CN112661893B - Main catalyst for copolymerization of ethylene and cycloolefin, polymerization method and application thereof - Google Patents
Main catalyst for copolymerization of ethylene and cycloolefin, polymerization method and application thereof Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000005977 Ethylene Substances 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 150000001925 cycloalkenes Chemical class 0.000 title claims abstract description 49
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 20
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims description 56
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 17
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 abstract description 11
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 8
- 125000004104 aryloxy group Chemical group 0.000 abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000011010 flushing procedure Methods 0.000 description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- -1 cyclic olefin Chemical class 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UKYGKNHLXAIOQN-UHFFFAOYSA-N 6-methylidenecyclohexa-2,4-dien-1-ol Chemical compound OC1C=CC=CC1=C UKYGKNHLXAIOQN-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000004377 microelectronic Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a main catalyst for copolymerization of ethylene and cycloolefin, a preparation method and application thereof, wherein the structure of the main catalyst is shown in the following formula,wherein X is selected from alkoxy, aryloxy, alkyl, aryl or halogen atom, cp' is cyclopentadienyl, indenyl or fluorenyl substituted or unsubstituted with hydrocarbyl groups, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from a hydrogen atom, a halogen atom, or a substituent containing 1 to 18 carbon atoms. The ethylene and cycloolefin copolymerization catalyst composition obtained by adopting the main catalyst for ethylene and cycloolefin copolymerization and alkyl aluminoxane can be used for copolymerization of ethylene and cycloolefin, and the obtained polymer has the advantages of high molecular weight, narrow molecular weight distribution and the like.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a main catalyst for copolymerization of ethylene and cycloolefin.
Background
The cycloolefin copolymer (COC) is a copolymer prepared by coordination polymerization or ring-opening metathesis polymerization using a cyclic olefin as a monomer, and has good heat resistance and optical properties. For example, norbornene and ethylene copolymers are thermoplastic polymers which have great industrial application prospects. It has high glass transition temperature (Tg), excellent moisture resistance, optical transparency and strong chemical corrosion resistance, and can be widely applied to the fields of medical equipment, automobiles, optical products, digital storage materials and the like. And the copolymer with high norbornene content has low dielectric constant, can be used as interface dielectric medium in microelectronic devices, realizes high-efficiency connection between interfaces, and has important application in the field of electronic appliances.
At present, the catalytic systems used for synthesizing norbornene and ethylene copolymers mainly comprise: front transition metal compound catalyst systems typified by titanium, zirconium, hafnium, and rear transition metal catalyst systems typified by iron, cobalt, nickel. Metallocene compounds are a classical class of catalysts in pre-transition metal catalytic systems. Metallocene catalysts for olefin polymerization have been the focus of research in metal organic chemistry, catalytic chemistry, polymer chemistry and materials for decades. The metallocene catalyst can be used for obtaining olefin polymers with very uniform molecular weight distribution and chemical composition distribution; meanwhile, the molecular structure and the molecular weight of the polymer can be controlled highly by adjusting the catalyst structure; in addition, by using a metallocene catalyst, it is also possible to obtain olefin polymers which are not obtainable by conventional Ziegler-Natta catalysts. For example, the Kaminsky group (macromol. Chem.1989,190,515-526; polym. Bull. (Berlin) 1993,31,175-182; macromol. Chem. Phs.1996,197, 3907-394), the Fink group (Macromolecules 1998,31,4669-4673) and the Waymouth group (Macromolecules 1999,32,2816-2825) have all been studied for copolymerization of ethylene with norbornene using homogeneous metallocene catalysts, and the resulting copolymers have a molecular weight of several tens of thousands to hundreds of thousands. With the development of cycloolefin polymerization catalyst systems, there are 4 companies that successively push out COC products: ethylene/norbornene copolymer available under the trade name TOPAS from Ticona; ethylene/tetracyclodecene copolymer sold under the trade name APEL by Mitsui corporation; ZEONEX and ZEONOR, commercial products of Zeon corporation; JSR company's product ARTON.
Although chinese patents also disclose catalytic systems for a variety of COCs, for example: CN101117366A, CN109467660A, CN106749781A, CN107141375A, CN107141377A, CN106749911a. However, there is still a lack of industrially applicable catalyst for efficient cycloolefin copolymerization, which makes a large amount of norbornene byproducts wastefully consumed in petrochemical industry every year. In summary, however, in order to effectively utilize domestic norbornene resources and reduce the import dependence of norbornene polymers, development and research of a novel COC catalyst have been the main research subject in this field.
Disclosure of Invention
The invention provides a main catalyst for copolymerization of ethylene and cycloolefin.
The invention aims to provide a main catalyst for the copolymerization of ethylene and cycloolefin, which has a structure shown in a formula (I):
in formula (I), X is selected from an alkoxy group, an aryloxy group, an alkyl group, an aryl group or a halogen atom, cp' is a cyclopentadienyl group, an indenyl group or a fluorenyl group substituted or unsubstituted with a hydrocarbon group, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from a hydrogen atom, a halogen atom, or a substituent containing 1 to 18 carbon atoms.
The description herein of the cyclopentadienyl, indenyl or fluorenyl substituted or unsubstituted with a hydrocarbyl group refers to a cyclopentadienyl substituted or unsubstituted with a hydrocarbyl group, an indenyl substituted or unsubstituted with a hydrocarbyl group, or a fluorenyl substituted or unsubstituted with a hydrocarbyl group, described directly as: cyclopentadienyl, indenyl or fluorenyl substituted with a hydrocarbyl group may also be described as cyclopentadienyl, indenyl, fluorenyl or derivatives thereof substituted with a hydrocarbyl group.
In the present invention, the compound represented by the formula (1) has smaller steric hindrance and the polymerization activity of the same kind may be higher.
In a preferred embodiment, in formula (I), X is selected from C 1 ～C 5 Alkoxy, C 6 ～C 9 Aryloxy group, C 1 ～C 5 Alkyl, C of (2) 6 ～C 9 Aryl or halogen atoms of (a); and/or Cp' is C 1 ～C 3 Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; and/or R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from hydrogen atom, halogen atom, C 6 ～C 9 Aryl, C of (2) 1 ～C 5 Alkyl or C of (2) 1 ～C 5 Substituted alkyl of (a).
In a further preferred embodiment, in formula (I), X is selected from chlorine atom, methoxy, phenoxy, methyl, phenyl or benzyl; and/or Cp' is selected from pentamethylcyclopentadienyl, cyclopentadienyl or indenyl; and/or R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from hydrogen atoms, C 1 ～C 3 Alkyl, C of (2) 1 ～C 3 Is substituted by halogen of alkyl or halogen atom.
In a still further preferred embodiment, in formula (I), X is selected from a chlorine atom or a methoxy group; and/or Cp' is selected from pentamethylcyclopentadienyl or cyclopentadienyl; and/or R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from a hydrogen atom, a chlorine atom, or a methyl group.
The second object of the present invention is to provide a process for preparing a procatalyst for the copolymerization of ethylene and cycloolefin, which comprises using the compounds of the formula (II) and the formula (III) as main raw materials.
In a preferred embodiment, in formula (II), X is selected from the group consisting of alkoxy, aryloxy, alkyl, aryl or halogen atoms, preferably from the group consisting of C 1 ～C 5 Alkoxy, C 6 ～C 9 Aryloxy group, C 1 ～C 5 Alkyl, C of (2) 6 ～C 9 Aryl or halogen atoms of (C)More preferably selected from a chlorine atom, methoxy, phenoxy, methyl, phenyl or benzyl, for example a chlorine atom, methoxy, phenoxy, methyl, phenyl or benzyl.
In a preferred embodiment, in formula (II), cp' is cyclopentadienyl, indenyl or fluorenyl substituted or unsubstituted with hydrocarbyl groups, preferably C 1 ～C 3 Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, more preferably pentamethylcyclopentadienyl, cyclopentadienyl or indenyl, for example pentamethylcyclopentadienyl or cyclopentadienyl.
In a preferred embodiment, in formula (III), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from a hydrogen atom, a halogen atom or a substituent containing 1 to 18 carbon atoms, preferably each independently selected from a hydrogen atom, a halogen atom, C 6 ～C 9 Aryl, C of (2) 1 ～C 5 Alkyl or C of (2) 1 ～C 5 More preferably each independently selected from the group consisting of hydrogen atom, C 1 ～C 3 Alkyl, C of (2) 1 ～C 3 For example, each independently selected from a hydrogen atom, a chlorine atom or a methyl group.
In the invention, the compound shown in the formula (III) is prepared by taking the compounds shown in the formulas (III-1) and (III-2) as main raw materials according to the method disclosed in the prior art.
Wherein in the formula (III-1) and the formula (III-2), R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Is defined as in formula (III) above.
In a preferred embodiment, the method is carried out under a protective atmosphere, comprising the steps of:
step 1, mixing a compound shown in a formula (II), a solvent and optional triethylamine to obtain a solution A;
when X is halogen, triethylamine is needed to be adopted, HX is removed in the reaction, the triethylamine reacts with HX to generate triethylamine hydrochloride which is insoluble in an organic solvent and easy to separate, and meanwhile, if the triethylamine is not added, the generated HX can be combined with N atoms in the formula (III) to obtain no target product, so that the triethylamine plays a role of an acid binding agent; when X is selected from alkoxy, aryloxy, alkyl or aryl, then triethylamine is not required.
Step 2, mixing a compound shown in a formula (III) with a solvent to obtain a solution B;
and 3, dropwise adding the solution B into the solution A, and reacting to obtain the main catalyst for copolymerization of ethylene and cycloolefin.
Wherein the protective atmosphere is preferably nitrogen.
The method of the invention is carried out under anhydrous and anaerobic conditions. The ligand shown in the formula (I) is simple in synthesis, does not involve dangerous butyl lithium, and is simple in treatment process, safe and environment-friendly in process.
In a preferred embodiment, the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1.
In a preferred embodiment, in step 1 and step 2, the solvent is an organic solvent, including tetrahydrofuran, dichloromethane, toluene, preferably tetrahydrofuran.
In a preferred embodiment, in step 1, when triethylamine is used, the molar ratio of triethylamine to the compound of formula (II) is greater than 1:1, preferably (2-4): 1.
in a preferred embodiment, in step 1, the weight concentration of the solution a is 15wt% or less, preferably 5wt% or less.
In a preferred embodiment, in step 2, the weight concentration of the solution B is 15wt% or less, preferably 5wt% or less.
In a preferred embodiment, in step 3, the reaction is carried out at 0 to 100 ℃, preferably 20 to 50 ℃, more preferably at room temperature, which is 20 to 30 ℃.
In a further preferred embodiment, in step 3, the reaction is carried out for 12 to 72 hours, preferably 24 to 36 hours.
In a preferred embodiment, the reaction of step 3 is followed by a post-treatment comprising sequentially desolventizing, extracting and freeze-crystallizing.
In a further preferred embodiment, the mother liquor is removed after freeze crystallization and the remaining solid is dried to give the main catalyst for the copolymerization of ethylene with cycloolefins.
The third object of the present invention is to provide a catalyst composition for copolymerizing ethylene with cycloolefin comprising alkylaluminoxane and the main catalyst for copolymerizing ethylene with cycloolefin according to one of the objects of the present invention or the main catalyst for copolymerizing ethylene with cycloolefin obtained by the two methods of the object of the present invention.
In a preferred embodiment, the alkylaluminoxane is selected from compounds of formula (i) and/or formula (ii).
In formula (i) and formula (ii), R represents an alkyl group, preferably C 1 ～C 6 More preferably methyl; n represents an integer of 4 to 30, preferably an integer of 10 to 30.
In a preferred embodiment, the molar ratio of the main catalyst for copolymerizing ethylene with cycloolefin to the alkylaluminoxane is 1 (50 to 20000), wherein the molar amounts of the Ti element and the Al element are calculated respectively.
In a further preferred embodiment, the molar ratio of the main catalyst for copolymerizing ethylene with cycloolefin to the alkylaluminoxane is 1 (200 to 10000), wherein the molar amounts of the Ti element and the Al element are calculated respectively.
In a still further preferred embodiment, the molar ratio of the main catalyst for copolymerizing ethylene with cycloolefin to the alkylaluminoxane is 1 (500 to 3000), wherein the molar amounts of the Ti element and the Al element are calculated respectively.
It is a fourth object of the present invention to provide the use of the catalyst composition for copolymerization of ethylene with cycloolefin according to the third object of the present invention in copolymerization of ethylene with cycloolefin.
The fifth object of the present invention is to provide a copolymerization system of ethylene and cycloolefin, comprising the third object of the present invention of the catalyst composition and ethylene and cycloolefin.
In a preferred embodiment, the copolymerization system further comprises an organic solvent, preferably toluene and/or hexane, more preferably toluene.
Wherein the alkylaluminoxane and the main catalyst for copolymerizing ethylene and cycloolefin are added into a polymerization vessel together or separately at the time of copolymerization.
In a preferred embodiment, the cycloolefin is a cycloolefin having 5 to 24 carbon atoms, preferably at least one selected from norbornene, cyclopentene and cyclohexene, more preferably norbornene.
In a preferred embodiment, the procatalyst concentration in the polymerization system is 1X10 -8 Molar/liter-1×10 -2 Moles/liter, preferably 1X10 -7 Molar/liter-1×10 -3 Moles/liter.
The sixth object of the present invention is to provide a method for copolymerizing ethylene and cycloolefin, which is carried out using the copolymerization system of ethylene and cycloolefin of the fifth object of the present invention.
In a preferred embodiment, the polymerization temperature is from-50℃to 200℃and preferably from-20℃to 150℃and more preferably from 25 to 100 ℃.
Compared with the prior art, the invention has the following beneficial effects: the polymerization system adopts the main catalyst for the copolymerization of ethylene and cycloolefin with special structures, the raw materials for preparing the main catalyst are low in cost, the preparation is simple, safe and efficient, and meanwhile, the polymer obtained by using the polymerization system has the advantages of high molecular weight, narrow molecular weight distribution and the like.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
The raw materials of the examples and comparative examples of the present invention are commercially available or can be prepared by themselves according to the methods disclosed in the prior art.
EXAMPLE 1 Synthesis of N, N' - (2-methylenephenol) -2-iminopyridine
Putting the magnetons into a dry 250 ml three-mouth bottle, and putting the bottle into a magnetic stirring device with oil bath temperature control; the three-necked flask was evacuated and repeatedly flushed with nitrogen three times. 2.26 g of 2-aminopyridine, 2.44 g of salicylaldehyde and 60 ml of ethanol are added under the protection of nitrogen, and the mixture is stirred and refluxed for 6 hours at 90 ℃. Half of the solvent was removed in vacuo, frozen and crystallized, and a yellow solid formed at the bottom of the flask, the solvent mother liquor was removed by syringe, and the solvent was removed in vacuo to give 2.91 g of a yellow powder, which was N, N' - (2-methylenephenoxy) -2-iminopyridine, in 73% molar yield.
1 H-NMR(CDCl 3 ,25℃):δ＝6.9-7.4(5H),7.3(1H),7.5-7.7(2H),9.0(1H),11.1(1H)。
EXAMPLE 2 Synthesis of cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride
Putting the magnetons into a dry 250 ml three-mouth bottle, and putting the bottle into a magnetic stirring device with oil bath temperature control; the three-necked flask was evacuated and repeatedly flushed with nitrogen three times. And 0.50 g of N, N' - (2-methylenephenol) -2-iminopyridine, 3 ml of triethylamine and 40 ml of tetrahydrofuran were added under nitrogen atmosphere, followed by stirring to obtain a solution A. The magneton is put into another dry 250 ml three-mouth bottle, the three-mouth bottle is repeatedly flushed with nitrogen for three times after being vacuumized, 0.55 g of cyclopentadienyl-titanium trichloride and 40 ml of tetrahydrofuran are added under the protection of nitrogen, and the solution B is obtained after being stirred uniformly. Solution A was added dropwise to solution B, and the reaction was stirred at room temperature for 24 hours. The solvent was removed in vacuo, the solid was extracted with dichloromethane, the extract was filtered to give a red transparent solution, which was freeze-crystallized, the bottom of the flask was clouded with a brownish red solid, the solvent mother liquor was removed by syringe, and the solvent was removed in vacuo to give 0.78 g of brownish red powder, which was cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride, in a molar yield of 82%.
1 H-NMR(CDCl 3 ,25℃):δ＝6.58(Cp,5H),6.9-7.4(5H),7.3(1H),7.5-7.7(2H),9.0(1H)。
EXAMPLE 3 Synthesis of pentamethylcyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride
Putting the magnetons into a dry 250 ml three-mouth bottle, and putting the bottle into a magnetic stirring device with oil bath temperature control; the three-necked flask was evacuated and repeatedly flushed with nitrogen three times. And 0.40 g of N, N' - (2-methylenephenol) -2-iminopyridine, 3 ml of triethylamine and 40 ml of tetrahydrofuran were added under nitrogen atmosphere, followed by stirring to obtain a solution A. The magneton is put into another dry 250 ml three-mouth bottle, the three-mouth bottle is repeatedly flushed with nitrogen for three times after being vacuumized, and 0.58 g of pentamethyl cyclopentadienyl-titanium trichloride and 40 ml of tetrahydrofuran are added under the protection of nitrogen, and the mixture is stirred uniformly to obtain solution B. Solution A was added dropwise to solution B, and the reaction was stirred at room temperature for 24 hours. The solvent is removed in vacuum, the solid is extracted by using methylene dichloride, the extract is filtered to obtain red transparent solution, the red transparent solution is frozen and crystallized, the brown solid is formed at the bottom of a bottle, the solvent mother liquor is pumped out by a syringe, the solvent is removed in vacuum, 0.76 g of brown red powder is obtained, and the cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride is obtained, and the molar yield is 85%.
1 H-NMR(CDCl 3 ,25℃):δ＝1.76(Cp*,15H),6.9-7.4(5H),7.3(1H),7.5-7.7(2H),9.0(1H)。
EXAMPLE 4 copolymerization of ethylene with norbornene Using cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride as a catalyst
Adding 0.94 g of norbornene into a dried polymerization bottle, repeatedly flushing with nitrogen for three times after vacuumizing, repeatedly flushing with ethylene gas for three times after vacuumizing, and maintaining the ethylene atmosphere; polymerization temperature at 30℃13 ml of toluene, 6.0 ml of methylaluminoxane toluene solution containing 10.0 mmol of methylaluminoxane, and 1.0 ml of toluene solution containing 5. Mu. Mol of catalyst according to example 2 of cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride were successively added. After 20 minutes of polymerization time, the reaction solution is carefully poured into a beaker, acidified ethanol is added, stirring is carried out for more than 6 hours, a polymer is obtained by filtration, a filter cake is dried in vacuum for 24 hours at 60 ℃, and 0.16 g of polymer is obtained by weighing; gel permeation chromatography detection of weight average molecular weight mw=24x10 of ethylene and norbornene copolymer 4 g/mol, molecular weight distribution mwd=1.97, and glass transition temperature Tg of the copolymer of ethylene and norbornene was 72 ℃.
EXAMPLE 5 copolymerization of ethylene with norbornene Using cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride as a catalyst
Adding 1.88 g of norbornene into a dried polymerization bottle, repeatedly flushing with nitrogen for three times after vacuumizing, repeatedly flushing with ethylene gas for three times after vacuumizing, and maintaining the ethylene atmosphere; polymerization temperature at 30℃13 ml of toluene, 6.0 ml of methylaluminoxane toluene solution containing 10.0 mmol of methylaluminoxane, and 1.0 ml of toluene solution containing 5. Mu. Mol of catalyst according to example 2 of cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride were successively added. After 20 minutes of polymerization time, the reaction solution is carefully poured into a beaker, acidified ethanol is added, stirring is carried out for more than 6 hours, a polymer is obtained by filtration, a filter cake is dried in vacuum for 24 hours at 60 ℃, and 0.53 g of polymer is obtained by weighing; gel permeation chromatography detection of weight average molecular weight mw=29×10 of ethylene and norbornene copolymer 4 g/mol, molecular weight distribution mwd=2.03, bThe glass transition temperature Tg of the alkene-norbornene copolymer was 111 ℃.
EXAMPLE 6 copolymerization of ethylene with norbornene Using cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride as a catalyst
Adding 3.76 g of norbornene into a dried polymerization bottle, repeatedly flushing with nitrogen for three times after vacuumizing, repeatedly flushing with ethylene gas for three times after vacuumizing, and maintaining the ethylene atmosphere; polymerization temperature at 30℃13 ml of toluene, 6.0 ml of methylaluminoxane toluene solution containing 10.0 mmol of methylaluminoxane, and 1.0 ml of toluene solution containing 5. Mu. Mol of catalyst according to example 2 of cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride were successively added. After 20 minutes of polymerization time, pouring the reaction solution into a beaker carefully, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake in vacuum at 60 ℃ for 24 hours, and weighing to obtain 0.05 g of the polymer; gel permeation chromatography detection of weight average molecular weight mw=31x10 of ethylene and norbornene copolymer 4 g/mol, molecular weight distribution mwd=2.01, glass transition temperature Tg of the ethylene and norbornene copolymer is 155 ℃.
EXAMPLE 7 copolymerization of ethylene with norbornene Using cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride as a catalyst
Adding 7.52 g of norbornene into a dried polymerization bottle, repeatedly flushing with nitrogen for three times after vacuumizing, repeatedly flushing with ethylene gas for three times after vacuumizing, and maintaining the ethylene atmosphere; polymerization temperature at 30℃13 ml of toluene, 6.0 ml of methylaluminoxane toluene solution containing 10.0 mmol of methylaluminoxane, and 1.0 ml of toluene solution containing 5. Mu. Mol of catalyst according to example 2 of cyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride were successively added. After 20 minutes of polymerization time, the reaction solution is carefully poured into a beaker, acidified ethanol is added, stirring is carried out for more than 6 hours, a polymer is obtained by filtration, a filter cake is dried in vacuum for 24 hours at 60 ℃, and 0.04 g of polymer is obtained by weighing; gel permeation chromatography for detecting weight of ethylene and norbornene copolymerAverage molecular weight mw=32x10 4 g/mol, molecular weight distribution mwd=1.99, glass transition temperature Tg of the ethylene and norbornene copolymer is 173 ℃.
EXAMPLE 8 copolymerization of ethylene with norbornene Using pentamethylcyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride as catalyst
Adding 1.88 g of norbornene into a dried polymerization bottle, repeatedly flushing with nitrogen for three times after vacuumizing, repeatedly flushing with ethylene gas for three times after vacuumizing, and maintaining the ethylene atmosphere; polymerization temperature at 30℃13 ml of toluene, 6.0 ml of methylaluminoxane toluene solution containing 10.0 mmol of methylaluminoxane, and 1.0 ml of toluene solution containing 5. Mu. Mol of catalyst according to example 3 of pentamethylcyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride were successively added. After 20 minutes of polymerization time, the reaction solution is carefully poured into a beaker, acidified ethanol is added, stirring is carried out for more than 6 hours, a polymer is obtained by filtration, a filter cake is dried in vacuum for 24 hours at 60 ℃, and 0.34 g of polymer is obtained by weighing; gel permeation chromatography detection of weight average molecular weight mw=37x10 of ethylene and norbornene copolymer 4 g/mol, molecular weight distribution mwd=2.13, glass transition temperature Tg of the ethylene and norbornene copolymer is 76 ℃.
EXAMPLE 9 copolymerization of ethylene with norbornene Using pentamethylcyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride as catalyst
Adding 3.76 g of norbornene into a dried polymerization bottle, repeatedly flushing with nitrogen for three times after vacuumizing, repeatedly flushing with ethylene gas for three times after vacuumizing, and maintaining the ethylene atmosphere; polymerization temperature at 30℃13 ml of toluene, 6.0 ml of methylaluminoxane toluene solution containing 10.0 mmol of methylaluminoxane, and 1.0 ml of toluene solution containing 5. Mu. Mol of catalyst according to example 3 of pentamethylcyclopentadienyl-N, N' - (2-methylenephenoxy) -2-iminopyridine-titanium dichloride were successively added. After 20 minutes of polymerization time, the reaction solution is carefully poured into a beaker, acidified ethanol is added, the mixture is stirred for more than 6 hours, the polymer is obtained by filtration, and a filter cake is vacuumized at 60 DEG CDrying for 24 hours and weighing to obtain 0.15 g of polymer; gel permeation chromatography detection of weight average molecular weight mw=42x10 of ethylene and norbornene copolymer 4 g/mol, molecular weight distribution mwd=2.20, glass transition temperature Tg of the ethylene and norbornene copolymer is 46 ℃.
Claims (22)
1. A main catalyst for the copolymerization of ethylene and cycloolefin has the structure shown in formula (I):
formula (I);
in formula (I), X is selected from halogen atoms, cp' is C 1 ~C 3 Alkyl-substituted or unsubstituted cyclopentadienyl, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from hydrogen atom, halogen atom, C 6 ~C 9 Aryl, C of (2) 1 ~C 5 Alkyl or C of (2) 1 ~C 5 Is a halogen substituted alkyl group.
2. The procatalyst for the copolymerization of ethylene and cycloolefin according to claim 1, characterized in that in the formula (I),
x is selected from chlorine atoms; and/or
Cp' is selected from pentamethylcyclopentadienyl or cyclopentadienyl.
3. The procatalyst for the copolymerization of ethylene and cycloolefin according to claim 1, characterized in that in the formula (I), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from hydrogen atoms, C 1 ~C 3 Alkyl, C of (2) 1 ~C 3 Is substituted by halogen of alkyl or halogen atom.
4. The procatalyst for the copolymerization of ethylene and cycloolefin according to claim 3, characterized in that it is represented by the formula [ ], whereinI) Wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from a hydrogen atom, a chlorine atom, or a methyl group.
5. A process for preparing a procatalyst for the copolymerization of ethylene with cycloolefins according to any one of claims 1 to 4, which comprises using the compounds of the formulae (II) and (III) as main raw materials; the method is carried out under a protective atmosphere and comprises the following steps:
step 1, mixing a compound shown in a formula (II), a solvent and triethylamine to obtain a solution A;
step 2, mixing a compound shown in a formula (III) with a solvent to obtain a solution B;
step 3, dropwise adding the solution B into the solution A, and reacting to obtain the main catalyst for copolymerization of ethylene and cycloolefin; in the step 3, the reaction is carried out at 20-50 ℃;
formula (II) formula (III).
6. The method according to claim 5, wherein the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1.
7. The method of claim 5, wherein the protective atmosphere is nitrogen.
8. The method of claim 5, wherein the step of determining the position of the probe is performed,
in the step 1 and the step 2, the solvent is an organic solvent comprising tetrahydrofuran, dichloromethane and toluene; and/or
In the step 1 and the step 2, the molar ratio of the compound shown in the formula (II) to the compound shown in the formula (III) is 1:1; and/or
In step 1, the molar usage ratio of triethylamine to the compound represented by formula (II) is greater than 1:1.
9. The method of claim 8, wherein the step of determining the position of the first electrode is performed,
in the step 1 and the step 2, the solvent is tetrahydrofuran; and/or
In the step 1, the molar usage ratio of triethylamine to the compound shown in the formula (II) is (2-4): 1.
10. the method of claim 5, wherein the step of determining the position of the probe is performed,
in the step 3, the reaction is carried out at room temperature, wherein the room temperature is 20-30 ℃; and/or
In the step 3, the reaction is carried out for 12-72 h; and/or
The reaction in step 3 is followed by a post-treatment comprising sequentially desolventizing, extracting and freeze-crystallizing.
11. The method of claim 10, wherein the step of determining the position of the first electrode is performed,
in the step 3, the reaction is carried out for 24-36 hours.
12. A catalyst composition for copolymerization of ethylene with cycloolefin comprising alkylaluminoxane and a main catalyst for copolymerization of ethylene with cycloolefin according to any one of claims 1 to 4 or a main catalyst for copolymerization of ethylene with cycloolefin obtained by the method according to any one of claims 5 to 11.
13. The catalyst composition according to claim 12, wherein the alkylaluminoxane is selected from compounds of formula (i) and/or formula (ii);
formula (i) formula (ii)
In the formula (i) and the formula (ii), R represents an alkyl group, and n represents an integer of 4 to 30.
14. The catalyst composition of claim 13 wherein in formulas (i) and (ii), R is C 1 ~C 6 Alkyl of (a); n is an integer of 10 to 30.
15. The catalyst composition for copolymerization of ethylene and cycloolefin according to claim 12, wherein a molar ratio of the main catalyst for copolymerization of ethylene and cycloolefin to the alkylaluminoxane is 1 (50 to 20000), wherein the molar amounts of the Ti element and the Al element are calculated respectively.
16. The catalyst composition for copolymerization of ethylene and cycloolefin according to claim 15, wherein a molar ratio of the main catalyst for copolymerization of ethylene and cycloolefin to the alkylaluminoxane is 1 (200 to 10000), wherein the molar amounts of the Ti element and the Al element are calculated respectively.
17. Use of the ethylene and cycloolefin copolymerization catalyst composition according to any of claims 14 to 16 in the copolymerization of ethylene and cycloolefin.
18. A copolymer system of ethylene and cycloolefin comprising the catalyst composition according to any one of claims 14 to 16 and ethylene and cycloolefin.
19. The copolymerization system according to claim 18, wherein the polymerization system further comprises an organic solvent.
20. The copolymerization system according to claim 19, wherein the concentration of the procatalyst in the polymerization system is 1X10 -8 Molar/liter to 1X10 -2 Moles/liter.
21. A method for copolymerizing ethylene and cycloolefin, which is carried out by using the copolymerization system of ethylene and cycloolefin according to any one of claims 18 to 20, wherein the polymerization temperature is-50 ℃ to 200 ℃.
22. The copolymerization process according to claim 21, wherein the polymerization temperature is from-20 ℃ to 150 ℃.
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