JPS62292814A - Production of fluoroolefin copolymer having hydroxyl group - Google Patents

Abstract

PURPOSE:To obtain a fluoroolefin copolymer having hydroxyl groups in good reproducibility, by polymerizing a monomer mixture comprising a fluoroolefin and a hydroxyl group-containing vinyl ether in the presence of specified compond. CONSTITUTION:In producing a hydroxyl group-containing fluoroolefin copolymer by using a monomer mixture comprising a fluoroolefin and a hydroxyl group- containing vinyl ether as essential components and other copolymerizable monomers as optional components, said monomer mixture is radical-polymerized in the presence of a compound having a 2,2,6,6-tetra-substituted piperidinyl group. As said other copolymerizable monomer, an alkyl vinyl ether or a cycloalkyl vinyl ether is desirable to attain a sufficiently high conversion.

Description

[Detailed Description of the Invention] 3. Detailed Description of the Invention [Field of Industrial Application] The present invention provides a method for producing a fluoroolefin polymer containing a hydroxyl group useful for paints, sealants, films, etc. More specifically, a fluoroolefin, a vinyl ether containing a hydroxyl group, and optionally other copolymerizable monomers are subjected to radical polymerization in the presence of a compound containing a 2,2,6,6-tetra-substituted piperidinyl group. The present invention relates to a method for producing a hydroxyl group-containing fluoroolefin polymer.

[Conventional technology and its problems]

In recent years, solution-type fluoroolefin copolymers containing hydroxyl groups have been developed and have come to be used mainly for paints. However, when producing a fluoroolefin copolymer containing a hydroxyl group, if one attempts to increase the amount of the hydroxyl group-containing additive, increase the non-volatile content of one polymerization, or increase the target molecular weight of the copolymer, During one polymerization, gelation may occur or the dispersion ratio (ratio of weight average molecular weight layer to number average molecular weight layer) of the resulting copolymer may become significantly large, making it difficult to produce the desired copolymer with good reproducibility. [Problems to be Solved by the Invention] The present inventors have conducted intensive research to solve the problems of the prior art described above, and as a result, they have discovered that 2,2,6,6-tetra By radically polymerizing a monomer mixture containing a fluoroolefin and a vinyl ether containing a hydroxyl group as essential components in the presence of a substituted piperidinyl group-containing compound, gelation does not occur during polymerization and the dispersion ratio does not increase significantly. discovered that a fluoroolefin copolymer containing the desired hydroxyl group can be obtained with good reproducibility,
The present invention has now been completed.

[Structure of the invention]

(Means for Solving the Problems) To summarize the present invention, the present invention uses a fluoroolefin and a vinyl ether containing a hydroxyl group as essential monomer components, and if necessary, other copolymerizable monomers. 2
．． The present invention provides a method for producing a fluoroolefin copolymer containing a hydroxyl group by radical polymerization in the presence of a compound containing a 2,6,6-tetra-substituted piperidinyl group.

The configuration of the present invention will be explained in detail below.

The fluoroolefin component used in the present invention includes vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, promotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, or (per)fluoropropylene. Alkyl trifluorovinyl ether [However, the number of carbon atoms in the (bar)fluoroalkyl group is 1 to 1]
8] is a typical example.

Next, as the hydroxyl group-containing vinyl ether which is a hydroxyl group-containing monomer component used in the present invention, 2-
Hydroxyethyl vinyl ether, 3-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyethyl vinyl ether, etc. is a typical example.

In the method for producing a hydroxyl group-containing fluoroolefin copolymer of the present invention, in addition to the above-mentioned essential monomer components, other monomers that can be copolymerized with these essential monomer components are required. Can be used accordingly. Examples of such other copolymerizable monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, and n-hexyl vinyl ether. , n-octyl vinyl ether, 2-ethylhexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methyl cyclohexyl vinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether or phenethyl vinyl ether: 2,2,3.3 -tetrafluoropropyl vinyl ether, 2,2,3,3
゜4.4,5. S-octafluoropentyl vinyl ether.

2, 2, 3, 3, 4, 4, 5. S, 6, 6, 7, 7, 8
(per)fluoroalkyl vinyl ethers such as , 8,9.9-hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether, perfluorocyclohexyl vinyl ether; vinyl acetate; Vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persatate,
Carboxylic acid vinyl esters such as vinyl laurate, vinyl stearate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl salicylate, and vinyl cyclohexanecarboxylate; furthermore, ethylene, vinyl chloride, vinylidene chloride, (meth) Acrylonitrile, various (
Typical examples include meth)acrylic acid esters.

Among such copolymerizable monomers, it is preferable to use alkyl vinyl ethers or cycloalkyl vinyl ethers in combination in order to sufficiently increase the polymerization rate. When used as a paste resin component, from the viewpoint of coating hardness, vinyl esters of aliphatic monocarboxylic acids having branched alkyl groups of 04 to Cut, vinyl benzoate, vinyl p'''tert-butylbenzoate, It is particularly preferable to use at least one member selected from the group consisting of vinyl cyclohexanecarboxylate.

When producing a hydroxyl group-containing fluoroolefin copolymer from the above monomer components by the method of the present invention, the ratio of each monomer component to be used is determined from the viewpoint of yield and weather resistance of the copolymer. 10-70 mol%
, 2 to 40 mol% of hydroxyl group-containing vinyl ether, 0 to 88 mol% of copolymerizable monomer, preferably 20 to 60 mol% of fluoroolefin, 5 to 40 mol% of hydroxyl group-containing vinyl ether
The copolymerizable monomer content is controlled to be 25 mol% and 15 to 75 mol%.

Next, as a compound containing a 2,2,6,6-tetra-substituted piperidinyl group used in the present invention, at least four hydrogen atoms on the carbon atoms at the 2- and 6-positions are substituted with an organic group. Refers to a compound containing a piperidine ring,
At the same time, the four hydrogen atoms at the 2nd and 6th positions are substituted with organic groups, and at the same time, at least one of the seven hydrogen atoms on the nitrogen atoms or carbon atoms at the 1st, 3rd, 4th and 5th positions is replaced with an organic group. It also includes compounds containing a piperidine ring substituted with a group or a hydroxyl group.

A typical compound containing such a 2,2,6,6-tetra-substituted piperidinyl group has a structure represented by the following general formula (1).

Here, R", R", R3, R in formula (I)
' are each independently a methyl group, an ethyl group, a propyl group,
01-1. such as dodecyl group and stearyl group. Alkyl groups; cycloalkyl groups such as cyclopentyl or cyclohexyl; substituted alkyl groups such as 2-hydroxyethyl, 2-methoxycarbonylethyl, and 3-hydroxypropyl; allyl groups such as phenyl and naphthyl groups:
In addition to representing an aralkyl group such as a phenethyl group or a benzyl group, R1 and R2 or R3 and R4 may also be taken together to form a C1-C1 aliphatic ring. Among these organic groups, from the point of view of price and ease of acquisition, 01 to 2. An alkyl group, especially a methyl group, is preferred.

Next, RS in formula (1) is a hydrogen atom or a methyl group,
Alkyl groups such as ethyl group, propyl group, butyl group, dodecyl group, stearyl group; 2-hydroxyethyl group, 2
- Substituted alkyl groups such as methoxycarbonylethyl group, 2-acetoxyethyl group, 2-(3-methoxycarbonylpropionyloxy)ethyl group, and 3-hydroxypropyl group; Allyl groups such as phenyl group, naphthyl group, and hydroxyphenyl group; Furthermore, it has an organic group represented by a phenethyl group, a benzyl group, a hydroxyphenylalkyl group, a cyclohexyl group, and the like.

Further, R6 in formula (1) is a hydrogen atom, a hydroxyl group or a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group,
Alkyl groups such as stearyl group: substituted alkyl groups such as 2-hydroxyethyl group, 2-methoxycarbonylethyl group, 2-acetoxyethyl group, 2-(3-methoxycarbonylpropionyloxy)ethyl group, and 3-hydroxypropyl group; Allyl groups such as phenyl group and naphthyl group; Aralkyl groups such as phenethyl group and benzyl group; Acetoxy group, propionyloxy group, butyryloxy group, lauroyloxy group, substituted alkylcarbonyloxy group, benzoyloxy group, substituted benzoyloxy group, etc. Ester-bonded gold group; further alkoxycarbonylamino group,
It represents an organic group represented by an amino group-containing group such as an N-monoalkylcarbamoylamino group or an N,N-dialkylcarbamoylamino group.

Representative examples of the compound represented by the general formula (1) include 2,2,6,6-titramethylpiperidine, 1.
2,2,6.6-pentamethylpiperidine, 2,2,6
．． 6-tetramethyl-4-hydroxypiperidine, 1゜2.2,6.6-bentamethyl-4-hydroxypiperidine, 1-ethyl-2,2,6,6-titramethylpiperidine, 1-ethyl-2,2, 6,6-tetramethyl-
4-hydroxypiperidine, 1-butyl-2,2,6゜6-tetramethyl-4-hydroxypiperidine, 1-dodecyl-2,2,6,6-titramethylpiperidine, 1
-Phenyl-2,2,6,6-titramethylbiperidine, 1-(2-hydroxyethyl)-2,2,6,6-titramethylpiperidine, 1-(2-hydroxyethyl)
-4-Hydroxy-2,2,6,6-titramethylpiperidine, 4-acetoxy-2,2,6,6-titramethylpiperidine, 4-acetoxy-1,2,2゜6.6-
Pentamethylpiperidine, 1-(2-acetoxyethyl)-4-acetoxy-2,2,6,6-titramethylbiperidine, 1-(2-benzoyloxyethyl)-4-
Benzoyloxy-2,2,6,6-titramethylpiperidine, 4-ethyl-2,2,6゜6-titramethylpiperidine, 4-ethyl-1,2゜2.6.6-pentamethylpiperidine, 4 -Butyl-2,2,6,6-titramethylpiperidine, 4-octyl-2,2,6,6-titramethylpiperidine, 4-dodecyl-2,2,6,6
-Titramethylbiperidine, 4-stialyl-2,2,
6.6-thitramethylpiperidine, 4-stearyl-1
, 2,2,6,6-pentamethylpiperidine.

Furthermore, compounds represented by the general formula (1) include 4-hydroxy-2,2,6,6-titramethylbiperidine, 4-hydroxy-1°2.2,6.
6-pentamethylpiperidine, 1-hydroxyethyl-
2,2,6.6 having a hydroxyl group such as 4-hydroxy-2,2,6,6-titramethylpiperidine, 1-hydroxyethyl-2,2゜6.6-titramethylpiperidine
-Tetramethylpiperidines are added to succinic acid, adipic acid,
Sebacic acid, azelaic acid.

Two or more 2.2, There are compounds containing a 6.6-titramethylpiperidinyl group.

Representative examples of such compounds containing two or more 2,2,6,6-titramethylpiperidinyl groups in one molecule include those represented by the following structural formulas (II) to (■). .

[However, n in the formula shall be an integer ranging from 1 to 20. ] These piperidinyl compounds can be used alone or as a mixture of two or more.

The amount of the piperidinyl compound to be used is 0.002 to 0.5 equivalents, more preferably 0.01 to 0.5 equivalents of the 2,2,6.6-tetra-substituted piperidinyl group per 1000 y of total monomers to be copolymerized. The amount is preferably within the range of 2 equivalents; if it is less than 0.002 equivalents, it may gel during polymerization or the dispersion ratio of the resulting copolymer will become large, and if it exceeds 0.5 equivalents, it will be difficult to increase the polymerization rate. This is not preferable because the resulting copolymer solution may become significantly colored.

In carrying out the method for producing a fluoroolefin copolymer containing a hydroxyl group according to the present invention, known and commonly used radical polymerization initiators are used as the polymerization initiators, and representative examples of such polymerization initiators include: Azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; t-butylperoxypivalate, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-t-
Butyl peroxide, dicumyl peroxide, t-
Peroxides include butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, and diisopropyl peroxycarbonate.

The amount of the radical polymerization initiator to be used is appropriately determined depending on the type of polymerization initiator, polymerization temperature, molecular weight of the copolymer, etc., but is generally from 0.01 to 0.01 of the total amount of monomers to be copolymerized.
About 10% by weight is sufficient.

In order to produce a fluoroolefin copolymer containing a hydroxyl group using each of the above-described heavy components, known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization can be applied. Polymerization and solution polymerization methods are preferred, and solution polymerization methods are particularly preferred because the obtained copolymer can be used as is as a curable resin composition such as a base resin component for solution-based paints. Typical solvents used in producing copolymers by polymerization include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; n-pentane, n-hexane,
Aliphatic hydrocarbons such as n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane; methanol, ethanol, n-propanol, impropanol, n-butanol, imbutanol, tert -butanol, n-pentanol, isopentanol, n-hexanol, n
- Alcohols such as octatool, 2-ethylhexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether, di-n
- Ethers such as butyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone; methyl acetate, ethyl acetate, acetic acid n-
Esters such as propyl, isopropyl acetate, isobutyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; chloroform, methylene chloride, Chlorinated hydrocarbons such as carbon chloride, trichloroethane and tetrachloroethane; furthermore, there are N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate and the like. Such solvents may be used alone or as a mixture of two or more types, but it is preferable to select them so as to dissolve the resulting copolymer, and the amount used depends on the monomer used. Approximately 5 to 1000 parts by weight per 100 parts by weight of the total amount of monomers To produce a fluoroolefin copolymer containing a hydroxyl group by a solution polymerization method from each of the above-mentioned monomer components,
All monomers, a solvent, a compound containing a 2,2,6,6-tetra-substituted piperidinyl group, and a polymerization initiator are charged all at once and polymerized.
, 2,6,6-Tetra-substituted piperidinyl group-containing compound is added to the reactor containing other monomers and a polymerization initiator, either continuously or in portions. The polymers, the 2,2,6,6-tetra-substituted piperidinyl group-containing compound, and the polymerization initiator are added continuously or in portions. ■Methods such as adding a solvent, a 2,2,6,6-tetra-substituted piperidinyl group-containing compound, a polymerization initiator, and other comonomers continuously or in portions to a reactor containing fluoroolefins. can be applied.

The reaction temperature and reaction pressure of the method of the present invention are appropriately selected depending on the type of polymerization initiator and polymerization solvent, and the molecular weight of the desired copolymer, but the reaction temperature is 0 to 140°C, preferably 40 to 100°C. is adopted, and the reaction pressure is usually 100 kg/c! # or less, preferably 70 kg/cd or less is adopted.

The copolymer thus obtained can be used as it is, or it can be used as a curing agent, pigment, or filler that can react with hydroxyl groups.

It can be used in various applications such as paints, sealants, and films by adding curing catalysts and the like.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Reference Examples. In the following, all parts mean parts by weight unless otherwise specified.

Example 1 Ethyl vinyl ether (EV, E) 25! ) (
s mol%), hydroxybutyl vinyl ether (HBV
E) 509 (10 mol%), cyclohexyl vinyl ether 175# (32,2 mol%), methyl isobutyl ketone (MIB) 215i, azobisisovaleronitrile (ABNV) 5f t-butyl peroxyoctoate (TBO) 5 g and 2,2,6.6-tetrapiperidine 2.89 were charged, then liquefied and collected chlorotrifluoroethylene 2501i (49,
8 mol %) was injected under pressure, reacted at 55°C for 15 hours with stirring, then heated to 85°C and reacted for 4 hours.

V, ) 69.2%, number average molecular weight (stone) 32,00
A solution of a hydroxyl group-containing copolymer called 0 and Gardner Color (G, C,) 3 was obtained.

Example 2 In a reactor similar to Example 1, 50 particles of IBVE (10
, 3 mol%), cyclohexyl vinyl ether 200
i (38,2-T-/L/%), butylacetate/L/21
514. ABNV 5 #, TBO5t and 1,2
, 2,6,6-bentamethylpiperidine were charged. Next, 250 # (51.5 mol%) of liquefied and collected chlorotrifluoroethylene was injected under pressure, and the reaction was carried out in the same manner as in Example 1 to obtain 67.5% of N and V.

A solution of a copolymer containing hydroxyl groups of 26,000, G, C, and 1 was obtained.

Example 3 In a reactor similar to Example 1, 6-hydroxyl vinyl ether lOO# (14,9-T-/Lz%), EVE
50 g (14,9 mol%), vinyl pivalate 100
t (16,7 mol%), MIBK 215@, ABN
V5g, TBO5# and 4-hydroxy-1,2,2
, 250 t (53
, 5 mol %), the reaction was carried out in the same manner as in Example 1, and N, V, 69.2%, G, C, 1, h 31,0
A solution of a copolymer containing 00 hydroxyl groups was obtained.

Example 4 In a reactor similar to Example 1, 50 g of HBVE (12,
6 mol%), isobutyl vinyl ether 509 (14
, 7 mol%), Beover 9 (C3 manufactured by Shell, Netherlands)
vinyl ester of branched fatty acid) 150 g (2
3.9 mol%), MIBK 2151 ABNV 5
t TBO59 and 4-hydroxy-2,Z, 6.
5 g of ester of 6-titramethylpiperidine and sebacic acid (molar ratio 2:1) was charged.Next, liquefied hexafluoropropylene 2509 (48.8 mol%) was injected, and then the same procedure as in Example 1 was carried out. perform the reaction, N
, V, 67.7%.

A solution of a hydroxyl group-containing copolymer of Ayu 17,000, G, C, 3, was obtained.

Example 5 In a reactor similar to Example 1, )IBVE 100# (
17 mol%), EVE 50i (13.6 mol%
), vinyl acetate 501i (11,4 mol%), vinyl benzoate 100y (13,3 mol%), MIBK 2
151i, ABNV5g, TBO59 and ester of 4-hydroxy-1,2,2,6,6-bentimethylpiperidone and sebacic acid (molar ratio 2:1) 59 were charged. Then, tetrafluoroethylene 1509 (29
, 4 mol%) and vinylidene fluoride 50) (15,
3 mol%), the reaction was carried out in the same manner as in Example 1, and N, V, 68.6%, G, C, 1, stone 33.000
A solution of a copolymer containing hydroxyl groups was obtained.

Example 6 In a reactor similar to Example 1, HBVE 51 (11,
7 mol%), EVE soy (18.8 mol%)
, p-tert-butylbenzoate vinyl so9 (6
, 6 mol%), vinyl cyclohexanecarboxylate 100
? (17.6 mol%), MIBK 2151, TBO
5t, ABNV 5t and 4-hydroxy-1,2
, ester of 2,6,6-pentamethylpiperidine and adipic acid (molar ratio 2:1).
Hexafluoropropylene 251 (45
, 3 mol %) was then reacted in the same manner as in Example 1 to obtain a solution of a copolymer containing hydroxyl groups of N, V, 67.5%, V 20.000, G, C, 1. Ta.

Comparative Example 1 When the reaction was carried out in the same manner as in Example 1 except that 2.89-titramethylpiperidine was not used, a jelly-like gelled product was produced and the desired polymer solution was not obtained. There wasn't.

Comparative Example 2 1.2,2.6.6-bentamethylpiperidine 2.99
When the reaction was carried out in the same manner as in Example 2 except that 2Q was not used, a jelly-like gelled product was produced and a solution of the desired copolymer could not be prepared.

Comparative Example 3 A reaction was carried out in the same manner as in Example 3 except that 4-hydroxy-1,2,2,6,6-bentamethylpiperidine 3.29 was not used. No polymer solution was obtained.

Comparative Example 4 When the reaction was carried out in the same manner as in Example 4 except that the ester of 4-hydroxy-2,2,6,6-titramethylpiperidine and sebacic acid 5g was not used, a jelly-like gelled product was produced. However, the desired copolymer solution could not be obtained.

Comparative Example 5 When the reaction was carried out in the same manner as in Example 5 except that the ester of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine and sebacic acid was not used, a jelly-like gelled product was obtained. was produced, and the desired copolymer solution could not be obtained.

Reference Example 1 100 parts of the solution of the vinyl polymer containing hydroxyl groups obtained in Example 1, 54.5 parts of Taibake CR-93 (rutile type titanium oxide manufactured by Ishihara Sangyo ■) and xylene/butyl acetate = 70/30 ( (weight ratio) A mixture consisting of 30 parts of mixed solvent was kneaded to obtain a white mill base. Coronate EH (Nippon Polyurethane Industry na hexamethylene diisocyanate trimer type polyisocyanate)
A white paint was obtained by adding 11.8 parts of . This paint was applied to a zinc phosphate treated steel plate using an applicator and left at room temperature for 7 days to obtain a cured paint film with a 60° gloss of 87 and a good appearance. This coating film was exposed to a Sunshine Weatherometer for 3,000 hours, but almost no decrease in gloss was observed and it showed good weather resistance.

Reference Example 2 Solution 100 of the copolymer containing hydroxyl groups obtained in Example 4
A white paint was obtained in the same manner as in Reference Example 1 from 5 parts of Tybake CR-9354, 30 parts of a 70/30 mixed solvent of xylene/butyl acetate, and 11.8 parts of Coronate EH. Next, 60% of the cured coating film obtained in the same manner as in Reference Example 1 was
The gloss was good at 89, and when this coating film was exposed to a sunshine weatherometer for 3,000 hours, there was almost no decrease in gloss and it showed good weather resistance.

〔Effect of the invention〕

A monomer mixture containing a fluoroolefin and a hydroxyl group-containing vinyl ether as essential components according to the present invention is 2.2, 6.6
The method of producing a hydroxyl group-containing fluoroolefin copolymer by radical polymerization in the presence of a compound containing a -tetra-substituted piperidinyl group can effectively suppress gelation during polymerization.

Therefore, the method of the present invention provides an excellent hydroxyl group-containing fluoroolefin copolymer that can be used in various applications such as paints, sealants, and films.

Claims (1)

[Scope of Claims] 1. Fluoroolefins and vinyl ethers containing hydroxyl groups are used as essential monomer components, and if necessary, other copolymerizable monomers are used to copolymerize fluoroolefins containing hydroxyl groups. A fluoroolefin copolymer containing a hydroxyl group, characterized in that, in producing the polymer, the monomer mixture is radically polymerized in the presence of a compound containing a 2,2,6,6-tetra-substituted piperidinyl group. manufacturing method. 2. The manufacturing method according to claim 1, wherein the radical polymerization is carried out in the presence of an organic solvent. 3. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are alkyl vinyl ethers. 4. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are cycloalkyl vinyl ethers. 5. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are alkyl vinyl ethers and cycloalkyl vinyl ethers. 6. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are carboxylic acid vinyl esters. 7. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are carboxylic acid vinyl ester, alkyl vinyl ether, and/or cycloalkyl vinyl ether. 8. The carboxylic acid vinyl ester is at least selected from the group consisting of a vinyl ester of an aliphatic monocarboxylic acid having a branched alkyl group of C_4 to C_1_7, vinyl benzoate, vinyl p-tert-butylbenzoate, and vinyl cyclohexanecarboxylate. The manufacturing method according to claim 6 or 7, which is one type. 9. The fluoroolefin is hexafluoropropylene,
The manufacturing method according to claim 1, which is at least one selected from the group consisting of chlorotrifluoroethylene, tetrafluoroethylene, and vinylidene fluoride.