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Process for preparation of polynorbornene

A polynorbornene and addition polymerization technology is applied in the field of preparing polynorbornene by a three-coordination nickel olefin polymerization catalyst, which can solve the problems of insolubility in organic solvents, low catalytic activity, difficult processing, etc., and achieve good dissolution properties, unique physicochemical properties, wide application range, high molecular weight effect

Inactive Publication Date: 2007-10-24
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, there are few studies on cationic or free radical polymerization, and the resulting product is a norbornene oligomer connected at the 2 and 7 positions with low relative molecular weight
In 1963, Sartori et al. first reported the addition polymerization of norbornene, but there were shortcomings such as low catalytic activity and low molecular weight.
After Kaminsky et al. discovered the efficient catalytic system of metallocene / methylaluminoxane, great progress was made in the addition polymerization of norbornene by using this catalytic system. The obtained polynorbornene had good thermal stability, but the product was insoluble in organic solvent, difficult to process
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  • Process for preparation of polynorbornene
  • Process for preparation of polynorbornene
  • Process for preparation of polynorbornene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Ligand o-C 6 h 4 [NH(C 6 h 3 -i-Pr 2 -2,6)] (CH=NC 6 h 3 -i-Pr 2 -2,6)(L 1 ) preparation:

[0026] (a)o-C 6 h 4 F(CH=NC 6 h 3 -i-Pr 2 -2,6)

[0027] Take 5.0mL (47.1mmol) of o-fluorobenzaldehyde and 9.77mL (51.8mmol) of 2,6-diisopropylaniline in a 100mL single-necked flask, then add 20mL of n-hexane and 2.0g of anhydrous magnesium sulfate. The resulting mixed solution was stirred at room temperature for 2 hours, filtered, and the filtrate was sucked dry to obtain a yellow solid powder. The solid powder was recrystallized with n-hexane to obtain yellow crystals, and some other products could be obtained by concentrating the mother liquor, totaling 9.88g, with a yield of about 74%.

[0028] (b)o-C 6 h 4 [NH(C 6 h 3 -i-Pr 2 -2,6)] (CH=NC 6 h 3 -i-Pr 2 -2,6)

[0029] Dissolve 7.65mL (40.6mmol) of 2,6-diisopropylaniline in 40mL of tetrahydrofuran, and slowly add 17.5mL (2.3M, 40.2mmol) of n-BuLi’s n-hexane solution dropwise at -78°C, and th...

Embodiment 2

[0030] Example 2; Ligand o-C 6 h 4 [NH(C 6 h 3 -i-Pr 2-2,6)] (CH=NC 6 h 3 -Me 2 -2,6)(L 2 ) preparation:

[0031] (a)o-C 6 h 4 F(CH=NC 6 h 3 -Me 2 -2,6)

[0032] Take 5.0 mL (47.1 mmol) of o-fluorobenzaldehyde and 6.0 mL (48.5 mmol) of 2,6-dimethylaniline in a 100 mL single-necked flask, then add 20 mL of n-hexane and 2.0 g of anhydrous magnesium sulfate. The resulting mixed solution was stirred at room temperature for 2 hours, filtered, and the filtrate was sucked dry to obtain a yellow solid powder. The solid powder was recrystallized with n-hexane to obtain yellow crystals, and some other products could be obtained by concentrating the mother liquor, totaling 10.6 g, with a yield of about 99%.

[0033] (b)o-C 6 h 4 [NH(C 6 h 3 -i-Pr 2 -2,6)] (CH=NC 6 h 3 -Me 2 -2,6)

[0034] Dissolve 4.0mL (32.4mmol) of 2,6-dimethylaniline in 40mL of tetrahydrofuran, and slowly add 12.96mL (2.5M, 32.4mmol) of n-BuLi in n-hexane solution dropwise at -78°C. After the a...

Embodiment 3

[0035] Embodiment 3: Ligand (2,6-i-Pr 2 (C 6 h 3 )N=C(CH 3 )) 2 CH 2 (L 3 ) preparation

[0036] Get 4.56mL2, 4-pentanedione (44.4mmol) and 19.49mL 2,6-diisopropylaniline (103mmol) are dissolved in the middle of 200mL ethanol, and this solution is placed in a 250mL single-necked flask, then to Add 5.0 mL of concentrated hydrochloric acid (12 mol / L) to the solution. After the resulting mixed solution was heated to reflux for 3 days, the solvent was removed to obtain a brownish-yellow solid residue. The solid residue was treated with 300 mL of dichloromethane and 200 mL of saturated sodium carbonate solution, and after stirring for 20 minutes, the organic layer was separated and dried over anhydrous magnesium sulfate. After filtration, the organic solvent was removed from the filtrate, and the resulting solid was recrystallized from methanol to obtain 13.6 g of a large amount of white crystalline solid product, with a yield of 73%.

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Abstract

This invention is the addition and aggregation method of norbornene with the catalysis N_N_dual-dentate ligand nickel-olefin in one valent state. The catalysis consists of two components A and B. A's component expression is [L-MR]. L means the N_N_dual-dentate ligand atom which could coordinate with metal. R means PPh3. M means metal Ni. B's component expression is MAO or MMAO. This invention is advantageous in high catalytic activity, simplied manipulation of the catalysis and stability. Meanwhile, we obtain our product norbornene with the high-macromolecule, high-glass transition temperature and high solubility.

Description

technical field [0001] The invention relates to a method for preparing polynorbornene by using a three-coordinated nickel olefin polymerization catalyst formed by a nitrogen-nitrogen bidentate ligand and a late transition metal nickel. Background technique [0002] The development and research of polyolefin synthesis process is one of the hot research topics in polymer chemistry and plastic industry. Polyolefin is the pillar industry of modern polymer material industry, and olefin polymerization catalyst is the core and driving force of the development of polyolefin industry. Because organometallic olefin polymerization catalysts can not only efficiently catalyze olefin polymerization under mild conditions, but also can tailor the microstructure of polymers, it is possible to design new functional polyolefin materials and improve the performance of existing polymers at the molecular level. Research in the field has always been one of the frontiers and hotspots of contempora...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F132/08C08F4/80
Inventor 金国新王海玉
Owner FUDAN UNIV