JPS62104814A - Fluoroalkyl-substituted styrene polymer - Google Patents

Abstract

PURPOSE:To provide the titled novel polymer useful as a coating material which is capable of such treatments as to afford the surface of glass with water- repellency, oil-repellency, reflectionproofness or chemical resistance without impairing its light transmittancy, having specific recurring unit. CONSTITUTION:For example, a fluoroalkyl-substituted styrene derivative of formula I which can be synthesized from chloromethylstyrene, etc. is radically polymerized, using an initiator such as benzoyl peroxide in an organic solvent such as benzene at 40-100 deg.C to obtain the objective polymer with a molecular weight >=1,000 having a recurring unit of formula II [R<1> is H or lower alkyl; R<2> is H or lower polyfluoroalkyl; R<3> is polyfluoroalkyl; X is -O- or of formula III (R<4> and R<5> are each lower alkyl); Y<1>-Y<4> are each H or halogen; n is 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to the treatment of surfaces such as glass to increase their light transmittance, 18 water, T8 oil treatment, anti-reflection treatment, and body treatment.

The fluoroalkyl-substituted styrene polymer of the present invention is a new compound that has not been described in any literature. The polymer can be used as a coating material that allows the surface of glass or the like to be treated with water, oil, antireflection or chemicals without impairing its light transmittance.

[Conventional technology]

Conventionally, fluorine-containing polymers have superior corrosion resistance and chemical resistance compared to hydrocarbon polymers, and also have water repellency and FFL oil resistance, so they have been used as antifouling and non-adhesive materials that take advantage of these properties. has been applied.

[Problem that the invention seeks to solve]

However, polymers with fluorine atoms introduced into the main chain, such as polytetrafluoroethylene and polyvinylidene polyfluoride, are insoluble in ordinary organic solvents, so they cannot be coated onto substrates such as glass or metal. requires an operation of heating and melting and then press-bonding, and cannot be coated on substrates with complicated shapes.Furthermore, polymers of fluorine-containing acrylic esters or fluorine-containing methacrylic esters cannot be coated with ethyl acetate. It is soluble in organic solvents such as, and by coating with this polymer solution, it is used for fiber to water treatment, antifouling treatment, optical fiber coating material, etc. However, since these polymers contain hydrolyzable ester bonds, properties such as water repellency and light transmittance inevitably deteriorate when used for a long period of time.

The present inventors conducted extensive research to solve the above-mentioned problems, and as a result, the fluoroalkyl-substituted styrene polymer of the present invention has a high value! The present inventors have discovered that they have excellent coating properties and stability as well as 8 aqueous properties, 18 oil properties, and light transmittance, and have completed the present invention.

[Means for solving problems]

The fluoroalkyl-substituted styrene polymer of the present invention has the general formula (wherein R1 represents a hydrogen atom or a lower alkyl group, R1 represents a hydrogen atom or a lower polyfluoroalkyl group, and R3 represents a polyfluoroalkyl group). , X represents 10- or -St-, Y'
-Y' each represents a hydrogen atom or a halogen atom, provided that R4 and R5 each represent a lower alkyl group, and n is an integer of 0 or 1. ) Repetition □
It is a polymer with a molecular weight of 11,000 or more and has a unit.

As the lower polyfluoroalkyl group represented by R1,
difluoromethyl group, perfluoromethyl group, 2 to 4
Ethyl group substituted with 2 to 6 fluorine atoms, perfluoroethyl group, propyl group substituted with 2 to 6 fluorine atoms, perfluoropropyl group, butyl group substituted with 2 to 8 fluorine atoms, perfluorobutyl group Among them, perfluoromethyl group and perfluoroethyl group are particularly preferable in terms of providing suitable reactivity, ]water, and 1B oiliness.As the polyfluoroalkyl group represented by R3, an ether bond is added in the alkyl chain. It may have a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluorooctyl group, a perfluorononyl group, a perfluorodecyl group, a difluoromethyl group, ethyl group substituted with 2 to 4 fluorine atoms, 2
Propyl group substituted with 6 fluorine atoms, butyl group substituted with 2 to 8 fluorine atoms, 3-oxa-
2-trifluoromethyl-2゜4.4.5,5,6,6
．． Examples include 6-octafluorohexyl group. Especially perfluoroalkyl groups or 2.2.
An alkyl group whose alkyl end is completely fluorinated, such as a 3,3,4°4.5,5.5-nonafluoropentyl group, is preferred in that it exhibits high to-water and to-oil properties.

The fluoroalkyl M-substituted styrene polymer of the present invention has the general formula C112.-C (wherein, R1, Rg, Rs, x, y', yt,
It can be easily produced by polymerizing monomers represented by (y 2 , Y 4 and n are the same as above) using a conventional radical polymerization method. (ii) As a method for using the polymerization reaction, known methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Radical polymerization reaction involves heat,
Radical initiators suitable for use in the zero reaction that is rapidly initiated by ultraviolet irradiation or addition of a radical initiator include organic peroxides such as dilauroyl peroxide and benzoyl peroxide, and α,α′-azobisisobutylene. Examples of organic solvents that can be used in the polymerization reaction include azo compounds such as lonitrile. In order to obtain a high molecular weight product, it is preferable that the organic solvent that can be used in the polymerization reaction is soluble in the resulting polymer; examples include benzene, toluene, and chlorobenzene. , tetrahydrofuran, carbon tetrachloride, chloroform, methyl ethyl ketone, fluorobenzene, hexafluorobenzene, penzotrifluoride, 1,4-bis(trifluoromethyl)benzene, etc., but are not limited to these. The reaction is usually carried out at a temperature in the range of 40°C to 100°C.

Furthermore, among the fluoroalkyl-substituted styrene polymers of the present invention, those in which X is 10- are represented by the general formula (wherein, Y5 represents a halogen atom,
2, Yl, Y4 and n are the same as above. ) by reacting an excess amount of a fluorine-containing alcohol represented by the general formula (R'' and R3 are the same as above) with a homopolymer obtained by a polymerization reaction of a monomer represented by the above in the presence of a base. The reaction that can be obtained is preferably carried out in a solvent, and solvents that can be used include tetrahydrofuran, 1
．． Examples include 4-bis(trifluoromethyl)benzene.

Bases used in the reaction include alkali metal hydrides such as sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkali metals such as sodium, potassium, and lithium, and diazabicyclo(3,4,0
) nonene-5 (DBN), 1.5-diazavinchlo (5
, 4,0) Undecene-5-(DBU) Styrene derivatives are easily produced from chloromethylstyrene, chlorostyrene, fluoroacetophenone, hydroxyacetophenone, pentafluorostyrene, etc. (See reference side)

In addition, examples of the fluorine-containing alcohol include 2,2゜2-trifluoroethanol, 2.2.3.3゜3-pentafluoro-1-propatol, 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-octatool, 2.2.2
-) Lifluoro-1-(trifluoromethyl)ethanol, 2.2-difluoroethanol, 2.2.3.3.
4゜4-hexafluoro-J-butanol, 2,2,3
．． 3-tetrafluoro-1-propertool, 2°2.3
．． 3.4.4,5.5-octafluoro-1-pentanol, 3,3,4,4.4-pentafluoro-1-butanol, 4,4.4-)lifluoro-1-butanol,
1.1.1,3.3゜3-hexafluoro-2-propertool, 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-heptatool, 3-oxa-2-trifluoromethyl- Examples include 2,4,4,5,5,6,6,6-octafluorohexanol.

The molecular weight of the fluoroalkyl-substituted polymer of the present invention is 100
Although the molecular weight is 0 or more, it is desirable that the molecular weight is 10,000 or more when using the polymer as a coating material.

The present invention will be specifically explained below using Reference Examples, Examples, Test Examples, and Comparative Examples.

Reference example 1 1i2C1 9 g of 2,2,2-trifluoroethanol and 20.37 g of tetra-n-butylammonium hydrogen sulfate (TBAS)
g and 300 ml of toluene were placed in a tri-Solo flask, stirred under an argon stream, and then 17.5 ml of a 5 Qwt% sodium hydroxide aqueous solution was added thereto and stirred for 15 minutes. After that, 9.15 g of p-chloromethylstyrene was added, and the mixture was heated to room temperature. Diluted hydrochloric acid was added to the reaction mixture, which was stirred overnight at , to neutralize it, and then the organic layer was taken into a separatory funnel and thoroughly washed with water. after that,
Dry over anhydrous magnesium sulfate, and remove toluene under reduced pressure. The residue was purified by passing it through a silica gel column using n-hexane as an eluent, and by distilling off the n-hexane, 15.8 g of p-(2,2,2-) was obtained with a yield of 27%.
(lifluoroethyloxymethyl)styrene (p-TFE
S) was obtained.

Elemental analysis value (%); Actual value: c: 6t, s, H: 5.2 Calculated value: C261.1. H: 5. IIR (low')
;2800-3000.1610°1510 (aromatic ring), 1630 (CH,=CH), 1210.1150
(C-F).

1100-1180 (-〇-).

NMR (ppm); 3.6-4.0 (-CHz
).

4.6 (-CHID-), 5.1-5.8 (CHt
-).

6.5 to 6.8 (-CH=).

Reference Examples 2 to 9 (Results of synthesis of fluoroalkyl-substituted styrene m4) Fluoroalkyl-substituted styrene derivatives were synthesized in the same manner as in Reference Example 1, except that the fluorine-containing alcohol, hyhaloalkyl styrene, and solvent were changed. The results are shown in Table 1.

Reference Example IO 2.6 g of 50% sodium hydride (oil-based) was added to 50 ml of hexamethylphosphoramide (HMPA) and stirred under an argon stream. Cool this to below 10℃ 2,
2.2-) Add 10.0g of refluoroethanol and
p-Fluoroacetophenine 6.06 minutes after stirring
Add ml of
The reaction mixture, which was kept stirring for 5 hours, was poured into water, and the organic phase was extracted with ether. This is dried over magnesium sulfate and the ether is distilled off under reduced pressure. The crude product was purified by a silica gel column using a chloroform/ethyl acetate (10/1) mixture as the eluent. The eluate was distilled off under reduced pressure to obtain 118.54 g of p-(2,2
,2-)lifluoroethoxy)acetophenone (p-T
FEA) was obtained.

Elemental analysis value (%): Theoretical value: C: 55. l, H: 4.2 Actual measurement: c: ss, t, H: 4. I IR(3-'); From 3000 to 2800,1610°<Yoshi*'s! >, 1690 (C-0), 1
280°1240 (CF,).

NMR (ppm); 2.56 (3H), 4.19~
4.63 (2H), 6.80-7.07 (2H).

7.75-8.06 (2H).

Reference Example 11 Reference Example 1 except that the fluorine-containing alcohol was replaced with 2.2, 3.3.4, 4゜4-hebutafluoro-1-butanol.
p-(2,2°3.3.4,4.
4-Hebutafluorobutoxy)acetophenone (p-H
FBA) was obtained in a yield of 50%.

Elemental analysis value (%); Theoretical value: C: 45.3. Hl, 9 Actual value: C: 45.2. H:2. I NMR (ppm); 2.53 (3H), 4.33~
4.72 (2H), 6.83-7.11 (2H)
.

7.8-8.07 (2H).

Reference example 12 Fluorine-containing alcohol at 3.3, 4, 4, 5, 5°6.6
．． p-(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. O, Hl, 9 Actual value: C: 43.7. H:2. T 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 13 Add HMP to 1.26 g of 50% sodium hydride (oil-based)
4.76 g of p-hydroxyacetophenone dissolved in 30 ml of A was added dropwise under an argon stream. 20 of this
After fraction alT, trifluoromethanesulfonic acid 2.2
．． 3.3.4.4.4-Hebutafluorobutyl (TF)
IB) 12.8g was subjected to WJM. ml was dropped into HMP81. This was stirred at 140°C for 20 hours, and 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) RA mixture as the eluent, yielding 18.0 g and 71.0 g.
p-1-IFPA was obtained at 8%.

Elemental analysis value (%); Theoretical value: C: 45.3. H: 2.9 Actual value: C: 45.5. Hl, 8 IR (value -'); 3000-2800, 1610° (fragrance, 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 14 TFHB was mixed with trifluoromethanesulfone ff12°2.
3.3.4.4.5.5.6.6.7, 7°8.8.8
-Reference example 1 except for changing to pentadecafluorooctyl
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. O NMR (ppm); 2.52 (3H), 4.33~
4.73 (2H), 6.9-7.1 (2H).

7.87-8.1 (2H).

Reference Example 15 40 ml of ether in which 8.54 g of p-TFEA obtained in Reference Example 10 was dissolved was mixed with 0 ml of lithium aluminum hydride.
．． It was dropped into 40 ml of ether containing 52 g under an argon stream. After stirring at room temperature for 1 hour, ether was distilled off under reduced pressure, and the crude product was dissolved in chloroform/ethyl acetate (10
/I) The mixed solution was purified using a silica gel column as an eluent, and the yield was 8.0 g, 92%. p -(2,2,2-
) refluoroethoxy) phenylmethyl carbinol (
p-TFEC) was obtained.

Elemental analysis value (%); Theoretical value: C: 54.5. H:　s.

Actual value: C: 54.8. H: 5.2IR(cs-'
); 3700-3100 (OH).

1610.1510. (aromatic ring), to7゜(C-
0), 1280. 1240 (CF,).

NMR (ppm); 1.42-1.49 (
3H).

1.93 (I H, OH), 4.12-4.4
6 (2H), 4.67-4.97 (IH),
6.77-6.99 (2H), 7.17-7
゜41 (2H).

Reference Example 16 p-TFHA was converted into p-TFHA obtained in Reference Example 11 and Reference Example 13.
p- in the same manner as in Reference Example 15 except that HFBA was used.
(2,2,3,3,4,4,4-heptafluorobutoxy)phenylmethylcarbinol (p-HFBC) was obtained in a yield of 75%.

IR (cm-'): 3700-3100 (OH).

1620.1520. (aromatic ring), 1300-11
60 (C-F).

NMR (ppm); 1.27-1.53 (3H
).

2.37 (IH), 4.17-4.6 (2H)
.

4.6-4.92 (IH), 6.7-6.97 (
2H), 7.1-7.37 (2H).

Reference Example 17 p-(2,2,3,
3,4,4,5,5,6,6,7°7°8,8.8-pentadecafluorooctyloxy)phenylmethylcarbinol<p-PFOC) was obtained in a yield of 72%.

NMR (ppm); 1.37-1.57 (3H).

1.92 (I H), 4.23-4.63 (2
H).

4.63-4.98 (IH), 6.8-7.05 (
2H), 7.2-7.47 (2H).

Reference Example 1B 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 (IH), 2.2-2.9 (2H),
3.8-4.2 (2H), 4.52-4.85 (
IH).

6.75-7.0 (2H), 7.13-7.41 (2H)
H).

Reference Example 19 One drop of 84% 'A water g water was added to 5.7 g of tribromophosphine, and p-TFECllg obtained in Reference Example 14 was added dropwise thereto under an argon stream, followed by stirring at 10°C for 1 hour. After stirring at room temperature for 15 hours, 12.4 ml of quinoline and a small amount of p-tert-butylcatechol were added and distilled at 120° C. and 2 mmHg. After diluted hydrochloric acid was added to the distillate, organic Y 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 (as-'): 3000-2800.1610 (aromatic ring), 1615. (CHs”CH).

1280.1240 (CF,).

NMR (ppm): 4.12-4.47 (2H).

5.03-5.73 (2H), 6.43-6.77 (
IH), 6.77~7.00 (2H), 7.17~
7.45 (2H).

Reference Example 20 p-(2,2,3
, 3,4,4,4-hebutafluorobutoxy)styrene (HFBS) was obtained in a yield of 36%.

Elemental analysis value (%); Theoretical value: C: 47.7. H:3.0 Actual value: C: 41.6. Hl,I NMR (ppm); 4.2-4.6 (2H).

5.03-5.27 (IH), 5.47-6.75 (
IH), 6.47-6.8 (IH), 6.8-6
．． 9 (2H), 7.7-7.47 (2H).

Reference Example 21 p-(2,2,3,
3,4,4,5,5,6,6,7゜7.8,8.8-pentadecafluorooctyloxy)styrene (PFO3
) was obtained in a yield of 26%.

Elemental analysis (a (%); Science X Bird II direct: C18, 3, Hl, 8 Actual value: C: 3B, 2.H: 1.9HMR (ppm
); 4.23-4.65 (2H).

5.03-5.29 (18), 5.45-5.77 (
IH), 6.45-6.77 (IH), 6.77-7
．． 03 (2H), 7.23~? , 47 (2) ().

Reference Example 22 p-TFEC was obtained in Reference Example 18. p-(3,3,4,4
,5,5,6,6,6-nonafluorohexyloxy)
Styrene (NFH3) was obtained with a yield of 30%.

Elemental analysis value (%); PI! Theory (Direct: C: 45.9. Hl, 0 Actual value: C
: 45.7. H: 2.9HMR (ppm);
2.2-3.0 (2H).

4.0-4.3 (214), 4.95-5.2 (
IH).

5.4-5.7 (IH), 6.4-6.7
(IH).

6.7-6.9 (2H), 7.2-7.45
(2H).

Reference Example 23 Under an argon stream, a small amount of ethyl bromide was added to 0.495 g of magnesium and 5 ml of tetrahydrofuran (THF) to initiate a reaction.

Add 2.82 g of p-chlorostyrene to 15 ml of THF.
The solution was slowly added dropwise. *After finishing the above, stir at 80°C for 1 hour and add log dimethyl (3°3.4, 4.5.5
．． 6.6,7,7.8.8゜9.9,10.10.10
-heptadecafluorodecyl)chlorosilane was added dropwise. After heating under reflux for about 30 minutes, the reaction solution was cooled, and then the aqueous layer was opened and extracted with ether. The ether extract 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℃/1mm
Hg) further purified by silica gel column chromatography,
4-[dimethyl (3,3゜4.4,5,5..6.6,
7.7.8.8.9゜9.10.10.10-heptadecafluorodecyl)silyl]styrene (SiFS) 4
．． I got 8g.

Yield 40.5% Elemental analysis value (%); Actual value: C: 39.4. Hl, 9 Theoretical value: C: 39.5. H: 2.8HMR(pi)
m); 0.51-0.80 (2H).

1.3-1.97 (2H), 4.79-5.0 (L
H).

5.25-5.34 (IH), 6.15-6.53
(IH), 7.05 (4H).

Reference example 24 60% sodium hydride (oil-based) 0 in THF 80ml
．． 78 g was added and stirred under an argon stream. 2.
Added 7.8 g of 2,3.3,4,4.4-heptadecafluoro-1-butanol and stirred at room temperature for 15 minutes. Next, extracted with pentafluorostil, and extracted with dilute hydrochloric acid and water. After washing, it was dried with magnesium sulfate. After distilling off the ether under reduced pressure, 4-(2,2,3
゜3.4.4.4-hebutafluorobutoxy)-2゜3
．． 5.6-titrafluorostyrene (HFBS) was obtained.

Boiling point; 91-b NMR (ppm); 4.46-4.83 (-0CHt
~), 5.57~6.2 <-c) (ri.

6.47-6.87 (-CH=).

'Itiit analysis; 374 (M") 205 (M'
-CF, CFICF, ), 191 (M”~CHyoC
F tc F tc F 3) - Reference Examples 25 to 27 Fluoroalkyl-substituted styrene derivatives were obtained using the same method as in Reference Example 24 except that the type of fluorine alcohol was changed. The compounds of Reference Example 25 and Reference Example 26 were purified using a silica gel column. Table 2 shows the results.
Shown below.

Example 1 CH20CI-12CF5 Reference Example 1 Obtained p-TFES 1.08 g and α, α'
-Azobisisobutyronitrile (AIBN) 4.111
11r was charged into a polymerization ampoule, degassed by a conventional method, and then sealed under high vacuum (1 (I'mmHg or less).
The polymerization reaction was carried out at 0°C for 1.5 hours while shaking,
The reaction mixture was poured into a large amount of methanol to precipitate the polymer. This was filtered and dried to obtain a white solid of 83 cm (yield: 7.
7%) was recovered.

It was confirmed by elemental analysis and IR measurement that it was poly(p-TFES). The weight average molecular weight measured by GPC was 2.9×10' in terms of polystyrene, and the glass transition temperature (Tg) measured by DSC was 30°C.

Elemental analysis value (%); Actual value: C: 61.1. H+5.1 Logic X Teeth A+ti: C: 6 1.1. H:
5. IIR(c+a-')2800~3000 (-
CH, -).

1610.1500 (aromatic ring), 1210°1150
(C-F), 1100-1180 (-〇-).

Examples 2 to 8 Polymers of fluoroalkyl-substituted styrene derivatives were obtained in the same manner as in Example 1, except that the type of the fluoroalkyl-substituted styrene derivative was changed.

The results are shown in Table 3.

Example 9 TFES607■ obtained in Reference Example 19 was placed in a polymerization ampoule, 2.46 qr of AlBN was added as a polymerization initiator and 2.4 ml of THF was added as a solvent, and after degassing according to a conventional method,
The tube was sealed under high vacuum (1 (I'mmHg or less).The tube was shaken at 60°C for 24 hours to perform a polymerization reaction.The polymer was precipitated by pouring the reaction mixture into a large amount of methanol. This was filtered and dried under vacuum. Yield 1134■,
Yield 22%.

Elemental analysis value (%); Theoretical value: C: 59.4. H: 4.5 Actual value: C: 58.9, H: 4.4 Molecular weight i 3.7X I O' (polystyrene equivalent)
Examples 1O to 12 Homopolymers were obtained in the same manner as in Example 9 except that the type of fluoroalkyl-substituted styrene derivative was changed. Table 4 shows the results.
Shown below.

Example 13 51.521 g of 5iF obtained in Reference Example 23 was placed in a polymerization ampoule, and 2.06 cm of AlBN was added as a polymerization initiator and 1 ml of 1,4-bis(trifluoromethyl)benzene was added as a solvent, followed by decomposition according to a conventional method. After air, under high vacuum (10-
The tube was sealed at a temperature of 0.1 mmHg or less). This was heated to 60°C for 29.
The reaction mixture, which had undergone a polymerization reaction by shaking for 2 hours, was poured into a large amount of methanol to precipitate a polymer, which was filtered and dried under vacuum. Yield: 489■ Yield: 32%
Elemental analysis value (%); Actual value: C: 39.3. lI: 2.7 Theoretical value: C19.5, H: 2.8 Example 14 51.13 g of HFB obtained in Reference Example 24 was charged into a polymerization ampoule, and 2.47 cm of AlBN was added as a polymerization initiator and 9 ml of THFl was used as a solvent. added.

After degassing this +1 by the usual method, it was vacuumed under high vacuum (10-'mm H
The polymer was precipitated by pouring the reaction mixture into a large amount of methanol into a large amount of methanol. This was filtered, thoroughly washed with methanol, and then vacuum dried to yield 10.69 g of I(
An FBS homopolymer was obtained.

Elemental analysis value (%); Theoretical value: C18.5, H: 1.4 Actual value: C: 38.5. H: 1.3 molecules; 9.7
xlO' (polystyrene equivalent) glass transition point (℃); 4
6°IR (3-'); 3000-2800.1510° (benzene ring), 1300-1100 (C-F).

Examples 15 to 17 Fluoroalkyl-substituted styrene polymers were obtained using the same method as in Example X4, except that the types of fluoroalkyl-substituted styrene derivatives and solvents used were changed. Table 5 shows the results.
Nishimesu.

Example 18 60% sodium hydride (oil-based) 60■ in THF5m+
and 2. 2. 3. 3.4. 4. 60 (Ig) of 4-heptafluoro-1-butanol was added, and the mixture was stirred at room temperature under an argon atmosphere for 20 minutes. To this was added 194 μl of THFloml in which polypentafluorostyrene was dissolved, and the mixture was allowed to react at room temperature for 40 hours. The reaction mixture was poured into a large amount of methanol to precipitate a polymer, which was filtered off and further poured into l.

The solution was dissolved in 4-bis(trifluoromethyl)benzene, washed with IN hydrochloric acid, and thoroughly washed with water repeatedly.

The polymer was purified by pouring this solution into a large amount of methanol. The precipitate was filtered and dried under vacuum to obtain poly[4-(2,2,3
,3,4,4,4-heptafluorobutoxy)-2,3
, 5,6-titrafluorostyrene] was obtained. “F-N
MR showed that the absorption based on the fluorine atoms at the bara position of the raw material polypentafluorostyrene completely disappeared, and 2.
The predetermined structure was confirmed from the observation of absorption based on the 2.3,3,4.4.4-hebutafluorobutoxy group.

Elemental analysis value (%); Theoretical value: C: 3 B, 5. H: 1.34 Actual value: (,: 38.1.H: 1.34 Test Example 1
(Evaluation of water repellency and oil repellency) A solution of Q, 5 wt % THF of the polymers obtained in Examples 1 to 8 was prepared, and this solution was cast on a glass plate. After keeping at 40°C for 24 hours to distill off THF, it was vacuum dried for 2 days. The angle of approach 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 6. 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 6 [Journal
of Applied Polymer Science (J, App 1
．． Pol ym.

Sci, Vol. 13, p. 1741 (1969) and Journal of Polymer Science (J.

Po l ym, Sc i, Po I ym, 5)'m
p.), Vol. 66, p. 313).

Test Example 2 (FA water and oil repellency evaluation) Examples 8 to 1
Q of the fluoroalkyl monostyrene polymer obtained in step 2
, a 5 wt% THF solution was prepared, and this solution was cast onto a glass plate. After keeping at 40°C for 24 hours to distill off THF, it was vacuum dried for 2 days. The contact angles of water and n-octane on the surface of the obtained glass plate were measured using a contact angle goniometer (Kyowa Kagaku type). The results are shown in Table 7.
For comparison, the results of measuring droplet contact angles on the surfaces of polystyrene and polydimethylsiloxane are as follows:
These are shown in Table 7 as Comparison 2 and Comparative Example 3, respectively.

Table 7 Surface droplet contact angle measurement result type Coalescence Droplet contact angle (degrees) Water n-
Octane Example 8 109 45 Example 9 113 48 Example 10 117 49 Example 11 124 54 Example 12 120 49 Comparative Example 2 90 <t.

Comparative Example 3 101 <10 Test Example 3
(Evaluation of Ω water, 18 oiliness) Q, 5wL% TIIF solutions of the polymers obtained in Examples 14 to 17 were prepared, and this solution was cast onto a glass plate. It was kept at 40°C for 24 hours. After distilling off THF, it 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 (1! manufactured by Wasakagaku Co., Ltd.).The results are shown in Table 8.
As a further comparative example! Table 8 shows the droplet contact angle on the surface of polydimethylsiloxane, which is known as an aqueous material.

Test Example 4 (Evaluation of Light Transmittance) Q and 5 of the polymers obtained in Examples 1.2.3.4 and 5
Cast the ivL% bovine THF solution onto a quartz plate and place! 18I
UV-240). The results are shown in Figure 1.

However, when measuring the light transmittance, a quartz plate having the same shape as above but not coated with a polymer was used on the reference side.

[Effects of the Invention] The fluoroalkyl-110 styrene polymer of the present invention has high to water and oil repellency, extremely high light transmittance, and is soluble in organic solvents. By applying a coalescing solution, a thin film can be easily formed, and antifouling and antireflection treatments can be performed. Furthermore, it is chemically stable compared to known fluorine-containing acrylic esters or fluorine-containing methacrylic esters, so for example, when a glass surface coated with the polymer is brought into contact with an alkaline solution for a long period of time, Even when the glass surface is eroded, it is possible to maintain antifouling properties and light transmittance.

[Brief explanation of drawings]

The first drawing shows Example 1 of the present invention coated on a quartz plate.
, 2.3.4 and 5. The light transmittance of the fluoroalkyl-substituted styrene polymers obtained in , 2.3.4 and 5 is shown.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (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; Each R^5 is a lower alkyl group, and n is an integer of 0 or 1. A fluoroalkyl-substituted styrene polymer having a molecular weight of 1000 or more and having a repeating unit represented by the following.