JPH0475900B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel fluorostyrene 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 fluorostyrene 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. As a result of intensive research to solve the above problems, the present inventors have found that the polymer obtained from the fluorostyrene derivative of the present invention has high water repellency, oil repellency, and permeability, as well as excellent coating properties and stability. They discovered this and completed the present invention. [Means for solving the problems] The fluorostyrene 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, 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 ² 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 2,2,3,
An alkyl group such as a 3,4,4,5,5,5-nonafluoropentyl group in which the alkyl terminal end is completely fluorinated is preferable because it exhibits high water and oil repellency. The fluorostyrene derivative of the present invention can be synthesized in good yield by reacting pentafluorostyrene and a fluorine-containing alcohol in the presence of a base. As a base, especially sodium hydride,
Alkali metal hydrides such as potassium hydride, alkali metals such as sodium, potassium, lithium, and diazabicyclo[3.4.0]nonene-5 (DBN),
1,5-diazabicyclo[5.4.0]undecene-
Examples include amines such as 5 (DBU). The fluorine-containing alcohol used is 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,
Examples include 5,6,6,6-octafluorohexanol. Examples of reaction solvents include tetrahydrofuran, hexamethylphosphoramide, dimethylacetamide, and N-methylpyrrolidone. The reaction temperature is 0℃~150℃, preferably 10℃~80℃
Although the temperature range is 50°C or lower, it is preferable to conduct the reaction at a temperature of 50°C or lower in order to prevent thermal polymerization reactions of raw materials and products. The fluorostyrene 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 is performed 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 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. For example, tetrahydrofuran, fluorobenzene, hexafluorobenzene, 1,4-
Bis(trifluoromethyl)benzene and the like can be used, but are not limited thereto. The reaction is usually carried out at a temperature ranging from 40°C to 100°C. Furthermore, a copolymer can be obtained by mixing the fluorostyrene derivative of the present invention and one or several 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,
Methyl methacrylate, ethyl methacrylate,
Methacrylic acid esters such as propyl methacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and polyfluoroalkyl methacrylate, acrylonitrile, acrylamide, methacrylamide, acrolein, acrylic acid, methacrylic acid, and the like 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 and 1,4-bis(trifluoromethyl)benzene are preferably used because they are difficult to cause termination reactions due to radical chain transfer and can yield high molecular weight products. The present invention will be explained in more detail by Examples, Reference Examples, Test Examples, and Comparative Examples. Example 1 0.78 g of 60% sodium hydride (oil base) was added to 80 ml of tetrahydrofuran (THF) and stirred under an argon stream. 2, 2, 3, 3, 4,
4,4-heptadecafluoro-1-butanol
7.8 g was added and stirred at room temperature for 15 minutes. Next, 2.91 g of pentafluorostyrene was added and reacted overnight at room temperature, and then the reaction mixture was poured into a large amount of water. The organic phase was extracted with ether, thoroughly washed with dilute hydrochloric acid and water, and then dried over magnesium sulfate.
After distilling off the ether under reduced pressure, 4-(2,
2,3,3,4,4,4-heptafluorobutoxy)-2,3,5,6-tetrafluorostyrene (HFBS) was obtained. Boiling point: 91-93℃/6.5mmHg. NMR (ppm): 4.46-4.83 (−OCH ₂ −), 5.57-6.2
(= _CH2 ), 6.47-6.87 (-CH=). Mass spectrometry; 374 (M ⁺ ), 205 (M ⁺ −CF ₂ CF ₂ CF ₃ ),
191 (M ⁺ −CH ₂ CF ₂ CF ₂ CF ₃ ). Examples 2 to 4 Fluorostyrene derivatives were obtained using the same method as in Example 1 except that the type of fluorine-containing alcohol was changed. Note that the compounds of Example 2 and Example 3 were purified using a silica gel column.

[Table] Reference example 1 1.13 g of HFBS obtained in Example 1 was placed in a polymerization ampoule, and 2.47 mg of α,α'-azobisisobutyronitrile (AIBN) as a polymerization initiator and 1.9 ml of THF as a solvent were added. After degassing this in a conventional manner, the tube was sealed under high vacuum (10 ^-5 mmHg or less), and the tube was shaken at 60° C. for 25 hours to carry out a polymerization reaction. The polymer was precipitated by pouring the reaction mixture into a large amount of methanol. This was separated by filtration, thoroughly washed with methanol, and then vacuum-dried to obtain an HFBS homopolymer in a yield of 0.69 g and a yield of 61.4%. Elemental analysis value (%); Theoretical value: C: 38.5, H: 1.4 Actual value: C: 38.5, H: 1.3 Molecular weight: 9.7 x 10 ⁴ (polystyrene equivalent) Glass transition point (°C): 46. IR (cm ^{- 1} ); 3000-2800, 1510 (benzene ring),
1300-1100 (C-F). Reference Examples 2 to 4 Fluorostyrene homopolymers were obtained in the same manner as in Reference Example 1, except that the types of fluorostyrene derivatives and solvents used were changed. The results are shown in Table 2.

[Table] Reference example 5 1.05 g of HFBS and 0.13 g of St were charged into a glass polymerization ampoule so that the molar ratio of HFBS and styrene (St) obtained in Example 1 was HFBS/St = 0.70/0.30, and further 3.29 mg of AIBN and 0.13 g of St were charged.
After adding 2.8 ml of THF and degassing in a conventional manner, the tube was sealed under high vacuum. A copolymerization reaction was carried out by shaking and mixing the mixture at 60°C for 23 hours. After the reaction was completed, the mixture was poured into a large amount of methanol to precipitate the polymer. This was filtered, thoroughly washed with methanol, and vacuum dried to yield 0.78g.
An HFBS-St copolymer was obtained with a yield of 66.8%. The HFSB mole fraction of the copolymer was 0.72 based on elemental analysis. Also, the molecular weight is 3.2×10 ⁴ (polystyrene equivalent)
It was hot. Elemental analysis values (%); C: 43.8, H: 2.2 IR (cm ^-1 ); 3000-2800, 1650, 1510 (benzene ring), 1300-1100 (C-F). Reference Examples 6 to 11 Fluorostyrene-styrene copolymers were obtained in the same manner as in Reference Example 5, by varying the type of fluorostyrene derivative and the molar composition with styrene. The results are shown in Table 3.

[Table] Example 3

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.)