3,60,601 United States Patent Office Patented Dec. 3, 1964 2 fied by oxygen atoms attached to other silicon atoms to 3,60,601 form siloxane linkages, monovalent hydrocarbon radicals, AMNE SALTS OF PHOSPHORIC ACED AND AANE SALS OF CAR30XYECAC AS hydrocarbon radicals which are polyvalent, i.e. which SLANO, CONDENSATON CATALYSTS have a valence higher than one, each valence of which James Franklia Hyde, Midland, Mich, assigaor ig Bow is attached to another silicon atom to form silcarbane Corning Corporation, Midland, Mich., a corporation linkages and similar monovalent and polyvalent hydro of Michigan carbon radicals containing such functions as ether link No Drawing. Filed July 3, 1959, Ser. No. 826,421 ages, aromatic halogen atoms, aliphatic fluorine atoms, 7. Caimas. (C. 260-46.5) hydroxyl groups and nitrile groups. Any aliphatic fluo 0 line atoms should be separated from any silicon atom This invention relates to the use of amine salts as by at least three carbon atoms. catalysts for the condensation of silicon-bonded hydroxyl More specifically, the silicon valences of the organe groups. silicon compound employed in this invention can be The condensation of silicon-bonded hydroxyl groups Satisfied by, for example, any alkyl radical such as the employing as catalysts alkali metal and quaternary am 5 Inethyl, ethyl, isopropyl, tert-butyl, 2-ethylhexyl, dodecyl, Inonium hydroxides and organosilicon salts thereof is ccitadecyl and myricyl radicals; any alkenyl radical such now well known in the art. However, these catalysts have as the vinyl, allyl and hexadienyl radicals; any cycloalkyl a primary disadvantage of breaking siloxane bonds causing radical such as the cyclopentyl and cyclohexyl radicals; random rearrangement of siloxane units in a polymer. any cycloalkenyl radical such as the cyclopentenyl and While this is not a problem where all the siloxane units 20 cylohexenyl radicals; any aryl hydrocarbon radical such are alike, it is undesirable where, for instance, there is as the phenyl, naphthyl and xenyl radicals; any aralkyl initially in a polymer a planned distribution of siloxane radical Slich as the benzyl, phenylethyl and xylyl radicals units containing functional groups. Rearrangement of and any alkaryl radical such as the tolyl and dimethyl such siloxane units may well reduce or negate the useful phenyl radicals. These monovalent hydrocarbon radicals ness of the functional groups. There has been a search can also contain aromatic halogen atoms as, for example, by those skilled in the art for a compound which would in the 2,4,6-trichlorobenzyl, perchlorophenyl, 2-bromo catalyze the condensation of silicon-bonded hydroxyl naphthyl, p-iodo-phenylethyl and 4-fluorophenyl radicals; groups in a polymer without attacking siloxane bonds aliphatic fluorine atoms as, for example, in the 3,3,3-tri and permitting unit rearrangement within the polymer. fluoropropyl, c.,a,c-trifluorotolyl, 3,3,4,4,5,5,5-heptafluoro The objects of this invention are primarily two-fold. 30 penty and 5,5,5-trifluoro-2-trifiuoromethylamyl radicals; The first object is to provide a new condensation catalyst hydroxyl radicals as, for example, in the 4-ethyl-4-hy for silicon-bonded hydroxyl groups. The second object droxyhexyl, 3-hydroxyallyl, cresy), p-hydroxyphenyl and is to provide such a condensation catalyst which is not a siloxane bond rearrangement catalyst. Other objects and advantages of this invention will become apparent 35 -CHCHK s >ot as the invention is explained. - radicals; nitrile radicals as, for example, in the gamma This invention relates to the method which comprises cyanopropyl and beta-cyanoethyl radicals and ether link condensation of silicon-bonded hydroxyl groups by con ages as, for example, in the -CHCHOCHCH, tacting (A) an organosilicon compound containing at least one silicon-bonded hydroxyl group per molecule, 40 any remaining silicon valences in said organo-silicon reno CCECE compound being satisfied by radicals selected from the -CH2(OCH2CH2)2OCH, -CHOCH2CH=CH and group consisting of silicon-bonded oxygen atoms, hydro furyl radicals. These radicals can contain more than one carbon radicals and hydrocarbon radicals containing func of the above functions in radicals such as, for example, tions selected from the group consisting of ether linkages, aromatic halogen atoms, nitrile groups, hydroxyl groups -CHCH-CHCHCHOHCHOCHs and aliphatic fluorine atoms, the last being separated from any silicon atom by at least three carbon atoms, with (B) -CH2CH2CH2O CH, CHOEICHk X a composition compatible with (A) and selected from the -CH2CH2OCFCF group consisting of (1) a salt of a phosphoric acid, the 50 only active hydrogen atoms in said acid being attached to the phosphorous through an oxygen atom, and a basic horroctor amino compound, any active hydrogen in said amino and compound being attached to nitrogen, and any remaining valences of the nitrogen atom in said amino compound 55 being satisfied by carbon atoms, the total number of car -C2CHCHO chschoichk Xci bon atoms in (1) being at least 18, and (2) a salt of a These silicon valences can also be satisfied by poly carboxylic acid, the only active hydrogen atoms in said Valent hydrocarbon radicais attached to other silicon acid being a part of carboxyl groups, and a basic amino atoms. These polyvalent hydrocarbon radicals can con compound, any active hydrogen in said amino compound 60 tain singly or in any combination such polyvalent groups being attached to nitrogen, and any remaining valences as methylene, vinylene, vinylidene, cyclohexylidene, phen of the nitrogen being satisfied by carbon atoms, the total - ylene, toylene, toluenyl, toluylene, tertiary carbon atoms, number of carbon atoms in (2) being at least 6, whereby and quaternary carbon atoms as well as any monovalent the silicon-bonded hydroxyl groups in (A) condense to hydrocarbon radicals. These polyvalent hydrocarbon form siloxane linkages producing water as a by-product. 65 radicais can contain the various functions permissible in The organosilicon compound can be any silane, siloxane the monovalent radicals as previously, described. Exam or silcarbane or any mixture thereof in which the only functional groups attached directly to any silicon atom pies of operative polyvalent hydrocarbon radicals contain are hydroxyl groups. The silicon valences not satisfied ing Such functions include - by hydroxyl groups can be satisfied by any groups which 70 -CH(OCH2CH3)6OCH, CHCH do not interfere with the condensation of silicon-bonded OH...... hydroxyl groups. Thus the silicon valences can be satis -CH3CH, CH, CH, CHCHO CH 3,160,601 ?e 4. -CHCHCHFCH2CH2-, iodophenylene and allylamine, N-methylallylamine, amylamine, N,N-dimeth ylamylamine, aniline, p-bromoaniline, 2,6-dinitroaniline, B m-fluoroaniline, sym-bis-gamma-aminopropyl-tetramethyl disiloxane, gamma (N-aminoethylamino)propyldiphenyl -CHK XCH 5 methylsilane, o-iodoaniline, o-nitroaniline, 2,3,4,5-tetra Thus, where R represents any of the abovedescribed chloroaniline, o-anisidine, 9-anthrylamine, 4,4'-diamino monovalent radicals and R represents any of the above azobenzene, anthranilonitrile, benzylamine, p-methoxy described polyvalent radicals, the organosilicon compound benzylamine, decylamine, diallylamine, dicyclohexyl employed as a starting material can be, for example, any amine, diethylenetriannine, difurfurylamine, di-m-tolyl one or any combination of the following types of mono amine, 3-ethoxyethylamine, tetrahydrofurfurylamine, his meric compounds or can contain any of the specific types O tamine, benzylhydrazine, p-bromophenylhydrazine, 1 of the following polymer units: methyl-1-phenylhydrazine, 4,4'-diaminohydrazobenzene, RSiOH, RSiOH2, RSi(OH)3, R3SiO5, p-leucaniline, methylamine, morpholine, 5-nitronaphthyl R2SiO, RSiO5, SiO2, RSi(OH)Os, amine, 1,2-dimethyl-4-pentenylamine, N,N-diethyl-p- RSi(OH)O, RSiR'Si(OH), RSiR'SiROH, phenylenediamine, piperazine, piperidine, 2-aminopyri dine, 6-nitro-o-toluidine, 2-amino-p-tolunitrile, 9-phenan HORSiR'SiR (OH), Hors--SIROH thrylamine, and tribenzylamine. SiRO As state above the salts which are operative catalysts ORSiR'SiRO.5 and the like. in this invention are the reaction products of any of the In any one molecule of the organosilicon compound there 20 basic amino compounds described above, i.e. ammonia must be at least one silicon-bonded hydroxyl group. and primary, secondary and tertiary amines, both organic While the above list does not include all the possible and silylorganic, with either a phosphoric acid or a variations, it is sufficiently representative to show the carboxylic acid in which any carboxyl group is attached scope of the materials which can be employed in this to a carbon atom. As in the basic amino compounds invention. 25 where any active hydrogen atoms are attached to nitrogen The method of this invention is especially advantageous atoms, so in the acids any active hydrogen atoms must be for producing polysiloxane fluids, gums and resins. Hy a part of the particular acid group, e.g. droxy-endblocked linear molecules, i.e. diorganopolysi O oxanes, can be polymerized without bond rearrangement by the condensation of the terminai silicon-bonded hy 30 RCOOH, O=P(OH)3 or ROP (OH), droxyl groups. If organosilyl endblocking is desired, the An “active hydrogen' atom is one which forms methane necessary proportion of triorganosilanol or other organo when a compound containing said "active hydrogen' is silicon compound containing one silicon-bonded hydroxyl reacted with methyl magnesium iodide at room tempera group per molecule can be added to condense with the ture, silicon-bonded hydroxyl on the polymer. If polyfunc 35 The salts employed in any particular system must be tionality is desired, the necessary organosilicon compound compatible in that system. The degree of compatibility containing more than two silicon-bonded hydroxyl groups of any salt in any system generally depends on the total per molecule, e.g. RSi(OH), number of carbon atoms and silicon atoms and their Ot configuration in the salt to be employed. Thus, for ex IOSiROSiROSiROE 40 ample, in a given system the n-hexylamine salt of octanoic or HO(SiRO)SiOOH)O(SiRO)H, can be added to acid is compatible while the di-n-hexylamine salt of suc condense with the terminal silicon-bonded hydroxyl cinic acid is incompatible. However, the di-eicosylamine groups on the polymer. Siloxane resin molecules, i.e. salt of succinic acid is compatible in that system. Simi molecules having an average of from 1 to 1.7 organic larly, the mono-2-ethylhexyl amine salt of phenylphos radicals per silicon atom, which contain silicon-bonded 45 phoric acid is compatible in a given system whereas it is hydroxyl groups can also be cured by the method of this necessary to go to the mono-eicosylamine salt of unsub invention. stituted phosphoric acid to achieve compatibility in the The crux of this invention resides in the discovery that same system. For any particular system suitable salts can certain amine salts catalyze the condensation of silicon be selected on the basis of compatibility. bonded hydroxyls under conditions where the amines or 50 The most compatible and therefore preferred salts are the acids alone are inactive. The amine salts are reac monocarboxylic acid salts which have at least six carbon tion products of basic amino compounds, i.e. ammonia atoms. Examples of the monocarboxylic acid which can or organic amines (including silylorganic amines), with be used in the preparation of these salts include the fol phosphoric acids or carboxylic acids. lowing: abietic acid, acetic acid, cyanoacetic acid, phen More specifically, the basic amino compound can be 55 oxyacetic acid, acrylic acid, S-benzoylacrylic acid, angelic ammonia, a primary amine, a secondary amine or a ter acid, anisic acid, N-acetylanthranilic acid, arachidic acid, tiary amine. The amine can contain one or more amino atropic acid, benzoic acid, o-bromobenzoic acid, p-cyano groups and can also contain carbon-bonded silicon atoms benzoic acid, 2,6-dichlorobenzoic acid, 2,5-dinitrobenzoic and other functional organic groups which are free of acid, m-fluoro-benzoic acid, brassidic acid, di-campholic active hydrogen. It is necessary that the only active hy 60 acid, capric acid, cinnamic acid, cyclohexanecarboxylic drogen atoms, if any, be attached to nitrogen atoms. acid, cyclopropanecarboxylic acid, formic acid, 3-furan Any other active hydrogen atoms would interfere with carboxylic acid, trimethylsilylacetic acid, 5-nitro-2-furoic the salt formation. The amino compound can, however, acid, 10-hendecenoic acid, isobutyric acid, lauric acid, contain various non-interferingfunctional groups as shown levulinic acid, ignoceric acid, linoleic acid, oleic acid, in the following examples. 65 stearic acid, tetrahydropyromucic acid, 3-ethylpentanoic In short the term “basic amino compound” means com acid and 2,4-xylic acid. pounds containing at least one nitrogen atom attached to Polycarboxylic acids while not preferred can also be no more than three carbon atoms any of which, if double employed in preparing the amine salt catalyst of this in bonded, are double-bonded only to another carbon atom, 70 vention. Examples of such acids include: adipic acid, e.g. azelaic acid, o-carboxymethoxybenzoic acid, 1-camphoric acid, 1,2-cyclobutanedicarboxylic acid, sym-bis-(3-carboxy -CassC-NH ethyltetramethyldisiloxane, 1,2,3,4,5,6 - cyclohexanehexa Specific examples of operative amines are: o-amino carboxylic acid, 1,3-cyclopentanedicarboxylic acid, di acetanilide, iminodiacetonitrile, m-aminoacetophenone, phenic acid, ethylmalonic acid, pimelic acid, sebacic acid, 3,160,601 5 6 Succinic acid and traumatic acid. It requires more car the salts of any other of the amines and acids shown bon atoms in an amine salt of a polycarboxylic acid to above. These examples are by no means complete, but render it compatible with an organosilicon compound they do illustrate some of the types of amine-type salts operative in this invention than is the case with an amine which can be used. These salts can be prepared prior to salt of a monocarboxylic acid. For instance, in a given their inclusion in the condensation system, or they can system n-hexylamine 2-ethylhexoate is very compatible be prepared in situ. For in situ preparation the order and active whereas bis-eicosylamine succinate containing of addition of the acid and amine to the system is not over three times as many carbon atoms is still less com critical. patible and therefore less active. This problem can gen It should be emphasized that the invention herein does erally be somewhat alleviated by the use of silylorganic O not reside in the amine-type salts, which are generally amine salts of these acids. well-known as a class, but in the use of these salts as This problem of conpatibility also arises with the amine catalysts for the condensation of silicon-bonded hydroxyl salts of phosphoric acids which are also operative as cat groups. As catalysts the amount of the amine salts alysts in this invention. The salt can be prepared with which must be present to condense silicon-bonded hy phosphoric acid or with any acid esters of phosphoric acid 5 droxyl groups is not critical since even an infinitesimal Such as monovalent hydrocarbon substituted phosphoric amount of such salt will catalyze the reaction to a degree. acids, e.g. phenylphosphoric, monooctadecylphosphoric or However, the rate of condensation generally increases diethylphosphoric acids. An organic amine salt of phos with an increase in catalyst concentration. Preferably phoric acid must contain at least abort 18 carbon atoms there should be at least 0.01 percent by weight salt based to make it sufficiently compatible in a diorganopolysilox 20 on the weight of the organosilicon compound to be con ane to be active whereas a silylorganic amine salt may densed. An optimum rate of condensation can be achieved not require so much carbon to render the catalyst com in any system with less than 10 percent by weight salt. patible depending on the solubility characteristics of the The best range runs from 0.1 to 5.0 percent by weight systein. of the amine salt. Since the active part of the catalyst The amine-type salts are prepared by reacting ammonia, 25 is the amine salt group, the percent by weight of catalyst an organic amine or an aminoorganosilicon compound necessary in a given system may increase or decrease with with a phosphoric or carboxylic acid. This can be ac the molecular weight of the amine salt as a whole depend complished by merely mixing the components alone in ing on the effect of the other atoms present on the com a relatively anhydrous system or by mixing the com patibility of the salt in the system. 8 - ponents together in a common solvent. This preparation 30 It is has been found that any water present in the is well known. system slows the rate of SiOH condensation. Con The amine-type salts can be normal, acidic or basic. sequently, agitation of the system allows water to escape The normal salts are those in which there are no un more readily thereby accelerating SiOH condensation. reacted amine or acid groups present as, for example, The temperature and pressure of the system are not critical but affect the rate of condensation. Generally, O O ... O the rate increases as the temperature increases and the | pressure decreases. (CH3)3NHO &c.His CoHNHOP (OCH3)2, NH4O C1H35 The method of this invention is useful for the polymer 40 iztion of linear polymers in the preparation of rubber (CH3)3SiCHCHCHNHO C12H25 grade gums and for the curing of resins. This method O O is operative in the presence of organic solvents such as toluene without rearrangement of the siloxane units. CH5NHO l (CH2) t ONC12H25 The following examples are illustrative of the method and of this invention. These examples are not intended to O O limit this invention which is properly delineated in the C Hué ON(CH) NHot Cs claims. All viscosity measurements were made at 25 C. Actually, the normal salts, will often be acidic or basic EXAMPLE depending on the relative basic and acidic characters of The following amine salts were prepared by mixing the amine and acid used to form the salt. This acidity 50 together the appropriate amines and acids in the propor or basicity can be balanced by adding an excess of the tions corresponding to the mol ratios of each component necessary amine or acid. The acidic salts are those in in the final salt. Where one component was solid at which there are unreacted acid groups present as for room temperature as in the case of myristic acid, the mix example, in ture was heated until the system was entirely liquid. There was an exothermic reaction in every case. Holt (CH), ONC 129 and C6H3NHOPSH: (OH) (A) Primary Monoamine and Monoacid The basic salts are those in which there are unreacted n-Hexylamine 2-ethylhexoate anino groups present as, for example in Isobutylamine oleate O 60 t-Butylamine 2-ethylhexoate st-Butylamine decanoate NCHCHNICICINEO &c.H., t-Butylamine laurate Further examples of amine salts operative as catalysts t-Butylamine myristate in this invention include: di-2-ethylhexylamine acetate, is t-Butylamine trimethyl-n-caproate triphenylsilpropylamine formate, trimethylsiloxydimethyl Cyclohexylamine 2-ethylhexoate silhexylamine hexoate, 4,4'-diaminobenzophenone buty 65 Cyclohexylamine decanoate rate, 4,4'-diamino diphenyl ether decanoate, tri-n-butyl Cyclohexylamine laurate amine acrylate, 3,4-dichloroaniline caproate, aniline octa Cyclohexylamine myristate noate, didodecylamine o-chlorophenoxyacetate, ethyl t-Octylamine 2-ethylhexoate amine 3-ethoxypropionate, diethylene triamine monoole O t-Octylamine decanoate ate, diisopropylamine palmitate, trimethylamine stearate, t-Octylamine laurate benzyhydrazine hexoate, 2,5-dimethylpiperazine octoate, t-Octylamine myristate di(octadecylamine) sebacate, ethylenediamine di-hexoate, t-Octylamine trimethyl-n-caproate tetraethylene pentamine di-phosphate, 1,2-aminopropane t-Nonylamine 2-ethylhexoate phenylphosphate and ammonium stearate together with 75 t-Nonyiamine decanoate 3,160,601 7 8 t-Nonylamine laurate Dibenzylamine myristate t-Nonylamine myristate Di-n-hexylamine acetate t-Nonylamine trimethyl-n-caproate Di-n-hexylamine 2-ethylhexoate Decylamine 2-ethylhexoate Di-n-hexylamine formate Decylamine decanoate 5 Di-n-hexylamine hexoate Decylamine laurate Di-n-hexylamine benzoate Decylamine myristate Tridecylamine 2-ethylhexoate (D) Mono-Tertiary Amine.--Monoacid Tridecylamine decanoate Triethylamine 2-ethylhexoate Tridecylamine laurate 0 Triethylamine decanoate Tridecylamine myristate Triethylamine laurate Tridecylamine trimethyl-n-caproate Triethylamine myristate Eicosylamine 2-ethylhexoate N,N-dimethyldodecylamine 2-ethylhexoate Eicosylamine decanoate N,N-dimethyldodecylamine decanoate Eicosylamine laurate l5 N,N-dimethyldodecylamine laurate Eicosylamine myristate N,N-dimethyldodecylamine myristate Eicosylamine trimethyl-n-caproate Trisoamylamine 2-ethylhexoate Ammonium oleate Trisoamylamine decanoate Ammonium stearate Trisoamylamine laurate t-Butylamine acetate 20 Trisoamylamine myristate t-Butylamine 2,2-dimethylpropanoate Tri-n-hexylamine 2-ethylhexoate n-Hexylamine formate n-Hexylamine acetate (E) Di-Tertiary Amine--Monoacid n-Hexylamine hexoate Tetramethylethylenediamine 2-ethylhexoate (Mono Salt) Eicosylamine 2-ethylhexoate 25 Tetramethylethylenediamine decanoate (Mono Salt) Aniline 2-ethylhexoate Tetramethylethylenediamine laurate (Mono Salt) Tetramethylethylenediamine myristate (Mono Salt) (B) Primary Diamine +Monoacid Tetramethylguanidine 2-ethylhexoate Menthanediamine 2-ethylhexoate (Mono Salt) Menthanediamine decanoate (Mono Salt) 30 (F) Mono-Primary Amine--Polyacid Menthanediamine laurate (Mono Salt) (1) Monohexylamine phosphate Menthanediamine myristate (Mono Salt) monoeicosylamine phosphate (2) Bishexylamine phosphate (C) Mono-Secondary Amine--Monoacid biseicosylamine phosphate Tridecyldodecenylamine (CH2)(C12H23)NH 35 (3) Trishexylamine phosphate 2-ethylhexoate triseicosylamine phosphate Tridecyldodecenylamine decanoate Tridecyldodecenylamine laurate (4) Bis-eicosylamine succinate Tridecyldodecenylamine myristate Tridecyldodecylamine 2-ethylhexoate - 40 EXAMPLE 2. Tridecyldodecylamine decanoate The polymer employed in this example was initially Tridecyldodecylamine laurate a hydroxy-endblocked dimethylpolysiloxane having a vis Tridecyldodecylamine myristate cosity at 25 C. of 10,720 c.p.s. (M.W.239,000). In Diisopropylamine 2-ethylhexoate each case the catalyst was thoroughly mixed with the Diisopropylamine decanoate polymer in the weight percent shown based on the weight Diisopropylamine laurate of the polymer and maintained at a given temperature in Diisopropylamine myristate an open container. Periodically, the mixture was cooled Dibenzylamine 2-ethylhexoate to 25 C. if not already at that temperature and the Dibenzylamine decanoate viscosity was measured after which the mixture was then Dibenzylamine laurate 50 returned to its reaction temperature.

Catalyst Percent Temp. Time Wisc. by Wt. (° C.) Chr.) (cps.)

A mixture of 1 mol of n-hexyla nine and Taol of n-hexylamine 2 ethylhex0ate------0.92 25 : 16,960 n-Hexylamine 2-ethylhexoate------1.3 25 { 5. l, ci: G A mixture of Imol of 2-ethylhexoic acid and Inol of Il-hexylamine 2-ethylhexoate------2.07 25 52 128,000 - Amixture of 2Inols of 2-ethylhexoic acid and Imol of n-hexylamine 2-ethylhexoate------4.35 25 52 201,500 Arnixture of 1 Inol of n-hexylamine and mol of n-hexylamine 2- 24.5 167,000 ethylhexoate------0.92 10 47.0 672,000 760 44,800,000 n-Hexylamine 2-ethylhexoate------1.3 110 24.5 103,000 AImixture of limol of 2-ethylhexoic acid and mol of n-hexylainine 2-ethylhexoate------2,07 10 2.5 131,000 A mixture of2.nols of 2-ethylhexoic acid and Imol of n-hexylamine 2-ethylhexoate------4.35 10 24.5 137,600 D 2.7 10 25.5 168,000 09 10 25.5 216,000 0.54 10 20 200,000 0.27 10 is: 000 $85,000 0.44: 110"I K as as:58 Do------0.22 0 48 500,000 n-Hexylamine 2-ethylhexoate--- 0.6 0. 48 166, 500 Tri-n-hexylamine 2-ethylhexoate 0.28 10 162 55,700 Trisoamylanine 2-ethylhexoate- 0.24 10 A8 25,000 Do------96 110 48 410,000 Tetramethylethylene diamine 2-ethylhexoate. 69 O 48 194,000 3,160,601 9 10 Catalyst Percent Temp. Time Wisc. by wt. (o C.) Chr.) (cps.) n-Hexylamine 2-ethylhex0ate.------0.16 1 50-55 { 20.570 3, 620,00095,000 Do------0.08 150-55 { 24013 2,666,66685.8 Eicosylamine 2-ethylhexoate------2.33 450-70 K 3s.i? 10,888458 Do------2.33 25 16 2,500,000

At (1.0 mm. Hg 2At <0.5 nm. Hg EXAMPLE 3 ABLE The polymer employed in this example was initially 5 - a hydroxy-endblocked dimethylpolysiloxane havingw a CatalystattayS Timee (hr.)(hr. Wisc.isc. (cps.(cps.) viscosity at 25 C. of 2090 cps. (M.W.s.22,000). 116 10,72 Eicosylamine 2-ethylhexoate was mixed with the polymer n-Hexylamine 2-ethylhexoate------{ 545 - 40,000,600

in an wamount 4 equivalent to one nitrogen atom, for every 20 Tri-isoalayanineE.E.------2-ethylhexoate-- - 11616 7,4901,000 two silicon-bonded hydroxyls, i.e. 1.99% by weight based y y nex0ate on the weight of polymer. One sample was allowed to stand at room temperature, i.e. 23–25 C. A second EXAMPLE 5 sample was heated at 50-52 C. These runs were made A hydroxy-endblocked dimethylpolysiloxane having a for 4 hours at an absolute pressure of 46-54 mm. Hg and 2 viscosity of 46.1 cps. (M.W.s3000) was mixed with the pressure reduced to 8-10 mm. Hg for the remainder di-n-hexylamine 2-ethylhexoate in an amount equivalent of the runs. A third sample was heated at 50-55 C. to approximately 25 silicon-bonded hydroxyl groups per at an absolute pressure of less than 0.5 mm. Hg. The nitrogen atom and the mixture was heated to and main resulting increases in viscosity were measured by bring tained at 110° C. The viscosity increase was recorded. ing the samples to 25 C. and measuring the viscosity. 30 TABLE ABLE Time (hr.): Visc. (cps.) Temp. (C.) Time (hr.) Wisc. (cps.) 21.5 ------10,240 44.0 ------251,000 23-25------48 7,680 35 210.0 ------30,000,000 6052------4: SES 50-55 at <0.5 mm. Hg------{ 57,588 EXAMPLE 6 Samples of the 2090 cps. hydroxy-endblocked dimethyl EXAMPLE 4 polysiloxane employed in Example 3 were mixed with Three samples of the 10,720 cps. polymer employed the following amine salt catalysts and heated to and in Example 2 were mixed respectively with n-hexylamine maintained at 110° C. Viscosities were measured after 2-ethylhexoate, di-n-hexylamine 2-ethylhexoate and tri 135 hours and 200 hours.

Percent by Catalyst weight based Time (hr.) I Wisc. (cps.) on polymer Menthanedianine Inono-2-ethylhexoate.------0.6 { 5 3. 3. 88: MenthanediaInine InoFOInyristate------. 0.46 { SS y E.WWy 8 Tetramethylencguanidine 2-ethylhexoate...--- 0.08 20035 3,786,0008, 400,000 Aniline 2-ethylhexoate------0.109 { 38 SSS Di-n-hexylamine benzoate------0.109 { is ... 2.588a www. Tetramethylenediamine 2-ethylhexoate------0.06 { 35 swwy S isoamylamine 2-ethylhexoate in an amount equivalent EXAMPLE 7 to eight silicon-bonded hydroxyl groups per nitrogen atom. 60 75 grams of toluene were then added to each mixture, Three samples of the 2090 cps. hydroxy-endblocked the components were thoroughly mixed, and the resulting dimethylpolysiloxane employed in Example 3 were mixed mixtures having a viscosity of 430 cps. at 25 C. were with the following amine phosphate catalysts and heated heated to and maintained at 75 C. The increase in to 110° C. Viscosities were determined after 112 hours viscosity was recorded. - 65 and 200 hours.

Percent by , Catalyst weight based Time (hr.) Wisc. (cps.) on polymer . Eicosylamine phosphate------0.113 { i ;8:8 Di-eicosylamine phosphate------0.109 { is 388 - Tri-eicosylamine- phosphate------0.0 2002 5,500,000980 000 3,160,601 2 EXAMPLE 8 O 3,3,3-trifluoropropylmethylsilanediol was mixed with (CH3) SiCHCHCHNHCCHN3O C C15 0.2% by weight based on the weight of the silane of n O hexylamine 2-ethylhexoate to give a mixture having a viscosity of 320 cps. After heating for 75 hours at (HCH-NHocc.His 110° C. the resulting mixture had a viscosity of 1290 (CH3) (CH) (CH) Si (CH2) .NHg CCH cps. After heating for 166 hours at 110° C. the resulting and each of the amine salts of Example 1 with the excep mixture had a viscosity of 5200 cps. tion of t-butylamine acetate, t-butylamine 2,2-dimethyl EXAMPLE 9 O propanoate, n-hexylamine formate and n-hexylamine Hydroxyl-endblocked 3,3,3-trifluoropropylmethylpoly acetate shown in Example 13. siloxane having a viscosity of 450 CS. was mixed with 2 EXAMPLE 1.5 to 4 percent by weight based on the polysiloxane of iso When 2000 cs. hydroxyl-endblocked phenylmethylpoly butylamine oleate. After the mixture was heated for 15 5 siloxane was heated at 110 C. with approximately 2 to 20 hours at 150° C., it had a viscosity of between one percent by weight n-hexylamine 2-ethylhexoate until the million and two million cs. viscosity of the mixture had risen to 50,000 cs. and an excess of phenylmethylvinylsilanol was added to the mix EXAMPLE 10 ture, further heating of the mixture produced a product When 10 parts by weight of a 2000 cs. hydroxyl-end 20 composed of sym - diphenyldimethyldivinyldisiloxane blocked dimethylpolysiloxane and 1 part by Weight of which could be stripped off leaving approximately 50,000 (HO)SiOSi(CH5)(CH3)OJSi(C6H5)(CH3)OH added cs. phenylmethylvinylsiloxy-endblocked phenylmethyl as 40 percent by weight toluene solution are heated at polysiloxane. EXAMPLE 16 75° C. for 72 hours in contact with 0.1 part by weight 25 of n-hexylamine 2-ethylhexoate, the resulting mixture When the following hydroxyl-endblocked organosili gells in 72 hours. con compounds are each heated at 110 C. in the pres EXAMPLE 1. ence of approximately 2 percent by weight of n-hexyl A 243 cs. hydroxyl-endblocked dimethylpolysiloxane amine 2-ethylhexoate based on the weight of the organo was mixed with approximately one percent by Weight of 30 silicon compound, condensation of the silicon-bonded hy ammonium oleate prepared by mixing stoichiometric droxyl groups to form SiOSi linkages will take place as amounts of ammonia and oleic acid. This mixture was shown by the gradual increase in viscosity in each sys heated for 40 hours at 110° C. after which the viscosity tem proving an increase in molecular weight. of the mixture had risen to 1,000,000 cs. HOSi(CH3) (CH)OISi(CH3)O10(SiOCH3) EXAMPLE 12 (CH2CHCN) OJSi(CH3) (CH)OH Br A 2000 cs. hydroxyl-endblocked dimethylpolysiloxane was mixed 0.1% by weight of bis-eicosylamine Suc Host(CH-CHK XCHSiCHoosi(CH-OH cinate and heated for 24 hours at 110° C. The resulting 40 Cs O viscosity of the mixture was 6700 cs. HOSi(C6H5) CH2CH2CHCHCHCHO CHSiCCH3)2OH. EXAMPLE 1.3 (H, The resin employed herein was a copolymer of 45 mol percent monomethylsiloxane units, 40 mol percent mono phenylsiloxane units, 5 mol percent phenylmethylsiloxane 45 units and 10 mol percent diphenylsiloxane units and con tained approximately two percent by weight silicon IOSi(CH3) OSi(CEI)-CH=CH-Si (CH)OSi(CEI), OH bonded hydroxyl groups. Between 0.1 and 0.2 percent A copolymer of: by weight di-n-hexylamine acetate was mixed in the resin 50 mol percent dimethylsiloxane units solution and the solvent was stripped off. The resin 50 45 mol percent phenylmethylsiloxane units mixture was then press-molded at 1000 p.s. i. for /2 hour 3 mol percent perchlorophenylmethylsiloxane units at 175 C., cooled and baked for 16 hours at 90 C. 1 molpercent cyclohexylbenzylsiloxane units followed by heating with an increase in temperature of 1 mol percent dicresylsiloxane units. 16° C. per hour until the temperature reached 250° C. 55 That which is claimed is: The resin mixture was subsequently heated for from 4 to 1. The method for the condensation of silicon-bonded 12 hours at 250° C. When this resin was treated as hydroxyl groups which comprises contacting (A) an or stated, it was found to have cured to a hard resinous ganosilicon compound containing at least one silicon solid. bonded hydroxyl group per molecule, the remaining sili When this experiment is done employing di-n-hexyl 60 con Valences in said organo-silicon compound being sat amine formate instead of di-n-hexylamine acetate, the isfied by radicals selected from the group consisting of results are approximately the same. silicon-bonded oxygen atoms attached to other silicon When this experiment is done with n-hexylamine atoms to form siloxane linkage, hydrocarbon radicals formate, n-hexylamine acetate, t-butylamine acetate or and hydrocarbon radicals containing functions selected t-butylamine 2,2-dimethylpropanoate instead of di-n- 65 from the group consisting of ether linkages, aromatic hexylamine acetate, a cured resin is produced. halogen atoms, nitrile groups, hydroxyl groups and ali EXAMPLE 1.4 phatic fluorine atoms, the last being separated from any silicon atom by at least three carbon atoms, with from When the experiment of Example 5 is repeated em 0.01 to 10 percent by weight based on the weight of ploying the following amine salt catalysts instead of di-n- (A) of (B) a composition compatible with (A) and se hexylamine 2-ethylhexoate, similar results are obtained lected from the group consisting of (1) a salt of a phos through the condensation of silicon-bonded hydroxyl phoric acid, the only active hydrogen atoms in said acid groups: being attached to the phosphorus through an oxygen atom, and a compound selected from the group con (C6H5)2(CH3)SiOSi(CH3)2CHCHCHNEO (C5Hit sisting of ammonia and amines, any active hydrogen 3,160,601 3. 4. in said compound being attached to nitrogen and any 5. The method of claim 4 in which the polysiloxane remaining nitrogen valences being satisfied by carbon is essentially a diorganopolysiloxane. atoms, the total number of carbon atoms in (1) being 6. The method which comprises contacting a poly at least 18 and (2) a sat of a carboxylic acid, the only siloxane containing an average of from 1 to 3 mono active hydrogen in said carboxylic acid being a part of 5 valent hydrocarbon radicals per silicon atom and at carboxyl groups, and a compound selected from the group least one silicon-bonded hydroxyl group per molecule consisting of ammonia and amines, any active hydrogen with from 0.1 to 5.0 percent by weight based on the in said compound being attached to nitrogen and any Weight of the polysiloxane of a compatible salt of an remaining nitrogen valences being satisfied by carbon aliphatic hydrocarbon monocarboxylic acid and an amine atoms, the total number of carbon atoms in (2) being at O composed of carbon atoms, hydrogen atoms, nitrogen least 6, whereby the silicon-bonded hydroxyl groups in atons and silicon atoms attached only to carbon atoms, (A) condense to form siloxane linkages producing water there being a total of at least six carbon atoms in said as a by-product. salt, whereby the silicon-bonded hydroxyl groups con 2. A heat-curable composition consisting essentially dense to form siloxane linkages producing water as a of a mixture of (A) an organopolysiloxane containing 5 by-product. an average of from 1.0 to 1.7 monovalent hydrocarbon 7. A heat curable composition consisting essentially radicals per silicon atom and an average of greater than of a mixture of two silicon-bonded hydroxyl groups per molecule, and (A) an organopolysiloxane containing an average of from 0.01 to 10 percent by weightbased on the weight from 1.0 to 1.7 monovalent hydrocarbon radicals of (A) of (B) a salt of (1) a carboxylic acid, the only 20 per silicon atom and an average of greater than two active hydrogen in said acid being a part of carboxyl silicon-bonded hydroxyl groups per molecule, and groups, and (2) an amine, any active hydrogen in said from 0.1 to 10 percent by weight based on the weight anine being attached to nitrogen, any remaining nitro of (A) of (B) a salt of gen valences being satisfied by carbon atoms, the total (1) a phosphoric acid, the only active hydrogen number of carbon atoms in (B) being at east 6. atoms in said acid being attached to the phos 3. The method which comprises contacting a poly phorus through an oxygen atom, and siloxane containing an average of from 1 to 3 mono (2) an amine, any active hydrogen in said amine Valent hydrocarbon radicals per silicon atom and at being attached to nitrogen, any remaining nitro least one silicon-bonded hydroxyl group per molecule gen valences being satisfied by carbon atoms, with from 0.1 to 5.0 percent by weight based on the 30 Weight of the polysiloxane of a compatible salt of an the total number of carbon atoms in aliphatic hydrocarbon monocarboxylic acid and an amine (B) being at least 18. composed of carbon atoms, hydrogen atoms and nitro References (Cied in the file of this patent gen atoms, there being a total of at least 6 carbon atoms in said salt, whereby the silicon-bonded hydroxyl groups 35 UNITED STATES PATENTS condense to form siloxane linkages producing water as 2,830,967 Nitzsche et al. ------Apr. 15, 1958 a by-product. 2,830,968 Clark ------Apr. 15, 1958 4. The method of claim 3 in which the amine salt 2,902,468 Fianu ------Sept. 1, 1959 contains at least 10 carbon atoms. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,160, 601 December 8, 1964 James Franklin Hyde It is hereby certified that error appears in the above numbered pat correctedent requiring below. correction and that the said Letters Patent should read as Column 9, EXAMPLE 3, in the TABLE, under the heading "Visc. cps.)", line 2 thereof, for "525,00" read -- 525,000 --; column 10, EXAMPLE 4, in the TABLE, under the heading "Wisc. (cp.s.)", line 1 thereof, for '10, 72" read -- 10,720 - -; belowcolumn instead12, lines of as4 toin 7,the the patent formula: : Should appearO as shown (CH3) enclose?."

Column 14, line 22, for '0.1' read -- 0.01 - - . Signed and Sealed this 29th day of June 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J BRENNER Attesting Officer Commissioner of Patents