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Norbornene, hexafluoropropylene and 2,5-dihydro-2,5-dimethoxy furan ternary polymerization method

A dimethoxyfuran terpolymer and dimethoxyfuran ternary technology, applied in the field of norbornene-based copolymers, can solve the problems of harsh reaction conditions and insufficient heat resistance of copolymers, and achieve dangerous Small size, simple and effective polymerization method, and improved heat resistance

Inactive Publication Date: 2018-08-24
NINGBO UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Notification number is that CN106632852A discloses " norbornene class, vinyl acetate and perfluoromethyl vinyl ether three-way copolymerization catalyst and three-way copolymerization method ", and notification number is that CN106832123A discloses " norbornene class, vinyl ether and Perfluoromethyl vinyl ether ternary copolymerization catalyst and ternary copolymerization method", the announcement number is CN106832119A discloses "norbornene, tetrafluoroethylene and perfluoromethyl vinyl ether ternary copolymerization catalyst and ternary copolymerization method ", the notification number is CN107141377A discloses "norbornene, acrylonitrile and perfluoromethyl vinyl ether ternary copolymerization catalyst and ternary copolymerization method", the copolymers obtained by these technical solutions still have insufficient heat resistance Problem; the announcement number is CN107189013A disclosed "norbornene, octafluorocyclopentene and perfluoromethyl vinyl ether ternary copolymerization catalyst and ternary copolymerization method", the announcement number is CN107189014A disclosed "norbornene, Styrene and Perfluoromethyl Vinyl Ether Ternary Copolymerization Catalyst", the announcement number is CN106866884A disclosed "Norbornene, Vinyl Cyclohexane and Perfluoromethyl Vinyl Ether Ternary Copolymerization Catalyst and Ternary Copolymerization Method "The preparation of copolymers by these technical schemes is mainly obtained by catalytic polymerization of complex catalysts. The catalyst preparation process requires anhydrous and oxygen-free, the polymerization reaction requires anhydrous and oxygen-free, and the reaction conditions are harsh.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Add 0.01 mole of bicyclo[2,2,1]hept-2-ene, 0.01 mole of hexafluoropropene and 0.01 mole of 2,5-dihydro-2,5-dimethoxyfuran into the autoclave, add 20ml Benzene dissolves. The initiator was prepared according to the molar ratio of di-tert-butyl peroxide and tert-butyl peroxyacetate of 0.1:1, and the initiator dose was bicyclo[2,2,1]hept-2-ene, hexafluoropropene and 2,5- 0.1% of the total weight of the three dihydro-2,5-dimethoxyfuran, the initiator is added to the above-mentioned autoclave. React at a constant temperature of 80°C and a pressure of 1 MPa for 3 hours. The product was poured into ethanol solution to precipitate the copolymer, and the precipitate was washed with ethanol; after vacuum drying at 50°C, bicyclo[2,2,1]hept-2-ene, hexafluoropropene and 2,5-dicyclo[2,2,1]hept-2-ene were obtained. Hydrogen-2,5-dimethoxyfuran terpolymer. The calculated reaction yield was 56.1%.

[0015] The copolymer was analyzed by differential scanning calorimetry (DSC), and the gl...

Embodiment 2

[0019] Add 0.01 mole of 1-methylbicyclo[2,2,1]hept-2-ene, 0.01 mole of hexafluoropropene and 0.01 mole of 2,5-dihydro-2,5-dimethoxyfuran to the autoclave Add 20ml of toluene to dissolve. According to the molar ratio of di-tert-butyl peroxide and tert-butyl peroxyacetate is 0.3:1, the initiator dose is 1-methylbicyclo[2,2,1]hept-2-ene, hexafluoropropene and 2,5 -0.3% of the total weight of dihydro-2,5-dimethoxyfuran, adding the above initiator into the above autoclave, and reacting at a constant temperature of 90° C. and a pressure of 2 MPa for 4 hours. The product was poured into ethanol solution to precipitate the copolymer. The precipitate was washed with ethanol and dried under vacuum at 50°C to obtain 1-methylbicyclo[2,2,1]hept-2-ene, hexafluoropropylene and 2, 5-dihydro-2,5-dimethoxyfuran terpolymer. The calculated reaction yield was 59.8%.

Embodiment 3

[0021] Add 0.01 mole of 5-methylbicyclo[2,2,1]hept-2-ene, 0.01 mole of hexafluoropropene and 0.01 mole of 2,5-dihydro-2,5-dimethoxyfuran into the autoclave Add 20ml tetrahydrofuran to dissolve. According to the molar ratio of di-tert-butyl peroxide and tert-butyl peroxyacetate is 0.5:1, the initiator dose is 5-methylbicyclo[2,2,1]hept-2-ene, hexafluoropropene and 2,5 -0.5% of the total weight of dihydro-2,5-dimethoxyfuran, and the initiator is added to the above-mentioned autoclave. React at a constant temperature of 100°C and a pressure of 3MPa for 2 hours. The product was poured into ethanol solution to precipitate the copolymer. The precipitate was washed with ethanol and dried under vacuum at 50°C to obtain 5-methylbicyclo[2,2,1]hept-2-ene, hexafluoropropene and 2, 5-dihydro-2,5-dimethoxyfuran terpolymer. The calculated reaction yield was 74.6%.

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Abstract

The invention relates to a norbornene, hexafluoropropylene and 2,5-dihydro-2,5-dimethoxy furan ternary polymerization method. The norbornene, hexafluoropropylene and 2,5-dihydro-2,5-dimethoxy furan ternary polymerization method is characterized by comprising the following steps: adding polymerization monomer norbornene, hexafluoropropylene and 2,5-dihydro-2,5-dimethoxy furan into a high-pressure kettle in a molar ratio being 1 to 1 to 1, and adding a solvent to dissolve; adding an initiator, reacting for 1-4 hours at a temperature being 0-150 DEG C under pressure being 1-3 MPa, wherein the initiator is prepared from di-tert-butyl peroxide and tert-butyl peroxyacetate in a molar ratio being (0.1:1) to (1:0.1), and dose of the initiator accounts for 0.1%-1.5% of the total weight of the polymerization monomer; pouring the product obtained by reaction into an alcohol containing solution, washing obtained precipitates with alcohol, and vacuum-drying to obtain the norbornene, hexafluoropropylene and 2,5-dihydro-2,5-dimethoxy furan ternary polymer.

Description

Technical field [0001] The invention relates to the field of norbornene copolymers, in particular to a ternary copolymerization method of norbornenes, hexafluoropropylene and 2,5-dihydro-2,5-dimethoxyfuran. Background technique [0002] The Chinese patent No. ZL201610136476.7 "Norbornene, hexafluoropropylene and 1-hexene ternary copolymerization catalyst and ternary copolymerization method" and the Chinese patent No. ZL201610151343.7 "Norbornene, six Fluoropropene and acrylonitrile ternary copolymerization catalyst and ternary copolymerization method", which uses the iron-titanium complex catalyst composed of iron pentamethylene, titanium tetrachloride and ligands for catalytic polymerization and bis(pentamethylcyclopentane Dienyl) cerium chloride, titanium tetrachloride and ligand cerium-titanium complex catalyst for catalytic polymerization, the obtained terpolymer contains perfluoro monomer chain link, has good light transmittance, but in There are still shortcomings in heat ...

Claims

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Application Information

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IPC IPC(8): C08F210/14C08F214/28C08F234/02C08F2/00
CPCC08F210/14C08F2/00C08F214/28C08F234/02
Inventor 胡敏杰周国权李正辉王江波张亚静陈斌高浩其胡爱珠房江华
Owner NINGBO UNIVERSITY OF TECHNOLOGY
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