Application of para-position phenyl-containing alpha-nickel diimine (II) complex to catalysis of 3-heptene for chain walking polymerization

A technology of diimine nickel and complexes, which is applied in the field of olefin polymerization, can solve the problems that 3-olefin polymerization monomers have not been successfully reported, achieve fast chain walking polymerization behavior, improve catalytic ability, and weaken the effect of transfer rate

Active Publication Date: 2019-06-14
ANHUI UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, 3-alkenes have not been succes

Method used

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  • Application of para-position phenyl-containing alpha-nickel diimine (II) complex to catalysis of 3-heptene for chain walking polymerization
  • Application of para-position phenyl-containing alpha-nickel diimine (II) complex to catalysis of 3-heptene for chain walking polymerization
  • Application of para-position phenyl-containing alpha-nickel diimine (II) complex to catalysis of 3-heptene for chain walking polymerization

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preparation example Construction

[0050] Preparation of cocatalyst dMMAO:

[0051] Modified methylaluminoxane (MMAO, 20.0 mL, 41.8 mmol) in toluene was vacuum dried at 60°C for 3 hours. The resulting colorless solid was redissolved in 20 mL of toluene. The cycle of drying and redissolution was repeated seven times to yield 3.32 g of a colorless solid. Titration of an aliquot of the resulting solid showed an aluminum content of 11.1 mmol / g (88% aluminum recovered). The prepared MMAO was used as stock solution in toluene (2.0M).

[0052] (3) Application of para-phenyl-containing α-diimine nickel (II) complexes in the chain walking polymerization of 3-heptene.

[0053] In the field of olefin polymerization, the preparation of new polyolefins has always been a very interesting challenge. Common olefin monomers that can be polymerized are very limited, generally including ethylene, propylene, long-chain α-olefins, styrene derivatives and different types of polar monomers. Olefins with alkyl substituent groups ...

Embodiment 1

[0057] (1) 3-heptene polymerization:

[0058] in N 2 Under atmosphere, toluene was used as the polymerization solvent, and the polymerization was carried out in a 10 mL dry glass reaction tube equipped with a magnetic stirrer. First weigh 0.61g of trans and cis 3-heptene mixture (trans / cis=0.82 / 0.18) with a reaction tube, then inject 5mL of toluene and cocatalyst dMMAO (1.0mL, 2.0M, n(Al) / n (Ni)=500) was sequentially added into the reaction tube, kept at the set polymerization temperature, and the mixture was fully stirred for 10 minutes. Then, the toluene solution containing 10 μmol nickel catalyst was added into the reaction tube with a syringe to start polymerization, and the reaction time was recorded. The polymerization was terminated with 50 mL of 3% HCl-MeOH solution. The resulting polymer was thoroughly washed with methanol, and vacuum-dried at 60°C for 3 hours.

[0059] (2) Evaluation of polymerization performance and analysis of polymer structure: weighing the ob...

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Abstract

The invention discloses application of a para-position phenyl-containing alpha-nickel diimine (II) complex to catalysis of 3-heptene for chain walking polymerization. The para-position phenyl-containing alpha-nickel diimine (II) complex is used as a chain walking catalyst for catalyzing the monomer 3-heptane for a polymerization reaction; through the conjugate effect of phenyl, the chain walking speed of nonterminal olefin is accelerated; and under the activation of cocatalyst dried and modified methylaluminoxane (dMMAO), the 3-heptene is catalyzed for a chain walking polymerization reaction through the chain walking catalyst, wherein the structural general formula of the para-position phenyl-containing alpha-nickel diimine (II) complex and a relevant polymerization process are shown in the description. A catalysis system involved in the invention realizes the polymerization of the 3-heptane through chain walking behaviors; and an amorphous polymer with a stable branching degree (about139 branch chains/1000 carbon; and Tg is about minus 68 DEG C) is generated. It is shown, by the NMR (Nuclear magnetic resonance) analysis of the polymer, that obtained poly(3-heptene) has ethyl, propyl and butyl branch chains and a small number of methylene sequences with long chains isomerized by monomers.

Description

technical field [0001] The invention relates to a preparation method of a novel polyolefin, in particular to the application of a para-phenyl-containing α-diimine nickel (II) complex in catalytic 3-heptene chain walking polymerization, belonging to the technical field of olefin polymerization . It also involves the characterization of new polyolefins and the study of polymerization mechanism. Background technique [0002] In the field of olefin polymerization, late-transition metal catalysts are a new generation of metal-organic catalysts with high activity, especially Brookhart-type diimide nickel(Ⅱ) and palladium(Ⅱ) catalysts have a unique chain walking mechanism (Guo, L.H.; Dai, S.Y. ; Sui, X.L.; Chen, C.L. Palladium and nickel catalyzed chain walking olefin polymerization and copolymerization, ACS Catal. 2016, 6, 428-441). By changing the type of olefin monomer, catalyst structure and polymerization conditions can strongly affect the topology of the resulting polymer, ...

Claims

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Application Information

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IPC IPC(8): C08F10/14C08F4/70
Inventor 王福周陈昶乐徐国永张严朱文彬邢旭
Owner ANHUI UNIVERSITY
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