CN115894751A - 1-butene polymerization catalyst and preparation method and application thereof - Google Patents
1-butene polymerization catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN115894751A CN115894751A CN202310036623.3A CN202310036623A CN115894751A CN 115894751 A CN115894751 A CN 115894751A CN 202310036623 A CN202310036623 A CN 202310036623A CN 115894751 A CN115894751 A CN 115894751A
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- Prior art keywords
- compound
- butene
- electron donor
- polymerization catalyst
- titanium
- Prior art date
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Links
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- -1 magnesium halide Chemical class 0.000 claims abstract description 132
- 239000011777 magnesium Substances 0.000 claims abstract description 117
- 150000001875 compounds Chemical class 0.000 claims abstract description 108
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 239000012442 inert solvent Substances 0.000 claims abstract description 44
- 229920001748 polybutylene Polymers 0.000 claims abstract description 43
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 32
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000012265 solid product Substances 0.000 claims description 30
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 22
- 150000008282 halocarbons Chemical class 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 18
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 17
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 9
- 229920000193 polymethacrylate Polymers 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- FJZBADSJNSFVDO-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C(C)C)(C(C)C)COC FJZBADSJNSFVDO-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims description 6
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 4
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 4
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 4
- HBMODDNTUPGVFW-UHFFFAOYSA-N (1,3-dimethoxy-2-phenylpropan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(COC)(COC)C1=CC=CC=C1 HBMODDNTUPGVFW-UHFFFAOYSA-N 0.000 claims description 3
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 3
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 3
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 claims description 2
- ZALOHOLPKHYYAX-UHFFFAOYSA-L CO[Ti](Cl)(Cl)OC Chemical compound CO[Ti](Cl)(Cl)OC ZALOHOLPKHYYAX-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QSMLJCIHMPUAQG-UHFFFAOYSA-L [Cl-].[Cl-].CCCO[Ti+2]OCCC Chemical compound [Cl-].[Cl-].CCCO[Ti+2]OCCC QSMLJCIHMPUAQG-UHFFFAOYSA-L 0.000 claims description 2
- GKQZBJMXIUKBGB-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CCCO[Ti+3] Chemical compound [Cl-].[Cl-].[Cl-].CCCO[Ti+3] GKQZBJMXIUKBGB-UHFFFAOYSA-K 0.000 claims description 2
- GAHSOBODSWGWHR-UHFFFAOYSA-N bis(2,2-dimethylpropyl) benzene-1,2-dicarboxylate Chemical compound CC(C)(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)(C)C GAHSOBODSWGWHR-UHFFFAOYSA-N 0.000 claims description 2
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 claims description 2
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 claims description 2
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 claims description 2
- XUCKQPJKYWZURJ-UHFFFAOYSA-N cyclohexyl(dimethoxy)silane Chemical compound CO[SiH](OC)C1CCCCC1 XUCKQPJKYWZURJ-UHFFFAOYSA-N 0.000 claims description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 claims description 2
- MNLMLEWXCMFNFO-UHFFFAOYSA-K ethanol;trichlorotitanium Chemical compound CCO.Cl[Ti](Cl)Cl MNLMLEWXCMFNFO-UHFFFAOYSA-K 0.000 claims description 2
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 2
- QZCOACXZLDQHLQ-UHFFFAOYSA-M methanolate titanium(4+) chloride Chemical compound [Cl-].[Ti+4].[O-]C.[O-]C.[O-]C QZCOACXZLDQHLQ-UHFFFAOYSA-M 0.000 claims description 2
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 27
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 239000011949 solid catalyst Substances 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000005406 washing Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RGHIYOCUMCUWAQ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,5-dimethylhexane Chemical compound COCC(COC)(CC(C)C)C(C)C RGHIYOCUMCUWAQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JZBJIXRVUYHAQC-AOOOYVTPSA-N bis(2-methylpropyl) (2s,3r)-2,3-bis(sulfanyl)butanedioate Chemical compound CC(C)COC(=O)[C@@H](S)[C@@H](S)C(=O)OCC(C)C JZBJIXRVUYHAQC-AOOOYVTPSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 1
- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical compound C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 150000002148 esters Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical class C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a 1-butene polymerization catalyst and a preparation method and application thereof. The catalyst comprises: the titanium-halogen-free magnesium halide solid catalyst comprises a magnesium halide carrier, and a titanium compound and a compound internal electron donor compound which are loaded on the carrier and have a Ti-halogen bond, wherein the compound internal electron donor compound comprises a combination of a phthalate compound, a1,3-diether compound and a succinate compound. The preparation method of the catalyst comprises the following steps: the magnesium halide carrier, a titanium compound with a Ti-halogen bond, a non-ionic surfactant and a compound internal electron donor compound are subjected to contact reaction in an inert solvent to obtain the 1-butene polymerization catalyst. The invention also provides the application of the catalyst in the homopolymerization or copolymerization of 1-butene. The 1-butene polymerization catalyst can be used for preparing polybutene-1 resin with high isotacticity and adjustable molecular weight and molecular weight distribution.
Description
Technical Field
The invention relates to a 1-butene polymerization catalyst, a preparation method and application thereof, belonging to the technical field of polymerization catalysts.
Background
Polybutene-1 is prepared with butene-1 monomer as material and through bulk polymerization, solution polymerization or slurry polymerization in the presence of catalyst. It is a semi-crystalline polyolefin thermoplastic resin with good mechanical properties; outstanding environmental stress cracking resistance and heat resistance; excellent creep resistance, repeated winding and continuity, and good creep resistance even at elevated temperatures; good chemical resistance; and a wear resistance similar to that of ultra high molecular weight polyethylene; high filler filling property, etc. Therefore, the polybutene-1 may be used in producing pipe, film, plate, container, etc. and is especially suitable for use as ground heating pipe.
It is known that since the advent of Ziegler-Natta catalysts, the catalytic activity has been improved from the first few decades to the present tens of thousands, the isotacticity of the polymer product has been able to reach more than 98%, and the production process has been simplified. Wherein, mgCl 2 The carrier type Ziegler-Natta catalyst is an important catalyst for preparing polyolefin, wherein an electron donor plays a critical role, and the ideal electron donor compound is always searched forThe hot spot of research on reagent synthesis.
EP0201647A1 uses TiCl 4 /DNBP/Mg(C 2 H 5 O) 2 -AlEt 3 The polymerization activity of the catalyst system is 2667gPB/g Cat.3.8 h, namely 701gPB/g Cat.h, and the bulk density of the polybutene-1 is 0.30g/cm 3 . Although this production method gives granular polybutene-1, the polymerization activity is too low and a step of separating the catalyst residue is required in order not to deteriorate the physical properties of the obtained polymer. In US6306996B1 (CN 1256698A) TiCl is used 4 dNBP/magnesium chloride spheres (MgCl) 2 ·2.1C 2 H 5 OH)-AlEt 3 (or Al) i Bu 3 ) The catalyst system is diisopropyl Dimethoxysilane (DIPMS), and butene-1 is used as solvent and reaction monomer to prepare high stereoregular polybutene-1 with isotacticity higher than 95%, the ppm content of titanium in the polymer is lower than 50, the molecular weight distribution is not less than 6, and the catalytic activity is 3500g/g Cat.h. However, the catalytic activity of the preparation method is still far lower than those of the preparation methods of high-efficiency polyethylene and polypropylene polymers, so that the productivity of the method is low. US7345122bB2 (CN 1590417A) uses TiCl 4 1,3 diether/anhydrous magnesium chloride/isooctanol-AlEt containing silicon atom 3 (or Al) i Bu 3 ) The catalyst system of external silane electron donor (such as DPDMS, DIBDMS and the like) obtains polybutene-1 with isotacticity higher than 98%, polymerization activity of 9800-20000 gPB/g Cat.h, and polymer molecular weight distribution of 4-6. Although the preparation method has high catalytic activity and polymer isotacticity and can meet the requirement of large-batch commercial production, the polymer has narrow molecular weight distribution and is not beneficial to the development of more brands of products. CN1374327A adopts TiCl 4 2-isopropyl-2-isobutyl-1,3-dimethoxypropane (or diisobutylphthalate)/anhydrous magnesium chloride/isooctanol-AlEt 3 (or Al) i Bu 3 ) The polybutene-1 copolymer with isotacticity of 91-95% is obtained by a silane external electron donor (such as DPDMS, DIBDMS and the like) catalytic system, the polymerization activity is 4800g/g Cat.h, and the molecular weight of the polymer is distributed between 3.5 and 4.6. It can be seen that the activity of the catalystLower molecular weight and narrower molecular weight distribution of the polymer, which is not beneficial to improving the production efficiency and developing more brands of products.
CN101020728A reports a method for bulk precipitation synthesis of highly isotactic polybutene-1, using a catalyst comprising magnesium halide supported titanium compound and organoaluminum compound prepared by grinding method to initiate polymerization of 1-butene (e.g. TiCl 4 /9,9-bis (methoxymethyl) fluorene/MgCl 2 -AlEt 3 DDS catalytic system), the particle shape of the obtained polybutene-1 is irregular and easy to adhere, and the difficulties of mass transfer and heat transfer are caused. CN104193870A reports a catalyst for improving the isotacticity of polybutene-1 and accelerating the transformation of polybutene-1 crystal form and a preparation method thereof, the catalyst consists of a carrier-supported titanium compound-aluminum alkyl-external electron donor containing an internal electron donor, diisobutyl phthalate is used as the internal electron donor and methylcyclohexyl dimethoxysilane is used as the external electron donor, and the isotacticity of polybutene-1 is 95.8% at most. CN106554442A reports that organosilane is used as an external electron donor, N series, DQ series and TK-260 series Ziegler-Natta catalysts are used for synthesizing polybutene-1, and the strength of catalyst particles is improved through propylene prepolymerization so as to achieve the effect of reducing the content of low-molecular-weight products, but the isotacticity of the polybutene-1 is only 95.1%. CN103288993A discloses a catalyst of high isotactic polybutene-1, which is used for preparing polybutene with an isotacticity of more than 95% and a catalytic efficiency of not more than 440Kg polybutene-1/gTi. CN103304709B reports a solid catalyst for 1-butene polymerization, the main catalyst comprises magnesium halide, titanium halide and an internal electron donor, different substituted 5-norbornene compounds are used as the internal electron donor, when the catalyst is used for 1-butene polymerization, the catalyst activity is 27.0KgPB/gTi at most, the polymer isotacticity is 95.2 at most, and the molecular weight distribution is 11.4 at most. CN111269341A reports a catalyst for synthesizing high isotactic polybutene-1 and a preparation method thereof, wherein spherical magnesium chloride is adopted to load titanium tetrachloride/electron donor, the electron donor is esters or diethers, when the catalyst is used for 1-butene polymerization, the catalytic efficiency reaches 1200Kg polymer/g titanium, the isotacticity of polybutene-1 is more than 98%, and polymer particles areThe particle morphology was good.
As can be seen from the above prior art, the electron donor used in the Ziegler-Natta catalyst is one or two of ethyl benzoate monoester, phthalic acid ester such as diisobutyl phthalate, etc., or 1,3 diether such as 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, etc. Although the activity of the diester electron donor is not as good as that of the diether, the molecular weight distribution of the prepared polymer is wider, and the improvement of the processability of the product is facilitated; although the diether electron donor has high activity and strong orientation capability, the molecular weight distribution of the polymer prepared by the diether electron donor is narrow, which is not beneficial to the processing of products and the development of more product brands.
Therefore, the development of a novel 1-butene polymerization catalyst and a preparation method thereof remain one of the problems to be solved in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a 1-butene polymerization catalyst and a preparation method and application thereof. The 1-butene polymerization catalyst provided by the invention has the advantages of good sphericity, high catalytic activity and the like. The 1-butene polymerization catalyst can be used for preparing polybutene-1 resin with high isotacticity and adjustable molecular weight and molecular weight distribution.
In order to achieve the above object, a first aspect of the present invention provides a 1-butene polymerization catalyst comprising: the electron donor compound comprises a magnesium halide carrier, and a titanium compound and a compound internal electron donor compound which are loaded on the carrier and have a Ti-halogen bond, wherein the compound internal electron donor compound comprises a combination of a phthalate compound, a1,3-diether compound and a succinate compound; wherein, the total weight of the 1-butene polymerization catalyst is 100 percent, the weight percentage of Ti is 1.8-7.0 percent, the weight percentage of the compound internal electron donor compound is 1.0-12.0 percent, and the balance is the magnesium halide carrier.
In the above-mentioned 1-butene polymerization catalyst, preferably, the molar ratio of the phthalate compound, the 1,3-diether compound and the succinate compound is 1: (0.1-0.5): (0.2-0.8).
In the above-mentioned 1-butene polymerization catalyst, preferably, the phthalate compound includes one or a combination of several of dibutyl phthalate (DNBP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), diisooctyl phthalate (DIOP), and dipentanyl phthalate (DPP).
In the above-mentioned 1-butene polymerization catalyst, preferably, the 1,3-diether compound includes one or more of 2,2-diisopropyl-1,3-dimethoxypropane (DIPDOP), 2,2-diisobutyl-1,3-dimethoxypropane (DIBDMOP), 2,2-diphenyl-1,3-dimethoxypropane (DPDPDPDMP) and the like.
In the above-mentioned 1-butene polymerization catalyst, preferably, the succinate compound comprises one or a combination of 2,3-diethyl diisopropylsuccinate (DIPSDE), 2,3-diethyl diisobutylsuccinate (DIBSDE), 2,3-dimethyl diisopropylsuccinate (DIPSDM), 2,3-dimethyl diisobutylsuccinate (DIBSDM), and the like.
In the above-mentioned catalyst for polymerization of 1-butene, the titanium compound having a Ti-halogen bond preferably includes one or a combination of several of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, trichloroethoxytitanium, methoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, dichlorodiethoxytitanium, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n-butoxytitanium chloride, and the like. More preferably, the titanium compound is titanium tetrachloride.
In the above-mentioned 1-butene polymerization catalyst, preferably, the magnesium halide support is prepared by the following steps: under the protection of inert gas, mixing magnesium dihalide and organic alcohol in an inert solvent, reacting for a period of time at a proper temperature, then cooling the system to a proper temperature, adding halogenated hydrocarbon into the system, and reacting for a period of time to obtain a mixed system containing a magnesium halide carrier.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the step of preparing the magnesium halide support, the magnesium dihalide includes one or a combination of several of magnesium chloride, magnesium bromide, magnesium iodide and the like. More preferably, the magnesium dihalide is magnesium chloride (preferably anhydrous magnesium chloride).
In the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the organic alcohol includes one or a combination of several of C2 to C8 organic alcohols. More preferably, the organic alcohol comprises one or more of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol, isooctanol and the like. Further preferably, the organic alcohol is isooctyl alcohol.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the step of preparing the magnesium halide support, the molar ratio of the organic alcohol to the magnesium dihalide is (2.0 to 4.0): 1.
in the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the halogenated hydrocarbon includes one or a combination of several of 1-chloroethane, 1-chloropropane, 1-chlorobutane, 1-chlorohexane and the like. More preferably, the halogenated hydrocarbon is 1-chlorobutane.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the step of preparing a magnesium halide support, the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5 to 4): 1.
in the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, after mixing the magnesium dihalide and the organic alcohol in an inert solvent, the reaction is carried out at 110 to 135 ℃ for 1 to 4 hours.
In the above-mentioned 1-butene polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the system is cooled to 50 to 70 ℃, a halogenated hydrocarbon is added thereto, and the reaction is carried out for 0.5 to 1 hour.
In the above-mentioned 1-butene polymerization catalyst, preferably, the inert gas may include high-purity nitrogen gas in the preparation step of the magnesium halide support.
In the above-mentioned butene-1 polymerization catalyst, preferably, in the preparation step of the magnesium halide support, the inert solvent includes one or a combination of several of alkane solvents, and a conventional inert alkane solvent such as, but not limited to, n-decane, etc. may be used. More preferably, the inert solvent may be used in an amount of 20 to 50mL/g of magnesium dihalide.
In the above-mentioned 1-butene polymerization catalyst, the preparation step of the magnesium halide support may be carried out under stirring conditions, and the rotation speed of stirring may be adjusted by those skilled in the art according to the actual circumstances.
In the above-mentioned 1-butene polymerization catalyst, after the preparation step of the magnesium halide carrier obtains a mixed system containing the magnesium halide carrier, conventional operations such as rapidly cooling the system may be selectively performed to solidify the particles to obtain a solid magnesium halide carrier. It is also possible to use the mixed system containing the magnesium halide support directly for the subsequent preparation of the catalyst without a curing step.
According to a particular embodiment of the present invention, preferably, the 1-butene polymerization catalyst is prepared by the following steps: the magnesium halide carrier, a titanium compound with a Ti-halogen bond, a non-ionic surfactant and a compound internal electron donor compound are subjected to contact reaction in an inert solvent to obtain the 1-butene polymerization catalyst.
More preferably, the 1-butene polymerization catalyst is prepared by the following steps:
s1, adding a magnesium halide carrier into a mixed solution of a titanium compound with a Ti-halogen bond and an inert solvent, adding a nonionic surfactant, keeping the temperature at-10 to 25 ℃ for 0.5 to 1 hour, heating to 105 to 120 ℃ and keeping the temperature for 1 to 3 hours, and carrying out solid-liquid separation to obtain a first solid product;
s2, adding the first solid product into a mixed solution of a titanium compound with a Ti-halogen bond and an inert solvent, adding a compound internal electron donor compound at the temperature of 50-80 ℃, heating to 90-110 ℃, keeping for 1-3 hours, and then carrying out at least solid-liquid separation to obtain the 1-butene polymerization catalyst.
Among them, it is preferable that in step S1, the mixed system containing the magnesium halide support (obtained from the above-mentioned production step of the magnesium halide support) is dropped into a mixed solution of a titanium compound having a Ti-halogen bond and an inert solvent, which is maintained at a temperature of 0 ℃. The dropping can be completed within 1.5-2.5 hours by adopting a peristaltic pump.
Among them, preferably, in step S1, the inert solvent includes one or a combination of several of alkane solvent and aromatic hydrocarbon solvent, such as but not limited to toluene, etc. More preferably, the mass ratio of the inert solvent to the magnesium halide support in step S1 is (12 to 18): 1.
wherein, preferably, in the step S1, the mass ratio of the titanium compound having a Ti-halogen bond to the magnesium halide support is (25 to 32): 1.
preferably, in step S1, the nonionic surfactant includes one or more of polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene ether, polymethacrylate, and the like. More preferably, the nonionic surfactant is a polymethacrylate.
Wherein, in step S1, the dosage ratio of the nonionic surfactant to the magnesium halide support is preferably (0.1 to 0.3) mL:1g of the total weight of the composition.
Among them, it is preferable that in step S1, the temperature is raised to 105 to 120 ℃ within 6 hours and maintained for 1 to 3 hours.
In step S1, the solid-liquid separation may be performed by thermal filtration separation or the like.
Among them, preferably, in step S2, the inert solvent includes one or a combination of several of alkane solvent and aromatic hydrocarbon solvent, such as but not limited to toluene, etc. More preferably, the mass ratio of the inert solvent to the first solid product in step S2 is (12 to 18): 1.
wherein, preferably, in step S2, the mass ratio of the titanium compound having a Ti-halogen bond to the first solid product is (25 to 32): 1.
wherein, in step S2, preferably, 0.05 to 0.6mol of the compound internal electron donor compound is added per mol of Mg in the magnesium halide support.
In step S2, the solid-liquid separation may be performed by thermal filtration separation or the like. After the solid-liquid separation, the 1-butene polymerization catalyst can be obtained by washing or the like. Preferably, the washing process may specifically be: and (3) washing the second solid product obtained after the solid-liquid separation in the step (S2) for 1-3 times at the temperature of 80-100 ℃ by adopting toluene, and then fully washing by adopting n-hexane at the temperature of 50-70 ℃ until no precipitated titanium compound is detected in the cleaning solution, thus obtaining the 1-butene polymerization catalyst.
According to an embodiment of the present invention, the average particle size of the 1-butene polymerization catalyst is preferably 40 to 70 μm.
The invention provides a 1-butene polymerization catalyst, which comprises a magnesium halide carrier, a titanium compound loaded on the carrier and having a Ti-halogen bond as an active component, a compound internal electron donor compound as a modifier, and a nonionic surfactant as a form control agent in the preparation process. The catalyst provided by the invention creatively adopts a phthalate compound, a1,3-diether compound and a succinate compound to be compounded as internal electron donors, so that the defects of three internal electron donors, namely diethers, diesters and succinates, are avoided, the respective advantages of the internal electron donors are fully exerted, and the catalyst has the advantages of high catalytic activity, high directionality, excellent copolymerization performance, good hydrogen regulation and the like by matching with the carrier and the titanium compound. The 1-butene polymerization catalyst can be used for preparing polybutene-1 resin with high isotacticity and adjustable molecular weight and molecular weight distribution.
The second aspect of the present invention provides a method for preparing the above-mentioned 1-butene polymerization catalyst, which comprises the following steps:
s1, adding a magnesium halide carrier into a mixed solution of a titanium compound with a Ti-halogen bond and an inert solvent, adding a nonionic surfactant, keeping the temperature at-10 to 25 ℃ for 0.5 to 1 hour, heating to 105 to 120 ℃ and keeping the temperature for 1 to 3 hours, and carrying out solid-liquid separation to obtain a first solid product;
s2, adding the first solid product into a mixed solution of a titanium compound with a Ti-halogen bond and an inert solvent, adding a compound internal electron donor compound at the temperature of 50-80 ℃, heating to 90-110 ℃, keeping for 1-3 hours, and then carrying out at least solid-liquid separation to obtain the 1-butene polymerization catalyst.
In the above preparation method, preferably, the magnesium halide support is prepared by the following steps: under the protection of inert gas, mixing magnesium dihalide and organic alcohol in an inert solvent, reacting for a period of time at a proper temperature, then cooling the system to a proper temperature, adding halogenated hydrocarbon into the system, and reacting for a period of time to obtain a mixed system containing a magnesium halide carrier.
In the above-mentioned preparation method, preferably, in the preparation step of the magnesium halide support, the magnesium dihalide includes one or a combination of several of magnesium chloride, magnesium bromide, magnesium iodide and the like. More preferably, the magnesium dihalide is magnesium chloride (preferably anhydrous magnesium chloride).
In the above preparation method, preferably, in the preparation step of the magnesium halide support, the organic alcohol includes one or a combination of C2 to C8 organic alcohols. More preferably, the organic alcohol comprises one or more of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol, isooctanol and the like. Further preferably, the organic alcohol is isooctyl alcohol.
In the above-mentioned production method, preferably, in the production step of the magnesium halide support, the molar ratio of the organic alcohol to the magnesium dihalide is (2.0 to 4.0): 1.
in the above-mentioned preparation method, preferably, in the preparation step of the magnesium halide support, the halogenated hydrocarbon includes one or a combination of several of 1-chloroethane, 1-chloropropane, 1-chlorobutane, 1-chlorohexane and the like. More preferably, the halogenated hydrocarbon is 1-chlorobutane.
In the above production method, preferably, in the production step of the magnesium halide support, the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5 to 4): 1.
in the above-mentioned production method, preferably, in the production step of the magnesium halide support, after mixing the magnesium dihalide and the organic alcohol in an inert solvent, the mixture is reacted at 110 to 135 ℃ for 1 to 4 hours.
In the above preparation method, preferably, in the preparation step of the magnesium halide support, the system is cooled to 50 to 70 ℃, a halogenated hydrocarbon is added thereto, and the reaction is carried out for 0.5 to 1 hour.
In the above-described production method, preferably, in the production step of the magnesium halide support, the inert gas may include high-purity nitrogen gas.
In the above-mentioned preparation method, preferably, in the preparation step of the magnesium halide support, the inert solvent includes one or a combination of several of alkane solvents, and a conventional inert alkane solvent such as, but not limited to, n-decane and the like can be used. Preferably, the inert solvent may be used in an amount of 20 to 50mL/g of magnesium dihalide.
In the above-mentioned preparation method, the preparation step of the magnesium halide support may be performed under stirring conditions, and the rotation speed of stirring may be adjusted by those skilled in the art according to the actual circumstances.
In the above-mentioned preparation method, after the preparation step of the magnesium halide support obtains the mixed system containing the magnesium halide support, conventional operations such as rapidly cooling the system may be optionally performed to solidify the particles to obtain the solid magnesium halide support. It is also possible to use the mixed system containing the magnesium halide support directly for the subsequent preparation of the catalyst without a curing step. The present invention preferably does not cure, but rather directly uses the mixed system containing the magnesium halide support for the subsequent preparation of the catalyst.
In the above-mentioned production method, preferably, in step S1, the mixed system containing the magnesium halide support (obtained from the above-mentioned production step of the magnesium halide support) is dropped into a mixed solution of a titanium compound having a Ti-halogen bond and an inert solvent, which is maintained at a temperature of 0 ℃. The dropping can be completed within 1.5-2.5 hours by adopting a peristaltic pump.
In the above preparation method, preferably, in step S1, the inert solvent includes one or a combination of several of an alkane solvent and an aromatic hydrocarbon solvent, such as, but not limited to, toluene and the like. More preferably, the mass ratio of the inert solvent to the magnesium halide support in step S1 is (12 to 18): 1.
in the above production method, preferably, the mass ratio of the titanium compound having a Ti-halogen bond to the magnesium halide support is (25 to 32): 1.
in the above preparation method, preferably, in step S1, the nonionic surfactant includes one or a combination of several of polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene ether, polymethacrylate, and the like. More preferably, the nonionic surfactant is polymethacrylate.
In the above preparation method, preferably, in step S1, the amount ratio of the nonionic surfactant to the magnesium halide support is (0.1 to 0.3) mL:1g of the total weight of the composition.
In the above-mentioned production method, it is preferable that, in step S1, the temperature is raised to 105 to 120 ℃ within 6 hours and held for 1 to 3 hours.
In the above-mentioned production method, preferably, in step S1, the solid-liquid separation may be performed by thermal filtration separation or the like.
In the above preparation method, preferably, in step S2, the inert solvent includes one or a combination of several of an alkane solvent and an aromatic hydrocarbon solvent, such as, but not limited to, toluene and the like. More preferably, the mass ratio of the inert solvent to the first solid product in step S2 is (12 to 18): 1.
in the above production method, preferably, in step S2, the mass ratio of the titanium compound having a Ti-halogen bond to the first solid product is (25 to 32): 1.
in the above preparation method, preferably, in step S2, 0.05 to 0.6mol of the built internal electron donor compound is added per mol of Mg in the magnesium halide support.
In the above-mentioned production method, preferably, in step S2, the solid-liquid separation may be performed by thermal filtration separation or the like. After the solid-liquid separation, the 1-butene polymerization catalyst can be obtained by washing or the like. Preferably, the washing process may specifically be: and (3) washing the second solid product obtained after the solid-liquid separation in the step (S2) for 1-3 times at the temperature of 80-100 ℃ by adopting toluene, and then fully washing by adopting n-hexane at the temperature of 50-70 ℃ until no precipitated titanium compound is detected in the cleaning solution, thus obtaining the 1-butene polymerization catalyst.
The preparation method of the 1-butene polymerization catalyst provided by the invention adopts a one-step method to prepare the spherical magnesium halide supported solid catalyst, and avoids the defects of low titanium-supported temperature, large titanium tetrachloride dosage and the like of the conventional polymerization catalysts. The catalyst prepared by the method has the advantages of smooth surface, good sphericity, narrow particle size distribution, high catalytic activity, good catalyst copolymerization performance and the like.
The third aspect of the invention provides an application of the 1-butene polymerization catalyst in the homopolymerization or copolymerization of 1-butene.
According to a particular embodiment of the invention, preferably, said application comprises the following steps: homopolymerizing or copolymerizing a reactant containing 1-butene in the presence of the 1-butene polymerization catalyst, an alkyl aluminum compound and an external electron donor compound to obtain a polybutene-1 homopolymer or a polybutene-1 copolymer.
In the above application, preferably, the alkyl aluminum compound comprises one or more of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum and the like. Preferably, the alkyl aluminium compound is triethyl aluminium.
In the above-mentioned applications, the external electron donor compound may be an external electron donor compound that is conventional in the art, and preferably, the external electron donor compound includes an alkoxysilane compound. More preferably, the external electron donor compound includes one or a combination of several of diphenyldimethoxysilane, dicyclopentyldimethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, cyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, and the like. Further preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane.
In the above application, preferably, the ratio of the alkyl aluminum compound to the 1-butene polymerization catalyst is (10 to 1000) in terms of aluminum to titanium molar ratio: 1, more preferably (50 to 500): 1, more preferably 300:1.
in the above application, preferably, the molar ratio of the external electron donor compound to the titanium in the 1-butene polymerization catalyst is (10 to 50): 1; more preferably (15 to 20): 1.
in the above application, preferably, the 1-butene polymerization catalyst is used in an amount of: 30000-140000g of 1-butene/g of the catalyst for polymerizing 1-butene.
In the above application, preferably, the reactant comprising 1-butene comprises an alpha-olefin comonomer comprising a C2-C10 alpha-olefin; more preferably, the alpha-olefin comonomer may comprise ethylene and/or propylene.
In the above application, it is preferable that the homopolymerization or copolymerization is carried out at a reaction temperature of 20 to 100 ℃, a reaction pressure of 1.0 to 4.0MPa, and a reaction time of 0.5 to 5 hours. More preferably, the homopolymerization or copolymerization reaction temperature is 60-80 ℃, the reaction pressure is 1.5-2.5 MPa, and the reaction time is 1.5-2.5 hours.
In a specific embodiment of the present invention, the application comprises the steps of: replacing the reaction kettle with high-purity nitrogen for 3 times, adding 1-butene liquid and optionally adding a comonomer, introducing hydrogen, then pressing an external electron donor compound, an alkyl aluminum compound and the 1-butene polymerization catalyst into the reaction kettle by using the high-purity nitrogen, supplementing pressure to 1.0-4.0 MPa (preferably 1.5-2.5 MPa) by using the nitrogen, reacting for 0.5-5 hours (preferably 1.5-2.5 hours) at 20-100 ℃ (preferably 60-80 ℃), releasing pressure after the polymerization is finished, and pressing out a product by using the nitrogen to obtain the polybutene-1 homopolymer or the polybutene-1 copolymer. The polymerization reaction may be carried out without a solvent or in the presence of a solvent, and the solvent used may be a solvent conventionally used in the art, such as but not limited to hexane, and the amount thereof may be adjusted by a person skilled in the art.
The 1-butene polymerization catalyst provided by the invention is suitable for catalyzing 1-butene polymerization, and solves the problems of low polymer isotacticity and difficult regulation and control of polymer molecular weight distribution of conventional catalysts, and the catalyst provided by the invention can be used for preparing polybutene-1 resin with high and adjustable isotacticity and adjustable molecular weight and molecular weight distribution, so that the performance of the polybutene-1 resin is improved, the processability of the resin is improved, the processing cost is reduced, and the application field of the polybutene-1 resin is widened.
The invention provides a 1-butene polymerization catalyst and a preparation method and application thereof. The technical scheme of the invention at least has the following beneficial effects:
1. the defects of low titanium-carrying temperature and large titanium tetrachloride using amount of the conventional catalyst are avoided, the prepared catalyst has the advantages of smooth surface, good sphericity, narrow particle size distribution and the like, and has high catalytic activity, high directionality, excellent copolymerization performance and good hydrogen regulation performance, and the activity of the catalyst can reach 25.4KgPB/g Cat.h;
2. the catalyst solves the problems that the polymer prepared by the conventional catalyst has low isotacticity and is difficult to regulate, and the catalyst can be used for preparing high-isotacticity adjustable polybutene-1 resin, wherein the isotacticity of the polymer can be controlled to be 97.2-99.0%;
3. solves the problem that the molecular weight and the molecular weight distribution of the polymer are difficult to regulate, and the catalyst of the invention can be used for preparing the polybutene-1 resin with adjustable polymer molecular weight and molecular weight distribution, and the molecular weight of the polymer can be controlled at 15 multiplied by 10 4 ～85×10 4 g/mol, and the molecular weight distribution can be regulated and controlled between 3.0 and 16.
Therefore, the technical scheme of the invention improves the performance of the polybutene-1 resin, improves the processability of the resin, reduces the processing cost and widens the application field of the polybutene-1 resin.
Drawings
FIG. 1 is a topographical view of the catalyst provided in example 1.
FIG. 2 is a morphology of the catalyst provided in comparative example 2
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
In one embodiment of the present invention, the 1-butene polymerization catalyst provided by the present invention is prepared by the following steps:
(1) Under the protection of inert gas (such as high-purity nitrogen) and stirring conditions, mixing anhydrous magnesium chloride and organic alcohol in an inert solvent, heating to 110-135 ℃ and reacting for 1-4 hours to obtain a homogeneous reaction product; wherein the molar ratio of the organic alcohol to the anhydrous magnesium chloride is (2.0-4.0): 1; the organic alcohol comprises one or more of C2-C8 organic alcohol, preferably the organic alcohol comprises one or more of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol, isooctanol and the like, and more preferably the organic alcohol is isooctanol; the dosage of the inert solvent is 20-50 mL/g anhydrous magnesium chloride; the inert solvent comprises one or more of alkane solvents, such as but not limited to n-decane and the like;
(2) Cooling the homogeneous reaction product to 50-70 ℃, adding halogenated hydrocarbon, continuously stirring for 0.5-1 hour, and cooling to room temperature to obtain a mixed system containing a magnesium halide carrier; wherein the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5 to 4): 1; the halogenated hydrocarbon comprises one or a combination of more of 1-chloroethane, 1-chloropropane, 1-chlorobutane, 1-chlorohexane and the like, and preferably, the halogenated hydrocarbon is 1-chlorobutane;
(3) Under the condition of stirring, dropwise adding the mixed system containing the magnesium halide carrier into a mixed solution of titanium tetrachloride and an inert solvent, the temperature of which is kept at 0 ℃ within 1.5-2.5 hours, adding a nonionic surfactant after dropwise adding, keeping at-10-25 ℃ for 0.5-1 hour, heating to 105-120 ℃ within 6 hours under the condition of stirring, keeping for 1-3 hours, and carrying out solid-liquid separation (such as thermal filtration separation) to obtain a first solid product; wherein, a peristaltic pump can be adopted for a mixed system containing the magnesium halide carrier; the mass ratio of the inert solvent to the magnesium halide carrier is (12-18): 1; the inert solvent comprises one or a combination of several of alkane solvent, aromatic hydrocarbon solvent and the like, such as but not limited to toluene and the like; the mass ratio of the titanium tetrachloride to the magnesium halide carrier is (25-32): 1; the dosage ratio of the nonionic surfactant to the magnesium halide carrier is (0.1-0.3) mL:1g; the nonionic surfactant comprises one or a combination of more of polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene ether, polymethacrylate and the like, and preferably, the nonionic surfactant is polymethacrylate;
(4) Adding the first solid product into a mixed solution of titanium tetrachloride and an inert solvent, heating to 50-80 ℃ under the stirring condition, adding a compound internal electron donor compound, continuously heating to 90-110 ℃ under the stirring condition, keeping the temperature for 1-3 hours, and then carrying out solid-liquid separation (such as thermal filtration separation) to obtain a second solid product; wherein the mass ratio of the inert solvent to the first solid product is (12-18): 1; the inert solvent comprises one or a combination of several of alkane solvent, aromatic hydrocarbon solvent and the like, such as but not limited to toluene and the like; the mass ratio of the titanium tetrachloride to the first solid product is (25-32): 1; adding 0.05-0.6 mol of the compound internal electron donor compound into each mol of Mg based on the amount of Mg in the magnesium halide carrier; the compound internal electron donor compound comprises a combination of a phthalate compound, a1,3-diether compound and a succinate compound, wherein the molar ratio of the phthalate compound to the 1,3-diether compound to the succinate compound is 1: (0.1-0.5): (0.2-0.8), the phthalate compound comprises one or a combination of several of dibutyl phthalate (DNBP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), diisooctyl phthalate (DIOP), dineopentyl phthalate (DPP) and the like, the 1,3-diether compound comprises one or a combination of several of 2,2-diisopropyl-1,3-Dimethoxypropane (DIOP), 2,2-diisobutyl-1,3-Dimethoxypropane (DIMOP), 2,2-diphenyl-1,3-dimethoxypropane (DPDPDMMOP) and the like, and the succinate compound comprises one or a combination of several of 2,3-diisopropyl diethyl Succinate (SDE), 2,3-diisobutyl diethyl succinate (DIBSDE), 5283-diisopropyl succinate (DIPF 5383-DIPD) and dimethyl Succinate (SDDM) 5329;
(5) And washing the second solid product for 1-3 times at 80-100 ℃ by using toluene, and then fully washing the second solid product at 50-70 ℃ by using n-hexane until no precipitated titanium compound is detected in a cleaning solution, thereby obtaining the 1-butene polymerization catalyst which is a spherical magnesium chloride carrier type solid catalyst.
The composition of the catalysts prepared in the following examples and comparative examples was measured as follows:
measuring the content of Ti in the catalyst by using an ultraviolet spectrophotometer (CARY-300);
the content of internal electron donor in the catalyst was determined by gas chromatography (SP 3420).
The polymerization activity of the catalysts prepared in the following examples and comparative examples was calculated according to the following equation:
W poly ＝Q/w cat ，gPoly·g -1 cat, wherein W poly For the polymerization activity of the catalyst, Q is the yield (g) of the polymer in 2 hours of the polymerization reaction, w cat The amount of the catalyst is used.
The polymers prepared in the following examples and comparative examples were tested as follows:
isotacticity, the weight percentage of insoluble substances after ether extraction;
molecular weight M w -gas gel permeation chromatography (PL-220);
molecular weight distribution PD-gas gel permeation chromatography (PL-220).
Example 1
This example provides a 1-butene polymerization catalyst prepared by the following steps:
(1) Under the protection of high-purity nitrogen, sequentially adding 90mL of n-decane, 3.0g of anhydrous magnesium chloride and 12.4mL of isooctyl alcohol into a reactor with a mechanical stirrer under the stirring condition, heating to 130 ℃ and reacting for 2 hours to obtain a homogeneous reaction product;
(2) Cooling the homogeneous reaction product to 60 ℃, adding 10mL of 1-chlorobutane, continuously stirring for 0.5 hour, and cooling to room temperature to obtain a mixed system containing a magnesium halide carrier;
(3) Dropwise adding the mixed system containing the magnesium halide carrier into 50mL of TiCl with the temperature kept at 0 ℃ within 2 hours by using a peristaltic pump 4 And 50mL of toluene, adding 0.5mL of polymethacrylate after the dropwise addition is finished, keeping the temperature at 25 ℃ for 0.5 hour, heating to 110 ℃ within 6 hours, keeping the temperature at 110 ℃ for 2 hours, and performing thermal filtration and separation to obtain a first solid product;
(4) The first solid product was added to 50mL of TiCl 4 Heating to 60 ℃ in 50mL of toluene mixed solution, adding a compound internal electron donor compound, wherein the compound internal electron donor compound comprises 4.8mmoL of diisobutylphthalate, 0.5mmoL 2, 2-diisopropyl-1,3-dimethoxypropane and 1.0mmoL 2, 3-diisopropyl diethyl succinate, the molar ratio of the added compound internal electron donor compound to Mg in a magnesium halide carrier is 0.2;
(5) And washing the second solid product for 2 times at 90 ℃ by using 100mL of toluene, and then fully washing the second solid product at 60 ℃ by using n-hexane until no precipitated titanium compound is detected in the cleaning solution, so as to obtain the 1-butene polymerization catalyst, which is a spherical magnesium chloride supported solid titanium catalyst.
The morphology of the catalyst is shown in figure 1 (different magnifications), and it can be seen that the catalyst has smooth surface, good sphericity and average particle size of 49.2 μm.
The mass percentage of each component in the catalyst is Ti =2.54%, and ID (compound electron donor compound) =6.9% through detection.
The embodiment also provides an application of the 1-butene polymerization catalyst in 1-butene polymerization, and the application comprises the following steps:
replacing a 5L stainless steel reaction kettle with high-purity nitrogen for 3 times, adding 2.5L 1-butene liquid, introducing 0.1MPa hydrogen, then pressing 0.15mmol of cyclohexyl methyl dimethoxy silane (external electron donor compound), 3.0mmol of triethyl aluminum and 0.01mmol (based on the molar amount of titanium) of the 1-butene polymerization catalyst into the reaction kettle by using the high-purity nitrogen, supplementing pressure to the total pressure of 2.0MPa by using the nitrogen, heating to 70 ℃, and reacting for 2 hours; after the polymerization was complete, the pressure was released and the product was pressed out with nitrogen and dried at 45 ℃ in vacuo to constant weight to give 480g of polybutene-1.
The calculation and detection result shows that the catalytic activity is 25.4KgPB/gCat, the polymer isotacticity is 98.5 percent, and the molecular weight (M) w )＝62×10 4 g/mol, molecular weight distribution (PD) =7.6.
The preparation method and polymerization method of the catalysts of examples 2-6 are basically the same as those of example 1, except that the compound internal electron donor compound is different, the specific compound and amount added are shown in table 1, and the polymerization result is shown in table 2.
TABLE 1 internal Electron donors, amounts used and contents of the components of the catalysts in the preparation of the catalysts
Comparative example 1
This comparative example provides a 1-butene polymerization catalyst prepared by the steps of:
(1) Under the protection of high-purity nitrogen, sequentially adding 90mL of n-decane, 3.0g of anhydrous magnesium chloride and 12.4mL of isooctyl alcohol into a reactor with a mechanical stirrer under the stirring condition, heating to 130 ℃ and reacting for 2 hours to obtain a homogeneous reaction product;
(2) Adding 1g of Phthalic Anhydride (PA) into the homogeneous reaction product, reacting at 130 ℃ for 2 hours, and cooling to room temperature to obtain a mixed system containing a magnesium halide carrier;
(3) Dropping the mixed system containing the magnesium halide carrier into 100mL TiCl with the temperature kept at minus 10 ℃ within 2 hours by using a peristaltic pump 4 After the dropwise addition is finished, keeping the temperature at minus 10 ℃ for 0.5 hour, then heating to 110 ℃ within 6 hours, keeping the temperature at 110 ℃ for 2 hours, and obtaining a first solid product after thermal filtration and separation;
(4) The first solid product was added to 50mL of TiCl 4 And 50mL of toluene, heating to 100 ℃, adding 6.3mmol of an internal electron donor compound Diisobutylphthalate (DIBP), keeping the molar ratio of the added internal electron donor compound to Mg in a magnesium halide carrier at 0.2;
(5) The second solid product was added to 50mL of TiCl 4 Reacting the mixture with 50mL of heptane at 98 ℃ for 2 hours, and then obtaining a third solid product after thermal filtration and separation;
(6) And fully washing the third solid product by using normal hexane at 60 ℃ until no precipitated titanium compound is detected in the cleaning solution, thus obtaining the 1-butene polymerization catalyst which is a magnesium chloride supported solid titanium catalyst.
The mass percentage of each component in the catalyst is Ti =1.97%, DIBP =3.79%.
The comparative example also provides the use of the 1-butene polymerization catalyst in the polymerization of 1-butene, the use comprising the steps of:
replacing a 5L stainless steel reaction kettle with high-purity nitrogen for 3 times, adding 2.5L 1-butene liquid, introducing 0.1MPa hydrogen, then pressing 0.15mmol of cyclohexyl methyl dimethoxy silane (an external electron donor compound), 3.0mmol of triethyl aluminum and 0.01mmol (based on the molar amount of titanium) of the 1-butene polymerization catalyst into the reaction kettle by using the high-purity nitrogen, supplementing pressure by using the nitrogen until the total pressure is 2.0MPa of gauge pressure, heating to 70 ℃, and reacting for 2 hours; after the polymerization was complete, the pressure was released and the product was pressed out with nitrogen and dried at 45 ℃ in vacuo to constant weight to give 300g of polybutene-1.
The calculation and detection show that the catalytic activity is 12.1KgPB/gCat, the isotacticity of the polymer is 94.2 percent, and the molecular weight (M) w )＝54×10 4 g/mol, molecular weight distribution (PD) =6.0.
Comparative example 2
This comparative example provides a 1-butene polymerization catalyst prepared by the following steps:
(1) Adding anhydrous magnesium chloride and anhydrous ethanol into a stirring reactor subjected to anhydrous and anaerobic treatment according to a molar ratio of 1:4 and a weight ratio of 1:4, and stirring and reacting for 2 hours at 100 ℃ to obtain a transparent magnesium chloride alcoholic solution; then spraying the solution into octane at the temperature of 10 ℃ below zero, wherein the volume ratio of the octane to the magnesium chloride alcoholate solution is 5:1, standing at the temperature of 10 ℃ below zero for 2 hours, carrying out suction filtration, adding a large amount of hexane, washing for 6 times, carrying out suction filtration, and drying to obtain a spherical magnesium chloride carrier;
(2) Vacuumizing a reactor, introducing argon for replacing for 3 times, adding titanium tetrachloride, dropwise adding the spherical magnesium chloride carrier obtained in the step (1) into titanium tetrachloride at the temperature of-10 ℃, wherein the volume mass ratio of the titanium tetrachloride to the spherical magnesium chloride carrier is 20mL;
(3) Adding titanium tetrachloride into the product obtained in the step (2), wherein the volume mass ratio of titanium tetrachloride to the spherical magnesium chloride carrier is 20mL;
(4) Adding a large amount of hexane into the product obtained in the step (3), washing at 60 ℃, performing suction filtration, and repeating for 6 times;
(5) Adding a trihexylaluminum/hexane solution with the volume ratio of 1:1 into the product obtained in the step (4), wherein the molar ratio of trihexylaluminum to magnesium in the spherical magnesium chloride carrier is 0.05;
(6) And (3) adding a large amount of hexane into the product obtained in the step (5), washing for 1 time at 60 ℃, carrying out suction filtration, and carrying out vacuum drying to obtain the solid catalyst.
The morphology of the catalyst is shown in fig. 2, and it can be seen that the catalyst has a non-smooth surface, a poor sphericity and agglomeration.
The detection shows that the titanium content in the catalyst is 2.35wt%, the content of the internal electron donor compound 2-isopropyl-2-isoamyl-1,3-dimethoxypropane is 9.6wt%, and the aluminum content is 1.58wt%.
This comparative example also provides the use of the catalyst for the polymerization of 1-butene, the specific procedure for this use being the same as in comparative example 1, to obtain 350g of polybutene-1.
The calculation and detection show that the catalytic activity is 17.2KgPB/gCat, the polymer isotacticity is 96.8 percent, and the molecular weight (M) w )＝55×10 4 g/mol, molecular weight distribution (PD) =5.8.
Comparative example 3
The comparative example provides a 1-butene polymerization catalyst, the preparation method and the polymerization method of the catalyst are basically the same as those of the example 1, the difference is that the compound internal electron donor compound is different, and the compound internal electron donor compound added in the comparative example is as follows: 4.8mmoL diisobutyl phthalate and 1.5mmoL 2, 2-diisopropyl-1,3-dimethoxypropane, wherein the molar ratio of the added compound internal electron donor compound to Mg in the magnesium halide carrier is 0.2.
The detection shows that the mass percentage of each component in the catalyst is Ti =2.61%, and ID (compound electron donor compound) =4.8%.
320g of polybutene-1 is obtained by polymerization, and the catalytic activity is 17.4KgPB/gCat, the isotacticity of the polymer is 96.0 percent, and the molecular weight (M) is obtained by calculation and detection w )＝30×10 4 g/mol, molecular weight distribution (PD) =4.5.
Comparative example 4
The comparative example provides a 1-butene polymerization catalyst, the preparation method and the polymerization method of the catalyst are basically the same as those of the example 1, the difference is that the compound internal electron donor compound is different, and the compound internal electron donor compound added in the comparative example is as follows: 1.5mmol 2, 2-diisopropyl-1,3-dimethoxypropane and 4.8mmol 2, 3-diisopropyl diethyl succinate, wherein the molar ratio of the added compound internal electron donor compound to Mg in the magnesium halide carrier is 0.2.
The mass percentage of each component in the catalyst is Ti =2.89%, and ID (compound electron donor compound) =4.6% through detection.
300g of polybutene-1 is obtained by polymerization, and the catalytic activity is 18.1KgPB/gCat, the isotacticity of the polymer is 94.0 percent and the molecular weight (M) is obtained by calculation and detection w )＝28×10 4 g/mol, molecular weight distribution (PD) =8.9.
Comparative example 5
The comparative example provides a 1-butene polymerization catalyst, the preparation method and the polymerization method of the catalyst are basically the same as those in example 1, the difference is that the compound internal electron donor compound is different, and the compound internal electron donor compound added in the comparative example is as follows: 0.5mmoL diisobutylphthalate, 1.5mmoL 2, 2-diisopropyl-1,3-dimethoxypropane and 4.3mmoL 2, 3-diisopropyl diethyl succinate, wherein the molar ratio of the added compound internal electron donor compound to Mg in the magnesium halide carrier is 0.2.
The detection shows that the mass percentage of each component in the catalyst is Ti =2.15%, and ID (compound electron donor compound) =3.6%.
326g of polybutene-1 is obtained by polymerization, and the catalytic activity is 14.6KgPB/gCat, the isotacticity of the polymer is 94.4 percent, and the molecular weight (M) is obtained by calculation and detection w )＝25×10 4 g/mol, molecular weight distribution (PD) =8.6.
TABLE 2 polymerization results of catalysts of examples and comparative examples
As can be seen from the above results, in comparison with comparative examples 1 and 2,under the condition that the dosage of the internal electron donor compound is the same, the temperature of the titanium carrier in the embodiment 1 can be raised to room temperature, and the dosage of the titanium tetrachloride is obviously reduced, thereby reducing environmental pollution and harm to people. The catalyst prepared by the embodiment of the invention has the advantages of smooth surface, good sphericity, narrow particle size distribution and the like, and the catalytic activity can reach 25.4KgPB/g Cat.h. From examples 1 to 6, it can be seen that the isotacticity of the polymer can be controlled to 97.2% to 99.0% and the molecular weight of the polymer can be controlled to 15 × 10 by using the built internal electron donor compound of the present invention and adjusting the addition amount thereof 4 ～85×10 4 g/mol, and the molecular weight distribution is regulated between 3.0 and 16.
In conclusion, the spherical polybutene-1 catalyst prepared by the one-step method has the advantages of smooth surface, good sphericity, narrow particle size distribution and the like, and has the advantages of high catalytic activity, high directionality, excellent copolymerization performance, good hydrogen regulation and the like. The catalyst of the invention is used for catalyzing the polymerization of 1-butene, thereby improving the performance of polybutene-1 resin, improving the processability of the resin, reducing the processing cost and widening the application field of the polybutene-1 resin.
Claims (10)
1. A 1-butene polymerization catalyst comprising: the electron donor compound comprises a magnesium halide carrier, and a titanium compound and a compound internal electron donor compound which are loaded on the carrier and have Ti-halogen bonds, wherein the compound internal electron donor compound comprises a combination of a phthalate compound, a1,3-diether compound and a succinate compound; wherein, the total weight of the 1-butene polymerization catalyst is 100 percent, the weight percentage of Ti is 1.8-7.0 percent, the weight percentage of the compound internal electron donor compound is 1.0-12.0 percent, and the balance is the magnesium halide carrier.
2. The 1-butene polymerization catalyst according to claim 1, wherein the molar ratio of the phthalate compound, the 1,3-diether compound and the succinate compound is 1: (0.1-0.5): (0.2-0.8).
3. The 1-butene polymerization catalyst according to claim 1 or 2, wherein the phthalate compound comprises one or a combination of several of dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate and dineopentyl phthalate;
preferably, the 1,3-diether compound comprises one or a combination of 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane and 2,2-diphenyl-1,3-dimethoxypropane;
preferably, the succinate compound comprises one or a combination of 2,3-diethyl diisopropylsuccinate, 2,3-diethyl diisobutylsuccinate, 2,3-dimethyl diisopropylsuccinate and 2,3-dimethyl diisobutylsuccinate.
4. The catalyst for polymerization of 1-butene according to claim 1 wherein the titanium compound having Ti-halogen bond comprises one or a combination of several of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, trichloroethoxytitanium, methoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, dichlorodiethoxytitanium, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride and tri-n-butoxytitanium chloride; preferably, the titanium compound is titanium tetrachloride.
5. The 1-butene polymerization catalyst according to claim 1, wherein the magnesium halide support is prepared by the following steps: under the protection of inert gas, mixing magnesium dihalide and organic alcohol in an inert solvent, reacting for a period of time at a proper temperature, then cooling the system to the proper temperature, adding halogenated hydrocarbon into the system, and reacting for a period of time to obtain a mixed system containing a magnesium halide carrier;
preferably, the magnesium dihalide comprises one or a combination of several of magnesium chloride, magnesium bromide and magnesium iodide; more preferably, the magnesium dihalide is magnesium chloride;
preferably, the organic alcohol comprises one or a combination of several of C2-C8 organic alcohols; more preferably, the organic alcohol comprises one or more of ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-octanol and isooctanol; further preferably, the organic alcohol is isooctyl alcohol;
preferably, the molar ratio of the organic alcohol to the magnesium dihalide is (2.0 to 4.0): 1;
preferably, the halogenated hydrocarbon comprises one or more of 1-chloroethane, 1-chloropropane, 1-chlorobutane and 1-chlorohexane; more preferably, the halogenated hydrocarbon is 1-chlorobutane;
preferably, the mass ratio of the halogenated hydrocarbon to the magnesium dihalide is (2.5 to 4): 1;
preferably, mixing magnesium dihalide and organic alcohol in an inert solvent, and reacting for 1-4 hours at 110-135 ℃;
preferably, the temperature of the system is reduced to 50-70 ℃, halogenated hydrocarbon is added into the system, and the reaction is carried out for 0.5-1 hour;
preferably, the inert solvent comprises one or a combination of alkane solvents;
preferably, the inert solvent is used in an amount of 20 to 50mL/g of magnesium dihalide.
6. A process for the preparation of the butene-1 polymerization catalyst according to anyone of claims 1 to 5, comprising the steps of:
s1, adding a magnesium halide carrier into a mixed solution of a titanium compound with a Ti-halogen bond and an inert solvent, adding a nonionic surfactant, keeping the temperature at-10 to 25 ℃ for 0.5 to 1 hour, heating to 105 to 120 ℃ and keeping the temperature for 1 to 3 hours, and carrying out solid-liquid separation to obtain a first solid product;
s2, adding the first solid product into a mixed solution of a titanium compound with a Ti-halogen bond and an inert solvent, adding a compound internal electron donor compound at the temperature of 50-80 ℃, heating to 90-110 ℃, keeping for 1-3 hours, and then carrying out at least solid-liquid separation to obtain the 1-butene polymerization catalyst.
7. The preparation method of claim 6, wherein, in step S1, the mixture system containing the magnesium halide support is dropwise added to a mixed solution of a titanium compound having a Ti-halogen bond and an inert solvent, which is maintained at a temperature of 0 ℃;
preferably, in step S1, the inert solvent includes one or a combination of several of an alkane solvent and an aromatic hydrocarbon solvent; more preferably, the mass ratio of the inert solvent to the magnesium halide support in step S1 is (12 to 18): 1;
preferably, in step S1, the mass ratio of the titanium compound having a Ti-halogen bond to the magnesium halide support is (25 to 32): 1;
preferably, in step S1, the nonionic surfactant includes one or more of polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene ether and polymethacrylate; more preferably, the nonionic surfactant is a polymethacrylate;
preferably, in step S1, the dosage ratio of the nonionic surfactant to the magnesium halide support is (0.1 to 0.3) mL:1g of the total weight of the composition.
8. The preparation method according to claim 6, wherein, in step S2, the inert solvent comprises one or a combination of alkane solvent and aromatic hydrocarbon solvent; more preferably, the mass ratio of the inert solvent to the first solid product in step S2 is (12 to 18): 1;
preferably, in step S2, the mass ratio of the titanium compound having a Ti-halogen bond to the first solid product is (25 to 32): 1;
preferably, in step S2, 0.05 to 0.6mol of the built internal electron donor compound is added per mol of Mg in the magnesium halide support.
9. Use of the butene-1 polymerization catalyst according to any one of claims 1 to 5 in the homo-or copolymerization of butene-1.
10. The application of claim 9, wherein the application comprises the steps of: homopolymerizing or copolymerizing a reactant containing 1-butene in the presence of the 1-butene polymerization catalyst, an alkyl aluminum compound and an external electron donor compound to obtain a polybutene-1 homopolymer or a polybutene-1 copolymer;
preferably, the alkyl aluminum compound comprises one or a combination of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum;
preferably, the external electron donor compound includes an alkoxysilane compound; more preferably, the external electron donor compound comprises one or a combination of several of diphenyldimethoxysilane, dicyclopentyldimethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, cyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane and diisobutyldimethoxysilane;
preferably, the ratio of the alkyl aluminum compound to the 1-butene polymerization catalyst is (10 to 1000) in terms of aluminum to titanium molar ratio: 1, more preferably (50 to 500): 1;
preferably, the molar ratio of the external electron donor compound to the titanium in the 1-butene polymerization catalyst is (10-50): 1;
preferably, the reaction temperature of the homopolymerization or copolymerization is 20-100 ℃, the reaction pressure is 1.0-4.0 MPa, and the reaction time is 0.5-5 hours; more preferably, the homopolymerization or copolymerization reaction temperature is 60-80 ℃, the reaction pressure is 1.5-2.5 MPa, and the reaction time is 1.5-2.5 hours.
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| 王立娟;何书艳;王文燕;张若晨;高文宇;: "丙烯聚合用复合内给电子体催化剂的制备", 合成树脂及塑料, no. 03 * |
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