JPH0449569B2 - - Google Patents
Info
- Publication number
- JPH0449569B2 JPH0449569B2 JP58176966A JP17696683A JPH0449569B2 JP H0449569 B2 JPH0449569 B2 JP H0449569B2 JP 58176966 A JP58176966 A JP 58176966A JP 17696683 A JP17696683 A JP 17696683A JP H0449569 B2 JPH0449569 B2 JP H0449569B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyester
- wholly aromatic
- weight
- parts
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 125000003118 aryl group Chemical group 0.000 claims description 105
- 229920000728 polyester Polymers 0.000 claims description 97
- 239000000203 mixture Substances 0.000 claims description 50
- 150000003384 small molecules Chemical class 0.000 claims description 23
- 239000000155 melt Substances 0.000 claims description 21
- -1 p-phenylphenoxy Chemical group 0.000 claims description 17
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- VQIKAPKIEUECEL-UHFFFAOYSA-N 2-phenoxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(OC=2C=CC=CC=2)=C1 VQIKAPKIEUECEL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229940125898 compound 5 Drugs 0.000 claims 1
- 239000010408 film Substances 0.000 description 45
- 238000000605 extraction Methods 0.000 description 25
- 238000002844 melting Methods 0.000 description 24
- 230000008018 melting Effects 0.000 description 23
- 239000002253 acid Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 16
- 239000002657 fibrous material Substances 0.000 description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HRMCXDSWURAYFR-UHFFFAOYSA-N 3-phenoxyphthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1C(O)=O HRMCXDSWURAYFR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 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 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VJIDDJAKLVOBSE-UHFFFAOYSA-N 2-ethylbenzene-1,4-diol Chemical compound CCC1=CC(O)=CC=C1O VJIDDJAKLVOBSE-UHFFFAOYSA-N 0.000 description 2
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- FEEJVTNPADMWRN-UHFFFAOYSA-N diphenyl 2-phenoxybenzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C(OC=2C=CC=CC=2)=CC=1C(=O)OC1=CC=CC=C1 FEEJVTNPADMWRN-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 2
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PQHRHABVSWOYPG-UHFFFAOYSA-N 2,9-dioxatricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaene-3,8-dione Chemical group O1C(=O)C(C=C2)=CC=C2C(=O)OC2=CC=C1C=C2 PQHRHABVSWOYPG-UHFFFAOYSA-N 0.000 description 1
- LMXZDVUCXQJEHS-UHFFFAOYSA-N 2-(1-phenylethyl)benzene-1,4-diol Chemical compound C=1C(O)=CC=C(O)C=1C(C)C1=CC=CC=C1 LMXZDVUCXQJEHS-UHFFFAOYSA-N 0.000 description 1
- FKWOGPPGVRDIRZ-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=CC=C1O FKWOGPPGVRDIRZ-UHFFFAOYSA-N 0.000 description 1
- PFTXJIDFNWHIFT-UHFFFAOYSA-N 2-(2-methylhexan-2-yl)benzene-1,4-diol Chemical compound CCCCC(C)(C)C1=CC(O)=CC=C1O PFTXJIDFNWHIFT-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- DTFQMPQJMDEWKJ-UHFFFAOYSA-N 3-ethoxybenzoic acid Chemical compound CCOC1=CC=CC(C(O)=O)=C1 DTFQMPQJMDEWKJ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- CLMNUWIUDGZFCN-UHFFFAOYSA-N 4-[2-(4-hydroxyphenoxy)ethoxy]phenol Chemical compound C1=CC(O)=CC=C1OCCOC1=CC=C(O)C=C1 CLMNUWIUDGZFCN-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical group BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000470 poly(p-phenylene terephthalate) polymer Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Description
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INDUSTRIAL APPLICATION FIELD The present invention relates to a novel wholly aromatic polyester composition suitable for producing a multidimensionally oriented body and a method for producing the same. Conventional technology Traditionally, poly(paraoxypenzoate),
It is known that wholly aromatic polyesters such as poly(p-phenylene terephthalate) form high performance molded articles with high Young's modulus and high chemical resistance. However, since the melting point of these polymers is much higher than the decomposition temperature, it is extremely difficult and virtually impossible to produce a multidimensionally oriented body not only by melt molding but also by a stretching process. Therefore, as a fully aromatic polyester that can be melt-molded, for example,
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Amorphous or semi-crystalline wholly aromatic polyesters with a repeating structure such as [Formula] [bisphenol] and many bending points within the main chain have been extensively studied. However, from these amorphous, semicrystalline, wholly aromatic polyesters, it is not possible to obtain a high-performance oriented material as the object of the present invention. For example, the young modulus of a fiber or film is at most 100g/denier or 200g/denier.
It only has a value of ~300Kg/ mm2 . In recent years, JP-A-50-157619, JP-A-50-158695
In this issue, while maintaining the linearity of the polymer molecular chain as much as possible and maintaining the rod-like rigidity as much as possible, we have made it difficult to obtain a perfect crystal lattice by copolymerization and the use of left-right asymmetric monomers and non-linear monomers. A wholly aromatic polyester that forms an optically anisotropic melt in a molten state by lowering the temperature, and a method of improving performance by melt-forming the wholly aromatic polyester and heat-treating the obtained molded product. was suggested. Since this proposal, an extremely large number of wholly aromatic polyesters with new compositions that have the ability to form an optically anisotropic melt when melted have been proposed, and furthermore, these wholly aromatic polyesters have the ability to form optically anisotropic melts. High-performance oriented molded products by melt molding have been proposed. A wholly aromatic polyester that has the ability to form an optically anisotropic melt when melted can be used under shearing force or extensional flow.
By easily providing a highly oriented melt, solidifying and further crystallizing the melt, a highly oriented molded article can be obtained. Although such properties work very advantageously in improving the performance of one-dimensional oriented bodies, they work rather in the opposite way in producing higher-dimensional oriented bodies. In other words, when a wholly aromatic polyester that has the ability to form an anisotropic melt when melted is formed into a sheet or film by melt extrusion for the purpose of making a two-dimensionally oriented body, the molecular chains are arranged along the flow aroma. In the resulting film or sheet, there will be a large difference in physical properties in two orthogonal axial directions. In order to eliminate such variations in physical properties, measures such as lamination are taken (as disclosed in European Patent No. 72210), European Patent Application No. 24494, and U.S. Patent No.
As disclosed in the specification of No. 4333907, a method based on stretching the melt extrudate by 1.5 times or more in the extrusion direction and a direction orthogonal to this immediately after extrusion has been proposed, but this proposal also has an excellent method. Very restrictive conditions must be maintained to produce films with uniformity. Despite these disadvantages, various wholly aromatic polyesters that give an anisotropic melt when melted have been developed since the above-mentioned JP-A-50-157619 and JP-A-50-158695.
An extremely large number of proposals have been made not only because of (1) the industrial advantage of being able to manufacture molded products using the extremely efficient method of melt molding, but also (2) having anisotropic melt molding ability when melted. Fully aromatic polyester
Compared to fully aromatic polyesters, which form an isotropic melt when melted, molded products (e.g. fibers) that have more rigid molecular chains and can be obtained from an anisotropic melt produce only an isotropic melt. This is because it is believed that various physical properties such as Young's modulus and other mechanical properties are superior to molded products obtained from non-polyester (European Patent Application No. 70539). Will. In order to solve the above-mentioned problems, for example, a composition that gives an optically isotropic melt is produced by mixing a wholly aromatic polyester having an optically anisotropic melt forming ability when melted and a low molecular weight compound, A method of obtaining a substantially non-oriented unstretched film by melt extrusion while avoiding the self-orientation property of an anisotropic melt, especially spontaneous orientation along the direction of flow, and then stretching this. proposed a method for producing a substantially biaxially stretched film from polyester that forms an optically anisotropic melt, and the film. (European Patent Application No. 70539
The physical properties of the biaxially stretched film obtained by this method are as compared to a film obtained by melt-extruding an optically anisotropic melt without using a low molecular weight compound.
The mechanical and thermal properties along two orthogonal axes and their balance are extremely excellent. However, these physical property values and their balance are still not fully satisfactory. This may be due to the fact that the optically anisotropic melt-formable fully aromatic polyester known at the time has a molecular structure that is still insufficient to exhibit essentially high performance, or that the isotropic melt-formable polyester of such fully aromatic polyester This is presumed to be due to the fact that the composition that provides the above is not yet sufficient to form an unoriented, unstretched film that is uniform enough to provide a film with well-balanced physical properties. Purpose of the Invention The present invention provides a multidimensionally oriented body (for example, a biaxially oriented film) that has high performance, mechanical, thermal, and chemical properties, and also exhibits well-balanced physical properties along two orthogonal axes. The object of the present invention is to provide a wholly aromatic polyester composition that does not exhibit melt anisotropy and is suitable for producing a polyester, and a method for producing the same. Structure of the Invention The above-mentioned objects are achieved by the composition of the present invention and the method for producing the same as described below. (A) An ester bond between the phenoxyterephthalic acid component and an aromatic dihydroxy compound in which the two hydroxy groups bonded to the aromatic nucleus have chain elongation in opposite directions and are located on the same or parallel axes. A substantially linear wholly aromatic polyester with a main repeating bond and an intrinsic viscosity of 1.0.
and the melt viscosity at 380°C (shear rate γ =
100 parts by weight of a wholly aromatic polyester whose 100sec -1 ) is 1000 poise or more, and a compound represented by the following formula, which is substantially non-reactive with the above wholly aromatic polyester and has a molecular weight of 1000.
A wholly aromatic polyester composition comprising 5 to 400 parts by weight of the following high boiling point, low molecular weight compound. Ar-X-Ar (where Ar is a monovalent aromatic group, X is -SO 2 -
or -CO-. ) (B) Reacting the phenoxyterephthalic acid component with an aromatic dihydroxy compound in which the two hydroxy groups bonded to the aromatic nucleus have chain elongation properties in opposite directions and are coaxial or parallel axes. When producing a substantially linear wholly aromatic polyester, a compound represented by the following formula, which is substantially non-reactive with respect to the produced wholly aromatic polyester, and has a molecular weight of
A melt polycondensation reaction is carried out by coexisting a high boiling point, low molecular weight compound of 1000 or less at a ratio of 5 to 400 parts by weight per 100 parts by weight of the wholly aromatic polyester, and the wholly aromatic polyester has an intrinsic viscosity of 1.0 or more. The melt viscosity at 380°C (shear rate γ = 100 sec -1 ) measured as a mixture of 60 parts by weight and 40 parts by weight of 4,4'-bis(p-phenylphenoxy) diphenylsulfone is 1000 poise or more. 1. A method for producing a wholly aromatic polyester composition, comprising forming a composition containing a certain wholly aromatic polyester. Ar-X-Ar (where Ar and X have the same meanings as above) Phenoxyterephthalic acid, which is an acid component in the present invention, has the following structural formula: [Here, Y is hydrogen, chloro, bromine, carbon number 1-
4 alkyl or phenyl] Examples of the alkyl group having 1 to 4 carbon atoms as Y in the above structural formula include methyl, ethyl, propyl, butyl, and the like. Specific examples of the above phenoxyterephthalic acid include phenoxyterephthalic acid, chlorophenoxyterephthalic acid, bromophenoxyterephthalic acid,
Examples include methylphenoxyterephthalic acid and ethylphenoxyterephthalic acid. Among these, phenoxyphthalic acid in which Y is hydrogen is particularly preferred. The wholly aromatic polyester of the present invention has the above-mentioned phenoxyterephthalic acid as a main acid component, but a small proportion of other aromatic dicarboxylic acids may be copolymerized. Specific examples of these include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl etherdicarboxylic acid, methylterephthalic acid, methylisophthalic acid, etc. I can give an example. Among these, aromatic dicarboxylic acids in which two carboxyl groups are coaxial or parallel to each other and extend in opposite directions are preferably used. Specific examples of these include terephthalic acid, methyl terephthalic acid, naphthalene 1,4-dicarboxylic acid, naphthalene 1,5-dicarboxylic acid, naphthalene 2,6-dicarboxylic acid, diphenyl 4,4'-
Examples include dicarboxylic acids, and the total amount of these is usually 20 mol% or less of the total acid components, more preferably 10
Used in mole% or less. However, terephthalic acid can be used in larger amounts than the other aromatic dicarboxylic acids mentioned above. This is because when different types of acids are copolymerized, the polymer melting point usually decreases, but when terephthalic acid is copolymerized with phenoxyterephthalic acid, the copolymerization can be performed without decreasing the polymer melting point. For example, the melting point of a polyimer made of hydroxynon-phenoxyterephthalic acid is approximately 330.
â, but if the terephthalic acid component is added to this polymer,
Even with 20 mole percent copolymerization, the melting point of the copolymer is the same as above. In this case, if the copolymerization exceeds 50 mole percent, the melting point of the copolymer will greatly increase, which is undesirable, but if the copolymerization exceeds 20 to 30 mole percent, the molded product and fluidity will improve, which is preferable. Examples of aromatic dihydroxy compounds in which the two hydroxyl groups bonded to the aromatic nucleus of the dioxy component in the present invention have chain elongation properties in opposite directions and are located on the same or parallel axes, such as hydroquinone, chlorhydrochloride, etc. Quinone, promhydroquinone, methylhydroquinone, ethylhydroquinone, t-butylhydroquinone, t-amylhydroquinone, t-heptylhydroquinone,
Phenylhydroquinone, benzylhydroquinone, α-methylbenzylhydroquinone, α, α
-dimethylbenzylhydroquinone, 4,4'-dihydroxydiphenyl, 3,3'-dihydroxydiphenyl, 1,4-dihydroxynaphthalene,
Examples include 1,6-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. Among these, hydroquinone, chlorohydroquinone, methylhydroquinone, 4,4-dihydroxydiphenyl, 1,4-dihydroxynaphthalene, 2,6
-dihydroxynaphthalene is preferably used. Particularly preferred is hydroquinone. The wholly aromatic polyester of the present invention has the above-mentioned aromatic dihydroxy compound as the main diol component, but other aromatic dihydroxy compounds such as resorcinol, 4,4'-dihydroxy diphenyl ether, 2,2'-bis(4-hydroxy phenyl)
Propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)ethane, etc. are added in extremely small amounts and within the range that does not significantly impair the physical properties of the resulting molded product. Can be polymerized. In addition to the above-mentioned components, a small proportion of aromatic oxycarboxylic acid can be copolymerized. Examples of these aromatic oxycarboxylic acids include P-oxybenzoic acid, 4-oxydiphenyl-4'-carboxylic acid, 3-chloro-4-oxybenzoic acid, 3-methoxy-4-oxybenzoic acid, and 3-ethoxybenzoic acid. -4-
Oxybenzoic acid, 2-methyl-4-oxybenzoic acid, 3-methyl-4-oxybenzoic acid, 2-phenyl-4-oxybenzoic acid, 3-phenyl-4-
Examples include oxybenzoic acid, 2-chloro-4-oxydiphenyl-4'-carboxylic acid, and 2-hydroxynaphthalene-6-carboxylic acid. The wholly aromatic polyester of the present invention includes one selected from the above-mentioned aromatic carboxylic acids, aromatic dihydroxy compounds, and in some cases, aromatic oxycarboxylic acids or ester-formable derivatives thereof.
A polyester raw material mainly consisting of a species or two or more species, which is substantially non-reactive with the raw materials and the wholly aromatic polyester to be produced, and which is at least difficult to distill off under polycondensation reaction conditions and has a molecular weight of 1000 or less, specified below. It can be produced by polycondensation in the melt state in the presence of a high boiling point, low molecular weight compound, thereby converting the above raw material into a high molecular weight wholly aromatic polyester. At that time, the polycondensation is carried out so that the intrinsic viscosity of the polymer is 1.0 or more, and 60 parts by weight of the polymer and 4,4'-bis(p-phenylphenoxy) diphenylsulfone are
This is carried out until the melt viscosity at 380°C (shear rate γ = 100 sec -1 ) measured as a 40 parts by weight mixture becomes 1000 poise or more. As the wholly aromatic polyester molding composition of the present invention, the reaction product produced by the above method can be used as is. Although it is of course possible to produce a wholly aromatic polyester molding composition by melt-mixing a wholly aromatic polyester with the same low molecular weight compound as mentioned above,
Compared to such methods, the above method is superior in that the temperature at which the wholly aromatic polyester and the high boiling point low molecular weight compound can be loaded can be significantly lowered. Firstly, since fully aromatic polyesters generally have a high melting point and are easily thermally decomposed at molding temperatures exceeding their melting point, the advantage of suppressing thermal decomposition of fully aromatic polyesters is Not only that, but secondly, high molecular weight fully aromatic polyesters are produced at a lower polycondensation temperature than in conventional polycondensation methods in which polycondensation is carried out in the absence of high-boiling low molecular weight compounds. It also makes it possible to produce fully aromatic polyester with a higher degree of polymerization at the same polycondensation temperature.
Therefore, special polycondensation reactors that require high-temperature heating can be
Provides benefits that you may not necessarily need. Furthermore, according to the above polymerization method, the high boiling point, low molecular weight compound used in the present invention can significantly reduce the apparent melt viscosity of the wholly aromatic polyester, so that in the absence of the high boiling point, low molecular weight compound, Compared to the case where polycondensation is carried out, there is an advantage that the polycondensation reaction can proceed more quickly and that a wholly aromatic polyester having a higher molecular weight can be produced more quickly. In particular, in order to fully demonstrate the mechanical, thermal, and chemical properties of the oriented molded article of fully aromatic polyester of the present invention, it is essential to produce a polyester with a high molecular weight, that is, a high degree of polymerization. As mentioned above, an intrinsic viscosity of 1.0 is required. Generally, as the degree of polymerization increases, the wholly aromatic polyester of the present invention becomes less soluble in the solvent for measuring the degree of polymerization (mixed solvent of p-chlorophenol/tetrachloroethane = 60/40 (by weight)), and has a solid viscosity of 3 to 3. When it exceeds 4, it becomes insoluble. Those whose degree of polymerization has increased to such an extent that they become insoluble in the solvent for measuring the degree of polycondensation,
Particularly high performance is exhibited in a multidimensionally oriented body, which is one of the objects of the present invention. In general, relatively low molecular weight and low degree of polymerization are acceptable for producing one-dimensional oriented materials, but in order to achieve high performance, the intrinsic viscosity must be at least 1.0.
In addition, the melt viscosity measured as a composition of 40% by weight of 4,4'-bis(p-phenylphenoxynodiphenylsulfone and 60% by weight of polyester) is 1000 poise or more at 380°C (γ = 1001/sce). More preferably, the intrinsic viscosity is 3.0 or more and the melt viscosity is 5Ã10 5 or more.
Furthermore, when the purpose is to improve the performance of a high-dimensional oriented body, those having a melt viscosity of 1Ã10 4 poise or more are preferably used. A wholly aromatic polyester containing phenoxyterphthalic acid is described in US Pat. No. 3,723,388,
Phenoxyphthalic acid with low glass transition temperature, low heat distortion temperature, low melt viscosity and low molding temperature
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ã§ãããIt is described as one of the fully aromatic polyesters containing the formula: The '388 patent teaches that conventional wholly aromatic polyesters have high glass transition temperatures, high heat distortion temperatures, and therefore high melt viscosities. For this reason, high temperatures are required for melt extrusion or injection molding of films or other molded articles. In addition, ordinary injection molding machines
Many wholly aromatic polyesters have melting points above 400°C, whereas they cannot operate at temperatures as high as 400°C. On the other hand, it has been stated that a wholly aromatic polyester containing phenoxyphthalic acid has excellent melt moldability, as well as excellent heat resistance and flame retardancy. Specific examples described in the above US patent specification are summarized in Table 1 below, but none of them
It is a polymer with an extremely low degree of polymerization with an IV (intrinsic viscosity) of 0.57 or less, and the intrinsic viscosity targeted by the present invention is
IV is not shown to be more than 1.0, and in particular, in examples containing phenoxyterephthalic acid components, the IV is only 0.57 at most. Although polymers with such low degrees of polymerization are useful for the purposes described in the above-mentioned US patents, they cannot satisfy the purposes of the present invention. This is clear from Table 2 below.
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As can be understood from the fact that the composition of the present invention is provided by a melt polycondensation method as a composition containing a fully aromatic polyester with a high degree of polymerization that could not be conventionally obtained only by a melt polycondensation method, Comparing the degree of polymerization of fully aromatic polyesters, the composition of the present invention can be molded at a lower temperature than when melt molding the fully aromatic polyester itself, or even at the same molding temperature, it can be molded more easily with a lower load. It has the advantage of being moldable. Furthermore, since the composition of the present invention contains the high melting point low molecular weight compound as described above, even if the wholly aromatic polyester forms an optically anisotropic melt, the composition Melts that are optically isotropic can be formed. First, an unstretched film or fibrous material is formed from the composition of the present invention by melt molding the wholly aromatic polyester composition of the present invention. Melt molding itself can be carried out, for example, using equipment used for melt forming aromatic polyesters, such as polyethylene terephthalate, by extruding the wholly aromatic polyester melt through a slit or nozzle. The unstretched film or fibrous material thus obtained is then extracted with an organic solvent to extract at least a major portion of the high melting point, low molecular weight compound contained therein. Extraction with an organic solvent may be carried out using an unstretched film or fibrous material, or may be carried out after being stretched, further stretched, and further heat-set. Extraction with an organic solvent is preferably further carried out using an organic solvent which is capable of dissolving the high boiling low molecular weight compound and which does not substantially dissolve the wholly aromatic polyester used under the extraction conditions, and which is liquid at ambient temperature and normally It is carried out using an organic solvent having a boiling point below about 200° C. at pressure. Such an organic solvent may have, for example, a carbon number of 6 to 9.
aromatic hydrocarbon, halogenated aliphatic hydrocarbon having 1 or 2 carbon atoms, aliphatic ketone or aliphatic ester having 3 to 6 carbon atoms, 5- or 6-membered cyclic ether, or aliphatic having 1 to 3 carbon atoms. Group alcohols are preferably used. Specifically, aromatic hydrocarbons having 6 to 9 carbon atoms such as benzene, toluene, ethylbenzene, xylene, tamene, and butoidcumene; halogenated aliphatic hydrocarbons having 1 or 2 carbon atoms such as methylene chloride, chloroform, and dichloroethane; ; Aliphatic ketones having 3 to 6 carbon atoms, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aliphatic esters; 5- or 6-membered cyclic ethers such as tetrahydrofuran and dioxane; or 1 carbon atoms such as methanol, ethanol, and propanol.
-3 aliphatic alcohols may be mentioned. Among these, aromatic hydrocarbons having 6 to 9 carbon atoms, halogenated hydrocarbons having 1 or 2 carbon atoms, or 5
Particularly preferably used are 6-membered or 6-membered cyclic ethers. Extraction with organic solvents is advantageously carried out on films having a thickness of less than about 1 mm, preferably from about 1 micron to about 500 microns, or on fibrous materials having an average diameter of less than about 1 mm, preferably from about 3 to about 400 microns. Extraction with organic solvents is preferably carried out under tension and can be carried out at temperatures between ambient temperature and the boiling point of the organic solvent used. The optimum extraction time required for extraction depends on the organic solvent used, the thickness or diameter of the film-like material or fibrous material subjected to extraction, the amount of low molecular weight substances contained in the film-like material or fibrous material, and the extraction temperature. It varies depending on etc. Generally speaking, for example, the thinner the film-like material, the smaller the diameter of the fibrous material, or the higher the extraction temperature, the shorter the optimum time required for extraction. According to the present invention, extraction can be completed in several seconds to about an hour in most cases, and the high-boiling, low-molecular-weight compounds thus contained are about 70% by weight or more, preferably about 80% by weight or more, especially about 90% by weight
A film or fibrous material from which the above components are extracted can be obtained. Extraction with an organic solvent can be carried out by passing a moving film or fibrous material through an organic solvent, or by immersing a stopped film or fibrous material in an organic solvent. You can also do it by In either case, the organic solvent may be fluid or stationary, but it is desirable that at least one of the film (or fibrous material) or the organic solvent is fluid. It goes without saying that the amount of organic solvent used for extraction must be at least enough to dissolve all of the high-melting, low-molecular-weight compounds to be extracted; It is 10 times or more by weight, preferably about 15 times or more by weight. Stretching is carried out in a manner known per se uniaxially (fibers or films) or biaxially (films) simultaneously or successively. If the heat distortion temperature Tg (°C) and melting point of the wholly aromatic polyester composition used are Tm (°C), then the stretching temperature (T 1 , °C) for uniaxial stretching and simultaneous biaxial stretching is
is in a range that satisfies the following formula Tg-10âŠT 1 âŠTm-20, more preferably the following formula Tg-5âŠT 1 âŠTm-30. In addition, in the case of sequential biaxial stretching, the first stage stretching temperature is the temperature (T 1 ) that satisfies the above formula, and the second stage stretching temperature is
The stretching temperature (T 1 , °C) of the stage is set within a range that satisfies the following formula T 2 â§T 1 . The stretching ratio is usually about 2 to 10 times for fibrous materials, and the area ratio is usually about 2 to 10 times for film materials.
It is about 30 times larger. According to the method of the present invention, since the wholly aromatic polyester composition used contains the above-mentioned high boiling point low molecular weight compound, the melt viscosity of the wholly aromatic polyester composition is lower than that of the wholly aromatic polyester contained in the composition. The melt viscosity is lower than that of the single melt viscosity, thus making it possible to produce very fine fibers or very thin films even from compositions containing high molecular weight aromatic polyesters. Said heat fixation before extraction is carried out under tension.
The heat setting temperature (Ts, °C) of the material subjected to uniaxial stretching and simultaneous biaxial stretching is as follows, where the stretching temperature is T 1 (°C) and the melting point (Tm, °C) of the wholly aromatic polyester composition used is: This is a range that satisfies the following formula T 1 +5âŠTsâŠTmâ10. Further, in the case of a film subjected to sequential biaxial stretching, when the second stage stretching temperature is T 2 (° C.), the range satisfies the following formula T 2 +5âŠTsâŠTmâ10. Heat fixation is usually 1 second to 10
It can be done for minutes. In this way, the unstretched or stretched film or fibrous material of the wholly aromatic polyester from which at least the main portion of the high melting point low molecular weight compounds contained therein has been extracted and removed may be further stretched, heat set or fibrous as required. It is also possible to further heat set after stretching. Such stretching after extraction can be carried out under temperature conditions in which the heat distortion temperature of the wholly aromatic polyester composition is read as the heat distortion temperature of the wholly aromatic polyester in the stretching before extraction. The stretching ratio can be the same as the above-mentioned ratio before extraction, but
Generally, the sum of the stretching ratio before extraction and the stretching ratio after extraction falls within the range of the stretching ratio before extraction. Heat fixation after extraction can be carried out under the same conditions as the heat fixation before extraction. However, the condition is that the melting point of the wholly aromatic polyester composition is read as the melting point of the wholly aromatic polyester. Thus, according to the method of the present invention, a completely aromatic product containing substantially no high melting point low molecular weight compound or containing at most 1 part by weight of the above high melting point low molecular weight compound per 100 parts by weight of the wholly aromatic polyester. Films or fibers of the group polyesters can be produced. Since the film or fibrous material provided by the present invention has excellent organic properties and heat resistance, it can be used as a film for metal deposition, a film for flexible printed wiring, etc. It can be used as an electrical insulating film, a film for magnetic tape, etc., and in the case of fibrous materials, it can be used, for example, as a rubber reinforcing material. Examples Hereinafter, the present invention will be explained in further detail with reference to Examples.
However, the invention is not limited in any way by such embodiments. Various physical property values in Examples are measured or defined as follows. Parts represent parts by weight. Strength, elongation and Young's modulus were measured using an Instron measuring machine at a tensile rate of 100%/min. The intrinsic viscosity is a solution in a mixed solvent of p-chlorophenol/tetrachloroethane = 60/40 (weight ratio) (polymer concentration 0.1
g/dl) at 35°C. The melting point viscosity was measured using a flow tester after filling about 1 g of the residue into a cylinder with a cross-sectional area of 1 cm 3 equipped with a discharge nozzle of 1 mm in diameter and 5 mm in length. For wholly aromatic polyesters that are optically isotropic in their molten state, their melting point (for polymers teeth
Tm and Tmâ² for the composition were measured. In addition, for fully aromatic polyesters that form optically anisotropic melts, the temperature at which they transition from a solid to an optically anisotropic melt (for polymers, T N compositions
T N ') and the temperature of transition from a solid or optically anisotropic melt to an optically isotropic melt (T L for polymers and T L ' for compositions) were measured.
The heat distortion temperature (Tg) of the wholly aromatic polyester composition or wholly aromatic polyester is 500Ό in thickness and 1 in width.
cm, an amorphous test thin film with a length of about 6 cm was melt-molded,
It was placed on a support stand with two fulcrums spaced 3 cm apart (the width of each fulcrum was 2 cm), and a weight weighing 10 g was placed on top of the test thin set in this manner and approximately in the center of the two fulcrums. Place the weight on it, immerse it in a silicone oil bath, then raise the temperature of the bath at a rate of about 4â/min, and measure the temperature when the center of the test thin with the weight on it drops 1cm from the top of the fulcrum. I asked. Moreover, the extraction rate (weight %) of the high boiling point low molecular weight compound was calculated from the difference in weight of the sample before and after extraction. Reference example 1 Phenoxyterephthalic acid diphenyl ester
410 parts of hydroquinone and 132 parts of hydroquinone were charged together with 0.088 parts of stannous acetate as a polymerization catalyst into a polycondensation reactor equipped with a stirrer, and after replacing the atmosphere of the system with nitrogen gas, the temperature was raised from 250°C to 290°C for 120 minutes. Put it on,
The mixture was heated while distilling the produced phenol out of the reaction system. Next, the pressure of the reaction system was gradually reduced and the temperature of the reactor was raised, and after 60 minutes, the internal pressure of the reactor was reduced to 1 mm.
Hg or less, the reaction temperature was set to 340°C, and at this temperature, stirring was stopped and the reaction was allowed to proceed for 30 minutes. The melting point (DSC) of the obtained polymer was 325°C, but the flow initiation temperature measured by the Protester was approximately
It was 405â. Note that this flow start temperature is calculated using a flow tester for measuring melt viscosity at a load of 100 kg (polymer pressure of 100 kg).
Kg/cm 2 ), and the temperature is shown as the temperature at which the polymer starts flowing out from the cap. From the above results, the polyester of the present invention can be heated to 400°C.
It is understood that it cannot be molded below. Furthermore, even if an attempt was made to forcibly mold the material at temperatures above 405° C., thermal decomposition began to proceed, making it impossible to mold the material efficiently and while maintaining high quality. Example 1 In Reference Example 1, 220 parts of non-reactive 4,4'-bis-(p-phenylphenoxy) diphenylsulfone was added together with the above raw materials, and the same procedure as in Reference Example 1 was carried out. Polymerized. The thus obtained molten polymer
The resulting polymer composition, which was ground into 10-20 meshes and reacted for 10 hours at a temperature of 270°C and a pressure of 0.2 mmHg, was
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åŸããããã€ã«ã ã®æ§èœãäžèšè¡šïŒã«ç€ºãã60% by weight polyester consisting of [Formula] and 4,
It has a composition consisting of 40% by weight of 4'-bis-(paraphenylphenoxy) diphenyl sulfone, the melting point of the composition is 285°C, and the melting point viscosity at 380°C is 6.0 à 10 4 poise. Ta. The obtained composition was extruded to a width of 0.5 mm using a 15 mmÏ twin-screw extruder (cylinder temperature 360 to 70°C).
A raw film with a thickness of about 0.4 mm was obtained by melt extrusion through a T-die with a length of 100 mm. The obtained raw film was stretched at 200° C. twice in the machine axis direction (MD) and further twice in the transverse direction (TD). The film thus obtained was immersed in dioxane at a fixed length, treated under refluxing dioxane for 30 minutes, and then vacuum-dried at 150° C. for 5 hours. This treatment extracted more than 99% of 4,4'-bis-(paraphenylphenoxy)diphenylsulfone. The performance of the obtained film is shown in Table 3 below.
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ãã§ãã€ãã[Table] In addition, the above polyester composition was spun at 360°C without solid phase polymerization (intrinsic viscosity: 4.5) through a single nozzle cap with a diameter of 0.5 mm and a length of 3 mm, and the obtained raw yarn was fixed in a metal frame. The film was extracted in xylene at 120°C, and then stretched 1.5 times at 200°C. The physical properties of the obtained yarn were as follows. Strength: 5g/Denier Elongation: 5% Young Modulus: 450g/Denier Example 2 (Phenoxyterephthalic acid/Terephthalic acid =
(Example using 8/2 molar ratio) 328 parts of diphenyl phenoxyterephthalate, 63.6 parts of diphenyl terephthalate, hydroquinone
132 parts, 0.088 parts of stannous acetate as a polycondensation catalyst, and 4,4'-bis-(p-phenylphenoxy)
Melt polymerization was carried out in the same manner as in Example 1 using 210 parts of diphenyl ketone, followed by solid phase polymerization. The obtained composition exhibited a melt viscosity of 6.5Ã10 4 poise at 380° C. (shear rate γ=1001/sec). The obtained composition was melt-extruded from an extruder in the same manner as in Example 1 to obtain a raw film having a thickness of 300 ÎŒm. Next, the original film was fixed in a metal frame and extracted in dioxane at 100°C, followed by vacuum drying at 150°C for 5 hours. This treatment extracted more than 99% of 4,4'-bis(p-phenylphenoxy)diphenylsulfone. The physical properties of the obtained unstretched film were as shown in Table 4 below.
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ã§ãã€ãã[Table] This unstretched film was stretched 2.5 times in the machine direction (MD) and further 2.5 times in the transverse direction (TD) at 260°C. The physical properties of the obtained film were as shown in Table 5 below.
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ãåŸãã[Table] Examples 3 to 8 In Example 1, the type and amount of the low molecular weight compound were changed and solid phase polymerization was performed to obtain the compositions shown in Table 6 below.
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ãã®çµæãè¡šïŒã«ç€ºãã[Table] ** The units of these values are strength: Kg/mm 2 and elongation:
%, Young modulus: Kg/ mm2 .
When each of the above compositions was melt-formed into a film using an extruder at 370°C to 380°C, good original films were obtained. The obtained original fabric was stretched 3.0 times at 220°C, and then treated in the same manner as in Example 1. Examples 9 to 11 A wholly aromatic polyester composition was prepared in the same manner as in Example 1 except that 132 parts of hydroquinone in Example 1 was replaced with the diol shown in Table 7 below. A uniaxially stretched film was produced in the same manner as in Example 3 using the wholly aromatic polyester composition. The results are shown in Table 7.
Claims (1)
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ãã¯âCOâã§ãããïŒ[Claims] 1. An aromatic dihydroxy compound in which the phenoxyterephthalic acid component and the two hydroxy groups bonded to the aromatic nucleus have chain elongation properties in opposite directions and are coaxial or parallel axes. A substantially linear wholly aromatic polyester having ester bonds as the main repeating bonds, and having an intrinsic viscosity of 1.0 or more,
and 60 parts by weight of the wholly aromatic polyester and 4,4'-
100 parts by weight of a wholly aromatic polyester having a melt viscosity at 380°C (shear rate γ = 100 sec -1 ) of 1000 poise or more, measured as a mixture of 40 parts by weight of bis(p-phenylphenoxy) diphenylsulfone; and a high-boiling point, low-molecular-weight compound 5 to 1, which is a compound represented by the following formula, is substantially non-reactive with the above-mentioned wholly aromatic polyester, and has a molecular weight of 1000 or less.
A wholly aromatic polyester composition comprising 400 parts by weight. Ar-X-Ar (where Ar is a monovalent aromatic group, and X is -SO 2 - or -CO-) Reacting with an aromatic dihydroxy compound component whose groups have chain elongation in opposite directions and are located on the same or parallel axes,
When producing a substantially linear wholly aromatic polyester, a compound represented by the following formula that is substantially non-reactive with the produced wholly aromatic polyester and has a molecular weight of 1000 or less is added to the polymerization system. A high boiling point, low molecular weight compound is added to the wholly aromatic polyester.
A melt polycondensation reaction is carried out in the proportion of 5 to 400 parts by weight per 100 parts by weight. Determined as a mixture of 40 parts by weight of enylphenoxy)diphenylsulfone.
The melt viscosity at 380â (shear rate γ=100sec -1 ) is
1. A method for producing a wholly aromatic polyester composition, comprising forming a composition containing a wholly aromatic polyester having a poise of 1000 poise or more. Ar-X-Ar (Here, Ar is a monovalent aromatic group, and X is -SO2- or -CO-.)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17696683A JPS6069132A (en) | 1983-09-27 | 1983-09-27 | Fully aromatic polyester, its molding composition and production of molding using same |
JP20240790A JPH0395231A (en) | 1983-09-27 | 1990-08-01 | Manufacture of wholly aromatic polyester molding |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17696683A JPS6069132A (en) | 1983-09-27 | 1983-09-27 | Fully aromatic polyester, its molding composition and production of molding using same |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20240790A Division JPH0395231A (en) | 1983-09-27 | 1990-08-01 | Manufacture of wholly aromatic polyester molding |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6069132A JPS6069132A (en) | 1985-04-19 |
JPH0449569B2 true JPH0449569B2 (en) | 1992-08-11 |
Family
ID=16022817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17696683A Granted JPS6069132A (en) | 1983-09-27 | 1983-09-27 | Fully aromatic polyester, its molding composition and production of molding using same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6069132A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3710643A1 (en) * | 1987-03-31 | 1988-10-20 | Huels Chemische Werke Ag | AROMATIC POLYESTERS BASED ON PHENOXYTEREPHTHALIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3723388A (en) * | 1971-10-08 | 1973-03-27 | Eastman Kodak Co | Phenoxyphthalate polyesters |
JPS4921440A (en) * | 1972-06-19 | 1974-02-25 | ||
JPS5884823A (en) * | 1981-11-09 | 1983-05-21 | ã¢ã¢ã³ãã³ãŒãã¬ãŒã·ã§ã³ | Manufacture of polyester or poly(ester carbonate) in presence of treatment aid |
-
1983
- 1983-09-27 JP JP17696683A patent/JPS6069132A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3723388A (en) * | 1971-10-08 | 1973-03-27 | Eastman Kodak Co | Phenoxyphthalate polyesters |
JPS4921440A (en) * | 1972-06-19 | 1974-02-25 | ||
JPS5884823A (en) * | 1981-11-09 | 1983-05-21 | ã¢ã¢ã³ãã³ãŒãã¬ãŒã·ã§ã³ | Manufacture of polyester or poly(ester carbonate) in presence of treatment aid |
Also Published As
Publication number | Publication date |
---|---|
JPS6069132A (en) | 1985-04-19 |
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