JPH02605A - Fluorinated copolymer - Google Patents

Abstract

PURPOSE:To obtain a fluorinated copolymer useful for a room temperature- curable coating material by forming a copolymer of chlorotrifluoroethylene with tetrafluoropropyl vinyl ether and a functional vinyl ether. CONSTITUTION:The subject copolymer comprising 40-60mol% chlorotrifluoroethylene, 25-45mol% 2,2,3,3-tetrafluoropropyl vinyl ether and 0.5-25mol% functional vinyl ether (wherein the functional group is a hydroxyl group, a glycidyl group or an amino group) and having an intrinsic viscosity [eta]of, usually, 0.09-0.76dl/g, desirably, 0.115-0.23dl/g is used as a fluorinated copolymer useful as a component of a curable resin composition. This copolymer can be mixed homogeneous,y with a methyl methacrylate polymer, and when used as a component of a coating material, it can improve the chemical resistance, weathering resistance, stain resistance, etc., of the obtained coating. A composition containing a functional methyl methacrylate copolymer has room temperature curability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fluorine-containing copolymer containing a functional group. More specifically, a copolymer of lolotrifluoroethylene, 2.2.3.3-tetrafluoropropyl vinyl ether, and a vinyl ether having a functional group (hereinafter referred to as the copolymer of the present invention) is useful as a component of a curable resin composition. fluorine copolymer).

[Conventional technology and issues] Fluororesin paints have excellent chemical resistance, weather resistance, stain resistance, heat resistance, etc., and are used in a variety of applications that take advantage of these properties. It has poor solubility, and even if it does dissolve, the types of solvents that can be used are limited, and since these solvents have high boiling points, they have disadvantages such as the need for heat treatment at high temperatures after painting. have. In order to eliminate the above-mentioned drawbacks, the combined use of methyl methacrylate polymers and fluorine-based polymers has been studied. However, to date, only vinylidene fluoride polymers have been found, excluding fluorine-containing methacrylate copolymers with low fluorine content, as fluoropolymers that can be mixed homogeneously with methyl methacrylate-1 polymers. Generally, there are only a few types of solvents that can dissolve vinylidene fluoride polymers, and special solvents with high boiling points such as N,N-dimethylformamide and N,N-dimethylacetamide are required to dissolve them. Because it must be used, the drying temperature of the paint must be increased. Paints containing vinylidene fluoride polymers and methyl methacrylate polymers have also been commercialized, but high-temperature baking is required to form films.

In recent years, research has been conducted on cold-curing fluororesin paints that do not require baking at high temperatures. Some studies have been conducted to create room-temperature-curing fluororesin paints using copolymers with improved fluoride, but vinylidene fluoride has poor copolymerizability and requires the use of special fluorine-containing functional monomers. However, the current situation is that copolymers that can be cured at room temperature have not been replaced.

Furthermore, copolymers consisting of fluoroolefin, cyclohexyl vinyl ether, and other copolymerizable monomer components have been proposed for the purpose of room-temperature-curing paints (JP-A-55-25414, JP-A-57-34107). and Japanese Patent Application Laid-open No. 57-34108).

However, the above copolymers have the problem that they cannot be homogeneously mixed with methyl methacrylate polymers, which have good translucency.

[Means for Solving the Problems] In view of the above, the present inventors have conducted extensive research to create a fluorine-containing copolymer that can be used in fluorine-based room-temperature curing paints and can be homogeneously mixed with methyl methacrylate polymer. As a result of stacking chlorotrifluoroethylene 40-60
mol%, 2.2゜3.3-tetrafluoropropyl vinyl ether 25 to 45 mol% and one or two vinyl ethers having a hydroxyl group, glycidyl group or amino group as a functional group (hereinafter referred to as functional vinyl ether)
Consisting of 0.5 to 25 mol% of 8 or more, intrinsic viscosity [η]
(in methyl ethyl ketone, below 35°C), 1) is 0
．． It has been discovered that the above object can be achieved by a fluorine-containing copolymer having a hydrogen content of 0.09 to 0.78 dl/g, leading to the completion of the present invention.

That is, in the present invention, by selecting the above-mentioned specific fluorine-containing olefin compound as a component of the fluorine-containing copolymer, the copolymer can be produced by a normal polymerization method, and the resulting copolymer is a methyl methacrylate polymer. It has been discovered that it is possible to mix homogeneously with or without using a conventional solvent. The obtained copolymer can be used as a component of a paint to improve the chemical resistance, weather resistance, stain resistance, etc. of the paint. In addition, this copolymer and specific methyl methacrylate-1
・The composition containing the copolymer has room-temperature curability and has the remarkable effect of being usable for paints, etc.

[Function and Examples] The functional vinyl ether used in the present invention has good copolymerizability with chlorotrifluoroethylene and 2,23.3-tetrafluoropropyl vinyl ether, and always imparts one-episode curability. A material containing a functional group that can be used is used. Such functional vinyl ethers include vinyl ethers that bind hydroxyl, glycidyl or amino groups, and specific examples include hydroxypropyl vinyl ether, hydroxyisopropyl vinyl ether, hydroxybutyl vinyl ether, hydroxy-2-methylbutyl vinyl ether, glycidyl vinyl ether, Ethylene oxyglycidyl vinyl ether nyl ether (CH2-CHoC)12CH2N+
42), aminopropyl vinyl ether, etc., and preferably hydroxybutyl vinyl ether, glycidyl vinyl ether, etc.

The proportions of chlorotrifluoroethylene, 2,2.3.3-tetrafluorobrobyl vinyl ether and functional vinyl ether constituting the fluorine-containing copolymer of the present invention are 40 to 60 mol% of chlorotrifluoroethylene, 2,2,
3.3-Tetrafluoropropyl vinyl ether 25~
50 mol%, functional vinyl ether 0.5-25 mol%
A range of is preferred. When the amount of chlorotrifluoroethylene exceeds 60 mol%, the solubility of the copolymer decreases, and when it becomes less than 40 mol%, the chemical resistance, weather resistance, stain resistance, etc. of the copolymer are reduced. properties deteriorate.

When the amount of seedlings containing 2,2.3.3-tetrafluoropropyl vinyl ether exceeds 50 mol%, properties such as chemical resistance, weather resistance, and stain resistance decrease, and when the amount is less than 25 mol%, methyl methacrylate 1. It becomes difficult to mix homogeneously with the polymer. The amount of functional vinyl ether may be controlled in relation to hardness, chemical resistance, etc. depending on the application.
If it exceeds 25 mol%, problems may occur with the solubility of the co-electrolyte obtained due to the influence of functional groups, and the physical properties of the coating film may deteriorate. Curing property becomes irreversible.

The fluorine-containing copolymer of the present invention is produced by polymerizing chlorotrifluoroethylene, 2,2,3.3-tetrafluoropropyl vinyl ether and functional vinyl ether at a temperature of -20 to 150°C, preferably 5 to 95°C. and 0-30 kg/cd G, preferably 1 old<H
It is produced by polymerization using methods such as emulsion polymerization, suspension polymerization, or solution polymerization in an aqueous medium under pressure conditions of /c+JG or lower. The intrinsic viscosity [η] of the obtained copolymer of the present invention is usually 0.09 to 0.76 dl/g, and particularly preferably 0.115 to 0.23 dl/g.

Examples of the solvent used in the solution polymerization reaction include trichlorotrifluoroethane, 1,1,1.2-tetrachloro-2,2-difluoroethane, methyl ethyl ketone, ethyl acetate, and butyl acetate.

Examples of polymerization catalysts used in the reaction include persulfates such as ammonium persulfate and potassium persulfate, sulfites such as persulfates and potassium sulfite and sodium sulfite, and/or acidic acids such as acidic potassium sulfite and acidic sodium sulfite. Redox polymerization initiator using sulfite, diisopropyl peroxydicarbonate, t-
Peroxide polymerization initiators such as butyl peroxybutyrate or benzoyl peroxide, azo polymerization initiators such as azobisisobutyronitrile, and the like are preferably used. The amount of the polymerization initiator used is usually 0.01 to 5-6% (wt%, the same applies hereinafter), preferably 0.05 to 1.0%, based on the total amount of the Tlt polymer.

The fluorine-containing copolymer of the present invention obtained by the above method includes methyl ethyl ketone, trichlorotrifluoroethane,
It can be homogeneously mixed by dissolving it in a solvent such as ethyl acetate or butyl acetate and mixing it with the methyl methacrylate mixture in a solution state, or by kneading it with heated rolls in the absence of a solvent. By blending the fluorine-containing copolymer thus obtained with a methyl methacrylate copolymer having a functional group (hereinafter referred to as functional MMAJ':ffi copolymer), an excellent curable resin composition can be obtained.

Functional MMAjJ used in the curable resin S
[For the combination, a copolymer of methyl methacrylate and a monomer having a functional group such as hydroxyethyl methacrylate, grindyl methacrylate, acrylamide, or methacrylamide is used. The functional HMA copolymer may optionally include ethyl methacrylate-1., butyl methacrylate, trifluoroethyl methacrylate-1.,
Gold platinum may be obtained by copolymerizing a third component such as pentafluoropropyl methacrylate-1, methyl acrylate, butyl acrylate-1. The third component is a functional MM that improves the homogeneity of the curable resin composition or the coating film obtained therefrom.
Since the functional stripes of the A copolymer vary slightly depending on the type, they are used for adjustment.

Sensual MMAJ! :iff The ratio of the monomer that forms the functional group a of methyl methacrylate and the third component in the coalescence is methyl methacrylate-1.GO ~ 99.5 mol%, and the monomer that forms the functional group q 0.5 ~ 25 mol%, third component O~30
It is mole%. The amount of methyl methacrylate is 60 mol%
If it is less than this, the compatibility with the fluorine-containing copolymer of the present invention becomes poor, and a homogeneous mixture cannot be obtained. If the content of the monomer having a functional group exceeds 25 mol%, the compatibility with the fluorine-containing copolymer of the present invention deteriorates, and homogeneous mixing becomes impossible. The amount of functional groups during coalescence decreases and sufficient curability cannot be achieved.

The blending ratio of the fluorine-containing copolymer of the present invention and the functional group MMA copolymer is 1/9 to 9/1, preferably 37
A range of 7 to 7/3 is desirable. If the amount of functional HMA copolymer exceeds 90%, properties such as chemical resistance, weather resistance, and stain resistance, which are characteristics of fluorine-containing copolymers, will hardly be obtained, and if it becomes less than 10%, Sensual MM
The characteristics of copolymer A, such as a high glass transition temperature, are reduced.

Such a curable resin composition is cured by adding a curing agent. As a curing agent, functional (but hydroxylic acid 21) (
In this case, isocyanates, such as hexamethylene diisocyanate! - and its 3111 substance and 1 derivative, xylene diamine ane-1., tolylene diisocyanate and tolylene diisocyanate, hydrogenation -4.
4'-diphenylmethane diisocyanate-1, etc. are used, and can be used depending on the type of diisocyanate. When the functional group is a grindyl group, amines such as diethylenetriamine, triethylenetetramine, xylenediamine, metaphenylenediamine, benzyldimethylamine, bisaminobrobyltetraoxasbiroundecane, etc. are used as the curing agent, depending on the purpose. Can be used for different purposes. When the functional group is an amino group, a linear dieboxide represented by the formula: an integer of 4;
Examples include aromatic dieboxides and aromatic triepoxides.

This curable resin composition can be used as it is or by dissolving or dispersing it in a solvent as a paint, etc., and the paint prepared using this curable resin composition can be used as an outdoor or indoor paint like a normal paint. It is used for metals, wood, concrete, plastics, etc., and has excellent chemical resistance, weather resistance, and dye resistance. In particular, when the coating film has a transparency of 76% or more in the wavelength range of visible light when the coating film is 0.2 mm thick, the sharpness of the pigment added in the preparation of the coating material and the gloss of the coating film are good.

Next, the copolymer of the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 A 1000 ml glass autoclave was charged with 350 g of ion-exchanged water and 1 g of sodium carbonate, and after the space was sufficiently replaced with nitrogen gas to remove oxygen, 180 ml of trichlorotrifluoroethane was charged, and then 2.
2,3.3-tetrafluoropropyl vinyl ether 2
8.5F: 5.2g of hydroxybutyl vinyl ether
and chlorotrifluoroethylene 28sr were charged. The mixture was heated to 45°C with stirring, and 0.35 g of diisopropyl peroxydicarbonate was added as a polymerization initiator, followed by polymerization at the same temperature for 8 hours. The pressure at the start of polymerization was 2.0 kg/cdG, and the pressure after 8 hours of polymerization was 0.2 kg/cdG. The polymer was dissolved in trichlorotrifluoroethane, and this was added to petroleum ether with stirring to reprecipitate it.

Thereafter, the polymer was dried under reduced pressure to obtain 51 g of polymer (polymerization rate: 83%).

The intrinsic viscosity [η] of the obtained polymer at 35°C in methyl ethyl ketone was 0.23 (dl/g), and the thermal decomposition temperature (temperature at which reduction started in air at a heating rate of 10°C/min)
The glass transition temperature (heating rate 10
'c/min) was 43°C. The obtained polymer was also subjected to elemental analysis and infrared spectral analysis (hereinafter referred to as !R analysis). II? The analysis results confirmed that this polymer contains hydroxyl groups, and the hydroxyl value was determined (according to Its K 00761%6) and the elemental analysis results showed that it was chlorotrifluoroethylene/2,
2,3.3-tetrafluoropropyl vinyl ether/
Hydroquine butyl vinyl ether was found to be a copolymer with a molar ratio of approximately 5HA.

Elemental analysis value: Actual value (%): C31.7 (J13.3 F
43.8 Examples 2 to 5 Polymers having the compositions shown in Table 1 were prepared in the same manner as in Example 1. The amount of chlorotrifluoroethylene used was all the same as in Example 1, and the amounts of other components were varied to obtain copolymers having the compositions shown in Table 1.

The intrinsic viscosity, thermal decomposition temperature and glass transition temperature of the obtained polymer were determined in the same manner as in Example 1. The results are shown in Table 1.

Example 6 Methyl methacrylate-ti was added to a 300 ml four-tube flask.
G, 8g, pentafluoropropyl methacrylate 6g
7.2 g of 1-hydroxyethyl methacrylate, 60 g of methyl ethyl ketone as a solvent, 1.0 g of stearyl mercaptan as a 1-chain hyperactivity agent, and 0.5 g of azobisisobutyronitrile as a polymerization initiator were charged. The inside of the flask was evacuated, heated to 76° C. with stirring, and allowed to stand at the same temperature for 7 hours, resulting in a viscous polymer solution (polymerization rate of 98%).

The intrinsic viscosity, glass transition temperature and thermal decomposition temperature of the obtained polymer were determined in the same manner as in Example 1. The results are shown in Table 1.

The obtained polymer was subjected to IR analysis and elemental analysis. From the results of Il1 analysis, it was confirmed that this polymer contained hydroxyl groups, and the hydroxyl value was determined (JIS K
0076-1'lGG) and the results of elemental analysis revealed that methyl methacrylate/pentafluoropropyl methacrylate/hydroxyethyl methacrylate-1 was a copolymer with a molar ratio of approximately 85 to 5/10.

Example 7 In the same manner as in Example 6, 69 g of methyl methacrylate, 11 g of glycidyl methacrylate, 8 g of methyl ethyl ketone were prepared.
0g1 stearyl mercaptan 0.6g and azobisisobutyronitrile 0. Polymer (polymerization rate 9) using Gg
7.5%) was prepared.

The intrinsic viscosity, glass transition temperature and thermal decomposition temperature of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.

The obtained polymer was subjected to elemental analysis, and the results revealed that the molar ratio of methyl methacrylate/glycidyl methacrylate was approximately 90/10.

Example 8 In place of pentafluoropropyl methacrylate in Example 6, ethyl methacrylate was used in an equimolar amount for polymerization to obtain a polymer.

The intrinsic viscosity, glass transition temperature and thermal decomposition temperature of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.

From the results of hydroxyl value determination (according to JIS K 0076-1986) and elemental analysis, the obtained polymer has a molar ratio of methyl methacrylate-1/ethyl methacrylate/hydroxyethyl methacrylate-1 of approximately 80 halo Met.

Example 9 A 1000 ml glass autoclave was charged with 35 i of ion-exchanged water and 1.5 g of sodium carbonate, the space was sufficiently replaced with nitrogen gas to remove oxygen, and then 180 ml of trichlorotrifluoroethane was charged. 2,2,3.3-tetrafluoropropyl vinyl ether GO, 3g, hydroxybutyl vinyl ether g
and 59.3 [chlorotrifluoroethylene] were charged. Heat to 40°C with stirring and add 0.2 g of diisopropyl peroxydicarbonate I as a polymerization initiator.
was added and polymerized at the same temperature for 12 hours. The pressure at the start of polymerization was 2.4 kg/cdG, and the pressure after 12 hours of polymerization was 0.32 kg/cJG. The polymer was dissolved in trichlorotrifluoroethane, and this was added to petroleum ether with stirring to reprecipitate it. After that, the polymer is dried under reduced pressure, and 115
g (polymerization rate of 88%) was obtained.

The intrinsic viscosity [η] of the obtained polymer was 0.76 tll/g
Met.

Example 1O A polymerization reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 55°C and the polymerization time was 3 hours. The pressure at the start of polymerization was 3.1 kg/ci G, and the pressure after 3 hours of polymerization was 0.50 kg/cd G.

The obtained copolymer weighed 55 g (polymerization rate 89%), and its intrinsic viscosity [η] was 0.09 mol/g.

Examples 11-20 The copolymers obtained in Examples 1.6 and 8 were each
026 methyl ethyl ketone solution and were mixed in the proportions shown in Table 2, and homogeneous mixing was confirmed with the naked eye. 1 part of a 50% solution of hexamethylene diisocyanate trimer in methyl ethyl ketone as a curing agent per 100 parts of the mixture.
After adding 4 parts and mixing thoroughly, it was applied onto a sputter-etched tetrafluoroethylene/hexafluoropropylene copolymer film, cured at room temperature for 30 minutes, placed in a vacuum drying mold, and completely removed the solvent. Sa 0
．． Obtained coatings for 2 cities.

The glass transition temperature and light transmittance at G50 nm of the obtained coating film were measured in the same manner as in Example 1. The results are shown in Table 2.

In addition, regarding the sample of Example 13, the light transmittance of light of various wavelengths was also measured. The results are shown in Table 3.

The thickness of the composition containing the curing agent is sufficiently degreased.
It was applied onto a 0.2 mm aluminum plate, dried at room temperature for 30 minutes, and then placed in a vacuum dryer for 40 hours to completely remove the solvent. Using the obtained sample, the contact angle was determined using water, glycerin, diethylene glycol, methylene diiodide, and tetrachloroethylene using a contact angle A11j machine manufactured by Kyowa Kagakusha ■, and the critical surface tension was determined using a Zisman plot. I asked for. The results are shown in Table 2.

Examples 21 to 23 The copolymers obtained in Examples 2 and 7 were made into 20% methyl ethyl ketone solutions and mixed in the proportions shown in Table 2, and homogeneous mixing was confirmed with the naked eye. To 100 parts of the mixture, 12 parts of a 50% solution of bisaminopropyltetraoxaspiroundecane in methyl ethyl ketone was added as a curing agent and thoroughly mixed. Thereafter, a sample was prepared with the same L'Q as in Example 11, and the glass transition temperature, light transmittance, and critical surface tension were measured. The results are shown in Table 2.

[Margins below] The details of each copolymer (1+1 monomer) in Table 1 are as follows.

CTPIE: Chlorotrifluoroethylene 4PVIE:
2.2,3.3-Tetrafluoropropyl vinyl ether 1113VE: Hydroxybutyl vinyl ether GVE
Nigericidyl vinyl ether MMA: Methyl methacrylate 5FM: Pentafluoropropyl methacrylate IIIEMA: Hydroxymethyl methacrylate 0M Nigericidyl methacrylate 1.1: MA: Ethyl methacrylate [blank below] Table 3 Example 24 and Comparative Examples 1- 6 A copolymer was obtained in the same manner as in Example 1 except that the 2,2,3,3-tetrafluoropropyl vinyl ether used in Example 1 was replaced with an equimolar amount of the vinyl ether shown in Table 4.

Each of the copolymer obtained in Example 1 and the copolymer obtained by the above polymerization was made into a 20% methyl ethyl ketone solution, and the polymerization ratio was adjusted to 20% methyl ethyl ketone solution of the methyl methacrylate polymer shown in Table 4. /l into a 20 ml sample tube, capped and shaken, and the compatibility was observed. The results are shown in Table 4.

In Table 4, ◯ indicates that the mixed solution is homogeneous, and △ indicates that it is slightly non-uniform, × indicates that the mixed solution is cloudy or separated into two layers.

Comparative Examples 7 to 8 A four-component composition was prepared in the same manner as in Example 1 except that 1/2 ffl of the 2,2,3,3-tetrafluoropropyl vinyl ether used in Example 1 was replaced with the vinyl ether shown in Table 4. I got a polymer. Example 2 using the obtained copolymer
The compatibility with the methyl methacrylate polymer solution shown in Table 4 was determined as 4p1 in the same manner as in 4. The results are shown in Table 4.

(margin below c) The details of each vinyl ether in Table 4 are as follows.

8PVIE: CH2-Cll0CI-12(Cr
3CF2 )2 l118PVE: CH2-C11
0CH2(CF2CF2)4+1 [Effects of the Invention] The fluorine-containing copolymer of the present invention can be homogeneously mixed with other polymers such as functional MMA copolymers, and can produce excellent room-temperature curable resin compositions. can be provided.

Claims (1)

[Claims] 1. 40 to 60 mol% of chlorotrifluoroethylene,
2,2,3,3-tetrafluoropropyl vinyl ether in a range of 25 to 45 mol% and one or more vinyl ethers having a hydroxyl group, glycidyl group or amino group as a functional group in a range of 0.5 to 25 mol%. A fluorine-containing copolymer containing a fluorine-containing copolymer having an intrinsic viscosity [η] of 0.09 to 0.76 dl/g. 2. The copolymer according to claim 1, which has an intrinsic viscosity [η] of 0.115 to 0.23 dl/g.