Patent GB-1144594-A (GB)
Title: Curable polyesters
IPC: C07F7/18
Filed: 1966-06-10
Abstract: 1,144,594. Silyl-substituted polyesters. GENERAL ELECTRIC CO. 10 June, 1966 [2 May, 1966; 14 June, 1965], No. 26055/66. Heading C3R. A polyester consists essentially of units -R-OOC-R-COO- and contains at least one silyl radical Y (3-a) R<SP>1</SP> a Sijoined by a C-Si bond to a group -R<SP>11</SP>.COO-, -R<SP>11</SP>ÀOÀCOO-, -R<SP>11</SP>NHCOO- or [-R<SP>11,</SP>ZÀCONH]eÀWÀNHCOO- which is attached in turn to a C atom in an alcohol or phenol residue in the polyester, the groups R and R<SP>11</SP> being divalent hydrocarbon or halohydrocarbon radicals; R<SP>1</SP> being a monovalent hydrocarbon or halohydrocarbon radical; Y being an acyloxy, amino, ketoximato or halogen radical; Z being -O- -S-, or - NG-; G being H or R<SP>1</SP>; W being a divalent or trivalent hydrocarbon radical; a being 0, 1 or 2 and e being 1 or 2. The polyester may be prepared by reacting a silane Y (3-a) R<SP>1</SP> a SiH with a polyester containing unsaturated groups, in the presence of a platinum catalyst, the unsaturated polyester being obtained either (1) by reacting a compound R<SP>111</SP>ÀCOX, R<SP>111</SP>ÀOÀCOX or R<SP>111</SP>ÀNCO with a polyester consisting essentially of units -R-OOC-R-COO- and having free OH groups or (2) by reacting a compound R<SP>111</SP>ZH with an isocyanate-terminated polyester derived from that in (1) above and a polyisocyanate W(NCO) e , R<SP>111</SP> being a monovalent unsaturated aliphatic hydrocarbon group and X being a halogen atom. As components of the polyester suitable dicarboxylic acids are oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic and o-, m- and pphthalic acids, and suitable polyols are ethylene, diethylene, triethylene, propylene, 1: 3- and 1: 4-butylene glycols, cyclohexane dimethanol, the dihydroxybenzenes, bisphenols and halobisphenols, optionally containing e.g. glycerol, 1: 3: 6-hexanetriol, trimethylol-propane and pentaerythritol. Suitable silicon hydride silanes listed contain formate, acetate, propionate or acetone or MEK ketoximate radicals or F, Cl or Br atoms, and 0, 1 or 2 methyl or ethyl radicals; amino-silyl polyesters may be obtained by treating halosilyl polyester products with, e.g. NH, methyl-, ethyl- or isopropyl-amine, dimethylamine, ethylisobutylamine or ethylisopropylamine. Suitable unsaturated compounds R<SP>11I</SP>ÀNCO are vinyl, allyl, p-vinylphenyl, p-allylphenyl, 4-cyclopentenyl, 4-butenyl and pallyloxyphenyl isocyanates; R<SP>111</SP>ÀOCOX are allyl and p-vinylphenyl chloroformates; R<SP>111</SP>ÀCOX are acryloyl and vinylacetyl chlorides; R<SP>111</SP>ÀZH are allyl alcohol, allyl mercaptan, allylamine, p-allylphenol and p-aminostyrene. Curing accelerators may be added to the product, e.g. 0À001-10 wt. per cent of stannous octoate or oleate, dibutyl tin dilaurate, and also fillers, e.g. up to 50 parts per 100 of resin of C black, diatomaceous earth, fume silica, SiC fibres and glass fibres, and pigments, stabilizers and plasticizers. In examples, diacetoxymethylsilane is reacted with allyl isocyanate-modified polyadipates of diethylene glycol (1), 1: 2-propylene glycol (6) or 1: 3-butylene glycol (2); or with allyl alcohol-modified isocyanateterminated polyesters from toluene-2: 4-diisocyanate and polyadipates of diethylene glycol (3) or 1: 2-propylene glycol (8); or with allyl chloroformate-modified (8) or butenoyl chloridemodified (10) polyadipate of diethylene glycol. The product of Example (3) is filled with fume silica or carbon black.