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CN-117820383-B - Asymmetric acenaphthenyl alpha-diimine nickel complex containing amino and preparation method and application thereof

CN117820383BCN 117820383 BCN117820383 BCN 117820383BCN-117820383-B

Abstract

The invention provides an asymmetric acenaphthenyl alpha-diimine nickel complex containing amino, which has a structure shown in a formula (I). The invention also provides a preparation method and application of the nickel complex. The invention further provides a catalyst composition and a process for the polymerization of olefins, in particular for the preparation of polyethylene. The nickel complex provided by the invention has novel structure, has the advantages of high catalytic activity, good thermal stability and the like when being used for catalyzing olefin polymerization (especially ethylene polymerization), and has the potential of further preparing heterogeneous covalent supported catalysts. In addition, the preparation method of the nickel complex provided by the invention is simple and convenient, the reaction condition is mild, the operation is simple and easy to control, the industrial practicability is very strong,

Inventors

  • WANG JIANLI
  • WANG QUANCHAO
  • WANG YIZHOU
  • WEI ZHENG
  • FU JIANGFENG
  • LI YI
  • SUN WENHUA
  • WANG ZHIJUN
  • ZHANG SHIJIE
  • ZHANG QIUYUE
  • SUN GAOPAN
  • MA YANPING
  • ZOU SONG

Assignees

  • 中国神华煤制油化工有限公司
  • 中国科学院化学研究所

Dates

Publication Date
20260508
Application Date
20231207

Claims (20)

  1. 1. An amine group-containing asymmetric acenaphthylene alpha-diimine nickel complex having the structure of formula (I): Formula (I) Wherein R 1 is the same or different, and R 1 is selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C10 cycloalkyl; R 2 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, hydroxy, mercapto, nitro or C3-C10 cycloalkyl, said C1-C6 alkyl, C1-C6 alkoxy, hydroxy or mercapto being optionally substituted by one or more substituents selected from C1-C6 alkyl, C3-C10 cycloalkyl or R'; R 3 is the same or different, and R 3 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C10 cycloalkyl; x is the same or different and is selected from halogen.
  2. 2. The nickel complex according to claim 1, wherein, R 1 are the same or different and are selected from hydrogen or C1-C6 alkyl; The R 2 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, hydroxyl, mercapto, nitro, C3-C10 cycloalkyl or-O-C3-C10 cycloalkyl; R 3 are the same or different and are selected from C1-C6 alkyl; the X are the same or different and are selected from fluorine, chlorine or bromine.
  3. 3. The nickel complex according to claim 2, wherein, The R 2 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, hydroxy, mercapto, nitro, trifluoromethoxy, fluoro, chloro, bromo, iodo, cyclopropyl or cyclohexyl.
  4. 4. The nickel complex according to claim 1, wherein, R 1 are the same or different and are selected from hydrogen or C1-C6 alkyl; The R 2 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, hydroxyl, mercapto or nitro; R 3 are the same or different and are selected from C1-C6 alkyl; The X is selected from chlorine or bromine.
  5. 5. The nickel complex according to claim 4, wherein the C1-C6 haloalkoxy is selected from C1-C6 fluoroalkoxy.
  6. 6. The nickel complex according to claim 4, wherein, R 1 are the same or different and are selected from hydrogen or C1-C4 alkyl; The R 2 is selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, fluorine, chlorine, bromine or nitro; r 3 are the same or different and are selected from C2-C4 alkyl; The X is selected from chlorine or bromine.
  7. 7. The nickel complex according to any of claims 1-6, wherein the nickel complex is selected from one of the following:
  8. 8. A process for the preparation of an amine group-containing asymmetric acenaphthylenyl α -diimine nickel complex according to any of claims 1 to 7, wherein said process comprises the steps of: S1, carrying out ketoamine condensation reaction on acenaphthene Shan Tong with a structure shown in a formula (III) and benzidine with a structure shown in a formula (IV) to obtain a ligand compound with a structure shown in a formula (II), and S2, carrying out a complex reaction between the ligand compound and a nickel-containing reagent to obtain the nickel complex; Wherein R 1 、R 2 and R 3 are as defined in any one of claims 1 to 7.
  9. 9. The method of claim 8, wherein the nickel-containing reagent is selected from nickel-containing halides.
  10. 10. The method of claim 9, wherein the nickel-containing reagent is selected from (DME) NiBr 2 、NiCl 2 ·6H 2 O or NiBr 2 .
  11. 11. The process according to any one of claims 8 to 10, wherein, In the step S1, the acenaphthylenemonoketone and benzidine are subjected to a ketoamine condensation reaction in a first organic solvent in the presence of a catalyst; In the step S2, the ligand compound and the nickel-containing reagent undergo a complexation reaction in a second organic solvent.
  12. 12. The production method according to claim 11, wherein the first organic solvent is selected from aromatic hydrocarbon-based organic solvents.
  13. 13. The method of claim 12, wherein the first organic solvent is selected from toluene.
  14. 14. The method of preparation of claim 11, wherein the catalyst is selected from p-toluene sulfonic acid.
  15. 15. The preparation method according to claim 11, wherein the feeding molar ratio of the acenaphthylenemonoketone to the benzidine is 1:1-2.
  16. 16. The preparation method of claim 11, wherein the ketoamine condensation reaction is performed under reflux for 6-24 hours.
  17. 17. The preparation method according to claim 11, wherein the second organic solvent is one or more selected from halogenated alkanes and alcohol organic solvents.
  18. 18. The preparation method according to claim 17, wherein the second organic solvent is one or more selected from dichloromethane and ethanol.
  19. 19. The method according to claim 11, wherein the molar ratio of the ligand compound to the nickel-containing reagent is 1 to 2:1.
  20. 20. The preparation method of claim 11, wherein the reaction temperature of the complexing reaction is 0-35 ℃ and the reaction time is 8-16 h.

Description

Asymmetric acenaphthenyl alpha-diimine nickel complex containing amino and preparation method and application thereof Technical Field The invention relates to the technical field of olefin catalytic polymerization, in particular to an asymmetric acenaphthylene alpha-diimine nickel complex containing an amino group, a preparation method and application thereof, a catalyst composition containing the nickel complex, an olefin polymerization method, and particularly a preparation method of polyethylene. Background The development of polyolefin industry technology greatly benefits from the development of polyolefin catalysts, ihsmarkit data indicate that the polyolefin produced by the catalytic process in 2020 reaches 87% of the total yield of polyolefin, which indicates that the design synthesis of the novel polyolefin catalyst is a key ring in further advancing the development of polyolefin industry technology. Polyethylene catalysts which have been commercialized at present mainly include Phillips catalysts, ziegler-Natta catalysts and metallocene catalysts, and the design and development of these catalysts have greatly promoted the production and application of commercial high-performance polyolefin products. Late transition metal catalysts have received great attention in recent years and are in a state of rapid development due to their explorable mechanism, unique polar monomer tolerance and unusual catalytic properties. With the intensive research of researchers on the relationship between the structure of the late transition metal catalyst and the catalytic performance thereof, more and more excellent ligand frameworks are proposed and widely studied, and mainly comprise alpha-diimine, pyridylimine, phenoxyimine and pyridyldiimine ligands. Among these, the Brookhart type alpha-nickel diimine complex (a, formula 1) has the ability to convert a single ethylene monomer to polyethylene (1.2-300 branches/1000 carbons) with different degrees of branching due to unique chain walking mechanisms (j.am.chem.soc., 1995,117,6414). The group of inventors have been working on the design development of olefin polymerization catalysts and the exploration of catalytic processes, and have conducted a great deal of research and structural optimization work around late transition nickel complexes. For the Brookhart type alpha-nickel diimine complex, modification of the ligand structure mainly involves systematic modification of the ligand backbone and N-aryl substituent type, thereby modulating the catalytic performance (polymerization activity and polymer properties) of the complex. The mode of the ligand framework structure can determine the coordination environment of the metal center, and the regulation of the N-aryl substitution mode in terms of space effect and electronic effect can directly determine the property of the metal center, so that the catalytic activity and the thermal stability of the complex as well as the molecular weight and various microstructure properties of the obtained polyethylene are regulated. For example, when bulky benzhydryl and R groups having different electronic properties are disposed at the ortho-position and para-position of an N-aryl group, respectively, the catalytic activity and structural properties of the polymer can be adjusted by changing the electronic properties of para-substituents of acenaphthylenyl alpha-diimine nickel complex (B, formula 1) while ensuring the thermal stability of the complex (Coord. Chem. Rev.,2017,350,68-83). In general, all nickel complexes have excellent catalytic activity in ethylene polymerization, and nickel complexes containing electron donating groups exhibit better catalytic activity and thermal stability than nickel complexes having electron withdrawing groups, which have a direct effect on polymer properties, particularly molecular weight and branching degree. The above-mentioned complexes B (formula 1) all achieve structural optimization of the N-aryl group on one side and lack discussion of steric hindrance effect of the para-substituent of the N-aryl group. In addition, as a representative type in homogeneous late transition metal catalysts, it is still limited to impart sufficient thermal stability to the complex by structural modification under the premise of ensuring the catalytic activity of the complex. Recently, the inventors have combined a class of amine-terminated substituted nickel picolinamides complexes and have demonstrated that the presence of amine groups is beneficial to improving the catalytic activity of the complexes and the molecular weight of the resulting polymers (ACS Omega,2021,6,30157-30172), and that the presence of amine groups enables high concentrations of covalent loading of homogeneous nickel complex catalysts on certain supports. Although researchers have recognized the need to introduce ortho-sterically bulky N, N-diaryl groups into the catalyst structure to achieve high thermal stability and activity of the c