CN104725540B - Ethylene copolymer preparation method - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 62
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 51
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 29
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 30
- -1 Hydrogen furans Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 125000005466 alkylenyl group Chemical group 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- XKWANYSVNPEJMG-UHFFFAOYSA-N oxolane;zirconium Chemical compound [Zr].C1CCOC1 XKWANYSVNPEJMG-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 abstract description 23
- 230000037048 polymerization activity Effects 0.000 abstract description 17
- 239000004711 α-olefin Substances 0.000 abstract description 12
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 239000002685 polymerization catalyst Substances 0.000 abstract 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 83
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 230000003197 catalytic effect Effects 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 239000002243 precursor Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 16
- 238000010276 construction Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 230000005311 nuclear magnetism Effects 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 150000002466 imines Chemical class 0.000 description 5
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- SYZWSSNHPZXGML-UHFFFAOYSA-N dichloromethane;oxolane Chemical compound ClCCl.C1CCOC1 SYZWSSNHPZXGML-UHFFFAOYSA-N 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NOXLGCOSAFGMDV-UHFFFAOYSA-N 2,3,4,5,6-pentafluoroaniline Chemical group NC1=C(F)C(F)=C(F)C(F)=C1F NOXLGCOSAFGMDV-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229940061334 2-phenylphenol Drugs 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 0 C*1C=CCC1 Chemical compound C*1C=CCC1 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing 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
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides an ethylene copolymer preparation method, which comprises that: in the presence of an olefin polymerization catalyst, ethylene and alpha-olefin are subjected to a polymerization reaction in a solvent, wherein the olefin polymerization catalyst contains a bimetallic catalyst precursor having a structure represented by a formula (I) and alkyl aluminoxane, R1, R2, R3, R4, R1＜'＞, R2＜'＞, R3＜'＞ and R4＜'＞ are the same or different and are respectively and independently hydrogen, phenyl or C1-C20 alkyl, R5 and R5＜'＞ are the same or different and are respectively and independently hydrogen or C1-C20 alkyl, and M1 and M2 are the same or different and are respectively and independently one selected from titanium, zirconium and hafnium. According to the present invention, when the olefin polymerization catalyst is used for catalysis of ethylene and alpha-olefin copolymerization, the high polymerization activity is provided. The formula I is defined in the instruction.
Description
Technical field
The present invention relates to a kind of preparation method of ethylene copolymer.
Background technology
Because polyolefinic raw materials enrich cheap, it is easily worked shaping, the polyolefin products worldwide producing every year
Exceed 100,000,000 tons, become one of industry of maximum-norm.Polyolefine material has relatively small density, good chemically-resistant
The features such as medicine, resistance to water and good mechanical strength, electrical insulating property, can be used for film, tubing, sheet material, various shaping
Product, electric wire etc., not only have been widely used in terms of agricultural, the daily use Sundry goods such as packaging, automobile, electrical equipment, are the mankind's
Clothing, food, lodging and transportion -- basic necessities of life are provided convenience, but also play great function in the Strategic projects such as national defence, the energy, Aero-Space.
Wherein, ethylene copolymer product has superior performance, and alpha-olefin species is various, including 1- octene, 1- hexene, 1-
Butylene, propylene and polar monomer etc..By adjusting comonomer type and consumption, linear low density polyethylene both can be obtained
, it is also possible to obtain thermoplastic elastomer (TPE) moreover it is possible to obtain rubber, application is quite varied for alkene.The special construction of particularly elastomer is assigned
Give its excellent mechanical property, rheological property and ageing-resistant performance, as during plastics impact resilience agent, low-temperature flexibility is good, consumption is few,
Cost performance is high, is widely used in modifying plastics.
The booming ziegler-natta catalyst and metallocene catalyst of having benefited from of polyolefin industry is joining of representative
The fast development of position polymerization.It is developed so far, day by day become with the research of metallocene catalyst for ziegler-natta catalyst
Ripe, but in such catalyst, the catalyst type being capable of effectively catalyzed ethylene combined polymerization is simultaneously few.Therefore, Nonmetallocene is urged
Agent is increasingly becoming the emphasis of current research.Salicylaldimine ligand transition-metal catalyst belongs to one kind therein.
Cn101864010a discloses the bimetallic catalyst precursor of a kind of catalysis in olefine polymerization or combined polymerization.This catalyst
Precursor is based on salicylaldimine ligand and the i-th v group 4 transition metal, and it is mainly condensed to yield with bridging salicylide using pentafluoroaniline
Part, then part is obtained catalyst with ti complexing.However, the synthetic route of this catalyst precarsor is loaded down with trivial details, with high costs, and
In alpha-olefin and ethylene copolymer, ratio is relatively low, and molecular weight distribution is wider.
Cn101200404a discloses a kind of method of synthesizing short-chain olefin by ethylene oligomerization, the method include be supported on from
Carry out ethylene oligomerization reaction, wherein, catalyst is by double salicylaldehyde imine nickel complex in the presence of catalyst in sub- liquid
With alkyl aluminum composition, the method products therefrom is ethylene low polymer.However, double salicylaldehyde imine nickel disclosed in cn101200404a
The yield of complex is relatively low, in addition, ethylene polymerization activity is relatively low.
Therefore, how to obtain and there is the ethylene copolymer of high catalytic activity and preparation process is simple remain one urgently
The technical problem solving.
Content of the invention
It is an object of the invention to overcoming the defect of prior art, and provide a kind of preparation side of new ethylene copolymer
Method.
The invention provides a kind of preparation method of ethylene copolymer, the method includes the presence in olefin polymerization catalysis
Under, ethene and alpha-olefin are carried out polymerisation in a solvent, wherein, described olefin polymerization catalysis contain with formula () institute
Show bimetallic catalyst precursor and the alkylaluminoxane of structure,
Formula (),
Wherein, r1、r2、r3、r4、r1’、r2’、r3' and r4' identical or different, and it is each independently hydrogen, phenyl or c1-c20
Alkyl；r5And r5' identical or different, and it is each independently hydrogen or c1-c20Alkyl；m1And m2Identical or different, and each
It independently is one of titanium, zirconium and hafnium.
The olefin polymerization catalysis that the present invention provides contain the above-mentioned bimetallic catalytic based on salicylaldimine ligand structure
Agent precursor and alkylaluminoxane, because the bimetallic in bimetallic catalyst precursor structure has synergy, and on phenyl ring
There is organic substituent, the olefin polymerization catalysis that therefore present invention provides have higher catalytic efficiency.Specifically, the present invention
The olefin polymerization catalysis providing when for catalyzed ethylene and alpha-olefin copolymer, the monometallic close with structure in prior art
Catalyst is compared, and has higher catalytic efficiency, and catalytic efficiency (polymerization activity) can reach 105g/(mol·cat·h).This
Outward, 12mol% is reached using the introducing ratio that the olefin polymerization catalysis that the present invention provides enable to alpha-olefin, and
The preparation method of described bimetallic catalyst precursor is simple, low cost, reproducible it is easy to industrialization.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of ethylene copolymer, the method includes the presence in olefin polymerization catalysis
Under, ethene and alpha-olefin are carried out polymerisation in a solvent, wherein, described olefin polymerization catalysis contain with formula () institute
Show bimetallic catalyst precursor and the alkylaluminoxane of structure,
Formula (),
Wherein, r1、r2、r3、r4、r1’、r2’、r3' and r4' identical or different, and it is each independently hydrogen, phenyl or c1-c20
Alkyl；r5And r5' identical or different, and it is each independently hydrogen or c1-c20Alkyl；m1And m2Identical or different, and each
It independently is one of titanium, zirconium and hafnium.
According to the present invention, the m in different bimetallic catalyst precursors1And m2Can identical it is also possible to different, and each
It independently is one of titanium, zirconium and hafnium.Preferably, m1And m2It is titanium.
According to the present invention, r1、r2、r3、r4、r5、r1’、r2’、r3' and r4' and r5' can be identical, all for hydrogen atom；Or,
r1、r2、r3、r4、r1’、r2’、r3' and r4' it is each independently hydrogen, phenyl or c1-c20Alkyl, r5And r5' be each independently
Hydrogen or c1-c20Alkyl, and r1、r2、r3And r4At least one of be c1-c20Alkyl or phenyl, r1’、r2’、r3' and r4' in
At least one be c1-c20Alkyl or phenyl.
In the present invention, described alkyl can be straight chain or side chain.Described c1-c20Straight or branched alkane
Base can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, positive penta
Base, 2- methyl butyl, 3- methyl butyl, 2,2- dimethyl propyl, n-hexyl, 2- methyl amyl, 3- methyl amyl, 4- methylpent
Base, n-heptyl, 2- methylhexyl, 3- methylhexyl, 4- methylhexyl, 5- methylhexyl, n-heptyl, n-octyl, n-nonyl, just
Decyl, 3,7- dimethyl octyl group, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, just
Octadecyl, NSC 77136 base and n-eicosane base.
Specifically, the structure meeting above-mentioned requirements can include but is not limited to: r1、r2、r3、r4、r5、r1’、r2’、r3’、r4’
And r5' can be hydrogen；Or, r1And r1' can be c1-c20Alkyl or phenyl, r2、r3、r4、r2’、r3' and r4' can be hydrogen,
r5And r5' can be hydrogen or c1-c20Alkyl；Or, r2And r2' can be c1-c20Alkyl or phenyl, r1、r3、r4、r1’、
r3' and r4' can be hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r3And r3' can be c1-c20Alkyl or benzene
Base, r1、r2、r4、r1’、r2' and r4' can be hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r4And r4' can be
c1-c20Alkyl or phenyl, r1、r2、r3、r1’、r2' and r3' can be hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or
Person, r1、r2、r1' and r2' can be c1-c20Alkyl or phenyl, r3、r4、r3' and r4' can be hydrogen, r5And r5' can be hydrogen
Or c1-c20Alkyl；Or, r1、r3、r1' and r3' can be c1-c20Alkyl or phenyl, r2、r4、r2' and r4' can be hydrogen,
r5And r5' can be hydrogen or c1-c20Alkyl；Or, r1、r4、r1' and r4' it is c1-c20Alkyl or phenyl, r2、r3、r2' and
r3' can be hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r2、r3、r2' and r3' can be c1-c20Alkyl or
Phenyl, r1、r4、r1' and r4' can be hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r2、r4、r2' and r4' permissible
For c1-c20Alkyl or phenyl, r1、r3、r1' and r3' it is hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r3、
r4、r3' and r4' can be c1-c20Alkyl or phenyl, r1、r2、r1' and r2' can be hydrogen, r5And r5' can be hydrogen or c1-c20
Alkyl；Or, r1、r2、r3、r1’、r2' and r3' can be c1-c20Alkyl or phenyl, r4And r4' it is hydrogen, r5And r5' permissible
For hydrogen or c1-c20Alkyl；Or, r1、r3、r4、r1’、r3' and r4' can be c1-c20Alkyl or phenyl, r2And r2' permissible
For hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r1、r2、r4、r1’、r2' and r4' can be c1-c20Alkyl or
Phenyl, r3And r3' can be hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r2、r3、r4、r2’、r3' and r4' permissible
For c1-c20Alkyl or phenyl, r1And r1' can be hydrogen, r5And r5' can be hydrogen or c1-c20Alkyl；Or, r1、r2、r3、
r4、r1’、r2’、r3' and r4' can be c1-c20Alkyl or phenyl, r5And r5' can be hydrogen or c1-c20Alkyl.
The present inventor finds under study for action it is preferable that r1And r1' identical or different, and it is each independently c1-
c20Alkyl or phenyl；r2、r3、r4、r5、r2’、r3’、r4' and r5' it is hydrogen, by specific r above1-r5And r1’-r5' cooperation
The mixture of the bimetallic catalyst precursor being formed and alkylaluminoxane is as olefin polymerization catalysis catalyzed ethylene and α-alkene
Fabulous catalytic effect can be obtained during hydrocarbon copolymerization.
It is further preferred that r1And r1' identical or different, and it is each independently tertiary butyl or phenyl；r2、r3、r4、r5、
r2’、r3’、r4' and r5' it is hydrogen, m1And m2For titanium.It is highly preferred that r1And r1' it is tertiary butyl, r2、r3、r4、r5、r2’、r3’、
r4' and r5' it is hydrogen, m1And m2It is titanium, now, corresponding described bimetallic catalyst precursor has the knot shown in formula ()
Structure；Or, r1And r1' it is each independently phenyl, r2、r3、r4、r5、r2’、r3’、r4' and r5' it is hydrogen, m1And m2It is titanium,
Now, corresponding described bimetallic catalyst precursor has the structure shown in formula (),
Formula (),
Formula ().
According to the present invention, described bimetallic catalyst precursor can prepare according to existing various methods it is preferable that
Prepare in accordance with the following methods: under the conditions of complex reaction, by having the compound of structure and formula shown in formula () be
mcl4(thf)2Compound contact in organic solvent,
Formula (),
Wherein, r1、r2、r3、r4、r1’、r2’、r3' and r4' identical or different, and it is each independently hydrogen, phenyl or c1-c20
Alkyl；r5And r5' identical or different, and it is each independently hydrogen or c1-c20Alkyl；M is one of titanium, zirconium and hafnium.
Specifically, the preparation process of described bimetallic catalyst precursor is referred to following reaction equation and carries out.
With regard to r1、r2、r3、r4、r5、r1’、r2’、r3’、r4' and r5' concrete restriction can be closed by described above
Reason ground selects, and therefore not to repeat here.
According to the present invention, described formula is mcl4(thf)2Compound can close titanium, tetrachloro for tetrachloro double (oxolane)
One of double (oxolane) zirconiums and tetrachloro double (oxolane) conjunction hafnium are it is preferable that described formula is mcl4(thf)2Change
Compound is that tetrachloro double (oxolane) closes titanium.
The present invention has the compound of structure shown in formula () and formula for mcl to described4(thf)2Compound consumption
It is not particularly limited, for example, described have the compound of structure shown in formula () and formula for mcl4(thf)2Compound
Mol ratio can be 1:1.8-2.5, preferably 1:2-2.2.
According to the present invention, solvent used and described bimetallic catalyst precursor in the preparation process of described ethylene copolymer
In preparation process organic solvent used can identical it is also possible to different it is possible to be each independently existing various not with
The inert substance that reactant is reacted with generation product, for example, it is possible to be each independently oxolane, ether, Isosorbide-5-Nitrae-dioxy six
One or more of ring, dichloromethane, benzene, toluene, n-hexane and hexamethylene.These solvents can be used alone it is also possible to
It is used in mixed way.The consumption of described solvent can be selected according to the consumption of ethene and alpha-olefin, the consumption of described organic solvent
Can be mcl according to there is the compound of structure shown in formula () with formula4(thf)2The consumption of compound reasonably selected
Select, therefore not to repeat here.
The present invention is mcl to having the compound of structure shown in formula () with formula4(thf)2Compound organic molten
In agent, the condition of contact is not particularly limited, as long as ensure that having the compound of structure and formula shown in formula () is
mcl4(thf)2Compound occur complex reaction generate target product.Preferably, the condition of described contact include first-
Contact 0.5-3 hour at 85 DEG C to -70 DEG C, then contact 8-24 hour at 0-60 DEG C；It is highly preferred that the condition bag of described contact
Include and first at -80 DEG C to -75 DEG C, contact 1-2 hour, then contact 12-20 hour at 20-40 DEG C.
According to the present invention, in addition it is also necessary to by described organic solvent after the preparation of described bimetallic catalyst precursor completes
Remove.Wherein, the method removing described organic solvent can be carried out using various methods well known in the art, for example, vacuum line
Except organic solvent, revolving remove organic solvent etc., all being known, here will not be described in great detail to this those skilled in the art.
Additionally, the bimetallic catalyst precursor higher in order to obtain purity, the preparation side of described bimetallic catalyst precursor
Method can also include the step being purified the product obtaining.The method of described purifying can adopt well known in the art various
Purification process is carried out, such as recrystallization etc..Recrystallization solvent used can be for example dichloromethane and/or n-hexane.
The present invention does not have spy to the bimetallic catalyst precursor containing in described olefin polymerization catalysis and alkylaluminoxane
Do not limit, but so that the collaborative catalyzed ethylene that plays of both materials carries out copolymerization, described bimetallic catalytic with alpha-olefin
The mol ratio of agent precursor and alkylaluminoxane is preferably 1:200-2000, more preferably 1:200-1000.
The various alkyl as co-catalyst that can be commonly used for catalyst field according to the present invention, described alkylaluminoxane
Aikyiaiurnirsoxan beta, for example, it is possible to be c1-c5Straight or branched alkylaluminoxane, preferably MAO (mao) and/or modification
MAO (mmao).
The present invention mainly thes improvement is that the olefinic polymerization employing a kind of new inclusion bimetallic catalyst precursor
Catalyst, and the consumption of the species of alpha-olefin, ethene and alpha-olefin and specific polymeric reaction condition all can be with existing skills
Art is identical.
Specifically, the condition of described polymerisation can be the conventional selection of this area, for example, generally include reaction temperature
Can be -30 DEG C to 80 DEG C, preferably 20-60 DEG C；Reaction pressure can be 0.5-10atm, preferably 1-5atm；Reaction time
Can be 1-60min, preferably 20-40min.Additionally, in order to overcome oxygen inhibition, obtain the ethylene copolymer with larger molecular weight
Thing, described polymerisation is preferably carried out in an inert atmosphere.Described inert atmosphere refers to not occur chemistry anti-with reactant and product
Any one gas answered or admixture of gas, such as one or more of nitrogen and periodic table of elements zero group gas.Keep lazy
Property atmosphere method can be to be passed through above-mentioned with reactant and product, any of chemical reaction not to occur in polymerization reaction system
A kind of gas or admixture of gas.
Additionally, the preparation method of described ethylene copolymer adds terminator after the completion of being additionally included in polymerisation, so that live
Property center inactivation.Described terminator can be the various terminations that living polymer chains can be terminated in field of olefin polymerisation
Agent, for example, it is possible to be one or more of water, methyl alcohol, ethanol, normal propyl alcohol and isopropanol.
Hereinafter will be described the present invention by embodiment, but embodiments of the invention will be not only limited in following reality
Apply example.
In following examples, the method that the performance test of polymer is related to is as follows:
Fusing point is measured by differential scanning calorimetry (dsc), specifically adopts pe company of U.S. model pe dsc-7
Differential scanning calorimeter be measured, wherein, heating rate be 10 DEG C/min.Weight average molecular weight (mw) and number-average molecular weight
(mn) it is measured by exclusion chromatography (gpc), using the gel permeation chrommatograph of model lc-10at of Shimadzu Corporation, flow
It is mutually thf, standard sample is Narrow distribution polystyrene, and test temperature is 25 DEG C.
Unless stated otherwise, the compound used in following preparation example, embodiment and comparative example and reagent etc. are commercially available
Product.
Preparation example 1
This preparation example is used for the preparation that explanation has the formula (ii) bimetallic catalyst precursor of shown structure.
By 6,6'- (1e, 1'e)-(4,4' methylene bis (4,1- penylene) double (imines -1- replaces -1- subunit)) double (first
Base -1- replaces -1- subunit) double (2- t-butyl phenol) (system recorded according to eur.polym.j.2012,48,191-199 document
Preparation Method is obtained, similarly hereinafter) (1.77g, 3.41mmol) be dissolved in dichloromethane solvent (consumption of dichloromethane be 30ml) ,-
At 78 DEG C, this solution is added to the dichloromethane solution (two closing titanium (2.28g, 6.82mmol) containing tetrachloro double (oxolane)
The consumption of chloromethanes is 30ml) in, react 1 hour under low temperature, recover to 25 DEG C of room temperature, continue reaction 16 hours.Reaction terminates
Afterwards, with vacuum line, solvent is removed, residue from dichloromethane is washed and filtered by diatomite, and filtrate is drained, crude product
With dichloromethane/n-hexane recrystallization, obtain the red brown solid of 2.97g, be denoted as bimetallic catalyst precursor a1, be computed really
Fixed, yield is 90%.
Elementary analysis result shows, anal.calc.for c57h52cl6f10n2o5ti2(%):c,54.99;h,3.45;n,
3.09.found(%):c,54.73;h,3.79;n,2.89.fd-ms:m/z966.5(calcd966.1).
Preparation example 2
This preparation example is used for the preparation that explanation has the formula (ii) bimetallic catalyst precursor of shown structure.
By 6,6'- (1e, 1'e)-(4,4' methylene bis (4,1- penylene) double (imines -1- replaces -1- subunit)) double (first
Base -1- replace -1- subunit) double (2- t-butyl phenol) (0.24g, 0.46mmol) be dissolved in dichloromethane solvent (dichloromethane
Consumption is 30ml) in, at -78 DEG C, this solution is added and close titanium (0.32g, 0.96mmol) to containing tetrachloro double (oxolane)
Dichloromethane solution (consumption of dichloromethane be 30ml) in, react 1 hour under low temperature, recover to room temperature and be heated to 40
DEG C, continue reaction 12 hours.After reaction terminates, with vacuum line, solvent is removed, residue from dichloromethane washs and passes through silicon
Diatomaceous earth filters, and filtrate is drained, crude product dichloromethane/n-hexane recrystallization, obtains the red brown solid of 0.41g, is denoted as
Bimetallic catalyst precursor a2, yield is 93%.
Characterization result is identical with preparation example 1.
Preparation example 3
This preparation example is used for the preparation that explanation has the formula (ii) bimetallic catalyst precursor of shown structure.
By 6,6'- (1e, 1'e)-(4,4' methylene bis (4,1- penylene) double (imines -1- replaces -1- subunit)) double (first
Base -1- replace -1- subunit) double (2- t-butyl phenol) (0.57g, 1.10mmol) be dissolved in dichloromethane solvent (dichloromethane
Consumption is 30ml) in, at -78 DEG C, this solution is added and close titanium (0.81g, 2.42mmol) to containing tetrachloro double (oxolane)
Dichloromethane solution (consumption of dichloromethane be 30ml) in, react 1 hour under low temperature, recover to 20 DEG C of room temperature, continue anti-
Answer 20 hours.After reaction terminates, with vacuum line, solvent is removed, residue from dichloromethane is washed and filtered by diatomite,
Filtrate is drained, crude product dichloromethane/n-hexane recrystallization, obtain the red brown solid of 0.88g, be denoted as bimetallic catalytic
Agent precursor a3, yield is 83%.
Characterization result is identical with preparation example 1.
Preparation example 4
This preparation example is used for the preparation that explanation has the formula (ii) bimetallic catalyst precursor of shown structure.
By 6,6'- (1e, 1'e)-(4,4' methylene bis (4,1- penylene) double (imines -1- replaces -1- subunit)) double (first
Base -1- replace -1- subunit) double (2- t-butyl phenol) (0.22g, 0.42mmol) be dissolved in dichloromethane solvent (dichloromethane
Consumption is 30ml) in, at -78 DEG C, this solution is added and close titanium (0.28g, 0.84mmol) to containing tetrachloro double (oxolane)
Dichloromethane solution (consumption of dichloromethane be 30ml) in, react 1 hour under low temperature, recover to room temperature and be heated to 40
DEG C, continue reaction 12 hours.After reaction terminates, with vacuum line, solvent is removed, residue from dichloromethane washs and passes through silicon
Diatomaceous earth filters, and filtrate is drained, crude product dichloromethane/n-hexane recrystallization, obtains the red brown solid of 0.33g, is denoted as
Bimetallic catalyst precursor a4, yield is 80%.
Characterization result is identical with preparation example 1.
Preparation example 5
This preparation example has the preparation of the bimetallic catalyst precursor of structure shown in formula () for explanation.
By 6,6'- (1e, 1'e)-(4,4' methylene bis (4,1- penylene) double (imines -1- replaces -1- subunit)) double (first
Base -1- replaces -1- subunit) double (2- phenylphenol) material (0.51g, 0.91mmol, purchased from alfa company) is dissolved in dichloromethane
In solvent (consumption of dichloromethane is 30ml), at -78 DEG C, this solution is added and close titanium to containing tetrachloro double (oxolane)
In the dichloromethane solution (consumption of dichloromethane be 30ml) of (0.60g, 1.82mmol), react 1 hour under low temperature, recover to
Room temperature is simultaneously heated to 40 DEG C, continues reaction 12 hours.After reaction terminates, with vacuum line, solvent is removed, residue dichloromethane
Alkane is washed and is filtered by diatomite, and filtrate is drained, crude product dichloromethane/n-hexane recrystallization, obtains the red of 0.95g
Brown solid, is denoted as bimetallic catalyst precursor a5, and yield is 87%.
Elementary analysis result shows, anal.calc.for c60h83cl6n2o4ti2(%):c,59.82;h,6.94;n,
2.33.found(%):c,59.80;h,6.92;n,2.34.fd-ms:m/z1203.40(calcd1203.34).
Embodiment 1
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6ml(12mg/ml of MAO (mao)), 1- hexene 15ml,
The n-hexane 100ml that processes through anhydrous and oxygen-free and containing the bimetallic metal catalysts precursors with formula (ii) shown structure
4ml(2.5 μm of ol/ml of the toluene solution of a1).It is passed through the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25
DEG C reaction 20min, afterwards add ethanol terminating reaction, obtain polymer 0.103g, be computed determine, polymerization activity be 3.1 ×
104g·mol-1(ti)·h-1.
Dsc records fusing point and is 81 DEG C；Gpc records the m of polyethylenewFor 1.6 × 105, molecular weight distribution mw/mnFor 2.92；High
The content that warm nuclear-magnetism carbon spectrum records 1- hexene construction unit is 8.9mol%.
Embodiment 2
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 3.4ml(12mg/ml of MAO (mao)), 1- hexene
15ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a2).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.116g, be computed determining, polymerization activity is
3.5×104g·mol-1(ti)·h-1.
Dsc records fusing point and is 86 DEG C；Gpc records the m of polyethylenewFor 2.4 × 105, molecular weight distribution mw/mnFor 2.77；High
The content that warm nuclear-magnetism carbon spectrum records 1- hexene construction unit is 8.0mol%.
Embodiment 3
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
15ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a3).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.267g, be computed determining, polymerization activity is
8.0×104g·mol-1(ti)·h-1.
Dsc records fusing point and is 120 DEG C；Gpc records the m of polyethylenewFor 2.9 × 105, molecular weight distribution mw/mnFor 3.03；
The content that high temperature nuclear-magnetism carbon spectrum records 1- hexene construction unit is 2.9mol%.
Embodiment 4
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a4).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.202g, be computed determining, polymerization activity is
6.1×104g·mol-1(ti)·h-1.
Dsc records fusing point and is 108 DEG C；Gpc records the m of polyethylenewFor 2.0 × 105, molecular weight distribution mw/mnFor 2.69；
The content that high temperature nuclear-magnetism carbon spectrum records 1- hexene construction unit is 5.5mol%.
Embodiment 5
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
15ml, the n-hexane 300ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a1).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.131g, be computed determining, polymerization activity is
3.9×104g·mol-1(ti)·h-1.
Dsc records fusing point and is 115 DEG C；Gpc records the m of polyethylenewFor 2.3 × 105, molecular weight distribution mw/mnFor 2.82；
The content that high temperature nuclear-magnetism carbon spectrum records 1- hexene construction unit is 4.9mol%.
Embodiment 6
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
2ml(2.5 μm of ol/ml of toluene solution of agent precursor a2).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.176g, be computed determining, polymerization activity is
1.1×105g·mol-1(ti)·h-1.
Dsc records fusing point and is 93 DEG C；Gpc records the m of polyethylenewFor 1.8 × 105, molecular weight distribution mw/mnFor 2.52；High
The content that warm nuclear-magnetism carbon spectrum records 1- hexene construction unit is 7.2mol%.
Embodiment 7
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
2ml(2.5 μm of ol/ml of toluene solution of agent precursor a3).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.176g, be computed determining, polymerization activity is
1.1×105g·mol-1(ti)·h-1.
Dsc records fusing point and is 93 DEG C；Gpc records the m of polyethylenewFor 2.5 × 105, molecular weight distribution mw/mnFor 2.81；High
The content that warm nuclear-magnetism carbon spectrum records 1- hexene construction unit is 7.2mol%.
Embodiment 8
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a1).It is passed through the ethene that pressure is 5atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.296g, be computed determining, polymerization activity is
8.9×105g·mol-1(ti)·h-1.
Dsc records fusing point and is 118 DEG C；Gpc records the m of polyethylenewFor 2.9 × 105, molecular weight distribution mw/mnFor 2.99；
The content that high temperature nuclear-magnetism carbon spectrum records 1- hexene construction unit is 2.9mol%.
Embodiment 9
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a1).It is passed through the ethene that pressure is 1atm under mechanical stirring, and in this pressure
Under react 20min in 25 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.081g, be computed determining, polymerization activity is
2.4×105g·mol-1(ti)·h-1.
Dsc records fusing point and is 53 DEG C；Gpc records the m of polyethylenewFor 3.1 × 105, molecular weight distribution mw/mnFor 3.03；High
The content that warm nuclear-magnetism carbon spectrum records 1- hexene construction unit is 12.1mol%.
Embodiment 10
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- hervene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- hexene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a1).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 40 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.162g, be computed determining, polymerization activity is
4.9×105g·mol-1(ti)·h-1.
Dsc records fusing point and is 68 DEG C；Gpc records the m of polyethylenewFor 1.9 × 105, molecular weight distribution mw/mnFor 2.42；High
The content that warm nuclear-magnetism carbon spectrum records 1- hexene construction unit is 10.4mol%.
Embodiment 11
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- octene copolymer: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- octene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a1).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 40 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.185g, be computed determining, polymerization activity is
5.6×105g·mol-1(ti)·h-1.
Dsc records fusing point and is 62 DEG C；Gpc records the m of polyethylenewFor 2.3 × 105, molecular weight distribution mw/mnFor 2.72；High
The content that warm nuclear-magnetism carbon spectrum records 1- octene construction unit is 11.1mol%.
Embodiment 12
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Ethene and 1- decene copolymerization: the 500ml polymeric kettle after heat drying is vacuumized logical nitrogen twice, then takes out true
Sky after be passed through ethylene gas, then sequentially add the toluene solution 6.8ml(12mg/ml of MAO (mao)), 1- decene
10ml, the n-hexane 150ml processing through anhydrous and oxygen-free and containing the bimetallic metal catalytic with formula (ii) shown structure
4ml(2.5 μm of ol/ml of toluene solution of agent precursor a1).It is passed through the ethene that pressure is 3atm under mechanical stirring, and in this pressure
Under react 20min in 40 DEG C, add ethanol terminating reaction afterwards, obtain polymer 0.137g, be computed determining, polymerization activity is
4.1×105g·mol-1(ti)·h-1.
Dsc records fusing point and is 72 DEG C；Gpc records the m of polyethylenewFor 2.5 × 105, molecular weight distribution mw/mnFor 2.63；High
The content that warm nuclear-magnetism carbon spectrum records 1- decene construction unit is 9.3mol%.
Embodiment 13
This embodiment is used for the preparation method of the ethylene copolymer of present invention offer is described.
Method according to embodiment 12 prepares ethylene copolymer, except for the difference that, has the bimetallic of formula (ii) shown structure
Metal catalysts precursors a1 are substituted with bimetallic metal catalysts precursors a5 with structure shown in formula () of identical molal quantity,
Obtain polymer 0.158g, be computed determining, polymerization activity is 4.7 × 105g·mol-1(ti)·h-1.
Dsc records fusing point and is 85 DEG C；Gpc records the m of polyethylenewFor 3.1 × 105, molecular weight distribution mw/mnFor 2.55；High
The content that warm nuclear-magnetism carbon spectrum records 1- decene construction unit is 8.4mol%.
As can be seen from the above results, when the described olefin polymerization catalysis that the present invention is provided be used for catalyzed ethylene and α-
During olefin-copolymerization, there is higher polymerization activity.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The combination of energy no longer separately illustrates.
Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (14)
1. a kind of preparation method of ethylene copolymer, the method is included in the presence of olefin polymerization catalysis, by ethene and α-
Alkene carries out polymerisation in a solvent it is characterised in that described olefin polymerization catalysis contain has structure shown in formula ()
Bimetallic catalyst precursor and alkylaluminoxane,
Wherein, r1、r2、r3、r4、r1’、r2’、r3' and r4' identical or different, and it is each independently hydrogen, phenyl or c1-c20Alkane
Base；r5And r5' identical or different, and it is each independently hydrogen or c1-c20Alkyl；m1And m2Identical or different and each independent
Ground is one of titanium, zirconium and hafnium.
2. preparation method according to claim 1, wherein, m1And m2For titanium.
3. preparation method according to claim 1 and 2, wherein, r1And r1' identical or different, and it is each independently c1-
c20Alkyl or phenyl；r2、r3、r4、r5、r2’、r3’、r4' and r5' it is hydrogen.
4. preparation method according to claim 3, wherein, r1And r1' identical or different, and it is each independently tertiary butyl
Or phenyl；r2、r3、r4、r5、r2’、r3’、r4' and r5' it is hydrogen.
5. preparation method according to claim 4, wherein, described bimetallic catalyst precursor has formula () or formula ()
Shown structure,
6. the preparation method according to claim 1,2,4 or 5, wherein, described bimetallic catalyst precursor is according to lower section
Method prepares: under the conditions of complex reaction, will have the compound of structure shown in formula () with formula is mcl4(thf)2Change
Compound contacts in organic solvent,
Wherein, r1、r2、r3、r4、r1’、r2’、r3' and r4' identical or different, and it is each independently hydrogen, phenyl or c1-c20Alkane
Base；r5And r5' identical or different, and it is each independently hydrogen or c1-c20Alkyl；M is one of titanium, zirconium and hafnium.
7. preparation method according to claim 6, wherein, described formula is mcl4(thf)2Compound be tetrachloro double (four
Hydrogen furans) close one of titanium, double (oxolane) zirconium of tetrachloro and tetrachloro double (oxolane) conjunction hafnium.
8. preparation method according to claim 7, wherein, described have the compound of structure and formula shown in formula () and be
mcl4(thf)2Compound mol ratio be 1:1.8-2.5.
9. preparation method according to claim 8, wherein, described have the compound of structure and formula shown in formula () and be
mcl4(thf)2Compound mol ratio be 1:2-2.2.
10. preparation method according to claim 6, wherein, the condition of described contact is included first at -85 DEG C to -70 DEG C
Contact 0.5-3 hour, then contact 8-24 hour at 0-60 DEG C.
11. preparation methods according to claim 10, wherein, the condition of described contact is included first at -80 DEG C to -75 DEG C
Contact 1-2 hour, then contact 12-20 hour at 20-40 DEG C.
12. preparation methods according to claim 1, wherein, the rubbing of described bimetallic catalyst precursor and alkylaluminoxane
That ratio is 1:200-2000.
13. preparation methods according to claim 12, wherein, described alkylaluminoxane is c1-c5Straight or branched alkane
Base aikyiaiurnirsoxan beta.
14. preparation methods according to claim 13, wherein, described alkylaluminoxane is MAO.
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