CA1046198A - Method of preparing fire retardant siloxane foams and foams prepared therefrom - Google Patents
Method of preparing fire retardant siloxane foams and foams prepared therefromInfo
- Publication number
- CA1046198A CA1046198A CA234,761A CA234761A CA1046198A CA 1046198 A CA1046198 A CA 1046198A CA 234761 A CA234761 A CA 234761A CA 1046198 A CA1046198 A CA 1046198A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
-
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- 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
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/24—Flameproof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure Siloxane foams can be prepared by mixing an organohydrogensiloxane, a hydroxylated organsiloxane and a platinum catalyst in amounts such that the ratio of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals is from 2.5 to 40 and thereafter allowing the mixture to foam. The siloxane foams can be made to have an increased fire retardant property by adding 0.01 to 2 parts by weight carbon black based on the weight of the total composition. Siloxane foams are also prepared from mixing an organohydrogensiloxane, a hydroxylated organo-siloxane, a vinyl containing triorganosiloxy endblocked polydiorganosiloxane and a platinum catalyst. These foams can be used for cushioning, in acoustical applications and protective filling or coating applications and especially applications wherein fire retarding is important.
Description
This invention relates to fire retardant siloxane foams.
Slloxane foams are known to the art, however, these foams have not had an acceptance in commerce as has other types of foams, such as polyurethane foams. Such a slloxane foam is described by Leonard B. Bruner in U.S. Patent No. 3,070,555 in which he describes mixing a hydroxylated organopolysiloxane containing silicon-bonded hydrogen, a hydroxylated compound and a stannous salt of a hydrocarbon-soluble carboxylic acid and thereafter allowlng the mixture to foam to an elastic product.
Another siloxane foam is described by Siegfried Nitzsche et al. in U.S. Patent No. 3,338,847 in which a foam is prepared from a mixture of a linear hydroxyl endblock0d diorganosiloxane polymer, an organohydrogensilicon compound, an aliphatically unsaturated organohydroxy silicon compound and a metal salt of a monocarboxylic acid. Another foam is described by Harold-R. Hersh in --U.S. Patent No. 3,429,838 in which a siloxane foam is prepared by mixing a silicone rubber containing a linear, fluid methylpolysiloxane having terminal silicon-bonded --hydroxyl groups, diatomaceous earth, zinc oxide, calcined clay, polyethylsilicate and tin octoate with a silicone blowing agent which was a trimethylsilyl chain-stopped dimethylpolysiloxane fluid with some of the silicon-bonded ~-methyl groups replaced by silicon-bonded hydrogen atoms and stannous octoate catalyst.
Also known to the art are fire resistant and self-extinguishing siloxane foams. Ronald L. Joyce in U.S. Patent No. 2,956,032 describes a fire resistant -1- ~ :
~046~98 organosiloxane elastomer foam of the type described by the Bruner patent containing in addition a compound of ;~
nlckelous bromide, aromatic pentabromoethylbenzene or aromatic pentabromotoluene. Siegfried Nitzsche et al.
teach ln U.S. Patent No. 3,428,580 a self-extinguishing organopolyslloxane resin foam containing a resln organo-slloxane polymer having alkoxy and hydroxy functionality, a fluld organohydrogen slloxane polymer, a compound havlng non-acidic reactive hydroxyl groups and a catalyst of quaternary ammonium compounds and carboxylic acid salts of heavy metals.
Although foams can be prepared as described above, there is a problem in use over broad temperature ranges such as from room temperature up to 300C. and when flre retardant foams are made they often give off toxic vapor lngredlents when heated. Thus, a more useful elastomeric siloxane foam is desirable and one which is also non-toxic, particularly when it is fire retardant.
It is known that platinum provides fire retardant properties to gum based silicone rubbers as described in U.S. Patent No. 3,514,424 and from U.S. Patent No. 3,652,488 that certain silicone rubbers can be made fire retardant by using a combination of platinum and carbon black. From U.S. Patent No. 3,734,881, it is known that certain room temperature silicone elastomers, namely those containing acetoxy and ketoxime functionality, can be made self-extinguishing and non-toxic by using platinum and carbon black.
From the above prior art, siloxane foams have been prepared and fire retardant siloxane foams
Slloxane foams are known to the art, however, these foams have not had an acceptance in commerce as has other types of foams, such as polyurethane foams. Such a slloxane foam is described by Leonard B. Bruner in U.S. Patent No. 3,070,555 in which he describes mixing a hydroxylated organopolysiloxane containing silicon-bonded hydrogen, a hydroxylated compound and a stannous salt of a hydrocarbon-soluble carboxylic acid and thereafter allowlng the mixture to foam to an elastic product.
Another siloxane foam is described by Siegfried Nitzsche et al. in U.S. Patent No. 3,338,847 in which a foam is prepared from a mixture of a linear hydroxyl endblock0d diorganosiloxane polymer, an organohydrogensilicon compound, an aliphatically unsaturated organohydroxy silicon compound and a metal salt of a monocarboxylic acid. Another foam is described by Harold-R. Hersh in --U.S. Patent No. 3,429,838 in which a siloxane foam is prepared by mixing a silicone rubber containing a linear, fluid methylpolysiloxane having terminal silicon-bonded --hydroxyl groups, diatomaceous earth, zinc oxide, calcined clay, polyethylsilicate and tin octoate with a silicone blowing agent which was a trimethylsilyl chain-stopped dimethylpolysiloxane fluid with some of the silicon-bonded ~-methyl groups replaced by silicon-bonded hydrogen atoms and stannous octoate catalyst.
Also known to the art are fire resistant and self-extinguishing siloxane foams. Ronald L. Joyce in U.S. Patent No. 2,956,032 describes a fire resistant -1- ~ :
~046~98 organosiloxane elastomer foam of the type described by the Bruner patent containing in addition a compound of ;~
nlckelous bromide, aromatic pentabromoethylbenzene or aromatic pentabromotoluene. Siegfried Nitzsche et al.
teach ln U.S. Patent No. 3,428,580 a self-extinguishing organopolyslloxane resin foam containing a resln organo-slloxane polymer having alkoxy and hydroxy functionality, a fluld organohydrogen slloxane polymer, a compound havlng non-acidic reactive hydroxyl groups and a catalyst of quaternary ammonium compounds and carboxylic acid salts of heavy metals.
Although foams can be prepared as described above, there is a problem in use over broad temperature ranges such as from room temperature up to 300C. and when flre retardant foams are made they often give off toxic vapor lngredlents when heated. Thus, a more useful elastomeric siloxane foam is desirable and one which is also non-toxic, particularly when it is fire retardant.
It is known that platinum provides fire retardant properties to gum based silicone rubbers as described in U.S. Patent No. 3,514,424 and from U.S. Patent No. 3,652,488 that certain silicone rubbers can be made fire retardant by using a combination of platinum and carbon black. From U.S. Patent No. 3,734,881, it is known that certain room temperature silicone elastomers, namely those containing acetoxy and ketoxime functionality, can be made self-extinguishing and non-toxic by using platinum and carbon black.
From the above prior art, siloxane foams have been prepared and fire retardant siloxane foams
-2-have been prepared, however, it was not known heretofor that siloxane ~oams could be prepared using a platinum catalyst nor was it known that such foams would be both flre retardant and non-toxic and that increased fire retardancy would be obtained by using carbon black.
It was unexpected that a fire retardant foam could be obtained by using a platinum catalyst in that foams act as very thin section materials compared to the usual solid material and it is known that the same material in thinner section will burn more rapidly than a thicker section, thus foams are generally more combustible than solid materials and it is therefore unexpected that a siloxane foam would be made fire retardant without the conventional fire retardant additives.
It is an ob~ect of this invention to provide a method for making a siloxane foam using platinum catalysts and a fire retardant siloxane foam which is non-toxic.
This invention relates to a method of making an organosiloxane foam by mixing an organohydrogensiloxane, -a hydroxylated organosiloxane and a platinum catalyst and thereafter allowing a foam to form. These foams are particularly useful for applications of cushioning and sealing where fire retardancy is of importance.
This invention relates to a method of preparing an organosiloxane foam comprising mixing an organohydrogensiloxane having an average of at least three silicon-bonded hydrogen atoms per molecule, an average of no more than one silicon-bonded hydrogen atom per silicon atom and organic radicals selected from the ' group consisting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl, a hydroxylated organosiloxane having an average of from greater than 1.0 to 2.5 silicon-bonded hydroxyl radicals per molecule and having an average of at least one organic radical per silicon atom selected from the group conslsting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl and a platinum catalyst in an amount of from 5 to 200 parts by weight platinum per one million parts by weight total composition, said organohydrogensiloxane and said hydroxylated organo-siloxane being present in sufficient amounts to provide a molar ratio of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals of 2.5 to 40, where a mixture ls obtalned having a viscosity of less than 100,000 cs.
at 25C., thereafter allowing a foam to form.
The method of thls inventlon is to mix the lngredients and obtain a foam at room temperature. These ingredients can be mixed in any manner. Thus, the organo-hydrogensiloxane can be mixed with the platinum catalystand then mixed with the hydroxylated organosiloxane or the platinum catalyst can be mixed with the hydroxylated organosiloxane and then mixed with the organohydrogen-siloxane. Other methods of mixing are also suitable such as the hydroxylated organosiloxane can be divided into two proportions where one proportion is mixed with the platinum catalyst and the other proportion is mixed with the organohydrogensiloxane and then the two mixtures are combined to form a foam. Additionally, the various optional ingredients can be mixed with one or more of the 1(~46198 three required ingredients in any manner as long as a premature reaction does not take place before all three ingredlents are present in the mixture, For purposes of storage, the organohydrogenslloxane and the platinum catalyst should not be stored as a mlxture because gasing ~;
can occur, To control the foaming and curing reactions which are taking place simultaneously, a platinum catalyst inhibitor, such as polymethylvinylsiloxane cyclic compounds and acetylenic alcohols can be added. The platinum catalyst inhibitors are known in the art and many varieties are available. These inhibitors should however not interfere with the foaming and curing in such a manner that destroys the foam product of this lnventlon, The mixture of ingredients should be placed in the desired place where they are to be used as soon as they are mixed because foaming begins immediately, unless a platinum catalyst inhibitor is used to extend the pot life such that they can be mixed and then put in the desired place of use.
The amounts of inhibitors are present in relatively small amounts, such as up to 2 parts by weight polymethylvinyl-siloxane cyclics can be used to control the initiation of the foaming and curing. The polymethylvinylsiloxane cyclics are known in the art and can be prepared by hydrolyzing methylvinyldichlorosilane, for example.
This method can also be extended to include adding the mixture of organohydrogensiloxane, hydroxylated organosiloxane and platinum catalyst to other room temperature vulcanizing silicone elastomer compositions, such as those which contain a vinyl organopolysiloxane, an organohydrogensiloxane and a platinum catalyst wherein a useful foam is also obtained. The room temperature vulcanlzing sillcone elastomer can be mixed with the organohydrogensiloxane, or the platinum catalyst, or it can be mixed with both the organohydrogensiloxane and the platinum catalyst and then the hydroxylated organosiloxane can be added to the mixture. A convenient and preferred method is to add the organohydrogensiloxane last.
The organohydrogensiloxane can be any siloxane having an average of at least three silicon-bonded hydrogen atoms per molecule and an average of no more than one silicon-bonded hydrogen atom per silicon atom.
The remaining valences of the silicon atoms are satisfied by dlvalent oxygen atoms or by monovalent radlcals of alkyl havlng one to six carbon atoms per radical, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, cyclohexyl, or phenyl or 3,3,3-trifluoro-propyl. The organohydrogensiloxanes can be homopolymers, copolymers and mixtures thereof which contain siloxane units of the following types; RSiOl.5, R2SiO, R3SiOo., RHSiO, HSiOl.,, R2HSiOo.,, HzSiO, RH2SiOo., and SiO2, where R is the monovalent radical defined above. Some specific examples include polymethylhydrogensiloxane cyclics, copolymers of trimethylsiloxy and methylhydrogensiloxane, copolymers of dimethylhydrogensiloxy and methylhydrogen-siloxane, copolymers of trimethylsiloxy, dimethylsiloxane and methylhydrogensiloxane and copolymers of dimethyl-hydrogensiloxane, dimethylsiloxane and methylhydrogen-siloxane. Preferably, the organohydrogensiloxanes have an average of at least five silicon-bonded hydrogen atoms per molecule.
: .. , ,: . :
The hydroxylated or~anosiloxanes can be any organosiloxane mixture of organosiloxanes having an average of from greater than 1.0 to 2.5 silicon-bonded hyclroxyl radicals per molecule. The organic radicals can be any of those monovalent radicals described above for the organohydrogensiloxane. The hydroxylated organosiloxanes can be homopolymers, copolymers or mlxtures thereof. They can be mixtures of different molecular weight species and varying hydroxyl contents as long as the average falls within the defined range.
The hydroxylated organosiloxane contains at least one organic radical per silicon atom. Examples of the hydroxlyated organosiloxane include hydroxyl endblocked polydimethylsiloxane, hydroxyl endblocked polydiorgano-slloxane havlng slloxane unlts of dlmethylsiloxane and phenylmethylsiloxane, hydroxyl endblocked polymethyl-j 3,3,3-trlfluoropropylsiloxane and hydroxyl endblocked polyorganosiloxane having siloxane units of monomethyl-siloxane, dimethylsiloxane, monophenylsiloxane and diphenylsiloxane. The hydroxylated organosiloxanes of this invention also includes mixtures of hydroxylated organosiloxane polymers and hydroxylated organosilanes, such as a mixture of hydroxyl endblocked polydimethylsiloxane and diphenylmethylsilanol. As long as some hydroxylated organosiloxane polymer having two or more hydroxyl radicals per molecule is present, hydroxylated silanes can be used to provide from greater than 1.0 to 2.5 silicon-bonded hydroxyl radicals per moleculeO
Platinum catalyst can be any of the known forms, ranging from platinum as deposited on carriers , .~ .
10~6198 such as silica gel or powdered charcoa}, to platinic chlorlde, salts of platinum and chloroplatinic acid.
An~y of these forms will function in the instant curing system. A preferred form of platinum is the chloro-platinic acid either as the commonly obtainable hexahydrate or the anhydrous form, on account of lts easy dispersability in organosilicon systems and its non-effect on color of the mixture. Another preferred platinum catalyst is a chloroplatinic acid catalyst complex as prepared by the method described in U.S. Patent No. 3,419,593, where chloroplatinic acid hexahydrate is mixed with symetrical divinyltetramethyldisiloxane to provide the complex. Another ~ ~-similar complex is one prepared from the chloroplatinic acid hexahydrate, symetrical divinyltetramethyldisiloxane, symetrical tetramethyldlslloxane and alcohol solvent.
Additional platinum compounds which include, PtCl2[P(CH2CH2CH3)3]2, platinum bromides, a complex of platinous halide and an olefin such as ethylene, propylene, butylene, cyclohexene and styrene, Pt(CH3CN)2C12, [Pt(CH2CN)2(CH3)4]Cl2, Pt(NH3)2Cl2, K[PtCl3CH2CH2CHzOH], PtBr2(C2H4)2, K[PtBr3(C2H4)], PtC12(C2H4), (CH3)2C=CH2-PtC12, H2Pt(CN)4-5H2O, H[PtCl3(CH2CN)], Pt(NH3)2(CNS)2, PtCl2-PCl3, [Pt(NH3)4]-[PtCl4], PtC12[P(CH2CH3)3]2, PtC12-P(OH)3, PtCl2-P(OCH2CH3)3, PtCl2-[P(OCHzCH3)3]2, Pt(OOCH2SCH2CH3)2, Pt(CN)3, (CH3)4Pt, (CH3)3Pt-Pt(CH3)3, --O ~ .
(CH3)3Pt(CH2COCH=CCH3), PtC12CO and PtBr2CO.
The platinum catalyst can be present in amounts sufficient to provide from 5 to 200 parts by weight platinum per one million parts by weight total composition ~046198 (p.p.m.). Preferably, the platinum catalyst is present ln amounts to provide from 10 to 50 p.p.m. platinum.
Amounts of platinum catalyst which provide less than 5 p.p.m. platinum are insufflclent to cause a foam to form and amounts in excess of 200 p.p.m. platinum are uneconomical. For this invention the higher amoun~s of platinum catalyst should be used with a platinum catalyst lnhibitor because the rate of foaming and curing increases with increasing platinum concentration and if the rate becomes too fast, mixing the ingredients is a problem.
The amount of platinum should also be sufficient to provide fire retardant properties, either alone or in combination with carbon black.
The organohydrogensiloxane and hydroxylated -organosiloxane are comblned ln amounts sufficient enough to provlde a ratlo of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals of from 2.5 to 40, preferably from 4 to 10. Ratios of less than 2.5 provide foams, but these foams are too friablé and weak to be useful in the known applications. The same problem exists at the upper limit. Within the range of the molar ratio of silicon-bonded hydrogen to silicon-bonded hydroxyl, the foam density will decrease as the ratio increases where other factors are constant.
The molecular weight of any particular ingredient is not significant except that it is compatible or dispers-ible in the total combination and that the total combination has a viscosity of less than 100,000 centistokes (cs.) at 25C., preferably less than 25,000 cs. at 25C. Above 100,000 cs., the mixing of the ingredients becomes a .
problem The kind of mixing also influences the foam characterlstics, such as void size and density. Some mechanlcal mixing ls desirable to produce a foam hut extreme mixing should be avoided unless it ls predetermlned by actual testing that is it suitable. Because there are so many variables of mixing speeds, equipment types, shearing conditions and the like, it is not practical to define meaningful conditions. Additionally any set of conditions would vary as to suitability lf the nature and amounts of ingredlents were changed.
Other lngredients can be present and include, platinum catalyst inhibitors, such as polymethylvinylsiloxane cyclics and acetylenic inhibitors, for example 3-methyl-1-butyne-3-ol and others as described in U.S. Patent No.
It was unexpected that a fire retardant foam could be obtained by using a platinum catalyst in that foams act as very thin section materials compared to the usual solid material and it is known that the same material in thinner section will burn more rapidly than a thicker section, thus foams are generally more combustible than solid materials and it is therefore unexpected that a siloxane foam would be made fire retardant without the conventional fire retardant additives.
It is an ob~ect of this invention to provide a method for making a siloxane foam using platinum catalysts and a fire retardant siloxane foam which is non-toxic.
This invention relates to a method of making an organosiloxane foam by mixing an organohydrogensiloxane, -a hydroxylated organosiloxane and a platinum catalyst and thereafter allowing a foam to form. These foams are particularly useful for applications of cushioning and sealing where fire retardancy is of importance.
This invention relates to a method of preparing an organosiloxane foam comprising mixing an organohydrogensiloxane having an average of at least three silicon-bonded hydrogen atoms per molecule, an average of no more than one silicon-bonded hydrogen atom per silicon atom and organic radicals selected from the ' group consisting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl, a hydroxylated organosiloxane having an average of from greater than 1.0 to 2.5 silicon-bonded hydroxyl radicals per molecule and having an average of at least one organic radical per silicon atom selected from the group conslsting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl and a platinum catalyst in an amount of from 5 to 200 parts by weight platinum per one million parts by weight total composition, said organohydrogensiloxane and said hydroxylated organo-siloxane being present in sufficient amounts to provide a molar ratio of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals of 2.5 to 40, where a mixture ls obtalned having a viscosity of less than 100,000 cs.
at 25C., thereafter allowing a foam to form.
The method of thls inventlon is to mix the lngredients and obtain a foam at room temperature. These ingredients can be mixed in any manner. Thus, the organo-hydrogensiloxane can be mixed with the platinum catalystand then mixed with the hydroxylated organosiloxane or the platinum catalyst can be mixed with the hydroxylated organosiloxane and then mixed with the organohydrogen-siloxane. Other methods of mixing are also suitable such as the hydroxylated organosiloxane can be divided into two proportions where one proportion is mixed with the platinum catalyst and the other proportion is mixed with the organohydrogensiloxane and then the two mixtures are combined to form a foam. Additionally, the various optional ingredients can be mixed with one or more of the 1(~46198 three required ingredients in any manner as long as a premature reaction does not take place before all three ingredlents are present in the mixture, For purposes of storage, the organohydrogenslloxane and the platinum catalyst should not be stored as a mlxture because gasing ~;
can occur, To control the foaming and curing reactions which are taking place simultaneously, a platinum catalyst inhibitor, such as polymethylvinylsiloxane cyclic compounds and acetylenic alcohols can be added. The platinum catalyst inhibitors are known in the art and many varieties are available. These inhibitors should however not interfere with the foaming and curing in such a manner that destroys the foam product of this lnventlon, The mixture of ingredients should be placed in the desired place where they are to be used as soon as they are mixed because foaming begins immediately, unless a platinum catalyst inhibitor is used to extend the pot life such that they can be mixed and then put in the desired place of use.
The amounts of inhibitors are present in relatively small amounts, such as up to 2 parts by weight polymethylvinyl-siloxane cyclics can be used to control the initiation of the foaming and curing. The polymethylvinylsiloxane cyclics are known in the art and can be prepared by hydrolyzing methylvinyldichlorosilane, for example.
This method can also be extended to include adding the mixture of organohydrogensiloxane, hydroxylated organosiloxane and platinum catalyst to other room temperature vulcanizing silicone elastomer compositions, such as those which contain a vinyl organopolysiloxane, an organohydrogensiloxane and a platinum catalyst wherein a useful foam is also obtained. The room temperature vulcanlzing sillcone elastomer can be mixed with the organohydrogensiloxane, or the platinum catalyst, or it can be mixed with both the organohydrogensiloxane and the platinum catalyst and then the hydroxylated organosiloxane can be added to the mixture. A convenient and preferred method is to add the organohydrogensiloxane last.
The organohydrogensiloxane can be any siloxane having an average of at least three silicon-bonded hydrogen atoms per molecule and an average of no more than one silicon-bonded hydrogen atom per silicon atom.
The remaining valences of the silicon atoms are satisfied by dlvalent oxygen atoms or by monovalent radlcals of alkyl havlng one to six carbon atoms per radical, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, cyclohexyl, or phenyl or 3,3,3-trifluoro-propyl. The organohydrogensiloxanes can be homopolymers, copolymers and mixtures thereof which contain siloxane units of the following types; RSiOl.5, R2SiO, R3SiOo., RHSiO, HSiOl.,, R2HSiOo.,, HzSiO, RH2SiOo., and SiO2, where R is the monovalent radical defined above. Some specific examples include polymethylhydrogensiloxane cyclics, copolymers of trimethylsiloxy and methylhydrogensiloxane, copolymers of dimethylhydrogensiloxy and methylhydrogen-siloxane, copolymers of trimethylsiloxy, dimethylsiloxane and methylhydrogensiloxane and copolymers of dimethyl-hydrogensiloxane, dimethylsiloxane and methylhydrogen-siloxane. Preferably, the organohydrogensiloxanes have an average of at least five silicon-bonded hydrogen atoms per molecule.
: .. , ,: . :
The hydroxylated or~anosiloxanes can be any organosiloxane mixture of organosiloxanes having an average of from greater than 1.0 to 2.5 silicon-bonded hyclroxyl radicals per molecule. The organic radicals can be any of those monovalent radicals described above for the organohydrogensiloxane. The hydroxylated organosiloxanes can be homopolymers, copolymers or mlxtures thereof. They can be mixtures of different molecular weight species and varying hydroxyl contents as long as the average falls within the defined range.
The hydroxylated organosiloxane contains at least one organic radical per silicon atom. Examples of the hydroxlyated organosiloxane include hydroxyl endblocked polydimethylsiloxane, hydroxyl endblocked polydiorgano-slloxane havlng slloxane unlts of dlmethylsiloxane and phenylmethylsiloxane, hydroxyl endblocked polymethyl-j 3,3,3-trlfluoropropylsiloxane and hydroxyl endblocked polyorganosiloxane having siloxane units of monomethyl-siloxane, dimethylsiloxane, monophenylsiloxane and diphenylsiloxane. The hydroxylated organosiloxanes of this invention also includes mixtures of hydroxylated organosiloxane polymers and hydroxylated organosilanes, such as a mixture of hydroxyl endblocked polydimethylsiloxane and diphenylmethylsilanol. As long as some hydroxylated organosiloxane polymer having two or more hydroxyl radicals per molecule is present, hydroxylated silanes can be used to provide from greater than 1.0 to 2.5 silicon-bonded hydroxyl radicals per moleculeO
Platinum catalyst can be any of the known forms, ranging from platinum as deposited on carriers , .~ .
10~6198 such as silica gel or powdered charcoa}, to platinic chlorlde, salts of platinum and chloroplatinic acid.
An~y of these forms will function in the instant curing system. A preferred form of platinum is the chloro-platinic acid either as the commonly obtainable hexahydrate or the anhydrous form, on account of lts easy dispersability in organosilicon systems and its non-effect on color of the mixture. Another preferred platinum catalyst is a chloroplatinic acid catalyst complex as prepared by the method described in U.S. Patent No. 3,419,593, where chloroplatinic acid hexahydrate is mixed with symetrical divinyltetramethyldisiloxane to provide the complex. Another ~ ~-similar complex is one prepared from the chloroplatinic acid hexahydrate, symetrical divinyltetramethyldisiloxane, symetrical tetramethyldlslloxane and alcohol solvent.
Additional platinum compounds which include, PtCl2[P(CH2CH2CH3)3]2, platinum bromides, a complex of platinous halide and an olefin such as ethylene, propylene, butylene, cyclohexene and styrene, Pt(CH3CN)2C12, [Pt(CH2CN)2(CH3)4]Cl2, Pt(NH3)2Cl2, K[PtCl3CH2CH2CHzOH], PtBr2(C2H4)2, K[PtBr3(C2H4)], PtC12(C2H4), (CH3)2C=CH2-PtC12, H2Pt(CN)4-5H2O, H[PtCl3(CH2CN)], Pt(NH3)2(CNS)2, PtCl2-PCl3, [Pt(NH3)4]-[PtCl4], PtC12[P(CH2CH3)3]2, PtC12-P(OH)3, PtCl2-P(OCH2CH3)3, PtCl2-[P(OCHzCH3)3]2, Pt(OOCH2SCH2CH3)2, Pt(CN)3, (CH3)4Pt, (CH3)3Pt-Pt(CH3)3, --O ~ .
(CH3)3Pt(CH2COCH=CCH3), PtC12CO and PtBr2CO.
The platinum catalyst can be present in amounts sufficient to provide from 5 to 200 parts by weight platinum per one million parts by weight total composition ~046198 (p.p.m.). Preferably, the platinum catalyst is present ln amounts to provide from 10 to 50 p.p.m. platinum.
Amounts of platinum catalyst which provide less than 5 p.p.m. platinum are insufflclent to cause a foam to form and amounts in excess of 200 p.p.m. platinum are uneconomical. For this invention the higher amoun~s of platinum catalyst should be used with a platinum catalyst lnhibitor because the rate of foaming and curing increases with increasing platinum concentration and if the rate becomes too fast, mixing the ingredients is a problem.
The amount of platinum should also be sufficient to provide fire retardant properties, either alone or in combination with carbon black.
The organohydrogensiloxane and hydroxylated -organosiloxane are comblned ln amounts sufficient enough to provlde a ratlo of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals of from 2.5 to 40, preferably from 4 to 10. Ratios of less than 2.5 provide foams, but these foams are too friablé and weak to be useful in the known applications. The same problem exists at the upper limit. Within the range of the molar ratio of silicon-bonded hydrogen to silicon-bonded hydroxyl, the foam density will decrease as the ratio increases where other factors are constant.
The molecular weight of any particular ingredient is not significant except that it is compatible or dispers-ible in the total combination and that the total combination has a viscosity of less than 100,000 centistokes (cs.) at 25C., preferably less than 25,000 cs. at 25C. Above 100,000 cs., the mixing of the ingredients becomes a .
problem The kind of mixing also influences the foam characterlstics, such as void size and density. Some mechanlcal mixing ls desirable to produce a foam hut extreme mixing should be avoided unless it ls predetermlned by actual testing that is it suitable. Because there are so many variables of mixing speeds, equipment types, shearing conditions and the like, it is not practical to define meaningful conditions. Additionally any set of conditions would vary as to suitability lf the nature and amounts of ingredlents were changed.
Other lngredients can be present and include, platinum catalyst inhibitors, such as polymethylvinylsiloxane cyclics and acetylenic inhibitors, for example 3-methyl-1-butyne-3-ol and others as described in U.S. Patent No.
3,445,420, which shows acetylenic compounds and are used to extend the pot life before foaming occurs.
Benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxanes having an average of about two vinyl radicals per molecule can also be added in amounts up to 85 weight percent based on the combined weight of the vinyl containing triorganosiloxy endblocked polydiorganosiloxane and the hydroxylated organosiloxane.
These vinyl containing polydiorganosiloxanes can be mixtures or single specie types and can have organic radicals as defined for the organohydrogensiloxane above plus vinyl. Examples of these types of polymer are widely shown in the prior art such as in U.S. Patent No.
3,445,420 and U.S. Patent No. 3,453,234, which show vinyl containing triorganosiloxy endblocked polydiorganosiloxanes.
The vinyl containing triorganosiloxy endblocked polydiorgano-10~6198 siloxanes are preferably present in amounts of 50 weight percent or less, based on the combined weight of the vinyl containlng triorganosiloxy endblocked polydiorganoslloxane and the hydroxylated organosiloxane. Although useful foams can be prepared using between 50 and 85 weight percent vinyl containlng siloxane, better foams are obtained with mixtures having less than 50 weight percent vinyl containing siloxanes.
The addition of the benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxanes, whether added as such or added as part of a room temperature vulcanizing silicone elastomer composition can be used to increase the strength of the foam product. When these vinyl siloxanes are present in the mixture, the molar ratlo of silicon-bonded hydrogen to silicon-bonded hydroxyl can be varied over a range of from 0.5 to 40. It is not fully understood why this ratio can be varied more broadly with these ingredients, however, the reactions are apparently complex in such mixtures and have not been fully studied.
Fillers can also be added to the present mixtures which are used in the method of making foams, such as fume silica, diatomaceous earth, zinc oxide, calcium carbonate, crushed quartz, and the like. The maximum amounts of fillers used will be dependent upon the final viscosity of the composition.
The foams of the present invention have fire retardant properties, as prepared, but for many applications it is desirable to increase this property to give added protection and broaden its areas of use. The fire retardant properties of the foams can be increased without adding ingredients which can give off toxic vapors when burned or in contact Wit~l fire. By adding, to the ingredients to be mixed to make a foam, from 0.01 to 2 parts by weight carbon black based on the total weight of the composition, preferably from 0.05 to 1 parts by weight, the fire retardant property of the foam is increased. When the carbon black is used, the foams are self-extinguishing in short times and do not give off toxic fumes nor do they contain toxic ingredients.
The method of this invention provides a fire ;
retardant siloxane foam which is obtained at room temperature. The ingredients are mixed and then the resulting mixture foams and cures at the same time. The use of the inhibitors permits a level of control of the pot life or working time before foaming begins. The amount of platinum also permits some control of the pot life. The control of pot life is important to allow one to mix the ingredients in a container other than the place where the foam is to be used. Under some circumstances, the mixture does not immediately foam because the combination has a long pot life, as in cases where there is inhibitors present and where the molar ratio of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals is low and a benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxane is present. Where one -~
wishes to hasten the foam or foam on demand, mild heating will accelerate the foaming process.
The foams prepared as described herein are fire retardant and self-extinguishing and are useful for pads, cushions, pillows, ablative pads, fire retardant cushioning of electronic components, fire retardant walls, fire retardant seals, non-burning uses in areas where persons are confined such as buses, trains, airplanes, and the like.
These foams can be varied in density from 0.10 to 0.80 grams per cubic centimeter. These densitles can be changed by varying the ratio of silicon-bonded hydrogen to silicon-bonded hydroxyl as well as the filler loadings.
The above densities are suggested for conventional types of fillers, however, it may be possible to obtain densities outside this range by using certain non-conventional or exotic fillers.
The following examples are presented for illustrative purposes only and should not be construed as limiting the present invention which is properly delineated in the claims.
Example 1 , A siloxane foam was prepared by hand mixing at room temperature 50 parts by weight of a phenylmethyl-vinylsiloxy endblocked polydimethylsiloxane having a viscosity of 12,500 cs. at 25C., 10 parts by weight of a trimethylsiloxy endblocked polymethylhydrogensiloxane having about 1.5 weight percent silicon-bonded hydrogen atoms, 10 parts by weight of a hydroxyl endblocked polydimethylsiloxane having about 4 weight percent silicon-bonded hydroxyl radicals and 46 parts by weight platinum in the form of a chloroplatinic acid catalyst complex with symetrical divinyltetramethyldisiloxane containing about 0.65 weight percent platinum. The polymethylhydrogensiloxane was the last ingredient added to the mixture. The resulting mixture had a ... , ~ , , .
-1046~98 molar ratio of silicon-bonded ~Iydrogen atoms (SiH) to sllicon-bonded hydroxyl radicals (SiOH) of about 6.4 and began foaming almost before the mlxing was completed.
The resulting product was a cured, dry elastomeric foam.
The above procedure was followed except one part by weight of polymethylvinylsiloxane cyclics was added to the polymethylhydrogensiloxane which was then added to the other ingredients. The foaming and curing reactions were retarded for approximately 10 minutes after which time the mixture foamed and cured rapidly to a dry, elastomeric foam similar to the foam obtained without the polymethylvinylsiloxane cyclics.
Example 2 A siloxane foam was prepared by hand mixing 50 parts by weight of a phenylmethylvinylsiloxy endblocked polydimethylsiloxane having a viscosity of 12,500 cs. at 25C., 6 parts by weight of a phenylmethyl-vinylsiloxy endblocked polydimethylsiloxane having a viscosity of about 2,000 cs. at 25C., 10 parts by weight hydroxyl endblocked polydimethylsiloxane having about
Benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxanes having an average of about two vinyl radicals per molecule can also be added in amounts up to 85 weight percent based on the combined weight of the vinyl containing triorganosiloxy endblocked polydiorganosiloxane and the hydroxylated organosiloxane.
These vinyl containing polydiorganosiloxanes can be mixtures or single specie types and can have organic radicals as defined for the organohydrogensiloxane above plus vinyl. Examples of these types of polymer are widely shown in the prior art such as in U.S. Patent No.
3,445,420 and U.S. Patent No. 3,453,234, which show vinyl containing triorganosiloxy endblocked polydiorganosiloxanes.
The vinyl containing triorganosiloxy endblocked polydiorgano-10~6198 siloxanes are preferably present in amounts of 50 weight percent or less, based on the combined weight of the vinyl containlng triorganosiloxy endblocked polydiorganoslloxane and the hydroxylated organosiloxane. Although useful foams can be prepared using between 50 and 85 weight percent vinyl containlng siloxane, better foams are obtained with mixtures having less than 50 weight percent vinyl containing siloxanes.
The addition of the benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxanes, whether added as such or added as part of a room temperature vulcanizing silicone elastomer composition can be used to increase the strength of the foam product. When these vinyl siloxanes are present in the mixture, the molar ratlo of silicon-bonded hydrogen to silicon-bonded hydroxyl can be varied over a range of from 0.5 to 40. It is not fully understood why this ratio can be varied more broadly with these ingredients, however, the reactions are apparently complex in such mixtures and have not been fully studied.
Fillers can also be added to the present mixtures which are used in the method of making foams, such as fume silica, diatomaceous earth, zinc oxide, calcium carbonate, crushed quartz, and the like. The maximum amounts of fillers used will be dependent upon the final viscosity of the composition.
The foams of the present invention have fire retardant properties, as prepared, but for many applications it is desirable to increase this property to give added protection and broaden its areas of use. The fire retardant properties of the foams can be increased without adding ingredients which can give off toxic vapors when burned or in contact Wit~l fire. By adding, to the ingredients to be mixed to make a foam, from 0.01 to 2 parts by weight carbon black based on the total weight of the composition, preferably from 0.05 to 1 parts by weight, the fire retardant property of the foam is increased. When the carbon black is used, the foams are self-extinguishing in short times and do not give off toxic fumes nor do they contain toxic ingredients.
The method of this invention provides a fire ;
retardant siloxane foam which is obtained at room temperature. The ingredients are mixed and then the resulting mixture foams and cures at the same time. The use of the inhibitors permits a level of control of the pot life or working time before foaming begins. The amount of platinum also permits some control of the pot life. The control of pot life is important to allow one to mix the ingredients in a container other than the place where the foam is to be used. Under some circumstances, the mixture does not immediately foam because the combination has a long pot life, as in cases where there is inhibitors present and where the molar ratio of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals is low and a benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxane is present. Where one -~
wishes to hasten the foam or foam on demand, mild heating will accelerate the foaming process.
The foams prepared as described herein are fire retardant and self-extinguishing and are useful for pads, cushions, pillows, ablative pads, fire retardant cushioning of electronic components, fire retardant walls, fire retardant seals, non-burning uses in areas where persons are confined such as buses, trains, airplanes, and the like.
These foams can be varied in density from 0.10 to 0.80 grams per cubic centimeter. These densitles can be changed by varying the ratio of silicon-bonded hydrogen to silicon-bonded hydroxyl as well as the filler loadings.
The above densities are suggested for conventional types of fillers, however, it may be possible to obtain densities outside this range by using certain non-conventional or exotic fillers.
The following examples are presented for illustrative purposes only and should not be construed as limiting the present invention which is properly delineated in the claims.
Example 1 , A siloxane foam was prepared by hand mixing at room temperature 50 parts by weight of a phenylmethyl-vinylsiloxy endblocked polydimethylsiloxane having a viscosity of 12,500 cs. at 25C., 10 parts by weight of a trimethylsiloxy endblocked polymethylhydrogensiloxane having about 1.5 weight percent silicon-bonded hydrogen atoms, 10 parts by weight of a hydroxyl endblocked polydimethylsiloxane having about 4 weight percent silicon-bonded hydroxyl radicals and 46 parts by weight platinum in the form of a chloroplatinic acid catalyst complex with symetrical divinyltetramethyldisiloxane containing about 0.65 weight percent platinum. The polymethylhydrogensiloxane was the last ingredient added to the mixture. The resulting mixture had a ... , ~ , , .
-1046~98 molar ratio of silicon-bonded ~Iydrogen atoms (SiH) to sllicon-bonded hydroxyl radicals (SiOH) of about 6.4 and began foaming almost before the mlxing was completed.
The resulting product was a cured, dry elastomeric foam.
The above procedure was followed except one part by weight of polymethylvinylsiloxane cyclics was added to the polymethylhydrogensiloxane which was then added to the other ingredients. The foaming and curing reactions were retarded for approximately 10 minutes after which time the mixture foamed and cured rapidly to a dry, elastomeric foam similar to the foam obtained without the polymethylvinylsiloxane cyclics.
Example 2 A siloxane foam was prepared by hand mixing 50 parts by weight of a phenylmethylvinylsiloxy endblocked polydimethylsiloxane having a viscosity of 12,500 cs. at 25C., 6 parts by weight of a phenylmethyl-vinylsiloxy endblocked polydimethylsiloxane having a viscosity of about 2,000 cs. at 25C., 10 parts by weight hydroxyl endblocked polydimethylsiloxane having about
4 weight percent SiOH, 10 parts by weight of trimethylsiloxy endblocked polymethylhydrogensiloxane having about 1.5 weight percent SiH, 1 part by weight of zinc oxide, 0.5 part by weight carbon black, 0.5 part by weight poly-methylvinylsiloxane cyclics and 41 p.p.m. platinum in the form defined in Example 1. A mixture of the polymethyl-hydrogensiloxane and the polymethylvinylsiloxane cyclics was the last ingredient added to the mixture. The resulting product was a cured, elastomeric foam which did not burn when an attempt was made to ignite it. The foams of Example 1 in comparison could be ignited.
.. . . ..
_ample 3 Siloxane foams were prepared by mixing at room temperature the ingredients described in Tables 1 and 2. The combination of the ingredients of this example began to foam and cure from 25 to 60 seconds after the polymethylhydrogensiloxane was added. The ingredients were all comblned in each case except a mixture of the polymethylhydrogensiloxane and the polymethylvinylsiloxane cyclics was added last. In Tables 1 and 2, "Polymer A " refers to a hydroxyl endblocked polydimethylsiloxane having a viscosity of 12,500 cs. at 25C., "Polymer B " refers to a hydroxyl endblocked polydimethylsiloxane having about 4 weight percent SiOH, " Polymer C " refers to a phenylmethylvlnylsiloxy endblocked polydimethylsiloxane having a viscosity of about 400 cs. at 25C., " Polymer D'' refers to a trimethylsiloxy endblocked polymethylhydrogen-siloxane having about 1.5 weight percent SiH and "Cyclics " ~ -refers to polymethylvinylsiloxane cyclics. The p.p.m. of platinum was added in the form as described in Example 1.
The wt.% in Tables 1 and 2 are weight percentages based on the total weight of the composition. Elastomeric siloxane foams were obtained in all combinations defined in Tables 1 and 2. The foam prepared with the ingredients defined in Table 2, Ref. No. 1 did not rise as much as did the foam obtained with the ingredients defined in Table 2, Ref. No. 2. The foams obtained as defined by Table 2, Ref. No. 3 and Ref. No. 4 had densities of 0.32 grams per cubic centimeter and o.67 grams per cubic centimeter, respectively. Foams were also made using : . . . . ..
~046198 ~
calcium carbonate. The foams obtained ln accordance with both Table 1 and Table 2 were self-extinguishing.
The fire retardancy was determlned in accordance with the procedure set forth by Underwriters' Laboratories, Inc. "The Standard For Tests For Flammability Of Plastic Materials For Parts In Devices And Appliances, UL 94, First Edition, Second Impression, Dated June 1, 1973"
SE-l Foam classification. The results for the foam obtained with ingredients defined by Table 1, Ref. No. 1, after a 60 second flame exposure, the test specimen ;
extinguished in less than 2 seconds and had a burn distance of less than 1.27 cm. (0.5 in.).
The ingredients as defined by Table 1 Ref. No. 1 were combined as descrlbed above except the ~
polymethylvinylsiloxane cyclics were replaced by -50 p.p.m. 3-methyl-1-butyne-3-ol. The foaming and curing began approximately 120 seconds after the polymethylhydrogensiloxane was added.
Several samples of the foam product prepared from the ingredients defined by Table 1, Ref. No. 1 were tested and found to have a density of 0.16 to 0.27 grams per cubic centimeter, an average of 30 pores per linear inch, 85 to 95 percent closed cells, a tensile strength of about 6 p.s.i. and a compression deflection of about 1.5 p.s.i. at 25 percent compression where both tensile strength and compression deflection were determined by ASTM-D1564-59T and the acoustics were determined by ASTM C423 where the noise reduction coefficient was 47Ø
~046198 ExamPle 4 (A) A mixture was prepared by blending 11.4 parts by weight of Polymer C as defined ln Example 3, 11.4 parts by weight of five micron quartz, 1.42 parts by weight of a phenylmethylvinylsiloxy endblocked polydimethylsiloxane having a viscosity of about 2000 cs.
at 25C., 0.24 parts by weight zinc oxide, 0.12 parts ~
by weight carbon black and a platinum catalyst as defined ~ -in Example 1 in an amount sufficient to provide 130 p.p.m.
platinum.
(B) A mixture was prepared by blending 11.6 parts by weight of Polymer C, 11.6 parts by weight of five micron quartz, 1.3 parts by weight of a trimethyl- -siloxy endblocked polyorganosiloxane having an average of 5 methylhydrogensiloxane units and 3 dimethylsiloxane units and 0.5 part by weight of polymethylvinylsiloxane cycllcs.
(C) A blend of 25 parts by weight of mixture (A) and 25 parts by weight of mixture (B), 10 parts by weight of Polymer B as defined in Example 3, 70 parts by weight of diphenylmethylsilanol and 10 parts by weight of Polymer D as defined in Example 3 was prepared by mixing at room temperature which cured to an elastomeric foam with an increase in volume compared to the unfoamed mixture of about 50 percent. This foam had fire retardant properties and had greater than 90 percent closed cells.
The blend of (C) had a molar ratio of SiH to SiOH of about 0.5, had 23 p.p.m. platinum and about 0.08 weight percent carbon black.
- i 10~6i9~
(D) A blend of 24 parts by weight of mixture (A) and 25 parts by weight of mixture (B), 5 parts by weight of dlphenylmethylsilanol, 5 parts by weight of Polymer B and 30 parts by welght Gf Polymer D was prepared ~' by mlxlng at room temperature whlch cured to an elastomerlc foam with an expanslon of about 100 percent. This foam had flre retardant propertles, had a density of about 0.13 grams per cubic centimeter and had greater than 90 ~ , -percent closed cells. The blend of (D) had a molar ratio ~ ~ ~
of SlH to SlOH of about 13, had 36 p.p.m. platinum and ; -about 0.13 weight percent carbon black. ~ -~
Example 5 A siloxane foam was prepared by mixing at room temperature 25 parts by weight of a hydroxyl endblocked polydimethylslloxane having a vlsco~lty of about 4000 cs.
at 25C., 25 parts by welght calclum carbonate, 10 parts by welght of Polymer B, 10 parts by weight of diphenyl-methylsilanol, 32 p.p.m. platinum in the form of the platinum catalyst as defined in Example 1 and thereafter mixing therewith a mixture of 30 parts by weight of Polymer D and 0.5 parts by weight of polymethylvinyl-siloxane cyclics. The resulting mixture had a molar ratio of SiH to SiOH of about 6. An elastomeric foam which had fire retardant properties, was obtained.
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_ample 3 Siloxane foams were prepared by mixing at room temperature the ingredients described in Tables 1 and 2. The combination of the ingredients of this example began to foam and cure from 25 to 60 seconds after the polymethylhydrogensiloxane was added. The ingredients were all comblned in each case except a mixture of the polymethylhydrogensiloxane and the polymethylvinylsiloxane cyclics was added last. In Tables 1 and 2, "Polymer A " refers to a hydroxyl endblocked polydimethylsiloxane having a viscosity of 12,500 cs. at 25C., "Polymer B " refers to a hydroxyl endblocked polydimethylsiloxane having about 4 weight percent SiOH, " Polymer C " refers to a phenylmethylvlnylsiloxy endblocked polydimethylsiloxane having a viscosity of about 400 cs. at 25C., " Polymer D'' refers to a trimethylsiloxy endblocked polymethylhydrogen-siloxane having about 1.5 weight percent SiH and "Cyclics " ~ -refers to polymethylvinylsiloxane cyclics. The p.p.m. of platinum was added in the form as described in Example 1.
The wt.% in Tables 1 and 2 are weight percentages based on the total weight of the composition. Elastomeric siloxane foams were obtained in all combinations defined in Tables 1 and 2. The foam prepared with the ingredients defined in Table 2, Ref. No. 1 did not rise as much as did the foam obtained with the ingredients defined in Table 2, Ref. No. 2. The foams obtained as defined by Table 2, Ref. No. 3 and Ref. No. 4 had densities of 0.32 grams per cubic centimeter and o.67 grams per cubic centimeter, respectively. Foams were also made using : . . . . ..
~046198 ~
calcium carbonate. The foams obtained ln accordance with both Table 1 and Table 2 were self-extinguishing.
The fire retardancy was determlned in accordance with the procedure set forth by Underwriters' Laboratories, Inc. "The Standard For Tests For Flammability Of Plastic Materials For Parts In Devices And Appliances, UL 94, First Edition, Second Impression, Dated June 1, 1973"
SE-l Foam classification. The results for the foam obtained with ingredients defined by Table 1, Ref. No. 1, after a 60 second flame exposure, the test specimen ;
extinguished in less than 2 seconds and had a burn distance of less than 1.27 cm. (0.5 in.).
The ingredients as defined by Table 1 Ref. No. 1 were combined as descrlbed above except the ~
polymethylvinylsiloxane cyclics were replaced by -50 p.p.m. 3-methyl-1-butyne-3-ol. The foaming and curing began approximately 120 seconds after the polymethylhydrogensiloxane was added.
Several samples of the foam product prepared from the ingredients defined by Table 1, Ref. No. 1 were tested and found to have a density of 0.16 to 0.27 grams per cubic centimeter, an average of 30 pores per linear inch, 85 to 95 percent closed cells, a tensile strength of about 6 p.s.i. and a compression deflection of about 1.5 p.s.i. at 25 percent compression where both tensile strength and compression deflection were determined by ASTM-D1564-59T and the acoustics were determined by ASTM C423 where the noise reduction coefficient was 47Ø
~046198 ExamPle 4 (A) A mixture was prepared by blending 11.4 parts by weight of Polymer C as defined ln Example 3, 11.4 parts by weight of five micron quartz, 1.42 parts by weight of a phenylmethylvinylsiloxy endblocked polydimethylsiloxane having a viscosity of about 2000 cs.
at 25C., 0.24 parts by weight zinc oxide, 0.12 parts ~
by weight carbon black and a platinum catalyst as defined ~ -in Example 1 in an amount sufficient to provide 130 p.p.m.
platinum.
(B) A mixture was prepared by blending 11.6 parts by weight of Polymer C, 11.6 parts by weight of five micron quartz, 1.3 parts by weight of a trimethyl- -siloxy endblocked polyorganosiloxane having an average of 5 methylhydrogensiloxane units and 3 dimethylsiloxane units and 0.5 part by weight of polymethylvinylsiloxane cycllcs.
(C) A blend of 25 parts by weight of mixture (A) and 25 parts by weight of mixture (B), 10 parts by weight of Polymer B as defined in Example 3, 70 parts by weight of diphenylmethylsilanol and 10 parts by weight of Polymer D as defined in Example 3 was prepared by mixing at room temperature which cured to an elastomeric foam with an increase in volume compared to the unfoamed mixture of about 50 percent. This foam had fire retardant properties and had greater than 90 percent closed cells.
The blend of (C) had a molar ratio of SiH to SiOH of about 0.5, had 23 p.p.m. platinum and about 0.08 weight percent carbon black.
- i 10~6i9~
(D) A blend of 24 parts by weight of mixture (A) and 25 parts by weight of mixture (B), 5 parts by weight of dlphenylmethylsilanol, 5 parts by weight of Polymer B and 30 parts by welght Gf Polymer D was prepared ~' by mlxlng at room temperature whlch cured to an elastomerlc foam with an expanslon of about 100 percent. This foam had flre retardant propertles, had a density of about 0.13 grams per cubic centimeter and had greater than 90 ~ , -percent closed cells. The blend of (D) had a molar ratio ~ ~ ~
of SlH to SlOH of about 13, had 36 p.p.m. platinum and ; -about 0.13 weight percent carbon black. ~ -~
Example 5 A siloxane foam was prepared by mixing at room temperature 25 parts by weight of a hydroxyl endblocked polydimethylslloxane having a vlsco~lty of about 4000 cs.
at 25C., 25 parts by welght calclum carbonate, 10 parts by welght of Polymer B, 10 parts by weight of diphenyl-methylsilanol, 32 p.p.m. platinum in the form of the platinum catalyst as defined in Example 1 and thereafter mixing therewith a mixture of 30 parts by weight of Polymer D and 0.5 parts by weight of polymethylvinyl-siloxane cyclics. The resulting mixture had a molar ratio of SiH to SiOH of about 6. An elastomeric foam which had fire retardant properties, was obtained.
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Claims (2)
1. A method of preparing an organosiloxane foam comprising mixing an organohydrogensiloxane having an average of at least three silicon-bonded hydrogen atoms per molecule, an average of no more than one silicon-bonded hydrogen atom per silicon atom and organic radicals selected from the group consisting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl, a hydroxylated organosiloxane having an average of from greater than 1.0 to 2.5 silicon-bonded hydroxyl radicals per molecule and having an average of at least one organic radical per silicon atom selected from the group consisting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl and a platinum catalyst in an amount of from 5 to 200 parts by weight platinum per one million parts by weight total composition, said organo-hydrogensiloxane and said hydroxylated organosiloxane being present in sufficient amounts to provide a molar ratio of silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals of 2.5 to 40, where a mixture is obtained having a viscosity of less than 100,000 cs.
at 25°C., thereafter allowing a foam to form.
at 25°C., thereafter allowing a foam to form.
2. A method of preparing an organosiloxane foam comprising mixing an organohydrogensiloxane having an average of at least three silicon-bonded hydrogen atoms per molecule, an average of no more than one silicon-bonded hydrogen atom per silicon atom and organic radicals selected from the group consisting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl, a hydroxylated organosiloxane having an average of from 1.5 to 2.5 silicon-bonded hydroxyl radicals per molecule and having an average of at least one organic radical per silicon atom selected from the group consisting of alkyl radicals having from one to six carbon atoms per radical, phenyl and 3,3,3-trifluoropropyl, a benzene-soluble vinyl containing trigorganosiloxy endblocked polydiorganosiloxane having an average of about two vinyl radicals per molecule and present in an amount equal to no more than 85 weight percent of the combined weight of the hydroxylated organosiloxane and the benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxane, the organic radicals of the benzene-soluble vinyl containing triorganosiloxy endblocked polydiorganosiloxane being selected from the group consisting of alkyl radicals having from one to six carbon atoms per radical, phenyl, vinyl and 3,3,3-trifluoropropyl and a platinum catalyst in an amount of from 5 to 200 parts by weight platinum per one million parts by weight total composition, said organohydrogensiloxane and said hydroxylated organosiloxane being present in sufficient amounts to provide a molar ratio Or silicon-bonded hydrogen atoms to silicon-bonded hydroxyl radicals of 0.5 to 40, where a mixture is obtained having a viscosity of less than 100,000 cs.
at 25°C., thereafter allowing a foam to form.
at 25°C., thereafter allowing a foam to form.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US519380A US3923705A (en) | 1974-10-30 | 1974-10-30 | Method of preparing fire retardant siloxane foams and foams prepared therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1046198A true CA1046198A (en) | 1979-01-09 |
Family
ID=24068061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,761A Expired CA1046198A (en) | 1974-10-30 | 1975-09-04 | Method of preparing fire retardant siloxane foams and foams prepared therefrom |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3923705A (en) |
| JP (1) | JPS5242826B2 (en) |
| BE (1) | BE834988A (en) |
| CA (1) | CA1046198A (en) |
| DE (1) | DE2548510C2 (en) |
| GB (1) | GB1522637A (en) |
| HK (1) | HK15679A (en) |
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Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB804199A (en) * | 1955-12-22 | 1958-11-12 | Midland Silicones Ltd | Organosiloxane compositions |
| US2956032A (en) * | 1958-06-02 | 1960-10-11 | Dow Corning | Fire resistant organosiloxane elastomer foams and method of preparing same |
| US3070555A (en) * | 1959-04-20 | 1962-12-25 | Dow Corning | Method of preparing organosiloxane elastomer foams |
| DE1224040B (en) * | 1963-06-28 | 1966-09-01 | Wacker Chemie Gmbh | Process for the production of elastomeric cells, sponges or foam bodies from linear organopolysiloxanes that can be carried out at room temperature |
| DE1221010B (en) * | 1964-09-18 | 1966-07-14 | Wacker Chemie Gmbh | Process for the production of organopolysiloxane foams |
| NL131010C (en) * | 1965-02-04 | 1900-01-01 | ||
| US3429838A (en) * | 1966-02-11 | 1969-02-25 | Us Air Force | Elastomeric foamable ablation composition |
| US3514424A (en) * | 1969-05-19 | 1970-05-26 | Gen Electric | Flame retardant compositions |
| US3677981A (en) * | 1969-06-25 | 1972-07-18 | Shinetsu Chemical Co | Silicone elastomeric compositions and a method for preparing silicone sponge rubbers therefrom |
| US3652488A (en) * | 1969-07-16 | 1972-03-28 | Dow Corning | Flame resistant silicone elastomers containing carbon black and platinum |
| BE786220A (en) * | 1971-07-15 | 1973-01-15 | Dow Corning | SINGLE-PART SELF-EXTINGUISHING SILICONE ELASTOMER COMPOSITION |
| JPS5146352A (en) * | 1974-10-18 | 1976-04-20 | Toshiba Silicone | HATSUHOSEISHIRIKOONGOMUSOSEIBUTSU |
-
1974
- 1974-10-30 US US519380A patent/US3923705A/en not_active Expired - Lifetime
-
1975
- 1975-09-04 CA CA234,761A patent/CA1046198A/en not_active Expired
- 1975-10-10 GB GB41607/75A patent/GB1522637A/en not_active Expired
- 1975-10-29 JP JP50129437A patent/JPS5242826B2/ja not_active Expired
- 1975-10-29 DE DE2548510A patent/DE2548510C2/en not_active Expired
- 1975-10-29 BE BE161353A patent/BE834988A/en not_active IP Right Cessation
-
1979
- 1979-03-22 HK HK156/79A patent/HK15679A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BE834988A (en) | 1976-02-16 |
| US3923705A (en) | 1975-12-02 |
| JPS5242826B2 (en) | 1977-10-26 |
| JPS5169565A (en) | 1976-06-16 |
| GB1522637A (en) | 1978-08-23 |
| DE2548510C2 (en) | 1982-09-16 |
| DE2548510A1 (en) | 1976-05-06 |
| AU8449475A (en) | 1976-11-04 |
| HK15679A (en) | 1979-03-30 |
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