JPS62292813A - Production of fluoroolefin copolymer having hydroxyl group - Google Patents

Abstract

PURPOSE:To obtain a fluoroolefin copolymer having hydroxyl groups in good reproducibility, by radical-copolymerizing a fluoroolefin with a hydroxyl group- containing vinyl ether in the presence of an amine. CONSTITUTION:A monomer mixture comprising a fluoroolefin and a hydroxyl group-containing vinyl ether as essential components and other monomers copolymerizable therewith as optional components is radical-copolymerized in the presence of an amine. Examples of the hydroxyl group-containing vinyl ethers include 2-hydroxyethyl vinyl ether and 2-hydroxy-2-methylpropyl vinyl either. As said amine compound, a tert. amine is particularly desirably used because the coloration of the obtained copolymer is low. The obtained copolymer can be used in many uses such as paints, sealants and films as such or a mixture with a curing agent reactive with hydroxyl groups, a pigment, a filler, a curing catalyst, etc.

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 polymer containing a hydroxyl group is produced by radically polymerizing a fluoroolefin, a vinyl ether containing a hydroxyl group, and, if necessary, other copolymerizable monomers in the presence of an amine. The present invention relates to a method for manufacturing a combination.

[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 you try to increase the amount of hydroxyl group-containing monomer, increase the polymerization nonvolatile content, or increase the target molecular weight of the copolymer, the polymerization Sometimes gelation occurs, and the dispersion ratio (ratio of weight average molecular weight sieve to number average molecular weight sieve) of the resulting copolymer becomes extremely large, making it impossible to produce the desired copolymer with good reproducibility. There is a problem.

[Problem that the invention seeks to solve]

In order to solve the above-mentioned problems of the conventional technology, the present inventors conducted intensive research and found that, in the presence of amines, a monomer mixture containing a fluoroolefin and a vinyl ether containing a hydroxyl group as essential components was radically polymerized. It has been discovered that by allowing the polymerization to increase, a fluoroolefin copolymer containing the desired hydroxyl group can be obtained with good reproducibility without gelling during one polymerization or significantly increasing the dispersion ratio, and in order to complete the present invention. It's arrived.

[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. The present invention provides a method for producing a fluoroolefin copolymer containing a hydroxyl group, which is characterized by carrying out radical polymerization of a hydroxyl group-containing fluoroolefin copolymer in the presence of an amine.

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 ) Fluoroalkyl trifluorovinyl ether [However.

The (per)fluoroalkyl group typically has 1 to 18 carbon atoms.

Next, as a vinyl ether containing a hydroxyl group, which is a monomer component containing a hydroxyl group 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
゜4.4,5.5-octafluoropentyl vinyl ether, 2,2,3,3,4,4,5,5,6,6,7,
7,8,8,9,9-hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether,
(Per)fluoroalkyl vinyl ethers such as perfluorocyclohexyl vinyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, benzoic acid Carboxylic acid vinyl esters such as vinyl, vinyl p-tert-butylbenzoate, vinyl salicylate, and vinyl cyclohexanecarboxylate; Furthermore, ethylene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile,
Representative examples include various (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 base resin component, from the viewpoint of coating hardness, vinyl esters of aliphatic monocarboxylic acids having C4 to C1t branched alkyl groups, vinyl benzoate, vinyl p-tsrt-butylbenzoate, cyclohexane It is particularly preferred to use at least one member selected from the group consisting of vinyl carboxylates.

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 hinyl di-ter, 0 to 88 mol% of other copolymerizable monomers, preferably 20 to 60 mol% of fluoroolefins, 5 to 25 mol% of hydroxyl group-containing vinyl ethers, and other copolymerizable monomers. The polymerizable monomer content is controlled to be 15 to 75 mol%.

Next, typical amine compounds used in the present invention include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, 5C
Primary amines such as C-butylamine, n-hexylamine, n-octylamine, dodecylamine, cyclohexylamine, benzylamine, phenethylamine; dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n- Secondary amines such as butylamine, diisobutylamine, di-n-octylamine, didodecylamine, N-methylbenzylamine, piperidine, pyrrolidine, N-methylpiperazine, N-ethylpiperazine; trimethylamine, triethylamine, trilopropylamine , triisopropylamine, tri-n-butylamine, triisobutylamine, tri-n-hexylamine, N,N-dimethylbenzylamine, N,N-dimethyldodecylamine, N.

3 such as N-dimethylcyclohexylamine, N-methylpiperidine, N-methylpyrrolidine, tetramethylethylenediamine, tetramethylhexamethylenediamine, etc.
There are class amines.

Among these amine compounds, the use of tertiary amines is particularly preferred since the resulting copolymer is less colored.

Further, the amount of the above-mentioned amines to be used is 0.002 equivalent to 0.5 equivalent per 100 of the total amount of monomers to be copolymerized in terms of basic nitrogen atoms contained in the amines, and further, 0. It is preferably within the range of 0.2 equivalents from Ol.

If the amount of basic nitrogen atoms is less than 0.002 equivalents, gelation may occur during polymerization or the dispersion ratio of the resulting copolymer will become large, while if it exceeds 0.5 equivalents, it will be difficult to increase the polymerization rate or the resulting copolymer will have a high dispersion ratio. This is not preferable because the resulting copolymer solution becomes 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.

To produce a fluoroolefin copolymer containing a hydroxyl group using each of the monomer components described above.

Known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization can be applied, but bulk polymerization and solution polymerization methods are preferable. The solution polymerization method is particularly preferable because it can be used as a curable resin composition such as a base resin component. Typical solvents used in producing the copolymer by the solution polymerization method include benzene, toluene, etc. , xylene,
Aromatic hydrocarbons such as ethylbenzene; n-pentane, n
- Aliphatic hydrocarbons such as hexane and n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; methanol,
Ethanol, n-propertool, isopropertool, n
-butanol, isobutanol, tart-butanol, n-pentanol, impentanol, n-hexanol, n-octatool, 2-ethylhexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Alcohols such as butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; Ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether; acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone; methyl acetate, ethyl acetate,
n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate.

Esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; chloroform, methylene chloride, carbon tetrachloride, trichloroethane.

Chlorinated hydrocarbons such as tetrachloroethane: Furthermore, N
-Methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate, etc. 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. The amount may be about 5 to 1000 parts by weight per 100 parts by weight of the total amount.

In order to produce a fluoroolefin copolymer containing a hydroxyl group from each of the monomer components described above by a solution polymerization method,
All monomers, solvent, amines, and polymerization initiator are charged at once and polymerized. ■Solvent.

Adding other monomers and a polymerization initiator continuously or in portions to a reactor containing fluoroolefins and amines; Adding monomers, amines, and polymerization to a reactor containing only a solvent. Add the initiator continuously or in portions; Add the solvent, amines, polymerization initiator, and other comonomers continuously or in portions to the reactor containing the fluoroolefin. Methods such as the following 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/aJ or less.

The copolymer thus obtained can be used as it is or by adding a curing agent that can react with hydroxyl groups, a pigment, a filler, a curing catalyst, etc. for various purposes such as paints, sealants, and films.

〔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 (EVE) 25# (8 mol%) was placed in an IQ stainless steel autoclave that was sufficiently purged with nitrogen.
), hydroxybutyl vinyl ether ()IBVB)S
O# (10 mol%), cyclohexyl vinyl ether 1759 (32,2 mol%), methyl isobutyl ketone (MIBK) 2159, azobisisovaleronitrile (ABNV) 5f t-butylperoxyoctoate (TBO) 5t and triethylamine 2g
Next, 250 # (49.8 mol%) of liquefied and collected chlorotrifluoroethylene was introduced under pressure, and the reaction was carried out at 55°C for 15 hours with stirring, and then the temperature was raised to 85°C and the reaction was carried out for 4 hours. , non-volatile content (N, V,) 69
．． A solution of a hydroxyl group-containing copolymer having a number average molecular weight (stone) of 0% and a Gardner color (G, C,) of 3 was obtained.

Example 2 A reactor similar to Example 1 was charged with HBVE 50 effluent (10,
3 mol%), cyclohexyl vinyl ether 2004)
(38,2-T-/L/%), butyl acetate 215y,
ABNV5i, TBO5t and tri-n-butylamine 47 were charged.

Then 250 chlorotrifluoroethylene was liquefied and collected.
After injecting iF (51.5 mol%), a reaction was carried out in the same manner as in Example 1, and N, V, 67.0%, stone 28,
A solution of a copolymer containing 000, G, C, and 3 hydroxyl groups was obtained.

Example 3 In a reactor similar to Example 1, 100 g (14.9 mol%) of 6-bitroxyhexyl vinyl ether, EVE 5
0 g (14.9 mol%), vinyl pivalate 100 g (
16.7 mol%), Iris IBK 215 seeds, 7805%,
2509 (5
3.5 mol%) was injected, the reaction was carried out in the same manner as in Example 1, and N, V, 69.0%, G, C, 3, stone 33,0%.
A solution of a copolymer containing a 0.00 null hydroxyl group was obtained.

Example 4 In a reactor similar to Example 1, HBVE 50 i (1
2.6 mol%), isobutyl vinyl ether 51 (1
4.7 mol%), Beover 9 (C manufactured by Shell, Netherlands)
1 (vinyl ester of branched fatty acid) 150 t (
23.9 mol%), MIBK 215t, TBO5z
, ABNV 51i and N,N-dimethylbenzylamine 2.49 and then liquefied hexafluoropropylene 2509 (48.8 mol%)
After pressurizing N, V, a reaction was carried out in the same manner as in Example 1.
, 67.5%, 18,000, G, C, 3, a solution of a copolymer containing hydroxyl groups was obtained.

Example 5 HBVE 10i (1
7 mol%), EVE 50 (13.6 mol%),
Vinyl acetate 509 (11.4 mol%), Vinyl benzoate 100 (13.3 mol%), MIBK 2159,
ABNV 51 0 charged with 5 t of TBO and 2 ml of N-methylpiperidine, then 1 ml of tetrafluoroethylene
50 # (29.4 mol%) and vinylidene fluoride 509 (15.3 mol%) were reacted in the same manner as in Example 1 to form N, V, 68%, G, C, 3, A solution of a copolymer containing 34,000 hydroxyl groups was obtained.

Example 6 HBVE501 (
11,7 mol%), EVE 50# (18,8
mol%), vinyl p-tart-butylbenzoate 50#
(6,6 mol%), vinyl cyclohexanecarboxylate 1009 (17,6 mol%), MIBK 2159,
5 TBO, 5 ABNV, and 2 N-methylpyrrolidine were charged. Next, 250 units of liquefied hexafluoropropylene (45.3 mol%) were injected, and then
Reacted in the same manner as in Example 1 to obtain N, V, 67.0%, revision 2.
0,000. A solution of a copolymer containing G, C, and 3 hydroxyl groups was obtained.

Comparative Example 1 When the reaction was carried out in the same manner as in Example 1 except that triethylamine 2 was not used, a jelly-like gelled product was formed and the desired polymer solution could not be obtained.

Comparative Example 2 When the reaction was carried out in the same manner as in Example 2 except that tri-n-butylamine 4g was not used, a jelly-like gelled product was produced and the desired polymer solution could not be obtained.

Comparative Example 3 When the reaction was carried out in the same manner as in Example 3 except that four shots of tri-n-butylamine were not used, a jelly-like gelled product was produced and the desired polymer solution could not be obtained.

Comparative Example 4 When the reaction was carried out in the same manner as in Example 4 except that the N,N-dimethylbenzylamine 2.4 method was not used, a jelly-like gelled product was produced and the desired polymer solution could not be obtained.

Reference Example 1 Solution 100 of the copolymer containing hydroxyl groups obtained in Example 1
54.5 parts of Tybake CR-93 (rutile-type titanium oxide manufactured by Ishihara Sangyo ■) and xylene/butyl acetate = 7
A mixture consisting of 30 parts of a 0/30 (weight ratio) mixed solvent was kneaded to obtain a white mill base. Then Coronate EH
(Trimer type polyisocyanate of hexamethylene diisocyanate made by Nippon Polyurethane Industries) No. 11
．． 8 parts were added to obtain a white paint. This paint was applied to a zinc phosphate-treated steel plate using an applicator, and
After being left for days, a cured coating film with a 60° gloss of 85 and a good appearance was obtained.

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
parts, Tybake CR-9354, 5 parts, xylene/butyl acetate = 70. A white paint was obtained in the same manner as in Reference Example 1 from 30 parts of /30 mixed solvent and 11.8 parts of Coronate EH.
The coating film was exposed to a Sunshine Weather-Ometer for 3,000 hours, and showed good weather resistance with almost no decrease in gloss.

〔Effect of the invention〕

The method of the present invention for producing a hydroxyl group-containing fluoroolefin copolymer by radically polymerizing a monomer mixture containing a fluoroolefin and a hydroxyl group-containing vinyl ether as essential components in the presence of amines is effective for gelation during polymerization. can be suppressed to

Accordingly, 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 method for producing a fluoroolefin copolymer containing a hydroxyl group, which comprises radically polymerizing the monomer mixture in the presence of an amine when producing the polymer. 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 amine is a tertiary amine. 4. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are alkyl vinyl ethers. 5. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are cycloalkyl vinyl ethers. 6. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are alkyl vinyl ethers and cycloalkyl vinyl ethers. 7. The manufacturing method according to claim 1, wherein the other copolymerizable monomers are carboxylic acid vinyl esters. 8. 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. 9. 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 7 or 8, which is one type. 10. The manufacturing method according to claim 1, wherein the fluoroolefin is at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, and vinylidene fluoride.