WO1979001030A1 - Polyesters of 4-carboxybenzenepropionic acid - Google Patents
Polyesters of 4-carboxybenzenepropionic acid Download PDFInfo
- Publication number
- WO1979001030A1 WO1979001030A1 PCT/US1979/000267 US7900267W WO7901030A1 WO 1979001030 A1 WO1979001030 A1 WO 1979001030A1 US 7900267 W US7900267 W US 7900267W WO 7901030 A1 WO7901030 A1 WO 7901030A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- polyester
- polyesters
- naphthalenediol
- diphenol
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 68
- QSPCOYVUYYFWAU-UHFFFAOYSA-N 4-(2-carboxyethyl)benzoic acid Chemical compound OC(=O)CCC1=CC=C(C(O)=O)C=C1 QSPCOYVUYYFWAU-UHFFFAOYSA-N 0.000 title claims abstract description 20
- -1 aromatic diols Chemical class 0.000 claims abstract description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 3
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 3
- RBWZNZOIVJUVRB-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-3-bicyclo[2.2.1]heptanyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C(C2)CCC2C1 RBWZNZOIVJUVRB-UHFFFAOYSA-N 0.000 claims description 3
- YZYGDZRBLOLVDY-UHFFFAOYSA-N 4-[cyclohexyl-(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1CCCCC1 YZYGDZRBLOLVDY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 claims description 3
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims description 2
- NAQNEMNLLODUCG-UHFFFAOYSA-N 2,3-dichloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1Cl NAQNEMNLLODUCG-UHFFFAOYSA-N 0.000 claims description 2
- RYRZSXJVEILFRR-UHFFFAOYSA-N 2,3-dimethylterephthalic acid Chemical compound CC1=C(C)C(C(O)=O)=CC=C1C(O)=O RYRZSXJVEILFRR-UHFFFAOYSA-N 0.000 claims description 2
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 claims description 2
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 claims description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- AREMQPPGVQNRIE-UHFFFAOYSA-N acetic acid;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CC(O)=O.CC(O)=O.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 AREMQPPGVQNRIE-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008018 melting Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- YXZUGYXICVZUOK-UHFFFAOYSA-N benzene-1,4-diol;propanoic acid Chemical compound CCC(O)=O.CCC(O)=O.OC1=CC=C(O)C=C1 YXZUGYXICVZUOK-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- LABJFIBQJFPXHZ-UHFFFAOYSA-N 4-(carboxymethoxy)benzoic acid Chemical compound OC(=O)COC1=CC=C(C(O)=O)C=C1 LABJFIBQJFPXHZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- AKOGNYJNGMLDOA-UHFFFAOYSA-N (4-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C=C1 AKOGNYJNGMLDOA-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- TWFZFDAORMYZFE-UHFFFAOYSA-N acetic acid;4-(4-hydroxyphenyl)sulfanylphenol Chemical compound CC(O)=O.CC(O)=O.C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 TWFZFDAORMYZFE-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
Definitions
- This invention relates to new high molecular weight polyesters prepared from 4-carboxybenzenepro- pionic acid and unsubstituted aromatic diols.
- polyesters of improved mechanical properties are being sought, and in order to increase the mechanical properties it is usually necessary to increase the molecular weight of the polyesters.
- the melting point of the polyesters increases, resulting in polyesters that are difficult to process in present commercial equipment.
- the polyesters must have excellent processability and excellent mechanical properties.
- the polyesters must also be stable at elevated temperatures and for some uses good light stability is required.
- Heat stability is an important property for many polyester applications. For example, if a polyester is used close to an automobile engine or in an electronic apparatus in which the parts become heated by hot vacuum tubes, it is. necessary that the polyester be stable under these conditions.
- German Offenlegungesschrift 2,530,820 discloses polyesters that are prepared from 4-carboxy- benzene-oxyacetic acid and unsubstituted diols. These polyesters apparently have desirable properties, but the polyesters are not sufficiently stable at elevated temperatures.
- polyesters such as the polyesters prepared from terephthalic acid and bisphenol A diacetate, are severely discolored when exposed to light for long periods of time. Disclosure of Invention
- polyesters of this invention have excellent mechanical properties and they can be processed in current commercial melt-processing equipment. Also, these polyesters have better heat stability and light stability than prior art polyesters.
- the polyesters of this invention are prepared by polymerizing 4-carboxybenzenepropionic acid with an unsubstituted aromatic diol.
- an unsubstituted aromatic diol such as hydroquinone
- the polyester is a liquid crystal polyester.
- a nonlinear unsubstituted aromatic diol such as 4,4'-isopropylidenediphenol
- Table I demonstrates the surprising improvement in heat stability that the polyesters of this invention have.
- polyesters in Table I Thermal stability of the polyesters in Table I was determined by thermogravimetric analyses (TGA) in nitrogen. The thermal properties of these polymers are summarized in Table I.
- TGA thermogravimetric analyses
- the preparations of polyesters 1, 3 and 5 are given in Examples 1, 4 and 5.
- Polyester 2 (I.V. 0.54) was similarly prepared but a melt temperature of 275°C. was used.
- Polyesters 4 and 6 were prepared by solid-state polymerization of pre polymers (28 ⁇ °C, 0.1 mm) which had solidified inmelt at 300°C.
- Polyester 1 of the invention is more thermally stable than polyester 2 of the prior art
- polyester 3 is more stable than polyester 4
- polyester 5 is more stable than polyester 6.
- the polyesters of this invention have an inherent viscosity of at least 0.4 and preferably at least 0.8 and are prepared from 4-carboxybenzenepropionic acid and unsubstituted aromatic diols.
- The. acid portion of the polyesters can be modified with up to 50 mole percent of at least one aliphatic, alicyclic or aromatic dicarboxylic acid.
- These modifying acids include terephthalic acid, isoph ⁇ j-halic acid, 2,6-naphthalenedicarboxylic acid, cis or trans-l,4-cyclohexanedicarboxylic acid, 4,4 ' -oxydibenzoic acid, monochloroterephthalic acid, a dichloroterephthalic acid, methyl terephthalic acid, a dimethylterephthalic acid and 4,4 ' -diphenyldi- carboxylic acid.
- the unsubstituted aromatic diol portion of the polyesters of this invention includes hydroquinone, 4,4 '-isopropylidendiphenol, 4,4'-thiodiphenol, 4,4'- oxydiphenol, 4,4 ' -(2-norbornylidene)diphenol, 4,4'- (cyclohexylmethylene)diphenol, 4,4 ' -dihydroxybiphenyl, 1,4-naphthalenediol, 1,5-naphthalenediol and 2,6-naphthalenediol.
- diacyl derivatives of the aromatic diols can be used to prepare the polyesters of this invention.
- the acetyl and propionyl derivatives are preferred, but the butyryl, isobutyryl, or benzoyl derivatives are examples of others which may also be used.
- unsubstituted we mean that no group such as alkyl, alkoxy, or halogen is attached to an aromatic ring of the aromatic diol.
- the preferred diols are hydroquinone and 4 , 4 ' -isopropylidenediphenol.
- a polyester of this invention can be prepared from 4-carboxybenzenepropionic acid, a diacyl ester of hydroquinone and a p-acyloxybenzoic acid and can be fined as a polyester having a fiber-forming molecula weight and having the following divalent radicals :
- radical (C) is 10 to 90 mole per cent, based on the sum of radicals (A) and (C). In a preferred embodiment the range of radical (C) is from 30 to 80 mole percent.
- the polymers of the invention can be made by techniques such as by acidolysis of the aromatic diol diacetate with the 4-carboxybenzenepropionic acid. reactants are heated at about 260oC. until most of the monocarboxylic acid has evolved. The temperature of the melt is then increased to about 325oC. (up to 360oC. the higher-melting compositions), a vacuum of about 0.5 millimeter is applied, and stirring is continued until a high-melt viscosity polymer is obtained. If the polymer solidifies, its molecular weight may be increased to a sufficient value by heating particles of the polymer in an inert atmosphere or under reduced pressure at a temperature just below the softening point of the polymer.
- Tough films of the polymers are obtained by pressing or by extrusion. Molding plastics having very high impact strength and heat-deflection tempertures are obtained by injection molding at about 350°C.
- polyesters of this invention can be fabricated to give other types of shaped objects such as foamed plastics, fibers, films, extruded shapes and coatings .
- the compositions of this invention also may contain nucleating agents, fibers, pigments, glass fibers, asbestos fibers, antioxidants, stabilizers, plasticizers, lubricants, and other additives.
- polyesters prepared in these examples were tested and found to have excellent mechanical properties . All inherent viscosities were determined at
- polyesters were dried in an oven at 100oC. overnight and injection molded to give 2-1/2 x 3/8 x 1/16-inch tensile bars and 5 x 1/2 x 1/8-inch flexure bars for testing.
- ASTM procedures were used for mea- suring the tensile strength and elongation (ASTM D1708), flexural modulus (ASTM D790), Izod impact strength (ASTM D256 Method A), and heat-deflection temperature (ASTM D648).
- EXAMPLE 1 This example illustrates the preparation of a polyester from 4-carboxybenzenepropIonic acid and bisphenol A diacetate.
- Example 3 illustrates the preparation of copolyester using 50 mole percent of terephthalic acid.
- the procedure described in Example 1 was used to prepare a copolymer from 50 mole percent 4-carboxybenzenepropionic acid, 50 mole percent terephthalic acid, and bisphenol A diacetate.
- the tough, light amber polymer had an inherent viscosity of 0.70 and a glass transition temperature of 168°C.
- Example 4 Using the procedure described in Example 1, a polyester was prepared from 77 - 6 g (0.4 mole) 4-carboxy benzenepropionic acid and 120.8 g (0.4 mole) 4,4'-thio diphenol diacetate. The polyester had an inherent vis cosity of 0.74. A tough, creasable film can be pressed easily at 325°C. EXAMPLE 4
- Example 2 Using the procedure described in Example 1, a prepolymer was prepared from 19.4 g (0.1 mole) 4-carboxybenzenepropionic acid and 22.2 g (0.1 mole) hydroquinone dipropionate. The prepolymer, which had solidified in the flask, was ground to pass a 20-mesh screen for subsequent solid-state polymerization. Solidstate polymerization of the prepolymer was accomplished by heating the particles under reduced pressure (0.1 mm Hg) at 28O°C. for four hours. The polyester had a melting point of 425°C. EXAMPLE 5 The procedure of Example 1 was used (except the vacuum was applied at 340°C.
- Example 5 The procedure of Example 5 was used to prepare a copolyester with 0.20 mole 4-carboxybenzenepropionic acid, 0.20 mole terephthalic acid, 0.20 mole hydroquinone diacetate, and 0.20 mole bisphenol A diacetate.
- the copolyester had an inherent viscosity of 0.88.
- EXAMPLE 7 A mixture of 14.4 g. (0.08 mole) p-acetoxybenzoic acid,3.88 g. (0.02 mole) 4-carboxybenzenepropionic acid, and 4.44 g. (0.02 mole) hydroquinone dipropionate was placed in a 100-ml.
- a second polyester was prepared in a similar manner, except 4-carboxybenzeneoxyacetic acid was used in place of the 4-carboxybenzenepropionic acid in the first polyester and the final reaction temperature was 340oC. to limit the considerable color formation.
- polyesters of this invention also have improved light stability compared to similar polyesters prepared with aromatic dicarboxylic acids other than 4-carboxybenzenepropionic acid.
- a pressed film of a polyester prepared from this acid and bisphenol A diacetate turned only slightly yellow when exposed for 35 hrs. (40 fading units) in a fadeometer containing a xenon lamp.
- a film of a similar polyester prepared with terephthalic acid and bisphenol A diacetate turned deep yellow at the same time in the test.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE7979900483T DE2965268D1 (en) | 1978-05-04 | 1979-04-27 | Polyesters of 4-carboxybenzenepropionic acid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/902,574 US4140846A (en) | 1978-05-04 | 1978-05-04 | Liquid crystal copolyesters containing 4-carboxybenzenepropionic acid |
| US95982978A | 1978-11-13 | 1978-11-13 | |
| US959829 | 1978-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1979001030A1 true WO1979001030A1 (en) | 1979-11-29 |
Family
ID=27129330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1979/000267 WO1979001030A1 (en) | 1978-05-04 | 1979-04-27 | Polyesters of 4-carboxybenzenepropionic acid |
Country Status (4)
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3368998A (en) * | 1962-05-22 | 1968-02-13 | Ici Ltd | Crystalline polyester polymer |
| DE2520820A1 (de) * | 1974-05-10 | 1975-11-27 | Du Pont | Verfahren zur verbesserung der festigkeit geformter gebilde, insbesondere von faeden |
-
1979
- 1979-04-27 DE DE7979900483T patent/DE2965268D1/de not_active Expired
- 1979-04-27 JP JP50076079A patent/JPS55500213A/ja active Pending
- 1979-04-27 WO PCT/US1979/000267 patent/WO1979001030A1/en unknown
- 1979-12-04 EP EP19790900483 patent/EP0011640B1/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3368998A (en) * | 1962-05-22 | 1968-02-13 | Ici Ltd | Crystalline polyester polymer |
| DE2520820A1 (de) * | 1974-05-10 | 1975-11-27 | Du Pont | Verfahren zur verbesserung der festigkeit geformter gebilde, insbesondere von faeden |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55500213A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1980-04-10 |
| EP0011640A4 (en) | 1980-09-29 |
| EP0011640A1 (en) | 1980-06-11 |
| EP0011640B1 (en) | 1983-04-27 |
| DE2965268D1 (en) | 1983-06-01 |
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