Claims
- 1. An advanced resin composition prepared by reacting
- (A) at least one epoxy resin having an average of more than one vicinal epoxy group per molecule; with
- (B) at least one compound having an average of more than one active hydrogen atom and one or more mesogenic moieties per molecule represented by the following Formulas I, II or III ##STR14## wherein each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, --NO.sub.2 or --C.tbd.N; each X' is independently a hydroxyl group, a carboxylic acid group or the group represented by Formula IV ##STR15## each Z is independently --CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.N--N.dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --CO--O--CH.sub.2 --, --CR.sup.1 .dbd.CR.sup.1 --CO--O--CH.sub.2 --CH.sub.2 --, --CH.sub.2 --O--CO--CR.sup.1 .dbd.CR.sup.1 --, --CH.sub.2 --CH.sub.2 --O--CO--CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --CO--O--, --O--CO--CR.sup.1 .dbd.CR.sup.1 --, --N.dbd.N--, --CO--NR.sup.1 --, --NR.sup.1 --CO--, --CO--NR.sup.1 --NR.sup.1 --CO--, --C.tbd.C--, --C.tbd.C--C.tbd.C--, --CO--S--, --S--CO--, --CO--O--, --O--CO--, --CR.sup.1 .dbd.CR.sup.1 --O--CO--CH.sub.2 --CH.sub.2, --CH.sub.2 --CO--O--CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --O--CO--CH.sub.2 --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --CO--O--CR.sup.1 .dbd.CR.sup.1 --, --CH.sub.2 --CH.sub.2 --CO--O--, --O--CO--CH.sub.2 --CH.sub.2 --, --CO--O--CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --O--CO--, a direct single bond when n.gtoreq.1, ##STR16## Z' is independently --O--CO--, --CO--O--, --NR.sup.1 --CO--, or --CO--NR.sup.1 --; each n' is independently zero or 1; R.sup.1 is independently a hydrogen atom or an alkyl group having from 1 to about 4 carbon atoms; Z.sup.6 is a divalent hydrocarbyl group having from 1 to about 12 carbon atoms, --SO--, --SO.sub.2 --, --S--, --S--S--, --O--, or --CO--; each Z.sup.1 is independently --CO--NH--, or --NH--CO--; Z.sup.2 is a group represented by a cyclic or bicyclic ring system containing from 5 to about 12 carbon atoms or a group represented by Formula V; ##STR17## Z.sup.3 is NH.sub.2 --, NH.sub.2 --SO.sub.2 --, NH.sub.2 --CO--, NH.sub.2 --Z.sup.5 --O--CO--, or NH.sub.2 --Z.sup.5 --O--; each Z.sup.4 is independently --CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.N--N.dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --CO--O--CH.sub.2 --, --CR.sup.1 .dbd.CR.sup.1 --CO--O--CH.sub.2 --CH.sub.2 --, --CH.sub.2 --O--CO--CR.sup.1 .dbd.CR.sup.1 --, --CH.sub.2 --CH.sub.2 --O--CO--CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --CO--O--, --O--CO--CR.sup.1 .dbd.CR.sup.1 --, --N.dbd.N--, --CO--NR.sup.1 --, --NR.sup.1 --CO--, --CO--NR.sup.1 --NR.sup.1 --CO--, --C.tbd.C--, --C.tbd.C--C.tbd.C--, --CO--S--, -- S--CO--, --CR.sup.1 .dbd.N--, --N.dbd.CR.sup.1 --, --CO--O--, --O--CO--, --CR.sup.1 .dbd.CR.sup.1 --O--CO--CH.sub.2 --, --CH.sub.2 --CO--O--CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --O--CO--CH.sub.2 --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --CO--O--CR.sup.1 .dbd.CR.sup.1 --, --CH.sub.2 --CH.sub.2 --CO--O--, --O--CO--CH.sub.2 --CH.sub.2 --, --CO--O--CR.sup.1 .dbd.CR.sup.1 --, --CR.sup.1 .dbd.CR.sup.1 --O--CO--, a direct single bond, ##STR18## Z.sup.5 is an alkylene or cycloalkylene group having from 1 to about 10 carbon atoms; Z.sup.7 is the same as Z.sup.4 with the proviso that it can also independently be a divalent hydrocarbyl group having from 1 to about 4, carbon atoms, --SO--, --SO.sub.2 --, --S--, --S--S--, --O--, or --CO--; v has a value of 1 or 2, and n has an average value of zero to about 6;
- wherein components (A) and (B) are meltable or soluble at the reaction conditions and are employed in amounts which provide a ratio of active hydrogen atoms per vicinal epoxy group of from about 0.01:1 to about 1.05:1;
- with the proviso that
- (a) at least about 80 percent of the Z and X' groups are in the para position with respect to each other in Formula I, and
- (b) at least about 80 percent of the Z.sup.3 and Z.sup.4 groups are in the para position with respect to each other in Formula III,
- (c) component (B) cannot be a compound represented by the formula ##STR19## wherein each X.sup.a is independently hydrogen, hydroxyl, a nitro, alkyl, aryl, alkaryl, aralkyl, halogen, alkoxy alkaryloxy, aralkyloxy or aryloxy group;
- (d) when component (B) is a compound represented by Formula III wherein Z.sup.3 is NH.sub.2 --Z.sub.5 --O-- or NH.sub.2 --Z.sub.5 --O--CO--, Z.sub.5 is an alkylene group having from 1 to 10 carbon atoms, Z.sup.4 is a direct single bond, n has a value of zero, X is hydrogen at all occurrences with the proviso that the single X substituent on the aromatic ring not substituted by Z.sup.3 para to the direct single bond is --NO.sub.2 or --CN and with the proviso that Z.sup.3 is para to the direct single bond, components (A) and (B) are employed in amounts which provide a ratio of amine hydrogen atoms per vicinal epoxy group of from 0.01:1 to about 0.5:1.
- 2. An advanced resin composition of claim 1 wherein components (A) and (B) are employed in amounts which provide a ratio of active hydrogen atoms per vicinal epoxy group of from about 0.96:1 to about 1.05:1.
- 3. An advanced resin composition of claim 1 wherein components (A) and (B) are employed in amounts which provide a ratio of active hydrogen atoms per vicinal epoxy group of from about 0.01:1 to about 0.95:1.
- 4. An advanced resin composition of claim 1 wherein components (A) and (B) are employed in amounts which provide a ratio of active hydrogen atoms per vicinal epoxy group of from about 0.01:1 to about 0.5:1.
- 5. An advanced resin composition of claims 2 or 3 wherein
- (i) component A is an epoxy resin represented by the following Formulas VI, VII, VIII, IX or X ##STR20## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 12 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 6 carbon atoms; Q is a single bond, --CH.sub.2 --S--CH.sub.2 --, --(CH.sub.2).sub.n1 --, or ##STR21## each R is independently hydrogen or an alkyl group having from 1 to about 4 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 6 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, --NO.sub.2 or --C.tbd.N; m has a value from about 1 to about 10; m' has a value from about 0.01 to about 12; m.sup.1 has an average value from about 1 to about 12; m.sup.2 has a value from about 1 to about 12; n has a value of zero or 1; n' has an average value from about zero to about 3; and n.sup.1 has an average value from about 1 to about 10; and
- (ii) component (B) is a compound represented by Formula I wherein each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group containing from 1 to about 6 carbon atoms, a halogen atom or a --NO.sub.2 or --C.tbd.N group; each Z is independently --N.dbd.N--, --CO--NR.sup.1 --, --NR.sup.1 --CO--, --CO--O--, --O--CO--, --CR.sup.1 .dbd.CR.sup.1 --, ##STR22## where each R.sup.1 is independently a hydrogen atom or an alkyl group having from 1 to about 4 carbon atoms; and each Z.sup.6 is independently a divalent hydrocarbyl group having from 1 to about 12 carbon atoms, --SO--, --SO.sub.2 --, --S--, --S--S--, --O--, or --CO--.
- 6. An advanced resin composition of claim 5 wherein
- (i) in component (A) each A is independently a divalent hydrocarbyl group having from 1 to about 6 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 3 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 3 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 6 carbon atoms, chlorine or bromine, --NO.sub.2 or --C.tbd.N; m has a value from about 1 to about 4; m' has a value from about 1 to about 6; m.sup.1 has an average value from about 1 to about 6; m.sup.2 has a value from about 2 to about 6; n has a value of zero or 1; and n' has an average value from about zero to about 1.5; and
- (ii) component (B) is a compound represented by Formula I wherein each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group containing from 1 to about 4 carbon atoms, chlorine or bromine or a --NO.sub.2 or --C.tbd.N group; each X' is a hydroxyl group.
- 7. An advanced resin composition of claim 6 wherein:
- (i) in component (A) each A is independently a divalent hydrocarbyl group having from 1 to about 3 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 3 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 2 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbon atoms, bromine, --NO.sub.2 or --C.tbd.N; m has a value from about 1 to about 2; m' has a value from about 1 to about 3; m.sup.1 has an average value from about 1 to about 3; m.sup.2 has a value from about 2 to about 3; n has a value of 1; and n' has an average value from about zero to about 0.5;
- (ii) component (B) is bis(4-hydroxyphenyl)terephthalate or N,N'-bis(4-hydroxyphenyl)terephthalamide.
- 8. An advanced resin composition of claims 2 or 3 wherein
- (i) component A is an epoxy resin represented by the following Formulas VI, VII, VIII, IX or X ##STR23## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 12 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 6 carbon atoms; Q is a single bond, --CH.sub.2 --S--CH.sub.2 --, --(CH.sub.2).sub.n1 --, or ##STR24## each R is independently hydrogen or an alkyl group having from 1 to about 4 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 6 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, --NO.sub.2 or --C.tbd.N; m has a value from about 1 to about 10; m' has a value from about 0.01 to about 12; m.sup.1 has an average value from about 1 to about 12; m.sup.2 has a value from about 1 to about 12; n has a value of zero or 1; n' has an average value from about zero to about 3; and n.sup.1 has an average value from about 1 to about 10; and
- (ii)component (B) is a compound represented by Formula II wherein each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group containing from 1 to about 6 carbon atoms, a halogen atom or a --NO.sub.2 or --C.tbd.N group; each Z.sup.1 is independently --CO--NH-- or --NH--CO--; each Z.sup.2 is independently a cyclic or bicyclic ring system containing from 5 to about 10 carbon atoms or a group represented by Formula V; and each Z.sup.7 is independently a divalent hydrocarbyl group having from 1 to about 12 carbon atoms, --SO--, --SO.sub.2 --, --S--, --S--S-- --O--, --CO--, --N.dbd.N--, --CO--NR.sup.1 --, --NR.sup.1 --CO--, --CO--O--, --O--CO--, --CR.sup.1 .dbd.CR.sup.1 --, ##STR25## where each R.sup.1 is independently hydrogen or an alkyl group having from 1 to about 4 carbon atoms; and n has a value from zero to about 6.
- 9. An advanced resin composition of claim 8 wherein component (B) is a compound represented by Formula II wherein each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group containing from 1 to about 4 carbon atoms, chlorine or bromine or a --NO.sub.2 or --C.tbd.N group; and each Z.sup.2 is independently a cyclic ring system containing from 5 to about 10 carbon atoms or a group represented by Formula V.
- 10. An advanced resin composition of claim 9 wherein
- (i) in component (A) each A is independently a divalent hydrocarbyl group having from 1 to about 3 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 3 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 2 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbon atoms, bromine, --NO.sub.2 or --C.tbd.N; m has a value from about I to about 2; m' has a value from about 1 to about 3; m.sup.1 has an average value from about 1 to about 3; m.sup.2 has a value from about 2 to about 3; n has a value of 1; and n' has an average value from about zero to about 0.5;
- (ii) component (B) is N,N'-diphenylterephthalamide or a mixture of N,N'-diphenylterephthalamide and N-phenylbenzamide.
- 11. An advanced resin composition of claims 2 or 3 wherein
- (i) component A is an epoxy resin represented by the following Formulas VI, VII, VIII, IX or X ##STR26## wherein each A is independently a divalent hydrocarbyl group having from 1 to about 12 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 6 carbon atoms; Q is a single bond, --CH.sub.2 --S--CH.sub.2 --, --(CH.sub.2).sub.n1 --, or ##STR27## each R is independently hydrogen or an alkyl group having from 1 to about 4 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 6 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, --NO.sub.2 or --C.tbd.N; m has a value from about 1 to about 10; m' has a value from about 0.01 to about 12; m.sup.1 has an average value from about 1 to about 12; m.sup.2 has a value from about 1 to about 12; n has a value of zero or 1; n' has an average value from about zero to about 3; and n.sup.1 has an average value from about 1 to about 10; and
- (ii) component (B) is a compound represented by Formula III wherein each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group containing from 1 to about 6 carbon atoms, a halogen atom or a --NO.sub.2 or --C.tbd.N group; each Z.sup.3 is independently NH.sub.2 -- or NH.sub.2 --SO.sub.2 --; and each Z.sup.4 is independently --N.dbd.N--, --CO--NR.sup.1 --, --NR.sup.1 --CO--, --CO--O--, --O--CO--, --CR.sup.1 .dbd.CR.sup.1 --, ##STR28## where each R.sup.1 is independently a hydrogen atom or an alkyl group having from I to about 4 carbon atoms.
- 12. An advanced resin composition of claim 11 wherein
- (i) in component (A) each A is independently a divalent hydrocarbyl group having from 1 to about 6 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 3 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 3 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 6 carbon atoms, chlorine or bromine, --NO.sub.2 or --C.tbd.N; m has a value from about 1 to about 4; m' has a value from about 1 to about 6; m.sup.1 has an average value from about 1 to about 6; m.sup.2 has a value from about 2 to about 6; n has a value of zero or 1; and n' has an average value from about zero to about 1.5; and
- (ii) component (B) is a compound represented by Formula III wherein each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group containing from 1 to about 4 carbon atoms, chlorine or bromine or a --NO.sub.2 or --C.tbd.N group.
- 13. An advanced resin composition of claim 12 wherein
- (i) in component (A) each A is independently a divalent hydrocarbyl group having from 1 to about 3 carbon atoms, --O--, --S--, --S--S--, --SO--, --SO.sub.2 --, or --CO--; each A' is independently a divalent hydrocarbon group having from 1 to about 3 carbon atoms; each R.sup.2 and R.sup.3 is independently hydrogen, a hydrocarbyl or halohydrocarbyl group having from 1 to about 2 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbon atoms, bromine, --NO.sub.2 or --C.tbd.N; m has a value from about I to about 2; m' has a value from about 1 to about 3; m.sup.1 has an average value from about 1 to about 3; m.sup.2 has a value from about 2 to about 3; n has a value of 1; and n' has an average value from about zero to about 0.5; and
- (ii)component (B) is 4'-sulfonamido-N-phenylbenzamide.
- 14. The advanced resin composition of claim 2 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 15. The advanced resin composition of claims 1, 3 or 4 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 16. The advanced resin composition of claim 5 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 17. The advanced resin composition of claim 6 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 18. The advanced resin composition of claim 7 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 19. The advanced resin composition of claim 8 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 20. The advanced resin composition of claim 9 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 21. The advanced resin composition of claim 10 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 22. The advanced resin composition of claim 11 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 23. The advanced resin composition of claim 12 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
- 24. The advanced resin composition of claim 13 which has been subjected during processing to an electric field, magnetic field, drawing and/or shear flow.
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 07/834,033 filed Feb. 11, 1992 (now abandoned) which is a continuation-in-part of application Ser. No. 07/620,509 filed Nov. 11, 1990 (now abandoned), which is a continuation-in-part of application Ser. No. 07/553,930 filed Jul. 13, 1990 (now abandoned), which is a continuation-in-part of application Ser. No. 07/297,896 filed Jan. 17, 1989 (now abandoned), all of which are incorporated herein by reference in their entirety.
US Referenced Citations (10)
Foreign Referenced Citations (3)
Number |
Date |
Country |
0361852 |
Apr 1990 |
EPX |
361853 |
Apr 1990 |
EPX |
211799A |
Jul 1984 |
DEX |
Non-Patent Literature Citations (3)
Entry |
C. Noel & P. Navard, Prog. Polym. Sci., 16, 55-110 (1991). |
C. K. Ober & R. A. Weiss, "Liquid Crystalline Polymers", R. A. Weiss and C. K. Ober (eds), ACS Symp. Series 435, Am. Chem. Soc., Washington D.C. pp. 1-13 (1990). |
ACS Symposium Series 114, Chapter 17, pp. 259-262, (given Sep. 1978, at the 176th meeting of the American Chemical Society by James R. Griffith). |
Continuation in Parts (4)
|
Number |
Date |
Country |
Parent |
834033 |
Feb 1992 |
|
Parent |
620509 |
Nov 1990 |
|
Parent |
553930 |
Jul 1990 |
|
Parent |
297896 |
Jan 1989 |
|