JPH0475899B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel fluoroalkyl-substituted styrene derivative useful as a raw material for a coating material that can be used to make a glass surface water- and oil-repellent without impairing its light transmittance. The fluoroalkyl-substituted styrene derivative of the present invention is a new compound that has not been described in any literature. Polymers obtained from the derivatives can be used as coating materials that can make glass surfaces water-repellent, oil-repellent, anti-reflective, or chemical-resistant without impairing their optical transparency. [Prior art] Fluorine-containing polymers have superior corrosion resistance and chemical resistance compared to hydrocarbon polymers, and also have water and oil repellency, so they have been developed as antifouling materials and non-fouling materials that utilize these properties. It has been applied to adhesive materials. [Problems to be solved by the invention] However, polymers in which fluorine atoms are introduced into the main chain, such as polytetrafluoroethylene and polyvinylidene fluoride, are insoluble in ordinary organic solvents, so they cannot be used with glass, for example. When coating a base material such as metal or metal, it is necessary to heat and melt it and then press it, and it is not possible to coat a base material with a complicated shape. Also,
Polymers of fluorine-containing acrylic esters or fluorine-containing methacrylic esters are soluble in organic solvents such as ethyl acetate, and coating with this polymer solution can be used for water-repellent treatment, stain-proofing treatment of fibers, and for optical fibers. However, since these polymers contain hydrolyzable ester bonds, performance such as water repellency and light transparency inevitably deteriorates when used for long periods of time. The present inventors conducted extensive research to solve the above problems, and found that the polymer obtained from the fluoroalkyl-substituted styrene derivative of the present invention has high water repellency,
The present inventors discovered that it has excellent coating properties and stability as well as oil repellency and light transmittance, leading to the completion of the present invention. [Means for solving the problems] The fluoroalkyl-substituted styrene derivative of the present invention has the general formula (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a hydrogen atom or a lower polyfluoroalkyl group, R ³ represents a polyfluoroalkyl group, and X represents -O- or

[Formula] (However, R ⁴ and R ⁵ represent lower alkyl groups.) ). The lower polyfluoroalkyl group represented by ^R2 includes a difluoromethyl group, a trifluoromethyl group, an ethyl group substituted with 2 to 4 fluorine atoms, a perfluoroethyl group, and a perfluoroethyl group substituted with 2 to 6 fluorine atoms. Examples include substituted propyl groups, perfluoropropyl groups, butyl groups substituted with 2 to 8 fluorine atoms, perfluorobutyl groups, and the like. In particular, perfluoromethyl group and perfluoroethyl group are preferred in the sense that they provide suitable reactivity, water repellency, and oil repellency. The polyfluoroalkyl group represented by R ³ may have an ether bond in the alkyl chain, such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group,
Perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, difluoromethyl group, ethyl group substituted with 2 to 4 fluorine atoms, 2 to 6 Propyl group substituted with 2 to 8 fluorine atoms, Butyl group substituted with 2 to 8 fluorine atoms, 3-oxa-2-trifluoromethyl-2,4,4,5,5,6,6 , 6,-octafluorohexyl group and the like.
Especially perfluoroalkyl groups or 2,2,
An alkyl group in which the alkyl end is completely fluorinated, such as a 3,3,4,4,5,5,5-nonafluoropentyl group, is preferable because it exhibits high water and oil repellency. Among the fluoroalkyl-substituted styrene derivatives represented by the general formula () of the present invention, those where It can be synthesized by reducing an acetophenone derivative obtained by reacting a fluorine-containing alcohol with a trifluoromethanesulfonic acid ester in the presence of a base, and dehydrating the resulting carbinol. As a base,
Alkali metal hydrides such as sodium hydride and potassium hydride, alkali metals such as sodium, potassium, and lithium, and diazabicyclo [3.4.0]
Examples include amines such as nonene-5 (DBN) and 1,5-diazabicyclo[5.4.0]undecene-5 (DBU). In addition, fluorine-containing alcohols include 2, 2,
2-trifluoroethanol, 2,2,3,3,
3-pentanefluoro-1-propanol, 2,
2,3,3,4,4,4-heptafluoro-1-
Butanol, 2,2,3,3,4,4,5,5,
6,6,7,7,8,8,8-pentadecafluoro-1-octanol, 2,2,2-trifluoro-1-(trifluoromethyl)ethanol, 2,
2-difluoroethanol, 2,2,3,3,
4,4-hexafluoro-1-butanol, 2,
2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 3,3,4,4,4
-pentafluoro-1-butanol, 4,4,4
-trifluoro-1-butanol, 1,1,1,
3,3,3-hexafluoro-2-propanol, 4,4,5,5,6,6,7,7,8,8,
9,9,10,10,10-heptadecafluoro-1-
Decanol, 1,1,1,6,6,7,7,7-
Octafluoro-2-heptanol, 3-oxa-2-trifluoromethyl-2,4,4,5,
5,6,6,6-octafluorohexanol,
Examples include 3,3,4,4,5,5,6,6,6-nonafluorohexanol. Also, in the general formula (), X is

The fluoroalkyl-substituted styrene derivative represented by the formula is, for example, the general formula (In the formula, R ² to ^{R 5} are the same as above, and Y represents a halogen atom.) It can be synthesized by reacting a fluoroalkyl group-substituted halosilane represented by the following formula with a vinyl-substituted phenylmagnesium halide. The fluoroalkyl group-substituted halosilane represented by the general formula () can be used, for example, in addition to the hydrosilylation reaction to form an olefin having a fluoroalkyl group.
It is a compound that can be synthesized by a known method, and includes dimethyl(3,3,3-trifluoropropyl)chlorosilane, dimethyl(3,3,4,4,5,5,
6,6,7,7,8,8,8-tridecafluorooctyl)chlorosilane, diethyl(4,4,
5,5,6,6,7,7,7-nonafluoroheptyl)bromosilane, dimethyl[3-(trifluoromethyl)-3,4,4,4-tetrafluorobutyl)fluorosilane, dimethyl(2,2 ，
Examples include 3,3,4,4,4-heptafluorobutyl)chlorosilane. The fluoroalkyl-substituted styrene derivative of the present invention can be easily made into a high molecular weight polymer by a normal radical polymerization method, and in this case, the reaction can be carried out using known methods such as bulk polymerization, solution polymerization, and emulsion polymerization. can. The radical polymerization reaction is quickly initiated simply by heat, ultraviolet irradiation, or addition of a radical initiator. Examples of radical initiators suitably used in the reaction include organic peracid compounds such as dilauroyl peroxide and benzoyl peroxide, and azo compounds such as α,α'-azobisisobutyronitrile. In order to obtain a polymer, it is preferable to select a solvent in which the produced polymer is soluble as an organic solvent that can be used in the polymerization reaction, such as benzene, toluene, chlorobenzene, tetrahydrofuran,
Carbon tetrachloride, chloroform, methyl ethyl ketone, fluorobenzene, hexafluorobenzene, etc. can be used, but are not limited to these. The reaction is usually carried out at a temperature ranging from 40°C to 100°C. Further, a copolymer can be obtained by mixing the fluoroalkyl-substituted styrene derivative of the present invention with one or more other monomers and subjecting the mixture to radical polymerization. Monomers that can be copolymerized include styrene, p-methylstyrene, p-chlorostyrene, pentafluorostyrene, p-aminostyrene and other styrene derivatives, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate. , acrylic esters such as polyfluoroalkyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, polyfluoroalkyl methacrylate, acrylonitrile, acrylamide, methacrylamide,
Acrolein, acrylic acid, methacrylic acid, etc. can be used. The polymerization reaction is preferably carried out in a solvent, and any solvent that can uniformly dissolve the monomer and polymerization initiator can be used without any restriction. In particular, tetrahydrofuran (THF), benzene, and chlorobenzene are preferably used because they are less likely to cause termination reactions due to radical chain transfer and can yield high molecular weight products. Next, the present invention will be explained in more detail using reference examples, examples, test examples, and comparative examples. Reference example 1 Hexamethylphosphoramide (HMPA) 50ml
Add 2.6g of 50% sodium hydride (oil-based) to it,
Stir under a stream of argon. Cool this to below 10℃ and 10.0g of 2,2,2-trifluoroethanol.
Add and stir for 30 minutes. Next, 6.06 ml of p-fluoroacetophenone was added, and stirring was continued for 2.5 hours at 10° C. or lower, and then for 15 hours at room temperature. The reaction mixture is poured into water and the organic phase is extracted with ether. This is dried over magnesium sulfate and the ether is distilled off under reduced pressure. The crude product was purified using a silica gel column using a chloroform/ethyl acetate (10/1) mixture as the eluent. The eluate was distilled off under reduced pressure, and the yield
8.54 g, yield 77.6% p-(2,2,2-trifluoroethoxy)acetophenone (p-
TFEA) was obtained. Elemental analysis value (%); Theoretical value: C: 55.1, H: 4.2 Actual value: C: 55.1, H: 4.1 IR (cm ^-1 ): 3000-2800, 1610 (aromatic ring), 1690 (C
=O), 1280, 1240 (CF ₃ ). NMR (ppm); 2.56 (3H), 4.19-4.63 (2H), 6.80
~7.07 (2H), 7.75~8.06 (2H). Reference example 2 Fluorine-containing alcohol 2, 2, 3, 3, 4,
p-(2,
2,3,3,4,4,4-heptafluorobutoxy)acetophenone (p-HFBA) with a yield of 50%
I got it from Elemental analysis value (%); Theoretical value: C: 45.3, H: 2.9 Actual value: C: 45.2, H: 2.7 NMR (ppm); 2.53 (3H), 4.33-4.72 (2H), 6.83
~7.11 (2H), 7.8~8.07 (2H). Reference example 3 Fluorine-containing alcohol 3, 3, 4, 4, 5,
P by the same method as Reference Example 1 except that 5,6,6,6-nonafluoro-1-hexanol was used.
-(3,3,4,4,5,5,6,6,6,-nonafluorohexaoxy)acetophenone (p-
NFHA) was obtained in a yield of 57%. Elemental analysis value (%); Theoretical value: C: 44.0, H: 2.9 Actual value: C: 43.7, H: 2.7 NMR (ppm): 2.52 (3H), 2.3~3.0 (2H), 4.1~
4.4 (2H), 6.7~7.0 (2H), 7.9~8.1 (2H). Reference example 4 50% sodium hydroxide (oil-based) 1.26g
4.76 g of p-hydroxyacetophenone dissolved in 30 ml of HMPA was added dropwise under an argon stream. After stirring this for 20 minutes, 12.8 g of 2,2,3,3,4,4,4-heptafluorobutyl trifluoromethanesulfonic acid (TFHB) was dissolved. HMPA10
ml was added dropwise. This was stirred at 140℃ for 20 hours,
The reaction mixture was poured into ice water, and the organic phase was extracted with ether. After extracting the ether under reduced pressure, the crude product was purified using a silica gel column using a chloroform/ethyl acetate (20/1) mixture as the eluent.
p-HFBA was obtained in an amount of 8.0 g and a yield of 71.8%. Elemental analysis value (%); Theoretical value: C: 45.3, H: 2.9 Actual value: C: 45.5, H: 2.8 IR (cm ^-1 ): 3000-2800, 1610 (aromatic ring), 1690 (C
=O), 1280-1160(C-F). NMR (ppm); 2.54 (3H), 4.33-4.71 (2H), 6.78
~7.09 (2H), 7.78~8.04 (2H). Reference example 5 TFHB was converted into trifluoromethanesulfonic acid 2,
2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7,
p-(2,2,
3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8,
8,8-Pentadecafluorooctyloxy)acetophenone (p-PFOA) was obtained in a yield of 94%. Elemental analysis value (%); Theoretical value: C: 37.1, H: 1.8 Actual value: C: 37.2, H: 2.0 NMR (ppm); 2.52 (3H), 4.33-4.73 (2H), 6.9-
7.1 (2H), 7.87-8.1 (2H). Reference example 6 40ml of ether in which 8.54g of p-TFEA obtained in Reference Example 1 was dissolved was added to lithium aluminum hydride.
It was dropped into 40 ml of ether containing 0.52 g under an argon stream. After stirring at room temperature for 1 hour, 5.8ml
of water was added, and then 78 ml of 3N hydrochloric acid was added. The organic phase was extracted with ether, the ether was distilled off under reduced pressure, and the crude product was purified using a silica gel column using a chloroform/ethyl acetate (10/1) mixture as the eluent. p-(2,
2,2-trifluoroethoxy)phenylmethyl carbinol (p-TFEC) was obtained. Elemental analysis value (%); Theoretical value: C: 54.5, H: 5.0 Actual value: C: 54.8, H: 5.2 IR (cm ^-1 ); 3700-3100 (OH), 1610, 1510, (aromatic ring), 1070 (C-O), 1280, 1240 ( _CF3 ). NMR (ppm); 1.42-1.49 (3H), 1.93 (1H, OH),
4.12~4.46 (2H), 4.67~4.97 (1H), 6.77~6.99
(2H), 7.17-7.41 (2H). Reference Example 7 p-(2,2,3,3,4,4,4- Heptafluorobutoxy) phenylmethyl carbinol (p-HFBC) was obtained in a yield of 75%. IR (cm ^-1 ); 3700-3700 (OH), 1620, 1520, (aromatic ring), 1300-1160 (C-F). NMR (ppm); 1.27-1.53 (3H), 2.37 (1H), 4.17
~4.6 (2H), 4.6~4.92 (1H), 6.7~6.97 (2H),
7.1-7.37 (2H). Reference Example 8 p-(2,2,
3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8,
Yield of 8,8-pentadecafluorooctyloxy)phenylmethylcarbinol (p-PFOC)
Got it with 72%. NMR (ppm); 1.37-1.57 (3H), 1.92 (1H), 4.23
~4.63 (2H), 4.63~4.98 (1H), 6.8~7.05 (2H),
7.2-7.47 (2H). Reference Example 9 p-(3,3,
4,4,5,5,6,6,6-nonafluorohexyloxy)phenylmethylcarbinol (p-
NFHC) was obtained in a yield of 69%. NMR (ppm); 1.30~1.55 (3H), 2.20 (1H), 2.2~
2.9 (2H), 3.8~4.2 (2H), 4.52~4.85 (1H),
6.75-7.0 (2H), 7.13-7.41 (2H). Example 1 Add one drop of 48% hydrogen bromide to 5.7 g of tribromophosphine, and add Reference Example 6 to this under an argon stream.
11 g of p-TFEC obtained above was added dropwise, and the mixture was stirred at 10°C for 1 hour. Next, after stirring at room temperature for 15 hours, 20 ml of ice water was added to the reaction mixture, and the organic phase was extracted with ether. After distilling off the ether under reduced pressure, 12.4 ml of quinoline and a small amount of p-tert-butylcatechol were added thereto, followed by distillation at 120°C and 2 mmHg. After adding dilute hydrochloric acid to the distillate, the organic phase was extracted with ether. The ether was distilled off under reduced pressure, and the crude product was purified using a silica gel column using a n-hexane/ether (2/1) mixture as the eluent to obtain p-(2,2,2 -trifluoroethoxy)styrene (TFES) was obtained. Elemental analysis value (%); Calculated value: C: 59.4, H: 4.5 Actual value: C: 59.1, H: 4.4 IR (cm ^-1 ); 3000-2800, 1610 (aromatic ring), 1615
(CH ₂ = CH), 1280, 1240 (CF ₃ ). NMR (ppm); 4.12-4.47 (2H), 5.03-5.73 (2H),
6.43~6.77 (1H), 6.77~7.00 (2H), 7.17~7.45
(2H). Example 2 p-(2,
2,3,3,4,4,4-heptafluorobutoxy)styrene (HFBS) was obtained in a yield of 36%. Elemental analysis value (%); Theoretical value: C: 47.7, H: 3.0 Actual value: C: 47.6, H: 3.1 NMR (ppm): 4.2-4.6 (2H), 5.03-5.27 (1H),
5.47~5.75 (1H), 6.47~6.8 (1H), 6.8~6.98
(2H), 7.1-7.47 (2H). Example 3 p-(2,2,
3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8,
8,8-pentadecafluorooctyloxy)styrene (PFOS) was obtained in a yield of 26%. Elemental analysis value (%); Theoretical value: C: 38.3, H: 1.8 Actual value: C: 38.2, H: 1.9 NMR (ppm); 4.23-4.65 (2H), 5.03-5.29 (1H),
5.45~5.77 (1H), 6.45~6.77 (1H), 6.77~7.03
(2H), 7.23-7.47 (2H). Example 4 p-(3,3,
4,4,5,5,6,6,6-nonafluorohexyloxy)styrene (NFHS) was obtained in a yield of 30%. Elemental analysis value (%); Theoretical value: C: 45.9, H: 3.0 Actual value: C: 45.7, H: 2.9 NMR (ppm); 2.2-3.0 (2H), 4.0-4.3 (2H),
4.95~5.2 (1H), 5.4~5.7 (1H), 6.4~6.7 (1H),
6.7-6.9 (2H), 7.2-7.45 (2H). Example 5 THF to 0.495g of magnesium under argon flow
A small amount of ethyl bromide was added to start the reaction. 2.82g of p-chlorostyrene
15 ml of THF solution was slowly added dropwise. After the addition was completed, the mixture was stirred at 80°C for 1 hour, and 10g of dimethyl (3,3,4,4,5,5,6,6,7,7,8,
8,9,9,10,10,10-heptadecafluorodecyl)chlorosilane was added dropwise. Heat to reflux for about 30 minutes
After running for a minute, the reaction solution was cooled, then the water was poured off and the mixture was extracted with ether. The ether phase was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. After distillation, the crude product (boiling point 144-146℃/
1 mmHg) was further purified by silica gel column chromatography to obtain 4-[dimethyl (3,3,4,4,5,
5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10,
4.8 g of 10-heptadecafluorodecyl)silyl]styrene (SiFS) was obtained. Yield 40.5% Elemental analysis value (%); Actual value: C: 39.4, H: 2.9 Theoretical value: C: 39.5, H: 2.8 NMR (ppm); 0.51-0.80 (2H), 1.3-1.97 (2H),
4.79~5.0 (1H), 5.25~5.34 (1H), 6.15~6.53
(1H), 7.05 (4H). Reference example 10 607 mg of TFES obtained in Example 1 was placed in a polymerization ampoule, and 2.46 mg of α,α′-azobisisobutyronitrile (AIBN) was added as a polymerization initiator and as a solvent.
After adding 2.4 ml of THF and degassing according to a conventional method, the tube was sealed under high vacuum (10 ^-5 mmHg or less). This was heated to 60℃ for 24 hours.
The polymerization reaction was carried out by stirring for a period of time. The reaction mixture was poured into a large amount of methanol to precipitate a polymer, which was filtered and dried under vacuum. Yield 134mg,
Yield 22%. Elemental analysis value (%); Theoretical value: C: 59.4, H: 4.5 Actual value: C: 58.9, H: 4.4 Molecular weight: 3.7 × 10 ⁴ (polystyrene equivalent) Reference examples 11 to 13 Types of fluoroalkoxy-substituted styrene derivatives However, a homopolymer was obtained in the same manner as in Reference Example 10. The results are shown in Table 1.

[Table] Rifluorome
Chill)benze
hmm
13 Example 4 THF 48 30.1 2.8〓
10 ⁴

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a hydrogen atom or a lower polyfluoroalkyl group, R ³ represents a polyfluoroalkyl group, and X represents -O- or [Formula] (However, R ⁴ and R ⁵ represent lower alkyl groups.) A fluoroalkyl-substituted styrene derivative represented by the following formula.