CN104558290B - One kind being used for catalyst component for olefin polymerization and catalyst - Google Patents
One kind being used for catalyst component for olefin polymerization and catalyst Download PDFInfo
- Publication number
- CN104558290B CN104558290B CN201310517877.3A CN201310517877A CN104558290B CN 104558290 B CN104558290 B CN 104558290B CN 201310517877 A CN201310517877 A CN 201310517877A CN 104558290 B CN104558290 B CN 104558290B
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- Prior art keywords
- malonic acid
- ester
- acid
- allyl
- malonate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 title claims description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 4
- -1 ether compound Chemical class 0.000 claims abstract description 146
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 25
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 24
- 239000002585 base Substances 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 13
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002681 magnesium compounds Chemical class 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 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 claims description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- TXQLXNVQGYCSHQ-UHFFFAOYSA-N 2,2-bis(2-methylpropyl)propanedioic acid Chemical compound CC(C)CC(C(O)=O)(C(O)=O)CC(C)C TXQLXNVQGYCSHQ-UHFFFAOYSA-N 0.000 claims description 6
- VSJZBUJCPNVRET-UHFFFAOYSA-N 2,2-bis(prop-2-enyl)propanedioic acid Chemical compound C=CCC(C(=O)O)(CC=C)C(O)=O VSJZBUJCPNVRET-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 claims description 6
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 claims description 6
- HCWOVPZEAFLXPL-UHFFFAOYSA-N diphenyl propanedioate Chemical compound C=1C=CC=CC=1OC(=O)CC(=O)OC1=CC=CC=C1 HCWOVPZEAFLXPL-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 6
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- CEVFCYUJPROJPK-UHFFFAOYSA-N 1,2-dimethoxy-9h-fluorene Chemical class C1=CC=C2C3=CC=C(OC)C(OC)=C3CC2=C1 CEVFCYUJPROJPK-UHFFFAOYSA-N 0.000 claims description 3
- XYVIKUTYMMOQFT-UHFFFAOYSA-N 2,2-ditert-butylpropanedioic acid Chemical compound CC(C)(C)C(C(O)=O)(C(O)=O)C(C)(C)C XYVIKUTYMMOQFT-UHFFFAOYSA-N 0.000 claims description 3
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical class COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 claims description 3
- LRBMAAAUWBHGGI-UHFFFAOYSA-N C(CCC)OC(C(C(=O)OCCCC)(CCC)CC1=CC=CC=C1)=O Chemical compound C(CCC)OC(C(C(=O)OCCCC)(CCC)CC1=CC=CC=C1)=O LRBMAAAUWBHGGI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- ZQGWBPQBZHMUFG-UHFFFAOYSA-N 1,1-dimethylthiourea Chemical compound CN(C)C(N)=S ZQGWBPQBZHMUFG-UHFFFAOYSA-N 0.000 claims description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 2
- WUHHVDQBQZVSJV-UHFFFAOYSA-N 2,2-dibutylpropanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CCCC WUHHVDQBQZVSJV-UHFFFAOYSA-N 0.000 claims description 2
- QULKBFUIGUDXJB-UHFFFAOYSA-N C(CCC)OC(C(C(=O)OCCCC)(CC)CC1=CC=CC=C1)=O Chemical compound C(CCC)OC(C(C(=O)OCCCC)(CC)CC1=CC=CC=C1)=O QULKBFUIGUDXJB-UHFFFAOYSA-N 0.000 claims description 2
- OJJDCYFKIUEABN-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)(C(CC)C1=CC=CC=C1)CC(C)C)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(C(CC)C1=CC=CC=C1)CC(C)C)=O OJJDCYFKIUEABN-UHFFFAOYSA-N 0.000 claims description 2
- CYVQEGQZKMKMHA-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)(C(CC)CC1=CC=CC=C1)CC(C)C)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(C(CC)CC1=CC=CC=C1)CC(C)C)=O CYVQEGQZKMKMHA-UHFFFAOYSA-N 0.000 claims description 2
- BQJJGFYFDORHQA-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)(C)C1=CC=CC=C1)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(C)C1=CC=CC=C1)=O BQJJGFYFDORHQA-UHFFFAOYSA-N 0.000 claims description 2
- IGSONJMPPWMFGH-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)(CC)CC1=CC=CC=C1)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(CC)CC1=CC=CC=C1)=O IGSONJMPPWMFGH-UHFFFAOYSA-N 0.000 claims description 2
- CZLLXUCSHXPRAA-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)(CCC)CC1=CC=CC=C1)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(CCC)CC1=CC=CC=C1)=O CZLLXUCSHXPRAA-UHFFFAOYSA-N 0.000 claims description 2
- CUJDBFPCBAYIGP-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)CCC(CC1=CC=CC=C1)CC1=CC=CC=C1)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)CCC(CC1=CC=CC=C1)CC1=CC=CC=C1)=O CUJDBFPCBAYIGP-UHFFFAOYSA-N 0.000 claims description 2
- UHIBDNISXLTJGZ-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(C(=O)O)(C(=O)O)C Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(C(=O)O)(C(=O)O)C UHIBDNISXLTJGZ-AFEZEDKISA-N 0.000 claims description 2
- HYGCPIUZIRFDAS-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(C(=O)O)(C(=O)O)CC Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(C(=O)O)(C(=O)O)CC HYGCPIUZIRFDAS-AFEZEDKISA-N 0.000 claims description 2
- UAAPPFGKXJAWCI-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(C(=O)O)(C(=O)O)CCCC Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(C(=O)O)(C(=O)O)CCCC UAAPPFGKXJAWCI-AFEZEDKISA-N 0.000 claims description 2
- AFRBHCJXQQTOJC-LATCQUSVSA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(CC)C(C(=O)O)(C(=O)O)CC(C)C Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(CC)C(C(=O)O)(C(=O)O)CC(C)C AFRBHCJXQQTOJC-LATCQUSVSA-N 0.000 claims description 2
- OVFUIIQQCUTSPK-LATCQUSVSA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(CCC(C(=O)O)C(=O)O)CC1=CC=CC=C1 Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(C1=CC=CC=C1)C(CCC(C(=O)O)C(=O)O)CC1=CC=CC=C1 OVFUIIQQCUTSPK-LATCQUSVSA-N 0.000 claims description 2
- XYBJGHHGXBFQLP-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(CC)C(C(=O)O)C(=O)O Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(CC)C(C(=O)O)C(=O)O XYBJGHHGXBFQLP-AFEZEDKISA-N 0.000 claims description 2
- SELUUDDBMOXFLN-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(CCCC)C(C(=O)O)C(=O)O Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C(CCCC)C(C(=O)O)C(=O)O SELUUDDBMOXFLN-AFEZEDKISA-N 0.000 claims description 2
- MJLYVPQXAZVDDA-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)C Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)C MJLYVPQXAZVDDA-AFEZEDKISA-N 0.000 claims description 2
- LQRWRHPGRQOVTN-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)CCC Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)CCC LQRWRHPGRQOVTN-AFEZEDKISA-N 0.000 claims description 2
- KRELVVKUJPNJMR-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)CCC(C)C Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)CCC(C)C KRELVVKUJPNJMR-AFEZEDKISA-N 0.000 claims description 2
- GOKZZIDLOZDTDI-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)CCCC Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(C(=O)O)(C(=O)O)CCCC GOKZZIDLOZDTDI-AFEZEDKISA-N 0.000 claims description 2
- NSCCDGRTYUWFTN-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(CC)C(C(=O)O)(C(=O)O)CC(C)C Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)C(CC)C(C(=O)O)(C(=O)O)CC(C)C NSCCDGRTYUWFTN-AFEZEDKISA-N 0.000 claims description 2
- UBCDTCQXJPJYIW-AFEZEDKISA-N C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)CCC(C(=O)O)C(=O)O Chemical compound C(\C=C/C(=O)OC1CCCCC1)(=O)OC1CCCCC1.C1(=CC=CC=C1)CCC(C(=O)O)C(=O)O UBCDTCQXJPJYIW-AFEZEDKISA-N 0.000 claims description 2
- GIPXWTAMSNMNTD-UHFFFAOYSA-N C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)(C(CC)C1=CC=CC=C1)CC(C)C)=O Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)(C(CC)C1=CC=CC=C1)CC(C)C)=O GIPXWTAMSNMNTD-UHFFFAOYSA-N 0.000 claims description 2
- HTOLTLAHFREEHB-UHFFFAOYSA-N C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)(CCC)CC1=CC=CC=C1)=O Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)(CCC)CC1=CC=CC=C1)=O HTOLTLAHFREEHB-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- DABZTDVEFNLKNI-UHFFFAOYSA-N dibutyl 2-(3-methylbutyl)-2-phenylpropanedioate Chemical compound C1(=CC=CC=C1)C(C(=O)OCCCC)(C(=O)OCCCC)CCC(C)C DABZTDVEFNLKNI-UHFFFAOYSA-N 0.000 claims description 2
- RPZZSLWYUCDWTM-UHFFFAOYSA-N dibutyl 2-benzyl-2-(3-methylbutyl)propanedioate Chemical compound C(C1=CC=CC=C1)C(C(=O)OCCCC)(C(=O)OCCCC)CCC(C)C RPZZSLWYUCDWTM-UHFFFAOYSA-N 0.000 claims description 2
- CSNVNIWORHRRQE-UHFFFAOYSA-N dibutyl 2-butyl-2-phenylpropanedioate Chemical compound C(CCC)OC(C(C(=O)OCCCC)(CCCC)C1=CC=CC=C1)=O CSNVNIWORHRRQE-UHFFFAOYSA-N 0.000 claims description 2
- VBPRCPAJVAYMNK-UHFFFAOYSA-N dibutyl 2-propylpropanedioate Chemical compound CCCCOC(=O)C(CCC)C(=O)OCCCC VBPRCPAJVAYMNK-UHFFFAOYSA-N 0.000 claims description 2
- NNDOHYGFLASMFR-UHFFFAOYSA-N diethyl 2,2-dipropylpropanedioate Chemical compound CCOC(=O)C(CCC)(CCC)C(=O)OCC NNDOHYGFLASMFR-UHFFFAOYSA-N 0.000 claims description 2
- KEVMYFLMMDUPJE-UHFFFAOYSA-N diisoamyl Natural products CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 claims description 2
- OMHLNQQIHHOYAA-UHFFFAOYSA-N dipentyl 2,2-bis(2-methylpropyl)propanedioate Chemical compound C(C(C)C)C(C(=O)OCCCCC)(C(=O)OCCCCC)CC(C)C OMHLNQQIHHOYAA-UHFFFAOYSA-N 0.000 claims description 2
- NRZAIDWIZMOUEB-UHFFFAOYSA-N dipentyl 2,2-dibutylpropanedioate Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(CCCC)CCCC)=O NRZAIDWIZMOUEB-UHFFFAOYSA-N 0.000 claims description 2
- DIHXOZRZEVZLPW-UHFFFAOYSA-N dipentyl 2-(2-phenylethyl)propanedioate Chemical compound C1(=CC=CC=C1)CCC(C(=O)OCCCCC)C(=O)OCCCCC DIHXOZRZEVZLPW-UHFFFAOYSA-N 0.000 claims description 2
- NAGRUIOJVSNUID-UHFFFAOYSA-N dipentyl 2-benzyl-2-(3-methylbutyl)propanedioate Chemical compound C(C1=CC=CC=C1)C(C(=O)OCCCCC)(C(=O)OCCCCC)CCC(C)C NAGRUIOJVSNUID-UHFFFAOYSA-N 0.000 claims description 2
- LCAIHFBVDINVCU-UHFFFAOYSA-N dipentyl 2-benzyl-2-butylpropanedioate Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(CCCC)CC1=CC=CC=C1)=O LCAIHFBVDINVCU-UHFFFAOYSA-N 0.000 claims description 2
- JNTHFLZGCZMRIX-UHFFFAOYSA-N dipentyl 2-butyl-2-phenylpropanedioate Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(CCCC)C1=CC=CC=C1)=O JNTHFLZGCZMRIX-UHFFFAOYSA-N 0.000 claims description 2
- LICKCMZDZFKULR-UHFFFAOYSA-N diphenyl 2-(3-methylbutyl)-2-phenylpropanedioate Chemical compound C1(=CC=CC=C1)C(C(=O)OC1=CC=CC=C1)(C(=O)OC1=CC=CC=C1)CCC(C)C LICKCMZDZFKULR-UHFFFAOYSA-N 0.000 claims description 2
- GXRGGYXJFCGARC-UHFFFAOYSA-N diphenyl 2-benzyl-2-(3-methylbutyl)propanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)(CCC(C)C)CC1=CC=CC=C1)=O GXRGGYXJFCGARC-UHFFFAOYSA-N 0.000 claims description 2
- ARHQKMNSBIKZIQ-UHFFFAOYSA-N diphenyl 2-benzyl-2-butylpropanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)(CCCC)CC1=CC=CC=C1)=O ARHQKMNSBIKZIQ-UHFFFAOYSA-N 0.000 claims description 2
- OVJUSGRMZROGQZ-UHFFFAOYSA-N diphenyl 2-butyl-2-phenylpropanedioate Chemical compound C1(=CC=CC=C1)OC(C(C(=O)OC1=CC=CC=C1)(CCCC)C1=CC=CC=C1)=O OVJUSGRMZROGQZ-UHFFFAOYSA-N 0.000 claims description 2
- BQZPGJGXBDIJQU-UHFFFAOYSA-N diphenyl 2-pentylpropanedioate Chemical compound CCCCCC(C(=O)OC1=CC=CC=C1)C(=O)OC1=CC=CC=C1 BQZPGJGXBDIJQU-UHFFFAOYSA-N 0.000 claims description 2
- LWIWFCDNJNZEKB-UHFFFAOYSA-N dipropyl propanedioate Chemical compound CCCOC(=O)CC(=O)OCCC LWIWFCDNJNZEKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical group 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 5
- IUZIGXNXWJEZLU-UHFFFAOYSA-N 2-(2-phenylethyl)propanedioic acid Chemical compound OC(=O)C(C(O)=O)CCC1=CC=CC=C1 IUZIGXNXWJEZLU-UHFFFAOYSA-N 0.000 claims 2
- IJBYVSUZCRXTOD-UHFFFAOYSA-N 1-methoxy-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(OC)=CC=C2 IJBYVSUZCRXTOD-UHFFFAOYSA-N 0.000 claims 1
- PLSDKHHKHVHECX-UHFFFAOYSA-N 2-(3-methylbutyl)-2-phenylpropanedioic acid Chemical compound CC(C)CCC(C(O)=O)(C(O)=O)c1ccccc1 PLSDKHHKHVHECX-UHFFFAOYSA-N 0.000 claims 1
- JAEJSNFTJMYIEF-UHFFFAOYSA-N 2-benzylpropanedioic acid Chemical compound OC(=O)C(C(O)=O)CC1=CC=CC=C1 JAEJSNFTJMYIEF-UHFFFAOYSA-N 0.000 claims 1
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 claims 1
- OBOGEABBZDRUAH-UHFFFAOYSA-N 2-phenyl-2-propylpropanedioic acid Chemical compound CCCC(C(O)=O)(C(O)=O)C1=CC=CC=C1 OBOGEABBZDRUAH-UHFFFAOYSA-N 0.000 claims 1
- UBYVXDJCOMOOEW-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)(C)CC1=CC=CC=C1)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(C)CC1=CC=CC=C1)=O UBYVXDJCOMOOEW-UHFFFAOYSA-N 0.000 claims 1
- XEDLKJDTRKDHMS-UHFFFAOYSA-N C(CCCC)OC(C(C(=O)OCCCCC)(CCC)C1=CC=CC=C1)=O Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(CCC)C1=CC=CC=C1)=O XEDLKJDTRKDHMS-UHFFFAOYSA-N 0.000 claims 1
- YNRBOJHRLRNFKI-UHFFFAOYSA-N dibutyl 2-butylpropanedioate Chemical compound CCCCOC(=O)C(CCCC)C(=O)OCCCC YNRBOJHRLRNFKI-UHFFFAOYSA-N 0.000 claims 1
- FRNBHFRKFCEDGF-UHFFFAOYSA-N dipentyl 2,2-ditert-butylpropanedioate Chemical compound C(CCCC)OC(C(C(=O)OCCCCC)(C(C)(C)C)C(C)(C)C)=O FRNBHFRKFCEDGF-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000003701 inert diluent Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 150000002903 organophosphorus compounds Chemical class 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002220 fluorenes Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QWJUMUXQFFWLIF-UHFFFAOYSA-N 9,9-dimethoxyfluorene Chemical class C1=CC=C2C(OC)(OC)C3=CC=CC=C3C2=C1 QWJUMUXQFFWLIF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- CADAOKXOWMHTKV-UHFFFAOYSA-N C(C)O[Ti](OCC)OCC.[Cl] Chemical compound C(C)O[Ti](OCC)OCC.[Cl] CADAOKXOWMHTKV-UHFFFAOYSA-N 0.000 description 1
- NCYAFNKCFNOBFE-UHFFFAOYSA-N C(CCC)OC(C(C(=O)OCCCC)(C(CC)C1=CC=CC=C1)CC(C)C)=O Chemical compound C(CCC)OC(C(C(=O)OCCCC)(C(CC)C1=CC=CC=C1)CC(C)C)=O NCYAFNKCFNOBFE-UHFFFAOYSA-N 0.000 description 1
- AONUCNMULTTWEN-UHFFFAOYSA-N CCCC(C(OCCC)=O)(C(OCCC)=O)C1=CC=CC=C1 Chemical compound CCCC(C(OCCC)=O)(C(OCCC)=O)C1=CC=CC=C1 AONUCNMULTTWEN-UHFFFAOYSA-N 0.000 description 1
- DKRKZMALPHCUAW-UHFFFAOYSA-N CCCC(CC)(CCC)C(C(OCCC)=O)C(OCCC)=O Chemical compound CCCC(CC)(CCC)C(C(OCCC)=O)C(OCCC)=O DKRKZMALPHCUAW-UHFFFAOYSA-N 0.000 description 1
- WLYTZLXPEKFWIE-UHFFFAOYSA-N CCCOC(C(C)(CC1=CC=CC=C1)C(OCCC)=O)=O Chemical compound CCCOC(C(C)(CC1=CC=CC=C1)C(OCCC)=O)=O WLYTZLXPEKFWIE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000004067 aliphatic alkene group Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical class [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- VQAZCUCWHIIFGE-UHFFFAOYSA-N diethyl 2-ethylpropanedioate Chemical compound CCOC(=O)C(CC)C(=O)OCC VQAZCUCWHIIFGE-UHFFFAOYSA-N 0.000 description 1
- GRRSDGHTSMJICM-UHFFFAOYSA-N diethyl 2-propylpropanedioate Chemical compound CCOC(=O)C(CCC)C(=O)OCC GRRSDGHTSMJICM-UHFFFAOYSA-N 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- DETXDPJFXPJEEG-UHFFFAOYSA-N dipentyl 2-(3-methylbutyl)-2-phenylpropanedioate Chemical compound C1(=CC=CC=C1)C(C(=O)OCCCCC)(C(=O)OCCCCC)CCC(C)C DETXDPJFXPJEEG-UHFFFAOYSA-N 0.000 description 1
- MQISHJOYCCHABB-UHFFFAOYSA-N dipentyl 2-butylpropanedioate Chemical group C(CCCC)OC(C(C(=O)OCCCCC)CCCC)=O MQISHJOYCCHABB-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A kind of catalytic component for olefinic polymerization, it includes magnesium, titanium, halogen and Lewis alkali cpds, the Lewis alkali cpds include general formula（Ⅰ）Compound represented and compound selected from ether compound, benzoate compounds and phthalate compound；
Description
Technical field
It is specific a kind of for the catalytic component of olefinic polymerization and comprising described the present invention relates to a kind of field of olefin polymerisation
The catalyst of catalytic component.
Background technology
Ziegler-Natter catalyst is usually made of magnesium, titanium, halogen and Lewis alkali etc., and wherein Lewis alkali is to contain
Some organic compounds of oxygen, nitrogen, phosphorus, silicon etc..The Nomenclature Composition and Structure of Complexes of Lewis alkali is bigger on the influence of the performance of catalyst, together
A kind of feed postition that Lewis alkali is different is also obvious on the influence of the performance of catalyst.Currently, have document disclose it is special
Structure malonic acid ester type compound is as Lewis alkali, but the activity of catalyst and isotacticity be not high, poor practicability.In addition,
Special 1, the 3- bis- of ether group containing there are two is used in the catalytic component of olefinic polyreaction, there is document to disclose
Ether compound is as Lewis alkali, such as 9,9- bis-（Methoxy）Fluorenes etc. has higher poly- when for propylene polymerization
Activity and stereoselectivity are closed, but molecular weight distribution is narrow, poor processability, limits its application.
Invention content
For deficiency in the prior art, the catalytic component that the present invention provides a kind of for olefinic polymerization, preparation side
Method and catalyst, the catalyst that the component obtains are used for olefinic polymerization, and there is higher catalytic activity, the polymer to have
Higher isotacticity, melt index and wider molecular weight distribution.
According to an aspect of the invention, there is provided a kind of catalytic component for olefinic polymerization, it includes magnesium, titanium,
Halogen and Lewis alkali cpds, the Lewis alkali cpds include general formula（Ⅰ）Compound represented and selected from ether compound,
The compound of benzoate compounds and phthalate compound；
Wherein, R1And R2It is identical or different, it is selected from C1-C20Substituted or unsubstituted straight chained alkyl, branched alkyl, cycloalkanes
Base, aryl, alkaryl, aralkyl, alkylene and fused ring aryl；R3And R4It is identical or different, it is selected from hydrogen and C1-C20Substitution or
Unsubstituted straight chained alkyl, branched alkyl, naphthenic base, aryl, alkaryl, aralkyl, alkylene and fused ring aryl, R3And R4It can
It is optionally bonded cyclic or not cyclic.
Catalytic component according to the present invention, the Lewis alkali cpds include general formula（Ⅰ）Compound represented and
General formula（Ⅱ）Shown in diether compound,
Wherein, RI、RII、RIII、RIV、RVAnd RVIIt is identical or different, it is hydrogen or C1-C18Hydrocarbyl group, and RVIIAnd RVIII
It is identical or different, it is C1-C18Hydrocarbyl group；RI~RVIIIThe optionally bonded cyclization of one or more of group or not at
Ring.
According to the present invention, the substituted straight chained alkyl, branched alkyl, naphthenic base, aryl, alkaryl, aralkyl or alkene
Alkyl, as straight chained alkyl, branched alkyl, naphthenic base, aryl, alkaryl, aralkyl or alkylene carbon or hydrogen atom optionally
Replaced by one or several hetero atoms, the hetero atom is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom.In the present invention, R3And R4
When bonded cyclization, double bond or hetero atom can also be contained in ring.
In the catalytic component of the present invention, it is preferable that the R1And R2Selected from C1-C10Substituted or unsubstituted straight chain
Alkyl, branched alkyl, naphthenic base, aryl, alkaryl, aralkyl and alkylene.
In the catalytic component of the present invention, the general formula（Ⅰ）Compound represented and general formula（Ⅱ）Compound represented
Molar ratio be 1:50-50:1, preferably 1:20-20:1, more preferably 1:10-10:1, it is even more preferably 1:5-5:1.
In the catalytic component of the present invention, the general formula（Ⅰ）Compound represented can be selected from but be not limited only to：Two isobutyls
Propylmalonic acid diethylester, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate；Diisobutyl malonic acid dipropyl
Ester, di-n-butyl dipropyl malonate, di-t-butyl dipropyl malonate, diisobutyl dibutyl malonate, di-n-butyl third
Adipate, di-t-butyl dibutyl malonate, diisobutyl malonic acid diamyl ester, di-n-butyl malonic acid diamyl ester, two
Tertiary butyl malonic acid diamyl ester, diisobutyl malonic acid dihexyl, di-n-butyl malonic acid dihexyl, di-t-butyl malonic acid two
Own ester, two heptyl ester of diisobutyl malonic acid, two heptyl ester of di-n-butyl malonic acid, two heptyl ester of di-t-butyl malonic acid, dipropyl third
Dipropyl malona-te, diisoamyl dipropyl malonate, two n-amyl malonic acid dipropyls, dihexyl dipropyl malonate, two are just
Amyl malonic acid dipropyl, phenylethyl dipropyl malonate, phenyl methyl dipropyl malonate, phenyl propyl malonic acid dipropyl
Ester, phenyl n-butylmalonic acid dipropyl, phenyl isobutyl propylmalonic acid dipropyl, phenyl isoamyl-malonic acid dipropyl, phenyl
N-amyl malonic acid dipropyl, diphenylprop dipropyl malona-te, benzyl ethyl malonic acid dipropyl, benzyl methyl malonic acid dipropyl
Ester, benzyl propylmalonic acid dipropyl, benzyl n-butylmalonic acid dipropyl, benzyl isobutyl group dipropyl malonate, benzyl are different
Amyl malonic acid dipropyl, benzyl n-amyl malonic acid dipropyl, dibenzyl dipropyl malonate, two fourth of phenylethyl malonic acid
Ester, phenyl methyl dibutyl malonate, phenyl propyl dibutyl malonate, phenyl n-butylmalonic acid dibutyl ester, phenyl isobutyl
Propylmalonic acid dibutyl ester, phenyl isoamyl-malonic acid dibutyl ester, phenyl n-amyl malonic acid dibutyl ester, two fourth of diphenylprop diacid
Ester, benzyl ethyl malonic acid dibutyl ester, benzyl methyl dibutyl malonate, benzyl propylmalonic acid dibutyl ester, benzyl normal-butyl
Dibutyl malonate, benzyl isobutyl group dibutyl malonate, benzyl isoamyl-malonic acid dibutyl ester, benzyl n-amyl malonic acid two
Butyl ester, dibenzyl dibutyl malonate, phenylethyl malonic acid diamyl ester, phenyl methyl malonic acid diamyl ester, phenyl propyl third
Diacid diamyl ester, phenyl n-butylmalonic acid diamyl ester, phenyl isobutyl propylmalonic acid diamyl ester, phenyl isoamyl-malonic acid diamyl
Ester, phenyl n-amyl malonic acid diamyl ester, diphenylprop diacid diamyl ester, benzyl ethyl malonic acid diamyl ester, benzyl methyl third
Diacid diamyl ester, benzyl propylmalonic acid diamyl ester, benzyl n-butylmalonic acid diamyl ester, benzyl isobutyl propylmalonic acid diamyl
Ester, benzyl isoamyl-malonic acid diamyl ester, benzyl n-amyl malonic acid diamyl ester, dibenzyl propylmalonic acid diamyl ester, phenylethyl
Malonic acid dicyclohexyl maleate, phenyl methyl malonic acid dicyclohexyl maleate, phenyl propyl malonic acid dicyclohexyl maleate, phenyl n-butylmalonic acid
Dicyclohexyl maleate, phenyl isobutyl propylmalonic acid dicyclohexyl maleate, phenyl isoamyl-malonic acid dicyclohexyl maleate, phenyl n-amyl malonic acid two
Cyclohexyl, diphenylprop dicyclohexyl sulfosuccinnate ester, benzyl ethyl malonic acid dicyclohexyl maleate, benzyl methyl malonic acid dicyclohexyl maleate, benzyl
Base propylmalonic acid dicyclohexyl maleate, benzyl n-butylmalonic acid dicyclohexyl maleate, benzyl isobutyl propylmalonic acid dicyclohexyl maleate, benzyl are different
Amyl malonic acid dicyclohexyl maleate, benzyl n-amyl malonic acid dicyclohexyl maleate, dibenzyl propylmalonic acid dicyclohexyl maleate, phenyl methyl the third two
Diphenyl phthalate, phenyl propyl diphenyl malonate, phenyl n-butylmalonic acid diphenyl ester, phenyl isobutyl propylmalonic acid diphenyl ester,
Phenyl isoamyl-malonic acid diphenyl ester, phenyl n-amyl malonic acid diphenyl ester, diphenyl diphenyl malonate, benzyl ethyl the third two
Diphenyl phthalate, benzyl methyl diphenyl malonate, benzyl propylmalonic acid diphenyl ester, benzyl n-butylmalonic acid diphenyl ester, benzyl
Base isobutyl group diphenyl malonate, benzyl isoamyl-malonic acid diphenyl ester, benzyl n-amyl malonic acid diphenyl ester, dibenzyl the third two
Diphenyl phthalate, fluorenyl methyl malonic acid dicyclohexyl maleate, fluorenyl propylmalonic acid dicyclohexyl maleate, two hexamethylene of fluorenyl n-butylmalonic acid
Ester, fluorenyl isobutyl propylmalonic acid dicyclohexyl maleate, fluorenyl isoamyl-malonic acid dicyclohexyl maleate, two hexamethylene of fluorenyl n-amyl malonic acid
Ester, two fluorenyl malonic acid dicyclohexyl maleates, allyl methyl diphenyl malonate, allyl propylmalonic acid diphenyl ester, allyl
N-butylmalonic acid diphenyl ester, allyl isobutyl group diphenyl malonate, allyl isoamyl-malonic acid diphenyl ester, allyl are just
Amyl malonic acid diphenyl ester, diallyl diphenyl malonate, allyl methyl dimethyl malenate, allyl propylmalonic acid
Dimethyl ester, allyl n-butylmalonic acid dimethyl ester, allyl isobutyl group dimethyl malenate, allyl isoamyl-malonic acid two
Methyl esters, allyl n-amyl malonic acid dimethyl ester, diallyl dimethyl malenate, allyl methyl diethyl malonate, alkene
Propyl propylmalonic acid diethylester, allyl diethyl butylmalonate, allyl iso-butyl diethyl malonate, allyl
Isoamyl-malonic acid diethylester, allyl n-amyl malonic acid diethylester, diallyl diethyl malonate, allyl methyl third
Dipropyl malona-te, allyl propylmalonic acid dipropyl, allyl n-butylmalonic acid dipropyl, allyl isobutyl propylmalonic acid
Dipropyl, allyl isoamyl-malonic acid dipropyl, allyl n-amyl malonic acid dipropyl, diallyl malonic acid dipropyl
Ester, allyl methyl dibutyl malonate, allyl propylmalonic acid dibutyl ester, allyl n-butylmalonic acid dibutyl ester, alkene
Propyl isobutyl group dibutyl malonate, allyl isoamyl-malonic acid dibutyl ester, allyl n-amyl malonic acid dibutyl ester, diene
Propylmalonic acid dibutyl ester, allyl methyl malonic acid diamyl ester, allyl propylmalonic acid diamyl ester, allyl normal-butyl third
Diacid diamyl ester, allyl isobutyl propylmalonic acid diamyl ester, allyl isoamyl-malonic acid diamyl ester, allyl n-pentyl the third two
Sour diamyl ester, diallyl malonic acid diamyl ester, allyl methyl malonic acid dicyclohexyl maleate, two hexamethylene of allyl propylmalonic acid
Ester, allyl n-butylmalonic acid dicyclohexyl maleate, allyl isobutyl propylmalonic acid dicyclohexyl maleate, allyl isoamyl-malonic acid two
Cyclohexyl, allyl n-amyl malonic acid dicyclohexyl maleate and diallyl malonic acid dicyclohexyl maleate, are preferably selected from diisobutyl third
Diethyl adipate, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate；Diisobutyl dipropyl malonate, two
N-butylmalonic acid dipropyl, di-t-butyl dipropyl malonate, diethyl benzyl malonate, benzyl malonic acid dipropyl, benzene
Base ethyl malonic acid diethylester, phenylethyl dipropyl malonate, dipropyl diethyl malonate, dipropyl propylmalonic acid dipropyl
Ester, diallyl diethyl malonate and diallyl dipropyl malonate.
In the catalytic component of the present invention, the general formula（Ⅱ）Shown in diether compound be selected from 9,9- it is bis-（Methoxy
Ylmethyl）Fluorenes, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2,2- diisobutyls -1,3- dimethoxy propane and
9,9- bis-（Methoxy）Fluorenes, 1,2- phenylenes dibenzoate and 2- isopropyl -2- cyclopenta -1,3- dimethoxy third
Alkane.
In the catalytic component of the present invention, in the catalytic component, in the catalytic component, the content of magnesium is
The content of 10-30wt%, titanium are 1-5wt%, general formula（Ⅰ）The content of compound represented is 1-20wt%, general formula（Ⅱ）Shown in two
The content of ether compound is 1-20wt%.
According to another aspect of the present invention, a kind of method preparing above-mentioned catalytic component is provided, including following
Step：
1）Magnesium compound is dissolved in containing general formula（Ⅰ）In the system of compound represented, precipitation agent is added, solid is precipitated
Object；
2）With titanium compound processing step 1）The solids of precipitation, with titanium compound handle solids during and/
Or general formula is added before processing（Ⅱ）Compound represented.
Wherein step 1）In " magnesium compound is dissolved in containing general formula（Ⅰ）In the system of compound represented " comprising first by magnesium
Compound is dissolved in dicyandiamide solution and obtains solution, adds general formula（Ⅰ）Compound represented；Also include by magnesium compound be dissolved in containing
General formula（Ⅰ）In the system that compound represented and dicyandiamide solution collectively constitute.
In the above-mentioned methods, the precipitation agent such as can be selected from metal halide, such as halogenated titanium, iron halide, zinc halide.Its
In, preferably halogenated titanium, such as titanium tetrachloride or titanium tetrabromide；More preferable titanium tetrachloride.
In the present invention, the magnesium compound is selected from magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and dihalide
The derivative that one of halogen atom is replaced by oxyl or halogenated oxyl in magnesium molecular formula；Preferably magnesium dihalide or two
The alcohol adduct of magnesium halide, such as magnesium dichloride, dibrominated magnesium, magnesium diiodide and their alcohol adduct.
In the present invention, it is TiXm (OR that general formula, which can be selected, in the titanium compound1) 4-m compound, R in formula1For C1-C20
Alkyl, X is halogen, m=1~4.Such as：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide,
One chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine, preferably titanium tetrachloride.
It may be selected to prepare the present invention's by following methods（Solid）Catalytic component, but catalysis according to the present invention
The preparation method of agent is without being limited thereto.
First, magnesium compound is dissolved in and is made of organic epoxy compound object, organic phosphorus compound and inert diluent
In dicyandiamide solution, after forming homogeneous solution, in special construction precipitation additive, i.e., above-mentioned general formula（Ⅰ）In the presence of compound, with titanizing
Object mixing is closed, solids is precipitated in heating；This solids is handled using electron donor compound, makes its appendix in solids
On, when necessary, then with titanium tetrahalide or titanium tetrahalide and inert diluent solids is handled.
Above-mentioned organic epoxy compound object, organic phosphorus compound etc. are disclosed in Chinese patent CN85100997, related
Content is incorporated herein by reference.
It is emphasized that magnesium compound, may be dissolved in the dicyandiamide solution containing organic epoxide and organic phosphorus compound
In.Wherein organic epoxy compound object include carbon atom number in 2~8 aliphatic olefin, alkadienes or halogenated aliphatic alkene or
At least one of oxide, glycidol ether and inner ether of alkadienes.Particular compound is such as：Ethylene oxide, propylene oxide, ring
Oxygen butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, four
Hydrogen furans.
Wherein organic phosphorus compound includes the hydrocarbyl carbonate or halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid, specifically such as：Orthophosphoric acid
Trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, triethyl phosphite, phosphorous
Sour tributyl, phosphorous triphenyl phosphate methyl esters.
According to another method, magnesium compound is mixed with organic alcohol compound and atent solvent, rising temperature for dissolving is at uniform
Solution, in above-mentioned general formula（Ⅰ）It in the presence of compound, mixes, heats up with titanium compound, solids is precipitated, this solids uses
To general formula（Ⅱ）Shown in diether compound handled, make its appendix on solids, when necessary, then with titanium tetrahalide or
Titanium tetrahalide and inert diluent handle solids.
Specifically list several methods for preparing catalyst below, rather than by the system of catalyst according to the present invention
It is standby to be defined in this.
It prepares according to the method disclosed in patent CN85100997, first, magnesium compound is dissolved in by organic epoxidation
In the dicyandiamide solution for closing object, organic phosphorus compound and inert diluent composition, mixed with titanium compound after forming homogeneous solution,
Special construction precipitation additive, that is, above-mentioned general formula（Ⅰ）In the presence of compound, at -40~50 DEG C, preferably at -35~0 DEG C, titanizing is closed
Object instills above-mentioned magnesium halide solution, then reaction mixture is warming up to 60~80 DEG C, and general formula is added（Ⅱ）Shown in two ethers
Object is closed, suspension is stirred at this temperature 0~3 hour, mother liquor is filtered off, solids is obtained after inert diluent washs, then
It is handled 1~5 time at a temperature of 60~130 DEG C with the halide of titanium and the mixture of inert diluent, is washed with inert diluent
Solids obtains solid catalyst after dry.In terms of every mole of magnesium, the dosage of organic epoxy compound object is 0.2~10 mole；Have
The dosage of machine phosphorus compound is 0.1~3 mole；Above-mentioned general formula（Ⅰ）0.001~30 mole of the dosage of compound, preferably 0.05~
15 moles；3~40 moles of titanium compound, preferably 5~30 moles；General formula（Ⅱ）Shown in the dosage of diether compound be
0.005~15, preferably 0.05~5 mole.
According to another aspect of the present invention, a kind of catalyst for olefinic polyreaction is provided, it includes under
State the reaction product of component：
A. above-mentioned catalytic component；
B. alkyl aluminum compound；
C. optionally, external electron donor component.
In above-mentioned catalyst system, the general formula of the alkyl aluminum compound is AlRnX3-n, R is hydrogen or C in formula1-C20Hydrocarbon
Base, X are halogen, 0 n≤3 <.Specifically it can be selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminums, triisobutyl aluminium, three n-octyls
Aluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter second
Base aluminium chloride, ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.
" optionally, the external electron donor component " means as needed, and selection adds or be not added with external electron donor chemical combination
Object.For need stereoregularity very high olefin polymer in application, 3 need to be added）External donor compound, such as general formula
(R2)kSi(OR3)4-kShown in organo-silicon compound, 0≤k≤3, R in formula2Selected from halogen, hydrogen atom and C1-C20Alkyl, ring
Alkyl, aryl, halogenated alkyl or amino, R3For C1-C20Alkyl, naphthenic base, aryl, halogenated alkyl or amino.Such as：Front three
Methoxylsilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diphenyl two
Methoxy silane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyl trimethoxy
Base silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane, preferably cyclohexyl methyl dimethoxy silicon
Alkane, dimethoxydiphenylsilane.
In above-mentioned catalyst system, the component 1）With component 2）Molar ratio with titanium:Aluminium is calculated as 1:(5-1000), it is excellent
Select 1：(25-100)；The component 3）With component 1）Molar ratio with external electron donor：Titanium is calculated as 0-500:1, preferably 25-100:
1.When component 3）When external electron donor is above-mentioned organo-silicon compound, then the component 3）With component 1）Molar ratio with silicon：
Titanium is calculated as 0-500:1, preferably 25-100:1
According to another aspect of the present invention, a kind of Prepolymerized catalyst system for olefinic polymerization, institute are provided
It includes that a kind of above-mentioned catalytic component or above-mentioned catalyst system are carried out with alkene obtained by prepolymerization to state pre-polymerized catalyst
Prepolymer, pre-polymerization multiple be 0.1~1000g olefin polymers/g ingredients of solid catalyst.
In the present invention, it is preferred to which pre-polymerization multiple is about 0.2~500g polymer/g ingredients of solid catalyst.Prepolymerization
Process can in a liquid or in gas phase be carried out at a temperature of -20 to 80 DEG C, preferably 0~50 DEG C.Prepolymerized step can
To be carried out as the part in continuous polymerization technique is online, or independently carried out in intermittently operated.
According to another aspect of the present invention, a kind of method for olefinic polymerization is provided, the alkene is above-mentioned to urge
It is polymerize in the presence of agent component, above-mentioned catalyst system or the Prepolymerized catalyst system.
The catalyst of the present invention can be directly added into reactor in polymerization process or catalyst can be added
Prepolymerization is carried out before first polymer reactor and obtains pre-polymerized catalyst, and alkene carries out in the presence of pre-polymerized catalyst
Subsequent polymerisation.
In the present invention, the general formula of the preferably described alkene is CH2=CHR, R are hydrogen or C1-C12Alkyl or aryl group, more
It is preferred that the alkene is ethylene or propylene.
The olefinic polyreaction of the present invention is carried out according to well known polymerization, can be carried out in liquid phase or gas phase, or
Person can also carry out under the operation that liquid and gas polymerization stage combines.Using conventional technique such as slurry process, gas phase fluidization
Bed etc., wherein alkene be selected from ethylene, propylene, 1- butylene, 4-methyl-1-pentene and 1- hexenes, the homopolymerization of special propylene with or
The combined polymerization of other alkene of propylene.Preferably it is to use following reaction condition：0~150 DEG C of polymerization temperature, preferably 60~90 DEG C.
Polymerization pressure is 0.01~10MPa.
According to the present invention, in the preparation process of catalytic component, general formula is added（Ⅰ）Compound represented and general formula（Ⅱ）
Shown in diether compound, the good fluidity of the catalyst of gained, particle shape is good, even particle size distribution, the catalysis of gained
The high comprehensive performance of agent.When the catalyst is used for olefinic polymerization, especially propylene polymerization, there is higher activity, obtain
Polymer stereoregularity is high, molecular weight distribution that melt index is good and wider.
Specific implementation mode
Example given below is in order to further illustrate the present invention, rather than to carry out any limitation to the present invention.
Test method
Polymer isotactic index II：It is measured using heptane extraction process（Heptane boiling extracting 6 hours）：2 grams of dry polymerizations
Object sample is placed in extractor after being extracted 6 hours with boiling heptane, residue is dried to the polymer weight obtained by constant weight
（g）Ratio with 2 is isotactic index.
Melt index MI：Using fusion index instrument under 230 DEG C, 2.16kg pressure, according to ASTM D1238-99《With squeeze
Compactibility meter measures the standard test method of thermoplasticity fusing flow rate》It measures.
Polymer molecular weight and molecular weight distribution：It is oozed using Waters companies Waters Alliance GPC2000 gels
Saturating chromatograph measures, and 1,2,4- trichloro-benzenes is solvent, and styrene is standard specimen.
Embodiment 1
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4mL, tributyl phosphate 12.5mL are warming up to 50 DEG C, and maintain 2.5h under stirring, solid is completely dissolved, and diisobutyl is added
Diethyl malonate 10mmol, continues to 1h.Solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1h4Drop in 56mL, 1h
Add TiCl456mL drips and is at the uniform velocity warming up to 80 DEG C, solids is gradually precipitated in temperature-rise period, is added to the solids
6mmol9,9- are bis-（Methoxy）Fluorenes maintains temperature 1h, after filtering, is washed twice, obtained solid with toluene 70mL respectively
Sediment.Then toluene 60mL and TiCl are added into sediment440mL is warming up to 110 DEG C, maintains 2h, filtering；Same operation
It is repeated once.And then three times, the time is respectively 10min to washing precipitate, adds hexane at 110 DEG C with toluene 70mL
60mL is washed twice, and obtains ingredient of solid catalyst.
Embodiment 2
Method is with embodiment 1, the difference is that substituting diisobutyl malonic acid using di-n-butyl diethyl malonate
Diethylester.
Embodiment 3
Method is with embodiment 1, the difference is that substituting diisobutyl malonic acid two using dipropyl diethyl malonate
Ethyl ester.
Embodiment 4
Method is with embodiment 1, the difference is that substituting diisobutyl malonic acid using diallyl diethyl malonate
Diethylester.
Embodiment 5
Method is with embodiment 1, the difference is that being substituted using 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes
9,9- is bis-（Methoxy）Fluorenes.
Embodiment 6
Method is with embodiment 1, the difference is that diisobutyl diethyl malonate addition 2mmol；9,9- is bis-（Methoxy
Ylmethyl）Fluorenes addition 10mmol；
Embodiment 7
Method is with embodiment 1, the difference is that diisobutyl diethyl malonate addition 16mmol；9,9- is bis-（First
Oxygroup methyl）Fluorenes addition 4mmol.
Comparative example 1
Method is with embodiment 1, the difference is that substituting diisobutyl diethyl malonate using phthalic anhydride.
Comparative example 2
Method is with embodiment 1, the difference is that it is bis- to substitute 9,9- using diisobutyl diethyl malonate（Methoxy methyl
Base）Fluorenes.
Propylene polymerization
Volume is the stainless steel cauldron of 5L, and after gaseous propylene is sufficiently displaced from, AlEt32.5mmol, methyl cyclohexane is added
Base dimethoxysilane（CHMMS）0.l mmol add above-described embodiment and the ingredient of solid catalyst 8-10mg of comparative example
And 1.2L hydrogen, it is passed through liquid propene 2.3L, is warming up to 70 DEG C, maintains this temperature 1 hour.Cooling, pressure release obtain PP powder
Material.Data are shown in Table 1.
Table 1
The data from table 1 are it is known that according to catalyst provided by the invention（Such as embodiment 1-7）With in the prior art
（Comparative example 1 and 2）In catalytic component containing only general formula（Ⅰ）Compound represented or general formula（Ⅱ）Shown in diether compound
It compares, shows certain synergistic effect, there is very excellent comprehensive performance, not only there is higher catalytic activity, and
Resulting polymers have higher isotacticity, it is often more important that, resulting polymers have wider molecular weight distribution, are conducive to gather
Close shaping for object.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (20)
1. a kind of catalytic component for olefinic polymerization, it includes magnesium, titanium, halogen and Lewis alkali cpds, the Lewis
Alkali cpd includes general formula (I) compound represented and the diether compound shown in the general formula (II)；General formula (I) institute
The molar ratio of the compound shown and general formula (II) compound represented is 1:5-4:1,
Wherein, R1And R2It is identical or different, it is selected from C1-C20Substituted or unsubstituted straight chained alkyl, branched alkyl, naphthenic base, virtue
Base, alkaryl, aralkyl, alkylene and fused ring aryl；R3And R4It is identical or different, it is selected from hydrogen and C1-C20Substitution or unsubstituted
Straight chained alkyl, branched alkyl, naphthenic base, aryl, alkaryl, aralkyl, alkylene and fused ring aryl, R3And R4Optionally
It is bonded cyclic or not cyclic；
Wherein, RI、RII、RIII、RIV、RVAnd RVIIt is identical or different, it is hydrogen or C1-C18Hydrocarbyl group, and RVIIAnd RVIIIIt is identical
Or it is different, it is C1-C18Hydrocarbyl group；RI-RVIIIOne or more of group it is optionally bonded cyclic or not cyclic；
The catalytic component is prepared by method comprising the following steps：
1) magnesium compound is dissolved in the system containing general formula (I) compound represented, precipitation agent is added, solids is precipitated；
2) use titanium compound processing step 1) be precipitated solids, with titanium compound handle solids during and/or place
Diether compound shown in general formula (II) is added before reason.
2. catalytic component according to claim 1, which is characterized in that the R1And R2Selected from C1-C10Substitution or do not take
Straight chained alkyl, branched alkyl, naphthenic base, aryl, alkaryl, aralkyl and the alkylene in generation.
3. catalytic component according to claim 1, which is characterized in that general formula (I) compound represented and general formula
(II) molar ratio of compound represented is 5:3-4:1.
4. catalytic component according to claim 1, which is characterized in that general formula (I) compound represented and general formula
(II) molar ratio of compound represented is 1:5-5:3.
5. catalytic component according to claim 1, which is characterized in that general formula (I) compound represented is selected from two
Iso-butyl diethyl malonate, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate；Diisobutyl malonic acid two
Propyl ester, di-n-butyl dipropyl malonate, di-t-butyl dipropyl malonate, diisobutyl dibutyl malonate, di-n-butyl
Dibutyl malonate, di-t-butyl dibutyl malonate, diisobutyl malonic acid diamyl ester, di-n-butyl malonic acid diamyl ester,
Di-t-butyl malonic acid diamyl ester, diisobutyl malonic acid dihexyl, di-n-butyl malonic acid dihexyl, di-t-butyl malonic acid
Dihexyl, two heptyl ester of diisobutyl malonic acid, two heptyl ester of di-n-butyl malonic acid, two heptyl ester of di-t-butyl malonic acid, dipropyl
Dipropyl malonate, diisoamyl dipropyl malonate, two n-amyl malonic acid dipropyls, dihexyl dipropyl malonate, two
N-amyl malonic acid dipropyl, phenylethyl dipropyl malonate, phenyl methyl dipropyl malonate, phenyl propyl malonic acid two
Propyl ester, phenyl n-butylmalonic acid dipropyl, phenyl isobutyl propylmalonic acid dipropyl, phenyl isoamyl-malonic acid dipropyl, benzene
Base n-amyl malonic acid dipropyl, diphenylprop dipropyl malona-te, benzyl ethyl malonic acid dipropyl, benzyl methyl malonic acid two
Propyl ester, benzyl propylmalonic acid dipropyl, benzyl n-butylmalonic acid dipropyl, benzyl isobutyl group dipropyl malonate, benzyl
Isoamyl-malonic acid dipropyl, benzyl n-amyl malonic acid dipropyl, dibenzyl dipropyl malonate, phenylethyl malonic acid two
Butyl ester, phenyl methyl dibutyl malonate, phenyl propyl dibutyl malonate, phenyl n-butylmalonic acid dibutyl ester, phenyl are different
Butylmalonic acid dibutyl ester, phenyl isoamyl-malonic acid dibutyl ester, phenyl n-amyl malonic acid dibutyl ester, diphenylprop diacid two
Butyl ester, benzyl ethyl malonic acid dibutyl ester, benzyl methyl dibutyl malonate, benzyl propylmalonic acid dibutyl ester, the positive fourth of benzyl
Propylmalonic acid dibutyl ester, benzyl isobutyl group dibutyl malonate, benzyl isoamyl-malonic acid dibutyl ester, benzyl n-amyl malonic acid
Dibutyl ester, dibenzyl dibutyl malonate, phenylethyl malonic acid diamyl ester, phenyl methyl malonic acid diamyl ester, phenyl propyl
Malonic acid diamyl ester, phenyl n-butylmalonic acid diamyl ester, phenyl isobutyl propylmalonic acid diamyl ester, phenyl isoamyl-malonic acid two
Pentyl ester, phenyl n-amyl malonic acid diamyl ester, diphenylprop diacid diamyl ester, benzyl ethyl malonic acid diamyl ester, benzyl methyl
Malonic acid diamyl ester, benzyl propylmalonic acid diamyl ester, benzyl n-butylmalonic acid diamyl ester, benzyl isobutyl propylmalonic acid diamyl
Ester, benzyl isoamyl-malonic acid diamyl ester, benzyl n-amyl malonic acid diamyl ester, dibenzyl propylmalonic acid diamyl ester, phenylethyl
Malonic acid dicyclohexyl maleate, phenyl methyl malonic acid dicyclohexyl maleate, phenyl propyl malonic acid dicyclohexyl maleate, phenyl n-butylmalonic acid
Dicyclohexyl maleate, phenyl isobutyl propylmalonic acid dicyclohexyl maleate, phenyl isoamyl-malonic acid dicyclohexyl maleate, phenyl n-amyl malonic acid two
Cyclohexyl, diphenylprop dicyclohexyl sulfosuccinnate ester, benzyl ethyl malonic acid dicyclohexyl maleate, benzyl methyl malonic acid dicyclohexyl maleate, benzyl
Base propylmalonic acid dicyclohexyl maleate, benzyl n-butylmalonic acid dicyclohexyl maleate, benzyl isobutyl propylmalonic acid dicyclohexyl maleate, benzyl are different
Amyl malonic acid dicyclohexyl maleate, benzyl n-amyl malonic acid dicyclohexyl maleate, dibenzyl propylmalonic acid dicyclohexyl maleate, phenyl methyl the third two
Diphenyl phthalate, phenyl propyl diphenyl malonate, phenyl n-butylmalonic acid diphenyl ester, phenyl isobutyl propylmalonic acid diphenyl ester,
Phenyl isoamyl-malonic acid diphenyl ester, phenyl n-amyl malonic acid diphenyl ester, diphenyl diphenyl malonate, benzyl ethyl the third two
Diphenyl phthalate, benzyl methyl diphenyl malonate, benzyl propylmalonic acid diphenyl ester, benzyl n-butylmalonic acid diphenyl ester, benzyl
Base isobutyl group diphenyl malonate, benzyl isoamyl-malonic acid diphenyl ester, benzyl n-amyl malonic acid diphenyl ester, dibenzyl the third two
Diphenyl phthalate, fluorenyl methyl malonic acid dicyclohexyl maleate, fluorenyl propylmalonic acid dicyclohexyl maleate, two hexamethylene of fluorenyl n-butylmalonic acid
Ester, fluorenyl isobutyl propylmalonic acid dicyclohexyl maleate, fluorenyl isoamyl-malonic acid dicyclohexyl maleate, two hexamethylene of fluorenyl n-amyl malonic acid
Ester, two fluorenyl malonic acid dicyclohexyl maleates, allyl methyl diphenyl malonate, allyl propylmalonic acid diphenyl ester, allyl
N-butylmalonic acid diphenyl ester, allyl isobutyl group diphenyl malonate, allyl isoamyl-malonic acid diphenyl ester, allyl are just
Amyl malonic acid diphenyl ester, diallyl diphenyl malonate, allyl methyl dimethyl malenate, allyl propylmalonic acid
Dimethyl ester, allyl n-butylmalonic acid dimethyl ester, allyl isobutyl group dimethyl malenate, allyl isoamyl-malonic acid two
Methyl esters, allyl n-amyl malonic acid dimethyl ester, diallyl dimethyl malenate, allyl methyl diethyl malonate, alkene
Propyl propylmalonic acid diethylester, allyl diethyl butylmalonate, allyl iso-butyl diethyl malonate, allyl
Isoamyl-malonic acid diethylester, allyl n-amyl malonic acid diethylester, diallyl diethyl malonate, allyl methyl third
Dipropyl malona-te, allyl propylmalonic acid dipropyl, allyl n-butylmalonic acid dipropyl, allyl isobutyl propylmalonic acid
Dipropyl, allyl isoamyl-malonic acid dipropyl, allyl n-amyl malonic acid dipropyl, diallyl malonic acid dipropyl
Ester, allyl methyl dibutyl malonate, allyl propylmalonic acid dibutyl ester, allyl n-butylmalonic acid dibutyl ester, alkene
Propyl isobutyl group dibutyl malonate, allyl isoamyl-malonic acid dibutyl ester, allyl n-amyl malonic acid dibutyl ester, diene
Propylmalonic acid dibutyl ester, allyl methyl malonic acid diamyl ester, allyl propylmalonic acid diamyl ester, allyl normal-butyl third
Diacid diamyl ester, allyl isobutyl propylmalonic acid diamyl ester, allyl isoamyl-malonic acid diamyl ester, allyl n-pentyl the third two
Sour diamyl ester, diallyl malonic acid diamyl ester, allyl methyl malonic acid dicyclohexyl maleate, two hexamethylene of allyl propylmalonic acid
Ester, allyl n-butylmalonic acid dicyclohexyl maleate, allyl isobutyl propylmalonic acid dicyclohexyl maleate, allyl isoamyl-malonic acid two
Cyclohexyl, allyl n-amyl malonic acid dicyclohexyl maleate and diallyl malonic acid dicyclohexyl maleate.
6. catalytic component according to claim 1, which is characterized in that general formula (I) compound represented is selected from two
Iso-butyl diethyl malonate, di-n-butyl diethyl malonate, di-t-butyl diethyl malonate, diisobutyl malonic acid two
Propyl ester, di-n-butyl dipropyl malonate, di-t-butyl dipropyl malonate, diethyl benzyl malonate, benzyl malonic acid two
Propyl ester, ethyl benzoic acid, phenylethyl dipropyl malonate, dipropyl diethyl malonate, dipropyl the third two
Sour dipropyl, diallyl diethyl malonate and diallyl dipropyl malonate.
7. catalytic component according to claim 1, which is characterized in that diether compound shown in the general formula (II)
Selected from bis- (methoxy) fluorenes of 9,9-, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes, 2,2- diisobutyls -1,3-
Dimethoxy propane and (methoxy) fluorenes of 9,9- bis- and 2- isopropyl -2- cyclopenta -1,3- dimethoxy propanes.
8. catalytic component according to claim 1, which is characterized in that in the catalytic component, the content of magnesium is 10-
30wt%, the content of titanium are 1-5wt%, and the content of general formula (I) compound represented is 1-20wt%, two shown in general formula (II)
The content of ether compound is 1-20wt%.
9. catalytic component according to claim 1, which is characterized in that the precipitation agent is selected from metal halide.
10. catalytic component according to claim 1, which is characterized in that the precipitation agent is halogenated titanium.
11. catalytic component according to claim 1, which is characterized in that the precipitation agent is titanium tetrachloride.
12. a kind of catalyst for olefinic polyreaction, it includes the reaction products of following components：
A. the catalytic component described in any one of claim 1~11；
B. alkyl aluminum compound；
C. optionally, external electron donor component.
13. catalyst according to claim 12, which is characterized in that the alkyl aluminum compound is general formula AlRnX3-nIt is shown
Alkyl aluminum compound, R is hydrogen or C in formula1-C20Alkyl, X is halogen, 0 n≤3 <.
14. catalyst according to claim 12, which is characterized in that external electron donor component is general formula (R2)kSi
(OR3)4-kShown in organo-silicon compound, 0≤k≤3, R in formula2Selected from halogen, hydrogen atom and C1-C20Alkyl, naphthenic base, virtue
Base, halogenated alkyl or amino, R3For C1-C20Alkyl, naphthenic base, aryl, halogenated alkyl or amino.
15. according to the catalyst described in any one of claim 12-14, which is characterized in that the component a) and component b)
Molar ratio with titanium:Aluminium is calculated as 1:(5-1000)；The molar ratio of the component c) and component a) is with external electron donor：Titanium is calculated as 0-
500:1。
16. catalyst according to claim 15, which is characterized in that the molar ratio of the component a) and component b) is with titanium:
Aluminium is calculated as 1：(25-100)；The molar ratio of the component c) and component a) is with external electron donor：Titanium is calculated as 25-100:1.
17. a kind of pre-polymerized catalyst for olefinic polymerization, the pre-polymerized catalyst include it is a kind of according to claim 1~
Catalyst described in any one of catalytic component or claim 12-16 described in any one of 11 carries out pre-polymerization with alkene
The prepolymer of gained is closed, pre-polymerization multiple is 0.1~1000g olefin polymers/g ingredients of solid catalyst.
18. a kind of method of olefinic polymerization, catalytic component of the alkene described in any one of claim 1~11, power
Profit requires to carry out in the presence of the pre-polymerized catalyst described in catalyst or claim 17 described in any one of 12-16.
19. according to the method for claim 18, which is characterized in that the general formula of the alkene is CH2=CHR, wherein R are hydrogen
Or C1-C12Alkyl or aryl group.
20. according to the method for claim 19, which is characterized in that the alkene is ethylene or propylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6699814B2 (en) * | 1998-11-04 | 2004-03-02 | Basell Poliolefine Italia S.P.A. | Catalysts for the polymerization of olefins |
| CN1653092A (en) * | 2002-05-10 | 2005-08-10 | 出光兴产株式会社 | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin polymer |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst and catalyst application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6699814B2 (en) * | 1998-11-04 | 2004-03-02 | Basell Poliolefine Italia S.P.A. | Catalysts for the polymerization of olefins |
| CN1653092A (en) * | 2002-05-10 | 2005-08-10 | 出光兴产株式会社 | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin polymer |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst and catalyst application thereof |
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