CN115260364A - Application of diimine metal complex in catalyzing olefin polymerization - Google Patents
Application of diimine metal complex in catalyzing olefin polymerization Download PDFInfo
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Abstract
The invention belongs to the technical field of olefin polymerization catalysts, and discloses an application of a diimine metal complex in catalyzing olefin polymerization, wherein olefins comprise at least one C4-C20 internal olefin monomer and optional ethylene, propylene and C4-C20 terminal olefin monomers; the structure of the diimine metal complex is shown as formula I: r3、R4、R13、R14Each is hydrogen, substituted or unsubstituted C1-C30 hydrocarbyl; r1、R2、R11、R12Independently selected from C1-C30 hydrocarbyl with or without substituent; r15Selected from C1-C20 alkyl containing substituent or not containing substituent; y is selected from non-metal atoms of group VIA; m1、M2、M3Is a group VIII metal; x is selected from halogen, C1-C10 hydrocarbon containing substituent or notA C1-C10 alkoxy radical containing or not containing substituent.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to an application of a diimine metal complex in catalyzing olefin polymerization.
Background
In the field of olefin polymerization, late transition metal catalysts are a new generation of metal organic catalysts with high activity, in particular Brookhart type nickel (II) and palladium (II) diimine catalysts have a unique chain walking mechanism (ACS cat. 2016,6, 428-441). The topological structure of the generated polymer can be strongly influenced by changing the type of the olefin monomer, the structure of the catalyst and the polymerization conditions, so that the physical and mechanical properties and the processing performance of the polymer can be accurately controlled. Compared with traditional linear polyolefin, the branched polyolefin with chain topological structure has unique physical properties and can be used as elastomer, adhesive, lubricating oil, paint and the like.
The advent of each new generation of catalysts has brought about a tremendous growth in the field of olefin polymerization, but the variety of olefins that can be efficiently polymerized is limited. Any olefin in which the double bond is not at the end of the carbon chain is referred to as an internal olefin. Internal olefins are not easily intercalated with the double bond of internal olefins due to their large steric hindrance of the cationic metal center with bulky ligands. Therefore, almost all internal olefins and their derivatives are not active or have very low catalytic activity in homogeneous polymerization, so that a large amount of internal olefins have not been used as polymerization monomers. Currently, there are a few reports of the polymerization behavior of internal olefins (Polymer 2017, 127, 88. However, the internal olefin copolymerization activity is generally low. In industry, the technical difficulty of selectively producing long-chain alpha-olefin is higher, and the process flow of separating the alpha-olefin and the internal olefin is longer. And the polymerization properties of internal olefins and terminal olefins together as polymerization monomers have been reported. If these internal and terminal olefins can be polymerized together to obtain a polymer, not only can the separation process of internal olefin and terminal olefin be saved, but also the obtained new polymer material will present special properties different from the polyolefin material currently used.
Disclosure of Invention
In view of the above circumstances, the present inventors have conducted extensive and intensive studies to produce an olefin polymer by copolymerizing at least one internal olefin and optionally ethylene, propylene and a terminal olefin with high activity using a catalyst system comprising a specific diimine metal complex for olefin polymerization. Compared with the commercial polyolefin elastomer and the synthetic lubricating oil additive, the method does not need to separate the internal olefin from the mixed olefin, greatly simplifies the process flow and reduces the production cost.
The invention provides the use of a diimine metal complex in the catalysis of the polymerization of olefins, said olefins comprising at least one C4 to C20 internal olefin monomer and optionally ethylene, propylene, C4 to C20 terminal olefin monomers, said diimine metal complex being used as the procatalyst of a catalyst system for the polymerization of olefins;
the structure of the diimine metal complex is shown as a formula I:
in the formula I, R3、R4、R13、R14Each is hydrogen, substituted or unsubstituted C1-C30 hydrocarbyl; r1、R2、R11、R12The same or different, independently selected from C1-C30 alkyl containing substituent or not containing substituent; r is15Selected from C1-C20 alkyl containing substituent or not containing substituent; y is selected from non-metal atoms of group VIA; m1、M2、M3Is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent, and C1-C10 alkoxy with or without substituent.
Compared with the prior art, the invention has the main advantages that:
(a) The invention uses a specific catalyst system in the olefin polymerization of at least one C4-C20 internal olefin monomer and optional ethylene, propylene and C4-C20 terminal olefin monomers, can directly catalyze mixed olefins with high activity to prepare polyolefin, thereby reducing the processes of mixed olefin separation and the like, further leading the preparation of high-performance polyolefin products to not depend on expensive high-grade alpha-olefin seriously and greatly reducing the cost.
(b) The olefin of the present invention may include alkenes such as terminal olefins and internal olefins, and may also include mixed alkenes such as cyclic olefins, diolefins, and polyenes.
(c) The invention can avoid the complicated separation process flow in the production of high-grade alpha-olefin.
(d) The olefin polymer of the invention has molecular weight and molecular weight distribution which can be regulated and controlled in a wide range, and can be used in the fields of processing aids, polyolefin elastomers, plastomers and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides the use of a diimine metal complex in the catalysis of the polymerization of olefins, said olefins comprising at least one C4 to C20 internal olefin monomer and optionally ethylene, propylene, C4 to C20 terminal olefin monomers, said diimine metal complex being used as the procatalyst of a catalyst system for the polymerization of olefins;
the structure of the diimine metal complex is shown as a formula I:
in the formula I, R3、R4、R13、R14Each is hydrogen, substituted or unsubstituted C1-C30 hydrocarbyl; r1、R2、R11、R12The same or different, independently selected from C1-C30 alkyl containing substituent or not containing substituent; r15Selected from C1-C20 alkyl containing substituent or not containing substituent; y is selected from non-metal atoms of group VIA; m1、M2、M3Is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent, and C1-C10 alkoxy with or without substituent.
Preferably, in formula I, R1、R2、R11、R12Is selected from C1-C20 alkyl containing substituent or not containing substituent, and C6-C20 aryl containing substituent or not containing substituent.
Further preferably, in formula I, R1、R2、R11、R12Is a group of formula II:
in the formula II, R1～R5The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 linear alkyl with or without substituent, C3-C20 branched alkyl with or without substituent, and C2-C20 with or without substituentAlkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 linear alkoxy, substituted or unsubstituted C3-C20 branched alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C3-C20 cycloalkoxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C7-C20 alkaryl; r1～R5Optionally forming a ring with each other.
Preferably, in formula II, R1～R5The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 linear alkyl with or without substituent, C3-C10 branched alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 linear alkoxy with or without substituent, C3-C10 branched alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent, C7-C15 alkylaryl with or without substituent.
Preferably, in formula I, M1、M2、M3Selected from nickel and palladium.
Preferably, in formula I, Y is selected from O and S.
Preferably, in formula I, X is selected from halogen, C1-C10 alkyl with or without substituent, C1-C10 alkoxy with or without substituent, more preferably from halogen, C1-C6 alkyl with or without substituent, C1-C6 alkoxy with or without substituent.
Preferably, in formula I, R15Selected from C1-C20 alkyl containing or not containing substituents, more preferably from C1-C20 alkyl containing substituentsA substituent or a C1-C10 alkyl group having no substituent, and further preferably selected from a C1-C6 alkyl group having a substituent or no substituent.
According to a specific embodiment of the present invention, the structure of the diimine metal complex is shown in formula III:
in formula III, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 linear alkyl containing a substituent Q or not, C3-C10 branched alkyl containing a substituent Q or not, C3-C10 cycloalkyl containing a substituent Q or not, C1-C10 linear alkoxy containing a substituent Q or not, C3-C10 branched alkoxy containing a substituent Q or not, C3-C10 cycloalkoxy containing a substituent Q or not, C6-C15 aryl containing a substituent Q or not, C7-C15 aralkyl containing a substituent Q or not, C7-C15 alkaryl containing a substituent Q or not;
R3and R4Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen, more preferably independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, halogen;
m is nickel; y is O; x is independently selected from fluorine, chlorine and bromine;
R15independently selected from C1-C20 alkyl with or without substituent Q, preferably C1-C10 alkyl with or without substituent Q, more preferably C1-C6 alkyl with or without substituent Q;
the substituent Q is selected from halogen, hydroxyl, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy; the substituents Q are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy group may be selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, and 3,3-dimethylbutoxy. Preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.
According to one embodiment of the present invention, the structure of the diimine metal complex is represented by formula I':
the diimine metal complex shown in formula I' can be prepared by the following method:
reacting a diimine compound of formula IV with MXnAnd R15YH, generating a diimine metal complex shown as a formula I',
r in formula IV and formula I1～R4And R in formula I1～R4The definitions are the same;
MXn and X in the formula I 'are defined as the same as X in the formula I, M in the MXn and the formula I' is VIII group metal, and n in the MXn is the number of X satisfying M valence state;
R15YH, Y, R in formula I15And Y, R in formula I15The definitions are the same.
According to the invention, the catalyst system also comprises a cocatalyst which is an agent capable of promoting the catalytic polymerization of olefins and which can be chosen from organoaluminum compounds and/or organoboron compounds.
In the present invention, the organoaluminum compound is at least one selected from the group consisting of alkylaluminoxane, alkylaluminum, and alkylaluminum halide. The alkylaluminum or alkylaluminum halide can be represented by the general formula AlRnX1 3-nWherein R is H, C-C20 hydrocarbyl or C1-C20 hydrocarbyloxy, preferably C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl or C6-C20 aryl; x1Is halogen, preferably chlorine or bromine; n is more than 0 and less than 3.
According to the present invention, specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO).
In the present invention, the organoboron compound is selected from an arylboronic group and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
According to the invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (10-10)7) 1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000: 1, 10000: 1, 100000: 1, 1000000: 1, 10000000: 1, and any value therebetween, preferably (10-100000) 1, more preferably (100-10000) 1.
When the cocatalyst is an organic boron compound and an organic aluminum compound, the molar ratio of boron in the cocatalyst to M in the main catalyst is (0.1-1000): 1, for example, 0.1: 1. 0.2: 1. 0.5: 1, 1:1, 2:1, 3: 1, 5: 1, 8: 1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700: 1. 800: 1. 1000:1 and any value therebetween, preferably (0.1-500): 1. the molar ratio of the organic aluminum to the M in the main catalyst is (10-105): 1, e.g., 10: 1. 20: 1. 50: 1. 100, and (2) a step of: 1. 200: 1. 300: 1. 400: 1. 500: 1. 600: 1. 700: 1. 800: 1. 1000: 1. 2000: 1. 3000: 1. 5000: 1, 10000: 1, 100000: 1 and any value in between, preferably (10-5000): 1, more preferably (10-1000): 1.
symbols such as R used in different general formulas or structural formulae in this application1、R2、R3、R4、R5、R3、R4、R15And X, M, Y, and the like, have the same definitions in each general formula or structural formula unless otherwise specified.
In the present invention, C1-C20 alkyl refers to C1-C20 straight chain alkyl or C3-C20 branched chain alkyl, including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
Examples of C3-C20 cycloalkyl include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
Examples of C6-C20 aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.
C2-C20 alkenyl refers to C2-C20 linear alkenyl or C3-C20 branched alkenyl, including but not limited to: vinyl, allyl, butenyl.
Examples of C7-C20 aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl and phenyl-tert-butyl.
Examples of C7-C20 alkaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl groups.
The olefin polymerization of the present invention can produce branched polyolefins, and the branched polyolefins refer to branched polyolefins with a number of methyl groups of 20 to 200 per 1000 methylene groups in the polymer chain. The branched polyolefin has a structure consisting of13Molecular weights determined by CNMR and high temperature GPC were compared to actual molecular weights determined by high temperature laser light scattering.
In the present invention, in the polymerization of olefins, the olefin, the diimine metal complex and the cocatalyst may be reacted in an inert solvent or may be directly bulk polymerized in the olefin. The reaction time may be 0.5 to 72 hours, and the reaction temperature may be-50 to 200 deg.C, preferably 30 to 100 deg.C.
The inert solvent can be alkane, aromatic hydrocarbon and halogenated hydrocarbon, the alkane is preferably C5-C20 saturated hydrocarbon, such as hexane, heptane; the halogenated hydrocarbon can be dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane; the aromatic hydrocarbon can be toluene and xylene.
The internal olefin in the present invention refers to an olefin in which the double bond is not at the terminal position, and the internal olefin of one olefin may be a mixture of various isomers or a single internal olefin. For example, the butene may be cis 2-C4, trans 2-C4, or may be a mixture of one or more isomers. Terminal olefins are olefins in which the double bond is terminal, for example, 1-C4 for butene.
The present invention will be further described with reference to the following examples. But is not limited by these examples.
The analytical characterization instrument used in the following examples and comparative examples is as follows:
1. nuclear magnetic resonance apparatus: bruker DMX 300 (300 MHz) with internal standard Tetramethylsilicon (TMS).
2. Molecular weight and molecular weight distribution PDI of the polymer (PDI = Mw/Mn): measured at 150 ℃ using trichlorobenzene as a solvent by PL-GPC220 chromatography (wherein the standard sample was PS, flow rate: 1.0mL/min, column: 3 XPLGel 1 um M1 XED-B300X 7.5 nm).
3. The melting point of the polymer was measured using Differential Scanning Calorimetry (DSC): 10mg of the sample was placed in a crucible and measured on a Pekin Elmer DSC 8500 differential scanning calorimeter. In the nitrogen atmosphere, the temperature is raised from 30 ℃ to 180 ℃ at the temperature raising speed of 10 ℃/min, the lmin is kept, the temperature is lowered to 30 ℃ at the speed of 10 ℃/min, the temperature is kept for 3min, then the temperature is raised to 180 ℃ at the speed of 10 ℃/min, and the second temperature raising scanning data is recorded.
4. The activity measurement method comprises the following steps: weight of polymer (g)/nickel (mol). Times.2.
Example 1
Preparation of Complex Ni1(in the formula III, R1、R3、R3、R4Is methyl, R2、R4、R5Is hydrogen, R15Is ethyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.175g (0.6 mmol) of ligand L1To a solution of dichloromethane (10 mL), stirred at room temperature for 6h, and precipitated by addition of anhydrous ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain yellow powdery solid Ni1. Yield: 70.2 percent. Elemental analysis (C)44H58Br6N4Ni3O2): c,39.72; h,4.39; n,4.21; experimental values (%): c,39.38; h,4.60; and N,3.96.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 2h, vacuumizing while hot, and adding N2Replace qi for 3 times. 380mL of hexane, 120mL of 2-octene was charged into the polymerization system, and 1.0mL (1.0 mol/L heptane solution) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were added, together with 3.3mg (2.5. Mu. Mol) of Ni complex as a complex1The reaction was carried out at 30 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The results are shown in Table 1.
Example 2
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 2h, vacuumizing while hot, and adding N2Replace qi for 3 times. 380mL of hexane, 60mL of 2-octene, 60mL of 1-decene were charged into the polymerization system, and 1.0mL (1.0 mol/L heptane solution) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were added, together with 3.3mg (2.5. Mu. Mol) of complex Ni1The reaction was carried out at 60 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally neutralizing the mixture by using ethanol solution acidified by 10wt% hydrochloric acid,a polymer was obtained. The results are shown in Table 1.
Example 3
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 2h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 380mL of hexane, 60mL of 2-octene, 60mL of 1-hexadecene were charged into the polymerization system, and 1.0mL (1.0 mol/L heptane solution) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were further added, while 3.3mg (2.5. Mu. Mol) of complex Ni was added1The reaction was carried out at 60 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The results are shown in Table 1.
Comparative example 1
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 2h, vacuumizing while hot, and adding N2Replace qi for 3 times. 380mL of hexane, 120mL of 1-octene was charged into the polymerization system, and 1.0mL (1.0 mol/L heptane solution) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were added thereto, along with 3.3mg (2.5. Mu. Mol) of Ni complex as a complex1The reaction was carried out at 60 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The results are shown in Table 1.
Example 4
Preparation of Complex Ni2(in the formula III, R1、R3Is methyl, R2、R4、R5Is hydrogen, R3、R4Is p-fluorophenyl, R15Is ethyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.272g (0.6 mmol) of the ligand L2In dichloromethane (10 mL). The color of the solution immediately turned to a deep red color,and a large amount of precipitate was formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni2. The yield was 74.1%. Elemental analysis (C)64H62Br6F4N4Ni3O2): c,46.57; h,3.79; n,3.39; experimental values (%): c,46.72; h,3.97; and N,3.48.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 2h, vacuumizing while hot, and adding N2Replace qi for 3 times. 380mL of hexane, 60mL of 2-octene, 60mL of 1-hexadecene were injected, 1.0mL (1.0 mol/L heptane solution) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were added, and 4.1mg (2.5. Mu. Mol) of complex Ni were added2. The reaction was vigorously stirred at 60 ℃ for 30min while maintaining an ethylene pressure of 10 atm. The polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid, and the results are shown in Table 1.
Example 5
Preparation of Complex Ni3(in the formula III, R1、R3Is isopropyl, R2、R4、R5Is hydrogen, R3、R4Is methyl, R15Is ethyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9 mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.243g (0.6 mmol) of ligand L3To a solution of dichloromethane (10 mL), stirred at room temperature for 6h, and precipitated by addition of anhydrous ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain yellow powdery solid Ni3. The yield was 74.0%. Elemental analysis (C)60H90Br6N4Ni3O2): c,46.35; h,5.83; n,3.60; experimental values (%): c,46.48; h,6.12; and N,3.50.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 480mL of hexane, 2 mL of 2-octene, 5.0mL of MAO (1.53 mol/L in toluene) were injected into the polymerization system while 3.9mg (2.5. Mu. Mol) of complex Ni were added3The reaction was carried out at 60 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid. The results are shown in Table 1.
Example 6
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 460mL of hexane, 20mL of 2-octene, 20mL of 1-hexadecene and 5.0mL of MAO (1.53 mol/L in toluene) were charged into the polymerization system, and 3.9mg (2.5. Mu. Mol) of complex Ni was added3The reaction was carried out at 60 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid. The results are shown in Table 1.
Example 7
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 380mL of hexane, 60mL of 2-octene, 60mL of 1-hexadecene, 5.0mL of MAO (1.53 mol/L in toluene) were injected into the polymerization system, while 3.9mg (2.5. Mu. Mol) of complex Ni were added3The reaction was carried out at 60 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The results are shown in Table 1.
Example 8
Preparation of Complex Ni4(in the formula III, R1、R3Is isopropyl, R2、R4、R5Is hydrogen, R3、R4Is methyl, R15Is isobutyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0).9mmol)(DME)NiBr2To a solution of 2-methyl-1-propanol (10 mL) containing 0.243g (0.6 mmol) of ligand L3To a solution of dichloromethane (10 mL), stirred at room temperature for 6h, and precipitated by addition of anhydrous ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain yellow powdery solid Ni4. The yield was 74.5%. Elemental analysis (C)64H98Br6N4Ni3O2): c,47.71; h,6.13; n,3.48; experimental values (%): c,47.48; h,6.42; and N,3.29.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 460mL of hexane, 20mL of 2-octene, 20mL of 1-hexadecene and 5.0mL of MAO (1.53 mol/L in toluene) were charged into the polymerization system, and 4.0mg (2.5. Mu. Mol) of complex Ni was added thereto4The reaction was carried out at 80 ℃ under an ethylene pressure of 10atm with stirring for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. As a result, the polymerization activity and the performance parameters of the polymer are shown in Table 1.
Comparative example 2
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 380mL of hexane, 60mL of 2-octene, 60mL of 1-hexadecene were injected, and 1.0mL (1.0 mol/L heptane solution) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, and 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were added, while 1.9mg (3.75. Mu. Mol) of comparative catalyst A (whose structure is shown in formula V) was added, and the reaction was vigorously stirred at 60 ℃ for 30min while maintaining an ethylene pressure of 10 atm. The polymer was obtained by neutralizing with a 10wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst of the present invention exhibits higher polymerization activity when it catalyzes the copolymerization of ethylene and a mixed olefin, and the internal olefin in the system does not exhibit any toxicity to the catalyst system, as compared with the comparative catalyst. The copolymerization activity of the catalyst can reach 6.17 x 10at most6g·mol-1(Ni)·h-1The molecular weight of the obtained polymer can be regulated and controlled between 5 and 70 ten thousand, and the molecular weight distribution of the obtained polymer can be controlled between 2.1 and 5.0 by regulating and controlling the catalytic structure and the comonomer. The melting point of the polymer obtained in example 1 was 124.5 ℃ as measured by DSC, the melting point of the polymer obtained in example 4 was 94.7 ℃, and the melting points of the polymers obtained in examples 5 to 8 were not significant,13the results of C-NMR measurements showed that the polymers obtained in examples 2 to 8 had a methyl group content of more than 30 in 1000C atoms, indicating that the polymers were branched polyolefins. The chain structure such as molecular weight, distribution and the like of the polymer can be effectively regulated and controlled according to various different processing and application fields.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. Use of a diimine metal complex in catalyzing the polymerization of olefins, wherein the olefins comprise at least one C4 to C20 internal olefin monomer and optionally ethylene, propylene, C4 to C20 terminal olefin monomers, as a procatalyst for the polymerization of olefins;
the structure of the diimine metal complex is shown as a formula I:
in the formula I, R3、R4、R13、R14Each is hydrogen, substituted or unsubstituted C1-C30 hydrocarbyl; r1、R2、R11、R12The same or different, independently selected from C1-C30 alkyl containing substituent or not containing substituent; r15Selected from C1-C20 alkyl containing substituent or not containing substituent; y is selected from non-metal atoms of group VIA; m1、M2、M3Is a group VIII metal; x is selected from halogen, C1-C10 alkyl containing substituent or not containing substituent, C1-C10 alkoxy containing substituent or not containing substituent.
2. Use of a diimine metal complex as in claim 1 wherein R in formula I is1、R2、R11、R12Is selected from C1-C20 alkyl containing substituent or not containing substituent, and C6-C20 aryl containing substituent or not containing substituent.
3. Use of the diimine metal complex in the catalysis of olefin polymerization as claimed in claim 2 wherein in formula I, R1、R2、R11、R12Is a group of formula II:
in the formula II, R1～R5The same or different, each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 straight-chain alkyl, substituted or unsubstituted C3-C20 branched-chain alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 straight-chain alkoxy, substituted or unsubstituted C3-C20 branched-chain alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C3-C20 cycloalkoxy, substituted or unsubstituted C2-C20 alkenyloxyOptionally substituted C6-C20 aryl, optionally substituted C7-C20 aralkyl, optionally substituted C7-C20 alkaryl; r is1～R5Optionally forming a ring with each other.
4. Use of the diimine metal complex of claim 3 wherein in formula II, R is1～R5The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 linear alkyl with or without substituent, C3-C10 branched alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 linear alkoxy with or without substituent, C3-C10 branched alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent, C7-C15 alkylaryl with or without substituent.
5. Use of the diimine metal complex of claim 1 wherein in formula I, M is1、M2、M3Selected from nickel and palladium; y is selected from O and S; x is selected from halogen, C1-C10 alkyl with or without substituent, C1-C10 alkoxy with or without substituent, preferably selected from halogen, C1-C6 alkyl with or without substituent, C1-C6 alkoxy with or without substituent; r15Is selected from C1-C20 alkyl containing or not containing substituent, preferably is selected from C1-C10 alkyl containing or not containing substituent, and more preferably is selected from C1-C6 alkyl containing or not containing substituent.
6. The use of a diimine metal complex as in claim 3 wherein the diimine metal complex has the structure of formula III:
in the formula III, R1～R5Each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 straight chain alkyl with or without substituent Q, C3-C10 branched chain alkyl with or without substituent Q, C3-C10 cycloalkyl with or without substituent Q, C1-C10 straight chain alkoxy with or without substituent Q, C3-C10 branched chain alkoxy with or without substituent Q, C3-C10 cycloalkoxy with or without substituent Q, C6-C15 aryl with or without substituent Q, C7-C15 aralkyl with or without substituent Q, C7-C15 alkaryl with or without substituent Q;
R3and R4Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen, more preferably independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, halogen;
m is nickel; y is O; x is independently selected from fluorine, chlorine and bromine;
R15independently selected from C1-C20 alkyl with or without substituent Q, preferably C1-C10 alkyl with or without substituent Q, more preferably C1-C6 alkyl with or without substituent Q;
the substituent Q is selected from halogen, hydroxyl, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy, and is preferably selected from halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.
7. The use of a diimine metal complex as in claim 1 for the catalysis of olefin polymerization wherein the diimine metal complex has the structure of formula I':
the diimine metal complex shown in the formula I' is prepared by the following method:
reacting a diimine compound of formula IV with MXn and R15YH, generating a diimine metal complex shown as a formula I',
r in formula IV and formula I1～R4And R in formula I1～R4The definitions are the same;
MXn and X in the formula I 'are defined as the same as X in the formula I, M in the MXn and the formula I' is VIII group metal, and n in the MXn is the number of X satisfying M valence state;
R15YH, Y, R in formula I15And Y, R in formula I15The definitions are the same.
8. Use of a diimine metal complex in the catalysis of olefin polymerization as in claim 1 wherein the catalyst system further comprises a cocatalyst selected from organoaluminum compounds and/or organoboron compounds;
the organic aluminum compound is at least one of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate.
9. Use of a diimine metal complex in the catalysis of olefin polymerization as claimed in claim 8 wherein the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane and modified methylaluminoxane;
the organoboron compound is at least one selected from the group consisting of tris (pentafluorophenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and triphenylmethyl tetrakis (pentafluorophenyl) borate.
10. Use of a diimine metal complex according to any one of claims 1 to 9 in the catalysis of olefin polymerisation at a temperature of from-50 to 200 ℃, preferably from 30 to 100 ℃.
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