IL41008A - Disilaalkanes and disilaarenes and articles coated therewith - Google Patents

Description

ana Ο»ΒΙΙΜ Hovel disilaalkanea and dlallaareaea and articles coated therewith STAUFFER-WACKER SILICONE CORPORATION C 138740 ftais invention provides novel disilaalkanes and disilaarenes of the general formula xjherein R* is alk l having from 1 to 18 carbon atons, alkenyl aryl, alkaryl, aralkyl or haloaryl; R" is an alkylene or an arylene radical; Z is a hydrolyzable group, such as acyloxy, alkoxy having from 1 to 10 carbon atoms, aryloxy, dialkylamino-oxy, diar laminooxy, alk lidenaminooxy, dialkylphosphate or diarylphosphate; m is an integer of at least 1; n is 0, 1, 2 or 3» the sum of m and n is greater than 2\ and when Z is an acyloxy group, m is at least 2 and n is at least 1.

The novel compounds of formula I above are useful as cross-linking agents capable of reacting with terminal hydroxyl groups of organopolysiloxanes to form elastomeric compositions which are curable at room temperature. ihese curable organopolysiloxane compositions are described in Israel Patent Specifica ion No. 31068.

T e disilaorganic compounds of foimula I according to the invention, particularly those having four or more acyloxy groups linked:to the molecule, may also be used as primers for coating various substrates to which it is desired to apply an elastomeric room-temperature cured polysiloxane coating.

In formula I above, the organic radicals Il'may be, e»g. , alkyl radicals having from 1 to 18 carbon atoms such as methyl, ethyls rop ls, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecylj aryl radicals such as phenyl, diphenyl. naphthyl and the like? alkaryl radicals such as tolyl, xylyl, ethylphehyl and the like; aralkyl radicals such as benayl, phenylethyl and the likes haloaryl radicals such as chloro-phenyls, tetrachlorophenyl, d fluoro henyl and the like? alkenyl mdicals such as vinyl, allyl and. the likej R" are divalent alkylene or arylene radicals having from 2 to 18 carbon atoms such as methylene, ethylene, propylene, tetramethylene, hexamethylene, octamethylene, decamethylene, phenylene, phenylethylene, diphenylmethylenQ and the like,, Z represents groups which are hydrolyzable by ambient moisture such ass acyloxy - OOCR^ hydrocarbyloxy - ORa dialkyl- or diarylaminooxy, -ON. represent monovalent alkyl or aryl radicals. Examples of acyloxy groups are monoacyl radicals of carboxylic acids such as formyloxy, acetoxy, propionyloxy, valeryloxy, caproyloxy, myristoyloxy and stearoyloxy radicals. Other hydrolyzable gr¾ups are hydrocarbyloxy groups having from 1 to 10 carbon atoms such as methoxy, ethoxy, butoxy, heptoxy, octoxy, decoxy, phenoxy and the like; aminooxy groups such as dimethylaminooxy, diethylaminooxy, dipropylaminooxy, dibutylaminooxy, dioctylaminooxy, diphenylaminooxy, ethylmethyl-aminooxy, methylphenylaminooxy and the like. Suitable alkylidenamino oxy radicals are those derived from acetophenone oxime, acetoxime, benzophenone oxime, 2-butanone oxime, diisopropylketone oxime, chlorocyclohexanone oxime, and the like. Examples of suitable phosphato radicals are dimethylphosphato, diethylphosphato, di-propylphosphato, dibutylphosphato, dihexylphosphato, diootyl-phosphato, didodecylphosphato, dioctadecylphosphato, methylethyl-phosphato, ethylpropylphosphato methylhexylphosphato, butylhexyl-phosphato, methyldodecylphosphato, methyloctadecylphosphato, ethyltetradecylphosphato, diphenylphosphato, methylphenylphosphato, butylphenylphosphato and the like.

The disilaorganic compounds of this invention may be prepared by reacting unsaturated hydrocarbon or unsaturated halogenatod hydrocarbon groups with a silane or a halosilane to form the corre sponding hal odi si 1 aal kanes or -arcnes having halogen groups linked to the silicon atoms. 'These compounds containing hal ogen groups -are reacted with an appropriate functional group to form the correspondi g compounds having functional groups which are hydrolyzable at ambient moisture. For example, the reaction of 3,3-dichloro-3-silabutene-l with tri chl oros i 1 ane in. the presence of a catalyst such as chl oropl at i c acid, organic peroxides, metal i carbonyls and the like which promote the addition of the silane · moiety to an olefinic double bond forms 1 ,1 ,1 ,4,4-pentachloro-l ,4 di si 1 apentane in accordance wi h the following equation: ' CI . ' 'CI CH,-Si-CH=CH, + HSiCl3 —> CH3-Si-CH2-CH2-Si-Cl3 CI CI Reaction of the above pentachl orodi si 1 apentane with an anhydride, e.g. acetic anhydride, results in the substitution of acetoxy groups for the chlorine. toms which are hydrolyzable with ambient moisture.

CI I CH~ C .

CH3-Si CH2.-CH2-Si-Cl3 + 5 3 C H CI 3, C : ¾ I Instead of acetic a n h d r i de , t h e pentachl orodi si 1 apentane may be reacted with other o rg a n i c anhydrides and acids thereof, hydroxy1 am nes » oximcs o r p hos p iiato compounds to form the corresponding functional groups which a re also hydrolyzable in ambient moisture.

Halogen containing di s 1 aorgani c compounds contemplated in this invention have the following general formulae: R' X X X · ' - X X I I 1 . I I I R'-Si-R"-Si-X or R'-Si-R"-Si- or 1 -Si -R"-S -X I I I I I i R' X X X X X wherein R' and R" have the same meaning as in formula I above and X is a halogen. The compounds described by the above formulae are reacted with organic hydroxylamines , organic oximes, organic phosphates, organic acids and anhydrides thereof to form compounds having the corresponding functional groups.

In preparing such < 1aalkanes or disalaarenes of formula I which have acyloxy functional groups, the halogen containing disila organic compounds are reacted with organic acids or anhydrides thereof at a temperature of from about 25° to about 150°C, preferably from about 50° to 120°C. and if desired in the presence of a solvent.

Suitable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane; aromatic hydrocarbons such as benzes, toluene, xylene, naphthylene as well ,as halogenated solvents such as methylene dioride, chlorobenzene and the like. Other solvents which may be used are organic ethers such as petroleum ether, diethyl ether, dibutyl ether and hydroxy1-free fluid siloxanes.

In the f ormation of aminooxydisilaalkanes or -arenes an organohydroxylamine is reacted with a halogen containing dieilaorganie compound, preferably in the presence of an inert ^solvent such as chloroform, benzene, toluene, xylene, perchloroethylene, etc. at a te&perature of from about 50° to 60° C. to form the corresponding aminooxydisllaorgahic compound. Generally, the reaction is completed in a matter of from about 1 to 2 hours. - Disilaorganic compounds having phosphato functional groups may be pre ared by reacting halogen containing .·¾ disilaorganic compounds with phosphoric acid or an alkali metal or alkaline earth rretal salt of an organic phosphate and if desired, in the presence of an inert solvent.

"' To this mixture are added with agitation over a 30 minute] period about 600 parts of acetic anhydride 1n about 300 parts of benzene. The reaction mass is refluxed for about 45 minutes at a temperature of about 80°C. The volatile materials are removed n vacuo and a product identified as 1 ,1 ,1 ,4,4-penta-acetoxy-l ,4-di-silapentane is recovered.

EXAMPLE 2 To a reactor fitted with a mechanical agitator, reflux condenser, nitrogen inlet and an addition funnel are added about 384 parts of 2,2,5,5-tetrachloro-2,5-dis lahexane in about 400 parts of benzene. About 642 parts of acetic anhydride in about 400 parts of benzene are added dropwise through the addition funnel. The reaction mass is refluxed at a temperature between 90° and 102°C. for about 2 hours. The volatile materials are removed under vacuum yielding a product identified as 2,2,5,5-tetra-acetoxy-2 , 5-di si 1 ahexano .

EXAMPLE 3 - In accordance with the procedure described in Example 2, about 490 parts of acetic anhydride in about 300 parts of benzene are added to a reactor containing about 312 parts of 2 ,2 ,7 ,7-tetra-chloro-2,7-disilaoctane in about 500 parts of benzene. The reaction mass is refluxed at about 100°C. for about 2 hours. The volatile materials are then removed under vacuum yielding a product identified as 2,2,7,7-tetra-acetoxy-2,7-disi laoctane.

EXAMPLE 4 In accordance % wi th the procedure described in Example 2, approximately 490 parts of acetic anhyd-ride are added dropwise to a reactor containing about 424 parts of 2,2,11 , Π -tetrachl oro-2 , 11-di s i 1 adodecane. The reaction mass is refluxed fo a period of about 2.5 hours, and the volatile materials are then removed under vacuum. A product is recovered which is identified as 2,2, 11, litetra-acetoxy-2,11-di si 1 adodecane.

EXAMPLE 5 In accordance with the procedure described in Example 2, approximately 1,158 parts of decanoic acid are added dropwise to a reactor containing 312 parts of 2,2,7,7-tetrachloro-2,7-disila-octane. The reaction mass is refluxed for a' period of about 3 hours and the volatile materials are then removed under vacuum. A residual product is recovered which is identified as' 2 ,2 ,7 ,7-tetra decanoyl,oxy-2,7-disi laoctane. i , EXAMPLE 6 In accordance^ wi th the procedure described in Example 1, approximately 731 parts of Ν,Ν-diethylhydroxylamine dissolved in about 170 parts of dry heptane are added to a reactor containing · 235 parts of 1 ,1 , 1 -tri chl oro-4 ,4-dimethyl -1 ,4-d s i 1 apentane in about 250 parts of dry heptane and heated to reflux temperature for about 1 hour. A precipitate is formed which is removed by filtration and identified as , -di ethyl hydroxy! ami ne hydrochloride. The heptane solvent and excess N ,N-d ethyl hydroxyl ami ne · are removed in vacuo yielding a residual product which is identified as 1,1,1-tris(N,N-diethylaminooxy)-4,4-dimethyl-l ,4-d si 1 apentane.

EXAMPLE 7 Approximately 157 parts of Ν,Ν-dioctylhydroxylamine in about 410 parts of dry heptane are added to a reactor containing · about 58 parts of 1 ,1 ,l-trichloro-4,4-dimethyT-l ,4-di si 1 apentane ir about 110 parts of d heptane. The reaction mass is heated to reflux temperature for about 1 hour. After cooling to room temperature, a precipitate identified as Ν,Ν-dioctylhydroxylamine hydrochloride is removed by filtration and the heptane solvent and excess , -di octyl hydroxyl ami e is removed in vacuo. A residual product is recovered which is identified as 1 ,1 ,l-tris(N,N-di-octyl ami nooxy )-4,4-dimethyl,-l ,4-di si 1 apentane.

EXAMPLE 8 In accordance with the procedure described in Example 7, approximately 87 parts, of 1 , 1 , 1 -tri chloro-12 , 12-dimethyl -1 , 1 -di si 1 atri decane in about 200 parts of dry heptane are reacted with about 150 parts of N.N-diethylhydroxylamine. The product is recovered which is identified as 1 ,1 ,l-tris(N,N-diethylaminooxy)-12,12-dimethyl -1 ,12*di si 1 atr decane.

EXAMPLE 9 Approximately 70 parts of 1 , 1 , 1 , ,4-pentachl oro-1 ,4- .' ·· ■ di si 1 apentane in about(80 parts of dr heptane are reacted wit about 230 parts of Ν,Ν-diethyl hydroxy! ami ne in about 60 parts of dry heptane for about 1 hour at reflux temperature. A precipitate is formed which is removed by filtration and identified as N,N- ' di ethyl hydroxyl ami ne hydrochloride. The heptane solvent and excess Ν,Ν-diethylhydroxyl.amine are removed in vacuo and a residua product is recovered which is identified as 1 ,1 ,1 ,4 ,4-pentaki s(N,N di ethyl ami nooxy)-! ,4-di si 1 apentane.

EXAMPLE 10 In accordance with the procedure described in Example 9, approximately 650 parts of ,N-di octyl hydroxyl ami ne dissolved in about 400 parts of dry heptane are added to a reactor containing about 98 parts of 1 ,1 ,1 ,12,12-pentachloro-l ,12-dis latridecane dissolved in about 100 parts of dry heptane. A residual product is recovered which is identified as 1 ,1 »1 ,12,12-pentakis(N,N-dioctyl ami nooxy)-l ,12-disi latridecane.

EXAMPLE 11 In accordance with the procedure described in Example 9, about 300 parts of N-butyl -N-ethyl hydroxyl ami ne dissolved in about 200 parts of dry heptane axe added to a reactor containing about 83 parts of 1 ,1 ,1 ,8,8-pentachloro-l ,8-disi 1 anonane in about 100 parts of dry heptane. A residual product is recovered which is identified as 1,1,1 , 8,8-pentak s( -butyl -N-ethyl ami oox )-l ,8-disi 1 anonane. .

I EXAMPLE 12 About 75 parts of acetoxime dissolved in about 357 pa s' of ethyl ether are added dropwise with stirring to a reactor containing a solution of 50 parts of 1 ,1 ,1,4,4-pentachloro-l ,4-di s i 1 apentane dissolved in about 1,200 parts of toluene and about 90 parts of pyridine. As the exothermic reaction progresses, additional toluene is added in small increments to disperse the large volume of pyridine hydrochlor de which is formed. After the reaction is complete, the reaction mass is cooled to room temperature. The product mixture is filtered, stripped of toluene and excess pyridine. A residual product is recovered which is identified as: CH3-S1 [0N"C(CH3)2]2CH2-CH2-S1 [0N-C(CH3)2]3 EXAMPLE 13 In accordance with the procedure described in Example 12 approximately 197 parts of benzophenone oxime dissolved in 350 parts of ethyl ether are added dropwise with stirring to a solutior of 70 parts of 1 , ,1 ,12,12-pentachloro-l ,12-disilatridecane in about 1,400 parts of toluene and about 90 parts of pyridine. As the exothermic reaction progresses, additional toluene is added in small increments to disperse the large volume of pyridine hydrochloride thus formed. After the reaction is complete and the reacti on mass cooled to room temperature, the product mixture is filtered, stripped of toluene and excess pyridine. The residual product is identified as CH3-SI [0N-C(C6H5)2]2CH2-(CH2).8-CH2S1 [ON-C(C6H5)233 by chemical analysis.

EXAMPLE 14 Approximately 88 parts of butyral dox ime in about 300 parts of ethyl ether are added drop ise with stirring to a solution of 60 parts of 1 ,1 ,1 ,8,8-pentachloro-l ,8-d si 1 anonane in about 1,000 parts of toluene and about 92 parts of pyridine. As the reaction progresses, additional toluene is added in small amounts to disperse the large volume of pyridine hydrochlor de formed.

After the reaction is complete, it is cooled to room temperature. The reaction mass is filtered, stripped of toluene and excess pyridine. A residual product is recovered which is identified as CH3-Si (0N=CH-CH2C2H5)2CH2-(CH2)4-CH2Si (0N=CH-CH2C2H5)3 by chemical analysis.

EXAMPLE 15 To a reactor containing about 50 parts of pentachloro-1 ,4-disilapentane in about 500 parts of toluene are added about 105 parts of acetic anhydride with agitation over a period of 30 minutes. The reaction mass is refluxed for about 45 minutes and the volatile materials removed in vacuo. A product is recovered which is identified as 1 ,1 , , ,4-pentaacetoxy- ,4-disilapentane by chemical analysis.

EXAMPLE 16 In accordance with the procedure described in Example' 15, approximately 172 parts of decanoic acid are reacted with about 70 parts of 1 ,1 ,1 ,12,12-pentachlqro-l ,12-disilatridecane. A residual product is recovered which is identified as 1 ,1 ,1 ,12,12-penta-decanoyloxy-1 ,12-disilatridecane.

. ' EXAMPLE 17 .

In accordance with the procedure described in Example 15, approximately 116 parts of hexanoic acid are reacted with about' 60 parts of 1 ,1 ,1 ,8,8-pentachloro-l ,3-disilanonane. A residual product is recovered which is identified by chemical analysis as 1 , 1 » 1 ,8,8-hexanoyloxy-l ,8-di si 1 anonane.

EXAMPLE- 18 Approximately 154 parts of di ethyl ydrogenphosphate are added to about 500 parts of benzene and introduced into a reactor containing 50 parts of 1 ,1 ,1 ,4 ,4-pentachl oro-1 ,4-di s i 1 apentane in about 250 parts of benzene. The reactants are heated to reflux temperature for about 0.5 hours with agitation. Nitrogen i"s then' passed through the solution for approximately 4 hours and the solvent and volatile materials are removed under vacuum distillation. A residual product is recovered which is identified S 1 , 1 »1 ,4,4-pentakis(diethylphosphato)-l ,4-dis lapentane.

EXAMPLE 19 • Approximately 120 parts of dimethyl hydrogenphosphate in about 400 parts of benzene' are introduced .to a reactor containing about 70 parts' of 1,1,1, 12, 12-pentachloro-l,12-disilatridecane dissolved 'in about 300 parts of benzene.. The reactants are heated to reflux temperature for about 1 hour with agitation. Nitrogen is then passed through the solution for approximately 5 hours and the solvent and volatile materials removed under vacuum distillation. A residual product is recovered which is identified as 1 ,1 ,1 ,12,12-pe takis(dimethylphosphato)-l ,12-disilatridecane.

EXAMPLE 20 In accordance with the procedure described in Example 19 approximately 38 parts of dimethyl hydrogenphosphate are reacted with about 24 parts of 1 , 1 , 1 -tri chl oro-4 ,4-dimethyl -1 ,4-di si 1 a-pentane. A residual product is recovered which is identified as i s (dimethyl phosphato ) -4 ,4-dimethyl-l ,4-di si 1 apentane.

EXAMPLE" 21 In accordance, with the procedure described in Example 19 approximately 250 parts of d phenyl ydrogenphosphate are reacted with about 60 parts of 1 ,1 ,1 ,8,8-pentachl oro-1 ,8-di s i 1 anonane . A residual product is recovered which is identified as 1,1,1,8,8-pentaki s(di henyl hosphato)-! ,8-di si 1 anonane.

EXAMPLE 22 , to a reactor containing about 66 parts of 2 , 2 , 5 ,5-tetra-chloro-2,5-disilahexane dissolved in about 150 parts of benzene are added about 190 parts of , -di ethyl hydroxyl ami e dissolved in about 150 parts of benzene and heated to reflux temperature for about 1 hour. A precipitate is formed which is removed by filtration and identified as Ν,Ν-diethylhydroxylamine hydrochloride. The solvent and excess Ν,Ν-diethylhydroxylamine are removed i n vacuo yielding a residual product which is identified as 2,2,5,5-tetrakis(N, -di ethyl am ooxy)-2 , 5-di si lahexane.

EXAMPLE 23 In accordance wi th the procedure described in Example 22 approximately 70 parts of 2,2,7, 7-tetrachloro-2 ,7-di si 1 aoctane in about 250 parts of benzene are reacted with about 550 parts of N, N-di octyl hydroxyl ami ne in about 400 parts of benzene. A residual product is recovered which is identified as 2,2,7,7-tetrakis(N,N-' di oct l ami noox )-2 , 7-di s 1 octane .

EXAMPLE 24 In accordance with the procedure described in Example 22, 85 parts of 2 ,2 , 11 , 11 - tetrachl oro-2 , 11 -di si 1 adodecane are reacted with about 250 parts of N-butyl -N-ethyl hydroxyl am ne . A residual product is recovered which is identified as 2,2,11 ,11-tetrakis-( -butyl -N-ethylami nooxy )-2 , 11-di si ladodecane.

EXAMPLE 25 I About 80 parts of acetoxime dissolved in about 357 parts i ■' . of ethyl ether are added dropwise with stirring to a solution of 60 parts of 2,2,5,5-tetrachloro-2,5-disi lahexane in about 1,100 parts of toluene and about 90 parts of pyridine. As the exothermicj reaction progresses, additional toluene is added in small increments to disperse the large volume of pyridine hydrochlor de formed. After the reaction is complete, the reaction mass is cooled to room temperature and the product mixture filtered, stripped of toluene and excess pyridine and distilled. A residual product is recovered which is identified by chemical analysis as: . CH3S1[0N-C(CH3)2]2CH2-CH2Si [0 -C(CH3)2]2CH3 I.' ' i; r ■ ^ EXAMPLE 26 ' In accordance ith the procedure described in Example 25,] about 140 parts of hexapone pxime dissolved in about 200 parts of ethyl ether are added to a solution of about 65 parts of 2,2,7,7-tetrachloro-2,7-disilaoctane in about 1,100 parts of toluene. A residual product is recovered which is identified by chemical EXAMPLE 30 In accordance with the procedure described in Example 28, approximately 120 parts of acetic anhydride dissolved in about 150 parts of ethyl ether are added to a reactpr containing about 80 parts of 2,2,11 , 11 -tetrachl oro-2 , 1 -d s i 1 adodecane dissolved in about 1 ,100 parts of toluene. A residual product is recovered which is identified as .2 , 2 , 11 , 11 - tetraacetoxy-2 , 11 -di si 1 adodecane.

EXAMPLE 31 A primer composition consisting of 90 parts of 1,1,1,4,4 pentaacetoxy- 1 ,4-di s i 1 apentane dissolved in 10 parts of methylene chloride is applied to a previously cleaned and degreased stainless steel substrate. The primer is allowed to dry for approximately 3 hours at ambient moisture.

A room -temperature curing silicone rubber composition consisting of about 100 parts of a hydroxy1 -termi nated polydi-methyl si loxane fluid having a viscosity of 7,000 cs., 20 parts of Cab-0-Sil, 10 parts of 1 , 1 , 1 ,4 ,4-.pentaacetoxy-l ,4-d s i 1 apentane and 1.0 part of dibutyltin dilaurate is poured on the primed substrate. The silicone rubber is allowed to set up, after which the bond is tested by trying to peel the rubber from the metal substrate with a spatula; The adhesion is good as illustrated by the fact that only cohesive failure in the cured rubber is found.

In a controlled test, the silicone rubber is applied to an unprimed metal substrate. The rubber peeled cleanly off the metal with little effort.

When the above examples are repeated utilizing other di si 1 organi c compounds with hydroxy! -termi nated organopolysi 1 oxanes, the elas.tomeric materials are obtained which have properties sub stantially equivalent to those of the specified examples.^ ... )

Claims (1)

1. CLAIMS A compound of the general wherein is alkyl having from 1 to carbon lk l o is an alkylene or an arylene Z is a hydrolyzable such as alkoxy having 1 to 10 carbon dialkylphosphate or is an integer of at least n is 2 or the sum of and n is greater than and when is an acyloxy m is at least 2 and is at least Compounds of formula I in Claim wherein is a divalent alkylene radical having from 2 to 18 Compounds of formula I in Claim wherein is an acyloxy is an integer of at least 2 and n is 2 Compounds of formula I in Claim wherein Z is an alk is an integer of at least 2 and n is 2 or Compounds of formula I in Claim wherein Z is a or diar laminooxy is an integer of at least 2 and n is 2 or Compounds of formula I in Claim wherein Z is a or diarylphosphato is an integer of at least 2 and n is 2 or An article of manufacture comprising a substrate coated compound of the formula I in Claim wherein Z is an aeyloxy and n are integers each equal to at least 1 and the sum of m and n is equal to at least An article according to Claim wherein in the compound of formula Z is an acetoxy An article according to Claim 7 or a silicone compound curable at room teraperaturc is applied to the coated insufficientOCRQuality