WO2006132208A1

WO2006132208A1 - Method for producing fluorine atom-containing (meth)acrylic acid ester polymer and polymer obtained by such method

Info

Publication number: WO2006132208A1
Application number: PCT/JP2006/311274
Authority: WO
Inventors: Etsuo Horii; Hirosuke Kawabata; Toshikazu Hirao; Xiaoliang Xu; Akiya Ogawa
Original assignee: Kaneka Corporation; Osaka University
Priority date: 2005-06-08
Filing date: 2006-06-06
Publication date: 2006-12-14
Also published as: JPWO2006132208A1

Abstract

Disclosed is a method for producing a fluororesin which enables to produce a fluororesin in a short time without requiring a special polymerization equipment. In this method, a (meth)acrylic acid ester polymer and a fluorine atom-containing alcohol are mixed by using a shear kneader, preferably by using an extruder for producing a fluorine atom-containing (meth)acrylic acid ester polymer through an ester exchange reaction, and the thus-produced polymer is continuously extruded from the extruder and formed into pellets.

Description

Specification

Method for producing fluorine atom-containing (meth) acrylic acid ester polymer and polymer thereof

Technical field

The present invention relates to a method for producing a fluorine atom-containing (meth) acrylic acid ester polymer and a fluorine atom-containing (meth) acrylic acid ester polymer produced thereby. Background art

In recent years, organic fluorine compounds have low refractive index, water repellency, and slidability! Various characteristics have become apparent, and by introducing fluorine atoms into the molecular structure of the polymer, heat resistance, weather resistance, electrical properties, slidability, chemical resistance, repellent properties are improved compared to existing hydrocarbon plastics. It is known to improve water / oil repellency and mechanical properties. So far, various fluorine resins such as polytetrafluoroethylene and poly (vinylidene fluoride) have been promoted! /

[0003] In addition, (meth) acrylic acid ester-based polymers are very inexpensive general-purpose resins, and they can be used as raw materials to introduce new functional resins by introducing specific functional groups. Is also proposed! A (meth) acrylic acid ester polymer introduced with a fluorine atom is also known and used as an industrial material such as an optical material (see, for example, Patent Document 1).

[0004] There are two methods for introducing a fluorine atom into a (meth) acrylic acid ester polymer. A method of polymerizing a (meth) acrylic monomer substituted with a fluorine atom (for example, Patent Document 2, And a method of reacting a (meth) acrylic acid polymer or a (meth) acrylic ester polymer with a fluorine atom-containing amine (for example, Patent Documents 4 and 5). And a method using an existing polymer such as However, the former method requires special polymerization equipment, and the latter method is expensive and highly toxic!すると When using fluorine atom-containing amines! There is a problem.

[0005] In addition, as a method for producing fluorine resin used as a separating agent used for separating and purifying a target component from a mixed solution containing various components, a crosslinking component such as alkylene di (meth) acrylate is used. And a copolymer of a polymerizable vinyl group or isopropenyl group and an ester having a functional group, and the functional group is converted to a fluorine source such as fluoroalcohol. A method of chemical modification with a compound containing a child is known (see Patent Document 6;). Furthermore, as a method for producing a positive charge image developing toner used in electrophotography, a polymer containing acrylic acid and Z or methacrylic acid as a constituent component and a (meth) acrylic acid ester component is used. 2, 2-triflate Ruo b how to esterification by reacting an alcohol such as ethanol are also known (see Patent Document 7.) ₀

[0006] However, conventionally, the production of fluorine soot as described above generally requires special polymerization equipment or a long polymerization time.

[0007] Patent Document 1: Japanese Patent Laid-Open No. 58-193501

Patent Document 2: Japanese Patent Publication No. 55-23567

Patent Document 3: Japanese Patent Laid-Open No. 11-255829

Patent Document 4: JP-A-7-118339

Patent Document 5: JP-A-3-243609

Patent Document 6: Japanese Patent Laid-Open No. 62-54162

Patent Document 7: Japanese Patent Laid-Open No. 3-168650

Disclosure of the invention

Problems to be solved by the invention

[0008] An object of the present invention is to provide a method capable of producing a fluorine atom-containing resin with high productivity without requiring a special polymerization facility.

Means for solving the problem

[0009] The method for producing a fluorine resin according to the present invention comprises using a shear kneader to mix a (meth) acrylic acid ester polymer with a fluorine atom-containing alcohol and subjecting it to a transesterification reaction. This is a method for producing a (meth) acrylic acid ester polymer.

[0010] As the shear kneader, an extruder can be preferably used.

[0011] The transesterification reaction by mixing can be performed in the absence of a solvent or in the presence of a solvent.

[0012] The transesterification reaction by mixing is preferably performed in the presence of a transesterification catalyst. Further, in this case, the fluorine atom-containing alcohol and the transesterification catalyst are mixed in advance, and then supplied to the shear kneader and mixed with the (meth) acrylate polymer. It is preferable to carry out the transesterification reaction.

The fluorine atom-containing (meth) acrylic acid ester polymer according to the present invention is obtained by mixing the (meth) acrylic acid ester polymer and the fluorine atom-containing alcohol using the shear kneader as described above. To obtain a transesterification reaction.

The invention's effect

[0014] According to the present invention, the (meth) acrylic acid ester-based polymer and the fluorine atom-containing alcohol are simply mixed by a shear kneader, and no special polymerization equipment is required, and fluorine is produced with high productivity. An atom-containing (meth) acrylic acid ester polymer can be produced and is useful.

[0015] When an extruder is used as the shear kneader, the resin pellets of the fluorine atom-containing (meth) acrylate polymer produced by the reaction are produced following the transesterification reaction by mixing. Production efficiency.

[0016] Further, by performing the transesterification reaction by mixing in the absence of a solvent, a step of devolatilizing the solvent after the reaction is not required, and the fluorine atom-containing (meth) acrylic acid ester polymer is continuously obtained. Furthermore, it becomes possible to produce a resin pellet having the polymer strength, and the productivity is improved.

[0017] On the other hand, by performing the transesterification reaction in the presence of a solvent, even when using a viscous fluorine atom-containing alcohol, the (meth) acrylic acid ester-based polymer and the fluorine atom-containing alcohol are used. Alcohol can be easily and uniformly mixed, and a fluorine atom-containing (meth) acrylic acid ester-based polymer can be produced easily and efficiently.

[0018] Further, the reaction efficiency is improved by performing the transesterification reaction by mixing in the presence of a transesterification catalyst. Further, by previously mixing the fluorine atom-containing alcohol and the transesterification catalyst before being supplied to the shear kneader, the use of the catalyst which is difficult to handle in air becomes easy.

BEST MODE FOR CARRYING OUT THE INVENTION

[0019] The present invention is characterized in that a (meth) acrylic acid ester polymer and a fluorine atom-containing alcohol represented by the following general formula (1) are mixed and subjected to a transesterification reaction using a shear kneader. Is a method for producing a fluorine atom-containing (meth) acrylic acid ester polymer. R (CH) OH Formula (1)

f 2 n

(However, R is a fluoro having 1 to 15 carbon atoms and containing at least one fluorine atom.

A kill group or a fluoroalkyl ether group, and n represents an integer of 0 to 10. )

[0020] The (meth) acrylic acid ester polymer used in the present invention is not particularly limited! /, For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meta ) (Meth) acrylate monomers such as acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples thereof include copolymers of these (meth) acrylic acid ester monomers. Of these, methyl methacrylate is preferable from the viewpoint of reactivity and cost.

[0021] The (meth) acrylic acid ester polymer includes a copolymerizable monomer such as (meth) acrylic acid, styrene, a-methylstyrene, maleic anhydride, and the like with a (meth) acrylic acid ester monomer. It may be polymerized.

[0022] The fluorine atom-containing alcohol that can be used in the present invention can be represented by the following general formula (1).

R (CH) OH Formula (1)

f 2 n

(Wherein R is a fluoroalkyl group having 1 to 15 carbon atoms containing one or more fluorine atoms f

Or a fluoroalkyl ether group, n represents an integer of 0 to 10)

[0023] R in the general formula (1) is a full f having 1 to 15 carbon atoms and containing one or more fluorine atoms.

If it is a fluoroalkyl group or a fluoroalkyl ether group, there is no particular limitation.

In addition, examples of the fluoroalkyl group include CF (CF) (b is an integer of 0 to 14) and CF

3 2 b 2

H (CHF) (CF) (c and d are each an integer of 0 or more, and c + d = 0 to 14)

2d

Or a branched structure such as (CF 3) C may be used.

3 3

[0025] In addition, a fluoroalkyl ether group is, for example, CF 0 (CF) O (CF) (e + f = l to l

3 2 e 2 f

An integer of 4 and e is an integer of 1 or more) or CF HO (CHF) O (CF) (g + h = an integer of l to 14

2 2 h

Where g is an integer of 1 or more) and (CF) CO (CF) (j is 0 to

3 3 2 j

It may be of a branched structure such as an integer of 10! /. [0026] On the other hand, in the fluorine atom-containing alcohol represented by the general formula (1), n representing the number of repeating units may be an integer from 0 to L0, but fluorine having a very high electron withdrawing property. In order to prevent the reactivity from being reduced by atoms, n is particularly preferably 2 or more.

[0027] Examples of the fluorine atom-containing alcohol include 2, 2, 2 trifluoro-1 ethanol, 2, 2, 3, 3, 3 pentafluoro 1-pronool V, 7,7, 8, 8, 8 Pentafluoro 1-octanol, 2, 2, 3, 3, 4, 4, 4 Heptafluoro 1-butanol, 3, 3, 4, 4, 5, 5, 6, 6, 6 Nonafluoro 1-hexanol, 4, 4 , 5, 5, 6, 6, 7, 7, 7 Nonafnore low 1 Heptanonore 7, 7, 8, 8, 9, 9, 10, 10, 10 Nonafnore 1-decanol, 2 Perfluoro Propoxy 2, 2, 3, 3—Tetrafluoropropanol Norole, 2- (Perfluoro oral hexyl) ethanol, 2- (Perfluoro oral hexyl) propanol, 6 (Perfluoro oral hexyl) hexanol, 2 (Per Fluorooctyl) ethanol, 3— (Perfluorooctyl) propanol, 6— (Perfluorooctyl) hexanol, 2 Perfluorodecyl) ethanol, 1H, 1H-2,5 di (trifluoromethyl) -3, 6 dioxaundecafluororonanol, 6 (perfluoro-1-methylethyl) monohexanol, 2 (perfluoro-) 3-methylbutyl) ethanol, 2- (perfluoro-5-methylhexyl) monoethanol, 2- (perfluoro-7-methyloctyl) ethanol, 1H, 1H, 3H tetrafluoropropanol, 1H, 1H, 5 H octaful Olopenol, 1H, 1H, 7H Dodecafluoro-heptanol, 1H, 1H, 9H Hexadecafluorononanol, 2H Hexafluoro-2-propanol, 1H, 1H, 3H Hexafluorobutanol, 2, 2 Bis (trifluoromethyl) prono-V-l etc. can be exemplified.

[0028] The amount of fluorine atom-containing alcohol used in the present invention may be in any range as long as the transesterification proceeds by mixing with a shear kneader.

) Ratio of moles of fluorine atom-containing alcohol (B) to moles of ester groups (A) in acrylic acid ester polymer {(B) Z (A)} force Usually between 0.01 and 2.0 A range amount is preferred. A range of 0.0.2-1.5 is more preferred. When the amount of fluorine atom-containing alcohol used is less than this range, the progress of the reaction becomes difficult, and when it is large, the amount of fluorine atom-containing alcohol increases without involving the reaction, leading to an increase in production cost. [0029] The shear kneading apparatus used in the present invention may be any apparatus capable of mixing a (meth) acrylic acid ester polymer, a fluorine atom-containing alcohol, and, if necessary, a mixture containing a catalyst and an additive. In particular, there can be mentioned an extruder, a Banbury mixer, a roller, a kneader, etc. without any restrictions. Examples of the extruder include a screw extruder such as a single-screw extruder and a twin-screw extruder, a hide-mouth dynamic extruder, a ram-type continuous extruder, a roll-type extruder, and a gear-type extruder. However, among these, a screw extruder, particularly a twin screw extruder is preferable from the viewpoint of mixing and reaction efficiency. There are two types of twin screw extruders: non-matching type co-rotating type, mating type co-rotating type, non-matching type counter-rotating type, and mating type counter-rotating type. Rotating force in the same direction of the mold High-speed rotation is possible, and it is preferable because it can promote the mixing of the fluorine atom-containing alcohol with the (meth) acrylic acid ester polymer and the reaction between the two. A more preferable shear kneading apparatus is a twin-screw extruder provided with one or more deaeration ports having good deaeration efficiency. These extruders may be used alone, or a plurality of extruders may be connected in series. The mixing order of the (meth) acrylic acid ester polymer, the fluorine atom-containing alcohol and other components added as necessary is not particularly limited.

[0030] When a (meth) acrylic acid ester polymer and a fluorine atom-containing alcohol are mixed with an extruder to produce a fluorine atom-containing (meth) acrylic acid ester polymer by an ester exchange reaction, a reaction is performed. The product fluorine atom-containing (meth) acrylic ester polymer is extruded as a strand from, for example, a die provided at the exit of the extruder, and after cooling, pelletized with a pelletizer or the like, followed by the reaction step. A resin pellet of the polymer can be produced, and the production efficiency is extremely high.

[0031] In addition to the extruder as described above, as the shear kneader, for example, a horizontal biaxial reactor such as Bipolak manufactured by Sumitomo Heavy Industries, Ltd. or a rigid type such as Super Blend. A high-viscosity reactor such as a biaxial agitation tank can also be suitably used.

[0032] In the present invention, for the purpose of accelerating the transesterification reaction between a (meth) acrylic acid ester polymer and a fluorine atom-containing alcohol, in the presence of a transesterification catalyst, a (meth) acrylic acid ester heavy polymer is used. That is, the (meth) acrylate polymer and the fluorine atom-containing alcohol in a shear kneader. It is preferred that a transesterification catalyst is included in the mixture with the solvent.

[0033] The transesterification catalyst is a substance that promotes a transesterification reaction for converting a substituent of the ester group. In the present invention, the transesterification catalyst converts the substituent of the ester group of the (meth) acrylic acid ester polymer to a fluorine atom-containing alcohol, and converts the (meth) acrylic acid ester polymer into a fluorine atom-containing (meth) acrylic acid. Promotes the reaction to form ester polymers. In the present invention, any commonly used transesterification catalyst can be used, and examples thereof include alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, Lewis acids and the like.

[0034] Examples of the alkali metal carbonate include lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, francium carbonate and the like, and potassium carbonate and cesium carbonate are particularly preferable.

[0035] Alkali metal bicarbonates include lithium bicarbonate, potassium bicarbonate, sodium bicarbonate, rubidium bicarbonate, cesium bicarbonate, francium bicarbonate, etc., with potassium bicarbonate being particularly preferred. ,.

[0036] A Lewis acid is a compound that can accept an electron pair, and specifically includes a tin compound, a zinc compound, an ytterbium compound, a titanium compound, a vanadium compound, a zirconium compound, and a hafnium compound. Compounds, scandium compounds, manganese compounds, nickel compounds, samarium compounds, cadmium compounds, cobalt compounds, aluminum compounds, indium compounds, lanthanum compounds, and other metal compounds that can accept electrons. In particular, titanium compounds, vanadium compounds, zirconium compounds, hafnium compounds, and scandium compounds are preferable.

[0037] Further, among the above metal compounds, from the viewpoint of improving the reaction rate, metals such as a salty hivanadium compound, a salty titanium compound, a salty zirconium compound, a salty hafnium compound, etc. Salt-based compounds are preferred. For example, titanium tetrachloride, titanium trichloride, titanium dichlorodiisopropoxide, vanadyl chloride (VOC1), zirconium chloride,

2

Examples include salt and hafnium. Of these, titanium tetrachloride is more preferred because of its high reaction rate.

[0038] From the viewpoint of ease of handling in air, the salt-vanadium compound, salt The titanium fluoride compound, the salt-zirconium compound, and the salt hafnium are preferably a tetrahydrofuran complex. For example, tetrachromated bis (tetrahydrofuran) zirconium, etc. can be exemplified.

[0039] It is also conceivable to use an acetylylacetonate complex for the same reasoning force. For example, vanadyl acetate toner HVO (acac)), titanium acyl acetate toner diisopropyl

2

Poxide, acetylacetonate hafnium, acetylacetyltonate zirconium, etc. can be exemplified.

[0040] Further, when the titanium compound, vanadium compound, zirconium compound, or hafnium compound is an alkoxide, it is preferable because no harmful hydrogen chloride is generated during the reaction. For example, titanium tetramethoxide, titanium tetraisopropoxide, titanium n-tetrabutoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, haf-hum tetra Examples thereof include t-butoxide. The compound is more preferably a fluorine-containing alkoxide from the viewpoint of improving the reaction rate. For example Ti (OR) (R is at least fc 4 fc

Compounds such as those represented by a fluoroalkyl group or fluoroalkyl ether group having 1 to 15 carbon atoms and containing at least one fluorine atom) vanadyl triflate (VO (SO CF)

3 3

) Etc.

2

[0041] Among Lewis acids, those in the form of carbonates such as zirconium carbonate and scandium carbonate, copper trifluoromethanesulfonate, scandium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, Also suitable are those in the form of trifluoromethanesulfonate or alkylsulfonate, such as tin trifluoromethanesulfonate, indium trifluoromethanesulfonate, hafnium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, etc. Can be used.

[0042] As the protonic acid, various substances capable of releasing H + can be used. Specifically, hydrogen chloride, hydrogen sulfide, sulfuric acid, acetic acid, p-toluenesulfonic acid, trifluoromethane sulfonic acid Etc. are exemplified.

[0043] Further, the transesterification catalyst may be used alone, or a plurality of types may be mixed and used. Either may be used as long as the transesterification proceeds.

[0044] The amount of the transesterification catalyst added in the present invention may be in any range as long as the reaction proceeds, but the transesterification catalyst with respect to the number of moles of ester groups (A) in the (meth) acrylic acid ester polymer. The ratio {(C) Z (A)} of the number of moles (C) is usually preferably in the range of 0.0001 to 1.0, more preferably in the range of 0.001 to 0.5. If the amount of transesterification catalyst added is less than this range, the progress of the reaction becomes difficult, and if it is too large, side reactions may occur.

[0045] In the present invention, when a fluorine atom-containing alcohol is reacted with a (meth) acrylic acid ester polymer, it can also be produced using a solvent inert to this reaction. Inactive to the reaction means that the solvent does not react with the fluorine atom-containing alcohol and the (meth) acrylic acid ester polymer, and the solvent does not react with the transesterification catalyst or the catalytic activity. Do not decrease

[0046] The solvent is particularly defined as a method of adding it to a fluorine-containing alcohol, adding it to a molten (meth) acrylic acid ester polymer, or adding it to a transesterification catalyst. There is no. When the transesterification catalyst that is unstable in air is used in the production method of the present invention, the stability of the catalyst in the air can be improved by dispersing or dissolving the transesterification catalyst in a solvent. is there. The solvent can also be suitably used as a diluent in the case of adding a viscous fluorine-containing alcohol.

[0047] Solvents that are inert to the transesterification reaction include aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, and aromatic carbonization such as benzene, toluene, xylene, black benzene, and black toluene. Examples thereof include ketones such as hydrogen, methyl ethyl ketone, tetrahydrofuran and dioxane, ether compounds, fluorine compounds such as benzotrifluoride and 2-chloro-benzotrifluoride. These may be used alone or as a mixture of at least two.

[0048] The reaction temperature in the production method of the present invention is not particularly limited as long as the (meth) acrylic acid ester polymer can be melted and the transesterification proceeds. A range of 320 ° C is preferred. Below 100 ° C, the (meth) acrylic ester polymer is not sufficiently melted, and the transesterification reaction is difficult to proceed. 320 ° C When exceeding, there is a problem that the thermal decomposition of the (meth) acrylic acid ester polymer becomes remarkable.

[0049] The fluorine atom-containing (meth) acrylic acid ester-based polymer obtained by the production method of the present invention has a solvent resistance, water repellency, oil repellency, heat resistance, low refraction because fluorine atoms are introduced. It has excellent efficiency and slidability, and is useful for, for example, a water-repellent treatment agent for fibers and an antireflection film for displays. Further, according to the production method of the present invention, such a useful fluorine atom-containing (meth) acrylic acid ester-based polymer can be obtained using a general shear kneader and using a special polymerization facility. It can be manufactured with high productivity.

[0050] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the measuring methods of the physical properties measured in the following examples and comparative examples are as follows.

[0051] (1) Measurement of introduction rate

The prepared reaction product, lOmg, was dissolved in lg heavy form lg, and NMR was measured using a Varian Gemini-300 (300MHz) at room temperature. From the obtained spectrum, the integral intensity of 3.5 to 3.7 ppm attributed to the methyl ester group, and the C (= = of the ester group of the raw material methyl ester group and fluorine atom-containing (meth) acrylate polymer o) oc H 2 attributed to one methylene group 4.2 to 4.4

. This introduction rate means the mole fraction (%) of the fluorinated ester moiety in the alkyl ester moiety with respect to the alkyl ester moiety of the raw material (meth) acrylate polymer.

[0052] (2) Glass transition temperature (Tg)

Using a differential scanning calorimeter (DSC, model DSC-50 manufactured by Shimadzu Corporation), the temperature of 10 mg of the product was raised at 20 ° C Zmin in a nitrogen atmosphere. Used to determine the glass transition temperature (Tg). The glass transition temperature of Sumipex MH manufactured by Sumitomo Chemical Co., Ltd., which is a raw material (meth) acrylic ester polymer, is 118 ° C. Since the transition temperature decreases, the progress of the reaction can be easily confirmed by measuring the glass transition temperature.

[0053] (Example 1)

Using an extruder, the molten (meth) acrylic acid ester polymer (manufactured by Sumitomo Chemical Co., Ltd.) SUMIPEX MH), 3, 3, 4, 4, 5, 5, 6, 6, 6—nonafluoro-1-hexanol (CF 2 CH 2 CH 2 OH), and a transesterification catalyst

4 9 2 2

TiCl was added to produce a fluorine atom-containing (meth) acrylic acid ester polymer. Messenger

Four

The extruder used was a counter-rotating co-rotating twin screw extruder with a 15 mm diameter. The raw material supply port Katsura et al. (Meth) acrylic ester polymer was charged at 0.5 kgZhr at a set temperature of 250 ° C and a screw speed of 300 rpm in each temperature control zone of the extruder. TiCl 1 as catalyst

Four

A mixture having 0 parts by weight dissolved in the same amount of hexane was supplied to the extruder by an extruder upstream press-fit pump, and further, fluorine atom-containing alcohol was supplied to the extruder by an extruder downstream press-fit pump. The supply amount of the fluorine atom-containing alcohol was 65 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer. The resin was melted and filled with a single block, mixed with the catalyst, and further reacted with a fluorine atom-containing alcohol. A seal ring was placed at the end of the reaction zone to fill the resin. By-products after the reaction and excess fluorine atom-containing alcohol were devolatilized by reducing the pressure at the vent port to 0.02 MPa. The resin that came out as a strand from the die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer.

The introduction rate of the obtained fluorine atom-containing (meth) acrylic acid ester polymer was 9%, and the glass transition temperature was 92 ° C.

[0055] (Examples 2 to 13)

Production was carried out in the same manner as in Example 1 except that a fluorine atom-containing alcohol, a transesterification catalyst and a solvent were used in the amounts shown in Table 1, and each of them was added with the positional force shown in Table 1. However, in Example 5, the raw material supply port was a nitrogen atmosphere.

[0056] Table 1 summarizes the introduction rates and glass transition temperatures of the fluorine atom-containing (meth) acrylate polymers obtained in Examples 1 to 13 above.

[0057] [Table 1] table 1

[0058] As shown in Table 1, by using a shear kneader to react a (meth) acrylic acid ester polymer with a fluorine atom-containing alcohol, fluorine atoms having good workability with good efficiency are obtained. It was possible to produce a (meth) acrylic acid ester polymer. Industrial applicability

[0059] According to the present invention, a fluorine atom-containing (meth) acrylic acid ester-based polymer can be produced easily and inexpensively by using a general shear kneader and without requiring special polymerization equipment. Furthermore, when an extruder is used as the shear kneading apparatus, the production of fluorine atom-containing (meth) acrylate polymer and the production of resin pellets with the polymer strength are continuously performed, and the fluorine-containing resin pellets are efficiently produced. Can be manufactured. Further, since the fluorine atom-containing (meth) acrylate polymer of the present invention has high water repellency and good moldability, various types of water repellency required by a general molding method. It can be easily shaped into the shape of this material, which is extremely useful industrially.

Claims

The scope of the claims

[1] A (meth) acrylic acid ester polymer and a fluorine atom-containing alcohol represented by the following general formula (1) are mixed and subjected to a transesterification reaction using a shear kneader. A method for producing a fluorine atom-containing (meth) acrylic acid ester polymer.

R (CH) OH Formula (1)

f 2 n

[2] The fluorine atom-containing (meta) according to claim 1, wherein an extruder is used as the shear kneader.

) A process for producing an acrylic ester polymer.

[3] The process for producing a fluorine atom-containing (meth) acrylate polymer according to claim 1 or 2, wherein the reaction is carried out in the absence of a solvent.

[4] The process for producing a fluorine atom-containing (meth) acrylate polymer according to claim 1 or 2, wherein the reaction is carried out in the presence of a solvent.

[5] The method for producing a fluorine atom-containing (meth) acrylate ester polymer according to any one of claims 1 to 4, which is carried out in the presence of a transesterification catalyst.

6. The fluorine atom-containing (meth) acrylic acid ester according to claim 5, wherein the fluorine atom-containing alcohol represented by the general formula (1) and the transesterification catalyst are mixed in advance and then supplied to the shear kneader. A method for producing a polymer.

[7] A fluorine atom-containing (meth) acrylic ester polymer obtained by the production method according to any one of claims 1 to 6.