GB656774A - Improvements in or relating to processes of preparing new organic silicon compounds and the compounds resulting from said process - Google Patents

Abstract

Organo silicon resins are obtained by hydrolysing a di-tertiary carbinoxy dihalogeno silane or a tertiary carbinoxy trichlorosilane in the presence of an acid acceptor, e.g. pyridine, ammonia or sodium carbonate, and then heating the product. The tertiary carbinoxy groups may be the same or different and may be any of the following: the tertiary-butoxy, tertiaryamoxy, dichloro-tertiary butoxy, 1-ethylcyclohexoxy, terpineoxy, dihydroterpineoxy, linalooxy and 4-acetoxy-2-methyl-2-pentoxy groups. Each of the three carbon atoms joined to the carbonyl atom of the tertiary-carbinoxy group may be included in a chlorinated alkyl or an aliphatic, aromatic, alicyclic or heterocyclic group; the aliphatic groups may be saturated or unsaturated, while any of the groups may contain substituents which are inert to the reaction, e.g. the halogen, nitro, alkoxy or acetoxy groups. The aromatic groups may, in addition to the substituents mentioned above, have an alkyl substituent. Heterocyclic groups mentioned are the furan and thiophene groups. A resin is obtained, for example, by hydrolysing di-tertiary amoxy dichloro silane, separating the resulting oil and water layers, extracting the water layer with benzene and adding the extract to the oil, and the benzene is then distilled from the oil and the oil heated. In a similar way, di-tertiary carbinoxy diamino silanes yield a resin, but they may be hydrolysed with water alone. The resins are soluble in benzene, ethyl alcohol or petroleum ether. Alkdy type resins are obtained by reacting linseed monoglyceride and di-tertiary amoxy dichloro silane or di-tertiary butoxy dichloro silane or a mixture of di-tertiary butoxy dichloro silane and tertiary-butoxy trichloro silane in the presence of pyridine, refluxing after adding benzene and then distilling off the benzene.ALSO:Organo silicon compounds having at least one tertiary carbinoxy group and at least one halogen atom directly attached to a silicon atom are prepared by reacting a tertiary alcohol with a silicon compound having at least two halogen atoms each directly attached to a silicon atom in the presence of pyridine or a tertiary amine. The halogen may be chlorine. Tertiary carbinoxy groups mentioned are the tertiary-butoxy, tertiary amoxy, dichloro-tertiary butoxy, 1-ethylcyclohexoxy, terpineoxy, dihydroterpineoxy, linalooxy, and 4-acetoxy-2-methyl-2-pentoxy groups. Silicon compounds which may be used for the process are silicon tetrachloride (may be employed in the form of a reaction product of pyridine and silicon tetrachloride), silicon oxychloride, tertiary alkoxy trichlorosilane and di-tertiary-alkoxy dichlorosilane. Bromine compounds are mentioned as alternatives to the chlorine compounds. Each of the three carbon atoms joined to the carbonyl carbon atom may be included in a chlorinated alkyl or an aliphatic, aromatic, alicyclic or heterocyclic group; the aliphatic groups may be saturated or unsaturated, while any of the groups may contain substituents which are inert to the reaction, e.g. the halogen, nitro, alkoxy or acetoxy groups. The aromatic groups may, in addition to the substituents mentioned above, have an alkyl substituent. Heterocyclic groups mentioned are the furan and thiophene groups. In the case of the desired silicon compounds containing more than one tertiary carbinoxy group, the groups may be the same or different. The tertiary carbinoxy halogeno organo silicon compounds may be reacted with ammonia or primary or secondary amines to replace at least one of the halogen atoms with an amino group, e.g. di-tertiary butoxy diamino and dianilino silanes may be prepared. Silicates are obtained by reacting the tertiary carbinoxy halogeno organo silicon compounds with pyridine and an alcohol or glycol, and the following silicates are mentioned di-n-propyl di-tertiary amyl silicate di-tertiary-butyl di-allyl silicate, di-tertiary-butyl (diethylene glycol) silicate, di-tertiary butyl (2-ethyl-2-nitro-1,3-propanediol) silicate, and di-tertiary butyl (2-methyl-2,4-pentanediol) silicate. The tertiary carbinoxy halogeno organo silicon compounds may also be reacted with organic acids in the presence of pyridine to yield compounds such as di-tertiary butoxy diacetoxy silane. Silanols are obtained by hydrolysing under alkaline conditions the tertiary-carbinoxy halogeno silicon compounds, e.g. with aqueous ammonia or aqueous pyridine; specific silanols mentioned are di-tertiary-butoxy dihydroxy silane, tritertiary butoxy hydroxy silane and a compound of the formula [(CH3)3CO]2(OH)-Si-O-Si(OH)[OC(CH3) 3]2. The Specification as open to inspection under Sect. 91 refers to the use of any acid acceptor for the preparation of the tertiary carbinoxy halogeno organo silicon compounds, and to the use of any silicon compound containing a plurality of hydrolysable halogen atoms attached to silicon as a starting material. Additional starting materials mentioned are hexachlorodisilane and alkyl or aryl polychlorosilane. An additional product which may be made by the process is ethyl tertiary-butoxy dichlorosilane, i.e. from tertiary butyl alcohol and ethyltrichlorosilane. Phenoxy tertiary-butoxy dichlorosilane, n-butoxy tertiary-butoxy dichlorosilane and tertiary-butoxy octadecoxy dichlorosilane are prepared by reacting phenol, n-butylalcohol and octadecanol with tertiary-butoxy trichlorosilane. The Specification also states that boron, titanium or phosphorus compounds analogous to the silicon compounds may be prepared. This subject-matter does not appear in the Specification as accepted.