JPH03212410A - Preparation of fluorinated copolymer - Google Patents

Abstract

PURPOSE:To prepare the subject copolymer having excellent weather resistance and chemical resistance and useful for coatings, etc., by copolymerizing a fluoroolefin, a specific radical polymerizable monomer and a specified organic silicon compound. CONSTITUTION:(A) A fluoroolefin (e.g. tetrafluoroethylene) preferably in an amount of 30-55mol%, (B) a radical polymerizable monomer having an olefinic unsaturated bond and a hydrolytically hydroxyl group-producing group bonded to a carbon atom (e.g. 4-vinyloxybutyl tetrahydropyranyl ether) preferably in an amount of 1-50mol% and (C) an organic silicon compound having an olefinic unsaturated bond and a hydrolytically hydroxyl group-producing group bonded to a silicon atom (e.g. vinyltrimethoxysilane) preferably in an amount of 3-20mol% are copolymerized to provide the objective copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a fluorine-based copolymer that is soluble in organic solvents at room temperature and curable at room temperature.

[Conventional technology]

A fluorine-based copolymer that is soluble in organic solvents and can be cured can be easily applied by dissolving it in an appropriate solvent, and the coating film formed has weather resistance, chemical resistance, solvent resistance, water repellency, water resistance,
Since it has excellent heat resistance, low friction properties, and transparency, it is suitably used as a surface treatment agent for various base materials.

Examples of such fluorine-based copolymers include fluoroolefins and cyclohexyl vinyl ethers.

A fluorine-based copolymer made by copolymerizing the four components of alkyl vinyl ether and hydroxyalkyl vinyl ether (Japanese Patent Publication No. 60-21686), a fluorine-based copolymer made from a fluoroolefin, vinyl ether, and a specific organosilicon compound (Japanese Patent Publication No. 60-21686); 141713), a fluorine-based copolymer with an alkoxysilane group introduced into the side chain through a urethane bond (Japanese Unexamined Patent Publication No. 63-30571).
(Japanese Patent Application Laid-Open No. 63-264675), a fluorine-based copolymer consisting of a fluoroolefin and a vinyl ether
Publication No.) etc. have been disclosed.

[Problem to be solved by the invention]

An object of the present invention is to propose a method for producing a fluorine-based copolymer that polymerizes specific components, dissolves in an organic solvent at room temperature, cures at room temperature, and has excellent storage stability.

[Means to solve the problem]

The present invention is a method for producing the following fluorine-based copolymer.

(1) (a) a fluoroolefin; (b) a radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom; and (C) A method for producing a fluorine-based copolymer, which comprises copolymerizing an organosilicon compound having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom.

(2) (a) Fluoroolefin, (b) A radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom, (c) Olefin A fluorine-based copolymer characterized by copolymerizing an organosilicon compound having a sexually unsaturated bond and in which a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom, and (d) an alkyl vinyl ether. manufacturing method.

The fluoroolefins (a) used in the present invention include:
Preferably, perfluoroolefins or perhaloolefins have at least one fluorine atom in the molecule, and preferably all hydrogen atoms of the olefin are replaced with fluorine atoms or with fluorine atoms and other halogen atoms, Furthermore, from the viewpoint of polymerizability and properties of the resulting copolymer, those having 2 or 3 carbon atoms are preferred.

Specifically, such fluoroolefins (a) include CF2=CF, C)lF=cF, CH,=CF
,,CH,=CHF,CCMF=CF□,CHCΩ=C
F,,C(,Q,=CF,,CCΩF=CCQF,C
HF: CCQz%CH,, CCQF, CCQ, =CC
Fluoroolefins having 2 carbon atoms (fluoroethylene type) such as QF; CF3CF=CF, CF, CH=CH
2, CF, CH=CH2, CF3CF=CH,, CF2
CH=CHBrCF, CH=CH2, CH3CF=CF
,,CHCH=CF,,CH,CF=CH,,CF,
CQCF=CF1. CF, CCU=CF,, CF3C
F20FCQ, CF2CQCCQ=CF2, CF, C
QC,F=CFCD.

CCf1CF=CF, CF3CBr=CCQF, C
F,CCQ=CC et al.,CCΩF2CF=CCQ,,CC
f13CF=CF, CF, CIlccmCllc,
, CFCQ, CH=CH2,, CF, CF=CHC
Q%CIF, CH=CH2Ω.

CF, CH=CHCQ, CHF, CH=CH2, CF
, CHCHCH3,,CF,CQCCQ=CHCQ,
CC et CF=CH(,Q%CF, ICF=CF,.

CF2BrC)I=CF,,CF,CBr=C)lBr
,CF,CQCBr=C)l,,CH,BrCF=CC
Q,, CF3CBr=CH,, CF2CH=CHBr
.

CF, BrC) I=CHF, CF, BrCF=CF
, 3-carbon fluoroolefin (fluoropropene type): CF, CCU=CFCF, , CF, =CF
CF,CCQF,,CF,=CFCCQ,CCQ,,C
H,=CFCC et CCU, CF, (CF,) ,
CCIQ=CF2, CF, (CF,), CCQ=CF,
, CF, CF, CF=CF, CF, CF=CFCF
,,CF,CH=CHCH3,CF,=CFCF,C)
HF2. CF, CF, CF=CH,, CF, CH=CH
2F,,CF,=CFCF,CH,,CF,=CFCH
,CH,,CF,CH,CH=C)1. , CF, CH=
CHCH3, CF, =CHCH, CH,, CI, CF,
CH=CH,,CFH,CH=CHCFH,,CH,C
F, CH=CH,, CH,=CFCH, CH,, CF,
(CF2>2CF=CFCF, (CF, ), C
Examples include fluoroolefins having 4 or more carbon atoms such as H=CH2.

Among these, as mentioned above, fluoroethylene and fluoropropene are preferred, and fluoroethylene and fluoropropene, in which all hydrogen atoms are substituted with fluorine and chlorine atoms, are particularly preferred, and among them, chlorotrifluoroethylene (CCQF =CF, ) is suitable.

The fluoroolefins (a) may be used alone or in combination of two or more.

The radically polymerizable monomer (b) having an olefinic unsaturated bond and having a group that becomes a hydroxyl group upon hydrolysis bonded to a carbon atom used in the present invention is represented by the following general formula (I). Or a compound represented by [II) can be mentioned.

(In the formula, R1 is an alkylene group having 1 to 10 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z is a hydrolyzable group.) General formula (1) or (II) Examples of Z include tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 3-bromotetrahydropyranyl group, tetrahydrofuranyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, 1-iso Propoxyethyl group, trimethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, tert-butyldimethylsilyl group, methyldiisopropylsilyl group, tert-butyldiphenylsilyl group, methyl di-tert-butylsilyl group, tribenzylsilyl group, tri-p-xylylsilyl group group, triisopropylsilyl group, triphenylsilyl group, etc.

Specific compounds represented by the general formula [1] include, for example, 4-vinyloxybutyltetrahydrobilanyl ether, 2-vinyloxyethyltetrahydrobilanyl ether, 4-vinyloxybutyl-1'-ethoxyethyl ether, and 2-vinyloxybutyltetrahydrobilanyl ether. Vinyloxyethyl-1'-ethoxyethyl ether, 4-vinyloxybutoxytrimethylsilane, 2-vinyloxyethoxytrimethylsilane, 4-vinyloxybutoxytriethylsilane, 2-vinyloxyethoxytrimethylsilane, 4-vinyloxybutoxyisopropyldimethylsilane, Examples include 2-vinyloxyethoxyisopropyldimethylsilane.

Specific compounds represented by the general formula [11] include, for example, 2-acryloyloxyethyltetrahydropyranyl ether, 2-methacryloyloxyethyltetrahydropyranyl ether, 2-acryloyloxyethyl-1'-ethoxyethyl ether, 2- methacryloyloxyethyl-1'-ethoxyethyl ether,
2-acryloyloxyethoxytrimethylsilane, 2
-methacryloyloxyethoxytrimethylsilane, 2
-acryloyloxyethoxytriethoxysilane, 2
-methacryloyloxyethoxytriethoxysilane,
Examples include 2-acryloyloxyethoxyisopropyldimethylsilane and 2-methacryloyloxyethoxyisopropyldimethylsilane.

Among the specific compounds represented by the general formula [I] or (II), compounds in which Z is a trialkylsilyl group are preferred, and 4-vinyloxybutoxytrimethylsilane is particularly preferred.

The radically polymerizable monomer (b) may be used alone or in combination of two or more.

The organosilicon compound (c) having an olefinic unsaturated bond and having a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom for use in the present invention has the following general formulas (III) to (V ) can be mentioned.

R"R'5iY1Y"...(m)
R"X1SiYiY" - (IV) R"S
iY”Y”Y” ... [■] (In the formula, R
3, R4 has an olefinic unsaturated bond.

It consists of a carbon atom, a hydrogen atom, and in some cases an oxygen atom, each representing the same or different groups.

xl is an organic group having no olefinic unsaturated bond, Yl
, Y2 and Y3 each represent the same or different hydrolyzable groups. ) R3 or R4 specifically includes a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group,
Examples include a cyclopentadienyl group, and a terminal olefinically unsaturated group is particularly preferred. Further, R3 or R4 has an ester bond of a terminal unsaturated acid.

CH2=CI(Coo (CH,)a-.

(H2=C(CH,)COO(CH,)a-1CH2=
C(CH,)Coo (cHt')2-0- CCH
2) 3-1CH,=C(CH3)C00CH,CH,
It may be a group such as OCH, CHCH, O(C112), -, or the like. Among these, those in which R3 and R4 do not contain oxygen atoms and are composed of carbon atoms and hydrogen atoms are preferred, and vinyl groups are particularly optimal.

Specifically, x1 is a methyl group, an ethyl group, a propyl group, a tetradecyl group, or an octadecyl group.

Examples include monovalent hydrocarbon groups such as phenyl group, benzyl group, and tolyl group. These groups may be halogen-substituted hydrocarbon groups.

Yl, Y2 or Y3 specifically includes an alkoxy group or alkoxyalkoxy group such as a methoxy group, ethoxy group, butoxy group, or methoxyethoxy group; an acyloxy group such as a formyloxy group, an acetoxy group, or a propionoxy group; -ON2C (CHa)z,0N=CHCH,C2
Oxime such as H5, -0N=C(C6H5)2; and any other hydrolyzable organic group can be mentioned.

The organosilicon compound (c) is preferably a compound represented by the general formula EV), particularly an organosilicon compound in which Yl, Y2, and Y3 are the same. Among these, organosilicon compounds in which R3 is a vinyl group and Y1 to Y3 are an alkoxy group or an alkoxyalkoxy group are particularly preferred, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(methoxyethoxy)silane, and the like. Also preferably used are vinyloxypropyltrimethoxysilane, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, and the like.

The organosilicon compound (c) may be used alone or in combination of two or more.

As the alkyl vinyl ether (d) used in the present invention, a compound in which a vinyl group and an alkyl group are bonded via an ether bond can be used.

Examples of such alkyl vinyl ether (d) include ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, and 4-methyl vinyl ether.
Examples include chain alkyl vinyl ethers such as 1-pentyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether.

Among these, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and the like are particularly preferred.

Alkyl vinyl ether (d) may be used alone,
Moreover, two or more types may be mixed and used.

In the present invention, the above (a) to C) or (a)
In addition to ) to d), a small amount of other copolymerizable 7mers such as α-olefins, cycloolefins, vinyl carboxylates, allyl carboxylic esters, etc. may be copolymerized.

In the production method of the present invention, monomers (a) to b), (a) to d), or monomers obtained by adding other monomers to these monomers are randomly copolymerized in the presence of a radical initiator.

The usage ratio of each monomer is 25 to 60 mol% of (a), preferably 30 to 55 mol%, 0.5 to 60 mol% of (b), preferably 1 to 50 mol%, and 1 to 50 mol% of (c). 25 mol%, preferably 3 to 20 mol%, and (d) 0 to 50 mol%, preferably 10 to 40 mol%.

Various known radical initiators can be used in the copolymerization reaction. Specifically, organic peroxides, organic peresters such as benzoyl peroxide,
Dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate) hexyne-3,1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, Dilauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tart-butylperoxy)hexyne-3,2,5-dimethyl-2,5
-di(tert-butylperoxy)hexane, ter
tert-butyl perbenzoate, tert-butyl perphenylacetate, tqrt-butyl perisobutyrate, tert-butylperu 5eC-octoate, t
Azo compounds such as ert-butyl perpivalate, cumyl perpivalate, tart-butyl perdiethyl acetate, and the like, such as azobis(isobutyronitrile) and dimethylazoisobutyrate, are used. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxide),
Dialkyl peroxides such as -butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred.

The copolymerization reaction is preferably carried out in a reaction medium consisting of an organic solvent. Such organic solvents include benzene,
Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-hebutane:
Chlorobenzene, bromobenzene, iodobenzene, 0
- Halogenated aromatic hydrocarbons such as bromotoluene; halogenated aliphatic hydrocarbons such as tetrachloromethane, 1,1.1-trichloroethane, tetrachloroethylene, 1-chlorobutane, etc. can be used.

In the copolymerization reaction, a radical initiator is added in a molar ratio of lXl0- to the total number of moles of monomers in the reaction medium as described above.
It is preferable to add in the range of "~2X10-". Polymerization temperature is -30~200℃, preferably 20~10℃
The polymerization pressure at 0°C is 0 to 100 kg/d-G, preferably 0 to 50 kg/cd-G, and the reaction time is 0.5 to 60 hours, preferably 2 to 30 hours.

In addition, when a fluoroolefin containing chlorine is used as the fluoroolefin (a), during the polymerization reaction and/or
Alternatively, it is desirable to have a chlorine scavenger present in the system during purification of the obtained copolymer.

As such a chlorine scavenger, the following compounds (a) to (c) can be used.

(a) MxA[y(OH), x+3y-2z(A)z-
aH,0 (wherein M is Mg, Ca or Zn,
A is CO or HPO4, X, y, and Z are positive numbers, and a is O or a positive number. ) is a complex compound represented by

Specific examples of such a complex compound (a) include the following compounds.

Mg5AL(OH), 5cOa・4Jo, Mgl Af
l2 (OH)2 D co, -5H20, Mg,
AQt (OH)t'*cOi・4H20, Mg□. A
et al(OH)z□CO,・4H,01Mg,AQ, (O
R)icHPo4-41(,01Ca,AQ, (OH
),, CO3-4H,01Zn, i, (OH),
, Go, ・4H,0 Such a complex compound (a) may be a compound that is not exactly represented by the above formula, for example, Mg, Afl(OH), ・3H20 in which part of O)l is CO , may be a compound substituted with Mg,
+511. (OH) , , Co, -3,5)1
．． It may be a compound such as 0. Further, water of crystallization may be removed from these compounds.

Among these complex compounds (a), 1M is Mg,
Compounds in which A is 003 are preferred.

(b) Basic compounds of alkaline earth metals Basic compounds of alkaline earth metals (b) include MgO, C
Alkaline earth metal oxides such as aO; Mg(OH)2, C
a(OH), etc. alkaline earth metal hydroxide; MgC0
, , CaC0, and other alkaline earth metal carbonates.

Such basic compounds (b) of alkaline earth metals are
It may be a double salt such as (MgCOx ) 4.Mg(OH)z.5H20, or these compounds may have water of crystallization removed.

Among these alkaline earth metal basic compounds (b), Mg-containing compounds are preferred.

(c) Epoxy group-containing compound The epoxy group-containing compound (c) specifically includes γ-glycidoxyprobyltrimethoxysilane, β-(3,4
Examples include silicon-containing epoxy compounds such as -epoxycyclohexyl)ethyltrimethoxysilane; aliphatic epoxy compounds such as trimethylolpropane polyglycidyl ether and neopentyl glycol diglycidyl ether.

Among these, silicon-containing epoxy compounds such as γ-glycidoxypropyltrimethoxysilane are preferred.

Among the chlorine scavengers mentioned above, chlorine scavengers that are inorganic compounds react faster with chlorine (hydrochloric acid) than chlorine scavengers that are organic compounds, and do not dissolve in polymerization or purification systems. Therefore, it is preferably used because it can be easily removed from the system. Particularly preferred are the composite compounds shown in (a).

By making the chlorine scavenger present during the polymerization reaction, during the purification of the obtained copolymer, or both, coloring of the obtained fluorine-based copolymer can be effectively prevented. In particular, by allowing a chlorine scavenger to be present in the system during the polymerization reaction, coloring of the resulting fluorine-based copolymer can be effectively prevented.

When a chlorine scavenger is used during the polymerization reaction, the amount of chlorine scavenger is 0.0% per mole of chlorine atom contained in the fluoroolefin (a).
It is desirable to use amounts of 5 to 100 g, preferably 1 to 70 g.

After the reaction is completed, the chlorine scavenger is separated by a method such as filtration, and the unreacted monomer and solvent are distilled off by a method such as vacuum distillation, thereby obtaining a fluorine-based random copolymer.

The obtained fluorine-based copolymer may be further purified using an alcohol or the like. In this case, it is preferable to use a chlorine scavenger as described above. By using a chlorine scavenger during the purification process, it is possible to effectively prevent rust from forming on the base material when the obtained fluorine-based copolymer is used as a coating component of a paint.

When a chlorine scavenger is used during purification, it is desirably used in an amount of 0.5 to 100 g, preferably 1 to 70 g, per 100 g of the obtained fluorine-based copolymer.

By the above method, the number average molecular weight measured by gel permeation chromatography (GPC) is usually 3,000 to 200,000, dissolves in organic solvents at room temperature, hardens at room temperature, and has excellent storage stability. A fluorine-based copolymer is produced.

Specific examples of organic solvents in which the fluorine-based copolymer can be dissolved include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone and methyl ethyl ketone; diethyl ether, dipropyl ether, and methyl cellosolve; Examples include ethers such as ethyl cellosolve; esters such as ethyl acetate and butyl acetate; alcohols such as ethanol; halogenated hydrocarbons such as trichloromethane, dichloroethane, and chlorobenzene; and mixtures thereof.

The fluorine-based copolymer obtained by the production method of the present invention contains hydrolyzable organic groups derived from components (b) and (c), so when it comes into contact with moisture, the copolymer forms at room temperature. A cross-linking reaction occurs between the molecular chains and hardens. Therefore, as a matter of course, a crosslinking reaction occurs due to moisture in the atmosphere and the copolymer is cured, so that the fluorine-based copolymer can be suitably used as a paint by dissolving it in the organic solvent.

The coating film formed from the fluorine-based copolymer obtained by the production method of the present invention has excellent weather resistance, water resistance, heat resistance, chemical resistance, low friction, etc.

〔Effect of the invention〕

According to the present invention, the above (a) or C), or (a)
Since component d) is copolymerized, it is possible to produce a fluorine-based copolymer that dissolves in an organic solvent at room temperature, cures at room temperature, and has excellent storage stability.

〔Example〕

Next, examples of the present invention will be described.

Example 1 After replacing the interior of a stainless steel autoclave with an internal volume of 1.5 Q with nitrogen, 500% of benzene was added under a nitrogen stream.
m Q, trimethoxyvinylsilane (hereinafter abbreviated as TMVS) 31.1g, ethyl vinyl ether (hereinafter Ev
(abbreviated as E) 60.6 g, 4-vinyloxybutoxytrimethylsilane (hereinafter abbreviated as 4-VOBOTMS) 8
3.8g, synthetic hydrotalcite (Mg4.s)
z (OH), Co, .3.5H, O) powder (hereinafter abbreviated as 5) IT) 9.3 g and dilauroyl peroxide 5.43 g were charged. Then chlorotrifluoroethylene (hereinafter abbreviated as CTFE) 1
83. was introduced into an autoclave, heated to 65°C, and reacted for 7.5 hours.

After that, the autoclave was cooled with water to stop the reaction, and after cooling, unreacted monomer was expelled, and the autoclave was opened.
The reaction solution was taken out into an IQ eggplant flask. 150 g of xylene was added to this reaction solution, residual monomers and solvent were distilled off under reduced pressure using an evaporator, then 400 g of xylene was added, and the solvent was distilled off under reduced pressure using an evaporator again.

After that, 500 g of xylene was added, and the solution was filtered and S
Remove HT and concentrate under reduced pressure to obtain a colorless and transparent copolymer (1)
296g was obtained.

The number average molecular weight of the obtained copolymer (I) by GPC was 16,000. In addition, when the composition of this copolymer (I) was analyzed using elemental analysis and NMR, it was found that C
TFE/4-VOBOTMS/TMVS/EVE, 43
/22/7/28 (mol%).

52.1 parts by weight of the above copolymer (1), 2.6 parts by weight of tetrasilicic acid oligomer as a paint additive, 2.6 parts by weight of methyl orthoformate as a dehydrating agent, and 42 parts by weight of xylene.
A mixture consisting of 7 parts by weight was allowed to stand at room temperature in a sealed state, and the time required for the mixture to harden was measured. Table 1 shows the results.
Shown below.

Comparative Example 1 The interior of a stainless steel autoclave with an internal volume of 1.5Q and a stirrer was replaced with nitrogen, and 180mQ of benzene was added under a nitrogen stream.
EVE 115.1g, hydroxybutyl vinyl ether (hereinafter abbreviated as HyBVE) 24.4g, TMV
S 43.6g, and SHT 13. I prepared Og. Thereafter, 257 g of CTFE was introduced into the autoclave, and the temperature was raised to 65°C.

To this, add 7.6 g of dilauroyl peroxide to 1 part of benzene.
An initiator solution dissolved in 2(la+Ω) was fed over 4 hours. After further reaction at 65° C. for 6 hours, the autoclave was cooled with water to stop the reaction.

After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1.5Q eggplant-shaped flask. 210 g of xylene, 120 g of methanol, and 13.0 g of SHT were added to this, and the mixture was heated at 50° C. for 1.5 hours and then at 60° C. for 1.5 hours while stirring.

After the treatment, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to form a homogeneous solution. This solution was filtered to remove SHT and concentrated under reduced pressure to obtain a colorless and transparent copolymer (II) 3.
22g was obtained.

The number average molecular weight of the obtained copolymer (II) by GPC was 10,300. Furthermore, when the composition of this copolymer (II) was analyzed using elemental analysis and NMR, CTFE/TMVS/EVE/HyBVE=49
/6/39/6 (mol%).

In Example 1, storage stability was measured in the same manner as in Example 1 except that the copolymer (II) above was used instead of copolymer (1). The results are shown in Table 1.

Table 1

Claims (2)

[Claims] (1) (a) fluoroolefin, (b) a radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom, and (c) A method for producing a fluorine-based copolymer, which comprises copolymerizing an organosilicon compound having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom. (2) (a) Fluoroolefin, (b) A radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom, (c) Olefin A fluorine-based copolymer characterized by copolymerizing an organosilicon compound having a sexually unsaturated bond and in which a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom, and (d) an alkyl vinyl ether. manufacturing method.