JPH0291119A - Aromatic polyester and preparation thereof - Google Patents
Aromatic polyester and preparation thereofInfo
- Publication number
- JPH0291119A JPH0291119A JP24072188A JP24072188A JPH0291119A JP H0291119 A JPH0291119 A JP H0291119A JP 24072188 A JP24072188 A JP 24072188A JP 24072188 A JP24072188 A JP 24072188A JP H0291119 A JPH0291119 A JP H0291119A
- Authority
- JP
- Japan
- Prior art keywords
- ester
- aromatic
- arom
- formulas
- dihydroxynaphthalene
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 title claims description 28
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- -1 Aromatic diol Chemical class 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 150000002009 diols Chemical class 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 6
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 6
- 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 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 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 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- BRYRWETXZVMCQQ-UHFFFAOYSA-N 2-chloro-3-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1Cl BRYRWETXZVMCQQ-UHFFFAOYSA-N 0.000 description 1
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 description 1
- GUTJKXDLQINLLR-UHFFFAOYSA-N 2-heptylbenzene-1,4-diol Chemical compound CCCCCCCC1=CC(O)=CC=C1O GUTJKXDLQINLLR-UHFFFAOYSA-N 0.000 description 1
- NOUJHHZNUIXAEX-UHFFFAOYSA-N 2-hexylbenzene-1,4-diol Chemical compound CCCCCCC1=CC(O)=CC=C1O NOUJHHZNUIXAEX-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- ZZXILYOBAFPJNS-UHFFFAOYSA-N 2-octylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=CC=C1O ZZXILYOBAFPJNS-UHFFFAOYSA-N 0.000 description 1
- ZFMFIBDSZCASNS-UHFFFAOYSA-N 2-pentylbenzene-1,4-diol Chemical compound CCCCCC1=CC(O)=CC=C1O ZFMFIBDSZCASNS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 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
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、新規な芳香族ポリエステルに関するものであ
り、更に詳しくは溶融成形が可能で耐熱性1機械的特性
2寸法安定性、耐溶剤性、溶融時の酸化特性等に優れて
おり、かつ吸水性が低く、エンジニアリングプラスチッ
クスとして有用な液晶形成性の芳香族ポリエステルに関
するものでおる。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a novel aromatic polyester, more specifically, it is melt moldable and has excellent heat resistance, mechanical properties, dimensional stability, and solvent resistance. This invention relates to a liquid crystal-forming aromatic polyester that has excellent oxidation properties during melting, has low water absorption, and is useful as engineering plastics.
〈従来技術〉
これまでにもガラス繊維等の補強材を用いなくても、十
分に高い耐熱性、および機械的強度の得られる溶融成形
の可能なポリエステルとして、各種の液晶形成性ポリエ
ステルが提案されている。<Prior art> Various liquid crystal-forming polyesters have been proposed as polyesters that can be melt-molded and have sufficiently high heat resistance and mechanical strength without using reinforcing materials such as glass fibers. ing.
かかる液晶形成性ポリエステルの一種として、テレフタ
ル酸を主とする芳香族ジカルボン酸の残基、置換ヒドロ
キノンを主とする芳香族ジヒドロキシ化合物の残基より
構成された芳香族ポリエステルが種々提案されている(
特公昭58−45224号公報等)。これらの芳香族ポ
リエステルは、耐熱性が良好で、かつ成型物の機械的特
性に優れているため、成形材料等として有用である。し
かし、本発明者らの検討したところ、溶融温度が高いた
め成形しにくいことがわかった。また、融点を下げる目
的で、例えば特公昭59−78232号公報等に記載さ
れている共重合成分を添加して検討したところ、融点は
下がるものの、流動性、繊維形成性に問題が残ることが
わかった。As a type of such liquid crystal-forming polyesters, various aromatic polyesters composed of residues of aromatic dicarboxylic acids, mainly terephthalic acid, and residues of aromatic dihydroxy compounds, mainly substituted hydroquinone, have been proposed (
(Special Publication No. 58-45224, etc.). These aromatic polyesters have good heat resistance and excellent mechanical properties of molded products, so they are useful as molding materials and the like. However, upon investigation by the present inventors, it was found that molding is difficult due to the high melting temperature. Furthermore, in order to lower the melting point, we investigated adding a copolymer component described in Japanese Patent Publication No. 59-78232, etc., and found that although the melting point was lowered, problems remained in fluidity and fiber formation. Understood.
〈発明の目的〉
本発明者らは、かかる点に着目し、種々の検討を行なっ
た結果、特定構造の成分を共重合すると、流動性、繊維
形成性が著しく向上することを見出し、本発明に到達し
たものである。<Object of the Invention> The present inventors focused on this point and conducted various studies, and as a result, discovered that copolymerization of components with a specific structure significantly improves fluidity and fiber-forming property. has been reached.
〈発明の構成および効果〉
すなわち、本発明は
[ここで、Rは炭化水素基である。]
[ここで、Arはパラ配向性芳香族基である。]を主成
分とし、(A)および(B)のユニットのモル数をそれ
ぞれa、 bとした時、下記式(I)40、/60≦a
、/b≦85/15 ・(I >を満たし、かつ
固有粘度が0.5以上であることを特徴とする芳香族ポ
リエステルである。<Structure and Effects of the Invention> That is, the present invention provides [where R is a hydrocarbon group]. ] [Here, Ar is a para-oriented aromatic group. ] is the main component, and the number of moles of units (A) and (B) are a and b, respectively, the following formula (I) 40, /60≦a
, /b≦85/15 ·(I>), and is an aromatic polyester characterized by having an intrinsic viscosity of 0.5 or more.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
本発明の芳香族ポリエステルを構成するジオール成分は
、主として
[ここで、Rは炭化水素基である。]
および
GO−Ar−CO−
・・・(C)
・・・(B)
よりなる。The diol component constituting the aromatic polyester of the present invention is mainly [where R is a hydrocarbon group]. ] and GO-Ar-CO-...(C)...(B).
(A)成分においてRは炭化水素基であり、具体的には
アルキル基、アラルキル基、アリール基等が挙げられる
。好ましくは炭素数5〜8のアルキル基、炭素数7〜1
5のアラルキル基、炭素数6〜12のアリール基であり
、更に、好ましくは−C−AI”(ここで、R1および
R2は水素原子または低級アルキル基であり、Ar’は
炭素数6〜12の芳香族基である。)で示されるアラル
キル基およ■3
ルキル基である。)で示されるアリール基である。In component (A), R is a hydrocarbon group, and specific examples include an alkyl group, an aralkyl group, and an aryl group. Preferably an alkyl group having 5 to 8 carbon atoms, 7 to 1 carbon atoms
5 aralkyl group, an aryl group having 6 to 12 carbon atoms, and more preferably -C-AI'' (where R1 and R2 are a hydrogen atom or a lower alkyl group, and Ar' is an aryl group having 6 to 12 carbon atoms). (3) is an aromatic group represented by () and an aryl group ((3) is an alkyl group).
(A)成分の具体例としては、アミルハイドロキノン、
ヘキシルハイドロキノン、ヘプチルハイドロキノン、オ
クチルヒドロキノン、ベンジルヒドロキノン、α−メチ
ルベンジルヒドロキノン、α。Specific examples of component (A) include amylhydroquinone,
Hexylhydroquinone, heptylhydroquinone, octylhydroquinone, benzylhydroquinone, α-methylbenzylhydroquinone, α.
α−ジメチルベンジルヒドロキノン、フェニルヒドロキ
ノン、トリルヒドロキノン、クロルフェニルヒドロキノ
ン等が挙げられる。Examples include α-dimethylbenzylhydroquinone, phenylhydroquinone, tolylhydroquinone, and chlorphenylhydroquinone.
(B)成分の具体例としては1.5−ジヒドロキシナフ
タレン、2.6−ジヒドロキシナフタレン、2゜7−ジ
ヒドロキシナフタレン等を例示することができ、特に1
,5−ジヒドロキシナフタレンが好ましい。Specific examples of component (B) include 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2゜7-dihydroxynaphthalene, etc. In particular, 1
, 5-dihydroxynaphthalene is preferred.
なお、前記(^)成分および(8)成分の一部、例えば
30モル%以下、より好ましくは10モル%以下の割合
で他の芳香族ジオールおよび/または脂肪族ジオールを
用いることもできる。この他の芳香族ジオールとしては
ハイドロキノン、レゾルシン。Note that other aromatic diols and/or aliphatic diols can also be used in a part of the components (^) and (8), for example, in a proportion of 30 mol% or less, more preferably 10 mol% or less. Other aromatic diols include hydroquinone and resorcinol.
ビスフェノールA、ビスフェノールS、ビスフェノール
Z、4,4°−ジヒドロキシジフェニル、4.4゜−ジ
ヒドロキシジフェニルエーテル、ブチルハイドロキノン
、メチルハイドロキノン、クロルハイドロキノン等を例
示することができ、また脂肪族ジオールとしてはエチレ
ングリコール、ネオペンチレンゲリコール、シクロヘキ
サンジメチロール。Examples include bisphenol A, bisphenol S, bisphenol Z, 4,4°-dihydroxydiphenyl, 4.4°-dihydroxydiphenyl ether, butylhydroquinone, methylhydroquinone, chlorohydroquinone, and aliphatic diols include ethylene glycol, Neopentylene gellicol, cyclohexane dimethylol.
ビス−β−ヒドロキシビスフェノール類(殊にビス−β
−ヒドロキシビスフェノールA、ビス−β−ヒドロキシ
ビスフェノールS、ビスーβ−ヒドロキシビスフェノー
ルZ等)等の如き低級アルキレングリコールまたは脂環
族グリコールを挙げることができる。これらのうち、他
の芳香族ジオールがより好ましい。Bis-β-hydroxybisphenols (especially bis-β-hydroxybisphenols)
-hydroxybisphenol A, bis-β-hydroxybisphenol S, bis-β-hydroxybisphenol Z, etc.) or alicyclic glycols. Among these, other aromatic diols are more preferred.
全ジオール成分中に占める(A)成分および(8)成分
のモル数の合計の割合は、70モル%以上、更には80
モル%以上、特に90モル%以上であることが好ましい
。The total number of moles of component (A) and component (8) in all diol components is 70 mol% or more, more preferably 80 mol%.
It is preferably at least 90 mol%, particularly at least 90 mol%.
本発明の芳香族ポリエステルを構成する酸成分は主とし
て
−Go−Ar−Co−−−・(C)
[ここで、Arはパラ配向性芳香族基である。]よりな
る。The acid component constituting the aromatic polyester of the present invention is mainly -Go-Ar-Co---.(C) [Here, Ar is a para-oriented aromatic group. ] Consists of.
ここでArはパラ配向性芳香族基であるが、パラ位とは
、ベンゼン核において1位と4位の位置を、またナフタ
リン核においては2位と6位、2位と7位または1位と
5位の位置を更にまたジフェニル核においては4位と4
°位の位置を表わす。Here, Ar is a para-oriented aromatic group, and the para position refers to the 1st and 4th positions in the benzene nucleus, and the 2nd and 6th positions, the 2nd and 7th positions, or the 1st position in the naphthalene nucleus. and the 5th position, and the 4th and 4th positions in the diphenyl nucleus.
Represents the position in degrees.
(C)成分の具体例としては、テレフタル酸、クロルテ
レフタル酸、ブロムテレフタルl、 25−ジブロムテ
レフタル酸、メチルテレフタル酸、2゜6−ナツタ・リ
ンジカルボンl1fi、 4.4’−ジフェニルジカル
ボンM、 3,3°−ジブロム−4,4°−ジフェニル
ジカルボン酸等を挙げることができ、これらのうちテレ
フタル酸類、特にテレフタル酸が好ましい。Specific examples of component (C) include terephthalic acid, chlorterephthalic acid, bromoterephthalic acid, 25-dibromoterephthalic acid, methylterephthalic acid, 2゜6-natsuta lindicarbonylfi, 4,4'-diphenyldicarvone M , 3,3°-dibromo-4,4°-diphenyldicarboxylic acid, etc. Among these, terephthalic acids, particularly terephthalic acid, are preferred.
また、前記芳香族二官能性カルボン酸以外に他の二官能
性カルボン酸を小割合用いることもできる。この他の二
官能性カルボン酸としては、例えばイソフタル酸、コハ
ク酸、アジピン酸、シクロヘキサンジカルボン酸等を挙
げることができる。Further, in addition to the aromatic difunctional carboxylic acid, other difunctional carboxylic acids can also be used in small proportions. Examples of other difunctional carboxylic acids include isophthalic acid, succinic acid, adipic acid, and cyclohexanedicarboxylic acid.
全ジカルボン酸成分中に占める(C)成分のモル数の割
合は、70モル%以上、更には80モル%以上、特に9
0モル%以上であることが好ましい。The mole ratio of component (C) in all dicarboxylic acid components is 70 mol% or more, further 80 mol% or more, especially 9
It is preferably 0 mol% or more.
本発明のポリマーにおいては、(A)および(B)のユ
ニットのモル数をそれぞれa、 bとした時、下記式(
I)
40/80≦a、/b ≦85./15・・・(I>
であることが必要であり、好ましくは
50.150≦a、/b≦75/25
である。a 、/b <40/60. a /b >8
5/15の場合は、共に融点が高くなりすぎ、繊維形成
性が良くないばかり、か、良好な流動性を持つ液晶ポリ
マーが得られず好ましくない。In the polymer of the present invention, when the number of moles of units (A) and (B) are a and b, respectively, the following formula (
I) 40/80≦a, /b≦85. /15...(I> is required, preferably 50.150≦a, /b≦75/25. a, /b <40/60. a /b >8
In the case of 5/15, both the melting points are too high and not only the fiber forming properties are not good, but also a liquid crystal polymer having good fluidity cannot be obtained, which is not preferable.
また、(A)成分と(B)成分との和(モル比)および
(C)成分(モル比)は理論上1/1である。Moreover, the sum (molar ratio) of the component (A) and the component (B) and the component (C) (molar ratio) are theoretically 1/1.
本発明の芳香族ポリエステルの重合度は、固有粘度にし
て0.5以上であることが必要であり、好ましくは0.
8以上、特に好ましくは1.0以上である。The degree of polymerization of the aromatic polyester of the present invention needs to be 0.5 or more in terms of intrinsic viscosity, preferably 0.5 or more.
It is 8 or more, particularly preferably 1.0 or more.
なお、本発明でいう固有粘度はP−クロロフェノール/
テトラクロロエタン=L/1(重量比)の混合溶媒中3
5℃で測定した溶液粘度より、算出される値である。Note that the intrinsic viscosity in the present invention is P-chlorophenol/
3 in a mixed solvent of tetrachloroethane = L/1 (weight ratio)
This value is calculated from the solution viscosity measured at 5°C.
本発明の芳香族ポリエステルは下記の方法、(Ao)
[ここで、Rは炭化水素基である。]
で表わされる芳香族ジオールおよび/またはそのエステ
ル形成性誘導体、
(Bo)
で表わされるジヒドロキシナフタレンおよび/またはそ
のエステル形成性誘導体および
(Co)
−CO−^r−CO−・−(C)
[ここで、Arはパラ配向性芳香族基である。]で表わ
される芳香族ジカルボン酸および/またはそのエステル
形成性誘導体とを、上記各(A’)。The aromatic polyester of the present invention can be produced by the following method (Ao) [where R is a hydrocarbon group]. ] Aromatic diol and/or its ester-forming derivative represented by (Bo) Dihydroxynaphthalene and/or its ester-forming derivative represented by (Co) -CO-^r-CO-・-(C) [ Here, Ar is a para-oriented aromatic group. ] An aromatic dicarboxylic acid and/or an ester-forming derivative thereof represented by the above (A').
(B’)、 (C’)のモル数をそれぞれa’、 b’
、 c’とじた時、下記式(II)および<III)
40/ 60≦a ’ 、/ b ’≦85/15
−(n )a’+b’≧C
・・・(III)
を同時に満足する割合で反応せしめ、0.5以上の固有
粘度を有する実質的に線状のポリマーとすることを特徴
とする芳香族ポリエステルの製造法である。ここで(A
o)および(Bo)のエステル形成性誘導体としては、
好ましくは低級脂肪酸エステルが挙げられ、具体的には
酢酸ジエステル、プロピオン酸ジエステル、クロロ酢酸
ジエステル等が例示でき、中でも酢酸ジエステルが好ま
しい。The number of moles of (B') and (C') are a' and b', respectively.
, c' when closed, the following formulas (II) and <III) 40/60≦a', /b'≦85/15
-(n)a'+b'≧C...(III) An aromatic compound characterized by reacting at a rate that satisfies the following simultaneously and forming a substantially linear polymer having an intrinsic viscosity of 0.5 or more. This is a method for producing polyester. Here (A
As the ester-forming derivatives of o) and (Bo),
Preferably, lower fatty acid esters are mentioned, and specific examples include acetic acid diester, propionic acid diester, chloroacetic acid diester, etc. Among them, acetic acid diester is preferable.
また、(Co)のエステル形成性誘導体としては、好ま
しくは芳香族ヒドロキシ化合物エステルが挙げられ、具
体的にはフェニルエステル、トリルエステル、ナフチル
エステル等が例示できるが、中でもフェニルエステルが
好ましい。Preferably, the ester-forming derivative of (Co) includes esters of aromatic hydroxy compounds, and specific examples thereof include phenyl ester, tolyl ester, naphthyl ester, etc. Among them, phenyl ester is preferred.
好ましい製造方法を例示すると、
■ 芳香族ジオールジアセチルエステルとジカルボン酸
とを加熱反応せしめる方法、
■ 芳香族ジオールとジカルボン酸ジフェニルエステル
とを加熱反応せしめる方法、
等がある。Examples of preferred manufacturing methods include (1) a method in which an aromatic diol diacetyl ester and a dicarboxylic acid are subjected to a heat reaction, (2) a method in which an aromatic diol and a dicarboxylic acid diphenyl ester are caused to undergo a heat reaction.
各成分の割合は、成分(A’)/(B’) (モル比)
で40/60〜85/15、好ましくは50150〜7
5/25とし、かつ(成分A’十B’) /C’ (モ
ル比)で1以上、好ましくは1.05〜1.2となるよ
うにする。The ratio of each component is component (A')/(B') (molar ratio)
40/60 to 85/15, preferably 50150 to 7
5/25, and (component A'10B')/C' (molar ratio) is 1 or more, preferably 1.05 to 1.2.
反応は、上記(^’)、 (B’)、 (C’)成分を
所定の量混合し、溶融状態で行なう。反応温度は一般に
は180℃以上、好ましくは200℃以上、特に好まし
くは250℃以上350℃以下である。反応圧力は任意
の圧力を採用できるが、反応が進行するに従って減圧す
る方が好ましい。The reaction is carried out by mixing the above components (^'), (B'), and (C') in predetermined amounts in a molten state. The reaction temperature is generally 180°C or higher, preferably 200°C or higher, particularly preferably 250°C or higher and 350°C or lower. Although any reaction pressure can be used, it is preferable to reduce the pressure as the reaction progresses.
反応に当っては、各成分の添加順序は任意である。また
、一般にポリエステルの重合触媒として知られているも
のが、反応触媒として用いることができる。かかる反応
触媒としては、例えばナトリウム、カリウム、カルシウ
ム、マグネシウム。In the reaction, the order of addition of each component is arbitrary. Moreover, what is generally known as a polyester polymerization catalyst can be used as a reaction catalyst. Examples of such reaction catalysts include sodium, potassium, calcium, and magnesium.
亜鉛、マンガン、コバルト、チタニウム、錫、鉛。Zinc, manganese, cobalt, titanium, tin, lead.
アンチモン、ゲルマニウム等の単体およびこれらの化合
物(例えば酸化物、水素化物、水素酸化物。Simple substances such as antimony and germanium and their compounds (e.g. oxides, hydrides, hydrogen oxides).
ハロゲン化物、アルコラード、フェノラート、有機酸塩
、無機酸塩、錯塩、複塩等)等が挙げられる。halides, alcoholades, phenolates, organic acid salts, inorganic acid salts, complex salts, double salts, etc.).
なお、本発明においては、各種添加剤例えば酸化防止剤
、紫外線吸収剤等の如き安定剤、顔料。In the present invention, various additives such as antioxidants, stabilizers such as ultraviolet absorbers, and pigments are used.
蛍光増白剤等を添加してもよい。A fluorescent whitening agent or the like may be added.
く本発明の効果〉
本発明による芳香族ポリエステルは、液晶特性を有する
ものであり、かつ、溶融成形性、耐薬品性2機械的特性
に優れているだけでなく、耐熱性。Effects of the present invention> The aromatic polyester according to the present invention not only has liquid crystal properties and is excellent in melt moldability, chemical resistance, mechanical properties, and heat resistance.
流動特性、i維形成性にも極めて優れた性能を有するも
のである。It also has extremely excellent performance in terms of fluidity and i-fiber formation.
従って、これらの性能を生かして広範な用途に使用する
ことができ、特にエンジニアリングプラスチックス繊維
として好適に使用される。Therefore, these properties can be utilized in a wide range of applications, and it is particularly suitable for use as engineering plastic fibers.
〈実施例〉
以下実施例をあげて本発明を詳述する。なお、実施例中
の「部」は重量部を意味する。<Examples> The present invention will be described in detail with reference to Examples below. Note that "parts" in the examples mean parts by weight.
また、融点はDSCを用い、昇温速度10℃/分で測定
した値である。Further, the melting point is a value measured using DSC at a heating rate of 10° C./min.
また、流動開始温度は、圧力60Kg −cm−i!で
、半径0.5mm 、’長さ5mmの円柱状吐出孔から
、約10℃7/分の速さで昇温した時、吐出をはじめた
温度である。Moreover, the flow start temperature is a pressure of 60 kg-cm-i! This is the temperature at which discharge begins when the temperature is raised at a rate of about 10° C./min from a cylindrical discharge hole with a radius of 0.5 mm and a length of 5 mm.
実施例1,2および比較例1,2
攪拌機および窒素ガスの導入口と留出口を備えた三ツロ
フラスコに、α−メチルベンジルヒドロキノン、1,5
−ジヒドロキシナフタレンを第1表に示す量、およびジ
フェニルテレフタレート31.8部、酢酸第1スズを0
.003部、トリフェニルホスフィンを0.003部仕
込み、系内を窒素ガスで十分置換した後、窒素ガスをゆ
るやかに流しながら265℃に加熱攪拌した。約30分
後、反応温度を280℃に、ついで約1時間後に300
℃に、さらに約1時間後に330℃に上昇せしめ、さら
に徐々に減圧にし、約70分かけて絶対圧を0.5mm
Hgとし、更に90分間攪拌しつつ反応せしめた。Examples 1 and 2 and Comparative Examples 1 and 2 α-methylbenzylhydroquinone, 1,5
- dihydroxynaphthalene in the amounts shown in Table 1, 31.8 parts of diphenyl terephthalate, and 0 parts of stannous acetate.
.. After adding 0.003 parts of triphenylphosphine and sufficiently replacing the inside of the system with nitrogen gas, the mixture was heated to 265° C. and stirred while slowly flowing nitrogen gas. After about 30 minutes, the reaction temperature was increased to 280°C, and then after about 1 hour to 300°C.
℃, then raised to 330℃ after about 1 hour, and then gradually reduced the pressure to 0.5mm absolute pressure over about 70 minutes.
Hg, and the reaction was continued with stirring for an additional 90 minutes.
得られたポリマーは溶融異方性を示した。その固有粘度
を表1に示す。更に、前記の条件で測定したDSCによ
る融点および流動開始点も表1にボす。The obtained polymer exhibited melt anisotropy. Table 1 shows its intrinsic viscosity. Furthermore, the melting point and flow start point measured by DSC under the above conditions are also listed in Table 1.
また、比較として、実施例1において1,5−ジヒドロ
キシナフタレンの代りに他の芳香族ジオールを用い、あ
とは同様に反応せしめた場合について示した。共重合成
分として4,4゛−ジヒドロキシジフェニルを用いた場
合には1.5−ジヒドロキシナフタレンを用いた場合に
比べて流動性が劣っており、また2、2°−ビス(4−
ヒドロキシフェニル)プロパンを用いた場合には重合条
件下では等方性になり溶融粘度が高く攪拌が困難になり
重合度の低いものしか得ることができなかった。For comparison, a case was shown in which another aromatic diol was used instead of 1,5-dihydroxynaphthalene in Example 1, and the rest was reacted in the same manner. When 4,4'-dihydroxydiphenyl is used as a copolymerization component, the fluidity is inferior to that when 1,5-dihydroxynaphthalene is used, and 2,2'-bis(4-
When hydroxyphenyl)propane was used, it became isotropic under polymerization conditions and had a high melt viscosity, making stirring difficult and only a product with a low degree of polymerization could be obtained.
実施例3
実施例1と同様の反応器に、フェニルヒドロキノン13
.96部、1,5−ジヒドロキシナフタレン4.80部
、ジフェニルテレフタレート31.8部および酢酸第1
スズ0.003部、トリフェニルホスフィン0、004
部を仕込み、実施例1と同様に反応せしめた。Example 3 In a reactor similar to Example 1, phenylhydroquinone 13
.. 96 parts, 1,5-dihydroxynaphthalene 4.80 parts, diphenyl terephthalate 31.8 parts and acetic acid 1st
0.003 parts of tin, 0.004 parts of triphenylphosphine
and reacted in the same manner as in Example 1.
得られたポリマーはサーモトロピックな液晶であり、固
有粘度2.41. DSCに寄る融点は明確でなかった
が流動開始温度は274℃でおり、流動特性および繊維
形成性は非常に優れていた。The obtained polymer is a thermotropic liquid crystal with an intrinsic viscosity of 2.41. Although the melting point determined by DSC was not clear, the flow initiation temperature was 274°C, and the flow characteristics and fiber forming properties were very excellent.
実施例4
実施例1と同様の反応器に、ベンジルヒドロキノンジア
セテート18.46部、1,5−ジヒドロキシナフタレ
ンジアセテート9.76部、テレフタル酸16.6部、
および酢酸第1スズ0.003部、トリフェニルホスフ
ィン0.004部を仕込み、実施例1と同様に反応せし
めた。得られたポリマーは、サーモトロピックな液晶で
あり、固有粘度2.03.融点299°C1流動開始温
度255°Cであり、流動特性および繊維形成性は、非
常に優れていた。Example 4 In a reactor similar to Example 1, 18.46 parts of benzylhydroquinone diacetate, 9.76 parts of 1,5-dihydroxynaphthalene diacetate, 16.6 parts of terephthalic acid,
Then, 0.003 part of stannous acetate and 0.004 part of triphenylphosphine were added, and the reaction was carried out in the same manner as in Example 1. The obtained polymer is a thermotropic liquid crystal with an intrinsic viscosity of 2.03. The melting point was 299°C and the flow start temperature was 255°C, and the flow characteristics and fiber forming properties were very excellent.
実施例5
実施例1と同様の反応器にα、α−ジメチルベンジルヒ
ドロキノンジアセテート20.28部、1.5−ジヒド
ロキシナフタレンジアセテート9.76部。Example 5 In a reactor similar to Example 1, 20.28 parts of α,α-dimethylbenzylhydroquinone diacetate and 9.76 parts of 1,5-dihydroxynaphthalene diacetate were added.
2.6−ナフタレンジカルボン198.64部、および
酢酸第1スズ0.003部、トリフェニルホスフィン0
、004部を仕込み、実施例1と同じように反応せしめ
た。得られたポリマーはサーモトロピックな液晶であり
、固有粘度2.15.融点325℃、誘動開始温度は2
82℃であり、流動特性および繊維形成性は非常に優れ
ていた。2.6-naphthalenedicarbone 198.64 parts, stannous acetate 0.003 parts, triphenylphosphine 0
, 004 parts were charged and reacted in the same manner as in Example 1. The obtained polymer is a thermotropic liquid crystal with an intrinsic viscosity of 2.15. Melting point: 325℃, induction temperature: 2
The temperature was 82°C, and the flow characteristics and fiber forming properties were excellent.
比較例3
1.5−ジヒドロキシナフタレンジアセテート9.76
部の代りにヒドロキノンジアセテート7.76部を用い
、他は同様に反応せしめたところ減圧反応中にポリマー
が析出固化した。Comparative Example 3 1.5-dihydroxynaphthalene diacetate 9.76
When the reaction was carried out in the same manner except that 7.76 parts of hydroquinone diacetate was used instead of 1 part, the polymer precipitated and solidified during the reaction under reduced pressure.
実施例6〜7
実施例1と同様の反応容器に、α−メチルベンジルヒド
ロキノン17.55部、ジフェニルテレフタレート31
.8部、酢酸第1スズ0.003部、および表2に示す
物質を、同じく表2に示す量だけ仕込み、実施例1と同
様に反応せしめた。得られたポリマーは溶融異方性を示
した。その固有粘度、前記の条件で測定したDSCによ
る融点および流動開始点、流動特性をも表2に示す。Examples 6 to 7 In a reaction vessel similar to Example 1, 17.55 parts of α-methylbenzylhydroquinone and 31 parts of diphenyl terephthalate were added.
.. 8 parts of stannous acetate, 0.003 parts of stannous acetate, and the substances shown in Table 2 in the amounts shown in Table 2 were charged, and the reaction was carried out in the same manner as in Example 1. The obtained polymer exhibited melt anisotropy. Table 2 also shows its intrinsic viscosity, melting point and flow start point measured by DSC under the above conditions, and flow characteristics.
Claims (2)
分とし、(A)および(B)のユニットのモル数をそれ
ぞれa、bとした時、下記式( I )を満たし、かつ固
有粘度が0.5以上であることを特徴とする芳香族ポリ
エステル。(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(A) [Here, R is a hydrocarbon group. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(B) and -CO-Ar-CO-...(C) [Here, Ar is a para-oriented aromatic group. ] is the main component, and when the number of moles of units (A) and (B) are a and b, respectively, it satisfies the following formula (I) and has an intrinsic viscosity of 0.5 or more. Aromatic polyester.
ル形成性誘導体、 (B′) ▲数式、化学式、表等があります▼・・・(B) で表わされるジヒドロキシナフタレンおよび/またはそ
のエステル形成性誘導体および (C′) ▲数式、化学式、表等があります▼・・・(C) [ここで、Arはパラ配向性芳香族基である。]で表わ
される芳香族ジカルボン酸および/またはそのエステル
形成性誘導体とを、上記各(A′)、(B′)、(C′
)のモル数をそれぞれa′、b′、c′とした時、下記
式(II)および(III) 40/60≦a′/b′≦85/15・・・(II)a′
+b′≧c′・・・(III) を同時に満足する割合で反応せしめ、0.5以上の固有
粘度を有する実質的に線状のポリマーとすることを特徴
とする芳香族ポリエステルの製造法。(2) (A') ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(A) [Here, R is a hydrocarbon group. ] Aromatic diol and/or its ester-forming derivative, (B') ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(B) Dihydroxynaphthalene and/or its ester-forming derivative, and (C') ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (C) [Here, Ar is a para-oriented aromatic group. ] The aromatic dicarboxylic acid and/or its ester-forming derivative represented by (A'), (B'), (C'
), the following formulas (II) and (III) 40/60≦a'/b'≦85/15... (II) a'
+b'≧c'...(III) A method for producing an aromatic polyester, which is characterized by reacting at a ratio satisfying the following at the same time and producing a substantially linear polymer having an intrinsic viscosity of 0.5 or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63240721A JPH07113057B2 (en) | 1988-09-28 | 1988-09-28 | Aromatic polyester and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63240721A JPH07113057B2 (en) | 1988-09-28 | 1988-09-28 | Aromatic polyester and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0291119A true JPH0291119A (en) | 1990-03-30 |
JPH07113057B2 JPH07113057B2 (en) | 1995-12-06 |
Family
ID=17063714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63240721A Expired - Fee Related JPH07113057B2 (en) | 1988-09-28 | 1988-09-28 | Aromatic polyester and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07113057B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009128325A1 (en) * | 2008-04-16 | 2009-10-22 | 日東電工株式会社 | Birefringent film, polarizing plate, image display device and aromatic polyester |
JP5510764B1 (en) * | 2012-10-17 | 2014-06-04 | Dic株式会社 | Active ester resin, epoxy resin composition, cured product thereof, prepreg, circuit board, and build-up film |
WO2023190020A1 (en) * | 2022-03-29 | 2023-10-05 | 味の素株式会社 | Active ester resin |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01297425A (en) * | 1988-05-26 | 1989-11-30 | Agency Of Ind Science & Technol | High-elastic modulus copolyester |
-
1988
- 1988-09-28 JP JP63240721A patent/JPH07113057B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01297425A (en) * | 1988-05-26 | 1989-11-30 | Agency Of Ind Science & Technol | High-elastic modulus copolyester |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009128325A1 (en) * | 2008-04-16 | 2009-10-22 | 日東電工株式会社 | Birefringent film, polarizing plate, image display device and aromatic polyester |
JP2009256456A (en) * | 2008-04-16 | 2009-11-05 | Nitto Denko Corp | Birefringent film, polarizing plate, image display and aromatic polyester |
US8741399B2 (en) | 2008-04-16 | 2014-06-03 | Nitto Denko Corporation | Birefringent film, polarizing plate, image display, and aromatic polyester |
JP5510764B1 (en) * | 2012-10-17 | 2014-06-04 | Dic株式会社 | Active ester resin, epoxy resin composition, cured product thereof, prepreg, circuit board, and build-up film |
WO2023190020A1 (en) * | 2022-03-29 | 2023-10-05 | 味の素株式会社 | Active ester resin |
Also Published As
Publication number | Publication date |
---|---|
JPH07113057B2 (en) | 1995-12-06 |
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