CN114702520A - Vanadium complex catalyst containing large steric hindrance phenol oxygen ligand and preparation method and application thereof - Google Patents
Vanadium complex catalyst containing large steric hindrance phenol oxygen ligand and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 47
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003446 ligand Substances 0.000 title claims abstract description 35
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000012265 solid product Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001953 recrystallisation Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 15
- 229920000098 polyolefin Polymers 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000012718 coordination polymerization Methods 0.000 claims description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 4
- FEUFNKALUGDEMQ-UHFFFAOYSA-N 2-isocyanato-1,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=O FEUFNKALUGDEMQ-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- GZWGTVZRRFPVAS-UHFFFAOYSA-N 1-isocyanato-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1N=C=O GZWGTVZRRFPVAS-UHFFFAOYSA-N 0.000 claims description 2
- IHHUGFJSEJSCGE-UHFFFAOYSA-N 1-isocyanato-2-phenylbenzene Chemical compound O=C=NC1=CC=CC=C1C1=CC=CC=C1 IHHUGFJSEJSCGE-UHFFFAOYSA-N 0.000 claims description 2
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 claims description 2
- HNENEALJPWJWJY-UHFFFAOYSA-N 2,4-difluoro-1-isocyanatobenzene Chemical compound FC1=CC=C(N=C=O)C(F)=C1 HNENEALJPWJWJY-UHFFFAOYSA-N 0.000 claims description 2
- OTCSNGYANYPKAW-UHFFFAOYSA-N 2,6-bis(2,3,4,5,6-pentafluorophenyl)phenol Chemical compound OC1=C(C=CC=C1C1=C(F)C(F)=C(F)C(F)=C1F)C1=C(F)C(F)=C(F)C(F)=C1F OTCSNGYANYPKAW-UHFFFAOYSA-N 0.000 claims description 2
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 claims description 2
- DRWRVXAXXGJZIO-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl acetate Chemical compound C1C2C(OC(=O)C)CC1C=C2 DRWRVXAXXGJZIO-UHFFFAOYSA-N 0.000 claims description 2
- BLMIXWDJHNJWDT-UHFFFAOYSA-N 6-chlorohex-1-ene Chemical compound ClCCCCC=C BLMIXWDJHNJWDT-UHFFFAOYSA-N 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 11
- -1 diisopropylvanadium Chemical compound 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a vanadium complex catalyst containing a large steric hindrance phenol oxygen ligand, a preparation method and application thereof, wherein the method comprises the following steps: weighing a reagent A in a reaction bottle in an anhydrous and oxygen-free nitrogen environment, adding a solvent n-octane, slowly dropwise adding vanadium oxychloride, placing the reaction bottle in a marmite for reacting for 25 hours at 135 ℃, cooling, filtering to obtain a filtrate, drying the filtrate to remove the solvent to obtain a solid crude product, dissolving the solid crude product with dichloromethane, and dropwise adding n-hexane for low-temperature recrystallization to obtain a solid product a; weighing a solid product a, adding a solvent alpha into a single-mouth bottle, refrigerating at the temperature of minus 30 ℃ for 1 hour to obtain a solution a, stirring and adding a reagent B into the solution a, stirring at room temperature, filtering, and removing the solvent in vacuum to obtain the vanadium complex catalyst containing the large steric hindrance phenol-oxygen ligand. The vanadium complex catalyst prepared by the method is simple to synthesize, has no strict requirements on experimental conditions, is simple to operate and is easy to react.
Description
Technical Field
The invention relates to the field of olefin polymerization organic metal catalysts and olefin coordination polymerization, in particular to a vanadium complex catalyst containing a large steric hindrance phenol oxygen ligand and a preparation method and application thereof.
Background
The application fields of polyolefin materials in modern industrial production and daily life are wide, and the output of the materials is the most global. Olefin polymers not only provide a lot of convenience for people's daily life, but also drive the development of many industries in the industries of optical instruments, chemistry, medical instruments, electronic devices, insulating materials, and the like. But due to the non-polarity and low surface energy, the dyeing property, the adhesive property, the hydrophilicity, the antistatic property and the compatibility with other polar high polymers or inorganic fillers are poor, so that the expansion of the application range is limited. And the performance of the polymer can be obviously improved by introducing a polar group with rich reactivity into a polyolefin chain structure to prepare the functionalized polyolefin.
Disclosure of Invention
The invention aims to provide a vanadium complex catalyst containing a large steric hindrance phenol oxygen ligand, a preparation method and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing a vanadium complex catalyst containing a bulky phenolic oxygen ligand, the method comprising the steps of:
(1) weighing a reagent A in a reaction bottle in an anhydrous and oxygen-free nitrogen environment, adding a solvent n-octane, slowly dropwise adding vanadium oxychloride, placing the reaction bottle in a marmite at 135 ℃ for reacting for 25 hours, cooling a reaction system to room temperature, filtering with diatomite to obtain a filtrate, drying the filtrate in vacuum to remove the solvent to obtain a solid crude product, dissolving the solid crude product with dichloromethane, and dropwise adding n-hexane for low-temperature recrystallization to obtain a solid product a; wherein the reagent A is one of 2, 6-diisopropyl phenyl isocyanate, 2, 4-difluorophenyl isocyanate, 2-trifluoromethyl phenyl isocyanate and 2- (phenyl) phenyl isocyanate;
(2) weighing a solid product a in a single-mouth bottle under an anhydrous and oxygen-free nitrogen environment, adding a solvent alpha into the single-mouth bottle, refrigerating the solid product a for 1 hour at the temperature of minus 30 ℃ to obtain a solution a, stirring the solution a, adding a reagent B into the solution a, changing the solution from brown to a black solution, stirring the solution at room temperature for 3 hours, filtering the solution with diatomite to obtain a brown solution, and removing the solvent from the filtrate in vacuum to obtain the vanadium complex catalyst containing the large steric hindrance phenol-oxygen ligand; wherein the solvent alpha is one of toluene and n-hexane; wherein the reagent B is one of o-phenylphenol, 2, 6-diphenylphenol, o-pentafluorophenyl phenol and 2, 6-di (pentafluorophenyl) phenol.
Preferably, the ratio of the amount of the reagent A to the amount of the vanadium oxytrichloride is 1.0: 1.5; the ratio of the amounts of the substance of the reagent B to the solid product a is 1.0: 1.0.
the general formula of the synthetic reaction of the vanadium complex catalyst containing the large steric hindrance phenol oxygen ligand is as follows:
a vanadium complex catalyst containing a large steric hindrance phenol oxygen ligand, which is prepared by a preparation method of the vanadium complex catalyst containing the large steric hindrance phenol oxygen ligand.
Preferably, the vanadium complex catalyst containing the bulky phenol oxygen ligand has the following structural general formula:
wherein R is1、R2、R3、R4、R5、R′1、R′2、R′3、R′4、R1″、R2″、R3″、R4″、R5"is one or more of hydrogen atom, isopropyl group, trifluoromethyl group, phenyl group and pentafluorophenyl group respectively.
The application of a vanadium complex catalyst containing a large-steric-hindrance phenol-oxygen ligand in catalyzing olefin to carry out coordination polymerization.
Preferably, the vanadium complex catalyst is used for catalyzing ethylene polymerization and coordination copolymerization of ethylene and olefin monomers containing polar functional groups to prepare functionalized polyolefin materials.
Preferably, the vanadium complex catalyst is used for catalyzing coordination copolymerization of ethylene and an olefin monomer containing a polar functional group to prepare a functionalized polyolefin material, and the specific application process is as follows: sequentially adding a cocatalyst, a polar monomer D, a solvent beta and a vanadium complex catalyst into an ethylene reaction kettle in an anhydrous and oxygen-free nitrogen environment, introducing ethylene gas, keeping a certain pressure for polymerization for 3-10 minutes, then decompressing, adding a hydrochloric acid-ethanol mixed solution to terminate the reaction, and drying the product in vacuum until the quality is unchanged to obtain an olefin polymerization product; the polar monomer D is one of hexene, 3-chloropropene, 6-chloro-1-hexene, 10-undecenol, methyl 10-undecenoate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, tert-butyl acrylate, vinyl acetate, allyl acetate, vinyl ethyl ether, methyl 5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate, vinyl pyrrolidone and N-isopropyl acrylamide, and the cocatalyst is one of diethylaluminum chloride, methylaluminoxane and modified methylaluminoxane.
Preferably, ethylene and polar monomer D are polymerizable under the catalysis of vanadium catalyst and cocatalyst, wherein a total of 17 polar monomers are used, and the polymerization process and the structure of polar monomer D are as follows:
preferably, the solvent beta is one of benzene, toluene and chlorobenzene.
Preferably, the molar ratio of the vanadium complex catalyst to the polar monomer D is from 1: 500-3000.
Preferably, the reaction temperature of the ethylene reaction kettle is 0-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the vanadium complex catalyst containing the large-steric-hindrance phenol-oxygen ligand is simple to synthesize, has no harsh requirements on experimental conditions, is simple to operate, and is easy to react;
(2) the vanadium complex containing the high steric hindrance phenol-oxygen ligand is used for catalyzing coordination polymerization reaction of ethylene and polar monomers, the influence of steric hindrance and electronegativity of a substituent group on copolymerization is researched, and a new strategy is provided for synthesizing the functionalized polyolefin.
(3) The homopolymerized ethylene prepared by the vanadium complex containing the large-steric-hindrance phenol-oxygen ligand has the advantages of large molecular weight, high strength, stable chemical property and certain anti-aging performance; the copolymer prepared by the vanadium complex containing the large-steric-hindrance phenol-oxygen ligand successfully introduces polar groups with rich reactivity into a polyolefin chain structure to synthesize the functionalized polyolefin, obviously improves the surface adhesion, the hydrophilicity and the compatibility with other polar macromolecules of the polymer, and greatly improves the performance of the polymer.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the trichloride of diisopropylvanadium prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of catalyst Cat.1 prepared in example 2 of the present invention;
FIG. 3 is a nuclear magnetic carbon spectrum of catalyst Cat.1 prepared in example 2 of the present invention;
FIG. 4 is a DSC plot of homopolyethylene prepared in example 3 of the present invention;
FIG. 5 is a Fourier infrared spectrum of homopolyethylene prepared in example 3 according to the present invention;
FIG. 6 is a DSC graph of a copolymer obtained by copolymerizing ethylene and methyl 10-undecenoate using the catalyst Cat.1 in example 4 of the present invention;
FIG. 7 is a Fourier infrared spectrum of a copolymer obtained by copolymerizing ethylene and methyl 10-undecenoate using a catalyst Cat.1 in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the trichloride of the diisopropyl vanadium comprises the following steps:
under the environment of anhydrous oxygen-free nitrogen, 2, 6-diisopropyl phenyl isocyanate (1.5g,7.1mmol) is added into a Schlenk bottle, vanadium oxychloride (1.86g,10.7mmol) is added into the Schlenk bottle, 15mL of n-octane is added, then the mixture is stirred for 25 hours at 135 ℃, carbon dioxide gas generated is discharged at intervals during the reaction, and the system is a dark green solution after the reaction is finished. Filtration through celite and collection of the filtrate and vacuum drying of the filtrate left the bottom solid product to vacuum dry gave a tan powder, 2.6g of the trichloride of vanadium diisopropylate, 86% yield. The structural formula of the trichloride of diisopropyl vanadium is as follows:
fig. 1 is a nuclear magnetic hydrogen spectrum of the trichloride of diisopropylvanadium prepared in this example, and the structure of the prepared product is judged to be correct by distinguishing signal peaks.
Example 2
A preparation method of a vanadium complex catalyst containing a large-steric-hindrance phenol-oxygen ligand comprises the following steps:
the diisopropylvanadium trichloride (135.2mg, 0.3mmol) prepared in example 1 was dissolved in 20mL of toluene and allowed to stand at-30 ℃ for 1 hour under anhydrous oxygen-free nitrogen atmosphere; o-phenylphenol (51.1mg, 0.3mmol) was dissolved in 20mL of toluene and allowed to stand at-30 ℃ for 1 hour; and slowly dripping the cold o-phenylphenol solution into the diisopropyl vanadium trichloride solution, changing the solution from black brown into a black solution, stirring at room temperature for 3 hours, then carrying out vacuum drying to obtain a black oily substance, carrying out low-temperature refrigeration, washing with cold n-hexane for three times, removing the liquid, and carrying out vacuum drying on the retained solid product to obtain a black solid vanadium complex catalyst (Cat.1) containing the large steric hindrance phenol oxygen ligand, wherein the yield is 82%. The structural formula of the vanadium complex catalyst Cat.1 containing the sterically hindered phenol oxygen ligand is as follows:
fig. 2 and 3 are a nuclear magnetic hydrogen spectrum and a nuclear magnetic carbon spectrum corresponding to the catalyst cat.1 prepared in this example, respectively, and the structure of the prepared product is judged to be correct by distinguishing signal peaks.
Example 3
A vanadium complex catalyst (Cat.1) containing a large-steric-hindrance phenol oxygen ligand is used for catalyzing ethylene homopolymerization, and comprises the following steps:
(1) in an anhydrous and oxygen-free nitrogen glove box, taking 2.0 mu mol of a main catalyst (Cat.1) into a 10mL polymerization bottle, and adding 8g of toluene; 5.0mmol of diethylaluminum chloride as cocatalyst was added to another polymerization flask and 6.5g of toluene were added to ensure that the total reaction volume was 20 mL. And taking the two bottles out of the glove box, connecting the two tubes, and replacing nitrogen for later use. The polymerization reactor is dried for 6 hours at 100 ℃ and then vacuumized for 3 hours. The kettle body is placed in an ice-water mixed bath until the temperature of the kettle body is constantly maintained at 0 ℃ for later use.
(2) After the polymerization reaction device replaces nitrogen for three times, keeping the nitrogen continuously introduced, sequentially and respectively adding a cocatalyst diethyl aluminum chloride and a main catalyst Cat.1 into the reaction kettle, and starting stirring magnetons for stirring. Ethylene gas is rapidly introduced, and polymerization is started after nitrogen in the reaction kettle is discharged through a valve above the reaction kettle. During the reaction, the pot temperature and the ethylene gas pressure were kept constant until the polymerization was terminated.
(3) After the reaction, the pressure was released to remove the ethylene gas remaining in the tube, and then the reaction solution was poured into 100mL of ethanol and stirred continuously, followed by slowly adding 15mL of concentrated hydrochloric acid and stirring for 12 hours. And (3) carrying out suction filtration on the mixed solution to obtain a white solid polymer, and putting the polymer in a vacuum drying oven to be dried in vacuum for 6 hours at the temperature of 60 ℃ until the weight is constant.
The synthetic route of the vanadium complex catalyst containing the large-steric-hindrance phenol-oxygen ligand for catalyzing ethylene polymerization is as follows:
in this example, the molecular weight of the obtained polymer was 9.01X 105Da, PDI 3.1.
FIGS. 4 and 5 are a DSC chart and a Fourier infrared spectrum, respectively, of the homopolyethylene prepared in this example, showing that polyethylene was polymerized.
Example 4
A vanadium complex catalyst (Cat.1) containing a bulky phenol oxygen ligand catalyzes ethylene and 10-methyl undecylenate to copolymerize, and comprises the following steps:
(1) in an anhydrous and oxygen-free nitrogen glove box, taking 6.0 mu mol of a catalyst into a 10mL polymerization bottle, and adding 4g of toluene; adding 9.0mmol of cocatalyst diethyl aluminum chloride into another polymerization bottle, and adding 6.5g of toluene; methyl 10-undecenoate (595mg, 3.0mmol) was taken in a 10mL polymerization flask, and 4g of toluene was added to ensure that the total reaction volume was 20 mL. And taking the three polymerization bottles out of the glove box, connecting the three polymerization bottles with a double-row pipe, and replacing nitrogen for later use. The polymerization reactor is dried for 6 hours at 100 ℃ and then vacuumized for 3 hours. The kettle body is placed in an ice-water mixed bath until the temperature of the kettle body is constantly maintained at 0 ℃ for later use.
(2) After the polymerization reaction device replaces nitrogen for three times, keeping the nitrogen continuously introduced, sequentially and respectively adding a cocatalyst diethyl aluminum chloride and a main catalyst Cat.1 into the reaction kettle, and starting stirring magneton for stirring. Ethylene gas is rapidly introduced, and polymerization is started after nitrogen in the reaction kettle is discharged through a valve above the reaction kettle. During the reaction, the pot temperature and the ethylene gas pressure were kept constant until the polymerization was terminated.
(3) After the reaction, the pressure was released to remove the ethylene gas remaining in the tube, and the reaction solution was poured into 100mL of ethanol and stirred, followed by slowly adding 15mL of concentrated hydrochloric acid and stirring for 12 hours. And (3) carrying out suction filtration on the mixed solution to obtain a white solid polymer, and putting the polymer in a vacuum drying oven for vacuum drying at 40 ℃ for 6 hours until the weight is constant.
The molecular weight of the copolymer obtained by copolymerizing ethylene and methyl undecylenate is 2.1X 104Da and PDI are 2.5, wherein the insertion rate of the 10-methyl undecylenate monomer reaches 1.8 percent.
FIGS. 6 and 7 are a DSC graph and a Fourier infrared spectrum of a polymer prepared by using the catalyst Cat.1 to catalyze the copolymerization of ethylene and methyl 10-undecenoate in example 4 of the present invention, respectively. The success of copolymerization is judged by the melting point Tm and infrared characteristic peak of the polymer.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (10)
1. A preparation method of a vanadium complex catalyst containing a large-steric-hindrance phenol-oxygen ligand is characterized by comprising the following steps:
(1) weighing a reagent A in a reaction bottle in an anhydrous and oxygen-free nitrogen environment, adding a solvent n-octane, slowly dropwise adding vanadium oxychloride, placing the reaction bottle in a marmite at 135 ℃ for reacting for 25 hours, cooling a reaction system to room temperature, filtering with diatomite to obtain a filtrate, drying the filtrate in vacuum to remove the solvent to obtain a solid crude product, dissolving the solid crude product with dichloromethane, and dropwise adding n-hexane for low-temperature recrystallization to obtain a solid product a; wherein the reagent A is one of 2, 6-diisopropyl phenyl isocyanate, 2, 4-difluorophenyl isocyanate, 2-trifluoromethyl phenyl isocyanate and 2- (phenyl) phenyl isocyanate;
(2) weighing a solid product a in a single-mouth bottle under an anhydrous and oxygen-free nitrogen environment, adding a solvent alpha into the single-mouth bottle, refrigerating the solid product a for 1 hour at the temperature of minus 30 ℃ to obtain a solution a, stirring the solution a, adding a reagent B into the solution a, changing the solution from brown to a black solution, stirring the solution at room temperature for 3 hours, filtering the solution with diatomite to obtain a brown solution, and removing the solvent from the filtrate in vacuum to obtain the vanadium complex catalyst containing the large steric hindrance phenol-oxygen ligand; wherein the solvent alpha is one of toluene and n-hexane; wherein the reagent B is one of o-phenylphenol, 2, 6-diphenylphenol, o-pentafluorophenyl phenol and 2, 6-di (pentafluorophenyl) phenol.
2. The method for preparing the vanadium complex catalyst containing the bulky hindered phenol oxygen ligand according to claim 1, wherein: the mass ratio of the reagent A to the vanadium oxychloride is 1.0:1.5, and the mass ratio of the reagent B to the solid product a is 1.0: 1.0.
3. a vanadium complex catalyst containing a sterically hindered phenol oxygen ligand prepared according to the method for preparing a vanadium complex catalyst containing a sterically hindered phenol oxygen ligand as claimed in claim 1.
4. The vanadium complex catalyst containing a sterically hindered phenol oxygen ligand according to claim 3, characterized in that it has the following general structural formula:
wherein R is1、R2、R3、R4、R5、R′1、R′2、R′3、R′4、R1″、R2″、R3″、R4″、R5"is one or more of hydrogen atom, isopropyl group, trifluoromethyl group, phenyl group and pentafluorophenyl group respectively.
5. Use of a vanadium complex catalyst containing a sterically hindered phenol oxygen ligand according to claim 3 or 4, characterized in that: the vanadium complex catalyst is applied to catalyzing olefin to carry out coordination polymerization.
6. Use of a vanadium complex catalyst containing a sterically hindered phenol oxygen ligand according to claim 5, characterized in that: the vanadium complex catalyst is used for catalyzing ethylene polymerization and coordination copolymerization of ethylene and an olefin monomer containing a polar functional group to prepare a functionalized polyolefin material.
7. The use of the vanadium complex catalyst containing the bulky hindered phenol oxygen ligand according to claim 4, wherein the vanadium complex catalyst is used for catalyzing the coordination copolymerization of ethylene and an olefin monomer containing a polar functional group to prepare a functionalized polyolefin material, and the specific application process comprises the following steps: sequentially adding a cocatalyst, a polar monomer D, a solvent beta and a vanadium complex catalyst into an ethylene reaction kettle in an anhydrous and oxygen-free nitrogen environment, introducing ethylene gas for polymerization for 3-10 minutes, then decompressing, adding a hydrochloric acid-ethanol mixed solution to terminate the reaction, and drying the product in vacuum until the quality is unchanged to obtain an olefin polymerization product; the polar monomer D is one of hexene, 6-chloro-1-hexene, 3-chloropropene, 10-undecenol, methyl 10-undecenoate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, tert-butyl acrylate, vinyl acetate, allyl acetate, vinyl ethyl ether, methyl 5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate, vinyl pyrrolidone and N-isopropyl acrylamide, and the cocatalyst is one of diethylaluminum chloride, methylaluminoxane and modified methylaluminoxane.
8. Use of a vanadium complex catalyst containing a sterically hindered phenol oxygen ligand according to claim 7, characterized in that: the solvent beta is one of benzene, toluene and chlorobenzene.
9. Use of a vanadium complex catalyst containing a sterically hindered phenol oxygen ligand according to claim 7, characterized in that: the molar ratio of the vanadium complex catalyst to the polar monomer D is from 1: 500-3000.
10. Use of a vanadium complex catalyst containing a sterically hindered phenol oxygen ligand according to claim 7, characterized in that: the reaction temperature in the ethylene reaction kettle is 0-80 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249510A (en) * | 2001-02-26 | 2002-09-06 | Asahi Kasei Corp | Polymerization catalyst of olefin polymer and method for manufacturing olefin polymer |
| JP2006016533A (en) * | 2004-07-02 | 2006-01-19 | Asahi Kasei Chemicals Corp | Method for producing cyclic olefin copolymer |
| CN111848669A (en) * | 2020-08-10 | 2020-10-30 | 合肥工业大学 | Vanadium complex catalyst containing phenoxy ligand and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249510A (en) * | 2001-02-26 | 2002-09-06 | Asahi Kasei Corp | Polymerization catalyst of olefin polymer and method for manufacturing olefin polymer |
| JP2006016533A (en) * | 2004-07-02 | 2006-01-19 | Asahi Kasei Chemicals Corp | Method for producing cyclic olefin copolymer |
| CN111848669A (en) * | 2020-08-10 | 2020-10-30 | 合肥工业大学 | Vanadium complex catalyst containing phenoxy ligand and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| WEI WANG: "Remarkable Effects of Aluminum Cocatalyst and Comonomer in Ethylene Copolymerizations Catalyzed by (Arylimido)(aryloxo)vanadium Complexes: Efficient Synthesis of High Molecular Weight Ethylene/Norbornene Copolymer", 《MACROMOLECULES》, vol. 38, pages 5905 - 5913 * |
| 张树等: "钒配合物及其催化乙烯与α-烯烃共聚的研究进展", 《科学通报》, vol. 66, no. 30, pages 3849 - 3865 * |
| 高翔: "含大位阻酚氧配体钒配合物催化联烯聚合研究", 中国优秀硕士学位论文全文数据库 工程科技I辑》, vol. 2, pages 14 * |
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