CA1335394C - Polymeric materials with high oxygen permeability and low protein substantivity - Google Patents
Polymeric materials with high oxygen permeability and low protein substantivityInfo
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- CA1335394C CA1335394C CA000587884A CA587884A CA1335394C CA 1335394 C CA1335394 C CA 1335394C CA 000587884 A CA000587884 A CA 000587884A CA 587884 A CA587884 A CA 587884A CA 1335394 C CA1335394 C CA 1335394C
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- 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
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- 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
A fluorosilicone based polymeric material with a fluori-nated methacrylate functional crosslinker and an internal wetting agent. This polymeric material is useful in the manufacture of gas-permeable biomedical devices such as contact lenses.
Description
POLYMERIC MATERIALS WITH HIGH OXYGEN PERMEABILITY
AND LOW PROTEIN SUBSTANTIVITY
FIELD OF THE INVENTION
This invention relates to materials useful in gas-permeable biomedical devices such as contact lenses made from polymeric materials comprising activated unsaturated group end capped polysiloxanes with fluorinated side chains, toughening agents and internal wetting agents.
BACKGROUND
10 U.S. Patent No. 4,153,641 discloses contact lenses made from polymers and copolymers comprising poly(organosiloxane) polymers and copolymers formed by free radically polymerizing a poly(organosiloxane) monomer terminally bonded through divalent hydrocarbon groups to polymerized, free radical polymerizably activated, unsaturated groups forming a polymer in a crosslinked network. Additionally, specific comonomers are disclosed which include lower esters of acrylic and methacrylic acid, styryls and N-vinyl pyrrolidinone which may be copolymerized with the above-described poly(organosiloxane) to form a copolymer.
U.S. Patent No. 4,208,506 discloses soft contact lenses made from polymers and copolymers comprising polyparaffinsiloxane polymers and copolymers formed by polymerizing a polyparaffinsiloxane monomer alpha, omega terminally bonded through divalent hydrocarbon groups to polymerized, free radical polymerizably activated, unsaturated groups forming a polymer in a crosslinked network.
Additionally, specific comonomers are disclosed which include lower esters of acrylic and methacrylic acid, styryls and N-vinyl pyrrolidinone which may be copolymerized with the above-described polyparaffinsiloxane monomer to form a copolymer. The instant invention preferred polysiloxane monomers include the same polyparaffinsiloxane monomers described above.
1 3353~4 U.S. Patent No. 4,303,772 discloses polysiloxanyl alkyl esters of acrylic and methacrylic acids and its copolymerization with alkyl esters of acrylic, methacrylic acids and/or itaconate esters to produce highly permeable contact lens material. The copolymer preferably includes a crosslinking agent and hydrophilic monomer. Contact lenses manufactured from the material are easily machined and polished into hard or semi-hard contact lenses having excellent dimensional stability.
U.S. patent No. 4,330,383 discloses improved contact lens materials obtained from copolymers containing a siloxanyl alkyl ester vinyl monomer by exposing the materials to high energy radiation thereby reducing the amount of unreacted monomer and residual contaminants.
U.S. Patent No. 4,327,203 discloses articles for biomedical applications made from a polymer formed by polymerizing (a) one or more polysiloxane monomers alpha, omega terminally bonded through divalent hydrocarbon groups to an activated, unsaturated group with (b) a cycloalkyl modulus modifier, e.g. tertiary butylcyclohexyl methacrylate, menthyl acrylate or methylisopentyl cyclooctyl acrylate, and (c) a tear film stabilizer. The products are useful as hard contact lenses. U.S. Patent No. 4,341,889 discloses the modulus modifier above can be tertiarybutyl styrene. U.S. Patent No. 4,355,147 discloses the modulus modifier above can be a polycyclic acrylate or methacrylate such as isobornyl methacrylate, adamantyl acrylate or isopinocamphyl methacrylate.
U.S. Patent No. 4,652,622 discloses polymeric materials comprised of monomeric polysiloxanes end capped with activated unsaturated groups, a modulus modifier and small amounts of an internal wetting agent such as N-alkenoyltrialkylsilyl aminate.
- DETAILED DESCRIPTION OF THE INVENTION
The invention relates to polymeric materials particularly useful in biomedical devices including contact lenses. The polymeric compositions of the present invention are the product of copolymerizing a mixture comprising (a) 10 to 100 weight parts of activated unsaturated group end-capped polysiloxanes containing fluorinated side chains where said polysiloxane is represented by the general formula (I) - Rll R3 A(CH2)4 -- S~ O -- Si -- O -- (CH2)4 -- A
_ R2 _ _ _ m n where A denotes an activated unsaturated group, where Rl denotes alkyl radicals with 1 to 6 carbon atoms, phenyl radicals, R2, R3 and R4 independently denote alkyl radicals with 1 to 6 carbon atoms, phenylradicals, or fluorinated alkyl radicals with 1 to 6 carbon atoms, and where m+n is at least 1, and n is at least 1;
(b) 10 to 100 weight parts toughening agent, and (c) 1 to 12 weight parts internal wetting agent.
The polymeric material may also include an optional crosslinking agent.
The activated unsaturated group end-capped polysiloxanes containing fluorinated side chains can be synthesized in several ways. For instance, mixtures of cyclopolysiloxanes with fluorinated side chains, cyclopolydimethylsiloxanes and 1,3-bis-(methacryloxybutyl)tetramethyldisiloxanes can be copolymerized. The relative amounts of the various components can be used to control the mole % of fluorinated side chains and the average molecular weight of polymer produced.
- Alternately, linear polysiloxanes with fluorinated side chains can be equilibrated in the presence of an acid or a base with either cyclopolydimethylsiloxanes or linear polydimethylsiloxane to produce polymers which could then be end-capped with 1,3-bis(methacryloxybutyl) tetramethyldisiloxane or a similar disiloxane end-capper.
Other methods could be used by those skilled in the art to synthesize the fluorinated polysiloxanes of the present invention.
The end-caps of the polymers used in the present invention besides being methacryl functional may also be end capped with any activated unsaturated group. The term ~activated unsaturated group" refers to a group which has a substituent which functions through resonance to increase the free radical stability or activity of the double bond, thereby facilitating free radical polymerization of the monomer. These activated unsaturated groups become polymerized to form a polymer with a crosslinked three-dimensional network. Preferably the activating groups present are such that the monomers lend themselves to polymerization under mild conditions, such as ambient temperature. Preferred activating groups include:
AND LOW PROTEIN SUBSTANTIVITY
FIELD OF THE INVENTION
This invention relates to materials useful in gas-permeable biomedical devices such as contact lenses made from polymeric materials comprising activated unsaturated group end capped polysiloxanes with fluorinated side chains, toughening agents and internal wetting agents.
BACKGROUND
10 U.S. Patent No. 4,153,641 discloses contact lenses made from polymers and copolymers comprising poly(organosiloxane) polymers and copolymers formed by free radically polymerizing a poly(organosiloxane) monomer terminally bonded through divalent hydrocarbon groups to polymerized, free radical polymerizably activated, unsaturated groups forming a polymer in a crosslinked network. Additionally, specific comonomers are disclosed which include lower esters of acrylic and methacrylic acid, styryls and N-vinyl pyrrolidinone which may be copolymerized with the above-described poly(organosiloxane) to form a copolymer.
U.S. Patent No. 4,208,506 discloses soft contact lenses made from polymers and copolymers comprising polyparaffinsiloxane polymers and copolymers formed by polymerizing a polyparaffinsiloxane monomer alpha, omega terminally bonded through divalent hydrocarbon groups to polymerized, free radical polymerizably activated, unsaturated groups forming a polymer in a crosslinked network.
Additionally, specific comonomers are disclosed which include lower esters of acrylic and methacrylic acid, styryls and N-vinyl pyrrolidinone which may be copolymerized with the above-described polyparaffinsiloxane monomer to form a copolymer. The instant invention preferred polysiloxane monomers include the same polyparaffinsiloxane monomers described above.
1 3353~4 U.S. Patent No. 4,303,772 discloses polysiloxanyl alkyl esters of acrylic and methacrylic acids and its copolymerization with alkyl esters of acrylic, methacrylic acids and/or itaconate esters to produce highly permeable contact lens material. The copolymer preferably includes a crosslinking agent and hydrophilic monomer. Contact lenses manufactured from the material are easily machined and polished into hard or semi-hard contact lenses having excellent dimensional stability.
U.S. patent No. 4,330,383 discloses improved contact lens materials obtained from copolymers containing a siloxanyl alkyl ester vinyl monomer by exposing the materials to high energy radiation thereby reducing the amount of unreacted monomer and residual contaminants.
U.S. Patent No. 4,327,203 discloses articles for biomedical applications made from a polymer formed by polymerizing (a) one or more polysiloxane monomers alpha, omega terminally bonded through divalent hydrocarbon groups to an activated, unsaturated group with (b) a cycloalkyl modulus modifier, e.g. tertiary butylcyclohexyl methacrylate, menthyl acrylate or methylisopentyl cyclooctyl acrylate, and (c) a tear film stabilizer. The products are useful as hard contact lenses. U.S. Patent No. 4,341,889 discloses the modulus modifier above can be tertiarybutyl styrene. U.S. Patent No. 4,355,147 discloses the modulus modifier above can be a polycyclic acrylate or methacrylate such as isobornyl methacrylate, adamantyl acrylate or isopinocamphyl methacrylate.
U.S. Patent No. 4,652,622 discloses polymeric materials comprised of monomeric polysiloxanes end capped with activated unsaturated groups, a modulus modifier and small amounts of an internal wetting agent such as N-alkenoyltrialkylsilyl aminate.
- DETAILED DESCRIPTION OF THE INVENTION
The invention relates to polymeric materials particularly useful in biomedical devices including contact lenses. The polymeric compositions of the present invention are the product of copolymerizing a mixture comprising (a) 10 to 100 weight parts of activated unsaturated group end-capped polysiloxanes containing fluorinated side chains where said polysiloxane is represented by the general formula (I) - Rll R3 A(CH2)4 -- S~ O -- Si -- O -- (CH2)4 -- A
_ R2 _ _ _ m n where A denotes an activated unsaturated group, where Rl denotes alkyl radicals with 1 to 6 carbon atoms, phenyl radicals, R2, R3 and R4 independently denote alkyl radicals with 1 to 6 carbon atoms, phenylradicals, or fluorinated alkyl radicals with 1 to 6 carbon atoms, and where m+n is at least 1, and n is at least 1;
(b) 10 to 100 weight parts toughening agent, and (c) 1 to 12 weight parts internal wetting agent.
The polymeric material may also include an optional crosslinking agent.
The activated unsaturated group end-capped polysiloxanes containing fluorinated side chains can be synthesized in several ways. For instance, mixtures of cyclopolysiloxanes with fluorinated side chains, cyclopolydimethylsiloxanes and 1,3-bis-(methacryloxybutyl)tetramethyldisiloxanes can be copolymerized. The relative amounts of the various components can be used to control the mole % of fluorinated side chains and the average molecular weight of polymer produced.
- Alternately, linear polysiloxanes with fluorinated side chains can be equilibrated in the presence of an acid or a base with either cyclopolydimethylsiloxanes or linear polydimethylsiloxane to produce polymers which could then be end-capped with 1,3-bis(methacryloxybutyl) tetramethyldisiloxane or a similar disiloxane end-capper.
Other methods could be used by those skilled in the art to synthesize the fluorinated polysiloxanes of the present invention.
The end-caps of the polymers used in the present invention besides being methacryl functional may also be end capped with any activated unsaturated group. The term ~activated unsaturated group" refers to a group which has a substituent which functions through resonance to increase the free radical stability or activity of the double bond, thereby facilitating free radical polymerization of the monomer. These activated unsaturated groups become polymerized to form a polymer with a crosslinked three-dimensional network. Preferably the activating groups present are such that the monomers lend themselves to polymerization under mild conditions, such as ambient temperature. Preferred activating groups include:
2-cyanocryloxy, acrylonitryl, acryloaminido, acryloxy, methacryloxy, styryl and N-vinyl-2-pyrrolidinone-x-yl where x may be 3, 4 or 5. The most preferred activating groups are methacryloxy and acryloxy.
The second component of the polymer of this invention is a strengthing agent which improves the modulus property of the polysiloxane with a minimum reduction of the oxygen permeability property. For convenience, this function is referred to as a toughening agent. The toughening agent is selected from the group comprising tertiary butyl styrene, a fluorinated methacrylate toughening agent, a cycloalkyl toughening agent or a polycyclic toughening agent.
~ 33~394 -- The cycloalkyl toughening agents are described and defined in U.S. Patent No. 4,327,203. These agents are a cycloalkyl acrylate or methacrylate of the formula O
,C~-- O -- C -- C == CH2 Z~ \
(CH2)n wherein E is either hydrogen or methyl D is branched or normal alkyl having 3 to 6 carbon atoms, preferably 3 to 4 carbon atoms Z is either hydrogen or methyl and n is an integer from 3 to 8 and preferably from 4 to 6.
Illustrative of the foregoing cycloalkyl toughening agents are the following: Menthyl methacrylate, menthyl acrylate, tertiarybutylcyclohexyl methacrylate, isopropylcyclopentyl acrylate, tertiarypentylcycloheptyl methacrylate, tertiarybutylcyclohexyl acrylate, isohexylcyclopentyl acrylate and methylisopentyl cyclooctyl acrylate.
The polycyclic toughening agents are described and defined in U.S. Patent No. 4,355,147. These agents are a polycyclic acrylate or methacrylate selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl acrylate, adamantyl methacrylate isopinocamphyl acrylate and isopinocamphyl methacrylate.
Illustrative of the fluorinated methacrylate toughening agents are: octafluoropentylmethacrylate, trifluoromethylmethacrylate, pentafluoroethyl methacrylate, and the like.
The toughening agent is present in an amount from 90 to 10 parts by weight per 10 to 90 parts by weight of the above-described polysiloxane monomers. In each event, the total parts of modifier and polysiloxane present are 100 parts. More preferably the modifier is present in the amount of 70 to 10 parts, more preferably yet the modifier is 45 to 15 parts.
The relative hardness (or softness) of the polymer of this invention can be varied by the amount of modulus modifier employed. Further small changes in the relative hardness can be obtained by decreasing or increasing the molecular weight of the monomeric polysiloxane endcapped with the activated, unsaturated groups. As the ratio of siloxane units to endcap units increases, the softness of the material increases.
Conversely, as this ratio decreases, the rigidity and hardness of the material increases.
Internal wetting agents useful in the present invention include N-alkyenoyl trialkylsilyl aminates described in U.S.
Patent No. 4,652,622 represented by the general formula CH2 = C(E)C(O)N(H)CH(G)(CH2)mC(O)OSi(R)3 wherein E is H or CH3, G is (CH2)XC(O)OSi(R)3 or H, R is CH3, C2Hs or C3H7, m is an integer from 1 to 15, x is an integer from 1 to 10, and m+x is an integer from 1 to 15 hereinafter referred to as NATA. Acryloyl- and methacryloyl-, mono- and dicarboxylic amino acids, hereinafter NAA, impart desirable surface wetting characteristics to polysiloxane polymers, but precipitate out of siloxane monomer mixtures before polymerization is completed. NAA can be modified to form trialkylsilyl esters which are more readily incorporated into polysiloxane polymers. The preferred NATAs are trimethylsilyl-N-methacryloylglutamate, - triethylsilyl-N-methacryloylglutamate, trimethyl-N-methacryloyl-6-aminohexanoate, trimethylsilyl-N-methacryloyl-aminododecanoate, and bis-trimethylsilyl-N-methacryloyl aspartate.
The preferred internal wetting agents are oxazolones of the general formula ~I 11 L
Rl N__ __" O
where Rl and R2 independently denote H or CH3; and R3 and R4 independently denote methyl or cyclohexylradicals.
These preferred internal wetting agents specifically include 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one (IPDMO), 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDMO), cyclohexane spiro-4'-(2'isopropenyl-2'-oxazol-5'-one) (IPCO), cyclohexane-spiro-4'-(2'-vinyl-2'-oxazol-5'-one) (VCO), and 2-(-1-propenyl)-4,4-dimethyl-oxazol-5-one (PDMO).
These preferred internal wetting agents have two important features which make them particularly desirable wetting agents: (1) They are relatively non-polar and are compatible with the hydrophobic monomers (the polysiloxanes and the toughening agents), and (2) They are converted to highly polar amino acids on mild hydrolysis, which impart substantial wetting characteristics. When polymerized in the presence of the other components, a copolymer is formed. These internal wetting agents result through the carbon-carbon double bond with the endcaps of the polysiloxane monomers, and with the toughening agents to form copolymeric materials particularly useful in biomedical devices, especially contact lenses.
- These oxazolones are prepared by the general reaction sequence O R3~ R4 NaOH R2 ~ \ R3 R2 ~ Cl + H2N COOH Hoo2oc NH R4 Rl Rl COOH
(I) (II) Cl COC2H5 ~ o Hexane Rl N ~ O
The first step being a Shotten-Bauman acrylation of an amino acid. Upon completion of this step the polymerizable functionality is introduced by using either acryloyl or methacryloyl chloride.
The internal wetting agents may be present in the polymeric materials of the present invention in the range of 1 to 12 parts per 100 parts of toughening agent and polysiloxane.
The above polymer system may also contain from zero to 20 parts by weight, based on weight of polysiloxane and modulus modifier, of an auxiliary modifier. These auxiliary modifiers are reactive with the three components of this invention. Minor but often desirable changes of physical properties, e.g. tear strength and tensile strength, are obtained by the use of auxiliary modifiers.
Useful auxiliary modifiers include, but are not limited to, tertiary-butyl acrylate, polyethylene glycol acrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, divinyl benzene, neopentylglycol diacrylate, ~ 33539~
- ethylene glycol dimethacrylate, ethylene glycol diacrylate, neopentylglycol dimethacrylate, polyvinyl alkyl benzenes, especially divinyl alkyl benzenes, e.g. divinyl toluene, 1,4-butane diglycol dimethacrylate and mixtures thereof. The foregoing polyethylene glycols will contain from 2 to 9 repeating ethylene glycol units. The most preferred polymeric materials employ ethylene glycol dimethacrylate as an auxiliary wetting agent.
The activated unsaturated end-capped polysiloxanes containing fluorinated side chains of the present invention are generally clear, colorless liquids, whose viscosity depends on the value of the sum of m plus n. To maintain viscosities which are useful, the degree of polymerization (m+n) should be within the range of 2 to about 100. These monomers can be readily cured to cast shapes by conventional methods, such as polymerization by free radical initiators.
Illustrative of free radical initiators which can be employed are bis(isopropyl)peroxydicarbonate, azo-bisisobutyronitrile, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, benzoyl peroxide, benzoin methyl ether, diethoxyacetophenone, tertiary butyl peroxypivalate and the like. The monomers are cured through the well known methods of heat and/or actinic light, depending on the nature of the catalyst.
The advantage of using the polymers of the instant invention are numerous. For example, (a) the advantages of using activated unsaturated terminal groups to cure the siloxane material are (a) the high reactivity systems permit rapid cure at or near room temperature if suitable initiators are used, (b) no fillers are needed to get useful physical strength as is common with most silicone resins in contact lenses. This is desirable since the use of fillers requires that other possibly undesirable materials be added to the composition in order to match the refractive index of the polymer to the filler.
1 3353~4 - Secondly, the contact lenses made from the polymer of the instant invention are oxygen permeable. A critical oxygen tension and flux under a lens should be about 10mm Hg and 2ml/(cm2 hr.) respectively below which corneal swelling occurs (Polse and Decker, Investigative Ophthalmology and Visual Science, vol. 18, p. 188, 1979). In order to meet these requirements, the lens material must have adequate oxygen permeability. When m in formula II and n in III above are at least about 2, the chain of siloxane is long enough in the instant compositions to exceed the oxygen requirements of the cornea. However, in specific situations m and n may be as low as 0 and still produce polymeric materials with significant oxygen permeability.
Additionally, these lenses are hydrolytically stable meaning that when the contact lenses are placed into an aqueous solution, e.g. on th eye, or during the disinfecting step, i.e. water plus heat, the lenses will not change in chemical composition, i.e. hydrolyze.
The most preferred contact lens of the instant invention is a fillerless, oxygen permeable, hydrolytically stable, wettable, biologically inert, transparent polymeric contact lens comprising a poly(organosiloxane) terminally bonded through a divalent hydrocarbon group to a polymerized activated, unsaturated group. These most preferred contact lenses have an oxygen permeability of at least 10 x 10~11cm3cm/(sec.cm2 mmHg), are hydrolytically stable, biologically inert and transparent.
The polymers of this invention can be formed into contact lenses by the spincasting process as disclosed in U.S. Patent Nos. 3,408,429 and 3,496,254 and by other conventional methods such as compression molding as disclosed in U.S. Patent Nos. 4,085,459 and 4,197,266.
When the term ~shaped article for use in biomedical applications" or ~biomedical device~ are used herein, it is meant that the materials disclosed herein above have physiochemical properties rendering them suitable for - prolonged contact with living tissue, blood and the mucous membrane. These properties are required for biomedical shaped articles, such as surgical implants, blood dialysis devices and membranes intended to come in contact with body fluid outside of the body, e.g. 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 synthetic surface which is antithrombogenic and nonhemolytic to blood is necessary for prostheses and devices used with blood. The instant polymers are compatible with living tissue.
The polymers disclosed herein can be boiled and/or autoclaved in water without being damaged whereby sterilization may be achieved. Thus, an article formed from the disclosed polymers may be used in surgery where an article compatible with living tissue or with the mucous membrane may be used.
The following examples are illustrative only and should not be construed as limiting the invention. All parts and percents referred to herein are on a weight basis, all viscosities measured at 25C unless otherwise specified and all temperatures are degrees Celsius.
EXAMPLES
A. Synthesis of 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one (IPDMO) 1. Methacryloylation: In a 500 ml 3-neck round bottom flask equipped with a mechanical stirrer, thermometer and an addition funnel, 51.5 grams (0.5 mole) of ~ -aminoisobutyric acid (Aldrich) and 40 grams (1 mole) of NaOH were dissolved in ~150 ml of H20. The reaction flask was cooled to 0~-5C
with MeOH-ice bath and 0.5 mole of methacrylate chloride (distilled, Aldrich) was added dropwise while the temperature of the reaction mixture kept below 0C. After stirring for an ~ 335394 additional hour, the reaction mixture was acidified with concentrated HCl to pH ~ 3 to precipitate out the intermediete, which was then filtered, washed with cold H2O
and air dried. Further drying was accomplished in vacuum oven at 80C overnight to obtain 44.9 grams (0.26 mole; 53%) n-methacryloyl-~ -aminoisobutyric acid (MAIBA), which was suitable for IPDMO synthesis. m.p. 157-159C.
2. Cyclization: Synthesis of IPDMO: In a 500 ml dry 3-neck round bottom flash, 0.26 mole of MAIBA was dispersed in 300 ml of dry hexane and this was allowed to react with mechanical stirring by dropwise addition of triethylamine (0.52 mole) while the temperature of the reaction mixture was maintained at 45 ~50C. During the addition, the copious evolution of carbon dioxide and the formation of white precipitate of TEA-HCl were observed. The reaction mixture was stirred for an additional two hours. After cooling to room temperature, white precipitate was filtered off and hexane evaporated off yielding an oil. Pure IPDMO was obtained after two times of recrystallization in hexane at dry ice-acetone temperature. Yield was 29 grams (73~).
B. Synthesis of 2-vinyl-4,4-dimethYl-2-oxazolin-5-one ~VDMO) 1. Acrylolation was achieved by adopting a procedure similar to step 1 of the synthesis of IPDMO except acryloyl chloride was used in place of methacryloyl chloride. The intermediete n-acryloyl-d-aminobutyric acid (AAIBA) was produced.
2. AAIBA was reacted with triethylamine in a fashion similar to step 2 of the synthesis of IPDMO to produce VDMO.
~ C. Synthesis of cYclohexane spiro-4'-(2~
isopropenyl-2-oxazolin-5'-one) (IPCO) The synthetic method used to synthesize IPDMO was followed except d-aminobiscyclohexylformic acid was used in place of ~ -aminoisobutyric acid.
D. Synthesis of Cyclohexane Spiro-4'-(2'-vinyl-2'-oxazolin-5'-one (VCO) The synthetic method employed in the synthesis of VDMO was used except l-amino-l-cyclohexane carboxylic acid was used in place of ~ -aminoisobutyric acid.
E. Synthesis of 2-(-1-propenYl)-4,4-dimethyl-oxazolin-5-one (PDMO) The method employed in the synthesis of VDMO was employed except crotonyl chloride was used in place of methacrylate chloride.
F. Synthesis of Polysiloxanes with Fluorinated Side Chains 1,3,5-trimethyl, 1,3,5-trifluoropropylcyclotrisiloxane, octamethylcyclotetrasiloxane and 1,3-Bis-(methacryloxybutyl) tetramethyldisiloxane is rapidly stirred upon the addition of trifluoromethane sulfonic acid for 24 hours. The mixture is charged with a 5 mole excess of sodium bicarbonate and reacted overnight, then diluted with CHC13, dried over MgSO4, filtered and devolatilized. The polymer is washed with methanol.
This general method was used with various amounts of 1,3,5-trimethyl, 1,3,5-trifluoropropylcyclotrisiloxane (TPTMCPS), 1,3-Bis-(methacryloxybutyl) tetramethyldisiloxane (BMTMDS) and octamethylcyclotetrasiloxane (OMCTS) to yield copolymers with varying degrees of fluoropropyl containing siloxane content.
The following weight parts of each component were used in the above general method to produce polymer with a degree of polymerization of about 100 possessing varying degrees of fluorination.
Mole % trifluoropropyl-methYlsiloxane wt. TFTMCPS wt. OMCTS wt. BMTMDS
65% 154g 39g 6.3g 40% 94g 67g 6.3g 25% 59g 84g 6.3g 18% 43g 91g 6.3g 12.5% 30g 97.5g 6.3g G. SYnthesis and Characterization of Polymeric Materials 1. Polydimethylsiloxane Based Materials Methacrylate end capped polydimethylsiloxane (PDMS) with an average degree of polymerization of about 180 was compounded with isobornylmethacrylate (IBOMA) and VDMO in the weight proportion of 85/5/5 (PDMS/IBOMA/VDMO). The mixture was stirred, a free radical initiator was added and polymerized by exposure to ultraviolet radiation. The resultant polymeric material was characterized for modulus, tensile strength, elongation, oleic acid uptake, and oxygen permeability (DK). The material was purified by extraction with toluene and also the internal wetting agent (VDMO) was hydrolyzed in the polymeric material by boiling in buffered saline solution for 20 minutes. Both the toluene extracted sample and toluene extracted/hydrolyzed sample were characterized. The results of these tests are reported in Table 1.
Polydimethylsiloxane Based Material Modulus Tensile Elongation Oleic Material(g/mm2) (g/mm2) % % DK
95/5/5(PDMS
/IBOMA/VDMO) 107 94 127 4.7 200 toluene extracted 521 142 35 4.4 200 extracted/
hydrolyzed 908 199 37 6.0 200 2. Polydimethylsiloxane Based Materials with Various Amounts of Internal Wetting Agent and Fluorinated Tougheninq Agent Various polymeric materials were made by reaching methacrylate end capped polydimethylsiloane with an average degree of polymerization of about 50 (M2Dso) with fluorinated toughening agent octafluoropentylmethacrylate (OFPMA), auxiliary toughening agent ethylene glycol dimethacrylate (EGDMA) and VDMO. The various ratios of the components and the physical characteristics of the polymeric material produced by reaching the components is reported in Table 2.
Polydimethylsiloxane Materials With Internal Wettinq Aqents M2Dso/OFPMA/ Modulus Tensile % %
EGDMA/VDMO (q/mm2) (q/mm2) Elongation Oleic DK
87/10/0/3 107 94 127 4.7 200 75/20/2/3 521 142 35 4.4 200 73/20/2/S 908 199 37 6.0 200 These samples were soaked in buffered saline solutions for 1, 3, 7 and 14 days and recharacterized. The results of the hydrolysis are reported in Table 3.
~ 15 ~ TABLE 3 Hydrolysis of Polydimethylsiloxane Materials M2Dso/OFPMA/ Modulus Tensile % %
EGDMA/VDMO (g/mm2) (q/mm2) Elonqation Oleic DK
87/10/0/3 1 day 333 182 46 3.9 3 days 535 129 32 6.4 7 days 519 128 32 2.0 14 days 549 126 33 3.9 75/20/2/3 1 day 581 187 40 4.8 3 days 521 142 35 4.4 7 days 661 147 32 5.4 14 days 746 167 34 5.9 73/20/2/5 1 day 666 197 41 7.0 3 days 908 199 37 3.9 7 days 906 211 43 7.1 14 days 1,020 202 36 7.3 3. Fluorinated PolYsiloxane Based Materials With Internal Wetting Agents Methacrylate end-capped polysiloxanes with varying degrees of fluoropropyl side chains (fluorosiloxanes), prepared by the method of Example F, were reacted with various amounts of strengthening agent (IBOMA) and internal wetting agent (VDMO). Various weight ratio mixtures of the three components were made, polymerized by free radical polymerization, and characterized. The results are summarized in Table 4.
Fluoro- Fluoro-silicone/ silicone/ Modulus Tensile Elongation Oleic 2 IBOMA/VDMO Mole % (q/mm2) (g/mm2) % % DK
95/5/5 65 Mole % 81 45 80 3.1 700 90/10/5 65 Mole % 122 104 106 5.8 550 85/15/5 65 Mole % 273 197 99 10.1 310 95/5/5 40 Mole % 90 52 89 5.11,200 90/10/5 40 Mole % 116 87 107 8.5 1,000 85/15/5 40 Mole % 245 201 130 12.0 258 95/5/5 40 Mole % 85 41 68 5.6 --90/10/5 40 Mole % 115 78 93 8.9 --85/15/5 40 Mole % 308 163 101 13.1 --95/5/5 25 Mole %118 56 66 7.2 --90/10/5 25 Mole % 153 83 80 10.2 --85/15/5 25 Mole % 390 192 104 14.1 --95/5/5 18 Mole %112 55 74 7.9 --90/10/5 18 Mole % 158 110 109 18.0 --95/5/5 12.5 Mole %139 60 57 10.9 --90/10/5 12.5 Mole % 179 76 62 14.4 --85/15/5 12.5 Mole % 333 122 70 11.5 --The oleic acid measurements were based upon the weight of material which could be extracted using toluene from a sample which had been immersed in oleic acid for a fixed period of time.
Synthesis of Polymeric Materials Comprising PolYsiloxanes with Fluorinated Side Chains, Fluorinated MethacrYlate Touqheninq Agent and an Internal Wettinq Aqent A series of mixtures comprising polydimethylsiloxane/
polymethyltrifluoropropylsiloxane in varying mole ratios, octafluoropropylmethacrylate (OFPMA) and the internal wetting agent VDMO were made. These mixtures were then polymerized, the volatiles were removed from the reactive product, and then the product was characterized. The test results are reported in Table 5.
The samples were then placed in a buffered saline solution at 80C and hydrolyzed for 1, 3 and 5 days. The samples were recharacterized, the results of which are reported in Table 6.
M2Dloo - (65 mole % trifluoropropyl)/OFPMA/VDMO
Siloxane/OFPMA/VDMO Modulus Tensile Elonqation Oleic 2 80/20/5 65 Mole %120 136 135 1.4 234 60/40/5 65 Mole %409 427 145 -0.2 206 55/45/5 65 Mole %712 400 136 0.7 240 50/50/5 65 Mole %1,571 563 153 0.7 186 40/60/5 65 Mole %7,630 730 135 1.2 102 20/80/5 65 Mole %27,200 983 91 0.9 42 80/20/5 40 Mole %127 89 102 1.5 346 60/40/5 40 Mole %224 248 120 1.1 --55/45/5 40 Mole %709 535 125 1.0 267 50/50/5 40 Mole %1,593 698 150 0.9 192 40/60/5 40 Mole %15,000 725 177 1.0 67 20/80/5 40 Mole %34,4001,030 62 0.9 30 80/20/5 25 Mole %126 65 81 2.7 --60/40/5 25 Mole %475 380 109 1.8 --80/20/5 12.5 Mole % 148 104 97 3.4 --60/40/5 12.5 Mole % 544 453 106 2.3 --40/60/5 12.5 Mole % 2,509 742 133 1.8 --20/80/5 12.5 Mole % 10,760887 142 1.3 --Series III M2Dloo (65% mole % trifluoropropyl)/OFPMA/VDMO
80/20/X X = 1,3,5 Parts VDMO Time Modulus Tensile Elongation 1 1 day 84 51 98 3 1 day 87 53 90 1 day 98 62 93 1 3 days 93 48 88 3 3 days 175 100 108 3 days 281 126 100 1 7 days 101 52 87 3 7 days 171 98 108 7 days 205 118 110 1 14 days 109 64 106 3 14 days 169 113 121 14 days 171 104 111
The second component of the polymer of this invention is a strengthing agent which improves the modulus property of the polysiloxane with a minimum reduction of the oxygen permeability property. For convenience, this function is referred to as a toughening agent. The toughening agent is selected from the group comprising tertiary butyl styrene, a fluorinated methacrylate toughening agent, a cycloalkyl toughening agent or a polycyclic toughening agent.
~ 33~394 -- The cycloalkyl toughening agents are described and defined in U.S. Patent No. 4,327,203. These agents are a cycloalkyl acrylate or methacrylate of the formula O
,C~-- O -- C -- C == CH2 Z~ \
(CH2)n wherein E is either hydrogen or methyl D is branched or normal alkyl having 3 to 6 carbon atoms, preferably 3 to 4 carbon atoms Z is either hydrogen or methyl and n is an integer from 3 to 8 and preferably from 4 to 6.
Illustrative of the foregoing cycloalkyl toughening agents are the following: Menthyl methacrylate, menthyl acrylate, tertiarybutylcyclohexyl methacrylate, isopropylcyclopentyl acrylate, tertiarypentylcycloheptyl methacrylate, tertiarybutylcyclohexyl acrylate, isohexylcyclopentyl acrylate and methylisopentyl cyclooctyl acrylate.
The polycyclic toughening agents are described and defined in U.S. Patent No. 4,355,147. These agents are a polycyclic acrylate or methacrylate selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl acrylate, adamantyl methacrylate isopinocamphyl acrylate and isopinocamphyl methacrylate.
Illustrative of the fluorinated methacrylate toughening agents are: octafluoropentylmethacrylate, trifluoromethylmethacrylate, pentafluoroethyl methacrylate, and the like.
The toughening agent is present in an amount from 90 to 10 parts by weight per 10 to 90 parts by weight of the above-described polysiloxane monomers. In each event, the total parts of modifier and polysiloxane present are 100 parts. More preferably the modifier is present in the amount of 70 to 10 parts, more preferably yet the modifier is 45 to 15 parts.
The relative hardness (or softness) of the polymer of this invention can be varied by the amount of modulus modifier employed. Further small changes in the relative hardness can be obtained by decreasing or increasing the molecular weight of the monomeric polysiloxane endcapped with the activated, unsaturated groups. As the ratio of siloxane units to endcap units increases, the softness of the material increases.
Conversely, as this ratio decreases, the rigidity and hardness of the material increases.
Internal wetting agents useful in the present invention include N-alkyenoyl trialkylsilyl aminates described in U.S.
Patent No. 4,652,622 represented by the general formula CH2 = C(E)C(O)N(H)CH(G)(CH2)mC(O)OSi(R)3 wherein E is H or CH3, G is (CH2)XC(O)OSi(R)3 or H, R is CH3, C2Hs or C3H7, m is an integer from 1 to 15, x is an integer from 1 to 10, and m+x is an integer from 1 to 15 hereinafter referred to as NATA. Acryloyl- and methacryloyl-, mono- and dicarboxylic amino acids, hereinafter NAA, impart desirable surface wetting characteristics to polysiloxane polymers, but precipitate out of siloxane monomer mixtures before polymerization is completed. NAA can be modified to form trialkylsilyl esters which are more readily incorporated into polysiloxane polymers. The preferred NATAs are trimethylsilyl-N-methacryloylglutamate, - triethylsilyl-N-methacryloylglutamate, trimethyl-N-methacryloyl-6-aminohexanoate, trimethylsilyl-N-methacryloyl-aminododecanoate, and bis-trimethylsilyl-N-methacryloyl aspartate.
The preferred internal wetting agents are oxazolones of the general formula ~I 11 L
Rl N__ __" O
where Rl and R2 independently denote H or CH3; and R3 and R4 independently denote methyl or cyclohexylradicals.
These preferred internal wetting agents specifically include 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one (IPDMO), 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDMO), cyclohexane spiro-4'-(2'isopropenyl-2'-oxazol-5'-one) (IPCO), cyclohexane-spiro-4'-(2'-vinyl-2'-oxazol-5'-one) (VCO), and 2-(-1-propenyl)-4,4-dimethyl-oxazol-5-one (PDMO).
These preferred internal wetting agents have two important features which make them particularly desirable wetting agents: (1) They are relatively non-polar and are compatible with the hydrophobic monomers (the polysiloxanes and the toughening agents), and (2) They are converted to highly polar amino acids on mild hydrolysis, which impart substantial wetting characteristics. When polymerized in the presence of the other components, a copolymer is formed. These internal wetting agents result through the carbon-carbon double bond with the endcaps of the polysiloxane monomers, and with the toughening agents to form copolymeric materials particularly useful in biomedical devices, especially contact lenses.
- These oxazolones are prepared by the general reaction sequence O R3~ R4 NaOH R2 ~ \ R3 R2 ~ Cl + H2N COOH Hoo2oc NH R4 Rl Rl COOH
(I) (II) Cl COC2H5 ~ o Hexane Rl N ~ O
The first step being a Shotten-Bauman acrylation of an amino acid. Upon completion of this step the polymerizable functionality is introduced by using either acryloyl or methacryloyl chloride.
The internal wetting agents may be present in the polymeric materials of the present invention in the range of 1 to 12 parts per 100 parts of toughening agent and polysiloxane.
The above polymer system may also contain from zero to 20 parts by weight, based on weight of polysiloxane and modulus modifier, of an auxiliary modifier. These auxiliary modifiers are reactive with the three components of this invention. Minor but often desirable changes of physical properties, e.g. tear strength and tensile strength, are obtained by the use of auxiliary modifiers.
Useful auxiliary modifiers include, but are not limited to, tertiary-butyl acrylate, polyethylene glycol acrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, divinyl benzene, neopentylglycol diacrylate, ~ 33539~
- ethylene glycol dimethacrylate, ethylene glycol diacrylate, neopentylglycol dimethacrylate, polyvinyl alkyl benzenes, especially divinyl alkyl benzenes, e.g. divinyl toluene, 1,4-butane diglycol dimethacrylate and mixtures thereof. The foregoing polyethylene glycols will contain from 2 to 9 repeating ethylene glycol units. The most preferred polymeric materials employ ethylene glycol dimethacrylate as an auxiliary wetting agent.
The activated unsaturated end-capped polysiloxanes containing fluorinated side chains of the present invention are generally clear, colorless liquids, whose viscosity depends on the value of the sum of m plus n. To maintain viscosities which are useful, the degree of polymerization (m+n) should be within the range of 2 to about 100. These monomers can be readily cured to cast shapes by conventional methods, such as polymerization by free radical initiators.
Illustrative of free radical initiators which can be employed are bis(isopropyl)peroxydicarbonate, azo-bisisobutyronitrile, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, benzoyl peroxide, benzoin methyl ether, diethoxyacetophenone, tertiary butyl peroxypivalate and the like. The monomers are cured through the well known methods of heat and/or actinic light, depending on the nature of the catalyst.
The advantage of using the polymers of the instant invention are numerous. For example, (a) the advantages of using activated unsaturated terminal groups to cure the siloxane material are (a) the high reactivity systems permit rapid cure at or near room temperature if suitable initiators are used, (b) no fillers are needed to get useful physical strength as is common with most silicone resins in contact lenses. This is desirable since the use of fillers requires that other possibly undesirable materials be added to the composition in order to match the refractive index of the polymer to the filler.
1 3353~4 - Secondly, the contact lenses made from the polymer of the instant invention are oxygen permeable. A critical oxygen tension and flux under a lens should be about 10mm Hg and 2ml/(cm2 hr.) respectively below which corneal swelling occurs (Polse and Decker, Investigative Ophthalmology and Visual Science, vol. 18, p. 188, 1979). In order to meet these requirements, the lens material must have adequate oxygen permeability. When m in formula II and n in III above are at least about 2, the chain of siloxane is long enough in the instant compositions to exceed the oxygen requirements of the cornea. However, in specific situations m and n may be as low as 0 and still produce polymeric materials with significant oxygen permeability.
Additionally, these lenses are hydrolytically stable meaning that when the contact lenses are placed into an aqueous solution, e.g. on th eye, or during the disinfecting step, i.e. water plus heat, the lenses will not change in chemical composition, i.e. hydrolyze.
The most preferred contact lens of the instant invention is a fillerless, oxygen permeable, hydrolytically stable, wettable, biologically inert, transparent polymeric contact lens comprising a poly(organosiloxane) terminally bonded through a divalent hydrocarbon group to a polymerized activated, unsaturated group. These most preferred contact lenses have an oxygen permeability of at least 10 x 10~11cm3cm/(sec.cm2 mmHg), are hydrolytically stable, biologically inert and transparent.
The polymers of this invention can be formed into contact lenses by the spincasting process as disclosed in U.S. Patent Nos. 3,408,429 and 3,496,254 and by other conventional methods such as compression molding as disclosed in U.S. Patent Nos. 4,085,459 and 4,197,266.
When the term ~shaped article for use in biomedical applications" or ~biomedical device~ are used herein, it is meant that the materials disclosed herein above have physiochemical properties rendering them suitable for - prolonged contact with living tissue, blood and the mucous membrane. These properties are required for biomedical shaped articles, such as surgical implants, blood dialysis devices and membranes intended to come in contact with body fluid outside of the body, e.g. 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 synthetic surface which is antithrombogenic and nonhemolytic to blood is necessary for prostheses and devices used with blood. The instant polymers are compatible with living tissue.
The polymers disclosed herein can be boiled and/or autoclaved in water without being damaged whereby sterilization may be achieved. Thus, an article formed from the disclosed polymers may be used in surgery where an article compatible with living tissue or with the mucous membrane may be used.
The following examples are illustrative only and should not be construed as limiting the invention. All parts and percents referred to herein are on a weight basis, all viscosities measured at 25C unless otherwise specified and all temperatures are degrees Celsius.
EXAMPLES
A. Synthesis of 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one (IPDMO) 1. Methacryloylation: In a 500 ml 3-neck round bottom flask equipped with a mechanical stirrer, thermometer and an addition funnel, 51.5 grams (0.5 mole) of ~ -aminoisobutyric acid (Aldrich) and 40 grams (1 mole) of NaOH were dissolved in ~150 ml of H20. The reaction flask was cooled to 0~-5C
with MeOH-ice bath and 0.5 mole of methacrylate chloride (distilled, Aldrich) was added dropwise while the temperature of the reaction mixture kept below 0C. After stirring for an ~ 335394 additional hour, the reaction mixture was acidified with concentrated HCl to pH ~ 3 to precipitate out the intermediete, which was then filtered, washed with cold H2O
and air dried. Further drying was accomplished in vacuum oven at 80C overnight to obtain 44.9 grams (0.26 mole; 53%) n-methacryloyl-~ -aminoisobutyric acid (MAIBA), which was suitable for IPDMO synthesis. m.p. 157-159C.
2. Cyclization: Synthesis of IPDMO: In a 500 ml dry 3-neck round bottom flash, 0.26 mole of MAIBA was dispersed in 300 ml of dry hexane and this was allowed to react with mechanical stirring by dropwise addition of triethylamine (0.52 mole) while the temperature of the reaction mixture was maintained at 45 ~50C. During the addition, the copious evolution of carbon dioxide and the formation of white precipitate of TEA-HCl were observed. The reaction mixture was stirred for an additional two hours. After cooling to room temperature, white precipitate was filtered off and hexane evaporated off yielding an oil. Pure IPDMO was obtained after two times of recrystallization in hexane at dry ice-acetone temperature. Yield was 29 grams (73~).
B. Synthesis of 2-vinyl-4,4-dimethYl-2-oxazolin-5-one ~VDMO) 1. Acrylolation was achieved by adopting a procedure similar to step 1 of the synthesis of IPDMO except acryloyl chloride was used in place of methacryloyl chloride. The intermediete n-acryloyl-d-aminobutyric acid (AAIBA) was produced.
2. AAIBA was reacted with triethylamine in a fashion similar to step 2 of the synthesis of IPDMO to produce VDMO.
~ C. Synthesis of cYclohexane spiro-4'-(2~
isopropenyl-2-oxazolin-5'-one) (IPCO) The synthetic method used to synthesize IPDMO was followed except d-aminobiscyclohexylformic acid was used in place of ~ -aminoisobutyric acid.
D. Synthesis of Cyclohexane Spiro-4'-(2'-vinyl-2'-oxazolin-5'-one (VCO) The synthetic method employed in the synthesis of VDMO was used except l-amino-l-cyclohexane carboxylic acid was used in place of ~ -aminoisobutyric acid.
E. Synthesis of 2-(-1-propenYl)-4,4-dimethyl-oxazolin-5-one (PDMO) The method employed in the synthesis of VDMO was employed except crotonyl chloride was used in place of methacrylate chloride.
F. Synthesis of Polysiloxanes with Fluorinated Side Chains 1,3,5-trimethyl, 1,3,5-trifluoropropylcyclotrisiloxane, octamethylcyclotetrasiloxane and 1,3-Bis-(methacryloxybutyl) tetramethyldisiloxane is rapidly stirred upon the addition of trifluoromethane sulfonic acid for 24 hours. The mixture is charged with a 5 mole excess of sodium bicarbonate and reacted overnight, then diluted with CHC13, dried over MgSO4, filtered and devolatilized. The polymer is washed with methanol.
This general method was used with various amounts of 1,3,5-trimethyl, 1,3,5-trifluoropropylcyclotrisiloxane (TPTMCPS), 1,3-Bis-(methacryloxybutyl) tetramethyldisiloxane (BMTMDS) and octamethylcyclotetrasiloxane (OMCTS) to yield copolymers with varying degrees of fluoropropyl containing siloxane content.
The following weight parts of each component were used in the above general method to produce polymer with a degree of polymerization of about 100 possessing varying degrees of fluorination.
Mole % trifluoropropyl-methYlsiloxane wt. TFTMCPS wt. OMCTS wt. BMTMDS
65% 154g 39g 6.3g 40% 94g 67g 6.3g 25% 59g 84g 6.3g 18% 43g 91g 6.3g 12.5% 30g 97.5g 6.3g G. SYnthesis and Characterization of Polymeric Materials 1. Polydimethylsiloxane Based Materials Methacrylate end capped polydimethylsiloxane (PDMS) with an average degree of polymerization of about 180 was compounded with isobornylmethacrylate (IBOMA) and VDMO in the weight proportion of 85/5/5 (PDMS/IBOMA/VDMO). The mixture was stirred, a free radical initiator was added and polymerized by exposure to ultraviolet radiation. The resultant polymeric material was characterized for modulus, tensile strength, elongation, oleic acid uptake, and oxygen permeability (DK). The material was purified by extraction with toluene and also the internal wetting agent (VDMO) was hydrolyzed in the polymeric material by boiling in buffered saline solution for 20 minutes. Both the toluene extracted sample and toluene extracted/hydrolyzed sample were characterized. The results of these tests are reported in Table 1.
Polydimethylsiloxane Based Material Modulus Tensile Elongation Oleic Material(g/mm2) (g/mm2) % % DK
95/5/5(PDMS
/IBOMA/VDMO) 107 94 127 4.7 200 toluene extracted 521 142 35 4.4 200 extracted/
hydrolyzed 908 199 37 6.0 200 2. Polydimethylsiloxane Based Materials with Various Amounts of Internal Wetting Agent and Fluorinated Tougheninq Agent Various polymeric materials were made by reaching methacrylate end capped polydimethylsiloane with an average degree of polymerization of about 50 (M2Dso) with fluorinated toughening agent octafluoropentylmethacrylate (OFPMA), auxiliary toughening agent ethylene glycol dimethacrylate (EGDMA) and VDMO. The various ratios of the components and the physical characteristics of the polymeric material produced by reaching the components is reported in Table 2.
Polydimethylsiloxane Materials With Internal Wettinq Aqents M2Dso/OFPMA/ Modulus Tensile % %
EGDMA/VDMO (q/mm2) (q/mm2) Elongation Oleic DK
87/10/0/3 107 94 127 4.7 200 75/20/2/3 521 142 35 4.4 200 73/20/2/S 908 199 37 6.0 200 These samples were soaked in buffered saline solutions for 1, 3, 7 and 14 days and recharacterized. The results of the hydrolysis are reported in Table 3.
~ 15 ~ TABLE 3 Hydrolysis of Polydimethylsiloxane Materials M2Dso/OFPMA/ Modulus Tensile % %
EGDMA/VDMO (g/mm2) (q/mm2) Elonqation Oleic DK
87/10/0/3 1 day 333 182 46 3.9 3 days 535 129 32 6.4 7 days 519 128 32 2.0 14 days 549 126 33 3.9 75/20/2/3 1 day 581 187 40 4.8 3 days 521 142 35 4.4 7 days 661 147 32 5.4 14 days 746 167 34 5.9 73/20/2/5 1 day 666 197 41 7.0 3 days 908 199 37 3.9 7 days 906 211 43 7.1 14 days 1,020 202 36 7.3 3. Fluorinated PolYsiloxane Based Materials With Internal Wetting Agents Methacrylate end-capped polysiloxanes with varying degrees of fluoropropyl side chains (fluorosiloxanes), prepared by the method of Example F, were reacted with various amounts of strengthening agent (IBOMA) and internal wetting agent (VDMO). Various weight ratio mixtures of the three components were made, polymerized by free radical polymerization, and characterized. The results are summarized in Table 4.
Fluoro- Fluoro-silicone/ silicone/ Modulus Tensile Elongation Oleic 2 IBOMA/VDMO Mole % (q/mm2) (g/mm2) % % DK
95/5/5 65 Mole % 81 45 80 3.1 700 90/10/5 65 Mole % 122 104 106 5.8 550 85/15/5 65 Mole % 273 197 99 10.1 310 95/5/5 40 Mole % 90 52 89 5.11,200 90/10/5 40 Mole % 116 87 107 8.5 1,000 85/15/5 40 Mole % 245 201 130 12.0 258 95/5/5 40 Mole % 85 41 68 5.6 --90/10/5 40 Mole % 115 78 93 8.9 --85/15/5 40 Mole % 308 163 101 13.1 --95/5/5 25 Mole %118 56 66 7.2 --90/10/5 25 Mole % 153 83 80 10.2 --85/15/5 25 Mole % 390 192 104 14.1 --95/5/5 18 Mole %112 55 74 7.9 --90/10/5 18 Mole % 158 110 109 18.0 --95/5/5 12.5 Mole %139 60 57 10.9 --90/10/5 12.5 Mole % 179 76 62 14.4 --85/15/5 12.5 Mole % 333 122 70 11.5 --The oleic acid measurements were based upon the weight of material which could be extracted using toluene from a sample which had been immersed in oleic acid for a fixed period of time.
Synthesis of Polymeric Materials Comprising PolYsiloxanes with Fluorinated Side Chains, Fluorinated MethacrYlate Touqheninq Agent and an Internal Wettinq Aqent A series of mixtures comprising polydimethylsiloxane/
polymethyltrifluoropropylsiloxane in varying mole ratios, octafluoropropylmethacrylate (OFPMA) and the internal wetting agent VDMO were made. These mixtures were then polymerized, the volatiles were removed from the reactive product, and then the product was characterized. The test results are reported in Table 5.
The samples were then placed in a buffered saline solution at 80C and hydrolyzed for 1, 3 and 5 days. The samples were recharacterized, the results of which are reported in Table 6.
M2Dloo - (65 mole % trifluoropropyl)/OFPMA/VDMO
Siloxane/OFPMA/VDMO Modulus Tensile Elonqation Oleic 2 80/20/5 65 Mole %120 136 135 1.4 234 60/40/5 65 Mole %409 427 145 -0.2 206 55/45/5 65 Mole %712 400 136 0.7 240 50/50/5 65 Mole %1,571 563 153 0.7 186 40/60/5 65 Mole %7,630 730 135 1.2 102 20/80/5 65 Mole %27,200 983 91 0.9 42 80/20/5 40 Mole %127 89 102 1.5 346 60/40/5 40 Mole %224 248 120 1.1 --55/45/5 40 Mole %709 535 125 1.0 267 50/50/5 40 Mole %1,593 698 150 0.9 192 40/60/5 40 Mole %15,000 725 177 1.0 67 20/80/5 40 Mole %34,4001,030 62 0.9 30 80/20/5 25 Mole %126 65 81 2.7 --60/40/5 25 Mole %475 380 109 1.8 --80/20/5 12.5 Mole % 148 104 97 3.4 --60/40/5 12.5 Mole % 544 453 106 2.3 --40/60/5 12.5 Mole % 2,509 742 133 1.8 --20/80/5 12.5 Mole % 10,760887 142 1.3 --Series III M2Dloo (65% mole % trifluoropropyl)/OFPMA/VDMO
80/20/X X = 1,3,5 Parts VDMO Time Modulus Tensile Elongation 1 1 day 84 51 98 3 1 day 87 53 90 1 day 98 62 93 1 3 days 93 48 88 3 3 days 175 100 108 3 days 281 126 100 1 7 days 101 52 87 3 7 days 171 98 108 7 days 205 118 110 1 14 days 109 64 106 3 14 days 169 113 121 14 days 171 104 111
Claims (9)
1 A composition formed by polymerizing a mixture comprising:
(a) 5 to 100 wt. parts polysiloxane containing fluorinated side chains represented by the general formula where A denotes a radical chosen from the group consisting of methacrylate or acrylate radicals, where R1 and R2 independently denote alkyl radicals with 1 to 6 carbon atoms or phenyl radicals, where R3 and R4 independently denote radicals chosen from the group consisting of alkyl radicals with 1 to 6 carbon atoms, phenyl radicals or fluorinated alkyl radicals with 1 to 6 carbon atoms, and either R3 or R4 denotes a fluorinated alkyl radical with 1 to 6 carbon atoms, and where m+n is at least 1, and n is at least 1;
(b) 5 to 80 wt. parts of a toughening agent; and (c) 1 to 20 wt. parts of an internal wetting agent.
(a) 5 to 100 wt. parts polysiloxane containing fluorinated side chains represented by the general formula where A denotes a radical chosen from the group consisting of methacrylate or acrylate radicals, where R1 and R2 independently denote alkyl radicals with 1 to 6 carbon atoms or phenyl radicals, where R3 and R4 independently denote radicals chosen from the group consisting of alkyl radicals with 1 to 6 carbon atoms, phenyl radicals or fluorinated alkyl radicals with 1 to 6 carbon atoms, and either R3 or R4 denotes a fluorinated alkyl radical with 1 to 6 carbon atoms, and where m+n is at least 1, and n is at least 1;
(b) 5 to 80 wt. parts of a toughening agent; and (c) 1 to 20 wt. parts of an internal wetting agent.
2. The composition of claim 1 wherein A denotes a methacrylate radical.
3. The composition of claim 2 wherein either R3 or R4 is a fluorinated alkyl radical chosen from the group of radicals consisting of 3,3,3 trifluoropropyl, perfluoropropyl, trifluoromethyl, 2,2,2 trifluoroethyl, perfluoroethyl, 4,4,4 trifluorobutyl, perfluorobutyl, 5,5,5 trifluoropentyl, per-fluoropentyl, 6,6,6 trifluorohexyl and perfluorohexyl radi-cals.
4. The composition of claim 3 wherein R1 and R2 denote methyl radicals.
5. The composition of claim 4 wherein the ratio of n to the sum of m+n is between 2 and 100.
6. The composition of claim 5 wherein R4 denotes the fluorinated alkyl radical, 3,3,3-trifluoropropyl and R3 denotes a methyl radical.
7. The composition of claim 1 wherein said toughening agent is a fluorinated methacrylate functional compound chosen from the group consisting of octafluoropentylmetha-crylate, hexafluoroisopropylmethacrylate, and decylfluoro-dodecylmethacrylate.
8. The composition of claim 7 wherein the fluorinated methacrylate functional compound is octafluoropentylmetha-crylate.
9. The composition of claim 1 wherein the internal wetting agent is an oxazolone which can be represented by the general formula where R1 and R2 independently denote a hydrogen atom or a methyl radical and R3 and R4 independently denote methyl or cyclohexyl radicals.
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| US07/153,856 US4810764A (en) | 1988-02-09 | 1988-02-09 | Polymeric materials with high oxygen permeability and low protein substantivity |
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|---|---|---|---|---|
| US4910277A (en) * | 1988-02-09 | 1990-03-20 | Bambury Ronald E | Hydrophilic oxygen permeable polymers |
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-
1988
- 1988-02-09 US US07/153,856 patent/US4810764A/en not_active Expired - Lifetime
-
1989
- 1989-01-10 CA CA000587884A patent/CA1335394C/en not_active Expired - Fee Related
- 1989-01-10 IE IE5689A patent/IE63184B1/en not_active IP Right Cessation
- 1989-01-27 AT AT89300823T patent/ATE102225T1/en not_active IP Right Cessation
- 1989-01-27 DE DE68913328T patent/DE68913328T2/en not_active Expired - Fee Related
- 1989-01-27 ES ES89300823T patent/ES2051995T3/en not_active Expired - Lifetime
- 1989-01-27 EP EP89300823A patent/EP0338656B1/en not_active Expired - Lifetime
- 1989-02-01 JP JP1020934A patent/JP2894711B2/en not_active Expired - Fee Related
- 1989-02-02 BR BR898900469A patent/BR8900469A/en not_active IP Right Cessation
- 1989-02-06 MX MX014797A patent/MX165652B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IE63184B1 (en) | 1995-03-22 |
| ES2051995T3 (en) | 1994-07-01 |
| EP0338656A2 (en) | 1989-10-25 |
| JPH01308419A (en) | 1989-12-13 |
| EP0338656B1 (en) | 1994-03-02 |
| ATE102225T1 (en) | 1994-03-15 |
| EP0338656A3 (en) | 1990-10-17 |
| BR8900469A (en) | 1989-10-03 |
| JP2894711B2 (en) | 1999-05-24 |
| MX165652B (en) | 1992-11-25 |
| IE890056L (en) | 1989-08-09 |
| DE68913328D1 (en) | 1994-04-07 |
| DE68913328T2 (en) | 1994-07-07 |
| US4810764A (en) | 1989-03-07 |
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