KR20120057087A - The monomer and preparation method for multi-functional acrylate containing perfluoropolyether - Google Patents

Abstract

PURPOSE: A polyfunctional acylate monomer is provided to form solid phase thin film, to improve physical property, and to form a thin film having low refractivity and stain resistance. CONSTITUTION: A polyfunctional acylate monomer comprises perfluoroether in chemical formula 1. In chemical formula 1, R^1 is -CF(CF3)O-[CF2(CF3)CFO]a-CF2CF2CF3, -Rf1-[OCF2CF2]b-[OCF(CF3)]c-[OCF(CF3)CF2]d-[OCF2]e-Rf2 or -CF2CF2-[OCF2CF2CF2]f-OCF2CF2CF3, R^2 and R^3 is independently R^1 or -CXCH2, Rf1 and Rf2 is independently F(CF2)n, n is integer from 1-10, X is hydrogen or methyl, and a, b, c, d, e and f are integer from 1-10.

Description

The multifunctional acrylate monomer containing a perfluoroether, and its manufacturing method {The monomer and preparation method for multi-functional acrylate containing perfluoropolyether}

The present invention relates to a polyfunctional acrylate monomer comprising a perfluorinated ether and a preparation method thereof.

Since fluorine-based functional materials have very excellent characteristics such as low refractive index, high light transmittance, extremely low coefficient of friction, excellent corrosion resistance, and stain resistance, they can be used not only in the textile and paper industries, but also in the existing traditional industries utilizing water and oil repellent stain resistance. In addition, it is drawing attention as one of the next generation core material technologies in the semiconductor, optical communication, and computer industries. In recent years, the application and application of the display industry, which is annually billions of units worldwide, have been expanded. As a simple example, it is applied as a low refractive index material of an anti-fouling coating of a display frame mainly made of plastic and an anti-reflection film of a front screen. have.

As an example of application to a display frame, a representative home appliance maker has recently developed excellent display frame injection processing technology and released a series of products with a very beautiful surface, which has received great acclaim worldwide. On the other hand, if the surface is damaged by external contamination such as fingerprints due to the excellent gloss and excessively clean surface, a situation that gives too much visual rejection occurs. Therefore, it is urgent to develop materials and technologies capable of giving a fluorine-based antifouling transparent low refractive index thin film coating of 100 nm or less, which does not change the color or beauty of the frame itself and does not cause optical interference on the surface.

In addition, as an example of using a fluorine-based functional coating on the front of the display is the most representative anti-reflective coating. All displays such as LCDs, PDPs, and OLEDs with different driving methods are finally detected by the human eye, and the light emitted from the device by external light reflection or light interference is the same as the external light source such as the sun or indoor light. An external light source causes reflections or interference on the surface of the display and finally the combined rays are perceived by the human eye. Therefore, the anti-reflective layer on the external light source of the display surface is necessary to increase the added value by securing a better image quality and view regardless of the rapidly developing display driving method.

The antireflection layer is typically a liquid crystal or polarization functional layer, a 10 to 20 μm thick hard coating layer for protecting and flattening the liquid crystal, and a λ / 4 thickness (about 100 nm) to provide clear image quality by canceling external light interference. The low refractive index / high refractive index composite layer or the low refractive index single antireflection layer is coated on the outermost layer, and the outermost layer is coated with a 10-20 nm thick antifouling layer to minimize light reflection and interference and prevent contamination. Among them, the low refractive index layer having a refractive index of 1.40 or less and the anti-fouling layer on the outermost surface cannot be replaced with other materials, so it is popular to use a functional fluorine compound material. The performance of the antireflective layer also depends on the presence of additional contaminant thin films and the ease of removing the formed contaminant layer. Therefore, the surface pollution prevention and removal function is an important factor that determines the appearance and performance of the product, so there is a great industrial demand to solve this problem. In order to meet these demands, a surface coating material having high durability, antifouling properties, transparency, and low refractive index properties is required.

Fluorine has a strong electron density, the smallest atomic radius after the hydrogen atom, and strong electronegativity, forming a strong carbon-fluorine bond. Due to the fluorine-based properties, the monomer containing a perfluorinated alkyl group exhibits extremely small hydrophobicity of about 6-8 dynes / cm, and has a very low surface energy, which repels both water and oil. As a result, fluorine-based compounds are relatively expensive and are used for high value-added resins, films, lubricants, and paints because of their excellent chemical stability, heat resistance, and weather resistance.They are non-tacky, low surface energy, The area of use is expanding to antifouling agents, optical materials, functional dyes, electronic materials and the like which require properties such as water repellency and low refractive index.

However, it is derived from perfluoroalkyl [F (CF ₂ ) nC ₂ H ₄ OH or F (CF ₂ ) nC ₂ H ₄ CH = CH ₂ , n = 6 ~ 12] compounds, which are representative of low refractive index and low energy surface materials. The coating agent is excellent in initial contamination prevention but poor in decontamination, and is a homopolymer of F (CF ₂ ) ₇ CH ₂ CH = CH ₂ and F (CF ₂ ) ₅ CH, which are representative acrylates using perfluoroalkyl compounds. ₂ CH = CH ₂ , homopolymer shows relatively low refractive index of about 1.3390 and 1.3560, but poor permeability to light due to crystal structure by side chain.

Perfluoropolyether compounds may be mentioned as compounds which overcome the disadvantages of perfluorinated alkyl compounds in terms of surface contamination removal properties and optical properties and are promising replacements. Perfluorinated polyether compounds consist of C, O and F chemical structures only, and are connected to highly flexible ether groups to remove contamination resulting from excellent flexibility, antifouling and lubricity as well as low energy surface properties of perfluoroalkyl compounds. Hold the castle. In addition, it has excellent optical properties such as transparency and low refractive index [poly (hexafluoropropylene oxide), nD = 1.3010, T300 ~ 800 nm> 95%]. However, in terms of physical properties, there is still a problem in forming and utilizing the solid-state thin film by maintaining the liquid phase in almost the entire molecular weight region because of the chemical structure including the ether group having excellent flexibility of the molecular chain.

Thus, the present inventors controlled the reaction ratio of the perfluoropolyether compound having a terminal group of -COF as a starting material of a tetrafunctional alcohol to acryloyl chloride in an intermediate in which two or three of the four functional groups were substituted with perfluoropolyether. A perfluoropolyether-modified acrylate monomer which is polymerizable by reaction and has a low refractive index; After combining two -OH groups of the tetrafunctional alcohol with a protecting group and reacting with a perfluorinated polyether, a perfluorinated polyether-modified diacrylate in which only two functional groups were optionally substituted was prepared. In addition, in the case of trifunctional acrylate in which one of the four functional groups is optionally substituted by using a tetrafunctional acrylate containing one hydroxyl group, the present technology was completed.

An object of the present invention is to provide a polyfunctional acrylate monomer comprising a fluorine-containing polyether capable of forming a solid thin film, to form a thin film having improved mechanical properties and a transparent and extremely low refractive index and stain resistance. .

Another object of the present invention is to provide a method for producing a multifunctional acrylate monomer comprising the perfluorinated polyether.

In order to achieve the above object, the present invention provides a polyfunctional acrylate monomer comprising a perfluorinated polyether represented by the following formula (1).

[Formula 1]

(The above substituents are as described herein.)

In addition, the present invention provides a method for producing a multifunctional acrylate monomer comprising the perfluoropolyether.

 Since the perfluoropolyether prepared in the present invention has one or two substituted acrylates having two or three polymerizable devices, an improvement in low refractive index and mechanical strength can be expected in polymerization and thin film formation. Acrylate can be utilized in the manufacture of very low refractive index thin films.

Therefore, the multifunctional acrylate monomer containing perfluoropolyether according to the present invention can be used as a raw material for thermosetting or UV curing transparent coating, so it is useful for coating and surface processing of various components requiring transparency, low refractive index and antifouling property. Can be used. In addition, it can be widely used in various applications, such as textile industry, paint industry, adhesive industry, fine chemical industry, biological, biochemical industry, electrical and electronic industry, automotive industry and metal industry.

1 shows a ¹ H-NMR graph analyzed by nuclear magnetic resonance (NMR) of a monomer substituted with a compound according to an embodiment of the present invention.
Figure 2 shows a ¹⁹ F-NMR graph analyzed by nuclear magnetic resonance (NMR) of the monomer substituted with a compound according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a polyfunctional acrylate monomer comprising a perfluorinated polyether represented by the following formula (1).

In Chemical Formula 1,

R ¹ is -CF (CF ₃ ) O- [CF ₂ (CF ₃ ) CFO] _a -CF ₂ CF ₂ CF ₃ , -R _f1- [OCF ₂ CF ₂ ] _b- [OCF (CF ₃ )] _c- [OCF (CF ₃ ) CF ₂ ] _d- [OCF ₂ ] _e -R _{f 2} or -CF ₂ CF _2- [OCF ₂ CF ₂ CF ₂ ] _f -OCF ₂ CF ₂ CF ₃ ;

R ² and R ³ are independently R ¹ Or -CXCH ₂ ;

R _f1 and R _f2 are independently F (CF ₂ ) _n , where n is an integer from 1 to 10;

X is hydrogen or methyl;

a, b, c, d, e and f are integers from 1 to 10.

Preferably, the acrylate monomer including the specific perfluoropolyether represented by the formula (1) is as follows.

1) acrylic acid 3- (2,3,3,3-tetrafluoro-2-heptafluoropropyloxypropionyloxy) -2,2-bis (2,3,3,3-tetrafluoro-2-heptafluoro Propyloxypropionyloxymethyl) propyl ester;

2) acrylic acid 3-acryloyloxy-2,2-bis- (2,3,3,3-tetrafluoro-2-heptafluoropropyl-oxypropionyloxymethyl) propyl ester;

3) acrylic acid 3-acryloyloxy-2,2-bis- [2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3-hexa-fluor-2- Heptafluoropropyloxypropoxy) propionyloxymethyl] propyl ester);

4) 2,2-bis ((2,3,3,3-tetrafluoro-2- (perfluoropropoxy) propanoyloxy) methyl) propane-1,3-diyl diacrylate;

5) acrylic acid 3-acryloyloxy-2-acryloyloxymethyl-2- (2,3,3,3-tetrafluoro-2-heptafluoro propyloxy propionyloxymethyl) propyl ester; And

6) acrylic acid 3-acryloyloxy-2-acryloyloxymethyl-2- [2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3-hexafluoro -2-heptafluoropropyloxypropoxy) propionyloxymethyl] propyl ester.

In addition, the present invention provides a method for producing a multifunctional acrylate monomer comprising a perfluorinated polyether represented by the formula (1).

Preparation 1:

As the present invention is shown in Scheme 1,

Reacting a tetrahydric alcohol of Formula 2 with perfluorinated polyether acid fluoride in an organic solvent and a base to prepare a compound of Formula 3 (step 1-1); And

Provided is a method for preparing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising reacting a compound of Formula 3 with acryloyl chloride in an organic solvent to prepare a compound of Formula 1a (Step 1-2). .

Scheme 1

(In Scheme 1,

The compound of Formula 1a is a monomer of Formula 1,

R ¹ is as defined in Formula 1).

Hereinafter, the production method of Preparation Method 1 according to the present invention will be described in detail step by step.

Step 1-1

Step 1-1 according to the present invention is a step of preparing a compound of formula 3 in a base and an organic solvent by reacting a compound of formula 2, which is a starting material, with perfluorinated polyether acid fluoride.

The starting material of the compound of formula (2) can be obtained by using a commercially available or synthesized by methods known in the art.

In the preparation method of the present invention, the base of step 1-1 may use any one or more selected from the group consisting of potassium carbonate, sodium carbonate, dimethylaminopyridine, triethylamine or pyridine, and the solvent is methylene chloride. And any one selected from the group consisting of tetrahydrofuran can be used.

Preferably, methylene chloride can be used as the reaction solvent, and dimethylamino pyridine and triethylamine can be used together as a base.

Steps 1-2

Step 1-2 according to the present invention is a step of preparing an compound of Formula 1a by introducing an acrylic group into the hydroxyl group of Formula 3 prepared in Step 1-1 in an organic solvent.

Preferably, methylene chloride may be used as the organic solvent, and (meth) acryloyl chloride or acryloyl chloride may be used to introduce an acryl group.

Recipe 2:

In addition, the present invention, as shown in Scheme 2,

Reacting pentaerythritol of Formula 2 with a perfluoropolyether acid fluoride in an organic solvent and a base to prepare a compound of Formula 4 (step 2-1); And

Provided is a method for preparing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising reacting a compound of Formula 4 with acroyl chloride in an organic solvent to prepare a compound of Formula 1b (Step 2-2).

Scheme 2

(In Scheme 2,

The compound of Formula 1b is a monomer of Formula 1,

R ¹ is as defined in Formula 1).

Hereinafter, the production method of Preparation Method 2 according to the present invention will be described in detail step by step.

Step 2-1

Step 2-1 according to the present invention is a step of preparing a compound of formula 4 using a perfluorinated polyether acid fluoride and a base and an organic solvent as a starting compound.

Preferably, methylene chloride may be used as the organic solvent, and dimethylaminopyridine and triethylamine may be used together as the base.

Step 2-2

Step 2-2 according to the present invention is a step of preparing a compound of Formula 1b by introducing an acrylic group into each of the two hydroxyl groups of Formula 4 prepared in Step 1 under an organic solvent.

Preferably, methylene chloride may be used as the organic solvent and (meth) acryloyl chloride may be used to introduce the acrylic group.

Recipe 3:

Furthermore, the present invention, as shown in Scheme 3 below,

Reacting a tetrahydric alcohol of Formula 2 with p-anisaldehyde to prepare a compound of Formula 5 (step 3-1);

Reacting the compound of formula 5 with perfluorinated polyether acid fluoride in an organic solvent and a base to prepare a compound of formula 6 (step 3-2);

Removing the protecting group of the compound of formula 6 to prepare a compound of formula 7 (steps 3-3); And

A method of preparing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising reacting a compound of Formula 7 with acryloyl chloride under an organic solvent and a base to prepare a compound of Formula 1b (steps 3-4) to provide.

Scheme 3

(In Scheme 3,

Formula 1b is a monomer of Formula 1,

R ¹ is as defined in Formula 1).

Hereinafter, the manufacturing method of the manufacturing method 3 according to the present invention will be described in detail step by step.

Step 3-1

Step 3-1 according to the present invention is a step of preparing a compound of Formula 5 by reacting a compound of Formula 2, which is a starting material, with p-anisaldehyde.

Specifically, in Step 3-1, the compound of Formula 2 may be dissolved in water at 80 to 90 ° C., cooled to room temperature, and p-anisaldehyde may be added to prepare the compound of Formula 5.

Step 3-2

Step 3-2 according to the present invention is a step of preparing a compound of Formula 6 by reacting a compound of Formula 5 with a perfluorinated polyether acid fluoride in an organic solvent and a base.

Specifically, in Step 3-2, the compound of Formula 5 and the perfluorinated polyether acid fluoride are dissolved in methylene chloride, triethylamine base is added, and the compound of Formula 6 is prepared by stirring at room temperature.

Step 3-3

Step 3-3 according to the present invention is a step of preparing a compound of Formula 7 by removing the protecting group of the compound of Formula 6.

Specifically, in Step 3-3, the compound of Formula 6 may be added to acetic acid and water, and stirred at 70 ° C. to remove the protecting group, thereby preparing the compound of Formula 7.

Steps 3-4

Step 3-4 according to the present invention is a step of preparing a compound of formula 1b by reacting a compound of formula 7 with acryloyl chloride in an organic solvent and a base.

Preferably, methylene chloride can be used as the organic solvent and triethylamine can be used as the base.

Preparation 4:

In addition, the present invention as shown in Scheme 4,

It provides a method of producing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising the step of reacting the compound of formula 8 in an organic solvent and a base to prepare a compound of formula (1c).

Scheme 4

(In Scheme 4,

Formula 1c is a monomer of Formula 1,

R ¹ is as defined in Formula 1).

The preparation 4 according to the present invention may prepare a compound of Formula 1c by reacting a compound of Formula 8 with a perfluorinated polyether acid fluoride in an organic solvent and a base.

Specifically, the compound of Formula 8, which is a starting material, is dissolved in methylene chloride, an organic solvent, and then perfluorinated polyether acid fluoride is added, and the compound of Formula 1c is reacted by using dimethylaminopyridine and triethylamine as a base. It can manufacture.

In the method for producing the polyfunctional acrylate monomer containing the perfluorinated polyether of the present invention, the perfluorinated polyether compound can be produced by the following known method [JAMES T. HILL, J. Macromol. Sci. Chem. , A8, (3), p 499 (1974)]. In particular, hexa fluoro propylene oxide (HFPO) and cesium fluoride may be prepared by placing in a solvent and stirring, wherein the solvent is not particularly limited as commonly used in the art, for example, triglyme, tetra Solvents selected from the group consisting of glyme, butyl diglyme and ethyl diglyme can be used. The degree of polymerization (molecular weight) of the perfluorinated polyether compound prepared by the above method can be controlled by the injection rate of HFPO, the HFPO injection amount, the ratio with cesium fluoride and the reaction temperature.

The multifunctional acrylate monomer including perfluorinated polyether according to the present invention has excellent effect of low energy surface modification during coating hardening, antifouling property and easy removal of contaminants, and transparent and low refractive index. Can be. In particular, it has excellent antifouling, water and oil repelling and decontamination performance and high transparency, thus preventing display frame contamination, surface coating of photomemory media, water repellent for industrial and textiles, oil repellent, outdoor large structures, stain-resistant paint, precision It can be widely used for moldable nano imprinting release agent or exterior protective coating.

Hereinafter, the present invention will be described in detail with reference to examples.

However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

< Manufacturing example  1> Hexafluoropropylene Oxide ( HFPO ) Preparation of Oligomer

2.49 g of tetraglyme, 1.69 g of cesium fluoride, 87.75 g of hexafluoropropylene (HFP) and 420 g of hexafluoropropylene oxide were charged to a stainless high pressure reactor including a stirrer, a cooling jacket, a thermometer, and a pressure gauge. It reacted and obtained the hexafluoropropylene oxide (HFPO) oligomer which is a target object. At this time, the total reaction time was 36 hours. The spectral data of the hexafluoropropylene oxide (HFPO) oligomer was measured by ¹⁹ F-NMR, and the average molecular weight was 870 as a result of gel permeation chromatogram (GPC) analysis.

¹⁹ F-NMR (CDCl ₃ , 300 MHz): δ-83.8 (3F, s, CF ₃ CF ₂ CF ₂ ),-131.3 (2F, m, CF ₃ CF ₂ CF ₂ ),-83.2 [(2F, m , CF ₃ CF ₂ CF ₂ ), (3F, s, CF (CF ₃ ) COF)],-146.2 (1F, t, OCFCF ₃ CF ₂ ),-81.6 [(3F, m, OCF (CF ₃ ) CF ₂ ), (m, 2F, OCF (CF ₃ ) CF ₂ )],-132.0 (1F, t, CFCOF).

Hexafluoropropylene oxide (HFPO) oligomers obtained above were subjected to atmospheric distillation using a glass bead-filled inner diameter 4 cm and 80 cm length of a vitreous distillation column, each of dimer, trimer, tetra Tetramer and pentamer were obtained. Each distillation temperature at the top of the column is as follows.

Dimer 52-54 degreeC, trimer 103-106 degreeC, tetramer 143-148 degreeC, pentamer 173-176 degreeC.

< Example  1> Acrylic acid  3- (2,3,3,3- Tetrafluorine -2- Heptafluoropropyloxypropionyloxy ) -2,2-bis (2,3,3,3- Tetrafluorine -2- Heptafluoropropyloxy Ropionyloxymethyl) propyl ester ( Acrylic acid  3- (2,3,3,3- tetrafluoro -2-heptafluoropropyloxypropionyloxy) -2,2-bis- (2,3,3,3- tetrafluoro -2-heptafluoropropyloxypropionyloxymethyl) propyl ester Manufacturing

2,3,3,3-tetrafluoro-2-heptafluoropropyloxypropionyl fluoride (3.8) in a mixed solution of pentaerythritol (500 mg, 3.6 mmol) and methylene chloride (MC) (1 mL) g, 11.3 mmol) was added dropwise. Dimethylaminopyridine (45 mg, 0.3 mmol) and triethylamine (2.6 mL, 18.3 mmol) were added dropwise under 30 ° C., the reaction solution was stirred for 2 hours, and then acryloyl chloride (358 μL, 4.4 mmol) was slowly added. And stirred for 12 hours. The reaction solution was treated with 1N-HCl aqueous solution, and the methylene chloride layer was extracted and concentrated. Then, the target compound was obtained in a liquid state by flash column chromatography (ethyl acetate: hexane = 1: 15) (800 mg, 20). %).

¹ H NMR (CDCl ₃ , 300 MHz): δ 6.41 (d, J = 17.1 Hz, 1H), 6.07 (q, J = 17.1 Hz, 1H), 5.89 (d, J = 10.4 Hz, 1H), 4.38 (d , J = 27.1 Hz, 6H), 4.16 (2H, s)

¹⁹ F NMR (CDCl ₃ , 282.5 MHz): δ -81.37 (3F, t), -82.42 (3F, t), -82.99 (6F, t), -83.21 (3F, s), -83.73 (6F, s ), -87.59 (3F, q), -130.74 (3F, s), -131.20 (3F, s), -132.86 (3F, dd)

¹³ C NMR (CDCl ₃ , 75 MHz): δ 164.50, 158.17, 157.62, 132.26, 131.83, 126.28, 122.83, 119.27, 115.47, 110.59, 106.41, 102.34, 98.10, 64.11, 59.72, 42.23

n ^D ₂₅ = 1.33091

< Example  2> Acrylic acid  3- Acryloyloxy -2,2- Vis -(2,3,3,3- Tetrafluorine -2-hep Tafluoropro Phil Oxypropionyloxymethyl ) Profile ester Acrylic acid  3-acryloyloxy-2,2-bis- (2,3,3,3-tetrafluoro-2-heptafluoropropyl-oxypropiony loxymethyl) propyl ester Manufacturing

2,3,3,3-tetrafluoro-2-heptafluoropropyloxypropionyl fluoride (51.2 g, 154.2) in a mixed solution of pentaerythritol (10.0 g, 73.4 mmol) and methylene chloride (100 mL) mmol) was added dropwise. Dimethylaminopyridine (897 mg, 7.3 mmol) and triethylamine (51.6 mL, 367.2 mmol) were added dropwise under 30 ° C, and the reaction solution was stirred for 2 hours, followed by acryloyl chloride (13.1 mL, 161.5 mmol). Slowly added and stirred for 12 hours. After treating the reaction solution with 1N-HCl aqueous solution, the methylene chloride layer was extracted and concentrated, and then the target compound was obtained as a liquid using flash column chromatography (ethyl acetate: hexane = 1: 10) (20 g, 16%). ).

¹ H NMR (CDCl ₃ , 300 MHz): δ 6.43 (dd, J = 17.2 Hz, 2H), 6.10 (d, J = 17.2 Hz, 2H), 5.90 (dd, J = 10.4 Hz, 2H), 4.53 (dd , J = 11.5 Hz, 2H), 4.41 (dd, J = 11.5 Hz, 2H), 4.23 (4H, s)

¹⁹ F NMR (CDCl ₃ , 282.5 MHz): δ -80.68 (1F, m), -81.20 (1F, m), -82.19 (6F, t), -82.92 (6F, s), -86.73 (1F, s ), -87.26 (1F, s), -130.50 (4F, s), -132.38 (2F, d)

¹³ C NMR (CDCl ₃ , 75 MHz): δ 164.93, 158.36, 132.23, 126.86, 132.26, 119.46, 114.98, 11.96, 106.05, 102.30, 98.76, 65.59, 61.07, 42.29

n ^D ₂₅ = 1.35262

< Example  3> Acrylic acid  3- Acryloyloxy -2,2- Vis -[2,3,3,3- Tetrafluorine -2- (1,1,2,3,3,3-hexa-fluor-2- Heptafluoropropyloxypropoxy ) Propionyloxy Methyl] propyl ester) ( Acrylic acid  3-acryloyloxy-2,2-bis- [2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3- hexa - fluoro -2-heptafluoropropyloxypropoxy) propionyloxymethyl] propyl ester Manufacturing

To a mixed solution of pentaerythritol (5.0 g, 36.7 mmol) and methylene chloride (50 mL), 2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3-hexafluoro 2-heptafluoropropyloxypropoxy) propionyl fluoride (25.6 g, 77.1 mmol) was added dropwise. Dimethylamidopyridine (449 mg, 3.6 mmol) and triethylamine (25.8 mL, 183.6 mmol) were added dropwise under 30 ° C, and the reaction solution was stirred for 2 hours, followed by acryloyl chloride (6.6 mL, 80.7 mmol). Slowly added and stirred for 3 hours. The reaction solution was extracted with 1N HCl and the organic layer was extracted again with saturated NaHCO ₃ solution. The organic layer was collected, dried over sodium sulfate, and then purified by flash column chromatography (ethyl acetate: hexane = 1: 10) to obtain a target compound in a liquid state (16 g, 50%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 6.41 (dd, J = 17.1 Hz, 2H), 6.08 (d, J = 17.2 Hz, 2H), 5.88 (dd, J = 10.5 Hz, 2H), 4.51 (d , J = 11.4 Hz, 2H), 4.39 (dd, J = 11.5 Hz, 2H), 4.21 (4H, s)

¹⁹ F NMR (CDCl ₃ , 282.5 MHz): δ -80.91 (8F, t), -82.77 (10F, d), -83.43 (7F, d), -85.36 (1F, t), -130.88 (4F, s ), -132.56 (2F, t), -146.15 (2F, q)

¹³ C NMR (CDCl ₃ , 75 MHz): δ 164.74, 157.90, 131.75, 126.72, 123.13, 119.33, 115.94, 112.14, 106.51, 104.19, 102.22, 100.61, 98.70, 76.73, 65.38, 60.91, 42.18

n ^D ₂₅ = 1.34078

< Example  4> 2,2-bis ((2,3,3,3- Tetrafluorine -2- (perfluoropropoxy) propanoyloxy) methyl Propane-1,3- Dill Diacrylate (2,2- Bis ((2,3,3,3- tetrafluoro -2- (perfluoropropoxy) propanoyloxy) methyl) propane -1,3- diyl diacrylate Manufacturing

Step 1: (5- Hydroxymethyl -2- (4- Methoxy - Phenyl )-[1,3] dioxan-5-yl] -methanol

Pentaerythritol (13.6 g, 99.8 mmol) was added to 100 mL of distilled water, and dissolved at 80 ° C to 90 ° C. After cooling down to room temperature, 0.5 mL of c-HCl was added, followed by p-anisaldehyde (1.35 mL). , 1.35 mmol) was added dropwise. After 5 minutes, p-anisaldehyde (11.5 mL, 94.7 mmol) was further added dropwise to the reaction solution, followed by stirring for 2 hours. Na ₂ CO ₃ saturated solution was added to the reaction solution, and the mixture was extracted using ethyl ether. The combined organic layers were dried over sodium sulfate and separated by flash column chromatography to obtain the title compound as a white solid (23.3 g, 88%).

¹ H NMR (CD ₃ OD, 300 MHz): δ 7.37 (2H, d), 6.89 (2H, d), 5.39 (1H, s), 4.02 (2H, d), 3.90 (2H, s), 3.86 (1H , s), 3.83 (1H, s), 3.78 (3H, s), 3.41 (2H, s).

Step 2: 2,3,3,3- Tetrafluorine -2- Heptafluoropropyloxy - Propionic acid  2- (4-methoxy Phenyl ) -5- (2,3,3,3- Tetrafluorine -2- Heptafluoropropyloxypropionyl Oxy methyl )-[1,3] dioxane-5- Yl methyl  Manufacture of ester

5-hydroxymethyl-2- (4-methoxy-phenyl)-[1,3] dioxan-5-yl] -methanol (7.0 g, 27.5 mmol) obtained in step 1 was dissolved in 10 mL of methylene chloride. 2,3,3,3-tetrafluoro-2-heptafluoropropyl-oxypropionyl fluoride (22.8 g, 68.8 mmol) and triethylamine (11.6 mL, 82.5 mmol) obtained in Example 1 were added thereto. Stir at room temperature for 3 hours. The reaction solution was concentrated and separated and purified using flash column chromatography (ethyl acetate: hexane = 1: 7) to obtain the target product (14 g, 58%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 7.37 (2H, d), 6.91 (2H, d), 5.42 (1H, s), 4.87-4.70 (2H, m), 4.31-4.05 (4H, m), 3.86 (2H, d), 3.81 (3H, s).

Step 3: 2,3,3,3- Tetrafluorine -2- Heptafluoropropyloxy - Propionic acid  3-hydroxy-2- Hydroxy - methyl -2- (2,3,3,3- Tetrafluorine -2- Heptafluoropropyl Jade Cipropionyloxy methyl Production of propyl ester

Compound 2,3,3,3-tetrafluoro-2-heptafluoropropyloxy-propionic acid 2- (4-methoxy phenyl) -5- (2,3,3,3-tetrafluoro) obtained in step 2 above To 2-heptafluoropropyloxypropionyloxy methyl)-[1,3] dioxan-5-ylmethyl ester (900 mg, 1.02 mmol), add 7 mL of acetic acid and 3 mL of water, and stir at 70 ° C. for 3 days. I was. After adding a small amount of methylene chloride to separate the organic layer and dried over sodium sulfate to give the target product by flash column chromatography (ethyl acetate: hexane = 1: 5) (252 mg, 32%).

¹ H NMR (CD ₃ OD, 300 MHz): δ 4.52-4.47 (4H, m), 3.58 (4H, s).

Step 4: 2,2-bis ((2,3,3,3- Tetrafluorine -2-( Perfluoropropoxy ) Propanoyloxy ) methyl Propane-1,3- Dill Diacrylate  Produce

2,3,3,3-tetrafluoro-2-heptafluoropropyloxy-propionic acid 3-hydroxy-2-hydroxy-methyl-2- (2,3,3,3) Tetrafluoro-2-heptafluoropropyloxypropionyloxy methyl) propyl ester (252 mg, 0.33 mmol) was dissolved in 2 mL of methylene chloride, triethylamine (140 μL, 0.99 mmol) and acryloyl chloride (100 μL, 3.65 mmol) was added dropwise and stirred at room temperature for 10 minutes. The reaction solution was concentrated to give the target product by flash column chromatography (ethyl acetate: hexane = 1: 7) (240 mg, 84%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 6.41 (2H, d), 5.88 (2H, d), 4.52 (2H, d), 4.40 (2H, d), 1.31 (12H, s).

n ^D ₂₅ = 1.34215

< Example  5> Acrylic acid  3- Acryloyloxy -2- Acryloyloxymethyl -2- (2,3,3,3-tetrafluor-2- Heptafluor Propyloxy Propionyloxymethyl )profile s foundation( Acrylic acid  3- acryloyloxy -2- acryloyloxymethyl -2- (2,3,3,3- tetrafluoro -2-heptafluoro propyloxy propionyloxymethyl ) propyl ester Manufacturing

Methylene chloride (10 mL) was added to pentaerythritol triacrylate (4.0 g, 13.4 mmol), followed by 2,3,3,3-tetrafluoro-2-heptafluoropropyloxypropionyl sulffluoride (6.7 g, 20.1 mmol) was added dropwise. Dimethylaminopyridine (164 mg, 1.3 mmol) and triethylamine (3.8 mL, 26.8 mmol) were added under 30 ° C conditions. After stirring the reaction solution for 16 hours, the reaction solution was extracted with 1N HCl and the organic layer was extracted again with saturated NaHCO ₃ solution. The organic layers were collected, dried over sodium sulfate, and then purified by flash column chromatography (ethyl acetate: methylene chloride: hexane = 1: 1: 20) to obtain a target compound in a liquid state (0.2 g, 20%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 6.43 (dd, J = 17.2 Hz, 3H), 6.12 (q, J = 17.2 Hz, 3H), 5.89 (dd, J = 10.4 Hz, 3H), 4.50 (d , J = 11.1 Hz, 1H), 4.34 (d, J = 11.1 Hz, 1H), 4.16 (6H, s).

¹⁹ F NMR (CDCl ₃ , 282.5 MHz): δ -80.62 (1F, m), -81.71 (3F, t), -82.48 (3F, s), -86.88 (1F, m), -130.14 (2F, s ), -132.06 (1F, d)

¹³ C NMR (CDCl ₃ , 75 MHz): δ 165.650, 158.51, 131.74, 127.72, 121.32, 120.51, 119.04, 118.41, 116.76, 115.94, 113.36, 106.32, 101.40, 99.30, 68.47, 63.62, 41.11, 23.08, 7.25

n ^D ₂₅ = 1.35894

< Example  6> Acrylic acid  3- Acryloyloxy -2- Acryloyloxymethyl -2- [2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3- Hexafluorine -2- Heptafluoropropyloxypropoxy Propionyloxymethyl] propyl ester Acrylic acid  3- acryloyloxy -2-acryloyloxymethyl-2- [2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3- hexafluoro -2-heptafluoropropyloxypropoxy) propionyloxymethyl] propyl ester Manufacturing

Methylene chloride (10 mL) was added to pentaerythritol triacrylate (5.0 g, 16.7 mmol), and then 2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3 Hexafluoro-2-heptafluoropropyloxypropoxy) propionyl fluoride (16.7 g, 33.5 mmol) was added dropwise. Dimethylaminopyridine (1.0 g, 8.3 mmol) and triethylamine (7 mL, 50.2 mmol) were charged under 30 ° C. After stirring the reaction solution for 14 hours, the reaction solution was extracted with 1N HCl and the organic layer was re-extracted with a saturated NaHCO ₃ solution. The combined organic layers were dried over sodium sulfate and then flash column chromatography (ethyl acetate: methylene chloride: hexane = 1: 1: 20) to obtain the target product in a liquid state (0.15 g, 10%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 6.38 (dd, J = 17.2 Hz, 3H), 6.07 (q, J = 17.2 Hz, 3H), 5.84 (dd, J = 10.4 Hz, 3H), 4.47 (d , J = 11.1 Hz, 1H), 4.29 (d, J = 11.1 Hz, 1H), 4.11 (6H, s).

¹⁹ F NMR (CDCl ₃ , 282.5 MHz): δ -80.50 (4F, t), -81.83 (3F, q), -82.12 (2F, m), -82.62 (3F, d), -84.87 (1F, m ), -130.07 (2F, s), -131.79 (1F, dd), -145.60 (1F, m)

¹³ C NMR (CDCl ₃ , 75 MHz): δ 165.64, 158.67, 131.71, 127.72, 121.58, 118.58, 116.27, 113.15, 106.41, 103.98, 101.44, 99.64, 68.45, 63.59, 41.14, 23.05, 7.23

n ^D ₂₅ = 1.34387

Claims (10)

A polyfunctional acrylate monomer comprising a perfluorinated polyether represented by Formula 1 below:
[Formula 1]

(In Formula 1,
R ¹ is -CF (CF ₃ ) O- [CF ₂ (CF ₃ ) CFO] _a -CF ₂ CF ₂ CF ₃ , -R _f1- [OCF ₂ CF ₂ ] _b- [OCF (CF ₃ )] _c- [OCF (CF ₃ ) CF ₂ ] _d- [OCF ₂ ] _e -R _{f 2} or -CF ₂ CF _2- [OCF ₂ CF ₂ CF ₂ ] _f -OCF ₂ CF ₂ CF ₃ ;
R ² and R ³ are independently R ¹ or -CXCH ₂ ;
R _f1 and R _f2 are independently F (CF ₂ ) _n , where n is an integer from 1 to 10;
X is hydrogen or methyl;
a, b, c, d, e and f are integers from 1 to 10.)
The multifunctional acrylate monomer of claim 1, wherein the polyfunctional acrylate monomer comprises a perfluorinated polyether.
1) acrylic acid 3- (2,3,3,3-tetrafluoro-2-heptafluoropropyloxypropionyloxy) -2,2-bis (2,3,3,3-tetrafluoro-2-heptafluoro Propyloxypropionyloxymethyl) propyl ester;
2) acrylic acid 3-acryloyloxy-2,2-bis- (2,3,3,3-tetrafluoro-2-heptafluoropropyl-oxypropionyloxymethyl) propyl ester;
3) acrylic acid 3-acryloyloxy-2,2-bis- [2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3-hexa-fluor-2- Heptafluoropropyloxypropoxy) propionyloxymethyl] propyl ester);
4) 2,2-bis ((2,3,3,3-tetrafluoro-2- (perfluoropropoxy) propanoyloxy) methyl) propane-1,3-diyl diacrylate;
5) acrylic acid 3-acryloyloxy-2-acryloyloxymethyl-2- (2,3,3,3-tetrafluoro-2-heptafluoro propyloxy propionyloxymethyl) propyl ester; And
6) acrylic acid 3-acryloyloxy-2-acryloyloxymethyl-2- [2,3,3,3-tetrafluoro-2- (1,1,2,3,3,3-hexafluoro 2-heptafluoropropyloxypropoxy) propionyloxymethyl] propyl ester. A multifunctional acrylate monomer comprising a perfluorinated polyether, characterized in that it is selected from the group consisting of.
As shown in Scheme 1 below,
Reacting a tetrahydric alcohol of Formula 2 with perfluorinated polyether acid fluoride in an organic solvent and a base to prepare a compound of Formula 3 (step 1-1); And
A method of preparing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising reacting a compound of Formula 3 with acryloyl chloride in an organic solvent to prepare a compound of Formula 1a (step 1-2):
[Reaction Scheme 1]

(In Scheme 1,
The compound of Formula 1a is a monomer of Formula 1,
R ¹ is the same as defined in Formula 1 of claim 1.
4. The perfluorinated polyether according to claim 3, wherein the organic solvent of steps 1-1 and 1-2 is methylene chloride, and the base of step 1-1 uses dimethylaminopyridine and triethylamine together. Method for producing a multifunctional acrylate monomer comprising.
As shown in Scheme 2 below,
Reacting pentaerythritol of Formula 2 with a perfluoropolyether acid fluoride in an organic solvent and a base to prepare a compound of Formula 4 (step 2-1); And
A process for preparing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising reacting a compound of Formula 4 with acroyl chloride in an organic solvent to prepare a compound of Formula 1b (step 2-2):
Scheme 2

(In Scheme 2,
The compound of Formula 1b is a monomer of Formula 1,
R ¹ is the same as defined in Formula 1 of claim 1.
6. The perfluorinated polyether according to claim 5, wherein the organic solvent of steps 2-1 and 2-2 is methylene chloride, and the base of step 2-1 uses dimethylaminopyridine and triethylamine together. Method for producing a multifunctional acrylate monomer comprising.
As shown in Scheme 3 below,
Reacting a tetrahydric alcohol of Formula 2 with p-anisaldehyde to prepare a compound of Formula 5 (step 3-1);
Reacting the compound of formula 5 with perfluorinated polyether acid fluoride in an organic solvent and a base to prepare a compound of formula 6 (step 3-2);
Removing the protecting group of the compound of formula 6 to prepare a compound of formula 7 (steps 3-3); And
A process for preparing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising reacting a compound of Formula 7 with acryloyl chloride in an organic solvent and a base to prepare a compound of Formula 1b (steps 3-4):
[Reaction Scheme 3]

(In Scheme 3,
Formula 1b is a monomer of Formula 1,
R ¹ is the same as defined in Formula 1 of claim 1.
8. The method of claim 7, wherein the organic solvents of steps 3-2 and 3-4 are methylene chloride and the base is triethylamine.
As shown in Scheme 4,
A method of preparing a multifunctional acrylate monomer comprising a perfluorinated polyether comprising reacting a compound of Formula 8 in an organic solvent and a base to produce a compound of Formula 1c:
[Reaction Scheme 4]

(In Scheme 4,
Formula 1c is a monomer of Formula 1,
R ¹ is the same as defined in Formula 1 of claim 1.
10. The method according to claim 9, wherein the organic solvent is methylene chloride, and the base is dimethylaminopyridine and triethylamine.

Images