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CN-122011001-A - Bisindolyl diphenoxy ether complex, preparation method thereof and olefin polymerization method

CN122011001ACN 122011001 ACN122011001 ACN 122011001ACN-122011001-A

Abstract

The invention discloses a bisindolyl diphenoxy ether complex, a preparation method thereof and an olefin polymerization method. The complex of the invention has extremely high catalytic activity, temperature resistance and cycloolefin insertion capability when being used for catalyzing ethylene and/or alpha-olefin to be copolymerized with cycloolefin, and the prepared copolymer has extremely good optical properties, such as good transparency, high refractive index, abbe number and the like, and simultaneously has extremely good mechanical properties, such as high strength and good toughness. Therefore, the complex provided by the invention is very suitable for catalyzing the copolymerization reaction of ethylene and/or alpha-olefin and cycloolefin, and the obtained copolymerization product has good industrial prospect in the processing application of the optical field.

Inventors

  • XU ZHEN
  • LI HAIXI
  • Lv Yingdong

Assignees

  • 万华化学集团股份有限公司

Dates

Publication Date
20260512
Application Date
20241112

Claims (10)

  1. 1. A bisindolyl diphenoxy ether complex with a structure shown in a formula I, Wherein M is selected from titanium, zirconium or hafnium; R 1 ～R 9 is independently selected from hydrogen, substituted or unsubstituted C1-C40 alkyl, C3-C40 cycloalkyl, C6-C40 aryl, heteroatom-containing group or silane group containing 1-3 Si atoms, wherein a plurality of R 1 ～R 9 can be mutually bonded to form cycloalkyl; X is selected from halogen, -NH 2 , substituted or unsubstituted C1-C20 alkyl, -NR ' 2 , C6-C20 aryl or benzyl, wherein R' is selected from C1-C20 alkyl; y is selected from a substituted or unsubstituted C1-C20 hydrocarbon group, a C3-C20 cyclic hydrocarbon group, a heteroatom-containing hydrocarbon group or a silane group containing 1-3 Si atoms.
  2. 2. The bisindolyl diphenoxy ether complex according to claim 1, wherein R 1 ～R 9 is each independently selected from hydrogen, C1-C12 hydrocarbyl, C3-C16 cycloalkyl, C6-C18 aryl or heteroatom-containing group, preferably, R 1 ～R 9 is each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, phenyl, substituted phenyl, methoxy, or R 1 ～R 9 wherein a plurality of may be bonded to each other to form a cycloalkyl group; The X is selected from halogen, C1-C4 alkyl, benzyl or-NR ' 2 , wherein R' is selected from C1-C4 alkyl, preferably, the X is selected from halogen, including F, cl, br, I.
  3. 3. The bisindolyl diphenoxy ether complex according to claim 1 or 2, characterized in that the bisindolyl diphenoxy ether complex is preferably selected from any one of the following complexes cat.1-cat.6: Cat.1 Cat.2 Cat.3 Cat.4 Cat.5 Cat.6
  4. 4. A process for the preparation of the bisindolyl diphenoxy ether complex of any one of claims 1-3, comprising the steps of: s1, synthesizing a phenoxy ether compound IV by a Williamson reaction by using the compounds II and III; S2, dissolving the compound IV in a solvent, adding alkyl lithium at a low temperature for lithiation, adding trimethyl borate for reaction, and then adding an aqueous solution of hydrochloric acid for hydrolysis to obtain the compound V; s3, carrying out a Suzuki coupling reaction on the compound V and a brominated compound VI of indole or a derivative thereof under an alkaline condition through a palladium catalyst to obtain a ligand compound; S4, reacting the ligand compound with alkyl lithium to obtain lithium salt of the ligand compound, then reacting with MX 4 or ether complex thereof, or directly reacting the ligand compound with MR 2 X 2 or ether complex thereof to obtain the bisindolyl diphenoxy ether complex,
  5. 5. The method according to claim 4, wherein X 1 is selected from the group consisting of halogen, preferably Br, wherein in the formula II, IV the alkyl lithium is one or more of C1-C6 alkyl lithium, preferably one or more of methyl lithium, n-butyl lithium, n-hexyl lithium, wherein in the step S2Z is borate-B (OH) 2 , wherein in the formula S4 the alkyl lithium is one or more of C1-C6 alkyl lithium, preferably one or more of methyl lithium, n-butyl lithium, n-hexyl lithium, wherein MX 4 is selected from the group consisting of one or more of TiCl 4 、ZrCl 4 、HfCl 4 , wherein in the step S4R in MR 2 X 2 is selected from the group consisting of C1-C20 alkyl, aryl or benzyl, preferably ZrBn 2 Cl 2 、HfBn 2 Cl 2 .
  6. 6. Use of a bisindolyl diphenoxy ether complex according to any one of claims 1-3 as a procatalyst for olefin polymerization.
  7. 7. Use according to claim 6, characterized in that the olefin polymerization is a copolymerization of ethylene and/or an α -olefin with a cycloolefin; Preferably, the alpha-olefin is C3-C12 alpha-olefin, preferably one or more selected from 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and the cycloolefin is C6-C21 cycloolefin, preferably one or more selected from cyclohexene, norbornene and tetracyclododecene.
  8. 8. An olefin polymerization method, comprising the following steps of carrying out polymerization reaction on ethylene and/or alpha-olefin and cycloolefin in the presence of a main catalyst and a cocatalyst to form an olefin copolymer, wherein the main catalyst is the bisindolyl diphenoxy ether complex according to any one of claims 1-3; Preferably, the alpha-olefin is C3-C12 alpha-olefin, preferably one or more selected from 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and the cycloolefin is C6-C21 cycloolefin, preferably one or more selected from cyclohexene, norbornene and tetracyclododecene.
  9. 9. The process for the polymerization of olefins according to claim 8, wherein the molar ratio of the procatalyst to the cocatalyst is 1:1 to 5000, preferably 1:1 to 2000, and/or, The cocatalyst is selected from one or more of alkylaluminum, alkylaluminum chloride, aluminoxane and boron-containing auxiliary agent, preferably, the alkylaluminum is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, the alkylaluminum chloride is selected from one or more of diethylaluminum chloride, ethylaluminum dichloride and diethylaluminum sesquichloride, the aluminoxane is selected from one or more of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane, and the boron-containing auxiliary agent is selected from one or two of tris (pentafluorophenyl) borane and triphenylcarbon tetra (pentafluorophenyl) borate; More preferably, the cocatalyst is selected from methylaluminoxane or a combination of methylaluminoxane and triisobutylaluminum in a molar ratio of 1-50:1, preferably 2-30:1.
  10. 10. The method for polymerizing olefins according to claim 8 or 9, wherein the reaction temperature of the polymerization reaction is 50-200 ℃, preferably 90-180 ℃, and/or the reaction pressure of the polymerization reaction is 0.01-10 mpa, preferably 0.1-3 mpa, and/or the reaction time of the polymerization reaction is 0.1-1000 min, preferably 1-100 min.

Description

Bisindolyl diphenoxy ether complex, preparation method thereof and olefin polymerization method Technical Field The invention relates to the field of olefin polymerization, in particular to a bisindolyl diphenoxy ether complex, a preparation method and application thereof, and also relates to an olefin polymerization method. Background COC is an amorphous engineering plastic obtained by addition copolymerization of ethylene and/or alpha-olefin and cycloolefin under the action of a coordination polymerization catalyst. Currently, the main COC in the market is Japanese Bao Liu plastics and TOPAS and APEL series commercial products developed by Mitsui chemistry. Compared with conventional optical materials such as polymethyl methacrylate (PMMA), polycarbonate (PC), and the like, COC has comparable light transmittance, refractive index, birefringence, and the like, but the latter has excellent characteristics of low hygroscopicity, low specific gravity, and the like. In order to obtain temperature resistance comparable to or even better than PMMA and PC, it is necessary to increase the insertion rate of cyclic olefin in COC, but the brittleness of COC is increased while the temperature resistance is improved, which is disadvantageous for processing, so that development of a novel catalyst and catalytic system is required. COC catalysts mainly include Ziegler-Natta catalysts, metallocene and non-metallocene catalysts, and the like. The Ziegler-Natta catalyst is a multi-active-center catalyst, can obtain polymers with wide molecular weight distribution, but has two polymerization modes of addition copolymerization and ring-opening metathesis polymerization when catalyzing COC polymerization, and has low catalytic activity, and the metallocene catalyst is a single-active-center catalyst, and has good catalytic activity when catalyzing polymerization reaction, but the product is generally narrower in relative molecular weight distribution, and the processability of polymer resin is reduced. To solve this problem, it is possible to achieve this by adjusting the molecular weight distribution, for example by preparing a bimodal polyolefin. For example, chinese patents CN114736321A, CN114853947a and CN105524217a respectively provide a method for preparing polymers of different molecular weight distribution. As described above, two or more catalysts are usually needed for preparing the bimodal or multimodal polyolefin, the catalyst is realized by a special process, the non-metallocene catalyst is an olefin polymerization catalyst with prospect and has more catalyst framework design and modification space, the appearance of the catalyst can possibly make up for the defects of the existing catalytic system in preparing the polymer structure diversity, such as copolymerization of catalytic ethylene with alpha-olefin, diolefin, cycloolefin and even polar monomer, but the existing non-metallocene catalyst has the problems of low catalytic activity, low insertion rate of cycloolefin monomer (i.e. low glass transition temperature T g of COC), difficult regulation and control of polymer structure, molecular weight (M w) and distribution (PDI) and the like. Disclosure of Invention In order to develop a wider variety of olefin coordination polymerization catalysts and improve the catalytic performance thereof, an object of the present invention is to provide a bisindolyl diphenoxy ether complex which can be used as a main catalyst for catalyzing the polymerization of ethylene and/or alpha-olefin and cycloolefin to obtain COC having excellent optical properties of mechanical strength and toughness, and which has extremely high catalytic activity, temperature resistance and cycloolefin insertion capability. The invention also aims to provide a preparation method of the bisindolyl diphenoxy ether complex. It is a further object of the present invention to provide a process for the polymerization of olefins. In a first aspect, the present invention provides a bisindolyl diphenoxy ether complex of the structure shown in formula I, Wherein M is selected from titanium, zirconium or hafnium; R 1～R9 is independently selected from hydrogen, substituted or unsubstituted C1-C40 alkyl, C3-C40 cycloalkyl, C6-C40 aryl, heteroatom-containing group or silane group containing 1-3 Si atoms, wherein a plurality of R 1～R9 can be mutually bonded to form cycloalkyl; X is selected from halogen, -NH 2, substituted or unsubstituted C1-C20 alkyl, -NR '2, C6-C20 aryl or benzyl, wherein R' is selected from C1-C20 alkyl; y is selected from a substituted or unsubstituted C1-C20 hydrocarbon group, a C3-C20 cyclic hydrocarbon group, a hydrocarbon group containing hetero atoms (such as oxygen) or a silane group containing 1-3 Si atoms; when the above groups are substituted groups, the number of substituents is 1,2, 3,4 or 5, each independently selected from halogen, C1-C10 alkyl, C1-C10 alkoxy, C3-C10 cycloalkyl, C6-C20 aryl or benzyl. Preferably, in the bisindol