MXPA97008180A - Procedure for preparing auto-curable and alkylene-siloxan hydroxide co-polymers and reversing composition - Google Patents

Abstract

A sequence catalysis of the ring-opening polymerization of cyclic organosiloxanes using a base catalyst which can be neutralized by a Lewis acid catalyst of subsequent redistribution or condensation, preferably a phosphonitryl compound, allows rapid synthesis of functionalized and polyfunctional silicone copolymers such as alkenyl hydride copolymers, a new material composition, which is a silicone component curable by means of hydrosilylation or radical polymerization with peroxide, the alkenyl hydride copolymer is formulated into a curable composition, emulsified and coated in a Airbag for car and it is subsequently cured

Description

PROCEDURE TO PREPARE AUTO-CURABLE COIL-SILOXAN HIDRURQ COPOLYMERS AND COATING COMPOSITION FIELD OF THE INVENTION The present invention relates to a catalyst and process for the preparation of siloxane copolymers of hydrogen. The process of the present invention makes possible the synthesis of new compositions of matter, mixed ilicon polymers having mixed functionalities. These new compositions allow the manufacture of new articles of manufacture especially air bag coverings.

BACKGROUND OF THE INVENTION The majority of the coating compositions used for automobile air bags are chloroprene resin blends. These chloroprene resin blends are also used in the treatment of fibrous base materials in the form of woven, spunbond and non-woven fabrics of polyarnide fibers by impregnation, coating or lamination. The resulting mixed body materials have excellent properties inherent to both polyarylene fibers and chloroprene resin and are useful in a variety of applications.

However, these mixed-body materials have some disadvantages. They tend to gradually lose their strength when they are allowed to stand at a certain temperature for a long term since the chloroprene resin releases hydrogen chloride which acts to cut the amide ligatures of the polyamide fibers. Since the chloroprene resin is relatively inelastic, the resin restrains poiiarnide fibers from the fibrous base material in the rnix + body material or to an excessive degree, thus preventing free movement of the fibers. In this way, mixed-body materials have a relatively hard feel and tear resistance. In order to overcome these disadvantages, it has been proposed to use coating compositions comprising silicone resins which are superior to chloroprene resins with respect to heat resistance, metatherism, and flexibility. Typical compositions are mixtures of a heat-curable ilicon resin and an adhesive and mixtures of an addition-cure type silicone rubber and an adhesive. These silicone coating compositions are applied to air bag base materials, particularly for automobiles or the like to form coatings thereon which are generally about 40 microns thick. However, to meet market demand for lightweight, compact and low-cost products, it is desired to reduce the thickness of the coating.

As the thickness of the coating is reduced, conventional coating compositions tend to increase in burn rate. When applied to automotive airbags, such thin liners allow the airbags to have holes during the explosive expansion of an inflator. As a result, air pockets lose gas impermeability and thus are impractical as they do not work for their intended purpose. The polydirnethylsi loxane fluids can be conveniently prepared by any of the different synthetic methods. A widely used industrial process for preparing such fluids involves the hydrolysis of halofunctional silanes followed by condensation. A second process begins with cyclic organosiloxanes using an open ring polymerization to produce a mixture of linear or cyclically controlled organosiloxane or equilibrium cyclic compounds. Open ring polymerization of cyclic organosiloxanes has generally been by acid or base catalysis. Catalysts that have been used successfully vary from numerous catalysts such as tri-loromethane sulfonic acid to very basic such as potassium hydroxide or potassium silanolate. A wide variety of acid catalysts have been employed to catalyze open ring polymerization, sulfuric acid, acid washed clays, acid ion exchange resins and linear phosphonitrilic chlorides (LPNC). Although open ring polymerization can be accomplished with an acid or basic catalyst, the preservative chemistry of hydrogen-containing siloxanes (ie, silyl hydrides) is restricted to acid catalysts. When a basic catalyst is used, open ring polymerization continues, but the abstraction of base catalyzed hydride yields hydroxy functionalities instead of the hydrogen functionalities and the material is condensed through the silanol groups. The hydride functionality of es + a way does not survive the basic reaction conditions. Although this produces a polymer, it produces an entangled polymer in contrast to a linear polymer. Process considerations in the choice of an acid catalyst for the preparation of hydrogen organosiloxanes tend to require mild acidic catalysts in contrast to sulfuric acid and trifluoromethanesulphonic acid since these acids are very strong and highly corrosive. The use of such strong acids requires the use of special alloys in process vessels to prevent acid-induced corrosion and contamination of the resulting product. The softer acid catalysts such as the acid-washed clays and acid ion exchange reams have disadvantages which, while avoiding the corrosion and contamination problems associated with the attack of strong acid in metal process vessels, cause other problems. Acid ion exchange reams do not maintain the catalytic activity well for a significant and economically useful period, requiring frequent regeneration or refrigeration. The acid-washed clays are generally used as powders to improve the efficiency of the contact between the reaction substrate and the catalyst, which requires a downstream filtration to remove the fine particles of the acid-washed clay catalyst from the product. In addition, the acid-washed clays usually contain residual amounts of water which contribute to a hydride silanol exchange which results in a gradual and undesired condensation polymerization of the hydride product. By comparison with the strong acid catalysts, these softer acid catalysts suffer from lower reaction rates and thus lower production of the product per unit time at any given temperature. Although the differences in the emetic velocity of any given catalyst can be biased by an increase in temperature, this solution has at least two serious disadvantages. The first is that as the temperature changes, ie increases, the relative proportions of reagents, desired products and unwanted byproducts change. This change may benefit the desired procedure or may impair depending on the relative amounts of the desired product as a function of the increased temperature since the equilibrium constant for reaction is a function of temperature. As the temperature increases, the amount of energy supplied to the reaction to increase the temperature must increase (for endothermic reactions) and this almost always adversely affects the economics of the procedure. In this way, there is a complex balance between the desired reaction rate, the desired product mixture, the catalyst activity and the process operation variables. In contrast to the acid catalysts that must be neutralized, for example sulfuric acid, or separated from the product, for example, acid washed clays, phosphomethyl halides, particularly linear phosphonitrile chlorides (LPNC), have found particular use for redistribution and condensation. of organosiloxane oligomers. These LPNC catalysts must be used at sufficiently low levels in the reaction to be catalyzed, for example between 25 and 2,000 pprn. An additional advantage is that the catalyst must be left in the product and thermally deactivated if desired. This procedure usually does not result in significant product contamination. Although LPNC catalysts have been particularly useful for the redistribution and condensation reactions having silicones and siloxanes, they have not been used for open-ring polymerization because of the low velocities associated with these catalysts in reactions of this type. Although it is possible to obtain acceptable reaction rates in the synthesis of hydride siloxane organosiloxane copolymers when the hydride level is above about 1,000 ppm, the speed of the ring-open polymerization in the presence of a low hydride level siloxane ( - 300 ppm) is extremely slow requiring a matter of days instead of hours. Thus, LPNC materials would not be expected to be well suited particularly to catalyze open-ring polymerization in the presence of low-hydride siloxanes to make siloxane polymers with low hydride content.

BRIEF DESCRIPTION OF THE INVENTION The invention comprises a curable silicone composition comprising: a) an ilicon hydrocarbon copolymer having the formula: having at least two Dq where Dq is different from any other Dq and each Dq has the formula: D , = SlR * R2? 2/2 wherein each R * and R2 in each D, is independently selected from the group consisting of hydrogen monovalent hydrocarbon radicals of one to forty carbon atoms wherein each subscribed q of Dq is independently one or more with M = R4 R5 R6 S03 / 2 wherein R *, S and R * are independently selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms wherein the stoichiometric subscript or M is non-zero and positive; T = R? Yes? 3/2 where R? is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms with the stoichiometric subscript r of T zero or positive; and 0 = SÍO4 / 2 with the subscribed stoiquerometric s of 0 is zero or positive; subject to the limitation that one of R1, R2, R3 t R * f RS t ß and R7 is hydrogen and that one of Rl, 2, R *, RS, Rβ7 qUT is not hydrogen is an alkenyl group having two to forty carbon atoms wherein said silicon hydride copolymer comprises an alkenyl group; b) a catalyst. The invention further provides for a curable emulsion comprising: having at least two Dq where Dq is different from any other Dq and each Dq has the formula: D, = lRlR202 / 2 wherein each R1 and R in each D, is independently selected from. from the group consisting of hydrogen monovalent hydrocarbon radicals of one to forty carbon atoms wherein each subscript q of D is independently one or more with M = R * R5 R6 _? 03/2 where R *, "&Rt; are independently selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms wherein the stoichione subscript u of M is non-zero and positive, T = R? Sl? 3/2 where R? selects from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms with the subscribed stoicheornetpco of zero or positive T, and 0 = S1O4 / 2 with the subscribed stoic acid s of 0 is zero or positive; subject to The limitation that one of R *, R2, R3 and R * t RS t Rß R7 is hydrogen and that one of Rl, R2, R *, R51 Rβ and R7 which is not hydrogen is an alkenyl group having two to forty carbon atoms wherein said silicon hydride copolymer comprises an alkenyl group; b) a catalyst. c) an ernulsifying agent; and d) water.

As a consequence of these two new compositions, the invention further provides for articles of manufacture comprising both curable compositions and the curable emulsions of the present invention. Since these curable compositions and emulsions can be used as coatings, the invention also provides for laminates made with these novel compositions and emulsions.

DETAILED DESCRIPTION OF THE INVENTION It will now be described that the silanolate catalysts can be used for an initial open ring polymerization reaction of cyclic organosiloxanes followed by the introduction of phosphonitryl halide catalyst and hydrogen-containing organosiloxane for the subsequent redistribution and condensation reaction to produce an organosiloxane copolymer which contains hydrogen driven in the same reaction vessel. In this way, the method of the present invention comprises the following steps: l) D? > H0SlRlR2 (D,) SlRlR20H base catalyst wherein D = S1RIR202 2 with Rl and R2 is independently selected from monovalent hydrocarbon radicals of one to forty carbon atoms and q > x, with x that varies usually as follows 3 <; x < B. The base catalyst may be any generally known in the art for polyrnering cyclic organosiloxanes, however, the catalyst must be capable of neutralizing by an acid species, be it Arrhenius acid, Bronsted acid or Le is acid. The preferred acid neutralizing agent is a Lewis acid selected from the group of phosphonitrile halides. Catalysts such as an alkali metal silanolate, an alkali metal hydroxide, and a tetra-organo-substituted ammonium hydroxide such as tetrarnetillarylonium hydroxide and the like are preferred. 2) Base catalyst (from reaction 1)) + Lewis acid catalyst > neutralization complex, 3) MDHp + H0SlRlR2 (D,) SlRlR20H > MDHpDqM Lewis acid catalyst where DH =? R3H02 2 where R3 is selected from monovalent hydrocarbon radicals of one to forty carbon atoms (alternatively DH = 1RIR202 / 2 with RI and R2 selected from the hydrogen group and monovalent hydrocarbon radicals of one to forty carbon atoms wherein one of R1 and R2 is hydrogen) and wherein M = R * RSRßS? 0? 2 wherein R *, RS and Rβ are independently selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms wherein the subscripts p and q are positive integers ranging independently from about 1 to about 1,000, preferably from about 1 to about 700, more preferably from about 1 to about 500, and most preferred from about 1 to about 400. It should be noted that the process of the present invention is very advantageous when it is desired to make copolymers having sufficiently low levels of hydride present, that is, when the subscribed stoichiometric product in the copolymer is much larger than the stoichiiornetric subscript P- The Le? Is acid catalyst for reaction 3) is selected from the group consisting of phosphonitrilic halide catalysts as described and taught in the Patent E.U.A. 5,420,221; as well as those and including but not limiting to: (X3P (NPX2) n P 3) + PXß- where n is an integer from 1 to 6 and X is a halide selected from the group consisting of F, Cl, Br , and I. (X3PINPX2) nNPX3) + PXß ~ where n is an integer from 1 to 6 and X is a halide selected from the group consisting of F, Cl, Br, and I; (X3PINPX2) nNPX3) + EXm- where E is an element that has an electronegativity value of 1.2 to 2 such as Al, b, P, Sn, Zn, and Fe with n an integer from 3 to 8; 0 (X) 2-_Y_P (NPX2) bNPX3-cYc where b is an integer ranging from 0 to 8, is O or l, c is O ol, and is selected from the group consisting of OH, OR ' and R'CO? wherein R 'is alkyl or aplo; 0 (X) 2- * Y_P (NPX2) bNP (0) X2-cYc where b is an integer that varies from 0 to 8, a is 0 or 1, c is 0 or 1, X is a halogen selected from of the group consisting of fluorine, chlorine, bromine and iodine, and is selected from the group consisting of OH, OR 'and R'C02 wherein R' is alkyl or aryl; X3-P (H0) pP (NPX2) mNP (0) X2, wherein X is a halogen selected from the group consisting of F, Cl, Br, and I, and is an integer ranging from 0 to 6 and p is 0 or 1; and X3PINPX2) m PX2 (0) wherein the values of m may vary from 0 to 6. It is preferred that the initial open ring polymerization be carried out in the presence of a rich chain termination source of M. In this manner , although it is preferred to use short-chain low molecular weight M-rich compounds to control the equilibrium distribution of polymer, the use of M-rich compounds of greater structural complexity such as those incorporating branching points T or 0 thus produces polymers branched The reaction of the product polymer, either co or the linear or branched polymer, with the hydride of reaction 3) produces a copolymer which is also linear or branched. The molar ratio of the M-rich siloxane compound to the cyclic siloxane compound governs the equilibrium distribution of the resulting polyrnomeric siloxane. Although it is desired to use M-rich chain termination compounds in reaction 1), the nature of the substituents in unit M may vary to impart additional functionality to the reaction product 3). For example, one of the R groups in the M group may contain olefinic msaturation. In this manner, a copolymer which is simultaneously a hydride and an alkene organosiloxane can be prepared by reacting a rich compound of M containing an alkene substitution in the initial open ring polymerization to produce an alkene intermediate which is then condensed and redistribute to produce the difunctional compound M "* DHp Dq v * where Mvi = M where one or more of R *, R5 and R6 is a monovalent alyl radical. Alternatively, the rich M-compound used as a chain-retaining agent in the initial open-ring polymerization may be just conventional, such as with a threptenium-retained compound, but the cyclic compound is functionalized, for example, a tetra-in where one of the groups R in each unit D is a monovalent alkene radical, for example Dvi, an idiosyncratic symbol for a group D containing alchem, where the superscript vi indicates that one or more of R1 and R2 is a monovalent alkenyl radical . Similarly, the overwritten Ph indicates that one or more of R1 and R2 is a phenyl radical or other aromatic radical. Due to the unique selectivity of this reaction sequence, the cyclic compounds that are the starting materials can also be functionalized. Thus, if one of the groups R in the units D comprising the cyclic organosiloxanes is an alkenyl group, a chain alkenyl, hydride in chain copolymer can be prepared, for example, iDHp viqMvi Instead of using a single cyclic species for the ring-open polymerization, mixtures of cyclic species can be employed and each cyclic species can be functionalized differently to prepare complex copolymers which are then reacted to form complex hydride copolymers. These materials have the general formula: DHpDlqiD2q2 - - .DnqnTrO. u where Hp f -. D qi? D2q2? . . . ? Dnqn, ie none of the different D's are alike, and the subscribed qi to qn, for all n different D groups, satisfy the definition for the subscribed q as previously described and the subscribed r, syu in the units Tr, 0 *, Mu that are tri functional, tetra functional or rnonofunctional units that vary over the same values as po q. In this way the di functional compound M «* DH p Dq« • where Mv = M where one or more of R *, R5 and Rβ is an alkenyl group is a member of this series; the di-functional compound DHpD "i where Dv * = D where R or R2 is an alkenyl group is a member of this series, the tri-functional compound Mvi DHpDwiq wl is a member of this series. Two cyclic species, for example Dqi and D, give rise to a copolymer of the first stage reaction. By an open-ring polymerization of more than two cyclic species, for example D i D2q2 ... D "qn and D, a polymer of Higher order of the first stage reaction. The precursors that contain the different groups D, Diqi? D2q2? - 4 D "n, can be functionalized differently leading to a multifunctional first stage product.In addition, the choice of a compound rich in functionalized or non-functionalized M leads to an initial product that is not functionalized or functionalized in the terminal positions of The second-stage reagent can be differeted from the product of the first stage so that copolymers or di, tri, tetrafunctionalized, and similar copolymers of the second stage reaction can arise. Thus, the method of the present inven allows the production of the following new material compositions: wi HpDq i, the variants T, 0 and TO Mvi DHP D TG Mvi, MviDHpDqO «M« i and M iDHpDqTrO «« i; MDHpDviq the variants T, 0 and TQ MDHpD iqTrM, MDHpDvi, Q, M, and MDHpD iqTrQt; viDHpD "iqMvi the variants of T, Q and TQ Mvi DHp Dv i, Tr Mvi, M" i DHP D «q Q, Mv, yvi DHp D" iq Tr Q, i; iDHpD'qiDq2 vi, the variants of T, Q and TQ MviDHpD'qiD, 2TrMvi, M i DHp D 'qi Dq2 Qß Mv i and Mv i DHp D'q D, 2 Tr Q »Mv i; DHpD i,? Dq2M, the vanantes of T, Q and TQ DHp iqiDq2Tr M, MDHpDviqiDq2Q «M, and MDHpDviqiDq2TrQ« M; M iDHp iqiDq2 vi, the variants of T, Q and TQ M iDHp iqlDq2TrM i, i DHp D iq? üq 2Q «vi, and MviDHpD iq Dq2TrQtM i; the higher order polymers based on D qi D2q2? - D "qn and the variants T, Q and TQ thereof, and the like, including the H variants. The curable compositions of the present invention comprise: (a) alkenyl hydride having the formula: M" D, rrQ ., which has at least two Dq where Dq is different from any other Dq and each Dq has the formula: D, = S1R1R202 / 2 where each Rl and R2 in each D is independently selected from the group consisting of hydrogen monovalent hydrocarbon radicals of one to forty carbon atoms wherein each q subscript of Dq is independently one or more with wherein R *, Rβ and Rβ are independently selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms wherein the subscribed stoichiomernet of M is non-zero and positive, T = R7.103 / 2 wherein R? is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms. arbono with the subscribed stoiquerometric r of T zero or positive; and Q = Si0 «/ 2 with the stoichiometric subscript s of Q is zero or positive; subject to the limitation that one of R, R 2, R 31 R *, RS t R b and R * is hydrogen and that one of R 1, R 2, R *, R, R 7 R 7 which is not hydrogen is an alkenyl group having two to forty carbon atoms wherein said silicon hydride copolymer comprises an alkenyl group; b) a hydrosilylation catalyst. The curable compositions of the present invention comprise the curable silicone composition of the present invention in an emulsion form, comprising: (a) an alkenyl hydride having the formula: M "D, TrQt, having at least two Dq where Dq is different from any other Dq and each Dq has the formula: D, = SÍR1R202 / 2 where each Rl and R2 in each D, is independently selected from the group consisting of hydrogen monovalent hydrocarbon radicals of one to forty carbon atoms in which each subscript q of Dq is independently one or more with ti - R * RS R6 SÍ03 / 2 wherein R *, Rβ and Rβ are independently selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms in which the stoichiometric subscript u of M is non-zero and positive; T = R7S03 2 wherein R7 is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms with the stoichiometric subscript r of T zero or positive; and Q = SÍO4 / 2 with the stoichiometric subscript of Q is zero or positive; subject to the limitation that one of R, R2, R3 R * t RS t Rß and R7 is hydrogen and that one of R, R2, R *, Rβ and R7 that is not hydrogen is an alkenyl group having from two to forty carbon atoms wherein said silicon hydride copolymer comprises an alkenyl group; b) a hydrosilylation catalyst; (c) an emulsifier; and (d) water. As a curable silicone composition, component (a), the alkenyl hydride (MuDqTrQ «), ranges from about 99.99% by weight, preferably from about 10 to about 99.99% by weight, most preferably from about from 20 to about 99.99% by weight, and most preferably from about 30 to about 99.99% by weight of the total composition; component (b), the catalyst, varies from around 0. 01 to about 5% by weight; preferably from about 0.01 to about 3% by weight; preferably from about 0.01 to about 1.5% by weight, and most preferred from about 0.01 to about 0.75% by weight. Component (b) is a catalyst for the curing of alkenyl hydride. Since alkenyl hydride contains both olefinic saturation and active hydrogen functionalities, the catalyst that can be employed is a hydrosilylation catalyst, typically a hydrosilylation catalyst comprising a noble metal. Also, since the alkene hydride contains olefinic unsaturation, the olefin moieties can be polymerized by the addition of a free radical initiator, typically organic peroxides including but not limited to peroxycarboxylic acids and their derivatives. Combination catalysis, such as combination hydrosilylation catalysts with free radical catalyst may also be employed depending on the circumstances of use. When component (a) and component (b) do not add 100.00% by weight, additional optional ingredients have been added. For example, extension or reinforcement fillers may be added, such fillers including, but not limited to, molten silicon, precipitated silicon, ground quartz, carbon black, carbon fiber, carbon fibrils, graphite, calcium carbonate, alumina, silica. , silazane, treated silica, silica airgel, high surface areas of silica / crystalline and non-crystalline alunmas, titanium, magnesium, iron oxide, diatomaceous earth, chromic oxide, zirconium oxide, zirconium silicate, calcined clay and the like . Both the ream composition and the emulsion composition comprise the self-healing alkenyl hydride and a hydrosilylation catalyst. In this way, it can also be advantageous to employ hydrosilylation catalyst inhibitors. The Patents of E.U.A. 3,445,420; 4.256870; and 5,506,289, incorporated herein and by reference herein teach compositions suitable for use as inhibitors with noble catalyzed hydrosilylation catalysts. The compositions of the present invention may further comprise other materials added to improve the properties of the curable formulation or the properties of the cured formulation. Such materials include, for example, stabilizers ... When used as an emulsion, the emulsion comprises: (1) from about 0.1 to about 99, preferably from about 1 to about 95, more preferably from about 25 to about 90, and most preferred from about 50 to about 80% by weight of alkenyl hydride ((MuDqTrQt); (2) of about 0.0000001 to about 10, preferably from about 0.0000005 to about 5, more preferably from about 0.000001 to about 1, and most preferably from about 0.0000005 to about 0.5% by weight of a hydrosilylation catalyst; (3) from about 0.001 to about 50, preferably from about 0.01 to about 20, preferably from about 0.1 to about 10, and most preferred from about 1 to about 5% by weight of an emulsifier, and (4) from about 1 to about 99, preferably from above from about 10 to about 95, preferably from about 20 to about 90, and most preferably from about 40 to about 80% by weight of water. The emulsifying agents used to prepare the curable emulsions of the present invention may be any known in the art to ernulsify silicones as long as: 1) the agent and ulsifier does not interfere with the cure of the alkenyl hydride; 2) the emulsifying agent does not deactivate the hydrosilylation catalyst; and 3) the emulsifying agent does not participate in any unwanted chemical reaction. An emulsion is prepared by mixing the alkenyl hydrides of the invention together with any other silicone that can be mixed with surfactants, followed by the slow addition of water. A mill that creates a high shear stress can be used to invert the mixture in an oil-in-water emulsion. The emulsion can be cured by the addition of a platinum catalyst. The emulsifying agent is selected from the group consisting of ammonium, nonionic and cationic emulsifying agents. The ammonium emulsifying agents are preferably selected from the group consisting of alkyl, aryl, and alkyl sulfyl acid, wherein the alkyl groups are alkyl groups of 1 to 20 carbon atoms and the aplo groups are aryl groups of 6 to 30. carbon atoms. Preferred non-ionic ernulsifying agents are selected from the group consisting of C11-C15 secondary alcohol ethoxylate, ethoxylated non-lphenol, polyglypic fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene, polyoxyethylene secondary alkyl ethers wherein the alkyl group varies from 6 to 40 carbon atoms, polyoxyethylene alkyl ethers wherein the alkyl group ranges from 6 to 40 carbon atoms, polyoxyethylene alkyanolanes wherein the alkyl group is selected independently and vain from 6 to 40 carbon atoms, polyoxythylene alkylamides in which the alkyl group is independently selected and ranges from 6 to 40 carbon atoms, polyoxyethylene lanolins, lauplic ether P0E (4), laepentyl ether POE (9), laurel ether POE (23), sterile ether POE (20) sorbitol rnonopalrnitato POE (20), amphotenon betama surfactant, lauplrneti acid betaine iaminoacetic, beta-propyl-iron-n-diminoacetic acid betaine of coconut fat amide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, sodium N-lauryl sarcosine, and lanolin derivatives of quaternary ammonium salts. The cationic emulsifying agents are preferably selected from the group consisting of ethynylated monono-methyl quaternary ammonium halides, rnonornetylethylated ammonium sulfate, alkyl t-phenyl-ammonium halides, and alkyl phenyl-alkyl sulfate wherein the alkyl group of said cationic surfactant varies from about 9 to about 30 carbon atoms. A preferred group of emulsifying agents are nonionic emulsifying agents, preferably those nonionic emulsifying agents having a hydrophilic to lipophilic balance ratio ranging from about 6 to about 17, more preferably ranging from about 7 to about 7. to about 16 and most preferred to range from about 8 to about 15. Particularly preferred emulsifying agents are ethoxylate of C11-C15 secondary alcohol and ethoxylated nonyl phenol. These ernulifying agents can be used either individually or in combination. The various emulsifying agents which can be used in the production of emulsions of the present composition are not strictly limited to the preferred emulsifying agents listed since almost any emulsifying agent can be used as long as it meets the established functional criteria.

Curable compositions and curable emulsions as described are used primarily in coating substrates. As coating agents, many compositions can benefit from the incorporation of adhesion promoters. In the present ilicon coating composition, an adhesion promoter, reaction inhibitor and other additives can be mixed in addition to the aforementioned components. In addition, other types of organopolysiloxane can be mixed. Such additives that can be mixed further include adhesion promoters, which are typically an organosilane compound (often referred to as a silane coupling agent) having two or three alkoxy groups and a functional group (eg, alkenyl group, acnloxy, rnetacnloxy group, glycidoxy group, etc.), such as vmtrtrimethoxysilane, 3-rnetacr? lox? prop? l-tpmethoxysilane, 3-acplox? rop? ltpmethox? -s? lano, t-glycidoxypropylmethoxysilane and 3-glycidoxypropyltromethoxysilane, Reaction inhibitors such as rnethylvimlcyclo-polysiloxane, acetylene alcohols, and tnalylisocyanurate or as taught in US Patents 3,445,420; 4.256870; and 5,506,289 plasticizers such as non-functional dirnenylpolysiloxane, and viscosity modifiers. Also, siliconee consisting of MD, MDQ MDQ and MDTQ where the units M, D, T and Q are subject as previously defined to the limitation that the silicone is sensitive to the hydride of it, can be used as a mechanical force improver. These additives can be added in any desired quantity. Additional components can be added to the compositions of the present invention to impart improved properties to the curable composition (alkali hydride and catalyst) or to the curable emulsion (alkenyl hydride, catalyst, emulsifier and water). For example, if desired, benzotnazole and / or benzindazole can be added as an additional component in the composition comprising alkenyl hydride. It is effective to further improve the high temperature resistance of a base material coated with silicone. It is added in an amount of up to one part, usually 0.01 to one part, preferably 0.05 to 0.5 part by weight per 100 parts by weight of alkenyl hydride. Said minor amounts of the compound are fully effective to improve resistance to high temperature. A lot of one part by weight of benzotnazole and / or benzidnidazole can retard the cure of the silicone coating composition. However, this can usually be compensated for by the addition of additional catalyst or by increasing the curing temperature to compensate for the retardation of the curing process. The addition of benzotpazole and / or benzimidazole ensures improved high temperature resistance. Curable compositions and curable emulsions using the curable compositions of the present invention can be coated on substrates and subsequently cured. The coating on such a substrate separates a sheet. The substrates can be rigid or flexible. In this way, rigid substrates comprise, but are not limited to glass, thermoplastic sheet derived from homopolymers and organic copolymers, metals such as steel, copper and the like, wood, carpentry and the like. Flexible substrates include, but are not limited to fabrics, flexible films, aluminos, and the like. Curable compositions and curable emulsions using these compositions can be cast into films and used as a separation medium. The curable compositions of the present invention can be used in a system without a solvent and aqueous emulsion system or a system diluted with a compatible organic solvent. In any case, the composition is usually adjusted to a viscosity of 1 to 50,000 centipoise, preferably 10 to 30,000 centipoise at 25 ° C, before being applied to a base material (or substrates). When applied to a flexible substrate, the substrate is selected from the group consisting of cotton, wool, silk, polyamide fibers, polyester fibers, cellulose fibers, woven and non-woven fabrics thereof, films or sheets of thermoplastic polymers and homopolymers and the like. A coating is formed at a dryness thickness of about 5 to 20 microns. For the purpose of application, coating, impregnation and sprinkling techniques are used. If the viscosity of the composition exceeds 50,000 centipoise at 25 ° C it is difficult to form a uniform coating of 5 to 20 microns thick. After application, the coating is usually cured by heating at 60 to 180 ° C for 1 / 1U for 10 minutes. In this way, a silicone-coated base material (or substrate) is obtained which is entirely or partially covered with a coating of the silicon coating composition at a thickness of 50 to 20 microns. All U.S. Patents referenced herein are incorporated herein by reference.

DEFINITIONS It is explicitly stated that where example reactions recite generic reagents mixtures of reagent species that satisfy the definition of the genus can be substituted. M-rich silicon compounds are defined as those silicones in which the ratio of M groups to the sum of D, T and Q groups present in the molecule is 0.04 or more. That is, by means of a given explanation of a silicon of the general formula M_D_TkQh the subscripts j, and h are integers that are zero or positive and i is a non zero positive integer, a rich silicon of M is defined as one in which the subscripts satisfy the criterion (? / (j + + h)) > 0.04, preferably this ratio is 0.30 or more, preferably this ratio is 0.15 or more, and this ratio is preferably 0.20 or more. M, D, T and Q have the usual definitions of structural silicon chemistry, ie M is an organosiloxyl group determination of non-functional chain, that is, M = R4R5Rβ? 0? 2 wherein R *, R5 and R6 are independently selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms, D is an organosiloxyl group of di-functional chain construction or repeat, i.e., D = S? Ri? 2/2 with R1 and R2 independently selected from hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms (when Rl or R2 is hydrogen D = DH and when one of the R groups is alquem, Dvi ), T is an organofunctional unit of trifunctional chain branching, ie, T = R7S 3/ 3/2 wherein R7 is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms and Q is a tetrafunctional unit S1O4 / 2 - A broad genus of substituent groups that can be used to prepare compounds of the present invention have been cited. The phrase monovalent hydrocarbon radicals of one to forty carbon atoms includes linear alkyl, branched alkyl, straight alkene, branched alkene, linear alkyl, branched alkyl, substituted linear halogen alkyl, substituted halogen branched alkyl, substituted linear halogen alkenyl, branched halogen alkenyl substituted, substituted halogen linear alkylated, substituted halogen branched alkylo, anlo, alkylamino, alchemlanlo, alkynylaplo, substituted halogen aplo, substituted halogen alkylo substituted halogen, alkenylanlo substituted halogen, and substituted halogen alkylamino. By substituted halogen, a substituent is defined which satisfies the requirement that at least one hydrogen position of the hydrocarbon radical is replaced with or substituted by a halogen selected from the group consisting of fluorine, chlorine, bromine or iodine. A preferred subset of monovalent hydrocarbon radicals of one to forty carbon atoms includes the group of monovalent radicals consisting of hydrogen, linear or branched alkyl radicals having from one to about 10 carbon atoms, straight or branched alkene radicals having 2 to about 10 carbon atoms, linear or branched alkyl radicals having from 2 to approximately 10 carbon atoms, cycloalkyl radicals having from 3 to about 12 carbon atoms, cycloalkenyl radicals having from about 3 to 12 carbon atoms. carbon, cycloalkyl radicals having from about 8 to about 16 carbon atoms, branched branched alkyl radicals of fluorine having from 1 to about 10 carbon atoms, linear or branched alkyl radicals of chlorine having from one to about 10 carbon atoms. carbon, linear or branched alkyl radicals of bromine having from 1 to approximately and 10 carbon atoms, linear or branched alkenyl radicals of fluorine having from 2 to about 10 carbon atoms, linear or branched alkenyl radicals of chlorine having from 2 to about 10 carbon atomslinear or branched alkenyl radicals of bromine having from 2 to about 10 carbon atoms, linear or branched alkylamino radicals of fluorine having from 2 to about 10 carbon atoms, linear or branched alkynyl radicals of chlorine having from 2 to about 10 carbon atoms, linear or branched alkynyl radicals of bromine having from 2 to about 10 carbon atoms, hydrocarbonoxy radicals containing at least 2 carbon atoms, hydrocarbon radicals of fluorine containing at least 2 carbon atoms, radicals chlorine hydrocarbonoxys containing at least 2 carbon atoms, hydrocarbonoxy radicals of bromine containing at least 2 carbon atoms, aryl radicals, linear or branched alkylalkal radicals, radicals of fluorine, chlorine radicals, bromine aryl radicals; linear or branched alkyl or alkynyl alkyl or alkylamine radicals, linear or branched alkyl-, alkenyl- or alkylanyl radicals of chlorine; linear or branched alkyl-, alkenyl- or alkylanyl radicals of bromine. The most preferred monovalent hydrocarbon radicals are selected from the group consisting of methyl, ethyl, propyl, tnfluoropropyl, butyl, vilyl, aillo, estem, femlo and benzyl. The preferred monovalent hydrocarbon radicals are selected from the group consisting of methyl, vinyl, trifluopropyl and fe lo. A copolymer is usually defined as the polyrnened product of two monomers; copolymers is used in this specification in a broad sense. This definition of copolirners includes not only copolymer itself, but also mixed polymers of higher order such as terpolines (three monomers) and mixed polymers of higher order (four or more). The process of the present invention makes the synthesis of mixed polymers of particular higher order as a mixture of cyclic siloxanes which can be employed in the first stage open ring polymerization leading to a mixed polymer of order n where n is the number of cyclic species or rnonorneros used in the open ring polymerization. In this way, the second stage reaction increases the polirnepco order of n + 1 if only one species is used in the second stage and if a mixture having rn members is used then the final polymer is a higher order polymer having order of n + n. As used herein, a polymer of order 2 is a copolymer, a polymer of order 3 is a terpolymer, etc. In this way, the polirnepco order is defined on the basis of groups D that are chemically distinguished present in the resulting polymer, the number of different D groups being the polymeric order. The term D "qn refers to a row Dq that has two or more members where the n is a count index that counts the different number of Dq. Thus, the first row consists of Di i and D2q2. consists of Di i, D2q2 and D393 The counting index n defines both the minimum number of different D groups and the minimum number of polymer order of the resulting compound When using superscripts indicative of functionalization, ie an idioeincratic overwriting, in the specification, they have been used to define a present functionality of a group D, for example H, vi, Ph, ie D «, Dy and DPh, and the like, which denotes a particular species of group D. If the superscribed These terms are not used, n absolutely defines the number of different groups and the order of polymer.The term Dq means an individual D unit that can vary as desired EXPERIMENTAL The following non-limiting examples should illustrate it in expiration EXAMPLE 1 A flask with the round bottom of 50 nmol was charged with 229.55 g, 3.10 moles, of octa ethylcyclotetrasiloxane (D "), 1.92 g, 0.0124 moles, of decarnetyltetrasiloxane (MD2, rich compound of M, M / (M + D) = 0.50 molar basis), and 0.27 g of 4.3 weight percent KOH in a low molecular weight polydimethylsiloxane oil (a silanolate catalyst) having an effective base concentration of 50 pprn. The reaction was heated for 3 hours at 150 ° C. Having achieved equilibrium, solids of 87-88 weight percent, The reaction mixture was cooled to 80-90 ° C and 1.62 g of 2 weight percent solution in a linear 20 centistokes polydimethylsiloxane (cSt) oil. of a phosphomethyl chloride having the formula (CI3 P (NPCl2) 2 PCl3 + PClβ was added (effective concentration of 138 pprn) The phosphonitrilic chloride neutralized the potassium silanolate catalyst leaving approximately 100 ppm of the linear phosphomethyl chloride to act as a catalyst The mixture was stirred for one hour at 80-90 ° C at which time 2.23 g of 1.62 weight percent of hydride linear silicon hydride polymer (MDH ^ o-soM) was added.The reaction was stirred for two hours. additional hours at 80-90 ° C. The resulting product was clear and colorless and had a hydride content of 155 ppm with a viscosity of 2275 cSt at 25 ° C. The NMR of S? l? con-29 indicated that the Si-H groups were randomly placed through the chain of po The hydride polymer thus produced was subsequently successfully used for hydrosilation without further purification or filtration.

EXAMPLE 2 The procedure of example 1 was repeated using 282 59 kg of octarnetiicicotetrasiloxane, 2.359 kg of decarnetyl tetrasiloxane, 0.18 kg of 4.9 weight percent of potassium hydroxide in silicone oil to give 30 pprn of catalyst-effective, 1.79 kg of 2 weight percent chloride catalyst phosphonitrile in silicone oil of 20 cSt, and 2.82 kg of 1,622 weight percent of hydride silicon hydride polymer. The resulting product had a viscosity of 2210 cSt at 25 ° C and a hydride content of 160 ppm. Silicon-29 NMR indicated that the Si-H groups were randomly placed through the polymer chain. The hydride polymer thus produced was subsequently successfully used for hydrosilation without further purification or filtration.

EXAMPLE 3 The rapid equilibrium obtaining in the open ring polymerization requires the presence of the base catalyst. The following attempts (table 1) to polyrize with open ring using only the phosphonitrilic halide catalyst which indicates that the synthesis of the hydride copolymer is significantly faster using two catalysts in sequence.

Table 1: Preparation of hydride silicone copolymers using only a single catalyst.

Reagents Conditions% by weight viscosity% of Scope of solidity at equilibrium Viscasil ™ 80 ° C, 6 hrs., 95 1910 40 MD2M, 60 pprn Polymer LPNC2 silicone hydride D,, MD2M, 80 ° C, 24 hrs., 86 2192 98 Polymer 100 ppm of silicon LPNC2 hydride D «, MD2M, 80 ° C, 24 hrs., 82 1600 94 Polymer 50 ppm silicon LPNC2 hydride Notes to Table 1: 1. 1.62 weight percent linear hydride silicon hydride polymer. 2. The LPNC used had the formula (CI3 P (NPC_2) 2 PC13 + PC.

The results in Table 1 indicate that unlike obtaining equilibrium in a total of approximately 5 to 10 hours (open ring polymerization 3-6 hours, redistribution and condensation 2-6 hours), the non-assisted LPNC catalyst requires more 24 hours In this way, the reaction efficiency increases by catalyzing the two reactions separately and using a first stage catalyst that can be neutralized by the second stage catalyst.

EXAMPLE 4: Preparation of (p = 3, q = 219): ÍDH3D21 Í, Mvi = (CH3) 2CH2 = CHSl03 / 2, DH = (CH3) HB ?? 2/2, D = (CH3) 2S ?? 2 2, One bottle was loaded with the round bottom of 500 mL with 223.63 octamethylcyclotetrasiloxane g, 2.24 g of 1, 3-d? V? N? Ll, l, 3,3-tetrarnet? L disiloxane in the presence of a silanolate catalyst, 0.27 g of 4.3 wt.% KOH in a siloxane oil (50 g. pprn). The reaction was stirred for 3 hours at 150 ° C. The resulting product was 87.3% solids, indicating an equilibrium product. The reaction was cooled to 80-90 ° C. After cooling, the LPNC catalyst was added, 1.62 g of 2% by weight of solution in a silicon oil with a viscosity of 20 cSt (143 ppm). The reaction was stirred at the lower temperature for 1 hour before the addition of 2.46 g of a linear silicon hydride polymer having 1.62 weight percent hydride. The reaction was stirred at 80-90 ° C for an additional 2 hours. The product was a slightly misty fluid that was filtered through a mixture of 2: 1 by weight of Cel? Te «R and Fuller's Earth. The filtered product was clear and colorless having a viscosity of 544 cSt at 25 ° C and a hydride content of 170 ppn. NMR of Silicon-29 indicated that both the presence of terminal alkenyl groups and the hydride have been randomly incorporated into the silicone chain.

EXAMPLE 5: Preparation of MD, iD i, 2DH, M (p = 10, q = 350, q2 = 10): MD350 VÍ10DH 0M: The procedure of Example 4 was repeated using 175.77 g of octanethylcyclotetrasiloxane, 1.92 g of decarnetyltetrasiloxane, 4.97 g of tetramethyltetravinylcyclotetrasiloxane, 0.21 g of 0.27 g of 4.3% by weight of KOH in a siloxane oil (49 pprn), 1.62. of LPNC catalyst solution (177 pprn) and 3.46 g of a linear silicon hydride polymer having 1.62 weight percent hydride. The clear and colorless product had a viscosity of 883 cSt at 25 ° C and a hydride content of 288 pprn. Silicon-29 NMR indicated that both the alkenyl group and the hydride groups had been randomly incorporated into the silicone chain (chemical changes: DH = -37.5 ppm, Dvi = -35.8 pprn). This reaction is an example of using a mixture of cyclic species in the ring-open polymerization to synthesize a silicone terpolymer, three (common) precursors containing three different D groups, minimum polymer order = 3.

EXAMPLE 6: Preparation of MD,? DPh, 2Dv i, 3DHp (p = 10, ql = 350, q2 = 10, q3 = 10): MD3S? Ph10Dvi1oDH? O: D ^ h is an idiosyncratic designation for a group D having both R groups substituted by phenyl groups. The procedure employed in Examples 4 and 5 was repeated using 490.0 g of octarnetylcyclotetrasiloxane, 164.5 g of octaphenylcyclotetrasiloxane, 12.92 g of decamethyltetrasiloxane, 35 g of tetramethyltetravinylcyclotetrasiloxane, 0.82g of 4.3% by weight of KOH in a siloxane oil (50 ppm). , 4.92 LPNC catalyst solution (140 ppm) and 24.4 g of a linear silicon hydride polymer having 1.62 weight percent hydride. The clear, colorless product had a viscosity of 613 cSt at 25 ° C and a hydride content of 555 ppm. NMR of Silicon-29 indicated that both the phenyl, hydride and alkenyl groups were randomly incorporated into the silicone chain (chemical changes: Dph = -48.0 ppm, Dfh? Or H = -37.5 ppm, D i = -35.8 ppm). This reaction is an example of using a mixture of cyclic species in the ring-open polymerization to synthesize a silicone terpolymer, at least four precursors containing four different D groups, minimum polynomeric order = 4.

EXAMPLE 7: Synthesis of alkenyl hydride To a resin pot was charged 230 grams of dirnethylsiloxane polymer, which contains 0.022 vinylnilhols of polymer / g having a viscosity of 78,000 cps at 25 ° C, and 6.58g of silicon hydride polymer, which contains 0.58 rnilirnoles of hydride / g of polymer and having a viscosity of 800 cps. The mixture was heated to 90 ° C at the same time mixing. After mixing for half an hour, 2.3 grams of LPNC solution, a 2% solution in viscosity 20 silicone oil was added. The mixture was allowed to mix at 90 ° C for another hour. 1.56 g of LPNC was added and mixed at 90 ° C for another hour before leaving the charge to cool to room temperature. A sample of the resulting compound was mixed with a catalytic amount of platinum complex (11% platinum in i vi) and cured at 150 ° C for 5 minutes to give a strong film.

EXAMPLE 8: Synthesis of alkenyl hydride To a resin pot was charged 1.4 g of hexamethyldisiloxane, 428.08 grams of a polymer / resin mixture containing 0.022 millimoles of vinyl / g of polymer and having a viscosity of 78,000 cps at 25 ° C and 10 g of hydride polymer. of silicone, which contains 16 millimoles of hydride / g of polymer and which has a viscosity of 23 cps. After mixing for half an hour, 1.27 grams of LPNC solution, such as 2% LPNC in viscosity 20 silicone oil, was added. The mixture was further mixed at 90 ° C for 2 more hours before leaving the load to cool to room temperature. ambient. The product had a viscosity of 2000 cps at 25 ° C. A sample of the resulting compound was mixed with a catalytic amount of platinum complex (11% platinum in iM i) and cured at 150 ° C for 5 minutes to give a strong film.

EXAMPLE 9; Synthesis of alchemlo hydride To a jar of 226.80 grams of LPNC solution, such as 2% LPNC in silicone oil with viscosity 20, 212.17 grams of a polymer / resin mixture containing 25% of Mo.βDv o.iQ and 75% dimethylsiloxane polymer, which contains 0. 022 viml / g polymer rnilirnolee and having a viscosity of 78,000 cps at 25 ° C, and 8.38 g of silicone hydride ream, MHQ containing 9.5 hydride hydride / g of polymer. The mixture had a viscosity of 19,000 cps at 25 ° C.

The bottle was sealed with a metal cover and placed in an oven at 50 ° C for 16 hours. The viscosity of the mixture dropped to 800 cps after heating. A sample of the resulting compound was mixed with a catalytic amount of platinum complex (11% platinum in i) and cured at 150 ° C for 5 minutes to give a strong film.

EXAMPLE 10; Alkenyl hydride emulsion To a metal vessel was charged 164.1 g of the alkenyl hydride prepared in Example 3, 3.74 g of secondary alcohol ethoxylate of Cn-Cis, V 1.5 g of 70% ethoxylated nonylphenol (30 moles of ethylene oxide) in water . The mixture was mixed with a mixer with a distillation head at room temperature. After mixing the mixture well, 184.5 g of water was added slowly to the mixture at the same time mixing. The addition became 1 hour and the mixture was gradually converted to a white emulsion with viscosity of 320 cps at 25 ° C. A sample of the resulting emulsion was mixed with a catalytic amount of a platinum emulsion (containing 0.16% platinum, 1.25% M iM i, 39% polydimethyisiloxane vinyl terminate having a viscosity of 20 cps, 2.2% alcohol polyvinyl, 2% propylene glycol, and 55.6% water) and cured at 150 ° C for 5 minutes to give a strong film.

EXAMPLE lis Synthesis of alkenyl hydride A flask with a round bottom of 500 mL with 75 grams of cyclooctarnetyltetrasiloxane (CD4), 1.01 mole D), 25 grams of cyclo-l, 2,3,4-tetravinyl-l, 2, 3,4-tetrarnetyltetrasiloxane was loaded. ([Dvi *]), 27 grams of decamethyl tetrasiloxane (0.175 moles of D, 0.17 moles of M), and 0.18 grams of 4.3% KOH silanolate catalyst (60 ppm). The reaction was stirred for 3 hours at 150 ° C. The completion of the reaction was tested by making a solids test, noting that equilibrium is reached when the percent of solids reaches a plane (in this case the level of solids at 80% solids). The reaction was cooled to 80-90 ° C. When cooled to a lower temperature, 2.5 grams of a 2% solution in silicone oil with viscosity 20 of LPNC (138 pprn of LPNC catalyst) was added. The reaction was stirred at a temperature for 1 hour at which point 173 grams of hydride containing 16 millirnoles / g of silicon hydride polymer was added. The reaction mixture was stirred at 80-90 ° C for an additional 2 hours. The clear product had a low viscosity and 0.90% hydride. NMR of Silicon-29 indicated that the Si-H group reacted randomly in the polymer base structure.

EXAMPLE 12s Alkenyl hydride emulsion Premix: 6832 was charged to a metal reactor. 5 g of a polymer / resin mixture containing 25% Mo. 6 Dv i 0. ? Q and 75% of dimetusi loxane polymer, which contains 0. 022 my vinyl limes / g of polymer and having a viscosity of 78,000 cps at 25 ° C, 142.7 g of secondary alcohol ethoxylate of Cn-Cis, and 266.2 g of 70% ethoxylated nonylphenol (30 moles of ethylene oxide ) in water. The mixture was heated to 80 ° C at the same time mixing. After mixing the mixture well, 1161.6 g of water was slowly added to the mixture. The mixture was further mixed and the charge allowed to cool to 46 ° C. The viscosity measured at this temperature was 82,000 cps. The mixture was then ground with a colloid mill. The heat generated by the mechanical shear warmed the mixture to 71 ° C.

Thickening solution: 10.560 g of water, 135 g of a biocide (Phenonip from ipa Laboratories, Inc., Lilmington, DE), 117 g of an anti-spurious emulsion (AF9010 available from GE? Ilicones, Uaterford) were charged to a separate container. , NY), and 120 g of carboxymethylcellulose (CMC). The mixture was mixed at room temperature until the carboxymethyl cellulose completely dissolved.

Emulsion: The emulsion was prepared by mixing the ground premix in the thickener solution at room temperature to produce a white emulsion with a viscosity of 3,800 cps at 25 ° C.

Coating formulation: 100 parts of the vmilo emulsion of example 12 was mixed with 0.35 part of an inhibitor, (+/- 3.5 d? Rnet? L-1-hex? N-3-ol, 4 parts of the example 11, 5.6 parts of 50% of an aqueous dispersion of colloid silica with an average particle size of 20 microns, and 1.75 parts of t-glycidoxypropyltrirnetoxyieilane After mixing the dispersion well, a platinum emulsion containing 0.16% of platinum, 1.25% viMvi, 39% polydimethylsiloxane vinyl terminated having a viscosity of 20 cps, 2.2% polyvinyl alcohol, 2% propylene glycol, and 55.6% water and the material was coated on a nylon cloth with a The cure was implemented by heating the coated cloth in an oven at 1 ° C for 3 minutes to result in a tight and tight coating on the cloth.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A curable silicone composition comprising: a) a silicone hydride copolymer having the formula: MM, TrQt, having at least two Dq where Dq is different from any other Dq and each Dq has the formula: Dq = S1RIR202 / 2 wherein each R1 and R2 in each D is independently selected from the group consisting of hydrogen monovalent hydrocarbon radicals of one to forty carbon atoms wherein each subscript q of Dq is independently one or more with M = R * RßRβs 3/ 3/2 wherein R *, Rβ and Rß are independently selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms wherein the subscribed stoichiomernet of M is non-zero and positive; T = R S ?? 2 wherein R7 is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms with the subscribed stoichiometric T of zero or positive; and Q = S? 0 * / 2 with the subscribed stoiqueometpco s of Q is zero or poetic; subject to the limitation that one of R1, R2, RS, R "RS, R1 and R7 is hydrogen and that one of R1, R2, R *, R1, R1 and R7 which is not hydrogen is an alkenyl group having two to forty carbon atoms wherein said silicon hydride copolymer comprises an alkenyl group; b) a catalyst.

2. The composition according to claim 1, further characterized in that said catalyst is a hydrosilylation catalyst.

3. The composition according to claim 2, further characterized in that the subscript r is zero.

4. The composition according to claim 3, further characterized in that the subscript s is zero.

5. The composition according to claim 4, further characterized in that R, R2, R3, R4 RS and Rβ are methyl or fe lo.

6. The composition according to claim 5, further characterized in that R1, R2, R3, R *, Rβ and Rβ are methyl.

7. The composition according to claim 6, further characterized in that R, R2, R3, R4, RS and Rβ are phenyl.

8. The cured composition according to claim 5.

9. A curable emulsion comprising: a) a silicon hydride copolymer having the formula: MMD9 TrQβ, which has at least two Dq where Dq is different from any other Dq and each Dq has the formula: D, = S1R R202 where each Rl and R2 in each D, is independently selected from the group consisting of hydrogen monovalent hydrocarbon radicals of one to forty carbon atoms wherein each subscript q of Dq is independently one or more with M = R * RßRβS 3/ 3/2 where R *, Rβ and Rβ are independently selected from the group it consists of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms in which the stoichiometric subscript of M is non-zero and positive; T = R7S 3/ 3/2 wherein R7 is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals of one to forty carbon atoms with the one subscribed to be stoichiometric of T zero or positive; and Q = S1O4 / 2 with the stoichiometric subscript of Q is zero or positive; subject to the limitation that one of Rl, R2, R3 t R * f RS; Rβ and 7 is hydrogen and one of Rl, R2, R *, Rβ t Rβ and 7 e is not hydrogen is an alkenyl group having from two to forty carbon atoms wherein said silicon hydride copolymer comprises an alkenyl group; b) a catalyst; c) an ernulsifying agent; and d) water.

10. The composition according to claim 9, further characterized in that said catalyst is a hydrosilylation catalyst.