CN104557855B - Dibenzothiophenes barium formate compound and preparation method thereof and anionic initiation system and the preparation method of conjugated diene polymer - Google Patents
Dibenzothiophenes barium formate compound and preparation method thereof and anionic initiation system and the preparation method of conjugated diene polymer Download PDFInfo
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- CN104557855B CN104557855B CN201310488258.6A CN201310488258A CN104557855B CN 104557855 B CN104557855 B CN 104557855B CN 201310488258 A CN201310488258 A CN 201310488258A CN 104557855 B CN104557855 B CN 104557855B
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- China
- Prior art keywords
- alkyl
- barium
- conjugated diene
- initiator
- dibenzothiophene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 92
- -1 Dibenzothiophenes barium formate compound Chemical class 0.000 title claims abstract description 86
- 150000001993 dienes Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 21
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003999 initiator Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 37
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 35
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 11
- DYSJMQABFPKAQM-UHFFFAOYSA-N 1-benzothiophene-2-carboxylic acid Chemical compound C1=CC=C2SC(C(=O)O)=CC2=C1 DYSJMQABFPKAQM-UHFFFAOYSA-N 0.000 claims description 10
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 10
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 125000001979 organolithium group Chemical group 0.000 claims description 7
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 6
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 3
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000009826 distribution Methods 0.000 description 18
- 238000004821 distillation Methods 0.000 description 17
- 239000007791 liquid phase Substances 0.000 description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 229940093476 ethylene glycol Drugs 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- VMGLLMDIYIPVHX-UHFFFAOYSA-N 1-benzothiophene-6-carboxylic acid Chemical compound OC(=O)C1=CC=C2C=CSC2=C1 VMGLLMDIYIPVHX-UHFFFAOYSA-N 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 159000000009 barium salts Chemical class 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- NUNQKTCKURIZQX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-2-methylpropane Chemical compound CCOCCOC(C)(C)C NUNQKTCKURIZQX-UHFFFAOYSA-N 0.000 description 1
- 0 C[U]C(C1=CC(*)C=C2SC=CC2=C1)=O Chemical compound C[U]C(C1=CC(*)C=C2SC=CC2=C1)=O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GRQJZSJOACLQOV-UHFFFAOYSA-N [Li].[N] Chemical compound [Li].[N] GRQJZSJOACLQOV-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BBCDCWSBHCIZJI-UHFFFAOYSA-L barium(2+);2-dodecylbenzenesulfonate Chemical compound [Ba+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O BBCDCWSBHCIZJI-UHFFFAOYSA-L 0.000 description 1
- HMOHOVASWYMMHA-UHFFFAOYSA-L barium(2+);diphenoxide Chemical compound [Ba+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 HMOHOVASWYMMHA-UHFFFAOYSA-L 0.000 description 1
- PJUABEIFHYROAC-UHFFFAOYSA-L barium(2+);naphthalene-1-sulfonate Chemical compound [Ba+2].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PJUABEIFHYROAC-UHFFFAOYSA-L 0.000 description 1
- VKZPHLURZLVMPJ-UHFFFAOYSA-N barium;ethyl hexanoate Chemical compound [Ba].CCCCCC(=O)OCC VKZPHLURZLVMPJ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a kind of dibenzothiophenes barium formate compound, the preparation method of a kind of dibenzothiophenes barium formate compound, a kind of anionic initiation system containing described dibenzothiophenes barium formate compound and the preparation method of a kind of conjugated diene polymer.Described dibenzothiophenes barium formate compound has structure shown in formula I, wherein, R1And R3Identical or different, and each stand alone as H, C1‑C16Alkyl or C1‑C16Alkoxyl；R2And R4Identical or different, and each stand alone as H, C1‑C6Alkyl, C1‑C6Alkoxyl or C3‑C6Ethylene glycol alkoxyl.The anionic initiation system using the present invention can not only obtain the polymer of high trans structural content, and solvent can also reclaim easily.
Description
Technical Field
The invention relates to a dibenzothiophene barium formate compound, a preparation method of the dibenzothiophene barium formate compound, an anion initiation system containing the dibenzothiophene barium formate compound and a preparation method of a conjugated diene polymer.
Background
High trans polymers refer to polymers having a molar content of trans structure of greater than 65%. The diene polymer with a high trans-structure has good dynamic properties, such as low rolling resistance and compression heat generation, excellent flexing resistance and the like, and is an ideal rubber compound for developing high-performance tires. However, trans-structured polymers such as trans-polyisoprene (TPI) and trans-polybutadiene (TPBD) are crystalline polymers and need to be prevented from crystallizing by vulcanization crosslinking or other methods before they can be used as rubbers. TPI gives elastomers at high sulphur levels, however, the use of sulphur affects certain properties of the polymer such as elongation and breaking strength. TPBD is difficult to prepare elastomers using conventional vulcanization processes due to high crystallinity and crystalline melting temperature. Copolymerization has also been found to be an effective means of preventing polymer crystallization.
Generally, coordination polymerization enables relatively high trans structures to be obtained, while anionic polymerization has somewhat poorer trans control capability. However, the anionic polymerization has a high activity and is easily controlled in relative molecular mass, Mooney viscosity and solution viscosity, and thus has a significant advantage in controlling the microstructure. Therefore, anionic polymerization is also currently used to obtain polymers of high trans structure.
The research on high trans-styrene-conjugated diene copolymers has been started in foreign countries as early as the end of the 20 th century in the 60's, mainly focusing on the former soviet union, the united states, japan and the like. It has been found that the high trans-form styrene-conjugated diene copolymer can be prepared mainly by using titanium-based, nickel-based, lanthanide-based, chromium-based, vanadium-based, alcohol (sodium) olefin catalysts and by using an anionic polymerization method. However, these methods have not been put into industrial production at a later time because they have different defects and are not suitable for practical production. With the increasing demand for energy saving of automobiles and high performance tires, further research on high trans butadiene-isoprene copolymers has been conducted.
US4020115 discloses the copolymerization of butadiene (Bd) and isoprene (Ip) using an organolithium/barium salt initiation system, wherein the barium salt has the structure shown in formula (1). Research shows that the melting point of the butadiene-isoprene copolymer is reduced along with the increase of the content of isoprene in the formulation ratio, and the copolymer can be stretched and crystallized, so that the green strength and the viscosity are increased, and the butadiene-isoprene copolymer is very suitable for being used as a tire tread rubber.
Wherein R is1Is methyl or cyclohexyl, and the molar ratio of a to b is 99.5:0.5 to 88: 12.
In the above-mentioned initiation system, organic barium salt is a key component for synthesizing high-trans conjugated diene. However, most of the organic barium salts used in the initiator at present are barium alkoxide and barium phenoxide, such as barium diethylene glycol ether salt, barium diethylene glycol ammonium salt, barium 2-ethyl hexanoate salt, and the like, and during the steam desorption process in the polymerization completion stage, such organic barium alkoxide can react with water to generate corresponding alcohol, and the alcohol and solvents such as cyclohexane and the like can form an azeotrope to affect the recycling of the solvents, which can cause serious industrial loss. In addition, the existing organic barium salts are generally difficult to synthesize, difficult to store and expensive.
In order to solve the above technical problems, CN102199232A discloses an initiation system of organic barium sulfonate/organic lithium/aluminum alkyl, wherein the structure of the organic barium sulfonate is:
R2-SO3-Ba-SO3-R2formula (2), or;
or;
wherein R is2Is C1-C26Alkyl of R3Is C1-C22Alkyl of R4Is C1-C5Alkyl of R5And R6Is C1-C10Alkyl group of (1). Research shows that the boiling point of benzenesulfonic acid generated after the organic barium sulfonate is hydrolyzed is high, and the benzenesulfonic acid cannot be azeotroped with a solvent or form a compound to pollute the solvent. However, the polybutadiene obtained by using the initiation system containing the organic barium sulfonate generally has a 1, 4-trans structure content of 40 to 60% by weight, and therefore, the requirement of a high trans structure is not met.
Disclosure of Invention
The invention aims to overcome the defects that a polymer with high trans-structure content cannot be obtained and solvent recovery is facilitated when the conventional anion initiation system containing organic barium salt is adopted, and provides a dibenzothiophene barium formate compound, a preparation method of the dibenzothiophene barium formate compound, an anion initiation system containing the dibenzothiophene barium formate compound and a preparation method of a conjugated diene polymer.
According to a first aspect of the present invention, there is provided a dibenzothiophene barium formate compound having the structure represented by formula (i):
wherein R is1And R3Identical or different and each independently H, C1-C16Alkyl or C1-C16Alkoxy group of (a); r2And R4Identical or different and each independently H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
According to a second aspect of the present invention, there is provided a process for producing a dibenzothiophene barium formate compound, the process comprising: reacting benzothiophenecarboxylic acid with a structure shown in a formula (II) with barium hydroxide under an esterification reaction condition;
wherein R is1Is H, C1-C16Alkyl or C1-C16Alkoxy of R2Is H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
According to a third aspect of the present invention, there is provided an anionic initiation system comprising a primary initiator and a co-initiator, wherein the primary initiator is a dibenzothiophene barium formate compound having a structure represented by formula (i):
wherein R is1And R3Identical or different and each independently H, C1-C16Alkyl or C1-C16Alkoxy group of (a); r2And R4Identical or different and each independently H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
According to a fourth aspect of the present invention, there is provided a process for producing a conjugated diene polymer, the process comprising: under the condition of anionic polymerization, polymerizing a conjugated diene-containing polymerized monomer and an anionic initiation system in a solvent, wherein the anionic initiation system is the anionic initiation system.
The anion initiation system of the invention can not only obtain polymers with high trans-structure content, but also ensure that organic acid generated after the dibenzothiophene barium formate compound with the structure shown in the formula (I) is hydrolyzed does not form azeotropy with a solvent or form a compound, and the solvent can be easily recycled. In addition, the dibenzothiophene barium formate compound with the structure shown in the formula (I) has simple preparation process and extremely wide industrial application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a dibenzothiophene barium formate compound having the structure represented by formula (i):
wherein R is1And R3Identical or different and each independently H, C1-C16Alkyl or C1-C16Alkoxy group of (a); r2And R4Identical or different and each independently H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
Particularly preferably, R1-R4Is H; or,
R1and R3Is H, R2And R4Are the same or different and are each independently C1-C5Alkyl groups of (a); or,
R1and R3Are the same or different and are each independently C10-C14Alkyl of R2And R4Are the same or different and are each independently C3-C6(ii) a glycol alkoxy group; or,
R1and R3Are the same or different and are each independently C1-C5Alkoxy of R2And R4Is H.
Wherein, the C1-C5Specific examples of the alkyl group of (a) may be, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl. Said C is10-C14Specific examples of the alkyl group of (a) may be, but are not limited to: decyl, n-undecyl, n-dodecyl, n-tridecyl and n-tetradecyl. Said C is3-C6The glycol alkoxy group is represented by the general formula-R' OCH2CH2A radical of OH, wherein R' is C1-C4An alkylene group of (a). Said C is3-C6Specific examples of the ethyleneglycol alkoxy group of (a) may be, but are not limited to: ethylene glycol methoxy, ethylene glycol ethoxy, ethylene glycol n-propoxy, ethylene glycol isopropoxy, ethylene glycol n-butoxy and ethylene glycol t-butoxy. Said C is1-C5Specific examples of the alkoxy group of (a) may be, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy and neopentoxy.
According to a second aspect of the present invention, a method for producing the dibenzothiophene barium formate compound comprises: reacting benzothiophenecarboxylic acid with a structure shown in a formula (II) with barium hydroxide under an esterification reaction condition;
wherein R is1Is H, C1-C16Alkyl or C1-C16Alkoxy of R2Is H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
Particularly preferably, R1And R2Is H; or,
R1is H, R2Is C1-C5Alkyl groups of (a); or,
R1is C10-C14Alkyl of R2Is C3-C6(ii) a glycol alkoxy group; or,
R1is C1-C5Alkoxy of R2Is H.
Wherein, the C1-C5Alkyl of (C)10-C14Alkyl of (C)3-C6Glycol alkoxy group and C1-C5The alkoxy group of (a) can be appropriately selected according to the above.
The esterification reaction conditions in the present invention are not particularly limited as long as the esterification reaction of benzothiophenecarboxylic acid having a structure represented by formula (II) with barium hydroxide to produce dibenzothiophenecarboxylic acid barium compound having a structure represented by formula (I) can be carried out, and for example, the esterification reaction conditions include a reaction temperature of 100-150 ℃, preferably 120-140 ℃. In addition, the time of the esterification reaction can be judged according to the amount of separated water in the reaction process, and the reaction end point is determined when no liquid is separated from the water separator basically.
According to the invention, the amount of barium hydroxide and benzothiophenecarboxylic acid having a structure represented by formula (II) can be selected as appropriate according to the actual situation, and for example, the molar ratio of barium hydroxide to benzothiophenecarboxylic acid having a structure represented by formula (II) can be 1:1-2, preferably 1: 1.2-1.8.
The benzothiophenecarboxylic acid having the structure represented by formula (ii) can be obtained commercially or prepared by a conventional method, and will not be described herein again.
According to a third aspect of the present invention, the anionic initiator system comprises a main initiator and a co-initiator, wherein the main initiator is a dibenzothiophene barium formate compound having a structure represented by formula (i):
wherein R is1And R3Identical or different and each independently H, C1-C16Alkyl or C1-C16Alkoxy group of (a); r2And R4Identical or different and each independently H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
Particularly preferably, R1-R4Is H; or,
R1and R3Is H, R2And R4Are the same or different and are each independently C1-C5Alkyl groups of (a); or,
R1and R3Are the same or different and are each independently C10-C14Alkyl of R2And R4Are the same or different and are each independently C3-C6(ii) a glycol alkoxy group; or,
R1and R3Are the same or different and are each independently C1-C5Alkoxy of R2And R4Is H.
The content of the main initiator and the co-initiator is not particularly limited in the present invention, and for example, the molar ratio of the main initiator to the co-initiator may be 0.03 to 1:1, preferably 0.1 to 0.8: 1.
According to the present invention, the kind of the co-initiator may be conventionally selected in the art, and for example, may be a co-initiator containing an aluminum alkyl and an organolithium. Wherein the aluminum alkyl is preferably of the general formula Al (R)7)3And/or AlH (R)8)2In which R is7And R8Each independently is C1-C6Alkyl group of (1). Specifically, examples of the aluminum alkyl include, but are not limited to: trimethylaluminum (TMA), Triethylaluminum (TEA), Tripropylaluminum (TPA), Triisopropylaluminum (TIPA), Triisobutylaluminum (TIBA), Tributylaluminum (TBA). The organolithium may be selected from one or more of alkyl lithium, alkoxy lithium and nitrogen lithium, with alkyl lithium being particularly preferred. Examples of such alkyl lithium include, but are not limited to: one or more of ethyllithium, propyllithium, isopropyllithium, n-butyllithium (n-BuLi), sec-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, phenyllithium, methylphenyllithium, and naphthyllithium.
The amount of the aluminum alkyl and the organolithium used in the present invention is not particularly limited, and for example, the molar ratio of the aluminum alkyl to the organolithium is, for example, 0.1 to 1.5:1, preferably 0.1 to 1:1.
According to a fourth aspect of the present invention, the process for producing a conjugated diene polymer comprises: under the condition of anionic polymerization reaction, the polymerized monomer containing conjugated diene and the above-mentioned anionic initiating system are undergone the process of anionic polymerization reaction in the solvent.
The amount of the anionic initiator system to be used according to the invention can be chosen appropriately according to the amount of the polymerized monomers, and can be, for example, from 0.02 to 0.65 part by weight, preferably from 0.05 to 0.5 part by weight, based on 100 parts by weight of the polymerized monomers.
The conditions for the anionic polymerization reaction in the present invention are not particularly limited, and for example, it is generally included that the polymerization temperature may be 50 to 120 ℃ and preferably 50 to 90 ℃; the polymerization time may be 0.5 to 4 hours, preferably 0.5 to 3 hours. In addition, in the polymerization process, the polymerization monomer and the solvent are generally uniformly mixed, the obtained mixture is preheated at 30-50 ℃ for 5-20 minutes, the main initiator and the auxiliary initiator are added in the preheating process, and then the temperature is raised to the polymerization temperature for reaction.
The polymerized monomer may be only a conjugated diene, or may contain a monovinylarene in addition to a conjugated diene. When the polymerized monomer contains both conjugated diene and monovinyl aromatic hydrocarbon, the monovinyl aromatic hydrocarbon may be used in an amount of 20 to 60 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of the conjugated diene.
According to the present invention, the conjugated diolefins refer to various unsaturated chain hydrocarbons having a conjugated double bond (i.e., -C = C-) in the molecular structure. Specifically, examples of the conjugated diene include, but are not limited to: butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, with butadiene and/or isoprene being particularly preferred.
According to the present invention, the monovinylarene may be any of the arene monomers commonly used in the art having a vinyl substituent on the aromatic ring, and in general, the monovinylarene may have a structure represented by formula (iii):
wherein R is5Can be C6-C20Is preferably phenyl and substituted or unsubstituted aryl, preferably by one or more C1-C5Alkyl-substituted phenyl of (a).
According to the invention, said C6-C20Examples of substituted or unsubstituted aryl groups of (a) may be, but are not limited to: phenyl, tolyl, ethylphenyl, tert-butylphenyl, dodecylphenylDi-n-butylphenyl (including o-di-n-butylphenyl, m-di-n-butylphenyl and p-di-n-butylphenyl), n-propylphenyl and diethylphenyl (including o-di-n-ethylphenyl, m-di-n-ethylphenyl and p-di-n-ethylphenyl).
According to the invention, the monovinyl aromatic hydrocarbon is particularly preferably one or more of styrene, vinyltoluene, alpha-methylstyrene, 4-tert-butylstyrene and 4-methylstyrene.
According to the present invention, the solvent may be any of various existing solvents capable of being used as a reaction medium in the preparation of the conjugated diene polymer, and for example, may be a hydrocarbon solvent and/or an ether solvent. The hydrocarbon solvent may be C5-C7And (3) one or more of cycloalkanes, aromatics and isoparaffins. Specific examples of the hydrocarbon solvent may include, but are not limited to: one or more of benzene, toluene, n-hexane, cyclohexane, pentane, and heptane. The ether solvent may be C4-C15Monoethers and/or polyethers. Specific examples of the ether solvent may include, but are not limited to: t-butoxyethoxyethane and/or tetrahydrofuran. These solvents may be used alone or in combination. Particularly preferably, the solvent is n-hexane and/or cyclohexane. The amount of the solvent to be used may be appropriately selected depending on the amount of the polymerizable monomer, and for example, the solvent may be used in such an amount that the total concentration of the polymerizable monomer is 5 to 20% by weight.
Generally, anionic polymerization systems do not have significant termination and transfer reactions, and the reactive sites remain when all of the monomer is consumed. Therefore, after the polymerization reaction is completed, the resultant product containing the conjugated diene polymer should be contacted with a terminator to inactivate the active center. The amount of the terminator to be used may be appropriately selected depending on the amount of the anionic initiator system used for preparing the conjugated diene polymer, and in general, the weight ratio of the terminator to the anionic initiator system used for preparing the conjugated diene polymer may be from 0.1 to 1:1. the terminator may be any of various agents capable of inactivating the anionic active sites, and may be, for example, one or more selected from the group consisting of water, methanol, ethanol and isopropanol, preferably isopropanol.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
cyclohexane: industrial grade, production in a brocade chemical plant. Soaking with 5A molecular sieve for two weeks before use, and deoxidizing with high purity nitrogen to make its water content and oxygen content less than 10 ppm.
Styrene: polymer grade, manufactured by synthetic rubber factories of Beijing Yanshan petrochemical division.
Butadiene: polymer grade, manufactured by synthetic rubber factories of Beijing Yanshan petrochemical division. Before use, butadiene in a storage tank is transferred into a small steel cylinder filled with KOH, the butadiene is soaked for 2 weeks to remove impurities such as polymerization inhibitor, moisture and the like, so that the water content is less than 20ppm, and the obtained clear liquid is added with n-butyl lithium and treated at 0 ℃ for half an hour. Wherein, the using amount of KOH is 5 weight parts and the using amount of n-butyl lithium is 0.002 weight part based on 100 weight parts of butadiene.
Isoprene: industrial grade, Puyang, a new yun chemical materials Co. Before use, isoprene is poured into a wide-mouth bottle filled with KOH, soaked for 2 weeks to remove polymerization inhibitor, and then soaked in refined N2Under protection with calcium hydride (CaH)2) Reflux treatment for 4 hours, distillation at atmospheric pressure and cutting of 34. + -. 1 ℃ fractions. Storing in a container filled with gamma-alumina at low temperature for later use. The water content of the isoprene is less than 10 ppm. Wherein, based on 100 weight parts of isoprene, the using amount of KOH is 5 weight parts, the using amount of calcium hydride is 3 weight parts, and the using amount of gamma-alumina is 5 weight parts.
1, 3-pentadiene: purchased from Puyang corporation, New Henan petrochemical company, Inc. Before use, the treatment was carried out in the same manner as for isoprene.
Ethylbenzene: analytically pure, Tianjin, Kemiou chemical reagent company, the rectification pretreatment is carried out before use according to the following method, 135-plus 137 ℃ fractions are cut and stored in a dryer in a sealing way. The water content is less than 10 ppm.
In the following preparation examples, the concentration of the dibenzothiophene barium formate compound was measured and calculated as follows: adding 2mL of a solution containing dibenzothiophene barium formate compound and 3 drops of phenolphthalein into a 100mL conical flask, shaking up, titrating to neutrality by using standard dilute hydrochloric acid, and recording the volume V of hydrochloric acid used for titrationHCl. The concentration of the dibenzothiophene barium formate compound is calculated according to the following formula:
VHCl: titrating the volume of the used hydrochloric acid, mL;
CHCl: titrating the concentration of hydrochloric acid used, mol/L;
v: volume of the solution containing dibenzothiophene barium formate compound, mL;
CBa: concentration of the solution containing dibenzothiophene barium formate compound, mol/L.
In the following examples and comparative examples:
the number average molecular weight and the molecular weight distribution coefficient of the polymer were measured by using a TDA302 Gel Permeation Chromatograph (GPC) of Viscotek corporation, USA, THF as a mobile phase, a flow rate of 1.0mL/min, a test sample concentration of 2-3mg/mL, narrow distribution polystyrene as a standard sample, and a test temperature of 25 ℃. The polymer microstructure was determined using a US Varian INOVA400NMR nuclear magnetic resonance spectrometer.
Preparation example 1
This preparation example is intended to illustrate the method for producing a dibenzothiophene barium formate compound provided by the present invention.
0.05mol of 1-benzothiophene-6-carboxylic acid (available from Li Yang Kai Xin chemical industry Co., Ltd., having a structure represented by the formula (II); R1And R2H, the same below), 0.03mol of barium hydroxide and 150mL of ethylbenzene were added to a 250mL two-necked flask equipped with a water separator, and the mixture was placed in an oil bath at 130 ℃ under the protection of high purity nitrogen to keep boiling reflux reaction until substantially no liquid was separated from the water separator, and the reaction was stopped to obtain a solution containing a dibenzothiophene barium formate compound (denoted as B1) at a concentration of 0.2 mol/L.
Preparation example 2
This preparation example is intended to illustrate the method for producing a dibenzothiophene barium formate compound provided by the present invention.
0.05mol of 1-benzothiophene-6-carboxylic acid, 0.05mol of barium hydroxide and 150mL of ethylbenzene were added to a 250mL two-neck flask, and the mixture was placed in an oil bath at 100 ℃ under the protection of high-purity nitrogen to keep boiling reflux reaction until substantially no liquid was separated from the water separator, and the reaction was stopped to obtain a solution containing a dibenzothiophene barium formate compound (denoted as B2) at a concentration of 0.2 mol/L.
Preparation example 3
This preparation example is intended to illustrate the method for producing a dibenzothiophene barium formate compound provided by the present invention.
0.05mol of 1-benzothiophene-6-carboxylic acid, 0.025mol of barium hydroxide and 150mL of ethylbenzene were added to a 250mL two-neck flask, and the mixture was placed in an oil bath at 150 ℃ under the protection of high-purity nitrogen to maintain boiling reflux reaction until substantially no liquid was separated from the water separator, and the reaction was stopped to obtain a solution containing a dibenzothiophene barium formate compound (denoted as B3) at a concentration of 0.18 mol/L.
Preparation example 4
This preparation example is intended to illustrate the method for producing a dibenzothiophene barium formate compound provided by the present invention.
A barium dibenzothiophene formate compound was prepared according to the procedure of preparation example 1, except that the 1-benzothiophene-6-carboxylic acid was used in the same molar amount of 1-benzohexylthiophene-6-carboxylic acid (available from Kjepellin Seiki chemical Co., Ltd., Shanghai) having a structure represented by formula (II), R1Is H, R2N-hexyl) to give a solution containing the barium dibenzothiophene carboxylate compound (denoted as B4) at a concentration of 0.2 mol/L.
Preparation example 5
This preparation example is intended to illustrate the method for producing a dibenzothiophene barium formate compound provided by the present invention.
A barium dibenzothiophene formate compound was prepared according to the procedure of preparation example 1, except that the 1-benzothiophene-6-carboxylic acid was prepared using the same number of moles of benzothiophenecarboxylic acid (available from Kjepellin Fine chemical Co., Ltd., Shanghai, having the structure of formula (II), R1Is n-dodecyl radical, R2Is ethylene glycol methoxy (namely-CH)2OCH2CH2OH)) was substituted, a solution containing the dibenzothiophene barium formate compound (denoted as B5) at a concentration of 0.2mol/L was obtained.
Preparation example 6
This preparation example is intended to illustrate the method for producing a dibenzothiophene barium formate compound provided by the present invention.
A barium dibenzothiophene formate compound was prepared according to the procedure of preparation example 1, except that the 1-benzothiophene-6-carboxylic acid was prepared using the same number of moles of benzothiophenecarboxylic acid (available from Kjepellin Fine chemical Co., Ltd., Shanghai, having the structure of formula (II), R1Is tert-butoxy, R2Is H), a solution containing 0.2mol/L dibenzothiophene barium formate compound (denoted as B6) is obtained.
Example 1
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
Under the condition of vacuumizing, a 500mL polymerization bottle for polymerization is firstly dehydrated by open fire, then is sequentially filled with high-purity nitrogen, is baked by flame and is vacuumized, and the steps are circulated for three times and are sealed and stored under the protection of the high-purity nitrogen. Adding a prepared cyclohexane solution of styrene, isoprene and butadiene (the mass percentage of the three monomers is 1:1.5:7.5, and the total concentration of the monomers is 20 wt%) into a polymerization bottle which is evacuated, baked and filled with nitrogen for three times, preheating for 10 minutes in a constant-temperature water bath at the temperature of 50 ℃, adding a main initiator and an auxiliary initiator (the molar ratio of a dibenzothiophene barium formate compound B1 and TIBA to n-BuLi is 1:4:3, and the total dosage of the main initiator and the auxiliary initiator is 0.36 wt% of the total dosage of the monomers) in the preheating process, then raising the temperature to 60 ℃ for polymerization for 2 hours, terminating the reaction by using distilled water after the polymerization reaction is finished, then settling by using absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven at the temperature of 40 ℃ until the mass is constant. The polymer was found to have a 1, 4-trans structure content of 92 wt%, a 1, 2-structure content of 2.2 wt%, a number average molecular weight Mn of 58840, and a molecular weight distribution coefficient MWD of 1.36. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 2
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
Under the condition of vacuumizing, a 500mL polymerization bottle for polymerization is firstly dehydrated by open fire, then is sequentially filled with high-purity nitrogen, is baked by flame and is vacuumized, and the steps are circulated for three times and are sealed and stored under the protection of the high-purity nitrogen. Adding a prepared cyclohexane solution of styrene, 1, 3-pentadiene and butadiene (the mass percentage of the three monomers is 1:1.5:7.5, and the total concentration of the monomers is 20 wt%) into a polymerization bottle which is evacuated, baked and filled with nitrogen for three times, preheating for 10 minutes in a constant-temperature water bath at the temperature of 40 ℃, adding a main initiator and an auxiliary initiator (the molar ratio of a dibenzothiophene barium formate compound B2 to TIBA to n-BuLi is 1:4:3, and the total dosage of the main initiator and the auxiliary initiator is 0.36 wt% of the total dosage of the monomers) in the preheating process, then heating to 50 ℃ for polymerization for 3 hours, terminating the reaction by deionized water after the polymerization reaction is finished, then settling by using absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven at the temperature of 40 ℃ until the mass is constant. The polymer was found to have a 1, 4-trans structure content of 87 wt%, a 1, 2-structure content of 3.2 wt%, a number average molecular weight Mn of 57340, and a molecular weight distribution coefficient MWD of 1.56. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 3
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
Under the condition of vacuumizing, a 500mL polymerization bottle for polymerization is firstly dehydrated by open fire, then is sequentially filled with high-purity nitrogen, is baked by flame and is vacuumized, and the steps are circulated for three times and are sealed and stored under the protection of the high-purity nitrogen. Adding a prepared cyclohexane solution of styrene, 1, 3-hexadiene and butadiene (the mass percentage of the three monomers is 1:1.5:7.5, and the total concentration of the monomers is 20 wt%) into a polymerization bottle which is evacuated, baked and filled with nitrogen for three times, preheating for 10 minutes in a constant-temperature water bath at the temperature of 50 ℃, adding a main initiator and an auxiliary initiator (the molar ratio of a dibenzothiophene barium formate compound B3 to TIBA to n-BuLi is 1:4:3, and the total dosage of the main initiator and the auxiliary initiator is 0.36 wt% of the total dosage of the monomers) in the preheating process, then heating to 90 ℃ for polymerization for 0.5 hour, terminating the reaction by using deionized water after the polymerization reaction is finished, then settling by using absolute ethyl alcohol, and baking the obtained polymer in a vacuum oven at the temperature of 40 ℃ until the mass is constant. The polymer was found to have a 1, 4-trans structure content of 88 wt%, a 1, 2-structure content of 2.9 wt%, a number average molecular weight Mn of 59400, and a molecular weight distribution coefficient MWD of 1.48. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 4
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
Under the condition of vacuumizing, a 500mL polymerization bottle for polymerization is firstly dehydrated by open fire, then is sequentially filled with high-purity nitrogen, is baked by flame and is vacuumized, and the steps are circulated for three times and are sealed and stored under the protection of the high-purity nitrogen. Adding a prepared cyclohexane solution of styrene, 2, 3-dimethylbutadiene and butadiene (the mass percentage of the three monomers is 1:1.5:7.5, and the total concentration of the monomers is 20 wt%) into a polymerization bottle which is evacuated, baked and filled with nitrogen for three times, preheating for 10 minutes in a constant-temperature water bath at the temperature of 50 ℃, adding a main initiator and an auxiliary initiator (the molar ratio of a dibenzothiophene barium formate compound B1 to TIBA to n-BuLi is 1:4:3, and the total dosage of the main initiator and the auxiliary initiator is 0.36 wt% of the total dosage of the monomers) in the preheating process, then heating to 60 ℃ for polymerization for 2 hours, terminating the reaction by deionized water after the polymerization reaction is finished, then settling by using absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven at the temperature of 40 ℃ until the quality is constant. Through detection, the content of the 1, 4-trans structure in the polymer is 90 weight percent, the content of the 1, 2-structure is 3.0 weight percent, the number average molecular weight Mn is 56840, and the molecular weight distribution coefficient MWD is 1.76. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 5
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared according to the procedure of example 1, except that the molar ratio of the dibenzothiophene barium formate compound B1, TIBA and n-BuLi was 1:4: 4. The polymer was found to have a 1, 4-trans structure content of 86 wt%, a 1, 2-structure content of 4.2 wt%, a number average molecular weight Mn of 58840, and a molecular weight distribution coefficient MWD of 1.88. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 6
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared according to the procedure of example 1, except that the molar ratio of the dibenzothiophene barium formate compound B1, TIBA to n-BuLi was 1:0.5: 2. It was found that the content of 1, 4-trans structure was 78% by weight, the content of 1, 2-structure was 6.4% by weight, the number average molecular weight Mn was 55800, and the molecular weight distribution coefficient MWD was 2.18. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 7
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
Under the condition of vacuumizing, a 500mL polymerization bottle for polymerization is firstly dehydrated by open fire, then is sequentially filled with high-purity nitrogen, is baked by flame and is vacuumized, and the steps are circulated for three times and are sealed and stored under the protection of the high-purity nitrogen. Adding a prepared cyclohexane solution of styrene, isoprene and butadiene (the mass percentage of the three monomers is 1:1.5:7.5, and the total concentration of the monomers is 20 wt%) into a polymerization bottle which is evacuated, baked and filled with nitrogen for three times, preheating for 10 minutes in a constant-temperature water bath at the temperature of 50 ℃, adding a main initiator and an auxiliary initiator in the preheating process to perform polymerization reaction (the molar ratio of a dibenzothiophene barium formate compound B2 to TBA to n-BuLi is 1:4:3, and the total dosage of the main initiator and the auxiliary initiator is 0.36 wt% of the total dosage of the monomers), then raising the temperature to 60 ℃ to perform polymerization for 2 hours, terminating the reaction by using deionized water after the polymerization reaction is finished, then settling by using absolute ethyl alcohol, and baking the obtained polymer in a vacuum oven at the temperature of 40 ℃ until the mass is constant. The polymer was found to have a 1, 4-trans structure content of 82 wt%, a 1, 2-structure content of 4.2 wt%, a number average molecular weight Mn of 58000 and a molecular weight distribution coefficient MWD of 1.78. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 8
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared according to the procedure of example 7, except that the molar ratio of the dibenzothiophene barium formate compound B2, TBA and n-BuLi was 1:4: 4. Through detection, the content of the 1, 4-trans structure in the polymer is 78 weight percent, the content of the 1, 2-structure in the polymer is 5.0 weight percent, the number average molecular weight Mn is 56500, and the molecular weight distribution coefficient MWD is 1.48. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 9
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared according to the procedure of example 7, except that the molar ratio of the dibenzothiophene barium formate compound B2, TBA and n-BuLi was 1:0.5: 2. The polymer was found to have a 1, 4-trans structure content of 68 wt%, a 1, 2-structure content of 8.0 wt%, a number average molecular weight Mn of 54500, and a molecular weight distribution coefficient MWD of 2.24. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 10
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared according to the procedure of example 7, except that the dibenzothiophene barium formate compound B2 was replaced with the same number of moles of the dibenzothiophene barium formate compound B4 obtained in preparation example 4. Through detection, the content of the 1, 4-trans structure in the polymer is 88 weight percent, the content of the 1, 2-structure is 2.6 weight percent, the number average molecular weight Mn is 59600, and the molecular weight distribution coefficient MWD is 1.63. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 11
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared according to the procedure of example 7, except that the dibenzothiophene barium formate compound B2 was replaced with the same number of moles of the dibenzothiophene barium formate compound B5 obtained in preparation example 5. The polymer was found to have a 1, 4-trans structure content of 95 wt%, a 1, 2-structure content of 1.6 wt%, a number average molecular weight Mn of 59200, and a molecular weight distribution coefficient MWD of 1.31. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 12
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared according to the procedure of example 7, except that the dibenzothiophene barium formate compound B2 was replaced with the same number of moles of the dibenzothiophene barium formate compound B6 obtained in preparation example 6. The polymer was found to have a 1, 4-trans structure content of 91 wt%, a 1, 2-structure content of 1.83 wt%, a number average molecular weight Mn of 59490, and a molecular weight distribution coefficient MWD of 1.73. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 13
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared by following the procedure of example 1 except that a cyclohexane solution of styrene, isoprene and butadiene (the mass percentages of the three monomers were 1:1.5:7.5, the total monomer concentration was 20% by weight) was replaced with a cyclohexane solution of isoprene and butadiene (the mass percentages of the two monomers were 2:8, the total monomer concentration was 20% by weight). The polymer was found to have a 1, 4-trans structure content of 94 wt%, a 1, 2-structure content of 2.1 wt%, a number average molecular weight Mn of 59220, and a molecular weight distribution coefficient MWD of 1.26. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Example 14
This example serves to illustrate the process for the preparation of conjugated diene polymers provided by the present invention.
A conjugated diene polymer was prepared by following the procedure of example 2 except that a cyclohexane solution of styrene, 1, 3-pentadiene and butadiene (the mass percentage of the three monomers was 1:1.5:7.5, the total concentration of the monomers was 20% by weight) was replaced with a cyclohexane solution of 1, 3-pentadiene and butadiene (the mass percentage of the two monomers was 2:8, the total concentration of the monomers was 20% by weight). The polymer was found to have a 1, 4-trans structure content of 89 wt%, a 1, 2-structure content of 2.5 wt%, a number average molecular weight Mn of 57060, and a molecular weight distribution coefficient MWD of 1.40. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Comparative example 1
This comparative example serves to illustrate a reference preparation of a conjugated diene polymer.
A conjugated diene polymer was prepared according to the procedure of example 9, except that the dibenzothiophene barium formate compound B2 was replaced with the same number of moles of barium dodecylbenzenesulfonate. The polymer was found to contain 49 wt% of 1, 4-trans structure, 15.6 wt% of 1, 2-structure, 53800 number average molecular weight Mn and 2.18 molecular weight distribution coefficient MWD. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
Comparative example 2
This comparative example serves to illustrate a reference preparation of a conjugated diene polymer.
A conjugated diene polymer was prepared according to the method of example 9, except that the dibenzothiophene barium formate compound B2 was prepared using the same number of moles of barium dinaphthalenesulfonate (available from Kjepellin Fine chemical Co., Ltd., Shanghai) having a structure represented by formula (4) wherein R is5And R6Methyl) is substituted. The polymer was found to have a 1, 4-trans structure content of 45 wt%, a 1, 2-structure content of 16.4 wt%, a number average molecular weight Mn of 567000, and a molecular weight distribution coefficient MWD of 2.24. The liquid phase product after settling to separate the polymer was recovered from the solvent by distillation.
From the above results, it can be seen that not only can polymers with high trans content (65-95%) be obtained with the anionic initiator system of the present invention, but also the solvent can be easily recycled. In addition, the dibenzo-barium-pyrrole-formate compound with the structure shown in the formula (I) has a simple preparation process and has great industrial application prospects.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A dibenzothiophene barium formate compound having the structure shown in formula (I):
wherein R is1And R3Identical or different and each independently H, C1-C16Alkyl or C1-C16Alkoxy group of (a); r2And R4Identical or different and each independently H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
2. The dibenzothiophene barium formate compound according to claim 1, wherein,
R1-R4is H; or,
R1and R3Is H, R2And R4Are the same or different and are each independently C1-C5Alkyl groups of (a); or,
R1and R3Are the same or different and are each independently C10-C14Alkyl of R2And R4Are the same or different and are each independently C3-C6(ii) a glycol alkoxy group; or,
R1and R3Are the same or different and are each independently C1-C5Alkoxy of R2And R4Is H.
3. A method for preparing a dibenzothiophene barium formate compound, which comprises the following steps: reacting benzothiophenecarboxylic acid with a structure shown in a formula (II) with barium hydroxide under an esterification reaction condition;
wherein R is1Is H, C1-C16Alkyl or C1-C16Alkoxy of R2Is H, C1-C6Alkyl of (C)1-C6Alkoxy or C3-C6The alkoxy group of ethylene glycol.
4. The production method according to claim 3, wherein,
R1and R2Is H; or,
R1is H, R2Is C1-C5Alkyl groups of (a); or,
R1is C10-C14Alkyl of R2Is C3-C6(ii) a glycol alkoxy group; or,
R1is C1-C5Alkoxy of R2Is H.
5. The production method according to claim 3 or 4, wherein the conditions of the esterification reaction include: the reaction temperature is 100-150 ℃, and the molar ratio of the barium hydroxide to the benzothiophenecarboxylic acid with the structure shown in the formula (II) is 1: 1-2.
6. An anionic initiator system comprising a main initiator and a co-initiator, wherein the main initiator is the barium dibenzothiophene carboxylate compound according to claim 1 or 2.
7. The anionic initiating system of claim 6, wherein the molar ratio of the primary initiator to the co-initiator is 0.03-1: 1.
8. The anionic initiating system of claim 6 or 7, wherein the co-initiator comprises an aluminum alkyl and an organolithium; preferably, the molar ratio of the aluminum alkyl to the organolithium is 0.1 to 1.5: 1.
9. A process for preparing a conjugated diene polymer, the process comprising: polymerizing a conjugated diene-containing monomer and an anionic initiator system in a solvent under anionic polymerization conditions, wherein the anionic initiator system is the anionic initiator system of any one of claims 6 to 8.
10. The method of claim 9, wherein the anionic initiator system is used in an amount of 0.02 to 0.65 parts by weight based on 100 parts by weight of the polymerized monomers.
11. The production method according to claim 9 or 10, wherein the anionic polymerization reaction conditions include: the polymerization temperature is 50-120 ℃, and the polymerization time is 0.5-4 hours.
12. The production method according to claim 9 or 10, wherein the polymerized monomer further contains a monovinylaromatic hydrocarbon; preferably, the monovinylarene is used in an amount of 20 to 60 parts by weight, based on 100 parts by weight of the conjugated diene.
13. The preparation method according to claim 12, wherein the conjugated diene is selected from one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene; the monovinyl aromatic hydrocarbon is selected from one or more of styrene, vinyl toluene, alpha-methyl styrene, 4-tert-butyl styrene and 4-methyl styrene.
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| US20020183469A1 (en) * | 1999-12-31 | 2002-12-05 | The Goodyear Tire & Rubber Company | Process for synthesizing trans polydiene rubber |
| CN102199232A (en) * | 2011-03-24 | 2011-09-28 | 北京化工大学 | Anion trigger system and polymerization method for synthesizing trans polybutadiene and copolymer thereof |
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| US20020183469A1 (en) * | 1999-12-31 | 2002-12-05 | The Goodyear Tire & Rubber Company | Process for synthesizing trans polydiene rubber |
| CN102199232A (en) * | 2011-03-24 | 2011-09-28 | 北京化工大学 | Anion trigger system and polymerization method for synthesizing trans polybutadiene and copolymer thereof |
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