CN101300288A - 纺丝液及使用该纺丝液的纤维的制造方法 - Google Patents
纺丝液及使用该纺丝液的纤维的制造方法 Download PDFInfo
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- CN101300288A CN101300288A CNA2006800410118A CN200680041011A CN101300288A CN 101300288 A CN101300288 A CN 101300288A CN A2006800410118 A CNA2006800410118 A CN A2006800410118A CN 200680041011 A CN200680041011 A CN 200680041011A CN 101300288 A CN101300288 A CN 101300288A
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- polymeric amide
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- 238000000034 method Methods 0.000 title claims abstract description 30
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- 239000002904 solvent Substances 0.000 claims abstract description 25
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- 238000009987 spinning Methods 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 52
- 150000001408 amides Chemical class 0.000 claims description 39
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000007669 thermal treatment Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 abstract description 5
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- 239000002245 particle Substances 0.000 abstract description 4
- -1 polyparaphenylene benzo-dioxazole Polymers 0.000 description 8
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
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- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 230000000739 chaotic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- KDISMIMTGUMORD-UHFFFAOYSA-N 1-acetylpiperidine Chemical class CC(=O)N1CCCCC1 KDISMIMTGUMORD-UHFFFAOYSA-N 0.000 description 1
- LNWWQYYLZVZXKS-UHFFFAOYSA-N 1-pyrrolidin-1-ylethanone Chemical compound CC(=O)N1CCCC1 LNWWQYYLZVZXKS-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- PEPBFCOIJRULGJ-UHFFFAOYSA-N 3h-1,2,3-benzodioxazole Chemical compound C1=CC=C2NOOC2=C1 PEPBFCOIJRULGJ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- YVORUSXCOOTKBR-UHFFFAOYSA-N C(C1=CC=C(C(=O)N)C=C1)(=O)N.OC1=CC=C(C=C1)C1=CC=C(C=C1)O Chemical compound C(C1=CC=C(C(=O)N)C=C1)(=O)N.OC1=CC=C(C=C1)C1=CC=C(C=C1)O YVORUSXCOOTKBR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101100240886 Rattus norvegicus Nptx2 gene Proteins 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N anhydrous dimethyl-acetamide Natural products CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
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- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229940047889 isobutyramide Drugs 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- HBJPJUGOYJOSLR-UHFFFAOYSA-N naphthalene-2,7-diamine Chemical compound C1=CC(N)=CC2=CC(N)=CC=C21 HBJPJUGOYJOSLR-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- ABYXFACYSGVHCW-UHFFFAOYSA-N pyridine-3,5-diamine Chemical compound NC1=CN=CC(N)=C1 ABYXFACYSGVHCW-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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Abstract
本发明的目的在于提供成形性优异、通过湿式法可以成形为纤维、薄膜、浆状粒子等的纺丝液。本发明的目的还在于提供制造耐热性、强度和弹性率优异的纤维的方法。本发明为下述纺丝液及使用该纺丝液的纤维的制造方法,所述纺丝液含有上式(I)所示重复单元、含有特性粘度为1以上的聚酰胺和碱性溶剂,在聚酰胺浓度超过10重量%且为25重量%以下时,在50℃下显示光学各向异性,式(I)中,Ar1为选自上式(a)和(b)中的至少一种取代基。
Description
技术领域
本发明涉及制造耐热性和力学性质优异的聚噁唑的成形体有用的纺丝液及使用该纺丝液的纤维的制造方法。
背景技术
已知Twaron、Kevlar所代表的聚对苯二甲酰对苯二胺(以下有时称作PPTA),Zylon所代表的聚对亚苯基苯并双噁唑(以下有时称作PBO)是耐热性、机械特性优异的纤维,作为其它成形品的原料有用。
专利文献1记载了苯并双噁唑和吡啶-苯并双噁唑的共聚物的制造。
专利文献2记载了将具有联苯基羟基作为取代基的芳香族聚酰胺的碱金属盐的水溶液挤出成形至凝固液中后,进行拉伸,获得薄膜或纤维。
(专利文献1)WO85/04178号小册子
(专利文献2)GB1142071号公报
发明内容
本发明的目的在于提供成形性优异、可以通过湿式法成形为纤维、薄膜、浆状粒子等的纺丝液。本发明的目的还在于提供仅通过成形即可形成分子取向、弹性率和耐热性优异的成形体的纺丝液。本发明的目的还在于提供使用对金属的腐蚀性小的溶剂可以抑制装置腐蚀的纺丝液。
本发明的目的还在于提供制造耐热性、强度和弹性率优异的纤维的方法。
本发明人发现当在碱性溶剂中高浓度含有具有羟基的高分子量芳香族聚酰胺时,可以获得光学各向异性的纺丝液。发现当将该光学各向异性的纺丝液湿式纺丝后进行热处理时,则高度地取向,获得强度和弹性率等机械特性优异的聚噁唑的纤维,进而完成本发明。
另外,还发现将纺丝液纺丝后进行拉伸,在凝固液中使其凝固时,与凝固后拉伸的情况相比,可以获得机械特性优异的纤维,进而完成本发明。
即,本发明为含有下式(I)所示重复单元、含有特性粘度为1以上的聚酰胺和碱性溶剂,聚酰胺浓度超过10重量且为%30重量%以下,在50℃下显示光学各向异性的纺丝液。
式(I)中Ar1为选自中的至少一种取代基。
另外,本发明为制造纤维的方法,其包括将含有下式(I)所示重复单元,含有特性粘度为1以上的聚酰胺和碱性溶剂,聚酰胺浓度超过10重量%且为30重量%以下,在50℃下显示光学各向异性的纺丝液纺丝后进行拉伸,在凝固液中使其凝固,在200~900℃下热处理所得纤维,制造含有选自下述式(I-a)和(I-b)中至少一种重复单元的聚噁唑的纤维。
具体实施方式
(纺丝液)
本发明的纺丝液含有聚酰胺和碱性溶剂,聚酰胺浓度超过10重量%且为30重量%以下,在50℃下显示光学各向异性。
(聚酰胺)
聚酰胺含有下式(I)所示重复单元、特性粘度为1以上,
聚酰胺优选含有50~100摩尔%式(I)所示重复单元和50~0摩尔%下式(II)所示重复单元。另外,聚酰胺更优选含有80~100摩尔%式(I)所示重复单元和20~0摩尔%式(II)所示重复单元。聚酰胺进一步优选含有90~100摩尔%式(I)所示重复单元和10~0摩尔%式(II)所示重复单元。聚酰胺特别优选含有95~100摩尔%式(I)所示重复单元和5~0摩尔%式(II)所示重复单元。
聚酰胺的特性粘度(ηinh)优选为1以上、更优选为1.5~50、进一步优选为3~10。特性粘度为在95重量%浓硫酸ldl中溶解0.5g该聚酰胺的溶液在30℃下测定的值。
(溶剂)
溶剂为碱性溶剂。碱性溶剂可以举出氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂等。另外,可以举出碱金属、碱土类金属的氢氧化物水溶液。这些物质可以单独使用还可以并用。碱性溶剂优选为氢氧化钠或氢氧化钾。纺丝液的pH优选为7以上、更优选为10~14。
本发明的纺丝液的特征在于在50℃下显示光学各向异性。这里光学各向异性是指例如在2张玻璃板间夹住纺丝液用显微镜在正交尼科尔棱镜下观察光学各向异性的状态。由于纺丝液显示光学各向异性,因此聚酰胺有必要高浓度地溶解。纺丝液的聚酰胺浓度为超过10重量%且为30重量%以下、优选为12~30重量%、更优选为15~30重量%、特别优选为15~25重量%。
(纺丝液的制备)
本发明的纺丝液可以如下制备:使用(a)芳香族二羧酸化合物和(b)芳香族二胺进行溶液聚合,将聚酰胺从溶液中分离后,将其溶解在溶剂中从而制备。
(a)芳香族二羧酸化合物可以举出下述式(A)所示的化合物。
式(A)中,X为OH、卤原子或OR所示的基团,R表示碳原子数6~20的1价芳香族基团。芳香族基团可以举出苯基等芳基。
(a)芳香族二羧酸化合物优选为X=Cl的对苯二甲酰氯。为了改良所得聚酰胺的性质,还可以共聚上述式(A)以外的二羧酸类。具体可以举出间苯二甲酰氯、2,6-萘二酰氯。
本发明使用的(b)芳香族二胺可以举出下述式(B)所示的芳香族二胺(3,3’-二羟基联苯胺)、下述式(C)所示芳香族二胺(1,4-二氨基-2,5-二羟基苯)或它们的盐酸盐、硫酸盐、磷酸盐。
予以说明,为了改良所得聚酰胺的性质还可以将下述二胺共聚。二胺的具体例子可以举出对苯二胺、间苯二胺、1,4-二氨基萘、1,5-二氨基萘、1,8-二氨基萘、2,6-二氨基萘、2,7-二氨基萘、2,5-二氨基吡啶、2,6-二氨基吡啶、3,5-二氨基吡啶、3,3’-二氨基联苯、3,3’-二氯联苯胺、3,3’-二氨基二苯基醚、3,4’-二氨基二苯基醚、4,4’-二氨基二苯基醚等。其中优选对苯二胺。
对于进行聚合所使用的溶剂并无特别限定,也可以使用溶解上所述原料单体(A)、(B)、(C)、且与它们基本为非反应性、可以获得优选特性粘度至少为1.0以上、更优选1.2以上的聚酰胺的任何溶剂。例如N,N,N’,N’-四甲基脲(TMU)、N,N-二甲基乙酰胺(DMAC)、N,N-二乙基乙酰胺(DEAC)、N,N-二甲基丙酰胺(DMPR)、N,N-二甲基丁酰胺(NMBA)、N,N-二甲基异丁酰胺(NMIB)、N-甲基-2-吡咯烷酮(NMP)、N-环己基-2-吡咯烷酮(NCP)、N-乙基吡咯烷酮-2(NEP)、N-甲基己内酰胺(NMC)、N,N-二甲基甲氧基乙酰胺、N-乙酰基吡咯烷(NARP)、N-乙酰基哌啶、N-甲基哌啶酮-2(NMPD)、N,N’-二甲基乙烯脲、N,N’-二甲基丙烯脲、N,N,N’,N’-四甲基丙二酰胺、N-乙酰基吡咯烷酮等酰胺系溶剂,对氯苯酚、苯酚、间甲酚、对甲酚、2,4-二氯苯酚等酚系溶剂或它们的混合物。其中优选的溶剂是N,N-二甲基乙酰胺(DMAC)、N-甲基-2-吡咯烷酮(NMP)。
此时,为了提高溶解性,可以在聚合前、途中或结束时添加适当公知的无机盐。这种无机盐例如可以举出氯化锂、氯化钙等。
聚酰胺的制造与将上述单体(A)、(B)、(C)脱水的上述溶剂中通常的聚酰胺溶液聚合法同样地制造。此时的反应温度为80℃以下、优选为60℃以下。此时的浓度作为单体浓度优选为1~20重量%左右。
另外,本发明中为了聚酰胺的高聚合度化还可以使用三烷基氯甲硅烷。
另外,为了捕获在通常所用酰氯与二胺的反应中所产生的氯化氢的类似酸,可以并用脂肪族、芳香族胺、季铵盐。
这里,所得聚酰胺由于不能高浓度地溶解于上述聚合溶剂中(一般来说数重量%左右为浓度的上限值),因此为了获得目标纺丝液,在聚合后将聚酰胺分离后,溶解于碱性溶剂中。
(纤维的制造方法)
本发明包括将上述纺丝液纺丝后拉伸,在凝固液中使其凝固,在200~900℃下热处理所得纤维,制造含有聚噁唑的纤维。
(纺丝)
本发明中通过纺丝喷头挤出纺丝液形成纤维。纺丝喷头优选含有金、铂、钯、铑、它们的合金的耐腐蚀性者。
(拉伸)
在凝固液中使其凝固之前,将所纺丝的纤维拉伸。拉伸优选在空隙部分进行。空隙是指设置于纺丝喷头与凝固液之间的空间。
纺丝液在从纺丝喷嘴的细孔挤出时,细孔处的剪切使液晶域在流动方向上取向,但在细孔的出口处由于纺丝液的粘弹性特性而出现液晶域取向混乱。通过在空隙部分进行拉伸,可以使该混乱恢复。纤维被拉伸、由于张力而变细,因此取向的混乱容易恢复。
拉伸倍率优选为1.5~300、更优选为2~100、进一步优选为3~30倍。拉伸倍率由从喷嘴的纺丝液喷出速度和凝固丝的卷绕速度之比求出。
(凝固)
由于拉伸而变细的纤维在保持高取向的分子结构的状态下在凝固液中凝固。结果,可以获得高结晶性、高取向性的纤维。
凝固液优选硫酸或盐酸的水溶液、氯化铵水溶液或丙酮。凝固液的温度优选为-30~150℃、更优选为0~100℃、进一步优选为5~50℃。
之后,优选进行洗涤、中和、洗涤、干燥。
(热处理)
本发明中,在200~900℃下对所得纤维热处理。热处理温度优选为250~700℃、更优选为300~550℃。热处理可以在空气中、氮气、氩气等惰性气氛下进行。
通过进行热处理,式(I)中取代为Ar1的-OH基团与酰胺键之间发生环化反应,获得具有式(I-a)、式(I-b)或式(I-a)和(I-b)的重复单元的聚噁唑。
而且,优选在张力下进行热处理。热处理时施加的张力优选为热处理前纤维的断裂强度的0.1~8.0%、更优选为1~30%。热处理时间优选为0.01~1800秒、更优选为0.1~600秒、进一步优选为1~300秒。
通过本发明方法获得的纤维包含含有选自下述选自下述式(I-a)和(I-b)中至少一种重复单元的聚噁唑。
优选聚噁唑含有50~100摩尔%选自式(I-a)和(I-b)的至少一种重复单元和50~0摩尔%下式(II)所示重复单元。
更优选聚噁唑含有由80~100摩尔%选自式(I-a)和(I-b)的至少一种重复单元和20~0摩尔%式(II)所示重复单元。进一步优选聚噁唑含有90~100摩尔%选自式(I-a)和(I-b)的至少一种重复单元和10~0摩尔%式(II)所示重复单元。最优选聚噁唑含有95~100摩尔%选自式(I-a)和(I-b)的至少一种重复单元和5~0摩尔%下式(II)所示重复单元。
(纤维的物性)
构成本发明所得纤维的聚噁唑的特性粘度(ηinh)优选为1.5~100、更优选为2.0~50、进一步优选为3.0~40。特性粘度(ηinh)为使用甲磺酸在聚合物浓度0.03g/100mL、30℃下测定的值。
本发明所得纤维中磷原子含量优选为30ppm以下、更优选为0~20ppm、进一步优选为0~10ppm。
本发明所得纤维的弹性率为10Gpa以上、优选为30~500Gpa、进一步优选为70~350Gpa。
本发明所得纤维的纤度优选为0.01~100dtex、更优选为0.1~10dtex、进一步优选为0.5~5dtex。
本发明所得纤维的强度优选为100~10000mN/tex、更优选为300~5000mN/tex、进一步优选为500~4000mN/tex。
本发明所得纤维的断裂伸长率优选为0.1~30%、更优选为0.5~10%、进一步优选为1.0~8%。
本发明所得含有聚噁唑的纤维通过下式(III)求得的取向系数F优选为0.3以上。取向系数F更优选为0.5以上、进一步优选为0.8以上。取向系数F的值越高则成为弹性率越高的纤维,优选。完全取向时的理论上取向系数F的上限值为1.0。
式中Φ为X射线衍射测定的方位角、I为X射线的衍射强度。
实施例
以下示出实施例,更加具体地说明本发明,本发明并非局限于这些实施例。实施例中的物性值通过以下方法测定。
(1)特性粘度(ηinh)
聚酰胺的特性粘度使用95重量%的浓硫酸、在聚合物浓度0.5g/dl、30℃下测定。Polyazole的特性粘度使用甲磺酸在聚合物浓度0.03g/100mL、30℃下测定。
(2)强度、断裂伸长率、弹性率
使用ォリェンテック株式会社制坦锡伦万能试验机1225A在拉伸速度10mm/min下拉伸单纤维进行测定。
(3)磷原子的含量
将试样采集至带有回流冷却的湿式分解容器,添加浓硫酸后进行加热,同时慢慢滴加硝酸以使试样不飞散,完全地分解有机物。放冷后,加入纯水定容至白色透明玻璃容器中,通过ICP发光分析法定量磷原子。
(4)X射线衍射测定
在X射线产生装置(理学电机社制RU-B型)为靶CuKa线、电压45kV、电流70mA的条件下测定。入射X射线通过ォスミック社制多层膜镜聚光和单色化,利用垂直透射法测定试样的截面。衍射X射线的检测使用大小200mm×250mm的成像板(富士胶卷制),在相机长250mm的条件下测定。
实施例1
(聚酰胺制造)
在氮气气流下、烧瓶内、250℃下干燥氯化钙30重量份1小时,将烧瓶内的温度返回至室温后,加入N-甲基-2-吡咯烷酮(NMP)562重量份。加入4,4’-二氨基-3,3’-联苯二醇18.75重量份溶解。通过外部冷却将该溶液保持在0℃,加入对苯二甲酰氯17.6037重量份,在0℃下反应1小时、50℃下反应2小时,加入12.84重量份氢氧化钙,停止反应。
反应结束后,投入到大量离子交换水中,使聚酰胺析出。过滤所得聚酰胺,进一步用乙醇、丙酮洗涤,真空干燥。聚酰胺的特性粘度(ηinh)为5.73。
(纺丝液的制备)
将所得聚酰胺6g投入到不锈钢制的带机械搅拌机的干燥圆形烧瓶中。在真空下将烧瓶加热至100℃30分钟,除去残留的水分。将烧瓶冷却至室温(约25℃)后,添加34g的1N的NaOH水溶液,搅拌。在该温度下保持数小时,每隔一定时间用光学显微镜检查该溶液,监测溶解的状况。将95%的聚酰胺粒子溶解时的该溶液加热至50℃。搅拌40分钟,获得均一、粘稠的纺丝液。用显微镜在正交尼科尔棱镜下观察所得纺丝液,在50℃下观察到光学各向异性。纺丝液得到光学各向异性的温度Tni由于高于溶剂的沸点因此无法检测。
实施例2
(纺丝)
将实施例1获得纺丝液移至气缸中,在减压、脱气的同时加热至70℃。使用机械驱动的气缸从带有100微米直径的孔的薄金属纺丝喷头中喷出。
(拉伸)
所喷出的纤维通过设置于纺丝喷头和凝固浴之间的1.0cm的空隙的过程中被拉伸2倍,经由凝固浴卷绕至电驱动的卷绕机。
(凝固)
使用含有1.5当量盐酸的溶液作为凝固液。凝固液设定为25℃。通过30cm凝固液后,以偏离水45度的角度拉起丝,卷绕至上述电驱动的卷绕机上。以20m/分将纤维卷绕至不锈钢制的筒管上,在筒管上用室温的水洗涤1小时,用80℃的热风干燥机干燥,获得纤维。
(热处理)
将所得聚对二羟基联苯对苯二甲酰胺丝卷在坚硬的金属框上,在450℃下加热10分钟。暗红色丝的化学结构经IR光谱鉴定为苯并噁唑。纺丝前体纤维的TGA分析(升温速度10℃/分钟、氮气气氛下测定)中,410℃附近最大减量速度在450和610℃之间,可观察到稳定的区域。由所测定的环化导致的减量为10.8%,该值接近10.5%这一理论值。这说明转变定量地进行。分解开始温度为630℃(5%减量)。所得纤维的特性粘度(ηinh)为7.6、磷原子含量为12ppm。表1表示热处理前纤维和热处理后纤维的物性的测定结果。
表1
弹性率(GPa) | 强度(mN/tex) | 伸长率(%) | 取向系数 | |
热处理前的纤维 | 12.8 | 193 | 7.4 | 0.55 |
热处理后的纤维 | 31.3 | 304 | 1.3 | 0.83 |
发明效果
本发明的纺丝液的成形性优异,通过湿式法可以成形为纤维、薄膜、浆状粒子等。本发明的纺丝液仅通过成形,即可成为分子取向的、弹性率、耐热性优异的成形体。另外,本发明的纺丝液由于使用对金属腐蚀性小的溶剂,因此可以抑制纺丝液对装置的腐蚀。
通过本发明纤维的制造方法,可以制造耐热性、强度和弹性率优异的纤维。
通过本发明的制造方法,可以制造多磷酸等磷化合物含量少的芳香族聚噁唑纤维。本发明的制造方法具有可以通过短时间水洗除去残留有机溶剂的优点。
产业实用性
将本发明的纺丝液纺丝获得的纤维可以广泛用于绳索、传送带、绝缘布、热固化性或热塑性纤维的加固材料、防护服等领域中。
Claims (17)
2.权利要求1所述的纺丝液,其中所述碱性溶剂为氢氧化钠或氢氧化钾。
4.权利要求3所述的纺丝液,其中所述聚酰胺含有80~100摩尔%式(I)所示重复单元和20~0摩尔%式(II)所示重复单元。
5.权利要求3所述的纺丝液,其中所述聚酰胺含有90~100摩尔%式(I)所示重复单元和10~0摩尔%式(II)所示重复单元。
8.权利要求7所述的方法,其中纺丝液中的聚酰胺含有80~100摩尔%式(I)所示重复单元和20~0摩尔%式(II)所示重复单元。
9.权利要求7所述的方法,其中纺丝液中的聚酰胺含有90~100摩尔%式(I)所示重复单元和10~0摩尔%式(II)所示重复单元。
10.权利要求6所述的方法,其中凝固液为硫酸或盐酸的水溶液、氯化铵的水溶液或丙酮。
11.权利要求6所述的方法,其在张力下进行热处理。
13.权利要求12所述的方法,其中聚噁唑含有80~100摩尔%选自式(I-a)和(I-b)中至少一种重复单元和20~0摩尔%式(II)所示重复单元。
14.权利要求12所述的方法,其中聚噁唑含有90~100摩尔%选自式(I-a)和(I-b)中至少一种重复单元和10~0摩尔%式(II)所示重复单元。
15.权利要求6所述的方法,其中所得纤维的磷原子含量为30ppm以下。
16.权利要求6所述的方法,其中所述纤维的弹性率为10GPa以上。
17.权利要求6所述的方法,对于所得纤维,使用下述式(III)求得的取向系数F为0.3以上,
式中,Φ为X射线衍射测定的方位角、I为X射线的衍射强度。
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EP2398942B1 (de) * | 2009-02-17 | 2012-11-14 | Teijin Aramid B.V. | Verfahren zur herstellung eines filamentgarns aus einem aromatischen polyamid |
US20100227984A1 (en) * | 2009-03-05 | 2010-09-09 | Dang Thuy | HYDROLYSIS-RESISTANT POLY (p-PHENYLENEBENZOBISOXAZOLE) (PBO) FIBERS |
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DE1595723A1 (de) | 1965-02-09 | 1970-04-30 | Gen Electric | Verfahren zur Herstellung von stickstoffhaltigen Polymeren |
WO1984001162A1 (en) | 1982-09-17 | 1984-03-29 | Stanford Res Inst Int | Liquid crystalline polymer compositions, process, and products |
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US4703103A (en) | 1984-03-16 | 1987-10-27 | Commtech International | Liquid crystalline polymer compositions, process and products |
US5322916A (en) * | 1993-03-16 | 1994-06-21 | The Dow Chemical Company | Method for the preparation of amide oligomers and polybenzazole polymers therefrom |
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US20090127735A1 (en) | 2009-05-21 |
US7838622B2 (en) | 2010-11-23 |
CN101300288B (zh) | 2011-02-23 |
TW200732381A (en) | 2007-09-01 |
CA2628267A1 (en) | 2007-05-10 |
KR20080064952A (ko) | 2008-07-10 |
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