CA1167586A - Liquid copolymeric organopolysiloxanes comprising sio.sub.2 and method therefor - Google Patents
Liquid copolymeric organopolysiloxanes comprising sio.sub.2 and method thereforInfo
- Publication number
- CA1167586A CA1167586A CA000389345A CA389345A CA1167586A CA 1167586 A CA1167586 A CA 1167586A CA 000389345 A CA000389345 A CA 000389345A CA 389345 A CA389345 A CA 389345A CA 1167586 A CA1167586 A CA 1167586A
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- CA
- Canada
- Prior art keywords
- copolymeric
- silicon
- siloxane
- bonded
- resinous
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
Abstract
LIQUID COPOLYMERIC ORGANOPOLYSILOXANES COMPRISING
SiO2 AND METHOD THEREFOR
Abstract of the Disclosure Copolymeric organopolysiloxanes comprising SiO2 are prepared by forming an acidic, homogeneous mixture of a silanol-containing resinous copolymeric siloxane comprising R3SiO1/2 siloxane units and SiO2 siloxane units, an organohydrogenpolysiloxane and an organic solvent and heating the resulting mixture to remove substantially all of the organic solvent. The copolymeric organosiloxanes contain silicon-bonded hydroxyl radicals and/or silicon-bonded hydrogen radicals in varying amounts which depends upon the acidity of the homogeneous mixture that is formed and the ratio of silicon-bonded hydrogen radicals to silicon-bonded hydroxyl radicals therein. The copolymeric organopolysiloxanes are useful as a reactive component in various types of curable silicone compositions.
SiO2 AND METHOD THEREFOR
Abstract of the Disclosure Copolymeric organopolysiloxanes comprising SiO2 are prepared by forming an acidic, homogeneous mixture of a silanol-containing resinous copolymeric siloxane comprising R3SiO1/2 siloxane units and SiO2 siloxane units, an organohydrogenpolysiloxane and an organic solvent and heating the resulting mixture to remove substantially all of the organic solvent. The copolymeric organosiloxanes contain silicon-bonded hydroxyl radicals and/or silicon-bonded hydrogen radicals in varying amounts which depends upon the acidity of the homogeneous mixture that is formed and the ratio of silicon-bonded hydrogen radicals to silicon-bonded hydroxyl radicals therein. The copolymeric organopolysiloxanes are useful as a reactive component in various types of curable silicone compositions.
Description
7S~
LI~UID COP~LYMERIC ORGANOPOLYSILOXANE~ COMPRISING
Si~2 ~ ME'r~O~ TH~REFOR
Background of the InVention The present invention relates to copolymeric oryanopolysiloxanes comprisiny SiO~ and to a method for their preparation. More particularly the present invention relates to the preparation of li~uid copolyrQeric oryanopolysiloxanes comprisiny SiO2. In a ~referred em~odiment the present invention relates to the ~reparation of li~ui~ copolyQleric oryanopolysiloxanes comprisiny SiO2 and bearing silicon-bonded hydroxyl radicals and silicon-bonded hydroyen radicals.
~ opolymeric siloxanes comprising SiO~ have been disclosed by Daudt et al., U.S. Patent Wo.
~,67~,182 issued A~ril 20, lY54, which are pre~ared by reacting a silica hydrosol havin~ a pH of less than 5 with an organosilane haviny the ~orrQula RnSiX4_n or an oryanosiloxane naviny the forlllula Rn~iO(4-n)/~ wherein R is alkyl, monocyclic aryl or halogenated monocyclic aryl and X is chlorine or alkoxy. The reaction products are sai~ to ranye from viscous oils to thermoplastic resiIlsO Some of the copolymeric siloxanes of Daudt et al. are preferred starting materials fo~ the ~rocess of this invention.
Organopolysiloxane resins containing R3SiO
UllitS arld Si~ UllitS~ along With ~ISiO units and/or HS103/~ unlts, wherein R is a mollovalent hydrocarbon yroup, are disclosed ~y Flannigan, U.S. Patent No.
3,772,~47, issued Novem~er 13, lg73. The resins of Flannigan are said to ~e preparable in any one of a varie-~y of ways; however, cohydrolysis of hydrolyzable silanes and tne reaction of hydrolyzable silanes with a silica hydrosol are the only methods disclosed and only brittle, solid resins are ~isclosed.
Solventless, flowable organo~olysiloxane encapsulating fluids comprisiny SiO2 are disclosed by Modic, U.S. Patent No~ 3,~05,2~3 issued September 7, 1965, which are prepared by neating a nomoyeneous mix~ure of an oryanic solvent solution of a resinous copolymer containin~ R3SiOl/~ units, wherein ~ is a monovalent hydrocarbon radical, and sio2 units and a liquid silanol chain-stopped diorganopolysiloxane to remove the organic solvent therefrom.
Brady, U.S~ Patent No. 3,6~7,351 issued December 14, 1971, discloses benzene-soluble copolymeric siloxanes consisting of (CH333SiOl/2 units, (CH3)~H5iO1/~ units and Si~2 units which are prepared by modifying tne procedure of Daudt et al.
noted above to include (CH3)~HSiCl or (CH3)2HSioSiH(C~3)2 as one o the components to react with the acidic silica hydrosol.
l 167~
Summary_of the_Invention It is an ob]ect of this invention to provide a method for pre~ariny liquid copolyineric oryanopolysiloxanes comprisiny ~ . It is a particular ob]ect of this invention to provide liquid copolymeric organopolysiloxanes cosn~risiny SiO~ and bearing silicon-bonded hydroxyl radicals and silicon-bonded hydroyen radicals.
These ob]ects~ and others which will be obvious to one skilled in the or9anopolysiioxane art upon consideriny the following disclosure and appended claims, are obtained by the method of this invention comprisiny ~A) forming a homogeneous mixture havin~ an acid number greater than zero and comprisiny (a) an oryanic solvent solution of a resinous copolymeric ~
siloxane containing silicon~bonded hydroxyl radicals and consistin~ essentially of R3SiOl/2 siloxane units and SiV4/2 siloxane units whereirl the ratio of the number of said R3SiOl/2 siloxane units to the number of sald ~iO4/~ siloxane units has a value of from 0.6/1 to 0.9/1 and each R denotes, independently, a monovalent hydrocarbon radical, and (b~ a liquid or~anohydrogenpolysiloxane wherein each oryanic radical is, independently, a monovalent hydrocarbon radical, there being an average of at least one silicon-bonded hydroyen radical per molecule of said oryanohydrogenpolysiloxane, and (~) heatiny said omogeneous mixture to remove substantially all of said organic solvent therefrorn.
3 167~36 ~rie~ ~escrlption o~ the ~rawin~
The sole drawing is a com~oslte o~ tnree ~el-permeation chromatograms. Curve 1 is a chromatogram of a Xylelle solution of a resinous co~olymer siloxane con~istilly o~ (CH3)3Siol/~ siloxane .units and Si~/2 siloxane units anci naviny a silicon-bonded nydroxyl content of about 3.6~ percent by weight, the ratio of ~CH3)3~iOl/2 units to SiO4/2 UllitS haviny a value of about 0.75. Curve 2 is a chromatogram of a mixture of 6~ parts by weight o~ the composition represented ~y Curve 1 and 40 parts by weight of a li~uid organohydrogenpolysiloxane havin~
the ~ormula (C~3)3SiOl(C~3)(~)SiO]35Si(C~3)~. Curve 3 is a chromatogram of a composition o~ this invention obtained by heating the mixture represented by Curve according to the process o~ this invention. The material havin~ an elution time exceedillg 26 minutes in ~urves 1 and ~ is substantially silanol-free volatile material which may have simply Deen removed from the composition represented by Curve 3 duriny the ileating and solvent removal process. Speci~ically the material elutiny at ap~roxilllately ~6 minutes and ~7 minutes is L(C~3)~SiO~40 and [(C~3)2SiO~4, respectively.
5 ~ ~
~etalled ~escriptlon of the Inventlon The products of the process of this invention are ~esignated herein as copolymeric oryanopolysiloxanes. 'l~hey are prepared ~y reactin~, by the process of tnis invention, a first reactant, designated herein as a resinous copolymeric siloxane, with a second reactant, ~esignated herein as a liquid oryanohydroyenpolysiloxane.
The products of the process of this invention have a structure which is not completely known at this time; however, their copolymeric nature is revealed by the sole drawing whicn shows a yel-permeation chromatogram (Curve 3), which is displaced and different from the gel-permeation chromatogram for the mixture of starting materials (Curve 2), when measured under identical instrumental conditions. Under identical gel-permeation cnromatoyraphy instrumental conditions lar~er molecules have a shorter elution time t~lan smaller molecules; therefore, a large portion of the copolymeric oryanopolysiloxane of this invention ~las larger molecular size tilan either of its precursors.
Component (a3 that is used in the method of this invention is an organic solvent solution of a resinous copolymeric siloxane wnich CollSiStS
essentially of ~SiOl/~ siloxane units and Si04/~
siloxane units. The resinous co~olymer siloxane has a complex, as-yet-undetermined structure; however, for the purposes of this disclosure it is fully characterize~ ~y the ratio of said siloxane units therein, by its silanol, i~e. silicon-bonded hydroxyl, content and by its solubility in organic solvents, such as benzene.
"
~ ~B7586 The resinous coyolymeric siloxane portion of component (a) consists o frorn ~.~ to 0.9 R3SiO
units for every ~iO4/2 unit. Eacn R denotes a monovalent hydrocarbon radical; sucn as an alkyl radical, such as methyl, ethyl, isopro~yl, butyl and hexyl; an alkenyl radical, such as vinyl and allyl; an aryl radical, such as phenyl, tolyl and xylyl; an arylalkyl radical~ such as beta-phenylethyl and ~eta-phenylpropyl; and a cycloaliphatic radicalt such as cyclopentyl, cyclohexyl and cyclohexenyl.
Preferably all ~ ra~icals in component (a) are lower alkyl radicals al~hough a minor portion of them can be replaced with other monovalent nydrocarbon radicals such as the vinyl radicai and/or the phenyl radical to provide additional properties for the resinous copol~ner such as the reactivity attendent therewith.
The resinous copolymeric siloxane portion further comprises from 0.1 to 5 percent by weight of silicon-bonded hydroxyl radicals and fre~uently comprises trace amounts of silicon-bonded alkoxy radicals such as methoxy, ethoxy or isopropoxy radicals which arise from the particular rnethod that is used to prepare said resin copolylneric siloxane.
In a preferred embodiment o~ this invention the resinous copolymeric siloxane portion of component (a) consists essentially of (CH3)3ciOl/2 siloxane units and ~iO4/2 siloxane units, in the number ratio stated above, and has a silicon bonded hydroxyl content of from 1 to 5 percent by weight.
~ 1~75~
--7~
Resinous copolymeric siloxanes cons1stiny of iUl/~ unlts and ~i~4/~ units are well known in the art and are described ~y Daudt et a~ . S r Patent No.
LI~UID COP~LYMERIC ORGANOPOLYSILOXANE~ COMPRISING
Si~2 ~ ME'r~O~ TH~REFOR
Background of the InVention The present invention relates to copolymeric oryanopolysiloxanes comprisiny SiO~ and to a method for their preparation. More particularly the present invention relates to the preparation of li~uid copolyrQeric oryanopolysiloxanes comprisiny SiO2. In a ~referred em~odiment the present invention relates to the ~reparation of li~ui~ copolyQleric oryanopolysiloxanes comprisiny SiO2 and bearing silicon-bonded hydroxyl radicals and silicon-bonded hydroyen radicals.
~ opolymeric siloxanes comprising SiO~ have been disclosed by Daudt et al., U.S. Patent Wo.
~,67~,182 issued A~ril 20, lY54, which are pre~ared by reacting a silica hydrosol havin~ a pH of less than 5 with an organosilane haviny the ~orrQula RnSiX4_n or an oryanosiloxane naviny the forlllula Rn~iO(4-n)/~ wherein R is alkyl, monocyclic aryl or halogenated monocyclic aryl and X is chlorine or alkoxy. The reaction products are sai~ to ranye from viscous oils to thermoplastic resiIlsO Some of the copolymeric siloxanes of Daudt et al. are preferred starting materials fo~ the ~rocess of this invention.
Organopolysiloxane resins containing R3SiO
UllitS arld Si~ UllitS~ along With ~ISiO units and/or HS103/~ unlts, wherein R is a mollovalent hydrocarbon yroup, are disclosed ~y Flannigan, U.S. Patent No.
3,772,~47, issued Novem~er 13, lg73. The resins of Flannigan are said to ~e preparable in any one of a varie-~y of ways; however, cohydrolysis of hydrolyzable silanes and tne reaction of hydrolyzable silanes with a silica hydrosol are the only methods disclosed and only brittle, solid resins are ~isclosed.
Solventless, flowable organo~olysiloxane encapsulating fluids comprisiny SiO2 are disclosed by Modic, U.S. Patent No~ 3,~05,2~3 issued September 7, 1965, which are prepared by neating a nomoyeneous mix~ure of an oryanic solvent solution of a resinous copolymer containin~ R3SiOl/~ units, wherein ~ is a monovalent hydrocarbon radical, and sio2 units and a liquid silanol chain-stopped diorganopolysiloxane to remove the organic solvent therefrom.
Brady, U.S~ Patent No. 3,6~7,351 issued December 14, 1971, discloses benzene-soluble copolymeric siloxanes consisting of (CH333SiOl/2 units, (CH3)~H5iO1/~ units and Si~2 units which are prepared by modifying tne procedure of Daudt et al.
noted above to include (CH3)~HSiCl or (CH3)2HSioSiH(C~3)2 as one o the components to react with the acidic silica hydrosol.
l 167~
Summary_of the_Invention It is an ob]ect of this invention to provide a method for pre~ariny liquid copolyineric oryanopolysiloxanes comprisiny ~ . It is a particular ob]ect of this invention to provide liquid copolymeric organopolysiloxanes cosn~risiny SiO~ and bearing silicon-bonded hydroxyl radicals and silicon-bonded hydroyen radicals.
These ob]ects~ and others which will be obvious to one skilled in the or9anopolysiioxane art upon consideriny the following disclosure and appended claims, are obtained by the method of this invention comprisiny ~A) forming a homogeneous mixture havin~ an acid number greater than zero and comprisiny (a) an oryanic solvent solution of a resinous copolymeric ~
siloxane containing silicon~bonded hydroxyl radicals and consistin~ essentially of R3SiOl/2 siloxane units and SiV4/2 siloxane units whereirl the ratio of the number of said R3SiOl/2 siloxane units to the number of sald ~iO4/~ siloxane units has a value of from 0.6/1 to 0.9/1 and each R denotes, independently, a monovalent hydrocarbon radical, and (b~ a liquid or~anohydrogenpolysiloxane wherein each oryanic radical is, independently, a monovalent hydrocarbon radical, there being an average of at least one silicon-bonded hydroyen radical per molecule of said oryanohydrogenpolysiloxane, and (~) heatiny said omogeneous mixture to remove substantially all of said organic solvent therefrorn.
3 167~36 ~rie~ ~escrlption o~ the ~rawin~
The sole drawing is a com~oslte o~ tnree ~el-permeation chromatograms. Curve 1 is a chromatogram of a Xylelle solution of a resinous co~olymer siloxane con~istilly o~ (CH3)3Siol/~ siloxane .units and Si~/2 siloxane units anci naviny a silicon-bonded nydroxyl content of about 3.6~ percent by weight, the ratio of ~CH3)3~iOl/2 units to SiO4/2 UllitS haviny a value of about 0.75. Curve 2 is a chromatogram of a mixture of 6~ parts by weight o~ the composition represented ~y Curve 1 and 40 parts by weight of a li~uid organohydrogenpolysiloxane havin~
the ~ormula (C~3)3SiOl(C~3)(~)SiO]35Si(C~3)~. Curve 3 is a chromatogram of a composition o~ this invention obtained by heating the mixture represented by Curve according to the process o~ this invention. The material havin~ an elution time exceedillg 26 minutes in ~urves 1 and ~ is substantially silanol-free volatile material which may have simply Deen removed from the composition represented by Curve 3 duriny the ileating and solvent removal process. Speci~ically the material elutiny at ap~roxilllately ~6 minutes and ~7 minutes is L(C~3)~SiO~40 and [(C~3)2SiO~4, respectively.
5 ~ ~
~etalled ~escriptlon of the Inventlon The products of the process of this invention are ~esignated herein as copolymeric oryanopolysiloxanes. 'l~hey are prepared ~y reactin~, by the process of tnis invention, a first reactant, designated herein as a resinous copolymeric siloxane, with a second reactant, ~esignated herein as a liquid oryanohydroyenpolysiloxane.
The products of the process of this invention have a structure which is not completely known at this time; however, their copolymeric nature is revealed by the sole drawing whicn shows a yel-permeation chromatogram (Curve 3), which is displaced and different from the gel-permeation chromatogram for the mixture of starting materials (Curve 2), when measured under identical instrumental conditions. Under identical gel-permeation cnromatoyraphy instrumental conditions lar~er molecules have a shorter elution time t~lan smaller molecules; therefore, a large portion of the copolymeric oryanopolysiloxane of this invention ~las larger molecular size tilan either of its precursors.
Component (a3 that is used in the method of this invention is an organic solvent solution of a resinous copolymeric siloxane wnich CollSiStS
essentially of ~SiOl/~ siloxane units and Si04/~
siloxane units. The resinous co~olymer siloxane has a complex, as-yet-undetermined structure; however, for the purposes of this disclosure it is fully characterize~ ~y the ratio of said siloxane units therein, by its silanol, i~e. silicon-bonded hydroxyl, content and by its solubility in organic solvents, such as benzene.
"
~ ~B7586 The resinous coyolymeric siloxane portion of component (a) consists o frorn ~.~ to 0.9 R3SiO
units for every ~iO4/2 unit. Eacn R denotes a monovalent hydrocarbon radical; sucn as an alkyl radical, such as methyl, ethyl, isopro~yl, butyl and hexyl; an alkenyl radical, such as vinyl and allyl; an aryl radical, such as phenyl, tolyl and xylyl; an arylalkyl radical~ such as beta-phenylethyl and ~eta-phenylpropyl; and a cycloaliphatic radicalt such as cyclopentyl, cyclohexyl and cyclohexenyl.
Preferably all ~ ra~icals in component (a) are lower alkyl radicals al~hough a minor portion of them can be replaced with other monovalent nydrocarbon radicals such as the vinyl radicai and/or the phenyl radical to provide additional properties for the resinous copol~ner such as the reactivity attendent therewith.
The resinous copolymeric siloxane portion further comprises from 0.1 to 5 percent by weight of silicon-bonded hydroxyl radicals and fre~uently comprises trace amounts of silicon-bonded alkoxy radicals such as methoxy, ethoxy or isopropoxy radicals which arise from the particular rnethod that is used to prepare said resin copolylneric siloxane.
In a preferred embodiment o~ this invention the resinous copolymeric siloxane portion of component (a) consists essentially of (CH3)3ciOl/2 siloxane units and ~iO4/2 siloxane units, in the number ratio stated above, and has a silicon bonded hydroxyl content of from 1 to 5 percent by weight.
~ 1~75~
--7~
Resinous copolymeric siloxanes cons1stiny of iUl/~ unlts and ~i~4/~ units are well known in the art and are described ~y Daudt et a~ . S r Patent No.
2,676,18~, and by Goodwin, U.~0 Patent No. 2,857,356, which teach how to pre~are resinous copolymeric siloxanes which are suitable for use in the method of this invention. Briefly, iTI these methods, an aqueous solution of sodiwn silicate (e.~ ~o. 9 sodium silicate sold ~y DuPont~) is acidified to the proper p~ by addin~ it to a mixture of hydrochloric acid and isopropanol and the resultiny acidic silica hydrosol is then treated with a source of R3SiOl/~ siloxane units sucn as ~3SioCH3, R~SiCl or ~3Si~SiR3 dissolved in a mixture of isopropanol and xylene. After bein~
heated the reaction mixture is cooled and is separated into an aqueous phase, which is discarded, and a non-ayueous phase comprising the resinous copolymeric siloxane, which is further washed with water to reduce its acid num~er and to remove water-soluble components, such as isopropyl àlcohol. Preferably the acidic resinous copoly~neric slloxanes which ~re prepared by these metho~s are washed with water to remove most, but not all, of the acid therein. For exam~le, resinous copolyMeric siioxanes which have been prepared by the met~od of ~audt et al. typically nave sufficient acid remainin~ therein to provide an acid nwnber of from ~.2 to ~.U, as measured ~y the method ~lereinafter disclosed, base~ on tne solvent-free resinous copolymeric siloxane. These materials are preferred.
"7 ~
Resinous copolymeric siloxanes are tyuically pre~ared in an oryal-ic solvent whlch can convenierltly serve as the oryanic solvent portion of colnponent (a) in the method of this invention. Alternatively, the resinous copolyrneric siloxane can be pre~ared in one oryanic solvent and subse~uently can be transferred to a second organic solvent, if desired, to form component (a) for the method of this invention. If the resinous copol~neric siloxane does not contain any oryanic solv~nt, one or more organic solvents snould be rnixed therewith before or duriny preparation of holnoyeneous mixture to be heated.
'~he particular oryanic solvènt portion of component: (a) is not critical and can be for example an ali~hatic hydrocarbon, an aromatic hydrocarbon or haloyenate~ derivatives of either or mixtures thereof.
Preferably the or~anic solvent is one tnat forms an azeotrope with water so that any water that is formed during the heatiny step in the method of this inven~ion can be conveniently removed ~y azeotropic distillation. ~articularly useful or~anic solvents include benzene, toluene, xylene, trichloroethylene and mineral spirits.
The amount of resinous copolymeric siloxane containe~ in component (a) is not critical and can ranye from 10 to 90 percent by weiyht. It is preferred that only as mucn organic solvent as is needed to pre~are a ~lomo~eneous mixture of resinous copolylneric siLoxane and li~luid oryanohy~rogenpoly~
siloxane be used in or~er to Jninimize the amount of time and/or eneryy needed to subse~uently remove it froln the mixture as described hereinafter. A
preferred component (a) contains approximately 6~ to 70 percent by weight resinous copolyrneric siloxane and the balance solvent.
Component (b) is any liquid organohydro~en-polysiloxane containin~ an averaye of at least one silicon-bonded hydroyen radical per molecule, and can nave a linear, cyclic or ~ranched structure or combinations thereof. Thus, component (b) has the unit formuld R~mHn~io(4-m-n)/~ wherein m and n denote positive num~ers whose sum is less than 4, preferably from 1.~ to 2.1. The oryanic radicals (~') in component (b) can oe any of the R radicals denoted above ~refera~ly, althouyh not necessarily, the organic radicals (~') in component (b) are the same as the organic radicals (~) in colnponent (a).
Exam~les of organollydroyenpolysiloxanes that are suitable for use as component (b~ in the process of this invention include cyclic organohydro~en polyslloxanes of the unit formula ~n~_mSiO such as [(CH3)(H)SiOJX wherein x is ~, 4, 5, 6 and nigher and L(~3)(H)Sio]yL(cH3)2siolz wherein the sum of y plus æ
is 3, 4, ~, 6 and hiy}ler; and linear or~3anohydrogen-polysiloxanes of the formula 5`~ ~
~"R'~Sio(~'~Si~a(R'~Sio~b~iR'~R", such as Rll(c~l3)~sioL(c~ )2~;io~a~(cE~3)~ o~bsi(c~3)2~ll wherein R" denotes H or methyl and _ and b each denote zero or a nu~nber yreater than zero, provided there is at least one silicon-~onded hydroyen radical ~er molecule, such as H(C~3)~sioL(c~3)~io]asi(cH3) )3sio[(cH3)(H)~iolb~i(cH3) (c~3)3sio~(c~3)(~)sioJbL(c~3)~si~asi(c~3)3 An~
H(C:113) ~SiO[(C~3)~SiOjaL(C1~3)~H)SiO]bSi(cH3)~
An oryanohydrogenpolysiloxane haviny the formula (CH3)3~i~L~CH~)(H)SioJbSi(cH3)3 wherein b has an averaye value of frorn 30 to 70 is a hiyhly ~referred component (b) in the ~rocess of this invention~ particularly when it is desired that the product of this invention have relatively large amounts of silicon-bonded hydroyell radicals.
Liquid organonydrogenpolysiloxane (b) can have any viscosity; however, it preferably has a viscosity of less than 1 pascal-second at ~5~C when used in amounts of less than 6U rparts by weight for every 40 parts by weiyht of resinous copoly~eric siloxane.
7~6 Oryanohydrogenpolysiloxanes and their pre~aration are well known in the oryanosilicon ~olymer art; some are commercially available. ~riefly the preparation of orgallohydro~enpolysiloxanes can be accomplished in any suitable manner SUC~I as ~y hydrolyziny a mixture of suita~le hyaroly~able silanes, such as chlorosilanes, and e~uilibrating the resultiny hydrolyzate under acid catalysis.`
~lternatively~ a mixture of suitable siloxanes, such as cyclic siloxanes and linear siloxanes, can be copolymerized and equilibrated under acid catalysis.
In tlle rnethod of this invention the amounts of resinous copolymeric siloxane and li~uid oryanohydroyenpolysiloxane that are mixed may vary widely. Generally, the viscosity of the copol~neric organopolysiloxane that is produced by the method of this invention varies directly with the viscosity of the organo~ydroyenpolysiloxane ànd inversly with its weiyht percent in the homoyeneous mixture of components (a) and ~b). Li~ui~ copolymeric oryanopolysiloxanes can be obtained when as little as about 1~ ~ercent by weiyht of oryanoilydroyenpolysiloxane is used, based on the weiyht of resinous copolymeric siloxane plus oryanohydrogenpolyslloxane. Li~uid co~olymeric organo~olysiloxanes of this invention whlch contain less than about lu percent ~y weight of resinous copolymeric silox~ne coln~onent are not expected to significarltl~ demonstrate the benefits for w~ich the resinous copol~neric siloxane is used, SUCh as a strengtneniny component in curable silicone compositiorls.
~ lB7586 A hi~hly preferrea com~ositioll of ti~is invention is o~tained when the honlogeneous mixture that is heated in the proce~s of this invention comprises from 40 to 6~ parts ~y weight of resinous copolymeric siloxane consistiny of (C~3)3~iOl/~ units and SiO4/2 units and containing from 1 to ~ percent by weiyht of silicon-bonded hydroxyl radicals and from 40 to 6~ ~arts by weiyht of oryanohy~royenpolysilvxane haviny the forMula (C~3)3SiO[(CH3)(~)SiO~3~ to 7~Si(CH3)3. The resultiny copol~neric or~anopolysiloxanes have demonstrated unexpected utility as a controlled release additive for curable silicone coatin~ com~ositions, as disclosed inCdn.
Application ~erlal No. 3~,520.
In the ~netho~ of this invention a homogeneous ~nixture ls formed by thorouyhly mixing the desired amounts of component (a) and component (~) and, if necessary, an acid, preferabiy a strong acid such as hydrochloric acid, to provide an acid nurnber greater than zero therefor. Preferably the acid number of the homoyeneous mixture, extrapolated to zero solvent content, has a value of froM 0.1 to 1. Preferably co~nponent (aJ is sufficiently acidic, as ~repared, to ~rovide this acidity for the hornogeneous mixture.
The resultiny homogeneous mixture is immediately or subse~uently heated to volatilize the oryanic solvent therefrom. ~aid heatin~ is preferably initially done at atmospheric pressure and is then continued at reduced pressure to accelerate the removal of said solvent.
In a preferred embodiment of this invention the homogeneous Jnixture of ~a) plus (b) is heated to about 15~C at atmospheric pressure and is then su~ected to a gradually decreasin~ pressure, without an increase in temperature/ to remove substantially all of the oryanic solvent therefrom. By substantially it is mednt ~erein that the product of this invention contains less than about 5 percent, and prefera~ly less than about 1 percent, by weiyht organic solvent.
Alternatively the homogeneous lnixture can be partially devolatili7ed at room temperature, suc~ as by evaporation, and the partially devolatilized mixture then heated to remove substantially all of the organic solvent therefrom.
While not wishiny to ~e limited by theory we ~elieve that the copolymerlc oryanopolysiloxanes of this invention are formed by a reaction between the resinous copolymeric siloxane and the oryanohydroyenpolysiloxane to form by-product water and/or by-~roduct hydroyen. The heating step of the process of this invention serves not only to remove substantially all of the organic solvent from the homoyeneous mlxture of reactants but also to facilitate said reaction. Said reaction is also facilitated by the acid in the homo~eneous mixture, yreater reaction ~einy obtained in mixtures haviny a hiyher acid number.
The copolymeric oryanopolysiloxanes that are produced by the method of this invention contain silicon-bonded hydroxyl radicals arld/or silicon-bonded nydroyen radicals which provide chemical xeactivity therefor. The amount of silicon-bonded hydroyen radicals and/or silicon-bonded hydroxyl radicals therein de-~ends upon the ratio of said radicals in, and the acid num~er of, the homogeneows mixture that is used ~or its preparation.
To assure that the copolymeric oryanopolysiloxane that is prepared by the method of this invention contains silicon-bonded hydroyen radicals it is believed that the llomoyeneous mixture tnat is prepared should ilave at least 2, and preferably at least 3, silicon-bonded hydroyen radicals for every silicon-bonded hydroxyl radical.
An up~er limit of 2580 for the ratio of silicon-bonded hydroyen radicals to silicon-bonded hydroxyl radicals in the homogeneous mixture occurs in a mixture of 10 parts ~y weiyht of resinous copolymeric siloxane haviny a silanol content of 0.1 percent by weiyht and 9~ parts by weight of an oryanohydroyenpolysiloxane haviny a silicon-bonded hydroyen content of 1.7 percent by weiyht.
To assure that the copolymeric oryanopolysiloxane that is ~repared by tne method vf this invention contains silicon-bonded hydroxyl radicals it is believed that the aci~ number of the holnogeneous inixture that is heated shquld have a value of less than about 2.
The copolymeric organopolysiloxanes of this invention are useful ~ se as tin-catalyzed or platinum-catalyzed curable encapsulatiny compositions.
.
7 ~
They have also been foun~ to be useful as a reactive component in curable silicone compositions such as in silicone coating compositions comprisiny hydroxyl-conta.inin~ silicone fluid polymers or vinyl-containing silicone fluid polymers.
The followirly examples are disclosed to further illustrate, but not limit, the present invention. All parts and yercentayes are ~y weiyht unless otherwise stated.
The non-volatile content, also denoted ~lerein as N.V.C., of a material was determined by placing 1.5U grams of the material in an aluminum foil dish, 60 mm. in diameter and 15 mm. deep and heating the sample for 1 hour at 150C in an a.ir-circulating oven.
The neated sample was then cooled to room temperatur~
and reweiyhed to determine the wei~ht of the non-volatile material (w). N.V.C., in percent, is e~ual to 100 w/l.S0.
'rhe acid num~er, also denoted herein as A.N., of a material was determined by titratiny 1.00 grams of the material to a bromcresol purple endpoint, using alcoho~ic KO~j and is e~ual to the number of my. of ~O~ so useo.
i i7 ~ .~3 ~;
The viscosity of a material was measured at ~5C with a Brookfield~ viscometer Model RVF and the vaLue obtained ~as converted from centipoise to pascal-seconds (Pa-s) for this disclosure by multi~lyiny by ~.0~1.
The following components were used in the examples.
~ esin A-l ~ A xylene solution of a resinous . . .
copol~neric siloxane, ~repared from 4~ parts of sodium silicate (41.6~e) and 20 ~arts of 1CH3)3Si~l accordiny to the method of ~audt et al. noted aobve, containlny (C~3)3SiOl/~ siloxane units and SiO4/2 siloxane units of a~proximately 0.75/1.0 an~ having A.N. = O. 8U, SiO~ = 2.56~, Si~ = 0% and N.V.C. = 7 By extrapolation to 100% N.V.C. the resinous copolymeric siloxane itself had A.N. = 1.14, SiH = 0% and SiO~ = 3.66%.
Resin A-2 - Resin A-l with substantially all of its solvent removed by evaporation at room temperature and atmospheric pressure to N.V.C. = ~5~;
a solid material.
Resin A-3 - Similar to, and prepare~ dS, Resin A~l except having N.V.C. = ~7.35~, A.N. = U.64, SiH = 0.003% and SioH = 1. 91%. By extrapolation to l~U~ N.V.C. the resinous copolymeric siloxane had A.N.
= ~.95, ~iH = ~ 4~ and ~iOH = ~.~4~.
Resin A-4 - Similar to, and pre~ared as, Resin A-l exceut having N~V~C~ = 6~7~ A.N. = U.33, SiH = 0~ and SioH = 2.02%. By extrapolation to l00 N.V.C. the resinous copol~neric siloxane had A.N. -0.48, SiH = 0~ and SiOH = 2.94~.
~esin A-5 - Similar to, and ~repared as, -Resin A-l except having an N.V.C. = 67.6~, A~No = 1~1 and a Turbidity Index = 12.4 (an indirect measurement of SiOH). By extrapolation to l00~ N.V.C. the resinous copolymer siloxane had A.N. = l.66.
Flu~d B-l - An or~anohydroyenpolysiloxane liqui~ having the formula (CH3)3SioL~CH3)2Sio]3-L(CH3)(H)SiO~5Si~CH3)3; N~V~Co = lU0%~ R~N~ = O~U()5 SiH = 0.74~ and SiOH = 0.025~.
Fluid B-2 - An oryanohydrogenpolysiloxane liquid having the formula (C~3)3SioL(CH3)(H)Siol3s-Si(CH3)3, N.V,C. = 100%, A.N. = 0.0l, SiH = l.~h%, SiOH = U% and a viscosity of 0.~3 Pa~s.
Fluid B-3 ~ Same as Fluid ~-~ except having AoN~ = 0.U2, Si~H -- 0~ and SiH = l.71~.
I ~75~
Fluid B-4 ~ame as Fluid B-~ except haviny A.M. = ~.00~, SioH = ~.03~ and SiH = 1.56~.
Exanl~_e 1 Thls example illustrates the pre~aration of a com~osition of this invention at atmos~heric ~ressure.
Fort~ parts of Fluid B-3 and 85.7 parts of ~esin A-l (6~ parts of resinous copolymeric siloxane and 25.7 parts of xvlene) were mixed to form a ho-mogeneous mixture having 5.3 silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical.
The mixture was devolatilized at room temperature and atmospheric ~ressure to a N~V.C. = 97~. This devolatilized, but not heated, Inixture had SioH =
heated the reaction mixture is cooled and is separated into an aqueous phase, which is discarded, and a non-ayueous phase comprising the resinous copolymeric siloxane, which is further washed with water to reduce its acid num~er and to remove water-soluble components, such as isopropyl àlcohol. Preferably the acidic resinous copoly~neric slloxanes which ~re prepared by these metho~s are washed with water to remove most, but not all, of the acid therein. For exam~le, resinous copolyMeric siioxanes which have been prepared by the met~od of ~audt et al. typically nave sufficient acid remainin~ therein to provide an acid nwnber of from ~.2 to ~.U, as measured ~y the method ~lereinafter disclosed, base~ on tne solvent-free resinous copolymeric siloxane. These materials are preferred.
"7 ~
Resinous copolymeric siloxanes are tyuically pre~ared in an oryal-ic solvent whlch can convenierltly serve as the oryanic solvent portion of colnponent (a) in the method of this invention. Alternatively, the resinous copolyrneric siloxane can be pre~ared in one oryanic solvent and subse~uently can be transferred to a second organic solvent, if desired, to form component (a) for the method of this invention. If the resinous copol~neric siloxane does not contain any oryanic solv~nt, one or more organic solvents snould be rnixed therewith before or duriny preparation of holnoyeneous mixture to be heated.
'~he particular oryanic solvènt portion of component: (a) is not critical and can be for example an ali~hatic hydrocarbon, an aromatic hydrocarbon or haloyenate~ derivatives of either or mixtures thereof.
Preferably the or~anic solvent is one tnat forms an azeotrope with water so that any water that is formed during the heatiny step in the method of this inven~ion can be conveniently removed ~y azeotropic distillation. ~articularly useful or~anic solvents include benzene, toluene, xylene, trichloroethylene and mineral spirits.
The amount of resinous copolymeric siloxane containe~ in component (a) is not critical and can ranye from 10 to 90 percent by weiyht. It is preferred that only as mucn organic solvent as is needed to pre~are a ~lomo~eneous mixture of resinous copolylneric siLoxane and li~luid oryanohy~rogenpoly~
siloxane be used in or~er to Jninimize the amount of time and/or eneryy needed to subse~uently remove it froln the mixture as described hereinafter. A
preferred component (a) contains approximately 6~ to 70 percent by weight resinous copolyrneric siloxane and the balance solvent.
Component (b) is any liquid organohydro~en-polysiloxane containin~ an averaye of at least one silicon-bonded hydroyen radical per molecule, and can nave a linear, cyclic or ~ranched structure or combinations thereof. Thus, component (b) has the unit formuld R~mHn~io(4-m-n)/~ wherein m and n denote positive num~ers whose sum is less than 4, preferably from 1.~ to 2.1. The oryanic radicals (~') in component (b) can oe any of the R radicals denoted above ~refera~ly, althouyh not necessarily, the organic radicals (~') in component (b) are the same as the organic radicals (~) in colnponent (a).
Exam~les of organollydroyenpolysiloxanes that are suitable for use as component (b~ in the process of this invention include cyclic organohydro~en polyslloxanes of the unit formula ~n~_mSiO such as [(CH3)(H)SiOJX wherein x is ~, 4, 5, 6 and nigher and L(~3)(H)Sio]yL(cH3)2siolz wherein the sum of y plus æ
is 3, 4, ~, 6 and hiy}ler; and linear or~3anohydrogen-polysiloxanes of the formula 5`~ ~
~"R'~Sio(~'~Si~a(R'~Sio~b~iR'~R", such as Rll(c~l3)~sioL(c~ )2~;io~a~(cE~3)~ o~bsi(c~3)2~ll wherein R" denotes H or methyl and _ and b each denote zero or a nu~nber yreater than zero, provided there is at least one silicon-~onded hydroyen radical ~er molecule, such as H(C~3)~sioL(c~3)~io]asi(cH3) )3sio[(cH3)(H)~iolb~i(cH3) (c~3)3sio~(c~3)(~)sioJbL(c~3)~si~asi(c~3)3 An~
H(C:113) ~SiO[(C~3)~SiOjaL(C1~3)~H)SiO]bSi(cH3)~
An oryanohydrogenpolysiloxane haviny the formula (CH3)3~i~L~CH~)(H)SioJbSi(cH3)3 wherein b has an averaye value of frorn 30 to 70 is a hiyhly ~referred component (b) in the ~rocess of this invention~ particularly when it is desired that the product of this invention have relatively large amounts of silicon-bonded hydroyell radicals.
Liquid organonydrogenpolysiloxane (b) can have any viscosity; however, it preferably has a viscosity of less than 1 pascal-second at ~5~C when used in amounts of less than 6U rparts by weight for every 40 parts by weiyht of resinous copoly~eric siloxane.
7~6 Oryanohydrogenpolysiloxanes and their pre~aration are well known in the oryanosilicon ~olymer art; some are commercially available. ~riefly the preparation of orgallohydro~enpolysiloxanes can be accomplished in any suitable manner SUC~I as ~y hydrolyziny a mixture of suita~le hyaroly~able silanes, such as chlorosilanes, and e~uilibrating the resultiny hydrolyzate under acid catalysis.`
~lternatively~ a mixture of suitable siloxanes, such as cyclic siloxanes and linear siloxanes, can be copolymerized and equilibrated under acid catalysis.
In tlle rnethod of this invention the amounts of resinous copolymeric siloxane and li~uid oryanohydroyenpolysiloxane that are mixed may vary widely. Generally, the viscosity of the copol~neric organopolysiloxane that is produced by the method of this invention varies directly with the viscosity of the organo~ydroyenpolysiloxane ànd inversly with its weiyht percent in the homoyeneous mixture of components (a) and ~b). Li~ui~ copolymeric oryanopolysiloxanes can be obtained when as little as about 1~ ~ercent by weiyht of oryanoilydroyenpolysiloxane is used, based on the weiyht of resinous copolymeric siloxane plus oryanohydrogenpolyslloxane. Li~uid co~olymeric organo~olysiloxanes of this invention whlch contain less than about lu percent ~y weight of resinous copolymeric silox~ne coln~onent are not expected to significarltl~ demonstrate the benefits for w~ich the resinous copol~neric siloxane is used, SUCh as a strengtneniny component in curable silicone compositiorls.
~ lB7586 A hi~hly preferrea com~ositioll of ti~is invention is o~tained when the honlogeneous mixture that is heated in the proce~s of this invention comprises from 40 to 6~ parts ~y weight of resinous copolymeric siloxane consistiny of (C~3)3~iOl/~ units and SiO4/2 units and containing from 1 to ~ percent by weiyht of silicon-bonded hydroxyl radicals and from 40 to 6~ ~arts by weiyht of oryanohy~royenpolysilvxane haviny the forMula (C~3)3SiO[(CH3)(~)SiO~3~ to 7~Si(CH3)3. The resultiny copol~neric or~anopolysiloxanes have demonstrated unexpected utility as a controlled release additive for curable silicone coatin~ com~ositions, as disclosed inCdn.
Application ~erlal No. 3~,520.
In the ~netho~ of this invention a homogeneous ~nixture ls formed by thorouyhly mixing the desired amounts of component (a) and component (~) and, if necessary, an acid, preferabiy a strong acid such as hydrochloric acid, to provide an acid nurnber greater than zero therefor. Preferably the acid number of the homoyeneous mixture, extrapolated to zero solvent content, has a value of froM 0.1 to 1. Preferably co~nponent (aJ is sufficiently acidic, as ~repared, to ~rovide this acidity for the hornogeneous mixture.
The resultiny homogeneous mixture is immediately or subse~uently heated to volatilize the oryanic solvent therefrom. ~aid heatin~ is preferably initially done at atmospheric pressure and is then continued at reduced pressure to accelerate the removal of said solvent.
In a preferred embodiment of this invention the homogeneous Jnixture of ~a) plus (b) is heated to about 15~C at atmospheric pressure and is then su~ected to a gradually decreasin~ pressure, without an increase in temperature/ to remove substantially all of the oryanic solvent therefrom. By substantially it is mednt ~erein that the product of this invention contains less than about 5 percent, and prefera~ly less than about 1 percent, by weiyht organic solvent.
Alternatively the homogeneous lnixture can be partially devolatili7ed at room temperature, suc~ as by evaporation, and the partially devolatilized mixture then heated to remove substantially all of the organic solvent therefrom.
While not wishiny to ~e limited by theory we ~elieve that the copolymerlc oryanopolysiloxanes of this invention are formed by a reaction between the resinous copolymeric siloxane and the oryanohydroyenpolysiloxane to form by-product water and/or by-~roduct hydroyen. The heating step of the process of this invention serves not only to remove substantially all of the organic solvent from the homoyeneous mlxture of reactants but also to facilitate said reaction. Said reaction is also facilitated by the acid in the homo~eneous mixture, yreater reaction ~einy obtained in mixtures haviny a hiyher acid number.
The copolymeric oryanopolysiloxanes that are produced by the method of this invention contain silicon-bonded hydroxyl radicals arld/or silicon-bonded nydroyen radicals which provide chemical xeactivity therefor. The amount of silicon-bonded hydroyen radicals and/or silicon-bonded hydroxyl radicals therein de-~ends upon the ratio of said radicals in, and the acid num~er of, the homogeneows mixture that is used ~or its preparation.
To assure that the copolymeric oryanopolysiloxane that is prepared by the method of this invention contains silicon-bonded hydroyen radicals it is believed that the llomoyeneous mixture tnat is prepared should ilave at least 2, and preferably at least 3, silicon-bonded hydroyen radicals for every silicon-bonded hydroxyl radical.
An up~er limit of 2580 for the ratio of silicon-bonded hydroyen radicals to silicon-bonded hydroxyl radicals in the homogeneous mixture occurs in a mixture of 10 parts ~y weiyht of resinous copolymeric siloxane haviny a silanol content of 0.1 percent by weiyht and 9~ parts by weight of an oryanohydroyenpolysiloxane haviny a silicon-bonded hydroyen content of 1.7 percent by weiyht.
To assure that the copolymeric oryanopolysiloxane that is ~repared by tne method vf this invention contains silicon-bonded hydroxyl radicals it is believed that the aci~ number of the holnogeneous inixture that is heated shquld have a value of less than about 2.
The copolymeric organopolysiloxanes of this invention are useful ~ se as tin-catalyzed or platinum-catalyzed curable encapsulatiny compositions.
.
7 ~
They have also been foun~ to be useful as a reactive component in curable silicone compositions such as in silicone coating compositions comprisiny hydroxyl-conta.inin~ silicone fluid polymers or vinyl-containing silicone fluid polymers.
The followirly examples are disclosed to further illustrate, but not limit, the present invention. All parts and yercentayes are ~y weiyht unless otherwise stated.
The non-volatile content, also denoted ~lerein as N.V.C., of a material was determined by placing 1.5U grams of the material in an aluminum foil dish, 60 mm. in diameter and 15 mm. deep and heating the sample for 1 hour at 150C in an a.ir-circulating oven.
The neated sample was then cooled to room temperatur~
and reweiyhed to determine the wei~ht of the non-volatile material (w). N.V.C., in percent, is e~ual to 100 w/l.S0.
'rhe acid num~er, also denoted herein as A.N., of a material was determined by titratiny 1.00 grams of the material to a bromcresol purple endpoint, using alcoho~ic KO~j and is e~ual to the number of my. of ~O~ so useo.
i i7 ~ .~3 ~;
The viscosity of a material was measured at ~5C with a Brookfield~ viscometer Model RVF and the vaLue obtained ~as converted from centipoise to pascal-seconds (Pa-s) for this disclosure by multi~lyiny by ~.0~1.
The following components were used in the examples.
~ esin A-l ~ A xylene solution of a resinous . . .
copol~neric siloxane, ~repared from 4~ parts of sodium silicate (41.6~e) and 20 ~arts of 1CH3)3Si~l accordiny to the method of ~audt et al. noted aobve, containlny (C~3)3SiOl/~ siloxane units and SiO4/2 siloxane units of a~proximately 0.75/1.0 an~ having A.N. = O. 8U, SiO~ = 2.56~, Si~ = 0% and N.V.C. = 7 By extrapolation to 100% N.V.C. the resinous copolymeric siloxane itself had A.N. = 1.14, SiH = 0% and SiO~ = 3.66%.
Resin A-2 - Resin A-l with substantially all of its solvent removed by evaporation at room temperature and atmospheric pressure to N.V.C. = ~5~;
a solid material.
Resin A-3 - Similar to, and prepare~ dS, Resin A~l except having N.V.C. = ~7.35~, A.N. = U.64, SiH = 0.003% and SioH = 1. 91%. By extrapolation to l~U~ N.V.C. the resinous copolymeric siloxane had A.N.
= ~.95, ~iH = ~ 4~ and ~iOH = ~.~4~.
Resin A-4 - Similar to, and pre~ared as, Resin A-l exceut having N~V~C~ = 6~7~ A.N. = U.33, SiH = 0~ and SioH = 2.02%. By extrapolation to l00 N.V.C. the resinous copol~neric siloxane had A.N. -0.48, SiH = 0~ and SiOH = 2.94~.
~esin A-5 - Similar to, and ~repared as, -Resin A-l except having an N.V.C. = 67.6~, A~No = 1~1 and a Turbidity Index = 12.4 (an indirect measurement of SiOH). By extrapolation to l00~ N.V.C. the resinous copolymer siloxane had A.N. = l.66.
Flu~d B-l - An or~anohydroyenpolysiloxane liqui~ having the formula (CH3)3SioL~CH3)2Sio]3-L(CH3)(H)SiO~5Si~CH3)3; N~V~Co = lU0%~ R~N~ = O~U()5 SiH = 0.74~ and SiOH = 0.025~.
Fluid B-2 - An oryanohydrogenpolysiloxane liquid having the formula (C~3)3SioL(CH3)(H)Siol3s-Si(CH3)3, N.V,C. = 100%, A.N. = 0.0l, SiH = l.~h%, SiOH = U% and a viscosity of 0.~3 Pa~s.
Fluid B-3 ~ Same as Fluid ~-~ except having AoN~ = 0.U2, Si~H -- 0~ and SiH = l.71~.
I ~75~
Fluid B-4 ~ame as Fluid B-~ except haviny A.M. = ~.00~, SioH = ~.03~ and SiH = 1.56~.
Exanl~_e 1 Thls example illustrates the pre~aration of a com~osition of this invention at atmos~heric ~ressure.
Fort~ parts of Fluid B-3 and 85.7 parts of ~esin A-l (6~ parts of resinous copolymeric siloxane and 25.7 parts of xvlene) were mixed to form a ho-mogeneous mixture having 5.3 silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical.
The mixture was devolatilized at room temperature and atmospheric ~ressure to a N~V.C. = 97~. This devolatilized, but not heated, Inixture had SioH =
3.82~, Si~ = 0.35%, A.N. = 0.19 and a viscosity of 900 ~a-sc The devolatillzed mixture was heated at 150C
for ~ hours in an air-circulating oven. The resulting li~uid composition of this invention had SiOH = 0.48%, Si~ = ~.56% and A.N. = 0.~. It was useful as a controlle~ release additive in a solventLess silicone coatiny com~osition.
Wl~erl this exarnple was re~eated with solid Resin A-2 a small ~ercentaye of the resin could not be homoyeneously mixe~ witn Fluid B-3. When this 5 ~ ~
~,, heterogeneous mixture haviny ~iOH = ~.09~, Si~ =
.67%, A~N. - ~.0~, N.V.C. = ~7~ and a viscosity of 38.5 Pa-s was neated~ as above, a li~uid co,nposition havin~ SiO~I = 0.35~, Si~ = ~.64~ and A.N. = 0.0~ was obtained which provided su~stantially the same controlled adhesive release for a solventless silicone coating composition as the above solvent-prepared COlllpO S i t ion.
Example ~
This example illustrates the preparation of a composition of this invention at reduced pressure.
; Forty parts of Fluid B-3 and 85.7 parts of Resin A 1 were Inixed to form a homogeneous mixture which was heated to 15~C at abnospheric pressure after which the pressure was reduced sufficiently to volatilize xylene and water. After water ceased to be evolved the mixture was heated at 15~C at a pressure of ~ Torr (267 Pa~ to remove substantially all of the remaining xylene. The copolymeric oryanopolysiloxane of this invention had SiO~ = l.Y~ iH = ~.15~, A.N.
= ~.35 and a viscosity of ~50 Pa~s. It was useful dS
a controlled-release additive in a curable silicone ~aper-coating composition.
Example 3 The preparation described in ~xample ~ was repeated except that 60 parts of Fluid B-3 and 57.1 parts of the Resin ~-1 (4~ parts of resinous copolyrneric siloxane and 17.1 parts of xylene) were mixed to form a homoyeneous mixture haviny 1 1~7~
11.~ silicon-bonded hydro~en radicals for every sllicon-~onded hydroxyl radical. The resulting co~olymeric oryanopolysiloxane of tllis inventiorl nad SiOH = 0.87~, SiH = U.91~, A.N. = 0.10 and a viscosity of 0031 Pa-s. It was useful as a reinforcing component in a curable a~ueous silicone emulsion composition.
Example 4 The preparation described in Example 2 was repeated except that 40 parts of Fluid B 2 and 87.3 parts of Resin A-4 (60 parts of resinous copolymeric siloxane and ~7.3 parts of xylene) were mixed to form a homogeneous mixture haviny 7.6 silicon-bonded hydroyen radicals for every silicon-bonded hydroxyl radical. The resultin~ copolymeric oryanopolysiloxane of this invention had SiOH = 0.30%~ SiH = U.5U~ and a viscosity of 71 Pa-s. It provided smooth adhesive release at hiyh release force for a silicone yaper-coatirlg composition when mixed therewith. The gel~permeation chromatoyraMs of the sole drawiny in this disclosure were derived from this preyaration.
Exam~le 5 The ~re~aration described in Example ~ was repeated except that 4U parts of Fluid B~l and ~
parts of Resin A~3 (60 parts of resinous copol~meric 1 ~7~
,~ ~
siloxane and ~.1 parts of xylene) were mixed to form a homogeneous mixture haviny ~9 silicon-~onded hy~royen radicals for every silicon-bonded nydroxyl radical. The resultiny copolymeric or~anopolysiloxane of tnis invention nad SiO~ = 1.64%, ~iH = ~.002%; A.N. = U.~5 and a viscosity of 77.5 Pa-s. It was useful as a controlled release additive for a platinum-catalyzed curable silicone paper coatiny composition for releasin~ ayrressive acrylic adhesive.
xam~le 6 The pre~aration described in ~xample 2 was repeated except that 6~U parts of Fluid B-4 and 1331 parts of Resin A-5 (90~ parts of resinous copolymeric siloxane and 431 parts of xylene) were mixed to form a homoyeneous inixture. ~uring the heatiny of ttliS
mixture pressure was reduced at 9~"C after 45 minutes of ileatin~ an~ was yradually reduced thereafter over a period of ~5 Ininutes as the temperature was increased to 150C. The resultiny co~olymeric organosiloxane of thiS invention had SiOH = 1~7~%, SiH = 0.~%, A.N. =
1.4~ N.V.C. = ~8.~% and a viscosity of 354 Pa~s. It was useful as a stren~thenin~ component for à
tin-catalyzed curable sllicone mold coating for releasing molded polyurethane fo~n articles.
for ~ hours in an air-circulating oven. The resulting li~uid composition of this invention had SiOH = 0.48%, Si~ = ~.56% and A.N. = 0.~. It was useful as a controlle~ release additive in a solventLess silicone coatiny com~osition.
Wl~erl this exarnple was re~eated with solid Resin A-2 a small ~ercentaye of the resin could not be homoyeneously mixe~ witn Fluid B-3. When this 5 ~ ~
~,, heterogeneous mixture haviny ~iOH = ~.09~, Si~ =
.67%, A~N. - ~.0~, N.V.C. = ~7~ and a viscosity of 38.5 Pa-s was neated~ as above, a li~uid co,nposition havin~ SiO~I = 0.35~, Si~ = ~.64~ and A.N. = 0.0~ was obtained which provided su~stantially the same controlled adhesive release for a solventless silicone coating composition as the above solvent-prepared COlllpO S i t ion.
Example ~
This example illustrates the preparation of a composition of this invention at reduced pressure.
; Forty parts of Fluid B-3 and 85.7 parts of Resin A 1 were Inixed to form a homogeneous mixture which was heated to 15~C at abnospheric pressure after which the pressure was reduced sufficiently to volatilize xylene and water. After water ceased to be evolved the mixture was heated at 15~C at a pressure of ~ Torr (267 Pa~ to remove substantially all of the remaining xylene. The copolymeric oryanopolysiloxane of this invention had SiO~ = l.Y~ iH = ~.15~, A.N.
= ~.35 and a viscosity of ~50 Pa~s. It was useful dS
a controlled-release additive in a curable silicone ~aper-coating composition.
Example 3 The preparation described in ~xample ~ was repeated except that 60 parts of Fluid B-3 and 57.1 parts of the Resin ~-1 (4~ parts of resinous copolyrneric siloxane and 17.1 parts of xylene) were mixed to form a homoyeneous mixture haviny 1 1~7~
11.~ silicon-bonded hydro~en radicals for every sllicon-~onded hydroxyl radical. The resulting co~olymeric oryanopolysiloxane of tllis inventiorl nad SiOH = 0.87~, SiH = U.91~, A.N. = 0.10 and a viscosity of 0031 Pa-s. It was useful as a reinforcing component in a curable a~ueous silicone emulsion composition.
Example 4 The preparation described in Example 2 was repeated except that 40 parts of Fluid B 2 and 87.3 parts of Resin A-4 (60 parts of resinous copolymeric siloxane and ~7.3 parts of xylene) were mixed to form a homogeneous mixture haviny 7.6 silicon-bonded hydroyen radicals for every silicon-bonded hydroxyl radical. The resultin~ copolymeric oryanopolysiloxane of this invention had SiOH = 0.30%~ SiH = U.5U~ and a viscosity of 71 Pa-s. It provided smooth adhesive release at hiyh release force for a silicone yaper-coatirlg composition when mixed therewith. The gel~permeation chromatoyraMs of the sole drawiny in this disclosure were derived from this preyaration.
Exam~le 5 The ~re~aration described in Example ~ was repeated except that 4U parts of Fluid B~l and ~
parts of Resin A~3 (60 parts of resinous copol~meric 1 ~7~
,~ ~
siloxane and ~.1 parts of xylene) were mixed to form a homogeneous mixture haviny ~9 silicon-~onded hy~royen radicals for every silicon-bonded nydroxyl radical. The resultiny copolymeric or~anopolysiloxane of tnis invention nad SiO~ = 1.64%, ~iH = ~.002%; A.N. = U.~5 and a viscosity of 77.5 Pa-s. It was useful as a controlled release additive for a platinum-catalyzed curable silicone paper coatiny composition for releasin~ ayrressive acrylic adhesive.
xam~le 6 The pre~aration described in ~xample 2 was repeated except that 6~U parts of Fluid B-4 and 1331 parts of Resin A-5 (90~ parts of resinous copolymeric siloxane and 431 parts of xylene) were mixed to form a homoyeneous inixture. ~uring the heatiny of ttliS
mixture pressure was reduced at 9~"C after 45 minutes of ileatin~ an~ was yradually reduced thereafter over a period of ~5 Ininutes as the temperature was increased to 150C. The resultiny co~olymeric organosiloxane of thiS invention had SiOH = 1~7~%, SiH = 0.~%, A.N. =
1.4~ N.V.C. = ~8.~% and a viscosity of 354 Pa~s. It was useful as a stren~thenin~ component for à
tin-catalyzed curable sllicone mold coating for releasing molded polyurethane fo~n articles.
Claims (10)
1. A method for preparing a liquid copolymeric organopolysiloxane, said method comprising (A) forming a homogeneous mixture having an acid number greater than zero and comprising (a) an organic solvent solution of a resinous copolymeric siloxane containing silicon-bonded hydroxyl radicals and consisting essentially of R3SiO1/2 siloxane units and SiO4/2 siloxane units wherein the ratio of the number of said R3SiO1/2 siloxane units to the number of said Si04/2 siloxane units has a value of from 0.6/1 to 0.9/1 and each R denotes, independently, a monovalent hydrocarbon radical, and characterized by adding (b) a liquid organohydrogenpolysiloxane wherein each organic radical is, independently, a monovalent hydrocarbon radical, there being an average of at least one silicon-bonded hydrogen radical per molecule of said organohydrogenpolysiloxane, and (B) heating said homogeneous mixture to remove substantially all of said organic solvent therefrom.
2. A method according to claim 1 wherein the homogeneous mixture is sufficiently acidic to provide an acid number of from 0.1 to 1 for the homogeneous mixture, extrapolated to the solvent-free state.
3. A method according to claim 2 wherein the ratio of the total number of silicon-bonded hydrogen atoms in component (b) to the total number of silicon-bonded hydroxyl radicals in component (a) has a value of at least about 2.
4. A method according to claim wherein the resinous copolymeric siloxane consists of (CH3)3SiO1/2 siloxane units and SiO4/2 siloxane units and has a silicon-bonded hydroxy content of from 1 to 5 percent by weight and an acid number of from 0.3 to 1.4.
5. A method according to claim 3 wherein the organohydrogenpolysiloxane has the formula (R")(CH3)2SiO[(CH3)2SiO]a[(CH3)(H)SiO]bSi(CH3)2(R") wherein each R" denotes, independently, a methyl radical or a hydrogen radical and a and b denote numbers, each having an average value of zero or more.
6. A method according to claim 5 wherein the organohydrogenpolysiloxane has the formula (CH3)3SiO[(CH3)(H)SiO]bSi(CH)3 wherein b has an average value of from 30 to 70.
7. A method according to claim 6 wherein the homogeneous mixture contains from 40 to 60 parts by weight of resinous copolymeric siloxane and from 40 to 60 parts by weight of organohydrogenpolysiloxane.
8, A copolymeric organopolysiloxane prepared by the method of claims 1, 2, or 3.
9. A copolymeric organopolysiloxane prepared by the method of claim 4, 5 or 6.
10. A copolymeric organopolysiloxane prepared by the method of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/212,188 US4310678A (en) | 1980-12-02 | 1980-12-02 | Liquid copolymeric organopolysiloxanes comprising SiO2 and method therefor |
| US212,188 | 1980-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1167586A true CA1167586A (en) | 1984-05-15 |
Family
ID=22789932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000389345A Expired CA1167586A (en) | 1980-12-02 | 1981-11-03 | Liquid copolymeric organopolysiloxanes comprising sio.sub.2 and method therefor |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4310678A (en) |
| EP (1) | EP0053472B1 (en) |
| JP (1) | JPS6317290B2 (en) |
| AU (1) | AU542158B2 (en) |
| BR (1) | BR8108899A (en) |
| CA (1) | CA1167586A (en) |
| DE (1) | DE3171943D1 (en) |
| MX (1) | MX160984A (en) |
| WO (1) | WO1982001876A1 (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1243434A (en) * | 1983-01-28 | 1988-10-18 | Leroy E. Thayer | Siloxane-pva coating compositions |
| US4423095A (en) * | 1983-01-28 | 1983-12-27 | Dow Corning Corporation | Silicone-organic coating compositions |
| US4554331A (en) * | 1984-07-02 | 1985-11-19 | Dow Corning Corporation | Liquid copolymeric organosiloxanes |
| US4595610A (en) * | 1984-07-02 | 1986-06-17 | Dow Corning Corporation | Curable silicone compositions for the protection of polyurethane foam |
| US4537829A (en) * | 1984-09-20 | 1985-08-27 | Dow Corning Corporation | Curable silicone compositions comprising resins |
| US4562096A (en) | 1984-12-24 | 1985-12-31 | Dow Corning Corporation | Heat-curable silicone compositions, use thereof and stabilizer therefor |
| US4788001A (en) * | 1985-04-02 | 1988-11-29 | Dow Corning Corporation | Oil-in-water emulsion |
| US4731191A (en) * | 1985-12-31 | 1988-03-15 | Dow Corning Corporation | Method for protecting carbonyl iron powder and compositions therefrom |
| GB8615862D0 (en) * | 1986-06-28 | 1986-08-06 | Dow Corning Ltd | Making siloxane resins |
| US5026769A (en) * | 1987-12-09 | 1991-06-25 | Dow Corning Corporation | Method of producing silicone emulsion |
| US5026768A (en) * | 1987-12-09 | 1991-06-25 | Dow Corning Corporation | Method of producing silicone emulsion |
| US4978710A (en) * | 1987-12-09 | 1990-12-18 | Dow Corning Corporation | Method of producing silicone emulsion |
| US5037886A (en) * | 1988-01-25 | 1991-08-06 | Dow Corning Corporation | Crosslinkable pressure-sensitive adhesives containing a liquid copolymeric organopolysiloxane |
| US5001186A (en) * | 1989-09-11 | 1991-03-19 | Dow Corning Corporation | Method of producing silicone emulsion |
| CA2035964A1 (en) * | 1990-03-06 | 1991-09-07 | Carl R. Kessel | Solventless silicon release coating |
| JP3161786B2 (en) * | 1991-11-20 | 2001-04-25 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane and method for producing the same |
| US5356585A (en) * | 1993-07-01 | 1994-10-18 | Dow Corning Corporation | Process of extruding snythetic thermoplastic resins using organosilicon resinous compositions as extrusion lubricants |
| US5891548A (en) * | 1996-10-03 | 1999-04-06 | Dow Corning Corporation | Encapsulated silica nanoparticles |
| JP3993373B2 (en) * | 2000-09-14 | 2007-10-17 | 信越化学工業株式会社 | Polyorganosiloxane compound and coating composition containing the same |
| US20080242744A1 (en) * | 2003-07-23 | 2008-10-02 | Kathleen Barnes | Process for making silicone-in-water emulsions |
| ATE466911T1 (en) * | 2003-07-23 | 2010-05-15 | Dow Corning | MECHANICAL INVERSION PROCESS FOR PRODUCING SILICONE OIL-IN-WATER EMULSIONS |
| ES2487894T3 (en) | 2003-08-27 | 2014-08-25 | Dow Corning Corporation | Silicone emulsions or compositions of the oil / water (O / W) type useful for water repellent applications |
| US20070218115A1 (en) * | 2003-10-27 | 2007-09-20 | Bott Richard R | Preparation for Topical Application and Methods of Delivering an Active Agent to a Substrate |
| DK1680097T3 (en) * | 2003-10-27 | 2009-07-06 | Dow Corning | Topical application compositions and methods for delivering an active agent to a substrate |
| JP5132027B2 (en) * | 2004-05-12 | 2013-01-30 | 株式会社Ａｄｅｋａ | Silicon-containing curable composition and cured product obtained by thermally curing the same |
| US8933177B2 (en) * | 2008-07-11 | 2015-01-13 | Dow Corning Toray Company, Ltd. | Release modifier and release coating organopolysiloxane composition |
| EP2635621B1 (en) * | 2010-11-02 | 2016-08-17 | Henkel AG & Co. KGaA | Hydrosilicone resin and preparation process thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3205283A (en) * | 1965-09-07 | Solventless liquid organopolysiloxane encapsulating compositions | ||
| US2676182A (en) * | 1950-09-13 | 1954-04-20 | Dow Corning | Copolymeric siloxanes and methods of preparing them |
| US2814601A (en) * | 1954-04-29 | 1957-11-26 | Dow Corning | Organopolysiloxane adhesive and pressure-sensitive adhesive tape containing same |
| US3529035A (en) * | 1968-05-01 | 1970-09-15 | Gen Electric | High strength silicone elastomers |
| US3629358A (en) * | 1969-07-02 | 1971-12-21 | Gen Electric | Tough unsupported films formed from organopolysiloxanes |
| US3627851A (en) * | 1970-10-23 | 1971-12-14 | Dow Corning | Flexible coating composition |
| BE786656A (en) * | 1971-07-30 | 1973-01-24 | Ici Ltd | SILOXANES |
| US3992426A (en) * | 1973-08-22 | 1976-11-16 | Union Carbide Corporation | Quadripolymer siloxanes containing Si-H bonds |
-
1980
- 1980-12-02 US US06/212,188 patent/US4310678A/en not_active Expired - Lifetime
-
1981
- 1981-10-28 JP JP56503567A patent/JPS6317290B2/ja not_active Expired
- 1981-10-28 BR BR8108899A patent/BR8108899A/en not_active IP Right Cessation
- 1981-10-28 AU AU78053/81A patent/AU542158B2/en not_active Expired
- 1981-10-28 WO PCT/US1981/001458 patent/WO1982001876A1/en unknown
- 1981-11-03 CA CA000389345A patent/CA1167586A/en not_active Expired
- 1981-11-25 EP EP81305568A patent/EP0053472B1/en not_active Expired
- 1981-11-25 DE DE8181305568T patent/DE3171943D1/en not_active Expired
- 1981-11-26 MX MX190298A patent/MX160984A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0053472B1 (en) | 1985-08-21 |
| EP0053472A2 (en) | 1982-06-09 |
| BR8108899A (en) | 1982-10-26 |
| AU7805381A (en) | 1982-06-17 |
| US4310678A (en) | 1982-01-12 |
| MX160984A (en) | 1990-06-29 |
| WO1982001876A1 (en) | 1982-06-10 |
| EP0053472A3 (en) | 1982-09-08 |
| DE3171943D1 (en) | 1985-09-26 |
| AU542158B2 (en) | 1985-02-07 |
| JPS6317290B2 (en) | 1988-04-13 |
| JPS57501856A (en) | 1982-10-14 |
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