CN105482003B - Carrier and its catalyst used in a kind of ethylene rolymerization catalyst - Google Patents
Carrier and its catalyst used in a kind of ethylene rolymerization catalyst Download PDFInfo
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- CN105482003B CN105482003B CN201410532200.1A CN201410532200A CN105482003B CN 105482003 B CN105482003 B CN 105482003B CN 201410532200 A CN201410532200 A CN 201410532200A CN 105482003 B CN105482003 B CN 105482003B
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- ethylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000005977 Ethylene Substances 0.000 title claims abstract description 26
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 33
- -1 alcohol compound Chemical class 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 24
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 230000003197 catalytic effect Effects 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 150000002681 magnesium compounds Chemical class 0.000 claims description 14
- 150000003254 radicals Chemical class 0.000 claims description 13
- 150000002924 oxiranes Chemical class 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 239000003701 inert diluent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- ZTHNOZQGTXKVNZ-UHFFFAOYSA-L dichloroaluminum Chemical compound Cl[Al]Cl ZTHNOZQGTXKVNZ-UHFFFAOYSA-L 0.000 claims description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 3
- LSCQUUWETLEULM-UHFFFAOYSA-N ethyl 2-butoxybenzoate Chemical class CCCCOC1=CC=CC=C1C(=O)OCC LSCQUUWETLEULM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002194 fatty esters Chemical class 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 229910010386 TiI4 Inorganic materials 0.000 claims description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical group C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- MMHHOWWUUCNZSX-UHFFFAOYSA-N ethyl 2-hexoxybenzoate Chemical class CCCCCCOC1=CC=CC=C1C(=O)OCC MMHHOWWUUCNZSX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- UBCXJXNSJYQNGO-UHFFFAOYSA-N propyl 2-butoxybenzoate Chemical compound C(CC)OC(C1=C(C=CC=C1)OCCCC)=O UBCXJXNSJYQNGO-UHFFFAOYSA-N 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 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
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- BUKSCRKGJVCWGE-UHFFFAOYSA-N methyl 2-butoxybenzoate Chemical class CCCCOC1=CC=CC=C1C(=O)OC BUKSCRKGJVCWGE-UHFFFAOYSA-N 0.000 claims 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 10
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 115
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 235000011147 magnesium chloride Nutrition 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000284 extract Substances 0.000 description 11
- 239000013049 sediment Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 235000010210 aluminium Nutrition 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 239000011949 solid catalyst Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000969 carrier Substances 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- YWNYZQTZOONLGU-UHFFFAOYSA-N C(CC)Cl.[O] Chemical compound C(CC)Cl.[O] YWNYZQTZOONLGU-UHFFFAOYSA-N 0.000 description 1
- WKLNPIPUIVGQIY-UHFFFAOYSA-N C1=CC=CC=C1.C(=O)OCC Chemical compound C1=CC=CC=C1.C(=O)OCC WKLNPIPUIVGQIY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical group C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000014483 powder concentrate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst, include the reactant of following components：Magnesium chloride/gallic acid-derivate/epoxide/alcohol compound/radical initiator with carbon-carbon double bond.The mixed solution of said components triggers in temperature-rise period through radical initiator, and polymerisation can occur for the carbon-carbon double bond in system, and so as to separate out, particle diameter distribution is narrow and the carrier of doped polymer.The polyethylene catalysts prepared by the carrier not only have the characteristics of particle diameter distribution is narrow, and hydrogen response is high, and the particle diameter distribution of gained polymerization powder is especially concentrated and fine powder is less.
Description
Technical field
It is used for vinyl polymerization or polymer-doped type carrier, the ingredient of solid catalyst of combined polymerization the present invention relates to a kind of,
And catalyst containing the ingredient of solid catalyst and preparation method thereof.
Background technology
Since Ziegler-Natta types polyolefin catalyst comes out, by the development of nearly 60 years, the poly- of its production is passed through
The resin such as ethene and polypropylene has turned into the most important naval stores in the whole world.In recent years, Ziegler-Natta types catalyzed polyolefin
A kind of common preparation method of agent is：First prepare with certain particle shape and particle diameter distribution magnesium compound (or magnesium compound and
The solid complex that electron donor is formed) carrier, the alkoxyl magnesium carrier as described in patent CN102020534A, or patent
Magnesium chloride/ethanolic vehicle described in CN1091748A etc..Again by dealcoholysis, chlorination the methods of, carrier is converted into magnesium chloride
Skeleton structure, the preparation process of polyolefin catalyst is completed finally by load titanium chloride.
In this area, most common magnesium compound (or magnesium compound/electron donor) carrier is magnesium chloride/ethanolic vehicle, existing
There is technology to be closed usually using ethanol and anhydrous magnesium chloride in 110-130 degree alcohol, then distribute it in white oil/silicone oil dispersion media
High-speed stirred and emulsify, most chlorination magnesium alcoholate ball type carrier is obtained through chilling afterwards, as described in patent CN1091748A.This
Outside, polymer can also be introduced into magnesium chloride/ethanolic vehicle, such as polyethers (CN101544710A) and polyester
(CN101550205A) etc., so as to assign support/catalyst higher resistant to breakage ability.
In addition, art also discloses the support preparation method compared with multiple types.Such as CN102020534A and
CN101663332A etc. discloses the method for preparing alkoxyl magnesium carrier.As WO2011/044761A1 discloses magnesium chloride/second
Alcohol/varsol reacts with epoxide, and the method for preparing novel ball magnesium compound carrier, its principle is ethanol/ring
Reacted between oxygen chloropropane and magnesium chloride, so as to generate the magnesium compound insoluble in solution system.Such as CN101554595A
Disclose the system of the polymer-doped type carrier comprising magnesium chloride/styrol copolymer/silica gel/tetrahydrofuran/butanediol component
Preparation Method.
The mechanical strength of carrier and catalyst possesses corresponding relation, if the mechanical strength of carrier is relatively low, is processed
To catalyst be also easily broken, a certain amount of polyethylene fine powder can be produced in polymerization.Toughness and the machinery for strengthening carrier are strong
Degree is to avoid catalyst breakage, and then reduces the necessary ways of fine powder content in industrial production, and polymer is introduced into carrier
It is effective method.
In addition, according to the replication capacity of Ziegler-Natta type olefin polymerization catalysis particles, if catalyst particle
Particle diameter distribution is wider (span values are larger), then the polyethylene powder prepared is also by with the wider property of particle diameter distribution
(span values are larger).The powder of wide distribution is generally also including a certain amount of compared with coarse powder material and less than 190 targeted fine powders, and this is for stream
The stable operation for changing bed is unfavorable.
Therefore, it is necessary to prepare a kind of polymer-doped type carrier and catalyst, and the catalyst particle size narrow distribution.
The present inventor it has been investigated that, magnesium chloride/gallic acid-derivate/carry carbon-carbon double bond epoxide/alcohol
Class compound can form the solution of clear in inert hydrocarbon solvent, and the solution draws in temperature-rise period through free radical
Send out agent to trigger, polymerisation can occur for the carbon-carbon double bond in system, generate the polymer insoluble in solution system, and then can
Gradually separate out that particle diameter distribution is narrow and the carrier of doped polymer.Gallic acid-derivate not only acts as molten in this solution system
The effect of the scattered magnesium chloride of solution and its derivative, is also used as electron donor, is advantageous to improve the hydrogen response of catalyst.
The content of the invention
The technical problem to be solved in the present invention is to provide the polymer-doped type carrier that a kind of ethylene rolymerization catalyst uses
Preparation method, this method is simple to operate, without being adjusted to conventional equipment.And one kind is provided and carried by polymer-doped type
Ethene polymerization catalyst component prepared by body, its catalytic component can be with polymerising ethylenes with co-catalyst.Prepared by the carrier
Polyethylene catalysts not only there is the characteristics of particle diameter distribution is narrow, and hydrogen response is high, and gained polymerize the particle diameter distribution of powder
Especially concentrate and fine powder is less.
Polymer-doped type carrier used in a kind of ethylene rolymerization catalyst of the present invention, the carrier include following group
The reaction product divided：
(1) magnesium compound；
(2) gallic acid-derivate；
(3) epoxide of carbon-carbon double bond is carried；
(4) alcohol compound；
(5) radical initiator；
Described magnesium compound be in magnesium dihalide, magnesium dihalide molecular formula one of halogen atom by oxyl or
One kind in the derivative that halo oxyl is replaced, or their mixture；
The formula of described gallic acid-derivate isR in formula1For C1~C8Alkyl, R2
For C1~C4Alkyl；
The described epoxide with carbon-carbon double bond includes the aliphatic olefin with carbon-carbon double bond, alkadienes, halogen
At least one of fat subsitutes race alkene, the oxide of alkadienes, glycidol ether and inner ether；
Described alcohol compound includes carbon number at least one of 1~18 fatty alcohol or aromatic alcohol；
Described radical initiator includes azo-initiator and peroxide initiator.
Magnesium compound described in component (1) includes MgCl2、MgBr2、MgI2, MgCl (OEt) and MgCl (OBu) etc..
Gallic acid-derivate described in component (2) includes：The butoxybenzoic acid ethyl esters of 3,4,5- tri-, the fourth oxygen of 3,4,5- tri-
Yl benzoic acid methyl esters, the butoxybenzoic acid propyl ester of 3,4,5- tri-, 3,4,5- triethoxies ethyl benzoate, 3,4,5- triethoxies
At least one of compound such as methyl benzoate and the hexyloxybenzoate ethyl esters of 3,4,5- tri-.
The epoxide with carbon-carbon double bond described in component (3) includes GMA and acrylic acid
Ethylene oxidic ester etc..
Alcohol compound described in component (4) include methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol,
Hexanol, cyclohexanol, octanol, isooctanol, phenmethylol, benzyl carbinol etc..
Radical initiator described in component (5) includes benzoyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide
Hydrogen, di-t-butyl peroxide, cumyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, idol
At least one of nitrogen bis-isobutyronitrile, ABVN.
Ratio between each reactant is in terms of every mole of magnesium, and gallic acid-derivate is 0.1~5.0 mole, with carbon carbon
The epoxide of double bond is 0.1~5.0 mole, and alcohol compound is 0.1~5.0 mole, radical initiator 0.0001
~0.05 mole.
A kind of preparation method of polymer-doped type carrier for used in ethylene rolymerization catalyst of the present invention, bag
Include following step：
(1) magnesium compound described in component (1) is dispersed in hydro carbons atent solvent, obtains suspension；
(2) gallic acid-derivate described in component (2) is added into suspension, carries carbon carbon pair described in component (3)
Alcohol compound described in the epoxide and component (4) of key, formation is uniformly saturating after reacting the regular hour at 20~50 DEG C
Bright solution；
(3) at 20~50 DEG C, the radical initiator described in component (5) is added into the homogeneous transparent solution of step (2),
Solids is separated out in slow temperature-rise period, after reacting the regular hour, removes unreacted reactant, and wash using inert diluent
Wash, obtain the polymer-doped type carrier of the present invention.
The invention further relates to a kind of catalytic component for vinyl polymerization, and it includes the reaction product of following components：
(1) above-mentioned polymer-doped type carrier；
(2) one or more are by formula Ti (OR3)nX4-nShown titanium compound, R in formula3For C1~C8Alkyl, X is halogen
Atom, 0≤n≤3；
(3) one or more are by formula Al R 'aXbHcShown organo-metallic compound, R ' is C in formula1~C14Hydrocarbon
Base, X are halogen, and a, b, c are 0~3 integer, and a+b+c=3；
(4) one or more electron donor compounds, selected from fatty ester/aromatic ester, aliphatic ether/cycloaliphatic ether and fat
Ketone；
Ratio between wherein each reactant in terms of every mole of magnesium in the polymer-doped type carrier described in component (1),
Component (2) titanium compound is 0.1~15.0 mole；Component (3) organo-metallic compound is 0.1~5.0 mole；Component (4) is given
Electron compound is 0.1~5.0 mole.
Titanium compound formula described in component (2) is Ti (OR3)nX4-n, R in formula3For C1~C8Alkyl, X is halogen atom, 0
≤ n≤3, including：TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti
(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I etc..
The formula of organo-metallic compound described in component (3) is AlR 'aXbHcShown, R ' is C in formula1~C14Hydrocarbon
Base, X are halogen, and a, b, c are 0~3 integer, and a+b+c=3.Particular compound is such as：Al(CH3)3、Al(CH2CH3)3、Al
(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、AlCl
(CH2CH3)2、AlCl2(CH2CH3) etc. alkyl aluminum compound, wherein preferably Al (CH2CH3)3、Al(n-C6H13)3、Al(i-Bu
)3.Most preferably Al (CH2CH3)3.These organo-metallic compounds both may be used alone, two or more kinds can also be used in combination.
Electron donor compound described in component (4) is selected from fatty ester/aromatic ester, aliphatic ether/cycloaliphatic ether and fat
Ketone etc., preferably C1~C4Arrcostab, the C of aliphatic saturated monocarboxylic acid1~C8Arrcostab, the C of aromatic carboxylic acids2~C12Aliphatic ether, C3~
C4Cyclic ethers, C3~C6Saturated fat ketone.Particular compound is such as：Methyl formate, ethyl acetate, butyl acetate, acetic acid n-octyl, benzene
Ethyl formate, butyl benzoate, ether, hexyl ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK) etc., these electron donors
Compound both may be used alone, two or more kinds can also be used in combination.
The preparation method of catalytic component of the present invention for ethylene polymerization, it comprises the following steps：
(1) the polymer-doped type support dispersion described in component (1) is obtained into suspension in hydro carbons atent solvent；
(2) by suspension in -40~50 DEG C and component (3) organo-aluminum compound and component (4) one or more electrons
Body compound carries out haptoreaction；
(3) mixture of step (2) is to slowly warm up to 20~60 DEG C, after reacting the regular hour, removes unreacted reactant,
And washed using inert diluent；
(4) add component (2) titanium compound to be reacted, then washed using inert diluent, obtain urging for the present invention
Agent component.
It is used for vinyl polymerization or the catalyst of combined polymerization present invention also offers a kind of, it includes reaction of following components and produced
Thing：
(1) catalytic component of the invention described above；
(2) formula is AlRdX3-dOrgano-aluminum compound, the alkyl that R is hydrogen or carbon number is l~20 in formula, X is halogen
Plain atom, 0<d≤3.
Component (2) formula of is AlRdX3-dOrgano-aluminum compound, R can be hydrogen in formula or carbon number is l~20
Alkyl, particularly alkyl, aralkyl, aryl；X is halogen atom, particularly chlorine and bromine；0<d≤3.Particular compound is such as：Al
(CH3)3、Al(CH2CH3)3、Al(i-Bu)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、
AlCl(CH2CH3)2、AlCl2(CH2CH3) etc. alkyl aluminum compound.Preferably Al (CH2CH3)3、Al(i-Bu)3.Wherein component
(2) mol ratio of aluminium and titanium in component (1) is 5~500, preferably 20~200 in.
Liquid polymerization medium includes：Iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, hydrogasoline, kerosene,
The atent solvent such as the aliphatic saturated hydrocarbons such as benzene,toluene,xylene or aromatic hydrocarbon.
In order to adjust the molecular weight of final polymer, molecular weight regulator is made using hydrogen.
The present inventor it has been investigated that, magnesium chloride/gallic acid-derivate/carry carbon-carbon double bond epoxide/alcohol
Class compound can form the solution of clear in inert hydrocarbon solvent, and the solution draws in temperature-rise period through free radical
Send out agent to trigger, polymerisation can occur for the carbon-carbon double bond in system, and so as to separate out, particle diameter distribution is narrow and doped polymer
Carrier.The polyethylene catalysts prepared by the carrier not only have the characteristics of particle diameter distribution is narrow, and hydrogen response is high, institute
The particle diameter distribution especially concentration of powder must be polymerize and fine powder is less.
Embodiment
Method of testing：
1. the relative weight percents of titanium elements in catalyst system：Using AAS；
2. the relative weight percents of polymer in catalyst system：Using core magnetic survey；
3rd, in catalyst system polymer molecular weight, measured by gel chromatography PL220；
4th, the measure (MI/2.16Kg) of melt index：According to ASTM D1238-99；
The present invention is described with embodiment below, but the not limitation scope of the invention.
Embodiment 1
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 90ml toluene, 15g 3,4,5- tripropoxy methyl benzoates, the contracting of 8.0ml methacrylic acids
Water glyceride, 3ml ethanol are added in reactor, under conditions of speed of agitator 450rpm, temperature are 40 DEG C, constant temperature 2 hours.
Azodiisobutyronitrile 0.08g is added to system, is to slowly warm up to 90 degree, carrier particle gradually separates out.Constant temperature 1 hour, filter off female
Liquid, through inert diluent washing for several times.Transferred them to by hexane in chromatography funnel, dried up with high pure nitrogen, obtain particle diameter
The polymer-doped type carrier of narrowly distributing.
Embodiment 2
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 100ml toluene, the butoxybenzoic acid ethyl ester of 25g 3,4,5- tri-, 5.0ml acrylic acid shrinks
Glyceride, 6ml ethanol are added in reactor, under conditions of speed of agitator 400rpm, temperature are 30 DEG C, constant temperature 2 hours.To
System adds benzoyl peroxide 0.05g, is to slowly warm up to 90 degree, carrier particle gradually separates out.Constant temperature 1 hour, mother liquor is filtered off,
Through inert diluent washing for several times.Transferred them to by hexane in chromatography funnel, dried up with high pure nitrogen, obtain particle diameter distribution
Narrow polymer-doped type carrier.
Embodiment 3
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, the polymer-doped type carriers of 4.0g are sequentially added (by reality
Example 1 is applied to prepare), hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (triethyl aluminum of 40ml triethyl aluminums is added dropwise：
1.2M) and 0.5ml ethyl benzoates, 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspension
Be layered quickly, extract supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to
0 DEG C, titanium tetrachloride 6ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension divides quickly
Layer, extracts supernatant liquor, after sediment washs twice with hexane, is transferred them to by hexane in chromatography funnel, uses High Purity Nitrogen
Air-blowing is done, and obtains the narrow ingredient of solid catalyst of good fluidity, particle diameter distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：
Volume is 2L stainless steel cauldron, and after high pure nitrogen is sufficiently displaced from, it is 1M to add 1L hexanes and 1.0ml concentration
Triethyl aluminum, add the ingredient of solid catalyst (contain 0.6 milligram of titanium) prepared by the above method, be warming up to 70 DEG C, it is logical
Entering hydrogen makes pressure in kettle reach 0.28Mpa, then being passed through ethene makes stagnation pressure in kettle reach 0.73Mpa (gauge pressure), in 80 DEG C of conditions
Lower polymerization 2 hours, polymerization result is shown in Table 2.
(3) polymerisation：
Volume is 2L stainless steel cauldron, and after high pure nitrogen is sufficiently displaced from, it is 1M to add 1L hexanes and 1.0ml concentration
Triethyl aluminum, add the ingredient of solid catalyst (contain 1.8 milligrams of titaniums) prepared by the above method, be warming up to 70 DEG C, it is logical
Entering hydrogen makes pressure in kettle reach 0.58Mpa, then being passed through ethene makes stagnation pressure in kettle reach 0.73Mpa (gauge pressure), in 80 DEG C of conditions
Lower polymerization 2 hours, polymerization result is shown in Table 3.
Embodiment 4
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, the polymer-doped type carriers of 5.0g are sequentially added (by reality
Example 1 is applied to prepare), hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (triethyl aluminum of 50ml triethyl aluminums is added dropwise：
1.2M) and 0.5ml acetic acid n-octyls, 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspension
Be layered quickly, extract supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to
0 DEG C, titanium tetrachloride 8ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension divides quickly
Layer, extracts supernatant liquor, after sediment washs twice with hexane, is transferred them to by hexane in chromatography funnel, uses High Purity Nitrogen
Air-blowing is done, and obtains the narrow ingredient of solid catalyst of good fluidity, particle diameter distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 1, polymerization result is shown in Table 2.
Embodiment 5
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, the polymer-doped type carriers of 3.0g are sequentially added (by reality
Example 2 is applied to prepare), hexane 100ml, -10 DEG C are cooled under stirring, hexane solution (three n-hexyls of 20ml tri-n-hexyl aluminums are added dropwise
Aluminium：1.0M) and 0.5ml butyl benzoates, 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspend
Liquid is layered quickly, extracts supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled down
To 0 DEG C, titanium tetrachloride 20ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension is quickly
Layering, extracts supernatant liquor, after sediment washs twice with hexane, is transferred them to by hexane in chromatography funnel, use is high-purity
Nitrogen dries up, and obtains the narrow ingredient of solid catalyst of good fluidity, particle diameter distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 1, polymerization result is shown in Table 2.
Embodiment 6
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, the polymer-doped type carriers of 3.0g are sequentially added (by reality
Example 2 is applied to prepare), hexane 100ml, -10 DEG C are cooled under stirring, hexane solution (three n-hexyls of 20ml tri-n-hexyl aluminums are added dropwise
Aluminium：1.0M) and 0.5ml tetrahydrofurans, 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspension
Be layered quickly, extract supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to
0 DEG C, titanium tetrachloride 30ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension divides quickly
Layer, extracts supernatant liquor, after sediment washs twice with hexane, is transferred them to by hexane in chromatography funnel, uses High Purity Nitrogen
Air-blowing is done, and obtains the narrow ingredient of solid catalyst of good fluidity, particle diameter distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 1, polymerization result is shown in Table 2 and table 3.
Comparative example 1
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, 4.0g ball type carriers MgCl is sequentially added2·
2.6C2H5OH, hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (triethyl aluminum of 40ml triethyl aluminums is added dropwise：
1.2M), 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts upper strata
Clear liquid, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to 0 DEG C, tetrachloro is slowly added dropwise
Change titanium 6ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, stand, suspension is layered quickly, extracts supernatant liquor, is sunk
After starch washs twice with hexane, transferred them to by hexane in chromatography funnel, dried up with high pure nitrogen, obtain good fluidity
Solid spherical catalytic component.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 1, polymerization result is shown in Table 2 and table 3.
Comparative example 2
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, 5.0g ball type carriers MgCl is sequentially added2·
2.6C2H5OH, hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (tri-n-hexyl aluminum of 50ml tri-n-hexyl aluminums is added dropwise：
1.0M), ethyl benzoate 2ml, then heats to 50 DEG C, and maintenance reaction 2 hours.Stop stirring, stand, suspension is quickly
Layering, extracts supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to 0 DEG C,
Titanium tetrachloride 15ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension is layered, taken out quickly
Except supernatant liquor, after sediment washs twice with hexane, transferred them to by hexane in chromatography funnel, with High Purity Nitrogen air-blowing
It is dry, obtain the solid spherical catalytic component of good fluidity.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 1, polymerization result is shown in Table 2.
Comparative example 3
By 4.0 grams of magnesium chlorides, 90ml toluene, 15g 3,4,5- tripropoxy methyl benzoates, 8.0ml epoxychloropropane,
3ml ethanol is added in reactor, under conditions of speed of agitator 450rpm, temperature are 40 DEG C, constant temperature 2 hours.Slowly heating
To 90 degree, constant temperature 2 hours.
Experimental phenomena：After 40 DEG C of constant temperature 2 hours, magnesium chloride is completely dissolved dissolution system, obtains the solution of clear.
But 90 degree and constant temperature are warming up to after 2 hours, system remains as the solution of clear, is separated out without any solids.Thus may be used
See, in the solution system temperature-rise period of the embodiment of the present invention 1/2, trigger through radical initiator, the carbon-carbon double bond in system
Generation polymerisation, the polymer insoluble in solution system is generated, be that solution system can gradually separate out polymer-doped type load
The key of body.
The composition of the catalytic component of table 1
It was found from the data of table 1, the catalytic component particle diameter distribution obtained by the present invention is very narrow, and span values are not higher than 0.7.It is poly-
The narrower span values of compound doping type carrier come from its slow precipitation mode.And the span values of comparative example catalyst be limited to it is spherical
The particle diameter distribution of magnesium chloride/ethanolic vehicle.
The particle diameter distribution of the catalyst performance of table 2 and powder
It was found from the data of table 2, the polyethylene powder that is gone out by catalyst preparation obtained by the present invention, melt index is higher, and
Particle diameter distribution is especially concentrated, and more than 70wt% powder concentrates on 55 mesh, more than 16 mesh is less than 3wt% compared with coarse powder material content, and 190
Fine powder content below mesh is less than 0.5wt%.As can be seen here, present invention gained catalyst particle is not fragile in the course of the polymerization process
It is broken.
The hydrogen response of the catalyst of table 3
The catalyst hydrogen response that the present invention is can be seen that from the data of table 3 is good.
Claims (17)
1. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst, the carrier include the reaction product of following component：
(1) magnesium compound；
(2) gallic acid-derivate；
(3) epoxide of carbon-carbon double bond is carried；
(4) alcohol compound；
(5) radical initiator；
Described magnesium compound be in magnesium dihalide, magnesium dihalide molecular formula one of halogen atom by oxyl or halo
One kind in the derivative that oxyl is replaced, or their mixture；
The formula of described gallic acid-derivate isR in formula1For C1~C8Alkyl, R2For C1
~C4Alkyl；
The described epoxide with carbon-carbon double bond includes the aliphatic olefin with carbon-carbon double bond, alkadienes, halo fat
At least one of fat race alkene, the oxide of alkadienes, glycidol ether and inner ether；
Described alcohol compound includes carbon number at least one of 1~18 fatty alcohol or aromatic alcohol；
Described radical initiator includes azo-initiator and peroxide initiator.
2. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Ratio between each reactant is in terms of every mole of magnesium, and gallic acid-derivate is 0.1~5.0 mole, the ring with carbon-carbon double bond
Oxygen compound is 0.1~5.0 mole, and alcohol compound is 0.1~5.0 mole, and radical initiator rubs for 0.0001~0.05
You.
3. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described gallic acid-derivate be the butoxybenzoic acid ethyl esters of 3,4,5- tri-, the butoxybenzoic acid methyl esters of 3,4,5- tri-, 3,4,
The butoxybenzoic acid propyl ester of 5- tri-, 3,4,5- triethoxies ethyl benzoate, 3,4,5- triethoxies methyl benzoate and 3,4,
At least one of hexyloxybenzoate ethyl esters of 5- tri-.
4. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
The described epoxide with carbon-carbon double bond is selected from GMA and glycidyl acrylate.
5. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described radical initiator is selected from benzoyl peroxide, isopropyl benzene hydroperoxide, TBHP, two tertiary fourth of peroxidating
Base, cumyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile, azo
At least one of two different heptonitriles.
6. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described alcohol compound is selected from methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol, hexanol, cyclohexanol, pungent
At least one of alcohol, isooctanol, phenmethylol, benzyl carbinol.
7. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described magnesium compound is selected from MgCl2、MgBr2、MgI2, MgCl (OEt) and MgCl (OBu).
8. the preparation of the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to one of claim 1-7
Method, comprise the steps：
(1) magnesium compound is dispersed in hydro carbons atent solvent, obtains suspension；
(2) gallic acid-derivate, epoxide and alcohol compound with carbon-carbon double bond are added into suspension, 20
Homogeneous transparent solution is formed after~50 DEG C of reaction regular hours；
(3) radical initiator is added into the homogeneous transparent solution of step (2) at 20~50 DEG C, is analysed in slow temperature-rise period
Go out solids, after reacting the regular hour, remove unreacted reactant, and washed using inert diluent, obtain polymer-doped type
Carrier.
9. a kind of catalytic component for ethylene polymerization, it is characterised in that include the reaction product of following components：
(1) the polymer-doped type carrier used in the ethylene rolymerization catalyst described in one of claim 1-7；
(2) at least one formula is Ti (OR3)nX4-nTitanium compound, R in formula3For C1~C8Alkyl, X is halogen atom, 0≤n
≤3；
(3) at least one is by formula AlRa’XbHcShown organo-metallic compound, R ' is C in formula1~C14Alkyl, X is halogen
Element, a, b, c are 0~3 integer, and a+b+c=3；
(4) at least one electron donor compound, selected from fatty ester/aromatic ester, aliphatic ether/cycloaliphatic ether and aliphatic ketone；
In terms of every mole of magnesium in described polymer-doped type carrier, titanium compound is ratio between wherein each reactant
0.1~15.0 mole；Organo-metallic compound is 0.1~5.0 mole；Electron donor compound is 0.1~5.0 mole.
A kind of 10. catalytic component for ethylene polymerization according to claim 9, it is characterised in that particle diameter distribution
Span is less than or equal to 0.7.
A kind of 11. catalytic component for ethylene polymerization according to claim 9, it is characterised in that described titanium
Compound is selected from TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti
(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I。
12. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that described has
Machine metallic compound is selected from Al (CH3)3、Al(CH2CH3)3、Al(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlH(i-
Bu)2、AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、AlCl(CH2CH3)2、AlCl2(CH2CH3)。
13. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that described gives
Electron compound be selected from methyl formate, ethyl acetate, butyl acetate, acetic acid n-octyl, ethyl benzoate, butyl benzoate,
Ether, hexyl ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK).
14. a kind of preparation method of catalytic component for ethylene polymerization described in claim 9, it includes following step
Suddenly：
(1) described polymer-doped type support dispersion is obtained into suspension in hydro carbons atent solvent；
(2) suspension is subjected to haptoreaction in -40~50 DEG C and organo-aluminum compound and at least one electron donor compound；
(3) mixture of step (2) is to slowly warm up to 20~60 DEG C, after reacting the regular hour, removes unreacted reactant, and adopt
Washed with inert diluent；
(4) add titanium compound to be reacted, then washed using inert diluent, obtain the catalytic component.
15. a kind of catalyst for ethylene polymerization, it includes the reaction product of following components：
(1) catalytic component described in claim 9；
(2) formula is AlR "dX3-dOrgano-aluminum compound, the alkyl that R " is hydrogen or carbon number is l~20 in formula, X is that halogen is former
Son, 0<d≤3.
16. the catalyst according to claim 15 for ethylene polymerization, it is characterised in that aluminium and group in component (2)
The mol ratio for dividing titanium in (1) is 20~200.
17. the catalyst for ethylene polymerization described in claim 15 is in ethylene homo closes reaction or copolymerization
Application.
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