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Fluorosulfonyl group-containing monomer and its polymer, and sulfonic acid group-containing polymer

a technology of fluorosulfonyl group and polymer, which is applied in the field of fluorosulfonyl group-containing monomer and its polymer, and sulfonyl group-containing polymer, can solve the problems of low molecular weight of copolymer, insufficient mechanical strength and durability of low molecular weight, and inapplicability, etc., to achieve high molecular weight, high polymerization reactivity, and easy to

Inactive Publication Date: 2009-02-19
ASAHI GLASS CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0013]The present invention has an object to provide an electrolyte material for polymer electrolyte fuel cells, which is an electrolyte material having a high ion-exchange capacity and low resistance, and which has a higher softening point than a commonly used electrolyte material and is excellent in durability. Further, the present invention has an object to provide a new monomer and a polymer to prepare such a material.
[0016]The monomer of the present invention is a perfluoromonomer having a perfluoro(2-methylene-1,3-dioxolane) structure having a high polymerization reactivity and two fluorosulfonyl groups, whereby it is easy to obtain a copolymer having a high molecular weight by copolymerizing it with a copolymerizable monomer such as tetrafluoroethylene, and it is easy to obtain a sulfonic acid polymer having high mechanical strength and durability. Further, since the monomer of the present is invention has two fluorosulfonyl groups, it is possible to obtain a sulfonic acid polymer having a high ion-exchange capacity even if its copolymerization ratio is low, as compared with a monomer having one fluorosulfonyl group.

Problems solved by technology

However, if the proportion of the fluorosulfonyl group-containing monomer to be used for copolymerization, is increased for a purpose of increasing the ion-exchange capacity of the sulfonic acid polymer, there has been a problem such that the molecular weight of the copolymer becomes low.
A membrane formed by the copolymer having low molecular weight is insufficient in mechanical strength and durability, and thus it is not practically useful.
Further, in order to obtain a sulfonic acid polymer having a high molecular weight, the fluorosulfonyl group-containing monomer is required to have high copolymerizability with other fluoromonomers such as tetrafluoroethylene, but the conventional fluorosulfonyl as group-containing monomer did not sufficiently have such copolymerizability.

Method used

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  • Fluorosulfonyl group-containing monomer and its polymer, and sulfonic acid group-containing polymer
  • Fluorosulfonyl group-containing monomer and its polymer, and sulfonic acid group-containing polymer
  • Fluorosulfonyl group-containing monomer and its polymer, and sulfonic acid group-containing polymer

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0080]

[0081]A 5 L 4-necked flask was equipped with a thermometer, a Dimroth condenser and a stirrer. Under an atmosphere of nitrogen, 1,800 ml of diglyme was added. Then, AgF (593 g, 4.68 mol) was added with stirring. A reactor was equipped with a dropping funnel, and the reactor was cooled in an ice bath until its inner temperature became at most 10° C. While maintaining the inner temperature of at most 10° C., sulfone (10b) (843 g, 4.68 mol) was dropped from a dropping funnel over a period of 2 hours, followed by stirring for 1 hour in a water bath.

[0082]Again, the reactor was cooled in an ice bath, and while maintaining the inner temperature of at most 10° C., trans-1,3-dibromo-2-butene (10a-1) (500 g, 2.34 mol) dissolved in 500 g of diglyme was dropped from a dropping funnel over a period of 1.5 hours. After the dropping, stirring was continuously carried out for 11 hours. When the crude liquid of the reaction was subjected to a GC analysis, it was confirmed that the reaction wa...

example 2

[0087]

[0088]A 5 L 4-necked flask was equipped with a thermometer, a Dimroth condenser and a stirrer. Under an atmosphere of nitrogen, the compound (1-1) (475 g, 1.05 mol), 2,800 g of 1,2-dichloroethane and 352 g of m-chloroperbenzoic acid (m-CPBA) (purity >65%) were added, and reflux was carried out for 7 hours. When the mixture was subjected to a GC analysis, the degree of conversion was 36.4%. 1,029 g of 1,2-dichloroethane and 352 g of M-CPBA (purity >65%) were further added into a reactor, and reflux was carried out for 31 hours. The degree of conversion was 94.6%.

[0089]The crude liquid of the reaction was filtrated to recover 5,132 g. It was washed twice with a saturated sodium carbonate aqueous solution and with 4.8 mol / l of a sodium chloride aqueous solution, and it was subjected to liquid separation to obtain 4,859 g of a crude liquid of the reaction.

[0090]Such a crude liquid was dried over sodium sulfate and filtrated, and then it was concentrated by an evaporator and dried ...

example 3

[0093]

Acetonide Formation

[0094]A 1 L 4-necked flask was equipped with a thermometer, a stirrer and a Dean-Stark trap. Under an atmosphere of nitrogen, 71.32 g (152.3 mmol) of the compound (11-1), 263 g of dried acetone, 290 g of dried toluene, 58.77 g (152.2 mmol) of a compound (15-1) and BF3.OEt2 (2.67 g, 18.8 mmol) were sequentially added.

[0095]The reactor was heated in an oil bath and heated to the inner temperature of 90° C. under a normal pressure to distill 300 ml of the solvent. Then, stirring was carried out for 4 hours at the inner temperature of 100° C. The degree of conversion analyzed by gas chromatograph was 97%.

Ketal Exchange

[0096]The Dean-Stark trap was removed from the flask and a simple distillation device was attached thereto. It was heated to the inner temperature of 90° C. at 33 kPa to distill 239 g of toluene. Into the reactor, BF3.OEt2 (1.33 g, 9.37 mmol) was added, and a reaction was carried out at 40 kPa at the inner temperature of 90° C. for 2.5 hours. Furth...

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Abstract

To provide a fluorosulfonyl group-containing monomer having a high polymerization reactivity and plural fluorosulfonyl groups. Further, to provide a fluorosulfonyl group-containing polymer and a sulfonic acid group-containing polymer, obtained by using the monomer.A perfluoro(2-methylene-1,3-dioxolane) derivative which is represented by the following formula (3) and which has two fluorosulfonyl groups, and its production process and its synthetic intermediate. A fluorosulfonyl group-containing polymer having monomer units represented by the following formula (3U) obtained by polymerizing the compound (3) by itself or with a comonomer, and a sulfonic acid group-containing polymer having the following units (5U) obtained by hydrolyzing a fluorosulfonyl group of the polymer. In the following formulae, each of Rf1 and Rf2 which are independent of each other, is a C1-8 perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms.

Description

BACKGROUND OF THE INVENTION[0001]1. Field of the Invention[0002]The present invention relates to a fluorosulfonyl group-containing polymer which is a precursor of a sulfonic acid group-containing polymer useful as an ion-exchange membrane (e.g. a membrane to be used for brine electrolysis or polymer electrolyte fuel cells) or an electrolyte membrane to be used for a catalyst layer of a fuel cell; and a new fluorosulfonyl group-containing monomer which can be a raw material of the polymer. Further, the present invention relates to a process for producing the fluorosulfonyl group-containing monomer and a new compound useful as an intermediate for production of the monomer. Furthermore, it relates to a sulfonic acid group-containing polymer obtainable from the above fluorosulfonyl group-containing polymer and an electrolyte material for polymer electrolyte fuel cells, which comprises the sulfonic acid group-containing polymer.[0003]2. Discussion of Background[0004]Heretofore, a copolym...

Claims

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Application Information

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IPC IPC(8): C08G75/20C07D317/10
CPCC07D317/42Y02E60/523C08G75/23
Inventor WATAKABE, ATSUSHIYAMAMOTO, HIROMASAIWAYA, MASAOSAITO, SUSUMU
Owner ASAHI GLASS CO LTD
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