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CN-122011002-A - Bicarbazolyl diphenoxy ether complex, preparation method thereof and olefin polymerization method

CN122011002ACN 122011002 ACN122011002 ACN 122011002ACN-122011002-A

Abstract

The invention discloses a biscarbazolyl diphenoxy ether complex, a preparation method thereof and an olefin polymerization method. The bis-carbazolyl diphenoxy ether complex is used as a main catalyst for catalyzing ternary polymerization of ethylene, alpha-olefin and cycloolefin, and the complex provided by the invention has good copolymerization insertion capability on the alpha-olefin and cycloolefin, and the prepared copolymerization product has uniform structure distribution, easy regulation and control of molecular chain entanglement and excellent mechanical properties such as high strength, good toughness and excellent tensile property. The ternary cycloolefin copolymer provided by the invention has good industrial prospect in the fields of optics, medical treatment and the like.

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 biscarbazolyl diphenoxy ether complex with a structure shown in a formula I, Wherein M is selected from titanium, zirconium or hafnium; R 1 ～R 11 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 11 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 biscarbazolyl diphenoxy ether complex according to claim 1, wherein in the biscarbazolyl diphenoxy ether complex, each R 1 ～R 11 is independently selected from hydrogen, C1-C12 hydrocarbyl, C3-C16 cycloalkyl or C6-C18 aryl, preferably, each R 1 ～R 11 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, substituted phenyl, or a plurality of R 1 ～R 11 groups which may be bonded to each other to form a cyclic hydrocarbyl 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 dicarbazolyl diphenoxy ether complex according to claim 1 or 2, wherein the dicarbazolyl diphenoxy ether complex is 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 biscarbazolyl diphenoxy ether complex according to any 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 bromo-compound VI of carbazole or a derivative thereof under an alkaline condition through catalysis of 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 biscarbazolyl 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 a borate, preferably from-B (OH) 2 , wherein in the formula V 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 S4 MX 4 is selected from one or more of TiCl 4 、ZrCl 4 、HfCl 4 , wherein R in the 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 biscarbazolyl diphenoxy ether complex according to any of claims 1-3 as a primary catalyst for olefin polymerization.
  7. 7. The use according to claim 6, characterized in that the olefin polymerization is a copolymerization of ethylene, an α -olefin and a cyclic olefin; 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 comprises the following steps of carrying out polymerization reaction on ethylene, 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 biscarbazolyl 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 the group consisting of methylaluminoxane or triphenylcarbon tetrakis (pentafluorophenyl) borate in combination with triisobutylaluminum in a molar ratio of 1:1 to 500, preferably 1:10 to 100.
  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

Bicarbazolyl 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 biscarbazolyl diphenoxy ether complex, a preparation method and application thereof, and also relates to an olefin polymerization method. Background Commercial COC is an amorphous engineering plastic obtained by addition copolymerization of ethylene 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 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 or introduce bulky comonomer, but the brittleness of COC is increased while the temperature resistance is improved, which is disadvantageous for processing, so that development of novel cyclic olefin copolymer is required. 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 generally required for preparing bimodal or multimodal distribution polyolefins, and are achieved by special processes, another strategy is to introduce alpha-olefins as third monomers into the copolymer, improving the polymer physical properties by regulating the polymer chain structure and chain entanglement (CN 116262796A, macromol. Chem. Phys.,2007,208 (13): 1341-1348, macromolecules,2011,44 (4): 795-804.). The non-metallocene catalyst is an olefin polymerization catalyst with prospect and has more framework design and modification space, the appearance of the catalyst can possibly make up for the defects of the existing catalytic system in the aspect of preparing Polymer structure diversity, such as copolymerization of catalytic ethylene and alpha-olefin, diolefin and cycloolefin even with polar monomers, but the existing non-metallocene catalyst has the problems of low catalytic activity, low alpha-olefin and/or cycloolefin insertion rate, difficult regulation of Polymer structure and the like (Polymer, 2010,51 (16): 3636-3643.). Disclosure of Invention In order to develop a plurality of kinds of COC with excellent optical and mechanical properties, an object of the invention is to provide a biscarbazolyl diphenoxy ether complex, which is used as a main catalyst for catalyzing polymerization of ethylene, alpha-olefin and cycloolefin to obtain the COC with excellent mechanical strength and toughness and optical properties, and the complex of the invention has good high temperature stability. The invention also aims to provide a preparation method of the biscarbazolyl diphenoxy ether complex. It is a further object of the present invention to provide a process for the polymerization of olefins. The first aspect of the invention provides a biscarbazolyl diphenoxy ether complex with a structure shown in a formula I, Wherein M is selected from titanium, zirconium or hafnium; R 1～R11 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～R11 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 biscarbazolyl diphenoxy ether complex provided by the invention, R 1～R11 is independently selected from hydrogen, C1-C12 alkyl, C3-C16 cycloalkyl or C6-C18 aryl. In some preferred embodiments, each of the R 1～R11 groups is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, or (substituted) phenyl, etc., or a plurality of R 1～R11 groups may be bonded to each other to form a cyclic hydrocarbon group. Preferably, in the biscarbazolyl diphenoxy ether complex provided by the inventio