JP2550526C - - Google Patents

Description

The present invention relates to a method for producing a hydroxyl group-containing fluoroolefin polymer useful for paints, sealants, films, etc. A hydroxyl group-containing fluoropolymer characterized in that solution radical polymerization of an olefin, a hydroxyl group-containing vinyl ether, an alkyl vinyl ether and / or a cycloalkyl vinyl ether and, if necessary, other copolymerizable monomers is carried out in the presence of an amine. The present invention relates to a method for producing an olefin polymer. [Prior art and its problems] In recent years, solution-type hydroxyl group-containing fluoroolefin copolymers have been developed and used mainly for coatings. However, when producing such a hydroxyl group-containing fluoroolefin copolymer, if the amount of the hydroxyl group-containing monomer used is increased, the non-volatile content of the polymerization is increased, or the target molecular weight of the copolymer is increased, the Gelation sometimes occurs, and the dispersion ratio of the resulting copolymer (weight-average There is a problem that a polymer cannot be produced with good reproducibility. [Problems to be Solved by the Invention] The present inventors have conducted intensive studies in order to solve the above-mentioned problems in the prior art, and as a result, in the presence of amines, a fluoroolefin and a vinyl ether containing a hydroxyl group were used. By subjecting a monomer mixture containing an alkyl vinyl ether and / or a cycloalkyl vinyl ether as an essential component to solution radical polymerization, it does not gel during polymerization and the dispersion ratio does not increase significantly. It has been found that a fluoroolefin copolymer containing is obtained, and the present invention has been completed. [Constitution of the Invention] (Means for Solving the Problems) In summary of the present invention, the present invention comprises a fluoroolefin, a vinyl ether containing a hydroxyl group, an alkyl vinyl ether and / or a cycloalkyl vinyl ether as essential monomer components. And a method for producing a hydroxyl group-containing fluoroolefin copolymer characterized by further performing a solution radical polymerization of another copolymerizable monomer with an amine if necessary, in the presence of an amine. is there. Hereinafter, the configuration of the present invention will be described in detail. As the fluoroolefin component used in the present invention, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene or (per) fluoro Representative examples include alkyl trifluorovinyl ethers (provided that the (per) fluoroalkyl group has 1 to 18 carbon atoms). Next, as a hydroxyl group-containing vinyl ether which is a hydroxyl group-containing monomer component used in the present invention, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, Representative examples include 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether. Further, as the alkyl vinyl ether used in the present invention, 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, n-hexyl vinyl ether, n-hexyl vinyl ether -Octyl vinyl ether, 2-ethylhexyl vinyl ether and the like are typical examples, and as cycloalkyl vinyl ethers, cyclopentyl vinyl ether, cyclohexyl vinyl ether and methylcyclohexyl vinyl ether are typical examples. The combination can sufficiently increase the polymerization rate. In the method for producing a hydroxyl group-containing fluoroolefin copolymer according to the present invention, in addition to the essential monomer components, other monomers that can be copolymerized with these essential monomer components are required. Can be used accordingly. Such other copolymerizable monomers include 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 fluorocyclohexyl vinyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate Vinyl carboxylate esters such as vinyl p-tert-butyl benzoate, vinyl salicylate and vinyl cyclohexanecarboxylate;
Further, ethylene, vinyl chloride, vinylidene chloride, (meth) acrylonitrile, various (meth) acrylates, and the like are typical examples. Further, when the copolymer obtained by the method of the present invention is used as a base resin component for paint, from the viewpoint of coating film hardness, among such copolymerizable monomers, C4
A vinyl ester of an aliphatic monocarboxylic acid having a branched alkyl group of ~ C17,
It is particularly preferable to use at least one selected from the group consisting of vinyl benzoate, vinyl p-tert-butyl benzoate and vinyl cyclohexanecarboxylate. When a hydroxyl group-containing fluoroolefin copolymer is produced from each of the above-mentioned monomer components by the method of the present invention, the ratio of each monomer component used from the viewpoint of the copolymer yield, weather resistance, and the like is the same as that of the fluoroolefin. 20 to 60 mol%, hydroxyl group-containing vinyl ether 5 to 25 mol%, a total of 15 to 75 mol% of alkyl vinyl ether and / or cycloalkyl vinyl ether and other copolymerizable monomers, or 20 to 60 mol% of fluoroolefin, Controlled at 5 to 25 mol% of hydroxyl group-containing vinyl ether and 15 to 75 mol% of alkyl vinyl ether and / or cycloalkyl vinyl ether. Next, typical amines used in the present invention include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sc
Primary amines such as c-butylamine, n-hexylamine, n-octylamine, dodecylamine, cyclohexylamine, benzylamine, phenethylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine , Diisobutylamine, di-n-octylamine,
Didodecylamine, N-methylbenzylamine, piperidine, pyrrolidine, N-
Secondary amines such as methylpiperazine and N-ethylpiperazine; trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine,
Tri-n-butylamine, triisobutylamine, tri-n-hexylamine,
Tertiary amines such as N, N-dimethylbenzylamine, N, N-dimethyldodecylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine, N-methylpyrrolidine, tetramethylethylenediamine, tetramethylhexamethylenediamine is there. Of these amines, the use of tertiary amines is particularly preferred in that the resulting copolymer is less colored. Further, the amount of the amines used is, in terms of the basic nitrogen atoms contained in the amines, per 1000 g of the total amount of the monomers to be copolymerized, from 0.002 equivalents to 0.5 equivalents, and more preferably from 0.01 to 0.2 equivalents. It is preferable to be within the range. If the amount of the basic nitrogen atom is less than 0.002 equivalent, gelation occurs during polymerization, or the dispersion ratio of the obtained copolymer becomes large, and if it exceeds 0.5 equivalent, the polymerization rate becomes difficult to increase or the obtained copolymer becomes It is not preferable because the coloring of the solution becomes remarkable. In carrying out the method for producing a hydroxyl group-containing fluoroolefin copolymer according to the present invention, a known and commonly used radical polymerization initiator is used as a polymerization initiator to be used.As a typical example of such a polymerization initiator, Azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; t-butyl peroxypivalate, t-
Butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, There are peroxides such as cumene hydroperoxide, methyl ethyl ketone peroxide and diisopropyl peroxycarbonate. The amount of the radical polymerization initiator used is appropriately determined according to the type of the polymerization initiator, the polymerization temperature, the molecular weight of the copolymer, and the like.
It may be about 01 to 10% by weight. In order to produce a hydroxyl group-containing fluoroolefin copolymer using each of the above monomer components, a solution polymerization method is applied. The copolymer obtained by the solution polymerization method,
It can be used as it is as a curable resin composition such as a base resin component for a solution type paint. Representative solvents used for producing the copolymer by the solution polymerization method include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; n-pentane, n-hexane, and n-octane. Aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, Pentanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether And alcohols such as propylene glycol monoethyl ether; ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether and di-n-butyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone Ketones such as methyl acetate, ethyl acetate,
Esters such as n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; chloroform, methylene chloride, carbon tetrachloride , Chlorinated hydrocarbons such as trichloroethane and tetrachloroethane; and further, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate and the like. Such solvents may be used alone or as a mixture of two or more, but it is preferable to select them so as to dissolve the resulting copolymer. The amount used may be about 5 to 1000 parts by weight based on 100 parts by weight of the total amount of the monomers used. To produce a hydroxyl group-containing fluoroolefin copolymer by a solution polymerization method from each of the above-mentioned monomer components, all monomers, a solvent, amines and a polymerization initiator are charged together and polymerized, a solvent, Adding other monomers and a polymerization initiator to the reactor charged with the fluoroolefin and the amine continuously or separately;
Monomers, amines, and polymerization initiators are added continuously or separately to a reactor charged only with a solvent.
A method such as adding amines, a polymerization initiator, and other comonomer continuously or dividedly can be applied. The reaction temperature and the reaction pressure of the method of the present invention are appropriately selected depending on the type of the polymerization initiator and the polymerization solvent, and the molecular weight of the target copolymer.
Preferably, a temperature of 40 to 100 ° C. is employed, and a reaction pressure of usually 100 kg / cm 2 or less is employed. The copolymer thus obtained can be used for various applications such as paints, sealing agents, films and the like as it is, or by blending a curing agent capable of reacting with a hydroxyl group, a pigment, a filler, a curing catalyst and the like. [Examples] Next, the present invention will be described more specifically with reference to Examples, Comparative Examples and Reference Examples.
In the following, all parts mean parts by weight unless otherwise specified. Example 1 In a 1 l stainless steel autoclave sufficiently purged with nitrogen, 25 g (8 mol%) of ethyl vinyl ether (EVE) and 50 g (10 mol%) of hydroxybutyl vinyl ether (HBVE) were added.
Mol%), 175 g (32.2 mol%) of cyclohexyl vinyl ether, 215 g of methyl isobutyl ketone (MIBK), 5 g of azobisisovaleronitrile (ABNV), 5 g of t-butyl peroxyoctoate (TBO) and 2 g of triethylamine. Next, 250 g (49.8 mol%) of liquefied and collected chlorotrifluoroethylene was injected, and the mixture was reacted at 55 ° C. for 15 hours with stirring, then heated to 85 ° C. and reacted for 4 hours. A solution of a copolymer containing an acid group was obtained. Example 2 In the same reactor as in Example 1, 50 g (10.3 mol%) of HBVE, 200 g (38.2 mol%) of cyclohexyl vinyl ether, 215 g of butyl acetate, 5 g of ABNV, 5 g of TBO and 5 g of tri-n-
4 g of butylamine was charged. Then liquefied and collected chlorotrifluoroethylene 25
After injecting 0 g (51.5 mol%), the reaction was carried out in the same manner as in Example 1, and NV67.0%, Example 3 100 g of 6-hydroxyhexyl vinyl ether (14.9 g) was placed in the same reactor as in Example 1.
Mol%), EVE50g (14.9mol%), vinyl pivalate 100g (16.7mol%), MIBK
215 g, 5 g of TBO, 5 g of ABNV and 4 g of tri-n-butylamine were charged. Then, after injecting 250 g (53.5 mol%) of tetrafluoroethylene, the reaction was carried out in the same manner as in Example 1. Obtained. Example 4 In the same reactor as in Example 1, 50 g (12.6 mol%) of HBVE, 50 g (14.7 mol%) of isobutyl vinyl ether, and 150 g (23.9 mol%) of Veovar 9 (vinyl ester of a branched fatty acid C9 manufactured by Shell, The Netherlands) ), MIBK215g, TBO5g, ABNV5g and N, N-
2.4 g of dimethylbenzylamine was charged. Then, after injecting 250 g (48.8 mol%) of liquefied and collected hexafluoropropylene, the reaction was carried out in the same manner as in Example 1,
NV Example 5 In the same reactor as in Example 1, 100 g (17 mol%) of HBVE, 50 g (13.6 mol%) of EVE,
Vinyl acetate 50g (11.4 mol%), vinyl benzoate 100g (13.3 mol%), MIBK215g
, ABNV5g, TBO5g and N-methylpiperidine 2g. Then, 150 g (29.4 mol%) of tetrafluoroethylene and 50 g (15.3 mol%) of vinylidene fluoride
Press fit A solution of the copolymer containing groups was obtained. Example 6 50 g of HBVE (11.7 mol%) and 50 g of EVE (18.8 mol) were placed in a 1-liter stainless steel autoclave.
Mol%), 50 g (6.6 mol%) of vinyl p-tert-butylbenzoate, 100 g (17.6 mol%) of vinyl cyclohexanecarboxylate, 215 g of MIBK, 5 g of TBO, 5 g of ABNV and 2 g of N-methylpyrrolidine. Then, liquefied and collected hexafluoropropylene
250g A 000, GC3 hydroxyl group-containing copolymer solution was obtained. Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that 2 g of triethylamine was not used. As a result, a jelly-like gel was formed, and a target polymer solution was not obtained. Comparative Example 2 The reaction was carried out in the same manner as in Example 2 except that 4 g of tri-n-butylamine was not used. As a result, a jelly-like gel was formed and the desired polymer solution was not obtained. Comparative Example 3 The reaction was carried out in the same manner as in Example 3 except that 4 g of tri-n-butylamine was not used. As a result, a jelly-like gel was produced and the desired polymer solution was not obtained. Comparative Example 4 A reaction was carried out in the same manner as in Example 4 except that 2.4 g of N, N-dimethylbenzylamine was not used. As a result, a jelly-like gel was produced, and a target polymer solution was not obtained. Reference Example 1 100 parts of a solution of the hydroxyl group-containing copolymer obtained in Example 1, TYPAQUE CR-93 (
54.5 parts of rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd. and xylene / butyl acetate = 70
A mixture comprising 30 parts of a 30/30 (weight ratio) mixed solvent was ground to obtain a white mill base.
Next, 11.8 parts of Coronate EH (trimer type polyisocyanate of hexamethylene diisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to obtain a white paint. The paint was applied to a zinc phosphate-treated steel sheet using an applicator, and allowed to stand at room temperature for 7 days to obtain a cured coating film having a good appearance of 60 ° gloss 85. When this coating film was exposed to a sunshine weatherometer for 3000 hours, there was almost no decrease in gloss and good weather resistance was exhibited. Reference Example 2 100 parts of a solution of the hydroxyl group-containing copolymer obtained in Example 4, TYPAQUE CR-9354
A white paint was obtained in the same manner as in Reference column 1 from .5 parts, 30 parts of a mixed solvent of xylene / butyl acetate = 70/30 and 11.8 parts of coronate EH. Next, the cured coating film obtained in the same manner as in Reference Example 1 had a good 60 ° gloss of 89, and this coating film was exposed to a sunshine weatherometer for 3000 hours. Showed sex. [Effects of the Invention] A method 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 according to the present invention in the presence of amines, Gelation can be effectively suppressed. Therefore, an excellent hydroxyl group-containing fluoroolefin copolymer which can be used in various applications such as coatings, sealing agents, films and the like by the method of the present invention is provided.

Claims (1)

Claims: 1. A fluoroolefin and a hydroxyl group-containing vinyl ether, an alkyl vinyl ether and / or a cycloalkyl vinyl ether are used as essential monomer components, and if necessary, another copolymerizable monomer is used. When producing a hydroxyl group-containing fluoroolefin copolymer using the copolymers, a hydroxyl group-containing fluoroolefin copolymer characterized in that the monomer mixture is subjected to solution radical polymerization in the presence of amines. Production method. 2. The method according to claim 1, wherein the amine is a tertiary amine. 3. The process according to claim 1, wherein the other copolymerizable monomer is vinyl carboxylate. 4. A vinyl ester of an aliphatic monocarboxylic acid having a branched alkyl group of C _{4 to} C _17, a vinyl carboxylate, vinyl benzoate, p-tert-
4. The method according to claim 3, wherein the method is at least one selected from the group consisting of vinyl butyl benzoate and vinyl cyclohexanecarboxylate. 5. The method according to claim 1, wherein the fluoroolefin is at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene and vinylidene fluoride.