Patent GB-810284-A (GB)
Title: Improvements in or relating to resins
IPC: C08G59/40
Filed: 1956-02-03
Abstract: The invention comprises reaction products of (1) 1 to 99 per cent by weight of a siloxane containing the units <FORM:0810284/IV (a)/1> in which X is a saturated non-aromatic hydrocarbon radical having substituted thereon at least 3 carbon atoms away from the silicon atom 1 or 2 of the groups OH, COOH, COOalkyl, NH2 and CONHR1NH2 in which R1 is an alkylene radical, R is a monovalent hydrocarbon or halogenated hydrocarbon radical free from aliphatic unsaturation and n has an average value of 0 to 2, and (2) 1 to 99 per cent by weight of an epoxide polymer prepared by reacting a polyhydric phenol with a polyfunctional chlorohydrin or polyepoxide.  The siloxane may contain up to 95 mol. per cent of units of the formula <FORM:0810284/IV (a)/2> , in which R11 is a monovalent hydrocarbon or halogenated hydrocarbon radical or a halophenoxy radical and m has an average value of 1 to 3.  Examples of the radical X are gamma-hydroxypropyl, 4-hydroxybutyl, 12-hydroxyoctadecyl, <FORM:0810284/IV (a)/3> gammacarboxypropyl, 4-carboxybutyl, 10-carboxydecyl, carboxyheptadecyl, HOOCCH2CH2 CH(COOH)CH2CH2-, HOOC(CH2)5CH(COOH) (CH2)6-, HOOC(CH2)3CH(COOH) (CH2)6-, carboxycyclohexyl, carboxycyclopentyl and other carboxylated cyclic radicals many of which are specified, and their alkyl esters; gamma-aminopropyl, 4-aminobutyl, 12-aminooctadecyl, aminocyclopentyl and -hexyl, <FORM:0810284/IV (a)/4> and radicals obtained by reacting carboxy substituted siloxanes with diamines, e.g. -CH2CH2 CONHCH2CH2NH2, -(CH2)3CONH2(CH2)4 NH2, -(CH2)17CONH(CH2)6NH2, -CH2CH2 CH(COOH)CH2CH2CONH2(CH2)5NH2 and cyclic radicals with such substituents, a number of which are specified.  The radical R in the functional siloxane may be alkyl, cycloalkyl, aryl, aralkyl and chloro, bromo and fluoro substituted radicals.  The radical R11 in the copolymeric portion may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl; chloro-, bromo- and fluoro-hydrocarbon radicals; and chloro- and bromo-phenoxy methyl.  The epoxide resins may be prepared from any polyhydric phenol, e.g. resorcinol, hydroquinone, catechol, phloroglucinol, bis - p,p1 - dihydroxydiphenyldimethylmethane, p,p1 - dihydroxybenzophenonep,p1 - dihydroxy - diphenyl and - dibenzyl, bis - (4 - dihydroxyphenyl) sulphone, 2,21 - dihydroxy - 1,11 - dinaphthylmethane, polyhydroxy naphthalenes and anthracenes and o,p,o1,p1 - tetrahydroxydiphenyldimethylmethane; condensation products of polyhydric phenols with dichlorides, of the formula HOR [OCH2CH2OCH2CH2OR]nOH and/or HOR [OCH2CH = CHCH2OR]nOH, where R is the phenol residue and n is at least 1; and condensation products of complex polyhydric phenols with dibasic acids, e.g. of the formula HOR[OOC(CH2)4COOR]nOH, where R is the phenol residue and n is at least 1.  The polyepoxide used for preparing the epoxide resin should be substantially free from reactive groups other than epoxy and hydroxyl groups, but may be admixed with monoepoxides.  Examples are 1,2 - epoxy - 3,4 - epoxy - butane, bis - (2,3-epoxy - propyl) ether, bis - (2,3 - epoxy - 2-methyl - propyl) ether; reaction products of a diepoxide with a di- or tri-hydric phenol; and polyepoxides derived from polyhydric alcohols such as mannitol, sorbitol, erythritol and polyallyl alcohol, and epichlorhydrin.  The polyfunctional chlorhydrins which may alternatively be used include epichlorhydrin, glycerol dichlorhydrin, bis - (3 - chloro - 2 - hydroxypropyl) ether, 1,4 - dichloro - 2,3 - dihydroxybutane, 2 - methyl - 2 - hydroxy - 1,3 - dichloropropane, bis - (3 - chloro - 2 - methyl - 2-hydroxypropyl) ether, and other mono- and dichlorhydrins derived from aliphatic olefins, mannitol, sorbitol and other alcohols.  The reaction temperatures vary from room temperature for siloxanes containing amino groups to temperatures above 200 DEG  C.  The mixture may also contain long chain fatty acids or other resins, e.g. phenolic, melamine and alkyd resins.  The reaction products may be thermoplastic or thermosetting and may be used for moulded articles, laminates and coating compositions.  Curing may be aided by heat and catalysts, e.g. amines, or, when alkenyl groups are present, by organic peroxides.  In the examples: (1) a copolymer comprising phenylmethylsiloxane (55 per cent), monophenylsiloxane (15 per cent), monomethylsiloxane (15 per cent) and 15 per cent of <FORM:0810284/IV (a)/5> prepared by reacting the corresponding carboxy copolymer with hexamethylenediamine, is mixed as a 70 per cent solution in toluene, with the epoxy resin prepared from epichlorhydrin and bis-phenol. The reaction product cures at room temperature on standing.  A portion is cured between glass plates by heating at 135 DEG  C. and the plates are bonded.  (2) A siloxane copolymer containing 15 per cent of <FORM:0810284/IV (a)/6> is reacted with the epoxy resin of (1).  (3) The siloxane is gamma-hydroxypropyl methylsiloxane.  (4) The siloxane contains 10 per cent chlorophenylmethylsiloxane, 25 per cent phenylvinylsiloxane, 10 per cent a ,a ,a -trifluorotolylsiloxane, 25 per cent pentachlorophenoxymethyl methyl siloxane and 30 per cent <FORM:0810284/IV (a)/7> and is heated with the epoxy resin in an inert atmosphere at 260 DEG  C.  (5) The siloxane is <FORM:0810284/IV (a)/8> Specifications 769,496, 769,498 and 810,283 are referred to.