Patent GB-991788-A (GB)
Title: Improvements in or relating to organosilicon compounds
IPC: C08G77/14
Filed: 1962-11-09
Abstract: Acyloxyalkyl polysiloxanes are prepared by reacting a compound of the formula <FORM:0991788/C3/1> where R1 is halogen or alkoxy, R2 is a halogen, alkoxy or monovalent hydrocarbon group, M is a divalent hydrocarbon group of at least 3 carbon atoms and n is an integer, with an acid of the formula XR3COOH, where XR3 is an organo group of which X is hydrogen when the group is unsubstituted or may be a carboxyl group, or an anhydride or acid chloride of such acid, and when the acid chloride is used, hydrolysing and condensing the reaction product. Among the products are the novel siloxanes of the formula <FORM:0991788/C3/2> where (1) R2 is alkyl or aryl, M is as above, R3 is a divalent substituted or unsubstituted, saturated or unsaturated hydrocarbon groups of 5 to 21 carbon atoms, and X is hydrogen or fluorine; also (2) where R2 is CH3, M is (CH2)3, R3 is CH2 and X is SH; and (3) where X is F, R3 is a fluorinated hydrocarbon group, R2 is CH3 and M is (CH2)3. Suitable starting materials of Formula 1 are 1-methyl-1-alkoxy-1, 2-siloxacyclopentane; 1,1-dialkoxy-1,2-siloxacyclopentane; and the corresponding siloxacyclohexane derivatives. They are described in Specification 991,786. They may be monomeric or polymeric, cyclic or in chain form. Suitable acid reactants are capric, caprylic, caproic, lauric, stearic, oleic, linolenic and behenic acids and acid chlorides, trifluoracetic, perfluoroctanoic, benzoic, maleic, fumaric, phthalic, terephthalic, salicylic and thioglycollic acids.  With polybasic acids, the products may additionally comprise ester-linked polymers having the units <FORM:0991788/C3/3> The reaction may be carried out at temperatures of 50 DEG  to 300 DEG  C. at various pressures and inert solvents may be used. Esterification catalysts which may be used include acids, Friedel-Crafts catalysts, tin and aluminium salts, and metal alkoxides.  In addition to the above reactants, the reaction mixture may contain a silane of the formula R1aSiR44-a where R1 is as above, R4 is a monovalent hydrocarbon group and a is 1 to 4, or a polysiloxane of the formula R1bR4cSiO2 - <FORM:0991788/C3/4> , where b is between 0.1 and 3, c is 0 to 2.9 and b+c is not greater than 3.  In a modification, the compounds of Formula 1 may be hydrolysed and condensed before reacting with the acid or acid chloride; this includes adding the water simultaneously with the acid.  When an acid chloride is used, initial products having the group Cl-Si-M-OOCR are formed, which on hydrolysis give polysiloxanes, siloxanols or silanols.  These may be condensed with other silanes or siloxanes.  Hardeners such as zirconium alkoxides and acetate and tin and cobalt salts may be added to the products. Many examples are given.  Where specified, the polysiloxanes have 2, 3, 4, 6 and 8 repeating units.  In Example XX, the product has the formula <FORM:0991788/C3/5> where n has a high value.  Uses: treating textiles, paper, leather etc.; polyester- and other resin-forming components; coating metals. Specification 859,375 also is referred to.ALSO:Organosilicon compounds which may be used in sun tan lotions and other cosmetic preparations comprise aryloxyalkyl polysiloxanes of the formula <FORM:0991788/A5-A6/1> where R2 is alkyl or aryl, M is a divalent hydrocarbon group of at least 3 carbon atoms, R3 is a divalent organo group, X is H, F or SH, and n is an integer (see Division C3).  In Example 18, a polymeric oil comprising units of the above formula and obtained from 1-methyl-1-ethoxy - 1,2 - siloxacyclopentane, trimethylethoxysilane, salicylic acid and water, is used as in U.V. absorbent in sun tan lotions.  Specifications 859,375 and 991,786 are referred to.ALSO:Metal surfaces are coated with acyloxyalkyl polysiloxanes of the formula <FORM:0991788/B1-B2/1> where R2 is alkyl or aryl, M is a divalent hydrocarbon group of at least 3 carbon atoms, R3 is a divalent organo group, X is H, F or SH, and n is an integer (see Division C3).  In Example 12, a metal surface is sprayed with a benzene solution of a resin comprising units of the above formula where R2 is CH3, M is (CH2)3 and XR3COO is derived from terephthalic acid.  In Example 13, the acid radical is linoleic and the oily product is mixed with a cobalt salt and painted on to a metal surface.  Specifications 859,375 and 991,786 are referred to.ALSO:Textiles, leather, paper &c. are rendered hydrophobic and oleophobic by impregnating with acyloxyalkyl silicon compounds of the formula <FORM:0991788/D1-D2/1> where R2 is alkyl or aryl, M is a divalent hydrocarbon group of at least 3 carbon atoms, R3 is a divalent, substituted or unsubstituted, saturated or unsaturated hydrocarbon group, X is H, F or SH, and n is an integer, e.g. 2 to 8 (see Division C3).  High molecular waxes used for textile purposes are softened by some of the above compounds.  The compounds may be applied as solutions in organic solvents, e.g. trichloroethylene, to which hardeners, e.g. zirconium alkoxides and acetate and tin compounds, may be added (see Examples 6 and 19). Specifications 859,375 and 991,786 are referred to.