CN107098992B - Cyclic annular multicore salicylic alidehyde imine nickel-metal catalyst precursor and its preparation and application - Google Patents
Cyclic annular multicore salicylic alidehyde imine nickel-metal catalyst precursor and its preparation and application Download PDFInfo
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- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 11
- 239000012685 metal catalyst precursor Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 150000002466 imines Chemical class 0.000 title description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 polyethylene Polymers 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 4
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 26
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 239000007868 Raney catalyst Substances 0.000 claims description 11
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 230000005595 deprotonation Effects 0.000 claims description 2
- 238000010537 deprotonation reaction Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims 1
- MHNHYTDAOYJUEZ-UHFFFAOYSA-N triphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MHNHYTDAOYJUEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 abstract description 21
- 229920000573 polyethylene Polymers 0.000 abstract description 10
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 abstract 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
- 150000001721 carbon Chemical group 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000006073 displacement reaction Methods 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 5
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 5
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
-
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Landscapes
- 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
Multicore nickel-metal catalyst precursor (shown in formula I) the invention discloses one kind based on cyclic annular salicylaldimine ligand, and preparation method thereof and application in olefin polymerization.The catalyst precarsor and three (phenyl-pentafluoride) borines or bis- (1,5- cyclo-octadiene) caltalyst of nickel composition shows high thermal stability when tying up to vinyl polymerization, obtain the polyethylene of high molecular weight, reduced branching degree, and region and the stereocpecificity polymerization that propylene is realized within the scope of mild temperature, obtain dystectic crystallinity isotatic polypropylene.
Description
Technical field
The invention belongs to olefin coordination polymerization field, be related to a kind of cyclic annular multicore nickel-metal catalyst precursor synthesis and by
Its application of catalyst formed in terms of catalysis in olefine polymerization.
Background technique
Polyolefin is the maximum a kind of high molecular material of current production rate, due to its abundant raw material, cheap, easy processing at
The advantages that type, has a wide range of applications in real life.Polyolefin has lesser density, good mechanical strength, electricity absolutely
The features such as edge and chemical resistance, can be used for making tubing, film, all kinds of moulded products etc., be widely used in its people
Economic every field, also plays great function on the Strategic projects such as the energy and national defence.
It is promoted using Ziegler-Natta catalyst and metallocene catalyst as the Catalysts for Olefin Polymerization of representative poly-
Alkene industry flourishes.Nowadays, rear transition non-metallocene catalyst due to its single site catalysed, to the tolerance of polar monomer
Property it is good the advantages that, become the hot spot of coordination polymerization area research, mainly include alpha-diimine palladium catalyst
(J.Am.Chem.Soc.1995,117,6414), phosphorus sulfonic acid palladium catalyst (Chem.Commun.2011,47,6948) and water
Poplar aldimine Raney nickel (Science 2000,287,460) etc..
At this stage, late transition metal catalyst there are the problem of essentially consist in: 1) thermal stability of catalyst is poor, it is difficult to
Vinyl polymerization is realized at high temperature.Research shows that introducing the thermal stability that big steric hindrance structure is conducive to improve catalyst
(J.Am.Chem.Soc.2013,135,16316).2) since regio- and stereo-selectivity is poor and chain walking process is deposited
It usually can only obtain random unformed shape polypropylene when being catalyzed propylene polymerization, be inserted into primitive containing 3 more, 1-.It is logical
Often need to improve the solid and regioselectivity of propylene polymerization by the way of chiral ligand and low temperature polymerization
(Coord.Chem.Rev.2009,253,2082)。
Summary of the invention
It is an object of the invention to synthesize a kind of multicore nickel-metal catalyst precursor based on cyclic annular salicylaldimine ligand,
New strategy is provided suitable for the ethylene rolymerization catalyst of industrial gaseous polymerization to develop, prepares region at room temperature to realize
New method is provided with the polypropylene of stereoregular.
The technical scheme is that
A kind of multicore nickel-metal catalyst precursor based on cyclic annular salicylaldimine ligand, structure are shown in formula I:
In Formulas I, R1It for hydrogen atom or is the linear or branched alkyl group that carbon atom number is 1-10；R2For hydrogen atom or it is
Carbon atom number is the linear or branched alkyl group of 1-20；R3It for hydrogen atom or is the linear chain or branched chain alkane that carbon atom number is 1-20
Base, or be phenyl or substituted-phenyl；R is 1- naphthalene, phenyl or methyl；L is triphenylphosphine, trimethyl-phosphine or pyridine；N is
Integer more than or equal to 1.
Wherein, R1Preferably H, C1~C6 alkyl, C1~C6 alkyl such as methyl, ethyl, propyl, isopropyl, fourth
Base, sec-butyl, isobutyl group and tert-butyl etc.；
R2Preferably H, C1~C10 alkyl, C1~C10 alkyl for example methyl, ethyl, propyl, isopropyl, butyl,
Sec-butyl, isobutyl group, tert-butyl, amyl, hexyl, heptyl etc.；
R3Preferably H, C1~C10 alkyl, phenyl or substituted-phenyl, C1~C10 alkyl such as methyl, ethyl, third
Base, isopropyl, butyl, sec-butyl, isobutyl group, tert-butyl, amyl, hexyl, heptyl etc., the substituted-phenyl are preferably C1~C6
Alkyl-substituted phenyl etc..
Particularly, R and L is respectively 1- naphthalene and triphenylphosphine, or respectively phenyl and triphenylphosphine, methyl and front three
Base phosphine or methyl and pyridine, n are preferably the integer of 1-4.
Compound shown in above-mentioned Formulas I general structure, works as R1For hydrogen atom, R2For isopropyl, R3For methyl, L is triphenyl
Phosphine, R is 1- naphthalene, is metal catalysts precursors shown in Formula II when n=1:
The present invention provides the method for preparing compound shown in above-mentioned Formulas I general structure, includes the following steps:
1) under conditions of palladium catalyst, by compound shown in compound shown in formula III and formula IV in organic solvent into
Row Suzuki coupling reaction, obtains compound shown in Formula V；
2) under conditions of palladium catalyst, compound 3- shown in compound shown in Formula V and Formula IV is replaced into -5- bromosalicylaldehyde
Suzuki coupling reaction is carried out in organic solvent, obtains compound shown in Formula VII；
3) under conditions of acid catalyst, compound shown in the Formula VII is self condensed in organic solvent, obtains formula
Compound shown in VIII；
4) compound shown in the Formula VIII is reacted into deprotonation with hydrofining or sodium hydride in organic solvent, then
It is reacted again with compound shown in Formula IX, obtains multicore nickel-metal catalyst precursor shown in Formulas I.
In above-mentioned reaction equation, R1It for hydrogen atom or is the linear or branched alkyl group that carbon atom number is 1-10；R2For hydrogen atom
Or the linear or branched alkyl group for for carbon atom number being 1-20；R3It for hydrogen atom or is straight chain or branch that carbon atom number is 1-20
Alkyl group, or be phenyl or substituted-phenyl；R is 1- naphthalene, phenyl or methyl；L is triphenylphosphine, trimethyl-phosphine or pyrrole
Pyridine；N is the integer more than or equal to 1.
For the step 1) into step 4), the organic solvent is one of tetrahydrofuran, toluene or methylene chloride；Institute
It states in Suzuki coupling reaction, temperature is 60-100 DEG C, and preferably 75 DEG C, the time is 6-24 hours, preferably 12 hours.
In the step 3), preferably acid catalyst is p-methyl benzenesulfonic acid, and compound and p-methyl benzenesulfonic acid shown in Formula VII rub
You are than being 1:0.003；Reaction temperature is 140-160 DEG C, and preferably 150 DEG C, the time is 10-24 hours, preferably 12 hours.
In the step 4), nickel shown in the phenolic hydroxyl group number and hydrofining (or sodium hydride) and formula IV of compound shown in Formula VIII
The molar ratio of metal chloride is 1:1-4:0.90-1.10, preferably 1:2:0.95；In the reaction, temperature is 0-40 DEG C, preferably
20 DEG C, the time is 8-24 hours, preferably 12 hours.
The present invention also provides by above-mentioned cyclic annular multicore nickel-metal catalyst precursor and three (phenyl-pentafluoride) borines or it is bis- (1,
5- cyclo-octadiene) nickel composition catalyst, wherein nickel metal center and three (phenyl-pentafluoride) borines or bis- (1,5- cyclo-octadiene) nickel
Molar ratio be 1:1-4, preferably 1:2.
Above-mentioned catalyst is used for catalysis in olefine polymerization, such as under the action of the catalyst polymerization reaction occurs for ethylene, gathers
Closing temperature is 0-100 DEG C；Polymerization reaction occurs under the action of the catalyst for propylene, and polymerization temperature is -10-50 DEG C.
Polymerization reaction of the invention can carry out in atent solvent, and solvent for use is usually aromatic solvent, preferably toluene
Or benzene.
Compared with the prior art, the present invention has following technical advantage:
1. having synthesized the novel cyclic annular multicore salicylic alidehyde imine nickel-metal catalyst precursor of structure for the first time.
2. cyclic annular multicore Raney nickel precursor has high activity, high thermal stability and institute when carrying out vinyl polymerization
Secure satisfactory grades sub- weight northylen, provides new strategy to develop industrial gas-phase polymerization catalyst.For example, the Cat1 in Formula II can
Obtain reduced branching degree (11-36/1000C), high molecular weight (Mw> 200kDa), the polyethylene material of high-melting-point (112.9-129.5 DEG C)
Material, and there is fabulous thermal stability (80-100 DEG C).
3. the solid and regional choice of propylene polymerization processes are realized in salicylic alidehyde imine nickel-metal catalyst field for the first time
Property.Such as three core Raney nickel precursor Cat1 of ring-type can be catalyzed propylene polymerization within the scope of relatively high temperature and can obtain
High regioregular, high stereospecificity ([mmmm] > 0.90), high-melting-point (138 DEG C) and high-crystallinity isotatic polypropylene.
Specific embodiment
Below by specific embodiment, present invention is further described in detail:
Embodiment 1
The preparation of compound Cat1 shown in Formula II, reaction process are as follows:
1) 5- (4- (3,5- diisopropyl -4- aminophenyl) -9,9- dimethyl -9H- xanthene -5- substitution) -3- methyl
The synthesis of salicylide (compound 2)
Under nitrogen protection, compound 9, bis- substituted boracic acid (compound 1) of 9- dimethyl -9H- xanthene -4,5-
(6.10g, 14.2mmol), the bromo- 3- cresotinic acid aldehyde (3.67g, 17.0mmol) of 5-, sodium carbonate (7.53g, 71.0mmol) and four
(triphenylphosphine) palladium (0.89g, 0.85mmol) is dissolved in the in the mixed solvent of 300mL tetrahydrofuran and 100mL water, is heated to 75
DEG C reaction 12 hours.It is cooled to room temperature, revolving removes organic solvent, is successively extracted with dichloromethane, washes and saturated salt solution
Washing, liquid separation are simultaneously dry with anhydrous sodium sulfate.Filtrate uses silica gel column separating purification after being spin-dried for, solvent is petroleum ether/dichloromethane
Alkane (5:1), obtaining product is white powder (5.21g, 71%).1H NMR(400MHz,CDCl3)δ11.18(s,2H),8.81
(s,2H),7.45-7.37(m,6H),7.23-7.19(m,4H),7.17-7.09(m,6H),7.03(s,4H),3.66(s,4H),
2.78-2.62 (m, 4H), 2.20 (s, 6H), 1.73 (s, 12H), 1.07 (d, J=6.8Hz, 24H)13C NMR(100MHz,
CDCl3)δ195.8,158.7,147.9,147.4,140.2,138.6,133.6,131.9,131.6,131.3,130.4,
129.4,128.9,128.6,128.2,128.1,126.3,125.4,124.6,124.4,123.2,119.6,34.7,32.6,
28.1,22.1,15.1.HRMS(ESI,m/z):Calculated for C35H38NO3[(M+H)+]:520.2846,found
520.2829.
2) synthesis of cyclic ligand
By 5- (4- (3,5- diisopropyl -4- aminophenyl) -9,9- dimethyl -9H- xanthene -5- substitution) -3- methyl
Salicylide (5.70g, 11.0mmol) and p-methyl benzenesulfonic acid (0.054g, 0.27mmol) are dissolved in toluene, are heated to 150 DEG C instead
It answers 12 hours and uses fraction water device water-dividing.It is cooled to room temperature, washes and is dried over anhydrous sodium sulfate.Filtrate is spin-dried for through silica gel column purification
Separation, solvent are petroleum ether/methylene chloride (5:1), obtain 2.90g principal product L-Trimer (51%) and by-product
0.40g L-Tetramer (7%) and 0.22g L-Hexamer (4%).
L-Trimer:1H NMR(400MHz,CDCl3)δ12.85(s,3H),8.32(s,3H),7.52-7.38(m,6H),
7.38-7.08(m,24H),3.09(br,3H),2.81(br,3H),1.96-1.58(m,27H),1.43(br,18H),0.96
(br,9H),0.55(br,9H).13C NMR(100MHz,CDCl3)δ167.4,159.1,147.7,147.1,138.2(br),
137.7(br),136.3,135.1,131.0,130.9,130.6,130.3,130.1,129.5,129.0,128.5,126.3,
125.4(br),125.0,124.3(br),124.3,123.3,123.1,117.9,35.0(br),34.6,30.3(br),28.4
(br),24.8(br),24.1(br),23.2(br),20.9(br),15.7.HRMS(ESI,m/z):C105H106N3O6[(M+H)+]:
1504.8076,found 1504.8123.
L-Tetramer:1H NMR(400MHz,CDCl3)δ12.71(s,4H),8.39(s,4H),7.52-7.37(m,
8H),7.31-7.06(m,32H),2.96(m,8H),1.92(s,12H),1.76(s,24H),1.05(br,48H).13C NMR
(100MHz,CDCl3)δ166.7,159.6,147.4,146.5,137.8,135.9,134.6,131.0,130.7,130.3,
129.8,129.6,129.3,129.1,127.9,126.7,125.0,124.9,124.6,123.1,123.9,117.8,34.5,
32.9(br),29.7,28.1,15.5.HRMS(ESI,m/z):Calculated for C140H141N4O8[(M+H)+]:
2006.0743,found 2006.0812.
L-Hexamer:1H NMR(400MHz,CDCl3)δ13.36(s,6H),8.46(s,6H),7.38-7.29(m,
18H),7.27-7.18(m,18H),7.13-7.03(m,18H),6.95(s,6H),3.03(br,6H),2.51(br,6H),
1.77(s,18H),1.70(s,18H),1.45(s,18H),1.29(br,18H),1.17(br,18H),0.63(br,18H),
0.29(br,18H).13C NMR(100MHz,CDCl3)δ166.8,158.4,147.2,147.04,144.8,137.0,135.1,
133.8,130.6,130.3,129.80,129.76,129.0,128.61,128.60,124.9,124.8,123.2,122.8,
118.3,34.7,34.3,30.9,28.6(br),27.5(br),23.6,23.1(br),22.6(br),15.3.MALDI MS:
Calculated for C210H211N6O12[(M+H)+]:3009.61,found 3009.29.
3) synthesis of catalyst precarsor Cat1
In glove box, ligand L-Trimer (1.00g, 1.21mmol) and KH (0.097g, 2.41mmol) are dissolved in 4mL
Tetrahydrofuran is extremely clarified for stirring 8 hours.It drains solvent and q. s. toluene dissolution is added, be added dropwise to trans- [Ni (PPh3)2
(Naph) Cl] (0.90g, 1.21mmol) toluene solution in, stir 12 hours.Reaction solution is filtered to remove inorganic through diatomite
Salt removes solvent with oil pump.Obtained solid is dissolved with a small amount of toluene, filters off insoluble matter, and n-hexane recrystallization is added.Again through dichloro
Methane/n-hexane repeated recrystallize to nuclear-magnetism no longer changes, and obtains yellow solid (1.20g, 66%).HRMS(ESI,m/z):
Calculated for C189H168KN3Ni3O6P3[(M+K)+]:2880.9838,found 2880.9862.
Embodiment 2
The synthesis of polyethylene: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 0 DEG C three times for displacement, are balanced 5 minutes.Inject the ethylene of 90psi, dimension
Reaction temperature polymerization 10min is held, the methanol solution for adding hydrochloric acid terminates reaction, then reaction solution is poured into 150mL methanol
And half an hour is stirred, it filters, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Polymer 0.020g is obtained, activity
3.0×103g·mol-1(Ni)·h-1。
It is 129.5 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 111.1 × 103Da, Mw/MnIt is 2.8,1H NMR
Measuring the degree of branching is 12 branches/every 1000 carbon atom.
Embodiment 3
The synthesis of polyethylene: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 15 DEG C three times for displacement, are balanced 5 minutes.Inject the ethylene of 90psi, dimension
Reaction temperature polymerization 10min is held, the methanol solution for adding hydrochloric acid terminates reaction, then reaction solution is poured into 150mL methanol
And half an hour is stirred, it filters, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Polymer 0.130g is obtained, activity
19.5×103g·mol-1(Ni)·h-1。
It is 127.1 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 194.6 × 103Da, Mw/MnIt is 3.8,1H NMR
Measuring the degree of branching is 11 branches/every 1000 carbon atom.
Embodiment 4
The synthesis of polyethylene: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 25 DEG C three times for displacement, are balanced 5 minutes.Inject the ethylene of 90psi, dimension
Reaction temperature polymerization 10min is held, the methanol solution for adding hydrochloric acid terminates reaction, then reaction solution is poured into 150mL methanol
And half an hour is stirred, it filters, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Polymer 0.151g is obtained, activity
22.7×103g·mol-1(Ni)·h-1。
It is 125.8 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 229.4 × 103Da, Mw/MnIt is 3.6,1H NMR
Measuring the degree of branching is 16 branches/every 1000 carbon atom.
Embodiment 5
The synthesis of polyethylene: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 50 DEG C three times for displacement, are balanced 5 minutes.Inject the ethylene of 90psi, dimension
Reaction temperature polymerization 10min is held, the methanol solution for adding hydrochloric acid terminates reaction, then reaction solution is poured into 150mL methanol
And half an hour is stirred, it filters, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Polymer 0.269g is obtained, activity
40.4×103g·mol-1(Ni)·h-1。
It is 123.5 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 184.4 × 103Da, Mw/MnIt is 7.6,1H NMR
Measuring the degree of branching is 18 branches/every 1000 carbon atom.
Embodiment 6
The synthesis of polyethylene: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 80 DEG C three times for displacement, are balanced 5 minutes.Inject the ethylene of 90psi, dimension
Reaction temperature polymerization 10min is held, the methanol solution for adding hydrochloric acid terminates reaction, then reaction solution is poured into 150mL methanol
And half an hour is stirred, it filters, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Polymer 0.295g is obtained, activity
44.3×103g·mol-1(Ni)·h-1。
It is 120.7 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 85.4 × 103Da, Mw/MnIt is 8.2,1H NMR is surveyed
Obtaining the degree of branching is 26 branches/every 1000 carbon atom.
Embodiment 7
The synthesis of polyethylene: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 100 DEG C three times for displacement, are balanced 5 minutes.The ethylene of 90psi is injected,
Maintaining reaction temperature polymerize 10min, and the methanol solution that hydrochloric acid is added terminates reaction, then reaction solution is poured into 150mL methanol
And half an hour is stirred, it filters, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Polymer 0.180g is obtained, activity
27.0×103g·mol-1(Ni)·h-1。
It is 112.9 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 33.6 × 103Da, Mw/MnIt is 3.4,1H NMR is surveyed
Obtaining the degree of branching is 36 branches/every 1000 carbon atom.
Embodiment 8
The synthesis of polyethylene: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 40 μm of ol catalyst precarsors are taken
Cat2、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 25 DEG C three times for displacement, are balanced 5 minutes.Inject the ethylene of 90psi, dimension
Reaction temperature polymerization 10min is held, the methanol solution that hydrochloric acid is added terminates reaction, then reaction solution is poured into 150mL methanol simultaneously
It stirs half an hour, filtering, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Obtain polymer 0.010g, activity 1.5
×103g·mol-1(Ni)·h-1。
It is 95.3 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 3.7 × 103Da, Mw/MnIt is 2.1.
1 vinyl polymerization result of tablea
aPolymerizing condition: 13.3 μm of ol Cat1 or 40 μm of ol Cat2,80 μm ol cocatalyst B (C6F5)3, 25mL toluene,
Ethylene pressure is 90psi, polymerization time 10min.b g/(mmol Ni·h)。cFrom polymer1H NMR is obtained, and unit is every
The branch number of 1000 carbon.dThe endothermic peak that fusing point is recycled using second.eMolecular weight unit is 103G/mol, through high temperature GPC
Test, using polystyrene as reference substance and the K through polyethylene and α correct to obtain.
Embodiment 9
Polyacrylic synthesis: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are -10 DEG C three times for displacement, are balanced 5 minutes.The propylene of 30psi is injected,
Maintaining reaction temperature polymerize 60min, and the methanol solution that hydrochloric acid is added terminates reaction, then reaction solution is poured into 150mL methanol
And half an hour is stirred, it filters, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Polymer 0.020g is obtained, activity
0.50×103g·mol-1(Ni)·h-1。
It is 138.4 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 22.4 × 103Da, Mw/MnIt is 2.2, Quan Tongli
Structure regularity [mmmm] > 0.90.
Embodiment 10
Polyacrylic synthesis: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 0 DEG C three times for displacement, are balanced 5 minutes.Inject the propylene of 30psi, dimension
Reaction temperature polymerization 60min is held, the methanol solution that hydrochloric acid is added terminates reaction, then reaction solution is poured into 150mL methanol simultaneously
It stirs half an hour, filtering, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Obtain polymer 0.037g, activity 0.93
×103g·mol-1(Ni)·h-1。
It is 137.8 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 18.5 × 103Da, Mw/MnIt is 3.2, Quan Tongli
Structure regularity [mmmm]=0.81.
Embodiment 11
Polyacrylic synthesis: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 15 DEG C three times for displacement, are balanced 5 minutes.Inject the propylene of 30psi, dimension
Reaction temperature polymerization 60min is held, the methanol solution that hydrochloric acid is added terminates reaction, then reaction solution is poured into 150mL methanol simultaneously
It stirs half an hour, filtering, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Obtain polymer 0.046g, activity 1.15
×103g·mol-1(Ni)·h-1。
It is 134.1 DEG C that DSC, which measures fusing point, and GPC measures the M of polyethylenewIt is 12.1 × 103Da, Mw/MnIt is 2.9, Quan Tongli
Structure regularity [mmmm]=0.80.
Embodiment 12
Polyacrylic synthesis: 350mL Andrew Glass polymerization bottle is dried overnight for 120 DEG C in vacuum drying oven, and addition is stirred
Magneton is mixed, then places it in the big storehouse of glove box to vacuumize and is cooled to room temperature.In glove box, 13.3 μm of ol catalyst precarsors are taken
Cat1、80μmol B(C6F5)3It is added in polymerization bottle with 20mL toluene, connects polyplant, take out glove box.Then poly-
It attaches together to set and is connected to high vacuum line, nitrogen, set temperature are 50 DEG C three times for displacement, are balanced 5 minutes.Inject the propylene of 30psi, dimension
Reaction temperature polymerization 60min is held, the methanol solution that hydrochloric acid is added terminates reaction, then reaction solution is poured into 150mL methanol simultaneously
It stirs half an hour, filtering, resulting polymers are dried in vacuo 12 hours in 80 DEG C, weighing.Obtain polymer 0.035g, activity 0.88
×103g·mol-1(Ni)·h-1。
GPC measures the M of polyethylenewIt is 11.6 × 103Da, Mw/MnIt is 4.3, isotacticity [mmmm]=0.49,
It is 3% that 1,3%-, which is inserted into content,.
2 propylene polymerization result of tablea
aPolymerizing condition: 13.3 μm of ol Cat1,80 μm ol cocatalyst B (C6F5)3, 25mL toluene, propylene pressure is
30psi, 25 DEG C, polymerization time 60min.b g/(mmol Ni·h)。cThe endothermic peak that fusing point is recycled using second.dPoint
Son amount unit is 103G/mol is tested through high temperature GPC, corrects to obtain using polystyrene as reference substance and through polyacrylic K and α.e
By the high temperature of polymer13C NMR is calculated.
The ring-type for describing catalyzed ethylene polymerization or propylene polymerization provided by the present invention above by specific embodiment is more
Catalyst core salicylic alidehyde imine nickel-metal catalyst precursor and be made from it, it will be understood by those of skill in the art that not
It is detached from the range of present invention essence, certain transformation or modification can be made to the present invention, and be not limited to disclosed in embodiment
Content.
Claims (10)
1. a kind of Raney nickel precursor is the multicore nickel-metal catalyst precursor based on cyclic annular salicylaldimine ligand, structure
It is shown in formula I:
In Formulas I, R1For the straight chained alkyl of H or C1-C10 or the branched alkyl of C3-C10；R2For H or C1-C20 straight chained alkyl or
The branched alkyl of C3-C20；R3For the straight chained alkyl of H, C1-C20 or branched alkyl, phenyl or the substituted-phenyl of C3-C20；R is
1- naphthalene, phenyl or methyl；L is triphenylphosphine, trimethyl-phosphine or pyridine；N is positive integer.
2. Raney nickel precursor as described in claim 1, which is characterized in that the substituted-phenyl is C1~C6 alkyl substituted benzene
Base.
3. Raney nickel precursor as described in claim 1, which is characterized in that R is 1- naphthalene or phenyl, and L is triphenylphosphine；Or
Person, R are methyl, and L is trimethyl-phosphine or pyridine.
4. Raney nickel precursor as described in claim 1, which is characterized in that the structure of the Raney nickel precursor such as Formula II institute
Show:
Wherein, PPh3Triphenylphosphine is represented, R is 1- naphthalene.
5. the preparation method of Raney nickel precursor described in claim 1, comprising the following steps:
1) compound shown in formula III and compound Suzuki coupling reaction shown in formula IV, obtain compound shown in Formula V；
2) with 3- substitution -5- bromosalicylaldehyde shown in Formula IV Suzuki coupling reaction occurs for compound shown in Formula V, obtains Formula VII institute
Show compound；
3) under conditions of acid catalyst, compound shown in VII is self condensed, and obtains compound shown in Formula VIII；
4) compound shown in Formula VIII reacts deprotonation with hydrofining or sodium hydride, then again with nickel metal chloride NiRL2Cl
Reaction, obtains Raney nickel precursor shown in Formulas I；
In reaction equation, R1For the straight chained alkyl of H or C1-C10 or the branched alkyl of C3-C10；R2For the straight chained alkyl of H or C1-C20
Or the branched alkyl of C3-C20；R3For the straight chained alkyl of H, C1-C20 or branched alkyl, phenyl or the substituted-phenyl of C3-C20；R
For 1- naphthalene, phenyl or methyl；L is triphenylphosphine, trimethyl-phosphine or pyridine；N is positive integer.
6. preparation method as claimed in claim 5, which is characterized in that the reaction of step 1) to step 4) in organic solvent into
Row, organic solvent used are selected from one of tetrahydrofuran, toluene and methylene chloride.
7. preparation method as claimed in claim 5, which is characterized in that the temperature of the Suzuki coupling reaction of step 1) and step 2)
Degree is 60-100 DEG C, and the time is 6-24 hours；Acid catalyst described in step 3) is p-methyl benzenesulfonic acid, compound shown in Formula VII
Molar ratio with p-methyl benzenesulfonic acid is 1:0.003, and self-condensation reaction temperature is 140-160 DEG C, and the time is 10-24 hours；Step
4) molar ratio of compound shown in Formula VIII and hydrofining or sodium hydride, nickel metal chloride is 1:3-6:2.90-3.10 in, instead
Answering temperature is 0-40 DEG C, and the time is 8-24 hours.
8. a kind of catalyst system, including Claims 1 to 4 any the Raney nickel precursor and three (phenyl-pentafluoride) borines or
Bis- (1,5- cyclo-octadiene) nickel.
9. the application of catalyst system described in claim 8 in olefin polymerization.
10. application as claimed in claim 9, which is characterized in that the alkene is ethylene or propylene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361183A (en) * | 2000-12-25 | 2002-07-31 | 中国科学院长春应用化学研究所 | Catalyst for multinuclear alpha-diimine nickel olefine polymerization |
| CN1637023A (en) * | 2004-12-09 | 2005-07-13 | 中山大学 | Mononuclear and multinuclear polyvinyl acenaphthenyl diimido nickel catalyst and its prepn process |
| CN101864010A (en) * | 2010-06-21 | 2010-10-20 | 北京大学 | Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization |
-
2017
- 2017-05-15 CN CN201710337580.7A patent/CN107098992B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361183A (en) * | 2000-12-25 | 2002-07-31 | 中国科学院长春应用化学研究所 | Catalyst for multinuclear alpha-diimine nickel olefine polymerization |
| CN1637023A (en) * | 2004-12-09 | 2005-07-13 | 中山大学 | Mononuclear and multinuclear polyvinyl acenaphthenyl diimido nickel catalyst and its prepn process |
| CN101864010A (en) * | 2010-06-21 | 2010-10-20 | 北京大学 | Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization |
Non-Patent Citations (4)
| Title |
|---|
| Double-Decker-Type Dinuclear Nickel Catalysts for Olefin Polymerization:Efficient Incorporation of Functional Co-Moneomers;Daisuke Takeuchi et al;《Angewandte Chemie》;20131107;第125卷(第48期);第12536-12540页 |
| Ethylene (Co)polymerization by Binuclear Nickel Phenoxyiminato Catalysts with Cofacial Orientation;Zhongtao Chen et al;《Macromolecules》;20161130;第49卷;第8848-8854页 |
| Ethylene Polymerization with a Highly Active and Long-Lifetime Macrocycle Trinuclear 2,6-Bis(imino)pyridyliron;Jingyu Liu et al;《Macromolecules》;20050222;第38卷;第2559-2563页 |
| Multinuclear Olefin Polymerization Catalysts;Massimiliano Delferro et al;《CHEMICAL REVIEWS》;20110217;第111卷;第2450-2485页 |
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