CN116178595B - Supported metallocene catalyst for olefin polymerization and preparation method and application thereof - Google Patents
Supported metallocene catalyst for olefin polymerization and preparation method and application thereof Download PDFInfo
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- CN116178595B CN116178595B CN202111420299.2A CN202111420299A CN116178595B CN 116178595 B CN116178595 B CN 116178595B CN 202111420299 A CN202111420299 A CN 202111420299A CN 116178595 B CN116178595 B CN 116178595B
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 43
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 39
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 16
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000741 silica gel Substances 0.000 claims description 31
- 229910002027 silica gel Inorganic materials 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012442 inert solvent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 8
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 7
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000006539 C12 alkyl 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 claims 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a supported metallocene catalyst for olefin polymerization, a preparation method and application thereof, wherein the catalyst has a structure shown in a formula (I): Wherein Cp ' and Cp ' are each independently cyclopentadienyl or substituted cyclopentadienyl, and Cp ' may be the same or different; m is Ti, zr or Hf of IVB group element; q is halogen; n is N of a main group element of V; si' is a carrier. The load of the metallocene of the catalyst is high; the catalyst still has good fluidity after being loaded, the catalyst cost is low, and the carbonyl in the organosilicon can coordinate with metallocene M (Zr, ti, hf) to enhance the stability.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a supported metallocene catalyst, a preparation method and application thereof.
Background
Olefin polymerization catalysts are the core of polyolefin polymerization, and in view of the development of olefin polymerization catalysts, there are mainly two general directions: (1) The development of polyolefin resin catalysts, such as metallocene catalysts, which can produce specific properties and unique or more excellent properties; (2) For the production of most polyolefin resins, on the premise of further improving the catalyst performance, the catalyst preparation process flow is simplified, the catalyst cost research and development and the technical requirements on environmental friendliness are reduced, so that the benefit is improved, and the product competitiveness is enhanced. The olefin catalyst developed at present mainly comprises a chromium-based catalyst, a Ziegler-Natta catalyst (Z-N), a metallocene catalyst, a post-transition metal catalyst, a bifunctional catalyst, a bimodal or broad-peak molecular weight distribution polyolefin composite catalyst and the like. In recent years, the market share of metallocene catalysts in polyolefin is improved year by year, the role of the metallocene catalysts in controlling polymer composition, molecular weight distribution and the like is more and more prominent, and the development prospect is quite optimistic.
Silica gel is currently the main support for metallocene catalysts for polyethylene synthesis. But the disadvantage of using pure inorganic silica gel carrier in the industrial production of polyolefin is also revealed gradually. The method is characterized in that the method is mainly characterized in that the problem that organic components in the metallocene are similar to the pure inorganic surface of the silica gel in a certain degree and are not matched with the pure inorganic surface of the silica gel is solved, the phenomenon that the metallocene falls off from the surface of the silica gel carrier is caused, the content of the metallocene on the carrier is reduced, and the catalytic efficiency of the composite catalyst is affected.
Bianchini found that immobilization of the metallocene on both silica gel and polyorganosiloxane microgel resulted in high activity of the catalyst at low Al/Zr molar ratio. Although metallocene homogeneously catalyzed olefin polymerizations exhibit higher activity, the polymerization product is severely stuck to the pot. In addition, the space congestion phenomenon exists when the active center and the catalyzed monomer act in homogeneous catalysis, and the catalytic activity of the catalyst cannot be fully exerted.
Although the former has made some work on silica gel surface modification by using organosilicon, we have found that most of the work is concentrated on improving the polarity of silica gel surface, and the integrated synthesis of metallocene structure and silica gel is not really realized, i.e. the metallocene is anchored to the surface of the organized silica gel, so that the activity of the synthesized supported composite catalyst does not reach an ideal state.
Disclosure of Invention
The invention aims to provide a supported metallocene catalyst for olefin polymerization.
The invention also aims to provide a preparation method of the supported metallocene catalyst for olefin polymerization.
The invention also aims to provide an application of the supported metallocene catalyst for olefin polymerization.
In order to achieve the above object, the present invention provides a supported metallocene catalyst for olefin polymerization, having a structure represented by formula (I):
Wherein Cp ' and Cp ' are each independently cyclopentadienyl or substituted cyclopentadienyl, and Cp ' may be the same or different;
M is Ti, zr or Hf of IVB group element;
Q is halogen;
n is N of a main group element of V;
Si' is a carrier.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein the substituent in a substituted cyclopentadienyl is one or more of C1-C12 alkyl, alkoxy, silane, aryl and aralkoxy.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein Cp 'and Cp' are each independently substituted or unsubstituted indenyl or fluorenyl.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein the substituent groups in substituted indenyl and fluorenyl are one or more of methyl, ethyl, propyl, isopropyl, butyl and isobutyl.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein Q is chlorine.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein M is Ti or Zr.
The supported metallocene catalyst for olefin polymerization provided by the invention is characterized in that the carrier is one or more of silica gel, alumina and magnesium chloride, and silica gel is preferred.
In order to achieve the above purpose, the present invention also provides a preparation method of the catalyst, comprising the following steps:
The surface of the carrier is subjected to organic modification containing carbonyl and imino groups, and then the carrier is reacted with a metallocene catalyst Cp 'MQ 2, wherein Cp' and Cp 'are respectively and independently cyclopentadienyl or substituted cyclopentadienyl, and Cp' can be the same or different; m is Ti, zr or Hf of IVB group element; q is halogen.
The method of the invention comprises the following specific preparation methods:
(1) Synthesis of organosilicon precursors
Mixing anhydrous dichloromethane and triethylamine under the protection of nitrogen, uniformly stirring, adding aminopropyl triethoxysilane, then dropwise adding a dichloromethane solution of oxalyl chloride at 0-10 ℃, and stirring at 20-40 ℃ for 6-12h after the dropwise adding is finished to obtain an organosilicon precursor;
(2) Organosilicon precursor modified carrier
Activating the carrier, dissolving the activated carrier in an anhydrous inert solvent under inert atmosphere, then adding an organosilicon precursor, and continuously stirring to obtain an organosilicon modified carrier;
(3) Synthesis of organosilicon supported metallocene catalyst:
Mixing the metallocene catalyst Cp' MQ 2 with the organosilicon modified carrier solution obtained in the step (2), reacting for 4-10h at 30-60 ℃, washing with an inert solvent, and filtering to obtain the organosilicon supported metallocene catalyst.
The method of the present invention, wherein in the step (2), the activated support is obtained by treating under vacuum at 400 to 900 ℃, preferably 500 to 700 ℃ for 8 to 12 hours.
The method of the present invention, wherein in the step (2), the concentration of the activated carrier after the carrier is dissolved in an anhydrous inert solvent is 0.04 to 0.1g/ml.
The method of the invention, wherein in the step (2), the mass ratio of the organosilicon precursor to the carrier is 1-50:100, preferably 10-30:100.
The method of the present invention, wherein in the step (2), stirring conditions are 30 to 100 ℃, preferably 40 to 60 ℃, for 8 to 16 hours.
The method of the invention, wherein in the step (2), the carrier particle size is 10-60 microns, and the inert solvent is one or more of toluene, normal hexane and benzene.
The process of the present invention, wherein in step (3), the molar ratio of Cp' MQ 2 to the organosilicon precursor is from 2 to 6:1.
In order to achieve the aim, the invention also provides an application of the catalyst in olefin homo-polymerization or copolymerization.
The application of the invention is characterized in that the promoter methylaluminoxane is added in the application process.
The use according to the invention, wherein the molar ratio of methylaluminoxane to catalyst, calculated as Al/M, is 500-3000:1, preferably 500-2000:1.
The beneficial effects of the invention are as follows:
The invention utilizes the organosiloxane containing ligand on the chain to modify the surface of the carrier microsphere to obtain the organized carrier microsphere, thereby realizing the integrated synthesis of the coordination supported metallocene@carrier, better solving the problem that the catalytic active points fall off from the surface of the carrier microsphere and realizing the efficient catalysis of the carrier supported metallocene composite catalyst to ethylene. The development of the synthesis technology of the organosiloxane modified carrier supported metallocene composite catalyst containing the coordination group has important significance for promoting the development of polyolefin catalyst industry in China.
The catalyst utilizes the organic silicon with large spacing groups to reduce the steric hindrance between the carrier and the metallocene, thereby improving the load capacity of the metallocene; the catalyst still has good fluidity after being loaded, the catalyst cost is low, and the carbonyl in the organosilicon can coordinate with metallocene M (Zr, ti, hf) to enhance the stability.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectrum of organosilicon precursor Silicone-1 of the invention.
FIG. 2 shows the nuclear magnetic carbon spectrum of the organosilicon precursor Silicone-1.
Fig. 3 and 4 show the X-ray photoelectron spectra of the catalyst prepared in example 1.
FIG. 5 is a FT-IR spectrum of the catalyst prepared in example 1.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
A supported metallocene catalyst for olefin polymerization having a structure represented by formula (I):
Wherein Cp ' and Cp ' are each independently cyclopentadienyl or substituted cyclopentadienyl, and Cp ' may be the same or different;
M is Ti, zr or Hf of IVB group element;
Q is halogen;
n is N of a main group element of V;
Si' is a carrier.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein the substituent in a substituted cyclopentadienyl is one or more of C1-C12 alkyl, alkoxy, silane, aryl and aralkoxy.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein Cp 'and Cp' are each independently substituted or unsubstituted indenyl or fluorenyl.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein the substituent groups in substituted indenyl and fluorenyl are one or more of methyl, ethyl, propyl, isopropyl, butyl and isobutyl.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein Q is chlorine.
The invention relates to a supported metallocene catalyst for olefin polymerization, wherein M is Ti or Zr.
The supported metallocene catalyst for olefin polymerization provided by the invention is characterized in that the carrier is one or more of silica gel, alumina and magnesium chloride, and silica gel is preferred.
Taking a carrier as an example of silica gel, the preparation method of the catalyst comprises the following steps:
(1) Synthesis of organosilicon precursor Silicones-1:
The 50mL Schlenk flask was dried under nitrogen. Then, anhydrous dichloromethane (DCM, 15 mL) and triethylamine (3.7 mL,27 mmol) were added to the flask, and after the mixed solution was stirred well, aminopropyl triethoxysilane (APTES, 6mL,27 mmol) was added to the mixed solution, and the Schlenk flask was placed in an ice bath at 0 ℃. Subsequently, a solution of oxalyl chloride in DCM was added dropwise (1.0 mL,13.6 mmol) to the above solution. After the addition, the whole reaction system is removed from the ice bath and stirred at 40 ℃ for reaction for 6 hours; gradually yellowing colorless solution along with the progress of the reaction, cooling the reaction system to room temperature after the reaction is finished, filtering the obtained product to remove generated triethylamine hydrochloride, and removing the solvent by a rotary evaporator to obtain an organosilicon precursor (1) containing amino groups and carbonyl groups; labeled Silicone-1.
(2) Silicone precursor Silicone-1 modified silica gel:
Activating the carrier silica gel under vacuum (P <10 -5 bar) at 400-800deg.C (preferably 500-600deg.C) for about 10 hr, and storing under argon atmosphere; under inert atmosphere, dissolving a certain amount of activated carrier silica gel in an anhydrous inert solvent, wherein the concentration of the carrier silica gel is 0.04-0.1g/ml; after stirring for 20-60min at 85-110 ℃, adding (1-50 wt%) Silicone-1, stirring for 8-16h at 30-100deg.C (preferably 40-60 ℃) to obtain the organosilicon modified carrier silica gel.
(3) Synthesis of supported metallocene catalyst:
Mixing a metallocene catalyst Cp' MQ 2 with the organosilicon modified carrier silica gel solution obtained in the step (2), and reacting for 4-10h at 30-60 ℃. The molar ratio of Cp' MQ 2 to Silicone-1 is 3-6:1, respectively washing with inert solvents, and filtering to obtain gray powder. Namely the organosilicon supported metallocene catalyst. The catalyst needs to be stored under an inert atmosphere.
The preparation flow chart of the synthetic metallocene catalyst is as follows:
In the method, in the step (2), the mass ratio of the organic silicon precursor to the silica gel is 5-40:100.
In the method, in the step (2), the particle size of the silica gel carrier is 10-60 microns, and the inert solvent is one or more of toluene, normal hexane and benzene.
The catalyst is applied to olefin homo-polymerization or copolymerization. The olefin polymerization reaction comprises: ethylene homopolymerization, propylene homopolymerization, ethylene and propylene copolymerization, and ethylene and/or propylene copolymerization with other alpha-olefins.
The alpha-olefin is one or more of butene, pentene, hexene, octene and 4-methylpentene-1.
In specific application, under the protection of N 2, a certain amount of cocatalyst MAO (Al/M ratio is 1000) is weighed, a certain amount of supported catalyst is added, olefin gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. Wherein the ethylene homopolymerization polymerization activity is higher and can reach 1.80 multiplied by 10 6 (gPE/Mol Zr.h), and the ethylene-octene copolymerization polymerization activity can reach 6.1 multiplied by 10 5 (gPE/Mol Zr.h).
According to the method, the catalyst conforming to the synthetic thought further comprises: the surfaces of all the carrier microspheres are organically modified and then contain ligand modification bodies.
Trade name, basic composition, model, specification, manufacturer
Preparation of organosilicon precursor Silicones-1
The 50mL Schlenk flask was dried under nitrogen. Then, anhydrous dichloromethane (DCM, 15 mL) and triethylamine (3.7 mL,27 mmol) were added to the flask, and after the mixed solution was stirred well, aminopropyl triethoxysilane (APTES, 6mL,27 mmol) was added to the mixed solution, and the Schlenk flask was placed in an ice bath at 0 ℃. Subsequently, a solution of oxalyl chloride in DCM was added dropwise (1.0 mL,13.6 mmol) to the above solution. After the addition, the whole reaction system is removed from the ice bath and stirred at 40 ℃ for reaction for 6 hours; the colorless solution gradually turns yellow with the progress of the reaction, after the reaction is finished, the reaction system is cooled to room temperature, the obtained product is filtered to remove the generated triethylamine hydrochloride, and the solvent is removed by a rotary evaporator to obtain the organosilicon precursor containing amino and carbonyl, which is marked as Silicone-1. The nuclear magnetic spectrum of Silicones-1 is shown in FIG. 1 and FIG. 2.
Example 1
The silica gel was activated under vacuum (P <10 -5 bar) at 500-600℃for 10h. 1.5g of activated silica gel is dissolved in 20-30mL of anhydrous toluene, stirred at 100 ℃ for 30min, and then 15wt% of organosilicon precursor Silicone-1 containing amino groups and carbonyl groups is added and stirred at 40 ℃ for 16h. Mixing zirconocene dichloride with the organosilicon modified silica gel carrier solution obtained in the previous step, and reacting for 6-8h at 40-50 ℃. The molar ratio of zirconocene dichloride to organosilicon Silicone-1 is 5:1, respectively washing with toluene and n-hexane, filtering, and vacuum drying to obtain gray powder. Namely the organosilicon supported metallocene catalyst. The catalyst needs to be stored under an inert atmosphere. The Zr content of the catalyst was 0.81% by ICP analysis.
Under the protection of N 2, a certain amount of MAO toluene solution is weighed, 10mg of catalyst (Al/Zr molar ratio is 1000) is added, ethylene gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. The catalyst polymerization activity was 2.29X 10 6 (gPE/mol. Zr h).
FIG. 3 shows X-ray photoelectron spectroscopy (XPS) of N1s in the catalyst prepared in this example.
FIG. 4 is an X-ray photoelectron spectrum of Zr3d in the catalyst prepared in this example.
The energy bands of N1s and Zr3d in the catalyst were analyzed by XPS, and 400.8ev (N-Zr bond), 399.8ev (N-H bond) and 399.2ev (C-N bond) were found in the N1s spectrum of the catalyst; in the Zr3d map of the catalyst, 185.4ev (N-Zr bond) and 184.1ev (Zr-cyclopentadienyl bond) and 182.7ev (Zr-Cl bond) were present. The formation of the organosilicon supported catalyst was confirmed.
FIG. 5 is a FT-IR spectrum of the catalyst prepared in this example.
FT-IR spectrum of the organosilicon supported metallocene catalyst. The band at 2968cm -1 corresponds to the vibration of the cyclopentadienyl ligand, at wavenumber 2827cm -1 to hydrocarbon vibration (vc-H), 1668cm -1 to carbonyl vibration (vc=o); at the same time, an imino (. Nu.N-H) absorption peak was found at 1514cm -1. The results indicate that catalysts prepared by organosilicon-modified synthesis complex our expectations.
Example 2
The silica gel was activated under vacuum (P <10 -5 bar) at 500-600℃for 10h. 1.5g of activated silica gel is dissolved in 20-30mL of anhydrous toluene, stirred at 100 ℃ for 30min, and then 25wt% of organosilicon precursor Silicone-1 containing amino groups and carbonyl groups is added and stirred at 40 ℃ for 16h. Mixing zirconocene dichloride with the organosilicon modified silica gel carrier solution obtained in the previous step, and reacting for 4-10h at 30-60 ℃. The molar ratio of zirconocene dichloride to organosilicon Silicone-1 is 5:1, respectively washing with toluene and n-hexane, filtering, and vacuum drying to obtain gray powder. Namely the organosilicon supported metallocene catalyst. The catalyst needs to be stored under an inert atmosphere. The Zr content of the catalyst was 0.48% by ICP analysis.
Under the protection of N 2, a certain amount of MAO toluene solution is weighed, 10mg of catalyst (Al/Zr molar ratio is 1000) is added, ethylene gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. The catalyst polymerization activity was 1.80X 10 6 (gPE/mol. Zr h).
Example 3
The silica gel was activated under vacuum (P <10 -5 bar) at 500-600℃for 10h. 1.5g of activated silica gel is dissolved in 20-30mL of anhydrous toluene, stirred at 100 ℃ for 30min, and then 15wt% of organosilicon precursor Silicone-1 containing amino groups and carbonyl groups is added and stirred at 40 ℃ for 16h. Mixing the dichloro titanocene with the organosilicon modified silica gel carrier solution obtained in the steps, and reacting for 4-10h at 30-60 ℃. The molar ratio of the dichloro titanocene to the organosilicon Silicone-1 is 5:1, respectively washing with toluene and n-hexane, filtering, and vacuum drying to obtain gray powder. Namely the organosilicon supported metallocene catalyst. The catalyst needs to be stored under an inert atmosphere. The Ti content of the catalyst was 0.63% by ICP analysis.
Under the protection of N 2, a certain amount of MAO toluene solution is weighed, 10mg of catalyst (Al/Ti molar ratio is 2000) is added, ethylene gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. The catalyst polymerization activity was 7.98X10 5 (gPE/mol. Ti h).
Example 4
The silica gel was activated under vacuum (P <10 -5 bar) at 500-600℃for 10h. 1.5g of activated silica gel is dissolved in 20-30mL of anhydrous toluene, stirred at 100 ℃ for 30min, and then 25wt% of organosilicon precursor Silicone-1 containing amino groups and carbonyl groups is added and stirred at 40 ℃ for 16h. Mixing the dichloro titanocene with the organosilicon modified silica gel carrier solution obtained in the steps, and reacting for 4-10h at 30-60 ℃. The molar ratio of the dichloro titanocene to the organosilicon Silicone-1 is 5:1, respectively washing with toluene and n-hexane, filtering, and vacuum drying to obtain gray powder. Namely the organosilicon supported metallocene catalyst. The catalyst needs to be stored under an inert atmosphere. The Ti content of the catalyst was 0.57% by ICP analysis.
Under the protection of N 2, a certain amount of MAO toluene solution is weighed, 10mg of catalyst (Al/Zr molar ratio is 500) is added, ethylene gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. The catalyst polymerization activity was 7.23X10 5 (gPE/mol. Ti h).
Example 5
The silica gel was activated under vacuum (P <10 -5 bar) at 500-600℃for 10h. 1.5g of activated alumina was dissolved in 20-30mL of anhydrous toluene, stirred at 100℃for 30min, then 15wt% of Silicone precursor Silicone-1 containing amino and carbonyl groups was added and stirred at 40℃for 16h. Mixing zirconocene dichloride with the organosilicon modified alumina carrier solution obtained in the previous step, and reacting for 4-10h at 30-60 ℃. The molar ratio of zirconocene dichloride to organosilicon Silicone-1 is 4:1, respectively washing with toluene and n-hexane, filtering, and vacuum drying to obtain gray powder. Namely the organosilicon supported metallocene catalyst. The catalyst needs to be stored under an inert atmosphere. The Zr content of the catalyst was 0.59% by ICP analysis.
Under the protection of N 2, a certain amount of MAO toluene solution is weighed, 10mg of catalyst (Al/Zr molar ratio is 1000) is added, ethylene gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. The catalyst polymerization activity was 1.26X10 6 (gPE/mol. Zr h).
Example 6
The silica gel was activated for 10h at 600℃under vacuum (P <10 -5 bar). 1.5g of activated silica gel is dissolved in 20-30mL of anhydrous toluene, stirred at 100 ℃ for 30min, and then 15wt% of organosilicon precursor Silicone-1 containing amino groups and carbonyl groups is added and stirred at 40 ℃ for 16h. Mixing zirconocene dichloride with the organosilicon modified silica gel carrier solution obtained in the previous step, and reacting for 4-10h at 30-60 ℃. The molar ratio of zirconocene dichloride to organosilicon Silicone-1 is 5:1, respectively washing with toluene and n-hexane, filtering, and vacuum drying to obtain gray powder. Namely the organosilicon supported metallocene catalyst. The catalyst needs to be stored under an inert atmosphere. The Zr content of the catalyst was 0.48% by ICP analysis.
A certain amount of MAO toluene solution is weighed, stirred for 20min, then 0.1mol/L octene 1.8mL is added under the protection of N 2, 10mg of catalyst (Al/Zr molar ratio is 1000) is added, ethylene gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. The catalyst copolymerization activity was 6.39X10 5 (gPE/mol. Zr h).
Comparative example 1
The silica gel was activated at 600℃for 10 hours and stored under argon atmosphere (glove box). 1.5g of activated silica gel and 25mL of anhydrous toluene and 5mL of MAO were added to a 100mL Schlenk flask, stirred at 100℃for 30min, then 30mg of zirconocene dichloride was added to the flask and stirred for 10h, after which three washes with toluene and n-hexane, respectively, were performed, and the filtration was performed under nitrogen protection, and the toluene and n-hexane washes were performed twice. The solid was finally dried under vacuum and stored in a glove box.
Under the protection of N 2, 60mL of toluene solvent is added, 10mg of catalyst is added, ethylene gas of 0.04Mpa is introduced, and the mixture is placed in an oil bath at 60 ℃ for polymerization for 1h. The catalyst polymerization activity was 6.12X10 5 (gPE/mol. Zr h).
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (24)
1. A supported metallocene catalyst for olefin polymerization, characterized by having a structure represented by the formula (I):
Wherein Cp ' and Cp ' are each independently cyclopentadienyl or substituted cyclopentadienyl, and Cp ' may be the same or different;
M is Ti, zr or Hf of IVB group element;
Q is halogen;
n is N of a main group element of V;
Si' is a carrier.
2. The supported metallocene catalyst for olefin polymerization according to claim 1, wherein the substituent in the substituted cyclopentadienyl group is one or more of a C1 to C12 alkyl group, an alkoxy group, a silane group, an aryl group and an aralkyloxy group.
3. The supported metallocene catalyst for olefin polymerization according to claim 1, wherein Cp' and Cp "are each independently a substituted or unsubstituted indenyl or fluorenyl group.
4. The supported metallocene catalyst for olefin polymerization according to claim 3, wherein the substituents in the substituted indenyl and fluorenyl groups are one or more of methyl, ethyl, propyl and butyl.
5. The supported metallocene catalyst for olefin polymerization according to claim 3, wherein the substituents in the substituted indenyl and fluorenyl groups are isopropyl and/or isobutyl.
6. The supported metallocene catalyst for olefin polymerization according to claim 1, wherein Q is chlorine.
7. The supported metallocene catalyst for olefin polymerization according to claim 1, wherein M is Zr or Ti.
8. The supported metallocene catalyst for olefin polymerization according to claim 1, wherein the carrier is one or more of silica gel, alumina and magnesium chloride.
9. The supported metallocene catalyst for olefin polymerization according to claim 1, wherein the support is silica gel.
10. A method for preparing a catalyst according to any one of claims 1 to 9, comprising the steps of:
The surface of the carrier is subjected to organic modification containing carbonyl and imino groups, and then the carrier is reacted with a metallocene catalyst Cp 'MQ 2, wherein Cp' and Cp 'are respectively and independently cyclopentadienyl or substituted cyclopentadienyl, and Cp' can be the same or different; m is Ti, zr or Hf of IVB group element; q is halogen.
11. The method according to claim 10, characterized in that the specific preparation method is:
(1) Synthesis of organosilicon precursors
Mixing anhydrous dichloromethane and triethylamine under the protection of nitrogen, uniformly stirring, adding aminopropyl triethoxysilane, then dropwise adding a dichloromethane solution of oxalyl chloride at 0-10 ℃, and stirring at 20-40 ℃ for 6-12h after the dropwise adding is finished to obtain an organosilicon precursor;
(2) Organosilicon precursor modified carrier
Activating the carrier, dissolving the activated carrier in an anhydrous inert solvent under inert atmosphere, then adding an organosilicon precursor, and continuously stirring to obtain an organosilicon modified carrier;
(3) Synthesis of organosilicon supported metallocene catalyst:
Mixing the metallocene catalyst Cp' MQ 2 with the organosilicon modified carrier solution obtained in the step (2), reacting for 4-10h at 30-60 ℃, washing with an inert solvent, and filtering to obtain the organosilicon supported metallocene catalyst.
12. The method according to claim 11, wherein in step (2), the activated support is obtained by treating under vacuum at 400 to 900 ℃ for 8 to 12 hours.
13. The method according to claim 11, wherein in step (2), the activated support is obtained by treating at 500 to 700 ℃ under vacuum for 8 to 12 hours.
14. The method according to claim 11, wherein in step (2), the activated carrier is dissolved in an anhydrous inert solvent to give a carrier concentration of 0.04 to 0.1g/ml.
15. The method of claim 11, wherein in step (2), the mass ratio of the organosilicon precursor to the carrier is from 1 to 50:100.
16. The method of claim 11, wherein in step (2), the mass ratio of the organosilicon precursor to the carrier is from 10 to 30:100.
17. The method according to claim 11, wherein in the step (2), the stirring condition is 30 to 100 ℃ for 8 to 16 hours.
18. The method according to claim 11, wherein in the step (2), the stirring condition is 40 to 60 ℃ for 8 to 16 hours.
19. The method according to claim 11, wherein in the step (2), the carrier has a particle size of 10 to 60 μm, and the inert solvent is one or more of toluene, n-hexane and benzene.
20. The method of claim 11, wherein in step (3), the molar ratio of Cp' Cp "MQ 2 to silicone precursor is from 2 to 6:1.
21. Use of the catalyst of any one of claims 1-9 in olefin homo-or co-polymerization.
22. Use according to claim 21, characterized in that the cocatalyst methylaluminoxane is added during the application.
23. Use according to claim 22, characterized in that the molar ratio of methylaluminoxane to catalyst in Al/M is 500-3000:1.
24. Use according to claim 22, characterized in that the molar ratio of methylaluminoxane to catalyst in Al/M is 500-2000:1.
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