JPS6128687B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel fluorine-containing polymer. More specifically, the present invention relates to a novel fluorinated polymer having a fluorosulfonyl group or/and a functional group derived therefrom in its side chain and an ether bond in its main chain. Conventionally, fluorine-based copolymers containing a fluorosulfonyl group or an ion exchange functional group derived therefrom in a side chain are known (see Japanese Patent Publication No. 1664/1983). However, these known copolymers are complicated,
It was manufactured through a wide variety of processes, and the copolymerization was carried out through the vinyl ether double bond formed during the process as shown in the following formula. However, as shown below, the fluorine-containing polymer of the present invention can be prepared by using the intermediate of the known process alone,
or other monomers, the manufacturing process is extremely simplified, and the copolymerization reaction is also copolymerization via the carbonyl group of the intermediate, so the resulting fluorine-containing The type of copolymer is also completely different from those mentioned above, and has an ether bond in the main chain. Thus, the present invention aims to provide a novel fluorine-containing resin that can be produced using an advantageous method that cannot be predicted from the known methods for producing fluorosulfonyl group-containing fluoropolymers. That is, the present invention provides the following: 1 General formula () [However, in the formula, R _f is -CFY- or

[Formula] (However, Y represents F or CF ₃ , n is 0 or 1
Represents an integer from ~3. ), Z is -F, -
Represents OM, -NRR' or -NRM. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium group, and R and R' are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an aralkyl group. ] It is a fluorine-containing polymer consisting of a structural unit represented by the following and a structural unit derived from perfluoroolefin, and containing at least 0.5 mol% of the structural unit of formula (). The fluorosulfonyl group-containing acid fluoride, which is a monomer unit constituting the fluorine-containing polymer of the present invention, is produced by a known method (for example, see Japanese Patent Publication No. 1664/1983) using tetrafluoroethylene or hexafluoropropylene as a raw material. It can be obtained easily and in high yield by the following process. This acid fluoride can be used alone or copolymerized with other ethylenically unsaturated monomers to give the polymer of the present invention. Examples of monomers that can be copolymerized include ethylene, propylene, etc. - Olefin: Dienes such as butadiene: Vinyl halides such as vinyl chloride and vinyl fluoride: Vinylidene halides such as vinylidene chloride and vinylidene fluoride:
Perhaloolefins such as chlorotrifluoroethylene and tetrafluoroethylene; vinyl compounds such as acrylic acid or its esters, vinyl ethers and vinyl esters are preferably used. These can be copolymerized with the above acid fluoride alone or in combination. Acid fluoride units occupied in copolymer

[Formula] is 0.5 mol% or more. If the content is less than this amount, it is difficult to obtain the functionality specific to the polymer of the present invention. In particular, in copolymerization with tetrafluoroethylene, the acid fluoride unit is
When the content is 0.5 mol% or more, flexibility is imparted and moldability is greatly improved. In obtaining the polymer of the present invention, both ionizing radiation and a radical polymerization initiator may be used for polymerization. As radical polymerization initiators, commonly used diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, ditertiary butyl peroxide, dicumyl peroxide, perfluoroalkyl peroxide, azoisobutyronitrile (AIBN) are commonly used. , fluorinated azide (F ₂ N−NF ₂ ), and the like. Furthermore, in producing the polymer of the present invention, non-aqueous solution polymerization, non-aqueous suspension polymerization or bulk polymerization is possible, but non-aqueous solution polymerization is most preferred. The polymerization solvent is preferably a lower fluorocarbon, such as dichlorotetrafluoroethane, trichlorotrifluoroethane, perfluorocyclobutane, perfluoro-1,3-dimethylcyclobutane, and the like. Further, ionizing radiation includes α rays, β rays, γ rays, radiation, neutron rays, X rays, and the like. The novel fluorosulfonyl group-containing fluorine-containing polymer of the present invention is characterized in that the fluorosulfonyl group is converted to an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonia, a secondary amine or (-SO ₃ -) _n M [where M is an alkali metal (m = 1) or an alkaline earth metal (m = 2)], respectively, by heat treatment with an amine as necessary.
It can be converted into the fluorine-containing polymer of the present invention having a functional group of -SO ₂ NRR' (R and R' are any one of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and an aralkyl group). Also −SO ₃ H and

A polymer having a functional group of the formula can be easily obtained by hydrolyzing a polymer having a functional group of -SO ₃ M (M is an alkali metal) with an acid. In addition, by treating this −SO ₃ H group-containing polymer with a primary tertiary amine,

It is possible to obtain a polymer having the formula: In addition, a polymer having a functional group (-SO ₂ NR) _n M is treated with an organic alkali metal compound such as methyllithium or butyllithium after converting the -SO ₂ F group into a functional group -SO ₂ NHR. Alternatively, it can be easily obtained by treatment with an organic alkaline earth metal compound, such as Grignard reagent. The degree of polymerization of these fluorine-containing polymers is not particularly limited, but is generally 50 to 10,000. The fluorine-containing polymer of the present invention, that is, the polymer containing in the main chain a monomer unit having a specific fluorosulfonyl group or a specific functional group derived therefrom, can be used to form, for example, a film, a filament, or a plastic molded article. used in any form, such as Furthermore, it has excellent uses as a functional polymer with extremely excellent oxidation resistance, chemical resistance, weather resistance, etc., and can be used, for example, in ion exchange membranes for salt electrolysis. As detailed above, the polymer of the present invention can be produced by a very simple process, and can easily provide a functional polymer that is extremely useful industrially. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Dry in a 300ml Hastelloy autoclave,
100ml of distilled trichlortrifluoroethane, 1
-Fluorosulfonyl perfluoroacyl fluoride

A system containing 18 g of [Formula] and 0.3 g of diisopropyl peroxydicarbonate was closed, cooled to -78°C, and after purging the system with dry nitrogen, 10 g of tetrafluoroethylene was charged. After warming the system to 50°C and stirring for 4 hours,
The system was returned to room temperature, the autoclave was opened, and the resulting polymer dispersion was filtered, washed with water, and dried to obtain 20 g of a white polymer (conversion rate: 71%). This one has 35.7 mol%

It contains the unit [Formula] and showed an absorption based on -SO ₃ F at 1460 cm in infrared absorption. The obtained copolymer was made into a 0.5% ethanol solution, and the weight average molecular weight in terms of polystyrene was determined by gel permeation.The degree of polymerization obtained by calculating from this was 264. Example 2 In the same apparatus as in Example 1, 21 g of 1-fluorosulfonyl perfluoroacyl fluoride and 8 g of tetrafluoroethylene were mixed in 100 ml of anhydrous trichlorotriflurochlorothane in the presence of 0.3 g of diisopropyl peroxydicarbonate. Copolymerization was carried out to obtain 18 g of a white solid polymer. This thing is
41 mol%

[Formula] unit, and in the infrared absorption spectrum, it showed an absorption based on -SO ₂ F at 1460 cm ^-1 and a broad absorption based on C-F bond at 1200 to 1050 cm ^-1 . The degree of polymerization was determined in the same manner as in Example 1. Example 3 The copolymers obtained in Examples 1 and 2 were
10 wt%, 20 wt% caustic soda in aqueous solution, 60
After stirring at ℃ for 24 hours, the infrared absorption spectrum (KB ^r ) of the dried product was measured.
1069, 665 cm ^-1 −SO ₃ Na νSO ₂ and νS−O
The absorption based on -SO ₂ F at 1460 cm ^-1 disappeared. This copolymer was immersed in a 10% KCl aqueous solution and its ion exchange capacity was measured.
It showed a value of 2.31 meq/g of dry resin, and that derived from Example 2 showed a value of 2.53 meq/g of dry resin. Example 4 In the same manner as in Example 1, 3 g of tetrafluoroethylene and 5.8 g of

[Formula] and 0.1 in 30 ml of trichlorotrifluoroethane
Copolymerization was carried out at 50° C. for 6 hours in the presence of g of diisopropyl peroxydicarbonate to obtain 3.6 g of a white polymer. This one has an infrared absorption of 1465
It shows an absorption based on -SO ₂ F at cm ^-1 , and elemental analysis shows 5 mol% acid furoshide units.

It contained [formula]. The degree of polymerization was determined in the same manner as in Example 1 and found to be 248.

Claims (1)

[Claims] 1 General formula () [However, in the formula, R _f is -CFY- or [Formula] (However, Y represents F or CF ₃ , and n is 0 or 1
Represents an integer from ~3. ), Z is -F, -
Represents OM, -NRR' or -NRM. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium group, and R and R' are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an aralkyl group. ] Consisting of the structural unit represented by and a structural unit derived from perfluoroolefin, and containing at least 0.5 mol% of the structural unit of formula (), a degree of polymerization
50 to 10,000 fluorine-containing polymers.