Patent GB-1009019-A (GB)
Title: Bisphenols and polyesters derived therefrom
IPC: C08G63/80
Filed: 1962-09-14
Abstract: The invention comprises linear polymers in which at least 10% o the units have the formula:  <FORM:1009019/C3/1> where R11 represents a hydrogen atom, halogen atom, or alkyl group having up to four carbon atoms, and X represents a gem-bivalent radical of a saturated polycyclic compound having at least one bicyclic carbon-bridged hydrocarbon ring, preferably of the formula <FORM:1009019/C3/2> <FORM:1009019/C3/3> <FORM:1009019/C3/4> <FORM:1009019/C3/5> <FORM:1009019/C3/6> <FORM:1009019/C3/7> <FORM:1009019/C3/8> <FORM:1009019/C3/9> <FORM:1009019/C3/100> <FORM:1009019/C3/111> <FORM:1009019/C3/122> <FORM:1009019/C3/133> <FORM:1009019/C3/144> <FORM:1009019/C3/155> <FORM:1009019/C3/166> <FORM:1009019/C3/177> wherein each of R, R1, R11, R1, R11 and R2 represent a hydrogen atom, halogen atom, or alkyl group containing up to 4 carbon atoms, and R1, R11 and R2 can also be aryl groups, and one of the carbon positions marked by an asterisk is the position at which the phenyl groups are joined to the radical.  The polymers may be linear polycarbonates in which at least 10% of the units have the formula <FORM:1009019/C3/188> in which X represents a gem-bivalent radical as above and Y is a bifunctional organic residue, which may be prepared from bisphenols by adding phosgene and/or a bischloroformate of a diol, to a cooled, stirred aqueous mixture containing sodium hydroxide, the bisphenol, a catalyst and methylene chloride.  The catalyst may be a quaternary ammonium salt or hydroxide, or a tertiary amine.  Copolycarbonates are made by using more than one bisphenol or a mixture of diacid chlorides.  Block copolycarbonates are made by condensing a mixture of low-molecular weight homopolycarbonates with phosgene.  Mixed copolymers are prepared by condensing a bisphenol with a bischloroformate of a polymeric diol, e.g. polyethylene oxide bischloroformates.  The polymers may also be linear polyester in which at least 10% of the units have the formula <FORM:1009019/C3/199> in which Z represents a bifunctional organic residue.  The polyesters are made by condensing the said bisphenols with dicarboxylic acids, by ester interchange reactions between the novel bisphenols and esters of aliphatic, cycloaliphatic and aromatic dicarboxylic acids. Mixtures containing two or more acids, two or more bisphenols or an aliphatic or cycloaliplatic glycol with the bisphenol, may be used to give co-polyesters.  The ester interchange is catalysed by the oxide, hydride or amide of an alkaline earth metal, or zinc oxide, lead oxide, dibutyl tin oxide, and sodium aluminate. Polyester may also be obtained by heating a mixture of equivalent amounts of bisphenol and acid chloride at temperatures from 160-280 DEG  C. or reacting them in a basic solvent such as pyridine or a two-phase system of aqueous alkali and organic phase. Another method involves ester interchange of a monobasic aliphatic acid ester of the bisphenol with a dicarboxylic acid.  A catalyst such as manganese may be used.  Specifications 621,102, 636,429, 648,513, 772,627, 777,215 and 1,009,020 are referred to.ALSO:The invention comprises a bisphenol having the formula <FORM:1009019/C2/1> wherein X has one of the structures <FORM:1009019/C2/2> wherein each of R, R1, R11, R1, R11 and R2 represents a hydrogen atom, halogen atom, or alkyl group containing up to 4 carbon atoms, and R1, R11 and R2 can also be aryl groups and one of the carbon positions marked by an asterisk is the position at which the phenyl groups are joined to the radical.  The bisphenols may be made by condensation of phenol with an appropriate polycyclic ketone or aldehyde, preferably in the presence of concentrated hydrochloric acid, though other acids such as sulphuric, toluenesulphonic or methionic acid may also be used as a catalyst. Detailed examples describe the preparation of the various polycyclic bis-phenols from the appropriate ketone or aldehyde.  The starting materials are prepared by known methods with the exception of the following:  (2) a substituted ethylene, e.g. propylene, 2-butene, styrene, stilbene, p-chloro-styrene, or other homologue containing 3-20 carbon atoms and which may contain up to 6 chlorine atoms, is heated at 200 DEG  C. with dicyclopentadiene (which cracks to form cyclopentadiene) to form a bicycloheptene by Diels-Alder reaction, which is hydrated to a norcamphanol followed by oxidation with nitric acid to a substituted norcamphor; (3) 4,7-hexahydromethanoidan-5-ol is oxidized with nitric acid to 4,7-hexahydromethanoidan - 5 - one; (6) decahydro - 1,4-exoendo - 5,8 - dimethano - naphthalene - 2 - one is made by oxidation of the corresponding hydroxy compound with nitric acid; (18) dihydrodicyclopentadiene is reacted with hydrogen and carbon monoxide in the presence of dicobalt octacarbonyl to form hexahydro-4,7-methano-indan-2 (or 3) carboxaldehyde; (22)-(29) describe chlorination of the polycyclic diphenols with chlorine or sulphuryl chloride. Specifications 621,102, 636,429, 648,513, 772,627, 777,215 and 1,009,020 are referred to.