3,357,949 United States Patent Office Patented Dec. 12, 1967

1. 2 3,357,949 , can be reacted with borazanes, with splitting off POLYMERC ORGANIC BORON-. of the component R of the borazane COMPOUNDS Elmar-Manfred Hora, Aachen, and Hans Niederprun, Monnheim, Germany, assignors to Farbenfabriken 5 and with splitting off of hydrogen, to form high-molecular Bayer Aktiengesellschaft, Leverkusen, Germany, a organic polymers containing boron, nitrogen and sulfur. German corporation The proportions of starting substances are preferably No Drawing. Fied May 1, 1964, Ser. No. 355,563 Selected in such a manner that one mol of borazane is Claims priority, application Germany, May 9, 1963, used per mol of thiocyanate group. When starting from F39,692 thiocyanate/ mixtures, one mol of borazane is pref 30 Clairas. (C. 260-46.5) O erably used for every mol of thiocyanate group as well as for every mol of nitrile group; however, the process according to the invention can also be carried out with ABSTRACT OF THE DISCLOSURE other molar proportions of boraZane and thiocyanate, or Production of thermally stable polymeric organic thiocyanate and nitrile. For example, when using olefini boron-nitrogen-sulfur compounds by mixing, e.g., at cally or acetylenically unsaturated thiocyanates and/or 0-600 C, a borane amine of the formula nitriles, it is in some cases of advantage to choose a high er molecular ratio, referred to the borazane employed. Dependent upon the conditions of production and the in which R is primary, secondary or tertiary amine with 20 thiocyanates or thiocyanate/nitrile mixtures used, there one or more thiocyanates of the formula are obtained resins, pastes or oils which chiefly exhibit a surprising thermal stability and can be used as plant R (SCN), protectives, as intermediates, as additives to motor fuels in which R1 is a hydrocarbon radical, optionally contain and lubricants, and for the production of polymers with ing silicon, phosphorus, tin, , halogen and/or nitro 25 neutron-absorbing properties. gen, and m is an integer from 1 to 6, and optionally with For the present process, borazanes are used, the amino one or more nitriles of the formula components of which can be primary, secondary or ter tiary C1-C18-, cycloalkyl or aryl , mixed alk R2(CN), yl-cycloalkyl-aryl amines, or possibly alkylated hetero in which R2 is a hydrocarbon radical, optionally contain 30 cyclic amines, preferably and piperidines. ing halogen and/or nitrogen. Because they are easily obtainable, N-triorgano-bora Zanes are preferably used, for example, N-trimethyl-bora Zane, N-triethyl-borazane, N-tripropyl-borazane, N-di The present invention relates to polymeric organic ethyl-N-butyl-borazane, N-dimethyl-N-cyclohexyl-bora boron-nitrogen-sulfur compounds and a process for the 35 Zane, N-dimethyl-N-phenyl-borazane or the -bo production thereof. rine; however, other borazanes, such as e.g. N-diethyl It is an object of the present invention to provide novel borazane or N-laurylborazane can also be used as start polymeric organic boron-nitrogen-sulfur compounds. It ing substances. is another object of the present invention to provide a Mono- or polythiocyanates of the general formula process for the production of polymeric organic boron nitrogen-Sulfur compounds. Still further objects of the 40 can be used. In this formula m. denotes an integer prefer present invention shall become apparent as the descrip ably from 1 to 6, p denotes an integer from 0 to 1. If p tion proceeds. is 0, Z has the meaning of R. R4 denotes alkyl, alkenyl, The process for the production of the polymeric organic alkinyl, cycloalkyl or aryl groups or alkyl-, cycloalkyl-, boron-nitrogen-Sulfur compounds is characterized in that aryl-alkoxy-, aroxy-, halogen-, primary, secondary or ter borazanes of the general formula 45 tiary amine, mono- or polysubstituted derivatives thereof. If p is 1, Z denotes alkylene, oxyalkylene, cycloalkylene, cyclooxyalkylene, arylene or oxyarylene groups with 1 to wherein R can be a primary, secondary or tertiary amine, 6 atoms. R has the meaning of are reacted at temperatures between 0° C. and 600° C. with thiocyanates of the general formula 50 R(SCN), possibly in the presence of nitriles of the general formula R2(CN), or with m (Z-SCN)-groups substituted disiloxane or polysiloxane groups. R5 denotes hydrogen, alkyl, alkenyl, wherein R. denotes a hydrocarbon radical which may alkinyl, cycloalkyl, aralkyl aryl, alkoxy, aryloxy-groups, contain silicon, phosphorus, tin and/or oxygen atoms, R3 When organo-silicon, organo-phosphorus or organo denotes a hydrocarbon radical, and m and n are integers. tin mono- or polythiocyanates are used, the silicon, phos It has been found that organic, organo-silicon, organo 60 phorus or tin atom in these compounds is always sepa phosphorus and organo-tin thiocyanates, mixtures of the rated from the thiocyanate group either by at least one said thiocyanates, and mixtures which may consist of carbon atom, or by one oxygen atom and at least one one or more of the said thiocyanates and one or more carbon atom. 3,357,949 3. 4. As examples of suitable monothiocyanates there may on the one hand and nitriles on the other hand be mentioned: possibly substituted aliphatic monothio are suitable for the reaction on which the process accord cyanates, such as methylthiocyanate, ethylthiocyanate, n ing to the invention is based; thereby organic mono- or and i-propylthiocyanate, n-, i- and tert.-butylthiocyanate, polycyanides of the general formula hexylthiocyanate, octylthiocyanate, dodecylthiocyanate, hexadecylthiocyanate, octadecylthiocyanate, methoxy R2(CN), methylthiocyanate, benzylthiocyanate, 4-chloro-benzyl thiocyanate, 2-fluoro-ethylthiocyanate, 2-bromo-1-meth can be used, wherein R2 is an aliphatic, cycloalphatic or yl-propylthiocyanate, 5,5,5-trifluoro-pentyl-thiocyanate, 2 aromatic radical which may be mono- or poly-substituted methyl-2-thiocyanatobutane, 3,5,5-trimethyl-hexyl-thio by alkyl, cycloalkyl, aryl, alkoxy, aroxy, primary, sec , allyl-thiocyanate, 3-chloro-allyl-thiocyanate, 3 10 ondary or tertiary amino groups and/or halogen atoms, ethyl-allyl-thiocyanate, oleylthiocyanate, 2-thiocyanato and n is an integer, preferably from 1 to 6. butadiene-(1,3); possibly nuclear-substituted cyclohexyl Examples of monoitriles are: , propionitrile, thiocyanates, such as cyclohexylthiocyanate and 4-methyl butyronitrile, the nitriles of octane-, dodecane- and cyclohexyl-thiocyanate; possibly nuclear-substituted aro 5 hexane-, possibly nuclear-substituted hexa matic thiocyanates, such as phenylthiocyanate, 1-naph hydro-benzoic acid nitriles, possibly nuclear-substituted thyl-thiocyanate, 3-methylphenyl-thiocyanate or 4-di benzonitriles (e.g. benzonitrile and 2-chloro-benzonitrile) methylamino-phenyl-thiocyanate. and possibly nuclear-substituted naphthaonitriles. Exam Examples of compounds with several thiocyanate ples of compounds with several nitrile groups in the groups in the molecule are: 20 molecule are: malonic acid dinitrile, glutaric acid dinitrile, adipic acid dinitrile, cyanoform and 1,1,3,3-tetracyano 1,4-dithiocyanto-butene-(2), propane. The organic radical containing one or more 2,3-dibromo-1,4-dithiocyanato-butane, nitrile groups may moreover be saturated or aromatically, bis(2-thiocyanto-ethoxy)-methane, olefinically or acetylenically unsaturated. di-(2,2'-thiocyanto-ethyl) 25 If organic thocyanates or silicon-, phosphorus- or tin and di-(4,4'-thiocyanto-n-butyl) ether. containing organic thiocyanates are used, which are ole The mono- or polythiocyanates containing silicon, or finically or acetylenically unsaturated, and/or olefinically silicon and oxygen are either silane derivatives, such as or acetylenically unsaturated nitriles such as allyl-thio for example, cyanate, 2 - thiocyanto - butadiene-(1,3)- allyl-dimethyl trimethyl-thiocyanto-methylsilane, 30 thiocyanathomethyl-silane, 1,4-dicyano-butane - (2) or ethyl-dimethyl-thiocyanto-methylsilane, 1,1,2,2-tetracyanoethylene, then there usually also occurs, phenyl-dimethyl-thiocyanto-methylsilane, in addition to the reaction of the borazane with the thio methoxy-dimethyl-thiocyanto-methylsilane, cyanate group and, possibly, the reaction of the borazene ethoxy-methyl-ethyl-thiocyanto-methylsilane, with the nitrile group, a hydroboration of the double or phenoxy-diphenyl-thiocyanto-methylsilane, 35 triple bond which frequently leads to an additional cross trimethyl-(p-thiocyanto-phenyl)-silane, linking of the polymeric organic boron-nitrogen-sulfur trimethyl-(o-thiocyanto-ethyl)-silane, compounds. trimethyl-(y-thiocyanto-propyl)-silane, An additional cross-linking or the polymeric com bis-(thiocyanto-methyl)-dimethylsilane, pounds according to the invention which contain boron, triphenyl-(y-thiocyanto-propyl)-silane 40 nitrogen, Sulfur and possibly silicon, phosphorus or tin, or triethyl-(2-thiocyanto-ethoxy)-silane, can also be achieved by using nitriles and/or thiocyanates which are substituted by primary or secondary amino or they are open-chain or cyclic poly-siloxanes which con groups. In this case an additional condensation takes tain one or more thiocyanate groups in the end position or place which proceeds, for example, according to the side position, whereby in these siloxane derivatives, as known scheme also in the above-mentioned silane derivatives, the silicon atom is always separated from the thiocyanate group by at least one carbon atom, or by one oxygen atom and at least one carbon atom. Examples of siloxane derivatives The reactions, forming the basis of the process accord which can be used for the process according to the inven ing to the invention, of borazanes with organic, organo tion are: silicon, -phosphorus and/or -tin thiocyanates, or with 1,3-bis-(thiocyanto-methyl)-1,1,3,3-tetramethyl mixtures consisting of the said thiocyanates and nitriles, disiloxane, are carried out at temperatures between 0° C. and 600 heptamethyl-thiocyanto-methyl-cyclo-tertasiloxane, C., expediently at temperatures above 100° C., whereby trimethyl-tris-(thiocyanto-methyl)-cyclo-trisiloxane 5 5 it is possible to work under normal pressure, under for and the cy,ay-bis-(thiocyanto-methyl)-polymethyl eign gas pressure (e.g. under nitrogen pressure) or also polysiloxanes. under the hydrogen pressure caused by the hydrogen which is split off during the reaction. As examples of organo-phosphorous- or organo-tin Apart from using, for example, olefinically or acetylen thiocyanates there may be mentioned: 60 ically unsaturated thiocyanates or nitriles, a further pos tris-(thiocyanto-methyl)-phosphine, sibility of influencing the properties of the boron-nitrogen tris-(p-thiocayanto-phenyl)-phosphine oxide, sulfur compounds produced according to the invention tris-(p-thiocyanato-phenyl)-phosphate, consists in that the thiocyanate component is not employed diethyl-thiocyanatomethyl-phosphine oxide, in the form of a well-defined uniform compound but that p-thiocayanto-phenyl-phosphonic acid dimethyl , any thiocyanate mixtures are used, possibly mixed with tris-(6-thiocyanato-ethyl)-phosphate one or more nitriles. or triphenyl-(y-thiocyanato-propyl)-tin, The properties of the polyners produced according to tripropyl-(y-thiocyanato-propyl)-tin, the present process can also be modified to a large extent dibutyl-bis-(y-thiocyanato-propyl)-tin by adopting a specific procedure for their production, for or triphenyl-(6-thiocyanato-ethoxy)-tin. 70 example, A process for the production of polymeric organic boron-nitrogen compounds has already been developed, (1) mixing the borazane and the thiocyanate and, pos which consists in reacting borazanes with nitriles. It has sibly, the nitrile and subsequently heating to the reac now been found that also mixtures which consist of or tion temperature under normal pressure or increased ganic, organo-silicon, -phosphorus and/or -tin thio preSSure, or 3,357,949 5 6 (2) heating one of the starting products to the reaction EXAMPLE 6 temperature and then adding the other component or 115 g. (1 mol) of N-triethyl-borazane dissolved in components, for example through a dropping funnel or, 500 ml. of diethyl- are mixed in a round flask when working under pressure, for example by means of fitted with stirrer, descending condenser, immersed a dosage pump, or 5 thermometer and dropping funnel, this mixture is heated (3) carrying out the reaction according to the methods to about 130 C, 115 g. (1 mol) of n-butyl-thiocyanate mentioned under (1) and (2) in an inert or are then added dropwise within about 40 minutes, and dispersing agent. For example, hydrocarbons, such as the separated triethylamine and the bulk of the diethyl benzene, toluene,or , xylene, such asdiethylbenzene dibutyl ether and and trimethyl dibenzyl io benzenenormal pressure.used as Duringsolvent theseare finallyoperations distilled a total off ofunder 2.8 ether, can be used for this purpose. litres (measured at 20.5 C.) of hydrogen evolve (identi The following examples are given for the purpose of fied by gas chromatography). After removal of the illustrating the invention. residual volatile components in a vacuum, 12.3 g of a EXAMPLE 1. yellow oil are obtained, which contains 7.3% of boron, s 15 23.9% of sulfur, 9.3% of nitrogen and 0.28% of H a mixtureIn an autoclave consisting of 0.9of litre79.5 capacity,g. (0.5 mol)fitted withof ethyl-di- stirrer, and possesses thes following physicalo constants 89 methyl-thiocyanatomethyl-silane, 57.5 g. (0.5 mol) of n20=1.5280, d0= 1.003, maoi=26.8 cp. N-triethyl-borazane and 150 ml. of dry benzene is heated and is soluble, for example, in benzene, dioxan, n-hexane, at about 200° C. for 1% hours, whereby the pressure ad- 20 di-n-butyl ether and . justs itself to 21.5 atmospheres. After cooling to room temperature, the final pressure amounts to 3.5 atmos- EXAMPLE 7 pheres. The practically pure hydrogen (identified by gas To a solution of 126.5 g. (1.1 mol) of N-triethyl chromatography) is blown off, the content of the auto- borazane in 250 ml. of diethylbenzene, heated to about clave is transferred to a round flask, the triethylamine 25 150° C., are added dropwise, in the apparatus described which has been split off and the benzene used as solvent above, within about 15 minutes, 582 g. of a linear o, co are distilled off under normal pressure, residual volatile bis-(thiocyanato-methyl) - poly-dimethyl-siloxane which, compounds are removed in a vacuum at temperatures of with a thiocyanate content of 9.9 percent by weight of about 130-140° C., and 86 g. of a brown-coloured oil SCN, has the approximate composition sulfur,are obtained, 9.0% ofwhich nitrogen, contains 15.4% 7.0% of siliconof boron, and 18.5%0.13% of 30 12Si(CH3)2O.2(NCSCH2)Si(CH3)2O2 of active hydrogen (hydridic-hydrogen, probably directly E. g Pitt i. up i it is ity linked with boron, determined gas-volumetrically by E. 1.7 i. O f e 'gy s fly E. hydrolysis with warm semi-concentrated ). ains 1.7% of boron, 5.15% of sulphur, 2.2%, or nitro This oil possesses the following physical constants: 35 gen, 32.1% of silicon and 0.31% of active hydrogen. 20=1 so d=1.007 "SF y d i lub The oil is characterised by the following constants: D"=1.53UU, d20-1.UU/, 20=98.0 cp, and is soluble, n20=1.4352, d0=1.005, moor-77.9 cp. and soluble in for example, in benzene, carbon tetrachloride, dioxan, e.g. dioxan, hexane, benzene, carbon tetrachloride and di di-n-butyl ether and n-hexane. n-butyl ether. - Further reactions which are carried out in an auto- 40 Further polymers containing boron, nitrogen and clave, are summarised in the following Table 1. Therein sulfur, and obtained by reaction under normal pressure %He denotes content of active hydrogen in percent. are described in Tables 2 and 3.


Ex. - Starting Substances Borazane Thiocyanate Nitrile Solvent

2----- (C2H5)3N.BB3, 115 g. = Innol------CH5SCN, 87 g. mol------5------I- - - - 8ENEEEEEEI.8:ENEES'12U.5 g. Fl (S.E.S.E.'"RIAgipicinitia,... --- I SESSN:36:33,57.5 g. F0.5 Rii.I.01------fgStars),itrile, 37 goas- u, Eglas|Diegbenzene, not.I.E.E.------Di 150 ml O.

ConditionsReaction Product obtained Ex. Soluble in e.g. Time Tag: Aynt Appearance Analyses Physical constants .

2----- 30 min. 160 93 Grey-brown oil--- 9.5%; S nD20 = 1,5031, d0= 0.980, 0's 44.7 cp----- Dioxan, benzene, CC14. 6.6%ii, 14.8% N. 3----- 1 hour- 160-180 44 Dark brown oil--- 10.4% B, D=1,5374, d40=1.036------Dioxan, benzene, hexane 25.9% S, CCls. 12.9% N, 0.42%. 4----- 1 hour - 170-180 98 Yellowish resin --- 10.8% B, Turns pale brown in closed tube at Little soluble in hot CCl4. 12.0% S, 400 C.; no melting or sintering up to % N: 525° C. 5----- 45 min-- 170 135 Yellow resin.------10.9% f As Turns pale brown in closed tube at Dioxan, benzene, dibutyl E3% Š S. : no melting or sintering up to ether, CCls. - Užo ly 0.21% H. 3,357,949


Starting substances Ex. Borazane Thiocyanate Nitrile Solvent

8----- (CH3)3N.BH3, il5g. = 1 Inol------. n-C4H9SCN, 57.5 g. = 0.5 mol------CH5CH2C=N, 58.5 g. = 0.5 mol------Pybenzene,ill.

9----- (CEs)3N.BEHs, 1.15g. = 1 noi------n-C4HgSCN, 86.3g. = 0.75 mol------ClCH2CHC=N, 22.4 g. = 0.25 mol---- Psybenzene,I 10---- N-BH, 46.5 g. =0.5 mol. C- CH-SCN, 91.7 g. ------Di-n-butyl ether, -- 250 Iml, -0.5 m.o. 1l---- (CEs)3N.BE3, 26.5 g. c.1.1 mol.------(H3C) N( )-scN, 17.8 g. HC-N(CH-CH CEN)------Dybenzene, =0.1 Linol.

Reaction Conditions Product obtained Ex. Soluble in e.g. Time Tegg Agnt Appearance Analyses Physical constants C.) 9. 8----- 1 hour - 140-160 106 Yellow oil------8.0% , 720=1.4675, d20-1.034, 720° =723 cp----- Dioxan, benzene, dibutyl 1.4% S, ether, C.C. 10.1% N, 0.77% H. 9.---- 40 min- 150-170 96 ----- do------8%, S in 20=1.5211, d420=1.025, 200 = 60.8 cp----- Benzene, dioxane, CCl. ió36N, 5.1%, Cl, 0.31%, Ea. 10 - 1 hour-- 100-150 103 Pale yellow resin. 4%, S M.P. =235-237 C------Dioxan, benzene, hexane. ;34°N 14.7%, Cl, 0.14% H.A. 11---- 20 min- 30-i60 81 -----do------'S's M.P. = 135-138 C------Benzene, dioxan, C.C. 55.6%N, 0.47% H.


Starting substances Ex. Borazane Thiocyanate Nitrile Solvent (H, 12---- { X--BH 1,3-bis-(thiocyanatomethyl)-1,1,3,3-tetramethyldisiloxane, 69g. = 0.25 (CH3)2N-CH-CH-C49 g. = 0.5 mol. EN, Diethylbenzene,250 ml. CH3 mol. 148.5g. = i.1 mol. C=N

13--- (n-C4H)3N-BF3, 29 g. = 1.1 mol----- ( )-CH-scN, Diisoamylether,200 ml. 50.6 g. = 0.4 no. N/ -- {O-scN, 76.5 g. sc. O.5 mol. 4.1 g. = 0.1 mol. 14---- (C2H5)3N-B3, 190g. = 1.65 mol------CH2=CHCH2SCN, 99 g. r1 mol------p-Cymol, 250 ml. 15.---- (n-C3H7).N.BE3, 80.5 g. = 0.5 Inol--- ( )-CH-scN, ()-CH-c as N, 0-Xylene, 800 ml. 7.5 g. = 0.05 mol. 52.7 g. = 0.45 mol. 3,357,949 TABLE 8-Continued E Reaction Conditions Product obtained X. - Time g Alpent Appearance Analyses Physical constants Soluble in e.g. 9.

12---- 40 min-- 20-140 101 Yellow oil------4.9% B, 7D'-1.5253------Benzene, dioxan, C Cla. 0.29% a i3---- 1 hour--- 125-40 60 Yellow to orange 53%. np20 = 1.6061, n2O=1.2003, 00 = 682.3 cp- Dioxan, benzene, CS, CCl4. Ol. 8.6% N.y 14---- 15min-- 135-175 70 Yellow resin.------1%s M.P.: 130 C------Dioxan tetrahydrofuran. 1.3%N. 15.-- 4 hours-- up to 140 63 Yellow-orange oil- 8:s in D20=1.5392, d0=1.150, nor = 21.1 cp--- Dioxan, CCl4, CS. i.S.

EXAMPLE 16 member selected from the group consisting of hydrogen, In the apparatus described in Example 6, a mixture of alkyl, alkenyl, phenyl, alkoxy, and phenoxy, and recover 103.5 g. (0.9 mol) of N-triethyl-borazane and 200 ml. ing the resultant polymeric compound. of isopropyl-benzene is heated to about 135-140 C. 25 2. Process according to claim 1 wherein said borane while stirring, and then there are added dropwise within amine is selected from the group consisting of N-trimethyl about 5 minutes 203 g. of a polymethyl-siloxane substi borazane, N-triethyl-borazane, N-tripropyl-borazane, N tuted by thiocyanato-methyl and having, with a thiocy tributyl borazane, N-diethyl-N-butyl-borazane, N-dimeth anate content of 16.9 percent by weight of SCN, the yl-N-cyclohexyl-borazane, N-dimethyl-N-phenyl-borazane, approximate composition 30 pyridine-borine, N-diethyl-borazane, and N-lauryl-bora Zane, and said thiocyanate is selected from the group consisting of methylthiocyanate, ethylthiocyanate, n- and In order to complete the reaction, the reaction temper i-propylthiocyanate, n-, i- and tert-butylthiocyanate, hexyl ature is subsequently raised to about 155 C. for about thiocyanate, octylthiocyanate, dodecylthiocyanate, hexa 10 minutes, and the reaction product then worked up as 35 decylthiocyanate, octadecylthiocyanate, methoxy-methyl described before. 214 grams of a colourless, rubber-like thiocyanate, benzylthiocyanate, 4-chloro-benzylthiocya material are obtained, which contains 2.6% of boron, nate, 2-fluoro-ethylthiocyanate, 2-bromo-1-methyl-propyl 5.3% of sulfur, 2.4% of nitrogen and 33.2-0.8% of thiocyanate, 5,5,5-trifluoro-pentylthiocyanate, 2-methyl-2- silicon and is soluble, for example, in benzene and dioxan. thiocyanato-butane, 3,5,5 - trimethylhexyl-thiocyanate, What is claimed is: 40 allyl-thiocyanate, 3-chloro-allyl-thiocyanate, 3-ethyl-allyl 1. Process for the production of polymeric organic thiocyanate, oleylthiocyanate, 2-thiocyanato-butadiene boron-nitrogen-sulfur compounds which comprises mixing (1,3), cyclohexylthiocyanate, 4-methylcyclohexyl-thiocya at a temperature between about 0-600 C. borane amine nate, phenylthiocyanate, 1-naphthylthiocyanate, 3-methyl having the formula - phenyl-thiocyanate, 4 - dimethylaminophenyl-thiocyanate, 1,4-dithiocyanato-butene-(2), 2,3-dibromo-1,4-dithiocya nato-butane, bis-(2-thiocyanato-ethoxy)-methane, di-(2,2'- in which R is a member selected from the group consist thiocyanato-ethyl) ether, di-(4,4'-thiocyanato-n-butyl) ing of pyridine, alkylated pyridine, piperidine, alkylated. ether, trimethyl-thiocyanato-methylsilane, ethyldimethyl piperidine, and primary, secondary and tertiary amines thiocyanato - methylsilane, phenyi - dimethylthiocyanato substituted with a selected from the group methylsilane, methoxy-dimethyl-thiocyanato-methylsilane, consisting of C-1s alkyl, cyclohexyl, phenyl and corre 50 ethoxy-methyl-ethyl-thiocyanato-methylsilane, phenoxy sponding mixtures of such , with thiocyanate diphenyl - thiocyanato-methylsilane, trimethyl-(p-thiocya having the formula . ' nato-phenyl) - silane, trimethyl-(o-thiocyanato-ethyl)-sil R8-(Z-SCN), ane, trimethyl-(y-thiocyanato-propyl)-silane, bis-(thio in which m is an integer from 1 to 6 and p is an integer cyanato-methyl)-dimethylsilane, triphenyl-(y-thiocyanato from 0 to 1, such that when p is 0, Z is R4 which is a 55 propyl)-silane, triethyl-(2-thiocyanato-ethoxy)-silane, 1,3- member selected from the group consisting of alkyl, bis-(thiocyanato-methyl)-1,1,3,3 - tetramethyl-disiloxane, alkenyl, alkynyl, cyclohexyl, phenyl, naphthyl, and each. heptamethyl - thiocyanato-methyl-cyclo-tetrasiloxane, tri such member which is substituted with a substituent se methyl-tris - (thiocyanato - methyl)-cyclo-trisiloxane, ox,y- lected from the group consisting of alkyl, phenyl, alkoxy, bis - (thiocyanato-methyl)-polymethyl-polysiloxane, tris halo, haloalkyl, halophenyl, alkyl substituted amino, and 60 (thiocyanato-methyl) - phosphine, tris - (p-thiocyanato mixtures thereof, and such that when p is 1, Z is a mem phenyl), -phosphine oxide, tris-(p-thiocyanato-phenyl)- ber selected from the group consisting of alkylene, oxy phosphate, diethyl-thiocyanatomethyl-phosphine oxide, p alkylene, phenylene and oxyphenylene, and R3 is a mem thiocyanato-phenyl-phosphonic acid dimethyl ester, tris ber selected from the: group consisting of (f3-thiocyanato-ethyl) - phosphate, triphenyl - (-y-thiocya O- O 65 nato-propyl)-tin, tripropyl-(y-thiocyanato-propyl)-tin, di ?y butyl-bis-(y-thiocyanato-propyl) - tin, triphenyl - (6-thio P4, o-P4. o-P40- R-6 o-f-co-R), R-P^ cyanato - ethoxy)-tin, allyl - thiocyanate, 2 - thiocyanato N. N. N. N N butadiene - (1,3) and allyl - dimethyl - thiocyanatomethyl / / / silane. (R) P-, -Sn-(R'), (R) Sn , (R5)Si-, (R)-st R-se 70 3. Process according to claim 1 wherein said mixing and corresponding disiloxane and polysiloxane groups is carried out with one mol of borane amine per mol of having 1 to 6 free valences, in which m in each instance corresponding thiocyanate group present. corresponds in value to the number of free valences 4. Process according to claim 1 wherein said mixing present in each said R3 member and in which R5 is a 75 is carried out with a mixture of such thiocyanates. 3,357,949 1. 2 5. Process according to claim 1 wherein said borane 10. Process according to claim 7 wherein said mixing amine is N-triethylborazane. is carried out with a mixture of such thiocyanates and a 6. Process according to claim 1 wherein said mixing is mixture of such nitriles. carried out under pressure. 11. Process according to claim 7 wherein said borane 7. Process according to claim 1 wherein said mixing is amine is N-triethyl borazane. carried out in the presence of a nitrile having the formula 12. Process according to claim 7 wherein said mixing is carried13. Polymeric out under boron-nitrogen-sulfur pressure. compound pro R2(CN) duced14. Polymericaccording toboron-nitrogen-sulfur claim 1. compound pro in which R is a member selected from the group consist 10 duced according to claim 7. ing of alkyl, alkenyl, cyclohexyl, phenyl, naphthyl and 15. Polymeric boron-nitrogen-sulfur-silicon compounds each such member which is substituted with a substituent having the physical constants: n20=1.5300, do= 1.007, Selected from the group consisting of phenyl, halo, and m200=98.6 cp., prepared by reacting N-triethyl borazane alkyl-substituted amino, and n is an integer from 1 to 6. 5 and ethyl-dimethyl-thiocyanatomethyl-silane at about 8. The process according to claim 7 wherein said ni 200 C. trile is selected from the group consisting of acetonitrile, 16. A polymeric boron-nitrogen-sulfur compound hav propionitrile, g- chloro - propionitrile, 3 - (N-dimethyl ing the physical constants: n0=1.5031, d.20=0.980, amino) - propionitrile, butyronitrile, octane-carboxylic m20=44.7 cp., obtained by reacting N-triethyl borazane acid nitrile, dodecane - carboxylic acid nitrile, hexane and CHSCN at about 160° C. carboxylic acid nitrile, N - di (6-cyanoethyl)-N-methyl 20 17. A polymeric boron-nitrogen-sulfur compound hav amine, hexahydro - benzoic acid nitrile, benzonitrile, 2 ing the physical constants: np?0=1.5374, dot-1.036, chloro - benzonitrile, phenyl acetonitrile, naphthonitrile, obtained by reacting N-triethyl-borazane with malonic acid dinitrile, glutaric acid dinitrile, adipic acid dinitrile, 1,4-dicyanobutene-2, cyanoform, 1,1,3,3-tetra i-CHSCN cyanopropane, 1,4-dicyano-butane-(2), 1,1,2,2-teracyano 25 , said borane amine is selected from the group at about 160-180° C. consisting of N-trimethyl-borazane, N-triethyl-borazane, 18. A polymeric boron-nitrogen-sulfur compound hav N-tripropyl-borazane, N-tributyl borazane, N-diethyl-N- ing a boron content of 10.8% and a sulfur content of butyl - borazane, N-dimethyl-N-cyclohexyl-borazane, N 30 12.0% and a nitrogen content of 14.6%, obtained by re dimethyl-N-phenyl-borazane, pyridine-borine, N-diethyl acting N-triethyl-borazane with n-CHSCN and adipic borazane, and N-lauryl-borazane, and said thiocyanate dinitrile at about 170-180° C. is selected from the group consisting of methylthiocya 19. A polymeric boron-nitrogen-sulfur compound hav nate, ethylthiocyanate, n- and i-propylthiocyanate, n-, i ing a boron content of 10.9%, a sulfur content of 15.4% and tert-butylthiocyanate, hexylthiocyanate, octylthio and a nitrogen content of 14.3%, obtained by reacting cyanate, dodecylthiocyanate, hexadecylthiocyanate, octa N-triethyl-borazane with n-CHSCN and 1.4-dicyano decylthiocyanate, methoxy - methylthiocyanate, benzyl thiocyanate, 4 - chloro-benzylthiocyanate, 2-fluoro-ethyl butene-(2)20. A polymeric at about boron-nitrogen-sulfur 170° C. compound with thiocyanate, 2-bromo-1-methyl-propylthiocyanate, 5,5,5- the physical constants: n20=1.5280; d0=1.003, trifluoro - pentyl - thiocyanate, 2-methyl-2-thiocyanate butane, 3,5,5-trimethyl-hexyl-thiocyanate, allyl-thiocya 40 . nate, 3-chloro-allyl-thiocyanate, 3-ethyl-allyl-thiocyanate, 7200 26.8 Cp. oleylthiocyanate, 2 - thiocyanato-butadiene-(1,3), cyclo obtained by reacting N-triethyl-borazane with N-butyl hexylthiocyanate, 4-methyl-cyclohexyl-thiocyanate, phen thiocyanate at about 130° C. ylthiocyanate, 1 - naphthyl - thiocyanate, 3-methyl-phen 21. A polymeric boron-nitrogen-sulfur-silicon com y - thiocyanate, 4 - dimethylamino-phenyl-thiocyanate, pound having the physical constants: n20=1.4352, 1,4-dithiocyanato-butene-(2), 2,3-dibromo-1,4-dithiocya d=1.005, mos-77.9 cp., obtained by reacting N-trieth nato - butane, bis - (2-thiocyanato-ethoxy)-methane, di yi - borazane with ox,a)-bis-(thiocyanato-methyl)-poly-di (2,2' - thiocyanato - ethyl) ether, di-(4,4'-thiocyanato-n- methyl-siloxane at about 150° C. butyl) ether, trimethyl-thiocyanato-methylsilane, ethyl 22. A polymeric boron-nitrogen-sulfur compound hav dimethyl - thiocyanator - methylsilane, phenyl-dimethyl 50 ing the physical constants: n0=1.4675, d0= 1.034, thiocyanato - methylsilane, methoxy - dimethyl-thiocya 200-723 cp., obtained by reacting N-triethyl-borazane nato - methylsilane, ethoxy - methyl-ethyl-thiocyanaio methylsilane, phenoxy - diphenyl - thiocyanato-methyl with n-CHSCN and CHCH2C=N at about 140 silane, trimethyl - (p-thiocyanato-phenyl)-silane, trimeth 16023. C.A polymeric boron-nitrogen-sulfuro compound hav y - (or - thiocyanato-ethyl)-silane, trimethyl-(y-thiocya 55 ing the physical constants: n=1.5211, d0= 1.025, nato - propyl) - silane, bis-(thiocyanato-methyl)-dimeth noe=60.8 cp., obtained by reacting N-triethyl-borazane ylsilane, triphenyl - (y - thiocyanato-propyl)-silane, tri ethyl - (2 - thiocyanato - ethoxy)-silane, 1,3-bis-(thio with n-CHSCN and CICHCH2C=N at about 150 cyanato - methyl) - 1,1,3,3-tetramethyl-disiloxane, hepta 170°24. C.A polymeric boron-nitrogen-sulfur compound hav methyl - thiocyanato - methyl - cyclo-tetrasiloxane, tri 60 methyl - tris - (thiocyanato - methyl)-cyclotrisiloxane, ing a melting point between 235 and 237 C., obtained o,c) - bis - (thiocyanato - methyl)-polymethyl-polysilox by reacting pyridine borazane with ane, tris - (thiocyanato - methyl) - phosphine, tris - (p- thiocyanato - phenyl) - phosphine oxide, tris - (p-thio cyanato - phenyl) - phosphate, diethyl-thiocyanatomethyl 65 phosphine oxide, p-thiocyanato-phenyl-phosphonic acid dimethyl ester, tris-(6-thiocyanato-ethyl)-phosphate, tri at about 100-150° C. phenyl - (y - thiocyanato-propyl)-tin, tripropyl-(y-thio 25. A polymeric boron-nitrogen-sulfur compound hav cyanato - propyl) - tin, dibutyl-bis-(y-thiocyanato-pro ing a melting point of 135 to 138 C., obtained by re pyl)-tin, triphenyl-(6-thiocyanato-ethoxy)-tin, allyl-thio to acting N-triethyl-borazane with cyanate, 2-thiocyanato-butadiene-(1,3) and allyl-dimeth yl-thiocyanatomethyl-silane. 9. Process according to claim 7 wherein said mixing is carried out with one mol of borane amine per each mol of corresponding thiocyanate and nitrile group present. 75 and HC-N(CH2CH2C= N), at about 130-160° C. 3,357,949 13 14 26. A polymeric boron-nitrogen-sulfur compound hav ing the physical constant: n0=1.5253, obtained by re acting N-dimethyl-N-phenyl-borazane with { X-CH-scN and { X-CH-C=N at about 140 C. 30. A polymeric boron-nitrogen-sulfur silicon com and 1.3 - bis - (thiocyanato-methyl)- pound having a boron content of 2.6% and a sulfur con disiloxane at about 120-140' C. tent of 5.3% and a nitrogen content of 2.4% and a sili 27. A polymeric boron-nitrogen-sulfur compound hav con content of 33.2%, obtained by reacting N-triethyl ing the physical constants: n20=1.6061, d20-1.2003, borazane with a polymethyl-siloxane substituted by thio m200-682.3 cp., obtained by reacting N-tributyl-borazane O cyanato-methyl groups having the proximate composition with 38Si(CH3)30.14(NCS-CH2)Si(CH3)0.2(CH3)2SiO2 CN at about 135-140' C.

5 References Cited {X-CH-scN, { X-scN and UNITED STATES PATENTS at about 125-140 C. 3,238,152 3/1966 Horn ------260-78.4 28. A polymeric boron-nitrogen-sulfur compound hav FOREIGN PATENTS ing a melting point of 130 C., obtained by reacting N 20. triethylborazane with CHFCHCHSCN at about 135 1,000,425 8/1965 Great Britain. 175° C. 29. A polymeric boron-nitrogen-sulfur compound hav DONALD E. CZAJA, Primary Examiner. ing the physical constants: n20=1.5392, d0= 1.150, L. J. BERCOVITZ, Examiner. m20-21.1 cp., obtained by reacting N-dipropyl-borazane 25 M. I. MARQUIS, Assistant Examiner. with UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,357, 949 December 12, 1967 Elmar-Manfred Horn et al. It is hereby certified that error appears in the above numbered pat ent requiring correction and that the said Letters Patent should read as corrected below. Column 3, lines 61 and 64, for "p - thiocayanto', each occurrence, read - - p - thiocyanato - - ; column 4, line 33, for "borazene" read - - borazane - - ; line 38, for 'or' read - - of -- ; columns 7 and 8, TABLE 3, opposite EX. 13, Second column, for '50. 6 g. = 0. 4 mol.' read - - 59.6 g. = 0. 4 mol. -- ; column 11, line 50, for 'thiocyanator" read -- thiocyanato - -; column 14, 1ine 10, for 'proximate" read -- opproximate -- . Signed and sealed this 22nd day of April 1969.

(SEAL) Attest : EDWARD M. FLETCHER, JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents