CN114015047B - S-containing polymer and preparation method thereof - Google Patents
S-containing polymer and preparation method thereof Download PDFInfo
- Publication number
- CN114015047B CN114015047B CN202111432287.1A CN202111432287A CN114015047B CN 114015047 B CN114015047 B CN 114015047B CN 202111432287 A CN202111432287 A CN 202111432287A CN 114015047 B CN114015047 B CN 114015047B
- Authority
- CN
- China
- Prior art keywords
- containing polymer
- sodium
- solvent
- potassium
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000642 polymer Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 72
- 239000000243 solution Substances 0.000 claims abstract description 65
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011593 sulfur Substances 0.000 claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 64
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 114
- 238000002386 leaching Methods 0.000 claims description 93
- 239000003054 catalyst Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 33
- 238000011084 recovery Methods 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- -1 Succinic Acid Zinc lithium adipate Chemical compound 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 5
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 4
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910018503 SF6 Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229940072056 alginate Drugs 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019407 octafluorocyclobutane Nutrition 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- 229960003975 potassium Drugs 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- MCOGTQGPHPAUJN-UHFFFAOYSA-L zinc;2-hydroxyacetate Chemical compound [Zn+2].OCC([O-])=O.OCC([O-])=O MCOGTQGPHPAUJN-UHFFFAOYSA-L 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 3
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- FIJPWGLOBMXXSF-UHFFFAOYSA-M potassium;2-hydroxyacetate Chemical compound [K+].OCC([O-])=O FIJPWGLOBMXXSF-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229940023144 sodium glycolate Drugs 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 3
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 claims description 3
- ZAXDJTPYGXZIRG-JEDNCBNOSA-N (2s)-2,6-diaminohexanoic acid;lithium Chemical compound [Li].NCCCC[C@H](N)C(O)=O ZAXDJTPYGXZIRG-JEDNCBNOSA-N 0.000 claims description 2
- YFMKTVBRLDLWIQ-JEDNCBNOSA-N (2s)-2,6-diaminohexanoic acid;potassium Chemical compound [K].NCCCC[C@H](N)C(O)=O YFMKTVBRLDLWIQ-JEDNCBNOSA-N 0.000 claims description 2
- SCWWKKUJPHRBRV-JEDNCBNOSA-N (2s)-2,6-diaminohexanoic acid;sodium Chemical compound [Na].NCCCC[C@H](N)C(O)=O SCWWKKUJPHRBRV-JEDNCBNOSA-N 0.000 claims description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- IIGCYQPNZRSCLY-UHFFFAOYSA-N 1,1-dimethyl-3-prop-1-enylurea Chemical compound CC=CNC(=O)N(C)C IIGCYQPNZRSCLY-UHFFFAOYSA-N 0.000 claims description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- UGTQQVWBEBYHPZ-UHFFFAOYSA-N 1,3-dipropyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCN1C[NH+](CCC)C=C1 UGTQQVWBEBYHPZ-UHFFFAOYSA-N 0.000 claims description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- JRGGNXKNLBXHAK-UHFFFAOYSA-N 1-methyl-3-propan-2-yl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CC(C)N1C[NH+](C)C=C1 JRGGNXKNLBXHAK-UHFFFAOYSA-N 0.000 claims description 2
- AJRFBXAXVLBZMP-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;bromide Chemical compound [Br-].CCCN1C=C[N+](C)=C1 AJRFBXAXVLBZMP-UHFFFAOYSA-M 0.000 claims description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 2
- FHQRDEDZJIFJAL-UHFFFAOYSA-N 4-phenylmorpholine Chemical compound C1COCCN1C1=CC=CC=C1 FHQRDEDZJIFJAL-UHFFFAOYSA-N 0.000 claims description 2
- RCUPWYOHBHEVSG-UHFFFAOYSA-N C(CCCCCCC)OC(CCC(=O)OCCCCCCCC)=O.[Li] Chemical compound C(CCCCCCC)OC(CCC(=O)OCCCCCCCC)=O.[Li] RCUPWYOHBHEVSG-UHFFFAOYSA-N 0.000 claims description 2
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 claims description 2
- GLVGVODYDUXXQP-UHFFFAOYSA-L NCCCCCC(=O)[O-].[Zn+2].NCCCCCC(=O)[O-] Chemical compound NCCCCCC(=O)[O-].[Zn+2].NCCCCCC(=O)[O-] GLVGVODYDUXXQP-UHFFFAOYSA-L 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 239000004283 Sodium sorbate Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 2
- NZSIEUJMXKIAOM-UHFFFAOYSA-N [CH2]C[K] Chemical group [CH2]C[K] NZSIEUJMXKIAOM-UHFFFAOYSA-N 0.000 claims description 2
- FMQNKVGDYIXYDI-UHFFFAOYSA-N [Na].C=C.C=C Chemical group [Na].C=C.C=C FMQNKVGDYIXYDI-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- JCCYXJAEFHYHPP-OLXYHTOASA-L dilithium;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Li+].[Li+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O JCCYXJAEFHYHPP-OLXYHTOASA-L 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- QTTDHHKBHTUYCK-UHFFFAOYSA-L dilithium;propanedioate Chemical compound [Li+].[Li+].[O-]C(=O)CC([O-])=O QTTDHHKBHTUYCK-UHFFFAOYSA-L 0.000 claims description 2
- RCRBCNZJGBTYDI-UHFFFAOYSA-L dilithium;terephthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 RCRBCNZJGBTYDI-UHFFFAOYSA-L 0.000 claims description 2
- UQJNQOURCBKJJV-UHFFFAOYSA-N dioctyl butanedioate;potassium Chemical compound [K].CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC UQJNQOURCBKJJV-UHFFFAOYSA-N 0.000 claims description 2
- RZHBMYQXKIDANM-UHFFFAOYSA-N dioctyl butanedioate;sodium Chemical compound [Na].CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC RZHBMYQXKIDANM-UHFFFAOYSA-N 0.000 claims description 2
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- HCDITHVDEPPNIL-UHFFFAOYSA-L dipotassium;propanedioate Chemical compound [K+].[K+].[O-]C(=O)CC([O-])=O HCDITHVDEPPNIL-UHFFFAOYSA-L 0.000 claims description 2
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 claims description 2
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 claims description 2
- WHYUWYVXDNNLTR-UHFFFAOYSA-J dizinc;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Zn+2].[Zn+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O WHYUWYVXDNNLTR-UHFFFAOYSA-J 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 229940071260 lithium gluconate Drugs 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- WAHQBNXSPALNEA-UHFFFAOYSA-L lithium succinate Chemical compound [Li+].[Li+].[O-]C(=O)CCC([O-])=O WAHQBNXSPALNEA-UHFFFAOYSA-L 0.000 claims description 2
- 229960004254 lithium succinate Drugs 0.000 claims description 2
- MFOFTMYHLHUILU-STWYSWDKSA-M lithium;(2e,4e)-hexa-2,4-dienoate Chemical compound [Li+].C\C=C\C=C\C([O-])=O MFOFTMYHLHUILU-STWYSWDKSA-M 0.000 claims description 2
- ZOTSUVWAEYHZRI-JJKGCWMISA-M lithium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Li+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O ZOTSUVWAEYHZRI-JJKGCWMISA-M 0.000 claims description 2
- DSOSKIYNVXMGOA-UHFFFAOYSA-M lithium;2-hydroxyacetate Chemical compound [Li+].OCC([O-])=O DSOSKIYNVXMGOA-UHFFFAOYSA-M 0.000 claims description 2
- ZBAFARDUZOEUPJ-UHFFFAOYSA-M lithium;4-aminobenzenesulfonate Chemical compound [Li+].NC1=CC=C(S([O-])(=O)=O)C=C1 ZBAFARDUZOEUPJ-UHFFFAOYSA-M 0.000 claims description 2
- IOEDDFFKYCBADJ-UHFFFAOYSA-M lithium;4-methylbenzenesulfonate Chemical compound [Li+].CC1=CC=C(S([O-])(=O)=O)C=C1 IOEDDFFKYCBADJ-UHFFFAOYSA-M 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-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
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 2
- GCHCGDFZHOEXMP-UHFFFAOYSA-L potassium adipate Chemical compound [K+].[K+].[O-]C(=O)CCCCC([O-])=O GCHCGDFZHOEXMP-UHFFFAOYSA-L 0.000 claims description 2
- 239000001608 potassium adipate Substances 0.000 claims description 2
- 235000011051 potassium adipate 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
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000004302 potassium sorbate Substances 0.000 claims description 2
- 235000010241 potassium sorbate Nutrition 0.000 claims description 2
- 229940069338 potassium sorbate Drugs 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- 239000001472 potassium tartrate Substances 0.000 claims description 2
- 229940111695 potassium tartrate Drugs 0.000 claims description 2
- 235000011005 potassium tartrates Nutrition 0.000 claims description 2
- ORUCCVLWOQSRMC-UHFFFAOYSA-M potassium;2,3,4,5,6,7-hexahydroxyheptanoate Chemical compound [K+].OCC(O)C(O)C(O)C(O)C(O)C([O-])=O ORUCCVLWOQSRMC-UHFFFAOYSA-M 0.000 claims description 2
- GHKGUEZUGFJUEJ-UHFFFAOYSA-M potassium;4-methylbenzenesulfonate Chemical compound [K+].CC1=CC=C(S([O-])(=O)=O)C=C1 GHKGUEZUGFJUEJ-UHFFFAOYSA-M 0.000 claims description 2
- ANDAULZAMAPNOJ-UHFFFAOYSA-M potassium;6-aminohexanoate Chemical compound [K+].NCCCCCC([O-])=O ANDAULZAMAPNOJ-UHFFFAOYSA-M 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- TVOIPJPTFTYKQM-UHFFFAOYSA-N propanedioic acid;zinc Chemical compound [Zn].OC(=O)CC(O)=O TVOIPJPTFTYKQM-UHFFFAOYSA-N 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001601 sodium adipate Substances 0.000 claims description 2
- 235000011049 sodium adipate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 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
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 239000001540 sodium lactate Substances 0.000 claims description 2
- 235000011088 sodium lactate Nutrition 0.000 claims description 2
- 229940005581 sodium lactate Drugs 0.000 claims description 2
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 claims description 2
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 claims description 2
- 235000019250 sodium sorbate Nutrition 0.000 claims description 2
- 229940074404 sodium succinate Drugs 0.000 claims description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- FMYOMWCQJXWGEN-UHFFFAOYSA-M sodium;2,3,4,5,6,7-hexahydroxyheptanoate Chemical compound [Na+].OCC(O)C(O)C(O)C(O)C(O)C([O-])=O FMYOMWCQJXWGEN-UHFFFAOYSA-M 0.000 claims description 2
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 2
- CLUHWBURHNNGPK-UHFFFAOYSA-M sodium;6-aminohexanoate Chemical compound [Na+].NCCCCCC([O-])=O CLUHWBURHNNGPK-UHFFFAOYSA-M 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- UYISKGVFPMWFJV-UHFFFAOYSA-N terephthalic acid;zinc Chemical compound [Zn].OC(=O)C1=CC=C(C(O)=O)C=C1 UYISKGVFPMWFJV-UHFFFAOYSA-N 0.000 claims description 2
- MFXHJJWBUBCCSO-UHFFFAOYSA-K trilithium 2-[bis(carboxylatomethyl)amino]acetate Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O MFXHJJWBUBCCSO-UHFFFAOYSA-K 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- FYZXEMANQYHCFX-UHFFFAOYSA-K tripotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [K+].[K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O FYZXEMANQYHCFX-UHFFFAOYSA-K 0.000 claims description 2
- JEVFKQIDHQGBFB-UHFFFAOYSA-K tripotassium;2-[bis(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O JEVFKQIDHQGBFB-UHFFFAOYSA-K 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 2
- 239000011670 zinc gluconate Substances 0.000 claims description 2
- 235000011478 zinc gluconate Nutrition 0.000 claims description 2
- 229960000306 zinc gluconate Drugs 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- VRGNUPCISFMPEM-ZVGUSBNCSA-L zinc;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Zn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VRGNUPCISFMPEM-ZVGUSBNCSA-L 0.000 claims description 2
- OUZIZSDIHWTACR-UHFFFAOYSA-L zinc;2-[carboxylatomethyl(carboxymethyl)amino]acetate Chemical compound [Zn+2].OC(=O)CN(CC([O-])=O)CC([O-])=O OUZIZSDIHWTACR-UHFFFAOYSA-L 0.000 claims description 2
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 2
- YNKYXJFHDLXPTI-UHFFFAOYSA-L zinc;hexanedioate Chemical compound [Zn+2].[O-]C(=O)CCCCC([O-])=O YNKYXJFHDLXPTI-UHFFFAOYSA-L 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- UXYAJXBVMZFRMS-UHFFFAOYSA-N 2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound OP1(=O)OCCCCO1 UXYAJXBVMZFRMS-UHFFFAOYSA-N 0.000 claims 3
- CRQZBQZASKQJAN-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;potassium Chemical compound [K].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O CRQZBQZASKQJAN-BTVCFUMJSA-N 0.000 claims 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- MEAXKTSYYJWYMW-UHFFFAOYSA-N C=C.C=C.[Li] Chemical group C=C.C=C.[Li] MEAXKTSYYJWYMW-UHFFFAOYSA-N 0.000 claims 1
- WYLNFICFIJTWIH-UHFFFAOYSA-N C=C.[Li] Chemical group C=C.[Li] WYLNFICFIJTWIH-UHFFFAOYSA-N 0.000 claims 1
- NTZRDKVFLPLTPU-UHFFFAOYSA-N CC[Na] Chemical compound CC[Na] NTZRDKVFLPLTPU-UHFFFAOYSA-N 0.000 claims 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- UKQZSQATELWRIO-UHFFFAOYSA-N [K].C=C.C=C Chemical group [K].C=C.C=C UKQZSQATELWRIO-UHFFFAOYSA-N 0.000 claims 1
- WHWAHHKDNFPEQJ-UHFFFAOYSA-N [K].NC1=CC=CC=C1 Chemical compound [K].NC1=CC=CC=C1 WHWAHHKDNFPEQJ-UHFFFAOYSA-N 0.000 claims 1
- AAAZLFIIPWSVTD-UHFFFAOYSA-N [Li].OCC(O)CO Chemical compound [Li].OCC(O)CO AAAZLFIIPWSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229940099352 cholate Drugs 0.000 claims 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 claims 1
- 229960003067 cystine Drugs 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- FUSGWABNFVFNRV-UHFFFAOYSA-M lithium;6-aminohexanoate Chemical compound [Li+].NCCCCCC([O-])=O FUSGWABNFVFNRV-UHFFFAOYSA-M 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- GVVGQWPLZQAOSX-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;sodium Chemical compound [Na].NCCNCCN GVVGQWPLZQAOSX-UHFFFAOYSA-N 0.000 claims 1
- IPGOVDXOBDFUBM-UHFFFAOYSA-N oxalic acid;sodium Chemical compound [Na].OC(=O)C(O)=O IPGOVDXOBDFUBM-UHFFFAOYSA-N 0.000 claims 1
- 239000000737 potassium alginate Substances 0.000 claims 1
- 235000010408 potassium alginate Nutrition 0.000 claims 1
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims 1
- 239000004300 potassium benzoate Substances 0.000 claims 1
- 235000010235 potassium benzoate Nutrition 0.000 claims 1
- 229940103091 potassium benzoate Drugs 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 235000016804 zinc Nutrition 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 229920000412 polyarylene Polymers 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- WRWPPGUCZBJXKX-UHFFFAOYSA-N 1-fluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C=C1 WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- YYFGDUPKHLYWGL-UHFFFAOYSA-N CS(=O)(=O)C.C(=O)N Chemical compound CS(=O)(=O)C.C(=O)N YYFGDUPKHLYWGL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229960001078 lithium Drugs 0.000 description 1
- KEQHHFKPFQFWAJ-UHFFFAOYSA-M lithium;acetate;hydrate Chemical compound [Li+].O.CC([O-])=O KEQHHFKPFQFWAJ-UHFFFAOYSA-M 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- LDZHTQSBXDDUFB-UHFFFAOYSA-M potassium;4-aminobenzenesulfonate Chemical compound [K+].NC1=CC=C(S([O-])(=O)=O)C=C1 LDZHTQSBXDDUFB-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- RIUORJCWAHCMSA-UHFFFAOYSA-L zinc;4-aminobenzenesulfonate Chemical compound [Zn+2].NC1=CC=C(S([O-])(=O)=O)C=C1.NC1=CC=C(S([O-])(=O)=O)C=C1 RIUORJCWAHCMSA-UHFFFAOYSA-L 0.000 description 1
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- 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
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- 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
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种含硫聚合物的制备方法，属于高分子合成领域。The invention relates to a preparation method of a sulfur-containing polymer, and belongs to the field of polymer synthesis.
背景技术Background technique
含硫化合物聚芳硫醚如聚苯硫醚、聚苯硫醚酮、聚苯硫醚砜由于其耐高温、耐腐蚀、优良的电性能、机械性能和尺寸稳定性，而被广泛用于汽车、航天航空和电子技术方面。工业化生产中，目前聚芳硫醚生产的主要方法为：采用硫化钠与二卤代芳香化合物在高温高压下进行溶液缩聚，如Philips公司以硫化钠和对二氯苯在氮气中于极性溶剂NMP中加压反应制备(US 33544129)，这种方法能耗大，反应周期长；CN1793202A德阳科技股份有限公司以以硫化钠和对二氯苯为原料采用加压合成纤维级聚苯硫醚树脂，采用釜式反应器，效率一般，其溶剂、催化剂回收率低，且其产品没有进行后期封端处理，产品加工稳定性欠佳；中国专利CN1143652A报道在极性溶剂中以硫磺为原料加压合成韧性聚苯硫醚树脂，其反应过程中需要使用还原剂，工艺较为复杂，反应副产物较多，产品不易提纯，溶剂也都是采用脱水、再精馏的方式进行回收，能耗高，不经济。Sulfur-containing compounds polyarylene sulfides such as polyphenylene sulfide, polyphenylene sulfide ketone, polyphenylene sulfide sulfone are widely used in automobiles due to their high temperature resistance, corrosion resistance, excellent electrical properties, mechanical properties and dimensional stability , aerospace and electronic technology. In industrial production, the main method for the production of polyarylene sulfide at present is: using sodium sulfide and dihalogenated aromatic compounds to carry out solution polycondensation under high temperature and high pressure. For example, Philips company uses sodium sulfide and p-dichlorobenzene in a polar solvent in nitrogen. Prepared by pressurized reaction in NMP (US 33544129), this method has high energy consumption and long reaction period; CN1793202A Deyang Technology Co., Ltd. uses sodium sulfide and p-dichlorobenzene as raw materials and adopts pressurized synthetic fiber grade polyphenylene sulfide resin , using a kettle type reactor, the efficiency is average, the solvent and catalyst recovery rate is low, and the product is not subjected to post-capping treatment, and the product processing stability is not good; Chinese patent CN1143652A reported that the use of sulfur as a raw material to pressurize in a polar solvent Synthesis of tough polyphenylene sulfide resin requires the use of a reducing agent in the reaction process, the process is more complex, the reaction by-products are many, the product is not easy to purify, the solvent is also recovered by dehydration and re-rectification, and the energy consumption is high. Uneconomical.
发明内容SUMMARY OF THE INVENTION
本发明的目的是针对现有技术的不足而提供一种超高效低能耗含S聚合物的生产方法，其特点是采用含硫单体、二卤代单体、碱、端基控制剂、溶剂浸取剂、催化剂浸取剂等为原料，在催化剂作用下，通过微通道反应器进行溶液缩聚反应，进而制得高性能超高效低能耗含S聚合物。The object of the present invention is to provide a kind of production method of super-efficient and low-energy consumption S-containing polymer for the deficiencies in the prior art, which is characterized by adopting sulfur-containing monomer, dihalogenated monomer, alkali, end group control agent, solvent The leaching agent, catalyst leaching agent, etc. are used as raw materials, and under the action of the catalyst, the solution polycondensation reaction is carried out through the microchannel reactor, and then the S-containing polymer with high performance, ultra-high efficiency and low energy consumption is obtained.
本发明的技术方案：Technical scheme of the present invention:
本发明要解决的第一个技术问题是提供一种含S聚合物的制备方法，所述制备方法包括以下步骤：The first technical problem to be solved by the present invention is to provide a preparation method of S-containing polymer, and the preparation method comprises the following steps:
1)将含硫单体32～248份、催化剂0.5～50份、碱0.5～50份和溶剂100～400份于150～220℃脱水反应制得含硫反应溶液；将二卤代单体114～677份用溶剂100～200份溶解制得单体溶液；然后将含硫反应溶液和单体溶液于串联型微通道反应器(第一组)在165～260℃共混反应得含硫聚合物溶液；1) Dehydration reaction of 32-248 parts of sulfur-containing monomers, 0.5-50 parts of catalysts, 0.5-50 parts of alkalis and 100-400 parts of solvents at 150-220°C to obtain a sulfur-containing reaction solution; 114 parts of dihalogenated monomers ～677 parts are dissolved in 100～200 parts of solvent to obtain monomer solution; then sulfur-containing reaction solution and monomer solution are mixed and reacted in series-type microchannel reactor (first group) at 165～260 ℃ to obtain sulfur-containing polymerization substance solution;
2)将步骤1)所得含硫聚合物溶液送入另一组并联微通道反应器(第二组)中，与端基控制剂溶液于240～280℃反应制得含硫聚合物混合液；2) sending the sulfur-containing polymer solution obtained in step 1) into another group of parallel microchannel reactors (the second group), and reacting with the end-group control agent solution at 240-280° C. to obtain a sulfur-containing polymer mixed solution;
3)将步骤2)所得含硫聚合物混合液于100～210℃下通过高温过滤或密闭闪蒸，回收混合液中的部分溶剂，再分别加入溶剂浸取剂100～500份、催化剂浸取剂200～1000份进行剩余溶剂和催化剂的浸取；纯化处理后所得产品即为所述含S聚合物。3) The sulfur-containing polymer mixed solution obtained in step 2) is subjected to high-temperature filtration or closed flash evaporation at 100 to 210° C. to recover part of the solvent in the mixed solution, and then 100 to 500 parts of solvent leaching agent and catalyst leaching agent are added respectively. The remaining solvent and catalyst are leached with 200-1000 parts of the agent; the product obtained after purification treatment is the S-containing polymer.
进一步，步骤2)中，所述端基控制剂为：Further, in step 2), the end group control agent is:
进一步，步骤1)中，所述含硫单体选自：Further, in step 1), the sulfur-containing monomer is selected from:
中的任一种。any of the.
进一步，步骤1)中，所述二卤代芳香化合物的结构式为X-Ar-X，其中X＝F、Cl或Br，Further, in step 1), the structural formula of the dihalogenated aromatic compound is X-Ar-X, wherein X=F, Cl or Br,
进一步，步骤1)中，将含硫反应溶液和单体溶液于串联型微通道反应在165～260℃共混反应5～1800s得含硫聚合物溶液。Further, in step 1), the sulfur-containing reaction solution and the monomer solution are reacted in a series-type microchannel reaction at 165-260° C. for a blending reaction of 5-1800 s to obtain a sulfur-containing polymer solution.
进一步，步骤1)中，含硫反应溶液和单体溶液通过高压计量泵送入串联型微通道反应器，进料速度为15～1500g/min。Further, in step 1), the sulfur-containing reaction solution and the monomer solution are sent into the series-type microchannel reactor by a high-pressure metering pump, and the feeding rate is 15-1500 g/min.
进一步，步骤1)中，所述串联型微通道反应器的反应模块数为1～100组(优选为10～60组)，微通道直径为1～10000微米(优选为5～500微米)。Further, in step 1), the number of reaction modules in the series-type microchannel reactor is 1-100 groups (preferably 10-60 groups), and the diameter of the microchannel is 1-10000 microns (preferably 5-500 microns).
进一步，步骤1)中，含硫单体、催化剂、碱和溶剂惰性气体保护下于150～220℃脱水反应0.5～3h制得含硫反应溶液。Further, in step 1), a sulfur-containing reaction solution is prepared by dehydration reaction at 150-220° C. for 0.5-3 h under the protection of sulfur-containing monomer, catalyst, alkali and solvent inert gas.
进一步，步骤2)中，所述并联型微通道反应器的反应模块数为1～20组，微通道直径为1～20000微米(优选为100～600微米)。Further, in step 2), the number of reaction modules of the parallel microchannel reactor is 1-20 groups, and the diameter of the microchannel is 1-20000 microns (preferably 100-600 microns).
进一步，步骤2)中，所述端基控制剂溶液指端基控制剂0.01～10份和5～50ml溶剂制成的溶液。Further, in step 2), the end-group control agent solution refers to a solution prepared from 0.01-10 parts of end-group control agent and 5-50 ml of solvent.
进一步，步骤3)中，加入溶剂浸取剂进行剩余溶剂浸取的方法为：加入浸取剂，密闭条件下于温度10～150℃、压力0.5～40MPa下分2～5次浸取剩余溶剂；浸取后的混合气流体经过滤网送入气液分离器进行浸取剂和溶剂的分离。Further, in step 3), the method of adding a solvent leaching agent to carry out the remaining solvent leaching is as follows: adding a leaching agent, and leaching the remaining solvent in 2 to 5 times at a temperature of 10 to 150° C. and a pressure of 0.5 to 40 MPa under airtight conditions ; The mixed gas fluid after leaching is sent to the gas-liquid separator through the filter screen to separate the leaching agent and the solvent.
进一步，加入溶剂浸取剂进行剩余溶剂的浸取后的溶剂纯度≥97.5％，直接送入溶剂回收槽与高温过滤或密闭闪蒸回收的溶剂混用，无需再进行提纯或精制可直接应用于制备后续产品；所得浸取剂则进入闭路循环系统，经泵回收送至浸取剂回收储罐，循环使用。Further, the solvent purity after adding solvent leaching agent to carry out the leaching of the remaining solvent is ≥97.5%, which is directly sent to the solvent recovery tank to be mixed with the solvent recovered by high temperature filtration or closed flash evaporation, and can be directly applied to the preparation without further purification or refining Subsequent products; the obtained leaching agent enters the closed-circuit circulation system, and is recovered by the pump and sent to the leaching agent recovery storage tank for recycling.
进一步，步骤3)中，催化剂浸取的方法为：浸取剩余溶剂后得到的固体粗产品采用催化剂浸取剂进行催化剂的回收和分离；浸取完成后的液体进行多效蒸发，液体回收作为下一批催化剂浸取剂使用，固体则为回收的催化剂，无需后处理可直接使用。Further, in step 3), the method of catalyst leaching is as follows: the solid crude product obtained after leaching the remaining solvent adopts catalyst leaching agent to recover and separate the catalyst; The next batch of catalyst leaching agent is used, and the solid is the recovered catalyst, which can be used directly without post-treatment.
进一步，步骤1)～步骤3)中，所述溶剂选自：甲酰胺、乙酰胺、N,N,N’,N’-四甲基脲、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、异喹啉、N-苯基吗啉、环丁砜、2,4-二甲基环丁砜、1-甲基-3-丙基咪唑溴代盐、1-甲基-3-异丙基咪唑溴代盐、1，3-二丙基咪唑溴代盐、二甲基砜、2,4-二甲基环丁砜、二苯砜、六甲基磷酰三胺、二甲基甲酰胺、ε-己内酰胺、N-甲基己内酰胺、N,N-二甲基丙烯基脲、1,3-二甲基-2-咪唑啉酮、N-甲基吡咯烷酮、N-环己基吡咯烷酮或2-吡咯烷酮中的任一种。Further, in steps 1) to 3), the solvent is selected from: formamide, acetamide, N,N,N',N'-tetramethylurea, N,N-dimethylformamide, N,N, N-dimethylacetamide, isoquinoline, N-phenylmorpholine, sulfolane, 2,4-dimethylsulfolane, 1-methyl-3-propylimidazolium bromide, 1-methyl-3 -Isopropylimidazole bromide, 1,3-dipropylimidazole bromide, dimethyl sulfone, 2,4-dimethyl sulfolane, diphenyl sulfone, hexamethylphosphoric triamide, dimethyl sulfone Formamide, ε-caprolactam, N-methylcaprolactam, N,N-dimethylpropenylurea, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-cyclohexylpyrrolidone or Any of 2-pyrrolidone.
进一步，步骤1)中，所述催化剂为LiCl、CeCl2、乙二酸锂、乙二酸钠、乙二酸钾、乙二酸锌、丙二酸锂、丙二酸钠、丙二酸钾、丙二酸锌、丁二酸锂、丁二酸钠、丁二酸钾、丁二酸锌己二酸锂、己二酸钠、己二酸钾、己二酸锌、对苯二甲酸锂、对苯二甲酸钠、对苯二甲酸钾、对苯二甲酸锌、甲酸锂、甲酸钠、甲酸钾、甲酸锌、乙酸锂、乙酸钠、乙酸钾、乙酸锌、苯甲酸锂、苯甲酸钠、苯甲酸钾、苯甲酸锌、乙二胺四乙酸锂、乙二胺四乙酸钠、乙二胺四乙酸钾、乙二胺四乙酸锌、乙二胺四乙酸三锂、乙二胺四乙酸三钠、乙二胺四乙酸三钾、乙二胺四乙酸三锌、磷酸锂、磷酸钠、磷酸钾、酒石酸锂、酒石酸钠、酒石酸钾、酒石酸锌、乳酸钠、山梨酸锂、山梨酸钠、山梨酸钾、赖氨酸锂、赖氨酸钠、赖氨酸钾、胱氨酸锂、胱氨酸钠、胱氨酸钾、柠檬酸锂、柠檬酸钠、柠檬酸钾、柠檬酸锌、6-氨基己酸锂、6-氨基己酸钠、6-氨基己酸钾、6-氨基己酸锌、氮川三乙酸锂、氮川三乙酸钠、氮川三乙酸钾、氮川三乙酸锌、羟基乙酸锂、羟基乙酸钠、羟基乙酸钾、羟基乙酸锌、葡萄糖酸锂、葡萄糖酸钠、葡萄糖酸钾、葡萄糖酸锌、二乙烯三胺五羧酸锂、二乙烯三胺五羧酸钠、二乙烯三胺五羧酸钾、庚糖酸锂、庚糖酸钠、庚糖酸钾、甘胆酸锂、甘胆酸钠、甘胆酸钾、甘胆酸锌、二辛基琥珀酸锂、二辛基琥珀酸钠、二辛基琥珀酸钾、乙二胺四甲叉磷酸锂、乙二胺四甲叉磷酸钠、乙二胺四甲叉磷酸钾、海藻酸锂、海藻酸钠、海藻酸钾、海藻酸锌、对氨基苯磺酸锂、对氨基苯磺酸钠、对氨基苯磺酸钾、对氨基苯磺酸锌、对甲基苯磺酸锂、对甲基苯磺酸钠、对甲基苯磺酸钾、对甲基苯磺酸锌、15-冠-5、18-冠-6、硬脂酸钠、硬脂酸钾、硬脂酸锌、乙二胺四甲叉磷酸钠、二乙烯三胺五甲叉膦酸钠或胺三甲叉磷酸钠中的至少一种。Further, in step 1), the catalyst is LiCl, CeCl 2 , lithium oxalate, sodium oxalate, potassium oxalate, zinc oxalate, lithium malonate, sodium malonate, potassium malonate , Zinc malonate, lithium succinate, sodium succinate, potassium succinate, zinc succinate lithium adipate, sodium adipate, potassium adipate, zinc adipate, lithium terephthalate , sodium terephthalate, potassium terephthalate, zinc terephthalate, lithium formate, sodium formate, potassium formate, zinc formate, lithium acetate, sodium acetate, potassium acetate, zinc acetate, lithium benzoate, sodium benzoate, benzoic acid Potassium, Zinc Benzoate, Lithium EDTA, Sodium EDTA, Potassium EDTA, Zinc EDTA, Trilithium EDTA, Trisodium EDTA, Tripotassium EDTA, Trizinc EDTA, Lithium Phosphate, Sodium Phosphate, Potassium Phosphate, Lithium Tartrate, Sodium Tartrate, Potassium Tartrate, Zinc Tartrate, Sodium Lactate, Lithium Sorbate, Sodium Sorbate, Potassium Sorbate , lithium lysine, sodium lysine, potassium lysine, lithium cystinate, sodium cystinate, potassium cystinate, lithium citrate, sodium citrate, potassium citrate, zinc citrate, 6-amino Lithium hexanoate, sodium 6-aminocaproate, potassium 6-aminocaproate, zinc 6-aminocaproate, lithium nitrilotriacetate, sodium nitrilotriacetate, potassium nitrilotriacetate, zinc nitrilotriacetate, hydroxyl Lithium acetate, sodium glycolate, potassium glycolate, zinc glycolate, lithium gluconate, sodium gluconate, potassium gluconate, zinc gluconate, lithium diethylenetriaminepentacarboxylate, sodium diethylenetriaminepentacarboxylate, diethylenetriaminepentacarboxylate Potassium Ethylene Triamine Pentacarboxylate, Lithium Heptonate, Sodium Heptonate, Potassium Heptonate, Lithium Glycolate, Sodium Glycolate, Potassium Glycolate, Zinc Glycolate, Lithium Dioctyl Succinate, Sodium Dioctyl Succinate, Potassium Dioctyl Succinate, Lithium EDTA, Sodium EDTA, Potassium EDTA, Lithium Alginate, Sodium Alginate, Seaweed Potassium sulfonate, Zinc alginate, Lithium p-sulfanilate, Sodium p-sulfanilate, Potassium p-sulfanilate, Zinc p-sulfanilate, Lithium p-toluenesulfonate, Sodium p-toluenesulfonate , potassium p-toluenesulfonate, zinc p-toluenesulfonate, 15-crown-5, 18-crown-6, sodium stearate, potassium stearate, zinc stearate, ethylenediaminetetramethylene At least one of sodium phosphate, sodium diethylene triamine pentamethylidene phosphonate or sodium amine trimethylidene phosphate.
进一步，步骤1)中，所述碱为氢氧化锂、氢氧化钠、氢氧化钾、氢氧化镁、氢氧化钙、氢氧化钡、碳酸锂、碳酸钠、碳酸钾、乙酸钾、碳酸氢锂、碳酸氢钠或碳酸氢钾中的任一种。Further, in step 1), the alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, potassium acetate, lithium bicarbonate , any of sodium bicarbonate or potassium bicarbonate.
进一步，步骤3)中，所述溶剂浸取剂为二氯甲烷、氯仿、二氯乙烷、丙酮、丁酮、戊酮、环己酮、二氧六环、四氢呋喃、乙醚、二氧化碳、六氟化硫、二氟二氯甲烷、三氟甲烷、四氟甲烷、四氟二氯甲烷、六氟乙烷、四氟乙烷、六氟丙烷或全氟环丁烷中的任一种。Further, in step 3), the solvent leaching agent is dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, ether, carbon dioxide, hexafluoro Sulfur, difluorodichloromethane, trifluoromethane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
进一步，步骤3)中，所述催化剂浸取剂为甲醇、乙醇、丙醇、乙二醇、丙二醇、丙三醇、异丙醇、异丁醇、叔丁醇、正丁醇、正戊醇、异戊醇、正己醇、正庚醇、正辛醇或异辛醇中的任一种。Further, in step 3), the catalyst leaching agent is methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, tert-butanol, n-butanol, n-amyl alcohol , any of isoamyl alcohol, n-hexanol, n-heptanol, n-octanol or isooctanol.
本发明要解决的第二个技术问题是提供一种含硫聚合物，其采用上述方法制得。The second technical problem to be solved by the present invention is to provide a sulfur-containing polymer prepared by the above method.
进一步，所述含硫聚合物分子量分布窄，分子量分布为1.56～1.7。Further, the molecular weight distribution of the sulfur-containing polymer is narrow, and the molecular weight distribution is 1.56-1.7.
进一步，所述含硫聚合物的卤素含量≤250ppm。Further, the halogen content of the sulfur-containing polymer is less than or equal to 250 ppm.
本发明要解决的第三个技术问题是提供一种含硫聚合物的后处理方法，所述后处理方法包括下述步骤：The third technical problem to be solved by the present invention is to provide a post-processing method of a sulfur-containing polymer, and the post-processing method comprises the following steps:
(1)第一次回收溶剂：在采用现有技术公开的方法制备含S聚合物的过程中，将后处理前的含硫反应产物混合液240～1500份于150～210℃下通过高温过滤或密闭闪蒸，回收反应产物混合液中的部分溶剂，将回收的溶剂输送至溶剂回收槽；(1) Recovering the solvent for the first time: in the process of preparing the S-containing polymer by the method disclosed in the prior art, 240-1500 parts of the sulfur-containing reaction product mixture before the post-treatment is filtered at a high temperature at 150-210° C. Or airtight flash evaporation, recover part of the solvent in the reaction product mixture, and transport the recovered solvent to the solvent recovery tank;
(2)浸取法回收树脂中包裹的溶剂：将进行一次回收溶剂后的物料加入高压浸取釜中，加入浸取剂100～500份，密闭条件下于温度10～150℃、压力0.5～40MPa下分2～5次浸取剩余溶剂；浸取后的混合气流体经过滤网送入2级气液分离器进行浸取剂和溶剂的分离，溶剂经2级气液分离器后，自动液化得到纯度≥97.5％的高纯度溶剂，直接送入溶剂回收槽与步骤(1)的回收溶剂混用，无需再进行提纯或精制可直接应用于制备后续产品；浸取剂经2级气液分离器后进入闭路循环系统，经泵回收送至浸取剂回收储罐，循环使用；(2) Recover the solvent wrapped in the resin by leaching method: add the material after the first recovery of the solvent into the high-pressure leaching kettle, add 100-500 parts of leaching agent, and under airtight conditions at a temperature of 10-150 ° C and a pressure of 0.5-40 MPa The remaining solvent is leached in 2 to 5 times; the mixed gas fluid after leaching is sent to the 2-stage gas-liquid separator through the filter screen to separate the leaching agent and the solvent, and the solvent is automatically liquefied after passing through the 2-stage gas-liquid separator. The obtained high-purity solvent with a purity of ≥97.5% is directly sent to the solvent recovery tank to be mixed with the recovered solvent in step (1), and can be directly used in the preparation of subsequent products without further purification or refining; the leaching agent is passed through a 2-stage gas-liquid separator Then it enters the closed-circuit circulation system, and is recycled by the pump and sent to the leaching agent recovery storage tank for recycling;
(3)回收催化剂：经步骤(2)处理后得到的固体粗产品采用催化剂浸取剂200～1000份进行催化剂的回收和分离；浸取完成后的液体进行多效蒸发，液体回收作为下一批催化剂浸取剂使用，固体则为回收的催化剂，无需后处理可直接使用；浸取完成后的固体树脂粗产品采用脱盐水或上一批次产品的洗水进行3-6次逆流水洗和固液分离，分离后的含水含硫化合物通过干燥获得含硫聚合物(聚芳硫醚类物质)。(3) Recovering the catalyst: the solid crude product obtained after the treatment in step (2) adopts 200-1000 parts of catalyst leaching agent to recover and separate the catalyst; The batch of catalyst leaching agent is used, and the solid is the recovered catalyst, which can be used directly without post-treatment. The solid-liquid separation is performed, and the separated water-containing sulfur-containing compound is dried to obtain a sulfur-containing polymer (polyarylene sulfide).
进一步，所述溶剂浸取剂为二氯甲烷、氯仿、二氯乙烷、丙酮、丁酮、戊酮、环己酮、二氧六环、四氢呋喃、乙醚、二氧化碳、六氟化硫、二氟二氯甲烷、三氟甲烷、四氟甲烷、四氟二氯甲烷、六氟乙烷、四氟乙烷、六氟丙烷或全氟环丁烷中的任一种。Further, the solvent leaching agent is dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, ether, carbon dioxide, sulfur hexafluoride, difluoro Any of dichloromethane, trifluoromethane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
进一步，所述催化剂浸取剂为甲醇、乙醇、丙醇、乙二醇、丙二醇、丙三醇、异丙醇、异丁醇、叔丁醇、正丁醇、正戊醇、异戊醇、正己醇、正庚醇、正辛醇或异辛醇中的任一种。Further, the catalyst leaching agent is methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, tert-butanol, n-butanol, n-amyl alcohol, isoamyl alcohol, Any of n-hexanol, n-heptanol, n-octanol or isooctanol.
本发明中，所述原料份数除特殊说明外，均为重量份数。In the present invention, the raw material parts are all parts by weight unless otherwise specified.
本发明的有益效果：Beneficial effects of the present invention:
1、本发明首次将微通道反应器引入含S聚合物的制备过程，能够制得分子量分布窄(分子量分布为1.56～1.7)的聚合物；并且可通过控制含硫反应溶液和二卤代单体溶液的进料量、进料速度以及微通道反应器的反应模块数，实现控制反应的配比及含硫聚合物的分子量和分子量分布。1. The present invention introduces the microchannel reactor into the preparation process of the S-containing polymer for the first time, which can produce a polymer with a narrow molecular weight distribution (molecular weight distribution is 1.56-1.7); The feed amount, feed rate and the number of reaction modules of the microchannel reactor can control the proportion of the reaction and the molecular weight and molecular weight distribution of the sulfur-containing polymer.
2、由于采用了微通道反应器，反应效率更高，节省时间，且反应过程中的放热以及物料的传质可以得到更好的控制。2. Due to the use of a micro-channel reactor, the reaction efficiency is higher, time is saved, and the heat release during the reaction process and the mass transfer of materials can be better controlled.
3、反应分两段进行，相对于传统的技术方法，可以更有效地控制产品的端基，且用微通道反应器的方法使得其封端效率更高，产品的熔体加工稳定性更优异，同时有利于降低产品的卤素含量，制备超低卤素含量(所得产品卤素含量最低可达190ppm)高品质树脂品种，满足无卤或低卤要求。3. The reaction is carried out in two stages. Compared with the traditional technical method, the end group of the product can be controlled more effectively, and the end-capping efficiency of the micro-channel reactor method is higher, and the melt processing stability of the product is more excellent. At the same time, it is beneficial to reduce the halogen content of the product, and prepare high-quality resin varieties with ultra-low halogen content (the lowest halogen content of the obtained product can reach 190ppm), which meets the requirements of halogen-free or low-halogen.
4、溶剂回收过程中，采用闪蒸(或热过滤)和浸取的联用方式，使得其溶剂回收率得到大幅度提升，可达98～99％，且纯度≥97.5％，无需再进行精馏提纯，大幅度降低能耗，降低成本。4. In the process of solvent recovery, the combined method of flash evaporation (or hot filtration) and leaching is adopted, so that the solvent recovery rate is greatly improved, reaching 98-99%, and the purity is ≥97.5%, and no further refining is required. Distillation and purification can greatly reduce energy consumption and cost.
5、催化剂的回收采用逐级、分段的方式，且最后随催化剂浸取剂采用多效蒸发的方式进行回收、分离制得，能耗低，纯度高。5. The catalyst is recovered in a step-by-step and segmented manner, and finally recovered and separated with the catalyst leaching agent by a multi-effect evaporation method, with low energy consumption and high purity.
附图说明：Description of drawings:
图1为本发明实施例1所得含S聚合物的红外测试结果图。Fig. 1 is the infrared test result diagram of the S-containing polymer obtained in Example 1 of the present invention.
图2为本发明实施例1所得含S聚合物的DSC(差示扫描量热分析方法)结果图。2 is a graph showing the results of DSC (differential scanning calorimetry) of the S-containing polymer obtained in Example 1 of the present invention.
图3为本发明实施例2所得含S聚合物的红外表征结果。Fig. 3 is the infrared characterization result of the S-containing polymer obtained in Example 2 of the present invention.
图4为本发明实施例2所得含S聚合物的DSC结果。Figure 4 is the DSC result of the S-containing polymer obtained in Example 2 of the present invention.
图5为本发明实施例3所得含S聚合物的红外表征结果。FIG. 5 is the infrared characterization result of the S-containing polymer obtained in Example 3 of the present invention.
图6为本发明实施例3所得含S聚合物的DSC结果。FIG. 6 is the DSC result of the S-containing polymer obtained in Example 3 of the present invention.
具体实施方式Detailed ways
下面通过实施例对本发明进行具体的描述，有必要在此指出的是本实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。The present invention will be specifically described by the following examples. It is necessary to point out that this example is only used to further illustrate the present invention, and should not be construed as a limitation on the protection scope of the present invention. Those skilled in the art can Some non-essential improvements and adjustments are made to the content of the invention.
实施例1Example 1
(1)将50gCeCl2，50g碳酸钠，400g溶剂异喹啉和178g含水硫化钠加入预反应釜中，在氮气保护下，于温度220℃脱水反应0.5h，得到脱水后的预反应溶液，恒温；将147g对二氯苯和100g溶剂异喹啉加入到预混合器中，待二卤代单体溶解完后，分别采用高压计量泵将预反应溶液和预混合器中的单体溶液送入串联型微通道反应器中(模块数：50组)，控制预反应溶液和预混合器中的单体溶液的进料摩尔比为1:1.01(S单体：二卤代单体)、进料速度为40g/min，于温度260℃下聚合约1400s，得到一定分子量和分子量分布的含硫化合物溶液；(1) 50g CeCl 2 , 50g sodium carbonate, 400g solvent isoquinoline and 178g aqueous sodium sulfide were added to the pre-reaction kettle, and under nitrogen protection, the dehydration reaction was carried out at a temperature of 220°C for 0.5h to obtain a dehydrated pre-reaction solution, and the temperature was kept constant. ; 147g of p-dichlorobenzene and 100g of solvent isoquinoline are added to the premixer, and after the dihalogenated monomer is dissolved, the high-pressure metering pump is used to send the prereaction solution and the monomer solution in the premixer into the premixer. In the series-type microchannel reactor (number of modules: 50 groups), the feed molar ratio of the pre-reaction solution and the monomer solution in the pre-mixer was controlled to be 1:1.01 (S monomer: dihalogenated monomer), The feed rate is 40g/min, and the polymerization is carried out at a temperature of 260°C for about 1400s to obtain a sulfur-containing compound solution with a certain molecular weight and molecular weight distribution;
(2)再将得到的含硫化合物溶液送到另一组并联微通道反应器中(模块数：10组)，并通过高压计量泵将溶解在50ml溶剂异喹啉中的端基控制剂苯硫酚0.5g送入并联微通道反应器中与所得含硫化合物进行反应，反应温度为265℃，制得含S化合物混合液；(2) The obtained sulfur-containing compound solution is then sent to another group of parallel microchannel reactors (number of modules: 10 groups), and the end-group control agent benzene dissolved in 50ml of solvent isoquinoline is dissolved by a high-pressure metering pump. 0.5 g of thiophenol was sent into a parallel microchannel reactor to react with the obtained sulfur-containing compound, and the reaction temperature was 265° C. to obtain a mixed solution of S-containing compounds;
(3)将所得含S化合物混合液于150℃下通过高温过滤，回收混合液中的部分溶剂，再将所得固体物料加入高压浸取釜中，然后加入丙酮500g，密闭条件下于温度100℃、压力1MPa下分5次浸取剩余溶剂；浸取后的混合气流体经过滤网送入2级气液分离器进行浸取剂和溶剂的分离，溶剂经2级气液分离器后，自动液化得到纯度为98.2％的高纯度溶剂，直接送入溶剂回收槽与步骤(3)高温过滤后回收的溶剂混用，无需再进行提纯或精制可直接作为溶剂应用于制备后续产品；丙酮经2级气液分离器后进入闭路循环系统，经泵回收送至浸取剂回收储罐，循环使用；(3) at 150 ℃, the obtained mixed solution containing the S compound is filtered by high temperature, and part of the solvent in the mixed solution is recovered, then the gained solid material is added to the high-pressure leaching kettle, then 500 g of acetone is added, and the temperature is 100 ℃ under airtight conditions. , The remaining solvent is leached in 5 times under the pressure of 1MPa; the mixed gas fluid after leaching is sent to the 2-stage gas-liquid separator through the filter screen to separate the leaching agent and the solvent. After the solvent passes through the 2-stage gas-liquid separator, it is automatically Liquefaction obtains a high-purity solvent with a purity of 98.2%, which is directly sent to the solvent recovery tank to be mixed with the solvent recovered after high-temperature filtration in step (3), and can be directly used as a solvent to prepare subsequent products without further purification or refining; After the gas-liquid separator, it enters the closed-circuit circulation system, and is recovered by the pump and sent to the leaching agent recovery tank for recycling;
(4)经步骤(3)处理后得到的固体粗产品采用催化剂浸取剂乙醇1000g进行催化剂的回收和分离；浸取完成后的液体进行多效蒸发，液体回收作为下一批催化剂浸取剂使用，固体则为回收的催化剂，无需后处理可直接使用；浸取完成后的固体树脂粗产品采用脱盐水或上一批次产品的洗水进行3次逆流水洗和固液分离，分离后的含水含硫化合物通过干燥获得超高效低能耗含S聚合物；其产率为94％，特性粘数[η]＝0.36，重均分子量为61000，分子量分布为1.61(以DMF为溶剂，流动相也为DMF，配置树脂浓度为2mg/ml，进样速度0.200ml/min)，溶剂回收率为98.9％，催化剂回收率为97.3％，熔体指数为82g/10min，氯离子含量为210ppm。(4) The solid crude product obtained after the treatment in step (3) adopts 1000 g of catalyst leaching agent ethanol to recover and separate the catalyst; the liquid after the leaching is completed is subjected to multi-effect evaporation, and the liquid is recovered as the next batch of catalyst leaching agent Use, the solid is the recovered catalyst, which can be used directly without post-treatment; the crude solid resin product after leaching is subjected to three countercurrent washing and solid-liquid separation with desalinated water or the washing water of the previous batch of products. The water-containing sulfur-containing compound is dried to obtain an ultra-efficient and low-energy-consumption S-containing polymer; the yield is 94%, the intrinsic viscosity [η]=0.36, the weight average molecular weight is 61000, and the molecular weight distribution is 1.61 (with DMF as the solvent, the mobile phase It is also DMF, the resin concentration is 2mg/ml, the injection rate is 0.200ml/min), the solvent recovery rate is 98.9%, the catalyst recovery rate is 97.3%, the melt index is 82g/10min, and the chloride ion content is 210ppm.
本发明制备的超高效低能耗含S聚合物的结构经红外光谱测试得到了证实，如图1所示；采用差示扫描量热分析方法(DSC)测试含S聚合物的玻璃化温度及熔点，结果见图2所示：其熔点为292.1℃，证明本发明所得含S聚合物具有较好的热性能。The structure of the ultra-efficient and low-energy-consumption S-containing polymer prepared by the present invention has been confirmed by infrared spectroscopy, as shown in Figure 1; the glass transition temperature and melting point of the S-containing polymer are measured by differential scanning calorimetry (DSC). , the results are shown in Figure 2: its melting point is 292.1 °C, which proves that the S-containing polymer obtained by the present invention has good thermal properties.
实施例2Example 2
(1)将30g氯化锂，5g氢氧化钠，350g溶剂N-甲基吡咯烷酮和117g含水硫氢化钠加入预反应釜中，在氮气保护下，于温度200℃脱水反应1h，得到脱水后的预反应溶液，恒温；将287g4,4’-二氯二苯砜和100g溶剂N-甲基吡咯烷酮加入到预混合器中，待二卤代单体溶解完后，分别采用高压计量泵将预反应溶液和预混合器中的单体溶液送入串联型微通道反应器中(模块数：40组)，控制预反应溶液和预混合器中的单体溶液的进料摩尔比为1:1.02(S单体：二卤代单体)、进料速度为50g/min，聚合约1100s，温度为190℃，即得到一定分子量和分子量分布的含硫化合物溶液；(1) 30g lithium chloride, 5g sodium hydroxide, 350g solvent N-methylpyrrolidone and 117g water-containing sodium hydrosulfide were added to the pre-reactor, and under nitrogen protection, dehydration reaction was carried out at a temperature of 200 ° C for 1h to obtain dehydrated Pre-reaction solution, constant temperature; 287g of 4,4'-dichlorodiphenyl sulfone and 100g of solvent N-methylpyrrolidone were added to the pre-mixer. After the dihalogenated monomer was dissolved, the pre-reaction was carried out by a high-pressure metering pump respectively. The solution and the monomer solution in the premixer were sent into the series-type microchannel reactor (number of modules: 40 groups), and the feed molar ratio of the prereaction solution and the monomer solution in the premixer was controlled to be 1:1.02 ( S monomer: dihalogenated monomer), the feed rate is 50g/min, the polymerization is about 1100s, and the temperature is 190℃, that is, a sulfur-containing compound solution with a certain molecular weight and molecular weight distribution is obtained;
(2)再将得到的含硫化合物溶液送到另一组并联微通道反应器中(模块数：8组)，并通过高压计量泵将溶解在40g溶剂N-甲基吡咯烷酮中的端基控制剂苯酚1g与所得含硫化合物进行反应，温度为200℃，制得超高效低能耗含S化合物混合液；(2) The obtained sulfur-containing compound solution is then sent to another group of parallel microchannel reactors (number of modules: 8 groups), and the end groups dissolved in 40g of solvent N-methylpyrrolidone are controlled by a high-pressure metering pump 1 g of the agent phenol was reacted with the obtained sulfur-containing compound at a temperature of 200 °C to obtain an ultra-efficient and low-energy-consumption S-containing compound mixed solution;
(3)反应产物混合液于150℃下通过高温闪蒸，回收反应产物混合液中的部分溶剂，再将固体物料加入高压浸取釜中，加入二氧六环450g，密闭条件下于温度150℃、压力0.5MPa下分5次浸取剩余溶剂；浸取后的混合气流体经过滤网送入2级气液分离器进行浸取剂和溶剂的分离，溶剂经2级气液分离器后，自动液化得到纯度为97.8％的高纯度溶剂，直接送入溶剂回收槽与步骤(3)中高温闪蒸的回收溶剂混用，无需再进行提纯或精制可直接应用于制备后续产品；二氧六环经2级气液分离器后进入闭路循环系统，经泵回收送至浸取剂回收储罐，循环使用；(3) the reaction product mixed solution was flashed at a high temperature at 150 ° C, and a part of the solvent in the reaction product mixed solution was recovered, and then the solid material was added to the high-pressure leaching kettle, and 450 g of dioxane was added. The remaining solvent is leached in 5 times at ℃ and pressure of 0.5MPa; the mixed gas fluid after leaching is sent to the 2-stage gas-liquid separator through the filter screen to separate the leaching agent and the solvent, and the solvent is passed through the 2-stage gas-liquid separator. , automatic liquefaction to obtain a high-purity solvent with a purity of 97.8%, which is directly sent to the solvent recovery tank to be mixed with the recovered solvent of high-temperature flash evaporation in step (3), and can be directly used in the preparation of subsequent products without further purification or refining; After passing through the 2-stage gas-liquid separator, it enters the closed-circuit circulation system, and is recovered by the pump and sent to the leaching agent recovery storage tank for recycling;
(4)经前述步骤(3)处理后得到的固体粗产品采用催化剂浸取剂异丙醇900g进行催化剂的回收和分离；浸取完成后的液体进行多效蒸发，液体回收作为下一批催化剂浸取剂使用，固体则为回收的催化剂，无需后处理可直接使用；浸取完成后的固体树脂粗产品采用脱盐水或上一批次产品的洗水进行5次逆流水洗和固液分离，分离后的含水含硫化合物通过干燥获得超高效低能耗含S化合物聚芳硫醚砜；其产率为99％，特性粘数[η]＝0.62，重均分子量为76200，分子量分布为1.56，溶剂回收率为98.1％，催化剂回收率为97.9％，氯离子含量为190ppm；红外表征详见图3所示，DSC分析见图4所示：其玻璃化温度为223.2℃，具有较好的热性能。(4) The solid crude product obtained after the treatment in the aforementioned step (3) adopts the catalyst leaching agent isopropanol 900g to carry out the recovery and separation of the catalyst; the liquid after the leaching is completed is subjected to multi-effect evaporation, and the liquid is recovered as the next batch of catalysts The leaching agent is used, and the solid is the recovered catalyst, which can be used directly without post-treatment; the crude solid resin product after leaching is subjected to 5 countercurrent washing and solid-liquid separation with desalinated water or the washing water of the previous batch of products. The separated water-containing sulfur-containing compound is dried to obtain an ultra-efficient and low-energy-consumption S-containing compound polyarylene sulfide sulfone; the yield is 99%, the intrinsic viscosity [η]=0.62, the weight average molecular weight is 76200, and the molecular weight distribution is 1.56. The solvent recovery rate is 98.1%, the catalyst recovery rate is 97.9%, and the chloride ion content is 190 ppm; the infrared characterization is shown in Figure 3, and the DSC analysis is shown in Figure 4: its glass transition temperature is 223.2 ° C, with good thermal performance.
实施例3Example 3
(1)将50g乙酸钠，45g碳酸钾，350g溶剂N-甲基吡咯烷酮和117g含水硫氢化钠加入预反应釜中，在氮气保护下，于温度195℃脱水反应1h，得到脱水后的预反应溶液，恒温；将218g4,4’-二氟二苯甲酮和100g溶剂N-甲基吡咯烷酮加入到预混合器中，待二卤代单体溶解完后，分别采用高压计量泵将预反应溶液和预混合器中的单体溶液送入串联型微通道反应器中(模块数：80组)，控制预反应溶液和预混合器中的单体溶液的进料摩尔比为1:0.99(S单体：二卤代单体)、进料速度为350g/min，聚合约1800s，温度为240℃，即得到一定分子量和分子量分布的含硫化合物溶液；(1) 50g of sodium acetate, 45g of potassium carbonate, 350g of solvent N-methylpyrrolidone and 117g of water-containing sodium hydrosulfide were added to the pre-reaction kettle, and under nitrogen protection, dehydration reaction at a temperature of 195 ° C was performed for 1h to obtain the pre-reaction after dehydration solution, constant temperature; 218g 4,4'-difluorobenzophenone and 100g solvent N-methylpyrrolidone were added to the pre-mixer, after the dihalogenated monomer was dissolved, the pre-reaction solution was respectively mixed with a high-pressure metering pump The monomer solution in the premixer and the monomer solution in the premixer are sent into the series-type microchannel reactor (number of modules: 80 groups), and the feeding molar ratio of the prereaction solution and the monomer solution in the premixer is controlled to be 1:0.99 (S Monomer: dihalogenated monomer), the feed rate is 350g/min, the polymerization is about 1800s, and the temperature is 240℃, that is, a sulfur-containing compound solution with a certain molecular weight and molecular weight distribution is obtained;
(2)再将得到的含硫化合物溶液送到另一组并联微通道反应器中(模块数：10组)，并通过高压计量泵将溶解在40g溶剂N-甲基吡咯烷酮中的端基控制剂溴化苯1g与所得含硫化合物进行反应，温度为260℃，制得超高效低能耗含S化合物混合液；(2) The obtained sulfur-containing compound solution is then sent to another group of parallel microchannel reactors (number of modules: 10 groups), and the end groups dissolved in 40g of solvent N-methylpyrrolidone are controlled by a high-pressure metering pump 1 g of brominated benzene is reacted with the obtained sulfur-containing compound at a temperature of 260° C. to obtain an ultra-efficient and low-energy-consumption S-containing compound mixed solution;
(3)反应产物混合液于140℃下通过高温过滤，回收反应产物混合液中的部分溶剂，再将固体物料加入高压浸取釜中，加入六氟化硫450g，密闭条件下于温度50℃、压力35MPa下分4次浸取剩余溶剂；浸取后的混合气流体经过滤网送入2级气液分离器进行浸取剂和溶剂的分离，溶剂经2级气液分离器后，自动液化得到纯度为99.1％的高纯度溶剂，直接送入溶剂回收槽与步骤(3)高温过滤的回收溶剂混用，无需再进行提纯或精制可直接应用于制备后续产品；六氟化硫经2级气液分离器后进入闭路循环系统，经泵回收送至浸取剂回收储罐，循环使用；(3) The reaction product mixed solution is filtered at 140°C by high temperature, and part of the solvent in the reaction product mixed solution is recovered, and then the solid material is added to the high-pressure leaching kettle, and 450 g of sulfur hexafluoride is added. , The remaining solvent is leached in 4 times under the pressure of 35MPa; the mixed gas fluid after leaching is sent to the 2-stage gas-liquid separator through the filter screen to separate the leaching agent and the solvent. After the solvent passes through the 2-stage gas-liquid separator, it is automatically Liquefaction obtains a high-purity solvent with a purity of 99.1%, which is directly sent to the solvent recovery tank to be mixed with the recovered solvent of step (3) high-temperature filtration, and can be directly used in the preparation of subsequent products without further purification or refining; After the gas-liquid separator, it enters the closed-circuit circulation system, and is recovered by the pump and sent to the leaching agent recovery tank for recycling;
(4)经前述步骤(3)处理后得到的固体粗产品采用催化剂浸取剂乙二醇700g进行催化剂的回收和分离；浸取完成后的液体进行多效蒸发，液体回收作为下一批催化剂浸取剂使用，固体则为回收的催化剂，无需后处理可直接使用；浸取完成后的固体树脂粗产品采用脱盐水或上一批次产品的洗水进行5次逆流水洗和固液分离，分离后的含水含硫化合物通过干燥获得超高效低能耗含S化合物聚芳硫醚酮；其产率为96％，特性粘数[η]＝0.82，重均分子量为57000，分子量分布为1.65，溶剂回收率为99.0％，催化剂回收率为98.3％，卤素离子含量为250ppm；红外表征详见图5所示，DSC分析见图6所示：其熔点为346℃，具有较好的热性能。(4) The solid crude product obtained after the treatment in the aforementioned step (3) adopts the catalyst leaching agent ethylene glycol 700g to carry out the recovery and separation of the catalyst; the liquid after the leaching is completed is subjected to multi-effect evaporation, and the liquid is recovered as the next batch of catalyst The leaching agent is used, and the solid is the recovered catalyst, which can be used directly without post-treatment; the crude solid resin product after leaching is subjected to 5 countercurrent washing and solid-liquid separation with desalinated water or the washing water of the previous batch of products. The separated water-containing sulfur-containing compound is dried to obtain an ultra-efficient and low-energy-consumption S-containing compound polyarylene sulfide ketone; the yield is 96%, the intrinsic viscosity [η]=0.82, the weight average molecular weight is 57000, and the molecular weight distribution is 1.65, The solvent recovery rate is 99.0%, the catalyst recovery rate is 98.3%, and the halide ion content is 250 ppm; the infrared characterization is shown in Figure 5, and the DSC analysis is shown in Figure 6: its melting point is 346 ° C, and it has good thermal properties.
实施例4Example 4
(1)将20g乙酸钠和18g胺三甲叉磷酸钠，36g碳酸氢钾，400g溶剂N-环己基吡咯烷酮和142g对苯二硫酚加入预反应釜中，在氮气保护下，于温度215℃脱水反应1h，得到脱水后的预反应溶液，恒温；将218g4,4’-双(4-氟苯甲酰)间苯二胺和200g溶剂N-环己基吡咯烷酮加入到预混合器中，待二卤代单体溶解完后，分别采用高压计量泵将预反应溶液和预混合器中的单体溶液送入串联型微通道反应器中(模块数：60组)，控制预反应溶液和预混合器中的单体溶液的进料摩尔比为1:0.99(S单体：二卤代单体)、进料速度为80g/min，聚合约1800s，温度为230℃，即得到一定分子量和分子量分布的含硫化合物溶液；(1) 20g sodium acetate and 18g sodium amine trimethylidene phosphate, 36g potassium bicarbonate, 400g solvent N-cyclohexylpyrrolidone and 142g terephthalic acid are added in the pre-reaction kettle, under nitrogen protection, dehydration at temperature 215 ℃ The reaction was carried out for 1 h to obtain a pre-reaction solution after dehydration, and the temperature was kept constant; 218 g of 4,4'-bis(4-fluorobenzoyl) m-phenylenediamine and 200 g of solvent N-cyclohexylpyrrolidone were added to the premixer, and the dihalogen After the replacement monomer is dissolved, the pre-reaction solution and the monomer solution in the pre-mixer are respectively sent to the series-type micro-channel reactor (number of modules: 60 groups) by using a high-pressure metering pump, and the pre-reaction solution and the pre-mixer are controlled. The feed molar ratio of the monomer solution is 1:0.99 (S monomer: dihalogenated monomer), the feed rate is 80g/min, the polymerization is about 1800s, and the temperature is 230°C, that is, a certain molecular weight and molecular weight distribution are obtained. solution of sulfur-containing compounds;
(2)再将得到的含硫化合物溶液送到另一组并联微通道反应器中(模块数：6组)，并通过高压计量泵将溶解在50g溶剂N-环己基吡咯烷酮中的端基控制剂对氟甲苯2g与所得含硫化合物进行反应，温度为250℃，制得超高效低能耗含S化合物混合液；(2) The obtained sulfur-containing compound solution is then sent to another group of parallel microchannel reactors (number of modules: 6 groups), and the end group dissolved in 50g of solvent N-cyclohexylpyrrolidone is controlled by a high-pressure metering pump 2 g of p-fluorotoluene was reacted with the obtained sulfur-containing compound at a temperature of 250 °C to obtain an ultra-efficient and low-energy-consumption S-containing compound mixed solution;
(3)反应产物混合液于140℃下通过高温过滤，回收反应产物混合液中的部分溶剂，再将固体物料加入高压浸取釜中，加入四氢呋喃450g，密闭条件下于温度90℃、压力0.6MPa下分5次浸取剩余溶剂；浸取后的混合气流体经过滤网送入2级气液分离器进行浸取剂和溶剂的分离，溶剂经2级气液分离器后，自动液化得到纯度为99.2％的高纯度溶剂，直接送入溶剂回收槽与步骤(3)高温过滤的回收溶剂混用，无需再进行提纯或精制可直接应用于制备后续产品；四氢呋喃经2级气液分离器后进入闭路循环系统，经泵回收送至浸取剂回收储罐，循环使用；(3) the reaction product mixed solution was filtered through high temperature at 140 ℃, and the part of the solvent in the reaction product mixed solution was recovered, and then the solid material was added to the high-pressure leaching kettle, and 450 g of tetrahydrofuran was added. The remaining solvent is leached five times under MPa; the mixed gas fluid after leaching is sent to the 2-stage gas-liquid separator through the filter screen to separate the leaching agent and the solvent, and the solvent is automatically liquefied after passing through the 2-stage gas-liquid separator. The high-purity solvent with a purity of 99.2% is directly sent to the solvent recovery tank to be mixed with the recovered solvent of step (3) high-temperature filtration, and can be directly used in the preparation of subsequent products without further purification or refining; It enters the closed-circuit circulation system, and is recycled by the pump and sent to the leaching agent recovery storage tank for recycling;
(4)经前述步骤(3)处理后得到的固体粗产品采用催化剂浸取剂甲醇950g进行催化剂的回收和分离；浸取完成后的液体进行多效蒸发，液体回收作为下一批催化剂浸取剂使用，固体则为回收的催化剂，无需后处理可直接使用；浸取完成后的固体树脂粗产品采用脱盐水或上一批次产品的洗水进行6次逆流水洗和固液分离，分离后的含水含硫化合物通过干燥获得超高效低能耗含S化合物聚芳硫醚酰胺；其产率为96％，特性粘数[η]＝0.56，重均分子量为51400，分子量分布为1.70，溶剂回收率为98.6％，催化剂回收率为98.0％，氟离子含量为220ppm。(4) The solid crude product obtained after the treatment in the aforementioned step (3) adopts the catalyst leaching agent methanol 950g to recover and separate the catalyst; the liquid after the leaching is completed is subjected to multi-effect evaporation, and the liquid is recovered as the next batch of catalyst leaching. The solid resin is the recovered catalyst, which can be used directly without post-treatment; the crude solid resin product after leaching is subjected to 6 countercurrent washing and solid-liquid separation with desalinated water or the washing water of the previous batch of products. The water-containing sulfur-containing compound obtained was dried to obtain an ultra-efficient and low-energy-consumption S-containing compound polyarylene sulfide amide; the yield was 96%, the intrinsic viscosity [η] = 0.56, the weight average molecular weight was 51400, the molecular weight distribution was 1.70, and the solvent was recovered. The catalyst recovery rate was 98.6%, the catalyst recovery rate was 98.0%, and the fluoride ion content was 220 ppm.
对比例1Comparative Example 1
采用与实施例1相同的方法，区别仅在于：对比例1采用的物料为制备聚芳酯的各种原料，其它工艺参数均与实施例1类似，所得产品的重均分子量为35000～41000，分子量分布为8.9～11.6；而当采用传统的釜式反应器时，所得聚芳酯的产品的重均分子量为39000～51000，分子量分布为2～3.5；由此可见，并不是所有聚合物的制备过程中引入微通道反应器后，均能够实现制得分子量分布窄的材料的结果。The same method as in Example 1 is adopted, except that the materials used in Comparative Example 1 are various raw materials for preparing polyarylate, other process parameters are similar to those in Example 1, and the weight-average molecular weight of the obtained product is 35,000 to 41,000. The molecular weight distribution is 8.9-11.6; and when the traditional tank reactor is used, the weight-average molecular weight of the obtained polyarylate product is 39,000-51,000, and the molecular weight distribution is 2-3.5; it can be seen that not all polymers have the same molecular weight. After the microchannel reactor is introduced into the preparation process, the result of preparing the material with narrow molecular weight distribution can be achieved.
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