Patent GB-746498-A (GB)
Title: Reaction products of organosilanes and methylol phenolic ethers
IPC: C08G77/00
Filed: 1953-08-06
Abstract: Resins convertible by heat and useful for coating and laminating are obtained by condensing a silane of the formula Z(4-m)SiXm, Z being a monovalent hydrocarbon radical, X being halogen, alkoxy or aryloxy and m being 2 or 3 with a methylol phenol ether of the formula <FORM:0746498/IV(a)/1> where R is alkyl, aralkyl, alkenyl or hydroxyalkyl, R1 is halogen, alkyl or aryl, P is 0, 1 or 2 and n is 2 or 3. Alternatively the methylol phenol ether may be partially condensed before reaction with the silane, using acid catalysts such as sulphamic, p-toluene sulphonic, urea hydrochloride and aniline and morpholine sulphates.  Subsequent curing of the resin may be catalysed by the same acids.  Modified resins may be obtained by reacting methylol groups in the initial product with abietic acid or long chain fatty acids to give materials useful as plasticizers for vinyl resins.  In general, however, the silane and methylol phenol ether are reacted in equivalent proportions, having regard to the number of methylol groups and hydrolysable radicals, or an excess of silane is employed.  In examples (2) 2.6 dimethylol-4-methyl anisole was condensed at 190 DEG  C. for 20 minutes in the presence of sulphamic acid to give a tough polymer which was dissolved in butyl acetate and methyl triacetoxy silane added.  A film of the mixture was baked at 150 DEG  C. to give a tough flexible water white film only slightly attacked by toluene.  (3) 2.6-dimethylol-4-methyl anisole was reacted with dimethyldiacetoxysilane in the molar ratio 2 : 1 by heating while removing acetic acid.  After cooling, a small quantity of sulphamic acid was added resulting in vigorous condensation with evolution of water to give a viscous polymer, convertible by heat in the presence of sulphamic acid.  (4) The reaction product of methyl triacetoxysilane and 2.6 dimethylol-4-methyl anisole together with additional quantities of the ether was resinified by heating at 200 DEG  C. with 0.25 per cent sulphamic acid.  (5) A mixture of allyl ethers of methylol phenols was reacted with dimethyl dibutoxy silane in the presence of sodium methoxide to give a rubbery solid.  (6) A mixture of propanol ethers of methylol phenols was reacted with dimethyldibutoxysilane to give a resin convertible by heat to a tack-free film.  (7) Similar to (6) but using phenyltrichlorosilane.  (8) The reaction product of a mixture of propanol ethers of methylol phenols, lauric acid and phenyltrichlorosilane was used to deposit films which were baked at 200 DEG  C.  (9) Reaction product of a mixture of allyl ethers of methylol phenols and dimethyldichlorosilane.  (10) Reaction product of a mixture of propanol ethers of methylol phenols and dimethyldichlorosilane.  (11) Reactive product of a mixture of propanol ethers of methylol phenols, abietic acid and dimethyl dichlorosilane.  The Specification lists a large number of silanes and ethers of methylol phenols which may be used in the invention. The products may be reacted with additional methylol phenols. Specification 712,588 is referred to.ALSO:2,6-DDimethylol-para-cresol is prepared by adding 830 grams of 37 per cent formaldehyde to a cooled solution of 540 grams p-cresol and 220 grams caustic soda. The solution is held at 30-40 DEG C. for two hours and allowed to stand at room temperature for 16 hours.  The sodium salt which separates out is neutralized with acetic acid and the resulting phenol alcohol recrystallized from aqueous alcohol.  The methyl ether of 2,6-dimethylol-p-cresol is prepared by reacting the phenol alcohol in an aqueous solution of caustic soda with dimethyl sulphate for two hours at 70 DEG C.  The precipitate forming on cooling is purified. Other ethers may similarly be prepared by reaction with ethyl chloride, butyl chloride, ethylchlorohydrin, and epichlorohydrin.  A mixture of allyl ethers of mono-, di- and trimethylol phenols is prepared by reacting allyl chloride with a mixture of sodium mono-, di- and tri-methylol phenates obtained by reacting formaldehyde phenol and caustic soda.  A mixture of the propanol ethers is prepared by reacting propylene oxide with a mixture of mono-, di- and tri-methylol phenols in caustic soda solution.  The various ethers or mixtures of ethers may be reacted with hydrolysable hydrocarbon-substituted silanes.  In example 3 a compound of the formula <FORM:0746498/IV(a)/1> is formed.  In example 4 a compound of the formula <FORM:0746498/IV(a)/2> is formed.  Specification 712,588 is referred to.