Patent GB-1116379-A (GB)
Title: Copolyimides
IPC: C09D5/25
Filed: 1965-07-08
Abstract: Polyimides have a main chain composed of organic residues interconnected by imide links and by carboxylic ester, urethane, carboxylic anhydride, carbonate, urea or amide links, the ester links when present being derived from a dihydroxy compound or an aliphatic monohydroxy compound, the urethane links being derived from a dihydroxy compound free from hydrolysable links and the amide groups being accompanied by at least one of the other linking groups.  The organic residues may be C1- 40 aliphatic, C3- 20 alicyclic or polyalicyclic or C6- 20 aromatic radicals or polymer residues. Elastomeric polymers may contain 40-91% of organic residues derived from a polymer, e.g. a polyester, polyether or polyformaldehyde, of m.p. less than 45 DEG  C. and M.W. 500-5000 and a fibre-forming polymer of m.p. above 200 DEG  C. joined by urethane links.  The polymers may be prepared from a bifunctional monomer containing 1-4 imide links.  These may be reacted with dicarboxylic acids, amino acids, hydroxyacids, aminoalcohols, aminophenols, glycols, diamines, phosgene or diisocyanates. Ester links may be formed by ester-interchange at 0-300 DEG  C. in the presence of a catalyst or by use of an acid chloride.  Urea links may be formed from a diamine and a diisocyanate at 0-200 DEG  C., the imide group being present in either reactant, a diamine and phosgene, CO2 or urea or a diamine and a urethane. Anhydride links may be formed at 0-300 DEG  C. from an imide-containing dicarboxylic acid, a non-imide containing dicarboxylic acid and acetic anhydride in pyridine. Carbonate links may be formed at 300 DEG  C. from an imide containing diol, e.g. a bis-phenol, and a phosgene or a bischloroformate of a diol.  Urethane links may be formed at 30-150 DEG  C. from an imido-diisocyanate and a diol or from a bis-chloroformate of a diol and a diamine. The diol may be a polyester or polyether. Products containing ester and amide links may be formed.  The products may be linear and fibre forming. In Examples (6-14, 16-23 and 41) polyesters are formed from: <FORM:1116379/C3/1> butane diol, cyclohexanedimethanol, ethylene glycol, polytetramethylene glycol <FORM:1116379/C3/2> <FORM:1116379/C3/3> sebacic acid, dimethyl terephthalate, <FORM:1116379/C3/4> dimethyl sebacate, dimethyl isophthalate and <FORM:1116379/C3/5> using titanium tetrapropoxide and titanium tetrabutoxide as catalyst.  In Examples (15, 32, 42 and 43) polycarbonates are prepared from diphenyl carbonate, diol IV, phenol, a polyether of tetrahydrofuran and oxa-bicyclononane bisphenol-A and phosgene using pyridine and methylene chloride as solvents and lithium in mineral oil as a catalyst.  In Examples (24-27 and 36-40) polyurethanes are prepared from diol IV, tolylene diisocyanate, p-xylylene diisocyanate, <FORM:1116379/C3/6> the bischloroformate of neopentylene glycol, <FORM:1116379/C3/7> polytetramethylene glycol, <FORM:1116379/C3/8> a polyether of tetrahydrofuran and oxabicyclononane, poly-(ethylene terephthalate) containing some propylene glycol residues, 1,4-bis-(isocyanatomethyl) cyclohexane, bis-(4 - isocyanatophenyl) methane, <FORM:1116379/C3/9> and <FORM:1116379/C3/100> using dimethylacetamide and dimethylformamide, as solvents and aq. NaOH as an acid acceptor.  In Examples (28-30) polyesteramides are formed from dicarboxylic acid I, 1-hydroxymethyl, 4 - aminomethyl - cyclohexane, ethylene glycol, hexamethylene diamine, diol IV, xylylene diamine and sebacic acid in the presence of water.  In Example (31) a polyanhydride was formed from dicarboxylic acid I, hydroquinone diacetic acid and acetic anhydride. In Examples (33-36 and 38-40) polyureas are formed from decamethylene diisocyanate, <FORM:1116379/C3/111> bis - (4 - isocyanatophenyl) methane, diamine X, hexamethylene diisocyanate, decamethylene diamine and diamine VIII, poly-(tetramethylene) glycol, p-xylylene diisocyanate, a polyether of tetrahydrofuran and oxabicyclononane, diamine IX and 1,4-bis-(isocyanatomethyl) cyclohexane using dimethylformamide and dimethyl acetamide as solvents.ALSO:In Example 1 <FORM:1116379/C2/1> was prepared from 1,4-bis (aminomethyl) cyclohexane and trimellitic anhydride by heating in DMF and later in mineral oil under N2. In Example 2 the procedure was repeated replacing the diamine by m-xylylene diamine and hexamethylene diamine.  In Example 3 <FORM:1116379/C2/2> was prepared from 1-hydroxymethyl, 4-aminomethylcyclohexane and pyromellitic anhydride in DMF, the resulting solution being poured into water to precipitate the product.  In Example 4 trimellitic acid/anhydride was heated in diphenyl ether to convert the acid to anhydride and the resulting solution condensed with hexamethylene diamine.  In Example 5 trimellitic anhydride was condensed with epsilon-caprolactam.