Claims
- 1. A process for preparing an aromatic 1,3,5-triazine compound from an aromatic nitrile compound which comprises heating the aromatic nitrile compound to a temperature in the range of from about 100.degree. C. to about 700.degree. C. in the presence of a catalyst or mixture of catalysts selected from one or more of the following groups: (A) organic sulfonic and sulfinic acids,
- (B) organic phosphonic and phosphinic acids, and (C) metallic acetylacetonates, at a pressure in the range of from about atmospheric pressures to about 10,000 p.s.i., said process being conducted in the presence of reinforcing filler material.
- 2. An aromatic nitrile-modified (terminated and/or appended) imide prepolymer having one of the following four general structural formulas: ##STR69## which is the reaction product of a tetracarboxylic acid dianhydride (Va), or its derivatives (Vb) having the structural formulas: ##STR70## a diamine having the structural formula:
- (VI) H.sub.2 N--R.sub.2 --NH.sub.2,
- with a nitrile having one of the following structural formulas, if prepolymer (I), (II) or (III) is to be made: ##STR71## or without a nitrile if prepolymer (IV) is to be made, wherein
- n is an integer from 0 to 50, depending on the chemical structural formula or the solubility of the aromatic nitrile-modified prepolymer in organic solvents; n.sub.1 is either 0 or greater than 1, n.sub.2 is a positive integer greater than 1, and the sum of n.sub.1 and n.sub.2 is an integer from 1 to 50;
- R.sub.1, r.sub.2, r.sub.3, and R.sub.4 are aryl radicals, heterocyclic radicals, particularly those heterocyclic radicals containing one, two, or three nitrogen atoms in the ring, or combination of both aryl and heterocyclic radicals; in prepolymer (IV), R.sub.1 and R.sub.2 in the brackets followed by the subscript n.sub.1 cannot contain a nitrile group, whereas R.sub.1 and/or R.sub.2 in the brackets followed by the subscript n.sub.2 must contain a nitrile group; and in the preferred embodiments R.sub.1 is a tetravalent aromatic radical selected from the group consisting of: ##STR72## R.sub.2 is a bivalent aromatic radical selected from the group consisting of: ##STR73## nitrile (VII) is an aromatic nitrile selected from the group consisting of: ##STR74## nitrile (VIIIa) is an aromatic nitrile selected from the group consisting of: ##STR75## nitrile (VIIIb) is the derivative of aromatic nitrile (VIIIa), wherein the dicarboxylic acid anhydride moiety becomes either a diacid, a diester, a halfester or a dicarbonyl halide having the two carboxyl or carbonyl groups in the ortho positions on the aryl ring;
- X.sub.1 and X.sub.2 are monovalent radicals selected from the group consisting of --H, --CN, --F, --Cl, --Br, --NO.sub.2, --CH.sub.3, and ##STR76## where X.sub.1 may or may not be the same group as X.sub.2, and X may be either X.sub.1 or X.sub.2 ; Y is a bivalent radical selected from the group consisting of: ##STR77## and Z.sub.1 and Z.sub.2 are monovalent radicals selected from the group of: hydroxyl, alkyoxyls, aroxyls, and halides, where Z.sub.1 may or may not be the same group as Z.sub.2, and Z may be either Z.sub.1 or Z.sub.2.
- 3. An imide prepolymer of claim 2 wherein the tetracarboxylic acid dianhydride (Va), or its derivatives (Vb) are selected from the group consisting of: ##STR78##
- 4. An imide prepolymer of claim 2 wherein the diamine (VI) is selected from the group consisting of: ##STR79##
- 5. A triazine ring containing or cross-linked polymer composition made by catalytically trimerizing an aromatic nitrile-modified imide prepolymer of claim 2.
- 6. The polymer composition of claim 5 which is catalytically trimerized in the presence of reinforcing filler material.
- 7. An aromatic nitrile-modified (terminated and/or appended) benzimidazole prepolymer having one of the following four general structural formulas: ##STR80## which is the reaction product of a dicarboxylic acid or its derivatives having the structural formula: ##STR81## a tetra-amine having the structural formula: ##STR82## with a nitrile having one of the following structural formulas, if prepolymer (IX), (X) or (XI) is to be made: ##STR83## or without a nitrile if prepolymer (XII) is to be made, wherein n is an integer from 0 to 50, depending on the chemical structural formula or the solubility of the aromatic nitrile-modified prepolymer in organic solvents; n.sub.1 is either 0 or greater than 1, n.sub.2 is a positive integer greater than 1, and the sum of n.sub.1 and n.sub.2 is an integer from 1 to 50;
- R.sub.1, r.sub.2, r.sub.3, and R.sub.4 are aryl radicals, heterocyclic radicals, particularly those heterocyclic radicals containing one, two, or three nitrogen atoms in the ring, or combination of both aryl and heterocyclic radicals; in prepolymer (XII), R.sub.1 and R.sub.2 in the brackets followed by the subscript n.sub.1 cannot contain a nitrile group, whereas R.sub.1 and/or R.sub.2 in the brackets followed by the subscript n.sub.2 must contain a nitrile group; and in the preferred embodiments R.sub.1 is a tetravalent aromatic radical selected from the group consisting of: ##STR84## R.sub.2 is a bivalent aromatic radical selected from the group consisting of: ##STR85## nitrile (XV) is an aromatic nitrile selected from the group consisting of: ##STR86## nitrile (XVI) is an aromatic nitrile selected from the group consisting of: ##STR87## X.sub.1 and X.sub.2 are monovalent radicals selected from the group consisting of --H, --CN, --F, --Cl, --Br, --NO.sub.2, --CH.sub.3, and ##STR88## where X.sub.1 may or may not be the same group as X.sub.2, and X may be either X.sub.1 or X.sub.2 ;
- Y is a bivalent radical selected from the group consisting of: ##STR89## and Z is a monovalent radical selected from the group consisting of: hydroxyl, alkyoxyls, aroxyls, and halides.
- 8. A benzimidazole prepolymer of claim 7 wherein the dicarboxylic acid or its derivatives (XIII) is selected from the group consisting of: ##STR90##
- 9. A benzimidazole prepolymer of claim 7 wherein the tetra-amine (XIV) is selected from the group consisting of: ##STR91##
- 10. A triazine ring containing or cross-linked polymer composition made by catalytically trimerizing an aromatic nitrile-modified benzimidazole prepolymer of claim 7.
- 11. The polymer composition of claim 10 which is catalytically trimerized in the presence of reinforcing filler material.
- 12. An aromatic nitrile-modified (terminated and/or appended) imidazopyrrolone prepolymer having one of the following four general structural formulas: ##STR92## which is the reaction product of a tetracarboxylic acid dianhydride (XXIa), or its derivatives (XXIb) having the structural formulas: ##STR93## a tetra-amine having the structural formula: ##STR94## with a nitrile having one of the following structural formulas, if prepolymer (XVII), (XVIII) or (XIX) is to be made: ##STR95## or without a nitrile if prepolymer (XX) is to be made, wherein
- n is an integer from 0 to 30, depending on the chemical structural formula or the solubility of the aromatic nitrile-modified prepolymer in organic solvents; n.sub.1 is either 0 or greater than 1, n.sub.2 is a positive integer greater than 1, and sum of n.sub.1 and n.sub.2 is an integer from 1 to 50;
- R.sub.1 and R.sub.4 are aryl radicals, heterocyclic radicals, particularly those heterocyclic radicals containing one, two or three nitrogen atoms in the ring, or combination of both aryl and heterocyclic radicals; in prepolymer (XX), R.sub.1 in the brackets followed by the subscript n.sub.1 cannot contain a nitrile group, whereas R.sub.1 in the brackets followed by the subscript n.sub.2 must contain a nitrile group; and in the preferred embodiments R.sub.1 is a tetravalent aromatic radical selected from the group consisting of: ##STR96## nitrile (XXIIIa) is an aromatic nitrile selected from the group consisting of: ##STR97## nitrile (XXIIIb) is the derivative of aromatic nitrile (XXIIIa), wherein the dicarboxylic acid anhydride moiety becomes either a diacid, a diester, a halfester or a dicarbonyl halide having the two carboxyl or carbonyl groups in the ortho positions on the aryl ring; nitrile (XXIV) is an aromatic nitrile selected from the group consisting of: ##STR98## X.sub.1 and X.sub.2 are monovalent radicals selected from the group consisting of --H, --CN, --F, --Cl, --Br, --NO.sub.2, --CH.sub.3, and ##STR99## where X.sub.1 may or may not be the same group as X.sub.2, and X may be either X.sub.1 or X.sub.2 ; Y is a bivalent radical selected from the group consisting of: ##STR100## and Z.sub.1 and Z.sub.2 are monovalent radicals selected from the group consisting of: hydroxyl, alkyoxyls, aroxyls, and halides, where Z.sub.1 may or may not be the same group as Z.sub.2, and Z may be either Z.sub.1 or Z.sub.2.
- 13. An imidazopyrrolone prepolymer of claim 12 wherein the tetracarboxylic acid dianhydride (XXIa), or its derivatives (XXIb) are selected from the group consisting of: ##STR101## and their ester and halide derivatives, respectively.
- 14. An imidazopyrrolone prepolymer of claim 12 wherein the tetraamine (XXII) is selected from the group consisting of: ##STR102##
- 15. An imidazopyrrolone prepolymer of claim 12 wherein n is zero.
- 16. A triazine ring containing or cross-linked polymer composition made by catalytically trimerizing an aromatic nitrile-modified imidazopyrrolone prepolymer of claim 12.
- 17. The polymer composition of claim 16 which is catalytically trimerized in the presence of reinforcing filler material.
- 18. An aromatic nitrile-modified (terminated and/or appended) quinoxaline prepolymer having one of the following four general structural formulas: ##STR103## which is the reaction product of a diglyoxal having the structural formula: ##STR104## a tetra-amine having the structural formula: ##STR105## with a nitrile having one of the following structural formulas, if prepolymer (XXV), (XXVI) or (XXVII) is to be made: ##STR106## or without a nitrile if prepolymer (XXVIII) is to be made, wherein n is an integer from 0 to 100, depending on the chemical structural formula or the solubility of the aromatic nitrile-modified prepolymer in organic solvents; n.sub.1 is either 0 or greater than 1, n.sub.2 is a positive integer greater than 1, and the sum of n.sub.1 and n.sub.2 is an integer from 1 to 100;
- R.sub.1, r.sub.2, and R.sub.4 are aryl radicals, heterocyclic radicals, particularly those heterocyclic radicals containing one, two, or three nitrogen atoms in the ring, or a combination of both aryl and heterocyclic radicals; in prepolymer (XXVIII), R.sub.1 and R.sub.2 in the brackets followed by the subscript n.sub.2 must contain a nitrile group; and in the preferred embodiments R.sub.1 is a tetravalent aromatic radical selected from the group consisting of: ##STR107## R.sub.2 is a bivalent aromatic radical selected from the group consisting of: ##STR108## nitrile (XXXI) is an aromatic nitrile selected from the group consisting of: ##STR109## X.sub.1 and X.sub.2 are monovalent radicals selected from the group consisting of --H, --CN, --F, --Cl, --Br, --NO.sub.2, --CH.sub.3, and ##STR110## where X.sub.1 may or may not be the same group as X.sub.2, and X may be either X.sub.1 or X.sub.2 ;
- Y is a bivalent radical selected from the group consisting of: ##STR111## and A is a monovalent radical selected from the group consisting of: ##STR112##
- 19. A triazine ring containing or cross-linked polymer composition made by catalytically trimerizing an aromatic nitrile-modified quinoxaline prepolymer of claim 18.
- 20. The polymer composition of claim 19 which is catalytically trimerized in the presence of reinforcing filler material.
- 21. An aromatic nitrile-modified (terminated and/or appended) precopolymer made by combining two, three or four of the following groups of monomeric reactants:
- (A) a tetracarboxylic acid dianhydride (Va) or its derivatives (Vb) having the structural formulas: ##STR113## and a diamine having the structural formula:
- (VI) H.sub.2 N--R.sub.2 --NH.sub.2 ;
- (b) a dicarboxylic acid or its derivatives having the structural formula: ##STR114## and a tetra-amine having the structural formula: ##STR115## (C) a tetracarboxylic acid dianhydride (XXIa) or its derivatives (XXIb) having the structural formulas: ##STR116## and a tetra-amine having the structural formula: ##STR117## (D) a diglyoxal having the structural formula: ##STR118## and a tetra-amine having the structural formula: ##STR119## with or without one or more appropriate terminating nitrile reagents having the following structural formulas: ##STR120## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are aryl radicals, heterocyclic radicals, particularly those heterocyclic radicals containing one, two or three nitrogen atoms in the ring, or a combination of both aryl and heterocyclic radicals; and in the preferred embodiment R.sub.1 is a tetravalent aromatic radical selected from the group consisting of: ##STR121## R.sub.2 is a bivalent aromatic radical selected from the group consisting of: ##STR122## nitrile (VII) is an aromatic nitrile selected from the group consisting of: ##STR123## nitrile (VIIIa) is an aromatic nitrile selected from the group consisting of: ##STR124## nitrile (VIIIb) is the derivative of aromatic nitrile (VIIIa), wherein the dicarboxylic acid anhydride moiety becomes either a diacid, a diester, a halfester or a dicarbonyl halide having the two carboxyl or carbonyl groups in the ortho positions on the aryl ring;
- nitrile (XV) is an aromatic nitrile selected from the group consisting of: ##STR125## nitrile (XVI) is an aromatic nitrile selected from the group consisting of: ##STR126## nitrile (XXIV) is an aromatic nitrile selected from the group consisting of: ##STR127## X.sub.1 and X.sub.2 are monovalent radicals selected from the group consisting of --H, --CN, --F, --Cl, --Br, --NO.sub.2, --CH.sub.3, and ##STR128## where X.sub.1 may or may not be the same group as X.sub.2, and X may be either X.sub.1 or X.sub.2 ;
- Y is a bivalent radical selected from the group consisting of: ##STR129## Z.sub.1 and Z.sub.2 are monovalent radicals selected from the group consisting of: hydroxyl, alkyoxyls, aroxyls, and halides, where Z.sub.1 may or may not be the same group as Z.sub.2, and may be either Z.sub.1 or Z.sub.2
- and A is a monovalent radical selected from the group consisting of: ##STR130##
- 22. A triazine ring containing or cross-linked copolymer composition made by catalytically trimerizing an aromatic nitrile-modified precopolymer of claim 21.
- 23. The copolymer composition of claim 22 which is catalytically trimerized in the presence of reinforcing filler material.
ORIGIN OF THE INVENTION:
The invention described herein was made by an employee of the United States Government and may be manufactured and used by or for the Government for governmental purposes without the payment or any royalties thereon or therefor.
US Referenced Citations (14)
Divisions (1)
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Number |
Date |
Country |
Parent |
513613 |
Oct 1974 |
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