CN102234338B - Catalyst component for olefin polymerization and catalyst comprising same - Google Patents
Catalyst component for olefin polymerization and catalyst comprising same Download PDFInfo
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- CN102234338B CN102234338B CN2010101527911A CN201010152791A CN102234338B CN 102234338 B CN102234338 B CN 102234338B CN 2010101527911 A CN2010101527911 A CN 2010101527911A CN 201010152791 A CN201010152791 A CN 201010152791A CN 102234338 B CN102234338 B CN 102234338B
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- Prior art keywords
- electron donor
- compound
- catalyst component
- alkyl
- logical formula
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 55
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- -1 diol ester compound Chemical class 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 19
- 229920001155 polypropylene Polymers 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 239000004743 Polypropylene Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000012442 inert solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910052794 bromium Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011949 solid catalyst Substances 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 230000037048 polymerization activity Effects 0.000 abstract description 8
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-UHFFFAOYSA-N 0.000 description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 4
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 4
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- UDSAOZBLEFVCKE-UHFFFAOYSA-N (3-benzoyloxy-2,2-dimethylpentyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)(C)C(CC)OC(=O)C1=CC=CC=C1 UDSAOZBLEFVCKE-UHFFFAOYSA-N 0.000 description 3
- VSRWWHOJVGFSFA-UHFFFAOYSA-N (3-benzoyloxy-2-ethylpentyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CC)COC(=O)C1=CC=CC=C1 VSRWWHOJVGFSFA-UHFFFAOYSA-N 0.000 description 3
- YEGVZUITMUKKBN-UHFFFAOYSA-N 2-(1-benzoyloxypropyl)hexyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CCCC)COC(=O)C1=CC=CC=C1 YEGVZUITMUKKBN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- PAHBCCOGSLEKQS-UHFFFAOYSA-N (5-benzoyloxy-2,5-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)(CC)CC(C(C)C)OC(=O)C1=CC=CC=C1 PAHBCCOGSLEKQS-UHFFFAOYSA-N 0.000 description 2
- BUCBXHLZGJGGCA-UHFFFAOYSA-N (5-benzoyloxy-2,6-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)C)CC(C(C)C)OC(=O)C1=CC=CC=C1 BUCBXHLZGJGGCA-UHFFFAOYSA-N 0.000 description 2
- HDCPAWWIFPIIQB-UHFFFAOYSA-N (5-benzoyloxy-4,4-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)(C)C(CC)OC(=O)C1=CC=CC=C1 HDCPAWWIFPIIQB-UHFFFAOYSA-N 0.000 description 2
- ZARWPEMJZSRXHD-UHFFFAOYSA-N (5-benzoyloxy-4,5-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)(CC)C(C)C(CC)OC(=O)C1=CC=CC=C1 ZARWPEMJZSRXHD-UHFFFAOYSA-N 0.000 description 2
- UGVIHDDRPUSMBC-UHFFFAOYSA-N (5-benzoyloxy-4,6-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)C)C(C)C(CC)OC(=O)C1=CC=CC=C1 UGVIHDDRPUSMBC-UHFFFAOYSA-N 0.000 description 2
- IEUGUAOMTXYLED-UHFFFAOYSA-N (5-benzoyloxy-5-ethyl-4-methylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)(CC)C(C)C(CC)OC(=O)C1=CC=CC=C1 IEUGUAOMTXYLED-UHFFFAOYSA-N 0.000 description 2
- XTOLJLHPCKTDBE-UHFFFAOYSA-N (5-benzoyloxy-5-ethylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)CC(CC)(CC)OC(=O)C1=CC=CC=C1 XTOLJLHPCKTDBE-UHFFFAOYSA-N 0.000 description 2
- AIVJBANJWIGQPI-UHFFFAOYSA-N (5-benzoyloxy-5-methylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)CC(C)(CC)OC(=O)C1=CC=CC=C1 AIVJBANJWIGQPI-UHFFFAOYSA-N 0.000 description 2
- VVMMFVMLTGBMTQ-UHFFFAOYSA-N (5-benzoyloxy-6,6-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(C(C)(C)C)OC(=O)C1=CC=CC=C1 VVMMFVMLTGBMTQ-UHFFFAOYSA-N 0.000 description 2
- IIYIECVYGJTMQU-UHFFFAOYSA-N (5-benzoyloxy-6-methylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)CC(C(C)C)OC(=O)C1=CC=CC=C1 IIYIECVYGJTMQU-UHFFFAOYSA-N 0.000 description 2
- ODCRXIIYCSXTLW-UHFFFAOYSA-N 2-methylpropyl 2-methoxybenzoate Chemical compound COC1=CC=CC=C1C(=O)OCC(C)C ODCRXIIYCSXTLW-UHFFFAOYSA-N 0.000 description 2
- ASFLIXVTLOHGHE-UHFFFAOYSA-N 5-benzoyloxyheptan-3-yl benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)CC(CC)OC(=O)C1=CC=CC=C1 ASFLIXVTLOHGHE-UHFFFAOYSA-N 0.000 description 2
- QGUNIPCNTNBTOZ-UHFFFAOYSA-N 9,9-dimethoxy-1-methylfluorene Chemical class C1=CC(C)=C2C(OC)(OC)C3=CC=CC=C3C2=C1 QGUNIPCNTNBTOZ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FNODWEPAWIJGPM-UHFFFAOYSA-N ethyl 2-methoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OC FNODWEPAWIJGPM-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002680 magnesium Chemical class 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 210000001835 viscera Anatomy 0.000 description 2
- DYJIIMFHSZKBDY-UHFFFAOYSA-N (3-benzoyloxy-2,2-dimethylpropyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)(C)COC(=O)C1=CC=CC=C1 DYJIIMFHSZKBDY-UHFFFAOYSA-N 0.000 description 1
- RHGOUUKDYGOMSX-UHFFFAOYSA-N (4-benzoyloxy-3,3-dimethylpentan-2-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)C(C)(C)C(C)OC(=O)C1=CC=CC=C1 RHGOUUKDYGOMSX-UHFFFAOYSA-N 0.000 description 1
- LESIHUNAOSLPSU-UHFFFAOYSA-N (4-benzoyloxy-3-ethylpentan-2-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)C(CC)C(C)OC(=O)C1=CC=CC=C1 LESIHUNAOSLPSU-UHFFFAOYSA-N 0.000 description 1
- AXUIEEPFBMGZLS-UHFFFAOYSA-N (4-benzoyloxy-3-methylpentan-2-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)C(C)C(C)OC(=O)C1=CC=CC=C1 AXUIEEPFBMGZLS-UHFFFAOYSA-N 0.000 description 1
- CFMYNHGXOMKGNH-UHFFFAOYSA-N (5-benzoyloxy-3,5-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)(CC)CC(C)(CC)OC(=O)C1=CC=CC=C1 CFMYNHGXOMKGNH-UHFFFAOYSA-N 0.000 description 1
- ONRSEIMQKHJZOL-UHFFFAOYSA-N (5-benzoyloxy-4,4-dimethylpentyl) benzoate Chemical group C=1C=CC=CC=1C(=O)OCC(C)(C)CCCOC(=O)C1=CC=CC=C1 ONRSEIMQKHJZOL-UHFFFAOYSA-N 0.000 description 1
- UCYYLAMYFFDGJB-UHFFFAOYSA-N (5-benzoyloxy-4-ethyl-4-methylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)C(C)(CC)C(CC)OC(=O)C1=CC=CC=C1 UCYYLAMYFFDGJB-UHFFFAOYSA-N 0.000 description 1
- XMJNXWFJHKHVMY-UHFFFAOYSA-N (5-benzoyloxy-4-ethyl-5-methylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)(CC)C(CC)C(CC)OC(=O)C1=CC=CC=C1 XMJNXWFJHKHVMY-UHFFFAOYSA-N 0.000 description 1
- RAMDWQXDLFRDBH-UHFFFAOYSA-N (5-benzoyloxy-4-ethyl-6-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C(C)C)C(CC)C(CC)OC(=O)C1=CC=CC=C1 RAMDWQXDLFRDBH-UHFFFAOYSA-N 0.000 description 1
- MISPJWXLQJXWHM-UHFFFAOYSA-N (5-benzoyloxy-4-ethylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)C(CC)C(CC)OC(=O)C1=CC=CC=C1 MISPJWXLQJXWHM-UHFFFAOYSA-N 0.000 description 1
- YVVDKVRIXQXQGL-UHFFFAOYSA-N (5-benzoyloxy-4-methylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(CC)C(C)C(CC)OC(=O)C1=CC=CC=C1 YVVDKVRIXQXQGL-UHFFFAOYSA-N 0.000 description 1
- MPMYNDGYFIWDTE-UHFFFAOYSA-N (5-benzoyloxy-5,6-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(C)(C(C)C)OC(=O)C1=CC=CC=C1 MPMYNDGYFIWDTE-UHFFFAOYSA-N 0.000 description 1
- ARFPWPKGKXQGFI-UHFFFAOYSA-N (5-benzoyloxy-5-ethyl-2-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)(CC)CC(C(C)C)OC(=O)C1=CC=CC=C1 ARFPWPKGKXQGFI-UHFFFAOYSA-N 0.000 description 1
- AEOHLOSZQSEYTQ-UHFFFAOYSA-N (5-benzoyloxy-5-ethyl-3-methylheptan-3-yl) benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)(CC)CC(CC)(CC)OC(=O)C1=CC=CC=C1 AEOHLOSZQSEYTQ-UHFFFAOYSA-N 0.000 description 1
- VJDKWMYPQSPDMA-UHFFFAOYSA-N (5-benzoyloxy-5-ethyl-6-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(CC)(C(C)C)OC(=O)C1=CC=CC=C1 VJDKWMYPQSPDMA-UHFFFAOYSA-N 0.000 description 1
- ADYXBLCKGGPWFI-UHFFFAOYSA-N (5-benzoyloxy-5-ethylnonan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)(CCCC)CC(CC)OC(=O)C1=CC=CC=C1 ADYXBLCKGGPWFI-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 1
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 1
- MHXGFZFAFFHXGF-UHFFFAOYSA-N 3-(1-benzoyloxyethyl)heptan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)C(CCCC)C(C)OC(=O)C1=CC=CC=C1 MHXGFZFAFFHXGF-UHFFFAOYSA-N 0.000 description 1
- OTSYPBYKMMRMOU-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 3,5-diethylhept-1-ene Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CC)CC(C=C)CC OTSYPBYKMMRMOU-UHFFFAOYSA-N 0.000 description 1
- AHZRDVGIZDALCT-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 3-ethylhept-1-ene Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CCCC)C=C AHZRDVGIZDALCT-UHFFFAOYSA-N 0.000 description 1
- AEGBIISXWMUHKA-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 3-methylideneoctane Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CCCCC)=C AEGBIISXWMUHKA-UHFFFAOYSA-N 0.000 description 1
- AKBHIRYBHFWEPE-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 5,5-diethylhept-1-ene Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CC)(CCC=C)CC AKBHIRYBHFWEPE-UHFFFAOYSA-N 0.000 description 1
- QSZVMYNVVOYORC-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 5,5-dimethylhept-1-ene Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CC)(CCC=C)C QSZVMYNVVOYORC-UHFFFAOYSA-N 0.000 description 1
- UTAVJGWZHCMXGC-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 5-butyl-5-ethylnon-1-ene Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CC)(CCC=C)CCCC UTAVJGWZHCMXGC-UHFFFAOYSA-N 0.000 description 1
- UGHMZQPYANZIFC-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 5-ethenyl-7-ethylundecane Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CC)CC(C=C)CCCC UGHMZQPYANZIFC-UHFFFAOYSA-N 0.000 description 1
- LIDWUYKAPXLQER-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate 5-methylhept-1-ene Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CC)CCC=C LIDWUYKAPXLQER-UHFFFAOYSA-N 0.000 description 1
- TYTTZVDFWCBYPG-UHFFFAOYSA-N 6-benzoyloxyhexyl benzoate Chemical group C=1C=CC=CC=1C(=O)OCCCCCCOC(=O)C1=CC=CC=C1 TYTTZVDFWCBYPG-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
- GAKPQXFBBJDUJC-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CC)CCC=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CC)CCC=C GAKPQXFBBJDUJC-UHFFFAOYSA-N 0.000 description 1
- JMDAMOLIKISQLA-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CCC)CC=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(C)C(CCC)CC=C JMDAMOLIKISQLA-UHFFFAOYSA-N 0.000 description 1
- CISDQPNFQKALRZ-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CC)C(CC)(CCC=C)CCC Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CC)C(CC)(CCC=C)CCC CISDQPNFQKALRZ-UHFFFAOYSA-N 0.000 description 1
- JPEXUYLSDJBLOK-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CC)C(CC)CC(C=C)CCC Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CC)C(CC)CC(C=C)CCC JPEXUYLSDJBLOK-UHFFFAOYSA-N 0.000 description 1
- OESSSLGDMAZLCO-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CC)CCC=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CC)CCC=C OESSSLGDMAZLCO-UHFFFAOYSA-N 0.000 description 1
- RULUOTFKCFHFDO-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CCC)CC=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CCC)CC=C RULUOTFKCFHFDO-UHFFFAOYSA-N 0.000 description 1
- FRSDCKSRDCOLCX-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CCCC)C=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CCCC)C=C FRSDCKSRDCOLCX-UHFFFAOYSA-N 0.000 description 1
- PUFOCEUEGFISFV-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CCCCC)=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.C(CCC)C(CCCCC)=C PUFOCEUEGFISFV-UHFFFAOYSA-N 0.000 description 1
- JQLBNXFVJCXUDW-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(C)CCCC=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(C)CCCC=C JQLBNXFVJCXUDW-UHFFFAOYSA-N 0.000 description 1
- JBBQZYITGXBWNB-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CC)CC(C=C)C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CC)CC(C=C)C JBBQZYITGXBWNB-UHFFFAOYSA-N 0.000 description 1
- GLSLWLLCHXDMBN-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CCC)CC=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CCC)CC=C GLSLWLLCHXDMBN-UHFFFAOYSA-N 0.000 description 1
- SLYKMJRXXLUPEO-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CCCC)C=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CCCC)C=C SLYKMJRXXLUPEO-UHFFFAOYSA-N 0.000 description 1
- NVWGWCVLKBUGMD-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CCCCC)=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CC(CCCCC)=C NVWGWCVLKBUGMD-UHFFFAOYSA-N 0.000 description 1
- UIXTVCHMLAXVQU-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CCCCCC=C Chemical group C(C1=CC=CC=C1)(=O)OC(C)CC(CCC)OC(C1=CC=CC=C1)=O.CCCCCC=C UIXTVCHMLAXVQU-UHFFFAOYSA-N 0.000 description 1
- NTHKCSDJQGWPJY-UHFFFAOYSA-N CCCC[SiH](OC)OC Chemical group CCCC[SiH](OC)OC NTHKCSDJQGWPJY-UHFFFAOYSA-N 0.000 description 1
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- 0 C[C@](C1)(C1*=C1)C(C(*)=O)=C1O* Chemical compound C[C@](C1)(C1*=C1)C(C(*)=O)=C1O* 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PFYHAAAQPNMZHO-UHFFFAOYSA-N Methyl 2-methoxybenzoate Chemical compound COC(=O)C1=CC=CC=C1OC PFYHAAAQPNMZHO-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WDINQFCMBGFZCN-UHFFFAOYSA-N [3-(1-benzoyloxyethyl)-3-methylheptan-2-yl] benzoate Chemical group C=1C=CC=CC=1C(=O)OC(C)C(C)(CCCC)C(C)OC(=O)C1=CC=CC=C1 WDINQFCMBGFZCN-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-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
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- OUZCDRGUTZLAGO-UHFFFAOYSA-N ethyl 2-ethoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OCC OUZCDRGUTZLAGO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QAYQKAPOTVSWLS-UHFFFAOYSA-N methyl 2-ethoxybenzoate Chemical class CCOC1=CC=CC=C1C(=O)OC QAYQKAPOTVSWLS-UHFFFAOYSA-N 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-methoxybenzoate Natural products COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- DXFQVUJFXYGTNP-UHFFFAOYSA-N propan-2-yl 2-ethoxybenzoate Chemical compound CCOC1=CC=CC=C1C(=O)OC(C)C DXFQVUJFXYGTNP-UHFFFAOYSA-N 0.000 description 1
- WHVIVRXGERGYGC-UHFFFAOYSA-N propan-2-yl 2-methoxybenzoate Chemical compound COC1=CC=CC=C1C(=O)OC(C)C WHVIVRXGERGYGC-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-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
- 150000003608 titanium Chemical class 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
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a catalyst component for olefin polymerization and a catalyst comprising the same. The catalyst component comprises an addition compound shown as MgX2.m(R'OH).nE.qH2O in a general formula (I), at least one titanium compound shown as Ti(OR)4-kXk in a general formula (II), and at least two electron donor compounds a and b, wherein E is an o-alkoxy benzoate compound; the electron donor compound a is a diol ester compound, and the electron donor compound b is a diether compound; and the molar ratio of a to b is 0.55-50. When the catalyst is used for olefin polymerization, particularly propene polymerization, the catalyst has superhigh polymerization activity; and the prepared polymer has wide molecular weight distribution, high degree of isotacticity and low ash content. The invention also provides application of the catalyst in preparation of polypropylene with low ash content.
Description
Technical field
The present invention relates to a kind of catalyst component for olefinic polyreaction and catalyzer thereof, more particularly, relate to a kind of take the spherical adduct of magnesium halides that contains the o-alkoxyl benzoate compounds as carrier, spherical catalyst component and the catalyzer thereof of two or more internal electron donor of load, and adopt the low polyacrylic method of ash content of this catalyzer preparation.
Technical background
As everyone knows, solid titanium series catalysts component take magnesium, titanium, halogen and electron donor as basal component, be used for olefinic polyreaction, particularly when propylene polymerization, have higher polymerization activity and vertical structure directional property, along with the development of internal electron donor compound, polyolefin catalyst constantly updates.Adopt the catalyzer of different internal electron donors to have different characteristics, for example, some catalyzer has higher polymerization activity, and some catalyzer has preferably hydrogen response, and the polyolefin resin of some catalyzer preparation has wider molecular weight distribution etc.But in polyolefinic industrial production, be starved of employed catalyzer and have very good over-all properties.
In order to improve the over-all properties of catalyzer, carrying out a large amount of research work always.Adopt the composite deficiency that remedies single internal electron donor performance of two kinds of (or two or more) internal electron donors in some research, improve the over-all properties of catalyzer.As: in the disclosed technology of patent US 6825309B2, the characteristics that the composite wide molecular mass that has not only kept the polymkeric substance of succinate catalyst of succinate and phthalic ester is distributed, and further improve the vertical structure directional property of catalyzer; Chinese patent ZL 200410073623.8 disclosed catalyst component and catalyzer, the catalyzer of the method preparation that employing is composite with 1,3-diol ester and dibutyl phthalate is used for the polymkeric substance that propylene polymerization obtains and has higher degree of isotacticity and wider molecular weight distribution.The disclosed catalyst component of Chinese patent CN1743346 and catalyzer, employing is carried out three kinds of electron donors composite, concrete is with 1,3-diol ester, dibutyl phthalate and ethyl benzoate carry out composite, the catalyst activity that it obtains improves, and molecular weight distribution and the degree of isotacticity of resulting polymkeric substance also are improved simultaneously.But, yet there are no in the present disclosed compounded technology and make catalyzer have the report of superelevation polymerization activity (＞150kg PP/g cat).
Along with the further expansion of polypropylene range of application, the low ash content acrylic resin of high purity shows good application prospect in industries such as medicine, electronic apparatus, weavings, can be used for masking such as low ash content polypropylene, such as capacitor films in recent years; Fiber and non-woven fabrics are such as the staple fibre, spinning non-woven fabrics etc. of spinning usefulness; Also can be used for preparing medical treatment product etc.What obtain at present high-purity acrylic resin mainly is the last handling process that adopts washing after polymerization, but this washing process need to use a large amount of solvents, and need again drying after the washing, can bring like this problem that production process is complicated, energy consumption is high, cost is high.If can from polymerization reactor, directly obtain low ash content acrylic resin, then can address these problems.As everyone knows, the add-on of polypropylene powder ash content catalyzer, promotor, external electron donor during with polymerization is directly proportional, and be inversely proportional to output, and the ash content of being introduced by promotor accounts for larger proportion.So, if adopt a kind of high activated catalyst, especially can under low aluminum alkyls (cocatalyst component) concentration, keep the high polymerization activity catalyzer then might from polymerization reactor, directly prepare low ash content acrylic resin.
The inventor finds by repetition test in research process, adopt a kind of take the spherical adduct of magnesium halides that contains the o-alkoxyl benzoate compounds as carrier, load has diol-lipid compound and 1, the 3-diether compound is composite as the prepared spherical catalyst of internal electron donor, be used for olefinic polymerization, especially during propylene polymerization, the polymerization activity (＞150kg PP/g cat) and the higher vertical structure directional property that have shown wonderful superelevation, even particularly under low aluminum alkyls (cocatalyst component) concentration, still kept very high activity, and the molecular weight distribution of resulting polymers is wider, and ash content is relatively low.
Summary of the invention
The object of the present invention is to provide a kind of catalyst component for olefinic polymerization and catalyzer thereof, this catalyzer has the polymerization activity of superelevation and high vertical structure directional property, and the polymkeric substance that obtains has wider molecular weight distribution and lower ash content.
Another object of the present invention provides a kind of usefulness catalyzer of the present invention and prepares the low polyacrylic method of ash content.
Catalyst component for olefinic polymerization of the present invention, it is included in a kind of such as general formula (I) MgX
2.m (the .nE.qH of R ' OH)
2Load has at least a such as general formula (II) Ti (OR) on the adducts shown in the O
4 -kX
kShown titanium compound, and the reaction product of at least a electron donor compound a and at least a electron donor compound b, wherein:
In the general formula (I), X is chlorine or bromine; R ' is C
1-C
4Alkyl; E is the o-alkoxyl benzoic acid ester compounds shown at least a general formula (III):
R in the general formula (III)
1And R
2Be independently selected from C
1-C
12Alkyl, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl and C
7-C
10Aralkyl, preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-;
In the general formula (I), m is 1.0-5.0; N is 0.001-0.5; Q is 0-0.8.Preferred m is 1.5-3.5, and n is 0.01-0.2.
In the general formula (II), R is C
1～C
20Alkyl, X is F, Cl or Br, k is 1～4 integer;
Described electron donor compound a is the diol-lipid compound shown in general formula (IV):
In the general formula (IV), R
1And R
2Be independently selected from C
1-C
10Straight or branched alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20Aralkyl, the aromatic ring in described aryl, alkaryl or the aralkyl randomly further are selected from halogen, C
1-C
6Alkyl and C
1-C
6The substituting group of alkoxyl group replaces; R
3-R
6, R
1-R
2nGroup is independently selected from the C of hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl and ester group, R
3-R
6And R
1-R
2nGroup is optional to comprise one or more heteroatomss as carbon atom or hydrogen atom or both substituents, and described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus and halogen, R
3-R
6And R
1-R
2nThe one or more optional ring that links up in the group; N is the integer of 0-10;
Described electron donor compound b is the diether compound shown in logical formula V:
In the logical formula V, R
I, R
II, R
III, R
IV, R
VAnd R
VIBe independently selected from the C of hydrogen, halogen, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Aralkyl and C
7-C
20Alkaryl, R
VIIAnd R
VIIIBe independently selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20Aralkyl; R
I-R
VIGroup between randomly be keyed to ring; With
The mol ratio of described electron donor compound a and electron donor compound b is 0.55-50.
Comprising electron donor a and b in the catalyst component of the present invention is 5-25wt% at the content of interior internal electron donor.
The particular compound of the o-alkoxyl benzoates shown in the general formula (III) is such as methyl o-anisate, the o-methoxybenzoic acid ethyl ester, the o-methoxybenzoic acid n-propyl, the o-methoxybenzoic acid isopropyl ester, the positive butyl ester of o-methoxybenzoic acid, the o-methoxybenzoic acid isobutyl ester, the o-ethoxybenzoic acid methyl esters, the o-ethoxybenzoic acid ethyl ester, the o-ethoxybenzoic acid n-propyl, the o-ethoxybenzoic acid isopropyl ester, the positive butyl ester of o-ethoxybenzoic acid, o-methoxybenzoic acid isobutyl ester etc.
Adducts shown in the above-mentioned general formula (I) is by magnesium halide, Organic Alcohol R
1The spherical adduct particle that OH and o-alkoxyl Benzoyl chloride (or o-alkoxyl benzoate compounds) reaction obtains, it uses as carrier in the preparation process of catalyzer.
Titanium compound shown in the general formula (II) is specifically selected a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine three titanium butoxide, dichloro dibutoxy titanium, trichlorine one titanium butoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, the titanous chloride or their mixture, preferred titanium tetrachloride.
Preferably, the electron donor compound a is selected from the diol-lipid compound shown in the general formula (VI):
R in the formula
1-R
6Group is identical or not identical hydrogen, the C of straight or branched
1-C
20Alkyl.Particularly, can adopt: 1, the ammediol dibenzoate, the 2-methyl isophthalic acid, the ammediol dibenzoate, 2-ethyl-1,3-PD dibenzoate, 2-propyl group-1,3-PD dibenzoate, 2-butyl-1, the ammediol dibenzoate, 2,2-dimethyl-1,3-propylene glycol dibenzoate, 2-ethyl-2-butyl-1,3-PD dibenzoate, 2,2-diethyl-1, the ammediol dibenzoate, 2-methyl-2-propyl-1,3-PD dibenzoate, 2-sec.-propyl-2-isopentyl-1,3-PD dibenzoate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-propyl group-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl group-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2,4-trimethylammonium-1,3-pentanediol dibenzoate, 3-methyl-3-butyl-2,4-pentanediol dibenzoate, 2,2-dimethyl-1,5-pentanediol dibenzoate, 1,6-hexylene glycol dibenzoate, 6-heptene-2,4-heptanediol dibenzoate, 2-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2,4-heptanediol dibenzoate, 3-propyl group-6-heptene-2,4-heptanediol dibenzoate, 4-propyl group-6-heptene-2,4-heptanediol dibenzoate, 5-propyl group-6-heptene-2,4-heptanediol dibenzoate, 6-propyl group-6-heptene-2,4-heptanediol dibenzoate, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-2,4-heptanediol dibenzoate, 5-butyl-6-heptene-2,4-heptanediol dibenzoate, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, 3-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 5-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 3-propyl group-3,5-heptanediol dibenzoate, 4-propyl group-3,5-heptanediol dibenzoate, 3-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 3,3-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 3,4-dimethyl-3,5-heptanediol dibenzoate, 3,5-dimethyl-3,5-heptanediol dibenzoate, 3,6-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-3-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-ethyl-3,5-heptanediol dibenzoate, 3-methyl-5-ethyl-3,5-heptanediol dibenzoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-5-ethyl-3,5-heptanediol dibenzoate, 2-methyl-3-propyl group-3,5-heptanediol dibenzoate, 2-methyl-4-propyl group-3,5-heptanediol dibenzoate, 2-methyl-5-propyl group-3,5-heptanediol dibenzoate, 3-methyl-3-propyl group-3,5-heptanediol dibenzoate, 3-methyl-4-propyl group-3,5-heptanediol dibenzoate, 3-methyl-5-propyl group-3,5-heptanediol dibenzoate, 4-methyl-3-propyl group-3,5-heptanediol dibenzoate, 4-methyl-4-propyl group-3,5-heptanediol dibenzoate, 4-methyl-5-propyl group-3,5-heptanediol dibenzoate etc.More preferably pentadiol ester and heptanediol ester.
Preferably, the electron donor compound b is selected from 1 shown in the general formula (VI), the 3-diether compound:
R
1R
2C(CH
2OR
3)(CH
2OR
4)
(VI)
In the general formula (VI), R
1And R
2Can be identical or not identical, be selected from C
1-C
18Alkyl, C
3-C
18Cycloalkyl, C
6-C
18Aryl, C
7-C
18A kind of in the aralkyl optionally is keyed to ring between group; R
3And R
4Can be identical or not identical, be selected from C
1-C
10Alkyl.Specifically can adopt: 2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-butyl-1, the 3-Propanal dimethyl acetal, 2-sec-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-1, the 3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1, the 3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal, 2-(p-chloro-phenyl-)-1, the 3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2,2-dipropyl-1, the 3-Propanal dimethyl acetal, 2,2-di-isopropyl-1, the 3-Propanal dimethyl acetal, 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl ethyls)-1 of 2-, the 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-phenylbenzene-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1, the 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, the 3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1, the 3-Propanal dimethyl acetal, 9,9-dimethoxy-methyl fluorenes etc.Preferred 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal or 9,9-dimethoxy-methyl fluorenes.
Above-mentioned 1 among the present invention, the 3-diether compound is disclosed among Chinese patent CN1020448C, CN100348624C and the CN1141285A.Its disclosed associated viscera is all introduced the present invention as a reference.
Preferably, the mol ratio of electron donor compound a and b is: 0.6～30, more preferably 0.65～10.
Catalyst component for olefinic polymerization of the present invention, the reaction by following component prepares:
(1) a kind of such as general formula (I) MgX
2.m (R
1OH) .nE.qH
2Adducts shown in the O;
(2) general formula (II) Ti (OR)
4-kX
kAt least a in the shown titanium compound;
(3) at least two kinds of electron donor compound as and b;
Adducts shown in the above-mentioned general formula (I) is disclosed among Chinese patent CN1091748A, CN101050245A and the CN101486722A, and its disclosed associated viscera is all incorporated herein by reference.In one embodiment, the adducts shown in the described general formula (I) is prepared as follows: with anhydrous magnesium halide and C
1-C
4Lower alcohol mix, the described electron donor compd E of optional adding, then with described mixture heating up to for example 90～140 ℃ to generate the magnesium halide alcohol adduct melt, make this magnesium halide alcohol adduct melt in dispersion medium, experience high shear forces, then drain in the inertia heat-eliminating medium, to solidify to form the spherical magnesium halide alcohol polymer particle, this magnesium halide alcohol adduct particle obtains ball type carrier after washing and drying.High shear forces can obtain by conventional method, such as high-speed mixing method (such as CN1330086A), high-gravity rotating bed method (such as CN1580136A) and mulser method (CN1463990A) etc.The example of dispersion medium includes but not limited to kerosene, white oil, silicone oil, paraffin oil, vaseline oil.The example of heat-eliminating medium includes but not limited to pentane, hexane, heptane, sherwood oil, raffinates oil.
Catalyst component of the present invention can synthesize as follows: with general formula (I) MgX
2.m (R
1OH) .nE.qH
2Adducts shown in the O is suspended in the mixture of the titanium compound of precooling or titanium compound and inert solvent such as hexane, heptane, octane, decane, toluene etc., and the precooling temperature scope is at-30 ℃～0 ℃, preferred-20 ℃～-10 ℃.Then said mixture is heated to 80 ℃～130 ℃, then adding electron donor compound a and electron donor compound b in temperature-rise period add titanium compound and process repeatedly, last, repeatedly wash with inert solvent and obtain ingredient of solid catalyst.In preparation process, relative 1 mole of MgX
2, usually recently use titanium compound with 20 to 200 mole; With 0.04 to 0.6, preferred 0.07 to 0.5, more preferably 0.1 to 0.4 mole amount is used electron donor a.
In the final resulting catalyst component of the present invention, the weight content of electron donor compound a and electron donor compound b is: 5-25wt%.
Particularly, a specific embodiment of the above-mentioned catalyst component of the present invention is as follows:
(A) with in a kind of a kind of mixture by the titanium compound shown in the general formula (II) or titanium compound and inert solvent such as hexane, heptane, octane, decane, toluene etc. that is suspended in precooling by the adducts shown in the general formula (I), the precooling temperature scope is at-30 ℃～0 ℃, preferred-20 ℃～-10 ℃.Keep 20min～2h at precooling temperature after adding the adducts carrier shown in the general formula (I), preferred 0.5-1h.The concentration of adducts is lower than 200g/L in the liquid medium, preferably is lower than 100g/L.Relative 1 mole of MgX2, the mole number of titanium compound is the 4-50 mole, is preferably the 10-45 mole, more preferably the 15-40 mole.
(B) under agitation, said mixture slowly is heated to 10 ℃～100 ℃, adds electron donor compound a and electron donor compound b.A and b can add together, also can separate or the substep adding, just add after preferably described electron donor compound a or b or the two temperature at suspension reach more than 30 ℃.。
(C) continue slowly to be warmed up to 100～130 ℃ reaction 0.5～3h, preferred 0.5～1h.Subsequently, stop to stir, liquid is separated with solid with suction filtration by sedimentation.
(D) solid matter that (C) is obtained is processed with the titanium compound shown in the general formula (II), at 100～130 ℃ of lower reaction 0.5～3h, subsequently, stops to stir, and liquid is separated with solid with suction filtration by sedimentation.Process 1 time or repeatedly with titanium compound, preferred more than 2 times.The amount of each used titanium compound: (A) add-on in the step=1.0～3.0, preferred 1.0～1.5.
(E) with by step (D) or (E) (if having step (E)) solids of obtaining and dry of inert solvent washing, obtain ingredient of solid catalyst.
Another object of the present invention provides a kind of catalyzer for olefinic polymerization, and it comprises the reaction product of following component;
(1) catalyst component of the present invention;
(2) alkylaluminium cpd.
(3) randomly, a kind of external donor compound.
Component (2) alkylaluminium cpd wherein, its general formula is AlR ' "
3, R ' " is identical or not identical C
1-8Alkyl, wherein one or two alkyl can be replaced by chlorine, can select one or more aluminum alkyls mix to use, preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination aluminum alkyls, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3Deng, preferred 10～500 generally take the Al/Ti mol ratio as 1～2000, more preferably 20～300 use the abovementioned alkyl aluminum compounds;
Component (3) a kind of external donor compound randomly wherein, for example list or polyfunctional carboxylic acids, carboxylic acid anhydride and carboxylicesters, ketone, ether, alcohol, lactone, and organophosphorus and silicoorganic compound.When adding external electron donor, preferably have organic silicon compound, its consumption is that Al/ED (mol/mol) is 2-500, preferred 2.5-200.
Described external electron donor preferably contains at least one Si-OR key, general formula is R
1 aR
2 bSi (OR
3)
cSilicon compound, wherein a and b are 0 to 2 integer, c be the integer of 1-3 and (a+b+c) and be 4; R
1, R
2And R
3C
1-C
18Alkyl, randomly contain heteroatoms.Particularly preferred silicon compound, wherein a is that 1, b is that 1, c is 2, R
1And R
2In have at least one to be to be selected from branched-alkyl, alkenyl, alkylidene group, cycloalkyl or the aromatic yl group with 3-10 carbon atom, optional heteroatoms and the R of containing
3Be C
1-C
10Alkyl group, particularly methyl.The example of preferred silicon compound has Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-, three fluoro-2-propyl group)-methyl dimethoxysilane.In addition, preferred silicon compound also has, and wherein a is that 0, c is 3, R
2Be branched-alkyl or group of naphthene base, optional heteroatoms and the R of containing
3Be methyl.The example of optional silicon compound has cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and uncle's hexyl Trimethoxy silane like this.
Alkylaluminium cpd and optional external donor compound can be separately or as mixture and the active ingredient contact reacts of two kinds of compositions.
Above-mentioned catalyzer is suitable for alkene CH
2Homopolymerization and the copolyreaction of=CHR (wherein R is the alkyl or aryl of hydrogen or 1～6 carbon).
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or contain in the inert solvent of polymerization single polymerization monomer, or in gas phase, or operates by the polymerization mix technique in liquid phase.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～90 ℃.Polymerization pressure is normal pressure or higher.In polymerization process, hydrogen can be used as molecular weight and the melting index that the polymericular weight conditioning agent joins telomerized polymer in the polymerization reactor.
Catalyst component, aluminum alkyls and external donor compound can add respectively polymerization reactor, also can mix rear adding polymerization reactor, join polymerization reactor after also can adopting the known prepolymerization method of the industry with the propylene pre-polymerization.
It is worthy of note, use the directly low-ash polypropylene of preparation from polymeric kettle of catalyzer of the present invention.Particularly, polymerization process is in the presence of the above-mentioned catalyzer of the present invention, carry out the polyreaction of propylene, resulting polymers is without the washing last handling process, directly obtain low ash content polypropylene, preferably use abovementioned alkyl aluminum compound, more preferably 20-200 take the Al/Ti mol ratio as 10～300 in the described catalyzer.Can not add external electron donor.When adding external electron donor, its consumption is that Al/ external electron donor (mol/mol) is 5-200, preferred 10-100.
The polymerization of propylene is carried out according to currently known methods, in liquid monomer or contain in the inert solvent of polymerization single polymerization monomer, or in gas phase, or operates by the polymerization mix technique in liquid phase.Polymerization temperature is generally 0 ℃～120 ℃, preferably 60 ℃～80 ℃.Polymerization pressure is normal pressure or higher.In polymerization process, hydrogen can be used as molecular weight and the melting index that the polymericular weight conditioning agent joins telomerized polymer in the polymerization reactor.Catalyst component, aluminum alkyls and external donor compound can add respectively polymerization reactor, also can mix rear adding polymerization reactor, join polymerization reactor after also can adopting the known prepolymerization method of the industry with the propylene pre-polymerization.
The present invention also provides the propene polymer by above-mentioned preparation method's preparation, and the ash oontent of this propene polymer can be lower than 100ppm, further can be lower than 50ppm, further can be lower than 30ppm; Isotactic index (II),, can be regulated according to the purposes of polymkeric substance further greater than 98.0% further greater than 97.5% greater than 96.7%; Melting index (MI) is greater than 0.1g/10min, and is preferred: 1.0-100g/10min; Molecular weight distributing index (Mw/Mn) is greater than 5.5, preferred 6-8.
It is low that propene polymer of the present invention has an ash oontent, and degree of isotacticity is high and can regulate, and the characteristics that molecular weight distribution is wider can be used for masking, such as capacitor films, fiber and non-woven fabrics, such as the staple fibre of spinning usefulness, spinning non-woven fabrics etc.; Also can be used for preparing medical treatment product etc.
Embodiment
Provide following examples the present invention is described better, be not used for limiting the scope of the invention.
Testing method:
1, melt index (M.I): measure according to ASTM D1238-99.
2, polymkeric substance degree of isotacticity (II): adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): with the dry polymer samples of 2 grams, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with the ratio of 2 (g).
3, molecular weight distribution index (Mw/Mn): gel gas-chromatography (GPC) is measured.
4, the mensuration of polymkeric substance ash content: measure according to GB/T 9345-1988.
Embodiment 1
The preparation of spherical catalyst component
In the glass reaction bottle that the 300ml band of fully replacing through high pure nitrogen stirs, add the titanium tetrachloride of 90ml and the hexane of 10ml, be cooled to-20 ℃, add the spherical magnesium chloride alcohol adduct carrier 8g (preparation method is referring to Chinese patent CN101486722A) that contains the o-methoxybenzoic acid ethyl ester, under agitation, slowly heat up stage by stage, add 2 in the temperature-rise period, 4-pentanediol dibenzoate 1.3ml and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.3ml continues to be warming up to 110 ℃, behind the rear constant temperature 0.5h of temperature, suction filtration is removed liquid, adds titanium tetrachloride and processes three times.Then with hexane washing five times, obtain spherical catalyst after the vacuum-drying.The weight content of electron donor compound a and electron donor compound b is 18wt% in the gained spherical catalyst.
Propylene polymerization
In the autoclave of a 5L, adopt stream of nitrogen gas to purge, then in stream of nitrogen gas, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of triethyl aluminum, the hexane solution (the concentration 0.1mmol/ml of CHMMS) of Cyclohexyl Methyl Dimethoxysilane (CHMMS), anhydrous hexane and a certain amount of spherical catalyst component of 10ml.The add-on of triethyl aluminum and Cyclohexyl Methyl Dimethoxysilane represents with Al/Ti and Al/Si, sees Table 1.Close autoclave, the liquid propene of hydrogenation 2NL and 2.3L.Be warmed up to 70 ℃, polymerization 1.5 hours.Test result sees Table 1.
Embodiment 2
The preparation of spherical catalyst component: except 2,4-pentanediol dibenzoate 1.0ml and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.3ml is outer with embodiment 1.The weight content of electron donor compound a and electron donor compound b is 15wt% in the gained spherical catalyst.
Propylene polymerization is with embodiment 1.
Embodiment 3
The preparation of spherical catalyst component: except not adding 2,4-pentanediol dibenzoate, add 3,5-heptanediol dibenzoate 0.9ml and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal 1.3ml is outer with embodiment 1.
Propylene polymerization is with embodiment 1.The weight content of electron donor compound a and electron donor compound b is 13wt% in the gained spherical catalyst.
Comparative Examples 1
The preparation of spherical catalyst component: be carrier, only add outside 2, the 4-pentanediol dibenzoate 1.5ml with embodiment 1 divided by the magnesium chloride alcohol adduct.
Propylene polymerization is with embodiment 1.
Comparative Examples 2
The preparation of spherical catalyst component: be carrier, only add 2-sec.-propyl-2-isopentyl-1 divided by the magnesium chloride alcohol adduct, 3-Propanal dimethyl acetal 1.5ml is outer with embodiment 1.
Propylene polymerization is with embodiment 1.
Comparative Examples 3
The preparation of spherical catalyst component: divided by the magnesium chloride alcohol adduct be carrier, only take diisobutyl phthalate as internal electron donor, add-on is that 1.6ml is outer with Comparative Examples 1.
Propylene polymerization is with embodiment 1.
Comparative Examples 4
The preparation of spherical catalyst component: take diisobutyl phthalate as internal electron donor, add-on is that 1.5ml is outer with embodiment 1 except only.
Propylene polymerization is with embodiment 1.
Comparative Examples 5
The preparation of spherical catalyst component: except being internal electron donor with 2,4-pentanediol dibenzoate only, add-on is that 1.5ml is outer with embodiment 1.
Propylene polymerization is with embodiment 1.
Table 1
Annotate: represent not add external electron donor
The data of embodiment and Comparative Examples relatively can be found out from table 1, its polymerization activity superelevation of catalyzer of the present invention, and apparently higher than the catalyzer that only contains single internal electron donor; When not adding external electron donor, the polymkeric substance that obtains also has higher degree of isotacticity, and the polymkeric substance that obtains has wider molecular weight distribution and lower ash content.
Claims (20)
1. catalyst component that is used for olefinic polymerization, this catalyst component is included in a kind of as logical formula I MgX
2.m (the .nE.qH of R ' OH)
2Load has at least a as logical formula II Ti (OR) on the adducts shown in the O
4-kX
kShown titanium compound, and the reaction product of at least a electron donor compound a and at least a electron donor compound b, wherein:
In the logical formula I, X is chlorine or bromine; R ' is C
1-C
4Alkyl; E is the o-alkoxyl benzoic acid ester compounds shown at least a logical formula III:
In the logical formula III, R
1And R
2Be independently selected from C
1-C
12Alkyl, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl and C
7-C
10Aralkyl; M is 1.0-5.0; N is 0.001-0.5; Q is 0-0.8;
In the logical formula II, R is C
1～C
20Alkyl, X is F, Cl or Br, k is 1～4 integer;
Described a is the diol-lipid compound shown in logical formula IV:
In the logical formula IV, R
1And R
2Be independently selected from C
1-C
10Straight or branched alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl and C
7-C
20Aralkyl, the aromatic ring in the described aryl or aralkyl randomly further are selected from halogen, C
1-C
6Alkyl and C
1-C
6The substituting group of alkoxyl group replaces; R
3-R
6, R
1-R
2nGroup is independently selected from the C of hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Aralkyl, C
2-C
10Alkylene and ester group, R
3-R
6And R
1-R
2nGroup is optional to comprise one or more heteroatomss as carbon atom or hydrogen atom or both substituents, and described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus and halogen, R
3-R
6And R
1-R
2nThe one or more optional ring that links up in the group; N is the integer of 0-10;
Described b is the diether compound shown in general formula (V):
In the general formula (V), R
I, R
II, R
III, R
IV, R
VAnd R
VIBe independently selected from the C of hydrogen, halogen, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Aralkyl and, R
VIIAnd R
VIIIBe independently selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl and C
7-C
20Aralkyl; R
I-R
VIGroup between randomly be keyed to ring; With
Relative 1 mole of MgX
2, use electron donor a with 0.04 to 0.6 mole amount, the mol ratio of described electron donor compound a and electron donor compound b is 0.55-50.
2. catalyst component according to claim 1 is characterized in that, in this catalyst component, the gross weight content of electron donor compound a and electron donor compound b is 5-25wt%.
3. catalyst component according to claim 1, in its formula of (I), m is 1.5-3.5, n is 0.01-0.2.
4. the described catalyst component of one of claim 1-3, wherein said electron donor compound a are the diol ester compounds shown in the logical formula VI:
（Ⅵ）
R wherein
1-R
6Group is independently selected from the C of hydrogen and straight or branched
1-C
20Alkyl, R are independently selected from hydrogen, halogen, C
1-C
6Alkyl and C
1-C
6Alkoxyl group.
5. the described catalyst component of one of claim 1-3, wherein said electron donor compound b is 1 shown in the general formula (VII), the 3-diether compounds:
R
1R
2C（CH
2OR
3）（CH
2OR
4）
（Ⅶ）
R wherein
1And R
2Be independently selected from C
1-C
18Alkyl, C
3-C
18Cycloalkyl, C
6-C
18Aryl and C
7-C
18Aralkyl, and optionally be keyed to ring; R
3And R
4C independently
1-C
10Alkyl.
6. the described catalyst component of one of claim 1-3, the mol ratio of wherein said electron donor a and described electron donor b is 0.65-10.
7. the described catalyst component of one of claim 1-3, wherein said catalyst component are spherical.
8. the catalyst component for olefinic polymerization according to claim 1, this catalyst component synthesizes as follows:
(A) be suspended in a kind of mixture by the titanium compound shown in the logical formula II or titanium compound and inert solvent of precooling by leading to the adducts shown in the formula I a kind of, the precooling temperature scope is at-30 ℃ ~ 0 ℃, keep 20min ~ 2h at precooling temperature after adding the adducts carrier shown in the logical formula I, the concentration of adducts is lower than 200g/L in the liquid medium, relative 1 mole of MgX
2, the mole number of titanium compound is the 4-50 mole;
(B) under agitation, said mixture slowly is heated to 10 ℃ ~ 100 ℃, adds electron donor compound a and electron donor compound b;
(C) continue slowly to be warmed up to 100 ~ 130 ℃, reaction 0.5 ~ 3h subsequently, stops to stir, and liquid is separated with solid with suction filtration by sedimentation;
(D) solid matter that (C) is obtained is processed with the titanium compound shown in the logical formula II, at 100 ~ 130 ℃ of lower reaction 0.5 ~ 3h, subsequently, stop to stir, liquid is separated with solid with suction filtration by sedimentation, described step (D) is for repeating 1 time or repeatedly;
(E) also dry by the solids that step (D) obtains with the inert solvent washing, obtain ingredient of solid catalyst.
9. catalyzer that is used for olefinic polymerization, it comprises the reaction product of following component;
(1) catalyst component of one of claim 1-8;
(2) alkylaluminium cpd;
(3) optional a kind of external donor compound.
10. olefine polymerizing process, the method is included under the polymerizing condition, makes alkene CH
2=CHR, wherein R is the alkyl or aryl of hydrogen or 1～6 carbon, the optional another kind of described alkene as comonomer contacts with catalyzer claimed in claim 9 with the diolefine of conduct the second comonomer of choosing wantonly; With the polymkeric substance that reclaims generation.
11. method claimed in claim 10, it is used for directly at the low ash content polypropylene of polymerization reactor preparation.
12. the described method of claim 11, wherein the Al/Ti mol ratio is 10 ~ 300 in the employed catalyzer.
13. the described method of claim 11, wherein the Al/Ti mol ratio is 20 ~ 200 in the employed catalyzer.
14. each described method among the claim 10-13 does not wherein add external electron donor.
15. each described method is wherein used described external electron donor among the claim 10-13, and it is silicoorganic compound, its consumption is so that the mol ratio of Al/ silicoorganic compound is 5-500.
16. the described method of claim 15, the consumption of wherein said external electron donor is so that the mol ratio of Al/ silicoorganic compound is 10-200.
17. each described method among the claim 11-13, wherein the polyacrylic ash content of gained is lower than 100ppm.
18. method according to claim 14, wherein the polyacrylic ash content of gained is lower than 100ppm.
19. method according to claim 15, wherein the polyacrylic ash content of gained is lower than 100ppm.
20. method according to claim 16, wherein the polyacrylic ash content of gained is lower than 100ppm.
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| TWI644896B (en) * | 2013-05-21 | 2018-12-21 | 中國石油化工科技開發有限公司 | Catalyst component, catalyst and application for olefin polymerization |
| US9663595B2 (en) | 2014-08-05 | 2017-05-30 | W. R. Grace & Co. —Conn. | Solid catalyst components for olefin polymerization and methods of making and using the same |
| CN105622423B (en) * | 2014-10-28 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of adduct of magnesium halides and its preparation method and application |
| CN104672356B (en) * | 2015-03-09 | 2016-08-24 | 陈伟 | Catalyst component for olefin, the preparation method of this component and catalyst |
| CN109096424A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of catalyst and olefine polymerizing process for olefinic polymerization |
| CN109694429B (en) * | 2017-10-20 | 2022-01-04 | 中国石油化工股份有限公司 | Polypropylene, preparation method and application thereof |
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| CN1743348A (en) * | 2004-09-02 | 2006-03-08 | 中国石油化工股份有限公司 | Catalyst component for olefinic polymerization and its catalyst |
| CN101165074A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and catalyst thereof |
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| CN1743348A (en) * | 2004-09-02 | 2006-03-08 | 中国石油化工股份有限公司 | Catalyst component for olefinic polymerization and its catalyst |
| CN101165074A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and catalyst thereof |
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