CA1134539A - Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains - Google Patents
Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechainsInfo
- Publication number
- CA1134539A CA1134539A CA000361551A CA361551A CA1134539A CA 1134539 A CA1134539 A CA 1134539A CA 000361551 A CA000361551 A CA 000361551A CA 361551 A CA361551 A CA 361551A CA 1134539 A CA1134539 A CA 1134539A
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- CA
- Canada
- Prior art keywords
- carbon atoms
- equal
- group
- hydrocarbon
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Abstract
ABSTRACT
A hydrolytically stable, biologically inert, transparent, hydrophilic, contact lens comprising a polysiloxane containing hydrophilic sidechains is disclosed.
A hydrolytically stable, biologically inert, transparent, hydrophilic, contact lens comprising a polysiloxane containing hydrophilic sidechains is disclosed.
Description
. BACKGROUND OF THE INV~NTION
FIELD OF THE INVENTION
This invention relates to a novel contact lens. These contact lenses are hydrolytically stable~ biolog.ically inert, transparent and hydrophilic. The contact lens are prepared from the polymerization o~ polysiloxane monomers containing hydrophilic sidechains which form polymers in a crossllnked network. The polymers and/or copolymers are hydrophilic, optically clear and colorless. The polymers and copolymers described herein can be usually employed for making "hard"
or "soft" contact lenses, lntraocular implants, as well as other prostheses, more particuiarly "soft" contact lenses which are hydrophilic.
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PRIOR ART STATEMENT
__ __ U.S. Patent 4~153g641 teaches contact lenses made from polymers and copolymers comprising poly(organosiloxane) polymers and copolymers formed by polymer~zing a poly(organo-siloxane) monomer ~ terminally bonded through divalenthydrocarbon groups to polymerized~ free radical polymerizably activated3 unsaturated groups forming a polymer in a cross linked network. Additionally, specific comonomers are dis-- closed which lnclude lower esters o~ acrylic and methacrylic acid, styryls and N-vinyl pyrrolidinone which may ~e copoly-merized with the above described poly(organosiloxane) monomer to for~ a copolymer. The instant invention preferred poly-siloxane monomers lnclude the same poly(organosiloxane) monomers described above. However, it was unexpectedly dis-covered that when siloxane monomers one of the preferredembddiments of which is described above, have attached thereto hydrophillc sidechains, then the polysiloxanes become hydro-philic. The polymers are then extremely suitable for making hydrophilic, soft contact lenses. It is generally known in the siloxane art that siloxanes are hydrophobic. There are a few instances where the art teaches hydrophilic polysiloxanes.
U.S. Patent 4~136,250 teaches, in pertinenk part, a water absorbing polysiloxane which may be used to make soft contact lenses which is obtained by coploymerizing the follow-in~ 5iloxane monomer:
i2 r R2 HR3C - C - X ~ Y Rl -Y - X - C = CHR~
~ 1 or 2 in which Rl can be ~3 ,c~3 R6- ~ Si - O- ~ Si - O - R
x C~3 6 ._~ ~
with a variety of hydrophilic monomers including acr~lic acid.
The abo~e silo~ane monomers can be reduced to a forrnula similar to but yet critically different from the instant polyorgano-siloxane monomers. From the pertinent teachings o~ U.S. patent 4,136,250 the following siloxane monomer may be derived:
1 3 ll ~ E 1 ~3 1 e IH3 H2C = C C o ~CH2~ Li - ~ 9l _ O ~CH2~ O - C - C = CH2 The oxygen atom in the monomer backbone with the arrow pointing to it is present in the '250 formula but not present in the instant polyorganosiloxane monomers. This oxygen atom~
presents several problems. This particular oxygen atom, because of i~s placement between the silicone and carbon atoms, is subject to hydrolysis and alcoholysis. Furthermore, the material disclosed in '250 is unstable at room temperature when in water. This stability is important, if this material is to be used for biomedical devices, such as contact lenses, since these types of devices come in constant contact with water and are also usually heated in water in order to dis infect them. If, during heating, the contact lens loses its shape, then it loses its optics. This means that the material taught in '250 would be undesirable for use in certain medical devices including contact lenses. The instant polyorganosiloxane monomers result in copolymers which have superior hydrolytic stability since there is no Si-O-C linkage.
Also to be considered are the examples of '250. Only in these examples of '250 are there specific monomers dis-closed without this undesirable Si-O-C linkage. HOwe~er, these specific monomers have undesirable urethane linkages or couplings which present structures which are even more different from the instant monomers. The urethane linkage, i.e., R - N - C -- O is as mentioned, a]so undesirable for use in medical devices, particularly contact lenses. However, in addition, the instant polyorganosiloxane monomers have no urethane linkages.
U.S. patent 4,138,382 teaches, in pertinent part, a hydrophilic, water swellable, crosslinked copolymer gel. This eopolymer gel is a hydrogel, such as N-vinylpyrrolidone erosslinked with a low molecular weight siloxane. The siloxane component is a very small constituent and is present for the purpose of crosslinking. The siloxane is not present in amounts more than about 2 percent by weight. This does not teach a hydrophilic siloxane, much less a contact lens made therefrom.
Dutch patent 7,704,136 published 18 October, 1977 teaches, , in pertinent part, a wettable siloxane material for use in making contact lenses. The Dutch patent refers to some of tne~
monomers which may be reacted with the polysiloxanes taught in '136 which are esters of glycidyl al.cohol and esters of certain acids including acrylic acid and methacrylic acid.
' 136 also suggests the use of specific anhydrides such as maleic anhydride. This 3utch reference ' 136 does not dis-~ close the instant polysiloxanes.
U.S. patent 3,808,178 discloses, in pertinent part, a polymeric material containing a polymethacrylate backbone with relatively short poly(organosiloxane) ester sidechains on the baekbone polymer. There is no crosslinking involved in '178 since the monomers disclosed in '178 are monofunctional, i.e.~ have only one functional group on each monomer. ln order to get crosslinking in ' 178 it is taught at column 5 of ' 178 that different monomers must oe added for crosslinking ~ ~.3~
which have ~ore than one functionality. Not only does ' L78 not teach the polysiloxane monomers used in the instant invention but ' 178 does not teach making the instant hydrophilic siloxane for use as hydrophilic contact lens.
U.S. patent, 33228,741 teaches, in pertinent part, a silicone contact lens in general. However, nowhere are any sidechains disclosed. Neither does '741 teach a hydrophilic siloxane contact lens as in the lnstant invention.
U.S. patent 3,700,573 teaches, in pertinent part, radiation grafting of hydrophilic polymers to polysiloxanes.
These siloxanes are then used in making contact lens. One sXilled in the art would be taught that something must be done to polyslloxanes ln order to make them hydrophilic.
~ As taught in '573, sllicones are inherently hydrophobic. ~
:~ - 15 In ' 573 the surface is treated in order to make this material : : :: ~ :
hydrophilic. Surface treatment is not as effectlve as the ~;
; ~ instant lnvention for making a siloxane hydrophilic. Surface treatment only affects the surface on the contact lens.
This surface can be removed, for example, by abrasion.
However, in the instant invention the hydrophilic siloxane material is hydrophilic throughout.
U.S.~patent 3,249,586 teaches, ln pertinent part, a~
siloxane monomer with a cyclic amide sidechain. In ' 586 thls monomeric material is prepared by hydrosilation. The 25 siloxane monomeric material of ' 586 can be polymerized and used as thermoplasti.c~ elastomeric and resinous material.
Nowhere does ' 586 teach that the final material is hydrophilic or that it can be used to make contact lens.
U.S. patent 3,317,450 teaches, in pertinent part, a polyalcohol sidechain slloxane monomer, ' 460 teaches making copolymers with di~ and trifunctional siloxane monomers. These monomeric materials are useful as curing agents for isocyanate prepolymers, for preparing polyurethane rubbers and for making ~arnishes. This reference does not remotely teaeh eontaet lens, much less, hydrophilic siloxane contact, lens as in the instant invention.
u.s. 3,703,486 teaches, in pertinent part, a siloxane monomer which contains a sideehain whieh has a solubilizing group attaehed. The solubilizing group may be either COOH, ; carboxylic acid, earboxylic aeid ester, amide, amine, eyano, thio, hydroearbon or a ketone. This rnonomerie material is ploymerized and used as a polymer ~or foam. In the instant invention, the group sidechains tend to lnerease the solubilizing factors. '486 is using solubillzing sideehains but for a completely dlfferent reason. ' 486 is using a completely different type of s~ystem than in the instant invention.
U.S. patent 3,729,444 teaches, in perteinent part, a carboxylic acld~sidechain siloxane monomer, copolymerized with difunctional siloxanes. This material ls used to enhanee paper's resistance to wetting. '444 does not remotely teaeh or suggest maklng, eontaet lenses, much less, hydrophilic siloxane eontaet lenses.
U.S. patent 3,586,699 teaches, in pertinent part, an imido si.deehain siloxane monomer. This imido group is a nitrogen whieh has two carbonyl groups attached to it In ~699, it is taught that a cyclic siloxane eompound eontaining one of these sidechains can be polymerized to form a high molecular weight polymer. This material is cured to form an elastomer. Nowhere does ' 699 remotely teach or suggest making contaet lenses, mueh less, hydrophilie siloxane eontaet lenses.
U.S. patent 3,716,518 teaches, in pertinent part, diethy-lene glycol allyl methyldisiloxane sidechain siloxane monomer.
This is one of the preferred monomers used in the instant invention. The sidechain is attached by hydrosilation. This monomeric material is not polymerized so no shaped bodies are '`3~
formed as in the instant invention where hydrophllic contact lens are formed from siloxane material which is surprlsingly hydrophilic.
U.S. patent 3,915,~33 teaches, in pertinent part, grafting, by the use of radiation, hydrophilic polymers onto polyme~hyl siloxane in order to make it bydrophilic. This material is then used to make contact lens. More specifically, '033 teaches using polydimethysiloxane and radiation grafting onto the surface of this material. This is a completely di~ferent :
process than taught in the instant invention.
U.S. patent Re. 25,727 teaches, in pertinent part, an ether sidechain siloxane monomer which is made by hydrosilation.
The ether sidechain silicone monomer is used as a surfactant.
The slloxane~monomer;is end-capped with trimethylsllo groups~
Thls same monomer i~s polymerized in the instant~invention~
to~form hydrophilic contact lens. However '727 does no-t~
polymerize thé monomeric material disclosed therein to ~form shaped bodies~, much~less, hydrophilic siloxane contact lenses :-since the material~disclosed in '727 is for use as a surfactant and one does not polymerize a surfactant into a solid material if used as a~surfactant.
U.S. patent~2,723,g87 teaches, in pertlnent part, a car-; boxylate, i.e~.~, a~earboxylic acid sidechain siloxane monomer.
The carboxylic sidechains are reacted with either an alcohol ~25 or an~amine to make a~poLyamide or polyester. This lS an intermediate mater~ial. It is taught in '987 that these intermediates~ l.e.~, monomers, are particularly useful in the preparation of siloxane modi~ied alkyd resins. '987~does not teach that the material, i.e.~ either the ester sidechain ::- : :
siloxane monomers can be cured to form shaped bodies. Also, in '987 the curing is done through the carboxylate groups by combining this with the polyalcohol or polyamine. This type of curing is not done in the instant in~ention.
~ 7--: - 'i : :
U.S. patent 2,762,823, in pertinent part, teaches an amino sidechain siloxane monomer. '823 describes the preparation of amino sidechain siloxane monomers. These amino sidechain siloxane monomers are not cured to form shaped bodies. Also, the amino functionality is used to react with polyacids to form polyamide type resins. These monomeric materials dis-closed in '823 are cured through the amine groups by reacting with a diacid chloride, etc. This type of reaction is not used in the instant invention. In '823 the sidechain siloxane monomers are intermediates used to form further end products not relevant to the instant invention.
U.S. patent 2,770,631 teaches, in pertinent part, hydroxy ester substituted siloxane monomers. '631 teaches that a carboxyl group can be attached to the silicone via a CH2 radical. '631 does not teach any sidechains longer than a CH2. However~ the instant invention also utilizes short sidechains. However, the longer sidechains would be more hydrolitically stable. It is known that hydroxy groups and ester groups that are alpha to silicone are much more stable compounds than the beta substituted siloxanes.
Also, '631 does teach an ester that has a hydroxy group in the sidechains. However, these monomers are used in '631 as ~ ~ .
~ lubricants, sunscreen agents and these monomers, it is taught ~: :
in '631, are soluble in silicone fluids which make them valuable as antioxidants and stabilizers for greases, etc.
; ~ However, nowhere does '631 teach that the hydroxy ester sidechaîn siloxane monomers are cured to form shaped bodies, much less hydrophilic silo~ane contact lenses. '631 would not want a polymerized material since these materials, i.e., monomers, are used in lubricants and should remain fluid.
However, as mentioned, '631 does prepare an hydroxy ester sidechain siloxane monomer, a vinyl sidechain siloxane monomer, a phenyl sidechain siloxane monomer but, as mentioned, '631 does not cure these monomers into shaped bodies, much less polymerize these monomers to form hydrophilic siloxane contact lens.
U.S. patent 2,770 ~ 632 teaches, in pertinent part, an ester aci.d sidechain siloxane monomer. The only length of 5 the al~yl attaching the ester to the silicone is a CH2 group.
' 632 does not teach longer sidechains. However~ these short sidechains are used on the monomers taught in the instant invention. Most importantly, however, these monomers are used in ' 632 as lubricants, sunscreens~ emulsifying agents, etc. Also, ' 632 makes the metal salts of the carboxylic acid which are utilized in the instant invention as monomeric material but ' 632 uses this monomeric material simply as an emulsifying agent. In ' 632 these monomers should not be polymerized due to the end uses taught in ' 632.
U.S. patent 3,458,553 teaches, in pertinent part, a paraffinsiloxane monomer which contains either an amide or a cyano sidechain. '553 teaches the~instant monomeric inter-mediates used herein. Ho~ever, nowhere does ' 553 teach or suggest the instant hydrophilic siloxane polymeric materials or contact lens made therefrom.
U.S. patent 2,819,245 teaches, in pertinent part, hydroxy sidechain siloxane monomers, amino sidechain siloxane monomers, carboxylic acid sldechain siloxane monomers, amide amlno side-chain siloxane monomers, amide amino carboxylate sidechain : ~
siloxane monomersj all of which are utilized as monomeric material in the lnstant invention. However, ' 245 does not teach that these monomeric materials can be cured since these materials are used to react with epoxides. ' 245 uses the functionality present to react with an epoxy resin which `~ 30 is then cured. This reaction is irrelevant to the instant invention. Furthermore, '245 does not remotely teach contac lens or shaped bodies.
~ e U.S. patent 2,823,195 teaches, in pertin~nt part, reacting a carboxyllc acid sidechain siloxane monomer with a diamine to form a polyamide. The siloxane monomer is being used as an intermediate. The siloxane, as mentioned, is reacted with a diamino or a triamino compound to make a polyamide. This reaction is not used in the instant in-vention. Neither does '197 teach a shaped boyd, mueh less a contact lens.
U.S. patent 2,838,423 teaches, in pertinent partj an amide sidechain siloxane monomer which is then reaeted with formaldehyde and pyridine to make a pyridinium salt. This monomer is utilized in the instant invention. However, in ' 423 the material is used as a water repellent for fabrics.
The salt sidechain siloxane monomer is used in '423 in a~
relatively low pereentage in order to make the slloxane adhere to the fabric. '423 is actuallD teaching using the polar sidechain as a binding agent for the fabrie since 1423 is : :
mak1ng the fabric hydrophobic rather than hydrophiIic.
Therefor, ' 423 is using a salt ~or hydrophobic purposes.
T e instant invention is using this sideehain si~oxane monomer in order to make the po]ymerized crosslinked siloxane eontaet lens hydrophilie.
U.S. patent 2,838,515 teaehes, in pertinent p~rt, a ~ pyridine end-capped~siloxane monomer. However, ' 515 does :: 25 not teach attaching a hydrophilic sidechain to this monomer.
Therefore, ' 515 teaehes one of the backbones used in the instant invention without the sidechains. ' 515 teaches that these materials are~ useful as solvents and as lubricants.
U.S. patent 2,842,517 teaches, in pertinent part, an alcohol sidechain siloxane monomer or a carboxyllc acid side-chain siloxane monomer. These may be reacted with an unsaturated " ~
diacid to make polyester resins. '517 does teach some of the siloxane monomers utilized in the instant invention. How-ever, '517 uses a carboxylic group or the alcohol group as a curing functionality. This reaction :Ls not utilized in the instant invention. Furthermore, ' 5:L7 does not make shaped bodies with the siloxanes per se, but reacts these siloxanes with other materials, not uitlized in the instant invention, in order to make shaped bodies. Therefore, the end product is not the instant materials nor are the shaped bodies, contact lens, much less, hydrophilic siloxane contact lens as in the instant invention.
U.S. patent 2,855,381 teaches, in pertlnent part, amide sidechain siloxanes monomers. '381 cures these siloxanes monomers to ~orm rubber. '381 incorporates~ the amide side-chains into the siloxane monomers to make the sillcone rubbermore resistant to attack by hydrocarbon solvents and oils.
'38I cures these slloxanes with benzoyl peroxides which is~
one of the preferred types of cures used in the instant invention. However, ' 381 is only teaching how to make the silicone rubbers more resistant to oils. ' 381 does not teach that this makes the silicone rubber hydrophilic.
Neither does ' 381 teach hydrophilic contact lenses.
~; U.S0 patent 2,894,967 teaches, in pertinent part, ~
carboxylates and alcohol sidechain siloxane monomers. '967 teaches using these monomers as chromium complexing agents.
~hese materials are not used to form shaped bodies, much less9 hydrophilic slloxane contact lenses.
U.S. patent 2,924,587, U.S. patent 2,924,588 and U.S.
patent 2,925,402 teach, in pertinent part, either alcohol 3G sideGhain siloxane monomers or carboxyl sidechain siloxane monomers, both of which are utilized in the instant invention as monomeric material. However, nowhere do these re~erences -~2~
teach 'nydrophilic contact lenses, much less, hydrophilic siloxane contact lenses. In ' 402 the material is cured with diacids, diisocyanates, diols, diamines, etc. These re-actions are not used in the instant invention. l588 teaches 5 alcohol sidechain silo~ane monomers. '588 teaches that functional siloxane monomers can be used to react with polyfunctional organic compounds such as dicarboxylic acids or diisocyanates to give a resinous material. '588 ~;
does not teach that;one can take these monomeric materlals per se and cure them into useful shaped bodies. These monomeric materials must be reacted with other materials in order to form shaped bodies. These reactions are much different than in the instant application.
U.S. patent 3,057,901 teaches, in pertinent part, a polyether alcohol sidechain siloxane monomer. '901 teaches~
that this monomeric si~loxane may~be used as a surfactant.
U.S. patent 37215,643, in~pertinent part, teaches a~
; sulphate salt sidechain siloxane monomer. ~ 643 teaches . ~ ~ ~ : : : : :
using this monomerlc~material as a solvent.
;~ ~20 U.S. patent 3,215,718 teaches, in pertinent part, , sulphonic acid sidechain siloxane monomers. It is taught in ' 718 that these materials are useful in making textiles water ~; ~ repellent.
D.S. patent 3,a46,048 teaches, in pertinent part, a polyether sidechain siloxane monomer. The polyether side-- ~ chain siloxane monomer is endcapped with a hydroxyl group and this is one of the types of sidechains used~wlth the~ monomers :
in~the instant invention. However, ~o48 teaches using the hydroxyl group for curing with a polyurethane. This is not pertinent to the instant invention.
U.S. patent 3,317,577 ~eaches, in pertinent part, a polyamino sidechain siloxane monomer. '577 teaches that this material may be used as a surfactant. The monomers disclosed in ' 577 are not polymerized, since the end use is for use as a surfactant.
. : . . - .. - ~ . ~: .
- ~3-U.S. 3,328,449 teaches, in pertinent part, a salt sidechaln siloxane monomer. '449 teaches that this material may be used as detergents, lon exchange resins, wettin~ agents, antistatlc agents ~or synthetic fibers and polymeriæat~on catalysts for siloxanes. Nothing is taught in '44g which would remotely teach or suggest the instant hydrophilic siloxane cont~ct lenses.
U.S. 3,33~,943 teaches, in pertinent part9 an amino side-chain and carboxyl sidechain copolymer which is then formed into an internal salt. '943 teaches that this material can be used as a protective coating for metals, etc. Nowhere does '943 remotely teach contact lens, much less, hydrophilic siloxane contact lens.
U.S. 3,355,425 teaches, ln pertlnent part, a pyridine side-chain siloxane monomer. '425 teaches using these monomeric materials for dyeing fabrics. Notthing is taught or suggested in '425 concerning contact lenses, much less, hydrophilic siloxane contact lenses.
U.S. 3,3551455 teaches, in pertinent part, the same sort of composition as in U.S. 3,555,~425.
U.S. 3,398,104 and 3,402,192 teach, in pertinent part, ;
ether sidechaln siloxane monomers. The degree of polymerization of the ether sidechain is from 25 to 100. Neither '104 nor '192 ~ ~ remotely teach or suggest contact lenses, much less, hydrophilic ; 25 siloxane contact lenses, as in the instant invention.
U.S. 3,440,261 teaches, in pertinent part, an amino amide sidechain siloxane monomer. This monomeric material is used as textile treating agent to improve the dyeability of the textile and as crease-proofing and water repelling agents for textiles. Nowhere does '261 teach or suggest contact lenses, much less, hydrophilic siloxane contact lenses.
U.S. 3,460,981 teaches, in pertlnent par~ a diamino sidechain siloxane mon~mer which is copolymerized with a ~ .
difunct~onal siloxane. This material is be~ng used to prevent ice adherence. Nowhere does '981 remotely suggest contact :, . .
' . .
~ `
~.~3~
.
i lenses, much less, the instar.t hydrophilic siloxane contact lenses.
U.S. 3,508,959 teaches, in pertinent part, a siloxane monomer which contalns a sidechain which has sulfur, oxygen, ester, amide, amine, sulfonomide and multi-amino sidechains that are attaching the silicone to a sulfate salt. These monomeric materials are being used as surfactants.
Also, it is taught that these monomeric materials can be used as emulsifying agents. Nowhere is there suggested in '959 contact lenses,~much less~ hydrophilic siloxane con-~tact lenses.
U.S. patent 3,512,915 teaches, in pertinent part, a diamino sidechain siloxane monomer used for textile dyeing.
'915 does not remotely teach or suggest making contact lenses.
V.S. patent 3,518,288 teaches, in pertlnent part, a polyether sidechain siloxane monomer which is used~as a surfactant. ~'288 does not remotely teach or sugg~est~making contact lenses.
20 ~ ~ U.S. patent 3,560,543 teaches, in pertinent part~ a polyamino sidechain siloxane mono~er. '543 does not remotely teach or suggest making contact lenses. ;~
!: U.S. patent 3,560,544 teaches, in pertinent part~ a trimethylsilyl~endcapped siloxane monomer which has a polyether sidechain attached. '544 does not remotely teach i or suggest making contact lenses.
U.S. patent 3,627,806 teaches, ln pertinent part~ a mono or dicarboxylate sldecha~n slloxane monomer. This material is used as adhesion promoters for silicon rubber.
'806 does not remotely teach or suggest making contact lenses.
U.S. patent 3,7349763 and U.S. patent 3,843,52~ teach~
in per~inent par~, siloxane monomers which contain quaternary ~3c~
.~ . ' ' :
ammonium sldechains. These monomerlc materials are being used as surfactants and lubricants. '523 does not remotely teach or suggest making contact lenses.
U.S. 3,846,329 teachesJ in pertinent part, using a polyether sidechain siloxane monomer as a ~oam controller.
'329 does not remotely teach or suggest making contact lenses.
U.S. 2,971,864 teaches, in pertlnent part, a diamino sidecha~n siloxane monomer. This monomeric material is used ~n latexes. '864 does not remotely teach or suggest making contact lenses.
U.S. 3,884,860 teaches, in pertinent part, a carboxylic ; acld and sul~ide linkage sidechain siloxane monomers and co-polymers with difunctional siloxanes. ~hese materials are :
use~ul as resin~intermedlates in water-reducible coating ;
formulations. '860 does not remotely teach or suggest making , contact lenses.
U.S. 3,033,815 teaches, in pertlnent part, an amlno and cyano ester or amlde sidechain siloxane monomer. These materials are useful in making fibrous glass materials. '815 does not remotely teach or suggest maklng contact lenses.
U.S. patent 2~823,218 teaches~ ln pertinent part, hydrosilation~whlch ls one of the processes used herein to prepare the monomers disclosed herein. '218 does not remotely teach or suggest making contact lenses.
U.S. patent 2,928,858 teaches, in pertinent part~ an amlde carboxylate sidechain siloxane monomer. '858 teaches an amide linkage which has a craboxyllc acid and carboxylic acid chloride attached thereto. '858 does not remotely teach or suggest making contact lenses.
"3 ~ .S. patent 2 j~29~829 teaches, in pertinent part, an amide sidechain siloxane monomer. ' 829 does not remotely teach or suggest making contact lenses.
u.s. 2,989,559 teaches, in pertinent part, a ketone 5 sidechain siloxane monomer. ' 559 does not remotely teach or suggest making contact lenses.
U.S. patent 3,032,577 teaches, in pertinent part, an amino sidechain siloxane monomer whlch has an hydroxy alkyl ester attached to the amino group. ' 577 does not remotely teach or suggest making contact lenses.
U.S. patent 3,071,561 teaches, in pertinent part, a pyridine sidechain-siloxane monomer. ' 561 does not remotely teach or suggest making contact lenses.
U.S. patent 3,I52,161 teaches, in p~ertinent part~, a diamino siloxane monomer. ' 161 teaches that one of the amino : ~
groups has a hydroxy alkyl group attached. '161 does not remotely teach or suggest making contact lenses.
U.S. patent 3,598,785 teaches, in pertinent part, an amide endcapped silo~xane monomer which may be one o~ the 20 backbones o~ the)monomers used in the instant invent~ion.
~ However, '785 does not remotely teach oontact lenses, much ; ~ less, the instant hydrophilic~siloxane contact lenses.
U.S. patent 3,658,867 teaches, in pertinent part, a quaternary ammonium sidechain siloxane monomer. ~ 867 does not remotely teach or suggest making contact lenses.
U.S. patent 3,660,452 teaches, in pertinent part, an amino sulfate salt sidechain siloxane monomer~ '452 does not remotely teach or suggest rnaking contact lenses.
U.S.. patent 3,737,336 teaches, in pertinent part, an 30 amino sidechain siloxane monomer. In ' 336 it is taught that this amino endcapped siloxane monomer can be used as a hyd-rophobic coating. The instant invention uses this monomeric ~ material to make crossllnked polymeric hydrophilic slloxane ; contact lenses. '336 does not remotely teach or suggest making contact lenses.
U.S. patent 3~836~559 teaches, in pertinent part, quaternary a.~monium sidechain siloxane monomers. '559 does not remotely teach or suggest making contact lenses.
- U.S. patent 3,878,168 teaches, in pertinent part, amide, sulfonamlde and urea sidechain siloxane monomers. '168 does not remotely teach or suggest making contact lenses.
U.S. patent 4,018,723 teaches, in pertinent part, I morpholino modi~ied polyether sidechain polysiloxane monomers.
- '723 teaches that two different kinds of sidechains can be used. '723 uses a polyether to obtain certain ~oam properties ~ . ~
` . and then uses a poly urethane sidechain. Then~the morpholi~e group, which has an oxygen and nitrogen in a 6-membered ring, .
~ls~used to give a material used a a fire retardant. Also, these monomeric materials are being used in '723 as sur~actants.
:
Nowhere does '723 remotely teach or suggest making contact lenses.
;~ 20 U.S. patent 4,049,674, U.S. patent 4,049,675 and U.S.
patent 4,o49,676 teach, ln pertinent part, sulfolanyl siloxane~
monomers made by hydrosilation. These monomerlc materials are used as sur~actants and as fire retardants. Nowhere does either '674, '675 or '676 remotely teach or suggest making : ~ ~ 25 contact lenses.
U.S. patent 3~2499586 teaches) in pertinent part, cyclic amide sidechain siloxane monomers made by hydrosilation.
'586 does not remotely teach or suggest making contact lenses.
U.S. patent 3,993,606 teaches, in pertinent part, carboxylate salt o~ an am~no siloxane monomer.
This material is an amino endcapped siloxane monomer. '606 does not remotely teac~ or suggest making contact lenses.
~ , ~
U.S. patent 2,838,423 teaches, in pertinent part, an amide sidechain siloxane monomer~ To the amide group is attached methlpyridine salt. '423 does not remotely tea^h or suggest making contact lenses.
U.S. patent 3,700,713 teaches, in pertinent part, an ether amide sidechain siloxane monomer made by hydrosilation.
1713 does not remotely teach or suggest making contact lenses.
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_~q SUMMARY OF THE INVENTION
The polysiloxanes contal.ning hydrophilic sidechains of the instant invention can be used to prepare contact lenses. However, the polymars and copolymers can also be 5 employed for other uses, such as, shaped articles ~or use in biomedical applications.
: The contact lens of the instant invention comprise a ~ polyslloxane monomer having the following formula~
Yl ~ 3~rlsl ~ r'lsl 10 ` ~ )}~~ S~_Sl'l : ~
whereln Yl and~Y2 equal the same~or dlfferent and;are~
selected from~the group conslsting of~a monovalent hydrocarbon :~ ~having from l to:20 carbon atoms and a halogenated monovalent : hydrocarbon having from 1 to 20 carbon atoms, : : X is selected from the group consisting o~ a hydroxyl : :
: radical, a monovalent hydrocarbon having from 1 to~20~oarbon ~atoms, halogenated monovalent hydrocarbon having from 1 to : 2~ carbon atoms, wherein R ls a monovalent hydrocarbon having from 1 to 20 carbon atomsj Rl is a monovalent hydrocarbon having from 1 to 20 carbon atoms, nl is an integer from zero to 1 and n2 is an integer ~rom 1 to 3, ~ ~ .
~.~$~
--~~ ~ ~--- N R2 wherein R2 and R3 are the same or different and are monovalent hydrocarbons having from 1 to 20 carbon atoms and n3 is an integear from zero to 1, R4 A ~
wherein R4 is a divalent hydrocarbon having from 1 to~l about 22 carbon atoms and A is a free radical polymerizably activated monovalent unsaturated group, ~ ;
a is at least 1, b 1s~ zero or at least 2, c is 1 if b is zero and c is zero if b is at least 2, d is at least 1, except when b is zero and a is l~;~then d is zero or gr~eater,~
:
e is at least l and f is zero or~greater, Zl through Z7 are the same or different and at leas~t one of Zl through Z7 is equal to-a hydrophilic sidechain, said Zl through Z7 are selected from the group consisting of~
a monovalent hydrocarbon having from l to 20 carbon atoms, a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms and~a hydrophilic sidechain, polymerized to ~¦ ~ 20 form a poly~er in a crosslinked network.
;:~ :: : :: : : :
; When there are more than~one Zl on the backbone of the polymsr, all of these Zl's maybe the same or different.
~ Also, this applies to Z2 through Z7. For example, the :~ ~ following formula is illustratlve of this:
~: o CH CH3 CIH3- CH3 C-N-~CH3)2 CH3 CH3 X- Si--~ O - Si--~CH2~-3 Si----O - Si -~CH2 - CH - CH2~-- Si - - O - Si - X
CH3 CH3 CH3_ CH3 CH3_ CH3 In order to easily locate the Z's, compare the above formula with the broad general formula dlsclosed herein. In the above formula Zl' Z2' Z5' Z6 and 7 q 3 Z4's equal hydrogen and there are 250 Z~'s equal to hydrogen and 50 Z3's equal to 0 - C - N --~CH3)2 The monomeric polysiloxane containing the hydrophlllc sidechain groups may be polymerized by several techniques~, e.g., condensation, hydrosilation and free radical poly-merization, all of which are taught in H.S. Kaufman andJ.J. Falcetta, Introduction To Polymer Science and 'rech-nology, Chapter 2, pp. 25-108, Wlley-Interscience Publication 1977.
Qs is well established, the oxygen transportabillty of polysiloxanes~ is substantially greater in comparison to conventional contac~t 1ens polymers, such as, Dolymethyl methacrylate ~PMMA) or polyhydroxyethylmethacrylate (PHEMA).
Not only is the oxygen transportabllity of the lnstant materlal much higher than the conventlonal contact lens
FIELD OF THE INVENTION
This invention relates to a novel contact lens. These contact lenses are hydrolytically stable~ biolog.ically inert, transparent and hydrophilic. The contact lens are prepared from the polymerization o~ polysiloxane monomers containing hydrophilic sidechains which form polymers in a crossllnked network. The polymers and/or copolymers are hydrophilic, optically clear and colorless. The polymers and copolymers described herein can be usually employed for making "hard"
or "soft" contact lenses, lntraocular implants, as well as other prostheses, more particuiarly "soft" contact lenses which are hydrophilic.
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PRIOR ART STATEMENT
__ __ U.S. Patent 4~153g641 teaches contact lenses made from polymers and copolymers comprising poly(organosiloxane) polymers and copolymers formed by polymer~zing a poly(organo-siloxane) monomer ~ terminally bonded through divalenthydrocarbon groups to polymerized~ free radical polymerizably activated3 unsaturated groups forming a polymer in a cross linked network. Additionally, specific comonomers are dis-- closed which lnclude lower esters o~ acrylic and methacrylic acid, styryls and N-vinyl pyrrolidinone which may ~e copoly-merized with the above described poly(organosiloxane) monomer to for~ a copolymer. The instant invention preferred poly-siloxane monomers lnclude the same poly(organosiloxane) monomers described above. However, it was unexpectedly dis-covered that when siloxane monomers one of the preferredembddiments of which is described above, have attached thereto hydrophillc sidechains, then the polysiloxanes become hydro-philic. The polymers are then extremely suitable for making hydrophilic, soft contact lenses. It is generally known in the siloxane art that siloxanes are hydrophobic. There are a few instances where the art teaches hydrophilic polysiloxanes.
U.S. Patent 4~136,250 teaches, in pertinenk part, a water absorbing polysiloxane which may be used to make soft contact lenses which is obtained by coploymerizing the follow-in~ 5iloxane monomer:
i2 r R2 HR3C - C - X ~ Y Rl -Y - X - C = CHR~
~ 1 or 2 in which Rl can be ~3 ,c~3 R6- ~ Si - O- ~ Si - O - R
x C~3 6 ._~ ~
with a variety of hydrophilic monomers including acr~lic acid.
The abo~e silo~ane monomers can be reduced to a forrnula similar to but yet critically different from the instant polyorgano-siloxane monomers. From the pertinent teachings o~ U.S. patent 4,136,250 the following siloxane monomer may be derived:
1 3 ll ~ E 1 ~3 1 e IH3 H2C = C C o ~CH2~ Li - ~ 9l _ O ~CH2~ O - C - C = CH2 The oxygen atom in the monomer backbone with the arrow pointing to it is present in the '250 formula but not present in the instant polyorganosiloxane monomers. This oxygen atom~
presents several problems. This particular oxygen atom, because of i~s placement between the silicone and carbon atoms, is subject to hydrolysis and alcoholysis. Furthermore, the material disclosed in '250 is unstable at room temperature when in water. This stability is important, if this material is to be used for biomedical devices, such as contact lenses, since these types of devices come in constant contact with water and are also usually heated in water in order to dis infect them. If, during heating, the contact lens loses its shape, then it loses its optics. This means that the material taught in '250 would be undesirable for use in certain medical devices including contact lenses. The instant polyorganosiloxane monomers result in copolymers which have superior hydrolytic stability since there is no Si-O-C linkage.
Also to be considered are the examples of '250. Only in these examples of '250 are there specific monomers dis-closed without this undesirable Si-O-C linkage. HOwe~er, these specific monomers have undesirable urethane linkages or couplings which present structures which are even more different from the instant monomers. The urethane linkage, i.e., R - N - C -- O is as mentioned, a]so undesirable for use in medical devices, particularly contact lenses. However, in addition, the instant polyorganosiloxane monomers have no urethane linkages.
U.S. patent 4,138,382 teaches, in pertinent part, a hydrophilic, water swellable, crosslinked copolymer gel. This eopolymer gel is a hydrogel, such as N-vinylpyrrolidone erosslinked with a low molecular weight siloxane. The siloxane component is a very small constituent and is present for the purpose of crosslinking. The siloxane is not present in amounts more than about 2 percent by weight. This does not teach a hydrophilic siloxane, much less a contact lens made therefrom.
Dutch patent 7,704,136 published 18 October, 1977 teaches, , in pertinent part, a wettable siloxane material for use in making contact lenses. The Dutch patent refers to some of tne~
monomers which may be reacted with the polysiloxanes taught in '136 which are esters of glycidyl al.cohol and esters of certain acids including acrylic acid and methacrylic acid.
' 136 also suggests the use of specific anhydrides such as maleic anhydride. This 3utch reference ' 136 does not dis-~ close the instant polysiloxanes.
U.S. patent 3,808,178 discloses, in pertinent part, a polymeric material containing a polymethacrylate backbone with relatively short poly(organosiloxane) ester sidechains on the baekbone polymer. There is no crosslinking involved in '178 since the monomers disclosed in '178 are monofunctional, i.e.~ have only one functional group on each monomer. ln order to get crosslinking in ' 178 it is taught at column 5 of ' 178 that different monomers must oe added for crosslinking ~ ~.3~
which have ~ore than one functionality. Not only does ' L78 not teach the polysiloxane monomers used in the instant invention but ' 178 does not teach making the instant hydrophilic siloxane for use as hydrophilic contact lens.
U.S. patent, 33228,741 teaches, in pertinent part, a silicone contact lens in general. However, nowhere are any sidechains disclosed. Neither does '741 teach a hydrophilic siloxane contact lens as in the lnstant invention.
U.S. patent 3,700,573 teaches, in pertinent part, radiation grafting of hydrophilic polymers to polysiloxanes.
These siloxanes are then used in making contact lens. One sXilled in the art would be taught that something must be done to polyslloxanes ln order to make them hydrophilic.
~ As taught in '573, sllicones are inherently hydrophobic. ~
:~ - 15 In ' 573 the surface is treated in order to make this material : : :: ~ :
hydrophilic. Surface treatment is not as effectlve as the ~;
; ~ instant lnvention for making a siloxane hydrophilic. Surface treatment only affects the surface on the contact lens.
This surface can be removed, for example, by abrasion.
However, in the instant invention the hydrophilic siloxane material is hydrophilic throughout.
U.S.~patent 3,249,586 teaches, ln pertinent part, a~
siloxane monomer with a cyclic amide sidechain. In ' 586 thls monomeric material is prepared by hydrosilation. The 25 siloxane monomeric material of ' 586 can be polymerized and used as thermoplasti.c~ elastomeric and resinous material.
Nowhere does ' 586 teach that the final material is hydrophilic or that it can be used to make contact lens.
U.S. patent 3,317,450 teaches, in pertinent part, a polyalcohol sidechain slloxane monomer, ' 460 teaches making copolymers with di~ and trifunctional siloxane monomers. These monomeric materials are useful as curing agents for isocyanate prepolymers, for preparing polyurethane rubbers and for making ~arnishes. This reference does not remotely teaeh eontaet lens, much less, hydrophilic siloxane contact, lens as in the instant invention.
u.s. 3,703,486 teaches, in pertinent part, a siloxane monomer which contains a sideehain whieh has a solubilizing group attaehed. The solubilizing group may be either COOH, ; carboxylic acid, earboxylic aeid ester, amide, amine, eyano, thio, hydroearbon or a ketone. This rnonomerie material is ploymerized and used as a polymer ~or foam. In the instant invention, the group sidechains tend to lnerease the solubilizing factors. '486 is using solubillzing sideehains but for a completely dlfferent reason. ' 486 is using a completely different type of s~ystem than in the instant invention.
U.S. patent 3,729,444 teaches, in perteinent part, a carboxylic acld~sidechain siloxane monomer, copolymerized with difunctional siloxanes. This material ls used to enhanee paper's resistance to wetting. '444 does not remotely teaeh or suggest maklng, eontaet lenses, much less, hydrophilic siloxane eontaet lenses.
U.S. patent 3,586,699 teaches, in pertinent part, an imido si.deehain siloxane monomer. This imido group is a nitrogen whieh has two carbonyl groups attached to it In ~699, it is taught that a cyclic siloxane eompound eontaining one of these sidechains can be polymerized to form a high molecular weight polymer. This material is cured to form an elastomer. Nowhere does ' 699 remotely teach or suggest making contaet lenses, mueh less, hydrophilie siloxane eontaet lenses.
U.S. patent 3,716,518 teaches, in pertinent part, diethy-lene glycol allyl methyldisiloxane sidechain siloxane monomer.
This is one of the preferred monomers used in the instant invention. The sidechain is attached by hydrosilation. This monomeric material is not polymerized so no shaped bodies are '`3~
formed as in the instant invention where hydrophllic contact lens are formed from siloxane material which is surprlsingly hydrophilic.
U.S. patent 3,915,~33 teaches, in pertinent part, grafting, by the use of radiation, hydrophilic polymers onto polyme~hyl siloxane in order to make it bydrophilic. This material is then used to make contact lens. More specifically, '033 teaches using polydimethysiloxane and radiation grafting onto the surface of this material. This is a completely di~ferent :
process than taught in the instant invention.
U.S. patent Re. 25,727 teaches, in pertinent part, an ether sidechain siloxane monomer which is made by hydrosilation.
The ether sidechain silicone monomer is used as a surfactant.
The slloxane~monomer;is end-capped with trimethylsllo groups~
Thls same monomer i~s polymerized in the instant~invention~
to~form hydrophilic contact lens. However '727 does no-t~
polymerize thé monomeric material disclosed therein to ~form shaped bodies~, much~less, hydrophilic siloxane contact lenses :-since the material~disclosed in '727 is for use as a surfactant and one does not polymerize a surfactant into a solid material if used as a~surfactant.
U.S. patent~2,723,g87 teaches, in pertlnent part, a car-; boxylate, i.e~.~, a~earboxylic acid sidechain siloxane monomer.
The carboxylic sidechains are reacted with either an alcohol ~25 or an~amine to make a~poLyamide or polyester. This lS an intermediate mater~ial. It is taught in '987 that these intermediates~ l.e.~, monomers, are particularly useful in the preparation of siloxane modi~ied alkyd resins. '987~does not teach that the material, i.e.~ either the ester sidechain ::- : :
siloxane monomers can be cured to form shaped bodies. Also, in '987 the curing is done through the carboxylate groups by combining this with the polyalcohol or polyamine. This type of curing is not done in the instant in~ention.
~ 7--: - 'i : :
U.S. patent 2,762,823, in pertinent part, teaches an amino sidechain siloxane monomer. '823 describes the preparation of amino sidechain siloxane monomers. These amino sidechain siloxane monomers are not cured to form shaped bodies. Also, the amino functionality is used to react with polyacids to form polyamide type resins. These monomeric materials dis-closed in '823 are cured through the amine groups by reacting with a diacid chloride, etc. This type of reaction is not used in the instant invention. In '823 the sidechain siloxane monomers are intermediates used to form further end products not relevant to the instant invention.
U.S. patent 2,770,631 teaches, in pertinent part, hydroxy ester substituted siloxane monomers. '631 teaches that a carboxyl group can be attached to the silicone via a CH2 radical. '631 does not teach any sidechains longer than a CH2. However~ the instant invention also utilizes short sidechains. However, the longer sidechains would be more hydrolitically stable. It is known that hydroxy groups and ester groups that are alpha to silicone are much more stable compounds than the beta substituted siloxanes.
Also, '631 does teach an ester that has a hydroxy group in the sidechains. However, these monomers are used in '631 as ~ ~ .
~ lubricants, sunscreen agents and these monomers, it is taught ~: :
in '631, are soluble in silicone fluids which make them valuable as antioxidants and stabilizers for greases, etc.
; ~ However, nowhere does '631 teach that the hydroxy ester sidechaîn siloxane monomers are cured to form shaped bodies, much less hydrophilic silo~ane contact lenses. '631 would not want a polymerized material since these materials, i.e., monomers, are used in lubricants and should remain fluid.
However, as mentioned, '631 does prepare an hydroxy ester sidechain siloxane monomer, a vinyl sidechain siloxane monomer, a phenyl sidechain siloxane monomer but, as mentioned, '631 does not cure these monomers into shaped bodies, much less polymerize these monomers to form hydrophilic siloxane contact lens.
U.S. patent 2,770 ~ 632 teaches, in pertinent part, an ester aci.d sidechain siloxane monomer. The only length of 5 the al~yl attaching the ester to the silicone is a CH2 group.
' 632 does not teach longer sidechains. However~ these short sidechains are used on the monomers taught in the instant invention. Most importantly, however, these monomers are used in ' 632 as lubricants, sunscreens~ emulsifying agents, etc. Also, ' 632 makes the metal salts of the carboxylic acid which are utilized in the instant invention as monomeric material but ' 632 uses this monomeric material simply as an emulsifying agent. In ' 632 these monomers should not be polymerized due to the end uses taught in ' 632.
U.S. patent 3,458,553 teaches, in pertinent part, a paraffinsiloxane monomer which contains either an amide or a cyano sidechain. '553 teaches the~instant monomeric inter-mediates used herein. Ho~ever, nowhere does ' 553 teach or suggest the instant hydrophilic siloxane polymeric materials or contact lens made therefrom.
U.S. patent 2,819,245 teaches, in pertinent part, hydroxy sidechain siloxane monomers, amino sidechain siloxane monomers, carboxylic acid sldechain siloxane monomers, amide amlno side-chain siloxane monomers, amide amino carboxylate sidechain : ~
siloxane monomersj all of which are utilized as monomeric material in the lnstant invention. However, ' 245 does not teach that these monomeric materials can be cured since these materials are used to react with epoxides. ' 245 uses the functionality present to react with an epoxy resin which `~ 30 is then cured. This reaction is irrelevant to the instant invention. Furthermore, '245 does not remotely teach contac lens or shaped bodies.
~ e U.S. patent 2,823,195 teaches, in pertin~nt part, reacting a carboxyllc acid sidechain siloxane monomer with a diamine to form a polyamide. The siloxane monomer is being used as an intermediate. The siloxane, as mentioned, is reacted with a diamino or a triamino compound to make a polyamide. This reaction is not used in the instant in-vention. Neither does '197 teach a shaped boyd, mueh less a contact lens.
U.S. patent 2,838,423 teaches, in pertinent partj an amide sidechain siloxane monomer which is then reaeted with formaldehyde and pyridine to make a pyridinium salt. This monomer is utilized in the instant invention. However, in ' 423 the material is used as a water repellent for fabrics.
The salt sidechain siloxane monomer is used in '423 in a~
relatively low pereentage in order to make the slloxane adhere to the fabric. '423 is actuallD teaching using the polar sidechain as a binding agent for the fabrie since 1423 is : :
mak1ng the fabric hydrophobic rather than hydrophiIic.
Therefor, ' 423 is using a salt ~or hydrophobic purposes.
T e instant invention is using this sideehain si~oxane monomer in order to make the po]ymerized crosslinked siloxane eontaet lens hydrophilie.
U.S. patent 2,838,515 teaehes, in pertinent p~rt, a ~ pyridine end-capped~siloxane monomer. However, ' 515 does :: 25 not teach attaching a hydrophilic sidechain to this monomer.
Therefore, ' 515 teaehes one of the backbones used in the instant invention without the sidechains. ' 515 teaches that these materials are~ useful as solvents and as lubricants.
U.S. patent 2,842,517 teaches, in pertinent part, an alcohol sidechain siloxane monomer or a carboxyllc acid side-chain siloxane monomer. These may be reacted with an unsaturated " ~
diacid to make polyester resins. '517 does teach some of the siloxane monomers utilized in the instant invention. How-ever, '517 uses a carboxylic group or the alcohol group as a curing functionality. This reaction :Ls not utilized in the instant invention. Furthermore, ' 5:L7 does not make shaped bodies with the siloxanes per se, but reacts these siloxanes with other materials, not uitlized in the instant invention, in order to make shaped bodies. Therefore, the end product is not the instant materials nor are the shaped bodies, contact lens, much less, hydrophilic siloxane contact lens as in the instant invention.
U.S. patent 2,855,381 teaches, in pertlnent part, amide sidechain siloxanes monomers. '381 cures these siloxanes monomers to ~orm rubber. '381 incorporates~ the amide side-chains into the siloxane monomers to make the sillcone rubbermore resistant to attack by hydrocarbon solvents and oils.
'38I cures these slloxanes with benzoyl peroxides which is~
one of the preferred types of cures used in the instant invention. However, ' 381 is only teaching how to make the silicone rubbers more resistant to oils. ' 381 does not teach that this makes the silicone rubber hydrophilic.
Neither does ' 381 teach hydrophilic contact lenses.
~; U.S0 patent 2,894,967 teaches, in pertinent part, ~
carboxylates and alcohol sidechain siloxane monomers. '967 teaches using these monomers as chromium complexing agents.
~hese materials are not used to form shaped bodies, much less9 hydrophilic slloxane contact lenses.
U.S. patent 2,924,587, U.S. patent 2,924,588 and U.S.
patent 2,925,402 teach, in pertinent part, either alcohol 3G sideGhain siloxane monomers or carboxyl sidechain siloxane monomers, both of which are utilized in the instant invention as monomeric material. However, nowhere do these re~erences -~2~
teach 'nydrophilic contact lenses, much less, hydrophilic siloxane contact lenses. In ' 402 the material is cured with diacids, diisocyanates, diols, diamines, etc. These re-actions are not used in the instant invention. l588 teaches 5 alcohol sidechain silo~ane monomers. '588 teaches that functional siloxane monomers can be used to react with polyfunctional organic compounds such as dicarboxylic acids or diisocyanates to give a resinous material. '588 ~;
does not teach that;one can take these monomeric materlals per se and cure them into useful shaped bodies. These monomeric materials must be reacted with other materials in order to form shaped bodies. These reactions are much different than in the instant application.
U.S. patent 3,057,901 teaches, in pertinent part, a polyether alcohol sidechain siloxane monomer. '901 teaches~
that this monomeric si~loxane may~be used as a surfactant.
U.S. patent 37215,643, in~pertinent part, teaches a~
; sulphate salt sidechain siloxane monomer. ~ 643 teaches . ~ ~ ~ : : : : :
using this monomerlc~material as a solvent.
;~ ~20 U.S. patent 3,215,718 teaches, in pertinent part, , sulphonic acid sidechain siloxane monomers. It is taught in ' 718 that these materials are useful in making textiles water ~; ~ repellent.
D.S. patent 3,a46,048 teaches, in pertinent part, a polyether sidechain siloxane monomer. The polyether side-- ~ chain siloxane monomer is endcapped with a hydroxyl group and this is one of the types of sidechains used~wlth the~ monomers :
in~the instant invention. However, ~o48 teaches using the hydroxyl group for curing with a polyurethane. This is not pertinent to the instant invention.
U.S. patent 3,317,577 ~eaches, in pertinent part, a polyamino sidechain siloxane monomer. '577 teaches that this material may be used as a surfactant. The monomers disclosed in ' 577 are not polymerized, since the end use is for use as a surfactant.
. : . . - .. - ~ . ~: .
- ~3-U.S. 3,328,449 teaches, in pertinent part, a salt sidechaln siloxane monomer. '449 teaches that this material may be used as detergents, lon exchange resins, wettin~ agents, antistatlc agents ~or synthetic fibers and polymeriæat~on catalysts for siloxanes. Nothing is taught in '44g which would remotely teach or suggest the instant hydrophilic siloxane cont~ct lenses.
U.S. 3,33~,943 teaches, in pertinent part9 an amino side-chain and carboxyl sidechain copolymer which is then formed into an internal salt. '943 teaches that this material can be used as a protective coating for metals, etc. Nowhere does '943 remotely teach contact lens, much less, hydrophilic siloxane contact lens.
U.S. 3,355,425 teaches, ln pertlnent part, a pyridine side-chain siloxane monomer. '425 teaches using these monomeric materials for dyeing fabrics. Notthing is taught or suggested in '425 concerning contact lenses, much less, hydrophilic siloxane contact lenses.
U.S. 3,3551455 teaches, in pertinent part, the same sort of composition as in U.S. 3,555,~425.
U.S. 3,398,104 and 3,402,192 teach, in pertinent part, ;
ether sidechaln siloxane monomers. The degree of polymerization of the ether sidechain is from 25 to 100. Neither '104 nor '192 ~ ~ remotely teach or suggest contact lenses, much less, hydrophilic ; 25 siloxane contact lenses, as in the instant invention.
U.S. 3,440,261 teaches, in pertinent part, an amino amide sidechain siloxane monomer. This monomeric material is used as textile treating agent to improve the dyeability of the textile and as crease-proofing and water repelling agents for textiles. Nowhere does '261 teach or suggest contact lenses, much less, hydrophilic siloxane contact lenses.
U.S. 3,460,981 teaches, in pertlnent par~ a diamino sidechain siloxane mon~mer which is copolymerized with a ~ .
difunct~onal siloxane. This material is be~ng used to prevent ice adherence. Nowhere does '981 remotely suggest contact :, . .
' . .
~ `
~.~3~
.
i lenses, much less, the instar.t hydrophilic siloxane contact lenses.
U.S. 3,508,959 teaches, in pertinent part, a siloxane monomer which contalns a sidechain which has sulfur, oxygen, ester, amide, amine, sulfonomide and multi-amino sidechains that are attaching the silicone to a sulfate salt. These monomeric materials are being used as surfactants.
Also, it is taught that these monomeric materials can be used as emulsifying agents. Nowhere is there suggested in '959 contact lenses,~much less~ hydrophilic siloxane con-~tact lenses.
U.S. patent 3,512,915 teaches, in pertinent part, a diamino sidechain siloxane monomer used for textile dyeing.
'915 does not remotely teach or suggest making contact lenses.
V.S. patent 3,518,288 teaches, in pertlnent part, a polyether sidechain siloxane monomer which is used~as a surfactant. ~'288 does not remotely teach or sugg~est~making contact lenses.
20 ~ ~ U.S. patent 3,560,543 teaches, in pertinent part~ a polyamino sidechain siloxane mono~er. '543 does not remotely teach or suggest making contact lenses. ;~
!: U.S. patent 3,560,544 teaches, in pertinent part~ a trimethylsilyl~endcapped siloxane monomer which has a polyether sidechain attached. '544 does not remotely teach i or suggest making contact lenses.
U.S. patent 3,627,806 teaches, ln pertinent part~ a mono or dicarboxylate sldecha~n slloxane monomer. This material is used as adhesion promoters for silicon rubber.
'806 does not remotely teach or suggest making contact lenses.
U.S. patent 3,7349763 and U.S. patent 3,843,52~ teach~
in per~inent par~, siloxane monomers which contain quaternary ~3c~
.~ . ' ' :
ammonium sldechains. These monomerlc materials are being used as surfactants and lubricants. '523 does not remotely teach or suggest making contact lenses.
U.S. 3,846,329 teachesJ in pertinent part, using a polyether sidechain siloxane monomer as a ~oam controller.
'329 does not remotely teach or suggest making contact lenses.
U.S. 2,971,864 teaches, in pertlnent part, a diamino sidecha~n siloxane monomer. This monomeric material is used ~n latexes. '864 does not remotely teach or suggest making contact lenses.
U.S. 3,884,860 teaches, in pertinent part, a carboxylic ; acld and sul~ide linkage sidechain siloxane monomers and co-polymers with difunctional siloxanes. ~hese materials are :
use~ul as resin~intermedlates in water-reducible coating ;
formulations. '860 does not remotely teach or suggest making , contact lenses.
U.S. 3,033,815 teaches, in pertlnent part, an amlno and cyano ester or amlde sidechain siloxane monomer. These materials are useful in making fibrous glass materials. '815 does not remotely teach or suggest maklng contact lenses.
U.S. patent 2~823,218 teaches~ ln pertinent part, hydrosilation~whlch ls one of the processes used herein to prepare the monomers disclosed herein. '218 does not remotely teach or suggest making contact lenses.
U.S. patent 2,928,858 teaches, in pertinent part~ an amlde carboxylate sidechain siloxane monomer. '858 teaches an amide linkage which has a craboxyllc acid and carboxylic acid chloride attached thereto. '858 does not remotely teach or suggest making contact lenses.
"3 ~ .S. patent 2 j~29~829 teaches, in pertinent part, an amide sidechain siloxane monomer. ' 829 does not remotely teach or suggest making contact lenses.
u.s. 2,989,559 teaches, in pertinent part, a ketone 5 sidechain siloxane monomer. ' 559 does not remotely teach or suggest making contact lenses.
U.S. patent 3,032,577 teaches, in pertinent part, an amino sidechain siloxane monomer whlch has an hydroxy alkyl ester attached to the amino group. ' 577 does not remotely teach or suggest making contact lenses.
U.S. patent 3,071,561 teaches, in pertinent part, a pyridine sidechain-siloxane monomer. ' 561 does not remotely teach or suggest making contact lenses.
U.S. patent 3,I52,161 teaches, in p~ertinent part~, a diamino siloxane monomer. ' 161 teaches that one of the amino : ~
groups has a hydroxy alkyl group attached. '161 does not remotely teach or suggest making contact lenses.
U.S. patent 3,598,785 teaches, in pertinent part, an amide endcapped silo~xane monomer which may be one o~ the 20 backbones o~ the)monomers used in the instant invent~ion.
~ However, '785 does not remotely teach oontact lenses, much ; ~ less, the instant hydrophilic~siloxane contact lenses.
U.S. patent 3,658,867 teaches, in pertinent part, a quaternary ammonium sidechain siloxane monomer. ~ 867 does not remotely teach or suggest making contact lenses.
U.S. patent 3,660,452 teaches, in pertinent part, an amino sulfate salt sidechain siloxane monomer~ '452 does not remotely teach or suggest rnaking contact lenses.
U.S.. patent 3,737,336 teaches, in pertinent part, an 30 amino sidechain siloxane monomer. In ' 336 it is taught that this amino endcapped siloxane monomer can be used as a hyd-rophobic coating. The instant invention uses this monomeric ~ material to make crossllnked polymeric hydrophilic slloxane ; contact lenses. '336 does not remotely teach or suggest making contact lenses.
U.S. patent 3~836~559 teaches, in pertinent part, quaternary a.~monium sidechain siloxane monomers. '559 does not remotely teach or suggest making contact lenses.
- U.S. patent 3,878,168 teaches, in pertinent part, amide, sulfonamlde and urea sidechain siloxane monomers. '168 does not remotely teach or suggest making contact lenses.
U.S. patent 4,018,723 teaches, in pertinent part, I morpholino modi~ied polyether sidechain polysiloxane monomers.
- '723 teaches that two different kinds of sidechains can be used. '723 uses a polyether to obtain certain ~oam properties ~ . ~
` . and then uses a poly urethane sidechain. Then~the morpholi~e group, which has an oxygen and nitrogen in a 6-membered ring, .
~ls~used to give a material used a a fire retardant. Also, these monomeric materials are being used in '723 as sur~actants.
:
Nowhere does '723 remotely teach or suggest making contact lenses.
;~ 20 U.S. patent 4,049,674, U.S. patent 4,049,675 and U.S.
patent 4,o49,676 teach, ln pertinent part, sulfolanyl siloxane~
monomers made by hydrosilation. These monomerlc materials are used as sur~actants and as fire retardants. Nowhere does either '674, '675 or '676 remotely teach or suggest making : ~ ~ 25 contact lenses.
U.S. patent 3~2499586 teaches) in pertinent part, cyclic amide sidechain siloxane monomers made by hydrosilation.
'586 does not remotely teach or suggest making contact lenses.
U.S. patent 3,993,606 teaches, in pertinent part, carboxylate salt o~ an am~no siloxane monomer.
This material is an amino endcapped siloxane monomer. '606 does not remotely teac~ or suggest making contact lenses.
~ , ~
U.S. patent 2,838,423 teaches, in pertinent part, an amide sidechain siloxane monomer~ To the amide group is attached methlpyridine salt. '423 does not remotely tea^h or suggest making contact lenses.
U.S. patent 3,700,713 teaches, in pertinent part, an ether amide sidechain siloxane monomer made by hydrosilation.
1713 does not remotely teach or suggest making contact lenses.
:: :
:
' ~ ~
~: -:
:: :
: ~ , , ..
~3~V~
_~q SUMMARY OF THE INVENTION
The polysiloxanes contal.ning hydrophilic sidechains of the instant invention can be used to prepare contact lenses. However, the polymars and copolymers can also be 5 employed for other uses, such as, shaped articles ~or use in biomedical applications.
: The contact lens of the instant invention comprise a ~ polyslloxane monomer having the following formula~
Yl ~ 3~rlsl ~ r'lsl 10 ` ~ )}~~ S~_Sl'l : ~
whereln Yl and~Y2 equal the same~or dlfferent and;are~
selected from~the group conslsting of~a monovalent hydrocarbon :~ ~having from l to:20 carbon atoms and a halogenated monovalent : hydrocarbon having from 1 to 20 carbon atoms, : : X is selected from the group consisting o~ a hydroxyl : :
: radical, a monovalent hydrocarbon having from 1 to~20~oarbon ~atoms, halogenated monovalent hydrocarbon having from 1 to : 2~ carbon atoms, wherein R ls a monovalent hydrocarbon having from 1 to 20 carbon atomsj Rl is a monovalent hydrocarbon having from 1 to 20 carbon atoms, nl is an integer from zero to 1 and n2 is an integer ~rom 1 to 3, ~ ~ .
~.~$~
--~~ ~ ~--- N R2 wherein R2 and R3 are the same or different and are monovalent hydrocarbons having from 1 to 20 carbon atoms and n3 is an integear from zero to 1, R4 A ~
wherein R4 is a divalent hydrocarbon having from 1 to~l about 22 carbon atoms and A is a free radical polymerizably activated monovalent unsaturated group, ~ ;
a is at least 1, b 1s~ zero or at least 2, c is 1 if b is zero and c is zero if b is at least 2, d is at least 1, except when b is zero and a is l~;~then d is zero or gr~eater,~
:
e is at least l and f is zero or~greater, Zl through Z7 are the same or different and at leas~t one of Zl through Z7 is equal to-a hydrophilic sidechain, said Zl through Z7 are selected from the group consisting of~
a monovalent hydrocarbon having from l to 20 carbon atoms, a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms and~a hydrophilic sidechain, polymerized to ~¦ ~ 20 form a poly~er in a crosslinked network.
;:~ :: : :: : : :
; When there are more than~one Zl on the backbone of the polymsr, all of these Zl's maybe the same or different.
~ Also, this applies to Z2 through Z7. For example, the :~ ~ following formula is illustratlve of this:
~: o CH CH3 CIH3- CH3 C-N-~CH3)2 CH3 CH3 X- Si--~ O - Si--~CH2~-3 Si----O - Si -~CH2 - CH - CH2~-- Si - - O - Si - X
CH3 CH3 CH3_ CH3 CH3_ CH3 In order to easily locate the Z's, compare the above formula with the broad general formula dlsclosed herein. In the above formula Zl' Z2' Z5' Z6 and 7 q 3 Z4's equal hydrogen and there are 250 Z~'s equal to hydrogen and 50 Z3's equal to 0 - C - N --~CH3)2 The monomeric polysiloxane containing the hydrophlllc sidechain groups may be polymerized by several techniques~, e.g., condensation, hydrosilation and free radical poly-merization, all of which are taught in H.S. Kaufman andJ.J. Falcetta, Introduction To Polymer Science and 'rech-nology, Chapter 2, pp. 25-108, Wlley-Interscience Publication 1977.
Qs is well established, the oxygen transportabillty of polysiloxanes~ is substantially greater in comparison to conventional contac~t 1ens polymers, such as, Dolymethyl methacrylate ~PMMA) or polyhydroxyethylmethacrylate (PHEMA).
Not only is the oxygen transportabllity of the lnstant materlal much higher than the conventlonal contact lens
2~ polymer, but the instant material ls also hydrophilic. A
high percent of slloxane unlts ln the lnstant formula results in a product more capable of transporting oxygen as compared w1th a lower percentage of siloxane units. Ho~ever, it has been discovered that by the use o~ hydrophilic sidechains attached to these polysiloxanes that a polymer or copolymer may be obtained which is not only oxygen permeable but is hydrophilic. The instant polymers appear in the ~ormulas to be blocked copolymers. However, it is believed the instant polymers are random copolysiloxanes.
high percent of slloxane unlts ln the lnstant formula results in a product more capable of transporting oxygen as compared w1th a lower percentage of siloxane units. Ho~ever, it has been discovered that by the use o~ hydrophilic sidechains attached to these polysiloxanes that a polymer or copolymer may be obtained which is not only oxygen permeable but is hydrophilic. The instant polymers appear in the ~ormulas to be blocked copolymers. However, it is believed the instant polymers are random copolysiloxanes.
3~
DESCRIPTIO.~J OF PREFERR~D EMBODIMENTS
In accordance with one embodiment of this invention, contact lens may be fabricated which are hydrolytically stable, biologically inert, transparent and hydrophilic.
These contact lens.comprise a polysiloxane monomer having the following formula:
~ 33 ~ zl ~ 3 ~ z ~ yl Y 2 Z Z Z L~ Z Y 2 wherein Yl and Y2 equal the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, X is selected from the group consisting of a hydroxyl radical3 a monovalent hydrocarbon having from 1 to 20 carbon atoms, halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, ( ~ ) 3_n2~
_ O - Si ~ ( C ~ Rl) n2 ~ ' .. a.~, .
~ ,~
`, , : `
-~3 wherein R is a monovalent hydrocarbon having from l to 20 carbon atomsl Rl is a monovalent hydrocarbon having from l to 20 carbon atoms, nl is an integer from zero.to l and n2 is an integer from 1 to 3, ~ O ~ N - R2 T~
:
wherein R and R are the same or different and are monovalent hydrocarbons having from 1 to 20 carbon atoms and: ~ :
n3 is an integer from zero to 1, :
wherein R4 is a divalent hydrocarbon having from 1 ~
to about 22 carbon atoms and A is a free:~radical polymerizably : ~:
activated monovalent unsatura:ted...group~
a is at le:ast~l, b is zero or~at least 2, c is~;l if b : 15 is zero and c is zero if b ls at least 2, d is at lea~st l except when b is zero and a is l then d is zero or greater, e is at least 1 and f is zero or greater, Zl through~Z7 are the same or different and at~least : one~of Zl through Z7 is equal to a:hydrophilic:sidechain, ~ ~s~aid Zl through~Z:7 are selected from the group consisting:
of a monovalent hydrocarbon havlng from 1 to 20 carbon atoms, ~:~ a halogenated;monovalent hydrocarbon having from 1 to 20 : ~ carbon atoms and a hydrophilic sidechain with the following ~:~ formula selected from the group consisting of : :25 ~ R~
1 ) / I
- R5~ ~ ~ CH2 ~ CH ~ 0 - R7 : : ~ JnL~
wherein R5 is a divalent hydrocarbon having from l to lO
carbon atoms, R6 is selected from the group consisting of 3`~a .Y
methyl and hydrogen, R7 i.3 selected from the group consisting o~ hydrogen~ a monovalent hydrocarbon ha~ing from 1 to 10 o Il .
carbon atoms, - C - R8 wherein R8 is selected ~rom the group consisting o~ a monovalent hydrocarbon having from l to 10 carbon atoms and hydrogen) and n4 is at least 1, 2) - R9~ OH )n5 ~herein R9 is a hydrocarbon having from l to 20 carbon atoms and a valence of n5 + l, n5 is at least 1 and there cannot be an -OH
group on an aliphatic carbon atom beta to the Si atom, and no ~: carbon atom o~ Rg can have more than one~-OH group attached thereto, :
~ ~ t t ~t ) wherein Rlo ls a dlvalent hydrocarbon having ~rom l to lO
carbon atoms ? Rll is selected from the group consistlng o~ :
hydrogen and methyl and R12 is a hydrocarbon having from 2 to 20 carbon atoms and a valence o~ n8 + 1 and can have no ~ more than one oxygen atom attached to any one carbon atom,~
n6 is zero or greater, n7 ls an integer from zero to 1 and n8 lS at least l, ~
DESCRIPTIO.~J OF PREFERR~D EMBODIMENTS
In accordance with one embodiment of this invention, contact lens may be fabricated which are hydrolytically stable, biologically inert, transparent and hydrophilic.
These contact lens.comprise a polysiloxane monomer having the following formula:
~ 33 ~ zl ~ 3 ~ z ~ yl Y 2 Z Z Z L~ Z Y 2 wherein Yl and Y2 equal the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, X is selected from the group consisting of a hydroxyl radical3 a monovalent hydrocarbon having from 1 to 20 carbon atoms, halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, ( ~ ) 3_n2~
_ O - Si ~ ( C ~ Rl) n2 ~ ' .. a.~, .
~ ,~
`, , : `
-~3 wherein R is a monovalent hydrocarbon having from l to 20 carbon atomsl Rl is a monovalent hydrocarbon having from l to 20 carbon atoms, nl is an integer from zero.to l and n2 is an integer from 1 to 3, ~ O ~ N - R2 T~
:
wherein R and R are the same or different and are monovalent hydrocarbons having from 1 to 20 carbon atoms and: ~ :
n3 is an integer from zero to 1, :
wherein R4 is a divalent hydrocarbon having from 1 ~
to about 22 carbon atoms and A is a free:~radical polymerizably : ~:
activated monovalent unsatura:ted...group~
a is at le:ast~l, b is zero or~at least 2, c is~;l if b : 15 is zero and c is zero if b ls at least 2, d is at lea~st l except when b is zero and a is l then d is zero or greater, e is at least 1 and f is zero or greater, Zl through~Z7 are the same or different and at~least : one~of Zl through Z7 is equal to a:hydrophilic:sidechain, ~ ~s~aid Zl through~Z:7 are selected from the group consisting:
of a monovalent hydrocarbon havlng from 1 to 20 carbon atoms, ~:~ a halogenated;monovalent hydrocarbon having from 1 to 20 : ~ carbon atoms and a hydrophilic sidechain with the following ~:~ formula selected from the group consisting of : :25 ~ R~
1 ) / I
- R5~ ~ ~ CH2 ~ CH ~ 0 - R7 : : ~ JnL~
wherein R5 is a divalent hydrocarbon having from l to lO
carbon atoms, R6 is selected from the group consisting of 3`~a .Y
methyl and hydrogen, R7 i.3 selected from the group consisting o~ hydrogen~ a monovalent hydrocarbon ha~ing from 1 to 10 o Il .
carbon atoms, - C - R8 wherein R8 is selected ~rom the group consisting o~ a monovalent hydrocarbon having from l to 10 carbon atoms and hydrogen) and n4 is at least 1, 2) - R9~ OH )n5 ~herein R9 is a hydrocarbon having from l to 20 carbon atoms and a valence of n5 + l, n5 is at least 1 and there cannot be an -OH
group on an aliphatic carbon atom beta to the Si atom, and no ~: carbon atom o~ Rg can have more than one~-OH group attached thereto, :
~ ~ t t ~t ) wherein Rlo ls a dlvalent hydrocarbon having ~rom l to lO
carbon atoms ? Rll is selected from the group consistlng o~ :
hydrogen and methyl and R12 is a hydrocarbon having from 2 to 20 carbon atoms and a valence o~ n8 + 1 and can have no ~ more than one oxygen atom attached to any one carbon atom,~
n6 is zero or greater, n7 ls an integer from zero to 1 and n8 lS at least l, ~
4) ~i RllS
- Rl3 - C - N Rl4 wherein Rl3 is a divalent hydrocarbon having ~rom 2 to lO
1~
carbon atoms and the -C- group is not attached to a carbon atom of Rl3 which is alpha to the Si atoms, Rl4 and Rl5 - 2 ~_ can be the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to lO carbon atoms, hydrogen,-CH2~-~ CH2 ~ 0H whereln n9 R~17 is an integer from l to 3 and-CH2~ CH2 ~ N - R16 :~. wherein Rl6 and Rl7 are the same or different and are selected from the~group consisting of hydrogen and a mono-valent hydrocarbon having from l to lO carbon atoms and nl:0 : is an integer from l to 5, -Rl8 - N - C R20 wherein R18 is a divalent hydrocarbon having from l to 20~
carbon atoms and R19 and R20 are the same or dlfferent and are selected from the group consistlng of hydrogen and a~
: ~15 ~ monovalent hydrocarbon having from 1 to lO carbon atoms,~
;: :~ R21 R22 (O) nll wherein R2l is a divalent:or trivalent hydrocarbon ha~ing ~ from l to lO carbon atoms and S is not attached to R2l by an aliphatic carbon atom beta to the Si atoms, R2l may or may not be attached to R22 to form a ring which contains more than 3 carbon atoms and R22 is selected from the group : consisting of a hydrocarbon having from l to lO carbon : 25 atoms and 0~ ~ where M is selected from the group consisting ~ ~ :
of a monovalent metal ion and a quaternery ammonium ion, and nll is an integer from l to 2, - R23 ~ R24 ~) ' wherein R23 is a divalent hydrocarbon having from 3 to l0 carbon atoms and the ~ must be attached to a carbon atom of R23 which is at least 2 carbon atoms away from the Si atom, R24, R25 and R26 are the same or different and are monovalent hydrocarbons having from l to l0 carbon atoms, ~ is a monovalent anion selected from the group consisting of halides, R27 ~ CO ~ wherein Rz7 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from~
l to l0 carbon atoms and a halogenated monovalent hydrocarbon 10 having from l to I0 carbon atoms and R28 ~ S ~ wherein R28 is selected from the group consist1ng of a monovalent hydro-carbon having from l to l0 carbon atoms and a halogenated mono-valent hydrocarbon having from l to l0 carbon atoms, -.
- R29 --~ ~12R3 3l 13:~
wherein R29 lS a divalent hydrocarbon having from 1 to l0 ~
carbon atoms and nl2 is an integer from 0 to l and when nl2 ~ :
: : is l the oxygen cannot be attached to an aliphatic carbon atom in R29 which is beta to the Si atom, R30 is a divalent hydrocarbon having from l to l0 carbon atoms, R3l is a ~hydrocarbon hav1ng from 2 to 20 carbon atoms and a valence :: : : : : :: :
of nl3 + l and can:have no more than l oxygen atom attached to any one carbon:atom and nl3 is at least l, ~ ~ : 9) ~ O
32 ~ - C - R33 ~ OH ) wherein R32 1s a ~divalent hydrocarbon having from l to l0 : carbon atoms and the oxygen atom bonded to R32 cannot be attached to an a~liphatic carbon atom in R32 which is beta to : the Si atom, R33 is a hydrocarbon having from 2 to 20 carbon atoms and a vaIence of nl4 + l and can have no more than l : oxygen atom attached to any one carbon atom and nl4 is an integer of at least l, :' ` ,, ' :. ' ~ a7-.v 10) - R3 ~
wherein R34 is a divalent hydrocarbon having from 1 to 10 carbon atoms, 11) f ~3~ ~) wherein R35 is a divalent hydrocarbon having from 2 to 10 carbon atoms and nl5 is an integer from 1 to 10, 12) 0 ~ ~R3~
lo R36 c t ~ CH2 ~ CH t R38 wherein R36 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group is not attac~ed to a carbon atom alpha to the Si atom, R37 is selected from the group consisting of methyl and hydrogen, R38 is selected from the group consisting o~ hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and ~l wherein R39 is a monovalent hydrocarbon having ~rom 1 to 10 carbon atoms and nl6 is at least 1, 13) - R - N ~ R
wherein R40 is a divalent hydrocarbon having ~rom 1 to 10 carbon atoms, R41 and R42 can be the same or dif~erent and are selected from the group consisting o~ monovalent hydro--carbons having from 1 to 10 carbon atoms and ~ CH2 ~ OH
where nl7 is an integer from 2 to 4, 14) O
il O R45 ~:
wherein R43 is a divalent hydroca.rbon having from 1 to 10 carbon atoms and the S atom cannot be attached to a carbon atom ; of R43 which is alpha to the Si atom, R44 and R45 can be the same or different and are selected from the group con-sisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, :~ : . : :
153/ CH~ CH ~
R46 N \ ~ ~ :
~ ~ :
wherein R46 is a divalent hydrocarbon having from 1 to : 10 carbon atoms and nl8 is an integer from zero to 3, 16) : R48 - R~17 - C ~ H n 9 ~ Rhg - CH ~ N
ol wherein R47 and R48 are selected from the group con-sisting of hydrogen, divalent or monovalent hydrocarbon _~.q_ :
havin~ ~rom O to 10 carbon atoms and R49 is selected ~rom the group consisting of hydrogen, divalent or monovalent hydrocarbon having from 1 to 10 carbon atoms and only one o~ R47, R48 and R49 must be a divalent hydrocarbon and attached to the Si atom, R50 is selected from the group consistlng of hydrogen5 a mono-valent hydrocarbon having from 1 to 10 czrbon atoms and ~~ C~2 ~ OH where n20 is 2 to 4, and nl9 is an:interger from zero to 3, 17) e - R51 - C ~
wherein R51 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot:be attached to a carbon atom:of R51 alpha to the S1 atom and X2 ls a monovalent~
cation selected from the group consisting of monovalent ~ :
; ~ l53 metal catlons and R52 ~ N - R5~ wherein R52, R53, R54~and~R55 Rss :
: can be the same or different and selected from the group consisting of hydrogen and a monovalent hydrocarbon having from l to 10 carbon~atoms, and :
18) R ~ C - R5 ~ ~ 58 whereln R56 is~a:dlvalent hydrocarbon having from 1 to 10 carbon atoms and the carbonyl group cannot be attached to~
a oarbon atom of R56 which is alpha to the Si atom, R57 is a divalent hydrocarbon having from one to 10 carbon atoms, R58 is selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n21 is an integer from~zero to 10, polymerized to fo.rm a polymer ln a crosslinked network.
:
-3~
Preferably, the hydrophilic sidechains are one of ~ \ ,.
( CH2 ~ CH2 CH2 t CH3 n22 : ;;
wherein n22 is an integer from 2 to 3 -~ CH2 ~ CH ~ CH2 ' OH OH
;
:: : : : :
( CH2 ~ o ~ CH2 ~ CH - CH2 : OH OH
~ ~ :
~CH2 ~ C - N - R59 ~1 wherein R59 and R60 are the same or:dif~erent and are ~ :
selected from the group consisting o~ hydrogen, methyl and -~CH2 - CH2 - OH ~ ~ ;
~R~l : 15 -~CH2~-3~- N CH3 wherein R61 is selected from the group consisting of hydrogen and methyl~ :
O
CH2 ~ S - CH3 CH
'H2 ~ N - CH3 Cl~ ' : CH3 : O
11:
~CH2 ~ C ~ O ~CH2 ~ OH ) :
-$ ~ 3 ~3 O
~ CH2~ c tQ - CH2 CH2t ~ o CH3 Jn23 ::
wherein n23 is an integer from 2 to 3 ~ ', 2 ~
:~ : ~: : `
~-~ CH2 ~ OH
: 11 CH2 ~ le NH2 O
: ~ 10 ~t-~CH2 C - CH
( CH ~ CH - CH2 ~: 15 : CH~2 NH ~ ~
: ~ : : ~ : : ::
O
CH2 ~ C ~ , and:
~: 20 ~_CH2 ~ C--CH3 ~ ~
In a preferred embodiment of the instant invention, when the siloxane backbone is a poly (organo) siloxane the following is preferred.
PreEerably, ~ 1~ one of~- CH2 ~
CH=CH2 wherein n24 is an integer f`rom 0 to 2, CHaCH2 and - R62-~ wherein 62 -~ CH2~ 25 wherein n25 is an integer from 3 to 4 and Il , G is - O - C - CH2 wherein R63 is selected from the group consisting of hydrogen and methyl More preferably X is ~ CH2 ~ ~ C ;~C = CH2 whereln R64 is selected from the group consisting of hydrogen and methyl, most preferably R64 is methyl.
Preferably Yl is methyl and Y2 is phenyl. More preferably . Yl and Y2 are methyls.
15 ; ~ Preferably only.one of~Zl~ Z~, Z5 and Z6 is a hydr~ophi~ic sidechain and a is equal to 1 to about 1,000, b is equal to zero, c is equal to 1, d is equal to 1 to about l,OOO, e is~
equal to one and f lS equal to zero. The instant contact lens may be hard or soft.
More preferably only one of Zl~ Z2~ Z5 and Z6 is a hydrophilic ~sidechaln and a is equal to 10 to about 500, b is equal to zero, c is equal to one, d is equal to about 10 to about 500, e is equal to one and f is equal to zero.
The instant contact lens may be hard or soft.
Even more preferably when only one of Zl~ Z2~ Z5 and Z6 . .
is a hydrophilic sidechain and a is equal to about 75 to about 150, b is equal to zero, c is equal to one, d is equal to about 25 to about 50, e is equal to one and f is equal to zero, the instant contact lens is soft and flexible.
Most prePerabl~ when only one of Zl~ Z2~ Z5 and Z6 is a hydrophilic sidechaln and a is equal to about 75, b is equal to zero, c ls equal to one, d is equal to 25, e ~.s equal to one and f is equal to zero, the instant contact lens is soft and flexible.
ly Zl, Z2 and Z5 are methyls and mo~st pre-ferably Z6 is one of -~ CH2 ~ CH2 CH2 ~ CH3 wherein n26 is an integer from 2 to 3, CH2 ~ o _ CH2 - CH - CH
OH OH and 2 ~ ~ CH2 C - I - R66 wherein R~5 is~
selected from the group conslsting of methyl and hydrogen,~
R6~ is selected Prom the group consisting of methyl5 hydrogen and - CH2 - CH2 - OH.
In another preferred embodiment of the instant invention, ~when the siloxane backbone is a polyparaffinsiloxane, the following is preferred. When only one of Zl through i7 is a~hydrophillc~sidechain and a~may be equal to one, b is equal to about 2 to 4, c is equal to~zero, d is equal to~ore, e ~lS
equal to about 25 to 500 and f is equal to 5 to 500, the con-tact lens may be either hard or soft.
More preferably in this embodiment, only one of Zl ~; 25 through Z7 is a hydrophilic sldechain and a is equal to one, b is equal to about 2 ~o about 3, c is equal to zero, d is equal to one, e is equal to 25 to about 250 and f lS equal to about 10 to about 250, resulting in a soft and flexible contact lens.
- 3 g '~' ~ " :
~3 _3 ~
In this same embodiment, even more preferably one one f Zl through Z7 is a hydrophilic sidechain and a is equal ~
to one, b is equal to about 2 to about 3, d is equal to one, c is equal to zero, e is equal to from about 50 to about lO0 and f is equal to from about 10 to about lO0, resuIting in a soft and flexible contact lens.
In this same embodiment~ most preferably only one of Zl through Z7 is a hydrophilic sldechain and a is equal to , one, b is equal to from about 2 to about 3, c is equal to zero, d is equal~to one, e is equal to from about 50 to about 75 and f is equal to from about 10 to 75, resulting ;
in a soft and flexible contact lens.
In this same embodiment, most preferably Zl~ Z2~ Z5 :
Z6' Z7~ Yl and Y2 are equal to methyl and Z4 is eq~lal to hydrogen and at least one of Z3's in the methylene brldee is equal - C - N -~CH3)2 and~the other Z3's ln that bridgé
qual ~yd_og-n, and X eq~als -~ ^V2~ 0 - C - C - CH
When there are more than one Z on the backbone of the polymer, all of these Zl's maybe the same or different. Also 5 :
; this applies t~o ;Z2 through Z7. Por example, the following~
formuIa is illustratlve of this~
3 ~~ CH3~ CIH3 ~ I f - ~ H3)2 9 3 CH3 ;~
X - Si 0 li ~4CH2t-3 ll _ _~ o ~ Si -4CH2 - CH - CH2~---- Si ---0 ~ Si - X
3 CH3 CH3 CH3 CH~ C~3 ;o 5o In order to~easily locate the Z's, compare the above formula with the broad general formula disclosed hereln. In the above formula Zl~ Z2~ Z5~ Z6 and Z7 equal -CH3, all the Z4'8 equal hydrogen and there are 250 Z3's equal to hydro~en and 50 O
Z3's equal to - C - N -~CH3)2.
~ 3~ .,t,~
--3~-When X is a polymerizable group then the instant poly-siloxane monomers may be compolymerized with comonomers, such as, hydroxyethylmethacrylate (HEMA), methacrylates and acrylates, e.g., cyclohexylacrylate, methyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate and glycerine trimethacrylate, monoesters of acrylic or methacrylic acid and.an alcohol having an esterifiable hydroxy group and at least one additional hydroxy group, such as, 2-hydroxy ethyl methacrylate and 2,3-: dihydroxy propyl acrylate, acrylamide and methacrylamides,:
N-vinyl lactams, acrylonitrile and methacrylonitrile, derivatives of methacrylic acid, acrylic acid, itaconic acid and crotonic : acid, styryls, such as9 styrene, divinyl benzene, vinylethyl benzene, vinyltolune and allylic monomers, such as, diallyl diglycol dicarbonate, allylcyanide, allyl chloride, diallyl phthalate, allyl bromide, diallyl furmarate and diallyl carbonate and comonomers.
The followlng:are hydrophilic sidechains which are preferred.
: : ~ \ :~ ~
POLYETHERS ~ : R~ ~
1 ~ 1 R5 ~ O CH - CH t ~ R7 -~ fn4 wherein R5 is a divalent hydrocarbon having from 1 to 10 carbon : atoms, R6 i selected from the group consisting of methyl and hydrogen, R7 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms, O
1 1 :
~: - C~- R8 wherein R8 is selected from the group consisking of a monovalent hydrocarbon having from 1 to 10 carbon a.toms and hydrogen and n4 is at least 1.
The most preferred polyethers are 4,7,10-trioxaundecane 2 2 CH2 O - CH2 ~ CH2 - O - CH CH O C
and 4,7,10,13-tetraoxatetradecane -CH2 CH2-cH2-o-cH2-cH2-o-clI2-cH2-o-cH2~cp'2-o-cH3 :-`
~3C ~
POLYALGOHOLS
2) - R9 -4 OH~n wherein Rg is a hydrocarbon having from l to 20 carbon atoms and a valence of n + l, n5 is at least l and there cannot be an -OH group on an aliphatic carbon atom beta to the Si atom, POLYETHER-POLYALCOHOL
~ 3) ~ 71~ :
- Rlo t - CH2 - C~ ~ O ~ Rl ~ ~n8 n6 wherein Rlo is a divalent hydrocarbon having from l to lO
carbon atoms, Rll is selected from the group consisting of hydrogen and methy1 and Rl2 is a hydrocarbon having from l to 20 carbon atoms and a valence of n6 + l and can have no more than l oxygen atom attached to any one carbon atom,:
:
n6 is zero or greater, n7-is an integer from zero to l and :
n8 is at least l.
The most preferred polyalcohols are 4 oxa-6,7-dihydroxy : heptane - CH2-GH2-CH2-O-cH2 C~H CIH
OH OH
AMIDE AND AMIDE-ALCOHOL
4) f Rl5 :
Rl3 - C - N R14 ~ where1n Rl3 is a divalent hydrocarbon having from 2 to ~O
carbon atoms and the ¦~ group is not attached to a carbon -C-atom of Rl3 which is alpha to the Si atom, Rl4 and Rl5 can be the same or~different and are selected from the group consisting I of a monovalent h~drocarbon having from l to lO carbon atoms, hydrogen, CH2~-~ CH2 ~ OH wherein n~ is an integer from 1 to 3 and CH2--~CH2 ~ N - R16 wherein R16 and R17 are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n10 is an integer from 1 to 5, QMIDE
- Rl3 - C - N Rl4 wherein Rl3 is a divalent hydrocarbon having ~rom 2 to lO
1~
carbon atoms and the -C- group is not attached to a carbon atom of Rl3 which is alpha to the Si atoms, Rl4 and Rl5 - 2 ~_ can be the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to lO carbon atoms, hydrogen,-CH2~-~ CH2 ~ 0H whereln n9 R~17 is an integer from l to 3 and-CH2~ CH2 ~ N - R16 :~. wherein Rl6 and Rl7 are the same or different and are selected from the~group consisting of hydrogen and a mono-valent hydrocarbon having from l to lO carbon atoms and nl:0 : is an integer from l to 5, -Rl8 - N - C R20 wherein R18 is a divalent hydrocarbon having from l to 20~
carbon atoms and R19 and R20 are the same or dlfferent and are selected from the group consistlng of hydrogen and a~
: ~15 ~ monovalent hydrocarbon having from 1 to lO carbon atoms,~
;: :~ R21 R22 (O) nll wherein R2l is a divalent:or trivalent hydrocarbon ha~ing ~ from l to lO carbon atoms and S is not attached to R2l by an aliphatic carbon atom beta to the Si atoms, R2l may or may not be attached to R22 to form a ring which contains more than 3 carbon atoms and R22 is selected from the group : consisting of a hydrocarbon having from l to lO carbon : 25 atoms and 0~ ~ where M is selected from the group consisting ~ ~ :
of a monovalent metal ion and a quaternery ammonium ion, and nll is an integer from l to 2, - R23 ~ R24 ~) ' wherein R23 is a divalent hydrocarbon having from 3 to l0 carbon atoms and the ~ must be attached to a carbon atom of R23 which is at least 2 carbon atoms away from the Si atom, R24, R25 and R26 are the same or different and are monovalent hydrocarbons having from l to l0 carbon atoms, ~ is a monovalent anion selected from the group consisting of halides, R27 ~ CO ~ wherein Rz7 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from~
l to l0 carbon atoms and a halogenated monovalent hydrocarbon 10 having from l to I0 carbon atoms and R28 ~ S ~ wherein R28 is selected from the group consist1ng of a monovalent hydro-carbon having from l to l0 carbon atoms and a halogenated mono-valent hydrocarbon having from l to l0 carbon atoms, -.
- R29 --~ ~12R3 3l 13:~
wherein R29 lS a divalent hydrocarbon having from 1 to l0 ~
carbon atoms and nl2 is an integer from 0 to l and when nl2 ~ :
: : is l the oxygen cannot be attached to an aliphatic carbon atom in R29 which is beta to the Si atom, R30 is a divalent hydrocarbon having from l to l0 carbon atoms, R3l is a ~hydrocarbon hav1ng from 2 to 20 carbon atoms and a valence :: : : : : :: :
of nl3 + l and can:have no more than l oxygen atom attached to any one carbon:atom and nl3 is at least l, ~ ~ : 9) ~ O
32 ~ - C - R33 ~ OH ) wherein R32 1s a ~divalent hydrocarbon having from l to l0 : carbon atoms and the oxygen atom bonded to R32 cannot be attached to an a~liphatic carbon atom in R32 which is beta to : the Si atom, R33 is a hydrocarbon having from 2 to 20 carbon atoms and a vaIence of nl4 + l and can have no more than l : oxygen atom attached to any one carbon atom and nl4 is an integer of at least l, :' ` ,, ' :. ' ~ a7-.v 10) - R3 ~
wherein R34 is a divalent hydrocarbon having from 1 to 10 carbon atoms, 11) f ~3~ ~) wherein R35 is a divalent hydrocarbon having from 2 to 10 carbon atoms and nl5 is an integer from 1 to 10, 12) 0 ~ ~R3~
lo R36 c t ~ CH2 ~ CH t R38 wherein R36 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group is not attac~ed to a carbon atom alpha to the Si atom, R37 is selected from the group consisting of methyl and hydrogen, R38 is selected from the group consisting o~ hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and ~l wherein R39 is a monovalent hydrocarbon having ~rom 1 to 10 carbon atoms and nl6 is at least 1, 13) - R - N ~ R
wherein R40 is a divalent hydrocarbon having ~rom 1 to 10 carbon atoms, R41 and R42 can be the same or dif~erent and are selected from the group consisting o~ monovalent hydro--carbons having from 1 to 10 carbon atoms and ~ CH2 ~ OH
where nl7 is an integer from 2 to 4, 14) O
il O R45 ~:
wherein R43 is a divalent hydroca.rbon having from 1 to 10 carbon atoms and the S atom cannot be attached to a carbon atom ; of R43 which is alpha to the Si atom, R44 and R45 can be the same or different and are selected from the group con-sisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, :~ : . : :
153/ CH~ CH ~
R46 N \ ~ ~ :
~ ~ :
wherein R46 is a divalent hydrocarbon having from 1 to : 10 carbon atoms and nl8 is an integer from zero to 3, 16) : R48 - R~17 - C ~ H n 9 ~ Rhg - CH ~ N
ol wherein R47 and R48 are selected from the group con-sisting of hydrogen, divalent or monovalent hydrocarbon _~.q_ :
havin~ ~rom O to 10 carbon atoms and R49 is selected ~rom the group consisting of hydrogen, divalent or monovalent hydrocarbon having from 1 to 10 carbon atoms and only one o~ R47, R48 and R49 must be a divalent hydrocarbon and attached to the Si atom, R50 is selected from the group consistlng of hydrogen5 a mono-valent hydrocarbon having from 1 to 10 czrbon atoms and ~~ C~2 ~ OH where n20 is 2 to 4, and nl9 is an:interger from zero to 3, 17) e - R51 - C ~
wherein R51 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot:be attached to a carbon atom:of R51 alpha to the S1 atom and X2 ls a monovalent~
cation selected from the group consisting of monovalent ~ :
; ~ l53 metal catlons and R52 ~ N - R5~ wherein R52, R53, R54~and~R55 Rss :
: can be the same or different and selected from the group consisting of hydrogen and a monovalent hydrocarbon having from l to 10 carbon~atoms, and :
18) R ~ C - R5 ~ ~ 58 whereln R56 is~a:dlvalent hydrocarbon having from 1 to 10 carbon atoms and the carbonyl group cannot be attached to~
a oarbon atom of R56 which is alpha to the Si atom, R57 is a divalent hydrocarbon having from one to 10 carbon atoms, R58 is selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n21 is an integer from~zero to 10, polymerized to fo.rm a polymer ln a crosslinked network.
:
-3~
Preferably, the hydrophilic sidechains are one of ~ \ ,.
( CH2 ~ CH2 CH2 t CH3 n22 : ;;
wherein n22 is an integer from 2 to 3 -~ CH2 ~ CH ~ CH2 ' OH OH
;
:: : : : :
( CH2 ~ o ~ CH2 ~ CH - CH2 : OH OH
~ ~ :
~CH2 ~ C - N - R59 ~1 wherein R59 and R60 are the same or:dif~erent and are ~ :
selected from the group consisting o~ hydrogen, methyl and -~CH2 - CH2 - OH ~ ~ ;
~R~l : 15 -~CH2~-3~- N CH3 wherein R61 is selected from the group consisting of hydrogen and methyl~ :
O
CH2 ~ S - CH3 CH
'H2 ~ N - CH3 Cl~ ' : CH3 : O
11:
~CH2 ~ C ~ O ~CH2 ~ OH ) :
-$ ~ 3 ~3 O
~ CH2~ c tQ - CH2 CH2t ~ o CH3 Jn23 ::
wherein n23 is an integer from 2 to 3 ~ ', 2 ~
:~ : ~: : `
~-~ CH2 ~ OH
: 11 CH2 ~ le NH2 O
: ~ 10 ~t-~CH2 C - CH
( CH ~ CH - CH2 ~: 15 : CH~2 NH ~ ~
: ~ : : ~ : : ::
O
CH2 ~ C ~ , and:
~: 20 ~_CH2 ~ C--CH3 ~ ~
In a preferred embodiment of the instant invention, when the siloxane backbone is a poly (organo) siloxane the following is preferred.
PreEerably, ~ 1~ one of~- CH2 ~
CH=CH2 wherein n24 is an integer f`rom 0 to 2, CHaCH2 and - R62-~ wherein 62 -~ CH2~ 25 wherein n25 is an integer from 3 to 4 and Il , G is - O - C - CH2 wherein R63 is selected from the group consisting of hydrogen and methyl More preferably X is ~ CH2 ~ ~ C ;~C = CH2 whereln R64 is selected from the group consisting of hydrogen and methyl, most preferably R64 is methyl.
Preferably Yl is methyl and Y2 is phenyl. More preferably . Yl and Y2 are methyls.
15 ; ~ Preferably only.one of~Zl~ Z~, Z5 and Z6 is a hydr~ophi~ic sidechain and a is equal to 1 to about 1,000, b is equal to zero, c is equal to 1, d is equal to 1 to about l,OOO, e is~
equal to one and f lS equal to zero. The instant contact lens may be hard or soft.
More preferably only one of Zl~ Z2~ Z5 and Z6 is a hydrophilic ~sidechaln and a is equal to 10 to about 500, b is equal to zero, c is equal to one, d is equal to about 10 to about 500, e is equal to one and f is equal to zero.
The instant contact lens may be hard or soft.
Even more preferably when only one of Zl~ Z2~ Z5 and Z6 . .
is a hydrophilic sidechain and a is equal to about 75 to about 150, b is equal to zero, c is equal to one, d is equal to about 25 to about 50, e is equal to one and f is equal to zero, the instant contact lens is soft and flexible.
Most prePerabl~ when only one of Zl~ Z2~ Z5 and Z6 is a hydrophilic sidechaln and a is equal to about 75, b is equal to zero, c ls equal to one, d is equal to 25, e ~.s equal to one and f is equal to zero, the instant contact lens is soft and flexible.
ly Zl, Z2 and Z5 are methyls and mo~st pre-ferably Z6 is one of -~ CH2 ~ CH2 CH2 ~ CH3 wherein n26 is an integer from 2 to 3, CH2 ~ o _ CH2 - CH - CH
OH OH and 2 ~ ~ CH2 C - I - R66 wherein R~5 is~
selected from the group conslsting of methyl and hydrogen,~
R6~ is selected Prom the group consisting of methyl5 hydrogen and - CH2 - CH2 - OH.
In another preferred embodiment of the instant invention, ~when the siloxane backbone is a polyparaffinsiloxane, the following is preferred. When only one of Zl through i7 is a~hydrophillc~sidechain and a~may be equal to one, b is equal to about 2 to 4, c is equal to~zero, d is equal to~ore, e ~lS
equal to about 25 to 500 and f is equal to 5 to 500, the con-tact lens may be either hard or soft.
More preferably in this embodiment, only one of Zl ~; 25 through Z7 is a hydrophilic sldechain and a is equal to one, b is equal to about 2 ~o about 3, c is equal to zero, d is equal to one, e is equal to 25 to about 250 and f lS equal to about 10 to about 250, resulting in a soft and flexible contact lens.
- 3 g '~' ~ " :
~3 _3 ~
In this same embodiment, even more preferably one one f Zl through Z7 is a hydrophilic sidechain and a is equal ~
to one, b is equal to about 2 to about 3, d is equal to one, c is equal to zero, e is equal to from about 50 to about lO0 and f is equal to from about 10 to about lO0, resuIting in a soft and flexible contact lens.
In this same embodiment~ most preferably only one of Zl through Z7 is a hydrophilic sldechain and a is equal to , one, b is equal to from about 2 to about 3, c is equal to zero, d is equal~to one, e is equal to from about 50 to about 75 and f is equal to from about 10 to 75, resulting ;
in a soft and flexible contact lens.
In this same embodiment, most preferably Zl~ Z2~ Z5 :
Z6' Z7~ Yl and Y2 are equal to methyl and Z4 is eq~lal to hydrogen and at least one of Z3's in the methylene brldee is equal - C - N -~CH3)2 and~the other Z3's ln that bridgé
qual ~yd_og-n, and X eq~als -~ ^V2~ 0 - C - C - CH
When there are more than one Z on the backbone of the polymer, all of these Zl's maybe the same or different. Also 5 :
; this applies t~o ;Z2 through Z7. Por example, the following~
formuIa is illustratlve of this~
3 ~~ CH3~ CIH3 ~ I f - ~ H3)2 9 3 CH3 ;~
X - Si 0 li ~4CH2t-3 ll _ _~ o ~ Si -4CH2 - CH - CH2~---- Si ---0 ~ Si - X
3 CH3 CH3 CH3 CH~ C~3 ;o 5o In order to~easily locate the Z's, compare the above formula with the broad general formula disclosed hereln. In the above formula Zl~ Z2~ Z5~ Z6 and Z7 equal -CH3, all the Z4'8 equal hydrogen and there are 250 Z3's equal to hydro~en and 50 O
Z3's equal to - C - N -~CH3)2.
~ 3~ .,t,~
--3~-When X is a polymerizable group then the instant poly-siloxane monomers may be compolymerized with comonomers, such as, hydroxyethylmethacrylate (HEMA), methacrylates and acrylates, e.g., cyclohexylacrylate, methyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate and glycerine trimethacrylate, monoesters of acrylic or methacrylic acid and.an alcohol having an esterifiable hydroxy group and at least one additional hydroxy group, such as, 2-hydroxy ethyl methacrylate and 2,3-: dihydroxy propyl acrylate, acrylamide and methacrylamides,:
N-vinyl lactams, acrylonitrile and methacrylonitrile, derivatives of methacrylic acid, acrylic acid, itaconic acid and crotonic : acid, styryls, such as9 styrene, divinyl benzene, vinylethyl benzene, vinyltolune and allylic monomers, such as, diallyl diglycol dicarbonate, allylcyanide, allyl chloride, diallyl phthalate, allyl bromide, diallyl furmarate and diallyl carbonate and comonomers.
The followlng:are hydrophilic sidechains which are preferred.
: : ~ \ :~ ~
POLYETHERS ~ : R~ ~
1 ~ 1 R5 ~ O CH - CH t ~ R7 -~ fn4 wherein R5 is a divalent hydrocarbon having from 1 to 10 carbon : atoms, R6 i selected from the group consisting of methyl and hydrogen, R7 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms, O
1 1 :
~: - C~- R8 wherein R8 is selected from the group consisking of a monovalent hydrocarbon having from 1 to 10 carbon a.toms and hydrogen and n4 is at least 1.
The most preferred polyethers are 4,7,10-trioxaundecane 2 2 CH2 O - CH2 ~ CH2 - O - CH CH O C
and 4,7,10,13-tetraoxatetradecane -CH2 CH2-cH2-o-cH2-cH2-o-clI2-cH2-o-cH2~cp'2-o-cH3 :-`
~3C ~
POLYALGOHOLS
2) - R9 -4 OH~n wherein Rg is a hydrocarbon having from l to 20 carbon atoms and a valence of n + l, n5 is at least l and there cannot be an -OH group on an aliphatic carbon atom beta to the Si atom, POLYETHER-POLYALCOHOL
~ 3) ~ 71~ :
- Rlo t - CH2 - C~ ~ O ~ Rl ~ ~n8 n6 wherein Rlo is a divalent hydrocarbon having from l to lO
carbon atoms, Rll is selected from the group consisting of hydrogen and methy1 and Rl2 is a hydrocarbon having from l to 20 carbon atoms and a valence of n6 + l and can have no more than l oxygen atom attached to any one carbon atom,:
:
n6 is zero or greater, n7-is an integer from zero to l and :
n8 is at least l.
The most preferred polyalcohols are 4 oxa-6,7-dihydroxy : heptane - CH2-GH2-CH2-O-cH2 C~H CIH
OH OH
AMIDE AND AMIDE-ALCOHOL
4) f Rl5 :
Rl3 - C - N R14 ~ where1n Rl3 is a divalent hydrocarbon having from 2 to ~O
carbon atoms and the ¦~ group is not attached to a carbon -C-atom of Rl3 which is alpha to the Si atom, Rl4 and Rl5 can be the same or~different and are selected from the group consisting I of a monovalent h~drocarbon having from l to lO carbon atoms, hydrogen, CH2~-~ CH2 ~ OH wherein n~ is an integer from 1 to 3 and CH2--~CH2 ~ N - R16 wherein R16 and R17 are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n10 is an integer from 1 to 5, QMIDE
5) Rlg O
~ ~1 5~ R18 ~ N - C R2o wherein R18 is a divalent hydrocarbon havlng from 1 to 20 carbon atoms and Rl~ and R20 are the same or diff?rent~ and are selected from the group consisting of hydrogen and a hydrocarbon having from 1 to 10 carbon atoms, SULPHONE AND SULPHOXIDE '~~~~ ~~l -- R2~ SI -- R22 ()nl1 ~
where1n R21~is;a divalent or trivalent hydrocarbon having ~ :
from l to 10 oarbon atoms and the S atom is not attached to R21 by 15 : an aliphatic carbon atom beta to the Si atom, R21 may or may not be attached to R22 to form a ring which contains more than 3~carbon atoms and is selected from the group consistingg of a hydrocarbon having from 1 to 10 carbon atoms and O M
where M is selected from the group consisting of a monovalent metal ion and a quaternary ammonium ion, and n11 is an integer ~:
from 1 to 2, QUATERNARY_SALTS
7) ~:~ 25 - R23 -~N - R24 h~
wherein R is a divalent hydrocarbon having from 3 to 10 23 ~
carbon atoms and the l~ must be attached to a carbon atom of R23 which is at least 2 carbon atoms away fro~ the Si -3~
atoms, R2l~, R25 and R25 are the same or different and are mono~-valent hydrocarbons having from l to lO carbon atoms, ~ is a monovalent anion selected from the group consisting of halidesg R27 ~ CO ~ ~herein R27 is selected from the lO carbon atoms and a halogenated monovalent hydrocarbon having from l to lO carbon atoms and - R28 ~ S ~ wherein R28 is selected from the group consisting of a monovalent hydrocarbon having from 1 to lO carbon atoms and a halogenated monovalent hydrocarbon having from l to lO carbon atoms, ~;
lO HYDROXY ESTERS
; .
8) ~29 ~ )nl2R30 C O R3 ~ 0H~nl3 wherein R29 is a divalent hydrocarbon having ~rom l to lO
carbon atoms and n12is an integer from O to l and when nl2 ~ : ~ 15 is l the oxygen;cannot be attached to an aliphatic carbon~
; ~ ~ atom in R29 which is beta to the Si atom, R30 is a~divalent :~ hydrocarbon having~from 1 to lO carbon atoms, R3l is a:hydro-~: carbon having from 1 to 20 carbon atoms and a valence of nl3 + l and can have;no more than l oxygen atom attached to any one carbon atom, and nl3 is at least l, ~: :
9) 0 32~ 33 n 14 wherein R 32is a divalent hydrocarbon having from I to lO
carbon atoms and the ester oxygen~cannot be attached to an aliphatic ~- 25 carbon atom in R32 which is beta to the Si atom, R33 is a hydrocarbon havi.ng from l to 20 carbon atoms and a valence ;~ of n14~1 and can have no more than l oxygen atom attached to any one carbon a~om and n14 is at least 19 GYCLIC ETHERS
-10) ~, - R ~
:: ~ ~y ~9~ .
w.nerein R34 is a divalent hydrocarbon having from 1 to 10 carbon atoms, 11) ~ o _ CH 2 , CH 2 ' n 1~
- R ~ J
O--wherein R35 is a divalent hydrocarbon having from 2 to 10 :: carbon atoms and nl5 is an integer from 1 to 10, :
: ESTER-ETHERS
12) o ~ 13~ ;~
- R36 ~ C ~ 2 - CH ~ 8 : wherein R36 is~a divalent hydrocarbon having from 2 to l0:~
~ : carbon atoms and the carbonyl group ls not attached to a : ~ 15 carbon atom alpha to~the Si atom, R37 i:s~selected from the~
group consisting of methyl and hydrogen, R38 is selected from ;~
the group consisting of hydrogen, a~monovalent hydrocarbon~ :
o havlng from l to I0~carbon atoms and-C - R39 wherein R39 is a monovalent hydrocarbon ha~ing from 1 to 10 carbon atoms :
: : and n is at least 1, AMINES
13) ~ R40 ~ N - R
:~ I
; 25 : 42 wherein R40 is a divalent hydrocarbon having from 1 to 10 carbon atoms, R41 and R42 can be the same or different and are selected from the group consisting of monovalent hydro-carbons having from 1 to 10 carbon atoms and ~ CH2~n ;OH
where nl7 is 2 to 4, ~.3 SULPHONAMIDES
14) ~3 Il ~ .
0 . R45 wherein R43 is a divalent hydrocaroon having f'rom 1 to lO
carbon at~ms and the 3 cannot be attached to a carbon atom of R43 which is alpha to the Si atoms, R44 and R45 can be the same or diferent and are selected from the group consisting 10 of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, CYCLIC AMIDES
~CH2~ CH2~j~ ` :: :
15 ~ ~ _ R46 ~ - N j ~ ~ ;
wherein R46 is a divalent hydrocarbon havlng from 1 to 10:
carbon atoms and nl8 is an integer from ~ero to 3, CYCLIC AMIDES I ~ ;
16) ~ ; 1 ~ ~ _ q g \ ~ N--1¦ R50 : ~ ~ O ' ~
wherein nlg is an integer from zero to 3, R47 and R48 30 are selected f~rom the group consi3ting of hydrogen~ divalent or monovalent hydrocarbon having from O to 10 carbon atoms and R49 is selected from the group consisting of hydrogen, ~ ~0 .
' :
divalent or monovalent hydrocarbon having from 1 to 10 carbon atoms and one of R~7, R48 and R49 must be a divalent hydrocarbon and attached to the Si atom, R50 is selected from the group consisting of a monovalent hydrocarbon ha~i.ng from 1 to 10 carbon atoms and -~ CH2 ~ OH wherein n20 is an integer from 2 to 49 CARBOLYLATE SALTS
17) O
R51 ~ C ~ ~2 wherein R51 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group ca~mot be attached to a carbon atom of R51 alpha to the Si atoms and ~ lS a mono~alent cation:selected from the group consisting of monova:lent metal ~: 15 cations and R5~2 - N - R54 wherein R52~ R53~ ~54 and R55~are : ~ 55 :~
: the same or di~ferent and selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 oarbon atoms, and KETONES A~D ALDEHYDES
18) ~ :
: ~
- R5~ C R - l l 58 21 ~
wherein ~56 is a divalent hydrocarbon having from 2 to 10 carbon atoms and ~he carbonyl group cannot be attached to a carbon atom of R56 which is alpha to the Si atom, R57 is a divalent hydrocarbon having from one to 10 carbon atoms, R58 : is selected from the group consisting of hydrogen and a ~ ~ monovalent h~drocarbon havin~ from 1 to 10 carbon atoms and .. .
, . .
n21 is an integer from zero to 10.
When the term "soft" is used herein to describe the contact lens of the instant invention, it is meant that the material should have a softness preferably of about 60 or below on the Shore hardness A scale. Most preferably the Shore hardness should be 25 to 35 on the A scale.
When the term "hydrolytically stable" is used herein it is meant that when the contact lens or biomedical device ;
disclosed herein when placed into an aqueous solution, e.g., in the eye, or during the disinfecting step, i.e., water plus heat, the lens or device will not change in chemical composition, i.e., hydrolyze, which would cause a lens to change shape resulting in an undesirable change~in opti~cs or shape.
When the term "biologically inert" is used here in it is meant that the contact lens or biomedical device disclosed herein have phsiochemlcal properties renderlng them suitable :
for prolonged contact with living tissue, blood or the mucous membranes such as would be required for biomedical shaped articles. It also means that this material is antithrom-; bogenlc and nonhemolytic to blood which is necessary for prosthesis and devices sued with blood. These materials : ~ ;
~ disclosed herein are compatible with living tissue.
: ' j: ~; : :
: ::
When the term "oxygen transportability" or "oxygen transporting" or "that the contact lens has the capability o~ transporting oxygen sufficiently to meet the requirements of the human cornea" and used herein, ~t is meant that the instant material will allow sufficient transmission of oxygen throuæh itself to supply the necessary oxygen requirements of the human cornea. The oxygen requirements of the human cornea are about 2x10 6cm3/(sec.cm2atm.) as reported by ~ill and Fatt, American Journal of Optometry and Archives of the American Acade-my of Optometry, vol. 47, pg. 50, 1970.
When the term "flexible" is used herein, it is meant that the contact lens is capable of being folded or bent back upon itself without breaking.
When the term "resilient" is used herein, it is meant that after the lens has been deformed the lens wlll return quickly to its original shape.
The most preferred contact lens, i.e., polymers, of the instant invention are soft, hydrophilic, flexible, hydrolytically stable, biologically inert and have an oxygen transport rate of at least about 2x10 6cm3/(sec~cm2atm.).
These lens have a softness preferably of about 60 or below on the Shore hardness A scale. ~ost preferably, the Shore hardness should be 25 to 35 on the A scale.
To further illustrate the most preferred contact lens of the instant invention's physical properties, the tensile modulus of elasticity should be about 500g/mm2 or less. If ; the material is to be used as contact lens, then the Shore hardness and modulus may be related to the comfort of the lens to the wearer when used on the human eye.
There are commercially available~ both hydrophobic and hydrophilic contact lenses. The hydrophobic contact lenses available are primarily hard contact lenses made from such q ~
materials as (PMMA) polymethyl methacrylate. However, there are soft contact lenses available which are hydrophilic.
These lenses are usually made from polymers and copolymers based on (HEMA) hydroxyethylmethacrylate. However, neither of these materials made from PMMA or PHEMA are oxygen permeable enough to meet all the oxygen requirements of the human cornea.
Therefore, a materlal had to be de~eloped which was soft, for comfort, and also, oxygen permeable, to the extent that when the material was made into a contact lens, sufficient oxygen-would pass through the material to meet all the requirementsof the human cornea. It was found that polysiloxane materials are oxygen permeable to the extent that oxygen will pass through these materials when made into contact lenses suf-ficiently to meet the requirements of the human cornea.
Also, contact lenses made from polysiloxanes are soft, result-ing in more comfort for the wearer. Therefore, it was found that polysiloxane materials could be a good candidate for making soft contact lenses~ Howeverj it was found that when soft contact lenses were made from known polysiloxane materials, these lenses did not ride on the cornea of~the eye on a layer~
of tears but rather attach themselves to the cornea in a manner which altered the metabolic outflow and inflow of fluid from the eye. It is known that non-movement or sub-stantially non-movement of soft contact lenses on the eye can result in physical damage to the cornea. As mentioned, it has been noted that when a soft contact lens moves on the eye there is also an exchange of tear fluid under the lens resulting in the exchange of metabolic products supplying the cornea and metabolic byproducts being removed from the cornea.
This movement of tear fluid results in maintainin~ a healthy environment for the cornea. This has been generally reported by Roth and Iwasaki, Complications Caused by Silicone Elastomer Lenses in West ~ermany and Japan, paper presented at the ~3~
Second Contact Lens Conf`erence, February 1~, 1979, in ~okyo, Japan (Prof. Motoicni Itoi, r~.D., Kyoto, Prefectur-al University of Medicine, ~irokohji, Ka~ara Machi-Dohri, ~amikyo-Ku, Kyoto 602); Kreiner, Christine F., Meues Optikerjournal, No. 2 (21) February 10, 1979; ~onArens, Franz D., Neues Optikerjournal, ~o. 3 (21) March 10, 1979; and VonZimmermann, E., ~eues Optikerjournal, No. 4 (21) April 10, 1979.
The instant contact lens moves on the eye sufficiently so that no physical damage occurs to the cornea and sufficient tear exchange occurs so that the cornea metabolism proceeds normally. Therefore, the instant polymers make excellent material for manufacturing contact lens and~ as mentioned, do not stick to the eye but move sufficierltly during normal wear so that corneal metabolism will proceed normally.
When the term "moveable soft contact lens" lS used ; hereln, it is meant that when the lens is placed on the eye during normal wear the lens will move at least 0.5mm with each blink of the eyelid. Preferably, the lens should move from about 0.5mm to about l.Omm with each blink.
Further~ when the term "moveable soft contact Iens"
is used herein, lt i~s meant that the lens moves sufficiently on the eye so that (1) no physical damage occurs to the~
cornea and (2) sufficient tear fluid exchange occurs under the lens so that sufficient cornea metabolic activity is maintained resulting in a healthy environment for the cornea.
When the term "non-moveable soft contact lens" is used herein, it is meant that the lens will move less than about 0.5mm with each blink of the eyelid.
~hen the term i'hydrophilic soft contact lens" is used herein, it is meant that the soft contact lens surface will not repel water as opposed to the "hydrophobic" lens where the lens would tend to repel water.
:
- ~3 The following illustrates a preferred embodiment Or the instant invention: ~
f CH3 3\
I l 1 mole CH ~ C - COO ~CH? ~ Sli - ~ O
: ; 2 : 3(4-methacryolyloxy) butyl 1,1,3,3 tetramethyl disiloxane C ~ ~ :
18 75 moles~ S~ + 6.25~moles Si - O ~ 1) H2S04 or (CF350H) 1 1: 1 ~>' ~:: : ~ CH3, J 4 H J 2) RaHC0 Octamethyl cyclo 1,3,5,7 tetramethyl tetra slloxane cyclo tetra siloxane ~:
3 ~ H3 ~H3 ~ ~ ~ H3~ ~ ~ CH3 ~ ;0 CH3~
CH2-C:~- C-0 ~ CH2 ~ Si - O~ ~i ~ t , ; t siq~ ~CH2 ~ 0-C-G =CH2 : 3 ~ 3 ~75 ~ J 25 ~: : .
~:~ This is a representative general formula. ~he actual product is a random copolysiloxane.
;20 ~ CH2~= CH - CH2 - O - CH2 - IH eH2 : ~ :
~ ~ 0:
\C~ ~
C~3 so~ketal allyl ether or ~: 25 3~2,2 dimethyl 1,3-dioxolane-4 methyoxyl] - 1 - propene :
: Pt catalyst ~ \ Chromotography :~: ~ ` :
- f ~ r ~4Si~
~7 CH3 O f ~ ~ 1T ~ I 1l fH3 C~2SC c o {~ CH2~ si o--si ~ t ~S1 _ ~--Si __~L CH2 ~ -C ~ ~-CH2 CH3 ~ 3 /67 ~2 ~ CH3 CH2 o - CH2 - CH ~ CH2 . O O
~C~
¦ ~ CH3 CH3 : :
H20 , : :
HOCCH
\ / l~ 3 CH O CH ~ CH ~ CH3q CH3 O ~ C~H3 : 1 3 l~ 1 3 l 3 ~
GH2=C - C-O--~ CH2 ~ :Sl _ O - Si ~ ) - Si 0--Si ~CH ~ ~O - C~-~C~= CH2 ~ ~ ~ CH3 CH3/6 CIH2 33 CH3 : CH2 ~ ;:
: : ~ : :
OH OH-Peroxide \ /
Cured polymer or shaped body as product The product formed after standing in H2O was completely wettableand has absorbed 13 percent H20 by weight based on the total weieht of the material plus water. This is 33 mole percent 6,7-dihydroxy-3-oxyheptane hydrophilic sidechain methacrylate endcapped siloxane.
~: 25 These polymers and copolymers can be used to make biomedical devices, i.e.~ shaped articles, such as, dialyzer d~aphragms, to prepare arti~icial kidneys and other biomedi-cal implants, such as disclosed in Wichterle, U.S. patent 2,976,576 and Wichterle, U.S. 3,220,960. The instant poly~
mers and copolymers can be used in preparing therapeutic . .-~ ~. 3 ~
bandages as disclosed in Shepherd, U.S. patent 3,L12~,043;.
The instant polymers and copolymers can also be used in preparing medical surgical devices, e.g., heart valves, vessel substitutes, intrauterine devices, membranes and 5 other films, dialyzer diaphragms, catheters, mouth guards, denture liners and other such devices as disclosed in Shepherd, U.S. patent 3,520,949 and Shepherd U.S. 3,618,231.
The instant polymers and copolymers can be used to modify collagen to make blood vessels, urinary bladders and other 10such devices as disclosed in Kliment, U.S. patent 3,503,925.
The instant polymers and copolymers can be used to make catheters as disclosed in Shepherd, U.S. patent 3,566,874.
The instant polymers and copolymers can also be used as semi-permeable sheets for dialysis, artificial dentures and all of such disclosures as set forth in Spoy, U.S. patent 15`3,607,848. The instant polymers and~copoly~ers car also;be~
used in ophthalmic prostheses and all other uses~disclosed in Wichterle U.S. patent 3,679,50~. ~
When the term "shaped article for use in biomedical applications" or "biomedical devlce" are used herein, it lS
20 meant that the materials disclosed herein have physioGhemical properties rendering them suitable for prolonged contact with living tissue, blood and the mucous membrane such as wouId ~
; ~ be required for blomedical shaped articles, such as~ surgical implants, blood dialysis devices, blood vessels, artificial - 25 ureters, artificial breast tissue and membranes intended to come in contact T~ith body fluids outside of the body; for ; example, membranes for kidney dialysis and heart/lung machines, and the like. It is known that blood, for example, is rapidly damaged in contact with artificial surfaces. The design of a 30 synthetic surface which is antithrombogenic and nonagmolytic to blood is necessary for prosthesis and devices used with blood. The instant polymers and copolymers are compatible with living tissue.
.:
r ~MP LE_ 557 g o~ 1,3-bis(4-hydroxybutyl)tecramethyl disiloxane, 634 g o~ dry pyridine and 2 liters of hexane are charged to a 5 liter reaction llask equipped wi~h a mechanical st1rrer and dryin~ tube. The mixture is chilled to 0C and then 836 ~ of methacryloyl ch'oride is added dropwise. The mixture is a~itated continuously overnight. The reaction solution is extracted consecutively with 1~% water solutions of HCl and ;~H3 in order to remove excess re2gents and pyridine hydrochloride. The resulting solution of the product in hexane is dried with anhydrous MgSO4, filtered~ and solvent removed at reduced~pressure. ADout 459 g (55~ yield) 1,3-bis(4-methacryloxy butyl)tetr2meshyl~d1s11Oxane ls col-~
lected. The~structure is co~firmed~by in~rared spectra, ~ ~
1~5 proton magnetic resonance spectra and elemen.ial analysis.~ -IR spectra shows no 1ntense hydroxyl band between 3100 and 3600 cm 1 but does show strong ~ethacrylate absorp~ions at 1640 and 1720 cra 1. PMR spectra agreed with the p~oposed structure.
: _ _ ~ :
.
~ 20 . O ICX3 ;~ H ~C ~ ~ C.i--Cd2, 2 CH2 ~ _O
l, 3-bis( "-me.,h-c y:ox"~ _u yl ) vetræmethyl - 25 d.. s loxane ~ ~
-~, . . .
rXAMPLE II
14~.7 g of octamethylcyclotetrasiloxane, available from Silar Labs, 10 Alplaus Road, Scotia, NY 12302, 40.2 g of tetramethylcyclotetrasiloxane, available from Silar Labs, 7 ll.l g of 1,3-bis(4~methacryoxybutyl) tetramethyl disiloxane as prepared in E~ample I and 2.0 g of 95~-98% ~;2SO4 are charged, under dry air, ~o a 500 ml 2-neck reaction ~lask ecuipped with a mechanical stirrer. The mixture is agitated continuously for 20 hours at which time 17 g of powdered sodium bicarbonate is added to the reaction mixture and stlrred for two hours. The resulting mixture is then diluted with 500 mls of hexane, dried over anhydrous MgS04, filtered and the soIvent removed at reduced pressure. The~cyclics are removed under high vacuum (0.050mmj at 60C~ for one hour. 180 g of a methacrylate endcapped~25 ~ole percent ~
silicone hydride polydimethylsiloxane is collected. The~ ~ ;
polymer is a clear`colorless fluld which has a viscosity of 1.1 stokes-by Cannon viscometer. The structure is confirmed by infrared spectra, proton magnetic resonance spectra and ~silicone hydr~ide analysis ~o be:
0 CH CH~ CH~ ~ CH CH
G~ 3 I ~ I ~ ~ 3 ~ 3 -C-O~CH2 4 Si - O Si - 0 Si - O ~ Si~ CH2 4 f, ;~Cl.2 CH3 3 ~ ~ J ~ ~CH3 ~ ~5 3 : :
~ The product is a ranaom co~olysiloxane.
-3'3 EXAMPLE III
: ~ ' 122.4 g of octamethyl cyclotetrasiloxane, available from Silar Laboratories, 10 .41plaus Road, Scotia, New York 12302, 66.17 g of tetramethyl cyclotetrasiloxane, available from Silar Laboratories, 11.4 g of 1,3 - Bls (4-methacryoxybutyl) Tetramethyl disiloxane as prepared in Example I and 2 g of~
95% - 98% H2S04 are charged under dry air to a 500 ml 2--neck ~reaction flask equlpped~with a mechanical stirrer. ~Th~e~mixture is agitated continuously for 20 hours at which time 17 g of powdered sodium bicarbonate is added to the mixture and stirred for two hours. The resulting mixture is then diluted with 500 mls of hexane, drled with anhydrous MgS04~, filtered~and~
the solvent~removed at reduced pressure. Cyclics are removed under high vacuum (b .05 mmj at 60d for one~hour. 18~0 grams 15 ~of a methacrylate:~end~capped 40~mole~% silicone-hydride~
polydimethylsiloxane is collected. The polymer is a clear, colorless fluld wlth a viscosity~ of o. 8 stokes measured~by Cannon ~iscometer. Structure is confirmed by infrared spec~tra, ~ proton magneti~c resonance spectra and siloxane-hydride analysi~s ;;~ 20 to be: ~ ~
CH2 3 3 CH3 C~I3 O CH2 C-C-0-~CH2~ Si ~0-Si~0-Si-~-0-Si~CH2~ 0-C-C
CH3 ~H3 H CH3 CH3 3 : , ~ ~ne product is a random copolysiloxane.
: : ~ :~:: :
`
~: :
~$~
.
EXAMPLE IV
1,700 rnls of dried peroxide free tetrahydrofuran, available from Fisher Scientific Company, 15 Jet View Drive~ P.O. Box 8740, Rochester, NY 14624 and 158.7 g potassi~m metal, avall-~
able from Fisher Scientific, are charged under dry nitrogen ;~ into a 5,000 ml three-neck round oottom flask equipped t~lth mechanical s'irrer. The solution is chilled to 10C, uslng an icewater bath and 494 ~tl of diethylene ~lycoI monomethyl ether,available from Chemical Samples Comp2nyj 46g~2 Kenny Road~
Columbus, OH 43221, is added dropwise. The ?otassium metal reacts withln 24 hours at which time 350 mls of allyl chloride availab~le from Aldrich, 159 Forest Street, Metuchen NJ o8840, 1s added dropwise at such a rat~e to ma~intain a gentle reflux. Afte;r the reaction is allowed to contlnue ~15 overnight, one 1~1ter of distilled ~ater is added to the : ~ ~
reaction vessel to dlssolve the precipitated salts. The tetrahydrofuran layer is washed three times ~ivh a salt water solutio~n (270 g NaCl to 1 liter H2O) to remove excess alcohol.
The tetrahydrofuran is removed~Jith a water ~spirator and the product is distilled at reduced pressure. 4~0 c o~ diethy-:
~; lene glycol allyl methyl ether lS obtalned ~ D ~? ~ 109C/30mm) .
~- The anaIytical data is consis~ent with a product Gf the general formula:
~2 = CH-cE2-o-cH2-c~2-o-cH2-cH
~.3~$~
EXAMPL~ V
46.1 g of diethylene glycol allyl methyl ether, as prepared in Example IV, followed by 320 mls of hexane, are passed through 42.9 g of activated F-20 alumina~
available from Alcoa, Bauxite3 AR 72011, into a lO00 ml three-neck flask equipped with mechanical stirrer, ther-;
mometer and nitrogen inlet. 40 ~ of 20 parts per lO00~
Pt solution in the form of H2 Pt C15- 6 H20, availabIe from Fisher, in 2-propanol is added to the mixture. 40 mls of hexane~are distilled to remove water and alcohol. The mixture is cooled to 40C at which time 40 g of methacrylate endcapped 25 mole percent silicone hydride polydimethylsiloxane, as prepared in Example II, i~s added. Distillation is continued ~or oDe hour at which time the temperature is a~ 80C. About 200 mls of hexane have~been remoYed. Infrared spectra at 2175 cm l ~, :
~; shows no remaining~silicone hydride bond.
The mixture is cooled and diluted with hexane to a total volume of 500 mls. The mixture is divided and added to two slurry packed 600mm x 45mm fritted silica gel chromotography columns layered with 0.5 cm Celite and 1.5 cm sea sand. Each~
column is elu~ed with 2000 ml of a l:l hexane/ether mixture.
This fraction contains the excess allylic ether. Each column is then eluted with 2000 ml of a l:l hexane/2cetone mixture.
his fraction contains the polymer. The resulting solution 25 ~ of the product which is in hexane is dried with anhydrous MgS04, filtered and the solvent is removed at reduced pressure.
45 g of a methacrylate endcapped 2~ mole perce:~t silicone diethylene glycol propyl methyl ether ?o'ydimethylsiloxane is obtained. The product is a c1ear, colorless fluid ~:Ji h a viscosity of 4.0 Sto~es, using a C2nnon vi scometer. Analytical data confirms structure to be:
::
~ ~3 O CH ¦ CH ~CH ~ CH CH
~H 2 1I J 3 1 3 ~ 3 1 3 1 3 C-C-O ~ CH 2~ Si ~ ~ O-CH . . ~-Si ~ ~ Si ~ CH~ O ~C~ CH
c~3 CH3 ~ ~ - CHy ~5 3 5 . C~ 2 ' , ' - :
~: : . ` :
:: ~ :
S~_ f..
EXAMPLE VI
.
Films of the fluld product obtained in Example V are cast between glass plates by adding 1% diethoxyacetophenone, I
available from UpJohn Company, La Porte, Texas 77571, to .5the monomer. The material is then lrradiated with U V light -~
for two hours. The glass plates are separated and the film is removed. Colorless, optlcally clear fllms are obtained such as represented by the three dimensional network polymer below:
lOCH2 CH CH ~ ~H \ CH 0 CH2 3 ~ 3 \ ~ 3 \ 1 3 i!
CE3-C-C-0-~CH2 ~ Si-0- ~si-oJ si-o - Si-~CH2 ~ 0-C - C-CH3 Cl9~;~ ~CC~H2~ ~H3~ 3 I
-CH2-CH2~-o-CH
:
lS H2 CH3~ ~CIH3~ ~CI 3~ 1 3 0 2 CH -C-C-0-~CH ~ Si-0~ ~Sl-C Sl-0~-Si-4CH2 ~ 0-C - C-CH
2 1 l I ~ I ~ 3 0 CH3 ~H2~ ~H J75 ~H3 ~H~ ~
; ~h~ O - C~- C~- CH3 CH2-~0-CH2-CH2~-2~0-CH3 CH3 C~ l1 The following physlcal properties are measured on an ~: : :
~ Instron tester ASTM D 1708 using standard t'dog borett samples ' .
cut from 0.2 mm thick ~ilms. This test ls used on all the examples where tensile strength, modules and elongation are 2~ measured.
~ SS~
~ . ~
Tensile Strength 24 g/mm2 Tensile Modules 58 g/mm Elongation 56%
The oxygen permeability of the abo~re sample is determined by the following technique. The test is measuring the oxygen permeability of a material while it i~s wet with distilled water. This is an attempt to simulate the conditlon of a contact lens when on the human eye. Two chambers filled with distilled water at 32C are connected together by a common passageway. Across this passagewaD is place the material to be tested. The oxygen concentration in the first chamber is lowered by bubbling nitrogen gas into the second chamber until the oxygen concentration in the first chamber is below about 0.1 ppm. Aerated distilled water is introduced into the second :
chamber. There is-located in the first chamber~an~oxygen sensing electrode which measures the~oxygen concentration in~
the first chamber. This measures the oxygen permeability of the material covering the passageway between the two chambers.
The oxygen permeabillty of the sample can be calculated from~
the rate of oxygen concentration change in the first chamber.
c.c.(STP) cm The unit of oxygen permeability is sec cm2 mm Hg . The~
oxygen permeabllity of the above sample :lS 1.33 x 10 9 25 ~ cc - c ~ ~ 2 which is 18 t`imes~more oxygen permeable sec-cm -mm Hg ~ ~
than the control material polyhydroxy ethyl methacrylate hydrogel ~PHEMA).
::
~ 56 EXAMPLE ~
The fluid product of Example V together with 1%
diethoxyacetophenone is placed in a suit;able contact lens spin casting mold and a contact lens is prepared as taught in U.S. 3,408,42g. After 2 hours irradiation with UV light, a cured optically clear, hydrophilic contact lens is o~-tained. The sess~le drop contact angle~ using distilled water on this lens is 55. The lens ~as worn by a monkey~
during clinical testing without trauma. In contrast, a methacrylate endcapped polydimethylsiloxane as prepared in Example VI of U.S. Patent 4,153,641, has a sessile drop contact angle of 110C rneasured using distilled water.
::
:
~:
:
~:
:~ _ 5~ ~
E~AMPLE VIII
77.6 g of diethylene glycol allyl methyl ether as pre-pared in example IV and 320 mls of hexane are passed through 40.0 g of activated F-20 alumina into a lO00 ml 3~neck flask equipped with a mechanical stirrer~ a thermometer, and a nitrogen inlet. 40 microliters of a 20 parts per thousand Pt solution in the form of H2 Pt C}6 6H2o in 2-propanol is added to the mixture. 40 mls of hexane is distilled to re-move the water and alcohol. The mixture is cooled to 40C
: ~
at which time 40 g of methacrylate end capped 40 mole percent silicone hydride polydimethyl siloxane as prepared in Example III is added. Distillation is continued for one hour at which time the temperature is at 80C. About 200 mls of hexane is removed. In~rared spectra at 2175 cm 1 shows no ~;~ 15 remaining sillcone~hydride bond. Purification lS completed~
exactly like that of Example V. 50 g~rams o~ a methacrylate end~
capped 40 mole percent silicone diethyIene glycol propyl : `
methyl ether polydlmethylsiloxane is obtained. The product is a clear, colorless fluid with a viscosity of 8.5 stokes by Cannon ~is~cometer. Analytical data confirms structure to be:
~CT~2 ~ ! 3 ~ 1 3 CH3 ' CH3 //H3 : ~ C - C - O ~CH2~ Si: ~0 - Si~O - Si~ O - Si ~CH2~ 0 - C - C
40 i 60 ~ 11 \
CH2 ~0 - CH2 - CH2~ 0 - Cll ~:
,. ,~ .
; Q_ E~AMP1E lX
Films of the fluid product obtained in Example VIII are cast between glass plates by adding I% dlethoxy acetophenone to the monomer and irradiating with UV light for 'cwo hours.
The glass plates are separated and the film removed. Color-less~ optically clear films are obtained.
The oxygen permeability of the above sample is dete~rmined~ -by the procedure as described in Example VI. The oxygen permeability of the sample is 6.5 x 3~ lO cc cm/sec cm2`mm Hg which is 9.4 times more oxygen permeable than the control material polyhydroxyethylmethacrylate hydrogel (PHEMA).
:
::
:::: : : :
:: ~ : : : ; :
::
:
' ' ' ::: :
EXA~PLE X
_.
The ~luid product of Example VIII t;ogether with 1%
diethoxy acetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After 2 hours irrad1ation with UV light, a cured opticall~ clear, hydrophilic contact lens is obtained. The sessile drop contact angle using:dis-: tllled water on this lens is 50 .
:
: :
: ;
:~ : ::: :
:: :
:
:::
:
,i ~3~
_XAMP1E XI
59.7 g of peroxide free diethylene glycol allylmethyl ether prepared as in Example IV, 0.010 ~ H2 Pt C16 ' 6H2o in 1 ml of 2-propanol and 200 ml of toluene are added under dry nitrogen to a 500 ml round bottom 2-neck flask and mixed.
The mixture is heated to reflux and dried by azeotropic dis-tillation. The mixture is cooled and 100 mls of heptamethyl cyclotetrasiloxaneS available from Silar Laboratories, Inc., is added. The mixture is heated to reflux for two hours at 10 which time in~rared spectra bond at 2175 cm 1 shows no silicone hydride. The mixture is cooled and solvent is removed under aspirator vacuum. The crude product that remains is vacuum distilled. 135 g of 3 (diethylene glycol methyl ether) propyl heptamethylcyclotetraslloxane~is obtained (b.p. 96o/ ;
15 .025 mm). Analytical data confirms structure to be: ~ ~
:
CH CH
2 CH2~CH2-O-CH2-CH2-0-CH2-CH2-O-CH
O O
H3C - Sl - 0 - Si - CH3 : ~ :
.
EXAMPLE XII
50 g of peroxide free 3 (diethylene glycol ~ethyl ether) propyl heptamethylcyclotetrasiloxane as prepared in Example XI is added to a 100 ml round bottom 2-neck flask equipped with a mechanical stirrer, a reflux condensor and a nitrogen inlet. The flask is heated for one hour at 110C using an oil bath at which time 1.9 g of 1,3-bis;(4-methacryloxy- ;
butyltetramethyldisiloxane as prepared in Example I and 0.05 g of dry cesium hydroxide available from I.C.N. Pharmaceutlcal, Plainview, New Jersey, are added. A substantial increase in viscosity is observed within five minutes. The mixture i6 heated for an additional hour, then cooled to room temperature and neutralized with C.04 g of acetic acid for one hour. The mlxture is then diluted with hexane, dried for one hour~over anhydrous Mg SO4,~filtered and the solvent removed at r~educed pressure. The low molecular weight cyclics are removed by precipitation with a water methanol mixture. A clear color-less fluid material is obtained.
~: :
~:
: :
: ~ ;
.
- ~
_XAMPLE XIII
The ~luid product of Example XII together with 1%
diethoxy acetophenone is placed in a suitable contact mold and a contact lens is prepared by the same method as taught : 5 in U.S. 3,408,429. After two hours of lrradiatlon with DV
light, a cured optlcally clear, hydrophllic c;ontact lens lS
obtained. The sessile drop contact angle using distilled wa~er on the lens is 55. : ~ ~ ;
;: :
:~ :: :: : :
.
::
:
:::: ~ : :: :
:~ : : : :
:
::
EXAMPLE XIV
50 g of perox1de free 3 (diethylene glycol methyl ether) propyl heptamethycyclotetrasiloxane as prepared in Fxample ~I is added to a 100 ml round bottom 2-neck flask equipped with a mechanical stirrer, a reflux condensor and a nitrogen inlet. The flask is heated for one hour at 110C
usina an oil bath at which time 0.5 g of tetramethyltetra-~inylcyclotetrasiloxane, available from Silar Laboratories, is added. 0.05 g of dry cesium hydroxide is then added. A
high molecular weight immobile polymer forms in five minutes.
The mixture is heated for an additional hour then cooled to room temperature and neutralized with 0.04 g of acetic acid in 10 mls of hexane. The mixture is then diluted with an : ~
; addltional 100 mIs of hexane, dried~ov~er anhydrous Mg SO4,~
filtered and the solvent removed at reduced pressure. The polymer is purified by precipitation ~rom a water-methanol mixture. The~product is a clear, colorless hlgh molecular weight immobile~polymer. Analytical data confirms structure.
The polymer is: 25 mole percent 3(diethylene glycol methyl ether) x mole percent polydimethylsiloxane.
: : : :
' 3~341~
EXAMPLE XV
A film of the product obtained in Example XIV is cast between glass plates by adding 1~ benzoyl peroxide, available from the Pennwalt Corporation~ Pennwalt Bldg., Three Parkway, Philadelphia, Pennsylvania 19102~ and heating eight hours at 80C.
The glass plates are separated and the:film removed.
A colorless optiGally clear, hydrophilic film is obtained which has a sessile drop contact angle with di`sti~led~water of 55 , .
:
:~ :
: :: : : :
: ~ ~ : : :
:: : :
~ e~
:
~ .
EXAMPLE XVI
50 g of peroxide free 3-(diethylene glycol methyl ether) propyl heptamethylcyclotetrasiloxane as prepared in Example XI is added to a 100 ml round bottom 2-neck flask equipped with a mechanical stirrer, a reflux condensor and a n~trogen inlet. ~he material is heated for one hour at 110C uslng an oil bath. At this tlme 0.5 g of dry cesium hydroxide is added. A high molecular weight polymer is ~ormed~in five minutes. The reaction mixture is then cooled to 90C and 0.1 g of distilled water is added. A substantlal decrease in viscosity is observed w~thin five minutes. The~mixture is heated for an additional hour. The mixture is then cooled, diluted with 200 mls of hexane, washed with distilled water, dried over anhydrous Mg SO4 and the hexane removed at reduced ~ pressure- A clear ~luld silanol end capped 25~mole percent sllicone diethylene~glycol propyl methyl ether polydimethyl-~siloxane is obtained. Analytical data conf~irms structure.
, ~3~
~XAMPLE XVII
2.0 g o~ the material prepared in accordance with Example XVI is mixed with 0.15 g o~ ethylsilicate prepolymer (M~600) a~ailable ~rom Petrarch, PØ Box 141, I.evittown, PA 1905~, 0.025 g of trimethoxy phenylsilane available from Silar Lab. and 10 microliters of dibutyltin dilaurate available ~rom Alfa Products, Beverly Massachusetts. A ~ilm is cast ~rom the above mixture between glass plates by heating in an 80C
air oven for 8 hours. The glass plates are separated and the film removed. A colorless, optically clear, hydrophilic film is obtained which has a sessile drop contact angle with distilled water o~ 55.
: :
-::: :
: ~ :
: ~ :
_ ¢~_ r3~q EXAMPLE ~
To 72.7 parts of the monomer prepared as in Example V is added 18.2 parts of lsobornyl acrylate, available ~rom Rohm and Haas, Independence Hall West, Philadelphia, PA 19105 and 9.1 parts of acrylic acid and one part diethoxyacetophenone. After mixing, a film is cast between glass plates. The film is irradiated with UV light for two hours. The film i3 released, extracted for four hours in a 1:1 hexane/isopropanol mixture and buffered. This buffering procedure consists of placing the film to be tested, which is about 2" x 3" in size, into 100 cc of O.lN ammonium hydroxide for 24 hours. Then the film is soaked in an isotonic phosphate buffer (pH 7.2), i.e.
Na2HP04, NaHPO4 and NaCl for another 24 hours. This b~uffered saline solution is made by mixing 1.403 g of Na2HP04, 0-458 6 of NaH2P04 and 8. o 8 of NaCL with water to make a;final vo1ume of one liter. The film is then stored in an isotonic buffered :
saline solution (pH 7.2).
The test procedure for determining the percent of water ; in the film is as~follows:
A 0.3 g sample is taken from the above hydrated film.
The sample of film is roller dried and immediately weighed to the nearest milligram. The weighed film is placed into a vacuum oven (1 cm Hg) overnight at 80C. Then the material is cooled and the vacuum broken by admitting dry air. After the sample is at room temperature for about 15 minutes, the sample is weighed to the nearest milligram. The percent water is calculated as follows:
Wet Weight - Dry WeiQht PeFcent Water = Wet Weight x 100 The percent water for the above sample is 18%.
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J ~
~ ~3~
The oxygen permerability ot' the above sample, in the buffered ~orm, is determined by the same technique described in Example VI except bu~fered saline i.s used in place of disti].led T~ater.
The oxygen permeability of the above sample is 6~7 x 10 lcc cm/
sec-cm -mm Hg which is 8.2 times more oxygen permeable than the control material polyhydroxye~hyl methacrylate hydrogel.
The following physical properties are measured a~ des-cribed in Example VI:
Tensile strength 36 g/mm2 Tensile Modules 72 g/mm2 Elongation 84%
, :
:
:~
;
EXAMPLE XIX
72.7 parts of the monomer as prepared in Example ~
are mixed wit~ 18.2 parts o~ isobornyl acrylate and 9.1 parts o~ acrylic acid and one part diethoxyacetophenone. 30 ~Q of the mixture is placed in a suitable contact lens spincasting mold and a contact lens is prepared as taught in U.S. ~
patent 3,408,429. A~ter two hours irradiàtion~with W llght, a cured contact lens is obtained. The lens formed is soft, water absorbing, hydrophilic, optically clear, elastic and strong. The lens was worn during clinical testing without trauma ~or 24 hours by a monkey.
::
:: ~
:::
. ~0-~ ~ .
_AMPLE XX
540 mls of dried pero.Yide free tetrahydrofuran and 21.5 g of potassium metal are char~ed into a 2000 ml three-neck flask equipped with mechanical stirrer and a dry nitrogen inlet. 88.4 ml of triethylene glycol monomethyl ; ether, available from Chemical Samples Co., is added to the mi~ture dropwise. Arter the potassium metal has completely reacted, li8.6 ml of allyl chloride is added dropwise to the mixture at such a rate in order to maintain a gentle reflux.
After the reactlon is complete, 500 mls of distilled water are added in order to dissolve the preclpitated salt. The tetrahydrofuran layer is washed with salt water (270~g NaCl/1 11ter ~water) in order to remove the excess alcohol. The resulting product ln tetrahydrofuran is coll~ected and the tetrahydio-furan is removed with a water aspirator. The product is dlstilled at reduced pressure~. 75.5 g (74~ yield) of~tri~
ethylene ~lycol allyl methyl ether is obtained (b.p. 97C - 1~00C/~
2mm). The analytical data is consistent with a product of the general formula:
20~ C~ =CH-CH2-0-CH2-CH2-0-CH2-CH2-0-C~2 C~
:
~, : :
~ .
: ~ .
~3~
_. . . ._ .. ..... ~ . . . ..
. . .
EXAMPLE XXI
.
58.8 g of triethylene glycol allyl methyl ether, 25 prepared in Example XX followed by 320 mls of hexane , are passed through 54.7 ~ Or actlvated F-20 alumina into 2 1000 ml three-neck ~lask equipped with mechanical stirrer, thermometer and a dry nitrogen inlet. 40 ~Q of 2~ pp~c Pt, ln 2-propanol is added to tbe mixture. The mixture is warmed and dried by azeotropic distillation. The mixture ls cooled to 40C
at which time 40 g of the methacrylate endcapped 25 mole percent "
hydrlde polysiloxane as prepared in Example TI is added.
:
: Slow distillation ls continued ~or one hour at which time~ :
the mixture temperature is 80C a~d about 200 mls of hexane :: ha~e been removed. ~Infrared spectra shows that the reaction is complete. The polymer ls purified by precipitation ~rom~
:
a 1:1 mixture o~ me~hanol and wa~er. Analytlcal data con~irms the structure to be:
O CH : .tfCT~ CX3 O
C,~ 3 1 3 l 3 : t ~1 ~CH2 C-C_o ~ ~H27~ Sl ~ - O--Sl - O _ Si - O --Si ' C~;;~O-C-C
3 CH 3 ~CH 3 J25 I H 2 ~ S- CH 3 C~13 I
' C;~2--0-C~-r'X2~0-C~.3 :
:
:: ~ : : :
.
~ .
~ 7~ ~
.
$~3 q~
EXAMPLE XXII
The ~luid product obtained in Example XXI t,ogether with 1% diethoxyacetophenone is placed in a 3uitable contact lens spin casting mold and a con~act lens is prepared by the sa,me method as tau~ht in U.S. 3,408,429. A~ter two hours irradiation with W light, a cured optically clear, hydro-philic contact lens is obtained. The contact lens has a low contact angle with water.
:
:~
EXAMPLE XXIII
1200 mls of dried peroxide free tetrahydrofuran and 100 g Or potassium metal are charged into a 3000 ml 3-neck flask equipped with a mechanlcal stirrerJ a thermometer and a dry nitrogen inlet. 317.7 mls of solketal, available from Aldrich, is added dropwise. After react:Lng overnight the potassium metal is reacted completely. 188.5 mls of allyl chloride is added dropwise at such a rate to maintain a gentle reflux. After reacting the mixture again o~ernight, 850 mls of distilled water are added to dissolve the precipitated salt. The tetrahydrofuran (~HF) layer 1s washed with a salt water solution to remove excess solketaI. The~
resulting product in THF is collected and the THF removed~
with a water aspirator. The product is distilled at reduced pressure. 261.4 mis of solketal allyl ether (b.p. 76C/14~mm) is obtained. Analytical da~a con~irms structure to be:
2 CH2 0 CH2-lH_IH2 O O
\
C
` H C CH
~ ' ~
~' E'~A~ XXIV
49.5 g of solke~.llallylether as prepared ln ~xample XXI~ ~ollowed by 320 mls oL` hexane are passed through 46.1g of activa~ed ~-20 alumina intc a lOG0 ml three-neck flask equipped with mechanical stirrer~ thermolrleter and a nitrogen inlet. 40 ~Q or 20 p~t Pt in 2-propanol is added to the mixture followed by a~eotropic distillation to remove alcohol~
and water. The charge is cooled to 40C and 40 g of the methacrylate endcapped 25 mole percent hydride polysiloxane prepared as in Example II is added. Slow disti}lation continues for one hour during which time the mixture temperature increases to 80C and about 200 mls of hexane are removed.
In~rared spectra Gonfirms the reaction is complete. The polymer is puri~led by precipitation ~rom a l:l mixture of water and methanol. Analytical data conflrms the~structure ; Ol Cll3 ~l3~ ~I 3j ~ 3 ~ C~
C`-C-O-~ CH ~ Si-O- Si-~ _ ~Si-( ~Si~CH ~ O-C-C
2 ~ l ~ 1 2 ~ ~
CH3 CH3 ICH2~ ~5 ~CH3, 75 C~E~3 CH3 \ /
; ~ H3~ 3 : ~ :
:
~:
:
: ~ ~ 7g ~
~ ~4~ J~
EXAMPLE XXV
5.0 g of the polymer as prepared i:n Example XXIV
52 mls of glacial acetic acid available from Fisher, and 4.2 mls of distilled water are charged to a 100 ml round bottom flask and heated to 50C overnight at which time the acetic acid, acetone formed during reaction and water are removed under high vacuum. Infrared shows a large hydroxyl bond and the ketal doublet at 1380 cm 1 is gone~
The polymer is a clear fluid material of the following structure: .
CH2 O ~CH3 CH3 CH3 CH3 ~ H3 ;
:C - C - O-~CH2 ~:~Si --~O-Si~ O-Si3 - O-Si -~CH2 ~ O-C-C
~¦~-25 1 O CH
CH3 GH3 CH3 ~ Cf 2 CH2 : ~ :
- ~ CH
~ 2 QH OH
~:~ ': :
:
: :
:
~3~ `3 EXAMPLE XXVI
The flùid product Gbtained in Example XXIII together wlth 1% diethoxy acetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After two hours irradiation with UV light, a cured optically clear~ water : absorbing, hydrophilic contact lens is obtained. The percent~: water as determined by the procedure in Example XVIII lS ~13%~.
The sessile drop contact angle measured using distilled water ~:
is low. :
: : ::
.
:
:
:: :
- : :
:: :
: q1~
7r~
.~ ' r EXAMP1E XX~II
34.9 g of 0-trimethylsily1 allyl alcohol available from Petrarch Inc., PØ Box l4l, 1evittown, PA 19059, 40 ~ of 2~ ppt Pt in 2-propanol and 320 mls of hexane are charged into a 1000 ml three-neck flask equ~pped with a mechanical stirrer, a nitrogen inlet and a thermometer. The mixture is warmed to reflux and dried by azeotropic distillatlon followed by cooling to 40C. 40 g of the methacrylate endcapped 25 mole percent silicone hydride polysiloxane as prepared in Example II is added. Distillation is continued for one hour ; ; during which time~the mixture tempè~rature increases Co 80C~
and about 200 mls of hexane are~removed. Infrared spectra~
confirms tha~t the reaction is;~complete~. Th~e polymer is~purlfied by precipitation from a l:l mixture of methanol and water.
A clear ~luld polymer is obtalned having the followlng structure as confirmed by analytical data:
::
H ~CH CE~ ~ CH~ ~ CE~3 0 CH
C~2 ~ 3 ~ ~ 3 J 3 ~ ll ~ 2 C-~-0 ~CH2 ~ Si - 0 - ~Sl-0 _ Si-0 - Si ~ CH2 ~ 0-C-C
CH3 3 ~H2 25 C~3 ~ CH3 CH3 -Si-CH3 :
~ ' f~
EXAMPLE XXVIII
5.0 g of the polymer as prepared in Example XX~II, . 52 mls of glacial acetic acid and 4.2 mls of distilled water are chargeà to a 100 ml flask and heated to 50C over-night at which time the acetic acid and water are~removed:under high vacuum. Infrared shows a large hydroxyl band.
The polymer is a clear fluid material of the follow1ng structure:
CH2 ~I CIH3 ¦ I Cl 3 /jH2 jC - C - O -~CH2 ~ Sli - O -~Si - O~-~Sji ~ 0~- Si -~CH2 ~ 0 - C~ - C
~ 3 :CH3 CIH2 : CH3 CH3 O ~ CH3 : :~: : CIX2 : ~ ~ :
OH
: :~ ~: :
::
: , ~ ' :
~ 3 EXAMPLE XXIX
The fluid product obtained in Example XXVIII together with 1% dietho~yacetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After two hours irradiation with UV light, a cured optically clear, hydrophilic, as measured by its low contact angle with water, contact lens is obtained.
::
_80 ~
~3~43`.~
E`{AMPI,E XXX
In a 2 liter, three-nf?cked flask ~itted with mechanical stirrer, reflux condensor and a dropping funnel ls placed 714 g of 2-allyl oxyethanol available from Haven Chemical Co., 5000 Langdon Street, Philadelphia, PA 19124. 600 g of phosphorous tribromide is added to the rnixture dropwise while stirring. This is done over a period of about two hours. The temperature is permitted to rise until the reaction mixture gently refluxes. The mixture is then distilled and the distillate below 160C is collected in a 2-liter flask with 1 liter of distilled water. The crude 2-allyloxyethylbromide is dried over calcium chloride and d~stilled. Pure 2-allyloxyethylbromide is obtained.
750 mls of dried peroxide free tetrahydrofuran and 14.9 g of potassium metal are charged under dry nitrogen into a~2000 ml three-neck flask equipped with mechanical stlrrer, condensor and an addition funnel. 55 g of solketal is added dropwise. Potassium metal reacts completely within 24 hours at whlch time 68.9 g of the 2-allyloxyethylbromide is added at such a rate as to maintain a gentle reflux. After an overnight reaction, 500 mls of distllled water are added to the reaction vessel to dissolve the precipitated salts.
The THF is then removed with a water aspirator. The product is distilled at a reduced pressure. Pure 2-allyloxyethyl solketal is obtained. Analytical data confirms structure to be:
.
CH2 CH CH2 0 CH2 C~2 O CH2 ICI ~ 2 O O
C
_ 8~
~ ~3~S~3~
:~ :
62.2 ~ of' the 2-allyloxyethylsolketal as prepared in E~a~ple XXX f`ollowed by 320 mls of hexane ls passed through 57.9 g Or activated F-20 alumina into a three-neck flask equipped with mechanical stirrer and a dry nltrogen inlet. 40 ~ of 20 ppt Pt in 2-propanol is added to the mixture. 40 mls of hexane are distilled to remo-~e water and alcohol. ~he mixture is cooled to 40C, at which time 40~ g Or the methacrylate endcapped hydrlde polydimethylsiloxane~
as~prepared in Example II is added. Distillation is continued for one hour at which time the mixture temperature ls 80C.
About 200 mls of hexane are removed. Infrared spectra at 2175 cm 1 con~irms the reaction is complete. The polymer is purifled by~precipltatlon from a l:l methanol/water~mlx~ure~
15~ A~clear~fluld polymer is obtained. Analytical data confl~rms 'hc~;structu-e ~to b~
CH 0 ; ~ ~H3~ CH3 CH~ 1 3 IH
C -C-0-~ CH2 ~ Sl~-- ~0-Sl~ _ 0-Si~--O-Si~-~CH2 ~ 0-1~ C
~Z ~H3 ~ : CV3 CN2 5 ~ CH C~ 3 ~ 2 CH2-0-C~2-CHZ-O-cH2 ~H ICH2 C
~ ~ H3C CN3 :
: ~ :
:: : :
~: ::
: ~ :
EXAMPLE XXXll 5.0 g of the polymer as prepared in Example XXXI, 52 mls of glacial acetic acid and 4.2 mls of distilled water are charged to a 100 ml flask and heated to 50C overnight.
Then the acetic acid,~water and acetone formed are removed under high vacuum. Infrared shows a large hydroxyl bond and the ketal doublet at 13~0 cm 1 is gone. A clear fluid material of the following structure is obtained:
CH2 It CIH3 CIH3 CIH3 CIH3 C -- C -- O --CH2~ Sl ~0 -- Si~O - Si~ -- Sl ~CH2~ -- r-- C
CH3 ~ CH3 C~3 CIH2 C~3 CH3 CH2 - O CH2 - CH2 - O - ~H2-CH-CH2 OH OH
; ~
:
' _ ~3_ 3`~
:
EXAMPLE XXXIII
The fluid product obtained in Example XXXII together with 1~ diethoxyacetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the - 5 same method as taught in U.S. 3,408,429. After two hours irradiation with UV light~ a cured optically clear and hydro-philic, as measured by its low contact angle with water, contact lens is obtained.
::
;~ : : : :
:
~;
~.A~IPLE XXXIV
-163.3 g. o~ all~l alcohol a~ailable ~rorn Aldr~ch in one liter o~ toluene is charged under dry nitrogen to a 5-liter three-necked ~lask fitted ~ith a mechanical stirrer and a reflux condensor. 100 g o~ potassium metal is added, stirrlng begins and the charge is heatecl in an oil bath until the mixture refluxes gently.
A~ter the reaction mixture has refluxed for 15 hours, the temperature Or the oil bath is lowered to ~5C-90C, at which time a warm solution of 95 g of monochloracetic acid in 800 mls of toluene is added at such a rate to maintaln a gentle reflux. A precipitate of potassium chloroacetate ~orms. Arter all the cnloroacetic acid is :
added the mixture is refluxed and stirred ~or 48 hours.
When the reaction is complete, the flask is cooled ~
and the reactlon mlxture is transferred to a 5~1iter separatory funnel and extract~ed with three one-liter portions of water.
The water extract is~acidified with 20% HCl. The crude alIyl-oxyacetic acid that is produced is extracted three times with ether. The ether extracts are combined and the solvent removed by distillation on a steam bath. The residue is then ~ractionally~distilled under reduced pressure. Pure ~: :
allyloxyacetic acid is obtained.
200 ~ o~thiongl chloride is charged to a one-liter three-neck flask equipped with a 250 ml dropping funnel, an efficient condensor and a mechanical stirrer. To this mixture is added dropwise a~d with rapid stirring, 116 g of allyloxy-acetic acid. An evolution o~ hydrogen chloride and sulfur dioxide takes place. When all the acid has been added9 the mixture ls heated to 80C and kept at this temperature ~or t~o hours. Then the remaining thionyl chloride is removed on steam bath under reduc~d pressure. The crude acid chloride is obtalned.
In a one-liter f'lask, equipped wlth mechanical stlrrer and a 500 ml dropping ~unnel and surrounded by an ice salt freezing mixturle~ is placed 0.5 1 of 28% cold, concentrated aqueous di~ethylamine available from Aldrich. The crude acid chloride is added to this mixture slowly while stirrlng, Stlrring is continued for one hour after the addltion of the acid chloride. 'rhe aqueous mixture is extracted three~t~imes with 250 mls of d1ethyl ether in order to collect the amlde which forms. The collected ether is remo-~ed by heating the mixture on a steam bath. Then the product Ls fractionally distilled a~ reduced pressure. Yure allyloxy N,N-dimethyl ~
acetamide is obtained. hnalytical data confirms the~structure~ ~;
to~be~
: ~ o :
~: ~
:
::: ~:: : :
: ::
: ~
~ ~6 :
, .
~39L~
EXAMPL,F, ~
41.1 g of the allyloxyacetamide as prepared in Example XXXIV follqwed by 320 mls of hexane are passed through 38.3 g of activated F-20 alumina into a 1000 ml three~neck round bottom fla3k equipped with mechanlcal stlrrer and a nitrogen inlet. 40 ~Q of 20 ppt Pt, in 2-propanol is added to the mixture followed by azeotroplc distlllation ln order to remove water and alcohol. The mixture is cooled to 40C
at which time 40 g o~ the methacrylate endcapped 25 mole percent silicone hydride polydimethylsiloxane as prepared in Example II is added to the mixture. Distillation contlnues for one hour dur1ng which time the mlxture temperature ls increased to 80C resulting in about 200 mls of hexane belng removed. Infrared~spectra confirms the reaction ls complete.
The polymer is purified by precipitation from a 1:1 mixture of water and methanol. Analytical data confirms the structure to be:
0 CH ¦ CH~ ¦ CH ~ CH3 CH
CH2 ¦3 1 3 ~ ~ 3 1 3 1 1~ 3 ~PC-C-0~ CH2 ~ Sl - )-Si- ~ 0-Si ~ -O-Si~ CH2 ~ 0 C C~
CH3 ~H \ CH3~ ,5 CH3 2 CH2-0-CH2~ N'~ CH3)2 ,.
_ 8 7 .
_XAMPLE XXXVI
~he ~luid product obtalned in Example X.CXV together ~ith 1% diethoxyacetop'nenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After two hours irradiation with W light, a cured optically clear and hydrophilic, as measured by i.ts low contact:angle with water, contact lens is obtained.
, f : J
3~ 9 EXAMPLE XXXVII
Synthesis o~ 3,3-tetrarnethyl - 1,3-dislla - 2w oxacyclohexane - 5-(N,N-dimethyl carboxamide).
To 218 g. of 1,1,3,3-tetramethyl - 1,3-disila 2 oxacyclohexane - 5-carboxylic acid (synthesized according to the procedure of Omer W. Steward and Leo H.
Sommer, J. of Organic Chem., Vol. 26, page 4132, 1961) in _ 1000 ml o~ anhydrous tetrahydrofuran, cooled to -15C, is added (under anhydrous conditions) lOl g of triethylamine and 108.5 g of ethyl choroformate. After stirring for 15 minutes, dimethyl amine is bubbled through the solution at -15C for thirty minutes. The solvent is then removed at reduced pressure. Then 1000 ml of diethyl ether and lOO~ml of,.~ater is added. The ether phase ls separate ~ ~
extracted with O.l N aqueous NaHC03, O.lN aqueous HCl, and dried with~MgS04. ~After rilteringg the ether ls removed to give the cyclic slloxane amide Or the formula.
: :
O CH
ll 1 3 CH
` CH2 CH2 ~:
~;~ CH3 ¦ ~¦ CH
Si Si 25This material is Or sufficient puri~y such that no further purification is necessary.
~f _8q -.~ .
. . , . . ~ : ... :
5~
EXAMPLE XXXVIII
122.5 g of 1,1,3,3-tetramethyl - 1,3-disila-2-oxacyclohexane - 5-(NjN-dimethyl carboxamide), as prepared in Example XXXVII, 87 g of 1,1,3,3 tetramethyl - 1,3-disila -5 2-oxacyclohexane, available from Silar Laboratories, 10 Alplaus Road, Scotia, New York 12302 and 4.14 g of 1,3--bis(4-methacryloxbutyl) tetramethyl disiloxane, as prepared in Example I are combined in a 250 ml flask. While vigorously stirring 1.52 g of trifluoromethane solfonic acid is added.
The reaction is stirred for 12 hours~ Then 10 g of NaHC03 is added. The product is pressure filtered to give a random copolysiloxane represented by the average formula.
:
: :: : : ~
:~ -90-~ ll v ~
I
o - c~
I
o v r~
~ v~ ~
o o Lr~
~--~r ~
v v~
:
~ o v $ x v ` c~
v o : I o ~ ~ ~
i: ~ ~ l :
V
: l :
l~ :
v :
o .,~
:: ~
o o ~ ~, ~ I
V--C~
ll V
3~
When this random copolysiloxane is mixed with 1% by weight diethoxyacetophenone, cast between glass plates and subjected to ultraviolet radiation, a cast sheet is obtained which is hydrophilic as measured by its low contact angle with water.
: ~ .
:
:
~ 32-
~ ~1 5~ R18 ~ N - C R2o wherein R18 is a divalent hydrocarbon havlng from 1 to 20 carbon atoms and Rl~ and R20 are the same or diff?rent~ and are selected from the group consisting of hydrogen and a hydrocarbon having from 1 to 10 carbon atoms, SULPHONE AND SULPHOXIDE '~~~~ ~~l -- R2~ SI -- R22 ()nl1 ~
where1n R21~is;a divalent or trivalent hydrocarbon having ~ :
from l to 10 oarbon atoms and the S atom is not attached to R21 by 15 : an aliphatic carbon atom beta to the Si atom, R21 may or may not be attached to R22 to form a ring which contains more than 3~carbon atoms and is selected from the group consistingg of a hydrocarbon having from 1 to 10 carbon atoms and O M
where M is selected from the group consisting of a monovalent metal ion and a quaternary ammonium ion, and n11 is an integer ~:
from 1 to 2, QUATERNARY_SALTS
7) ~:~ 25 - R23 -~N - R24 h~
wherein R is a divalent hydrocarbon having from 3 to 10 23 ~
carbon atoms and the l~ must be attached to a carbon atom of R23 which is at least 2 carbon atoms away fro~ the Si -3~
atoms, R2l~, R25 and R25 are the same or different and are mono~-valent hydrocarbons having from l to lO carbon atoms, ~ is a monovalent anion selected from the group consisting of halidesg R27 ~ CO ~ ~herein R27 is selected from the lO carbon atoms and a halogenated monovalent hydrocarbon having from l to lO carbon atoms and - R28 ~ S ~ wherein R28 is selected from the group consisting of a monovalent hydrocarbon having from 1 to lO carbon atoms and a halogenated monovalent hydrocarbon having from l to lO carbon atoms, ~;
lO HYDROXY ESTERS
; .
8) ~29 ~ )nl2R30 C O R3 ~ 0H~nl3 wherein R29 is a divalent hydrocarbon having ~rom l to lO
carbon atoms and n12is an integer from O to l and when nl2 ~ : ~ 15 is l the oxygen;cannot be attached to an aliphatic carbon~
; ~ ~ atom in R29 which is beta to the Si atom, R30 is a~divalent :~ hydrocarbon having~from 1 to lO carbon atoms, R3l is a:hydro-~: carbon having from 1 to 20 carbon atoms and a valence of nl3 + l and can have;no more than l oxygen atom attached to any one carbon atom, and nl3 is at least l, ~: :
9) 0 32~ 33 n 14 wherein R 32is a divalent hydrocarbon having from I to lO
carbon atoms and the ester oxygen~cannot be attached to an aliphatic ~- 25 carbon atom in R32 which is beta to the Si atom, R33 is a hydrocarbon havi.ng from l to 20 carbon atoms and a valence ;~ of n14~1 and can have no more than l oxygen atom attached to any one carbon a~om and n14 is at least 19 GYCLIC ETHERS
-10) ~, - R ~
:: ~ ~y ~9~ .
w.nerein R34 is a divalent hydrocarbon having from 1 to 10 carbon atoms, 11) ~ o _ CH 2 , CH 2 ' n 1~
- R ~ J
O--wherein R35 is a divalent hydrocarbon having from 2 to 10 :: carbon atoms and nl5 is an integer from 1 to 10, :
: ESTER-ETHERS
12) o ~ 13~ ;~
- R36 ~ C ~ 2 - CH ~ 8 : wherein R36 is~a divalent hydrocarbon having from 2 to l0:~
~ : carbon atoms and the carbonyl group ls not attached to a : ~ 15 carbon atom alpha to~the Si atom, R37 i:s~selected from the~
group consisting of methyl and hydrogen, R38 is selected from ;~
the group consisting of hydrogen, a~monovalent hydrocarbon~ :
o havlng from l to I0~carbon atoms and-C - R39 wherein R39 is a monovalent hydrocarbon ha~ing from 1 to 10 carbon atoms :
: : and n is at least 1, AMINES
13) ~ R40 ~ N - R
:~ I
; 25 : 42 wherein R40 is a divalent hydrocarbon having from 1 to 10 carbon atoms, R41 and R42 can be the same or different and are selected from the group consisting of monovalent hydro-carbons having from 1 to 10 carbon atoms and ~ CH2~n ;OH
where nl7 is 2 to 4, ~.3 SULPHONAMIDES
14) ~3 Il ~ .
0 . R45 wherein R43 is a divalent hydrocaroon having f'rom 1 to lO
carbon at~ms and the 3 cannot be attached to a carbon atom of R43 which is alpha to the Si atoms, R44 and R45 can be the same or diferent and are selected from the group consisting 10 of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, CYCLIC AMIDES
~CH2~ CH2~j~ ` :: :
15 ~ ~ _ R46 ~ - N j ~ ~ ;
wherein R46 is a divalent hydrocarbon havlng from 1 to 10:
carbon atoms and nl8 is an integer from ~ero to 3, CYCLIC AMIDES I ~ ;
16) ~ ; 1 ~ ~ _ q g \ ~ N--1¦ R50 : ~ ~ O ' ~
wherein nlg is an integer from zero to 3, R47 and R48 30 are selected f~rom the group consi3ting of hydrogen~ divalent or monovalent hydrocarbon having from O to 10 carbon atoms and R49 is selected from the group consisting of hydrogen, ~ ~0 .
' :
divalent or monovalent hydrocarbon having from 1 to 10 carbon atoms and one of R~7, R48 and R49 must be a divalent hydrocarbon and attached to the Si atom, R50 is selected from the group consisting of a monovalent hydrocarbon ha~i.ng from 1 to 10 carbon atoms and -~ CH2 ~ OH wherein n20 is an integer from 2 to 49 CARBOLYLATE SALTS
17) O
R51 ~ C ~ ~2 wherein R51 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group ca~mot be attached to a carbon atom of R51 alpha to the Si atoms and ~ lS a mono~alent cation:selected from the group consisting of monova:lent metal ~: 15 cations and R5~2 - N - R54 wherein R52~ R53~ ~54 and R55~are : ~ 55 :~
: the same or di~ferent and selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 oarbon atoms, and KETONES A~D ALDEHYDES
18) ~ :
: ~
- R5~ C R - l l 58 21 ~
wherein ~56 is a divalent hydrocarbon having from 2 to 10 carbon atoms and ~he carbonyl group cannot be attached to a carbon atom of R56 which is alpha to the Si atom, R57 is a divalent hydrocarbon having from one to 10 carbon atoms, R58 : is selected from the group consisting of hydrogen and a ~ ~ monovalent h~drocarbon havin~ from 1 to 10 carbon atoms and .. .
, . .
n21 is an integer from zero to 10.
When the term "soft" is used herein to describe the contact lens of the instant invention, it is meant that the material should have a softness preferably of about 60 or below on the Shore hardness A scale. Most preferably the Shore hardness should be 25 to 35 on the A scale.
When the term "hydrolytically stable" is used herein it is meant that when the contact lens or biomedical device ;
disclosed herein when placed into an aqueous solution, e.g., in the eye, or during the disinfecting step, i.e., water plus heat, the lens or device will not change in chemical composition, i.e., hydrolyze, which would cause a lens to change shape resulting in an undesirable change~in opti~cs or shape.
When the term "biologically inert" is used here in it is meant that the contact lens or biomedical device disclosed herein have phsiochemlcal properties renderlng them suitable :
for prolonged contact with living tissue, blood or the mucous membranes such as would be required for biomedical shaped articles. It also means that this material is antithrom-; bogenlc and nonhemolytic to blood which is necessary for prosthesis and devices sued with blood. These materials : ~ ;
~ disclosed herein are compatible with living tissue.
: ' j: ~; : :
: ::
When the term "oxygen transportability" or "oxygen transporting" or "that the contact lens has the capability o~ transporting oxygen sufficiently to meet the requirements of the human cornea" and used herein, ~t is meant that the instant material will allow sufficient transmission of oxygen throuæh itself to supply the necessary oxygen requirements of the human cornea. The oxygen requirements of the human cornea are about 2x10 6cm3/(sec.cm2atm.) as reported by ~ill and Fatt, American Journal of Optometry and Archives of the American Acade-my of Optometry, vol. 47, pg. 50, 1970.
When the term "flexible" is used herein, it is meant that the contact lens is capable of being folded or bent back upon itself without breaking.
When the term "resilient" is used herein, it is meant that after the lens has been deformed the lens wlll return quickly to its original shape.
The most preferred contact lens, i.e., polymers, of the instant invention are soft, hydrophilic, flexible, hydrolytically stable, biologically inert and have an oxygen transport rate of at least about 2x10 6cm3/(sec~cm2atm.).
These lens have a softness preferably of about 60 or below on the Shore hardness A scale. ~ost preferably, the Shore hardness should be 25 to 35 on the A scale.
To further illustrate the most preferred contact lens of the instant invention's physical properties, the tensile modulus of elasticity should be about 500g/mm2 or less. If ; the material is to be used as contact lens, then the Shore hardness and modulus may be related to the comfort of the lens to the wearer when used on the human eye.
There are commercially available~ both hydrophobic and hydrophilic contact lenses. The hydrophobic contact lenses available are primarily hard contact lenses made from such q ~
materials as (PMMA) polymethyl methacrylate. However, there are soft contact lenses available which are hydrophilic.
These lenses are usually made from polymers and copolymers based on (HEMA) hydroxyethylmethacrylate. However, neither of these materials made from PMMA or PHEMA are oxygen permeable enough to meet all the oxygen requirements of the human cornea.
Therefore, a materlal had to be de~eloped which was soft, for comfort, and also, oxygen permeable, to the extent that when the material was made into a contact lens, sufficient oxygen-would pass through the material to meet all the requirementsof the human cornea. It was found that polysiloxane materials are oxygen permeable to the extent that oxygen will pass through these materials when made into contact lenses suf-ficiently to meet the requirements of the human cornea.
Also, contact lenses made from polysiloxanes are soft, result-ing in more comfort for the wearer. Therefore, it was found that polysiloxane materials could be a good candidate for making soft contact lenses~ Howeverj it was found that when soft contact lenses were made from known polysiloxane materials, these lenses did not ride on the cornea of~the eye on a layer~
of tears but rather attach themselves to the cornea in a manner which altered the metabolic outflow and inflow of fluid from the eye. It is known that non-movement or sub-stantially non-movement of soft contact lenses on the eye can result in physical damage to the cornea. As mentioned, it has been noted that when a soft contact lens moves on the eye there is also an exchange of tear fluid under the lens resulting in the exchange of metabolic products supplying the cornea and metabolic byproducts being removed from the cornea.
This movement of tear fluid results in maintainin~ a healthy environment for the cornea. This has been generally reported by Roth and Iwasaki, Complications Caused by Silicone Elastomer Lenses in West ~ermany and Japan, paper presented at the ~3~
Second Contact Lens Conf`erence, February 1~, 1979, in ~okyo, Japan (Prof. Motoicni Itoi, r~.D., Kyoto, Prefectur-al University of Medicine, ~irokohji, Ka~ara Machi-Dohri, ~amikyo-Ku, Kyoto 602); Kreiner, Christine F., Meues Optikerjournal, No. 2 (21) February 10, 1979; ~onArens, Franz D., Neues Optikerjournal, ~o. 3 (21) March 10, 1979; and VonZimmermann, E., ~eues Optikerjournal, No. 4 (21) April 10, 1979.
The instant contact lens moves on the eye sufficiently so that no physical damage occurs to the cornea and sufficient tear exchange occurs so that the cornea metabolism proceeds normally. Therefore, the instant polymers make excellent material for manufacturing contact lens and~ as mentioned, do not stick to the eye but move sufficierltly during normal wear so that corneal metabolism will proceed normally.
When the term "moveable soft contact lens" lS used ; hereln, it is meant that when the lens is placed on the eye during normal wear the lens will move at least 0.5mm with each blink of the eyelid. Preferably, the lens should move from about 0.5mm to about l.Omm with each blink.
Further~ when the term "moveable soft contact Iens"
is used herein, lt i~s meant that the lens moves sufficiently on the eye so that (1) no physical damage occurs to the~
cornea and (2) sufficient tear fluid exchange occurs under the lens so that sufficient cornea metabolic activity is maintained resulting in a healthy environment for the cornea.
When the term "non-moveable soft contact lens" is used herein, it is meant that the lens will move less than about 0.5mm with each blink of the eyelid.
~hen the term i'hydrophilic soft contact lens" is used herein, it is meant that the soft contact lens surface will not repel water as opposed to the "hydrophobic" lens where the lens would tend to repel water.
:
- ~3 The following illustrates a preferred embodiment Or the instant invention: ~
f CH3 3\
I l 1 mole CH ~ C - COO ~CH? ~ Sli - ~ O
: ; 2 : 3(4-methacryolyloxy) butyl 1,1,3,3 tetramethyl disiloxane C ~ ~ :
18 75 moles~ S~ + 6.25~moles Si - O ~ 1) H2S04 or (CF350H) 1 1: 1 ~>' ~:: : ~ CH3, J 4 H J 2) RaHC0 Octamethyl cyclo 1,3,5,7 tetramethyl tetra slloxane cyclo tetra siloxane ~:
3 ~ H3 ~H3 ~ ~ ~ H3~ ~ ~ CH3 ~ ;0 CH3~
CH2-C:~- C-0 ~ CH2 ~ Si - O~ ~i ~ t , ; t siq~ ~CH2 ~ 0-C-G =CH2 : 3 ~ 3 ~75 ~ J 25 ~: : .
~:~ This is a representative general formula. ~he actual product is a random copolysiloxane.
;20 ~ CH2~= CH - CH2 - O - CH2 - IH eH2 : ~ :
~ ~ 0:
\C~ ~
C~3 so~ketal allyl ether or ~: 25 3~2,2 dimethyl 1,3-dioxolane-4 methyoxyl] - 1 - propene :
: Pt catalyst ~ \ Chromotography :~: ~ ` :
- f ~ r ~4Si~
~7 CH3 O f ~ ~ 1T ~ I 1l fH3 C~2SC c o {~ CH2~ si o--si ~ t ~S1 _ ~--Si __~L CH2 ~ -C ~ ~-CH2 CH3 ~ 3 /67 ~2 ~ CH3 CH2 o - CH2 - CH ~ CH2 . O O
~C~
¦ ~ CH3 CH3 : :
H20 , : :
HOCCH
\ / l~ 3 CH O CH ~ CH ~ CH3q CH3 O ~ C~H3 : 1 3 l~ 1 3 l 3 ~
GH2=C - C-O--~ CH2 ~ :Sl _ O - Si ~ ) - Si 0--Si ~CH ~ ~O - C~-~C~= CH2 ~ ~ ~ CH3 CH3/6 CIH2 33 CH3 : CH2 ~ ;:
: : ~ : :
OH OH-Peroxide \ /
Cured polymer or shaped body as product The product formed after standing in H2O was completely wettableand has absorbed 13 percent H20 by weight based on the total weieht of the material plus water. This is 33 mole percent 6,7-dihydroxy-3-oxyheptane hydrophilic sidechain methacrylate endcapped siloxane.
~: 25 These polymers and copolymers can be used to make biomedical devices, i.e.~ shaped articles, such as, dialyzer d~aphragms, to prepare arti~icial kidneys and other biomedi-cal implants, such as disclosed in Wichterle, U.S. patent 2,976,576 and Wichterle, U.S. 3,220,960. The instant poly~
mers and copolymers can be used in preparing therapeutic . .-~ ~. 3 ~
bandages as disclosed in Shepherd, U.S. patent 3,L12~,043;.
The instant polymers and copolymers can also be used in preparing medical surgical devices, e.g., heart valves, vessel substitutes, intrauterine devices, membranes and 5 other films, dialyzer diaphragms, catheters, mouth guards, denture liners and other such devices as disclosed in Shepherd, U.S. patent 3,520,949 and Shepherd U.S. 3,618,231.
The instant polymers and copolymers can be used to modify collagen to make blood vessels, urinary bladders and other 10such devices as disclosed in Kliment, U.S. patent 3,503,925.
The instant polymers and copolymers can be used to make catheters as disclosed in Shepherd, U.S. patent 3,566,874.
The instant polymers and copolymers can also be used as semi-permeable sheets for dialysis, artificial dentures and all of such disclosures as set forth in Spoy, U.S. patent 15`3,607,848. The instant polymers and~copoly~ers car also;be~
used in ophthalmic prostheses and all other uses~disclosed in Wichterle U.S. patent 3,679,50~. ~
When the term "shaped article for use in biomedical applications" or "biomedical devlce" are used herein, it lS
20 meant that the materials disclosed herein have physioGhemical properties rendering them suitable for prolonged contact with living tissue, blood and the mucous membrane such as wouId ~
; ~ be required for blomedical shaped articles, such as~ surgical implants, blood dialysis devices, blood vessels, artificial - 25 ureters, artificial breast tissue and membranes intended to come in contact T~ith body fluids outside of the body; for ; example, membranes for kidney dialysis and heart/lung machines, and the like. It is known that blood, for example, is rapidly damaged in contact with artificial surfaces. The design of a 30 synthetic surface which is antithrombogenic and nonagmolytic to blood is necessary for prosthesis and devices used with blood. The instant polymers and copolymers are compatible with living tissue.
.:
r ~MP LE_ 557 g o~ 1,3-bis(4-hydroxybutyl)tecramethyl disiloxane, 634 g o~ dry pyridine and 2 liters of hexane are charged to a 5 liter reaction llask equipped wi~h a mechanical st1rrer and dryin~ tube. The mixture is chilled to 0C and then 836 ~ of methacryloyl ch'oride is added dropwise. The mixture is a~itated continuously overnight. The reaction solution is extracted consecutively with 1~% water solutions of HCl and ;~H3 in order to remove excess re2gents and pyridine hydrochloride. The resulting solution of the product in hexane is dried with anhydrous MgSO4, filtered~ and solvent removed at reduced~pressure. ADout 459 g (55~ yield) 1,3-bis(4-methacryloxy butyl)tetr2meshyl~d1s11Oxane ls col-~
lected. The~structure is co~firmed~by in~rared spectra, ~ ~
1~5 proton magnetic resonance spectra and elemen.ial analysis.~ -IR spectra shows no 1ntense hydroxyl band between 3100 and 3600 cm 1 but does show strong ~ethacrylate absorp~ions at 1640 and 1720 cra 1. PMR spectra agreed with the p~oposed structure.
: _ _ ~ :
.
~ 20 . O ICX3 ;~ H ~C ~ ~ C.i--Cd2, 2 CH2 ~ _O
l, 3-bis( "-me.,h-c y:ox"~ _u yl ) vetræmethyl - 25 d.. s loxane ~ ~
-~, . . .
rXAMPLE II
14~.7 g of octamethylcyclotetrasiloxane, available from Silar Labs, 10 Alplaus Road, Scotia, NY 12302, 40.2 g of tetramethylcyclotetrasiloxane, available from Silar Labs, 7 ll.l g of 1,3-bis(4~methacryoxybutyl) tetramethyl disiloxane as prepared in E~ample I and 2.0 g of 95~-98% ~;2SO4 are charged, under dry air, ~o a 500 ml 2-neck reaction ~lask ecuipped with a mechanical stirrer. The mixture is agitated continuously for 20 hours at which time 17 g of powdered sodium bicarbonate is added to the reaction mixture and stlrred for two hours. The resulting mixture is then diluted with 500 mls of hexane, dried over anhydrous MgS04, filtered and the soIvent removed at reduced pressure. The~cyclics are removed under high vacuum (0.050mmj at 60C~ for one hour. 180 g of a methacrylate endcapped~25 ~ole percent ~
silicone hydride polydimethylsiloxane is collected. The~ ~ ;
polymer is a clear`colorless fluld which has a viscosity of 1.1 stokes-by Cannon viscometer. The structure is confirmed by infrared spectra, proton magnetic resonance spectra and ~silicone hydr~ide analysis ~o be:
0 CH CH~ CH~ ~ CH CH
G~ 3 I ~ I ~ ~ 3 ~ 3 -C-O~CH2 4 Si - O Si - 0 Si - O ~ Si~ CH2 4 f, ;~Cl.2 CH3 3 ~ ~ J ~ ~CH3 ~ ~5 3 : :
~ The product is a ranaom co~olysiloxane.
-3'3 EXAMPLE III
: ~ ' 122.4 g of octamethyl cyclotetrasiloxane, available from Silar Laboratories, 10 .41plaus Road, Scotia, New York 12302, 66.17 g of tetramethyl cyclotetrasiloxane, available from Silar Laboratories, 11.4 g of 1,3 - Bls (4-methacryoxybutyl) Tetramethyl disiloxane as prepared in Example I and 2 g of~
95% - 98% H2S04 are charged under dry air to a 500 ml 2--neck ~reaction flask equlpped~with a mechanical stirrer. ~Th~e~mixture is agitated continuously for 20 hours at which time 17 g of powdered sodium bicarbonate is added to the mixture and stirred for two hours. The resulting mixture is then diluted with 500 mls of hexane, drled with anhydrous MgS04~, filtered~and~
the solvent~removed at reduced pressure. Cyclics are removed under high vacuum (b .05 mmj at 60d for one~hour. 18~0 grams 15 ~of a methacrylate:~end~capped 40~mole~% silicone-hydride~
polydimethylsiloxane is collected. The polymer is a clear, colorless fluld wlth a viscosity~ of o. 8 stokes measured~by Cannon ~iscometer. Structure is confirmed by infrared spec~tra, ~ proton magneti~c resonance spectra and siloxane-hydride analysi~s ;;~ 20 to be: ~ ~
CH2 3 3 CH3 C~I3 O CH2 C-C-0-~CH2~ Si ~0-Si~0-Si-~-0-Si~CH2~ 0-C-C
CH3 ~H3 H CH3 CH3 3 : , ~ ~ne product is a random copolysiloxane.
: : ~ :~:: :
`
~: :
~$~
.
EXAMPLE IV
1,700 rnls of dried peroxide free tetrahydrofuran, available from Fisher Scientific Company, 15 Jet View Drive~ P.O. Box 8740, Rochester, NY 14624 and 158.7 g potassi~m metal, avall-~
able from Fisher Scientific, are charged under dry nitrogen ;~ into a 5,000 ml three-neck round oottom flask equipped t~lth mechanical s'irrer. The solution is chilled to 10C, uslng an icewater bath and 494 ~tl of diethylene ~lycoI monomethyl ether,available from Chemical Samples Comp2nyj 46g~2 Kenny Road~
Columbus, OH 43221, is added dropwise. The ?otassium metal reacts withln 24 hours at which time 350 mls of allyl chloride availab~le from Aldrich, 159 Forest Street, Metuchen NJ o8840, 1s added dropwise at such a rat~e to ma~intain a gentle reflux. Afte;r the reaction is allowed to contlnue ~15 overnight, one 1~1ter of distilled ~ater is added to the : ~ ~
reaction vessel to dlssolve the precipitated salts. The tetrahydrofuran layer is washed three times ~ivh a salt water solutio~n (270 g NaCl to 1 liter H2O) to remove excess alcohol.
The tetrahydrofuran is removed~Jith a water ~spirator and the product is distilled at reduced pressure. 4~0 c o~ diethy-:
~; lene glycol allyl methyl ether lS obtalned ~ D ~? ~ 109C/30mm) .
~- The anaIytical data is consis~ent with a product Gf the general formula:
~2 = CH-cE2-o-cH2-c~2-o-cH2-cH
~.3~$~
EXAMPL~ V
46.1 g of diethylene glycol allyl methyl ether, as prepared in Example IV, followed by 320 mls of hexane, are passed through 42.9 g of activated F-20 alumina~
available from Alcoa, Bauxite3 AR 72011, into a lO00 ml three-neck flask equipped with mechanical stirrer, ther-;
mometer and nitrogen inlet. 40 ~ of 20 parts per lO00~
Pt solution in the form of H2 Pt C15- 6 H20, availabIe from Fisher, in 2-propanol is added to the mixture. 40 mls of hexane~are distilled to remove water and alcohol. The mixture is cooled to 40C at which time 40 g of methacrylate endcapped 25 mole percent silicone hydride polydimethylsiloxane, as prepared in Example II, i~s added. Distillation is continued ~or oDe hour at which time the temperature is a~ 80C. About 200 mls of hexane have~been remoYed. Infrared spectra at 2175 cm l ~, :
~; shows no remaining~silicone hydride bond.
The mixture is cooled and diluted with hexane to a total volume of 500 mls. The mixture is divided and added to two slurry packed 600mm x 45mm fritted silica gel chromotography columns layered with 0.5 cm Celite and 1.5 cm sea sand. Each~
column is elu~ed with 2000 ml of a l:l hexane/ether mixture.
This fraction contains the excess allylic ether. Each column is then eluted with 2000 ml of a l:l hexane/2cetone mixture.
his fraction contains the polymer. The resulting solution 25 ~ of the product which is in hexane is dried with anhydrous MgS04, filtered and the solvent is removed at reduced pressure.
45 g of a methacrylate endcapped 2~ mole perce:~t silicone diethylene glycol propyl methyl ether ?o'ydimethylsiloxane is obtained. The product is a c1ear, colorless fluid ~:Ji h a viscosity of 4.0 Sto~es, using a C2nnon vi scometer. Analytical data confirms structure to be:
::
~ ~3 O CH ¦ CH ~CH ~ CH CH
~H 2 1I J 3 1 3 ~ 3 1 3 1 3 C-C-O ~ CH 2~ Si ~ ~ O-CH . . ~-Si ~ ~ Si ~ CH~ O ~C~ CH
c~3 CH3 ~ ~ - CHy ~5 3 5 . C~ 2 ' , ' - :
~: : . ` :
:: ~ :
S~_ f..
EXAMPLE VI
.
Films of the fluld product obtained in Example V are cast between glass plates by adding 1% diethoxyacetophenone, I
available from UpJohn Company, La Porte, Texas 77571, to .5the monomer. The material is then lrradiated with U V light -~
for two hours. The glass plates are separated and the film is removed. Colorless, optlcally clear fllms are obtained such as represented by the three dimensional network polymer below:
lOCH2 CH CH ~ ~H \ CH 0 CH2 3 ~ 3 \ ~ 3 \ 1 3 i!
CE3-C-C-0-~CH2 ~ Si-0- ~si-oJ si-o - Si-~CH2 ~ 0-C - C-CH3 Cl9~;~ ~CC~H2~ ~H3~ 3 I
-CH2-CH2~-o-CH
:
lS H2 CH3~ ~CIH3~ ~CI 3~ 1 3 0 2 CH -C-C-0-~CH ~ Si-0~ ~Sl-C Sl-0~-Si-4CH2 ~ 0-C - C-CH
2 1 l I ~ I ~ 3 0 CH3 ~H2~ ~H J75 ~H3 ~H~ ~
; ~h~ O - C~- C~- CH3 CH2-~0-CH2-CH2~-2~0-CH3 CH3 C~ l1 The following physlcal properties are measured on an ~: : :
~ Instron tester ASTM D 1708 using standard t'dog borett samples ' .
cut from 0.2 mm thick ~ilms. This test ls used on all the examples where tensile strength, modules and elongation are 2~ measured.
~ SS~
~ . ~
Tensile Strength 24 g/mm2 Tensile Modules 58 g/mm Elongation 56%
The oxygen permeability of the abo~re sample is determined by the following technique. The test is measuring the oxygen permeability of a material while it i~s wet with distilled water. This is an attempt to simulate the conditlon of a contact lens when on the human eye. Two chambers filled with distilled water at 32C are connected together by a common passageway. Across this passagewaD is place the material to be tested. The oxygen concentration in the first chamber is lowered by bubbling nitrogen gas into the second chamber until the oxygen concentration in the first chamber is below about 0.1 ppm. Aerated distilled water is introduced into the second :
chamber. There is-located in the first chamber~an~oxygen sensing electrode which measures the~oxygen concentration in~
the first chamber. This measures the oxygen permeability of the material covering the passageway between the two chambers.
The oxygen permeabillty of the sample can be calculated from~
the rate of oxygen concentration change in the first chamber.
c.c.(STP) cm The unit of oxygen permeability is sec cm2 mm Hg . The~
oxygen permeabllity of the above sample :lS 1.33 x 10 9 25 ~ cc - c ~ ~ 2 which is 18 t`imes~more oxygen permeable sec-cm -mm Hg ~ ~
than the control material polyhydroxy ethyl methacrylate hydrogel ~PHEMA).
::
~ 56 EXAMPLE ~
The fluid product of Example V together with 1%
diethoxyacetophenone is placed in a suit;able contact lens spin casting mold and a contact lens is prepared as taught in U.S. 3,408,42g. After 2 hours irradiation with UV light, a cured optically clear, hydrophilic contact lens is o~-tained. The sess~le drop contact angle~ using distilled water on this lens is 55. The lens ~as worn by a monkey~
during clinical testing without trauma. In contrast, a methacrylate endcapped polydimethylsiloxane as prepared in Example VI of U.S. Patent 4,153,641, has a sessile drop contact angle of 110C rneasured using distilled water.
::
:
~:
:
~:
:~ _ 5~ ~
E~AMPLE VIII
77.6 g of diethylene glycol allyl methyl ether as pre-pared in example IV and 320 mls of hexane are passed through 40.0 g of activated F-20 alumina into a lO00 ml 3~neck flask equipped with a mechanical stirrer~ a thermometer, and a nitrogen inlet. 40 microliters of a 20 parts per thousand Pt solution in the form of H2 Pt C}6 6H2o in 2-propanol is added to the mixture. 40 mls of hexane is distilled to re-move the water and alcohol. The mixture is cooled to 40C
: ~
at which time 40 g of methacrylate end capped 40 mole percent silicone hydride polydimethyl siloxane as prepared in Example III is added. Distillation is continued for one hour at which time the temperature is at 80C. About 200 mls of hexane is removed. In~rared spectra at 2175 cm 1 shows no ~;~ 15 remaining sillcone~hydride bond. Purification lS completed~
exactly like that of Example V. 50 g~rams o~ a methacrylate end~
capped 40 mole percent silicone diethyIene glycol propyl : `
methyl ether polydlmethylsiloxane is obtained. The product is a clear, colorless fluid with a viscosity of 8.5 stokes by Cannon ~is~cometer. Analytical data confirms structure to be:
~CT~2 ~ ! 3 ~ 1 3 CH3 ' CH3 //H3 : ~ C - C - O ~CH2~ Si: ~0 - Si~O - Si~ O - Si ~CH2~ 0 - C - C
40 i 60 ~ 11 \
CH2 ~0 - CH2 - CH2~ 0 - Cll ~:
,. ,~ .
; Q_ E~AMP1E lX
Films of the fluid product obtained in Example VIII are cast between glass plates by adding I% dlethoxy acetophenone to the monomer and irradiating with UV light for 'cwo hours.
The glass plates are separated and the film removed. Color-less~ optically clear films are obtained.
The oxygen permeability of the above sample is dete~rmined~ -by the procedure as described in Example VI. The oxygen permeability of the sample is 6.5 x 3~ lO cc cm/sec cm2`mm Hg which is 9.4 times more oxygen permeable than the control material polyhydroxyethylmethacrylate hydrogel (PHEMA).
:
::
:::: : : :
:: ~ : : : ; :
::
:
' ' ' ::: :
EXA~PLE X
_.
The ~luid product of Example VIII t;ogether with 1%
diethoxy acetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After 2 hours irrad1ation with UV light, a cured opticall~ clear, hydrophilic contact lens is obtained. The sessile drop contact angle using:dis-: tllled water on this lens is 50 .
:
: :
: ;
:~ : ::: :
:: :
:
:::
:
,i ~3~
_XAMP1E XI
59.7 g of peroxide free diethylene glycol allylmethyl ether prepared as in Example IV, 0.010 ~ H2 Pt C16 ' 6H2o in 1 ml of 2-propanol and 200 ml of toluene are added under dry nitrogen to a 500 ml round bottom 2-neck flask and mixed.
The mixture is heated to reflux and dried by azeotropic dis-tillation. The mixture is cooled and 100 mls of heptamethyl cyclotetrasiloxaneS available from Silar Laboratories, Inc., is added. The mixture is heated to reflux for two hours at 10 which time in~rared spectra bond at 2175 cm 1 shows no silicone hydride. The mixture is cooled and solvent is removed under aspirator vacuum. The crude product that remains is vacuum distilled. 135 g of 3 (diethylene glycol methyl ether) propyl heptamethylcyclotetraslloxane~is obtained (b.p. 96o/ ;
15 .025 mm). Analytical data confirms structure to be: ~ ~
:
CH CH
2 CH2~CH2-O-CH2-CH2-0-CH2-CH2-O-CH
O O
H3C - Sl - 0 - Si - CH3 : ~ :
.
EXAMPLE XII
50 g of peroxide free 3 (diethylene glycol ~ethyl ether) propyl heptamethylcyclotetrasiloxane as prepared in Example XI is added to a 100 ml round bottom 2-neck flask equipped with a mechanical stirrer, a reflux condensor and a nitrogen inlet. The flask is heated for one hour at 110C using an oil bath at which time 1.9 g of 1,3-bis;(4-methacryloxy- ;
butyltetramethyldisiloxane as prepared in Example I and 0.05 g of dry cesium hydroxide available from I.C.N. Pharmaceutlcal, Plainview, New Jersey, are added. A substantial increase in viscosity is observed within five minutes. The mixture i6 heated for an additional hour, then cooled to room temperature and neutralized with C.04 g of acetic acid for one hour. The mlxture is then diluted with hexane, dried for one hour~over anhydrous Mg SO4,~filtered and the solvent removed at r~educed pressure. The low molecular weight cyclics are removed by precipitation with a water methanol mixture. A clear color-less fluid material is obtained.
~: :
~:
: :
: ~ ;
.
- ~
_XAMPLE XIII
The ~luid product of Example XII together with 1%
diethoxy acetophenone is placed in a suitable contact mold and a contact lens is prepared by the same method as taught : 5 in U.S. 3,408,429. After two hours of lrradiatlon with DV
light, a cured optlcally clear, hydrophllic c;ontact lens lS
obtained. The sessile drop contact angle using distilled wa~er on the lens is 55. : ~ ~ ;
;: :
:~ :: :: : :
.
::
:
:::: ~ : :: :
:~ : : : :
:
::
EXAMPLE XIV
50 g of perox1de free 3 (diethylene glycol methyl ether) propyl heptamethycyclotetrasiloxane as prepared in Fxample ~I is added to a 100 ml round bottom 2-neck flask equipped with a mechanical stirrer, a reflux condensor and a nitrogen inlet. The flask is heated for one hour at 110C
usina an oil bath at which time 0.5 g of tetramethyltetra-~inylcyclotetrasiloxane, available from Silar Laboratories, is added. 0.05 g of dry cesium hydroxide is then added. A
high molecular weight immobile polymer forms in five minutes.
The mixture is heated for an additional hour then cooled to room temperature and neutralized with 0.04 g of acetic acid in 10 mls of hexane. The mixture is then diluted with an : ~
; addltional 100 mIs of hexane, dried~ov~er anhydrous Mg SO4,~
filtered and the solvent removed at reduced pressure. The polymer is purified by precipitation ~rom a water-methanol mixture. The~product is a clear, colorless hlgh molecular weight immobile~polymer. Analytical data confirms structure.
The polymer is: 25 mole percent 3(diethylene glycol methyl ether) x mole percent polydimethylsiloxane.
: : : :
' 3~341~
EXAMPLE XV
A film of the product obtained in Example XIV is cast between glass plates by adding 1~ benzoyl peroxide, available from the Pennwalt Corporation~ Pennwalt Bldg., Three Parkway, Philadelphia, Pennsylvania 19102~ and heating eight hours at 80C.
The glass plates are separated and the:film removed.
A colorless optiGally clear, hydrophilic film is obtained which has a sessile drop contact angle with di`sti~led~water of 55 , .
:
:~ :
: :: : : :
: ~ ~ : : :
:: : :
~ e~
:
~ .
EXAMPLE XVI
50 g of peroxide free 3-(diethylene glycol methyl ether) propyl heptamethylcyclotetrasiloxane as prepared in Example XI is added to a 100 ml round bottom 2-neck flask equipped with a mechanical stirrer, a reflux condensor and a n~trogen inlet. ~he material is heated for one hour at 110C uslng an oil bath. At this tlme 0.5 g of dry cesium hydroxide is added. A high molecular weight polymer is ~ormed~in five minutes. The reaction mixture is then cooled to 90C and 0.1 g of distilled water is added. A substantlal decrease in viscosity is observed w~thin five minutes. The~mixture is heated for an additional hour. The mixture is then cooled, diluted with 200 mls of hexane, washed with distilled water, dried over anhydrous Mg SO4 and the hexane removed at reduced ~ pressure- A clear ~luld silanol end capped 25~mole percent sllicone diethylene~glycol propyl methyl ether polydimethyl-~siloxane is obtained. Analytical data conf~irms structure.
, ~3~
~XAMPLE XVII
2.0 g o~ the material prepared in accordance with Example XVI is mixed with 0.15 g o~ ethylsilicate prepolymer (M~600) a~ailable ~rom Petrarch, PØ Box 141, I.evittown, PA 1905~, 0.025 g of trimethoxy phenylsilane available from Silar Lab. and 10 microliters of dibutyltin dilaurate available ~rom Alfa Products, Beverly Massachusetts. A ~ilm is cast ~rom the above mixture between glass plates by heating in an 80C
air oven for 8 hours. The glass plates are separated and the film removed. A colorless, optically clear, hydrophilic film is obtained which has a sessile drop contact angle with distilled water o~ 55.
: :
-::: :
: ~ :
: ~ :
_ ¢~_ r3~q EXAMPLE ~
To 72.7 parts of the monomer prepared as in Example V is added 18.2 parts of lsobornyl acrylate, available ~rom Rohm and Haas, Independence Hall West, Philadelphia, PA 19105 and 9.1 parts of acrylic acid and one part diethoxyacetophenone. After mixing, a film is cast between glass plates. The film is irradiated with UV light for two hours. The film i3 released, extracted for four hours in a 1:1 hexane/isopropanol mixture and buffered. This buffering procedure consists of placing the film to be tested, which is about 2" x 3" in size, into 100 cc of O.lN ammonium hydroxide for 24 hours. Then the film is soaked in an isotonic phosphate buffer (pH 7.2), i.e.
Na2HP04, NaHPO4 and NaCl for another 24 hours. This b~uffered saline solution is made by mixing 1.403 g of Na2HP04, 0-458 6 of NaH2P04 and 8. o 8 of NaCL with water to make a;final vo1ume of one liter. The film is then stored in an isotonic buffered :
saline solution (pH 7.2).
The test procedure for determining the percent of water ; in the film is as~follows:
A 0.3 g sample is taken from the above hydrated film.
The sample of film is roller dried and immediately weighed to the nearest milligram. The weighed film is placed into a vacuum oven (1 cm Hg) overnight at 80C. Then the material is cooled and the vacuum broken by admitting dry air. After the sample is at room temperature for about 15 minutes, the sample is weighed to the nearest milligram. The percent water is calculated as follows:
Wet Weight - Dry WeiQht PeFcent Water = Wet Weight x 100 The percent water for the above sample is 18%.
~ 6~
, O . .
J ~
~ ~3~
The oxygen permerability ot' the above sample, in the buffered ~orm, is determined by the same technique described in Example VI except bu~fered saline i.s used in place of disti].led T~ater.
The oxygen permeability of the above sample is 6~7 x 10 lcc cm/
sec-cm -mm Hg which is 8.2 times more oxygen permeable than the control material polyhydroxye~hyl methacrylate hydrogel.
The following physical properties are measured a~ des-cribed in Example VI:
Tensile strength 36 g/mm2 Tensile Modules 72 g/mm2 Elongation 84%
, :
:
:~
;
EXAMPLE XIX
72.7 parts of the monomer as prepared in Example ~
are mixed wit~ 18.2 parts o~ isobornyl acrylate and 9.1 parts o~ acrylic acid and one part diethoxyacetophenone. 30 ~Q of the mixture is placed in a suitable contact lens spincasting mold and a contact lens is prepared as taught in U.S. ~
patent 3,408,429. A~ter two hours irradiàtion~with W llght, a cured contact lens is obtained. The lens formed is soft, water absorbing, hydrophilic, optically clear, elastic and strong. The lens was worn during clinical testing without trauma ~or 24 hours by a monkey.
::
:: ~
:::
. ~0-~ ~ .
_AMPLE XX
540 mls of dried pero.Yide free tetrahydrofuran and 21.5 g of potassium metal are char~ed into a 2000 ml three-neck flask equipped with mechanical stirrer and a dry nitrogen inlet. 88.4 ml of triethylene glycol monomethyl ; ether, available from Chemical Samples Co., is added to the mi~ture dropwise. Arter the potassium metal has completely reacted, li8.6 ml of allyl chloride is added dropwise to the mixture at such a rate in order to maintain a gentle reflux.
After the reactlon is complete, 500 mls of distilled water are added in order to dissolve the preclpitated salt. The tetrahydrofuran layer is washed with salt water (270~g NaCl/1 11ter ~water) in order to remove the excess alcohol. The resulting product ln tetrahydrofuran is coll~ected and the tetrahydio-furan is removed with a water aspirator. The product is dlstilled at reduced pressure~. 75.5 g (74~ yield) of~tri~
ethylene ~lycol allyl methyl ether is obtained (b.p. 97C - 1~00C/~
2mm). The analytical data is consistent with a product of the general formula:
20~ C~ =CH-CH2-0-CH2-CH2-0-CH2-CH2-0-C~2 C~
:
~, : :
~ .
: ~ .
~3~
_. . . ._ .. ..... ~ . . . ..
. . .
EXAMPLE XXI
.
58.8 g of triethylene glycol allyl methyl ether, 25 prepared in Example XX followed by 320 mls of hexane , are passed through 54.7 ~ Or actlvated F-20 alumina into 2 1000 ml three-neck ~lask equipped with mechanical stirrer, thermometer and a dry nitrogen inlet. 40 ~Q of 2~ pp~c Pt, ln 2-propanol is added to tbe mixture. The mixture is warmed and dried by azeotropic distillation. The mixture ls cooled to 40C
at which time 40 g of the methacrylate endcapped 25 mole percent "
hydrlde polysiloxane as prepared in Example TI is added.
:
: Slow distillation ls continued ~or one hour at which time~ :
the mixture temperature is 80C a~d about 200 mls of hexane :: ha~e been removed. ~Infrared spectra shows that the reaction is complete. The polymer ls purified by precipitation ~rom~
:
a 1:1 mixture o~ me~hanol and wa~er. Analytlcal data con~irms the structure to be:
O CH : .tfCT~ CX3 O
C,~ 3 1 3 l 3 : t ~1 ~CH2 C-C_o ~ ~H27~ Sl ~ - O--Sl - O _ Si - O --Si ' C~;;~O-C-C
3 CH 3 ~CH 3 J25 I H 2 ~ S- CH 3 C~13 I
' C;~2--0-C~-r'X2~0-C~.3 :
:
:: ~ : : :
.
~ .
~ 7~ ~
.
$~3 q~
EXAMPLE XXII
The ~luid product obtained in Example XXI t,ogether with 1% diethoxyacetophenone is placed in a 3uitable contact lens spin casting mold and a con~act lens is prepared by the sa,me method as tau~ht in U.S. 3,408,429. A~ter two hours irradiation with W light, a cured optically clear, hydro-philic contact lens is obtained. The contact lens has a low contact angle with water.
:
:~
EXAMPLE XXIII
1200 mls of dried peroxide free tetrahydrofuran and 100 g Or potassium metal are charged into a 3000 ml 3-neck flask equipped with a mechanlcal stirrerJ a thermometer and a dry nitrogen inlet. 317.7 mls of solketal, available from Aldrich, is added dropwise. After react:Lng overnight the potassium metal is reacted completely. 188.5 mls of allyl chloride is added dropwise at such a rate to maintain a gentle reflux. After reacting the mixture again o~ernight, 850 mls of distilled water are added to dissolve the precipitated salt. The tetrahydrofuran (~HF) layer 1s washed with a salt water solution to remove excess solketaI. The~
resulting product in THF is collected and the THF removed~
with a water aspirator. The product is distilled at reduced pressure. 261.4 mis of solketal allyl ether (b.p. 76C/14~mm) is obtained. Analytical da~a con~irms structure to be:
2 CH2 0 CH2-lH_IH2 O O
\
C
` H C CH
~ ' ~
~' E'~A~ XXIV
49.5 g of solke~.llallylether as prepared ln ~xample XXI~ ~ollowed by 320 mls oL` hexane are passed through 46.1g of activa~ed ~-20 alumina intc a lOG0 ml three-neck flask equipped with mechanical stirrer~ thermolrleter and a nitrogen inlet. 40 ~Q or 20 p~t Pt in 2-propanol is added to the mixture followed by a~eotropic distillation to remove alcohol~
and water. The charge is cooled to 40C and 40 g of the methacrylate endcapped 25 mole percent hydride polysiloxane prepared as in Example II is added. Slow disti}lation continues for one hour during which time the mixture temperature increases to 80C and about 200 mls of hexane are removed.
In~rared spectra Gonfirms the reaction is complete. The polymer is puri~led by precipitation ~rom a l:l mixture of water and methanol. Analytical data conflrms the~structure ; Ol Cll3 ~l3~ ~I 3j ~ 3 ~ C~
C`-C-O-~ CH ~ Si-O- Si-~ _ ~Si-( ~Si~CH ~ O-C-C
2 ~ l ~ 1 2 ~ ~
CH3 CH3 ICH2~ ~5 ~CH3, 75 C~E~3 CH3 \ /
; ~ H3~ 3 : ~ :
:
~:
:
: ~ ~ 7g ~
~ ~4~ J~
EXAMPLE XXV
5.0 g of the polymer as prepared i:n Example XXIV
52 mls of glacial acetic acid available from Fisher, and 4.2 mls of distilled water are charged to a 100 ml round bottom flask and heated to 50C overnight at which time the acetic acid, acetone formed during reaction and water are removed under high vacuum. Infrared shows a large hydroxyl bond and the ketal doublet at 1380 cm 1 is gone~
The polymer is a clear fluid material of the following structure: .
CH2 O ~CH3 CH3 CH3 CH3 ~ H3 ;
:C - C - O-~CH2 ~:~Si --~O-Si~ O-Si3 - O-Si -~CH2 ~ O-C-C
~¦~-25 1 O CH
CH3 GH3 CH3 ~ Cf 2 CH2 : ~ :
- ~ CH
~ 2 QH OH
~:~ ': :
:
: :
:
~3~ `3 EXAMPLE XXVI
The flùid product Gbtained in Example XXIII together wlth 1% diethoxy acetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After two hours irradiation with UV light, a cured optically clear~ water : absorbing, hydrophilic contact lens is obtained. The percent~: water as determined by the procedure in Example XVIII lS ~13%~.
The sessile drop contact angle measured using distilled water ~:
is low. :
: : ::
.
:
:
:: :
- : :
:: :
: q1~
7r~
.~ ' r EXAMP1E XX~II
34.9 g of 0-trimethylsily1 allyl alcohol available from Petrarch Inc., PØ Box l4l, 1evittown, PA 19059, 40 ~ of 2~ ppt Pt in 2-propanol and 320 mls of hexane are charged into a 1000 ml three-neck flask equ~pped with a mechanical stirrer, a nitrogen inlet and a thermometer. The mixture is warmed to reflux and dried by azeotropic distillatlon followed by cooling to 40C. 40 g of the methacrylate endcapped 25 mole percent silicone hydride polysiloxane as prepared in Example II is added. Distillation is continued for one hour ; ; during which time~the mixture tempè~rature increases Co 80C~
and about 200 mls of hexane are~removed. Infrared spectra~
confirms tha~t the reaction is;~complete~. Th~e polymer is~purlfied by precipitation from a l:l mixture of methanol and water.
A clear ~luld polymer is obtalned having the followlng structure as confirmed by analytical data:
::
H ~CH CE~ ~ CH~ ~ CE~3 0 CH
C~2 ~ 3 ~ ~ 3 J 3 ~ ll ~ 2 C-~-0 ~CH2 ~ Si - 0 - ~Sl-0 _ Si-0 - Si ~ CH2 ~ 0-C-C
CH3 3 ~H2 25 C~3 ~ CH3 CH3 -Si-CH3 :
~ ' f~
EXAMPLE XXVIII
5.0 g of the polymer as prepared in Example XX~II, . 52 mls of glacial acetic acid and 4.2 mls of distilled water are chargeà to a 100 ml flask and heated to 50C over-night at which time the acetic acid and water are~removed:under high vacuum. Infrared shows a large hydroxyl band.
The polymer is a clear fluid material of the follow1ng structure:
CH2 ~I CIH3 ¦ I Cl 3 /jH2 jC - C - O -~CH2 ~ Sli - O -~Si - O~-~Sji ~ 0~- Si -~CH2 ~ 0 - C~ - C
~ 3 :CH3 CIH2 : CH3 CH3 O ~ CH3 : :~: : CIX2 : ~ ~ :
OH
: :~ ~: :
::
: , ~ ' :
~ 3 EXAMPLE XXIX
The fluid product obtained in Example XXVIII together with 1% dietho~yacetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After two hours irradiation with UV light, a cured optically clear, hydrophilic, as measured by its low contact angle with water, contact lens is obtained.
::
_80 ~
~3~43`.~
E`{AMPI,E XXX
In a 2 liter, three-nf?cked flask ~itted with mechanical stirrer, reflux condensor and a dropping funnel ls placed 714 g of 2-allyl oxyethanol available from Haven Chemical Co., 5000 Langdon Street, Philadelphia, PA 19124. 600 g of phosphorous tribromide is added to the rnixture dropwise while stirring. This is done over a period of about two hours. The temperature is permitted to rise until the reaction mixture gently refluxes. The mixture is then distilled and the distillate below 160C is collected in a 2-liter flask with 1 liter of distilled water. The crude 2-allyloxyethylbromide is dried over calcium chloride and d~stilled. Pure 2-allyloxyethylbromide is obtained.
750 mls of dried peroxide free tetrahydrofuran and 14.9 g of potassium metal are charged under dry nitrogen into a~2000 ml three-neck flask equipped with mechanical stlrrer, condensor and an addition funnel. 55 g of solketal is added dropwise. Potassium metal reacts completely within 24 hours at whlch time 68.9 g of the 2-allyloxyethylbromide is added at such a rate as to maintain a gentle reflux. After an overnight reaction, 500 mls of distllled water are added to the reaction vessel to dissolve the precipitated salts.
The THF is then removed with a water aspirator. The product is distilled at a reduced pressure. Pure 2-allyloxyethyl solketal is obtained. Analytical data confirms structure to be:
.
CH2 CH CH2 0 CH2 C~2 O CH2 ICI ~ 2 O O
C
_ 8~
~ ~3~S~3~
:~ :
62.2 ~ of' the 2-allyloxyethylsolketal as prepared in E~a~ple XXX f`ollowed by 320 mls of hexane ls passed through 57.9 g Or activated F-20 alumina into a three-neck flask equipped with mechanical stirrer and a dry nltrogen inlet. 40 ~ of 20 ppt Pt in 2-propanol is added to the mixture. 40 mls of hexane are distilled to remo-~e water and alcohol. ~he mixture is cooled to 40C, at which time 40~ g Or the methacrylate endcapped hydrlde polydimethylsiloxane~
as~prepared in Example II is added. Distillation is continued for one hour at which time the mixture temperature ls 80C.
About 200 mls of hexane are removed. Infrared spectra at 2175 cm 1 con~irms the reaction is complete. The polymer is purifled by~precipltatlon from a l:l methanol/water~mlx~ure~
15~ A~clear~fluld polymer is obtained. Analytical data confl~rms 'hc~;structu-e ~to b~
CH 0 ; ~ ~H3~ CH3 CH~ 1 3 IH
C -C-0-~ CH2 ~ Sl~-- ~0-Sl~ _ 0-Si~--O-Si~-~CH2 ~ 0-1~ C
~Z ~H3 ~ : CV3 CN2 5 ~ CH C~ 3 ~ 2 CH2-0-C~2-CHZ-O-cH2 ~H ICH2 C
~ ~ H3C CN3 :
: ~ :
:: : :
~: ::
: ~ :
EXAMPLE XXXll 5.0 g of the polymer as prepared in Example XXXI, 52 mls of glacial acetic acid and 4.2 mls of distilled water are charged to a 100 ml flask and heated to 50C overnight.
Then the acetic acid,~water and acetone formed are removed under high vacuum. Infrared shows a large hydroxyl bond and the ketal doublet at 13~0 cm 1 is gone. A clear fluid material of the following structure is obtained:
CH2 It CIH3 CIH3 CIH3 CIH3 C -- C -- O --CH2~ Sl ~0 -- Si~O - Si~ -- Sl ~CH2~ -- r-- C
CH3 ~ CH3 C~3 CIH2 C~3 CH3 CH2 - O CH2 - CH2 - O - ~H2-CH-CH2 OH OH
; ~
:
' _ ~3_ 3`~
:
EXAMPLE XXXIII
The fluid product obtained in Example XXXII together with 1~ diethoxyacetophenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the - 5 same method as taught in U.S. 3,408,429. After two hours irradiation with UV light~ a cured optically clear and hydro-philic, as measured by its low contact angle with water, contact lens is obtained.
::
;~ : : : :
:
~;
~.A~IPLE XXXIV
-163.3 g. o~ all~l alcohol a~ailable ~rorn Aldr~ch in one liter o~ toluene is charged under dry nitrogen to a 5-liter three-necked ~lask fitted ~ith a mechanical stirrer and a reflux condensor. 100 g o~ potassium metal is added, stirrlng begins and the charge is heatecl in an oil bath until the mixture refluxes gently.
A~ter the reaction mixture has refluxed for 15 hours, the temperature Or the oil bath is lowered to ~5C-90C, at which time a warm solution of 95 g of monochloracetic acid in 800 mls of toluene is added at such a rate to maintaln a gentle reflux. A precipitate of potassium chloroacetate ~orms. Arter all the cnloroacetic acid is :
added the mixture is refluxed and stirred ~or 48 hours.
When the reaction is complete, the flask is cooled ~
and the reactlon mlxture is transferred to a 5~1iter separatory funnel and extract~ed with three one-liter portions of water.
The water extract is~acidified with 20% HCl. The crude alIyl-oxyacetic acid that is produced is extracted three times with ether. The ether extracts are combined and the solvent removed by distillation on a steam bath. The residue is then ~ractionally~distilled under reduced pressure. Pure ~: :
allyloxyacetic acid is obtained.
200 ~ o~thiongl chloride is charged to a one-liter three-neck flask equipped with a 250 ml dropping funnel, an efficient condensor and a mechanical stirrer. To this mixture is added dropwise a~d with rapid stirring, 116 g of allyloxy-acetic acid. An evolution o~ hydrogen chloride and sulfur dioxide takes place. When all the acid has been added9 the mixture ls heated to 80C and kept at this temperature ~or t~o hours. Then the remaining thionyl chloride is removed on steam bath under reduc~d pressure. The crude acid chloride is obtalned.
In a one-liter f'lask, equipped wlth mechanical stlrrer and a 500 ml dropping ~unnel and surrounded by an ice salt freezing mixturle~ is placed 0.5 1 of 28% cold, concentrated aqueous di~ethylamine available from Aldrich. The crude acid chloride is added to this mixture slowly while stirrlng, Stlrring is continued for one hour after the addltion of the acid chloride. 'rhe aqueous mixture is extracted three~t~imes with 250 mls of d1ethyl ether in order to collect the amlde which forms. The collected ether is remo-~ed by heating the mixture on a steam bath. Then the product Ls fractionally distilled a~ reduced pressure. Yure allyloxy N,N-dimethyl ~
acetamide is obtained. hnalytical data confirms the~structure~ ~;
to~be~
: ~ o :
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:
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: ::
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~ ~6 :
, .
~39L~
EXAMPL,F, ~
41.1 g of the allyloxyacetamide as prepared in Example XXXIV follqwed by 320 mls of hexane are passed through 38.3 g of activated F-20 alumina into a 1000 ml three~neck round bottom fla3k equipped with mechanlcal stlrrer and a nitrogen inlet. 40 ~Q of 20 ppt Pt, in 2-propanol is added to the mixture followed by azeotroplc distlllation ln order to remove water and alcohol. The mixture is cooled to 40C
at which time 40 g o~ the methacrylate endcapped 25 mole percent silicone hydride polydimethylsiloxane as prepared in Example II is added to the mixture. Distillation contlnues for one hour dur1ng which time the mlxture temperature ls increased to 80C resulting in about 200 mls of hexane belng removed. Infrared~spectra confirms the reaction ls complete.
The polymer is purified by precipitation from a 1:1 mixture of water and methanol. Analytical data confirms the structure to be:
0 CH ¦ CH~ ¦ CH ~ CH3 CH
CH2 ¦3 1 3 ~ ~ 3 1 3 1 1~ 3 ~PC-C-0~ CH2 ~ Sl - )-Si- ~ 0-Si ~ -O-Si~ CH2 ~ 0 C C~
CH3 ~H \ CH3~ ,5 CH3 2 CH2-0-CH2~ N'~ CH3)2 ,.
_ 8 7 .
_XAMPLE XXXVI
~he ~luid product obtalned in Example X.CXV together ~ith 1% diethoxyacetop'nenone is placed in a suitable contact lens spin casting mold and a contact lens is prepared by the same method as taught in U.S. 3,408,429. After two hours irradiation with W light, a cured optically clear and hydrophilic, as measured by i.ts low contact:angle with water, contact lens is obtained.
, f : J
3~ 9 EXAMPLE XXXVII
Synthesis o~ 3,3-tetrarnethyl - 1,3-dislla - 2w oxacyclohexane - 5-(N,N-dimethyl carboxamide).
To 218 g. of 1,1,3,3-tetramethyl - 1,3-disila 2 oxacyclohexane - 5-carboxylic acid (synthesized according to the procedure of Omer W. Steward and Leo H.
Sommer, J. of Organic Chem., Vol. 26, page 4132, 1961) in _ 1000 ml o~ anhydrous tetrahydrofuran, cooled to -15C, is added (under anhydrous conditions) lOl g of triethylamine and 108.5 g of ethyl choroformate. After stirring for 15 minutes, dimethyl amine is bubbled through the solution at -15C for thirty minutes. The solvent is then removed at reduced pressure. Then 1000 ml of diethyl ether and lOO~ml of,.~ater is added. The ether phase ls separate ~ ~
extracted with O.l N aqueous NaHC03, O.lN aqueous HCl, and dried with~MgS04. ~After rilteringg the ether ls removed to give the cyclic slloxane amide Or the formula.
: :
O CH
ll 1 3 CH
` CH2 CH2 ~:
~;~ CH3 ¦ ~¦ CH
Si Si 25This material is Or sufficient puri~y such that no further purification is necessary.
~f _8q -.~ .
. . , . . ~ : ... :
5~
EXAMPLE XXXVIII
122.5 g of 1,1,3,3-tetramethyl - 1,3-disila-2-oxacyclohexane - 5-(NjN-dimethyl carboxamide), as prepared in Example XXXVII, 87 g of 1,1,3,3 tetramethyl - 1,3-disila -5 2-oxacyclohexane, available from Silar Laboratories, 10 Alplaus Road, Scotia, New York 12302 and 4.14 g of 1,3--bis(4-methacryloxbutyl) tetramethyl disiloxane, as prepared in Example I are combined in a 250 ml flask. While vigorously stirring 1.52 g of trifluoromethane solfonic acid is added.
The reaction is stirred for 12 hours~ Then 10 g of NaHC03 is added. The product is pressure filtered to give a random copolysiloxane represented by the average formula.
:
: :: : : ~
:~ -90-~ ll v ~
I
o - c~
I
o v r~
~ v~ ~
o o Lr~
~--~r ~
v v~
:
~ o v $ x v ` c~
v o : I o ~ ~ ~
i: ~ ~ l :
V
: l :
l~ :
v :
o .,~
:: ~
o o ~ ~, ~ I
V--C~
ll V
3~
When this random copolysiloxane is mixed with 1% by weight diethoxyacetophenone, cast between glass plates and subjected to ultraviolet radiation, a cast sheet is obtained which is hydrophilic as measured by its low contact angle with water.
: ~ .
:
:
~ 32-
Claims (16)
1. A hydrophilic, hydrolytically stable, biologically inert.
contact lens with the capability of transporting oxygen sufficiently to meet the requirements of the human cornea, comprising a polysiloxane monomer having the following formula:
wherein Y1 and Y2 equal the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, X is selected from the group consisting of a hydroxyl radical, a monovalent hydrocarbon having from 1 to 20 carbon atoms, halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, wherein R is a monovalent hydrocarbon having from 1 to 20 carbon atoms, R1 is a monovalent hydrocarbon having from 1 to 20 carbon atoms, n1 is an integer from zero to 1 and n2 is an integer from 1 to 3, wherein R2 and R3 are the same or different and are monovalent hydrocarbons having from 1 to 20 carbon atoms and n3 is an integer from zero to 1, wherein R4 is a divalent hydrocarbon having from 1 to about 22 carbon atoms and A is a free radical polymerizably activated monovalent unsaturated group, a is at least 1, b is zero or at least 2, c is 1 if b is zero and c is zero if b is at least 2, d is at least 1, except when b is zero and a is 1 then d is zero or greater, e is at least 1 and f is zero or greater, Z1 through Z7 are the same or different and at least one of Z1 through Z7 is equal to a hydrophilic sidechain, said Z1 through Z7 are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms, a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms and a hydrophilic sidechain with the follow-ing formulas selected from the group consisting of wherein R5 is a divalent hydrocarbon having from 1 to 10 carbon atoms, R6 is selected from the group consisting of methyl and hydrogen, R7 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms, wherein R8 is selected from the group consisting of a monovalent hydrocarbon having from 1 to 10 carbon atoms and hydrogen, and n4 is at least 1, 2) wherein R9 is a hydrocarbon having from 1 to 20 carbon atoms and a valence of n5 + 1, n5 is at least 1, there cannot be an -OH group on an aliphatic carbon atom beta to the Si atom, and there cannot be more than one OH group on any one carbon atom, wherein R10 is a divalent hydrocarbon having from 1 to 10;
carbon atoms, R11 is selected from the group consisting of hydrogen and methyl and R12 is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n8 + 1 and can have no more than one oxygen atom attached to any one carbon atom, n6 is zero or greater, n7 is an integer from zero to l and n8 is at least 1, wherein R13 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the group is not attached to a carbon atom of R13 which is alpha to the Si atom, R14 and R15 can be the same or different and are selected from the group consist-ing of a monovalent hydrocarbon having from 1 to 10 carbon atoms, hydrogen, OH wherein n9 is an integer from 1 to 3 and wherein R16 and R17 are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n10 is an integer from 1 to 5, 5) wherein R18 is a divalent hydrocarbon having from 1 to 20 carbon atoms and R19 and R20 are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, 6) wherein R21 is a divalent or trivalent hydrocarbon having from 1 to 10 carbon atoms and the S atom is not attached to R21 by an ali-phatic carbon atom beta to the Si atom, R21 may or may not be attached to R22 to form a ring which contains more than 3 carbon atoms and R22 is selected from the group consisting of a hydrocarbon having from 1 to 10 carbon atoms and -0- M+
where M is selected from the group consisting of a monovalent metal ion and a quaternery ammonium ion, and n11 is an integer from 1 to 2, 7) wherein R23 is a divalent hydrocarbon having from 3 to 10 carbon atoms and the N+ must be attached to a carbon atom of R23 which is at least 2 carbon atoms away from the Si atom, R24, R25 and R26 are the same or different and are monovalent hydrocarbons having from 1 to 10 carbon atoms, is a monovalent anion selected from the group consisting of halides, R27-COO- wherein R27 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and a halogenated monovalent hydro-carbon having from 1 to 10 carbon atoms and R28 - SO? wherein R28 is selected from the group consisting of a monovalent hydrocarbon having from 1 to 10 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 10 carbon atoms, 8) wherein R29 is a divalent hydrocarbon having from 1 to 10 carbon atoms and n12 is an integer from 0 to 1 and when n12 is 1 the oxygen cannot be attached to an aliphatic carbon atom in R29 which is beta to the Si atom, R30 is a divalent hydro carbon having from 1 to 10 carbon atoms, R31 is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n13 + 1 and can have no more than one oxygen atom attached to any one carbon atom and n13 is at least 1, 9) wherein R32 is a divalent hydrocarbon having from 1 to 10 carbon atoms and the ester oxygen atom bonded to R32 cannot be at-tached to an aliphatic carbon atom in R32 which is beta to the Si atom, R33 is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n14 + 1 and can have no more than one oxygen atom attached to any one carbon atom and n14 is an integer of at least 1, 10) wherein R34 is a divalent hydrocarbon having from 1 to 10 carbon atoms, 11) wherein R35 is a divalent hydrocarbon having from 2 to 10 carbon atoms and n15 is an integer from 1 to 10, 12) wherein R36 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group is not attached to a carbon atom alpha to the Si atom, R37 is selected from the group consisting of methyl and hydrogen, R38 is selected from the group consisting or hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and wherein R39 is a monovalent hydrocarbon having from 1 to 10 carbon atoms and n16 is at least l, 13) wherein R40 is a divalent hydrocarbon having from 1 to 10 carbon atoms, R41 and R42 can be the same or different and are selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and wherein n17 is an integer from 2 to 4, 14) wherein R43 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the S atom cannot be attached to a carbon atom of R43 which is alpha to the Si atom, R44 and R45 can be the same or different and are selected from the group con sisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, 15) wherein R46 is a divalent hydrocarbon having from 1 to 10 carbon atoms and n18 is an integer from zero to 3, 16) wherein R47 and R48 are selected from the group consisting of hydrogen, divalent or monovalent hydrocarbon having from 0 to 10 carbon atoms and R49 is selected from the group con-sisting of hydrogen, divalent or monovalent hydrocarbon having from 1 to 10 carbon atoms and only one of R47, R48 and R49 must be a divalent hydrocarbon and attached to the Si atom, R50 is selected from the group consisting of hydrogen, a mono-valent hydrocarbon having from 1 to 10 carbon atoms and where n20 is an integer from 2 to 4, and n19 is an integer from zero to 3, 17) wherein R51 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot be attached to a carbon atom of R51 alpha to the Si atom and X? is a monovalent cation selected from the group consisting of monovalent metal cations and wherein R52, R53, R54 and R55 can be the same or different and selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, and 18) wherein R56 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot be attached to a carbon atom of R56 which is alpha to the Si atom, R57 is a divalent hydrocarbon having from one to 10 carbon atoms, R58 is selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n21 is an integer from zero to 10, polymerized to form a polymer in a crosslinked network.
contact lens with the capability of transporting oxygen sufficiently to meet the requirements of the human cornea, comprising a polysiloxane monomer having the following formula:
wherein Y1 and Y2 equal the same or different and are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, X is selected from the group consisting of a hydroxyl radical, a monovalent hydrocarbon having from 1 to 20 carbon atoms, halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms, wherein R is a monovalent hydrocarbon having from 1 to 20 carbon atoms, R1 is a monovalent hydrocarbon having from 1 to 20 carbon atoms, n1 is an integer from zero to 1 and n2 is an integer from 1 to 3, wherein R2 and R3 are the same or different and are monovalent hydrocarbons having from 1 to 20 carbon atoms and n3 is an integer from zero to 1, wherein R4 is a divalent hydrocarbon having from 1 to about 22 carbon atoms and A is a free radical polymerizably activated monovalent unsaturated group, a is at least 1, b is zero or at least 2, c is 1 if b is zero and c is zero if b is at least 2, d is at least 1, except when b is zero and a is 1 then d is zero or greater, e is at least 1 and f is zero or greater, Z1 through Z7 are the same or different and at least one of Z1 through Z7 is equal to a hydrophilic sidechain, said Z1 through Z7 are selected from the group consisting of a monovalent hydrocarbon having from 1 to 20 carbon atoms, a halogenated monovalent hydrocarbon having from 1 to 20 carbon atoms and a hydrophilic sidechain with the follow-ing formulas selected from the group consisting of wherein R5 is a divalent hydrocarbon having from 1 to 10 carbon atoms, R6 is selected from the group consisting of methyl and hydrogen, R7 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms, wherein R8 is selected from the group consisting of a monovalent hydrocarbon having from 1 to 10 carbon atoms and hydrogen, and n4 is at least 1, 2) wherein R9 is a hydrocarbon having from 1 to 20 carbon atoms and a valence of n5 + 1, n5 is at least 1, there cannot be an -OH group on an aliphatic carbon atom beta to the Si atom, and there cannot be more than one OH group on any one carbon atom, wherein R10 is a divalent hydrocarbon having from 1 to 10;
carbon atoms, R11 is selected from the group consisting of hydrogen and methyl and R12 is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n8 + 1 and can have no more than one oxygen atom attached to any one carbon atom, n6 is zero or greater, n7 is an integer from zero to l and n8 is at least 1, wherein R13 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the group is not attached to a carbon atom of R13 which is alpha to the Si atom, R14 and R15 can be the same or different and are selected from the group consist-ing of a monovalent hydrocarbon having from 1 to 10 carbon atoms, hydrogen, OH wherein n9 is an integer from 1 to 3 and wherein R16 and R17 are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n10 is an integer from 1 to 5, 5) wherein R18 is a divalent hydrocarbon having from 1 to 20 carbon atoms and R19 and R20 are the same or different and are selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, 6) wherein R21 is a divalent or trivalent hydrocarbon having from 1 to 10 carbon atoms and the S atom is not attached to R21 by an ali-phatic carbon atom beta to the Si atom, R21 may or may not be attached to R22 to form a ring which contains more than 3 carbon atoms and R22 is selected from the group consisting of a hydrocarbon having from 1 to 10 carbon atoms and -0- M+
where M is selected from the group consisting of a monovalent metal ion and a quaternery ammonium ion, and n11 is an integer from 1 to 2, 7) wherein R23 is a divalent hydrocarbon having from 3 to 10 carbon atoms and the N+ must be attached to a carbon atom of R23 which is at least 2 carbon atoms away from the Si atom, R24, R25 and R26 are the same or different and are monovalent hydrocarbons having from 1 to 10 carbon atoms, is a monovalent anion selected from the group consisting of halides, R27-COO- wherein R27 is selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and a halogenated monovalent hydro-carbon having from 1 to 10 carbon atoms and R28 - SO? wherein R28 is selected from the group consisting of a monovalent hydrocarbon having from 1 to 10 carbon atoms and a halogenated monovalent hydrocarbon having from 1 to 10 carbon atoms, 8) wherein R29 is a divalent hydrocarbon having from 1 to 10 carbon atoms and n12 is an integer from 0 to 1 and when n12 is 1 the oxygen cannot be attached to an aliphatic carbon atom in R29 which is beta to the Si atom, R30 is a divalent hydro carbon having from 1 to 10 carbon atoms, R31 is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n13 + 1 and can have no more than one oxygen atom attached to any one carbon atom and n13 is at least 1, 9) wherein R32 is a divalent hydrocarbon having from 1 to 10 carbon atoms and the ester oxygen atom bonded to R32 cannot be at-tached to an aliphatic carbon atom in R32 which is beta to the Si atom, R33 is a hydrocarbon having from 2 to 20 carbon atoms and a valence of n14 + 1 and can have no more than one oxygen atom attached to any one carbon atom and n14 is an integer of at least 1, 10) wherein R34 is a divalent hydrocarbon having from 1 to 10 carbon atoms, 11) wherein R35 is a divalent hydrocarbon having from 2 to 10 carbon atoms and n15 is an integer from 1 to 10, 12) wherein R36 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group is not attached to a carbon atom alpha to the Si atom, R37 is selected from the group consisting of methyl and hydrogen, R38 is selected from the group consisting or hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and wherein R39 is a monovalent hydrocarbon having from 1 to 10 carbon atoms and n16 is at least l, 13) wherein R40 is a divalent hydrocarbon having from 1 to 10 carbon atoms, R41 and R42 can be the same or different and are selected from the group consisting of hydrogen, a monovalent hydrocarbon having from 1 to 10 carbon atoms and wherein n17 is an integer from 2 to 4, 14) wherein R43 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the S atom cannot be attached to a carbon atom of R43 which is alpha to the Si atom, R44 and R45 can be the same or different and are selected from the group con sisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, 15) wherein R46 is a divalent hydrocarbon having from 1 to 10 carbon atoms and n18 is an integer from zero to 3, 16) wherein R47 and R48 are selected from the group consisting of hydrogen, divalent or monovalent hydrocarbon having from 0 to 10 carbon atoms and R49 is selected from the group con-sisting of hydrogen, divalent or monovalent hydrocarbon having from 1 to 10 carbon atoms and only one of R47, R48 and R49 must be a divalent hydrocarbon and attached to the Si atom, R50 is selected from the group consisting of hydrogen, a mono-valent hydrocarbon having from 1 to 10 carbon atoms and where n20 is an integer from 2 to 4, and n19 is an integer from zero to 3, 17) wherein R51 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot be attached to a carbon atom of R51 alpha to the Si atom and X? is a monovalent cation selected from the group consisting of monovalent metal cations and wherein R52, R53, R54 and R55 can be the same or different and selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms, and 18) wherein R56 is a divalent hydrocarbon having from 2 to 10 carbon atoms and the carbonyl group cannot be attached to a carbon atom of R56 which is alpha to the Si atom, R57 is a divalent hydrocarbon having from one to 10 carbon atoms, R58 is selected from the group consisting of hydrogen and a monovalent hydrocarbon having from 1 to 10 carbon atoms and n21 is an integer from zero to 10, polymerized to form a polymer in a crosslinked network.
2. The contact lens according to Claim 1 wherein said hydro-philic sidechains are selected from the group consisting of wherein n22 is an integer from 2 to 3, , , wherein R59 and R60 are the same or different and are selected from the group consisting of hydrogen, methyl and - CH2 - CH2 - OH, and R61 is selected from the group consisting of hydrogen and methyl, , , , wherein n23 is an integer from 2 to 3 , , , , , , and .
3. The contact lens according to Claim 1 wherein X is selected from the group consisting of wherein n24 is an integer from 0 to 2, - CH=CH2and -R62 - G
wherein R62is wherein n25 is an integer from 3 to 4 and G is wherein R63 is selected from the group consisting of hydrogen and methyl.
wherein R62is wherein n25 is an integer from 3 to 4 and G is wherein R63 is selected from the group consisting of hydrogen and methyl.
4. The contact lens according to Claim 1 wherein X is wherein R64 is selected from the group consisting of hydrogen and methyl.
5. The polysiloxane monomer according to Claim 1 wherein Y1 and Y2 are methyl.
6. The polysiloxane monomer according to Claim 1 wherein Y1 is methyl and Y2 is phenyl.
7. The contact lens according to Claim 1 wherein only one of Z1, Z2, Z5 and Z6 is a hydrophilic sidechain and wherein a is equal to l to about 1,000, b is equal to zero, c is equal to 1, d is equal to 1 to about 1,000, and f is equal to zero.
8. The contact lens according to Claim 7 wherein a is equal to about 10 to about 500, b is equal to zero, c is equal to 1, d is equal to about 10 to about 500, e is equal to 1 and f is equal to zero.
9. The contact lens according to Claim 8 wherein said contact lens is soft and flexible and a is equal to about 75 to about 150, b is equal to zero, c is equal to 1, d is equal to about 25 to about 50, e is equal to one and f is equal to zero.
10. The soft and flexible contact lens according to Claim 9 wherein a is equal to about 75, b is equal to zero, c is equal to 1, d is equal to about 25, e is equal to 1 and f is equal to zero.
11. The contact lens according to Claim 10 wherein Z1, Z2 and Z5 are methyls, and Z6 is selected from the group con-sisting of ; wherein n26 is an integer from 2 to 3, , wherein R65 is selected from the group consisting of methyl and hydrogen, R66 is selected from the group consisting of methyl, hydrogen and - CH2-CH2-OH, Yl and Y2 equal methyl and X equals wherein n27 is an integer from 3 to 4.
12. The contact lens according to Claim 1 wherein only one of Z1 through Z7 is a hydrophilic sidechain and wherein a is equal to 1, b is equal to about 2 to about 4, c is equal to zero, d is equal to 1, e is equal to about 25 to about 500 and f is equal to about 5 to about 500.
13. The contact lens according to Claim 12 wherein said contact lens is soft and flexible and a is equal to 1, b is equal to about 2 to about 3, c is equal to zero, d is equal to 1, e is equal to about 25 to about 250 and f is equal to about 10 to about 250.
14. The soft and flexible contact lens according to Claim 13 wherein a is equal to 1, b is equal to about 2 to about 3, d is equal to 1, c is equal to zero, e is equal to from about 50 to about 100 and f is equal to from about 10 to about 100.
15. The soft and flexible contact lens according to Claim 14 wherein a is equal to 1, b is equal to from about 2 to about 3, c is equal to zero, d is equal to 1, e is equal to from about 50 to about 75 and f is equal to from about 10 to about 75.
16. The soft and flexible contact lens according to Claim 15 wherein Z1' Z2' Z5' Z6' Z7, Y1 and Y2 equal methyl, and Z4 equals hydrogen, and at least one of the Z3's in the methylene bridge is equal and the other Z3's in that bridge equal hydrogen, and X equals
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/102,010 US4259467A (en) | 1979-12-10 | 1979-12-10 | Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains |
| US102,010 | 1979-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134539A true CA1134539A (en) | 1982-10-26 |
Family
ID=22287637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000361551A Expired CA1134539A (en) | 1979-12-10 | 1980-10-03 | Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4259467A (en) |
| EP (1) | EP0035080B1 (en) |
| JP (1) | JPS5694324A (en) |
| AU (1) | AU540143B2 (en) |
| CA (1) | CA1134539A (en) |
| DE (1) | DE3068973D1 (en) |
| ES (1) | ES8202721A1 (en) |
| IE (1) | IE50609B1 (en) |
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-
1979
- 1979-12-10 US US06/102,010 patent/US4259467A/en not_active Expired - Lifetime
-
1980
- 1980-10-03 CA CA000361551A patent/CA1134539A/en not_active Expired
- 1980-11-07 ES ES496633A patent/ES8202721A1/en not_active Expired
- 1980-11-28 EP EP80304295A patent/EP0035080B1/en not_active Expired
- 1980-11-28 DE DE8080304295T patent/DE3068973D1/en not_active Expired
- 1980-12-02 IE IE2502/80A patent/IE50609B1/en not_active IP Right Cessation
- 1980-12-10 AU AU65231/80A patent/AU540143B2/en not_active Ceased
- 1980-12-10 JP JP17336480A patent/JPS5694324A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6229777B2 (en) | 1987-06-29 |
| AU6523180A (en) | 1981-06-18 |
| JPS5694324A (en) | 1981-07-30 |
| AU540143B2 (en) | 1984-11-01 |
| EP0035080B1 (en) | 1984-08-15 |
| IE50609B1 (en) | 1986-05-28 |
| ES496633A0 (en) | 1982-03-01 |
| DE3068973D1 (en) | 1984-09-20 |
| EP0035080A1 (en) | 1981-09-09 |
| ES8202721A1 (en) | 1982-03-01 |
| US4259467A (en) | 1981-03-31 |
| IE802502L (en) | 1981-06-10 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |