Patent GB-1179173-A (GB)
Title: New Thermally Stable Nitrogenous Resins
Inventor: RABILLOUD GUY
IPC: C08G73/18
Filed: 1967-01-17
Abstract: 1,179,173. Glass fibre laminates. INSTITUT FRANCAIS DU PETROLE DES CARBURANTS ET LUBRIFIANTS. 17 Jan., 1967 [17 Jan., 1966; 12 Oct., 1966], No. 2472/67. Heading B5N. [Also in Divisions C2 and C3] Copolymer resins used in laminating glass fibre fabrics comprise in the polymer chain groups and -CO-NH-Ar 2 -Z 1 -(Ar 3 -Z 2 -) n -Ar 4  -NH-CO-Ar 1 -, wherein Ar 1 , Ar 2 , Ar 3  and Ar 4  are divalent heterocyclic or aromatic radicals, A is a tetravalent aromatic radical having the four valencies in two ortho pairs, Z 1  and Z 2  are -CO-NH- or -NH-CO-, and n is 0 or an integer. They may be prepared by reacting 2 moles of a diacid monohalide monoester ROOC-Ar 1 -COHa with one mole of a diamine H 2 N-Ar 2 -Z 1 -(-Ar 3 -Z 2 -) n - Ar 4 -NHg and reacting the product with one mole of a tetramine A(NH 2 ) 4  or by reacting 1 mole of a diester ROOC-Ar 1 -COOR with a total of substantially 1 mole of such diamine and tetramine, preferably in proportions of diamine: tetramine between 1: 9 and 9:1. Using the diester it is preferable also to react the diamine first but the diamine and tetramine may also be reacted simultaneously. Each of the radicals Ar and A may comprise several rings joined by direct bonds or by -CH 2 -, -CO-, -C(CH 3 ) 2 -, -O-, -S-, -SO-, -SO 2 -, -NR 1 - or -O-P.R 1 .O-O-, R 1  being alkyl or aryl. Numerous suitable reactants are specified those used in specific examples being: (diesters and ester halide) phenyl iso- and tere - phthalates; 4,4<SP>1 </SP>- diphenoxycarbonyl diphenyl ether; 3,5-diphenoxycarbonyl pyridine; and phenyl 3-chloroformylbenzoate; (diamines) 3,3<SP>1 </SP>- or 4,3<SP>1 </SP>- diaminobenzanilide; bis(m - aminobenzamido) - 3,3<SP>1</SP> - benzanilide; di(31 - amino - 4 - benzamido - phenyl) ether; and di(3 - aminophenyl) or di(3<SP>1</SP> - amino - 3 - benzamidophenyl) N,N<SP>1</SP>-isophthalamide; and (tetramine) 3,31-diaminobenzidine. Reaction may be effected in a polar solvent at 100 to 300 C. for 1 to 48 hours. If the resin is to be used as an adhesive the reaction is preferably stopped when the resin reaches an inherent viscosity (0À5% in dimethylsulphoxide at 30 C.) of 0À03 to 0À20 while the softening point is below 400 C. For such use the resin is preferably applied as a 5 to 70 wt. per cent solution in a polar organic solvent and cured at 310 to 400 C. under pressure. The resins may be used to manufacture fibres or films; as adhesive for wood, metals or glass; or as binders in laminates. Preparation of laminates.-In Examples 15- 17 solutions of the resins are used to impregnate glass fabrics (double satin weave, some with aminopropyl silane stiffening) and the solvent evaporated. A laminate of layers of the impregnated material is pressed according to the following schedule: 15 to 20 minutes at 135 C. without pressure; 14 to 15 kg/cm.<SP>2</SP> then applied while the temperature is raised to 330 to 340 C. at 1À5 C/min.; temperature and pressure maintained for 3¢ hours; pressure maintained while temperature is allowed to fall to 120 C. In variations (a) the press is initially at 300 C.; or (b) the pressure is 30 kg/cm.<SP>2</SP> and the cooled laminates are further treated in vacuum or an inert atmosphere for 1 day each at successive temperatures of 250, 300, 325 and 350 C.