Patent GB-1129617-A (GB)
Title: High molecular weight polybenzoxazine diones and a process for their production
Inventor: BOTTENBRUCH LUDWIG
IPC: C08L75/00
Filed: 1965-10-08
Abstract: 1,129,617. High molecular weight polybenzoxazine diones. FARBENFABRIKEN BAYER A.G. 8 Oct., 1965 [10 Oct., 1964], No. 42809/65. Heading C3R. High molecular weight polybenzoxazine diones of the general formula wherein X is a tetravalent aryl, diaryl or diarylmethane radical, each pair of O-and C- bonds being attached to adjacent C atoms of the aromatic radical, R is a divalent aliphatic, cycloaliphatic, araliphatic or aromatic radical and n is an integer from 50-200 are prepared by reacting a polyamide derived from an aromatic di-(o-hydroxy carboxylic acid) and a diamine at 0-350‹ C. with an acylating carbonic acid derivative. Suitable polyamides may be derived from aryl di-(o-hydroxy carboxylic) acids such as 4: 4<SP>1</SP> - dihydroxydiphenyl - 3: 3<SP>1</SP> - dicarboxylic acid, 3: 6-dihydroxyphthalic acid, resorcinol - 2: 4 - or - 4: 6 - dicarboxylic acid, 2: 5 - dihydroxyterephthalic acid, 4: 4<SP>1 </SP>- dihydroxydiphenylmethane - 3: 3<SP>1 </SP>- dicarboxylic acid, 4: 4<SP>1</SP> - dihydroxy - 5: 5<SP>1 </SP>- dimethyldiphenylmethane - 3: 31 - dicarboxylic acid and 1: 1<SP>1</SP> - (4: 4<SP>1</SP> - dihydroxy - 5: 5<SP>1</SP> - dimethyldiphenyl) - ethane - 3: 3<SP>1</SP>- dicarboxylic acids and diamines such as 1: 4-tetramethylene diamine 1: 6-hexamethylene diamine, 1: 11-undecamethylene diamine, 4: 41-diaminodiphenylmethane, 2: 2 - bis (4 - aminophenyl) - propane, m - xylylene diamine, 4: 4<SP>1</SP>-diaminodiphenyl ether, p - xylylene diamine, m - bis - (2 - aminoethyl)-benzene and p-bis-(2-aminoethyl)-benzene. The carbonic acid derivative may be e.g. phosgene, or alkyl or aryl chloroformates or carbonic diesters, e.g. ethyl or phenyl chloroformate or diphenyl carbonate. Polyamides containing residues of other acids may also be used, with reduced amounts of carbonic compound. Amounts of carbonic compound less than equivalent to all the hydroxy-amide groups may be used if products containing free hydroxyl and amide groups are required. The reaction of the polyamide with a diaryl carbonate may be carried out in the melt at 150- 350‹ C. or in e.g. phenol or cresol solution. Catalysts, e.g. NaOCH 3 , NaOPh, NaOOC.CH 3  and N,N-dimethylstearylamine or N,N,N<SP>1</SP>,N<SP>1</SP>- tetramethyl-tetramethylenediamine or -hexamethylene diamine, may be used. The reaction with alkyl or aryl (preferred) chloroformate is preferably conducted at 0-50‹ C. in solution, e.g. in tetrahydrofuran, dimethylformamide, tetrachlorethane or dichlorbenzene, i.p.o. an acid-combining agent, e.g. pyridine. The product polybenzoxazine diones have M.W. of at least 10,000 and intrinsic viscosities between 1À0 and 1À5. In Examples 1-6, 4: 4<SP>1</SP>-dihydroxy- 3: 3<SP>1</SP> - dimethyl - 5: 51 - dicarboxyl diphenylmethane or its diphenyl ester is condensed with hexamethylene diamine, m-xylylene diamine, bis - p - (2 - aminoethyl) benzene, methylene dianiline or dianiline ether; in Examples 7 and 8, 4: 4<SP>1</SP> - dihydroxy - 3: 3 - dicarboxyl diphenylmethane diphenyl ester and resorcinol-2: 4-dicarboxylic acid diphenyl ester are condensed with hexamethylene diamine and undecamethylene diamine respectively. The polyamide products are heated with phenyl chloroformate, in dichlorbenzene/pyridine (Examples 1-5) or tetrachlorethylene (Examples 7, 8), or with diphenyl carbonate in phenol. The polyamides are soluble in DMF, THF, DMSO, cresol, pyridine and aqueous methanolic NaOH, the polybenzoxazine diones in CH 2 Cl 2 , C 2 H 2 Cl 4 , cresol and pyridine; the relative viscosities are given for each, and films are cast from solutions in phenol or tetrachlorethane respectively.