Patent GB-667436-A (GB)
Title: Improvements in or relating to the manufacture of organo-silicon polymers
IPC: C08G77/00
Filed: 1950-02-08
Abstract: Cyclic or linear organo-silicon polymers containing units of the formula <FORM:0667436/IV (a)/1> are made by hydrolysing and condensing compounds of the formula R(R2SiCH2)mSiRY2 in which each R is an alkyl radical, e.g. methyl to octadecyl, or a monocyclic aryl radical, e.g. phenyl, tolyl or xylyl, m is 1 or 2, and each Y is an alkoxy radical or halogen atom.  Acid or alkaline catalysts may be used.  In examples: a mixture of (CH3)3SiCH2SiCH3(OC2H5)2 ethyl alcohol and 35 per cent HCl was refluxed, the acid-aqueous layer withdrawn, and the hydrolysate was washed, dried, filtered and distilled, yielding [(CH3)3SiCH2SiCH3O-]3 and [(CH3)3 <FORM:0667436/IV (a)/2> (2) a mixture of CH3 <FORM:0667436/IV (a)/3> and 10 per cent H2SO- was refluxed &c. to yield {CH3[(CH3)2\t <FORM:0667436/IV (a)/4> (3) is similar to (1) except that the water-layer and washings are extracted with benzene, the products obtained being the trimer and a mixture of the tetramer and <FORM:0667436/IV (a)/5> (4) hydrolysis &c. of <FORM:0667436/IV (a)/6> gave the trimer, tetramer, pentamer and a non-volatile liquid, <FORM:0667436/IV (a)/7> containing cyclics of this formula in which n had values up to 10; (5) hydrolysis &c. of (CH3)2 C6H5SiCH2SiCH3(OC2H5)2 yielded a mixture of compounds of the formula <FORM:0667436/IV (a)/8> (6) hydrolysis &c. of (CH3)3SiCH2SiCH3(OC2H5)2 yielded the cis and trans isomers of [(CH3)3 <FORM:0667436/IV (a)/9> The polymers of the invention are useful as hydrophobing agents, lubricants, hydraulic and heat transfer liquids and thermal expansion regulator liquids.ALSO:Cyclic or linear organo-silicon polymers containing units of the formula <FORM:0667436/IV (b)/1> are made by hydrolysing and condensing compounds of the formula R(R2SiCH2)mSiRY2, in which each R is an alkyl radical, e.g. methyl to octadecyl, or a monocyclic aryl radical, e.g. phenyl, tolyl or xylyl, m is 1 or 2, and each Y is an alkoxy radical or halogen atom.  Acid or alkaline catalysts may be used.  In examples: (1) a mixture of (CH3)3SiCH2SiCH3(OC2H5)2 ethyl alcohol and 35 per cent HCl was refluxed, the acid-aqueous layer withdrawn, and the hydrolysate was washed, dried, filtered and distilled, yielding <FORM:0667436/IV (b)/2> and <FORM:0667436/IV (b)/3> ; (2) a mixture of <FORM:0667436/IV (b)/4> and 10 per cent H2SO4 was refluxed &c. to yield {CH3 <FORM:0667436/IV (b)/5> ; (3) is similar to (1) except that the water-layer and washings are extracted with benzene, the products being the trimer and a mixture of the tetramer and <FORM:0667436/IV (b)/6> ; (4) hydrolysis &c. of (CH3)3SiCH2SiCH3Cl2 gave the trimer, tetramer, pentamer and a non-volatile liquid, <FORM:0667436/IV (b)/7> , containing cyclics of this formula in which n had values up to 10; (5) hydrolysis &c. of (CH3)2C6H5.SiCH2 SiCH3(OC2H5)2 yielded a mixture of compounds of the formula <FORM:0667436/IV (b)/8> ; (6) hydrolysis &c. of (CH3)3SiCH2SiCH3(OC2H5)2 yielded the cis and trans isomers of <FORM:0667436/IV (b)/9>  The starting materials of the general formula R3SiCH2SiRX2 may be prepared by reacting a compound of the formula X2RSiCH2SiRX2 in liquid phase with a Grignard reagent, RMgX, in which each R is as above, and each X is a halogen atom. (CH3)3SiCH2SiCH3(OC2H5)2 may be made by contacting in liquid phase ClCH2SiCH3(OC2H5)2 with an alkali metal in the presence of (CH3)3SiCl, and <FORM:0667436/IV (b)/100> may be similarly made from ClCH2SiCH3(OC2H5)2 and (CH3)3SiCH2Si(CH3)2Cl.