Curable mixture of mesogenic epoxy resins and mesogenic polyamines and cured compositions

Claim 2

A curable composition characterized by comprising (A) one or more epoxy resins containing one or more mesogenic or rodlike moieties represented by the following Formula II and Z⁴ is -CO-O-, -O-CO-, -NR¹-CO- or -CO-NR¹-; and X¹ is a hydrocarbyl group having from 1 to 10, carbon atoms which can contain one or more heteroatoms selected from N, O, or S and may be saturated or unsaturated; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; and each n' is independently zero or one; and with the proviso that Z⁴ is not -CO-O- or -O-CO- when R¹ is a group having only one carbon atom; and (B) a curing amount of one or more polyamines containing one or more mesogenic or rodlike moieties.

Claim 3

A curable composition characterized by comprising (I) an advanced epoxy resin prepared by reacting (A) one or more epoxy resins containing one or more mesogenic or rodlike moieties, said epoxy resin being those represented by either the following Formula I wherein at least 80 percent of the -(Z¹-Z²) n -Z¹-linkages and the glycidyl ether groups are in the para position with respect to each other; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; each Z¹ is independently -CR¹=CR¹-, -CR¹=CR¹-CR¹=CR¹-, -CR¹=N-N=CR¹-, -CR¹=CR¹-CO-O-CH₂-, -CR¹=CR¹-CO-O-CH₂-CH₂-, -CH₂-O-CO-CR¹=CR¹-, -CH₂-CH₂-O-CO-CR¹=CR¹-, -CR¹=CR¹-CO-O-, -O-CO-CR¹=CR¹-, -CO-NR¹, -NR¹-CO-, -CO-NR¹-NR¹-CO-, -C≡C-, -C≡C-C≡C-, -N=N-, -CO-S-, -S-CO-, -CR¹=CR¹-O-CO-CH₂-, -CH₂-CO-O-CR¹=CR¹, -CR¹=CR¹-O-CO-CH₂-CH₂-, -CH₂-CH₂-CO-O-CR¹=CR¹-, -CH₂-CH₂-CO-O-, -O-CO-CH₂-CH₂-, -CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-, a direct single bond when n ≧ 1, Z² is a group represented by a cyclic or bicyclic ring system containing from 5 to 12 carbon atoms and may be cycloaliphatic, polycycloaliphatic, aromatic or a combination thereof; n is 0 to 2; each Z' is independently a -CO-, -O-CO-, -CO-O-, -CO-NR¹-, or -NR¹-CO-group and each n' independently has a value of zero or one; with the proviso that each Z¹ can also independently be -CR¹=N-, -N=CR¹-, -CO-CR¹=CR¹-, -CR¹=CR¹-CO-, -CO-O-, and -O-CO- when Z² is not a benzene ring and when n≠0; or the following Formula II and Z⁴ is -CO-O-, -O-CO-, -NR¹-CO- or -CO-NR¹-; X¹ is a hydrocarbyl group having from 1 to about 10 carbon atoms which can contain one or more heteroatoms selected from N, O, or S and may be saturated or unsaturated; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to about 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; and each n' is independently zero or one; or any combination of any two or more epoxy resins represented by the aforementioned Formulas I and II; with (B) at least one compound having an average of more than one active hydrogen atom per molecule; and wherein components (A) and (B) are employed in quantities which provide a ratio of active hydrogen atoms per epoxide group of from 0.01:1 to 0.95:1; and (II) a curing amount of one or more polyamines containing one or more mesogenic or rodlike moieties.

Claim 4

A curable composition of Claim 3 wherein (a) component (B) is hydroquinone, bisphenol A, 4,4'-dihydroxydiphenylmethane, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide, 4,4'-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 3,3',5,5'-tetrachlorobisphenol A, 3,3'-dimethoxybisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-α,α'-diethylstilbene, 4,4'-dihydroxy-α-methylstilbene, 4,4'-dihydroxybenzanilide, 4,4'-dihydroxy-2,2'-dimethylazoxybenzene, 4,4'-dihydroxy-α-cyanostilbene, bis(4-hydroxyphenyl)terephthalate, N,N'-bis(4-hydroxyphenyl)terephthalamide, bis(4'-hydroxybiphenyl)terephthalate, 4,4'-dihydroxyphenylbenzoate, bis(4'-hydroxyphenyl)-1,4-benzenediimine, 4,4''-dihydroxybiphenylbenzoate, 1,4-bis(4'-hydroxyphenyl-1'-carboxamide)benzene, 1,4-bis(4'-hydroxyphenyl-1'-carboxy)benzene, 4,4'-bis(4''-hydroxyphenyl-1''-carboxy)biphenyl, terephthalic acid, 4,4'-benzanilide dicarboxylic acid, 4,4'-phenylbenzoate dicarboxylic acid, 4,4'-stilbenedicarboxylic acid, aniline, 4'-sulfonamido-N-phenylbenzamide, 4'-sulfonamido-N'-phenyl-4-chlorobenzamide, 4-amino-1-phenylbenzoate, 4-amino-N-phenylbenzamide, N-phenyl-4-aminophenyl-1-carboxamide, phenyl-4-aminobenzoate, biphenyl-4-aminobenzoate, 1-phenyl-4'-aminophenylterephthalate and mixtures thereof; and (b) components (A) and (B) are employed in amounts which provide a ratio of active hydrogen atoms per epoxide group of from 0.1:1 to 0.5:1.

Claim 5

A curable composition characterized by comprising (I) a blend comprising (A) one or more epoxy resins or monoepoxide compounds containing one or more mesogenic or rodlike moieties represented by either the following Formula I wherein at least 80 percent of the -(Z¹-Z²) n -Z¹- linkages and the glycidyl ether groups are in the para position with respect to each other; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having suitably from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; each Z¹ is independently -CR¹=CR¹-, -CR¹=CR¹-CR¹=CR¹-, -CR¹=N-N=CR¹-, -CR¹=CR¹-CO-O-CH₂-, -CR¹=CR¹-CO-O-CH₂-CH₂-, -CH₂-O-CO-CR¹=CR¹-, -CH₂-CH₂-O-CO-CR¹=CR¹-, -CR¹=CR¹-CO-O-, -O-CO-CR¹=CR¹-, -CO-NR¹-, -NR¹-CO-,-CO-NR¹-NR¹-CO-, -C≡C-, -C≡C-C≡C-, -CR¹=CR¹-O-CO-CH₂-, -CH₂-CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-CH₂-CH₂-, -CH₂-CH₂-CO-O-CR¹=CR¹-, -CH₂-CH₂-CO-O-, -O-CO-CH₂-CH₂-, -CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-, Z² is a group represented by a cyclic or bicyclic ring system containing from 5 to 12 carbon atoms and may be cycloaliphatic, polycycloaliphatic, aromatic or a combination thereof; n is 0 to 2; each Z' is independently a -CO-, -O-CO-, -CO-O-, -CO-NR¹-, or -NR¹-CO- group and each n' independently has a value of zero or one; with the proviso that: (a) both of the R¹ groups in the -CR¹=CR¹- group cannot simultaneously be a hydrogen atom; (b) each Z¹ can also independently be -CR¹=N-, N=CR¹-, -CO-CR¹=CR¹- and -CR¹=CR¹-CO- when Z² is not a benzene ring and n≠0; (c) R¹ in the -CR¹=N- and -N=CR¹- groups is other than hydrogen; (d) when n=1, either one of Z¹ can also be selected from the group consisting of -CH=CH-, -N=N-, -CO-S-, -S-CO-, -CH=N-, -N=CH-, -O-CO-,-CO-O- and a direct single bond provided that the other Z¹ group is not selected from this same group or is not selected from a group selected from the group consisting of and when (i) each n' is zero, or (ii) when one n'= zero and one n'=1 with Z' being -O-CO-or -CO-O- and R¹ is a group having only one carbon atom; (e) when n=2, one or two Z¹ groups can also independently be selected from the group consisting of -CH=CH-, -N=N-, -CO-S-, -S-CO-, -CH=N-, -N=CH-, -O-CO-, -CO-O-, and a direct single bond, provided that the remaining Z¹ groups are not selected from this group; (f) when one Z¹ is wherein (i) when each n'=1 with each Z' being - O-CO- or -CO-O-, or (ii) when one n'=1 with Z' being -O-CO- or -CO-O- and the other n'= zero resulting in the other Z' being a direct bond and R¹ is a group having only one carbon atom, then n must have a value of 1 or 2 and R¹ is a group having only one carbon atom; or the following Formula II and Z⁴ is -CO-O-, -O-CO-, -NR¹-CO- or -CO-NR¹-; and X¹ is a hydrocarbyl group having from 1 to 10, carbon atoms which can contain one or more heteroatoms selected from N, O, or S and may be saturated or unsaturated; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; and each n' is independently zero or one; and with the proviso that Z⁴ is not -CO-O- or - O-CO- when R¹ is a group having only one carbon atom; or the following Formula III wherein at least 80 percent of the -(Z⁵-Z²) n -Z⁵- linkages and the glycidyl ether groups are in the para position with respect to each other; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having suitably from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; each Z⁵ is independently -CR¹=CR¹-, -CR¹=CR¹-CR¹=CR¹-, -CR¹=N-N=CR¹-, -CR¹=CR¹-CO-O-CH₂-, -CR¹=CR¹-CO-O-CH₂-CH₂-, -CH₂-O-CO-CR¹=CR¹-, -CH₂-CH₂-O-CO-CR¹=CR¹-, -CR¹=CR¹-CO-O-, -O-CO-CR¹=CR¹-, -N=N-,-CO-NR¹-, -NR¹-CO-, -CO-NR¹-NR¹-CO-, -C≡C-, -C≡C-C≡C-, -CO-S-, -S-CO-, -CR¹=N-, -N=CR¹-, -CO-O-, -O-CO-, -CR¹=CR¹-O-CO-CH₂-, -CH₂-CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-CH₂-CH₂-, -CH₂-CH₂-CO-O-CR¹=CR¹-, -CH₂-CH₂-CO-O-, -O-CO-CH₂-CH₂-, -CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-, a direct single bond when n≧1, Z² is a group represented by a cyclic or bicyclic ring system containing from 5 to 12 carbon atoms and may be cycloaliphatic, polycycloaliphatic, aromatic or a combination thereof; n is zero or two; each Z' is independently a -CO-, -O-CO-, -CO-O-, -CO-NR¹-, or -NR¹-CO- group; and each n' is independently zero or one; or by the following Formula IV Z⁴ is -CO-O-, -O-CO-, -NR¹-CO or -CO-NR¹-; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 tot 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; X¹ is a hydrocarbyl group having from 1 to about 10 carbon atoms which can contain one or more heteroatoms selected from N, O or or S and may be saturated or unsaturated; and each n' is independently zero or one; or any combination of any two or more epoxy resins or monoepoxide compounds represented by the aforementioned Formulas I, II, III and IV; (B) one or more polyepoxides which are substantially free of mesogenic or rodlike moieties; and (II) a curing amount of one or more polyamines containing one or more mesogenic or rodlike moieties.

Claim 6

A curable composition characterized by comprising (I) a blend comprising (A) an advanced epoxy resin prepared by reacting (1) one or more epoxy resins containing one or more mesogenic or rodlike moieties, said epoxy resin being those represented by either the following Formula I wherein at least 80 percent of the -(Z¹-Z²) n -Z¹- linkages and the glycidyl ether groups are in the para position with respect to each other; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; each Z¹ is independently -CR¹=CR¹-, -CR¹=CR¹-CR¹=CR¹-, -CR¹=N-N=CR¹-, -CR¹=CR¹-CO-O-CH₂-, -CR¹=CR¹-CO-O-CH₂-CH₂-, -CH₂-O-CO-CR¹=CR¹-, -CH₂-CH₂-O-CO-CR¹=CR¹-, -CR¹=CR¹-CO-O-, -O-CO-CR¹=CR¹-, -CO-NR¹-, -NR¹-CO-, -CO-NR¹-NR¹-CO-, -C≡C-, -C≡C-C≡C-, -N=N-, -CO-S-, -S-CO-, -CR¹=CR¹-O-CO-CH₂-, -CH₂-CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-CH₂-CH₂-, -CH₂-CH₂-CO-O-CR¹=CR¹-, -CH₂-CH₂-CO-O-, -O-CO-CH₂-CH₂-, -CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-, a direct single bond when n ≧ 1, Z² is a group represented by a cyclic or bicyclic ring system containing from 5 to 12 carbon atoms and may be cycloaliphatic, polycycloaliphatic, aromatic or a combination thereof; n is 0 to 2; each Z' is independently a -CO-, -O-CO-, -CO-O-, -CO-NR¹-, or -NR¹-CO- group and each n' independently has a value of zero or one; with the proviso that each Z¹ can also independently be -CR¹=N-, -N=CR¹-, -CO-CR¹=CR¹-, -CR¹=CR¹-CO-, -CO-O-, and -O-CO- when Z² is not a benzene ring and when n≠0; or the following Formula II and Z⁴ is -CO-O-, -O-CO-, -NR¹-CO- or -CO-NR¹-; X¹ is a hydrocarbyl group having from 1 to 10 carbon atoms which can contain one or more heteroatoms selected from N, O, or S and may be saturated or unsaturated; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; and each n' is independently zero or one; or any combination of any two or more epoxy resins represented by the aforementioned Formulas I and II; with (2) at least one compound having an average of more than one active hydrogen atom per molecule; and wherein components (1) and (2) are employed in quantities which provide a ratio of active hydrogen atoms per epoxide group of from 0.01:1 to 0.95:1; and (B) one or more polyepoxides which are substantially free of mesogenic or rodlike moieties; and (II) a curing amount of one or more polyamines containing one or more mesogenic or rodlike moieties.

Claim 7

A curable composition characterized by comprising (I) a blend comprising (A) one or more epoxy resins containing an average of more than one vicinal epoxide group per molecule and one or more mesogenic or rodlike moieties per molecule; and (B) one or more compounds containing only one vicinal epoxide group per molecule and one or more mesogenic or rodlike moieties per molecule; and (II) at least one polyamine containing one or more mesogenic or rodlike moieties.

Claim 8

A curable composition of Claim 1, 2, 3, 4, 5, 6, or 7 wherein said polyamine containing one or more mesogenic or rodlike moieties is represented by the following Formula XIX wherein at least 80 percent of the -(Z¹-Z²) n -Z¹- linkages and the Z⁹ groups are in the para position with respect to each other; each R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 12 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having suitably from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; each Z¹ is independently -CR¹=CR¹-, -CR¹=CR¹-CR¹=CR¹-, -CR¹=N-N=CR¹-, -CR¹=CR¹-CO-O-CH₂-, -CR¹=CR¹-CO-O-CH₂-CH₂-, -CH₂-O-CO-CR¹=CR¹-, -CH₂-CH₂-O-CO-CR¹=CR¹-, -CR¹=CR¹-CO-O-, -O-CO-CR¹=CR¹-, -CO-NR¹-, -NR¹-CO-, -CO-NR¹-NR¹-CO-, -C≡C-, -C≡C-C≡C-, -N=N-, -CO-S-, -S-CO-, -CR¹=N-, -N=CR¹-, -CO-CR¹=CR¹-, -CR¹=CR¹-CO-, -CR¹=CR¹-O-CO-CH₂-, -CH₂-CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-CH₂-CH₂-, -CH₂-CH₂-CO-O-CR¹=CR¹-, -CH₂-CH₂-CO-O-, -O-CO-CH₂-CH₂-, -CO-O-CR¹=CR¹-, -CR¹=CR¹-O-CO-, Z² is a group represented by a cyclic or bicyclic ring system containing from 5 to 12 carbon atoms and may be cycloaliphatic, polycycloaliphatic, aromatic or a combination thereof; n is 0 to 2; each Z⁹ is independently a -NHR¹, -O-(CHR¹) n -CHR¹-NHR¹, -NR¹-(CHR¹) n -CHR¹-NHR¹, each Z' is independently a -CO-, -O-CO-,-CO-O-, -CO-NR¹-, or -NR¹-CO- group and each n' independently has a value of zero or one; or the following Formula XX Formula XX   Z⁹-Z³-Z⁹ wherein Z³ is and Z⁴ is -CO-O-, -O-CO-, -NR¹-CO- or -CO-NR¹-; X¹ is a hydrocarbyl group having from 1 to 10 carbon atoms which can contain one or more heteroatoms selected from N, O, S and the like and may be saturated or unsaturated; each R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having suitably from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; and each n' is independently zero or one; and Z⁹ is as hereinbefore defined.

Claim 9

The product resulting from curing the curable composition of Claim 8.

Claim 10

The product of Claim 9 wherein said curable composition is oriented prior to and/or during curing of the curable composition.

Claim 11

The product of Claim 10 wherein said orientation is accomplished by the application of an electric field or magnetic field or drawing and/or shear flow or any combination thereof.

Claim 12

The product resulting from curing a curable composition comprising (A) at least one epoxy resin containing one or more mesogenic or rodlike moieties, said epoxy resin being represented by the following Formula I wherein at least 80 percent of the -(Z¹-Z²) n -Z¹- linkages and the glycidyl ether groups are in the para position with respect to each other; each R and R¹ is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or - C≡N; Z², Z', n and n' are as hereinbefore defined; with the proviso that: (a) when n=1, either one of Z¹ is selected from the group consisting of -CH=CH-, -N=N-, -CO-S-, -S-CO-, -CH=N-, -N=CH-, -O-CO-,-CO-O- and a direct single bond provided that the other Z¹ group is selected from this same group or is selected from a group selected from the group consisting of and when (i) each n' is zero, or (ii) when one n'= zero and one n'=1 with Z' being -O-CO-or -CO-O- and R¹ is a group having only one carbon atom; (b) when n=2, one or two Z¹ groups are independently selected from the group consisting of -CH=CH-, -N=N-, -CO-S-, -S-CO-, -CH=N-, -N=CH-, -O-CO-, -CO-O-, and a direct single bond, provided that the remaining Z¹ groups are selected from this group; (c) when one Z¹ is wherein (i) when each n'=1 with each Z' being -O-CO- or -CO-O-, or (ii) when one n'=1 with Z' being -O-CO- or -CO-O- and the other n'= zero resulting in the other Z' being a direct bond and R¹ is a group having only one carbon atom, then n must have a value of 1 or 2 and R¹ is a group having only one carbon atom; and (B) a curing amount of one or more polyamines containing one or more mesogenic or rodlike moieties; and wherein said curing is conducted outside the liquid crystal transition temperature range of said epoxy resin and with the proviso that the epoxy resin and curing agent are not simultaneously the diglycidyl ether of 4,4'-dihydroxyphenylbenzoate and 4,4'-diaminophenylbenzoate, respectively.

Claim 13

The product characterized by resulting from curing a curable composition comprising (A) at least one epoxy resin containing one or more mesogenic or rodlike moieties said epoxy resin being represented by the following Formula II and Z⁴ is -CO-O- or -O-CO-; each R is independently hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms; R¹ is a group having only one carbon atom each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms, a halogen atom, -NO₂, or -C≡N; and (B) a curing amount of one or more polyamines containing one or more mesogenic or rodlike moieties; and wherein said curing is conducted outside the liquid crystal transition temperature range of said epoxy resin.

Claim 14

The product of Claim 12 resulting from the application of an electric field or magnetic field or drawing and/or shear flow or any combination thereof prior to and/or during cure.

Claim 15

The product of Claim 13 resulting from the application of an electric field or magnetic field or drawing and/or shear flow or any combination thereof prior to and/or during cure.