Process of curing methylhydrosiloxanes

Abstract: A process of curing and cross-linking methylhydrosiloxanes by contacting and forming a mixture of an allyl amide with at least one methylhydrosiloxane in the presence of a Group VIII metal catalyst and heating the mixture of the allyl amide, the methylhydrosiloxane and the Group VIII metal catalyst, in the presence of ambient moisture until the methylhydrosiloxane becomes cured and cross-linked.

Description: This invention relates to a method of curing and cross-linking methylhydrosiloxanes and includes compositions and mixtures of methylhydrosiloxanes prepared in accordance with the method. The cross-linking of silicones to form higher molecular weight polymers has been used to prepare many useful silicone products. One example is the hydrolysis of reactive chloro, alkoxy and amino silanes to form various fluids, resins and elastomers through silanol condensation. Low molecular weight resinous silicones have been formulated with high viscosity silanol fluids to prepare pressure sensitive adhesives. These pressure sensitive adhesives have medical utility such as surgical dressings as well as various non-medical applications. The cross-linking reaction of vinyl endblocked silicone fluids of about one thousand centistoke viscosity with methyl/hydrogen silicones in the presence of a platinum catalyst provides "pseudo" interpenetrating network gels. These gels are used in applications ranging from breast implants to paper coatings. Condensation curing has been employed to prepare room temperature vulcanizing sealants and adhesives. The room temperature vulcanizing and curable silicones have been composed of cross-linkers with moisture sensitive groups on silicon and are typically catalyzed by tin, zinc, titanium, iron or carboxylate salt catalysts. High temperature vulcanizing cures involve a method in which a peroxide initiates cure of a silcon hydride and an olefin substituted silicone at elevated temperature. Such technology has found application in penile prosthesis, for example. Since one of the major cure reactions used in sealants is, for example, acetoxy hydrolysis or moisture curing, amongst others it has been unexpectedly discovered that the foregoing technology for converting a silicon hydride to a silicon ester could be applied in a new and novel manner for creating an "in situ" acetoxy cure. Thus, and in accordance with the concept of the present invention, the silicon hydrogens on a silicone are converted to acetoxy groups and exposed to air and the material cures and cross-links through silanols to form new siloxane bonds. European Patent Application 0 063 863 describes a process for stabilizing organosilicone compositions which comprise an ethylenically unsaturated polysiloxane and a polyhydrogensiloxane together with a metal hydrosilation catalyst and an unsaturated amide. In addition, European Patent Application 0 412 564 describes a process for curing and cross-linking methylhydrosiloxanes by forming or mixing an allyl ester with at least one methylsiloxane in the presence of a group VIII metal catalyst. This invention relates to a process of curing and cross-linking methylhydrosiloxanes comprising contacting and forming a mixture of an allyl amide with at least one methylhydrosiloxane in the presence of a Group VIII metal catalyst and heating the mixture of the allyl amide, the methylhydrosiloxane and the Group VIII metal catalyst, in the presence of ambient moisture until the methylhydrosiloxane becomes cured and cross-linked characterised in that said mixture further comprises at least one chemically inert polyorganosiloxane in addition to the methylhydrosiloxane, wherein when the methylhydrosiloxane is cured and cross-linked it entraps the chemically inert polyorganosiloxane. In the process, the mixture of the allyl amide, the methylhydrosiloxane, the chemically inert polyorganosiloxane and the Group VIII metal catalyst is heated at a temperature in excess of about 125°C. There may also be included in the mixture at least two methylhydrosiloxanes. The invention is also directed to a methylhydrosiloxane cured and cross-linked in accordance with the method as described above and wherein the cured and cross-linked methylhydrosiloxane is formed into the shape of a film. The methylhydrosiloxane film is coated on the surface of a substrate such as aluminum, paper, polyesters, polycarbonates and acrylics. As noted hereinabove, a film is employed as a coating for a substrate. The film is prepared in accordance with a process of curing and cross-linking methylhydrosiloxanes by contacting and forming a mixture of an allyl amide with at least one methylhydrosiloxane and at least one chemically inert polyorganosiloxane in the presence of a Group VIII metal catalyst; and heating the mixture of the allyl amide, the methylhydrosiloxane, the chemically inert polyorganosiloxane and the Group VIII metal catalyst, in the presence of ambient moisture until the methylhydrosiloxane becomes cured and cross-linked. For purposes of the present invention, the siloxanes which may be used are methylhydrosiloxanes among which are bis(trimethylsiloxy)dimethyldisiloxane, bis(trimethylsiloxy)methylsilane, diphenyldimethyl-disiloxane, diphenyltetrakis(dimethylsiloxy)disiloxane, heptamethyltrisiloxane, hexamethyltrisiloxane, methylhydrocyclosiloxanes, methyltris(dimethylsiloxy)silane, octamethyltetrasiloxane, pentamethylcyclopentasiloxane, pentamethyldisiloxane, phenyltris(dimethylsiloxy)silane, polymethylhydrosiloxane, tetrakis(dimethylsiloxy)silane, tetramethylcyclotetrasiloxane, tetramethyldisiloxane and methylhydrodimethylsiloxane copolymers. The preferred Group VIII metal catalyst is RhCl₃, although other appropriate catalyst systems may be employed such as ClRh(PPh₃)₃; H₂PtCl₆; a complex of 1,3-divinyl tetramethyl disiloxane and H₂PtCl₆; and alkyne complexes of H₂PtCl₆. A more exhaustive list of appropriate catalyst systems is set forth in U.S. Patent No. 4,746,750. The most effective concentration of the Group VIII metal catalyst has been found to be from about ten parts per million to about two thousand parts per million on a molar basis relative to the allyl ester. As used herein, the term chemically inert polyorganosiloxane is intended to denote a polymer of the formula wherein n is an integer between zero and three and m is two or more. The simplest silicone materials are the polydimethylsiloxanes. Polydimethylsiloxanes have the structure where x is an integer of from one to about one hundred thousand. The repeating unit of the polymer is the dimethylsiloxane unit. The terminal unit is the trimethylsiloxy group. At low molecular weights, silicones are fluids and at high molecular weights, they are gums which may be cross-linked to form elastomeric products. The methyl group in a silicone may be substituted by a variety of other substituents including, for example, phenyl or ethyl. Conventional silicones are the trimethylsiloxy terminated polydimethylsiloxanes. Such materials are available in viscosities ranging from 0.65 to 2,500,000 centistokes. Substituents on the silicon consist of methyl groups. Termination of the polymer chain prevents viscosity change and other alterations of the physical properties of the silicone polymeric materials. The polydimethylsiloxanes exhibit characteristic properties of low viscosity change with temperature; thermal stability; oxidative stability; chemical inertness; non-flammability; low surface tension; high compressibility; shear stability; and dielectric stability. The polydimethylsiloxane fluid used herein as the chemically inert polyorganosiloxane is a high molecular weight polymer having a viscosity in the range from about 20 to 2,000,000 mm²s⁻¹ (centistokes), preferably from about 500 to 50,000 mm²s⁻¹ (centistokes), more preferably about 50 mm²s⁻¹ (centistokes)at 25°C. The siloxane polymer is generally end-blocked with trimethylsilyl groups but other end-blocking groups are also suitable. The polymer can be prepared by various techniques such as the hydrolysis and subsequent condensation of dimethyldihalosilanes or by the cracking and subsequent condensation of dimethylcyclosiloxanes. For purposes of the present invention, the term "skinned over" is defined as curing to a solid film on top of a fluid that can be touched and which does not leave a visibly wet residue, which is not tacky, but which is not fully cured. "Cured" is defined as the formation of a solid film that does not leave a visibly wet residue when touched. "Cheesy" is defined as a cured solid that when rubbed has the texture of cheese. "Tacky" is defined as cured to a gelatinous texture that adheres to the fingers when touched. "Orange peel" is defined as cured to a clear undulant appearance. "Spongy" is defined as cured to a porous solid. Allyl amides are employed in the method of the present invention for curing and cross-linking methylhydrosiloxanes. The most preferred allyl amide is of the type illustrated by the following generic formula: wherein R is selected from the group consisting of hydrogen, alkyl radicals having one to eight carbon atoms and aryl radicals. A preferred allyl amide species of this type is, for example, N-allyl-N-methylacetamide of the above formula in which R is methyl. There may also be included in the mixture a filler in order to strengthen, toughen or otherwise reinforce the endproduct. Typical of the fillers which may be employed in the compositions of the present invention are, for example, carbon black, silica aerogels, silica soots, treated silicas, alumina, clays, metal oxides, metal carbonates and metal silicas. Specific filler materials may be ground quartz, reinforcing silicas, titanium dioxide, diatomaceous earth, iron oxide, fume silica, precipitated silica and silica xerogel. The mixture can further include other materials which have been found to be useful in order to strengthen, toughen or otherwise reinforce the endproduct. Such materials which have been found useful are various silicone gums, silanol functional silicones, silane treated silicates and curable silicone resin compositions. Exemplary of a silane treated silicate is trimethylchlorosilane treated sodium silicate referred to hereinafter and in the examples as TMC treated silicate. A preferred silanol functional silicone is a silanol functional polydimethylsiloxane having a viscosity of about ninety Centistokes measured at 25°C. and having the formula HOSiMe₂(OSiMe₂) x SiHe₂OH in which Me is methyl and x is an integer having a value of about thirty to forty. This silanol functional silicone is referred to in the examples as SFS fluid. The particular details of the silicone gums and the curable silicone resin compositions which may be employed in accordance with the present invention are set forth below. The polydiorganosiloxane gum most suitable for use in the present invention is a polydimethylsiloxane gum. The polydiorganosiloxane gum can be represented by an average unit formula where each R³ is a methyl radical, a vinyl radical, a phenyl radical, an ethyl radical or a 3,3,3-trifluoropropyl radical and a has an average value of 1.95 to 2.005 inclusive. Since the polydiorganosiloxane gums are essentially polydimethylsiloxane gums, at least 90 percent of the total R³ groups are methyl radicals and the remaining R₃ groups are vinyl, phenyl, ethyl or 3,3,3-trifluoropropyl. Small amounts of other groups can be present such as 1 or 2 percent of the total R₃, where such groups are other monovalent hydrocarbon groups, such as propyl, butyl, hexyl cyclohexyl, beta-phenylethyl or octadecyl; other halogenated monovalent hydrocarbon radicals, such as chloromethyl, bromophenyl, α,α,α-trifluorotolyl, perfluoroheptylethyl or dichlorophenyl; cyanoalkyl; alkoxyl, such as, methoxy, propoxy, ethoxy or hexoxy; ketoxime; halogen; hydroxyl; and acyloxy. The groups which are present in small amounts are considered as incidental and not producing any significant characteristic changes of the polydimethylsiloxane gum. The polydiorganosiloxane gums suitable for the present invention are essentially composed of dimethylsiloxane units with the other units being represented by monomethylsiloxane, trimethylsiloxane, methylvinylsiloxane, methylethylsiloxane, diethylsiloxane, methylphenylsiloxane, diphenylsiloxane, ethylphenylsiloxane, vinylethylsiloxane, phenylvinylsiloxane 3,3,3-trifluoropropylmethylsiloxane, dimethylphenylsiloxane, methylphenylvinylsiloxane, dimethylethylsiloxane, 3,3,3-trifluoropropyldimethylsiloxane, mono-3,3,3-trifluoropropylsiloxane, monophenylsiloxane or monovinylsiloxane. The polydiorganosiloxane gums are well known in the art and can be obtained commercially and have viscosities greater than 1,000,000 mm²s⁻¹ (cs). at 25°C., preferably greater than 5,000,000 mm²s⁻¹ (cs). at 25°C. The resinous composition of the present invention is disclosed in U.S. Patent No. 4,322,518, issued March 30, 1982. This curable silicone resin composition can be best described as a mixture of (i) a resinous polymeric siloxane containing silicon-bonded hydroxyl radicals and consisting essentially of R₃SiO 1/2 siloxane units and SiO 4/2 siloxane units wherein the ratio of the number of said R₃SiO 1/2 siloxane units to the number of said SiO 4/2 siloxane units has a value of from 0.6/l to 0.9/l and each R denotes, independently, a monovalent hydrocarbon radical, and (ii) an 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. Following are examples illustrating the process of the present invention in which an allyl amide is included in the mixture for curing and cross linking methylhydrosiloxanes. Tetrahydrofuran has been referred to as THF and polymethylhydrosiloxane has been referred to as PMHS. Comparison Example 1 A mixture was prepared including HSiMe₂O(SiMe₂O)₁₃SiMe₂H, a catalyst prepared by stirring 10 grams of RhCl₃·3H₂O in 1200 grams of THF (tetrahydrofuran) at room temperature for 12 hours. This catalyst was employed in the examples unless otherwise specified and N-allyl-N-methylacetamide solution and a curable silicone resin composition as defined above. A solution of N-allyl-N-methylacetamide and the RhCl₃/THF catalyst was prepared in a five dram vial by combining the allyl amide and the catalyst in a weight ratio of 1:0.2. This solution is referred to in the examples as the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture including the siloxane, the catalyst-allyl amide solution and the curable silicone resin were combined in the weight ratio of 1:0.2:1. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full, soft and flexible cure had been obtained. Comparison Example 2 A mixture was prepared including HSiMe₂O(SiMe₂O)₁₃SiMe₂H, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and TMC treated silicate as defined above. The ingredients of the mixture were combined in the weight ratio of 1:0.2:1. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a smooth and tacky cure had been obtained. Comparison Example 3 A mixture was prepared including HSiMe₂O(SiMe₂O)₁₃SiMe₂H and the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full, soft and flexible cure had been obtained. Comparison Example 4 A mixture was prepared including polymethylhydrosiloxane having a viscosity of about thirty centistokes measured at 25°C. hereinafter referred to as PMHS, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and a curable silicone resin composition as defined above. The ingredients of the mixture were combined in the weight ratio of 1:0.2:1. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full, soft and flexible cure had been obtained. Comparison Example 5 A mixture was prepared including PMHS, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and TMC treated silicate as defined above. The ingredients of the mixture were combined in the weight ratio of 1:0.2:1. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a hard and brittle cure had been obtained. Comparison Example 6 A mixture was prepared including PMHS, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and SFS fluid as defined above. The ingredients of the mixture were combined in the weight ratio of 1:0.2:1. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a soft and flexible cure had been obtained. Comparison Example 7 A mixture was prepared including PMHS, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and fumed silica. The ingredients of the mixture were combined in the weight ratio of 1:0.2:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full soft and grainy cure had been obtained. Comparison Example 8 A mixture was prepared including PMHS, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and porous preciptitated silica. The ingredients of the mixture were combined in the weight ratio of 1:0.2:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full soft and flexible cure had been obtained. Comparison Example 9 A mixture was prepared including HSiMe₂O(SiMe₂O)₁₃SiMe₂H, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and fumed silica. The ingredients of the mixture were combined in the weight ratio of 1:0.2:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full soft cure had been obtained. Comparison Example 10 A mixture was prepared including HSiMe₂O(SiMe₂O)₁₃SiMe₂H, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and porous precipitated silica. The ingredients of the mixture were combined in the weight ratio of 1:0.2:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full soft cure had been obtained. Comparison Example 11 A mixture was prepared including PMHS, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution and a silicone gum as defined above. The ingredients of the mixture were combined in the weight ratio of 1:0.2:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full cure had been obtained. Example 1 A mixture was prepared including PMHS, a polydimethylsiloxane fluid having a viscosity of fifty centistokes and the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.25:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a full soft, cheesy, nontacky and flexible cure had been obtained. The same mixture was also placed into a 113.4g (four ounce) vial and after thirty minutes in the oven, a solid brittle cure was obtained. Example 2 A mixture was prepared including HSiMe₂O(SiMe₂O)₁₃SiMe₂H, a polydimethylsiloxane fluid having a viscosity of fifty centistokes and the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.25:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for five minutes. At the end of this time, the pan was removed from the oven evidencing that a soft cure had been obtained. Comparison Example 12 A mixture was prepared including Me₃SiO(SiMe₂O)₂₇(SiMeHO)₃SiMe₃ and the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for ten minutes. At the end of this time, the pan was removed from the oven evidencing that a soft, cheesy and flexible cure had been obtained. Comparison Example 13 A mixture was prepared including Me₃SiO(SiMe₂O)₂₇(SiMeHO)₃SiMe₃, the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.2. Ten drops of the combined mixture was coated on various substrates including paper, glass and MYLAR. Each of the substrates including the mixture was placed in a 135°C. oven for ten minutes. At the end of this time, the substrates were removed from the oven evidencing that a cure had been obtained in each instance. The coating on all of the substrates was soft. The paper and glass substrate coatings were both smooth and shiny and showed good adhesion. The MYLAR coating was cheesy and flexible and showed good adhesion. Comparison Example 14 A mixture was prepared including PMHS and the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.2. Thirty drops of the combined mixture was coated on various substrates including polycarbonate, acrylic and paper. A thin coating was applied to each substrate with a number eight wire wound rod. Each coated substrate was placed in a 135°C. oven for five minutes. At the end of this time, the substrates were removed from the oven evidencing that a cure had been obtained in each instance. The coating on all of the substrates was smooth and shiny and showed good adhesion. Comparison Example 15 A mixture was prepared including PMHS, Me₃SiO(SiMe₂O)₂₇(SiMeHO)₃SiMe₃ and the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.5:0.2. Thirty drops of the combined mixture was coated in an aluminum weighing pan and the pan was placed in a 135°C. oven for ten minutes. At the end of this time, the pan was removed from the oven evidencing that a soft cure had been obtained. The same mixture was also placed into a 113.4g (four ounce) vial and after thirty minutes in the oven, a solid brittle cure was obtained. Comparison Example 16 A mixture was prepared including PMHS, Me₃SiO(SiMe₂O)₂₇(SiMeHO)₃SiMe₃ and the catalyst of Comparison Example 1 and N-allyl-N-methylacetamide solution. The ingredients of the mixture were combined in the weight ratio of 1:0.5:0.2. Ten drops of the combined mixture was coated on various substrates including polycarbonate, poly(ethylene terephthalate), paper and glass. A thin coating was applied to each substrate with a number eight wire wound rod. Each coated substrate was placed in a 135°C. oven for five minutes. At the end of this time, the substrates were removed from the oven evidencing that a cure had been obtained in each instance. The coating on all of the substrates except glass was soft, shiny and showed good adhesion. The following example illustrates a procedure for preparing the allyl amide N-allyl-N-methylacetamide employed in the foregoing procedures. Comparison Example 17 Four hundred-fifty milliliters of toluene was placed in a one liter three neck round bottom flask equipped with a stirring bar, condenser and addition funnel. The flask was heated and 14.7 grams of sodium was added to the flask and allowed to melt. A mixture including 47.2 grams of N-methylacetamide and twenty milliliters of toluene was added. Heat to the flask was discontinued and the contents were allowed to cool to room temperature. Seventy grams of allyl bromide mixed with 75 milliliters of toluene was added to the flask and stirred overnight. The flask contents was placed in a medium frit funnel containing filter aid and the filtrate was distilled in a one liter three neck round bottom flask equipped with a stirring bar, J-head distillation apparatus, thermometer and stopper. Forty-one grams of product was isolated and the product was identified as N-allyl-N-methylacetamide by gas chromatographic mass spectroscopy, nuclear magnetic resonance and infrared analysis. It has been found, that the use of an allyl amide instead of an allyl ester such as an allyl acetate, produces a more rapid cure than can be obtained with the allyl esters.

Claims: A process of curing and cross-linking methylhydrosiloxanes comprising contacting and forming a mixture of an allyl amide with at least one methylhydrosiloxane in the presence of a Group VIII metal catalyst and heating the mixture of the allyl amide, the methylhydrosiloxane and the Group VIII metal catalyst, in the presence of ambient moisture until the methyl-hydrosiloxane becomes cured and cross-linked characterised in that said mixture further comprises at least one chemically inert polyorganosiloxane in addition to the methylhydrosiloxane, wherein when methyl-hydrosiloxane is cured and cross-linked it entraps the chemically inert polyorganosiloxane. A process according to claim 1, in which the chemically inert polyorganosiloxane is a high molecular weight polymer having a viscosity of between 20 to 2,000,000, mm²s⁻¹ (centistokes) at 25°C. A process according to claim 1, in which the cured and cross-linked methylhydrosiloxane is formed into the shape of a film. The process according to claim 3, in which the film is coated on the surface of a substrate selected from aluminum, paper, polyesters, polycarbonates and acrylics. The process according to claim 1, in which the mixture includes a filler. The process according to claim 1, in which the mixture includes a material to strengthen, toughen or reinforce the cured and cross-linked methyl-hydrosiloxane, the material being selected from silicone gums, silanol functional silicones, silane treated silicates and curable silicone resin compositions.

Inventors: CAMPBELL WILLIAM HENRY, REVIS ANTHONY, CAMPBELL, WILLIAM HENRY, REVIS, ANTHONY
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1991
Main classification: C08L83
IPC codes: C08G77, C08J3, C08L83