JP2010241831A - Fluorine-containing polyether carboxylic acid ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluorine-containing polyether carboxylic acid ester having not less than two polymerizable functional groups in a molecule, which is obtained by a one-step reaction of directly reacting an alcohol with an acid halide. <P>SOLUTION: This is a fluorine-containing polyether carboxylic acid ester represented by the general formula: R<SP>1</SP>OCOCF(CF<SB>3</SB>)[OCF<SB>2</SB>CF(CF<SB>3</SB>)]<SB>a</SB>O(CF<SB>2</SB>)<SB>b</SB>O[CF(CF<SB>3</SB>)CF<SB>2</SB>O]<SB>c</SB>CF(CF<SB>3</SB>)COOR<SP>1</SP>, wherein R<SP>1</SP>is a group represented by the general formula: CH<SB>2</SB>=CR<SP>2</SP>COO(CH<SB>2</SB>)<SB>d</SB>CH<SB>2</SB>- (R<SP>2</SP>is a hydrogen atom or methyl group, d is an integer of 1-3), a+c is an integer of not greater than 28 except 0, preferably an integer of 6-28 and b is an integer of not smaller than 2. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a fluorine-containing polyether carboxylic acid ester. More specifically, the present invention relates to a fluorine-containing polyether carboxylic acid ester having two or more polymerizable functional groups in one molecule.

Patent Document 1 discloses a general formula.
R ₁ OCH ₂ CFX ₁ (OCF ₂ CFX ₂ ) _l O (CF ₂ ) _m O (CFX ₃ CF ₂ O) _n CFX ₄ CH ₂ OR ₂
R ₁ and R ₂ : Vinyl group, allyl group, acryloyl group, methacryloyl group
Or epoxy alkyl group
X _{1 to} X ₄ : perfluoroalkyl group
l, n: An integer greater than or equal to 0
m: A fluorine-containing ether compound represented by an integer of 2 or more is described.

  This compound is subjected to three steps: methyl esterification of the corresponding acid fluoride, followed by reduction, and reaction of the acid halide with the resulting alcohol.

Japanese Patent No. 2,563,959

  An object of the present invention is to provide a novel fluorine-containing polyether carboxylic acid ester having two or more polymerizable functional groups in one molecule obtained by a one-step reaction in which an alcohol is directly reacted with an acid halide. It is in.

The object of the present invention is to provide a general formula
R ¹ OCOCF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _a O (CF ₂ ) _b O [CF (CF ₃ ) CF ₂ O] _c CF (CF ₃ ) COOR ¹
[Wherein, R ¹ is the general formula _{^{CH 2 = CR 2 COO (CH}} 2) d CH 2 - (R 2 is a hydrogen atom or a methyl group, d is an is an integer of 1 to 3) a group represented by There, a + c is 28 an integer except 0, b is thus achieved in the fluorine-containing polyether carboxylic acid ester represented by a is] an integer of 2 or more.

  The fluorine-containing polyether carboxylic acid ester according to the present invention has two or more polymerizable functional groups in one molecule and also has a large number of fluorine atoms in one molecule, so that it has thermal stability and chemical stability. In addition, it has excellent optical properties and surface active properties.

  Furthermore, this product can be cured by irradiation with energy rays such as visible light, ultraviolet rays, and electron beams, so photosensitive curable inks, paints, electron beam curable paints, ultraviolet curable adhesives, etc. Application to is possible. In addition, since it is a polyfunctional monomer, it can be cross-linked in a three-dimensional structure and used as a cross-linking agent, modifier, etc. for various resins and has physical properties such as hardness, strength, heat resistance, weather resistance, and chemical resistance. Improve and improve.

  This product also exhibits a low refractive index because of the high fluorine content in the molecule, and can therefore be used as an antireflection film for displays and the like, and a cladding material for optical fibers and the like. Furthermore, it can be used for various release coating agents, various surface coating agents, surface modifiers, water- and oil-repellent agents and the like by utilizing surface active properties.

The fluorine-containing polyether carboxylic acid ester has the general formula
XOCCF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _a O (CF ₂ ) _b O [CF (CF ₃ ) CF ₂ O] _c CF (CF ₃ ) COX
X: Halogen atom
a + c: an integer of 28 or less excluding 0 , preferably an integer of 6 to 28
b: Produced by reacting a perfluoropolyether dicarboxylic acid dihalide represented by an integer of 2 or more with a hydroxyl group-containing compound represented by the general formula R ¹ OH.

In the perfluoropolyether dicarboxylic acid dihalide used as the main raw material of this reaction, the halide group is preferably a fluorine atom because of the ease of raw material synthesis, and the value of b is 2 to 6 because of the availability of the raw material. It is preferable that Further, the value of a + c is an integer of 28 or less excluding 0 , preferably an integer of 6 to 28 , and particularly preferably 20 or less from the viewpoint of ease of production. Adjustment of the value of a + c is generally achieved by reacting the corresponding perfluoroalkyldicarboxylic acid difluoride with hexafluoropropene oxide in the presence of a catalyst and distilling the perfluoropolyether compound with the desired distribution. This is done by obtaining a dicarboxylic acid dihalide having a value of a + c.

The R ¹ group of the hydroxyl group-containing compound R ¹ OH that reacts with such a perfluoropolyether dicarboxylic acid dihalide is the following group.
CH ₂ = CR ² COO (CH ₂ ) _d CH _2-
R ² : hydrogen atom or methyl group
d: Integer from 1 to 3

Specific examples of the hydroxyl group-containing compound include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate. Etc.

  The reaction between them is carried out by a dehydrohalogen condensation reaction using a hydroxyl group-containing compound in an amount of about 2.0 to 3.0 times mol, preferably 2.0 to 2.2 times mol. Any reaction solvent can be used as long as it is inert to this reaction. Generally, dialkyl ethers, preferably diethyl ether, diisopropyl ether, tetrahydrofuran, etc., which have a low boiling point and are easy to remove are used. .

  Since this reaction is a dehydrohalogenation reaction, it is preferably carried out in the presence of a hydrogen halide scavenger. Alkali metal fluoride is generally used as the scavenger for hydrogen fluoride, and sodium fluoride is preferably used from the viewpoint of the ability to retain the generated hydrogen fluoride and the cost. The use ratio thereof is about 2 to 8 times mol, preferably 2.1 to 3.0 times mol for the fluorine-containing polyether dicarboxylic acid difluoride. In the case of other hydrogen halides, trialkylamines, pyridine derivatives and the like are used in a ratio of about 2 to 6 times moles with respect to perfluoropolyether dicarboxylic acid dihalide, preferably triethylamine is 2.0 to 3.0 times. Used in molar proportions.

  In order to suppress unwanted polymerization of the hydroxyl group-containing compound or product having a polymerizable functional group used, a polymerization inhibitor such as phenothiazine, hydroquinone, or methoquinone, preferably hydroquinone or methoquinone is added to the reaction system. Used. These polymerization inhibitors are generally used at a ratio of about 0.01 to 1% by weight with respect to the fluorine-containing polyether carboxylic acid ester expected to be produced, and the product has a high boiling point and may not be purified by distillation. Particularly preferably, it is added and used at a ratio of 0.03 to 0.1% by weight. Addition of the polymerization inhibitor within this range does not hinder the polymerization of the product.

  The reaction temperature can be selected widely from about -80 ° C to the boiling point of the reaction solvent used. However, in order to prevent polymerization of raw materials and products, it is desirable that the temperature be as low as possible. A range of about −20 to 10 ° C. is particularly preferable from the viewpoint of ease of treatment.

  Next, the present invention will be described with reference to examples.

Example 24.5 g of 2-hydroxyethyl acrylate (purity 95% by gas chromatography; 0.2 mol) was added to 1500 ml of diethyl ether suspended in 16.8 g (0.4 mol) of sodium fluoride under a nitrogen gas atmosphere. To the solution, 0.1 g of methoquinone was added and cooled in an ice bath. Slowly perfluoropolyether dicarboxylic acid difluoride FOCC (CF ₃ ) [OCF ₂ CF (CF ₃ )] _a O (CF ₂ ) ₂ O [CF (CF ₃ ) CF ₂ O _c 139 g of CF (CF ₃ ) COF (mixture of a + c = 6) (purity 95% of the mixture by gas chromatography; 0.1 mol) was added dropwise.

  After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred for 8 hours or more at room temperature. After the organic layer was dried over anhydrous magnesium sulfate, diethyl ether was removed under reduced pressure to obtain 154.8 g (purity 82.6% by F-NMR; yield 79.6%) of the target compound which was a high-viscosity liquid at room temperature.

This target product is judged to be a 2-hydroxyethyl acrylate derivative having the following structural formula from the data of H-NMR and F-NMR.
CH ₂ = CHCOO (CH) ₂ OCOCF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _a O-
-(CF ₂ ) ₂ O [CF (CF ₃ ) CF ₂ O] _c CF (CF ₃ ) COO (CH ₂ ) ₂ OCOCH = CH ₂
H-NMR (CDCl ₃ , TMS): δ4.45 (4H)
4.61 (4H)
5.88 (2H)
6.12 (2H)
6.44 (2H)
F-NMR (neat CFCl ₃ ); ppm -78.72 (CF ₃ )
-80.16 (CF ₂ )
-120.10 (CF)

Claims (5)

General formula
R ¹ OCOCF (CF ₃ ) [OCF ₂ CF (CF ₃ )] _a O (CF ₂ ) _b O [CF (CF ₃ ) CF ₂ O] _c CF (CF ₃ ) COOR ¹
[Wherein, R ¹ is the general formula _{^{CH 2 = CR 2 COO (CH}} 2) d CH 2 - (R 2 is a hydrogen atom or a methyl group, d is an is an integer of 1 to 3) a group represented by And a + c is an integer of 28 or less, excluding 0, and b is an integer of 2 or more ] . The fluorine-containing polyether carboxylic acid ester according to claim 1, wherein a + c is an integer of 6 to 28. General formula
XOCCF (CF _Three ) [OCF ₂ CF (CF _Three )] _a O (CF ₂ ) _b O [CF (CF _Three CF ₂ O] _c CF (CF _Three COX
(Wherein X is a halogen atom, a + c is an integer of 28 or less excluding 0, and b is an integer of 2 or more), a perfluoropolyether dicarboxylic acid dihalide represented by the general formula R ¹ OH (where R ¹ Is the general formula CH ₂ = CR ² COO (CH ₂ ) _d CH ₂ -(R ² Is a hydrogen atom or a methyl group, and d is a group represented by the formula (1) to (3)). Production method of acid ester. The method for producing a fluorinated polyether carboxylic acid ester according to claim 3, wherein a + c is an integer of 6 to 28. The process for producing a fluorinated polyether carboxylic acid ester according to claim 3 or 4, wherein the reaction is carried out in the presence of a hydrogen halide scavenger.