WO2006132208A1 - Procede de fabrication d'un polymere d'ester d'acide (meth)acrylique contenant un atome de fluor, et polymere obtenu par un tel procede - Google Patents

Procede de fabrication d'un polymere d'ester d'acide (meth)acrylique contenant un atome de fluor, et polymere obtenu par un tel procede Download PDF

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Publication number
WO2006132208A1
WO2006132208A1 PCT/JP2006/311274 JP2006311274W WO2006132208A1 WO 2006132208 A1 WO2006132208 A1 WO 2006132208A1 JP 2006311274 W JP2006311274 W JP 2006311274W WO 2006132208 A1 WO2006132208 A1 WO 2006132208A1
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Prior art keywords
meth
fluorine atom
acrylic acid
acid ester
polymer
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PCT/JP2006/311274
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English (en)
Japanese (ja)
Inventor
Etsuo Horii
Hirosuke Kawabata
Toshikazu Hirao
Xiaoliang Xu
Akiya Ogawa
Original Assignee
Kaneka Corporation
Osaka University
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Priority to JP2007520105A priority Critical patent/JPWO2006132208A1/ja
Publication of WO2006132208A1 publication Critical patent/WO2006132208A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/24—Haloalkylation

Definitions

  • 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.
  • (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.
  • 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).
  • a crosslinking component such as alkylene di (meth) acrylate is used.
  • 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;).
  • 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
  • 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.
  • 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.
  • an extruder can be preferably used as the shear kneader.
  • the transesterification reaction by mixing can be performed in the absence of a solvent or in the presence of a solvent.
  • 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 (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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a method for producing a fluorine atom-containing (meth) acrylic acid ester polymer R (CH) OH Formula (1)
  • 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.
  • 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.
  • 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.
  • the fluorine atom-containing alcohol that can be used in the present invention can be represented by the following general formula (1).
  • R is a fluoroalkyl group having 1 to 15 carbon atoms containing one or more fluorine atoms f
  • n represents an integer of 0 to 10.
  • R in the general formula (1) is a full f having 1 to 15 carbon atoms and containing one or more fluorine atoms.
  • examples of the fluoroalkyl group include CF (CF) (b is an integer of 0 to 14) and CF
  • a branched structure such as (CF 3) C may be used.
  • 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.
  • 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— (Perfluorooo
  • 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.
  • 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.
  • an extruder a Banbury mixer, a roller, a kneader, etc. without any restrictions.
  • 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.
  • a screw extruder particularly a twin screw extruder is preferable from the viewpoint of mixing and reaction efficiency.
  • twin screw extruders 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.
  • 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.
  • a (meth) acrylic acid ester heavy polymer is used for the purpose of accelerating the transesterification reaction between a (meth) acrylic acid ester polymer and a fluorine atom-containing alcohol. 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.
  • the transesterification catalyst is a substance that promotes a transesterification reaction for converting a substituent of the ester group.
  • 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.
  • 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.
  • alkali metal carbonate examples 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.
  • Alkali metal bicarbonates include lithium bicarbonate, potassium bicarbonate, sodium bicarbonate, rubidium bicarbonate, cesium bicarbonate, francium bicarbonate, etc., with potassium bicarbonate being particularly preferred. ,.
  • 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.
  • titanium compounds, vanadium compounds, zirconium compounds, hafnium compounds, and scandium compounds are preferable.
  • 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.
  • 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.
  • Examples include salt and hafnium. Of these, titanium tetrachloride is more preferred because of its high reaction rate.
  • the titanium fluoride compound, the salt-zirconium compound, and the salt hafnium are preferably a tetrahydrofuran complex.
  • tetrachromated bis (tetrahydrofuran) zirconium, etc. can be exemplified.
  • titanium compound, vanadium compound, zirconium compound, or hafnium compound is an alkoxide
  • the compound is more preferably a fluorine-containing alkoxide from the viewpoint of
  • 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.
  • 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.
  • 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.
  • 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.
  • a fluorine atom-containing alcohol when 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
  • 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.
  • 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.
  • 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.
  • aromatic carbonization such as benzene, toluene, xylene, black benzene, and black toluene.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 3, 3, 4, 4, 5, 5, 6, 6, 6—nonafluoro-1-hexanol
  • TiCl was added to produce a fluorine atom-containing (meth) acrylic acid ester polymer.
  • 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.
  • 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.
  • the introduction rate of the obtained fluorine atom-containing (meth) acrylic acid ester polymer was 9%, and the glass transition temperature was 92 ° C.
  • Example 5 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.
  • 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.
  • 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.

Abstract

L'invention concerne un procédé de fabrication d'une fluororésine permettant d'obtenir rapidement une fluororésine, sans nécessiter d'équipement spécial de polymérisation. Selon ce procédé, un polymère d'ester d'acide (méth)acrylique et un alcool contenant un atome de fluor sont mélangés à l'aide d'un malaxeur à cisaillement, en utilisant de préférence une extrudeuse, pour obtenir un polymère d'ester d'acide (méth)acrylique contenant un atome de fluor, par une réaction d'échange d'ester, et le polymère ainsi obtenu est extrudé de manière continue par l'extrudeuse, et mis sous forme de pastilles.
PCT/JP2006/311274 2005-06-08 2006-06-06 Procede de fabrication d'un polymere d'ester d'acide (meth)acrylique contenant un atome de fluor, et polymere obtenu par un tel procede WO2006132208A1 (fr)

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JP2007520105A JPWO2006132208A1 (ja) 2005-06-08 2006-06-06 フッ素原子含有（メタ）アクリル酸エステル系重合体の製造方法及びその重合体

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2325005B1 (fr) * 2008-06-10 2015-11-11 Kaneka Corporation Film de résine acrylique stratifié de fluororésine
WO2018042952A1 (fr) * 2016-09-05 2018-03-08 リケンテクノス株式会社 Procédé de production d'un film multicouche
CN111393289A (zh) * 2020-05-09 2020-07-10 安徽灵达高新材料有限公司 一种由氟化醇制备氟化丙烯酸酯的方法
US11396165B2 (en) 2017-06-13 2022-07-26 Riken Technos Corporation Multilayer film

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2325005B1 (fr) * 2008-06-10 2015-11-11 Kaneka Corporation Film de résine acrylique stratifié de fluororésine
WO2018042952A1 (fr) * 2016-09-05 2018-03-08 リケンテクノス株式会社 Procédé de production d'un film multicouche
EP3508323A4 (fr) * 2016-09-05 2020-04-29 Riken Technos Corporation Procédé de production d'un film multicouche
US11465323B2 (en) 2016-09-05 2022-10-11 Riken Technos Corporation Method for producing multilayer film
US11396165B2 (en) 2017-06-13 2022-07-26 Riken Technos Corporation Multilayer film
CN111393289A (zh) * 2020-05-09 2020-07-10 安徽灵达高新材料有限公司 一种由氟化醇制备氟化丙烯酸酯的方法
CN111393289B (zh) * 2020-05-09 2022-09-13 安徽灵达高新材料有限公司 一种由氟化醇制备氟化丙烯酸酯的方法

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