Patent GB-1130558-A (GB)
Title: Processes for preparing polyesters
IPC: C08G63/64
Filed: 1965-12-07
Abstract: 1,130,558. Polyesters. EASTMAN KODAK CO. 7 Dec., 1965 [7 Dec., 1964], No. 51885/65. Heading C3R. In the manufacture of linear polyesters by reacting an aliphatic diester of a dicarboxylic acid or carbonic acid with a dihydroxy compound at least 10 mol per cent of which consists of a 2:2:4:4-tetraalkyl-1 :3-cyclobutanediol, a lead compound is used as a catalyst. Specified lead compounds are the nitrate (which may be ethylene glycol treated), sulphate, silicate, phosphite, carbonate, borate, acetate, propionate, butyrate, stearate, tartarate, salicylate, phthalate, maleate, oxide (e.g. PhO, PhO 2  or Ph 3 O 4 ) and organo-lead compounds wherein the organic radicals are C 1-25  alkyls, C 6-10  cycloalkyls or C 6-10  aryls. Specified dicarboxylic acids are terephthalic, hexahydroterephthalic, p : p<SP>1</SP> - sulphonyldibenzoic, 4 : 1<SP>1</SP> - dipheylether dicarboxylic 4 : 4<SP>1</SP> - diphenic, 4 : 41 - ethylenedioxydibenzoic, 4 : 4<SP>1 </SP>- methylenedibenzoic, 4 : 4<SP>1</SP> - benzophenonedicarboxylic, 4 : 4<SP>1</SP> - vinylenedibenzoic, 1 : 4-, 1: 5- or 2 : 6-naphthalenedicarboxylic, 2 : 5- or 2 : 6-norcamphanedicarboxylic, isophthalic, orthophthalic, hexahydrophthalic, 1 : 4- phenylenediacetic, 1 : 4 - cyclohexanediacetic, oxalic, succinic, adipic, 2 : 2 : 4 - trimethyladipic, sebacic, azelaic 2 - ethylsuberic, 2 : 2- diethyladipic, dimethylmalonic and dimer acids; also dicarboxy diethyl ether. Suitable modifying glycols are C 2-10  polymethylene glycols, 2 : 2 - dimethyl - 1: 3 - propanediol, 2 - methyl - 1 : 5 - pentanediol, p - xylylene glycol, 1 :4 - di-(hydroxyethyl)benzene quinitol, 1 : 4 - cyclohexanedimethanol, dimer glycols and polyglycols of formula where R 4  is a hydrogen atom or an aliphatic, aromatic or cycloaliphatic hydrocarbon radical, a is 1-4 and b is 2-100. The reaction mixture may also include hydroxycarboxylic acids (e.g. 4 - hydroxybutanoic, 6-hydroxyhexanoic, 2 : 2 - dimethyl - 3 - hydroxypropionic or p - hydroxymethylbenzoic acids. The process for making the polyesters comprises a normal ester-interchange reaction followed by a normal melt polymerization or solid phase polymerization reaction. Examples describe the manufacture of polyesters by reacting (1)-(5) 2 : 2 4 : 4 - tetramethyl - 1 : 3 - cyclobutanediol and dialkyl esters of terephthalic, azalaic, 4 : 4<SP>1</SP> - sulphonyldibenzoic or transcyclohexane - 1 : 4 - dicarboxylic acids; (6) and (7) 2 : 4 - dimethyl - 2:4 - diisopropyl - 1:3 - cyclobutanediol (or a mixture thereof with 1 : 6 - hexanediol) and dimethyl terephthalate; (8), (9), (10), (12), (13), (14) and (15) 2 : 2 : 4 : 4- tetramethyl - 1 : 3 - cyclobutanediol, dimethyl terephthalate and 1 : 4 - cyclohexanedimethanol, polytetramethylene glycol (M.W. 3100), mixed polytetramethylene glycols (M.W.'s 1600 and 3100), polybutylene glycol (M.W. 1000), polyethylene glycol (M.W. 1000) and dimer glycol; (11) 2 : 2 : 4 : 4- (18) 2 : 2 : 4 : 4-tetramethyl - 1 : 3- cyclobutanediol and dimethyl hexahydroterephthalic acid; tetramethyl - 1 : 3 - cyclobutanediol, polytetramethylene glycol (M.W. 1000), dimethyl terephthalate and dimethyl azelate; (17) and (20) 2 : 2 : 4 : 4 - tetramethyl- 1 : 3 - cyclobutanediol and dimethylisophthalate or dimethyl - 2,6 - naphthalenedicarboxylate; (18), (19) and (21) 2 : 2 : 4 : 4 - tetramethyl - 1 : 3 - cyclobutane - diol and mixtures of dimethyl esters of terephthalic and succinic, azolaic, adipic, sepacic, dimer or isophthalic acids, mixtures of dimethyl esters isophathalic and azeloic or adipic acids and a mixture of the dimethyl esters of 2 : 6 - naphthalenedicarboxylic and sebacic acids; (18) 2 : 2 4 : 4- tetramethyl - plus 2 : 2 : 4 : 4 - tetraethyl- 1 : 3 - cyclobutanediol and dimethyl isophthalate (16) and (21) 2 :2 : 4 :4 - tetramethyl- : 1 : 3- cyclobutanediol and dibutyl carbonate with or without the dimethyl esters of sebacic, isophthalic or terephthalic acids.