CN113667122A - Gradient temperature-controlled continuous condensation method of polyarylene sulfide resin - Google Patents
Gradient temperature-controlled continuous condensation method of polyarylene sulfide resin Download PDFInfo
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- CN113667122A CN113667122A CN202110816570.8A CN202110816570A CN113667122A CN 113667122 A CN113667122 A CN 113667122A CN 202110816570 A CN202110816570 A CN 202110816570A CN 113667122 A CN113667122 A CN 113667122A
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- temperature
- polyarylene sulfide
- sulfide resin
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- sodium
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- 229920000412 polyarylene Polymers 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 239000011347 resin Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000009833 condensation Methods 0.000 title claims abstract description 17
- 230000005494 condensation Effects 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 230000014759 maintenance of location Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 13
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 12
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VSKSUBSGORDMQX-UHFFFAOYSA-N 1,2-dichloro-3-phenoxybenzene Chemical compound ClC1=CC=CC(OC=2C=CC=CC=2)=C1Cl VSKSUBSGORDMQX-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 claims description 2
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 claims description 2
- JTPZTKBRUCILQD-UHFFFAOYSA-N 1-methylimidazolidin-2-one Chemical compound CN1CCNC1=O JTPZTKBRUCILQD-UHFFFAOYSA-N 0.000 claims description 2
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 claims description 2
- YTBRNEUEFCNVHC-UHFFFAOYSA-N 4,4'-dichlorobiphenyl Chemical group C1=CC(Cl)=CC=C1C1=CC=C(Cl)C=C1 YTBRNEUEFCNVHC-UHFFFAOYSA-N 0.000 claims description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 2
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- CILZBARDXHWUSX-UHFFFAOYSA-M lithium;2-hydroxybutanoate Chemical compound [Li+].CCC(O)C([O-])=O CILZBARDXHWUSX-UHFFFAOYSA-M 0.000 claims description 2
- WIAVVDGWLCNNGT-UHFFFAOYSA-M lithium;butanoate Chemical compound [Li+].CCCC([O-])=O WIAVVDGWLCNNGT-UHFFFAOYSA-M 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- AXMOZGKEVIBBCF-UHFFFAOYSA-M lithium;propanoate Chemical compound [Li+].CCC([O-])=O AXMOZGKEVIBBCF-UHFFFAOYSA-M 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 claims description 2
- 239000004331 potassium propionate Substances 0.000 claims description 2
- 235000010332 potassium propionate Nutrition 0.000 claims description 2
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 claims description 2
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 claims description 2
- 239000004324 sodium propionate Substances 0.000 claims description 2
- 235000010334 sodium propionate Nutrition 0.000 claims description 2
- 229960003212 sodium propionate Drugs 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004671 saturated fatty acids Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- -1 sulfide sulfone Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 229940079101 sodium sulfide Drugs 0.000 description 4
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 125000005257 alkyl acyl group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000019086 sulfide ion homeostasis Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 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
- TWKKUWBBCHHMLT-UHFFFAOYSA-N disodium;sulfide;trihydrate Chemical compound O.O.O.[Na+].[Na+].[S-2] TWKKUWBBCHHMLT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/242—Tubular reactors in series
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
- C08G75/0218—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
- C08G75/0222—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur containing nitrogen
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides a gradient temperature-control continuous condensation method of polyarylene sulfide resin, which comprises the steps of mixing a sulfur-containing monomer, a chlorine-containing monomer, an aprotic polar solvent, a catalyst and an auxiliary agent in a certain proportion, and then continuously feeding the mixture into a kettle-type reactor or a tubular reactor which are connected in series by a metering pump for reaction, and ensuring the sufficient retention time of materials in different reactors; the temperature gradient control of the condensation reaction is realized by setting the temperature of each reactor to be constant at different temperatures or setting the temperature range of different tubular reactors. The invention adopts gradient temperature control to adapt to different schedules of polymerization reaction, and produces polyarylene sulfide resin with concentrated and stable molecular weight; meanwhile, the continuous production process of the multistage series kettle type reactor or the tubular reactor can effectively solve the problem of repeated temperature rise and temperature reduction of materials, reduce energy consumption, shorten production period and ensure safety, stability and reliability of the production process.
Description
Technical Field
The invention belongs to the field of synthesis of organic functional high molecular polymers, and relates to a gradient temperature control continuous condensation method of polyarylene sulfide resin.
Background
The polyarylene sulfide resin is a special high molecular polymer with a molecular main chain of sulfur and an aryl structure which are alternately connected. The polymer generally has the characteristics of excellent high temperature resistance, corrosion resistance and radiation resistance, excellent dimensional stability, excellent electrical insulation performance and the like, and is widely applied to the industrial fields of machining, electronics and electricity, light weight of automobiles, precision manufacturing, aerospace, 3D printing, ecological environmental protection, medicines, pesticides, new energy batteries, electronic information, intelligent communication and the like. The aryl group may be classified into polyarylene sulfide PAS, polyarylene sulfide sulfone (PASs), polyarylene sulfide ketone (PASK), polyarylene sulfide amide (PASA), and the like, according to the difference in the aryl structure, and the aromatic ring structure may further have other substituents such as alkyl group (e.g., methyl, ethyl, propyl, butyl, and the like), carboxyl group, amino group, hydroxyl group, aryl group, alkylacyl group, alkylacyloxy group, benzoyl group, benzoyloxy group, alkylamido group, alkylacyl group, and quaternary ammonium salt group, and the like, thereby imparting other functional effects such as antibacterial property, metal ion chelating property, antibacterial property, coloring property, antistatic property, electric conductivity, and the like to the polyarylene sulfide.
In a general polyarylene sulfide resin, polyphenylene sulfide (PPS), which has the simplest structure, has a main chain structure in which a sulfur atom and a benzene ring are alternately connected, and is a crystalline polymer resin. The high-performance flame-retardant plastic has excellent solvent resistance, corrosion resistance, flame retardance, insulativity and mechanical strength, and is one of special engineering plastics with the most industrial value and application prospect. Currently, para-dichlorobenzene (p-DCB) and sodium sulfide or sodium hydrosulfide are frequently used for pressure polymerization in NMP to generate polyphenylene sulfide resin industrially. The synthesis process is mostly intermittent operation, raw materials containing crystal water sodium sulfide or sodium hydrosulfide, sodium hydroxide solution and partial solvent are heated in a dehydration kettle for dehydration reaction, then the dehydrated materials are cooled and transferred into a high-pressure condensation reaction kettle, raw materials such as p-dichlorobenzene and catalyst are added, the reaction kettle is sealed, the temperature is raised, and the condensation reaction is carried out under the conditions of high temperature and high pressure to obtain the resin slurry. The intermittent condensation process needs repeated heating, cooling and material transfer, has long auxiliary time, thus causing the problems of long material retention time, solvent decomposition and the like, and consumes a large amount of manpower in intermittent production and consumes time in operations of loading, unloading and the like; the temperature rise and temperature drop courses of each batch are inconsistent, the process stability and reliability are poor, the product quality consistency cannot be ensured, and the subsequent purification and refining unit operation, processing application and the like of the resin are influenced; meanwhile, the thermal strain of the process equipment in the repeated heating and cooling processes is frequent, so that the equipment is easily damaged, and the safety of the production process is seriously influenced.
The foreign patent US4060520-A proposes a continuous polyarylene sulfide production process, in which the raw material is fed at 13.5-15.0 Kg/cm in the first reaction zone2Partially polymerizing under the pressure of (1), and then transporting the partially polymerized material to a second reaction area to make the partially polymerized material at 12.0-13.5 Kg/cm2Polymerization was complete under pressure, but the two reactions were kept at the same temperature. Domestic patent CN00116140.7 proposes a method for controlling the conditions of a synthetic process for polyphenylene sulfide production, in particular to continuously injecting a NMP solution containing p-DCB at a low temperature section of a polymerization reaction and simultaneously adjusting the injection rate according to the feedback of the reaction temperature. However, in the patent, other materials are fed intermittently, and the whole process is operated intermittently.
Disclosure of Invention
Aiming at the technical problem, the invention provides a method for continuously synthesizing polyarylene sulfide resin by gradient temperature control, which adopts gradient temperature control to adapt to different progress of polymerization reaction and produces polyarylene sulfide resin with concentrated and stable molecular weight; meanwhile, the continuous production process of the multistage series kettle type reactor or the tubular reactor can effectively solve the problem of repeated temperature rise and temperature reduction of materials, reduce energy consumption, shorten production period and ensure safety, stability and reliability of the production process.
The technical scheme adopted by the invention is as follows:
a process for continuously condensing the polyarylthioether resin by gradient temp control includes proportionally mixing the S-contained monomer, Cl-contained monomer, solvent for condensation reaction, catalyst and assistant, and continuously feeding them to n-stage serial reactor or tubular reactor by metering pump for reaction. The temperature range of the whole polymerization reaction is 150-300 ℃, the temperature of each serially connected kettle type reactor or tubular reactor is a low-temperature reaction zone and a high-temperature reaction zone along the material flowing direction, and the low-temperature section is beneficial to forming small molecules and oligomers; the high temperature section promotes the polymerization of small molecules and oligomers and increases molecular chains. The gradient temperature control of the polymerization reaction is realized by setting each reactor to be constant at different temperatures or setting each tubular reactor to be in different temperature intervals. And after the polymerization reaction is finished, continuously outputting the polyarylene sulfide resin slurry from the last-stage reaction kettle or the tubular reactor, and performing separation and purification procedures to obtain the polyarylene sulfide resin. The whole reaction process is carried out in a closed system, and inert gases such as nitrogen and the like are introduced to replace the air in the reactor before the reaction so as to prevent the solvent from oxidative denaturation.
In the raw material, the sulfur-containing monomer is one or more of anhydrous sodium sulfide, sodium sulfide containing crystal water, anhydrous sodium hydrosulfide, sodium hydrosulfide aqueous solution, crystal sodium hydrosulfide and the like; the chlorine-containing monomer is one or more of p-dichlorobenzene (p-DCB), p-chlorobenzoic acid, p-chloroaniline, dichlorobiphenyl, dichlorodiphenyl ether, dichlorobenzophenone, dichlorodiphenyl sulfone, dichloropyridine, dichlorodiphenyl ether and the like; the aprotic polar solvent is any one or more of N-methylpyrrolidone (NMP), hexamethylphosphoric triamide (HMPTA), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), sulfolane (CBS), N-methyl 2-imidazolidinone (NMI), and the like.
When the polymer is polyphenylene sulfide with the simplest structure, the sulfur-containing monomer is preferably anhydrous sodium sulfide, sodium sulfide with crystal water (sodium sulfide nonahydrate, sodium sulfide pentahydrate and sodium sulfide trihydrate), anhydrous sodium hydrosulfide and an aqueous solution of sodium hydrosulfide; the chlorine-containing monomer is preferably p-DCB; preferred aprotic polar solvents are NMP, HMPTA and CBS.
The catalyst is lithium chloride, lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium hydroxybutyrate, lithium salt of aromatic acid, and C10-C20, especially C12-C18 saturated fatty acid lithium salt.
The auxiliary agent is carboxylate of alkali metal, including sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium butyrate, potassium butyrate, and sodium salt or potassium salt of aromatic acid whose total carbon number in molecule is not more than 10, specially not more than 7.
The dosage of each material is based on a sulfur source compound, and the dosage of p-DCB is 1.0-1.5 times of the sulfur content (molar weight, the following is all the same); the total mass of NMP is 500-600 g NMP/1mol of sulfur source monomer; the total water content of the system is 1.0-4.5 times of the content of the sulfur source compound; the dosage of the catalyst is 0.5-1.0 time of that of the sulfur source compound; the dosage of the auxiliary agent is 0.1-0.5 time of the mole number of the sulfur-containing monomer.
The catalyst and the auxiliary agent can be added at one time, and can also be added in different stages of reaction kettles or tubular reactors in different times according to the requirements of the process.
Specifically, when a multistage series kettle type reactor is used for continuously carrying out polymerization reaction, the reaction temperature in each stage of reaction kettle connected in series is kept constant at different values to form a certain temperature gradient; liquid heating medium is introduced into each reaction kettle jacket from bottom to top or steam is introduced from top to bottom to adjust the temperature required by the materials in the reaction kettle, so as to realize the control of the temperature gradient. The complete uniform mixing of the slurry in the kettle type reactor is realized through the special stirring blade structure, the kettle accessories and the adjustable stirring strength of the kettle type reactors which are connected in series, thereby achieving the reaction effect similar to a full-mixing kettle.
The gas phases of all the kettle reactors can be communicated with each other, the gas phase washing and purifying process is unified, the operation pressure in all the reaction kettles is kept consistent, and the pressure of the polymerization reaction is controlled to be 0.1-3.0 MPa; or the gas phase of each reaction kettle is subjected to a washing and purifying process through different gas phase pipelines, the operation temperature and the operation pressure in each reaction kettle are different, and the pressure of the polymerization reaction is controlled to be 0.1-3.0 MPa. When the gas phases are mutually communicated and the operation pressure in the reaction kettle is kept consistent, the materials among the reaction kettles can be naturally overflowed and conveyed through the potential difference of the reaction kettles or conveyed through a high-temperature slurry pump; when the gas phase is respectively and independently led to the washing and purifying working procedure, the materials among the reaction kettles are transported by a pump. When the materials are conveyed by utilizing the reaction kettle potential difference natural overflow mode, the materials are directly conveyed to the bottom end in the kettle through a feed inlet guide pipe at the upper part of the reaction kettle, flow out from a discharge outlet at the upper end of the kettle body after certain retention time, and naturally overflow to a next-stage reaction kettle; when the high-temperature slurry pump is used for conveying materials, except the first-stage reaction kettle, the rest materials of each kettle are input into the reaction kettle from the bottom of the reaction kettle by the pump, and are output from the discharge port at the upper end after certain retention time, and the feed port of the first-stage reaction kettle is identical to that of the natural overflow reaction kettle.
When the polyarylene sulfide is continuously polymerized and produced by utilizing a multistage series tubular reactor, the temperature interval of different stages of tubular reactors is set to form the temperature gradient of polymerization reaction; the high-temperature heat conduction oil is reversely conveyed along the material flow direction to the outer jacket of the tubular reactor, the axial temperature of the oil is controlled to be constant in a certain range along the axial direction of the tubular reactor, and the gradient temperature control is realized. The tubular reactor is internally provided with a special flow guide structure and irregularly changed flow channels so as to realize the complex change of the material flow pattern and further realize the sufficient mixing and suspension of materials on different sections along the radial direction. Visual static mixers are arranged among the tubular reactor sections, and different additives can be supplemented through the mixers, so that the flexible production of polyarylene sulfides with different structures is realized; meanwhile, the reaction condition, the formation state of the polyarylene sulfide resin and the like can be observed, and the reaction condition can be adjusted in time. The materials in the tubular reactor are provided with conveying power by a high-temperature slurry pump.
The invention is characterized in that:
the condensation reaction temperature of each reaction kettle or each section of tubular reactor can be flexibly adjusted; secondly, the stirring strength of the kettle type reactors connected in series is controlled by designing stirring blades with special structures, so that the materials in the kettles are fully and uniformly mixed; the tubular reactor has a special flow guide structure, and realizes the complex change of material flow pattern, thereby realizing the full mixing and suspension of materials on different sections along the radial direction; thirdly, materials among all the kettle type reactors connected in series are naturally overflowed through potential difference or conveyed to slurry through a high-temperature slurry pump; conveying power is provided among all sections of tubular reactors through a high-temperature slurry pump; the process carries out the polymerization reaction at different temperatures of n sections (n is more than or equal to 2) by adjusting the temperature in all the serially connected fully mixed reaction kettles or tubular reactors, is favorable for realizing prepolymerization, condensation and final polymerization at different temperatures or temperature intervals, improves the conversion rate of monomers, and ensures that the molecular weight of the polymer is concentrated and stable. The polymer slurry obtained by the process can adopt the washing and purifying process technology commonly used in industry to separate the polyarylene sulfide resin and recover the solvent. Compared with the batch polymerization reaction technology generally adopted in the industry at present, the polyarylene sulfide gradient temperature control continuous condensation reaction process has higher production efficiency, more stable and controllable process, better resin quality and better economy.
The invention adopts gradient temperature control to adapt to different schedules of polymerization reaction, and produces polyarylene sulfide resin with concentrated and stable molecular weight; meanwhile, the continuous production process of the multistage series kettle type reactor or the tubular reactor can effectively solve the problem of repeated temperature rise and temperature reduction of materials, reduce energy consumption, shorten production period and ensure safety, stability and reliability of the production process.
Drawings
FIG. 1 is a schematic flow diagram of a production process of a gradient temperature-controlled multi-stage series tank reactor in which the material of example 1 flows to a next-stage reactor through natural overflow;
FIG. 2 is a schematic diagram of a production process of a gradient temperature-controlled multi-stage series tank reactor in which the material of example 1 is conveyed to a next-stage reactor by a high-temperature slurry pump;
FIG. 3 is a schematic diagram of the continuous polyarylene sulfide synthesis process using a gradient temperature-controlled multistage tubular reactor in example 2.
Detailed Description
The specific technical scheme of the invention is explained by combining the attached drawings.
Example 1
As shown in figure 1 or figure 2, polyphenylene sulfide resin is continuously synthesized through gradient temperature control of three-stage series kettle type reactors.
The flow rates of the materials are as follows: 56Kg/h of sulfur-containing monomer sodium hydrosulfide, 176.4Kg/h of chlorine-containing monomer p-dichlorobenzene, 550Kg/h of total weight of NMP, 29.7Kg/h of catalyst lithium chloride and 16.8Kg/h of auxiliary agent sodium acetate. The materials are input into a first reaction kettle according to the flow, the reaction temperature is controlled at 185 ℃, and the retention time is 90 minutes. The material overflows to the second reactor naturally through potential difference, the reaction temperature in the second reactor is controlled at 220 ℃, and the retention time is 150 minutes. And the resin slurry naturally overflows to a third reaction kettle through a potential difference, the reaction temperature is kept at 255 ℃, and the retention time is 190 minutes. The polyphenylene sulfide resin product can be obtained through subsequent solid-liquid separation, washing and purification, the yield can reach 91%, and the weight average molecular weight of the polyphenylene sulfide resin can reach 44251 g/mol.
Example 2
As shown in FIG. 3, the polyarylene sulfide resin is synthesized by gradient temperature control continuous synthesis of three-stage series tubular reactors. The material flow rates were the same as in example 1; the temperature interval of the first-stage tubular reactor is controlled to be 180-190 ℃, and the retention time is 50 minutes. And (3) inputting the mixed solution into a second-stage tubular reactor through a high-temperature slurry pump, wherein the temperature interval of the tubular reactor is controlled to be 215-225 ℃, and the retention time is 90 minutes. And (3) conveying the material to a third-stage tubular reactor through a pump, wherein the temperature interval of the tubular reactor is controlled to be 250-260 ℃, and the retention time is 120 minutes. The final resin yield can reach 95%, and the weight average molecular weight is 49280 g/mol. Compared with the tubular reactor in the example 1, the tubular reactor has no radial concentration gradient of materials and is more uniform in mixing, so that the reaction effect is better, and the required reaction residence time is shorter.
Claims (10)
1. The gradient temperature-control continuous condensation method of polyarylene sulfide resin is characterized in that a sulfur-containing monomer, a chlorine-containing monomer, an aprotic polar solvent, a catalyst and an auxiliary agent are continuously input into each stage of series-connected kettle-type reactor or tubular reactor for temperature-control condensation reaction by a metering pump according to a certain flow rate, and the temperature of the whole condensation reaction is controlled at 150-300 ℃; the polyarylene sulfide resin slurry thus produced is continuously subjected to the subsequent separation and purification steps to obtain a polyarylene sulfide resin.
2. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 1, wherein each of the tank reactors connected in series is kept at a different reaction temperature, the materials in each tank reactor are fully mixed and suspended by adjusting the stirring strength of the reaction tanks, and the materials in each reaction tank are conveyed by natural overflow or a pump; the retention time of the materials in each reaction kettle is set according to the requirements of different polyarylene sulfide resins; the gas phases of the kettle reactors connected in series are communicated with each other, and the gas phases are uniformly washed and purified or are independently washed and purified through different gas phase pipelines.
3. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 2, wherein when the gas phases of the tank reactors connected in series are connected, the pressure of the condensation reaction is controlled to be 0.1 to 3.0MPa at the same pressure at the operating pressure of each tank reactor.
4. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 2, wherein when the gas phase of each of the tank reactors connected in series is separately passed through a gas phase line to each of the independent gas phase washing purification processes, the operating pressure of each of the tank reactors is controlled within the range of 0.1MPa to 3.0 MPa.
5. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 1, wherein each of the tubular reactors connected in series is controlled to have a constant temperature in a certain range along the axial direction of the tubular reactor by an external heat exchanger, and has a stable temperature gradient; the material of each tubular reactor connected in series is provided with conveying power by a material conveying pump.
6. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin as claimed in claim 1, wherein different auxiliaries are added to different tank type condensation reactors or different tubular reactors according to the process requirements to adjust the molecular structure or molecular weight of polyarylene sulfide resin.
7. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 1, characterized in that:
the sulfur-containing monomer is any one or more of the following: anhydrous sodium sulfide, sodium sulfide containing crystal water, anhydrous sodium hydrosulfide, sodium hydrosulfide aqueous solution, and crystal sodium hydrosulfide;
the chlorine-containing monomer is any one or more of p-dichlorobenzene, p-chlorobenzoic acid, p-chloroaniline, dichlorobiphenyl, dichlorodiphenyl ether, dichlorobenzophenone, dichlorodiphenyl sulfone, dichloropyridine and dichlorodiphenyl ether;
the aprotic polar solvent is any one or more of: n-methylpyrrolidone NMP, hexamethylphosphoric triamide HMPTA and N, N-dimethylformamide DMF, N-dimethylacetamide DMAc, sulfolane CBS, N-methyl-2-imidazolidinone NMI.
8. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 1, wherein when the polymer is polyphenylene sulfide having the simplest structure, the sulfur-containing monomer is anhydrous sodium sulfide, sodium sulfide of crystal water, anhydrous sodium hydrosulfide, an aqueous solution of sodium hydrosulfide; the chlorine-containing monomer is p-DCB; the aprotic polar solvent is NMP, HMPTA and CBS;
according to the molar weight, the dosage of the p-DCB is 1.0-1.5 times of the sulfur content; the total mass of NMP is 500-600 g NMP/1mol of sulfur source monomer; the total water content of the system is 1.0-4.5 times of the content of the sulfur source compound.
9. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 1, wherein the catalyst is lithium chloride, lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium hydroxybutyrate, lithium salt of aromatic acid, lithium salt of saturated fatty acid of C10-C20; the dosage of the lithium salt serving as the catalyst is 0.5-1.0 time of the mole number of the sulfur-containing monomer.
10. The method for the gradient temperature-controlled continuous condensation of polyarylene sulfide resin according to claim 1, wherein the auxiliary agent is a carboxylate of an alkali metal, including sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium butyrate, potassium butyrate, and sodium salt or potassium salt of an aromatic acid having not more than 10 total carbons in the molecule; the dosage of the auxiliary agent is 0.1-0.5 time of the mole number of the sulfur-containing monomer.
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Application publication date: 20211119 |