JPH07118339A - Production of fluoroacrylic resin - Google Patents

Abstract

PURPOSE:To produce efficiently an acrylic resin having fluorine atoms in side chains and being excellent in heat resistance, lubricity, solvent resistance and water repellency. CONSTITUTION:An acrylic resin and a fluoroamine are heated to 100 deg.C or above to introduce fluorine atoms into the side chains of the resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fluorine atom-containing acrylic resin, more specifically, by incorporating a fluorine atom in the side chain of an acrylic resin, heat resistance, solvent resistance, water repellency, etc. And a method for producing a fluorine atom-containing acrylic resin having improved performance.

[0002]

2. Description of the Related Art Various acrylic resins are known such as (meth) acrylic acid [acrylic acid or methacrylic acid, or a mixture thereof] or a homopolymer or copolymer of its ester. Such acrylic resins are often produced as copolymers with other vinyl comonomers, and give various changes to their properties.

These acrylic resins are used in various fields, for example, as adhesives, paints, coating materials, films, separation membranes or plastic materials of various shapes, depending on their properties. Among them, there are many applications that make use of their excellent transparency, weather resistance, mechanical properties, etc., and they are widely used in various industrial fields such as automobile parts, electric / electronic device parts, and building materials.

However, these conventional acrylic resins have a low heat distortion temperature of about 100 ° C. and are more water resistant.
It had the drawback of poor water repellency. Therefore, it has been attempted to introduce a fluorine atom into the acrylic resin.

As a method of introducing a fluorine atom, a method of polymerizing an acrylic monomer substituted with a fluorine atom (Japanese Patent Publication No. 55-23567) and a method of polymerizing an acrylic acid ester monomer consisting of an alcohol substituted with a fluorine atom ( JP-A-3-26911, JP-A-63-
No. 507) has been proposed, but the obtained polymer is excellent in water repellency, but has a problem of insufficient heat resistance. Further, a method of reacting polyacrylic acid and 1,1-dihydroxyperfluoroalkylamine in the presence of a specific compound (JP-A-3-243609).
However, this method has a problem that a specific compound is required, the process is complicated, and the heat resistance of the obtained polymer is insufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention is a simple process of heating an acrylic resin and a fluorine atom-containing amine to obtain a heat resistance, a solvent resistance, and a heat resistance containing a fluorine atom in a side chain.
An object of the present invention is to provide an efficient production method capable of producing an acrylic resin having excellent water repellency.

[0007]

Means for Solving the Problems The present inventor has made an acrylic resin and a fluorine atom-containing amine react with each other by a simple operation of heating to thereby obtain a heat resistance, a solvent resistance, and a hydrophobic property which contain a fluorine atom in a side chain. It has been found that an acrylic resin having excellent water-based property can be obtained, and based on this finding, the present invention has been completed.

That is, according to the present invention, a method for producing a fluorine atom-containing acrylic resin is characterized in that the acrylic resin and the fluorine atom-containing amine are heated to 100 ° C. or higher to contain a fluorine atom in the side chain of the acrylic resin. Is provided.

In the method for producing a fluorine atom-containing acrylic resin of the present invention, the acrylic resin of which the fluorine atom-containing amine is reacted is of any kind and structure as long as it has a carbonyl group in the side chain. It may be a polymer. A carbonyl group easily reacts with a fluorine atom-containing amine at a temperature of 100 ° C or higher without a catalyst, and as a result, a fluorine atom is introduced into a side chain, and an acrylic resin excellent in heat resistance, solvent resistance and water repellency is obtained. can get.

The acrylic resin preferably used in the method of the present invention is, for example, at least the following general formula [I]

[0011]

[Chemical 1]{However, R in the formula [I]¹ Is a hydrogen atom or 1 to 4 carbon atoms
Alkyl group of R² Is a hydrogen atom or an alkane having 1 to 8 carbon atoms.
Represents a kill group. } Has a repeating unit [I]
Polymers may be mentioned.

The polymer having the repeating unit [I] represented by the general formula [I] may be a homopolymer or a copolymer composed of two or more kinds of repeating units.

Such a polymer has, for example, the following general formula [II]:

[0014]

[Chemical 2]{However, R in the formula [II]¹ , R² Has the same meaning as above
To do. } Acrylic acid and acrylic acid derivatives represented by
Homopolymerization of one or more of [II] or
Polymers obtained by copolymerization and these acrylic acids and
One or more of the acrylic acid derivatives [II],
Copolymerizable with the acrylic acid and / or acrylic acid derivative
At least one of other vinyl compounds [III]
Examples of various polymers obtained by copolymerizing
You can

In the case of a copolymer, acrylic acid and /
Alternatively, the copolymerization ratio of the acrylic acid derivative [II] is preferably 10 mol% or more.

Specific examples of [II] include acrylic acid,
Methacrylic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, 2-butylpropenoic acid and its ester form can be mentioned.

On the other hand, other vinyl compounds [III] copolymerizable with these acrylic acids and / or acrylic acid derivatives
As, there are various olefins and various functional group-containing olefins, and of these, typical examples include, for example, acrylonitrile, methacrylonitrile,
Other (meth) acrylic compounds such as acrylamide, methacrylamide, acrolein, and methacrolein, styrene, α-methylstyrene, p-methylstyrene, 2,4
-Dimethyl styrene, p-tert-butyl styrene,
styrenes such as p-chlorostyrene, vinyl pyridine,
Examples thereof include N-2-vinylpyrrolidone and maleic anhydride.

Specific examples of the acrylic resin include polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate and the like.

The fluorine atom-containing amine is preferably a fluorine atom-containing primary alkylamine represented by the general formula R-NH ₂ (wherein R represents a fluorinated alkyl group having 1 to 10 carbon atoms). Used for.

Specifically, trifluoromethylamine,
Examples include pentafluoroethylamine, heptafluoropropylamine, pentadecafluorooctylamine and the like.

These fluorine atom-containing amines are
One kind may be used alone, or two or more kinds may be used together as a mixture or the like, if necessary.

As the reaction conditions for reacting the acrylic resin with the fluorine atom-containing amine, the following conditions are usually preferably adopted.

That is, the reaction temperature is 100 ° C. or higher, usually 100 to 300 ° C., preferably 150 to 2
It is suitable to select in the range of 50 ° C, and the reaction time is
Usually, it is good to select in the range of 1 minute to 5 hours, preferably 30 minutes to 2 hours.

If the reaction temperature is less than 100 ° C., the predetermined reaction rate becomes slow, which is not practical.
If the reaction is carried out at a high temperature exceeding ℃, the polymer is likely to be decomposed or side reaction may occur.

The ratio of the fluorine atom-containing amine used is not particularly limited and may be appropriately determined in consideration of the purpose of use of the resulting fluorine atom-containing acrylic resin, but usually the composition of the acrylic resin to be reacted, especially the carbonyl group. Varies depending on the content ratio of the carbonyl group in the resin, but 0.01 to 3, preferably 0.02 to 2 (molar ratio)
It is preferable to select the above range, and by selecting these conditions, the effects of improving heat resistance, lubricity, solvent resistance and water repellency can be obtained.

The reaction is usually preferably carried out in a suitable solvent. As this solvent, various ones can be used, but usually, for example, N-methylpyrrolidone (NMP), N-cyclohexylpyrrolidone, dimethylformamide (DMF), dimethylacetamide (DM) are used.
Ac), dimethylimidazolidine (DMI), N-methylcaprolactam, dimethylsulfoxide (DMS)
O), sulfolane, dimethyl propylene urea (DMP
A neutral polar solvent such as U) can be preferably used. Among these, NMP, DMF and sulfolane are particularly preferable. These solvents can be used as a single solvent or a mixed solvent.

The amount of this solvent used is usually preferably selected in the range of 20 to 90% by weight based on the whole reaction system. The reaction pressure can be atmospheric pressure or reduced pressure.

As described above, heat resistance, solvent resistance and water repellency can be improved by reacting various acrylic resins with a fluorine atom-containing amine.

The fluorine atom-containing acrylic resin obtained as described above is separated from the reaction mixture by a conventional method and, if necessary, subjected to an appropriate purification treatment to obtain a desired product.

[0030]

EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited thereto.

In the following example, the reduced viscosity [η _sp / c] of the polymer was measured in NMP at a polymer concentration of 0.2.
The measurement was performed under the conditions of g / dl and a measurement temperature of 60 ° C. Further, the glass transition temperature was measured using DSC at a temperature rising rate of 20 ° C./minute, and the thermal decomposition initiation temperature was measured using TGA in air at a temperature rising rate of 10 ° C./minute. The temperature at the time of% weight loss was determined.

Example 1 In a 100 ml separable flask equipped with a stirrer and an argon gas inlet tube, polymethacrylic acid (reduced viscosity 1.
36 dl / g, thermal decomposition starting temperature 210 ° C.) 3.0 g, pentadecafluorooctylamine 5.0 g, and sulfolane 30 ml were added, and the mixture was heated and stirred at 190 ° C. for 2 hours. At the end of the reaction, the polymer was precipitated. The polymer was triturated in methanol, washed with methanol and dried. The yield of the obtained polymer was 4.6 g, the glass transition temperature was 136.7 ° C., and the thermal decomposition initiation temperature was 363 ° C. When this polymer was pressed at 220 ° C. to produce a film, the film was colorless and transparent, and the film was acetone, toluene, methylene chloride, chloroform, D
Immersion in MF did not change at all. The IR chart of this polymer is shown in FIG. Acid anhydride to 1750 cm ^-1, an imide group in 1700 cm ^-1, to 1205cm ^-1 C-
F-bond absorption was observed. As a result of elemental analysis of this polymer, 42% of F was contained, and from this result, it was found that 41% of the imide was formed in the polymer.

Example 2 Polymethacrylic acid was replaced with polyacrylic acid (reduced viscosity 3.05).
dl / g, thermal decomposition starting temperature 225 ° C.) Polymer was obtained in the same manner as in Example 1 except that the amount was changed to 3.0 g. The obtained polymer had a yield of 4.8 g and a glass transition temperature of 14
The temperature was 9.6 ° C and the thermal decomposition starting temperature was 287 ° C. When this polymer was pressed at 220 ° C. to produce a film, the film was colorless and transparent, and the film was
Immersion in toluene, methylene chloride, chloroform and DMF did not change at all. The IR chart of this polymer is shown in FIG. Acid anhydride at 1740 cm ^-1 , 170
0 cm ^-1 imide group, the absorption of C-F bond was observed at 1210cm ^-1. As a result of elemental analysis of this polymer,
The content of F was 49.5%, and from this result, it was found that the imide form was formed in 55% of the polymer.

Example 3 The same as Example 1 except that the polymethacrylic acid was changed to 3.0 g of polymethylmethacrylate (reduced viscosity 0.95 dl / g, glass transition temperature 116 ° C., thermal decomposition start temperature 365 ° C.). To obtain a polymer. The yield of the obtained polymer was 3.9 g, the glass transition temperature was 131.8 ° C, and the thermal decomposition initiation temperature was 375 ° C. When this polymer was pressed at 220 ° C. to prepare a film, the film was colorless and transparent, and this film was immersed in acetone, toluene, methylene chloride, chloroform, and DMF, but there was no change.

[0035]

Industrial Applicability According to the present invention, it is possible to obtain a fluorine atom-containing acrylic resin having excellent heat resistance, lubricity, solvent resistance and water repellency, and it is expected to have a wide range of uses.

[Brief description of drawings]

FIG. 1 is an IR spectrum of the polymer obtained in Example 1.

FIG. 2 is an IR spectrum of the polymer obtained in Example 2.

Claims (1)

[Claims] 1. A method for producing a fluorine atom-containing acrylic resin, which comprises heating the acrylic resin and a fluorine atom-containing amine to 100 ° C. or higher to contain a fluorine atom in a side chain of the acrylic resin.