[1]United States Patent Office p 32441@537, 3,441,537 ORGANOPOLYSILOXANES Guenther Fritz Lengnick, Manitou Beach, Mich., assignor to Stauffer Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Filed July 12, 1967, Ser. No. 652,672 Int. Cf. C08g 31128, 33110 U.S. Cl. 260-46.5 25 Claims ABSTRA,CT OF THE DISCLOSURE The invention relates to curable one-component organophosphatosiloxanes and to the preparation of these room temperature curin.a systems by reacting organophosphatosilanes with hydroxyl terminated organopolysiloxanes. The present invention relates to siloxane compositions,- particularly to liquid or viscous organopolysiloxanes which may be cured by atmospheric moisture at room temperature to form elastomeric materials. The desirability of having one-component siloxane compositions which cure at room temperature is well established. Heretofore, certain ffuid organopolysiloxanes containin- silicon-bonded acyloxy radicals as the reactive .@roups were stable in the absence of moisture, but cured in the presence of ynoisture to resinous or elastomeric solids depending on the organopolysiloxane structure and composition. The curing of this one-component system is accompanied by the evolution of a carboxylic acid, generally acetic acid with present commercial materials. This one-component system has been a great commercial success. However, there are some applications in which the presence of the carboxylic acid produced by this system is undesirable and detrimental. The preparation of a commercially acceptable product havin.- desirable properties and universal application is extremely important. Consequently, the discovery of a new class of organopolysiloxanes has made possible the preparation of a new one-co.mponent room temperature curing system. The characteristics of the final cured product can be widely varied by variation in the composition. For example, the newly discovered or,-anopolysiloxanes have improved proper-ties, such as low modulus values. These properties are extremely important, especially where the composition is used in caulking applications. In addition, the corrosive problems which heretofore have plagued the silicone industry have been alleviated -by these newly discovered organopolysiloxanes. It is therefore an object of this invention to provide a novel or.-anopolysiloxane. Another object of this inventiori is to provide an organopolysiloxane composition ,.vhich will cure at room temperature. Still another object of this invention is to provide an organopolysiloxane composition which will be less toxic than the ones heretofore known in the art. Still another object of this invention is to provide an organopolysiloxane composition which will be essentially non-corrosinie to a metal substrate. A further object of this invention is to provide an or-.anopolysil6xane composition Nvhich will rapidly cure to an elastomeric state. A still further object of this invention is to provide an organopolysiloxane composition which may be dispensed in a single packaged system. The foregoin. objects and others which will beco.me apparent from the following description are accomplished in accordance with this invention, generally speaking, by atented Apr. 29, 1969 2 providin,@ organopolysiloxane compositions having the following formulae: 0 R"114-. R R " 1 . 0 [( R ... 0)2p ol.-I-@iorjio 1'( OR ... )21.-I 5 P I L'. J. o r 0 RI,,, R R [(R ... 0) 10 2@0].-I--slio @io @i-O -SI!-IOP(OR ... )21-1 I R' @'ll" y wherein R and R', which may be the same or different, represent monovalent hydrocarbon radicals, halogenated 15 monovalent radicals or eyanoalkyl radicals; R" is a divalent hydrocarbon radical, halogenated divalent radical or divalent cyanoalkyl radical; R... is a monovalent hydrocarbon radical, - halogenated monovalent hydrocarbon 20 radical or eyanoalkyl radical; R.... is hydrogen, a nionovalent hydrocarbon radical, halogenated monovalent hydro@earbon radical, cyanoalkyl radical or radicals hydrolyzed by ambient moisture; R is a monomeric or polymeric organic group linked to R!' by a carbon to carbon 25 linkage; n is an integer greater than 3 and up to 4; x is an integer of from 0 to 20,000 and y is an integer of from 1 to 500. The phosphorus containing organopolysiloxanes illustrated above are prepared by reacting an organophos30 phatosilane of the for.mula 0 R"I't-@Si[OD(OR ... )21. with organopolysiloxanes ha-ving the general -formulae: 15 R R ' I I I HO -[-SiO-].+iH and HO s sio 11 I , I . I R R R" I'll 4( R wherein R, R', R", R"', R R x and y are the same as those represented above. R, R' and R.... are organic radicals selected from the class consisting of alkyl radicals having from I to 18 carbon atoms surh as methyl, 45 ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl; aryl radicals such as phenyl, diphenyl, naphthyl and the like; alkaryl radicals such as tolyl, xylyl, ethylphenyl and the like; aralkyl radicals such as benzyl, phenylethyl and the like; haloaryl radicals such as chloro50 phenyl, tetracblorophenyl, difluorophenyl and the like; alkenyl radicals such as vinyl, allyl and the like. R.... may also represent hydrolyzable groups such as carboxy, hydrocarbonoxy, aminooxy and oximo groups. Examples of carboxy groups are monoacyl radicals of carboxylic acids 55 such as formoxyl, acetoxyl, propionoxyl, valeroxyl, caproxyl, myristoxyl and stearoxyl radicals. Other hydrolyzable groups are hydrocarbonoxy groups having from I to 10 carbon atoms such as metboxy, ethoxy, butoxy, heptoxy, octoxy, decoxy, phenoxy and the like; aminoGo oxy groups such as dimethylaminooxy, diethylaminooxy, dipropylaminooxy, dibutylaminooxy, dioctylaminooxy, di phenylaminooxy, ethylmethylaminooxy, methylphenylaminooxy and the like. Other groups are the oximo radicals such as acetophenoximo acetonoxi ' mo, benzophenox(15 imo, 2-butanoximo, diisopropylketonoximo, chlorocyclohexanoximo, alpha-bromoacetophenoximo and the like. R" is a divalent radical stich as methylene, ethylene pro-
[2]3;4412537 3 pylene, butylene, hexylene, octylene, decylene, dodecylene, phenylene and the like. The groups represented by R..... are monomers, polymers or copolymers which are linked to a hydroxyl terminated organopolysiloxane backbone through a carbon to carbon linkage with an alkylene or arylene group represented by R" above. Examples of suitable phosphatosilanes which may be reacted with the hydroxyl terminated organopolysiloxanes are methyl-tris(dimethylphosphato)silane, ethyl-tris(dimdthylphosphato)silane, propyl-tris (dimethylphosphato) silane, butyl-tris (dim6thylphosphato) silane, hexyl-tris(dimethylphosphato)silane, octyltris(dimethylphosphato) silanc, dodecyl-tris(dimethylphosphato) silane, hexadecyl-tris(dimethylphosphato)silane, octadecyl-tris(dimethylphosphato)silane, methyl-tris(diethylphosphato)silane, ethyl-tris(dipropylphosphato) silane, propyl-tris(dibutylphosphato) silane, methyl-tris (dihexylphosphato) silane, hexyl-tris (ditdtradecylphosphato) silane, octyl-tris (dioctadecylphosphato) silane, methyl-tris (dihexylphospha,.-O) silane, methyl-tris(ethylpropylphosphato) silane, butyl-tris (methylhexylphos phato) silane, propyl-tris(inethyldodecylphosphato) silane, hexyl-tris (methyloctadecyl phosphato) silane, octyl-tris (ethyltetradecylpliosphato) silane, phenyl-tris(diphenylphosphato) silane, tolyl-tris(diphenylphosphato) silane, naphthyl-tris (diphenylphosphato) silane, methyl-tris(diphenylphosphato)silane, octyl-tris (diphenylphosphato) silane, phenyl-tris(methylphenylphosphato) silane, propyl-tris(butylphenylphosphato)silane and the like. Examples of other phosphatosilanes are tetrakis(dim ethylphosphato) silane, tetrakis(dibutylphosphato) silane, tetrakis(dihexyl phosphato)silane, tetrakis(dioetylphosphat:o)silane, tetrakis(didodec ylphospbato)silane, tetrakis(dioctadecylpho3phato)silane, tetrakis(meth yloctylphosphato)silane, tetrakis(methylethylphosphato)silane, tetrakis(ethy lbutylphor,phato)silane, tetrakis(propylbutylphosphato)silane, tetrakis (but ylhexylphosphato) silane, tetrakis (octadecylphosphato) silane, tetrakis(dodecyloctade cylphosphato)silane, tetrakis(diphenylphosphato)silane, tetrakis(dinapht hylphosphato)silane, tetrakis (methylphenylphosphato) silane, tetrakis (methyltolylphosphato) silane, tetrakis(propylxylylphosphato) silane and the like. These phosphorus compounds may be prepared by reacting dialkyl or diaryl hydrogen phosphates or mixtures thereof with organotrihalosilanes in the presence of a solvent at a temperature of from about 25' to 150' C., preferably from about 80' to 120' C. For example, diethylhydrogen phosphate may be reacted with an alkyl@ trihalosilane such as methyltrichlorosilane in the presence of a solvent and an acid acceptor. Acid acceptors such as alkylamines or pyridine are prcferably used in the formation of these phosphatosilane compounds. Also, these phosphato compounds may be prepared by react'mg alkali metal or alkaline earth metal salts of a.n organic phosphate with an organohalosilane in accord-ance with the following equation:' 0 0 11 11 zm[op(OR ... )27 + R .... 4-.SiX. @ R .... 4-.Si[OP(OR ... )21. + ZMX wherein R... and R.... are the same as those described above, X is a halogen, M is an alkali metal or alkaline 4 earth metal and z is an integer greater than 2 and up to 4 If desired, the formation of the phosphatosilanes may be carried outin the presence of an inert solvent. Suitable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane; aromatic. hydrocarbons such a,benzene, toluene, xylene, naphthylene, as well as hal(@genated solvents such as methylene chloride, chlorobenzene and the like. Other solvents which may be employed are organic ethers such as petroleum ethers, 10 diethyl cther. dibutyl ether and fluid hydroxyl-freesiloxanes. The conventional or.-anopolysiloxanes described here.tofore may be prepared from any di-functioral organnsilanes of the formula 1 5 RI Rsix2 wherein R and R' represent an unhalo-enated or halogen monovalent aliphatic, alicyclic or aro@matic hydrocarbon radical such as methyl, ethyl, vinyl, allyl, cyclohexyl, 20 cyclohexenyl, phenyl and tolyl and X represents a hydrolyzable atom or group such as a halogen atom or an alkoxy group. The dio rganopolysiloxanes may be homopolymers as well as copolymers, that is, compounds derived from two or more different dior.-anosilanes and 25 even the organic radicals linked to any particular silicon atom may be different organic radicals. Especially useful are the dimeth ylpolysiloxanes, the rnethylphenylpolysiloxanes and the methylvinylpolysiloxanes. In the formation of the grafted organopolysiloxanes, 30 the monomeric or polymeric groups are -rafted to theconventional hydroxyl terminated organopo'lysiloxanes by using a free-radicalinitiator, normally a peroxide. As little as 0.05 percent of the more active peroxide initiators based on the wei-ht of reactants is adequate in most cases. 35 Where increased@reaction rates are desired as much as 2 percent or even more of the initiator may be used. In general, it is advised not to exceed about I percent, since higher concentrations tend to promote coupling reactions which understandably increase the viscosity of the 40 reaction mixture. In using a free-radical initiator, the reaction when carried out in a batch-wise process generally proceeds at a satisfactory rate if a temperature is maintained in a range of from about 60' C. to 130' C. If a continuous 45 process is used or if the reaction is carried out batch-wise without a free-radical initiator, substantially higher temperatures such as up to about 160' C. may be advantageously employed. Examples of suitable peroxide initiators are those hav50 ing at least one of the peroxide oxygens attached to a tertiary-carbon atom such as dialkyl peroxides, i.e., ditert-butyl and dicurnyl peroxide; hydroperoxides such as tert@butyl hydroperoxide, cumyl hydroperoxide and decylene hydroperoxides; cyclic peroxides such as aseari55 dole and 1,5-dimethylhexane-1,5-peroxide; and peresters such as tertbutylperbenzoate, tert-butylperoxyisopropylcarbonate and tert-butylperoctoate. Other peroxides which may be used are ketone peroxides such as acetone peroxide and cyclic hexanone peroxide. 60 Acyl peroxides and peracids may be used as initiators in the formation of graft polymers. However, these initiators result in less grafting, i.e., lower yields of the grafted product. The difference is believed to lie in the nature of the radicals produced, thus tert-alkoxy radicals from 65 ditert-butyl peroxide, for example, have a strong tendency to extract hydrogen atoms which is a necessary step in the grafting procedure. On the other hand, acyloxy radicals produced from acyl peroxide, e.g., benzyl peroxide while effective initiators are relative ineffective as 7o hydrogen extractors. Although it may be possible to carry out the graftin.procedure using organopolysiloxane material free of terminal hydroxyl groups <)r groups hydrolyzable by ambient moisture and to subsequently treat the graft polymer to 75 incorporate such groups, it is preferred in the graftin.-
[3]5 operation to start with an organopolysiloxane having terminal hydroxyl groups. Following this procedure, the grafted polymer is appropriately treated to convert the hyd-roxyl groups to groups which are hydrolyzable by ambient moisture. The hydroxyl terminated organopolysiloxanes may contain in minor proportions molecules havin.- only one hydroxyl group or there may be a smaller number of molecules carryin.- an excess of two hydroxy groups. It is preferred, in any event, that the hydroxyl terminated organopolysiloxanes have on the avera.-e from about 1.75 to about 2.25 hydroxyl groups per molecule. The proportion of organic monomer or polymer used in the grafting reaction may be varied within wide limits; however, it has been found that greatly improved physical properties bave been obtained when the reaction mixture contains from about 25 to about 75 percent by weight of organic monomers or polymers. It is preferred that the organic monomer or polymer pottion account for from about 40 to 65 percent of the total wei.-ht of the reactants. Organic monomeric compounds which may be used in the formation of the grafted or.- anopolysitoxanes include both branched and strai,-ht chained monomeric olefins having from 1 to 18 carbon atoms such as ethylene, propylene, butylene, isobutylene, isoprene, butadiene, hexylene, octylene, 1-decene, dodecene, tetradecene, hexadecene, octadecene; unsaturated aromatic hydrocarbons such as styrene, alpha-methylstyrene, alpha-ethylstyrene, alpha-butylstyrene, vinyl toluene and the like. Other monomeric compounds which may be used are the halo,@enated mono-olefinic hydrocarbons such as chloroprene, chlorostyrene, alpha-bromostyrene, 2,5-dichlorostyrene, 2,5 - dibromostyrene, 3,4-dichlorostyrene, 3,4-difluorostyrene, ortho-, metaand parafluorostyrenes, 2,6-dichlorostyrene, 2,6-difluorostyrene, 3-chloro-4-fluorostyrene, 2,4,5- trichlorostyrene, dichloro-mono-fluorostyrene, chloroethylene, 1,1-dichloroethylene, phenylethylene, fluoroethylede, iod(>ethylene, 1, 1 -dibromoethylene, 1,1- difluoroethylene, 1,1-diiodoetbylene and the like. Examples of unsaturated acids wbich may be used are vinyl acetic acid, acrylic acid, methacrylic acid, crotonic acid, 3- butenoic acid, cinnamic acid, maleic acid, trimethyl maleic acid, lauric acid, oleic acid, linoleic acid, lenolenic acid and the like. Other compounds which may be used are esters of or.-anic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl caproate, vinyl benzoate, vinyl toluate, vinyl pchlorobenzoate, vinyl ochlorobenzoate, vinyl m-chlorobenzoate and similar vinyl halobenzoates, vinyl p-methoxybenzoate, vinyl o-methoxybenzoate, vinyl petboxybenzoate, methyl methacrylate, ethyl methacrylate, propyl methaerylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2- ethylhexyl acrylate, heptyl acrylate, octyl acrylate, 3,5,5-trimethylhexyl acrylate, decyl acrylate and dodecyl acrylate, tetra-decyl acrylate, octodecyl acrylate, isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl valerate, isoropenyl caproate, isopropenyl benzoate, isopropenyl pcblorobenzoate, isopropenyl o-bromobenzoate, isopropenyl m-chlorobenzoate, isopropenyl toluate, isopropenyl alpha-chloroacetate, isopropenyl alphabromopropionate, vinyl alpha-chloroacetate, vinyl a lphabromoacetate, vinyl alphachloroptopionate, vinyl alphabromopropionate, vinyl alpha-iodopropionate, vinyl alhachlorobutyrate, vinyl alpha-chlorovalerate, vinyl alphabromovalerate, allyl chlorocarbonate, allyl formate, allyl acetate, allyl propionate, allyl butyrate, allyl valerate, allyl caproate, diallyl phthalate, diallyl suceinate, diethylene c,,Iycol bis-(allyl carbonate), allyl-3,5-5-trimethylhexoate, diallyl adipate, diallyl subacate, diallyl fumarate, allyl benzoate, allyl acrylate, allyl crotonate, allyl oleate, allyl 3)441)537 6 chloroacetate, allyl trichloroacetate, allyl chloropropionate, allyl chlorovalerate, allyl lactate, allyl pyiruvate, allyl aminoacetate, allyl aceto acetate, allyl thioacetate, as well as methyl esters correspondin.- to th6 above allyl esters. Other vinyl compounds which may be used are the vinyl atomatics such as vinyl pyridine, vinyl naphthalene, divinyl benzene, as well as vinyl silicone compounds such as vinyl triethoxysilanes. In addition, organic nitriles such as acrylonitrile, meth10 acrylonitrile, ethacrylonitrile, crotonitrile and the like may be used in the formation of grafted polysiloxanes. As emphasized previously, the monomers may be used singly,or in combinations of two or three or even more. Exceptional results have been achieved by the use of 15 styrene and substituted styrenes in conjunction with acrylates and methacrylates. For purposes of this invention, the organopolysiloxanes and the organopolysiloxanes having organic groups grafted thereto are generally liquids having a viscosity of 20 from about 1,000 to about 500,000 centistokes at 25' C., preferably from about 2,000 to about 100,000 centistokes. The reaction between the phosphatosilanes and the o rganopolysiloxanes may be carried out at any convenient temperature although, in general, temperatures ranging 25 from about 20' C. to 100' C. are sufficient. It should be understood, of course, that higher or lower temperatures can be employed if desired although, preferably the reaction should be carried out at temperatures below about 200' C. 30 If desired, the reaction may be carried out in the presence of an inert solvent, that is, a solvent which will not react with the terminal hydroxyl groups on the organopolysiloxane. Solvents which may be used includehydrocarbons such as benzene, toluene, xylene; petroleum 35 ethers; halogenated solvents such as ethylene chloride, perchloroethylene, chlorobenzene and the like; organic ethers such as diethyl ether and dibutyl ether; and fluid hydroxyl-free siloxanes. The presence of solvents are particularly desirable when the hydroxyl terminated organo40 polysiloxane has a high viscosity. In these cases, the presence of a solvent reduces the overall viscosity of the mixture and facilitates the reaction. Although the ratio of phosphatosilanes to organopolysiloxanes is not critical, it is preferred that at least one 45 mole of the phosphorus compound be used per mole of silicon bonded hydroxyl group and more preferably from about 2 to 5 moles of the phosphorus compound be used per mole of silicon bonded hydroxyl group in the organopolysiloxane. It is possible to use up to about 12 moles of 50 the phosphorus compound per mole of silicon bonded hydroxyl group in the siloxane. A large excess of the phosphorus compound insures complete reaction with all silicon bonded hydroxyl groups and in addition, acts as a scavenger for any moisture which may be present. It is 55 preferred that the reaction be carried out in the absence of rnoisture, since the latter may interfere with the reaction. However, traces of moisture are not especially harmful if an excess of the phosphorus compound is used. The compositions of this invention may be cured by 60 merely exposing them to atmospheric moisture with or without any additional water vapor. Upon exposure to moisture, the compositions cure at times varying froin a few minutes to several hours or days depending upon the type of R, R', R... and R.... groups. In general, an in65 crease in the molecular weight of any of the groups will increase the time of cure. The compositions according to the present invention may consist solely of the reaction product of an organopolysiloxane and a phosphatosilane. However, for modi70 fying the consistency of the uncured composition or to reinforce the cured products or for some other purpose, mineral fillers in the form of very fine powders may be added. Examples of mineral fillers which may be used are 75 various kinds of silicas, oxides of iron, zinc, cadmiiim,
[4]3,441,537 7 aluminum and carbonates, especially calcium carbonate. The par-ticular filler and proportion in which it is used will depend to a certain extent on the particular use to which the composition is to be applied. Silica obtained by precipitation, for example, those sold under the trade 5 names Santocel and Hi-Sil and silicas obtained by combustion such as those sold under the trade name Aerosil, are particularly suitable for the production of reinforced elastomeric products. These silicas are micro fine - products formed of par-ticles having the size of the order of 10 10 to 20 millimicrons and have a high absorptive power. They have a large absorbent surface and are very effective even in small quantities. Fillers such as milled natural silicas and calcium carbonate can, on the other hand, be employed in larger proportions, for example, 200 percent 15 based on the weight of the organopolysiloxane. Apart from the fillers mentioned heretofore, compositions conforming to the invention may contain - coloring agents, thixotropic agents, agents capable of preventing the passage of ultraviolet light, desiccants and - antioxi- 20 dants. These compositions may be dissolved or dispersed in organic liquids which are compatible with the organopolysiloxanes. Examples of suitable diluents are aromatic hydrocarbons such as benzene, toluene or xylene; aliphatic 25 hydrocarbons such as hexane and heptane and halogenated aliphatic hydrocarbons such as methylene - chloride and the like. In addition to the constituents mentioned above, the compositions of this invention may contain, for the pur- 3( pose of accelerating the rate of cure, certain compounds which have a catalytic effect on the condensation reactions. Although several compounds are known which have a catalytic effect upon the curing rate, organotin compounds were found to be the most desirable. Examples of 35 suitable catalysts are the tin salts of organic carboxylic acids such as tin naphthenate, tin 2-ethylhexanate, tin benzoate, dibutyltindilaurate, dibutyltindiacetate and the like. These tin compounds may be used in an amount de- 40 termined as tin metal of from 0.001 to about 1.0 percent by weight based on the weight of the organop olysiloxanes. A convenient niethod for preparing the compositions of this invention comprises mixing liquid hydroxyl terminated organopolysiloxanes and a fuler in any conventional mixing apparatus such as a Sigma-Blade mixer, 45 roller mill, Banbury mixer and the like, and thereafter heating the mixture for a sufficient time to eliminate aH traces of moisture. Various methods may be used - together with the heating to facilitate the elimination of water such as, for example, sweeping with a current of dry inert gas. 50 The mass is then cooled and the phosphorus compound is added and if desired, a catalyst and an anhydrous organic diluent. The composition is then transferred under anhydrous conditions into dry containers which are then hermetically sealed. The products thus prepared may be kept 55 for several months and even several years. The compositions of this invention are stable in the absence of moisture. Consequently, they can be stored for prolonged periods of time without any deleterious - effects. During this period of storage, little or no change occurs in 60 the physical properties of the compositions. This is of particular importance from a commercial standpoint, since it assures that once a composition is prepared with a certain consistency and cure time that neither will change to any great extent upon storage. This stability on storage is 65 the characteristic which makes the composition of this invention particularly useful as one-component room temperature curing compositions. The products of this invention adhere to a variety of materials such as, for example, wood, metal, glass, ce- 7o ramics, plastics and the like. In the,case of metals, it may be desirable to apply an appropriate pretreatment to the metal before applying the composition of this invention. These self-curing compositions may serve for caulking, covering various articles such as electrical equipment, 75 8 coating glass, metals, fabrics, protecting various supports and producing films and molded articles. These compositions may be applied by any of the usual techniques such as by dipping, doctoring or spraying. Various aspects of the invention are further illustrated by the following examples which are not to be taken as in any way limiting the scope thereof. In the examples, all parts are by weight unless otherwise specified. Preparation of the phosphatosilanes Example I Approximately 18.3 parts of diethyl hydrogen phosphate is added to about 49.4 parts of benzene and introduced to a reactor along with about 5.2 parts of metbyltrichlorosilane dissolved in about 12 parts of benzene. The reactants are heated to reflux temperature for about 0.5 hour with agitation. Nitro.-en is then passed through the solution for approximately 5 hours and the solvent removed under vacuum distillation at a temperature of about 55' C. yielding a viscous liquid. The product is analyzed and found to be methyltris(diethylphosphato)silane. Example 2 To a reactor containing about 49.4 parts of benzene and 15.3 parts of diethyl hydrogen phosphate is added a solution containing about 12 parts of benzene, 5.2 parts of methyltrichlorosilane and about 7.8 parts of pyridine with a.@itation. The reactants are heated to reflux temperature and refluxed for approximately 2 hours and then cooled to room temperature. The pyridine hydrochloride thus formed is removed by filtration and the solvent removed by vacuum distillation. A reaction product is recovered. On analysis, it is determined to be methyltris(diethyl phosphato)silane. Example 3 To a reactor containing 38 parts of benzene and about 110 parts of diethyl hydrogen phosphate is added about 150 parts of benzene and about 38.2 parts of butyltrichlorosilane. The reactants are heated to reflux temperature and refluxed for about 0.5 hour. The solvent is removed by vacuum distillation and a product identified as butyltris(diethylphosphato)silane is recovered. Example 4 To a reactor containing approximately 405 parts of benzene and 153 parts of diethyl hydrogen phosphate is added about 176 parts of benzene containing about 66 parts of hexyltrichlorosilane and about 78 parts of pyridine. The reactants are heated with agitation to reflux temperature and refluxed for approximately 0.5 hour and then cooled to room temperature. The pyridine hydrochloride thus formed is removed by filtration and the solvent is removed under vacuum distillation. Infrared analysis of the product disclosed no OH groups or a phosphorus to hydro-en group. The product is identified as hexyltris(diethylp@hosphato)silane. Example 5 To a reactor containing approximately 80 parts of benzene and 210 parts of dibutyl hydrogen phosphate is added about 40 parts of benzene containing about 57.5 parts of butyltrichlorosilane and about 80 parts of pyridine. The reactants are heated to reflux temperature and maintained at this temperature for approximately 2 hours and then cooled to room temperature. The pyridine hydrochloride thus formed is removed by filtration and the solvent is removed by vacuum distillation at a temperature of about 60' C. A product is recovered which is identified as.butyltris (dibutylphosphato) silane. Example 6 Approximately 80 parts of benzene containing 83 parts of decyltrichlorosilane is added to a reactor containing about 140 parts of benzene and 266 parts of dihexyl hydrogen phosphate. Approximately 80 parts of pyridine are
[5]9 3,441,537 10 then added to the reactor -with agitation and heated to reflux temperature. The reactants are refluxed for approximately 2 hours and then cooled to room temperature. The pyridine hydrochloride tbus formed is removed by filtration and the solvent removed by vacuum distillation. 5 The recovered product is analyzed and identified as decyl- . tris(dihexylphosphate)silane. Example 7 To a reactor containin-, approximately 160 parts of benzene and 430 parts of didodecyl hydrogen phosphate 1 0 and about 80 parts of pyridine is added a solution containin- about 40 parts of benzene and about 108 parts of hexadecyltrichlorosilane over a period of about 23 minutes with agitation. The reactants are heated to reflux 15 temperature and refluxed over a period of about 2 hours and then cooled to room temperature. The pyridine hydrochloride thus formed is removed by filtration and the Solvent removed under vacuum at a temperature of about 60 . ' C. The product is analyzed and identified as hexadecyltris 2 0 (didodecylphosphato) silane. Example 8 In accordance with the procedure described in Example 5, approximately 250 parts of diphenyl hydrogen phos25 phate is reacted with about 45 parts of met hyltrichlorosilane in about 120 parts of benzene and about 80 parts of pyridine. A product is recovercd which is identified as methyltris (diphenyiphosphato) silane. Example 9 30 In accordance with the procedure described in Example 5, approximately 250 parts of diphenyl hydrogen phosphate is reacted with about 83 parts of decyltr ichlorosilane in about 120 parts of benzene and about 80 parts of py35 ridine. A product is recovered which is identified as decyltris (diphenylphosphato) silane. Example 10 In accordance with the procedure described in Exam40 ple 5, approximately 278 parts of dibenzyl hydro-en phosphate is reacted with about 63.3 parts of phe nyltrichlorosilane in about 120 parts of benzene and about 80 parts of pyridine. A product is recovered which is identified as phenyltris(dibenzylphosphato)silane. 4 @3 Example I I In accordance with the procedure described in Example 5, approximately 306 parts of diphenylethyl - hydrogen phosphate is reacted with about 78 parts of naphthyltri50 chlorosilane in about 220 parts of benzene and about 80 parts of pyridine. A product is recovered which is identifled as naphthyltris(diphenylethylphosphato)silane. Example 12 5- To a reactor containing approximately 60 parts of ben@' zene and about 154 parts of diethyl hydro.-en phospbate is added a complex formed by the reaction of about 34 parts of tetrachlorosilane and about 70 parts of pyridine in about 88 parts of benzene. The reactants are heated to reflux temperature and refluxed for a period of about 2 hours and then cooled to room temperature. The pyridine hydrochloride thus formed is removed by filtration and the solvent is removed by vacuum distillation at a temperature of about 60' C. A viscous product is recovered which is identified as tetrakis(diethylphosphato)silane. Example 13 In accordance with the procedure described in Example 8, approximately 210 parts of dibutyl hydrogen phosphate is reacted with about 34 parts of tetrachlorosilane in about 100 parts of benzene and about 80 parts of pyridine. A product is recovered which is identified as tetrakis(dibutylphosphato) silane. Example 14 In accordance with the procedure described in Example 13, 602 parts of dioctadecyl hydrogen phosphate is substituted for the dibutyl bydrogen phosphate. A product is recovered wbich is identified as tetrakis(dioctyldecylphosphato) silane. Example 15 In accordance with the procedure described in Example 5, approximately 210 parts of dibutyl hydrogen phosphate is reacted with about 49.5 parts of methoxytrichlorosilane in about 200 parts of benzene and about 80 parts of pyridine. A product is recovered which is identified as methoxytris(dibutylphosphato)silane. Example 16 In accordance with the procedure described in Example 5, approximately 378 parts of didecyl hydrogen phosphate is reacted with about 62.1 parts of butoxytrichlorosilane in about 200 parts of benzene and about 80 parts of pyridine. A product is recovered which is identified as butoxytris (didecylphosphato) silane. Exa-mple 17 In accordance with the procedure described in Example 5, approximately 250 parts of diphenyl hydrogen phosphate is reacted with about 68.1 parts of phenoxytrichlorosilane in abotit 200 parts of benzene and about 80 parts of pyridine. A product is recovered which is identifi,-d as phenoxytris (diphenylphosphato) silane. Preparation of grafted organopolysiloxanes Example 18 Grafted organopolysiloxanes are prepared by graftin.olefinic compounds to hydroxyl terminated polysiloxanes by reacting a mixture consisting of polydimethylsiloxanes and olefinic compounds in the presence of a free-radical initiator at a temperature of from about 601 to about 190' C. The unreacted olefinic compounds are removed at an elevated temperature by applyina a vacuum of about I mm. or less while continuin.- to heat and stir for an additional hour. The pertinent data is illustrated in Table 1. TABLEI Olefliiie compound Hydroxylated fluid Free-radical initiator Reaction conditions Example Viscosity, Final polymer "10. Type Parts CS. Parts Type Parts Temp., I C. Time, hr. viscosity, Cs. 18(a)--- -- Acrylonitrile ------------ 14.6 1,000 60 t-BP 0. 5 so 1.5 14, COO Butyl acrylate ---------- 35.4 18(b) Acrylonitrile ------------ 9.0 800 40 t-BP 0.5 80 1.7 7,800 Butyl acrylate ---------- 51'0 18(c) ------ Acrylon,trile ------------ 0.1 Ethyl acrylate ---------- 2.9 Soo 40 tBP 0.25 so 2.0 20,200 Butyl acrylate ---------- 48.0 18(d) Methaerylate ------------ 50.0 400 50 t-BP 0.5 so 4.0 15,500 18(e) ------ Lauryl methaerylate ---- 70. 0 400 30 tBP 0.5 80 5.0 19,400 18(f) ------ Styrene ----------------- 250. 0 610 304 tBP 2.0 125 24.0 14,500 Butyl acrylate ---------- 204.0 18(g) ------ Vinyl chloride ---------- 45.0 6,700 350 t-BPer 1.8 80 4. 0 17,800 t-BP=tertiary butyl peroxide. t-BPer=tertiary butyl peroctoate.
[6]32441)537 Preparation of phosphatopolysiloxanes Example 19 -A reactor containing approximately 31.3 parts of a grated hydroxyl terminated organopolysiloxane - prepared 5 in accordance with the procedure dcscribed in Example 18(a) is evacuated for about 10 minutes. About 3 parts of methyltris(diethylphosphato)silane prepared in accordance with the procedure described in Example 1 is added to the reactor and heated to a temperature of about 80' with agitation. After about I hour, the volatile materials 10 are removed by vacuum distillation and the residual product placed in a mold and allowed to cure at room - temperature. It cured to a tack-free condition in less than about 6 hours yieldin-, a cloudy, opaque elastomeric solid. 15 Example 20 To a reactor containing approximately 31.3 parts of a hydroxyl terminated organopolysiloxane having a viscosity of about 10,000 cs. is added about 3 parts of butyltris 20 (diethylphosphato)silane prepared in accordance with the procedure described in Example 3. The reactants are heated to a temperature of about 80' C. for about I hour with agitation. The volatile materials are removed under vacuum and the residual product is transferred to a mold 25 and allowed to cure at room temperature. The product cured to a tack-free state in less than 6 hours. Example 21 To a reactor containing about 33.3 parts of a hydroxyl 30 terminated or.-anopolysiloxane (viscosity 16,000 cs.) is added about 2 parts of methyltris(diet hylphosphato) silane prepared in accordance with the procedure described in Example 2. The reactants are heated to a temperature of about 80' C. for about 1 hour with agitation. The 35 volatile materials then are removed under vacuum distillation. The residual product cures at room temperature when exposed to ambient moisture, to a tack-free condition in less than about 2 hours. 40 Example 22 To a reactor containing approximately 33.3 parts of a hydroxyl terminated organopolysiloxane prepared in accordance with the procedure described in Example 18(b) is added about 3 parts of hexyltris(diet hylphosphato) 45 silane prepared in accordance with the procedure described in Example 4. The reactants are heated to a temperature of about 80' C. for a period of about 1 hour with agitation. The volatile materials are removed under 50 vacuum and the resulting product is placed in a mold and allowed to cure at room temperature in the - presence of ambient moisture. The transparent product is tack-free in about 34 minutes. Example 23 55 To a reactor containing about 33.3 parts of hydroxyl terminated organopolysiloxane (viscosity 18,000 cs.) is added about 2 parts of decyltris(dihe xylphosphato) silane with agitation. After heating the reactants to a 60 temperature of about 80' C. for I hour, the - volatile materials are removed under vacuum. The residual product is placed in a mold and allowed to cure at room temperature in the presence of ambient moisture. The product is tack-free in about 4.2 hours. 65 Example 24 To a reactor containing approximately 33.3 parts of a hydroxyl terminated organopolysiloxane prepared in ac12 3 hours at room temperature in the presence of ambient moisture. Example 25 Approximately 33.3 parts of a hydroxyl terminated o rganopolysiloxane having a viscosity of about 4,000 cs. is added to a reactor. Approximately 2 parts of decyltris (diphenylphosphato)silane prepared in accordance with the procedure described in Example 9 is added to the reactor with agitation and heated to about 80' C. for a period of about I hour. The volatile materials are removed under vacuum. The resulting product cures to a tack-free condition in less than about 6 hours when exposed to ambient moisture. Example 26 To a reactor containing about 33.3 part of a hydroxyl terminated organopolysiloxane prepared in accordance with the procedure described in Example 18(d) is added about 1 part of a tetrakis(diethylphosphato)silane with a.-itation. The reactants are heated to a temperature of about 80' C. for a period of about 1 hour. After removing the voiatile materials under vacuum, the residual product cures to a tack-free condition in about .3 hour upon exposure to ambient moisture. Example 27 In accordance with the procedure described in Example 20, 3 parts of phenyltris(oditolylphosphato)silane is substituted for butyltri s(diethylphosphato) silane. The product cured to a tack-free condition when exposed to ambient moisture. Example 28 In accordance with the procedure described in Example 20, 3 parts of hydro-en tris(,diphenylphosphato)silane is substituted for b utyltris(diethylphosphato)silane. A tackfree product is obtained when exposed to ambient moisture. Example 29 In accordance with the procedure described in Example 20, 3 parts of tetrakis(dibutylphosphato)silane is substituted for methyltris(diethylphosphato)silane. The product cured to a tack-free condition when exposed to ambient moisture. Example 30 In accordance with the procedure described in Example 20, 3 parts of tetrakis(dioctadecylphosphato)silane is substituted forbutyltris(diethylphosphato)silane. The prod. uct cured to a tack-free condition when exposed to ambient moisture. Example 31 In accordance with the procedure described in Example 19, 31.3 parts of a grafted hydroxyl terminated organopolysiloxane prepared according to Example 18(e) is reacted with about 3 parts of methoxytris(dibutylphos. phato)silane. A tack-free product is obtained upon exposure to ambient moisture. Example 32 In accordance with the procedure described in Example 20, 3 parts of butoxytris(didecylphosphate)silane is substituted for butyltris(diethylphosphato)silane. Exposure to ambient moisture resulted in a tack-free product. Example 33 In accordance with the procedure described in Example 19, 31.3 parts of a grafted hydroxyl terminated organopolysiloxane prepared according to Example 18(f) is recordance with the procedure described in Example 18(c) 7o acted with about 3 parts of phenoxytris(diphenylpbosis added about 2 parts of methyltris(diphenylphosphato) phato)silane. A tack-free product is obtained upon exposilane with agitation. The reactants are heated to a temsure to ambient moisture. perature of about 80' C. for about I hour with agitation. The volatile materials are removed under vacuum and the Example 34 residual product is cured to a tack-free condition in about 75 To a reactor containing about 15.4 parts of diethyl hy-
[7]3)4412537 13 drogen phosphate in about 30 parts toluene is added about 22 parts of methyltriacetoxysilane in about 100 parts of toluene. The reactants are heated to reflux temperature with agitation and maintained for about 2 hours and then cooled to room temperature. After evacuating the reactor for about 15 minutes, the reactants are again heated to reflux temperature and refluxed for an additional hour. The reactor is again evacuated and the solvent removed under a vacuuzn of <1 mm. Hg at 80' C. The residual product is analyzed and identified as methyl(diethylphosphato) diacetoxysflane. To a reactor containing approximately 33.3 parts of a hydroxyl-terminated dimethylpolysiloxane having a viscosity of about 4,000 cs. is added about 3 parts of the methyl(diethylphosphato)diacetoxysiIane prepared above. After heating the reactants to a temperature of about 80' C. for about I hour with agitation, the volatile materials are removed under vacuum. The residual prod. uct is transferred to a mold and exposed to ambient moisture and temperature. The material cured to a tack-fre condition in about 16 minutes. Example 35 In accordance with the procedure described in Example 34, a grafted hydroxylterminated organopolysiloxane prepared in accordance with the procedure described in Example 18 (a) is substituted for the hydroxyl-terminated dimethylpolysiloxane. The molded material cured to a tack-free condition in about 17 minutes. Example 36 To a reactor containing approximately 30.8 parts of diethyl hydrogen phosphate in about 40 parts of benzene is added about 22 parts of methyltriacetoxysilane dissolved in about 80 parts of benzene. The reactants are heated to reflux temperature and refluxed for about 2 hours and then cooled to room temperature. The reactor is evacuated for about 15 minutes and then reheated to reflux temperature and refluxed for an additiortal hour. The reactor is evacuated and the solvent removed under vacuum of <1 mm. Hg at 80' C. The residual product is analyzed and identified as methylbis-(diethylphosphato)acetoxysilane. To a reactor containing approximately 33.3 parts of a hydroxyl-terminated dimethylpolysiloxane having a viscosity of about 4,000 cs. is added about 3 parts of methylbis-(diethylphosphato)acetoxysilane prepared above and heated to a temperature of about 801 C. for about I hour with agitation. The volatile materials are removed under vacuum and the residual product is transferred to a mold and exposed to atmospheric moisture. The product cured to a tack-free condition in about 5.25 hours. Example 37 In accordance with the procedure described in Example 36, a grafted hydroxylterminated organopolysiloxane prepared in accordance with the procedure described in Example 18 (a) is substituted for the hydroxyl-terminated dimethylpoiysiloxane. A cured product is obtained in about 5.25 hours. Example 38 In accordance with the procedure described in Example 36, approximately 2 parts of methylbis(diethylphosphato)acetoxysilane is added to a hydroxyl-terminated dimethylpolysiloxane having a viscosity of about 4,000 cs. The product cured to a tackfree condition in about 5.25 hours. Example 39 Tn ar-cordance with the procedure described in Example 36, approximately 1 part of methylbis(diethylphosphato)acetoxysilane is added to about 33.3 parts of a hydroxylterminated dimethylpolysiloxane having a visr-osity of 4,000 cs. The product cured to a tack-free condition in about 5.16 hours. 14 When the above examples are repeated utilizing other organophosphato-silanes with bydroxyl-terminatcd organopolysiloxanes, elastomeric materials are obtained which have properties substantially equivalent to those of the specified examples. Although specific examples of the invention have been described herein, other variations and modifications falling within the spirit and scope of the appended claims are to be included therein. 10 The invention
