CN115141116A - Macromolecular diimine nickel-palladium catalyst and application thereof - Google Patents

Macromolecular diimine nickel-palladium catalyst and application thereof Download PDF

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CN115141116A
CN115141116A CN202210750494.XA CN202210750494A CN115141116A CN 115141116 A CN115141116 A CN 115141116A CN 202210750494 A CN202210750494 A CN 202210750494A CN 115141116 A CN115141116 A CN 115141116A
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陈敏
季明航
王福周
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Abstract

The invention discloses a macromolecular nickel-palladium diimine catalyst and application thereof, wherein the catalyst contains a polymer chain and a nickel-palladium diimine structure. The catalyst is used as a coordination polymerization catalyst for ethylene homopolymerization, ethylene copolymerization and long-chain olefin, the characteristic of forming a macromolecular catalyst can be realized by a ROMP method, and compared with the known diimine nickel palladium catalyst, the catalyst has the advantages of reducing the branching degree of a polymer, controlling the conversion efficiency of long-chain olefin internal alkene, obviously regulating and controlling the polymerization effect and the like.

Description

Macromolecular diimine nickel-palladium catalyst and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a macromolecular diimine nickel-palladium catalyst and application thereof.
Background
Polyolefin has low raw material price and excellent physical and chemical properties, and becomes an indispensable polymer resin material in the current society. In olefin polymerization, the catalyst determines the kinetics of the olefin polymerization reaction, the structure and properties of the polymer, and the morphology of the polymer particles, among other things. The development of olefin polymerization catalysts makes the types of polyolefin products more abundant and the performances more differentiated, thereby promoting the development of the whole polyolefin field.
Since the pioneering work of brueckhart and coworkers (j.am.chem.soc., 1995,117,6414.) (j.am.chem.soc., 1996,118,11664.), various strategies have emerged to design novel alpha-diimine palladium catalysts to regulate olefin polymerization processes. Many groups have developed a series of alpha-diimine palladium with electronic and steric regulation. (chem. Rev.2000,100, 1169-1204.) (ACS cat.2016, 6, 428-441.) (sci. China chem.2015,58, 1663-1673.) (angelw. Chem.int.ed.2019,58, 7192-7200.) in addition to the above electronic and steric hindrance modulation, alternative design strategies have emerged that provide novel olefin polymerization catalysts. (Angew. Chem., int.Ed.2020,59, 14884-14890.) (ACS Catal.2015,5, 456-464.) (Angew. Chem.2020,132, 14402-14408.) (Organometallics 2011,30,2432-2452.) (chem. Commun.2010,46, 7879-7893.) (Chem. Commun.2010,46, 7879-7893.) (which is a catalyst component of the catalyst system) is a complex catalyst that exhibits unique catalytic properties in olefin polymerization processes. (Angew. Chem. Int. Ed.2017,56, 11604-11609.) (J.am. Chem. Soc.2016,138, 774-777.)
Meanwhile, in recent years, the concept of polymer catalysts has attracted considerable attention in the fields of catalysis and synthetic organic chemistry. There are basically two different methods for synthesizing polymer catalysts: (1) Metallation by stirring a mixture of the polymeric ligand and the desired metal precursor; (2) The desired metal is already coordinated to the ligand building block prior to polymerization. One benefit of the second approach is that metallization can be almost quantitative, and in some cases complete metallization after formation of the polymeric ligand can be difficult. For polymer catalysts, the choice of building blocks has a crucial influence on the microenvironment of the final polymer. For the synthesis of polymer catalysts, many different methods have been reported in recent years, such as radical polymerization, friedel-Crafts reaction and satisfying and metal organic coordination reactions, etc. The development of new technologies for synthesizing polymer catalysts becomes necessary and will offer other possibilities for catalyst design.
Ring-opening metathesis polymerization (ROMP) has become a powerful and versatile tool for polymer synthesis since the advent of well-defined transition Ru metal catalysts. With the ROMP synthesis method, few polymerization catalysts have been used in recent years for the polymerization of olefins based only on norbornene backbones. From pioneering reports of Grubbs and co-workers, ru-catalyzed copolymerization of diene monomers and cyclic monomers was efficiently mediated. The advantage of this system is that the tolerances of the polar functional groups are large and the molecular weight of the produced polymer can be effectively adjusted. In this invention, we synthesize macromolecular nickel palladium diimine catalysts by ring opening metathesis polymerization of monocyclic rings.
Disclosure of Invention
In view of the above, the present invention provides a macromolecular nickel palladium diimine catalyst and applications thereof. Compared with the known diimine nickel palladium catalyst, the macromolecular catalyst has the advantages of reducing the branching degree of polymers, controlling the conversion efficiency of long-chain olefin internal alkene, obviously regulating and controlling the polymerization effect and the like.
In a first aspect, the present invention provides a ligand compound having the general structural formula (I) (II):
Figure BDA0003718116570000021
wherein:
R 1 、R 2 、R 3 、R 4 are each independently selected from
Figure BDA0003718116570000022
One kind of (1). R 1 、R 2 、R 3 、R 4 May be the same or different.
Preferably, R 1 、R 2 、R 3 、R 4 Are all isopropyl.
The synthetic route of the ligand compound of the present invention is as follows:
Figure BDA0003718116570000031
4-Bromophenylamine (10.00mmol, 1.0 equiv.) and R 1 the-OH (10.10 mmol,1.1 equiv.) mixture was heated to 120 ℃ and zinc chloride in hydrochloric acid was added to the mixture, the reaction rapidly exothermed and bubbled. The reaction temperature was raised to 160 ℃ and after 30 minutes of reaction, the reaction mixture was cooled to room temperature and dissolved in 200mL of dichloromethane. The dichloromethane layer was washed with water 3 times and dried over anhydrous sodium sulfate. Purification by flash chromatography on silica gel to give R 1 Substituted 4-bromoaniline. R is to be 1 Substituted 4-bromoaniline (10.00mmol, 1.0 equiv.) and R 2 the-OH (10.10 mmol,1.1 equiv.) mixture was heated to 120 ℃ and zinc chloride in hydrochloric acid was added to the mixture, the reaction rapidly exothermed and bubbled. The reaction temperature was raised to 160 ℃ and after 30 minutes of reaction, the reaction mixture was cooled to room temperature and dissolved in 200mL of dichloromethane. The dichloromethane layer was washed with water 3 times and dried over anhydrous sodium sulfate. Purification by flash chromatography on silica gel to give R 1 And R 2 Substituted 4-bromoaniline. Tetrakis (triphenylphosphine) palladium (0.47mmol, 0.01 equiv.) was then added to R 1 And R 2 Substituted 4-bromoaniline (9.50mmol, 1.0 equiv.), potassium vinyltrifluoroborate (19.00mmol, 2 equiv.), potassium carbonate (19.00mmol, 2 equiv.) and water (4 mL) were in toluene (30 mL) in a 200mL Schlenk flask under nitrogen. The mixture was stirred at 110 ℃ for 12 hours. Quenching with 100mL of water and 50mL of ethyl acetateThe ester was extracted twice. The organic layer was washed with brine and concentrated in vacuo. Purification by flash chromatography on silica gel to give 4-vinyl-2-R 1 -6-R 2 -aniline.
The R in the method is 1 -OH and R 2 -OH, substituted by R 3 -OH and R 4 -OH. 4-vinyl-2-R can be prepared in the same manner 3 -6-R 4 -aniline.
The potassium vinyltrifluoroborate used in the above process was replaced with 4-vinylphenylboronic acid in the same manner. 4-styryl-2-R can be prepared in the same manner 1 -6-R 2 -aniline and 4-styryl-2-R 3 -6-R 4 -aniline.
The obtained 4-vinyl-2-R 1 -6-R 2 Aniline (10.00mmol, 1.0 equiv.), 4-vinyl-2-R 3 -6-R 4 A solution of aniline (10.00mmol, 1.0 equiv.) and 2,3 butanedione (10.00mmol, 1.0 equiv.) and formic acid (1 mL) in methanol (30 mL) was stirred at 50 ℃ for 12h. After the reaction, a yellow solid precipitated from the solution. The yellow solid was isolated by filtration, washed 3 times with 20mL methanol and dried under high vacuum. The resulting complex 1.
Similarly, 4-vinyl-2-R in the above-mentioned method 1 -6-R 2 -aniline and 4-vinyl-2-R 3 -6-R 4 -aniline R 1 -OH, instead of 4-styryl-2-R 1 -6-R 2 -aniline and 4-styryl-2-R 3 -6-R 4 -aniline. Complex 2 can be prepared in the same manner.
In a second aspect, based on the above ligand compound, the present invention provides a nickel palladium complex, whose structure is shown in the following formulas (iii) (iv):
Figure BDA0003718116570000041
wherein M is nickel or palladium; x is one or more of Me, cl and Br.
Preferably, when M is nickel, X is Br and Br; when M is palladium, X is Me and Cl.
The synthetic route of the nickel-palladium complex is as follows:
Figure BDA0003718116570000051
a mixture of complex 1 (1.00mmol, 1.0 equiv.) and (COD) PdMeCl (1.00mmol, 1.0 equiv.) in 15mL of dichloromethane was stirred at room temperature for 12h. The resulting mixture was evaporated and the residue was washed with diethyl ether (30 mL). The solid was collected by filtration to give the palladium complex Pd1 as an orange solid.
Likewise, complex 1 in the above process was replaced by complex 2. The palladium complex Pd2 can be prepared in the same manner.
Likewise, the (COD) PdMeCl in the above process was replaced by (DME) NiBr 2 . Nickel complexes Ni1 and Ni2 can be prepared in the same manner.
In a third aspect, the present invention also provides a macromolecular diimine nickel-palladium catalyst, which has a structure shown in formula (v) (vi) below:
Figure BDA0003718116570000052
wherein R5 is
Figure BDA0003718116570000053
The polymerization degree is 1-1000, and the molecular weight range is 1000-110000.
An example of a preferred structure of a macromolecular nickel palladium diimine catalyst is as follows:
Figure BDA0003718116570000061
the synthetic route of the macromolecular diimine nickel-palladium catalyst is shown as follows:
Figure BDA0003718116570000062
cyclic monomer:
Figure BDA0003718116570000063
Figure BDA0003718116570000064
a solution of Hoveyda-Grubbs generation 2 catalyst (0.01mmol, 0.003 equiv.) in 1mL dry dichloromethane was added to a 50mL Schlenk's mixture of palladium complex 1 (0.16mmol, 0.05 equiv.), cyclooctene (3.20mmol, 1.0 equiv.) in 20mL dry dichloromethane in a flask under nitrogen. The mixture was stirred at 40 ℃ for 6 hours. The resulting mixture was quenched with ethyl vinyl ether, the solvent was removed in vacuo, and then anhydrous n-hexane was added to precipitate the polymer. The polymer was collected by filtration to give macromolecular palladium catalyst 1 as an orange solid.
Similarly, when cyclooctene in the above-mentioned method was replaced with norbornene, 5-norbornene-2,3-dicarboxylate and 5-norbornene-1-oxy-2,3-dicarboxylate, a large-molecular palladium catalyst 2, a large-molecular palladium catalyst 3 and a large-molecular palladium catalyst 4 were prepared in the same manner.
Similarly, by replacing the palladium complex 1 with the palladium complex 2 in the above-described method, the macromolecular palladium catalyst 5, the macromolecular palladium catalyst 6, the macromolecular palladium catalyst 7 and the macromolecular palladium catalyst 8 can be prepared in the same manner.
Similarly, the corresponding macromolecular nickel catalyst can be prepared in the same manner by replacing the palladium complex 1 with the nickel complex 1 and the nickel complex 2 in the above method.
In a fourth aspect, the macromolecular nickel-palladium diimine catalyst is used as a catalyst for catalyzing the polymerization of olefins.
Further, the polymerization reaction of the olefin includes ethylene homopolymerization, ethylene copolymerization, long-chain olefin homopolymerization and the like.
Specifically, the method comprises the following steps:
when ethylene homopolymerizes, a cocatalyst and an organic solvent are respectively added into a reaction kettle, then a macromolecular nickel palladium diimine catalyst is injected under the condition of introducing ethylene gas, so that coordination polymerization reaction is carried out in the ethylene gas with 8 atmospheric pressures, and after the reaction is finished, methanol is used for quenching.
When ethylene is copolymerized, a cocatalyst, a comonomer and an organic solvent are respectively added into a reaction kettle, then a macromolecular nickel palladium diimine catalyst is injected under the condition of introducing ethylene gas, so that coordination polymerization reaction is carried out in the ethylene gas with 8 atmospheric pressures, and after the reaction is finished, methanol is used for quenching.
When long-chain olefin homopolymerization is carried out, a cocatalyst, a long-chain olefin monomer and an organic solvent are respectively added into a reaction kettle, then a macromolecular nickel-palladium diimine catalyst is injected under the condition of nitrogen, so that coordination polymerization reaction is carried out at normal temperature and normal pressure, and after the reaction is finished, methanol is used for quenching.
The cocatalyst is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum, and alkali metals such as lithium, sodium, potassium and the like or alkali metal salts thereof.
The organic solvent is one or more of toluene, benzene and n-heptane.
The comonomer comprises methacrylic acid, methyl methacrylate, ethyl methacrylate 10-undecenol, 10-undecenoic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.
The long-chain olefin monomer comprises 10-undecenol, 10-undecenoic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.
The polymerization process is illustrated below:
and (3) carrying out ethylene polymerization reaction. In a typical experiment, a 350mL glass thick-walled pressure vessel was charged with 12. Mu. Mol NaBARF, 18mL toluene, and a magnetic stir bar in a glove box. 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. 2mL of CHCl was injected via syringe 3 The 10. Mu. Mol Pd catalyst in (1) was injected into the polymerization system. Under the condition of rapid stirringThe reactor was pressurized and maintained at 8.0atm of ethylene. After the desired time, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol/HCl = 50/1) and dried under vacuum at 50 ℃ for 24 hours. Alternatively in a typical experiment, a 350mL glass thick-walled pressure vessel was charged with 1mmol diethylaluminum chloride, 18mL toluene, and a magnetic stir bar in a glove box. 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. 2mL of CHCl was injected via syringe 3 2. Mu. Mol Ni catalyst in (1) was injected into the polymerization system. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid stirring. After the desired time, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol/HCl = 50/1) and dried under vacuum at 50 ℃ for 24 hours.
1-hexene polymerization. In a typical experiment, 1mL of 1-hexene, 12. Mu. MolNaBARF, 5mL of CHCl3, and a magnetic stir bar in a glove box were charged to a 50mL Schlenk flask. The flask was warmed to 30 ℃ and allowed to equilibrate for 15 minutes. 2mL of CHCl was injected via syringe 3 10. Mu. MolPd in (C) was injected into the polymerization system. Stir rapidly for 3 hours, precipitate the polymer in acidified methanol (methanol/HCl = 50/1) and dry under vacuum at 50 ℃ for 24 hours.
Ethylene-methyl acrylate copolymerization. In a typical experiment, a total of 18mL of 24. Mu. Mol NaBARF, toluene, and methyl acrylate, a magnetic stir bar in a glove box, was charged into a 350mL glass thick-walled pressure vessel. 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. 2mL of CHCl was injected via syringe 3 20. Mu. Mol of the metal complex in (1) was injected into the polymerization system. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid stirring. After 3 hours, the solvent was evaporated and the polymer was dried under vacuum at 50 ℃ for 24 hours.
The catalyst is used as a coordination polymerization catalyst for ethylene homopolymerization, ethylene copolymerization and long-chain olefin, the characteristic of forming a macromolecular catalyst can be realized by a ROMP method, and compared with the known diimine nickel palladium catalyst, the catalyst has the advantages of reducing the branching degree of a polymer, controlling the conversion efficiency of long-chain olefin internal alkene, obviously regulating and controlling the polymerization effect and the like.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectrum (CDCl 3) of Compound 1.
FIG. 2 shows nuclear magnetic hydrogen spectrum (CDCl 3) of Compound 2.
FIG. 3 nuclear magnetic carbon spectrum (CDCl 3) of Compound 2.
FIG. 4 shows nuclear magnetic hydrogen spectrum (CDCl 3) of Compound 3.
FIG. 5 shows nuclear magnetic hydrogen spectrum (CDCl 3) of Compound 4.
FIG. 6 shows nuclear magnetic hydrogen spectrum (CDCl 3) of Pd1 as a palladium complex.
FIG. 7 nuclear magnetic carbon spectrum (CDCl 3) of Pd1 as a palladium complex.
FIG. 8 shows nuclear magnetic hydrogen spectrum (CDCl 3) of Pd2 as a palladium complex.
FIG. 9 Nuclear magnetic carbon Spectroscopy (CDCl 3) of Pd2, a palladium complex.
FIG. 10 shows a macromolecular catalyst Pd1-COE 1:20 Nuclear magnetic hydrogen spectrum (CDCl 3).
FIG. 11 shows that the macromolecular catalyst Pd1-COE 1:20 Nuclear magnetic hydrogen-hydrogen relationship (CDCl 3).
FIG. 12 shows a macromolecular catalyst Pd2-COE 1:20 Nuclear magnetic hydrogen spectrum (CDCl 3).
FIG. 13 shows a macromolecular catalyst Pd2-COE 1:20 Nuclear magnetic hydrogen-hydrogen relationship (CDCl 3).
FIG. 14 shows a macromolecular catalyst Pd2-NB 1:20 Nuclear magnetic hydrogen spectrum (CDCl 3).
FIG. 15 shows a macromolecular catalyst Pd2-NB 1:20 Nuclear magnetic hydrogen-hydrogen relationship (CDCl 3).
FIG. 16 shows a macromolecular catalyst Pd2-NB 1:50 Nuclear magnetic hydrogen spectrum (CDCl 3).
FIG. 17 shows a macromolecular catalyst Pd2-NB 1:80 Nuclear magnetic hydrogen spectrum (CDCl 3).
FIG. 18 shows a macromolecular catalyst Pd2-NB COOMe Nuclear magnetic hydrogen spectrum (CDCl 3).
FIG. 19 shows a macromolecular catalyst Pd2-NB COOMe Nuclear magnetic hydrogen-hydrogen relationship (CDCl 3).
Detailed Description
In order to further understand the present invention, the following detailed description of the catalyst system and its application are provided in connection with the examples. The scope of the present invention is not limited by the following examples.
The following examples illustrate the details of the invention and give data including ligand synthesis, metal compound synthesis, ethylene polymerization or copolymerization processes wherein the synthesis of the complex, the polymerization process is carried out in the absence of water and oxygen, all sensitive materials are stored in a glove box, all solvents are rigorously dried to remove water, and the ethylene gas is purified by a water and oxygen removal column. All the raw materials were purchased and used without specific mention.
The nuclear magnetism detection is carried out by a Bruker 400MHz nuclear magnetism instrument. The elemental analysis was determined by the chemical and physical center of the university of science and technology in China. Molecular weight and molecular weight distribution were determined by high temperature GPC. Mass spectra were determined using Thermo LTQ Orbitrap XL.
The present invention preferably provides a macromolecular nickel palladium diimine catalyst.
Figure BDA0003718116570000091
Example 1: synthesis of N, N-bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine.
Figure BDA0003718116570000092
A solution of 4-bromo-2,6-diisopropylaniline (5.63g, 22.00mmol), 2,3 butanedione (0.86g, 10.00mmol) and formic acid (1 mL) in methanol (20 mL) was stirred at 50 ℃ for 12 hours. After the reaction was complete, a yellow solid precipitated from the solution. The yellow solid was isolated by filtration, washed 3 times with 20mL methanol and dried under high vacuum. The yellow solid obtained was compound 1 (5.32g, 9.50mmol,95% yield). Tetrakis (triphenylphosphine) palladium (0.54g, 0.47mmol) was added to compound 1 (5.32g, 9.50mmol), potassium vinyltrifluoroborate (5.09g, 38.00mmol), potassium carbonate (5.25g, 38.00mmol) and water (4 mL) in 200mL of Schlenk flask in toluene (30 mL), under nitrogen. The mixture was stirred at 110 ℃ for 12 hours. Quenched with 100mL of water and extracted twice with 50mL of ethyl acetate. The organic layer was washed with brine and concentrated in vacuo. Purification by flash chromatography on silica gel gave compound 2 (3.47g, 80% yield) as a yellow solid. 1 H NMR(400MHz,CDCl 3 )δ7.23(s,4H),6.73(dd,J＝17.5,10.9Hz,2H),5.72(d,J＝17.6Hz,2H),5.17(d,J＝10.9Hz,2H),2.70(dt,J＝13.7,6.8Hz,4H),2.06(d,J＝13.3Hz,6H),1.20(dd,J＝11.2,6.9Hz,24H). 13 C NMR(100MHz,CDCl 3 )δ168.28(s),146.06(s),137.28(s),135.27(s),133.02(s),121.17(s),111.59(s),28.53(s),22.96(s),22.61(s),16.67(s).
Example 2: synthesis of N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine.
Figure BDA0003718116570000101
Tetrakis (triphenylphosphine) palladium (0.58g, 0.50mmol) was added to a 100mL Schlenk flask of 4-bromo-2,6 diisopropylaniline (2.56g, 10.00mmol), 4-vinylphenylboronic acid (2.95g, 20.00mmol), potassium carbonate (2.76g, 20.00mmol), and water (2 mL) in toluene (15 mL) under nitrogen. Mixing the mixture at 110 stirring at deg.C for 12 hr. Quenched with 100mL of water and extracted twice with 50mL of ethyl acetate. The organic layer was washed with brine and concentrated in vacuo. Purification by flash chromatography on silica gel gave compound 3 (1.39g, 5.00mmol,52% yield) as a yellow solid. A solution of compound 3 (6.14g, 22.00mmol), 2,3-butanedione (0.86g, 10.00mmol) and formic acid (1 mL) in methanol (20 mL) was stirred at 50 ℃ for 12h. After the reaction was complete, a yellow solid precipitated from the solution. The yellow solid was isolated by filtration, washed 3 times with 20mL methanol and dried under high vacuum. The resulting yellow solid was compound 4 (4.92g, 81% yield) containing a small amount of α -iminoketone by-product. 1 HNMR(400MHz,CDCl 3 )δ7.60(t,J＝5.8Hz,4H),7.51–7.48(m,4H),7.40(s,4H),6.81–6.74(m,2H),5.83–5.78(m,2H),5.29–5.25(m,2H),2.77(dt,J＝13.7,6.8Hz,4H),2.14(s,6H),1.25(dd,J＝10.7,6.8Hz,24H)。
Example 3: synthesis of N, N-bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine palladium complex.
Figure BDA0003718116570000111
A mixture of compound 2 (0.45g, 1.00mmol), (COD) PdMeCl (0.26g, 1.00mmol) in 15mL of dichloromethane was stirred at room temperature for 12h. The resulting mixture was evaporated and the residue was washed with diethyl ether (30 mL). The solid was collected by filtration to give N, N bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine palladium complex Pd1 (0.55g, 89% yield) as an orange solid. 1 H NMR(400MHz,CDCl 3 )δ7.31–7.26(m,4H),6.77–6.67(m,2H),5.75(dd,J＝19.1,17.9Hz,2H),5.29–5.21(m,2H),3.11–2.99(m,4H),2.05(t,J＝6.5Hz,6H),1.44(t,J＝7.4Hz,6H),1.35(t,J＝6.1Hz,6H),1.17(dd,J＝6.9,2.0Hz,12H),0.57–0.53(s,3H). 13 C NMR(100MHz,CD 2 Cl 2 )δ173.64(s),169.01(s),140.68(s),140.37(s),137.81(s),137.29(s),135.80(s),135.74(s),135.38(s),134.86(s),120.85(s),120.22(s),112.73(s),111.96(s),27.88(s),27.43(s),22.44(s),22.32(s),22.04(s),21.83(s),20.08(s),18.67(s).MALDI-TOF-MS(m/z):561.3616[M-Me-Cl] + (ii) a Elemental analysis calculation C 33 H 47 ClN 2 Pd is C,64.59; h,7.72; n,4.57, actually measuring C,64.56; h,7.70; n,4.53.
Example 4: synthesis of N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine palladium complex.
Figure BDA0003718116570000112
The procedure is analogous to example 3, except that the compound 2-N, N-bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine from example 1 is replaced by 0.59g of the compound 4-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl]-4-yl) butane-2,3-diimine to give a polymer with 0.65gN, N bis (3,5-diisopropyl)-4-ethenyl- [1,1-biphenyl]-4-yl) butane-2,3-diimine palladium complex Pd2 (0.65g, 85% yield). 1 H NMR(400MHz,CDCl 3 )δ7.59(dd,J＝8.1,5.9Hz,4H),7.51(d,J＝9.4Hz,4H),7.46(d,J＝13.1Hz,4H),6.78(m,2H),5.81(dd,J＝18.3,7.5Hz,2H),5.29(t,J＝11.1Hz,2H),3.13(qd,J＝13.6,6.7Hz,4H),2.10(d,J＝3.5Hz,6H),1.50(d,J＝6.7Hz,6H),1.42(d,J＝6.7Hz,6H),1.23(dd,J＝6.8,2.2Hz,12H),0.61(s,3H). 13 C NMR(100MHz,CDCl 3 )δ173.20(s),168.57(s),140.24(s),140.01(s),139.67(s),139.06(s),139.00(s),138.07(s),138.00(s),137.36(s),135.80(s),135.46(s),135.34(s),135.29(s),126.21(s),126.17(s),125.66(s),125.50(s),121.62(s),121.05(s),113.08(s),112.68(s),28.13(s),27.62(s),22.85(s),22.82(s),22.46(s),22.23(s),20.31(s),18.87(s).MALDI-TOF-MS(m/z):713.4054[M-Me-Cl] + (ii) a Elemental analysis calculation C 45 H 55 ClN 2 Pd is C,70.58; h,7.24; n,3.66, actually measuring C,70.55; h,7.23; and N,3.64.
Example 5: synthesis of N, N-bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-nickel diimine complex.
Figure BDA0003718116570000121
Under a nitrogen atmosphere, compound 2 (0.45g, 1.00mmol), (DME) NiBr 2 A mixture (0.30g, 1.00mmol) in 15mL of dichloromethane was stirred at room temperature for 12h. The resulting mixture was evaporated and the residue was washed with diethyl ether (30 mL). The solid was collected by filtration to give N, N bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine nickel complex Pd1 (0.60g, 89% yield) as an orange solid. MALDI-TOF-MS (m/z): 595.2017[ M-Br ]] + (ii) a Elemental analysis calculation C 32 H 44 Br 2 N 2 Ni is C,56.92; h,6.57; n,4.15, actually measuring C,56.906; h,6.54; n,4.14.
Example 6: synthesis of N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine nickel complex.
Figure BDA0003718116570000122
The procedure is analogous to example 3, except that the compound 2-N, N-bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine from example 1 is replaced by 0.59g of the compound 4-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl]-4-yl) butane-2,3-diimine to give bis (3,5-diisopropyl-4-ethenyl- [1,1-biphenyl) from 0.74gN]-4-yl) butane-2,3-diimine nickel complex Pd2 (0.74g, 90% yield). MALDI-TOF-MS (m/z): 747.2610[ m-Br ]] + (ii) a Elemental analysis calculation C 44 H 52 Br 2 N 2 Ni is C,63.87; h,6.33; n,3.39, actually measuring C,63.85; h,6.30; n,3.38.
Example 7:1: synthesis of 20 ratio of polycyclooctene-N, N-bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine palladium complex.
Figure BDA0003718116570000123
A solution of Hoveyda-Grubbs generation 2 catalyst (6.2mg, 0.01mmol) in 1mL dry dichloromethane was added to a 50mL Schlenk's mixture of Pd1 (0.10g, 0.16mmol), cyclooctene (0.36g, 3.20mmol) in 20mL dry dichloromethane in a flask under nitrogen. The mixture was stirred at 40 ℃ for 6 hours. The resulting mixture was quenched with ethyl vinyl ether, the solvent was removed in vacuo, and then anhydrous n-hexane was added to precipitate the polymer. The polymer was collected by filtration to give a polycyclooctene-N, N-bis (2,6-diisopropyl-4-vinylphenyl) butane-2,3-diimine palladium complex, i.e., pd1-COE 1:20 As an orange solid (0.43g, 95% yield). 1 HNMR(400MHz,CDCl 3 )δ7.23(s,2H),7.20(s,2H),6.38(dd,J＝15.6,4.6Hz,2H),6.25(d,J＝19.6Hz,2H),5.86–5.77(m,1H),5.44–5.32(m,40H),4.96(dd,J＝25.4,13.5Hz,2H),3.04(d,J＝7.0Hz,4H),2.21(d,J＝6.5Hz,4H),2.04(s,6H),1.99(m,80H),1.36–1.16(m,184H),0.54(br,3H).
Example 8:1: synthesis of 20 proportions of polycyclooctene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine Palladium Complex.
Figure BDA0003718116570000131
A solution of Hoveyda-Grubbs generation 2 catalyst (6.2mg, 0.01mmol) in 1mL dry dichloromethane was added to a 50mL Schlenk's mixture of Pd2 (0.10g, 0.13mmol), cyclooctene (00.29g, 2.60mmol) in 20mL dry dichloromethane in a flask under nitrogen. The mixture was stirred at 40 ℃ for 6 hours. The resulting mixture was quenched with ethyl vinyl ether, the solvent was removed in vacuo, and then anhydrous n-hexane was added to precipitate the polymer. The polymer was collected by filtration to give polycyclooctene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl]-4-yl) butane-2,3-diimine palladium complex, i.e., pd2-COE 1:20 As an orange solid (0.37g, 95% yield). 1 H NMR(400MHz,CDCl 3 )δ7.59–7.52(m,4H),7.45(m,8H),6.42(d,J＝15.8Hz,2H),6.31(d,J＝7.0Hz,2H),5.81(d,J＝6.7Hz,1H),5.38(m,40H),4.96(dd,J＝24.1,13.3Hz,2H),3.12(s,4H),2.23(s,4H),2.10(s,6H),1.97(m,80H),1.31(m,185H),0.61(br,3H)。
Example 9:1: synthesis of 20 proportions of poly-2-norbornene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine palladium complex.
Figure BDA0003718116570000132
A solution of Hoveyda-Grubbs generation 2 catalyst (6.2mg, 0.01mmol) in 1mL of dry dichloromethane was added to a 50mL Schlenk's mixture of Pd2 (0.10g, 0.13mmol), 2-norbornene (0.24g, 2.60mmol) in 20mL of dry dichloromethane in a flask under nitrogen. The mixture was stirred at 40 ℃ for 6 hours. The resulting mixture was quenched with ethyl vinyl ether, the solvent was removed in vacuo, and then anhydrous n-hexane was added to precipitate the polymer. The polymer was collected by filtration to give poly-2-norbornene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl]-4-yl) butane-2,3-diimine palladium complex, i.e., pd2-NB 1:20 Is orange solidBody (0.32g, 95% yield). 1 HNMR(400MHz,CDCl 3 )δ7.55(m,4H),7.44(m,8H),6.39(s,2H),6.28(s,2H),5.83(s,2H),5.35(m,18H),5.21(m,22H),4.99(s,4H),3.14(s,4H),2.79(m,22H),2.44(m,18H),2.11(s,6H),1.80(m,40H),1.38(m,104H),0.61(br,3H)。
Example 10:1: synthesis of 50 proportions of poly-2-norbornene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine Palladium Complex.
Figure BDA0003718116570000141
Preparation was carried out in analogy to example 7, except that 2-norbornene (0.24g, 2.60mmol) from example 7 was changed to 2-norbornene (0.61g, 6.50mmol) to give poly-2-norbornene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl)]-4-yl) butane-2,3-diimine palladium complex, i.e., pd2-NB 1:50 As an orange solid (0.67g, 95% yield). 1 H NMR(400MHz,CDCl 3 )δ7.56(m,4H),7.45(m,8H),6.39(s,2H),6.28(s,2H),5.84–5.76(m,2H),5.35(m,46H),5.21(m,54H),4.91(dd,J＝39.7,13.5Hz,4H),3.13(s,4H),2.79(m,54H),2.44(m,46H),2.11(s,6H),1.88–1.77(m,100H),1.55–0.96(m,224H),0.61(br,3H)。
Example 11:1: synthesis of 80 ratio of poly-2-norbornene-N, N bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine Palladium Complex.
Figure BDA0003718116570000142
The procedure was analogous to example 7, except that 2-norbornene (0.24g, 2.60mmol) in example 7 was changed to 2-norbornene (0.98g, 10.40mmol) to give poly-2-norbornene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl)]-4-yl) butane-2,3-diimine palladium complex, i.e., pd2-NB 1:80 As an orange solid (1.02g, 95% yield). 1 H NMR(400MHz,CDCl 3 )δ7.52–7.48(m,4H),7.38(m,8H),6.34(m,2H),6.26–6.12(m,2H),5.76–5.68(m,2H),5.28(m,70H),5.14(m,90H),4.84(d,J＝26.3Hz,4H),3.06(d,J＝6.2Hz,4H),2.72(m,90H),2.37(m,70H),2.04(s,6H),1.75(m,160H),1.34–0.93(m,344H),0.54(br,3H)。
Example 12:1: synthesis of 20 proportions of poly-5-norbornene-2,3-dicarboxylate-N, N bis (3,5-diisopropyl-4-ethenyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine palladium complex.
Figure BDA0003718116570000151
A solution of Hoveyda-Grubbs generation 2 catalyst (6.2 mg, 0.01mmol) in 1mL dry dichloromethane was added to a 50mL Schlenk mixture of Pd2 (0.10g, 0.13mmol), 5-norbornene-2,3-dicarboxylate (0.55g, 2.60mmol) in 20mL dry dichloromethane in a flask under nitrogen. The mixture was stirred at 40 ℃ for 6 hours. The resulting mixture was quenched with ethyl vinyl ether, the solvent was removed in vacuo, and then anhydrous n-hexane was added to precipitate the polymer. The polymer was collected by filtration to give poly-5-norbornene-2,3-dicarboxylate-N, N bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl]-4-yl) butane-2,3-diimine palladium complex, i.e., pd2-NB COOME As an orange solid (0.61g, 95% yield). 1 H NMR(400MHz,CDCl 3 )δ7.54(m,4H),7.45(m,8H),6.45(s,2H),6.43(s,2H),5.89(s,2H),5.53(m,40H),5.09–4.89(m,4H),3.67(m,120H),3.12(m 44H),2.87(s,40H),2.11(s,6H),1.91(m,40H),1.49(d,J＝6.4Hz,6H),1.42(d,J＝5.9Hz,6H),1.24(d,J＝6.5Hz,12H),0.60(br,3H)。
Example 13:1: synthesis of poly-2-norbornene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl ] -4-yl) butane-2,3-diimine Nickel Complex N at 20 ratios.
Figure BDA0003718116570000152
A solution of Hoveyda-Grubbs generation 2 catalyst (6.2 mg, 0.01mmol) in 1mL dry dichloromethane was added to Ni2 (0.11g, 0.13mmol), 2-norbornene (0.24g, 2.60mmol) in 20mL dry dichloromethaneFlask under nitrogen in 50mL Schlenk mixture in mL dry dichloromethane. The mixture was stirred at 40 ℃ for 6 hours. The resulting mixture was quenched with ethyl vinyl ether, the solvent was removed in vacuo, and then anhydrous n-hexane was added to precipitate the polymer. The polymer was collected by filtration to give poly-2-norbornene-N, N-bis (3,5-diisopropyl-4-vinyl- [1,1-biphenyl]-4-yl) butane-2,3-diimine nickel complex, i.e., ni2-NB 1:20 As an orange solid (0.32g, 95% yield).
Example 14: macromolecular diimine palladium catalyst catalyzed ethylene polymerization
Procedure for ethylene polymerization. In a typical experiment, a 350mL glass thick-walled pressure vessel was charged with 12. Mu. Mol NaBAF, 18mL toluene, and a magnetic stir bar in a glove box. 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. 2mL of CHCl was injected via syringe 3 The 10. Mu. Mol Pd catalyst in (1) was injected into the polymerization system. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid stirring.
After the desired time, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol/HCl = 50/1) and dried under vacuum at 50 ℃ for 24 hours.
TABLE 1 macromolecular diimine Palladium catalyst catalyzed ethylene polymerization Table a
Figure BDA0003718116570000161
a Polymerization conditions: palladium catalyst =10 μmol,2mL CHCl 3 1.2 equivalents NaBAF, toluene =18mL, ethylene =8atm,1h. b Yield and activity averaged at least twice. The unit of activity is 10 5 g·mol -1 ·h -1 。 C Measured in trichlorobenzene at 150 ℃ by GPC. d The degree of branching is given per 1000 carbon atoms. Count per 1000C = (CH 3/3)/[ (CH + CH2+ CH 3)/2]*1000, by passage in Tol-d 8at 120 ℃ 1 H NMR measurement.
Example 15: 1-hexene polymerization catalyzed by macromolecular diimine palladium catalyst
1-hexene polymerization process. In a typical experiment, 1mL of 1-hexene, 12. Mu. MolNaBAF, 5mL of CHCl3, and a magnetic stir bar in a glove box were charged to a 50mL Schlenk flask. The flask was warmed to 30 ℃ and allowed to equilibrate for 15 minutes. 2mL of CHCl was injected via syringe 3 10. Mu. MolPd in (C) was injected into the polymerization system. Stir rapidly for 3 hours, precipitate the polymer in acidified methanol (methanol/HCl = 50/1) and dry under vacuum at 50 ℃ for 24 hours.
TABLE 2 polymerization of 1-hexene catalyzed by macrodiimine palladium catalyst Table a
Figure BDA0003718116570000171
a Polymerization conditions: palladium catalyst =10 μmol,2mL CHCl 3 1.2 equivalents of NaBAF, CHCl 3 =5ml, 1-hexene =1ml,30 ℃,3h. b Yield and activity averaged at least twice. The unit of activity is 10 5 g·mol -1 ·h -1 。 C Calculated from the ratio of the obtained polymer and the original 1-hexene feed. d GPC was measured in trichlorobenzene. d The degree of branching is given per 1000 carbon atoms. Count per 1000C = (CH 3/3)/[ (CH + CH2+ CH 3)/2]*1000, passage through Tol-d 8at 120 ℃ 1 HNMR determination. e One degree of branching is given per 1000 carbon atoms, = (CH 3/3)/[ (CH + CH2+ CH 3)/2) per 1000C branches]*1000 was determined by 1HNMR in CDCl 3. f The number of branches in the calculation was determined by 1H-NMR and 13C-NMR (CDCl 3).
Example 16: copolymerization and polymerization of ethylene-methyl acrylate catalyzed by macromolecular diimine palladium catalyst
Ethylene-methyl acrylate copolymerization process. In a typical experiment, a total of 18mL of 24. Mu. Mol NaBAF, toluene and methyl acrylate, a magnetic stir bar in a glove box, was charged into a 350mL glass thick-walled pressure vessel. The pressure vessel was connected to a high pressure line and the solution was degassed. The vessel was heated to the desired temperature and allowed to equilibrate using an oil bathFor 15 minutes. 2mL of CHCl was injected via syringe 3 20. Mu. Mol of the metal complex in (1) was injected into the polymerization system. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid stirring. After 3 hours, the solvent was evaporated and the polymer was dried under vacuum at 50 ℃ for 24 hours.
TABLE 3 copolymerization of ethylene-methyl acrylate catalyzed by Macro-diimine Palladium catalyst Table a
Figure BDA0003718116570000172
a Polymerization conditions: palladium catalyst =20 μmol,2mL chcl3,1.2 equivalents NaBAF,2.5M/L MA, toluene =18mL, ethylene =8atm,3h. b Yield and activity averaged at least twice. The unit of activity is 10 4 g·mol -1 ·h -1 。 C Calculated from the ratio of polymer obtained and of original 1-hexene feed, using that in CDCl3 1 H NMR measurement. d GPC was measured as THF at 40 ℃.
Example 17: macromolecular nickel diimine catalyst catalyzed ethylene polymerization
Procedure for ethylene polymerization. In a typical experiment, a 350mL glass thick-walled pressure vessel was charged with 1mmol diethylaluminum chloride, 18mL toluene, and a magnetic stir bar in a glove box. 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. 2mL of CHCl was injected via syringe 3 2. Mu. Mol Ni catalyst (II) was injected into the polymerization system. The reactor was pressurized and maintained at 8.0atm of ethylene with rapid stirring. After the desired time, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol/HCl = 50/1) and dried under vacuum at 50 ℃ for 24 hours.
TABLE 4 macromolecular diimine palladium catalyst catalyzed ethylene polymerization Table a
Figure BDA0003718116570000181
a Polymerization conditions: nickel catalyst =2 μmol,1mL CHCl 3 500 equivalents of diethylaluminum chloride, toluene =18mL, ethylene =8atm,1h. b Yield and activity averaged at least twice. The unit of activity is 10 6 g·mol -1 ·h -1 。 C Measured by GPC in trichlorobenzene at 150 ℃. d The degree of branching is given per 1000 carbon atoms. Count per 1000C = (CH 3/3)/[ (CH + CH2+ CH 3)/2]*1000, passage through Tol-d 8at 120 ℃ 1 H NMR measurement.

Claims (9)

1. A ligand compound characterized by the structural general formula as shown in the following formula (I) (II):
Figure FDA0003718116560000011
wherein:
R 1 、R 2 、R 3 、R 4 are each independently selected from
Figure FDA0003718116560000012
One kind of (1).
2. A nickel palladium complex based on the ligand compound according to claim 1, characterized by the following structures (iii) (iv):
Figure FDA0003718116560000013
wherein M is nickel or palladium; x is one or more of Me, cl and Br.
3. A macromolecular nickel palladium diimine catalyst based on the nickel palladium complex of claim 2 and having the structure of formula (v) (vi):
Figure FDA0003718116560000014
wherein R5 is
Figure FDA0003718116560000015
The polymerization degree is 1-1000, and the molecular weight range is 1000-110000.
4. A macromolecular nickel diimine palladium catalyst according to claim 3 which is characterized by being one of the compounds of the following structure:
Figure FDA0003718116560000021
5. use of a macromolecular nickel palladium diimine catalyst of claim 3 wherein:
the macromolecular nickel-palladium diimine catalyst is used as a catalyst for catalyzing the polymerization reaction of olefin.
6. Use according to claim 5, characterized in that:
the polymerization reaction of the olefin comprises ethylene homopolymerization, ethylene copolymerization and long-chain olefin homopolymerization.
7. Use according to claim 6, characterized in that:
respectively adding a cocatalyst and an organic solvent into a reaction kettle during ethylene homopolymerization, then injecting a macromolecular nickel palladium diimine catalyst under the condition of introducing ethylene gas, carrying out coordination polymerization reaction in the ethylene gas with 8 atmospheric pressures, and quenching with methanol after the reaction is finished;
the cocatalyst is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum and lithium, sodium, potassium alkali metal or alkali metal salt thereof;
the organic solvent is one or more of toluene, benzene and n-heptane.
8. Use according to claim 6, characterized in that:
when ethylene is copolymerized, respectively adding a cocatalyst, a comonomer and an organic solvent into a reaction kettle, then injecting a macromolecular nickel palladium diimine catalyst under the condition of introducing ethylene gas, carrying out coordination polymerization reaction in the ethylene gas with 8 atmospheric pressures, and quenching by using methanol after the reaction is finished;
the cocatalyst is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum and lithium, sodium, potassium alkali metal or alkali metal salt thereof;
the organic solvent is one or more of toluene, benzene and n-heptane;
the comonomer comprises methacrylic acid, methyl methacrylate, ethyl methacrylate 10-undecenol, 10-undecenoic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.
9. Use according to claim 6, characterized in that:
when long-chain olefin homopolymerization is carried out, respectively adding a cocatalyst, a long-chain olefin monomer and an organic solvent into a reaction kettle, then injecting a macromolecular diimine nickel palladium catalyst under the condition of nitrogen, carrying out coordination polymerization reaction at normal temperature and normal pressure, and quenching by using methanol after the reaction is finished;
the cocatalyst is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum and lithium, sodium, potassium alkali metal or alkali metal salt thereof;
the organic solvent is one or more of toluene, benzene and n-heptane;
the long-chain olefin monomer comprises 10-undecenol, 10-undecenoic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030060357A1 (en) * 2001-08-16 2003-03-27 Michael Arndt-Rosenau Catalysts for olefin polymerization
WO2003102005A1 (en) * 2002-05-30 2003-12-11 Exxonmobil Chemical Patents Inc. Soluble late transition metal catalysts for olefin oligomerizations
US20070043186A1 (en) * 2003-08-07 2007-02-22 Zhibin Guan Macrocyclic metal complexes and their uses as polymerization catylysts
CN102336846A (en) * 2011-07-07 2012-02-01 中山大学 Loaded alpha-palladium diimine and method for preparing hyperbranched polyethylene by catalyzing with same
JP2013184925A (en) * 2012-03-08 2013-09-19 Osaka Univ Tungsten complex, catalyst for metathesis reaction and production method of cyclic olefin ring-opened polymer
JP2017179022A (en) * 2016-03-29 2017-10-05 日本ポリエチレン株式会社 Manufacturing method of ethylene copolymer by specific catalyst and specific process
CN110317149A (en) * 2019-07-31 2019-10-11 安徽大学 Big steric hindrance flexibility diimide ligand, the diimine nickel based on it and palladium complex and its catalytic applications
CN110563862A (en) * 2019-08-09 2019-12-13 宁夏工商职业技术学院（宁夏化工技工学校、宁夏机电工程学校、宁夏农业机械化学校） High steric hindrance nickel catalyst and synthetic method and application thereof
CN112961110A (en) * 2021-02-10 2021-06-15 浙江工业大学 Olefin functionalized IPr HCl monomer and preparation method and application thereof
CN113480578A (en) * 2021-06-23 2021-10-08 浙江大学 (alpha-diimine) nickel complex compositions and uses thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030060357A1 (en) * 2001-08-16 2003-03-27 Michael Arndt-Rosenau Catalysts for olefin polymerization
WO2003102005A1 (en) * 2002-05-30 2003-12-11 Exxonmobil Chemical Patents Inc. Soluble late transition metal catalysts for olefin oligomerizations
US20070043186A1 (en) * 2003-08-07 2007-02-22 Zhibin Guan Macrocyclic metal complexes and their uses as polymerization catylysts
CN102336846A (en) * 2011-07-07 2012-02-01 中山大学 Loaded alpha-palladium diimine and method for preparing hyperbranched polyethylene by catalyzing with same
JP2013184925A (en) * 2012-03-08 2013-09-19 Osaka Univ Tungsten complex, catalyst for metathesis reaction and production method of cyclic olefin ring-opened polymer
JP2017179022A (en) * 2016-03-29 2017-10-05 日本ポリエチレン株式会社 Manufacturing method of ethylene copolymer by specific catalyst and specific process
CN110317149A (en) * 2019-07-31 2019-10-11 安徽大学 Big steric hindrance flexibility diimide ligand, the diimine nickel based on it and palladium complex and its catalytic applications
CN110563862A (en) * 2019-08-09 2019-12-13 宁夏工商职业技术学院（宁夏化工技工学校、宁夏机电工程学校、宁夏农业机械化学校） High steric hindrance nickel catalyst and synthetic method and application thereof
CN112961110A (en) * 2021-02-10 2021-06-15 浙江工业大学 Olefin functionalized IPr HCl monomer and preparation method and application thereof
CN113480578A (en) * 2021-06-23 2021-10-08 浙江大学 (alpha-diimine) nickel complex compositions and uses thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MINGHANG JI ET AL.: ""Polymeric a-diimine palladium catalysts for olefin (co)polymerization"", 《JOURNAL OF CATALYSIS》, vol. 415, pages 51 - 57 *

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