# US 4,393,194 A · Substituted-quaterphenylene polyamide > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,393,194 A - Document ID: US4393194A - Status: Granted - Kind: A - Application number: 06/239,180 - Filed: 1981-03-02 - Granted: 1983-07-12 - Earliest claimed: 1981-03-02 - Assignees: Polaroid Corporation - Inventors: Russell A. Gaudiana; Palaiyur S. Kalyanaraman - Web page: https://patentgrep.com/patent/US4393194A ## CPC - C07C 205/11: having nitro groups bound to carbon atoms of six-membered aromatic rings - C08G 69/26: derived from polyamines and polycarboxylic acids - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract A class of polyamides comprising recurring units having substituted-quaterphenylene radicals is disclosed. The polymers comprise recurring units of the formula ##STR1## wherein each of A and B is a divalent radical, except that B can represent a single bond; R and R.sup.1 are each hydrogen, alkyl, aryl, alkaryl or aralkyl; and c is zero or one; and wherein, when c is one, at least one of A and B is a substituted-quaterphenylene radical having the formula ##STR2## where each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, the U, W.sub.p and X.sub.r substitution being sufficient to provide the radical with a non-coplanar molecular configuration; and wherein, when c is zero, A is a substituted-quaterphenylene radical as aforedescribed. The polyamide materials exhibit solubility in select solvents including those of the non-amide type and are characterized by high electron density substantially cylindrically distributed about the long axis thereof. The molecularly oriented polymers are optically uniaxial and are suited to application in optical filter and other devices where a highly refractive and birefringent polymeric material is desired. ## Claims ### Claim 1 A rigid rod-like film- or fiber-forming polymer comprising recurring units of the formula ##STR39## wherein A is a divalent radical and B is a divalent radical or B represents a single bond; R and R.sup.1 are each hydrogen, alkyl, aryl, alkaryl or aralkyl; and c is zero or one; and wherein, when c is one, at least one of A and B is a divalent substituted-quaterphenylene radical having the formula: ##STR40## where each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide the aromatic nuclei of said radical with a non-coplanar molecular configuration with respect to each other; and wherein, when c is zero, A is a divalent substituted-quaterphenylene radical having the aforesaid formula. ### Claim 2 (depends on 1) The polymer of claim 1 wherein said c is the integer one. ### Claim 3 (depends on 2) The polymer of claim 2 wherein each of said A and B radicals is a divalent substituted-quaterphenylene radical having the formula ##STR41## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide each said radical with a non-coplanar molecular configuration. ### Claim 4 (depends on 3) The polymer of claim 3 wherein each said A and B radical is a divalent substituted-quaterphenylene radical having the formula ##STR42## wherein each of U and X is a substituent other than hydrogen. ### Claim 5 (depends on 4) The polymer of claim 4 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 6 (depends on 5) The polymer of claim 5 wherein each said U and X substituent is trifluoromethyl. ### Claim 7 (depends on 2) The polymer of claim 2 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR43## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 8 (depends on 7) The polymer of claim 7 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR44## wherein each of U and X is a substituent other than hydrogen. ### Claim 9 (depends on 8) The polymer of claim 8 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 10 (depends on 9) The polymer of claim 9 wherein each said U and X substituent is trifluoromethyl. ### Claim 11 (depends on 2) The polymer of claim 2 wherein said divalent radical B is substituted-quaterphenylene radical having the formula ##STR45## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is a hydrogen or a substituent other than hydrogen, and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 12 (depends on 11) The polymer of claim 11 wherein said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR46## wherein each of U and X is a substituent other than hydrogen. ### Claim 13 (depends on 12) The polymer of claim 12 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 14 (depends on 13) The polymer of claim 13 wherein each said U and X substituent is trifluoromethyl. ### Claim 15 (depends on 2) The polymer of claim 2 wherein said B represents a single bond and said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR47## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said divalent radical A with a non-coplanar molecular configuration. ### Claim 16 (depends on 15) The polymer of claim 15 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR48## wherein each of U and X is a substituent other than hydrogen. ### Claim 17 (depends on 16) The polymer of claim 16 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 18 (depends on 17) The polymer of claim 17 wherein each said U and X is trifluoromethyl. ### Claim 19 (depends on 2) The polymer of claim 2 wherein said divalent radical A is the radical having the formula ##STR49## and said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR50## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 20 (depends on 19) The polymer of claim 19 wherein said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR51## wherein each of U and X is a substituent selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 21 (depends on 20) The polymer of claim 20 wherein each of said U and X substituents is trifluoromethyl. ### Claim 22 (depends on 2) The polymer of claim 2 wherein said divalent radical A is the radical having the formula ##STR52## and said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR53## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 23 (depends on 22) The polymer of claim 22 wherein said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR54## wherein each of U and X is a substituent selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 24 (depends on 23) The polymer of claim 23 wherein each of said U and X substituents is trifluoromethyl. ### Claim 25 (depends on 1) The polymer of claim 1 wherein c is zero and said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR55## where each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide the aromatic nuclei of said radical with a non-coplanar molecular configuration with respect to each other. ### Claim 26 (depends on 25) The polymer of claim 25 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR56## wherein each of U and X is a substituent other than hydrogen. ### Claim 27 (depends on 26) The polymer of claim 26 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 28 (depends on 27) The polymer of claim 27 wherein each U and X substituent is trifluoromethyl. ### Claim 29 A molecularly oriented and birefringent rigid rod-like polymer in the form of a film or fiber and comprising recurring units of the formula ##STR57## wherein A is a divalent radical and B is a divalent radical or B represents a single bond; R and R.sup.1 are each hydrogen, alkyl, aryl, alkaryl or aralkyl; and c is zero or one; and wherein, when c is one, at least one of A and B is a divalent substituted-quaterphenylene radical having the formula: ##STR58## wherein each Y is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide the aromatic nuclei of said radical with a non-coplanar molecular configuration with respect to each other; and wherein, when c is zero, A is a divalent substituted-quaterphenylene radical having the aforesaid formula. ### Claim 30 (depends on 29) The polymer of claim 29 wherein said c is the integer one. ### Claim 31 (depends on 30) The polymer of claim 30 wherein each of said A and B radical is a divalent substituted-quaterphenylene radical having the formula ##STR59## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide each said radical with a non-coplanar molecular configuration. ### Claim 32 (depends on 31) The polymer of claim 31 wherein each said A and B radical is a divalent substituted-quaterphenylene radical having the formula ##STR60## wherein each of U and X is a substituent other than hydrogen. ### Claim 33 (depends on 32) The polymer of claim 32 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 34 (depends on 33) The polymer of claim 33 wherein each said U and X substituent is trifluoromethyl. ### Claim 35 (depends on 30) The polymer of claim 30 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR61## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p, and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 36 (depends on 35) The polymer of claim 35 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR62## wherein each of U and X is a substituent other than hydrogen. ### Claim 37 (depends on 36) The polymer of claim 36 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 38 (depends on 37) The polymer of claim 37 wherein each said U and X substituent is trifluoromethyl. ### Claim 39 (depends on 30) The polymer of claim 30 wherein said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR63## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 40 (depends on 39) The polymer of claim 39 wherein said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR64## wherein each of U and X is a substituent other than hydrogen. ### Claim 41 (depends on 40) The polymer of claim 40 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 42 (depends on 41) The polymer of claim 41 wherein each said U and X substituent is trifluoromethyl. ### Claim 43 (depends on 30) The polymer of claim 30 wherein said B represents a single bond and said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR65## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said divalent radical A with a non-coplanar molecular configuration. ### Claim 44 (depends on 43) The polymer of claim 43 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR66## wherein each of U and X is a substituent other than hydrogen. ### Claim 45 (depends on 44) The polymer of claim 44 wherein each of said U and X substituents is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 46 (depends on 45) The polymer of claim 45 wherein each said U and X in trifluoromethyl. ### Claim 47 (depends on 30) The polymer of claim 30 wherein said divalent radical A is the radical having the formula ##STR67## and said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR68## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 48 (depends on 47) The polymer of claim 47 wherein said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR69## wherein each of U and X is a substituent selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 49 (depends on 48) The polymer of claim 48 wherein each of said U and X substituents is trifluoromethyl. ### Claim 50 (depends on 30) The polymer of claim 30 wherein said divalent radical A is the radical having the formula ##STR70## and said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR71## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 51 (depends on 50) The polymer of claim 50 wherein said divalent radical B is a substituted-quaterphenylene radical having the formula ##STR72## wherein each of U and X is a substitutent selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 52 (depends on 51) The polymer of claim 51 wherein each of said U and X substituents is trifluoromethyl. ### Claim 53 (depends on 29) The polymer of claim 29 wherein c is zero and said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR73## wherein each U is a substituent other than hydrogen, each W is hydrogen or a substituent other than hydrogen, each p is an integer from 1 to 3, each X is hydrogen or a substituent other than hydrogen and each r is an integer from 1 to 4, said U, W.sub.p and X.sub.r substitution being sufficient to provide said radical with a non-coplanar molecular configuration. ### Claim 54 (depends on 53) The polymer of claim 53 wherein said divalent radical A is a substituted-quaterphenylene radical having the formula ##STR74## wherein each of U and X is a substituent other than hydrogen. ### Claim 55 (depends on 54) The polymer of claim 54 wherein each of said U and X substituent is selected from the group consisting of halogen, nitro, alkoxy and trifluoromethyl. ### Claim 56 (depends on 55) The polymer of claim 55 wherein each U and X substituent is trifluoromethyl. ### Claim 57 (depends on 29) The polymer of claim 29 in the form of a unidirectionally stretched film or fiber.