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Fluorine-containing pyridine imine ligand, transition metal complex thereof and application of ligand to polyisoprene synthesis

A technology of polyisoprene and pyridinium, which is applied in the direction of compounds containing Group 8/9/10/18 elements of the periodic table, iron organic compounds, cobalt organic compounds, etc., can solve the problems of low activity, poor selectivity, Problems such as low molecular weight of synthetic polymers

Inactive Publication Date: 2018-10-16
QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] In order to solve the above-mentioned catalyst structure or the problems of unclear active center, low activity, poor selectivity, low molecular weight of synthetic polymers, etc., the present invention provides a new high-efficiency catalyst, pyridine imine transition metal complex as the main catalyst (iminobenzene The ring substituent is connected with a strong electron-withdrawing group such as monofluorine, polyfluorine or trifluoromethyl groups), and catalyzes the polymerization of isoprene under the activation of a commercial cocatalyst methylaluminoxane (MAO). The present invention The transition metal complex catalyst system provided has extremely high activity, and a polymer with a high relative molecular weight (number average molecular weight of 10,000-5,000,000) and a controllable microstructure can be obtained. The microstructure of the polymer can be adjusted by the main catalyst. The modification of the body is regulated, and the selectivity of this type of system is not sensitive to the reaction temperature

Method used

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  • Fluorine-containing pyridine imine ligand, transition metal complex thereof and application of ligand to polyisoprene synthesis
  • Fluorine-containing pyridine imine ligand, transition metal complex thereof and application of ligand to polyisoprene synthesis
  • Fluorine-containing pyridine imine ligand, transition metal complex thereof and application of ligand to polyisoprene synthesis

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Experimental program
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Embodiment 1

[0060] Embodiment 1 Preparation of fluorine-containing pyridine imine ligands

[0061] All ligands described here are obtained by condensation reactions of substituted aldehydes or ketones with primary amines. Complex amines need to be synthesized in advance. Many commercially available amines and substituted aldehydes and ketones can be subjected to one-step synthesis of ligands (imine condensation).

[0062] (1) Synthesis of pyridine imine ligand compound L1

[0063]

[0064]Add 2-difluoroaniline (1.03g, 9.24mmol, 1.00eq.) to a 25mL two-necked flask, replace it with Ar three times, then add pyridine-2-carboxaldehyde (1.00g, 9.34mmol, 1.01eq.) Dichloromethane solution 10mL, formic acid (0.1mL), reflux reaction at 50°C, TLC tracking detection until 2-difluoroaniline raw material disappeared. The solvent was spin-dried, and recrystallized five times with 40 mL of n-hexane to obtain 1.21 g of a white solid with a yield of 64%.

[0065] (2) Synthesis of pyridine imine liga...

Embodiment 2

[0077] The synthesis of embodiment 2 fluorine-containing pyridinium transition metal complexes

[0078] (1) Synthesis of pyridinium iron complex 1a

[0079]

[0080] In the glove box, add anhydrous FeCl to a 10 mL Schlenk tube 2 (95.0mg, 0.75mmol, 1eq.), the pyridine imine ligand compound L1 (150.0mg, 0.75mmol, 1eq.) prepared in Example 1, and then added 5mL of anhydrous DCM, and stirred at room temperature for 2 days. After the reaction is over, dissolve the precipitated solids with 10mL×2 anhydrous DCM and filter them separately to obtain a purple-black liquid, drain the remaining DCM; then wash twice with 20mL of anhydrous n-hexane, remove the supernatant and The residue was dried to give a purple solid in 71% yield.

[0081] (2) Synthesis of pyridinium iron complex 2a

[0082]

[0083] In the glove box, add anhydrous FeCl to a 10 mL Schlenk tube 2 (95.0mg, 0.75mmol, 1eq.), the pyridine imine ligand compound L2 (150.0mg, 0.75mmol, 1eq.) prepared in Example 1, and ...

Embodiment 3

[0111] Take a 25mL Schlenk bottle, add cocatalyst MAO (4mmol, 500eq.), toluene 5mL successively therein, complex 1a (8μmol, 1eq.) is dissolved in 1mL dichloromethane, this mixture is stirred at room temperature for 2min, then Isoprene monomer (20mmol, 2500eq.) was added, and after polymerization at 25°C for 2h, 1M methanolic hydrochloric acid solution was added to terminate the reaction. Pour the viscous polymer solution into 50 mL of ethanol and allow the polymer to settle out. The polymer after the supernatant was discarded was washed with distilled water and ethanol in turn, and the obtained polymer was dried in a vacuum oven at 40° C. to a constant weight to obtain the product with a yield of 78%. The reaction selectivity was 59% cis-1,4 and 41% 3,4-polyisoprene.

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Abstract

The invention discloses a fluorine-containing pyridine imine ligand, a transition metal complex thereof and an application of the ligand to polyisoprene synthesis, and belongs to the field of new compounds and metal organic synthesis. The complex is used for polyisoprene synthesis including the steps: dissolving cocatalysts, a pyridine imine transition metal complex and an isoprene monomer in a solvent; performing stirring reaction for 2-4 hours under the condition of the temperature of 25 DEG C; performing separation and purification to obtain a polyisoprene product. The polyisoprene synthesis method is efficient and environmentally friendly, has quite high activity and selectivity, and provides guidance for preparation of novel iron and cobalt catalysts and catalytic isoprene polymerization reaction mechanisms.

Description

technical field [0001] The present invention relates to the field of novel compounds and polymer synthesis. Background technique [0002] The design and development of olefin polymerization catalysts is the key to the polyolefin industry, and the design and development of a new generation of high-efficiency olefin polymerization catalysts is of great significance to the development of my country's polyolefin industry. Conjugated diolefins (butadiene, isoprene, 1,3-pentadiene, etc.) are another large class of olefin monomers different from α-olefins and styrene, due to the presence of two conjugated bis Bonds, they can be polymerized by 1,4-addition to obtain cis-1,4- or trans-1,4-structured polymers, and can be 1,2- or 3,4-addition 1,2- or 3,4-structured polymers are obtained. Isoprene rubber (IR) is one of the most important polyconjugated dienes. It is a polymer material polymerized from isoprene monomers under catalyst conditions. 4) Same as natural rubber, commonly kn...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/53C07F15/03C07F15/06C08F136/08C08F4/70
CPCC07D213/53C07F15/03C07F15/065C08F136/08C08F4/7006
Inventor 王庆刚王晓武赵梦梦王亮咸漠张献辉朱广乾荆楚杨
Owner QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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