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US5114612A Expired / Lapsed US ⏱️ 0.0 years remaining

Liquid crystal polyester thermosets

Assignee: United States Department of Energy
•
Filing: 1991-01-22
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Granted: 1992-05-19
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Expires: 2011-01-22
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Abstract

Abstract The present invention provides (1) curable liquid crystalline polyester monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals selected from the group consisting of maleimide, substituted maleimide, nadimide, substituted naimide, ethynyl, and (C(R 3 ) 2 ) 2 where R 3 is hydrogen with the proviso that the two carbon atoms of (C(R 3 ) 2 ) 2 are bound on the aromatic ring of A 1 or A 3 to adjacent carbon atoms, A 1 and A 3 are 1,4-phenylene and the same where said group contains one or more substituents selected from the group consisting of halo, e.g., fluoro, chloro, bromo, or iodo, nitro lower alkyl, e.g., methyl, ethyl, or propyl, alkoxy, e.g., methoxy, ethoxy, or propoxy, and fluoroalkyl, e.g., trifluoromethyl, pentafluoroethyl and the like, A 2 is selected from the group consisting of 1,4-phenylene, 4,4'-biphenyl, 2,6-naphthylene and the same where said groups contain one or more substituents selected from the group consisting of halo, e.g., fluoro, chloro, bromo, or iodo, nitro, lower alkyl, e.g., methyl, ethyl, and propyl, lower alkoxy, e.g., methoxy, ethoxy, or propoxy, and fluoroalkyl or fluoroalkoxy, e.g., trifluoromethyl, pentafluoroethyl and the like, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--, (2) thermoset liquid crystalline polyester compositions comprised of heat-cured segments derived from monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 as described above, (3) curable blends of at least two of the polyester monomers and (4) processes of preparing the curable liquid crystalline polyester monomers.

Inventors

  • 👤 Brian C. Benicewicz
  • 👤 Andrea E. Hoyt

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-31 13:26
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/68; C08G63/685; C08G63/6854; C08G63/6858; C08G63/02; C08G63/12; C08G63/52; C08G63/682; C08G63/6824; C08G63/6828; C09; C09K; C09K19/00; C09K19/04; C09K19/38; C09K19/3804; C09K19/3823

Claims Analysis

Total Claims: 11
Claim 1
Independent Claim 134 words
A curable liquid crystalline polyester monomer represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals of ethynyl, A 1 and A 3 are 1,4-phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--.
Claim 2
Dependent Claim 134 words
A curable liquid crystalline polyester monomer represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals of ethynyl, A 1 and A 3 are 1,4-phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--.
Claim 3
Dependent Claim 71 words
The curable liquid crystalline polyester monomer of claim 1 wherein A 1 and A 3 are 1,4-phenylene, A 2 is a substituted 1,4-phenylene group containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, and B 1 and B 2 are --C(O)--O-- groups wherein the --C(O)-- functionalities of B 1 and B 2 are adjacent to A 1 and A 3 .
Claim 4
Dependent Claim 66 words
The curable liquid crystalline polyester monomer of claim 1 wherein R 1 and R 2 are ethynyl groups, A 1 and A 3 are 1,4-phenylene, A 2 is a 1,4-phenylene group containing a methyl substituent upon the ring, and B 1 and B 2 are --C(O)--O-- groups wherein the --C(O)-- functionalities of B 1 and B 2 are adjacent to A 1 and A 3 .
Claim 5
Dependent Claim 66 words
The curable liquid crystalline polyester monomer of claim 1 wherein R 1 and R 2 are ethynyl groups, A 1 and A 3 are 1,4-phenylene, A 2 is a 1,4-phenylene group containing a chloro substituent upon the ring, and B 1 and B 2 are --C(O)--O-- groups wherein the --C(O)-- functionalities of B 1 and B 2 are adjacent to A 1 and A 3 .
Claim 6
Dependent Claim 208 words
A curable blend comprised of at least two liquid crystalline polyester monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals selected from the group consisting of maleimide, nadimide, methyl nadimide, and ethynyl, A 1 and A 3 are 1,4-phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl where R 1 or R 2 are ethynyl or A 2 is selected from the group consisting of 1,4-phenylene, 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl where R 1 or R 2 are maleimide, nadimide, or methyl nadimide, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--.
Claim 7
Dependent Claim 208 words
A curable blend comprised of at least two liquid crystalline polyester monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals selected from the group consisting of maleimide, nadimide, methyl nadimide, and ethynyl, A 1 and A 3 are 1,4-phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl where R 1 or R 2 are ethynyl or A 2 is selected from the group consisting of 1,4-phenylene, 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl where R 1 or R 2 are maleimide, nadimide, or methyl nadimide, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--.
Claim 8
Dependent Claim 144 words
A thermoset liquid crystalline polyester composition comprised of cured segments derived from one or more monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals of ethynyl, A 1 and A 3 are phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--.
Claim 9
Dependent Claim 144 words
A thermoset liquid crystalline polyester composition comprised of cured segments derived from one or more monomers represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals of ethynyl, A 1 and A 3 are phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--.
Claim 10
Dependent Claim 273 words
A process of preparing a curable liquid crystalline polyester monomer represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals of ethynyl, A 1 and A 3 are phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--, said process comprising: reacting a difunctional compound represented by the formula B 3 --A 2 --B 4 wherein B 3 and B 4 are --OH, and A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, with an acid chloride represented by the formula: Cl--C(O)--A 1 --R 1 wherein A 1 is 1,4-phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, and R 1 is a radical of ethynyl.
Claim 11
Dependent Claim 273 words
A process of preparing a curable liquid crystalline polyester monomer represented by the formula: R.sup.1 --A.sup.1 --B.sup.1 --A.sup.2 --B.sup.2 --A.sup.3 --R.sup.2 where R 1 and R 2 are radicals of ethynyl, A 1 and A 3 are phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, and B 1 and B 2 are selected from the group consisting of --C(O)--O-- and --O--C(O)--, said process comprising: reacting a difunctional compound represented by the formula B 3 --A 2 --B 4 wherein B 3 and B 4 are --OH, and A 2 is selected from the group consisting of substituted 1,4-phenylene containing one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, or 4,4'-biphenyl, 2,6-naphthalene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, or fluoroalkyl, with an acid chloride represented by the formula: Cl--C(O)--A 1 --R 1 wherein A 1 is 1,4-phenylene and the same where said groups contain one or more substituents selected from the group consisting of halo, nitro, lower alkyl, lower alkoxy, fluoroalkoxy or fluoroalkyl, and R 1 is a radical of ethynyl.

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