JPH0475898B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel fluorinated styrene derivative useful as a raw material for a coating material that can make a glass surface water- and oil-repellent without impairing its light transmittance. The fluorine-containing 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 can be used as antifouling materials and non-adhesive materials that take advantage of these properties. It has been applied to 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. As a result of intensive research to solve the above problems, the present inventor has found that the polymer obtained from the fluorine-containing styrene derivative of the present invention has high water repellency, oil repellency, and permeability, as well as excellent coating properties and stability. This discovery led to the completion of the present invention. [Means for solving the problems] The fluorine-containing 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, and R ³ represents a polyfluoroalkyl group.) 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, perfluorothimel groups and perfluoroethyl groups are preferred in the sense that they provide suitable reactivity, water repellency, and oil repellency. Examples of the polyfluoroalkyl group represented by R ³ include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and perfluorodecyl group. group, difluoromethyl group, ethyl group substituted with 2 to 4 fluorine atoms, propyl group substituted with 2 to 6 fluorine atoms, butyl group substituted with 2 to 8 fluorine atoms For example, In particular, perfluoroalkyl groups are preferred because they exhibit high water and oil repellency. The fluorine-containing styrene derivative of the present invention can be synthesized in good yield by reacting a styrene derivative substituted with a halomethyl group and a fluorine-containing alcohol in the presence of a base. Bases include, in particular, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metals such as sodium, potassium, and lithium, and diazapicyclo[3.4.0]nonene- Examples include amines such as 5 (DBN) and 1.5-diazabicyclo[5.4.0]undecene-5 (DBU). It is also possible to carry out the reaction in a two-phase system of an organic phase and an aqueous phase using a phase transfer catalyst such as tetra-n-butylammonium hydrogen sulfate. Styrene derivatives substituted with a halomethyl group that can be used in the reaction include p-chloromethylstyrene, m-chloromethylstyrene, p-bromomethylstyrene, p-
Examples include chloromethyl-α-methylstyrene and m-bromomethyl-α-ethylstyrene. In addition, as a fluorine-containing alcohol,
2,2,2-trifluoroethanol, 2,2,
3,3,3-pentafluoro-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-pentadecafluoro-1-decanol, 1,1,1,6,6,7,
Examples include 7,7-octafluoro-2-heptanol. In addition, the reaction solvent and 2
Examples of the organic phase used in the phase-based reaction include benzene, toluene, xylene, diethyl ether, and cyclohexane. Reaction temperature is 0℃~
150°C, preferably in the range of 10°C to 80°C,
50℃ in preventing thermal polymerization reaction of raw materials and products
It is recommended to do the following. The fluorine-containing 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 by bulk polymerization,
Known methods such as solution polymerization and emulsion polymerization can be used. 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 peroxides such as dilauroyl peroxide and benzoyl peroxide, and azo compounds such as a,a'-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. Furthermore, a donor polymer can be obtained by mixing the fluorine-containing 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, styrene derivatives such as p-methylstyrene, p-chlorostyrene, pentafluorostyrene, and p-aminostyrene, methyl acrylate,
Acrylic acid esters such as ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, polyfluoroalkyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, polyfluoroalkyl Methacrylic acid esters such as 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, 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 substances. The present invention will be explained in more detail with reference to Examples, Reference Examples, and Comparative Examples. Example 1 9 g of 2,2,2-trifluoroethanol, 20.37 g of tetra-n-butylammonium hydrogen sulfate (TBAS), and 300 ml of toluene are placed in a three-necked flask and stirred under an argon stream. next
Add 17.5ml of 50wt% sodium hydroxide aqueous solution15
After stirring for a minute, p-chloromethylstyrene 9.15
g and stirred overnight at room temperature. Dilute hydrochloric acid is added to the reaction mixture to neutralize it, and then the organic layer is taken into a separatory funnel and thoroughly washed with water. Thereafter, it is dried over anhydrous magnesium sulfate, and toluene is distilled off under reduced pressure.
The residue was purified by passing it through a silica gel column using n-hexane as an eluent. By distilling off n-hexane, the yield was 5.8g, 27% p-(2,2,
2-trifluoroethyloxymethyl)styrene (TFES) was obtained. Elemental analysis (%): Actual value: C, 61.5; H, 5.2 Calculated value: C, 61.1; H, 5.1 IR (cm ^-1 ): 2800-3000, 1610, 1510 (aromatic ring),
1630 (CH ₂ = CH), 1210, 1150 (C-F), 1100
~1180 (-O-), NMR (ppm): 3.6-4.0 (-CH ₂ -), 4.6 (-CH ₂ O
−), 5.1 to 5.8 (CH ₂ =), 6.5 to 6.8 (CH =), Examples 2 to 9 (Synthesis results of fluorinated styrene derivatives) Except for changing the types of fluorinated alcohol, haloalkylstyrene, and solvent A fluorine-containing sturen derivative was synthesized by the same method as in Example 1. The results are shown in Table 1.

【table】

[Table] Reference Example 1 1.08 g of TFES obtained in Example 1 and 4.11 mg of azobisisobutyronitrile (AIBN) were charged into a polymerization ampoule, degassed by a conventional method, and then heated under high vacuum (10 ^-5 mm
The tube was sealed with Hg or less. A polymerization reaction was carried out at 60°C for 1.5 hours while shaking, and the reaction mixture was poured into a large amount of methanol to precipitate the polymer.
This was filtered and dried to obtain 83 mg of white solid (yield:
7.7%) obtained. Elemental analysis and IR measurements confirmed that it was poly(TFES). The weight average molecular weight measured by GPC is 2.9 in terms of polystyrene.
×10 ⁵ , and the glass transition temperature (Tg) measured by DSC was 30°C. Element molecule (%): Actual value: C, 61.1; H, 5.1 Theoretical value: C, 61.1; H, 5.1 IR (cm ^-1 ): 2800-3000 (-CH ₂ -), 1610, 1500
(aromatic ring), 1210, 1150 (C-F), 1100-1180
(-O-), Reference Examples 2 to 8 Homopolymers of the fluorine-containing styrene derivatives were obtained in the same manner as in Reference Example 1 except that the type of the fluorine-containing styrene derivative was changed. The results are shown in Table 2.

[Table] Reference Example 9 (Evaluation of water repellency and oil repellency) A 0.5 wt% tetrahydrofuran (THF) solution of a homopolymer obtained from a fluorine-containing styrene derivative was prepared, and this solution was cast on a glass plate. 40℃
After the THF was distilled off, the mixture was vacuum dried for 2 days. The contact angle of the droplet on the surface of the glass plate was measured using a contact angle goniometer (manufactured by Kyowa Kagaku). The results are shown in Table 3. Furthermore, as a comparative example, the droplet contact angle on the surface of polydimethylsiloxane, which is known as a water-repellent material, is shown in Table 3 [J.Appl.Polym.Sci., Vol. 13, No. 1741]
Mitsugu (1969) and Journal of Polymer Science (J.Polym.Sci.Polym.Symp.) Volume 66
See No. 313 Tribute (1979)].

【table】

[Table] Eta iodide α-bro
No methylene monafta polymer water run run

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, and R ³ represents a polyfluoroalkyl group.) A fluorine-containing styrene derivative represented by the formula: