Elastomers from silicone emulsions having self-catalytic crosslinkers

Abstract: A crosslinked polysiloxane dispersion comprising a product of a siloxane polymer or polymer mixture having a viscosity of 5000 to 500,000 mPa·s and at least one self catalyzing crosslinker, a surfactant and water.

Description: This invention relates to a method for making a crosslinked polysiloxane dispersion which upon drying yields an elastomer with improved durometer, tensile and elongation properties. The technical background of this invention is generally represented by: EP-A2 0 463 431; WO 94/09058; WO 94/09059; US-As 3,355,406; 4,788,001; 5,034,455; 5,037,878; 5,045,231 or 5,145,907. US-A-4,704,422 discloses a silicone emulsion having improved freeze/thaw resistance. EP-A-0,387,157 discloses aqueous silicone dispersions comprising aminosilanes and/or amidosilanes and crosslinkable into an elastomer. EP-A-0,415,254 discloses stable emulsions containing amino polysiloxanes and silanes for treating fibers and fabrics. EP-A-0,606,671 discloses organosilicon emulsions for rendering porous substrates water repellent. The present invention is distinguishable from the prior art because a self catalytic crosslinker is added to the siloxane polymer, instead of using a conventional catalyst and crosslinker. Thus, the system self cures without the need for a heavy metal catalyst, such as tin. The present invention provides a method for making a crosslinked polysiloxane dispersion, comprising the steps of blending components comprising a siloxane polymer or polymer mixture having a viscosity of 5000 to 500,000 mPa.s and a molecular formula (I) X 3-n R n -YO-(R 1 2 SiO) z -Y-R n X 3-n where n is 0, 1, 2 or 3 and z is an integer from 500 to 5000 and X is a hydrogen atom, a hydroxyl group or any condensable or any hydrolyzable group, Y is a Si atom or a Si-(CH 2 ) m -SiR 1 2 group, R is individually selected from alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl, alkenyl and aryl groups and R 1 is individually selected from X, alkyl, alkenyl and aryl groups, a surfactant, water and from 1 to 5 parts by weight, per 100 parts of siloxane polymer, of at least one self-catalysing crosslinker selected from R 4 SiQ 3 , SiQ 4 , partial hydrolysis products of R 4 SiQ 3 and SiQ 4 , and copolymers of the formula in which Q is selected from carboxylic groups, hydroxylamine groups and oxime groups and R 4 is an alkyl group of 1 to 8 carbon atoms inclusive or vinyl, a is 0 or a positive integer and b is an integer greater than 2, wherein the self-catalysing crosslinker is added to the siloxane polymer before mixing with the water and surfactant; mixing said components at a sufficiently high shear to transform the components into a gel phase and, optionally, diluting the gel phase with water, the method being carried out in the absence of a heavy metal catalyst. Optionally, in-situ resin reinforcers, stabilizers, fillers and the like may also be added to the mixture. The dispersion is produced by mixing the above components at a sufficiently high shear to transform the mixture into a gel phase and by then diluting the gel with water to the desired silicone content. The emulsion is transformed into an elastomer upon the evaporation of water. The present invention represents several significant advances in the art. First, the process of making the dispersion is surprising because a self catalytic crosslinker is added to the siloxane polymer before mixing with the water and surfactant; instead of mixing in crosslinker and catalyst in a separate, later step as in the art. Second, our invention teaches that the physical properties of the resulting elastomeric film are improved if an in situ resin reinforcer is added to the composition to promote the formation of an in situ resin. Finally, the present invention discloses that the addition of certain types of silicas, in particular, NH 4 + treated colloidal silica will also alter the physical characteristics of the resulting elastomer and produce excellent heat stability. In addition, we have unexpectedly found that selecting an appropriate surfactant alters the physical properties of the dispersion and the resulting elastomers, specifically properties such as freeze/thaw stability, high temperature stability and clarity. The present invention also has additional advantages over the prior art. For example, at high solids content the composition produced according to the invention does not require a thickener. Also, the composition produced according to the invention cures without the use of a tin catalyst which improves shelf-stability, compatibility and lowers the toxicity of the product dispersion. Finally, the dispersions produced in the present invention and the elastomers resulting therefrom have superior rheological properties, improved shelf stability, enhanced freeze/thaw characteristics, better high temperature characteristics and high clarity. The siloxane polymers or polymer mixtures used as starting materials for the present invention are well known in the art. These polymers have a viscosity between 5000 to 500,000 mPa·s. The siloxanes are described by the following molecular formula (I) X 3-n R n -YO-(R 1 2 SiO) z -Y-R n X 3-n where n is 0, 1, 2 or 3 and z is an integer from 500 to 5000 and X is a hydrogen atom, a hydroxyl group and any condensable or any hydrolyzable group, Y is a Si atom or a Si-(CH 2 ) m -SiR 1 2 group, R is individually selected from the group consisting of alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl, alkenyl or aromatic aryl groups and R 1 is individually selected from the group consisting of X, alkyl, alkenyl and aromatic groups. The siloxane polymer of the present invention can be a single siloxane represented by formula (I) or it can be mixtures of siloxanes represented by the aforesaid formula or solvent/polymer mixtures. The term "polymer mixture" is meant to include any of these types of polymers or mixtures of polymers. As used herein, the term "silicone content" means the total amount of silicone in the dispersed phase of the dispersion, from whatever source, including, but not limited to silicone polymer, polymer mixtures, self catalytic crosslinkers, in situ resin reinforcers and stabilizers. X can be a hydrogen atom, hydroxyl group and any condensable or hydrolyzable group. The term "hydrolyzable group" means any group attached to the silicon which is hydrolyzed by water at room temperature. The hydrolyzable group X includes hydrogen atom, halogen atoms such as F, Cl, Br or I; groups of the formula -OT where T is any hydrocarbon or halogenated hydrocarbon group such as methyl, ethyl, isopropyl, octadecyl, allyl, hexenyl, cyclohexyl, phenyl, benzyl, beta-phenylethyl; any hydrocarbon ether radical such as 2-methoxyethyl, 2-ethoxyisopropyl, 2-butoxyisobutyl, p-methoxyphenyl or -(CH 2 CH 2 O) 2 CH 3 ; or any N,N-amino radical such as dimethylamino, diethylamino, ethylmethylamino, diphenylamino or dicyclohexylamino. X can also be any amino radical such as NH 2 , dimethylamino, diethylamino, methylphenylamino or dicyclohexylamino; any ketoxime radical of the formula -ON=CM 2 or -ON=CM' in which M is any monovalent hydrocarbon or halogenated hydrocarbon radical such as those shown for T above and M' is any divalent hydrocarbon radical, both valences of which are attached to the carbon, such as hexylene, pentylene or octylene; ureido groups of the formula -N(M)CONM" 2 in which M is defined above and M" is hydrogen atom or any of the above M radicals; carboxyl groups of the formula -OOCMM" in which M and M" are defined above or carboxylic amide radicals of the formula -NMC=O(M") in which M and M" are defined above. X can also be the sulfate group or sulfate ester groups of the formula -OSO 2 (OM) where M is as defined above; the cyano group; the isocyanate group; and the phosphate group or phosphate ester groups of the formula -OPO(OM) 2 in which M is defined above. The most preferred groups of the invention are hydroxyl groups or alkoxy groups. Illustrative alkoxy groups are methoxy, ethoxy, propoxy, butoxy, isobutoxy, pentoxy, hexoxy and 2-ethylhexoxy; dialkoxy radicals such as methoxymethoxy or ethoxymethoxy and alkoxyaryloxy such as ethoxyphenoxy. The most preferred alkoxy groups are methoxy or ethoxy. R is individually selected from the group consisting of aliphatic, alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl, alkenyl organic and aromatic aryl groups. Most preferred are the methyl, ethyl, octyl, vinyl, allyl and phenyl groups. R 1 is individually selected from the group consisting of X, aliphatic, alkyl, alkenyl and aromatic aryl groups. Most preferred are methyl, ethyl, octyl, trifluoropropyl, vinyl and phenyl groups. When the siloxane polymer of formula (I) has an average of more than two condensable or hydrolyzable groups per molecule which are self catalytic, it is not necessary to have the self catalytic crosslinker present separately to form a crosslinked polymer. The condensable or hydrolyzable groups on the different siloxane molecules can react with each other to form the required crosslinks. The siloxane polymer produced according to the invention can be a mixture of different kinds of molecules, for example, long chain linear molecules and short chain linear or branched molecules. These molecules may react with each other to form a crosslinked network. Such siloxanes, which can take the place of more conventional crosslinkers, are illustrated by low molecular weight organosilicon hydrides, such as polymethylhydrogensiloxane, low molecular weight copolymers containing methylhydrogensiloxy and dimethylsiloxy groups, -(OSi(OEt) 2 )-, (ethylpolysilicate), (OSiMeC 2 H 4 Si(OMe) 3 ) 4 and (OSi-MeON=CR' 2 ) 4 , where Me is methyl and Et is ethyl. Advantageously, the siloxane polymer of the present invention also comprises mixtures of siloxane polymers of formula (I), exemplified by, but not limited to, mixtures of α,ω-hydroxysiloxy terminated siloxanes and of α,ω-bis(triorganosiloxy) terminated siloxanes, mixtures of α,ω-hydroxylsiloxy terminated siloxanes and of α-hydroxy, ω-triorganosiloxy terminated siloxanes, mixtures of α,ω-dialkoxysiloxy terminated siloxanes and of α,ω-bis(triorganosiloxy) terminated siloxanes, mixtures of α,ω-dialkoxysiloxy terminated siloxanes and of α,ω-hydroxysiloxy terminated siloxanes, mixtures of α,ω-hydroxysiloxy terminated siloxanes and of α,ω-bis(triorganosiloxy) terminated poly(diorgano)(hydrogenorgano)siloxane copolymers. The siloxane polymer of the invention can also comprise mixtures of siloxane polymers of formula (I) as described above with liquid, branched methylpolysiloxane polymers ("MDT fluids") comprising a combination of recurring units of the formulae: (CH 3 ) 3 Si 1/2 (CH 3 ) 2 SiO CH 3 SiO 3/2 and containing from 0.1 to 8% hydroxyl groups. The fluids may be prepared by co-hydrolysis of the corresponding chloro- or alkoxy-silanes, as described in U.S. Patents 3,382,205; 3,661,817; 3,714,089; 4,356,116; 4,468,760 and 5,175,057 or Belgian Patent 0,877,267. The proportion of MDT fluids added should not exceed 50 parts, preferably of 1 to 20 parts by weight, per 100 parts by weight of the polymer of formula (I), to achieve improved physical properties and adhesion of the resultant polymers. The siloxane polymer of the present invention can also comprise mixtures of siloxane polymers of formula (I) with liquid or solid, branched methylsiloxane polymeric resins comprising a combination of recurring units of the formulae: (CH 3 ) 3 Si 1/2 (CH 3 ) 2 SiO CH 3 SiO 3/2 SiO 2 and containing from 0.1 to 8% hydroxyl groups, the fluids may be prepared by co-hydrolysis of the corresponding chloro- or alkoxy-silanes, as described in US Patents 2,676,182; 2,441,320; 4,707,531 and 5,070,175; EP Patents 0,529,547 or 0,535,687; DE Patent 4,124,588; JP Patent 05-098,012 and WO 93/23455. The MDTQ fluid/resin may be added in a proportion not exceeding 50 parts, preferably of 1 to 10 parts by weight, per 100 parts by weight of the polymer of formula (I) to improve physical properties and adhesion of the resultant polymers. MDTQ fluids/resins can also be mixed with MDT fluids and the polymers of Formula (I). Finally, the siloxane polymer can comprise mixtures of siloxane polymers of Formula (I) with compatible organic solvents, to form organic polymer/solvent mixtures. These organic solvents are exemplified by organophosphate esters, such as trioleylphosphate, trioctylphosphate or tetraethyleneglycolmonolauryletherphosphate, as disclosed in US Patent 4,147,855 or German Patent 2,802,170; alkanes, such as hexane or heptane; higher paraffins; and aromatic solvents, such as toluene or benzene. The polymer solvent mixtures can also be added with MDT fluids and/or MDTQ fluids to the polymer of Formula I. Any of the above mixtures of polymers or polymer/solvents can be prepared by mixing the ingredients prior to emulsification or by emulsifying them individually and then mixing the prepared emulsions. The surfactant used in the present invention is selected from nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants or mixtures thereof. The surfactant is generally present in our composition in an amount of 0.5 to 10 parts by weight of siloxane polymer and is preferably present in the amount of 2 to 10 parts. Most preferred are nonionic surfactants known in the art as being useful in emulsification of polysiloxanes. Useful nonionic surfactants are polyoxyalkylene alkyl ethers, polyoxyalkylene sorbitan esters, polyoxyalkylene esters, polyoxyalkylene alkylphenyl ethers, ethoxylated amides and others. The surfactants useful in the instant invention may be further exemplified by TERGITOL™ TMN-6, TERGITOL™ 15S40, TERGITOL™ 15S9, TERGITOL™ 15S12, TERGITOL™ 15S15 and TERGITOL™ 15S20, produced by UNION CARBIDE CORPORATION (Danbury, CT); BRIJ™ 30 and BRIJ™ 35 produced by ICI CHEMICALS (Wilmington, DE); TRITON™ X405 produced by ROHM AND HAAS (Philadelphia, PA); MAKON™ 10 produced by STEPAN COMPANY, (Chicago, IL); and ETHOMID™ O/17 produced by AKZO INC, Chicago, IL. Cationic and anionic surfactants known in the art as being useful in emulsification of polysiloxanes are also useful as the surfactant in the instant invention. Suitable cationic surfactants are aliphatic fatty amines and their derivatives such as dodecylamine acetate, octadecylamine acetate and acetates of the amines of tallow fatty acids; homologues of aromatic amines having fatty chains such as dodecylanalin; fatty amides derived from aliphatic diamines such as undecylimidazoline; fatty amides derived from disubstituted amines such as oleylaminodiethylamine; derivatives of ethylene diamine; quaternary ammonium compounds such as tallow trimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, didodecyldimethyl ammonium chloride and dihexadecyldimethyl ammonium chloride; amide derivatives of amino alcohols such as betahydroxyethylsteraryl amide; amine salts of long chain fatty acids; quaternary ammonium bases derived from fatty amides of di-substituted diamines such as oleylbenzylaminoethylene diethylamine hydrochloride; quaternary ammonium bases of the benzimidazolines such as methylheptadecyl benzimidazole hydrobromide; basic compounds of pyridinium and its derivatives such as cetylpyridinium chloride; sulfonium compounds such as octadecylsulfonium methyl sulfate; quaternary ammonium compounds of betaine such as betaine compounds of diethylamino acetic acid and octadecylchloromethyl ether; urethanes of ethylene diamine such as the condensation products of stearic acid and diethylene triamine; polyethylene diamines and polypropanolpolyethanol amines. Cationic surfactants commercially available and useful in the instant invention include ARQUAD™ T27W, ARQUAD™ 16-29, ARQUAD™ C-33, ARQUAD™ T50, ETHOQUAD™ T/13 ACETATE, all manufactured by Akzo Inc. (Chicago, IL). Suitable anionic surfactants are carboxylic, phosphoric and sulfonic acids and their salt derivatives. The anionic surfactants useful in the instant invention are alkyl carboxylates; acyl lactylates; alkyl ether carboxylates; n-acyl sarcosinate; n-acyl glutamates; fatty acid-polypeptide condensates; alkali metal sulforicinates; sulfonated glycerol esters of fatty acids such as sulfonated monoglycerides of coconut oil acids; salts of sulfonated monovalent alcohol esters such as sodium oleylisethionate; amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride; sulfonated products of fatty acids nitriles such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate; condensation products of naphthalene sulfonic acids with formaldehyde; sodium octahydroanthracene sulfonate; alkali metal alkyl sulfates, ether sulfates having alkyl groups of 8 or more carbon atoms and alkylarylsulfonates having 1 or more alkyl groups of 8 or more carbon atoms. Anionic surfactants commercially available and useful in the instant invention include POLYSTEP™ A4, A7, A11, A15, A15-30K, A16, A16-22, A18, A13, A17, B1, B3, B5, B11, B12, B19, B20, B22, B23, B24, B25, B27, B29, C-OP3S; ALPHA-STEP™ ML40, MC48; STEPANOL™ MG; all produced by STEPAN CO., Chicago, IL; HOSTAPUR™ SAS produced by HOECHST CELANESE; HAMPOSYL™ C30 and L30 produced by W.R.GRACE & CO., Lexington, MA. Suitable amphoteric surfactants are glycinates, betaines, sultaines and alkyl aminopropionates. These include cocoamphglycinate, cocoamphocarboxy-glycinates, cocoamidopropylbetaine, lauryl betaine, cocoamidopropylhydroxysultaine, laurylsulataine and cocoamphodipropionate. Amphoteric surfactants commercially available and useful in the instant invention are REWOTERIC™ AM TEG, AM DLM-35, AM B14 LS, AM CAS and AM LP produced by SHEREX CHEMICAL CO, Dublin, OH. Selection of the surfactant can have an important impact on the properties of the dispersion or the elastomer resulting after the evaporation of water. The properties particularly controllable by surfactant selection are freeze/thaw stability, high temperature heat stability and clarity. Typical prior approaches to freeze/thaw stability include: 1) freezing point depression techniques, e.g., adding glycols or salts; 2) steric stabilization, e.g., adding additional surfactant to further stabilize the dispersion particle, or 3) bonding an anionic moiety onto the dispersion particle. These routes may add cost and negatively affect other aspects of the sealant's performance like adhesion, translucency or tack free time. The present invention introduces a method for preparing an aqueous crosslinked silicone dispersion that withstands freeze/thaw cycling. The freeze/thaw stability is achieved though judicious selection of surfactants. In general, surfactants improve the freeze/thaw properties of the resulting elastomers if the surfactant could emulsify the polydiorganosiloxane and if the surfactant is not selected from the group of surfactants comprising alkyl sulfates, linear alkylbenzene sulfonates, alkyl sulfonates and taurates. The surfactants which achieve desirable freeze/thaw results include non-ionic surfactants, such as ethoxylated alcohols and esters, polyoxypropylene compounds, amine oxides and fatty acid esters of polyhydric alcohols, cationic surfactants such as monoalkyl and dialkyl quaternary ammonium salts, amphoteric surfactants such as sulfobetaines, silicone surfactants such as silicone polyethers, florosurfactants and certain anionic surfactants such as sulfosuccinamates, paraffin sulfonates, phosphoric esters and carboxylates. The aforereferenced surfactants or classes of surfactants will all favorably influence the number of freeze/thaw cycles. Freeze/thaw stability is tested by subjecting the sealant in its original container to 10 freeze/thaw cycles, each cycle consisting of 16 hours of a freeze segment at -17°C. ± 1°C. (0°F. ± 2°F.) and 8 hours of a thaw segment at 23°C. ± 1°C. (73.4°F. ± 2°F.). After each cycle, a portion of the sealant is extruded and examined for appearance changes. If the extrudate is equivalent to the original unfrozen sealant by not exhibiting coagulation, gels, separation or other manifestations of instability, the sample is deemed to pass that freeze/thaw cycle. Appropriate selection of the surfactant in the present invention can also influence the thermal stability of the elastomeric film resulting from the evaporation of water from the dispersion. Through the judicious selection of surfactant, specifically one whose degradation products at high temperature (such as greater than 100°C.) do not include siloxane redistribution catalysts, heat stable elastomers from aqueous siloxane dispersions are made. The best types of surfactants which are used to improve the thermal stability are nonionic, cationic or anionic surfactants, which at elevated temperatures (above 100°C.) do not form siloxane redistribution catalysts. Specifically, the species which form siloxane redistribution catalysts include: 1) strong acidic species such as H 2 SO 4 , HSO 4 Na, H 3 PO 4 and H 2 PO 4 Na or 2) strong basic species such as NaOH, KOH and LiOH. Nonionic, cationic and amphoteric surfactants are preferred since the degradation products of these surfactants do not contain these species. Within the class of anionic surfactants, carboxylate and sulfonate surfactants are most preferred. Specifically, anionic surfactants include monovalent alkyl carboxylates; polyvalent alkyl carboxylates; acyl lactylates; alkyl ether carboxylates; n-acyl sarcosinate; n-acyl glutamates; and fatty acid - polypeptide condensates. Other anionic surfactants are ester linked sulfonates such as alkyl sulfo esters; taurates; sulfosuccinates, such as monoester, diester (both symmetrical and unsymmetrical), ethoxylated monoalkyl sulfosuccinates, alkyl amide 1/2 ester sulfosuccinate (mono/di M + ) such as where M + is Na + , Li + , K + or H + and ethoxylated amide sulfosuccinates; sulfosuccinamates; sulfonated ethers, (Na cocoglycerol ether sulfonate); linear alkylbenzenesulfonates; benzene, toluene, xylene, cumene sulfonate; ligninsulfonates such as sulfonated polymers having number average molecular weights of 1000-20,000; petroleum sulfonates, such as petroleum fractions of differing molecular weights reacted with oleum or H 2 SO 4 to sulfonate; paraffin sulfonates, such as sulfoxidation of n-paraffins via UV/SO 3 secondary alkane sulfonates C 14 -C 18 (e.g. HOECHST™ SAS); α-olefin sulfonates; alkylnapthalenesulfonates; diphenyl oxide sulphonates and linear alkylpolyethersulfonates. Specific non-ionic surfactants include ethoxylated alcohols, ethoxylated esters, polysorbate esters, ethoxylated amides; polyoxypropylene compounds such as propoxylated alcohols, ethoxylated/propoxylated block polymers and propoxylated esters; alkanolamides; amine oxides; fatty acid esters of polyhydric alcohols, such as ethylene glycol esters, diethylene glycol esters, propylene glycol esters, glyceryl esters, polyglyceryl fatty acid esters, sorbitan esters, sucrose esters and glucose esters. Specific cationic surfactants include monoalkyl quaternary ammonium salts, which are hydroxylated or ethoxylated, propoxylated; dialkyl quaternary ammonium compounds; amidoamines; and aminimides. Specific amphoteric surfactants include N-substituted alkyl amides (i.e. fatty acid plus aminoethanolamines e.g. cocoamphoglycinate or cocoamphocarboxyglycinate); N-alkyl betaines, including alkyl amidobetaines; sulfobetaines, such as laurylsultaine, cocoamidopropylhydroxysultaine; N-alkyl-b-aminopropionates, such as lauraminopropionic acids. Specific silicone surfactants which improve high temperature stability include branched or linear polyoxyalkylenes. Specific flourosurfactants include those selected from anionics (such as carboxylates and sulfonics), non-ionics and amphoterics. The selection of the surfactant in the present invention also influences the clarity of the elastomeric film resulting from the evaporation of water from the dispersion. To obtain clear elastomers from silicone latices, the refractive index must be matched in the final film between the crosslinked siloxane phase and the surfactant/residual water phase. The term "crosslinked siloxane phase" refers to the plurality of crosslinked siloxane particles remaining after water has evaporated to form an elastomeric film. The term "surfactant/residual water phase" refers to amount of residual surfactant and water remaining in the elastomeric film after the evaporation of substantially all the water from the dispersion. In the absence of refractive index additives, this is accomplished by using nonionic surfactants having the following structure R 2 -B y -(EO) x where R 2 is a hydrocarbon group having 8 to 18 carbon atoms with the -B y -(EO) x attached either terminally or pendently to the hydrocarbon chain or R 2 is a group having the formula x is an integer from 5 to 15; y is 1 or 0; and B is C(O) or C(O)N-. Further, the absence of refractive index additives, this can be accomplished by using anionic surfactants with the following structure R 3 -Z where R 3 is an aliphatic hydrocarbon group having 8 to 18 carbon atoms with the Z attached either terminally or pendently to the hydrocarbon chain and Z is anionic hydrophilic group containing sulfate or sulfonate attached directly to the carbon or through taurate, isethionate or succinate linkage. Specific anionic surfactants that will improve the clarity of the elastomeric film resulting from the composition of the present invention include sulfuric acid esters, such as alkyl sulfates, ethoxylanted alkyl sulfates, sulfated triglyceride oils, e.g., sulfated castor oil; ester linked sulfonates, such as alkyl sulfo esters (acyl isethionate), taurates and monoester sulfosuccinates; sulfosuccinamates; sulfonated ethers; paraffin sulfonates, i.e. sulfoxidation of n-paraffins via UV/SO 3 secondary alkane sulfonates (e.g. HOECHST™ SAS); α-olefin sulfonates; and linear alkylpolyether sulfonates. Specific non-ionic surfactants that will improve clarity include polyoxyethylene compounds, such as ethoxylated alcohols, ethoxylated esters and ethoxylated amides. Rake or comb type silicone polyether surfactants will also improve the clarity of the film, as will sulfonic and nonionic fluoro surfactants. In addition to adding the surfactant to the siloxane polymer, the mixture also includes a predetermined amount of water. The water is generally present in the mixture in an amount of 0.5 to 30 parts by weight of siloxane polymer and is preferably present in the amount of 2 to 10 parts. Water may also be added after mixing, in any amount, to dilute the gel phase. At least one self catalytic crosslinker is also present in the composition in the amount of 1 to 5 parts by weight per 100 parts of siloxane polymer. The term "self catalytic crosslinker" means a molecule that has at least one group serving as the catalytic species. While in certain circumstances only one self catalytic crosslinker may be needed to produce an elastomer having the desired physical properties, those skilled in the art will recognize that two or more self catalytic crosslinkers may be added to the reaction mixture to achieve excellent results. In addition, the self catalytic crosslinker or crosslinkers may be added with a conventional catalyst. However, adding the self catalytic crosslinker with a conventional catalyst is not required for the practice of this invention and the compositions contemplated by this invention may in fact be free of said conventional catalysts. Typical self catalytic crosslinkers include tri or tetra functional compounds, such as R 4 -Si-(Q) 3 or Si-(Q) 4 , where Q is carboxylic , OC(O)R 4 , e.g. acetoxy and R 4 is an alkyl group of 1 to 8 carbon atoms inclusive, preferably methyl, ethyl or vinyl. Other preferred Q groups are the hydroxyl amines, ON(R 4 ) 2 , where R 4 is the same or different alkyl group of 1 to 8 carbon atoms inclusive, e.g., ON(CH 2 CH 3 ) 2 . Q may also be an oxime group, such as O-N=C(R 4 ) 2 where R 4 is the same or different alkyl group of 1 to 8 carbon atoms inclusive, e.g., O-N=C(CH 3 )(CH 2 CH 3 ). Further, Q may be an amine group such as N(R 5 ) 2 where R 5 is the same or different alkyl group of 1 to 8 carbon atoms inclusive or cyclic alkyl group, e.g., N(CH 3 ) 2 or NH(cyclohexyl). Finally, Q may be an acetamido group, NRC(O)R 4 , where R 4 is the same or different alkyl group of 1 to 8 carbon atoms inclusive, e.g. N(CH 3 )C(O)CH 3 . In addition, partial hydrolysis products of the aforementioned compounds may also function as self catalytic crosslinkers. This would include dimers, trimers, tetramers and the like, for example, compounds of the formula: where Q and R 4 are defined in the preceding paragraph. Also useful as self catalytic crosslinkers are those polymeric or copolymeric species containing 3 or more (Q) sites located at either pendant or terminal positions or both on the backbone of a polydiorganosiloxane molecule of the following formula: where R 4 is the same or different alkyl group of from 1 to 8 carbon atoms inclusive and a is 0 or a positive integer and b is an integer greater than 2. Effective self catalytic crosslinkers are those compounds which form tack free elastomers when mixed with functional silicone polymers in the absence of additional catalysts such as tin carboxylates or amines. In the self catalytic crosslinkers, the acetoxy, oxime, hydroxyl amine (aminoxy), acetamide and amide groups catalyze the formation of Si-O-Si bonds in the reactions contemplated by this invention. One skilled in the art would recognize that the starting polymer itself could be pre-endblocked with self catalytic crosslinking moieties. Optionally, further self-catalytic crosslinkers can be added to such compositions. In addition, in situ resin reinforcers such as methyltrimethoxy silane, vinyltrimethoxy silane, tetraethyl orthosilicate (TEOS), normal propylorthosilicate (NPOS) may be added with the self catalyzing crosslinker. It is believed that adding in situ resin reinforcers to the polydiorganosiloxane/self catalytic crosslinker mixture forms an in situ resin having a highly branched and crosslinked structure, which results in improved physical properties of the elastomer, particularly the tensile, elongation and hardness properties. It also results in improved clarity of the resulting elastomer. Stabilizers may also be added to the composition. It is expected that any aminosilane containing polymeric or neat aminosilane will function as a stabilizer. Neat aminosilanes include compounds of the formula (R 4 O) 3-n R 4 n SiQ 1 NR 4 y H 2-y where n and y are independently 0, 1 or 2; R 4 is the same or different alkyl chain of 1 to 8 carbon atoms inclusive, Q 1 is (CH 2 ) z or {(CH 2 ) z N(R)} w , where z is an integer from 1 to 10 and w is from 0 to 3 inclusive. Polymeric amino silanes may also be used in the practice of the present invention, such as reaction products of silanol functional siloxane fluids and aminosilanes or silanol functional siloxane fluids and alkoxysilanes and aminosilanes. For example, one useful polymeric amino siloxane particularly useful to the practice of the present invention has the formula: where z is from 3 to 40. Fillers may be optionally added to the composition of the invention, such as colloidal silica, silica powders made by combustion and precipitation, semi-reinforcing agents such as diatomaceous earths or ground quartz. Nonsiliceous fillers may also be added, such as calcium carbonate, hydrated alumina, magnesium hydroxide, carbon black, titanium dioxide, aluminum oxide, vermiculite, zinc oxide, mica, talcum, iron oxide, barium sulfate and slaked lime. If necessary, liquid alkoxysilanes which are soluble in the siloxane polymer may also be added with the filler to compatibilize the filler with the siloxane polymers. The selection and addition of particular fillers to our compositions, such as certain types of silicas, may improve the physical properties of the resulting elastomer, particularly tensile properties, elongation properties, hardness and heat stability. Elastomers containing ammonium stabilized silicas are heat stable while sodium stabilized silicas are not. Acidic silicas, (those containing H+ as a stabilizer) also yield heat stable elastomers. In general, colloidal or dispersed silica which is not stabilized by Group IA or IIA elements of the periodic chart, will also yield heat stable elastomers. Volatile organic amines and volatile inorganic bases are useful as stabilizers for silicas that would yield heat stable elastomers, e.g., (R 7 ) 3-x N(H) x where x= 0, 1, 2 or 3, R 7 is an alkyl or aryl group such as (CH 3 ) 2 NH or R 7 is an alcohol group such as N(CH 2 CH 2 OH) 3 or NH(CH 2 CH 2 OH) 2 . The volatile organic amines include cyclohexylamine, triethylamine, dimethylaminomethylpropanol, diethylaminoethanol, aminomethyl propanol, aminobutanol, monoethanolamine, monoisopropanolamine, dimethylethanolamine, diethanolamine, aminoethylpropanediol, aminomethylpropanesiol, diisopropanolamine, morpholine, tris(hydroxymethyl)aminomethane, triisoproanolamine, triethanolamine, aniline and urea. In addition to the volatile organic amines, volatile inorganic bases such as ammonia and ammonium carbonate also yield heat stable elastomers. To prepare the compositions of the instant invention, siloxane polymer and the self catalyzing crosslinker are mixed. Water and surfactant are then added to the siloxane polymer and the self catalyzing crosslinker is mixed in until a high solids gel phase is formed. Any type of mixing equipment may be used including low shear mixing equipment, such as Turrello™, Neulinger™ or Ross™ mixers. The gel will have a silicone content of at least 85%. The gel will also exhibit excellent shelf stability and may be stored for long periods of time or even transported if required. After mixing, the gel may be diluted with water to the desired silicone content. The dispersion may be stored for long periods of time and will exhibit excellent freeze/thaw stability. The dispersion may then be dispensed and will form an elastomeric film upon the evaporation of water. Those skilled in the art will recognize that these crosslinked, oil in water dispersions may be prepared in other ways. For instance, the siloxane polymer and self catalytic crosslinker mixture may be added to a surfactant and water solution and then emulsified using colloid mills, homogenizers, sonolaters or other high shear devices as described in U.S. Patents 5,037,878 and 5,034,455. The dispersion may be formed by either a batch process, as described above, or a continuous process. If a continuous process is used, then a low shear dynamic mixer or static mixer is preferred. In the examples, the aforesaid wet dispersions were cast into films one day after the dispersions were made and the film was allowed to dry for a minimum of seven days prior to testing. Durometer results were obtained by the method described in ASTM C661 "Indentation Hardness of Elastomeric-Type Sealants by Means of a Durometer". Tensile and elongation results were obtained by the method described in ASTM D412 "Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers- Tension" using dumbell specimens with an L dimension equal to 1.3 cm (0.5 inch). The clarity test method was developed to assign a numerical value to the translucency of crosslinked silicone elastomers prepared from silicone latex. The value reported is the thickness through which black, printed letters can be read. The sealant is extruded between two graduated shims. The shims graduate from 0.25 mm to 5.1 mm (0.01 to 0.20 inch). After two weeks at ambient conditions, the film is placed on white paper containing printing of rows of random letters. The measured thickness at which the letters become difficult to resolve is the clarity value. Maximum readings indicate that the letters were readable even at the thickest portion of the film. Examples 1, 4, 5, 6, 7, 8, 18 and 20 illustrate the invention, the remaining Examples being for reference. Example 1 Using parts by weight based on siloxane polymer, 2 parts of (aminoxy-functional polysiloxane,"AOPS") were mixed into 100 parts of 50,000 mm 2 /s (centistokes) (Mw 110,000) of -OH endblocked polydimethylsiloxane ("PDMS") polymer in a laboratory mixer (Whip™ Mix, i.e. Combination Unit or Power-Mixer using the 200 mL or 500 mL Vac-U-Mixer™; Whip Mix Corporation, Louisville, KY). 4.0 parts of a 50/50 solution of water and TERGITOL™ TMN-6 were then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted with 20 parts of water and 1 part of a 5% acetic acid solution. This formulation produced a silicone elastomeric film after water evaporation with a tensile strength of 68.5 kPa (10 psi), an elongation of 310% and a Shore A durometer reading of 4. Example 2 Using weight parts based on siloxane polymer, 2 parts of AOPS were mixed into 100 parts of the PDMS polymer of Example 1 in the laboratory mixer of Example 1. Again, the water and TERGITOL™ solution were mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted with 19 parts of water and 1 part of 5% solution of acetic acid. 1 part of (aminoalkoxypolysiloxane, "AAPS", z having an average value of 12) was also mixed into the dispersion. This formulation dried to a silicone elastomeric film after water evaporation with a tensile strength of 144.8 kPa (21 psi), an elongation of 770% and a Shore A durometer of 5. Example 3 Using parts based on siloxane polymer, 2 parts of AOPS, 2 parts of methyltrimethoxysilane and 1 part of a 1:1 molar solution of AAPS and acetic acid were mixed into 100 parts of the PDMS polymer of Example 1 in the same laboratory mixer of Example 1. The same water and TERGITOL™ solution were then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted with 21 parts of water. This formulation made a tack free silicone elastomeric film after water evaporation with a tensile strength of 586.1 kPa (85 psi), an elongation of 1310% and a durometer of 8. Example 4 Using parts based on siloxane polymer, 2 parts of vinyltris(methylethylketoxime)silane were mixed into 100 parts of the PDMS polymer of Example 1 in the same laboratory mixer. 6.0 parts of a 50/50 solution of water and TERGITOL™ TMN-6 were then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted with 19.3 parts of water. This formulation produced a tack-free silicone elastomer after water evaporation. Example 5 Using parts based on siloxane polymer, 2 parts of vinyltris(methylethylketoxime)silane were mixed into 100 parts of the PDMS polymer of Example 1 in the laboratory mixer of the same example. The same water and TERGITOL™ solution was then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted with deionized water to achieve 80% silicone content. This formulation dried to a tack-free silicone elastomer after water evaporation with a tensile strength of 551.6 kPa (80 psi), an elongation of 1151 and a Shore A durometer of 7. Example 6 Using parts based on siloxane polymer, 2 parts of a 50/50 mixture of methyl and ethyl triacetoxysilane were mixed into 100 parts of the PDMS polymer in the same laboratory mixer. Then, the same amount of a water and TERGITOL™ solution was then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted with deionized water to 80% silicone content. This formulation made a silicone elastomer after water evaporation with a tensile strength of 358.5 kPa (52 psi), an elongation of 1160 and a Shore A durometer of 4. Example 7 Using parts based on siloxane polymer, 1 part of a 50/50 mixture of methyl and ethyl triacetoxysilane were mixed into 100 parts of the PDMS polymer of Example 1 in a laboratory mixer (Universal Mixing Machine AM501™, Hauschild & Co. KG, Hamm, Germany). 6.6 parts of a 35% solution of water and Avanel™ S150 (PPG Industries, Gurnee, IL) sulfonate surfactant were then mixed until a very high solids emulsion gel was formed. This emulsion gel was diluted with 20.4 parts of deionized water. This formulation yielded a tacky silicone elastomer after water evaporation. Example 8 Using parts based on siloxane polymer, 2.04 parts of a vinyltriacetoxysilane were mixed into 100 parts of 14,000 mm 2 /s (cs) of -OH endblocked PDMS polymer in the laboratory mixer of Example 7. 6.6 parts of a 35% solution of water and Avanel™ S150 sulfonate surfacatant were then mixed until a very high solids emulsion gel was formed. This emulsion gel was diluted with 20.8 parts of deionized water. This formulation produced a tack free silicone elastomer after water evaporation. Example 9 Using parts based on siloxane polymer, 2.0 parts of tris(dimethylamino)methylsilane were mixed into 100 parts of the PDMS polymer of Example 1 in the laboratory mixer of Example 7. 4 parts of a 45% solution of water and TERGITOL™ TMN6 nonionic surfactant were then mixed until a very high solids emulsion gel was formed. This emulsion gel was diluted with 17 parts of deionized water. This formulation yielded a slightly tacky silicone elastomer after water evaporation when the dispersion had been aged for 6 weeks. Example 10 Using parts based on siloxane polymer, 100 parts of the PDMS polymer of Example 1, 2.8 parts of methyldivinyldi(N-methylacetamido)silane, 1.7 parts of (CH 3 ) 3 SiO(((CH 3 )Si(ON(CH 2 CH 3 ) 2 ))O) 5 ((CH 3 ) 2 SiO) 3 Si(CH 3 ) 3 , 6.26 parts of Makon™ 10 nonionic surfactant and 10 parts of water were mixed in the laboratory mixer of Example 1 until an emulsion was formed. This emulsion had good handling properties and dried to a silicone elastomer after water evaporation. Example 11 Using parts based on siloxane polymer, 100 parts of the PDMS polymer of Example 1, 2.0 parts of AOPS, 2.0 parts of MTM (methyltrimethoxysilane) and 1.0 part of AAPS/acetic acid mixture (aminoalkoxypolysiloxane) were mixed with glacial acetic acid at a 1 g of AAPS/0.07g of AcOH ratio. This mixture was then mixed together in a 10L Turello™ Mixer, Turello, Italy. 4.0 parts of a 50/50 by weight mixture of TERGITOL™ TMN-6 and water (45% solid surfactant) were then mixed in until an emulsion gel was formed. This 96% silicone content oil in water (O/W) emulsion was then diluted with 21 parts of deionized water. This produced an 80% silicone content O/W crosslinked silicone latex. This material was evaluated for freeze/thaw stability. Material that had been freshly made survived 10 cycles of freeze/thaw cycling. Elastomers made from the silicone latex initially had a Shore A durometer of 8, tensile strength of 586.1 kPa (85 psi) and elongation of 1307. Elastomers made from the silicone latex after 10 F/T cycles had a Shore A durometer of 11, tensile strength of 586.1 kPa (85 psi) and elongation of 1193. Material that had not been cured but aged for 12, 24 and 48 weeks also survived 10 cycles of freeze/thaw cycling. Example 12 Using parts based on siloxane polymer, 100 parts of the PDMS polymer of Example 1, 2.0 parts of AOPS, 2.0 parts of MTM and 1.0 part of AAPS/acetic acid mixture of Example 11 were mixed together in the same mixer of Example 11. 7.4 parts of Arquad™ T-27, a cationic surfactant that comes as a 27% by weight aqueous solution, were then mixed in until an emulsion gel was formed. This 93% silicone content O/W emulsion was than diluted with deionized water to an 80% silicone content O/W crosslinked silicone latex. This material passed 10 cycles of freeze/thaw cycling without coagulating. Elastomers made from the silicone latex had a Shore A durometer of 10, a tensile strength of 262 kPa (38 psi) and an elongation of 222. Example 13 Using parts based on siloxane polymer, 100 parts of the PDMS polymer of Example 1, 2.0 parts of AOPS, 2.0 parts MTM and 1.0 part of the AAPS/acetic acid mixture of Example 11 were mixed together in the same mixer as Example 11. 6.0 parts of the same TERGITOL™ and water solution of Example 11 were then mixed in until an emulsion gel was formed. This 96% silicone content O/W emulsion was then diluted with 13.7 parts of deionized water. This produced an 84% silicone content O/W crosslinked silicone latex. A 75% solid slurry of calcium carbonate (OMYACARB™ 3) was then added to this material at different levels. Table 1 summarizes the results. Hereinafter, the columns D, T and E of the Tables stand for Durometer reading (Shore A), Tensile Strength (kPa) and Elongation, respectively. slurry pts Total Content % filler/PDMS ratio F/T cycles # D Shore A T kPa E % 0 78 0 10 6 510.2 1357 53.3 86.3 0.38 10 7 475.7 900 106.7 83.5 0.76 5 12 648.1 1148 133.3 81.8 0.95 2 14 593.0 1024 160 82.6 1.14 2 14 544.7 823 Example 14 Using parts based on siloxane polymer, 100 parts of the PDMS polymer of Example 1, 2.0 parts of AOPS, 2.0 parts of MTM and 1.0 part of the AAPS/acetic acid mixture of Example 11 were mixed together in the same mixer of Example 11. Then, the same amount of the TERGITOL™ and water mixture of Example 11 were mixed in until an emulsion gel was formed. This 96% silicone content O/W emulsion was than diluted with 21 parts of deionized water. This produced an 80% silicone content O/W crosslinked silicone latex. To this material various fillers were added. Table 2 reports the number of Freeze/Thaw cycles, hardness, tensile strength and elongation values of the elastomer after various fillers were added. Filler Total Content % filler /PDMS ratio F/T cycle # D Sh-A T kPa E % ATH S-3 a 74 0.40 10 22 627.4 1080 ATH S-23 b 77 0.65 10 24 661.9 1173 Al-Tab c 80 1.0 10 24 606.7 780 Omya-5 d 80 1.0 10 25 599.8 1107 Omya-21 e 80 1.0 10 27 503.3 867 10ES Wollas f 77 0.65 10 28 882.5 767 SparW-44 g 80 1.0 10 23 565.4 867 DicalWB5 h 70 0.15 10 22 923.9 1027 Siltex44 i 77 0.60 10 26 820.5 480 325Nova j 79 0.80 10 26 813.6 760 200Nova k 80 1.0 10 28 717.1 440 Example 15 Two silicone latices were prepared. Base #1 Using parts based on siloxane polymer, 100 parts of the PDMS polymer of Example 1, 2.0 parts of AOPS, 2.0 parts of MTM and 1.0 part of the AAPS/acetic acid mixture of Example 11 were mixed together in the mixer of Example 11. Then, the same amount of the TERGITOL™ and water solution (45% solid surfactant) were mixed in until an emulsion gel was formed. This 96% silicone content O/W emulsion was then diluted with 21 parts of deionized water. This produced an 80% silicone content O/W crosslinked silicone latex. Base #2 Using parts based on siloxane polymer, 100 parts of the PDMS polymer of Example 1 and 2.0 parts of AOPS were mixed together in a 10L Turello mixer. 4.0 parts of a 50/50 by weight mixture of TERGITOL™ TMN-6 and water (45% solid surfactant) were then mixed in until an emulsion gel was formed. This 96% silicone content O/W emulsion was then diluted with 21 parts of deionized water. This produced an 80% silicone content O/W crosslinked silicone latex. The following samples were prepared by mixing the above prepared materials with different fillers and diluting to the desired silicone content. For the silica samples, two silica/PDMS ratios, 4.9 and 9.8, were utilized. These gave latices with a total silicone content (silica + silicone)/total weight of 52% and 54%. For instance, 123 g of Base #1 would be mixed with 33.1 g of NALCO™ 2326 colloidal silica and 43.8 g of deionized water. This would give a silica/PDMS ratio of 4.9% and a total silicone content of 52%. The controls were Base #1 and Base #2 without any fillers. The fillers used were selected from groups of colloidal silicas, dispersed fumed silicas and non-siliceous fillers as follows: Colloidal silicas: Trade name % solids surface area (m 2 /g) stabilizing ion Nalco™ 2326 15 600 NH4+ Nalco™ TX8806 30 375 NH4+ Nalco™ 1115 15 750 Na+ Nalco™ 1034A 34 150 - Dispersed Fumed Silicas: Cabosperse™ S3810 14 380 Na+ Cabosperse™ S2095 17 200 Na+ Cabosperse™ A2095 17 200 NH4+ Non-siliceous Fillers: Omyacarb™ -3 2.5 - (calcium carbonate) Hydral™ 710 6-12 - (alumina trihydrate) These latices were allowed to dry for two weeks. Samples from the resulting elastomeric films were then stored in weighing pans and next placed into 150°C. and 200°C. ovens. Weight loss was tracked over time. Samples of a (non-latex) RTV silicone rubber were also tracked. The weight loss data is given in Table 3. Sample %filler/PDMS (pts) 150°C. 200°C 3wk 12wk 3wk 12wk %wt loss % wt loss RTV 2.6 6.5 6.1 13.9 Filler BASE #1 BASE #2 150°C. 200°C. 150°C 200°C. 3wk 12wk 3wk 12wk 3wk 12wk 3wk 12wk None 3.9 5.3 6.9 10.6 5.0 --- 37.2 47.3 Colloidal silicas Nalco™ 2326 4.9 3.6 6.9 4.5 6.6 4.3 4.5 4.9 7.3 9.8 -- -- 2.8 3.8 4.2 8.7 Nalco™ TX 8806 4.9 3.6 4.6 4.7 6.3 3.1 3.6 3.9 5.6 9.8 3.3 4.3 5.0 5.9 2.8 3.7 4.7 6.7 Nalco™ 1034 4.9 3.9 5.8 4.7 5.4* --- --- Nalco™ 1115 4.9 5.9 13.8 24.6 69 4.8 10.7 12.9 79.0 9.8 5.3 15.3 10.9 68 4.0 10.3 9.2 80.0 Dispersed Fumed Silicas C 1 S3810 4.9 3.7 4.6 8.4 58.0 3.5 4.4 -- 43.5 9.8 4.1 2.3 8.2 36.4 3.8 4.9 10.3 41.2 C A2095 4.9 -- -- 2.5 3.8 4.6 4.8 9.8 -- -- 3.2 3.8 4.3 3.9 C S2095 4.9 -- -- 3.4 4.2 9.8 20.4 9.8 -- -- 3.9 5.7 8.6 40.9 1=Cabosperse™ Calcium Carbonates Omya™ -3 12 4.3 5.9 19.7 32.2 4.4 9.8 36.6 41.8 80 4.0 14.0 38.0 40.5 6.2 27.3 54.0 99.5 This example clearly shows that the Base #1 control and Base #1 or #2 with ammonia stablized silicas are as stable or more stable than the RTV silicone rubbers. Additional data on the physical properties of these elastomers is shown in Table 4. D Shore A T kPa E % (RTV comparison) 22 7,694.6 1440 SELF-CATALYTIC CROSSLINKER= Base #1 formulation Parts D T E control (no filler) 17 765.3 1260 CaCO 3 12 22 717.1 1140 80 26 620.5 1253 Nalco™ 1034 4.9 21 579.2 800 Nalco™ 1115 4.9 33 1,999.5 1420 9.8 44 3,771.5 1573 SELF-CATALYTIC CROSSLINKER= Base #2 formulation Parts D T E control(no filler) 3 137.9 580 Cabosperse™ A2095 4.9 7 206.8 587 9.8 20 1,261.8 1747 Cabosperse™ S2095 4.9 8 275.8 687 9.8 16 1,048.0 1307 Cabosperse™ S3810 4.9 11 393.0 987 9.8 21 1,323.8 1293 Nalco™ 2326 4.9 25 986 1153 9.8 48 2,109.8 993 Nalco™ TX8806 4.9 13 434.4 946 9.8 32 1,737.5 1367 Nalco™ 1115 4.9 18 992.9 1320 9.8 30 1,537.5 1120 CaCO3 12 5 137.9 560 80 5 110.3 320 Example 16 A laboratory dynamic mixer of the rotor-stator type had a length of 25.4 cm (10 inch) with an internal diameter of 3.8 cm (1.5 inch). To the exit port was attached a static mixer containing an inlet port for dilution water. To the polymer feed line, prior to the entrance to the mixing zone, was also attached a static mixer containing an inlet port for the self catalytic crosslinker. In this case, a dimethylmethyldiethylhydroxylaminesiloxane copolymer was used. The dynamic mixer itself had inlet ports for a water/surfactant mixture and for a polymer feed. The self-catalytic crosslinker was fed into the polymer stream prior to the static mixer. This mixture was then fed into the mixing zone, while the surfactant/water was fed into another inlet and into the mixing zone. With the rotor turned on, and the dilution water turned off, a clear gel having 96% silicone content O/W emulsion was prepared. The dilution water was turned on to prepare a 91% silicone content latex which had a white, paste-like appearance. This material formed a very slightly tacky silicone elastomer after water evaporation. The following conditions were used: 50,000 mm 2 /s (cs) Si-OH terminated PDMS feed 115 g/min self-catalytic crosslinker feed 2.6 g/min 45% aqueous TERGITOL™ TMN-6 surfactant feed 4.4 g/min deionized water for feed dilution 7.2 g/min rotor RPM 900 Example 17 Using parts based on siloxane polymer, 100 parts of a polymer mixture consisting of 85% Si-OH terminated PDMS, 12% monosilanol terminated PDMS and 3% Si-Me 3 terminated PDMS, 2.0 parts of AOPS, 2.0 parts of MTM, 1.0 part of RAPS and 0.076 part of glacial acetic acid were mixed together in a 10L Turello mixer. 6.0 parts of a 50/50 by weight mixture of TERGITOL™ TMN-10 and water (45% solid surfactant) were then mixed in until an emulsion gel was formed. This 96% silicone content O/W emulsion was then diluted with 21 parts of deionized water. This produced an 80% silicone content O/W crosslinked silicone latex. For a 100 g sample, 45.3 g of the above material was mixed with 36.6 g of Alcoa Hydral™ 710 alumina trihydrate (ATH) (Alcoa Industrial Chemicals Div, Bauxite, AR), 2.16 g of Joncryl™ 61LV dispersant (Johnson Wax Speciality Chemicals, Racine, WI), 0.25 g of aminomethylpropanol (AMP-95) (Angus Chemical Co., Buffalo Grove, IL) and 15.7 g of water. This yielded a filled silicone latex with a total silicone content of 74.2% and a ATH/silicone ratio of 0.97. This resulting elastomer from this material was aged at 150°C. and 200°C. After 6 weeks at 150°C., this material had only lost 3.3% of its weight, while at 200°C. it had only lost 10.6% of its weight. This compares to the non-latex DC 3145 RTV silicone rubber which lost 3.7% after 6 weeks at 150°C. and 7.9% after 6 weeks at 200°C. Example 18 Using parts based on siloxane polymer, 2 parts of AOPS were mixed into 100 parts of the PDMS polymer of Example 1 in the laboratory mixer of Example 1. 4.0 parts of a 50/50 solution of water and TERGITOL™ TMN-6 was then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted to an 80% silicone content emulsion. This formulation formed a silicone elastomer after water evaporation. The clarity value equaled 2.15 mm (86 mils). Example 19 Using parts based on siloxane polymer, 2 parts of AOPS, 2 parts of MTM and 1 part of a 1:1 molar solution of AAPS and acetic acid were mixed into 100 parts of the PDMS polymer of Example 1 in a laboratory mixer (Whip™ Mix). 4.0 parts of a 50/50 solution of water and TERGITOL™ TMN-6 were then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted to an 80% silicone content emulsion. This formulation formed a silicone elastomer after water evaporation with a tensile strength of 703.3 kPa (102 psi) and an elongation of 1664. The clarity value equaled 4.5 mm (176 mils), the maximum reading. Example 20 Using parts based on siloxane polymer, in separate experiments 0.5, 1.0, 2.0 and 3.0 parts of AOPS, were mixed into 100 parts of 60,000 mm 2 /s (cs) trimethoxysilylethylene endblocked PDMS polymer in a laboratory mixer (Whip™ Mix). 4.0 parts of a 45% solution of water and TERGITOL™ TMN-6 were then mixed in until a very high solids emulsion gel was formed. This emulsion gel was diluted to an 80% silicone content emulsion. These formulations all formed a silicone elastomer after water evaporation. The 0.5 part and 1.0 part AOPS samples formed tacky elastomers even after 11 weeks of gestation of the wet dispersion. The 2.0 part AOPS sample formed a tack-free elastomer after 5 weeks of gestation of the wet dispersion. The 3.0 part AOPS sample formed a tack-free elastomer after 3.5 weeks of gestation of the wet dispersion.

Claims: A method for making a crosslinked polysiloxane dispersion, comprising the steps of blending components comprising a siloxane polymer or polymer mixture having a viscosity of 5000 to 500,000 mPa.s and a molecular formula (I) X 3-n R n -YO-(R 1 2 SiO) z -Y-R n X 3-n where n is 0, 1, 2 or 3 and z is an integer from 500 to 5000 and X is a hydrogen atom, a hydroxyl group or any condensable or any hydrolyzable group, Y is a Si atom or a Si-(CH 2 ) m -SiR 1 2 group, R is individually selected from alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl, alkenyl and aryl groups and R 1 is individually selected from X, alkyl, alkenyl and aryl groups, a surfactant, water and from 1 to 5 parts by weight, per 100 parts of siloxane polymer, of at least one self-catalysing crosslinker selected from R 4 SiQ 3 , SiQ 4 , partial hydrolysis products of R 4 SiQ 3 and SiQ 4 , and copolymers of the formula in which Q is selected from carboxylic groups, hydroxylamine groups and oxime groups and R 4 is an alkyl group of 1 to 8 carbon atoms inclusive or vinyl, a is 0 or a positive integer and b is an integer greater than 2, wherein the self-catalysing crosslinker is added to the siloxane polymer before mixing with the water and surfactant; mixing said components at a sufficiently high shear to transform the components into a gel phase and, optionally, diluting the gel phase with water, the method being carried out in the absence of a heavy metal catalyst. The method of claim 1 wherein the polysiloxane dispersion has a silicone content of from 1% to 98%. The method of claim 1 wherein 1 to 10 parts by weight of surfactant are present in the emulsion for 100 parts of siloxane polymer or polymer mixture. The method of claim 1 wherein 3 to 30 parts by weight of water are present in the emulsion for 100 parts of siloxane polymer or polymer mixture. The method of claim 1 wherein 0.1 to 5 parts by weight of self catalyzing crosslinker are present in the emulsion for 100 parts of siloxane polymer or polymer mixture. The method of claim 1 wherein the self catalyzing crosslinker is where R 4 is the same or different alkyl group of from 1 to 8 carbon atoms inclusive or vinyl and a is 0 or a positive integer and b is an integer greater than 3. The method of claim 1 comprising the additional step of adding, before or after mixing, a stabilizer of the formula: where Me is a methyl group and z is an integer from 3 to 40 inclusive. The method of claim 1 comprising the additional step of adding prior to mixing an in situ resin reinforcer selected from the group consisting of methyltrimethoxysilane, vinyltrimethoxysilane, tetraethylorthosilicate and normal propylorthosilicate. The method of claim 1 wherein the surfactant is not an alkyl sulfate, alkyl sufonate or taurate. The method of claim 1 wherein the surfactant's degradation products at a temperature greater than 100°C. do not include siloxane redistribution catalysts. The method of claim 1 comprising the additional step of adding a filler either before or after mixing. The method of claim 1 wherein the dispersion has a crosslinked siloxane phase and a surfactant/residual water phase and the refractive index of the crosslinked siloxane phase is the same as the refractive index of the surfactant/residual water phase.

Inventors: BERG DANIEL TRENT, JOFFRE ERIC JUDE, BERG, DANIEL TRENT, JOFFRE, ERIC JUDE
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1996
Main classification: C08L83
IPC codes: C08L83, C08J3