WO1982001876A1 - Liquid copolymeric organopolysiloxanes comprising sio2 and method therefor - Google Patents

Liquid copolymeric organopolysiloxanes comprising sio2 and method therefor Download PDF

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Publication number
WO1982001876A1
WO1982001876A1 PCT/US1981/001458 US8101458W WO8201876A1 WO 1982001876 A1 WO1982001876 A1 WO 1982001876A1 US 8101458 W US8101458 W US 8101458W WO 8201876 A1 WO8201876 A1 WO 8201876A1
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WIPO (PCT)
Prior art keywords
sio
copolymeric
silicon
siloxane
bonded
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PCT/US1981/001458
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French (fr)
Inventor
Corning Corp Dow
John D Blizzard
Terence J Swihart
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Dow Corning
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Priority to BR8108899A priority Critical patent/BR8108899A/en
Publication of WO1982001876A1 publication Critical patent/WO1982001876A1/en

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    • 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

Definitions

  • the present invention relates to copolymeric oryanopolysiloxanes comprising SiO 2 and to a method for their preparation. More particularly the present invention relates no the preparation of liquid copolymeric oryanopolysiloxanes comprisiny SiO 2 . In a preferred embodiment the present invention relates to the preparation of liquid copolymeric oryanopolysiloxanes comprisiny SiO 2 and bearing silicon-bonded hydroxyl radicals and silicon-bonded hydroyen radicals.
  • Copolymeric siloxanes comprisiny SiO 2 have been disclosed Dy Daudt et al., U.S. Patent No. 2 ,67b,182 issued April 20, 1954, which are prepared by reacting a silica hydrosol having a pH of less than 5 with an organosilane having tne formula R n SiX 4-n or an organosiloxane having the formula R n SiO (4-n/2 wherein R is alkyl, monocyclic aryl or haiogenated monocyclic aryl and X is chlorine or alkoxy.
  • the reaction products are said to range from viscous oils to thermoplastic resins.
  • Organopoiysiloxane resins containing R 3 SiO 1/2 units and SiO 2 units, along with KHSiO units and/or HSlO 3/2 units, wherein R is a monovifying hydrocarbon group, are disclosed Dy Flannigan, U.S. Patent No. 3,772,247, issued November 13, 1973.
  • the resins of Flannigan are said to be preparaole in any one of a variety of ways, however, cohycrolysis of nydrolyzable silanes and tne reaction of nydrolyzable silanes with a silica hy ⁇ rosol are the only methods disclosed and only brittle, solid resins are disclosed.
  • Curve 1 is a cnromatogram of a xyiene solution of a resinous copolymer siloxane consisting of (CH 3 ) 3 SiO 1/2 siloxane units and SiO 4/2 siloxane units and having a silicon-bonded nydroxyl content of about 3.66 percent oy weight, tne ratio of (CH 3 ) 3 SiO 1/2 units to SiO 4/2 units having a value of about 0.75.
  • Curve 2 is a chromatogram of a mixture of 60 parts by weight of the composition represented by Curve 1 and 40 parts by weight of a liquid organohydrogenpolysiloxane having the formula (CH 3 ) 3 SiOL(CH 3 )(H)SiO] 35 Si(CH 3 )3.
  • Curve 3 is a chromatogram of a composition of this invention obtained by heating the mixture represented by Curve 2 according to the process of this invention.
  • the material having an eiution time exceeding 26 minutes in Curves 1 and 2 is suostantially silanol-free volatile material which may have simply been removed from the composition represented by Curve 3 during the heating and solvent removal process.
  • tne material eluting at approximately 26 minutes and 27 minutes is [ (CH 3 ) 3 SiO] 4 O and [(CH 3 ) 2 SiO] 4 , respectively.
  • the products of the process of this invention are designated herein as copolymeric oryanopolysiloxanes. They are prepared oy reacting, by the process of this invention, a first reactant, designated herein as a resinous copolymeric siloxane, with a second reactant, designated herein as a liquid oryanonydrogenpoiysiloxane.
  • 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 wnich snows a gel-permeation chromatogram (Curve 3), which is displaced and different from the gel-permeation chromatogram for the mixture of starting materials (Curve 2), wnen measuredunder identical instrumental conditions. Under identical gel-permeation chromatography instrumental conditions larger molecules have a snorter elution time than smaller molecules; therefore, a large portion of the copolymeric organopoiysiloxane of this invention nas larger molecular size than either of its precursors.
  • Component (a that is used in the metnod of this invention is an organic solvent solution of a resinous copolymeric siloxane wnicn consists essentially of R 3 SiO 1/ 2 siloxane units and SiO 4/2 siloxane units.
  • the resinous copolymer siloxane has a complex, as-yet-undetermined structure; however, for tne purposes of this disclosure it is fully characterized by the ratio of said siloxane units tnerein, by its silanol, i.e. silicon-bonded hydroxyl, content and by its solubility in organic solvents, sucn as benzene.
  • the resinous copolymeric siloxane portion of component (a) consists of from 0.6 to 0.9 R 3 SiO 1/2 units for every SiO 4/2 unit.
  • Each R denotes a monovalent hydrocarbon radical; such as an alkyl radical, such as methyl, ethyl, isopropyl, butyl and hexyl; an alkenyl radical, such as vinyl and allyl; an aryl radical, such as pnenyl, tolyl and xylyl; an arylalkyl radical, such as beta-phenylethyl and oeta-phenylpropyl; and a cycloalipnatic radical, such as cyclopentyl, cyclohexyl and cyclohexenyl.
  • R radicals in component (a) are lower alkyl radicals although a minor portion of them can be replaced with other monovalent hydrocarbon radicals sucn as the vinyl radical and/or the pnenyl radical to provide additional properties for the resinous copolymer 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 frequently comprises trace amounts of silicon-bonded alkoxy radicals sucn as methoxy, ethoxy or isopropoxy radicals which arise from the particular method that is used to prepare said resin copolymeric siloxane.
  • the resinous copolymeric siloxane portion of component (a) consists essentially of (CH 3 ) 3 SiO 1/2 siloxane units and SiO 4/2 siloxane units, in the. number ratio stated above, and has a silicon-bonded hydroxyl content of from 1 to 5 percent by weight.
  • Resinous copolymeric siloxanes consisting of R 3 SiO 1/2 hits and SiO 4/2 units are well known in the art and are described by Dauot et al., U.S. Patent No. 2,676,182, and by Goodwin, U.S. atent No.
  • the reaction mixture After being neated the reaction mixture is cooled and is separated into an aqueous phase, which is discarded, and a non-aqueous phase comprising the resinous copolymeric siloxane, which is further washed with water to reduce its acid numoer and to remove water-soluble components, such as isopropyl alcohol.
  • the acidic resinous copolymeric siloxanes wnicn are prepared by tnese metnods are washed with water to remove most, but not all, of the acid therein.
  • resinous copolymeric siloxanes wnich have been prepared by tne method of Daudt et al.
  • Resinous copolymeric siloxanes are typically prepared in an organic solvent which can conveniently serve as the organic solvent portion of component (a) in the method of this invention. Alternatively, the resinous copolymeric siloxane can be prepared in one organic solvent and subsequently can be transferred to a second organic solvent, if desired, to form component (a) for the method of this invention. If the resinous copolymeric siloxane does not contain any organic solvent, one or more organic solvents should be mixed therewith before or during preparation of homogeneous mixture to be heated.
  • the particular organic solvent portion of component (a) is not critical and can be for example an aliphatic hydrocarbon, an aromatic nydrocaroon or halogenated derivatives of either or mixtures thereof.
  • the organic solvent is one that forms an azeotrope with water so that any water that is formed during the heating step in the method of this invention can be conveniently removed by azeotropic distillation.
  • Particularly useful organic solvents include uenzene, toluene, xylene, trichloroetnylene and mineral spirits.
  • component (a) The amount of resinous copolymeric siloxane contained in component (a) is not critical and can range from 10 to 90 percent by weight. It is preferred that only as much organic solvent as is needed to prepare a homogeneous mixture of resinous copolymeric siloxane and liquid organohydrogenpoly- siloxane be used in order to minimize the amount of time and/or energy needed to subsequently remove it from the mixture as described hereinafter.
  • a preferred component (a) contains approximately 60 to 70 percent by weight resinous copolymeric siloxane and the balance solvent.
  • Component (b) is any liquid organonydrogenpolysiloxane containing an average of at least one silicon-bonded hydrogen radical per molecule, and can nave a linear, cyclic or branched structure or comoinations thereof.
  • component (b) has the unit formula R' m H n SiO (4-m-n)/2 wherein m and n denote positive numbers wnose sum is less than 4, preferably from 1.9 to 2.1.
  • the organic radicals (R') in component (b) can be any of the R radicals denoted above.
  • tne organic radicals (R') in component (b) are the same as the organic radicals (R) in component (a).
  • organohydrogenpolysiloxanes that are suitable for use as component (b) m the process of this invention include cyclic organonydrogenpolysiloxanes of the unit formula R m H2-mSiO such as [(CH 3 )(H)SiO] x wherein x is 3, 4, 5, 6 and higher and [(CH 3 )(H)SiO]y[(CH3) 2 SiO] z wherein the sum of y plus z is 3, 4, 5, 6 and higher; and linear organonydrogenpolysiloxanes of the formula
  • R" (CH 3 ) 2 SiOC(CH 3 )2SiO] a [(CH 3 )(H)SiO] b Si(CH 3 ) 2 R" wherein R" denotes H or methyl and a and b each denote zero or a nuraoer greater than zero, provided there is at least one silicon-bonded hydrogen radical per molecule, such as H(CH 3 )2SiO[(CH 3 ) 2 SiO] a Si(CH 3 ) 2 H,
  • Liquid organonydrogenpolysiloxane (b) can have any viscosity; however, it preferaoly has a viscosity of less than 1 pascal-second at 25°C when used in amounts of less than 60 parts by weight for every 40 parts by weight of resinous copolymeric siloxane.
  • Organonydrogenpoiysiloxanes and their preparation are well known in the organosilicon polymer art; some are commercially available. briefly the preparation of organonydroyenpolysiloxanes can be accomplished in any suitable manner such as by hydrolyzing a mixture of suitable hydrolyzable silanes, such as chlorosilanes, and equilibrating the resulting nydrolyzate under acid catalysis, alternatively, a mixture of suitable siloxanes, such as cyclic siloxanes and linear siloxanes, can oe copolyraerized and equilibrated under acid catalysis.
  • suitable hydrolyzable silanes such as chlorosilanes
  • a mixture of suitable siloxanes such as cyclic siloxanes and linear siloxanes
  • the amounts of resinous copolymeric siloxane and liquid organonydrogenpolysiloxane that are mixed may vary widely.
  • the viscosity of the copolymeric organopoiysiloxane that is produced by the method of this invention varies directly with the viscosity of the oryanohydrogenpoiysiloxane and inversly with its weiyht percent in the homoyeneous mixture of components (a) and (b).
  • Liquid copolymeric oryanopolysiloxanes can oe obtained when as little as anout 10 percent by weight of oryanonydrogenpoiysiloxane is used, based on tne weiyht of resinous copolymeric siloxane plus oryanonydrogenpoiysiloxane.
  • Liquid copolymeric organopoiysiloxanes of this invention which contain less tnan aoout 10 percent by weight of resinous copolymeric siloxane component are not expected to significantly demonstrate tne oenefits for which the resinous copolymeric siloxane is used, sucn as a strenytheniny component in curable silicone compositions.
  • a nignly preferred composition of this invention is obtained when the homogeneous mixture that is heated in the process of this invention comprises from 40 to 60 parts by weight of resinous copolymeric siloxane consisting of (Cl 3 ) 3 SiO 1/2 , units and SiO 4/2 units and containing from 1 to 5 percent by weight of silicon-bonded hydroxyl radicals and from 40 to 60 parts by weight of organohydrogenpolysiloxane having the formula (CH 3 ) 3 SiO[(CH 3 )(H)SiO] 30 to 7 0 Si(CH 3 ) 3 .
  • the resulting copolymeric organopolysiloxanes have demonstrated unexpected utility as a controlled release additive for curable silicone coating compositions, as disclosed in U.S. Application Serial No. 212,189 filed December 2, 1980.
  • a homogeneous mixture is formed by thoroughly mixing the desired amounts of component (a) and component (b) and, if necessary, an acid, preferably a strong acid such as hydrocnioric acid, to provide an acid number greater than zero therefor.
  • an acid preferably a strong acid such as hydrocnioric acid
  • the acid numoer of the nomogeneous mixture extrapolated to zero solvent content, has a value of from 0.1 to 1.
  • component (a) is sufficiently acidic, as prepared, to provide this acidity for the homogeneous mixture.
  • the resulting homogeneous mixture is immediately or subsequently heated to volatilize the organic solvent therefrom. Said heating is preferably initially done at atmospheric pressure and is then continued at reduced pressure to accelerate the removal of said solvent.
  • the homogeneous mixture of (a) plus (b) is heated to about 150°C at atmospheric pressure and is then subjected to a gradually decreasing pressure, without an increase in temperature, to remove substantially all of the organic solvent therefrom.
  • the homogeneous mixture can be partially devolatilized at room temperature, such as by evaporation, and the partially devolatilized mixture then heated to remove substantially all of the organic solvent therefrom.
  • the copolymeric oryanopolysiloxanes of this invention are formed by a reaction between the resinous copolymeric siloxane and the oryanonydrogenpoiysiloxane to form by-product water and/or by-product hydrogen.
  • the heating step of the process of this invention serves not only to remove substantially all of the organic solvent from the homogeneous mixture of reactants but also to facilitate said reaction. Said reaction is alsofacilitated by the acid in the homogeneous mixture, greater reaction ⁇ eing obtained in mixtures having a higher acid number.
  • the copolymeric organopolysiloxanes that are produced by the method of this invention contain silicon-bonded hydroxyl radicals and/or silicon-bonded hydrogen radicals which provide chemical reactivity therefor.
  • the amount of silicon-bonded hydrogen radicals and/or silicon-bonded hydroxyl radicals therein depends upon the ratio of said radicals in, and the acid number of, tne homogeneous mixture that is used for its preparation.
  • the homogeneous mixture that is prepared by the method of this invention contains silicon-bonded hydrogen radicals it is believed that the homogeneous mixture that is prepared should have at least 2, and preferably at least 3, silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical.
  • An upper limit of 2580 for the ratio of silicon-bonded hydrogen radicals to silicon-bonded hydroxyl radicals in the homogeneous mixture occurs in a mixture of 10 parts by weight of resinous copolymeric siloxane having a silanol content of 0.1 percent by weiyht and 90 parts by weight of an organohydrogenpolysiloxane having a silicon-bonded hydrogen content of 1.7 percent by weight.
  • the acid number of the homogeneous mixture that is heated should have a value of less than about 2.
  • copolymeric organopolysiloxanes of this invention are useful per se as tin-catalyzed or platinum-catalyzed curable encapsulating compositions. They have also ⁇ een. found to be useful as a reactive component in curable silicone compositions sucn as in silicone coating compositions comprising hydroxyl-containing silicone fluid polymers or vinyl-containing silicone fluid polymers.
  • the non-volatile content, also denoted herein as N.V.C., of a material was determined by placing 1.50 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 150°C in an air-circulating oven. The heated sample was then cooled to room temperature and reweighed to determine the weight of the non-volatile material (w). N.V.C, in percent, is equal to 100 w/1. 50.
  • the acid number, also denoted herein as A.N., of a material was determined by titrating 1.00 grams of the material to a bromcresol purple endpoint, using alcoholic KOH, and is equal to the number of mg. of KOH so used.
  • the viscosity of a material was measured at 25°C with a Brookfield ® viscometer Model RVF and the value obtained was converted from centipoise to pascal-seconds (Pa.s) for this disclosure by multiplying by 0.001.
  • Example 1
  • This example illustrates the preparation of a composition of this invention at atmospheric pressure.
  • This example illustrates the preparation of a composition of this invention at reduced pressure.
  • Example 4 The preparation described in Example 2 was repeated except that 60 parts of Fluid B-3 and 57.1 parts of the Resin A-1 (40 parts of resinous copolymeric siloxane and 17.1 parts of xylene) were mixed to form a homogeneous mixture having 11.8 silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical.
  • Example 4 Example 4
  • Example 5 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 27.3 parts of xylene) were mixed to form a homogeneous mixture having 7.6 silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical.
  • the gel-permeation chromatograms of the sole drawing in this disclosure were derived from this preparation.
  • Example 5 Example 5
  • Example 2 The preparation descrioed in Example 2 was repeated except that 40 parts of Fluid B-1 and 89.1 parts of Resin A-3 (60 parts of resinous copolymeric
  • Example 2 The preparation described in Example 2 was repeated except that 600 parts of Fluid B-4 and 1331 parts of Resin A-5 (900 parts of resinous copolymeric siloxane and 431 parts of xylene) were'e mixed to form a homogeneous mixture. During the heating of this mixture pressure was reduced at 98°C after 45 minutes of neating and was gradually reduced thereafter over a period of 85 minutes as the temperature was increased to 150°C.

Abstract

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

LIQUID COPOLYMERIC ORGANOPOLYSILOXANES COMPRISING SiO2 AND METHOD THEREFOR
Background of the Invention The present invention relates to copolymeric oryanopolysiloxanes comprising SiO2 and to a method for their preparation. More particularly the present invention relates no the preparation of liquid copolymeric oryanopolysiloxanes comprisiny SiO2. In a preferred embodiment the present invention relates to the preparation of liquid copolymeric oryanopolysiloxanes comprisiny SiO2 and bearing silicon-bonded hydroxyl radicals and silicon-bonded hydroyen radicals.
Copolymeric siloxanes comprisiny SiO2 have been disclosed Dy Daudt et al., U.S. Patent No. 2 ,67b,182 issued April 20, 1954, which are prepared by reacting a silica hydrosol having a pH of less than 5 with an organosilane having tne formula RnSiX4-n or an organosiloxane having the formula RnSiO(4-n/2 wherein R is alkyl, monocyclic aryl or haiogenated monocyclic aryl and X is chlorine or alkoxy. The reaction products are said to range from viscous oils to thermoplastic resins. Some of the copolymeric siloxanes of Dauct et al. are preferred starting materials for the process of this invention. Organopoiysiloxane resins containing R3SiO1/2 units and SiO2 units, along with KHSiO units and/or HSlO3/2 units, wherein R is a monovaient hydrocarbon group, are disclosed Dy Flannigan, U.S. Patent No. 3,772,247, issued November 13, 1973. The resins of Flannigan are said to be preparaole in any one of a variety of ways, however, cohycrolysis of nydrolyzable silanes and tne reaction of nydrolyzable silanes with a silica hyαrosol are the only methods disclosed and only brittle, solid resins are disclosed.
Soiventiess, flowabie organopoiysiloxane encapsulating fluids comprising SiO2 are disclosed by Modic, U.S. Patent No. 3,205, 283 issued September 7, 1965, which are prepared by heading a homogeneous mixture of an organic solvent solution of a resinous copolymer containing R3SiO1/ 2 units, wherein R is a monovalent hydrocarbon radical, and SiO2 units and a liquid silanol chain-stopped diorgancpoiysiloxane to remove the organic solvent therefrom.
Brady, U.S. Patent No. 3,627,351 issued December 14, 1971, discloses benzene-soluole copolymeric siloxanes consisting of (CH3)3SiO1/2 units, (CH3)2HSH O1 /2 units and SiO2 units which are prepared Dy modifying tne procedure of Daudt et al. noted above to include (CH3)2HSiCl or (CH3) 2-HSiOSιH(CH3)2 as one of tne components to react with the acidic silica hydrosol. Summary of the Invention
It is an object of this invention to provide a method for preparing liquid copolymeric oryanopolysiloxanes comprising SiO2. It is a particular object of this invention to provide liquid copolymeric organopolysiloxanes comprising SiO2 and bearing silicon-bonded hydroxyl radicals and silicon-bonded hydrogen radicals.
These objects, and otners wnich will be obvious to one skilled in the organopoiysiloxane art upon considering the following disclosure and appended claims, are obtained by the metnoo of this invention comprisiny ( A) forming a homogeneous mixture having an acid number greater than zero and comprising (a) an organic solvent solution of a resinous copolymeric siloxane containiny silicon-bonded hydroxyl radicals and consistiny 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 SiO4/2 siloxane units has a value of from 0.6/1 to 0.9/1 and each R denotes, independently, a monovalent hydrocarbon radical, and (b) a liquid oryanonydrogenpoiysiloxane wherein each oryanic radical is, independently, a monovalent hydrocarbon radical, there being an average of at least one silicon-bonded hydrogen radical per molecule of said oryanonydrogenpoiyslioxane, and (B) heating said homogeneous mixture to remove substantially all of said organic solvent therefrom. Brief Description of the Drawing The sole drawing is a composite of three gel-permeation chromatograms. Curve 1 is a cnromatogram of a xyiene solution of a resinous copolymer siloxane consisting of (CH3)3SiO1/2 siloxane units and SiO4/2 siloxane units and having a silicon-bonded nydroxyl content of about 3.66 percent oy weight, tne ratio of (CH3) 3SiO1/2 units to SiO4/2 units having a value of about 0.75. Curve 2 is a chromatogram of a mixture of 60 parts by weight of the composition represented by Curve 1 and 40 parts by weight of a liquid organohydrogenpolysiloxane having the formula (CH3)3SiOL(CH3)(H)SiO]35Si(CH3)3. Curve 3 is a chromatogram of a composition of this invention obtained by heating the mixture represented by Curve 2 according to the process of this invention. The material having an eiution time exceeding 26 minutes in Curves 1 and 2 is suostantially silanol-free volatile material which may have simply been removed from the composition represented by Curve 3 during the heating and solvent removal process. Specifically tne material eluting at approximately 26 minutes and 27 minutes is [ (CH3)3SiO]4O and [(CH3)2SiO]4, respectively. Detailed Description of the Invention The products of the process of this invention are designated herein as copolymeric oryanopolysiloxanes. They are prepared oy reacting, by the process of this invention, a first reactant, designated herein as a resinous copolymeric siloxane, with a second reactant, designated herein as a liquid oryanonydrogenpoiysiloxane.
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 wnich snows a gel-permeation chromatogram (Curve 3), which is displaced and different from the gel-permeation chromatogram for the mixture of starting materials (Curve 2), wnen measuredunder identical instrumental conditions. Under identical gel-permeation chromatography instrumental conditions larger molecules have a snorter elution time than smaller molecules; therefore, a large portion of the copolymeric organopoiysiloxane of this invention nas larger molecular size than either of its precursors.
Component (a that is used in the metnod of this invention is an organic solvent solution of a resinous copolymeric siloxane wnicn consists essentially of R3SiO1/ 2 siloxane units and SiO4/2 siloxane units. The resinous copolymer siloxane has a complex, as-yet-undetermined structure; however, for tne purposes of this disclosure it is fully characterized by the ratio of said siloxane units tnerein, by its silanol, i.e. silicon-bonded hydroxyl, content and by its solubility in organic solvents, sucn as benzene. The resinous copolymeric siloxane portion of component (a) consists of from 0.6 to 0.9 R3SiO1/2 units for every SiO4/2 unit. Each R denotes a monovalent hydrocarbon radical; such as an alkyl radical, such as methyl, ethyl, isopropyl, butyl and hexyl; an alkenyl radical, such as vinyl and allyl; an aryl radical, such as pnenyl, tolyl and xylyl; an arylalkyl radical, such as beta-phenylethyl and oeta-phenylpropyl; and a cycloalipnatic radical, such as cyclopentyl, cyclohexyl and cyclohexenyl. Preferably all R radicals in component (a) are lower alkyl radicals although a minor portion of them can be replaced with other monovalent hydrocarbon radicals sucn as the vinyl radical and/or the pnenyl radical to provide additional properties for the resinous copolymer 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 frequently comprises trace amounts of silicon-bonded alkoxy radicals sucn as methoxy, ethoxy or isopropoxy radicals which arise from the particular method that is used to prepare said resin copolymeric siloxane.
In a preferred embodiment of tnis invention the resinous copolymeric siloxane portion of component (a) consists essentially of (CH3)3SiO1/2 siloxane units and SiO4/2 siloxane units, in the. number ratio stated above, and has a silicon-bonded hydroxyl content of from 1 to 5 percent by weight. Resinous copolymeric siloxanes consisting of R3SiO1/2 hits and SiO4/2 units are well known in the art and are described by Dauot et al., U.S. Patent No. 2,676,182, and by Goodwin, U.S. atent No. 2,857,356, which teach how to prepare resinous copolymeric siloxanes which are suitable for use in tne method of this invention. Briefly, in these methods, an aqueous solution of sodium silicate (e.g. No. 9 sodium silicate sold by DuPont®) is acidified to tne properpH by adding it to a mixture of hydrochloric acid and isopropanol and the resulting acidic silica hydrosol is then treated with a source of R3SiO1/2 siloxane units such as R3SiOCH3, R3SiCl or R3SiOSiR3 dissolved in a mixture of isopropanol and xylene. After being neated the reaction mixture is cooled and is separated into an aqueous phase, which is discarded, and a non-aqueous phase comprising the resinous copolymeric siloxane, which is further washed with water to reduce its acid numoer and to remove water-soluble components, such as isopropyl alcohol. Preferably the acidic resinous copolymeric siloxanes wnicn are prepared by tnese metnods are washed with water to remove most, but not all, of the acid therein. For example, resinous copolymeric siloxanes wnich have been prepared by tne method of Daudt et al. typically have sufficient acid remaining therein to provide an acid number of from 0.2 to 2.0, as measured by the method hereinafter disclosed, based on the solvent-free resinous copolymeric siloxane. These materials are preferred. Resinous copolymeric siloxanes are typically prepared in an organic solvent which can conveniently serve as the organic solvent portion of component (a) in the method of this invention. Alternatively, the resinous copolymeric siloxane can be prepared in one organic solvent and subsequently can be transferred to a second organic solvent, if desired, to form component (a) for the method of this invention. If the resinous copolymeric siloxane does not contain any organic solvent, one or more organic solvents should be mixed therewith before or during preparation of homogeneous mixture to be heated.
The particular organic solvent portion of component (a) is not critical and can be for example an aliphatic hydrocarbon, an aromatic nydrocaroon or halogenated derivatives of either or mixtures thereof. Preferably the organic solvent is one that forms an azeotrope with water so that any water that is formed during the heating step in the method of this invention can be conveniently removed by azeotropic distillation. Particularly useful organic solvents include uenzene, toluene, xylene, trichloroetnylene and mineral spirits.
The amount of resinous copolymeric siloxane contained in component (a) is not critical and can range from 10 to 90 percent by weight. It is preferred that only as much organic solvent as is needed to prepare a homogeneous mixture of resinous copolymeric siloxane and liquid organohydrogenpoly- siloxane be used in order to minimize the amount of time and/or energy needed to subsequently remove it from the mixture as described hereinafter. A preferred component (a) contains approximately 60 to 70 percent by weight resinous copolymeric siloxane and the balance solvent.
Component (b) is any liquid organonydrogenpolysiloxane containing an average of at least one silicon-bonded hydrogen radical per molecule, and can nave a linear, cyclic or branched structure or comoinations thereof. Thus, component (b) has the unit formula R'mHnSiO(4-m-n)/2 wherein m and n denote positive numbers wnose sum is less than 4, preferably from 1.9 to 2.1. The organic radicals (R') in component (b) can be any of the R radicals denoted above. Preferauly, although not necessarily, tne organic radicals (R') in component (b) are the same as the organic radicals (R) in component (a).
Examples of organohydrogenpolysiloxanes that are suitable for use as component (b) m the process of this invention include cyclic organonydrogenpolysiloxanes of the unit formula RmH2-mSiO such as [(CH3)(H)SiO]x wherein x is 3, 4, 5, 6 and higher and [(CH3)(H)SiO]y[(CH3)2SiO]z wherein the sum of y plus z is 3, 4, 5, 6 and higher; and linear organonydrogenpolysiloxanes of the formula
CMFI R"R'2SiO(R'2SiO)a(R'HSiO)bSiR'2R", such as
R" (CH3)2SiOC(CH3)2SiO]a[(CH3)(H)SiO]bSi(CH3)2R" wherein R" denotes H or methyl and a and b each denote zero or a nuraoer greater than zero, provided there is at least one silicon-bonded hydrogen radical per molecule, such as H(CH3)2SiO[(CH3)2SiO]aSi(CH3)2H,
(CH3)3SiO[(CH3)(H)SiO]bSi(CH3)3'
(CH3)3SiO[(CH3) (H)SiO]b[(CH3)2SiO]aSi(CH3)3 and
H(CH3)2SiO[(CH3)2SiO]a[(CH3)(H)SiO]bSi(CH3)2H.
An oryanonydrogenpoiysiloxane having the formula (CH3) 3SiO[(CH3)(H)SiO] bSi(CH3)3 wherein b has an average value of from 30 to 70 is a highly preferred component (b) in the process of this invention, particularly when it is desired that the product of this invention have relatively large amounts of silicon-bonded hydrogen radicals.
Liquid organonydrogenpolysiloxane (b) can have any viscosity; however, it preferaoly has a viscosity of less than 1 pascal-second at 25°C when used in amounts of less than 60 parts by weight for every 40 parts by weight of resinous copolymeric siloxane.
Organonydrogenpoiysiloxanes and their preparation are well known in the organosilicon polymer art; some are commercially available. briefly the preparation of organonydroyenpolysiloxanes can be accomplished in any suitable manner such as by hydrolyzing a mixture of suitable hydrolyzable silanes, such as chlorosilanes, and equilibrating the resulting nydrolyzate under acid catalysis, alternatively, a mixture of suitable siloxanes, such as cyclic siloxanes and linear siloxanes, can oe copolyraerized and equilibrated under acid catalysis.
In tne method of this invention the amounts of resinous copolymeric siloxane and liquid organonydrogenpolysiloxane that are mixed may vary widely. Generally, the viscosity of the copolymeric organopoiysiloxane that is produced by the method of this invention varies directly with the viscosity of the oryanohydrogenpoiysiloxane and inversly with its weiyht percent in the homoyeneous mixture of components (a) and (b). Liquid copolymeric oryanopolysiloxanes can oe obtained when as little as anout 10 percent by weight of oryanonydrogenpoiysiloxane is used, based on tne weiyht of resinous copolymeric siloxane plus oryanonydrogenpoiysiloxane. Liquid copolymeric organopoiysiloxanes of this invention which contain less tnan aoout 10 percent by weight of resinous copolymeric siloxane component are not expected to significantly demonstrate tne oenefits for which the resinous copolymeric siloxane is used, sucn as a strenytheniny component in curable silicone compositions.
\f~T A nignly preferred composition of this invention is obtained when the homogeneous mixture that is heated in the process of this invention comprises from 40 to 60 parts by weight of resinous copolymeric siloxane consisting of (Cl3)3SiO1/2, units and SiO4/2 units and containing from 1 to 5 percent by weight of silicon-bonded hydroxyl radicals and from 40 to 60 parts by weight of organohydrogenpolysiloxane having the formula (CH3)3SiO[(CH3)(H)SiO]30 to 70Si(CH3)3. The resulting copolymeric organopolysiloxanes have demonstrated unexpected utility as a controlled release additive for curable silicone coating compositions, as disclosed in U.S. Application Serial No. 212,189 filed December 2, 1980.
In the method of this invention a homogeneous mixture is formed by thoroughly mixing the desired amounts of component (a) and component (b) and, if necessary, an acid, preferably a strong acid such as hydrocnioric acid, to provide an acid number greater than zero therefor. Preferaoly the acid numoer of the nomogeneous mixture, extrapolated to zero solvent content, has a value of from 0.1 to 1. Preferably component (a) is sufficiently acidic, as prepared, to provide this acidity for the homogeneous mixture. The resulting homogeneous mixture is immediately or subsequently heated to volatilize the organic solvent therefrom. Said heating 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 mixture of (a) plus (b) is heated to about 150°C at atmospheric pressure and is then subjected to a gradually decreasing pressure, without an increase in temperature, to remove substantially all of the organic solvent therefrom. By substantially it is meant nerein that the product of this invention contains less than about 5 percent, and preferaoly less than about 1 percent, by weight organic solvent.
Alternatively the homogeneous mixture can be partially devolatilized at room temperature, such as by evaporation, and the partially devolatilized mixture then heated to remove substantially all of the organic solvent therefrom.
While not wishing to be limited by theory we oelieve that the copolymeric oryanopolysiloxanes of this invention are formed by a reaction between the resinous copolymeric siloxane and the oryanonydrogenpoiysiloxane to form by-product water and/or by-product hydrogen. The heating step of the process of this invention serves not only to remove substantially all of the organic solvent from the homogeneous mixture of reactants but also to facilitate said reaction. Said reaction is alsofacilitated by the acid in the homogeneous mixture, greater reaction σeing obtained in mixtures having a higher acid number.
The copolymeric organopolysiloxanes that are produced by the method of this invention contain silicon-bonded hydroxyl radicals and/or silicon-bonded hydrogen radicals which provide chemical reactivity therefor. The amount of silicon-bonded hydrogen radicals and/or silicon-bonded hydroxyl radicals therein depends upon the ratio of said radicals in, and the acid number of, tne homogeneous mixture that is used for its preparation.
To assure that the copolymeric organopoiysiloxane that is prepared by the method of this invention contains silicon-bonded hydrogen radicals it is believed that the homogeneous mixture that is prepared should have at least 2, and preferably at least 3, silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical. An upper limit of 2580 for the ratio of silicon-bonded hydrogen radicals to silicon-bonded hydroxyl radicals in the homogeneous mixture occurs in a mixture of 10 parts by weight of resinous copolymeric siloxane having a silanol content of 0.1 percent by weiyht and 90 parts by weight of an organohydrogenpolysiloxane having a silicon-bonded hydrogen content of 1.7 percent by weight.
To assure that the copolymeric organopoiysiloxane that is prepared by the method of this invention contains silicon-bonded hydroxyl radicals it is believed that the acid number of the homogeneous mixture that is heated should have a value of less than about 2.
The copolymeric organopolysiloxanes of this invention are useful per se as tin-catalyzed or platinum-catalyzed curable encapsulating compositions. They have also ύeen. found to be useful as a reactive component in curable silicone compositions sucn as in silicone coating compositions comprising hydroxyl-containing silicone fluid polymers or vinyl-containing silicone fluid polymers.
The following examples are disclosed to further illustrate, but not limit, the present invention. All parts and percentages are by weight unless otherwise stated.
The non-volatile content, also denoted herein as N.V.C., of a material was determined by placing 1.50 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 150°C in an air-circulating oven. The heated sample was then cooled to room temperature and reweighed to determine the weight of the non-volatile material (w). N.V.C, in percent, is equal to 100 w/1. 50.
The acid number, also denoted herein as A.N., of a material was determined by titrating 1.00 grams of the material to a bromcresol purple endpoint, using alcoholic KOH, and is equal to the number of mg. of KOH so used.
The viscosity of a material was measured at 25°C with a Brookfield® viscometer Model RVF and the value obtained was converted from centipoise to pascal-seconds (Pa.s) for this disclosure by multiplying by 0.001.
The following components were used in the examples.
Resin A-l - A xylene solution of a resinous copolymeric siloxane, prepared from 45 parts of sodium silicate (41.6°Be) and 20 parts of (CH3)3SiCl according to the method of Daudt et al. noted aobve, containing (CH3) 3SiO1/2 siloxane units and SiO4/2 siloxane units of approximately 0.75/1.0 and having A. N. = 0. 80 , SiOHi = 2. 56%., SiH = 0% and N . V. C. = 70% . By extrapolation to 100% N.V.C. the resinous copolymeric siloxane itself had A.N. = 1.14, SiH = 0% and SiOH = 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. = 95%; a solid material.
Resin A-3 - Similar to, and prepared as, Resin A-l except having N.V.C. = 67.35%, A.N. = 0.64, SiH = 0.003% and SiOH - 1.91%. By extrapolation to 100% N.V.C. the resinous copolymeric siloxane had A.N. = 0,95, SiH = 0.004% and SiOH = 2.84%. Resmin A-4 - Similar to, and prepared as, Resin A-l except having N.V.C. = 68.7%, A.N. = 0.33, SiH = 0% and SiOH = 2.02%. By extrapolation to 100% N.V.C. the resinous copolymeric siloxane had A.N. = 0.48, SiH = 0% and SiOH = 2.94%.
Resin A-5 - Similar to, and prepared as. Resin A-l except having an N.V.C. = 67.6%, A.N. = 1.12 and a Turbidity Index = 12.4 (an indirect measurement of SiOH). By extrapolation to 100% N.V.C. the resinous copolymer siloxane had A.N. = 1.66.
Fluid B-1. - An prganohydrogenpolysiioxane liquid having the formula (CH3 ) 3SiO[ (CH3 SiO] 3- [(CH3)(H)SiO]5Si(CH3)3, N.V.C. = 100%, A.N. = 0.005, SiH = 0.74% and SiOH = 0.025%.
Fluid B-2 - An organohydrogenpolysiloxane liquid having the formula (CH3)3SiO[(CH3)(H)SiO]35- Si(CH3)3, N.V.C. = 100%, A.N. = 0.01, SiH = 1.96%, SiOH = 0% and a viscosity of 0.03 Pa.s.
Fluid B-3 - Same as Fluid B-2 except having A.N. = 0.02, SiOH = 0% and SiH = 1.71%.
Fiuid B-4 - Same as Fluid B-2 except having A.N. = 0.008, SiOH = 0.03% and SiH = 1.56%. Example 1
This example illustrates the preparation of a composition of this invention at atmospheric pressure.
Forty parts of Fluid B-3 and 85.7 parts of Resin A-1 (60 parts of resinous copolymeric siloxane and 25.7 parts of xylene) were mixed to form a homogeneous mixture having 5.3 silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical. The mixture was devolatilized at room temperature and atmospheric pressure to a N.V.C. = 97%. This devolatilized, but not heated, mixture had SiOH = 3.82%, SiH = 0.35%, A.N. = 0.19 and a viscosity of 900 Pa.s. The devolatilized mixture was neated at 150°C . for 2 hours in an air-circulatiny oven. The resulting liquid composition of this invention had SiOH - 0.48%, SiH = 0.56% and A.N. = 0.22. It was useful as a controlled release additive in a solventiess silicone coating composition.
When tnis example was repeated with solid Resin A-2 a small percentage of the resin could not be homogeneously mixed with Fluid B-3. When this
heterogeneous mixture having SiOH = 2.09%, SiH = 0.67%, A.N. = 0.08, N.V.C. = 97% and a viscosity of 38.5 Pa.s was neated, as above, a liquid composition having SiOH = 0.35%, SiH = 0.64% and A.N. = 0.08 was obtained which provided suostantially the same controlled adhesive, release for a solventiess silicone coating composition as the above solvent-prepared composition. Example 2
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 mixed to form a homogeneous mixture which was neated to 150°C at atmospheric pressure after which the pressure was reduced sufficiently to volatilize xylene and water. After water ceased to be evolved the mixture was heated at 15ϋ°C at a pressure of 2 Torr (267 Pa) to remove suostantially all of the remaining xylene. The copolymeric organopoiysiloxane of this invention had SiOH = 1.98%, SiH = 0.15%, A.N. = 9.35 and a viscosity of 250 Pa.s. It was useful as a controlled-release additive in a curable silicone paper-coating composition. Example 3
The preparation described in Example 2 was repeated except that 60 parts of Fluid B-3 and 57.1 parts of the Resin A-1 (40 parts of resinous copolymeric siloxane and 17.1 parts of xylene) were mixed to form a homogeneous mixture having 11.8 silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical. The resulting copolymeric organopoiysiloxane of this invention had SiOH = 0.87%, SiH = 0.91%, A.N. = 0.10 and a viscosity of 0.31 Pa-s. It was useful as a reinforcing component in a curable aqueous 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 27.3 parts of xylene) were mixed to form a homogeneous mixture having 7.6 silicon-bonded hydrogen radicals for every silicon-bonded hydroxyl radical. The resulting copolymeric organopoiysiloxane of this invention had SiOH = 0.30%, SiH = 0.50% and a viscosity of 71 Pa.s. It provided smooth adhesive release at high release force for a silicone paper-coating composition when mixed therewith. The gel-permeation chromatograms of the sole drawing in this disclosure were derived from this preparation. Example 5
The preparation descrioed in Example 2 was repeated except that 40 parts of Fluid B-1 and 89.1 parts of Resin A-3 (60 parts of resinous copolymeric
Aζ/* siloxane and 29.1 parts of xylene) were mixed to form a homogeneous mixture having 2.9 silicon-oonded hydrogen radicals for every silicon-oonded nydroxyl radical. The resulting copoiymeric organopoiysiloxane of this invention nad SiOH = 1.64%, SiH = 0.002%, A.N. = 0.95 and a viscosity of 77.5 Pa-s. It was useful as a controlled release additive for a platinum-catalyzed curable silicone paper coating composition for releasing agrressive acrylic adhesive. Example 6
The preparation described in Example 2 was repeated except that 600 parts of Fluid B-4 and 1331 parts of Resin A-5 (900 parts of resinous copolymeric siloxane and 431 parts of xylene) wer'e mixed to form a homogeneous mixture. During the heating of this mixture pressure was reduced at 98°C after 45 minutes of neating and was gradually reduced thereafter over a period of 85 minutes as the temperature was increased to 150°C. The resulting copolymeric organosiloxane of this invention had SiOH = 1.78%, SiH = 0.02%, A.N. = 1.4, N.V.C. = 98.8% and a viscosity of 354 Pa.s. It was useful as a strengthening component for a tin-aatalyzed curaole silicone moid coating for releasing molded poiyurethane foam articles.

Claims

Claims :
1. A method for preparing a liquid copolymeric organopoiysiloxane, 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 nydroxyl radicals and consisting essentially of R3SiO1/2 siloxane units and SiO4/2 siloxane units wnerein the ratio of tne number of said R3SiO1/2 siloxane units to the numoer of said SiO4/2 siloxane units has a value of from 0.6/1 to 0.9/1 and eacn 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 oryanonydrogenpoiysiloxane, and
(B) heating said homogeneous mixture to remove substantially all of said organic solvent therefrom.
2. A method according to claim 1 wherein the nomogeneous 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 hyorogen 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 claims 1, 2 or 3 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 4 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) SiO[(CH3)(H)SiO]bSi(CH3)3 wherein b has an average value of from 30 to 70.
7. A metnod according to claim 6 wherein tne nomogeneous 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 organopoiysiloxane prepared by the method of claims 1, 2, or 3.
9. A copolymeric organopoiysiloxane prepared by the metnod of claim 4, 5 or 6.
10. A copolymeric organopoiysiloxane prepared by the method of claim 7.
PCT/US1981/001458 1980-12-02 1981-10-28 Liquid copolymeric organopolysiloxanes comprising sio2 and method therefor WO1982001876A1 (en)

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Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4423095A (en) * 1983-01-28 1983-12-27 Dow Corning Corporation Silicone-organic coating compositions
CA1243434A (en) * 1983-01-28 1988-10-18 Leroy E. Thayer Siloxane-pva 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
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
US5026769A (en) * 1987-12-09 1991-06-25 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
JP4857109B2 (en) * 2003-07-23 2012-01-18 ダウ・コーニング・コーポレイション Mechanical inversion process for producing silicone-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
CN1893931B (en) * 2003-10-27 2011-07-20 陶氏康宁公司 Preparations for topical application and methods of delivering an active agent to a substrate
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
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
WO2012058798A1 (en) * 2010-11-02 2012-05-10 Henkel China Co. Ltd. Hydrosilicone resin and preparation process thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US3205283A (en) * 1965-09-07 Solventless liquid organopolysiloxane encapsulating compositions
US3627851A (en) * 1970-10-23 1971-12-14 Dow Corning Flexible coating composition
US3772247A (en) * 1971-07-30 1973-11-13 Ici Ltd Siloxanes
US3992426A (en) * 1973-08-22 1976-11-16 Union Carbide Corporation Quadripolymer siloxanes containing Si-H bonds

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
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
US3627851A (en) * 1970-10-23 1971-12-14 Dow Corning Flexible coating composition
US3772247A (en) * 1971-07-30 1973-11-13 Ici Ltd Siloxanes
US3992426A (en) * 1973-08-22 1976-11-16 Union Carbide Corporation Quadripolymer siloxanes containing Si-H bonds

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AU542158B2 (en) 1985-02-07
US4310678A (en) 1982-01-12
CA1167586A (en) 1984-05-15
JPS57501856A (en) 1982-10-14
JPS6317290B2 (en) 1988-04-13
MX160984A (en) 1990-06-29
EP0053472B1 (en) 1985-08-21
EP0053472A3 (en) 1982-09-08
BR8108899A (en) 1982-10-26
AU7805381A (en) 1982-06-17
EP0053472A2 (en) 1982-06-09
DE3171943D1 (en) 1985-09-26

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