CN114478873A - N, O-type nickel catalyst containing fluorine effect and application thereof in coordination copolymerization of olefin - Google Patents
N, O-type nickel catalyst containing fluorine effect and application thereof in coordination copolymerization of olefin Download PDFInfo
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- CN114478873A CN114478873A CN202210224076.7A CN202210224076A CN114478873A CN 114478873 A CN114478873 A CN 114478873A CN 202210224076 A CN202210224076 A CN 202210224076A CN 114478873 A CN114478873 A CN 114478873A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000011737 fluorine Substances 0.000 title claims abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 230000000694 effects Effects 0.000 title claims abstract description 36
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 title abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000005977 Ethylene Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- -1 polyethylene Polymers 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 42
- 125000001153 fluoro group Chemical group F* 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003446 ligand Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 235000010290 biphenyl Nutrition 0.000 claims description 14
- 239000004305 biphenyl Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 150000004658 ketimines Chemical class 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003780 insertion Methods 0.000 claims description 8
- 230000037431 insertion Effects 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 239000003039 volatile agent Substances 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 claims description 5
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- KAVKNHPXAMTURG-UHFFFAOYSA-N n-(4-bromonaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C(Br)C2=C1 KAVKNHPXAMTURG-UHFFFAOYSA-N 0.000 claims description 4
- OJPSFJLSZZTSDF-UHFFFAOYSA-N 3-ethoxyprop-1-ene Chemical compound CCOCC=C OJPSFJLSZZTSDF-UHFFFAOYSA-N 0.000 claims description 3
- BLMIXWDJHNJWDT-UHFFFAOYSA-N 6-chlorohex-1-ene Chemical compound ClCCCCC=C BLMIXWDJHNJWDT-UHFFFAOYSA-N 0.000 claims description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 claims description 3
- 229930015698 phenylpropene Natural products 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000012546 transfer Methods 0.000 abstract description 5
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 229920000098 polyolefin Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000006519 CCH3 Chemical group 0.000 description 6
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000003818 flash chromatography Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 1
- NZESCINJPKXOML-UHFFFAOYSA-N 3-(3,5-dimethylphenyl)-2-hydroxybenzaldehyde Chemical compound CC1=CC(C)=CC(C=2C(=C(C=O)C=CC=2)O)=C1 NZESCINJPKXOML-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
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- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- 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)
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Abstract
The invention discloses a fluorine-effect-containing N, O-type nickel catalyst and coordination copolymerization thereof in olefinThe general structural formula of the N, O-type nickel-based catalyst containing fluorine effect is shown as the following formula (I) and formula (II):
the catalyst of the invention is applied to homogeneous polymerization of ethylene, and can efficiently prepare ultra-high molecular weight polyethylene (UHMWPE) products. Mainly because the complex has the influence of intermolecular fluorine effect, the chain transfer can be effectively inhibited in the ethylene polymerization, thereby improving the thermal stability and catalytic activity of the catalyst, obviously improving the molecular weight of the polymer and reducing the branching degree of the obtained polymer. More importantly, the catalyst also realizes the copolymerization of ethylene and polar monomers to obtain the functionalized polyethylene materials with different polarities. Therefore, the nickel-based catalyst has important industrial application value and wide application prospect in the field of olefin polymerization.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization, and particularly relates to an N, O-type nickel catalyst containing a fluorine effect and application thereof in coordination copolymerization of olefins.
Background
Because of the characteristics of rich raw materials, low price, easy processing and forming, excellent comprehensive performance and the like, the polyolefin is a high polymer material (M.Sturzel, S.Mihan, R.Mulhaupt, chem.Rev.2016,116,1398) with the largest global yield and demand at present, and is widely applied to the development of the social industry and the daily production and life of people. Olefin polymerization catalyst development is a core technology of the polyolefin industry, and thus development of new catalysts is a key to realizing high-performance polyolefin materials. Late transition metals can catalyze the copolymerization of olefin and polar monomer due to their low oxophilicity, so that they have been the hot research focus for preparing functionalized polyolefin materials in recent years, but some problems still need to be solved in order to achieve better copolymerization effect (F.Wang, C.Chen, Polymer.Chem.2019, 10, 2354-. Even though palladium catalysts exhibiting outstanding alpha-diimine palladium with nickel catalysts, phosphine sulfonic acid and related ligands show great potential in catalyzing the copolymerization of ethylene and many polar monomers, there still exist polymerization problems of low catalyst activity, low copolymer molecular weight, low polar monomer insertion ratio, etc., and only simple polar monomers can be catalyzed and copolymerized, and when other polar monomers such as allyltrimethoxysilane, methyl 10-undecenoate, 10-undecen-1-ol, vinyl ether, styrene, etc., are added, the performance of the catalyst is greatly reduced, even completely deactivated.
Therefore, the development of high-efficiency olefin metal catalysts is the key point for promoting the regeneration of industrial products of polyolefins. The invention mainly researches a cheap nickel-based high-efficiency catalyst and researches the application of the catalyst in olefin polymerization and copolymerization of polar monomers. In the field of olefin polymerization, the nickel-based catalyst has important industrial application value and wide application prospect.
Disclosure of Invention
The invention aims to provide an N, O-type nickel-based catalyst containing fluorine effect, a preparation method of the catalyst and application of the catalyst in homogeneous polymerization and copolymerization of polar monomers of ethylene.
(I) N, O-type nickel-based catalyst containing fluorine effect
The invention relates to a fluorine-effect-containing N, O-type nickel catalyst, which has the structural general formula shown as the following formulas (I) and (II):
wherein R is1Selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro substituted biphenyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C20 alkyl, nitro, hydroxyl, methyl, methoxy, trifluoromethyl, trifluoromethoxy and fluorine substituted biphenyl;
R3selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro-substituted phenyl, fluoro-substituted biphenyl;
R4selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, substituted C1-C6 alkyl, C6EOne or more of C12 aryl.
Formula (I) provides a fluorine substituted ketimine N, O-type nickel catalyst; formula (II) provides a fluorine substituted salicylaldehyde N, O-type nickel catalyst.
The preparation method of the N, O-type nickel catalyst containing fluorine effect introduces fluorine substitution into ligand aryl, accelerates the process of olefin insertion due to the influence of the fluorine effect on the active center, greatly improves the activity of the nickel catalyst, weakens the transfer rate of an active chain to a monomer, improves the thermal stability of the catalyst and obtains the ultrahigh molecular weight polyethylene (UHMWPE). Meanwhile, the nickel-based catalyst realizes the copolymerization of ethylene and polar monomers to obtain copolymers with different polarities.
The preparation method of the N, O-type nickel catalyst containing fluorine effect is divided into the following two types according to different catalyst types (namely, ketimine N, O-type nickel catalyst and salicylaldehyde N, O-type nickel catalyst):
preparation of fluorine substituted ketimine N, O-type nickel-based catalyst
The preparation method of the fluorine-substituted ketimine N, O-type nickel-based catalyst comprises the following steps:
under the atmosphere of nitrogen, dissolving a ketimine ligand, allyl nickel chloride and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate in dichloromethane respectively, and stirring to react for 8-12 hours at room temperature; after the reaction is finished, filtering and evaporating the obtained mixture by diatomite to obtain a fluorine substituted ketimine N, O-type nickel catalyst (I);
the structure of the ketimine ligand is shown as the following formula (III):
wherein R is1Selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro substituted biphenyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C20 alkyl, nitro, hydroxyl, methyl, methoxyl and trifluoromethylTrifluoromethoxy, fluoro substituted biphenyl.
The preparation method of the ketimine ligand (III) is particularly preferably performed by the following steps:
under the nitrogen atmosphere, adding phenylboronic acid, aniline and anhydrous potassium carbonate with corresponding structures into a mixed solvent containing toluene/anhydrous ethanol/water, stirring uniformly, and blowing nitrogen in a double-row pipe to inject Pd (PPh)3)4After the reaction is carried out for 24 hours at 95 ℃, the reaction is finished and aniline of the following formula (a) is obtained through column chromatography separation and purification; adding the obtained aniline of the formula (a) into a toluene solution containing 2, 3-butanedione, adding p-toluenesulfonic acid with a catalytic amount, reacting at the temperature of 85-90 ℃, and separating and purifying after the reaction is finished to obtain the ketimine ligand of the formula (III).
In the preparation method of the compound represented by the formula (III), the meanings and selection ranges represented by the substituents are consistent with those represented by the substituents in the compound represented by the formula (III), and are not repeated herein.
Preparation of N, O-type nickel catalyst containing fluorine substituted salicylaldehyde
The preparation method of the fluorine-substituted salicylaldehyde N, O-type nickel catalyst comprises the following steps:
stirring the salicylaldehyde ligand and NaH in THF overnight under nitrogen, then filtering the solution through celite and removing all volatiles in vacuo to obtain a yellow sodium salt solid which is used without further purification; the obtained sodium salt and trans-NiPhCl (PPh)3)2Dissolving in toluene solution and stirring overnight; after the reaction is finished, filtering the mixture by using kieselguhr, and removing volatile matters in vacuum to obtain a fluorine substituted salicylaldehyde N, O-type nickel catalyst (II);
the salicylaldehyde ligand has the structure shown as the following formula (IV):
wherein R is1Selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro substituted biphenyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C20 alkyl, nitro, hydroxyl, methyl, methoxy, trifluoromethyl, trifluoromethoxy and fluorine substituted biphenyl;
R3selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro-substituted phenyl, fluoro-substituted biphenyl;
R4one or more selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, substituted C1-C6 alkyl and C6-C12 aryl.
The preparation method of the salicylaldimine ligand (IV) is preferably the following steps:
adding aniline of formula (a), salicylaldehyde of formula (b) and p-toluenesulfonic acid of catalytic amount into a toluene solution under nitrogen atmosphere, reacting at 85-150 ℃ for 8-24 hours, and separating and purifying by column chromatography after the reaction is finished to obtain the salicylaldimine ligand of formula (IV).
In the preparation method of the compound represented by the formula (IV), the meanings and selection ranges represented by the substituents are consistent with those represented by the substituents in the compound represented by the formula (IV), and are not repeated herein.
Application of N, O-type nickel catalyst containing fluorine effect in ethylene homogeneous polymerization
The invention relates to an application of an N, O-type nickel catalyst containing fluorine effect as a catalyst for catalyzing the homogeneous polymerization of ethylene. The complex contains a large amount of fluorine atoms, which can effectively inhibit chain transfer in ethylene polymerization, thereby improving the thermal stability and catalytic activity of the catalyst, reducing the branching degree of the obtained polyethylene, and simply and efficiently preparing the ultra-high molecular weight polyethylene (UHMWPE) product.
A large number of experiments have proved that the prepared N, O-type nickel-based catalyst is put into a high-pressure reaction flask in the homogeneous polymerization of ethylene, wherein the N, O-type nickel-based catalyst formula (II) needs to be mixed with a cocatalyst (Ni (COD)2Or B (C)6F5)3) The composite catalytic system is formed by a molar ratio of 1: 1-1: 5, the reaction temperature is controlled at 0-200 ℃, the reaction time is 0.05-5.0 hours, and when the dosage of the catalyst is 1-20 mu mol, the catalytic system has high thermal stability and catalytic activity (can reach 6.93 multiplied by 10) for catalyzing ethylene polymerization6g/(mol Nih), ultra-high molecular weight polyethylene (up to M) having a low degree of branching is obtainedn＝279.2×104g/mol)。
Through nuclear magnetic analysis, the obtained polymer is low in branching degree and is 1-100 branches/1000 carbon atoms. (V) application of N, O-type nickel catalyst containing fluorine effect in copolymerization reaction of ethylene and polar monomer
The N, O-type nickel catalyst prepared by the invention can also be applied to copolymerization of ethylene and polar monomers, and can inhibit chain transfer effect in the polymerization process through the influence of fluorine effect among the molecules of the complex, so as to realize copolymerization of ethylene and polar monomers, thereby obtaining a functional polyethylene material with higher polar monomer insertion rate.
The polar monomer comprises one or more of methyl 10-undecylenate, 10-undecen-1-ol, allyltrimethoxysilane, allyl chloride, 6-chloro-1-hexene, styrene, allyl benzene, ethyl allyl ether, methyl methacrylate and vinyl ethyl ether.
A great deal of experiments show that the N, O-type nickel catalyst containing fluorine effect can realize the copolymerization of ethylene and polar monomers, such as 10-methyl undecylenate, 10-undecylen-1-ol, allyltrimethoxysilane and the like, and the prepared nickel catalyst is put into a high-pressure reaction bottle, wherein the salicylaldehyde N, O-type nickel catalyst needs to be mixed with a cocatalyst (Ni (COD)2Or B (C)6F5)3) The composite catalytic system is composed by a molar ratio of 1: 1-1: 5, the dosage of the catalyst is 5-40 mu mol/L, the polymerization pressure is 0.1-30 MPa, the reaction temperature is controlled at 0-120 ℃, and the reaction time is 0.1-5.0 hours, so that the functionalized polyolefin material with higher molecular weight, lower dispersity and higher polar monomer insertion ratio is obtained. Different concentrations of polar monomer can effectively intercalate into the ethylene polymer, thereby altering the branching structure of the copolymer to affect the properties of the resulting high molecular weight polyolefin.
Compared with the prior art, the invention aims at the problem of preparing a catalyst system by the existing olefin polymerization, particularly adopts a metal complex catalyst system containing a fluorine effect, and simultaneously aims at the inherent defects that the existing catalyst has a catalytic effect but is far from insufficient in selectivity and activity. The invention creatively applies the fluorine effect strategy to the olefin bulk polymerization and the copolymerization of the olefin and the polar monomer based on the intermolecular electronic effect and the steric effect, and obtains better technical effect. The invention considers that fluorine atoms close to the metal center can generate secondary interaction with a growing chain of the polymer to inhibit the chain transfer process, thereby inhibiting the elimination of beta-H and beta-X, but not preventing the normal coordination of ethylene, inhibiting the occurrence of chain walking, reducing the branching degree of polyethylene, and being capable of preparing ultrahigh molecular weight polyolefin materials and copolymers containing polar functional groups.
Drawings
FIG. 1 is a diagram of a single crystal structure by X-ray diffraction of a catalyst complex prepared in example 3 of the present invention;
FIG. 2 is a diagram of a single crystal structure by X-ray diffraction of a catalyst complex prepared in example 4 of the present invention;
FIG. 3 shows the molecular weight M of the polymer prepared by Entry1 in Table 1 of example 5 of the present inventionnData;
FIG. 4 shows the melting point T of a polymer prepared by Entry1 in Table 1 of example 6 of the present inventionmAnd (4) data.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
According to the embodiment of the application, an N, O-type nickel-based catalyst containing fluorine effect is provided, and the general structural formula of the catalyst is shown as the following formula (I) and formula (II):
wherein R is1Selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro substituted biphenyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C20 alkyl, nitro, hydroxyl, methyl, methoxy, trifluoromethyl, trifluoromethoxy and fluorine substituted biphenyl;
R3selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro-substituted phenyl, fluoro-substituted biphenyl;
R4one or more selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, substituted C1-C6 alkyl and C6-C12 aryl;
there is also provided, in accordance with an embodiment of the present application, the use of nickel catalysts (I) and (II) of the N, O-type containing a fluorine effect in coordination polymerization of olefins, including for catalyzing ethylene homopolymerization or olefin/polar monomer copolymerization.
The polar monomer comprises one or more of 10-methyl undecylenate, 10-undecen-1-ol, allyltrimethoxysilane, allyl chloride, 6-chloro-1-hexene, styrene, allyl benzene, ethyl allyl ether, methyl methacrylate and vinyl ethyl ether.
The data given in the examples of the present invention include the synthesis of ligands, the synthesis of metal compounds, and the olefin polymerization process, wherein the synthesis of metal compounds and the olefin polymerization process were carried out under anhydrous and oxygen-free conditions, all sensitive materials were stored in a glove box refrigerator at-30 ℃, all solvents were strictly dried to remove water, and no specific description was given, and all raw materials were purchased and used directly.
Silica gel with 200-300 meshes is used for the silica gel column, and a Bruker 400MHz nuclear magnetism instrument is used for nuclear magnetism. The elemental analysis was determined by the chemical and physical center of the university of science and technology in China. The molecular weight and molecular weight distribution of the amorphous polymer were determined by GPC (polystyrene type columns, HR2 and HR4, box temperature 45 ℃, using Water 1515 and Water 2414 pumps, tetrahydrofuran as the mobile phase, flow rate 1.0 ml per minute, polydispersed polystyrene as standard). The molecular weight and molecular weight distribution of the crystalline polymer were determined by high temperature GPC (at 120 ℃ C. using PL-GPC220 with an infrared probe (658 nm), 1, 2, 4 trichlorobenzene as the mobile phase at a flow rate of 1.0 ml per minute). The single crystal X-ray Diffraction analysis adopts an Oxford Diffraction Gemini S Ultra CCD single crystal Diffraction instrument, Cu Ka
And (5) irradiating at room temperature.
Example 1:
(1) ligand I-CF3Synthesis of-L
Under the condition of nitrogen, 3',5, 5' -penta (trifluoromethyl) - [1,1':3', 1' -terphenyl is put in]A mixture of (E) -2' -amine (0.59 g, 1 mmol), p-toluenesulfonic acid-hydrate (0.02 g, 0.1 mmol) and 2, 3-butanedione (0.18 g, 2 mmol) in 50 ml of toluene was refluxed at 85-90 ℃ for 12 hours. After cooling the mixture to room temperature, the solvent was evaporated and purified by flash chromatography on silica gel (CH)2Cl2/PE (1/20) separation and purification to obtain the target product as yellow solid I-CF3L (0.41 g, 62% yield).
The nuclear magnetic results were as follows:
1H NMR(400MHz,CDCl3)δ7.94(s,4H),7.88(s,2H),7.73(s,2H),2.27(s,3H,COCH3),1.42(s,3H,N＝CCH3).19F NMR(376MHz,CDCl3)δ-62.24(s,3F,aryl-CF3),-62.92(s,12F,aryl-CF3).13C NMR(100MHz,CDCl3)δ197.17(s,COCH3),168.21(s,N＝CCH3),148.21(s),139.48(s),132.71(s,aryl-CF3),132.38(s,aryl-CF3),132.04(s,aryl-CF3),131.71(s,aryl-CF3),129.17(s),127.68(d,J＝3.5Hz),127.05(s),124.34(s),122.02(s),121.62(s),23.65(s,COCH3),16.10(s,N＝CCH3).
(2) catalyst I-CF3Synthesis of-Ni
In a glove box, ligand I-CF3-L (0.33 g, 0.5 mmol), allylnickel chloride (0.07 g, 0.5 mmol) and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (0.44 g, 0.5 mmol) were mixed in dichloromethane (15 ml) and stirred at room temperature for 12 hours. Filtering the obtained mixture by using kieselguhr and evaporating to obtain the target product which is black red solid I-CF3Ni (0.72 g, 86% yield).
The nuclear magnetic results were as follows:
1HNMR(400MHz,CDCl3)δ7.98–7.80(m,9H),7.72(t,J＝22.7Hz,8H),7.49(s,3H),2.28(s,3H,COCH3),1.41(s,3H,N＝CMe).19F NMR(376MHz,CDCl3)δ-62.22(s,3F,aryl-CF3),-62.35(s,12F,aryl-CF3),-62.90(s,24F,aryl-CF3).
elemental analysis calculation C62H31BF39NNiO C46.07; h1.93; n, 0.87; c46.05, H1.91, N0.90 were found.
Example 2:
(1) ligand I-CH3Synthesis of-L
Under the condition of nitrogen gas making 3, 3',5, 5' -pentamethyl- [1,1':3', 1' -terphenyl]-2' -amine (0.32 g, 1 mmol), pA mixture of toluenesulfonic acid monohydrate (0.02 g, 0.1 mmol) and 2, 3-butanedione (0.18 g, 2 mmol) in 50 ml of toluene was refluxed at 85-90 ℃ for 12 hours. After cooling the mixture to room temperature, the solvent was evaporated and purified by flash chromatography on silica gel (CH)2Cl2/PE (1/20) separating and purifying to obtain the target product which is light yellow solid I-CH3L (0.30 g, 75% yield).
The nuclear magnetic results were as follows:
1H NMR(400MHz,d-DMSO)δ7.17(s,2H),6.95(s,4H),6.90(s,2H),2.37(s,3H,COCH3),2.24(s,12H,aryl-CH3),2.22(s,3H,aryl-CH3),1.27(s,3H,N＝CCH3).13C NMR(100MHz,CD2Cl2)δ199.31(s,COCH3),165.94(s,N＝CCH3),142.71(s),139.66(s),137.36(s),134.28(s),131.06(s),129.92(s),128.38(s),126.92(s),24.42(s,COCH3),20.99(s,aryl-CH3),20.54(s,aryl-CH3),14.98(s,N＝CCH3).
(2) catalyst I-CH3Synthesis of-Ni
In a glove box, ligand I-CH3-L (0.20 g, 0.5 mmol), allylnickel chloride (0.07 g, 0.5 mmol) and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (0.44 g, 0.5 mmol) were mixed in dichloromethane (15 ml) and stirred at room temperature for 12 hours. Filtering the obtained mixture by diatomite and evaporating to obtain the target product which is black red solid I-CH3Ni (0.61 g, 90% yield).
The nuclear magnetic results were as follows:
1H NMR(400MHz,CDCl3)δ7.67(s,10H,PhH),7.49(s,6H,PhH),7.26(s,16H,PhH),3.10(s,3H,COCH3),2.74(d,J＝31.5Hz,3H,N＝CMe),2.33(s,15H,Ph-CH3).19F NMR(376MHz,CDCl3)δ-62.28(s,24F,aryl-CF3).
elemental analysis calculation C62H46BF24NNiO is C55.30; h3.44; n, 1.04; found 55.27, H3.40, N1.07.
Example 3:
(1) ligand II-CF3Synthesis of-L
Under the condition of nitrogen, 3',5, 5' -penta (trifluoromethyl) - [1,1':3', 1' -terphenyl is put in]-2 '-amine (0.59 g, 1 mmol), p-toluenesulfonic acid-hydrate (0.02 g, 0.1 mmol) and 2-hydroxy-3', 5 '-bis (trifluoromethyl) - [1,1' -biphenyl]-3-Formaldehyde (0.40 g, 1.2 mmol) was added to 50 ml of toluene and the reaction mixture was refluxed with water in an oil bath at 136 ℃ for 24 hours. After the reaction is complete, the mixture is cooled to room temperature, the solvent is evaporated and the reaction mixture is purified by flash Chromatography (CH)2Cl2/PE-1/5) to isolate and purify the crude product. The target product is obtained as off-white solid II-CF3L (0.66 g, 73% yield).
The nuclear magnetic results were as follows:
1H NMR(400MHz,CDCl3)δ8.04(s,1H),7.97(s,2H),7.87(d,J＝12.3Hz,7H),7.80(s,2H),7.45(dd,J＝6.6,2.6Hz,1H),6.95(d,J＝6.7Hz,2H).19F NMR(376MHz,CDCl3)δ-62.29(s,6F,aryl-CF3),-62.93(s,3F,aryl-CF3),-63.06(s,12F,aryl-CF3).13C NMR(100MHz,CDCl3)δ170.23(s,N＝C-Ph),158.01(s,C-OH),148.18(s),139.42(s),138.71(s),135.53(s),133.24(s),132.92(d,J＝13.5Hz),132.52(s),132.18(s),132.09–131.55(m),131.32(s),130.99(s),129.85(s),129.23(d,J＝28.4Hz),128.03(d,J＝3.5Hz),127.17(s),126.97(s),124.73(d,J＝5.0Hz,CF3),124.26(s),121.88(dd,J＝27.2,23.2Hz,CF3),121.15(s),119.93(s),118.83(s),117.96(s).
(2) catalyst II-CF3Synthesis of-Ni
In a glove box, ligand II-CF3L (0.45 g, 0.5 mmol) and NaH (0.05 g, 2 mmol) were stirred in 25 ml THF overnight. The solution was then filtered through celite and all volatiles were removed in vacuo. The yellow solid obtained, i.e. the sodium salt II-CF3-Na. THF was used without further purification. The resulting sodium salt (0.46 g, 0.5 mmol) and trans-NiPhCl (PPh)3)2(0.34 g, 0.5 mmol) was placed in 25 ml of toluene solution and stirred overnight. After the reaction was completed, the mixture was filtered through celite. After removal of volatiles in vacuo, a dark brown solid was obtained. The solid was washed with 10 ml of n-hexane, filtered and dried in vacuo to give the desired product as an orange-red powder (0.60 g, 92% yield).
The nuclear magnetic results were as follows:
1H NMR(400MHz,CDCl3)δ8.16(d,J＝7.6Hz,1H,CH＝N),8.05(s,5H,PhH),7.92–7.78(m,1H,PhH),7.43(s,2H,PhH),7.29–6.91(m,20H,PhH),6.59(d,J＝7.1Hz,1H,PhH),6.47–6.20(m,3H,PhH),6.08(s,2H,PhH).13C NMR(100MHz,CDCl3)δ168.68(s),152.11(s),141.57(s),139.80(s),137.34(s),136.92(s),135.22(s),133.71(d,J＝9.9Hz),132.31(d,J＝24.6Hz),132.05–131.92(m),131.85(s),131.27(d,J＝50.3Hz),130.62–130.20(m),129.78(t,J＝30.4Hz),129.40–129.39(m),128.79(s),127.62(d,J＝10.1Hz,CF3),125.30(s,CF3),124.60(s,CF3),121.95(s,CF3),121.72(s,CF3),119.17(s,CF3),114.88(s,CF3).31P NMR(162MHz,CDCl3)δ25.90(s).19F NMR(376MHz,C6D6)δ-61.84(s),-62.37(s),-62.54(s).
elemental analysis calculation C62H35F21NNiOP, C57.34; h2.72; n, 1.08; c57.30, H2.70, N1.09 were found.
For the catalyst II-CF prepared in inventive example 33-Ni crystal structure for X-ray diffraction phase analysis.
Referring to FIG. 1, FIG. 1 shows the catalysts II-CF prepared in example 3 of the present invention3X-ray diffraction of-NiStructure of the crystal.
Example 4:
(1) ligand II-CH3Synthesis of-L
Under the condition of nitrogen gas making 3, 3',5, 5' -pentamethyl- [1,1':3', 1' -terphenyl]-2 '-amine (0.32 g, 1 mmol), p-toluenesulfonic acid monohydrate (0.02 g, 0.1 mmol) and 2-hydroxy-3', 5 '-dimethyl- [1,1' -biphenyl]-3-Formaldehyde (0.27 g, 1.2 mmol) was added to 50 ml of toluene and the reaction mixture was refluxed with water in an oil bath at 136 ℃ for 24 hours. After the reaction is complete, the mixture is cooled to room temperature, the solvent is evaporated and the reaction mixture is purified by flash Chromatography (CH)2Cl2/PE-1/5) to isolate and purify the crude product. The target product is orange yellow solid II-CH3L (0.49 g, 94% yield).
The nuclear magnetic results were as follows:
1H NMR(400MHz,CDCl3)δ13.38(s,1H),7.93(s,1H),7.30(dd,J＝6.3,2.9Hz,1H),7.19(s,4H),7.03(s,4H),6.98(s,1H),6.88(s,2H),6.79–6.73(m,2H),2.42(s,3H),2.37(s,6H),2.28(s,12H).13C NMR(100MHz,CDCl3)δ168.05(s,N＝C-Ph),158.33(s,C-OH),142.47(s),139.65(s),137.76(s),137.52(d,J＝7.4Hz),135.27(d,J＝10.8Hz),133.53(s),131.18(s),130.69(s),128.82(s),128.48(s),127.71(s),127.20(s),119.00(s),118.31(s),21.42(d,J＝10.1Hz,CH3),21.00(s).
(2) catalyst II-CH3Synthesis of-Ni
In a glove box, ligand II-CH3L (0.26 g, 0.5 mmol) and NaH (0.05 g, 2 mmol) were stirred in 25 ml THF overnight. The solution was then filtered through celite and all volatiles were removed in vacuo. The yellow solid obtained, i.e. the sodium salt II-CH3-Na. THF need not be taken inCan be used after one-step purification. The resulting sodium salt (0.30 g, 0.5 mmol) and trans-NiPhCl (PPh)3)2(0.34 g, 0.5 mmol) was placed in 25 ml of toluene solution and stirred overnight. After the reaction was completed, the mixture was filtered through celite. After removal of volatiles in vacuo, a dark brown solid was obtained. The solid was washed with 10 ml of n-hexane, filtered and dried in vacuo to afford the desired product as an orange-red powder (0.44 g, 96% yield).
The nuclear magnetic results were as follows:
1H NMR(400MHz,CDCl3)δ8.58(d,J＝6.8Hz,1H,PhH),7.97(s,1H,PhH),7.80(d,J＝26.6Hz,2H,PhH),7.59(d,J＝30.8Hz,6H,PhH),7.40(d,J＝24.1Hz,10H,PhH),7.10(d,J＝28.6Hz,7H,PhH),6.77(d,J＝28.5Hz,4H,PhH),6.56(s,2H,PhH),6.35(s,2H,PhH),2.55(d,J＝13.3Hz,15H,Ph-CH3),1.87(d,J＝22.8Hz,6H,Ph-CH3).31P NMR(162MHz,CDCl3)δ20.58(s).
elemental analysis calculation C62H56NNiOP C80.87; h6.13; n, 1.52; c80.83, H6.10, N1.55 were found.
For catalyst II-CH prepared in example 4 of the present invention3-Ni crystal structure for X-ray diffraction phase analysis.
Referring to FIG. 2, FIG. 2 shows the catalysts II-CH prepared in example 4 of the present invention3-X-ray diffraction single crystal structure diagram of Ni.
Example 5: catalytic ethylene polymerization
A stirring magneton and 28 ml of toluene were added to a 350 ml pressure bottle under a glove box nitrogen atmosphere. Catalyst (VI) is dissolved in CH2Cl2Medium (5 micromole, 2 ml) and poured into a pressure reaction flask. The pressure vessel was connected to a high pressure line and the solution was degassed. The vessel was heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. The vessel was pressurized and maintained at the desired ethylene pressure of 8 atm with rapid stirring, and reacted for 0.3 hour. The reaction was stopped, 5% methanolic hydrochloric acid solution was added to precipitate a solid, which was washed three times with pure methanol and dried in a vacuum oven for 24 hours to constant weight.
At handA350 ml pressure bottle was charged with a stirring magneton and 28 ml toluene under nitrogen atmosphere. Catalyst (VII) dissolved in CH2Cl2Medium (5 micromole, 2 ml) and poured into a pressure reaction flask. The pressure vessel was connected to a high pressure line and the solution was degassed. The vessel was heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. The vessel was pressurized and maintained at a relatively low ethylene pressure of-2 atm under rapid stirring, and a solution of cocatalyst (10. mu. mol, 2 ml) in methylene chloride was injected thereinto. And (5) closing the valve, adjusting the pressure of the ethylene to 8 atmospheric pressure after the reaction temperature is stable, and reacting for 0.3 hour. The reaction was stopped, 5% methanolic hydrochloric acid solution was added to precipitate a solid, which was washed three times with pure methanol and dried in a vacuum oven for 24 hours to constant weight.
Referring to table 1, table 1 shows specific experimental conditions (catalyst cat. and temperature T), Yield (Yield), catalytic activity (Act.), and polymer molecular weight (M) for ethylene polymerization provided by the present inventionn) Polymerization result data such as polymer molecular weight distribution (PDI) and degree of branching (B).
TABLE 1 investigation of ethylene polymerization
Polymerization conditions: dissolving Ni catalyst (5 micromoles) in 2 ml of dichloromethane, wherein the solvent is 28 ml of toluene, the ethylene pressure is 8 atmospheric pressures, and the reaction time is 0.3 hour;
a. the cocatalyst is 2 equivalents of B (C)6F5)3；
b. Unit of active Act. is 106g/(molNih)；
c. Molecular weight M of the PolymernAnd molecular weight distribution PDI was determined by Gel Permeation Chromatography (GPC) at 150 ℃ in trichlorobenzene and polystyrene standards;
d. the degree of branching is the number of branches per 1000 carbon atoms, consisting of1HNMR nuclear magnetic resonance method determination;
e. melting point TmBy differential scanningCalorimetry (DSC) measurements.
As can be seen from Table 1, the catalyst of the present application shows higher activity when catalyzing ethylene homogeneous phase polymerization, wherein the polymerization activity of the nickel-based catalyst containing fluorine effect is the highest, and can reach 6.93 x 106g/(mol Nih); the prepared polymer has higher thermal stability and molecular weight than the polymer prepared by the nickel catalyst without fluorine-containing effect, the melting point is up to 130.5 ℃, and the number average molecular weight is up to 279.2 multiplied by 104g/mol。
Referring to FIG. 3, FIG. 3 shows the number average molecular weight M of the polymer prepared by Entry1 in Table 1 of example 9 of the present inventionnAnd (4) data.
Referring to FIG. 4, FIG. 4 shows the melting point T of the polymer prepared by Entry1 in Table 1 of example 9 of the present inventionmAnd (4) data.
Example 6: catalytic copolymerization of ethylene and polar monomer
Under the nitrogen atmosphere of a glove box, a stirring magneton, 20 ml of toluene and polar monomers in corresponding concentration ratios are added into a 350 ml pressure-resistant bottle. Catalyst (VI) is dissolved in CH2Cl2Medium (20 micromoles, 2 ml) and poured into a pressure reaction flask. The pressure vessel was connected to a high pressure line and the solution was degassed. The vessel was heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. The vessel was pressurized and maintained at the desired ethylene pressure, 8 atm, with rapid stirring, and reacted for 1 hour. The reaction was stopped, 5% methanolic hydrochloric acid solution was added to precipitate a solid, which was washed three times with pure methanol and dried in a vacuum oven for 24 hours to constant weight. Finally, the obtained solid is extracted for 2 to 3 days, and the solid is drained and weighed.
Under the nitrogen atmosphere of a glove box, a stirring magneton, 20 ml of toluene and polar monomers in corresponding concentration ratios are added into a 350 ml pressure-resistant bottle. Catalyst (VII) dissolved in CH2Cl2Medium (20 micromoles, 2 ml) and poured into a pressure reaction flask. The pressure vessel was connected to a high pressure line and the solution was degassed. The vessel was heated to the desired temperature using an oil bath and allowed to equilibrate for 15 minutes. The container is pressurized and kept in relative position under rapid stirringThe lower ethylene pressure, 2 atm, was filled with a solution of cocatalyst (40. mu. mol, 2 ml) in dichloromethane. And (5) closing the valve, adjusting the pressure of the ethylene to 8 atmospheric pressure after the reaction temperature is stable, and reacting for 1 hour. The reaction was stopped, 5% methanolic hydrochloric acid solution was added to precipitate a solid, which was washed three times with pure methanol and dried in a vacuum oven for 24 hours to constant weight. Finally, the obtained solid is extracted for 2 to 3 days, and the solid is drained and weighed.
The polar monomer insertion ratio was calculated from the hydrogen spectrum of the polymer.
See table 2, table 2 for (catalyst cat. and polar monomer Co-monomer), concentration (M), Yield (Yield), catalytic activity (Act.), polymer molecular weight (M)n) Polymer molecular weight distribution (PDI), insertion ratio (X)M) And so on to aggregate the resulting data.
TABLE 2 investigation of ethylene and polar monomer polymerization
Polymerization conditions: dissolving Ni catalyst in 20 micromole in 2 ml of dichloromethane, wherein the solvent is 18 ml of toluene, the ethylene pressure is 8 atmospheric pressures, the reaction temperature is 50 ℃, and the reaction time is 1 hour;
a. the cocatalyst is 2 equivalents of B (C)6F5)3；
b. Unit of active Act. is 104g/(molNih)；
c. Polymer molecular weight Mn and molecular weight distribution PDI were determined by Gel Permeation Chromatography (GPC) at 150 ℃ in trichlorobenzene and polystyrene standards;
d. polar monomer insertion ratio XMBy1HNMR nuclear magnetic resonance method determination;
e. the melting point Tm is determined by Differential Scanning Calorimetry (DSC).
As can be seen from Table 2, the catalyst of the present application can catalyze copolymerization of ethylene and polar monomer to prepare polar polyolefin under certain conditions, and the nickel catalyst containing fluorine effect shows the best copolymerization activity and the highest activityUp to 6.9X 104g/(mol Nih); the melting point is 91.7-111.2 ℃; the number average molecular weight is up to 6.55X 104g/mol。
The foregoing detailed description of a compound, complex catalyst, catalyst composition and process for the preparation of olefin polymers provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are presented solely to aid in the understanding of the process and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. An N, O-type nickel catalyst containing fluorine effect is characterized in that the general structural formula of the catalyst is shown as the following formula (I) and formula (II):
wherein R is1Selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro substituted biphenyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C20 alkyl, nitro, hydroxyl, methyl, methoxy, trifluoromethyl, trifluoromethoxy and fluorine substituted biphenyl;
R3selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro-substituted phenyl, fluoro-substituted biphenyl;
R4one or more selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, substituted C1-C6 alkyl and C6-C12 aryl.
2. A preparation method of fluorine substituted ketimine N, O-type nickel-based catalyst is characterized by comprising the following steps:
in the nitrogen atmosphere, dissolving a ketimine ligand, allyl nickel chloride and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate in dichloromethane respectively, and stirring and reacting at room temperature for 8-12 hours; after the reaction is finished, filtering and evaporating the obtained mixture by diatomite to obtain a fluorine substituted ketimine N, O-type nickel catalyst (I);
the structure of the ketimine ligand is shown as the following formula (III):
wherein R is1Selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro substituted biphenyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C20 alkyl, nitro, hydroxyl, methyl, methoxy, trifluoromethyl, trifluoromethoxy and fluorine substituted biphenyl.
3. A preparation method of N, O-type nickel catalyst containing fluorine substituted salicylaldehyde is characterized by comprising the following steps:
stirring the salicylaldehyde ligand and NaH in THF for 8-12 hours under nitrogen, then filtering the solution through celite and removing all volatiles in vacuo to obtain a yellow sodium salt solid; the resulting sodium salt and trans-NiPhCl (PPh)3)2Dissolving in toluene solution and stirring for 8-12 hr; after the reaction is finished, filtering the mixture by using kieselguhr, and removing volatile matters in vacuum to obtain a fluorine substituted salicylaldehyde N, O-type nickel catalyst (II);
the salicylaldehyde ligand has the structure shown as the following formula (IV):
wherein R is1Selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro substituted biphenyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C20 alkyl, nitro, hydroxyl, methyl, methoxy, trifluoromethyl, trifluoromethoxy and fluorine substituted biphenyl;
R3selected from hydrogen, fluoro, methyl, trifluoromethyl, trifluoromethoxy, fluoro-substituted phenyl, fluoro-substituted biphenyl;
R4one or more selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, substituted C1-C6 alkyl and C6-C12 aryl.
4. Use of the fluorine effect-containing N, O-type nickel-based catalyst according to claim 1, wherein:
the N, O-type nickel catalyst containing fluorine effect is used as a catalyst to catalyze the homogeneous polymerization reaction of ethylene to prepare a polyethylene product with low branching degree and ultrahigh molecular weight.
5. Use according to claim 4, characterized in that:
in the homogeneous polymerization reaction of catalyzing ethylene, a composite catalytic system consisting of an N, O-type nickel catalyst shown in a formula (II) and a cocatalyst is used; the cocatalyst is Ni (COD)2Or B (C)6F5)3。
6. Use according to claim 5, characterized in that:
the molar ratio of the N, O-type nickel-based catalyst represented by the formula (II) to the cocatalyst is 1:1 to 1: 5.
7. Use of the fluorine effect-containing N, O-type nickel-based catalyst according to claim 1, wherein:
the N, O-type nickel catalyst containing the fluorine effect is used as a catalyst to catalyze the copolymerization reaction of ethylene and polar monomers to prepare the functionalized polyethylene material with higher polar monomer insertion rate.
8. Use according to claim 7, characterized in that:
the polar monomer comprises one or more of methyl 10-undecylenate, 10-undecen-1-ol, allyltrimethoxysilane, allyl chloride, 6-chloro-1-hexene, styrene, allyl benzene, ethyl allyl ether, methyl methacrylate and vinyl ethyl ether.
9. Use according to claim 7, characterized in that:
in the copolymerization reaction of catalyzing ethylene and polar monomer, a composite catalytic system consisting of an N, O-type nickel catalyst shown in a formula (II) and a cocatalyst is used; the cocatalyst is Ni (COD)2Or B (C)6F5)3。
10. Use according to claim 9, characterized in that:
the molar ratio of the N, O-type nickel-based catalyst represented by the formula (II) to the cocatalyst is 1:1 to 1: 5.
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