WO2022092716A1 - Fibre multi-filament de sulfure de polyarylène - Google Patents
Fibre multi-filament de sulfure de polyarylène Download PDFInfo
- Publication number
- WO2022092716A1 WO2022092716A1 PCT/KR2021/014920 KR2021014920W WO2022092716A1 WO 2022092716 A1 WO2022092716 A1 WO 2022092716A1 KR 2021014920 W KR2021014920 W KR 2021014920W WO 2022092716 A1 WO2022092716 A1 WO 2022092716A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polyarylene sulfide
- less
- carbon atoms
- sulfide resin
- Prior art date
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 331
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 329
- 239000000835 fiber Substances 0.000 title claims abstract description 138
- 239000011347 resin Substances 0.000 claims description 271
- 229920005989 resin Polymers 0.000 claims description 271
- 125000004432 carbon atom Chemical group C* 0.000 claims description 77
- 238000006116 polymerization reaction Methods 0.000 claims description 71
- 150000001491 aromatic compounds Chemical class 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 44
- 150000003464 sulfur compounds Chemical class 0.000 claims description 44
- 239000003112 inhibitor Substances 0.000 claims description 38
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 37
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 37
- 239000000654 additive Substances 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 239000012760 heat stabilizer Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000006224 matting agent Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 23
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 12
- 229940006487 lithium cation Drugs 0.000 claims description 12
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 150000007942 carboxylates Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000101 thioether group Chemical group 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 39
- 229920000069 polyphenylene sulfide Polymers 0.000 description 39
- 238000009987 spinning Methods 0.000 description 38
- 238000002156 mixing Methods 0.000 description 29
- 238000002360 preparation method Methods 0.000 description 26
- 239000011342 resin composition Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 15
- 229910010272 inorganic material Inorganic materials 0.000 description 14
- 239000011147 inorganic material Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- -1 diiodine aromatic compound Chemical class 0.000 description 12
- 239000000155 melt Substances 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 229910052740 iodine Inorganic materials 0.000 description 11
- 238000012805 post-processing Methods 0.000 description 11
- 230000001976 improved effect Effects 0.000 description 10
- 239000011630 iodine Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000003017 thermal stabilizer Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- VSIIHWOJPSSIDI-UHFFFAOYSA-N 1-ethoxy-4-iodobenzene Chemical compound CCOC1=CC=C(I)C=C1 VSIIHWOJPSSIDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XBNOMKROXZGMFW-UHFFFAOYSA-N 3-[(3-hydroxyphenyl)disulfanyl]phenol Chemical compound OC1=CC=CC(SSC=2C=C(O)C=CC=2)=C1 XBNOMKROXZGMFW-UHFFFAOYSA-N 0.000 description 2
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical compound [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 125000002346 iodo group Chemical group I* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QQFIQWBUKYSUHM-UHFFFAOYSA-N (2,3-diiodophenyl)-phenylmethanone Chemical compound IC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1I QQFIQWBUKYSUHM-UHFFFAOYSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- LSESTAVEDKBXPP-UHFFFAOYSA-N 1,2-diiodo-3,4-dimethylbenzene Chemical group CC1=CC=C(I)C(I)=C1C LSESTAVEDKBXPP-UHFFFAOYSA-N 0.000 description 1
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- UYHYZAYIQAVJCN-UHFFFAOYSA-N 1,2-diiodonaphthalene Chemical compound C1=CC=CC2=C(I)C(I)=CC=C21 UYHYZAYIQAVJCN-UHFFFAOYSA-N 0.000 description 1
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- IVUYGANTXQVDDG-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrolidin-2-one Chemical compound CC(C)CN1CCCC1=O IVUYGANTXQVDDG-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- MXEOFTCIEDUHCX-UHFFFAOYSA-N 1-cyclohexylazepan-2-one Chemical compound O=C1CCCCCN1C1CCCCC1 MXEOFTCIEDUHCX-UHFFFAOYSA-N 0.000 description 1
- JUJREUXKABNEFA-UHFFFAOYSA-N 1-ethoxy-2-iodobenzene Chemical compound CCOC1=CC=CC=C1I JUJREUXKABNEFA-UHFFFAOYSA-N 0.000 description 1
- GWCFTYITFDWLAY-UHFFFAOYSA-N 1-ethylazepan-2-one Chemical compound CCN1CCCCCC1=O GWCFTYITFDWLAY-UHFFFAOYSA-N 0.000 description 1
- GPYDMVZCPRONLW-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)benzene Chemical group C1=CC(I)=CC=C1C1=CC=C(I)C=C1 GPYDMVZCPRONLW-UHFFFAOYSA-N 0.000 description 1
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 1
- OFKCMFHRODHIGA-UHFFFAOYSA-N 1-methyl-2h-pyrrol-3-one Chemical compound CN1CC(=O)C=C1 OFKCMFHRODHIGA-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- NDDIKKNFARRUNI-UHFFFAOYSA-N 1-phosphorosopropane Chemical compound CCCP=O NDDIKKNFARRUNI-UHFFFAOYSA-N 0.000 description 1
- GHELJWBGTIKZQW-UHFFFAOYSA-N 1-propan-2-ylpyrrolidin-2-one Chemical compound CC(C)N1CCCC1=O GHELJWBGTIKZQW-UHFFFAOYSA-N 0.000 description 1
- BWISIXSYQURMMY-UHFFFAOYSA-N 1-propylazepan-2-one Chemical compound CCCN1CCCCCC1=O BWISIXSYQURMMY-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- YYLVCQOSKAFIKV-UHFFFAOYSA-N 1-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)C(S)CC YYLVCQOSKAFIKV-UHFFFAOYSA-N 0.000 description 1
- VALABLHQPAMOBO-UHFFFAOYSA-N 2,4-diiodo-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1I VALABLHQPAMOBO-UHFFFAOYSA-N 0.000 description 1
- FNXXLDHPVGHXEM-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)disulfanyl]phenol Chemical compound OC1=CC=CC=C1SSC1=CC=CC=C1O FNXXLDHPVGHXEM-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- WBNUVPGJLHTDTD-UHFFFAOYSA-N 4-ethyl-5-methylimidazolidin-2-one Chemical compound CCC1NC(=O)NC1C WBNUVPGJLHTDTD-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- XVYHFPMIBWTTLH-UHFFFAOYSA-N [Zn].[Mg].[Ca] Chemical group [Zn].[Mg].[Ca] XVYHFPMIBWTTLH-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005362 aryl sulfone group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- IBSGAWQJFSDRBJ-UHFFFAOYSA-M cesium sulfanide Chemical compound [SH-].[Cs+] IBSGAWQJFSDRBJ-UHFFFAOYSA-M 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- QTNDMWXOEPGHBT-UHFFFAOYSA-N dicesium;sulfide Chemical compound [S-2].[Cs+].[Cs+] QTNDMWXOEPGHBT-UHFFFAOYSA-N 0.000 description 1
- HIPNYJBGYFRVAY-UHFFFAOYSA-N diiodomethylbenzene Chemical compound IC(I)C1=CC=CC=C1 HIPNYJBGYFRVAY-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- XNFVGEUMTFIVHQ-UHFFFAOYSA-N disodium;sulfide;hydrate Chemical compound O.[Na+].[Na+].[S-2] XNFVGEUMTFIVHQ-UHFFFAOYSA-N 0.000 description 1
- XWKIXFQOFAVHQI-UHFFFAOYSA-N disodium;sulfide;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[S-2] XWKIXFQOFAVHQI-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- HXQGSILMFTUKHI-UHFFFAOYSA-M lithium;sulfanide Chemical compound S[Li] HXQGSILMFTUKHI-UHFFFAOYSA-M 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 1
- IFTIBNDWGNYRLS-UHFFFAOYSA-N n,n-dipropylacetamide Chemical compound CCCN(C(C)=O)CCC IFTIBNDWGNYRLS-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- BIHJEIFLAWVSQP-UHFFFAOYSA-N n-(anilinodisulfanyl)aniline Chemical compound C=1C=CC=CC=1NSSNC1=CC=CC=C1 BIHJEIFLAWVSQP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- SXCQOWSCNMKTFA-UHFFFAOYSA-N phosphorosobenzene Chemical compound O=PC1=CC=CC=C1 SXCQOWSCNMKTFA-UHFFFAOYSA-N 0.000 description 1
- XGCRFIXLYQQNSO-UHFFFAOYSA-N phosphorosomethane Chemical compound CP=O XGCRFIXLYQQNSO-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- LXOXXUIVMOYGST-UHFFFAOYSA-M rubidium(1+);sulfanide Chemical compound [SH-].[Rb+] LXOXXUIVMOYGST-UHFFFAOYSA-M 0.000 description 1
- AHKSSQDILPRNLA-UHFFFAOYSA-N rubidium(1+);sulfide Chemical compound [S-2].[Rb+].[Rb+] AHKSSQDILPRNLA-UHFFFAOYSA-N 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/30—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensation products not covered by indexing codes D10B2331/02 - D10B2331/14
- D10B2331/301—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensation products not covered by indexing codes D10B2331/02 - D10B2331/14 polyarylene sulfides, e.g. polyphenylenesulfide
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
Definitions
- the present invention relates to polyarylene sulfide multifilament fibers.
- Polyarylene sulfide is an important engineering plastic, and due to its high heat resistance, chemical resistance, nonflammability, high strength, and the like, the demand for polyarylene sulfide is increasing for various uses such as highly durable plastic molded products, electrical products, and fibers.
- Polyphenylene sulfide is the only polyarylene sulfide currently being mass-marketed, and its production method includes a solution polymerization method that polymerizes paradichlorobenzene and sodium sulfide as raw materials in N-methylpyrrolidone solvent (patented Reference 1), there is a melt polymerization method in which a diiodine aromatic compound and a sulfur compound are polymerized at a high temperature as raw materials without using a solvent.
- the polyphenylene sulfide resin prepared by the solution polymerization method has a high amount of outgas due to the use of a solvent and chlorine contained in raw materials, low molecular weight oligomers, and high inorganic substances such as sodium chloride, such outgas, oligomers and inorganic substances
- a solvent and chlorine contained in raw materials low molecular weight oligomers, and high inorganic substances such as sodium chloride, such outgas, oligomers and inorganic substances
- silver fiber acts as a defect in the spinning process and causes yarn breakage. Since such filaments make it difficult to obtain continuous fibers, it is a problem that must be overcome for the commercialization of polyarylene sulfide multifilament fibers.
- polyphenylene sulfide resin produced by the melt polymerization method has excellent productivity and cost structure because it is polymerized under high temperature and vacuum conditions without using a solvent, and has a low amount of outgassing and corrosion resistance because it does not use chlorine-based raw materials. It has an improved effect such as excellent.
- due to the non-polar end group of the resin it is difficult to modify it to have desired properties due to its low reactivity with processing additives, which limits its use and usage, and the disulfide bond derived from the sulfur compound used as a raw material has a weak structure in the resin. There is a limitation in that mechanical properties are insufficient because it acts as a
- Patent Document 1 US Patent No. 2,513,188
- polyarylene sulfide multifilament fibers having sufficiently low outgassing amount, oligomer content and inorganic material content to have a low single yarn rate and excellent mechanical strength such as elongation strength and elongation rate.
- the present inventors have found that when a polyarylene sulfide resin post-processed as a compatibilizer is used for the production of multifilament fibers, low single yarn rate and good mechanical strength can be achieved. found that there is In addition, by mixing the solution-polymerized polyarylene sulfide resin and the melt-polymerized polyarylene sulfide resin, the present invention was completed by discovering that multifilament fibers having remarkably excellent mechanical strength while lowering the single yarn rate can be produced. .
- the present invention relates to a first polyarylene sulfide resin in which a terminal group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; And it provides a multifilament fiber comprising at least one additive selected from the group consisting of a heat stabilizer and a matting agent.
- the present invention relates to a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor are melt-polymerized, and a second polyarylene sulfide in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized.
- polyarylene sulfide mixed resin composed of resin; And it provides a multifilament fiber comprising at least one additive selected from the group consisting of a heat stabilizer and a matting agent.
- the present invention provides a post-processed first polyarylene sulfide resin in which an end group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized, and a post-processed polyarylene sulfide mixed resin composed of a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized; And it provides a multifilament fiber comprising at least one additive selected from the group consisting of a heat stabilizer and a matting agent.
- the polyarylene sulfide multifilament fiber of the present invention may have a low single yarn rate and excellent mechanical strength.
- the first polyarylene sulfide resin is post-processed in which terminal groups derived from a compatibilizer are introduced into the first polyarylene sulfide resin in which the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are melt-polymerized; and at least one additive selected from the group consisting of a heat stabilizer and a matting agent, multifilament fibers (hereinafter, post-processed first polyarylene sulfide multifilament fibers) are provided.
- a post-processed first polyarylene sulfide resin in which an end group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized, and Preparing a post-processed first polyarylene sulfide resin composition including an additive; and spinning and/or stretching the post-processed first polyarylene sulfide resin composition.
- the first polyarylene sulfide resin may be prepared by melt polymerization of a composition including a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor.
- the diiodo aromatic compound refers to a compound having an aromatic ring and two iodine atoms directly bonded thereto.
- Diiodo aromatic compounds include diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether and diiododiphenyl. It may be at least one selected from the group consisting of sulfones, but is not limited thereto.
- the aromatic ring of the diiodo aromatic compound is a halo group excluding an iodo group, a phenyl group, a hydroxy group, a nitro group, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, a carboxylate, an arylsulfone, and an aryl ketone group It may be substituted by at least one substituent selected from.
- the diiodo aromatic compound having an aromatic ring substituted with the above substituent is a diiodo having an unsubstituted aromatic ring from the viewpoint of crystallinity and heat resistance of the resin.
- substitution positions of the two iodo groups in the diiodo aromatic compound are not particularly limited, but the two substitution positions may be far from each other in the molecule, and may be the para position or the 4,4'-position.
- the diiodo aromatic compound is present in an amount of 0.5 to 2.0 moles, 0.55 to 1.9 moles, 0.6 to 1.8 moles, 0.65 to 1.7 moles, 0.7 to 1.6 moles, 0.75 to 1.5 moles, or 0.8 to 1.4 moles based on 1 mole of the first sulfur compound. may be included as
- the diiodo aromatic compound may be, for example, p-diiodobenzene.
- the first sulfur compound may be a single sulfur.
- Single sulfur refers to a compound composed of sulfur atoms.
- the single sulfur may be at least one selected from the group consisting of S 8 , S 6 , S 4 and S 2 , and specifically, it may be a mixture including S 8 and S 6 that is generally available, but limited thereto doesn't happen
- the purity, form, and particle size of the single sulfur are not particularly limited.
- the form of single sulfur may be in the form of granules or powders that are solid at room temperature (23° C.).
- the particle diameter of the single sulfur may be 0.001 to 10 mm, 0.01 to 5 mm, or 0.01 to 3 mm, but is not particularly limited thereto.
- the polymerization inhibitor may be used without particular limitation as long as it is a compound that inhibits or stops the polymerization reaction of the first polyarylene sulfide resin.
- the polymerization inhibitor is a compound capable of introducing at least one functional group selected from the group consisting of -OR, -SR, -COOR, -NHR, -SO 3 R, -NHCOR, etc. at the end of the main chain of the polyarylene sulfide resin may be, wherein R may each independently be a hydrogen group, a metal cation such as sodium or lithium, a halo group, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
- the polymerization inhibitor may include the functional group, and the functional group may be generated by a polymerization stop reaction or the like.
- the polymerization inhibitor may be a compound not containing the functional group, specifically, diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole , N-cyclohexyl-2-benzothiazolylsulfenamide, 2-(morpholinothio)benzothiazole and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide It may be at least one compound.
- the polymerization inhibitor may be one or more of the compounds represented by the following Chemical Formulas 1 to 4, specifically, may be a compound represented by the Chemical Formula 1.
- X 1 and X 2 are each independently a hydrogen group, a halo group, an alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted phenyl group, -OA 1 , -SA 2 , -COOA 3 , -NA 4 A 5 , - SO 3 A 6 and -NHCOA 7 selected from the group consisting of,
- a 1 to A 7 are each independently a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted is selected from the group consisting of a substituted phenyl group
- Z 1 to Z 4 are each independently a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms It is selected from the group consist
- Z 1 and Z 2 are an alkenyl group having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.
- Z 3 and Z 4 are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.
- X 1 or X 2 bonded to one aromatic ring may be the same as or different from each other.
- Z 1 and Z 3 may be the same as or different from each other, and Z 2 and Z 4 may be the same or different from each other.
- the substituted phenyl group of X 1 or X 2 may have a substituent of -SH or -SS-Ph.
- the substituted alkyl group having 1 to 3 carbon atoms and the substituted phenyl group of A 1 to A 7 may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.
- Z 1 and Z 2 may be bonded to two adjacent carbon atoms
- Z 3 and Z 4 may be bonded to two adjacent carbon atoms.
- At least one or two or more of Z 1 to Z 4 may not be a hydrogen group.
- at least one of X 1 and X 2 may be selected from the group consisting of -OA 1 , -SA 2 , -COOA 3 , NA 4 A 5 , -SO 3 A 6 , and -NHCOA 7 .
- both X 1 and X 2 are hydrogen groups, at least one of a combination of Z 1 and Z 2 or a combination of Z 3 and Z 4 may be connected to each other to form a benzene ring.
- X 3 To X 6 are each independently a hydrogen group, a halo group, an alkyl group having 1 to 5 carbon atoms, -OA 8 , -SA 9 , -COOA 10 , -NA 11 A 12 , -SO 3 A 13 and -NHCOA is selected from the group consisting of 14 , and A 8 to A 14 are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms, and R 1 to R 4 are each independently It is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms and an alkoxy group.
- At least one of X 3 to X 6 may be selected from the group consisting of -OA 8 , -SA 9 , -COOA 10 , -NA 11 A 12 , -SO 3 A 13 and -NHCOA 14 .
- at least one of X 3 to X 6 may be -SA 9 in which A 9 is a hydrogen group.
- X 7 to X 12 are each independently a hydrogen group, a halo group, an alkyl group having 1 to 5 carbon atoms, -OA 15 , -SA 16 , -COOA 17 , -NA 18 A 19 , -SO 3 A 20 and -NHCOA is selected from the group consisting of 21 , A 15 to A 21 are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms, R 5 and R 6 are each independently It is an alkylene group having 1 to 5 carbon atoms.
- X 13 is a hydrogen group, a halo group, an alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted phenyl group, -OA 22 , -SA 23 , -COOA 24 , NA 25 A 26 , -SO 3 A 27 and -NHCOA is selected from the group consisting of 28 , and A 22 to A 28 are each independently a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group from the group consisting of selected, W is a halo group, Z 5 and Z 6 are each independently a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms It is selected from the group, and n is
- Z 5 and Z 6 are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.
- n is 2 or more, two or more X 13 bonded to one aromatic ring may be the same as or different from each other.
- Z 5 and Z 6 may be bonded to two adjacent carbon atoms. Also, at least one of Z 5 and Z 6 may not be a hydrogen group. In addition, at least one of X 13 may be selected from the group consisting of -OA 22 , -SA 23 , -COOA 24 , NA 25 A 26 , -SO 3 A 27 and -NHCOA 28 .
- the substituted phenyl group of X 13 may have a substituent of -SH or -SS-Ph.
- the substituted alkyl group having 1 to 3 carbon atoms or the substituted phenyl group of A 22 to A 28 may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.
- the polymerization inhibitor may be included in an amount of 0.0001 to 0.1 moles, 0.0002 to 0.08 moles, 0.0005 to 0.05 moles, or 0.001 to 0.05 moles based on 1 mole of the first sulfur compound.
- a catalyst may be additionally used.
- the catalyst may be, for example, a nitrobenzene-based catalyst, and specifically, may be at least one selected from the group consisting of 1,3-diiod-4-nitrobenzene and 1-iod-4-nitrobenzene, but is not limited thereto.
- the catalyst when used, it may be used in an amount of 0.0001 to 0.1 moles, 0.0002 to 0.05 moles, or 0.0005 to 0.01 moles based on 1 mole of the first sulfur compound.
- melt polymerization may proceed under any conditions as long as the polymerization reaction of the composition including the diiodo aromatic compound and the first sulfur compound can be initiated.
- melt polymerization may be carried out at a temperature of about 180 to 400 °C, 180 to 350 °C, or 180 to 300 °C, and at a pressure of about 0.001 to 500 torr, 0.001 to 450 torr, or 0.001 to 400 torr. .
- melt polymerization may proceed under elevated temperature and reduced pressure reaction conditions. In this case, temperature rise and pressure drop are performed at an initial reaction condition of about 180 to 250° C. and a pressure of about 50 to 450 torr, which is the final reaction condition. It is changed to about 270 to 350° C.
- melt polymerization may be performed under the final reaction conditions at a temperature of about 280 to 300° C. and a pressure of about 0.1 to 2 torr.
- the order of mixing the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor is not particularly limited, but the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are simultaneously mixed, or the diiodo aromatic compound and a polymerization inhibitor may be mixed with a mixture including the first sulfur compound to prepare a composition for melt polymerization.
- the timing of adding the polymerization inhibitor is not particularly limited, but may be determined in consideration of the final molecular weight of the target polyarylene sulfide. For example, about 0 to 30% by weight, 30 to 70% by weight, or 70 to 100% by weight of the diiodine aromatic compound contained in the initial reactant may be added at a time when the reaction is exhausted. Alternatively, the timing of the polymerization inhibitor may be added when the molecular weight of the polymerization product reaches a certain level.
- the molecular weight of the polymerization reactant is 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% of the final molecular weight of the target polyarylene sulfide. % or more, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, a polymerization inhibitor may be added.
- the molecular weight of the polymerization reactant can be determined, for example, through gel permeation chromatography.
- the composition including the diiodine aromatic compound and the first sulfur compound may be melt-mixed before the polymerization inhibitor is added.
- a catalyst may also be included in the composition in the melt mixing step.
- the melt mixing is not particularly limited as long as all of the compositions can be melt-mixed, but for example, may be performed at a temperature of about 130 to 200°C or about 160 to 190°C. In the case of performing such melt mixing, melt polymerization to be performed later may be more easily performed.
- the post-processed first polyarylene sulfide resin may be prepared by post-processing the first polyarylene sulfide resin using a compatibilizer.
- the post-processed first polyarylene sulfide resin may include a first polyarylene sulfide resin; and end groups derived from compatibilizers.
- the first polyarylene sulfide resin is as described above.
- the compatibilizer for post-processing the first polyarylene sulfide resin is a compound containing at least one functional group selected from the group consisting of a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.
- the compatibilizer may be one or more of the compounds represented by one of the following Chemical Formulas 5 to 8.
- Y 1 and Y 2 are each independently selected from the group consisting of a hydrogen group, a halo group, -OB 1 , -SB 2 , -COOB 3 , -NB 4 B 5 , -SO 3 B 6 and -NHCOB 7
- B 1 to B 7 are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted C1-C3 alkyl group, and a substituted or unsubstituted phenyl group
- Z 1' to Z 4 ' is each independently selected from the group consisting of a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms
- p 1 and p 2 are each independently an integer of 1 to 3, provided that at least one of Y 1 and Y 2 is -OB 1
- Z 1 ' and Z 2 ' are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring, and Z 3 ' and Z 4 ' are 2 carbon atoms When it is an alkenyl group and is bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.
- Y 1 or Y 2 bonded to one aromatic ring may be the same as or different from each other.
- Z 1 ′ and Z 3 ′ may be the same as or different from each other, and Z 2 ′ and Z 4 ′ may be the same or different from each other.
- the substituted alkyl group having 1 or 2 carbon atoms or the substituted alkenyl group having 1 or 2 carbon atoms of Z 1′ to Z 4′ may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.
- One of B 1 to B 7 may have a substituted alkyl group having 1 to 3 carbon atoms or a substituted phenyl group having 1 or 2 carbon atoms or a substituent to the phenyl group.
- Z 1 ′ and Z 2 ′ may be bonded to two adjacent carbon atoms, and Z 3 ′ and Z 4 ′ may be bonded to two adjacent carbon atoms. In addition, at least one or two or more of Z 1 ′ to Z 4 ′ may not be a hydrogen group.
- Y 3 To Y 6 are each independently selected from the group consisting of a hydrogen group, a halo group, -OB 8 , -SB 9 , -COOB 10 , -NB 11 B 12 , -SO 3 B 13 and -NHCOB 14
- B 8 to B 14 are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms
- R 1 ' to R 4 ' are each independently selected from the group consisting of 1 to 5 carbon atoms.
- At least one of Y 3 to Y 6 is -OB 8 , -SB 9 , -COOB 10 , -NB 11 B 12 , -SO 3 B 13 and -NHCOB 14 selected from the group consisting of
- at least one of Y 3 to Y 6 may be —SB 9 in which B 9 is a hydrogen group.
- Y 7 to Y 12 are each independently selected from the group consisting of a hydrogen group, a halo group, -OB 15 , -SB 16 , -COOB 17 , -NB 18 B 19 , -SO 3 B 20 and -NHCOB 21
- B 15 to B 21 are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation and an alkyl group having 1 to 5 carbon atoms
- R 5 ' and R 6 ' are each independently selected from the group consisting of 1 to 5 carbon atoms It is an alkylene group.
- Y 13 may be selected from the group consisting of a halo group, -OB 22 , -SB 23 , -COOB 24 , NB 25 B 26 , -SO 3 B 27 and -NHCOB 28 , and B 22 to B 28 are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group, W' is a halo group, and Z 5 ' and Z 6 ' are each independently selected from the group consisting of a hydrogen group, an alkyl group having 1 or 2 carbon atoms, and an alkenyl group having 1 or 2 carbon atoms, and q is an integer of 1 to 3.
- Z 5 ′ and Z 6 ′ are an alkenyl group having 2 carbon atoms and are bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.
- q is 2 or more, 2 or more Y 13 bonded to one aromatic ring may be the same as or different from each other.
- Z 5 ′ and Z 6 ′ may be bonded to two adjacent carbon atoms. Also, at least one of Z 5 ′ and Z 6 ′ may not be a hydrogen group. In addition, at least one of Y 13 may be selected from the group consisting of -OB 22 , -SB 23 , -COOB 24 , NB 25 B 26 , -SO 3 B 27 and -NHCOB 28 .
- the substituted alkyl group or substituted phenyl group having 1 or 2 carbon atoms of B 22 to B 28 may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.
- compatibilizers include dithiobisdibenzoic acid, dithiodianiline, bis(hydroxyphenyl)disulfide, (triethoxysilyl)propanethiol, bis((triethoxysilyl)propyl)disulfane and iodophenyl ethyl ether. It may be at least one selected from the group consisting of, but is not particularly limited thereto.
- the compatibilizer is 2,2'-dithiobisdibenzoic acid, 4,4'-dithiodianiline, bis(3-hydroxyphenyl) disulfide, bis(4-hydroxyphenyl) disulfide, 3-(tri It may be at least one selected from the group consisting of ethoxysilyl)propane-1-thiol, 1,2-bis(3-(triethoxysilyl)propyl)disulfane and 4-iodophenyl ethyl ether, but limited thereto doesn't happen
- the compatibilizer may perform a substitution reaction with an iodine atom that may be positioned at the terminal of the first polyarylene sulfide resin, or may serve as a compatibilizer by itself without a reaction. If the first polyarylene sulfide resin is post-processed with a compatibilizer, the atmosphere of the main chain and/or the terminal of the first polyarylene sulfide resin can be changed from hydrophobicity to hydrophilicity, and through this, other resins having hydrophilic functional groups and/or reactive groups , it is possible to improve the compatibility with inorganic fillers, etc., it is possible to improve the mechanical strength of the final product using the same and to significantly reduce the amount of outgas generated by heating.
- the compatibilizer may react with the first polyarylene sulfide resin to impart end groups to the first polyarylene sulfide resin. Accordingly, the post-processed first polyarylene sulfide resin may have end groups derived from the compatibilizer.
- the terminal group derived from the compatibilizer may mean a functional group of the compatibilizer.
- the compatibilizer may be a compound containing a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group, so the terminal group derived from the compatibilizing agent is also a carboxyl group , may be a functional group such as a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, a sulfonate group.
- the terminal group derived from the compatibilizer may have a structure represented by one of Chemical Formulas 9 to 12 below.
- Z 1 ', Z 2 ', Z 5 ', Z 6 ', Y 1 , Y 3 to Y 5 , Y 7 to Y 9 , Y 13 , R 1 ' to R 5 ', p 1 and q are As described above.
- the compatibilizer may be included in an amount of 0.001 to 10% by weight, 0.001 to 5% by weight, 0.01 to 3% by weight, or 0.1 to 2% by weight based on the total weight of the first polyarylene sulfide resin.
- the reaction efficiency of the compatibilizer is significantly better than when the same compound is added as a polymerization inhibitor during the polymerization of the resin.
- the content of the functional group can be maximized, and the target content of the functional group to be introduced into the final resin can be achieved through the compatibilizer while using a small amount of the compatibilizer.
- the reaction efficiency is low for reasons such as the compound is decomposed by a high temperature environment for a long time required for the polymerization reaction, or discharged during the reaction. Therefore, when the first polyarylene sulfide resin is post-processed with a compatibilizer, the residence time in a high-temperature environment is short, so decomposition can be minimized, and due to the process characteristics of the post-processing that imposes a vacuum, it can cause outgas. The amount of polymerization inhibitor / compatibilizer can be lowered, and by-products from side reactions can be minimized to reduce the amount of outgas and improve compatibility.
- the first polyarylene sulfide resin post-processed with a compatibilizer can exhibit a low single yarn rate by reducing the number of defects in the spinning process as the amount of outgas is reduced as described above, so the productivity per unit time is high and the production cycle may have the effect of reducing
- Post-processing using a compatibilizer may be performed by hot mixing.
- Hot mixing may be performed at a temperature of 280 to 330 °C.
- it can be carried out in a non-oxidizing atmosphere or vacuum conditions to achieve a high degree of polymerization while preventing oxidative crosslinking.
- the oxygen concentration of the gas phase may be less than 5% by volume or less than 2% by volume, and more specifically, the gas phase may be substantially free of oxygen.
- iodine that may be partially present at the terminal of the first polyarylene sulfide resin is sufficiently removed and the crystallinity is excellent to reduce shrinkage, so the post-processed first polyarylene sulfide is used to The dimensional stability of the manufactured final article can be improved.
- high-temperature mixing may be performed under a reactor capable of heating and stirring.
- the reactor may be a reactor of various materials such as SUS.
- High-temperature mixing may be performed in a twin screw extruder, and the diameter ratio (L/D) of the twin screw extruder may be about 30 to 50.
- the first polyarylene sulfide resin may be introduced through the main inlet of the twin-screw extruder, and the first polyarylene sulfide resin may be mixed with other additives and compatibilizers added in small amounts before being introduced into the main inlet. .
- the post-processed first polyarylene sulfide resin is mainly composed of arylene sulfide units, but is usually derived from the first sulfur compound of the raw material, and the units according to the disulfide bond represented by [-S-S-] are also the main chain can be included in
- the structural formula of the final polyarylene sulfide resin including a unit according to a disulfide bond may have the form of a copolymer suggested by Eastman (US Patent No. 47,680,000).
- the structural formula of the copolymer may be expressed as in Structural Formula 1 below.
- the content of x is 0.900 to 0.999, 0.950 to 0.999 or 0.990 to 0.999.
- the disulfide bond fraction of the post-processed first polyarylene sulfide may be 0.001 to 20.0 wt%, specifically, 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, or 0.7 wt% or more, and 20.0 wt% or less , 10.0 wt% or less, 5.0 wt% or less, 2.0 wt% or less, 1.8 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less or 1% by weight or less.
- the fraction (wt%) of disulfide bonds may be defined as the difference between the theoretical amount of sulfur in polyarylene sulfide and the amount of sulfur measured by elemental analysis with respect to the theoretical amount of sulfur in polyarylene sulfide.
- Disulfide bond fraction (wt%) ⁇ (total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide) ⁇ / (theoretical weight of sulfur in polyarylene sulfide)
- the post-processed first polyarylene sulfide resin may include iodine derived from a diiodo aromatic compound, and the content of iodine is 100 to 10,000 ppm based on the total weight of the post-processed first polyarylene sulfide resin, specifically , 250 ppm or more, 500 ppm or more, 750 ppm or more, or 900 ppm or more, 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less, 4,000 ppm or less, 3,000 ppm or less, 2,500 ppm or less, 2,250 ppm or less, 2,200 ppm or less, 2,100 ppm or less, 2,000 ppm or less, 1,900 ppm or less, or 1,800 ppm or less.
- the post-processed first polyarylene sulfide resin may include inorganic substances such as Fe, Na, Ca, and Li, and the content of these (metallic) inorganic substances is based on the total weight of the post-processed first polyarylene sulfide resin.
- the inorganic material content of the polyarylene sulfide resin falls within the above range, since it may cause yarn breakage when manufacturing fibers using the polyarylene sulfide resin.
- the inorganic material of the polyarylene sulfide resin acts as a nucleating agent to increase the crystallinity of the resin, and in the stretching process, the inorganic material serves to fix the stretching point on the stretching roller, so that it slips. This is prevented, so that the elongation becomes uniform, and the mechanical strength of the final fiber can be improved.
- the inorganic material of the polyarylene sulfide resin can be distinguished from the inorganic material added as a matting agent after the resin is prepared. After the resin is manufactured, the inorganic material included in the fiber together with the resin may be input during the polymerization process due to the difference in the process and may exhibit a difference in dispersibility, cohesiveness, etc. from the inorganic material included in the resin.
- the inorganic material means a metallic inorganic material such as Na, K, Li, Ca, Fe, Ni, and the inorganic material may exist in the form of a halogen salt such as NaCl or KCl.
- Si is excluded from the inorganic material.
- the inorganic content may be measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) by heating and decomposing the resin with a mixed acid (nitric acid/perchloric acid/sulfuric acid) and then diluting it with ultrapure water.
- the mixed acid may be a mixture of 65% nitric acid, 60% perchloric acid, and 98% sulfuric acid in a volume ratio of 1:1:1.
- the post-processed first polyarylene sulfide resin may have an oligomer content of 0.01 to 5 wt% based on the total weight of the post-processed first polyarylene sulfide resin, specifically, 0.10 wt% or more, 0.50 wt% or more, or 0.80 wt% or more, 3.00 wt% or less, 2.00 wt% or less, 1.50 wt% or less, 1.40 wt% or less, 1.30 wt% or less, 1.20 wt% or less, 1.10 wt% or less, 1.00 wt% or less, or 0.90 wt% or less may be below.
- the oligomer content of the post-processed first polyarylene sulfide resin is within the above range, the single yarn rate may be lowered when manufacturing fibers using the same.
- the post-processed first polyarylene sulfide resin may have a melt viscosity of 1 poise or more, 10 poise or more, 50 poise or more, 100 poise or more, 500 poise or more, 1,000 poise or more, 1,500 poise or more, or 1,700 poise or more, and 7,000 poise or more. or less, 5,000 poise or less, 4,000 poise or less, 3,000 poise or less, or 2,500 poise or less.
- the melt viscosity is measured at 300° C. with a rotating disk viscometer, and when the viscosity is measured in an angular frequency section of 0.6 to 500 rad/s by a frequency sweep method, the viscosity at an angular frequency of 1.84 rad/s can be defined as
- the nonlinearity index may be 0.50 or less, 0.40 or less, 0.30 or less, 0.20 or less, 0.15 or less, 0.14 or less, 0.13 or less, 0.12 or less, 0.11 or less, 0.10 or less, 0.05 or less, or 0.02 or less.
- the non-linearity index may be an index related to the molecular weight of the measurement target or molecular structure such as linear, branched, or cross-linked.
- the nonlinear index is measured at 300° C. with a rotating disk viscometer, and when the viscosity change rate in the shear rate section of 0.03 to 25 s ⁇ 1 is measured by the frequency sweep method, it can be defined through Equation 2 below.
- Nonlinearity index 1 - (melt viscosity at a shear rate of 17.3 s ⁇ 1 ) / (melt viscosity at a shear rate of 3.22 s ⁇ 1 ).
- the post-processed first polyarylene sulfide resin having the above-described nonlinearity index is, for example, a method of solution polymerization of a mixture for melt polymerization comprising a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor, It is possible to obtain this polyarylene sulfide resin by making it high molecular weight to some extent.
- the post-processed first polyarylene sulfide resin may have a branching index ( ⁇ ) of 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, or 0.60 or more, and 1.00 or less, 0.90 or less, 0.80 or less, or 0.70 or less.
- ⁇ is calculated through the Mark-Howink equation represented by Equation 3 below. In general, the closer ⁇ is to 1, the more it is a linear polymer, and the closer it is to 0, the more it is a branched polymer.
- ⁇ is an intrinsic viscosity
- M is a weight average molecular weight
- K is a constant.
- the post-processed first polyarylene sulfide resin may have a melting point of 250 to 300 °C, 260 to 300 °C, 265 to 300 °C, or 270 to 290 °C.
- the melting point is measured using a differential scanning calorimeter (DSC) from 30°C to 320°C at a rate of 10°C/min, cooled to 30°C, and then from 30°C to 320°C again. It may be measured while the temperature is raised at a rate of 10 °C / min.
- DSC differential scanning calorimeter
- the post-processed first polyarylene sulfide resin may have a crystallization temperature of 150 to 300 °C, 200 to 250 °C, 210 to 240 °C, 215 to 230 °C, or 216 to 225 °C.
- the crystallization temperature is lowered, the degree of orientation can be sufficiently increased during the spinning process because it takes a long time for the molten polymer that comes out through the spinning nozzle to crystallize during the spinning process. mechanical properties can be improved.
- the crystallization temperature is high, the time during which the orientation can occur during the spinning process is short, so it is difficult to increase the degree of spinning orientation and it is difficult to have a desirable effect on the mechanical properties of the final fiber.
- the crystallization temperature is increased at a rate of 10°C/min from 30°C to 320°C using a differential scanning calorimeter differential scanning calorimeter, cooled to 30°C, and then again from 30°C to 320°C at a rate of 10°C/min. It may be measured while raising the temperature to 30 °C and cooling at 10 °C/min to 30 °C.
- the molecular weight of the post-processed first polyarylene sulfide resin may be measured by weight average molecular weight, number average molecular weight, peak peak molecular weight, and the like.
- the weight average molecular weight of the post-processed first polyarylene sulfide resin is not particularly limited as long as the effects of the present invention are not impaired, but may be 25,000 g/mol or more, 30,000 g/mol or more, or 40,000 g/mol or more in terms of mechanical strength. and may be 100,000 g/mol or less, 80,000 g/mol or less, or 65,000 g/mol or less in terms of cavity balance.
- the number average molecular weight may be 1,000 g/mol or more, 5,000 g/mol or more, 7,500 g/mol or more, 9,000 g/mol or more, or 10,000 g/mol or more, and 30,000 g/mol or less, 25,000 g/mol or less , 20,000 g/mol or less, 15,000 g/mol or less, 13,500 g/mol or less, or 13,000 g/mol or less. If the number average molecular weight is too low, the melt strength is insufficient and single yarn easily occurs in the spinning and/or stretching process. ⁇ occurs, and in more severe cases, as the extruded strand sticks to the nozzle surface and kneading occurs, single yarn may occur and the spinning process may be poor.
- the peak peak molecular weight may be 10,000 g/mol or more, 15,000 g/mol or more, 20,000 g/mol or more, or 25,000 g/mol or more, and 140,000 g/mol or less, 100,000 g/mol or less, 75,000 g/mol or less , 50,000 g/mol or less, 45,000 g/mol or less, or 44,000 g/mol or less.
- the post-processed first polyarylene sulfide resin may have a polydispersity index (PDI) of 2.0 to 6.0, for example, 2.5 or more, 3.0 or more, 3.2 or more, or 3.3 or more, 5.0 or less, 4.0 or less, 3.8 or less or 3.7 or less.
- the polydispersity index may be calculated as a ratio of a weight average molecular weight to a number average molecular weight.
- the amount of outgas of the post-processed first polyarylene sulfide resin may be 0.001 to 0.50 wt%, 0.001 to 0.20 wt%, or 0.01 to 0.10 wt%.
- the amount of outgas is quantified in wt% by using a gas chromatograph (GC) mass spectrometer to measure the amount of gas generated when a sample of a predetermined amount of polyarylene sulfide resin or resin composition is heated at 330° C. for 20 minutes. it could be When the amount of outgassing of the resin falls within the above range, the number of defects in the fiber including the same may be reduced and the fiber may exhibit a low single yarn rate, thereby increasing productivity per unit time and reducing the production cycle.
- GC gas chromatograph
- the terminal of the post-processed first polyarylene sulfide resin may include a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, a sulfonate group, and the like. Specifically, it may include a functional group derived from a compound represented by one of Formulas 5 to 8 described above.
- the first polyarylene sulfide resin post-processed with a compatibilizing agent has excellent compatibility with other resins and inorganic fillers having a hydrophilic functional group and/or reactive group, and thus can be utilized in the development of a compounding product of a polyarylene sulfide resin.
- the residence time is shorter than that of polyarylene sulfide resin that is not post-processed, and due to the nature of the post-processing process that imposes a vacuum, the amount of outgas is lower than that of polyarylene sulfide resin prepared by using the same compound as a polymerization inhibitor during the polymerization of the resin.
- the additive is not limited as long as it does not impair the effects of the present invention, and specifically, it may include one or more selected from the group consisting of a heat stabilizer and a matting agent.
- the heat stabilizer can be used to prevent the resin from decomposing due to the action of heat and light during the manufacturing process or use of the resin, and when mixing or molding the polyarylene sulfide resin with other additives or resins, By minimizing side reactions occurring in a high-temperature environment, physical properties of the final polyarylene sulfide resin composition can be improved.
- Heat stabilizer is calcium magnesium zinc-based heat stabilizer, calcium zinc-based heat stabilizer, organotin-based heat stabilizer, metal ore-based heat stabilizer, barium zinc-based heat stabilizer, epoxy zinc-based heat stabilizer, magnesium aluminum carbonate-based heat stabilizer, zinc-based heat stabilizer and a metal-based thermal stabilizer such as a lead-based thermal stabilizer, and a non-metallic thermal stabilizer such as an epoxy-based thermal stabilizer and an organic phosphite-based thermal stabilizer.
- a commercially available thermal stabilizer includes CLC-120 from Dubon, a magnesium aluminum carbonate-based thermal stabilizer.
- heat stabilizer for example, a primary phenolic stabilizer, a secondary phosphorus stabilizer, and a primary and secondary mixed stabilizer may be used. It is preferred that the material has good thermal stability.
- preferred stabilizers include ADEKA's AO-60, AO-80, Chemtura's Ultanox627A, Doverphos S9228, and the like.
- the matting agent may be added for the matting effect of the fiber and/or the drapery property of the fabric or knitted fabric to be manufactured.
- a matting agent TiO 2 and BaSO 4
- An inorganic matting agent comprising at least one selected from the group consisting of may be used.
- the post-processed first polyarylene sulfide multifilament fiber may include the post-processed first polyarylene sulfide resin and additives.
- the multifilament fiber refers to a fiber including a plurality of filament fibers.
- the multifilament fiber of the present specification may include two or more filament fibers.
- the number of strands of the filament fibers included in the multifilament fiber is not particularly limited, but specifically, may be 6 or more and 392 or less.
- the multifilament fibers of the present specification have an average aspect ratio, that is, an average fiber length/fiber diameter of, for example, 100 It can be ideal, and theoretically, it can be infinite.
- the multifilament fiber of the present specification may have an average fineness of 50 to 2000 de ⁇ , and the average fineness of each strand of the multifilament fiber may be 2 to 10 de ⁇ .
- the post-processed first polyarylene sulfide multifilament fiber contains 3% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight of the post-processed first polyarylene sulfide resin based on the total weight of the multifilament fiber.
- Weight % or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 97% by weight or more may be included.
- the post-processed first polyarylene sulfide multifilament fiber may include an additive in an amount of 3 wt% or less based on the total weight of the multifilament fiber, specifically, 0.01 to 3 wt%.
- the post-processed first polyarylene sulfide multifilament fiber contains, based on the total weight of the multifilament fiber, 0.01 wt% or more or 0.05 wt% or more, or 2 wt% or less, 1 wt% or less, or 0.5 wt% It may include less than, specifically, may include 0.1% to 1.0% by weight, and may include a matting agent in an amount of 2.5% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less And, specifically, it may be included in an amount of 0.01 wt% or more or 2.5 wt% or less.
- the post-processed first polyarylene sulfide multifilament fiber may have a single yarn rate measured under undrawn yarn spinning conditions of 2 times/hour or less, 1.5 times/hour or less, or 1 time/hour or less.
- the tensile strength of the post-processed first polyarylene sulfide multifilament fiber may be 3.0 g/de ⁇ or more or 3.5 g/de ⁇ or more, and 3.5 g/de ⁇ to 5 g/de ⁇ days when measured under the conditions of the drawn yarn.
- the post-processed first polyarylene sulfide multifilament fiber may have a tensile elongation of 50% or less when measured under the conditions of the drawn yarn, for example, may have a tensile elongation of more than 35% and 50% or less.
- the post-processed first polyarylene sulfide multifilament fiber may have a shrinkage rate of 15% or less measured under the conditions of the drawn yarn, for example, 6 to 12%, or 8 to 10%. If the shrinkage ratio is higher than the above range, the orientation crystal may be insufficient, and thus the shape stability of the final woven, knitted or nonwoven fabric made of the fiber may be insufficient. Conversely, if the shrinkage rate is lower than the above range, there is a difficulty in that post-processing such as sewing becomes difficult due to insufficient pores in the final fabric, knitted fabric or nonwoven fabric manufactured. When the fiber has a shrinkage rate in the above range, it can have desirable shape stability and post-processing properties, particularly in industrial applications.
- the post-processed first polyarylene sulfide multifilament fiber is prepared by preparing a post-processed first polyarylene sulfide resin composition including the first polyarylene sulfide and an additive, and preparing the post-processed first polyarylene sulfide resin composition. It may be prepared by spinning and/or stretching.
- a specific composition of the post-processed first polyarylene sulfide resin composition may be set to be the same as that of the final multifilament fiber.
- the spinning step may be performed by melt spinning the post-processed first polyarylene sulfide resin composition, and may be performed using a generally used melt spinning apparatus, for example, a single or twin screw extruder type spinning machine. .
- the temperature of the spinning step is preferably a temperature sufficient to melt the polyarylene sulfide resin and as low as possible from the viewpoint of suppressing gelation.
- the spinning process may be performed under a condition that the temperature of the polyarylene sulfide resin discharged from the nozzle is 250 to 340°C or 270 to 320°C, and may be performed under a nitrogen atmosphere.
- a spinneret commonly used for melt spinning may be used.
- a nozzle having a discharge aperture of 0.1 to 1.0 mm ⁇ and a discharge hole depth of about 0.1 to 5.0 mm may be used.
- the cross-sectional shape of the fiber during spinning is not particularly limited, and may be a normal circular cross-section, triangular cross-section, rectangular cross-section, Y-shaped cross-section, cross-section, C-shaped cross-section, hollow cross-section, or typical cross-section.
- the fibers discharged from the spinneret are generally cooled and wound up by exposure to a wind having a wind speed of 5 to 100 m/min after discharging.
- an emulsion may be added as a bundling agent and used.
- the winding speed may be 300 to 5,000 m/min.
- the process method is to obtain an undrawn yarn (UDY) by spinning the post-processed first polyarylene sulfide resin composition at a low speed, or by spinning the post-processed first polyarylene sulfide resin composition at high speed to obtain a partially oriented yarn (partially oriented yarn) ; to obtain POY); winding the undrawn or partially drawn yarn; Drawing the wound undrawn yarn or partially drawn yarn may be carried out including the step of obtaining a fully drawn yarn (FDY). Alternatively, it may be carried out including the step of inputting the wound undrawn or partially drawn yarn to a false twisting machine to obtain a draw-textured yarn by false twisting and drawing.
- the spinning step may include a step of directly spinning the post-processed first polyarylene sulfide resin composition in one step to obtain a spin draw yarn (SDY).
- SDY spin draw yarn
- the post-processed first polyarylene sulfide multifilament fiber has a significantly lower single yarn rate, as well as tensile strength and/or tensile strength, as compared to the multifilament fiber including the first polyarylene sulfide resin that is not post-processed with a compatibilizer.
- the mechanical strength of the elongation may exhibit an excellent effect.
- a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor are melt-polymerized, and a second polyarylene sulfide in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized polyarylene sulfide mixed resin composed of resin; and at least one additive selected from the group consisting of a heat stabilizer and a matting agent, a multifilament fiber (hereinafter, polyarylene sulfide mixed multifilament fiber) is provided.
- a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor are melt-polymerized, and a second polyarylene in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized polyarylene sulfide mixed resin composed of sulfide resin; and preparing a polyarylene sulfide mixed resin composition comprising an additive; And comprising the step of spinning the polyarylene sulfide mixed resin composition, there is provided a method for producing a multi-filament fiber.
- the first polyarylene sulfide resin and additives are the same as described above.
- the second polyarylene sulfide resin may be prepared by solution polymerization of a dihalo aromatic compound and a second sulfur compound.
- the second polyarylene sulfide resin is not particularly limited as long as it is prepared including solution polymerization of a dihalo aromatic compound and a second sulfur compound.
- a commercial method for preparing such a polyarylene sulfide resin a Macallum process of solution polymerization of p-dichlorobenzene and sodium sulfide in the presence of a polar organic solvent such as N-methyl pyrrolidone (Macallum process) This is known A typical process is described in US Pat. No. 2,513,188.
- the melt polymerization may be performed in the presence of an organic polar solvent.
- the organic polar solvent is, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam.
- the dihalo aromatic compound refers to a compound having an aromatic ring and two halo groups directly bonded thereto.
- the halogen atom of the halo group may be each atom of fluorine, chlorine, bromine and iodine, and two halo groups present in the dihalo aromatic compound may be the same or different from each other. More specifically, both halogen atoms may be chlorine.
- Dihalo aromatic compounds include, for example, o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl It may be at least one selected from the group consisting of ether, dihalodiphenylsulfone, dihalodiphenylsulfoxide and dihalodiphenylketone.
- the dihalo aromatic compound may be, for example, 1,4-dichlorobenzene, but is not particularly limited thereto.
- the second sulfur compound may be at least one selected from the group consisting of an alkali metal sulfide and an alkali metal sulfide-forming compound capable of forming the alkali metal sulfide.
- the second sulfur compound may be at least one selected from the group consisting of alkali metal hydrosulfide and the alkali metal hydrosulfide-forming compound.
- the second sulfur compound includes, for example, alkali metal hydrosulfides such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide and cesium hydrosulfide, and alkali metal hydrosulfides such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. It may be a metal sulfide, but is not particularly limited thereto.
- the alkali metal sulfide-forming compound or the alkali metal hydrosulfide-forming compound may be, for example, hydrogen sulfide.
- alkali metal hydroxide eg NaOH
- alkali metal hydrosulfide eg NaSH
- alkali metal sulfide eg Na 2 S
- the second sulfur compound may be at least one selected from the group consisting of anhydrides, hydrates, and aqueous solutions.
- the second sulfur compound may be, for example, sodium sulfide hydrate, but is not particularly limited thereto.
- the polyarylene sulfide blended multifilament fiber includes a polyarylene sulfide blended resin composed of a melt-polymerized first polyarylene sulfide resin and a solution-polymerized second polyarylene sulfide resin; and at least one additive selected from the group consisting of a heat stabilizer and a matting agent.
- Solution-polymerized polyarylene sulfide resin prepared by solution polymerization of a dihalo aromatic compound and a sulfur compound has excellent physical properties such as high mechanical strength, but has a disadvantage in that the amount of outgas is high due to the use of a solvent that can cause outgas have
- the melt-polymerized polyarylene sulfide resin which is prepared by melt polymerization of a mixture containing a diiodo aromatic compound, a sulfur compound, and a polymerization inhibitor, has a remarkably low amount of outgas, but a disulfide bond with a weak structure due to the manufacturing method. It has a disadvantage in that mechanical strength is low as it is included.
- the present inventors surprisingly found that by mixing the solution-polymerized polyarylene sulfide resin and the melt-polymerized polyarylene sulfide resin, the amount of outgas is low at a level comparable to that of the melt-polymerized polyarylene sulfide resin, and the solution-polymerized poly It has been found that a polyarylene sulfide mixed resin having better physical properties than that of an arylene sulfide resin can be prepared.
- the effect of the mixed resin is not limited to a specific theory, but may be achieved by the reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, the disulfide bond of the first polyarylene sulfide resin is cleaved to further react with the terminal halogen of the second polyarylene sulfide. can do.
- the disulfide bond which is a weak structure of the first polyarylene sulfide, is removed and the molecular weight increases, and at the same time, the halogen of the second polyarylene sulfide can be additionally removed, so that not only mechanical properties are improved but also the amount of outgas This can be significantly reduced.
- melt mixing may be performed under any conditions as long as the first polyarylene sulfide resin and the second polyarylene sulfide resin can be melted.
- melt mixing may be performed in a single-screw or twin-screw kneader and extruder, a polymerization reactor, a kneader reactor, and the like. More specifically, melt mixing may be performed in a twin-screw extruder, and may be performed at a temperature of 280 to 330°C, preferably 290 to 310°C.
- the discharge amount of the resin component may be 5 to 400 kg/hr at a rotation speed of 100 to 450 rpm, and may be adjusted to 100 to 250 kg/hr in consideration of dispersibility.
- a polyarylene sulfide mixed resin with a further reduced amount of outgas can be prepared.
- the polyarylene sulfide mixed resin may include 1 to 99.9 wt% of the first polyarylene sulfide resin based on the total weight of the polyarylene sulfide mixed resin, and more specifically 2 wt% or more, 3 wt% or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 50% by weight or more, and 99.9% by weight, 99% by weight or less, 98% by weight or less, 97% by weight or less, 95% by weight or less , 90% by weight or less or 70% by weight may be included.
- the polyarylene sulfide mixed resin may include 1 to 99.9 wt% of the second polyarylene sulfide resin based on the total weight of the polyarylene sulfide mixed resin, and more specifically 2 wt% or more, 3 Weight % or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 50% by weight or more, 99.9% by weight, 99% by weight or less, 98% by weight or less, 97% by weight or less, 95% by weight % or less, 90% by weight or less, or 70% by weight or less.
- the nonlinearity index, molecular weight, polydispersity index, and melting point of the polyarylene sulfide mixed resin are the same as those described above for the post-processed first polyarylene sulfide resin.
- the polyarylene sulfide mixed resin may have a melt viscosity of 1 poise or more, 10 poise or more, 50 poise or more, 100 poise or more, 500 poise or more, 1,000 poise or more, 1,500 poise or more, or 1,700 poise or more, 7,000 poise or less, 5,000 poise or more or less, 4,000 poise or less, 3,000 poise or less, or 2,600 poise or less.
- the polyarylene sulfide mixed resin may have a disulfide bond fraction of 0.001 to 10.0% by weight, specifically, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, or 0.7% by weight or more, and 10.0% by weight or less, 5.0 weight % or less, 2.0 wt% or less, 1.8 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, or 1 wt% or less .
- the polyarylene sulfide mixed resin may contain iodine derived from a diiodo aromatic compound, and the content of iodine is 1 to 10,000 ppm, specifically, 5 ppm or more, based on the total weight of the polyarylene sulfide mixed resin; 10 ppm or more, 20 ppm or more, or 40 ppm or more, and 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less, 4,000 ppm or less, 3,000 ppm or less, 2,500 ppm or less, 2,300 ppm or less; 2,270 ppm or less, 2,200 ppm or less, 2,000 ppm or less, 1,900 ppm or less, 1,800 ppm or less, 1,700 ppm or less, 1,600 ppm or less, or 1,500 ppm or less.
- the polyarylene sulfide mixed resin may contain chlorine derived from a raw material used in the preparation of the second polyarylene sulfide resin, and the content of chlorine is less than 2,500 ppm based on the total weight of the polyarylene sulfide mixed resin; It may be 2,300 ppm or less or 2,000 ppm or less.
- the polyarylene sulfide mixed resin may include inorganic substances such as Fe, Na, Ca, and Li, and the content of these (metallic) inorganic substances is 1,000 ppm or less and less than 780 ppm based on the total weight of the polyarylene sulfide mixed resin. , 700 ppm or less, 600 ppm or less, or 500 ppm or less.
- the polyarylene sulfide mixed resin may have an oligomer content of 0.01 to 5 wt% based on the total weight of the polyarylene sulfide mixed resin, specifically, 0.10 wt% or more, 0.50 wt% or more, or 0.80 wt% It may be more than 3.00 wt%, 2.00 wt% or less, 1.50 wt% or less, 1.40 wt% or less, 1.30 wt% or less, 1.20 wt% or less, 1.10 wt% or less, 1.00 wt% or less, or 0.90 wt% or less .
- the polyarylene sulfide mixed resin may have a branching index ( ⁇ ) of 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, or 0.60 or more, and 1.00 or less, 0.90 or less, 0.80 or less, 0.76 or less, or 0.70 or less.
- the polyarylene sulfide mixed resin may have a crystallization temperature of 150 to 300 °C, 200 to 250 °C, 210 to 250 °C, 220 to 250 °C, or 225 to 245 °C.
- the amount of outgas of the polyarylene sulfide mixed resin may be 0.001 to 5% by weight, and specifically, 0.001% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, or 0.35% by weight or more. % or more, 3 wt% or less, 2 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.35 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1 wt% or less, It may be 0.8 wt% or less or 0.6 wt% or less.
- the polyarylene sulfide mixed multifilament fiber contains 3% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight of the polyarylene sulfide mixed resin based on the total weight of the multifilament fiber. or more, 90% by weight or more, 95% by weight or more, or 97% by weight or more.
- the polyarylene sulfide mixed multifilament fiber may include an additive in an amount of 3 wt% or less based on the total weight of the multifilament fiber, specifically, 0.01 to 3 wt%.
- the polyarylene sulfide blended multifilament fiber may contain 0.01 wt% or more, or 0.05 wt% or more, or 2 wt% or less, 1 wt% or less, or 0.5 wt% or less of the heat stabilizer based on the total weight of the multifilament fiber.
- the single yarn rate measured under the spinning conditions of the undrawn yarn may be 3 times/hour or less, specifically, less than 2.5 times/hour, 2 times or less, 1 to 3 times/hour hour or 1-2 times/hour.
- the tensile strength of the polyarylene sulfide mixed multifilament fiber may be 3.0 g/de' or more, 3.5 g/de' or more, or 4.1 g/de' or more, for example, 4.1 g/de' to 5 It can be g/de ⁇ .
- the polyarylene sulfide mixed multifilament fiber may have a tensile elongation of 50% or less when measured under the conditions of the drawn yarn, for example, may have a tensile elongation of more than 35% and 50% or less.
- the polyarylene sulfide mixed multifilament fiber may have a shrinkage ratio of 15% or less measured under the conditions of the drawn yarn, for example 6 to 12%, or 8 to 10%.
- the polyarylene sulfide mixed multifilament fiber is prepared by preparing a polyarylene sulfide mixed resin composition including the polyarylene sulfide mixed resin and additives, and spinning and/or stretching the prepared polyarylene sulfide mixed resin composition.
- the specific composition of the polyarylene sulfide mixed resin composition may be set to be the same as the composition of the final multifilament fiber, and the specific method of spinning is as described above with respect to the spinning of the post-processed first polyarylene sulfide resin composition. .
- the polyarylene sulfide mixed multifilament fiber has a single yarn rate as low as that of the multifilament fiber made of the first polyarylene sulfide resin, but has significantly superior mechanical strength such as tensile strength and tensile elongation. And, compared to the second polyarylene sulfide resin composition, the single yarn rate may be significantly superior.
- a post-processed first polyarylene sulfide resin in which an end group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized, and a post-processed polyarylene sulfide mixed resin composed of a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized; and at least one additive selected from the group consisting of a heat stabilizer and a matting agent, a multifilament fiber (hereinafter, post-processed polyarylene sulfide mixed multifilament fiber) is provided.
- a post-processed first polyarylene sulfide resin in which a terminal group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; and a post-processed polyarylene sulfide mixed resin composed of a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized; and preparing a post-processed polyarylene sulfide mixed resin composition comprising an additive; and spinning and/or stretching the post-processed polyarylene sulfide mixed resin composition.
- the post-processed first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives are the same as described above.
- the post-processed polyarylene sulfide mixed multifilament fiber is a post-processed polyarylene sulfide mixed resin composed of a first polyarylene sulfide resin post-processed to a melt-polymerized first polyarylene sulfide resin, and a second polyarylene sulfide resin. ; and additives. Their mixing is as described above.
- post-processing of the first polyarylene sulfide resin may be performed before mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin, may be performed with mixing, or may be performed after mixing there is. In addition, it may be carried out before mixing and additionally performed with or after mixing, and other combinations are possible without limitation.
- post-processing of the first polyarylene sulfide resin is performed by adding a compatibilizer to the twin-screw extruder when the first polyarylene sulfide resin and the second polyarylene sulfide resin are put into a twin-screw extruder and melt-mixed.
- the discharge amount of the resin component may be 5 to 400 kg/hr at a rotation speed of 100 to 450 rpm, and may be adjusted to 100 to 250 kg/hr in consideration of dispersibility.
- the mixing it is possible to prepare a polyarylene sulfide mixed resin in which the amount of outgas is further reduced by defoaming in a mixer or reactor equipped with a vacuum line.
- the terminal of the post-processed polyarylene sulfide mixed resin may include a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.
- a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.
- the post-processed polyarylene sulfide mixed resin may include 1 to 99.9 wt% of the post-processed first polyarylene sulfide resin based on the total weight of the post-processed polyarylene sulfide mixed resin, and more specifically, 2 wt. % or more, 3% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 50% by weight or more, 99.9% by weight, 99% by weight or less, 98% by weight or less, 97% by weight or more or less, 95% by weight or less, 90% by weight or less, or 70% by weight or less.
- the post-processed polyarylene sulfide mixed resin may include 1 to 99.9% by weight of the second polyarylene sulfide resin based on the total weight of the post-processed polyarylene sulfide mixed resin, and more specifically 2 weight percent % or more, 3% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 50% by weight or more, 99.9% by weight, 99% by weight or less, 98% by weight or less, 97% by weight or more or less, 95% by weight or less, 90% by weight or less, or 70% by weight or less.
- the melting point and shrinkage ratio of the post-processed polyarylene sulfide mixed resin in which the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed are as described above for the post-processed first polyarylene sulfide resin .
- the post-processed polyarylene sulfide mixed resin may have a disulfide bond fraction of 0.001 to 10.0% by weight, specifically, 0.1% by weight or more, 0.3% by weight or more, or 0.4% by weight or more, and 10.0% by weight or less, 5.0% by weight or less , 2.0 wt% or less, 1.8 wt% or less, 1.7 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, or 1 wt% or less can
- the post-processed polyarylene sulfide mixed resin may contain iodine derived from a diiodo aromatic compound, and the content of iodine is 1 to 10,000 ppm based on the total weight of the post-processed first polyarylene sulfide resin, specifically , 5 ppm or more, 10 ppm or more, 20 ppm or more, or 250 ppm or more, and 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less, 4,000 ppm or less, 3,000 ppm or less, 2,500 ppm or less , less than 2,300 ppm, less than 2,250 ppm, less than 2,200 ppm, less than 2,000 ppm, less than 1,500 ppm, less than 1,000 ppm, less than 800 ppm, or less than 600 ppm.
- the post-processed polyarylene sulfide mixed resin may contain chlorine derived from a raw material used for manufacturing the second polyarylene sulfide resin, and the content of chlorine is based on the total weight of the post-processed polyarylene sulfide mixed resin. It may be less than 2,500 ppm, less than 2,300 ppm, or less than 2,000 ppm.
- the post-processed polyarylene sulfide mixed resin may include inorganic substances such as Fe, Na, Ca, and Li, and the content of these (metallic) inorganic substances is 2,000 ppm or less based on the total weight of the post-processed polyarylene sulfide mixed resin. , 1,000 ppm or less, 780 ppm or less, 700 ppm or less, 600 ppm or less, or 500 ppm or less.
- the post-processed polyarylene sulfide mixed resin may have an oligomer content of 0.01 to 5 wt% based on the total weight of the post-processed polyarylene sulfide mixed resin, specifically, 0.10 wt% or more, 0.50 wt% or more or 0.80 wt% or more, 3.00 wt% or less, 2.00 wt% or less, 1.50 wt% or less, 1.40 wt% or less, 1.30 wt% or less, 1.20 wt% or less, 1.10 wt% or less, 1.00 wt% or less, or 0.90 wt% or less % or less.
- the post-processed polyarylene sulfide mixed resin may have a melt viscosity of 1 poise or more, 10 poise or more, 50 poise or more, 100 poise or more, 500 poise or more, 1,000 poise or more, 1,500 poise or more, 1,700 poise or more, 7,000 poise or less, 5,000 poise or less, 4,000 poise or less, 3,000 poise or less, or 2,800 poise or less.
- nonlinearity index of the post-processed polyarylene sulfide mixed resin may be 0.50 or less, 0.40 or less, 0.30 or less, 0.20 or less, 0.15 or less, 0.14 or less, 0.13 or less, or 0.12 or less.
- the post-processed polyarylene sulfide mixed resin may have a branching index ( ⁇ ) of 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, or 0.60 or more, and 1.00 or less, 0.90 or less, 0.80 or less, 0.77 or less, 0.75 or less, or 0.70 or less.
- the post-processed polyarylene sulfide mixed resin may have a crystallization temperature of 150 to 300 °C, 200 to 250 °C, 210 to 250 °C, 220 to 250 °C, or 225 to 245 °C.
- the weight average molecular weight of the post-processed polyarylene sulfide mixed resin is 25,000 g/mol or more, 30,000 g/mol or more, 35,000 g/mol or more, 40,000 g/mol or more, 43,000 g/mol or more, or 45,000 g/mol or more. and may be 100,000 g/mol or less, 80,000 g/mol or less, or 65,000 g/mol or less. Further, the number average molecular weight may be 1,000 g/mol or more, 5,000 g/mol or more, 7,500 g/mol or more, 9,000 g/mol or more, or 10,000 g/mol or more, and may be 30,000 g/mol or less, 25,000 g/mol or more.
- the melt strength is insufficient and single yarn easily occurs in the spinning and/or stretching process, and when it is higher than the above range, the die swell phenomenon in the spinneret is severe, so kneading) may occur, which may deteriorate the spinning process.
- the peak peak molecular weight may be 10,000 g/mol or more, 15,000 g/mol or more, 20,000 g/mol or more, 25,000 g/mol or more, or 30,000 g/mol or more, and 140,000 g/mol or less, 100,000 g/mol or more or less, 75,000 g/mol or less, or 60,000 g/mol or less.
- the post-processed polyarylene sulfide mixed resin may have a polydispersity index (PDI) of 2.0 to 6.0, for example, 2.5 or more, 3.0 or more, 3.2 or more, or 3.3 or more, and 5.0 or less, 4.0 or less, 3.8 or less, or 3.7 or less. there is.
- PDI polydispersity index
- the amount of outgas of the post-processed polyarylene sulfide mixed resin may be 0.001 to 5% by weight, and specifically, 0.001% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 0.15% by weight or more, or 0.2% by weight or more. and 3 wt% or less, 2 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.35 wt% or less, 1.25 wt% or less, 1 wt% or less, 0.8 wt% or less, 0.6 wt% or less, 0.5 wt% It may be less than, 0.4% by weight or less, 0.35% by weight or less, or 0.3% by weight or less.
- the post-processed polyarylene sulfide mixed multifilament fiber contains 3% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight of the polyarylene sulfide mixed resin based on the total weight of the multifilament fiber. It may be included in an amount of at least 90 wt%, at least 95 wt%, or at least 97 wt% by weight.
- the post-processed polyarylene sulfide mixed multifilament fiber may include an additive in an amount of 3 wt% or less based on the total weight of the multifilament fiber, specifically, 0.01 to 3 wt%.
- the post-processed polyarylene sulfide mixed multifilament fiber contains 0.01 wt% or more or 0.05 wt% or more of the heat stabilizer based on the total weight of the multifilament fiber, or 2 wt% or less, 1 wt% or less, or 0.5 wt% or less It may include, and may include a matting agent in an amount of 0.01 wt% or more or 2.5 wt% or less, or 2 wt% or less, 1 wt% or less, or 0.5 wt% or less.
- the tensile strength of the post-processed polyarylene sulfide mixed multifilament fiber may be 3.0 g/de' or more, 3.5 g/de' or more, or 4.1 g/de' or more, for example, 4.1 g/de' when measured under the conditions of the drawn yarn. to 5 g/de ⁇ .
- the post-processed polyarylene sulfide mixed multifilament fiber has a single yarn rate lower than that of the multifilament fiber made of the first polyarylene sulfide resin, and mechanical strength such as tensile strength and tensile elongation can also be remarkably excellent, and the second Compared to the polyarylene sulfide resin composition, the single yarn rate may be significantly superior.
- This effect is not limited to a specific theory, but may be achieved by the reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, the disulfide bond of the first polyarylene sulfide resin is cleaved to further react with the terminal halogen of the second polyarylene sulfide. can do.
- the disulfide bond which is a weak structure of the first polyarylene sulfide, is removed and the molecular weight increases, and at the same time, the halogen of the second polyarylene sulfide can be additionally removed, so that not only mechanical properties are improved but also the amount of outgas This is significantly reduced, and the single yarn rate may be lowered.
- the first polyarylene sulfide resin is post-processed using a compatibilizer, compatibility with other resins and inorganic fillers having a hydrophilic functional group and/or reactive group is improved, and the mechanical properties of the final fiber produced using the mixed resin strength can be improved.
- the reaction efficiency of the compatibilizer is remarkably excellent, so that the content of functional groups remaining in the final resin can be maximized.
- the reaction efficiency is remarkably excellent, it is possible to achieve the target content of the functional group to be introduced into the final resin through the compatibilizer while using a small amount of the compatibilizer. Therefore, in the case of post-processing with a compatibilizer, the amount of polymerization inhibitor / compatibilizer that can be a cause of outgas is lowered, and by-products due to side reactions that can be generated by the compatibilizer in a high temperature environment for a long time required for the polymerization reaction are minimized. It is possible to further reduce the amount of outgas, and at the same time improve the compatibility to improve the mechanical strength of tensile strength and/or tensile elongation.
- thermocouple capable of measuring the internal temperature of the reactor and a vacuum line capable of filling nitrogen and applying a vacuum were attached to the 5 L reactor, and 5,240 g of paradiiodobenzene and 450 g of elemental sulfur were added to the reactor.
- the composition in the reactor containing paradiiodobenzene and elemental sulfur was heated to 180° C. to completely melt and mix it, starting from the initial reaction conditions of a temperature of 220° C. and a pressure of 350 torr, the temperature is gradually increased and reduced, and the temperature is 300° C.
- the polymerization reaction was carried out under the final reaction conditions of a pressure of 1 torr or less.
- the filtered cake was further washed with 2,880 g of NMP, and 10 L of ion-exchanged water was added to the cake containing NMP, which was then stirred in an autoclave at 200° C. for 10 minutes, followed by further filtration.
- the final filtered cake was dried at 130° C. for 3 hours to prepare PPS b as a second polyarylene sulfide resin.
- PPS c2 was prepared as a post-processed first polyarylene sulfide resin.
- Preparation c1 except that 0.3 parts by weight of 3-(triethoxysilyl)propane-1-thiol (Power chemical (China) SiSiB-PC2310) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer
- PPS c4 was prepared as a post-processed first polyarylene sulfide resin.
- post-processed first poly PPS c6 was prepared as an arylene sulfide resin.
- a twin-screw kneading extruder ( Toshiba Kikai Co., Ltd., TEM-35B) was melt-kneaded at 300° C. and processed into pellets using a small strand cutter to prepare a polyarylene sulfide resin (resin before mixing additives).
- the polyarylene sulfide resin was uniformly mixed with a heat stabilizer and/or a matting agent at the weight ratio shown in Tables 1 to 4 using a tumbler, and a single/twin extruder type small spinning machine (Screw diameter 20 ⁇ , single screw) at a spinning speed of 800 m/min, and once wound in the undrawn (UDY) state, stretched using a stretching machine at a stretching speed of 400 m/min and a stretching ratio of 2.5 to 4.0, and non-contact A multifilament fiber was prepared by heat setting at 230°C using a heater (UDY-FDY method).
- a polyarylene sulfide fiber composed of a resin or a composition containing the same is once wound with a partially oriented yarn (POY) spun at high speed using a single/twin extruder type spinning machine and stretched using a stretching machine.
- Multifilament fibers may be manufactured by the method (POY-FDY method), or multifilament fibers may be manufactured by a direct spinning method (SDY method) in which spinning and drawing processes are continuously performed.
- the heat stabilizer and matting agent are specifically shown in Table 4 below.
- the temperature was raised from 30°C to 320°C at a rate of 10°C/min, and after cooling to 30°C at a rate of 10°C/min, The melting point and the crystallization temperature were measured again while the temperature was raised from 30°C to 320°C at a rate of 10°C/min, and cooled to 30°C at a rate of 10°C/min.
- DSC differential scanning calorimeter
- Melt viscosity is, with a rotating disk viscometer, when the viscosity is measured in the frequency range of 0.6 to 500 rad/s by a frequency sweep method at 300° C., the viscosity at each frequency condition of 1.84 rad/s has been defined
- the nonlinear index was calculated through Equation 2 below.
- Nonlinearity index 1 - (melt viscosity at a shear rate of 17.3 s ⁇ 1 ) / (melt viscosity at a shear rate of 3.22 s ⁇ 1 ).
- the number average molecular weight, weight average molecular weight, and peak peak molecular weight of the polyarylene sulfide resin were measured by gel permeation chromatography under the following measurement conditions, and the polydispersity index was calculated as the ratio of the weight average molecular weight to the measured number average molecular weight.
- the polydispersity index was calculated as the ratio of the weight average molecular weight to the measured number average molecular weight.
- six types of monodisperse polystyrene were used for calibration.
- the branching index was defined as an ⁇ value calculated by applying the viscosity measured from the triple system detector to the Mark-Howink equation of Equation 3 below.
- the Mark Howink equation is a relationship between molecular weight and intrinsic viscosity of a polymer, and the branching index ( ⁇ ) indicates the degree of branching of the polymer. That is, the closer ⁇ is to 1, the more linear the polymer, and the closer to 0, the more branched the polymer is.
- ⁇ is an intrinsic viscosity
- M is a weight average molecular weight
- K is a constant.
- the binding fraction of disulfide was calculated through Equation 1 below.
- Disulfide bond fraction (wt%) ⁇ (total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide) ⁇ / (theoretical weight of sulfur in polyarylene sulfide)
- the amount of gas generated by heating a sample of a predetermined amount of polyarylene sulfide resin at 330° C. for 20 minutes was quantified in weight % using a gas chromatograph (GC) mass spectrometer.
- GC gas chromatograph
- the iodine and chlorine contents of the polyarylene sulfide resin were measured by ion chromatograph (IC) using IC (AQF) Thermo Scientific, ICS-2500 (Mitsubishi AQF-100).
- the ratio of the polymer having a molecular weight of 1,000 g/mol or less was calculated as weight %, and the oligomer content was evaluated.
- the tensile strength and tensile elongation of the multifilament fibers in the stretched state were measured using Zwick's Z010 according to the ISO 527-2 method.
- PPS C1 to C7 containing the first polyarylene sulfide resin post-processed with a compatibilizer is PPS A1 containing the first polyarylene sulfide resin that is not post-processed with a compatibilizer, and the compound of Formula 5 Compared to PPS A2 containing the first polyarylene sulfide resin prepared by using a polymerization inhibitor, it was confirmed that the yarn breakage occurred less during the spinning process and the drawn yarn fiber strength was excellent.
- the strength of the drawn yarn is higher than in PPS A1 including the first polyarylene sulfide resin. It was excellent, and it was confirmed that the second polyarylene sulfide resin showed the same level of drawn yarn strength as compared to PPS B, and the number of single yarns was small, so that the stability in the spinning process was excellent.
- PPS E1 to E10 including the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin compared to PPS A1 including the first polyarylene sulfide resin, the drawn yarn It was confirmed that the fiber strength was excellent, and it exhibited an equivalent level of drawn yarn strength compared to PPS B including the second polyarylene sulfide resin, and the number of single yarns was small, so that the stability in the spinning process was excellent.
- PPS D4 including the first polyarylene sulfide resin and the second polyarylene sulfide resin the drawn yarn strength was excellent.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
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- Artificial Filaments (AREA)
Abstract
La présente invention concerne une nouvelle fibre multi-filament de sulfure de polyarylène. La fibre multi-filament selon la présente invention peut avoir un faible taux de rupture de fil et une excellente résistance mécanique.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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KR1020200139703A KR20220055346A (ko) | 2020-10-26 | 2020-10-26 | 폴리아릴렌 설파이드 멀티 필라멘트 섬유 |
KR10-2020-0139703 | 2020-10-26 |
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WO2022092716A1 true WO2022092716A1 (fr) | 2022-05-05 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/KR2021/014920 WO2022092716A1 (fr) | 2020-10-26 | 2021-10-22 | Fibre multi-filament de sulfure de polyarylène |
Country Status (3)
Country | Link |
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KR (1) | KR20220055346A (fr) |
TW (1) | TW202229687A (fr) |
WO (1) | WO2022092716A1 (fr) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4897454A (en) * | 1989-03-17 | 1990-01-30 | Eastman Kodak Company | Blends of poly(arylene sulfide) and copoly(arylene sulfide) modified with diphenyl ether |
EP0405135B1 (fr) * | 1989-06-29 | 1995-01-18 | General Electric Company | Polyarylènesulfides ayant des groupements terminaux réactives, procédé pour leur préparation et intermédiaires |
KR20150085087A (ko) * | 2013-03-25 | 2015-07-22 | 디아이씨 가부시끼가이샤 | 폴리아릴렌설피드 수지의 제조 방법 및 폴리아릴렌설피드 수지 조성물 |
KR20160050047A (ko) * | 2013-09-05 | 2016-05-10 | 디아이씨 가부시끼가이샤 | 폴리아릴렌설피드 섬유 및 그 제조 방법 |
KR20170105269A (ko) * | 2016-03-09 | 2017-09-19 | 이니츠 주식회사 | 표면 평활도 및 금속 증착성이 우수한 램프 리플렉터용 수지 조성물 |
KR20200002731A (ko) * | 2012-09-19 | 2020-01-08 | 에스케이케미칼 주식회사 | 폴리아릴렌 설파이드계 수지 조성물 및 성형품 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2513188A (en) | 1948-09-10 | 1950-06-27 | Macallum Alexander Douglas | Mixed phenylene sulfide resins |
-
2020
- 2020-10-26 KR KR1020200139703A patent/KR20220055346A/ko unknown
-
2021
- 2021-10-22 WO PCT/KR2021/014920 patent/WO2022092716A1/fr active Application Filing
- 2021-10-25 TW TW110139537A patent/TW202229687A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4897454A (en) * | 1989-03-17 | 1990-01-30 | Eastman Kodak Company | Blends of poly(arylene sulfide) and copoly(arylene sulfide) modified with diphenyl ether |
EP0405135B1 (fr) * | 1989-06-29 | 1995-01-18 | General Electric Company | Polyarylènesulfides ayant des groupements terminaux réactives, procédé pour leur préparation et intermédiaires |
KR20200002731A (ko) * | 2012-09-19 | 2020-01-08 | 에스케이케미칼 주식회사 | 폴리아릴렌 설파이드계 수지 조성물 및 성형품 |
KR20150085087A (ko) * | 2013-03-25 | 2015-07-22 | 디아이씨 가부시끼가이샤 | 폴리아릴렌설피드 수지의 제조 방법 및 폴리아릴렌설피드 수지 조성물 |
KR20160050047A (ko) * | 2013-09-05 | 2016-05-10 | 디아이씨 가부시끼가이샤 | 폴리아릴렌설피드 섬유 및 그 제조 방법 |
KR20170105269A (ko) * | 2016-03-09 | 2017-09-19 | 이니츠 주식회사 | 표면 평활도 및 금속 증착성이 우수한 램프 리플렉터용 수지 조성물 |
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TW202229687A (zh) | 2022-08-01 |
KR20220055346A (ko) | 2022-05-03 |
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