JPH02721A - Fluoroalkoxyethyl vinyl ether and polymer thereof - Google Patents

Abstract

NEW MATERIAL:A fluoroalkoxyethyl vinyl ether expressed by formula I (R<1> is H, lower alkyl or lower polyfluoroalkyl; R<2> is polyfluoroalkyl). EXAMPLE:2-(1H,1H,2H,2H)-Perfluorooctyloxy)ethyl vinyl ether. USE:Useful as a water and oil repellent agent, sheathing material for optical fibers, antithrombotic materials, etc., readily polymerizable by cationic or radical polymerization, providing polymers, having an ultralow refractive index and exhibiting excellent water and oil repellency and extremely stable to hydrolysis due to the absence of ester bonds. PREPARATION:2-Chloroethyl vinyl ether is reacted with a fluorine-containing alcohol expressed by formula II in the presence of a base to afford the compound expressed by formula I. Furthermore, the compound expressed by formula I can be obtained by a method for polymerization in the coexistence of a cationic polymerization initiator in, e.g., a solvent.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel fluorine-containing alkyl vinyl ether and a polymer thereof, and this polymer
It is useful as an oil agent, optical fiber sheath material, antithrombotic material, etc.

[Conventional technology]

Up to now, fluorine-containing polymers have been used as raw materials for TA water 10 oil agents, optical fiber sheath materials, antithrombotic materials, and the like. The main ones are polymers of polyfluoroalkyl esters of acrylic acid or methacrylic acid. This material is widely used because it is relatively inexpensive and easy to manufacture, but it has a somewhat high refractive index and contains ester bonds, which sometimes poses problems in terms of durability. Recently, fluorine-containing styrene polymers have been developed, and although the latter drawback is being solved, it has the drawback of a considerably high refractive index.

[Problems to be solved by the present invention]

The inventors of the present invention have conducted extensive studies on the development of a new fluorine-containing polymer that is expected to have good durability and tn-water-in-oil properties and has a low refractive index, and as a result, they have arrived at the fluorine-containing vinyl ether and its polymer of the present invention.

[Means for solving problems]

The present invention is a novel fluorine-containing superstructure represented by the general formula % (wherein R1 is a hydrogen atom, a lower alkyl group, or a lower polyfluoroalkyl group, and R1 is a polyfluoroalkyl group). It consists of fluoroalkoxyethyl vinyl ether and repeating units obtained by its polymerization expressed as mm formula % formula %), and has an intrinsic viscosity of 0.001 dl/g at 30°C in 1,4-bis(trifluoromethyl)benzene. The present invention provides a polymer of fluoroalkoxyethyl vinyl ether as described above (in the formula, R1 and Ra are the same as above).

Alkyl groups and polyfluoroalkyl groups may be of either linear or branched type, or polyfluoroargyl groups have at least 30%, preferably 50% or more of the hydrogen atoms in the alkyl group being fluorine atoms. It is a group substituted with.

As the lower polyfluoroalkyl group represented by R1,
difluoromethyl group, perfluoromethyl group, 2 to 5
Examples include an ethyl group substituted with 2 to 7 fluorine atoms, a propyl group substituted with 2 to 7 fluorine atoms, and a butyl group substituted with 2 to 9 fluorine atoms.

The polyfluoroalkyl group represented by R2 includes a difluoromethyl group, a perfluoromethyl group, an ethyl group substituted with 2 to 5 fluorine atoms, a propyl group substituted with 2 to 7 fluorine atoms, and 2 to 9 fluorine atoms. butyl group substituted with 2 to 1) fluorine atoms, pentyl group substituted with 2 to 1) fluorine atoms, hexyl group substituted with 2 to 13 fluorine atoms, Heptyl group substituted with 2 to 17 fluorine atoms, nonyl group substituted with 2 to 19 fluorine atoms, decyl group substituted with 2 to 21 fluorine atoms, 2 to 23 fluorine atoms undecyl group substituted with fluorine atoms, dodecyl group substituted with 2 to 25 fluorine atoms, tridecyl group substituted with 2 to 27 fluorine atoms, tetradecyl group substituted with 2 to 29 fluorine atoms Examples include groups. In particular, from the viewpoint of refractive index, an alkyl group substituted with six or more fluorine atoms is preferred, and from the viewpoint of tθ water and oil repellency, a perfluoroalkyl group is preferred.

The fluoroalkoxyalkyl vinyl ether of the present invention can be synthesized in good yield by reacting 2-chloroethyl vinyl ether with a fluorine-containing alcohol represented by the general formula % ([) in the presence of a base. Examples of bases include 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 and potassium, and diazabicyclo(3,4,
Examples include amines such as 0) to 5-nonene (DBN) and 1,5-diazabicyclo(5,4,0)-5-undecene (DBU). The base can be used in an amount of 1 equivalent to a large excess relative to the fluorine-containing alcohol, and in particular, in the following two-phase reaction, it is preferable to use a large excess in terms of reaction efficiency. Although it is possible to use a solvent, it is preferable from the viewpoint of yield to use a phase transfer catalyst such as tetra-n-butylammonium hydrogen sulfate to carry out the reaction in a two-phase system of an organic phase and an aqueous phase.

Examples of the fluorine-containing alcohol include 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-
1-Propertool, 2,2,3.3゜4.4.4-Pentafluoro-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-difluoro Ethanol, 2,2,3,3.4.4-hexafluoro-1-butanol, 2,2,3.3-tetrafluoro-1-propatol, 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-pentadecafluoro-1-decanol, 1.1
．． Examples include 1.6,6,7.7.7-octafluoro-2-heptatool. Examples of the solvent that can be used in the reaction and the organic phase in a two-phase reaction include benzene, toluene, xylene, diethyl ether, and cyclohexane. The temperature of the reaction is preferably 0°C to 150°C, preferably 20°C.
It is in the range of °C to 100 °C.

Further, the fluoroalkoxyalkyl vinyl ether polymer of the present invention can be obtained by cationic polymerization or radical polymerization of the fluoroalkoxyalkyl vinyl ether of the present invention represented by general formula (1).

Cationic polymerization can be carried out by coexisting a cationic polymerization initiator in a solvent that does not directly participate in polymerization. Any solvent can be used as long as it does not directly participate in the reaction, such as hexane, cyclohexane, benzene, toluene, chloroform, dichloroethane, trichlorotrifluoroethane (Triflon), 1,4-bistrifluoromethylbenzene ( B
TB), etc. As an initiator for cationic polymerization, initiators that are normally used for cationic polymerization can be used, but in terms of polymerization activity, BF3.
EtzO,'EtAICIt.

CFffSO! It is preferable to use H or the like.

The reaction temperature is -100°C to 70°C, preferably 80°C
Polymerization proceeds suitably in the range of ~50°C.

In addition, recently developed HI/IT, EtA
I C1t-ether compound, EtAICl.

It is also possible to carry out cationic living polymerization by using an initiator system such as an ester compound. By using this method, it is possible to synthesize block copolymers or terminally functional polymers.
romolecules.

1E 1 (1987)).

Radical polymerization can be performed using known methods such as bulk polymerization, solution polymerization, and emulsion polymerization, and is promptly initiated by heat, ultraviolet irradiation, or addition of a radical polymerization initiator. Examples of the radical initiator include organic peroxides such as dilauroyl peroxide, benzoyl peroxide, and t-butyl peroxide, and azo compounds such as α,α'-azobisisoputyronitrile. When using a solvent, any solvent can be used as long as it does not directly participate in the reaction, but examples include benzene, toluene, tetrahydrofuran, carbon tetrachloride, chloroform, dichloroethane, trichlorotrifluoroethane, and 1,4-bistrifluoroethane. Fluoromethylbenzene, N,N-didimethylformamide, and the like can be used.

The reaction is usually carried out at 40°C to 150°C, preferably 60°C to
The process is preferably carried out at a temperature of 120°C.

In addition to the above-mentioned repeating unit (■), the polymer of the present invention includes repeating units other than repeating unit (II) for the purpose of adjusting the film-forming properties, flexibility, solubility, viscosity, etc. of the polymer. Specific examples of such repeating units that may contain up to 50 mol % of the following include, for example, repeating units derived from the following monomers.

1)1 Acrylic acid or methacrylic acid 01~CI@
Alkyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-decyl acrylate,
Isooctyl acrylate, n-decyl acrylate, methyl methacrylate, isopropyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, etc.

+21 01-C8° polyfluoroalkyl ester of acrylic acid or methacrylic acid, such as acrylic acid 2.
2.2-trifluoroethyl, acrylic acid 2.2.3,
3,4.4.4-Heptafluorobutyl, acrylic acid 3
, 3,4,4,5,5,6゜6-octafluorohexyl, acrylic acid 3.3゜4.4,5,5,6,6,7,
7,8,8.8-tridecafluorooctyl, 1-trifluoromethyl-2,2,2-1-lifluoroethyl acrylate, 2.2,3.3.3-pentafluoropropyl methacrylate, methacryl fa3.3.4,4゜5.
5,6,6.7.7-decafluorohebutyl, methacryl fi4.4,5,5,6,6.7.7°8.8.9.
9.10.10.10-Pentadecafluorodecane and the like.

(3) Ct'' C4 hydroxyalkyl esters of acrylic or methacrylic acid, such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, ff12-hydroxypropyl acrylate, 5-hydroxypropyl acrylate
Hydroxypentyl, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, and its hydroxyl group protected form.

(4) Vinyl aromatic compounds, such as styrene, α-
Methylstyrene, p-chlorostyrene, pentafluorostyrene, p-hydroxystyrene, m-fluorostyrene, p-ethylstyrene, p-trimethylsilylstyrene, 2-vinylnaphthalene, 4-vinylpyridine, N
-Vinylpyrrole etc.

[5) Others, such as ethyl vinyl ether, vinyl chloride, octyl vinyl ether, CF, -CFOCF
*CFOCF! CFs, vinyltrimethylsilaCF.

acrylonitrile, N-vinylpyrrolidone, maleic anhydride, vinyl acetate, etc.

(6) Monomers having crosslinkable groups, such as acryloyloxyethyl vinyl ether, methacryloyloxyethyl vinyl ether, cinnamyloxyethyl vinyl ether, styrylmethyloxypropyl vinyl ether, glycidyl methacrylate, p-glycidyloxymethylstyrene, and the like.

The fluorine-containing polymer of the present invention has an intrinsic viscosity of 0.00 at 30°C in 1,4-bis(trifluoromethyl)benzene.
1 dl/g or more, and particularly when used as a coating material, it is preferably 0.01 dl/g or more from the viewpoint of film forming ability.

〔Effect of the invention〕

The fluorine-containing vinyl ether of the present invention is easily polymerized by cationic polymerization or radical polymerization to provide the novel fluorine-containing polymer of the present invention. Further, the obtained polymer generally has an extremely low refractive index of 1.40 or less and exhibits excellent 1a water (θ oiliness).

Furthermore, since it does not have an ester bond, it is extremely stable against hydrolysis. Therefore, highly durable water-repellent tB oil material,
It is thought to be useful as a sheath material for optical fibers.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Synthesis of 2-(IH,IH,2H,2H-perfluorooctyloxy)ethyl vinyl ether CHz "Cl
l0CIIzCHtC1--11--kai CH spirit "CH
OCHtCHtOCHtC)It"e-cFt'6hC
FsIH, IH, 2H, 2H-perfluorooctatotool 1.456 g (4 mmol), tetra-n-sulfate
Butylammonium 67.9w (0.2mm o +
) and 4 ml of a 40% aqueous sodium hydroxide solution were mixed and stirred at room temperature for 30 minutes. Next, 4 ml of 2-chloroethyl vinyl ether was added, and the mixture was stirred at 70'C for 20 hours. After cooling, the mixture was diluted with 15 ml of water and extracted with dichloromethane. The extract was washed with water and dried over anhydrous magnesium sulfate. Then, by distillation, the boiling point is 80-89℃/
8mmHH 2-(IH,IH,2H,2H-perfluorooctyloxy)ethyl vinyl ether 1.40
g (yield 80.6%) was obtained.

Elemental analysis (%): C++*H++F1! Ox.

Calculated value, c, 33.19; H, 2,55° actual measurement + a: c, 33.25; H, 2,50° NMR (ppm) (CDC1s): 2.02-2
．． 90 (2H), 3.63-4.02 (6H)
.

4.10-4.37 (2H), 6.34-6.70
(IH).

rR(am-') 1640, 1620° Refractive index: n
D' 1-3431-Mass m/s 434
(M'), 390° 327.77.69.57° Example 2 Synthesis of poly (IH, IH, 2H, 2H-perfluorooctyloxyethyl vinyl ether) CI! =CH 0CHzCHzOCHtCHtCJ+i-> +cuzcus0CH*CHtOCHtCHtC6P+ s Under argon stream, IH, IH, 2H, 2H-perfluorooctyloxyethyl vinyl ether 2.06 g (4,75
12.5 ml of Triflon solution (mmol) was heated to -15°C.
Boron trifluoride ethyl ether 6 μm (1 mo
1%) and stirred at the same temperature for 24 hours. The reaction was stopped by adding 0.2 ml of triethylamine, and the solvent was distilled off.

The residue was washed with hexane and tetrahydrofuran, and 1.90 g of pale yellow oily poly(IH, IH, 2H, 2H-perfluorooctyloxyethyl vinyl ether) was obtained.
(yield 92.2%).

The raw materials used in this reaction were calcium hydride, and the triflon was dried using phosphorus pentoxide and distilled. The same applies to the following cationic polymerization reaction.

Elemental analysis (%): (C+ t H+ + F
Calculated value as + s Ot ) -: C, 33, 19
; H, 2,55° Actual value: C, 33,57i H,
2,51°NMR(+)I)m)(CFtCI CFC
l5-CDCI3:1.52-2.02 (2H),
2.32-2.54 (2H), 3.44-4.04
(7H).

T R (cm-') (n a at) 2950.
2900, 1365, 1240°1) 90.1) 40,
1000.845° 810.730° Intrinsic viscosity (BT8 30°C) [η) = 0.087 dl/g.

Thermal properties -1'g, -60℃, "["mH-Tdeg
;1) 3°C・Refractive index: n” 1.3652°Contact angle (Hlo, 28°C), θ-926 Example 3 2- (IH, IH, 2H, 2H-Berf J rheolotyloxy) ethyl vinyl ether J-Synthesis-Saku'Ctlz'''CHOCthel (gcl-
kls Ctlz = Cll0CHtCH saving 〒τCFt dimension qcP
*IH,LH,2H,2H-perfluorodecanol 1
．． 954g (purity 95%, 4mmol), 67.9μ of tetra-n-butylammonium hydrogen sulfate (0.2m
mol) and 4 ml of 40% aqueous sodium hydroxide solution were mixed and stirred at room temperature for 30 minutes.

Next, add 2-chloroethyl vinyl ether aml and add 7
The mixture was stirred at 0°C for 20 hours. After cooling, add 15 m of water to the reaction solution.
1 was added to dilute the mixture, and the mixture was extracted with dichloromethane. The extract was washed with water and dried over anhydrous magnesium sulfate. after that,
Boiling point 92-98℃/3 mm Hg2 by distillation
- (IH, IH, 2H.

1.87 g (yield: 87.6%) of 2H-perfluorodecanyloxy)ethyl vinyl ether was obtained.

Elemental analysis (%): C+ a H+ + F I
? Ox.

Calculated value: C, 31,47; H, 2,08° Actual value:
C, 31,49; H, 2,05°NMR (ppm)
(CDCI z2.02~2.90 (2H),
3.63-4.02 (6H).

4.10~4.37 (21(), 6.35~6.
71 (IH).

! R (cm-') 1640, 1620° Refractive index: n"
1.341? .

Mass m/e 534 (M”), 490°4
27.169,131,1)9.9577, 69.
57° Example 4 Poly (IH, IH, 2H, 28-perfluorodecanyloxyethyl vinylot-CH OCHxCHxOCHtCIIzCJ + .

1000H. CHsuOCLClltOCHyo(:HxC*F+tlH obtained by the method of Example 3 under an argon stream.

LH,2H,2H-perfluorooctyloxyx-
j-nt vinyl x-full 2.13 7 g (4.0
mmo L)'s truffle 0f IQ. 5ml solution at -20℃
Boron trifluoride ethyl ether was added to 10 l (2
Mo1%) was added thereto, and the mixture was stirred at the same temperature for 25 hours. U
The reaction was stopped by adding 0.2 ml of ethylamine, and the solvent was distilled off. The residue was washed with hexane and tetrahydrofuran to obtain poly(LH, IH) as a colorless powder.

1.95 g (yield: 91.3%) of 2H,2H-perfluorodecani J leoxyethyl vinyl ether was obtained.

Elemental analysis (%): Calculated value as (C14H1)F+, 0ha: C. 33.47. H. 2.08.

Actual value: C, 3 1.4? , H, 2.1
5.

NMR (CF.CI CFCl*-CDCla)
.

(ppm): 1.52 ~ 2.03 (2H)
, 2.32-2.53 (2H), 3.47-4
．． 09 (7H).

IR (mouth) 1240° 970° intrinsic viscosity [η] thermal properties de Refractive index: contact angle ’) (KBr) 2900, 1370.　1330゜ 1205, 1) 50.　1000゜ 870, 820. 740° (BTB 30℃) = 0.067 dl/g.

Tg: -52°C, Tm: 36°C.

g; 1) 2°C.

n%,' 1.3605° (Hf0.28°C), θ-1076 Example 5 Synthesis of 2-(IH,IH,2H,2H-perfluorododecanyloxy)ethyl vinyl ether CI(,=C
l1OC1(,CH2Cl-1-CHt
-CHOCHtcll z)it CF zjqcF
sIH, IH, 2H, 2H Perfluorodododecanol 2.82g (5mmol), hydrogen sulfate tetra-n-butylammonium 169.8■ (0.5mmol)
1) and 5 ml of 40% aqueous sodium hydroxide solution were mixed and stirred at room temperature for 30 minutes. Next, 5 ml of 2-chloroethyl vinyl ether was added, and the mixture was stirred at 60°C for 24 hours. After cooling, the reaction solution was diluted with 20 ml of water and extracted with dichloromethane. The extract was washed with water and dried over anhydrous magnesium sulfate. Then, by distillation, 2-(IH,1) with a boiling point of 87-89℃10.35mmHH
-1,2H.

2.71 g (yield: 85.5%) of 2H-perfluorododecanyloxy)ethyl vinyl ether was obtained.

Elemental analysis (%): Clil (++Ft+Ot.

Calculated value: C, 30, 30; H, 1,75° Actual value: C
, 30, 29; H, t, 67°NMR (ppm) (C
DC1i): 2.02-2.90 (2H), 3.63
~4.02 (6H).

4.10-4.37 (2H), 6.35-6.72 (
IH).

IR(am-')1640. 1620° refractive index: n
'o' l -3360-Mass m/e
634 (M”), 590°131, 7?,
69. 57゜Example 6 Synthesis of poly(IH, LH, 2H, 2H-perfluorododecanyloxyethyl vinyl ether) C1 (2 Tom CI 0CHtCHtOCHtCHtC+.Fz+ -+Cl(,CH+ 0CR1CH!OCR,Cl1tCI.h.

IH and LH obtained in Example 5 under an argon stream.

2H,2H-perfluorododecanyloxyethyl vinyl ether 2.550 g (4.02 mmo 1) of Triflon 1). The 0 ml solution was cooled to -20°C, 5 μm of boron trifluoride ethyl ether (1 mo 1%) was added, and the mixture was stirred at the same temperature for 24 hours. Triethylamine Q,2
ml was added to stop the reaction, and the solvent was distilled off. The residue was washed with hexane and tetrahydrofuran to obtain 1.50 g of poly(LH, IH, 2H2H-perfluorododecanyloxyethyl vinyl ether) as a colorless powder (yield 6).
0.0%) was obtained.

Elemental analysis (%): Calculated value as (C+aH++Ft+0z)-: C, 30, 30, H, 1,75° Actual IN
Straight: C, 30, 28; H, 1, 72°NMR (CFt
CI CFCIt-CDCI,).

(ppm): 1.50-2.02 (2H), 2.3
4-2.55 (2H), 3.44-4.09 (7H
).

I R (cm-') (KB r) 2950.2900, 1375.1330°1240.
1210.1) 50,1000°900.880,74
0° Intrinsic viscosity rBTB 30°C] = 0.024 dl/g.

Tg: -38°C, Tm: 80°C.

g; 1) 1°C.

n'o 1-3360.

(HO 0.28°C), θ-128@(η) Thermal properties refractive index: Contact angle Example 7 Synthesis of 2- (IH, IH-perfluorooctyloxy)ethyl vinyl ether C1), CoCll0C)ltcHzcl −One ÷
cut -Cll0CHtCH! OCH*+ Ch f
hcFsLH,IH-Perfluorooctatool 1.6
0g (4mmol), tetra-n-butylammonium hydrogen sulfate 135.8■ (0.4mmol 1) and 40%
4 ml of sodium hydroxide aqueous solution was mixed and stirred at room temperature for 30 minutes. Next, 2-chloroethyl vinyl ether 4
ml and stirred at 60°C for 23 hours. After cooling, the reaction solution was diluted with 15 ml of water and extracted with dichloromethane. The extract was washed with water and dried over anhydrous magnesium sulfate. After that, the boiling point is 75~79℃75m by distillation.
m HH 2(IH,IH-perfluorooctyloxy)ethyl vinyl ether 1.76 g (yield 93.6%
) was obtained.

Elemental analysis (%): C+tHwFtang.

Calculated values: C, 30°65; H, 1,93° NMR (pp
m) (CDC1z): 3.90~(2H),
3.72-4.42 (6H).

6.35-6. 'IO(IH).

TR(csi-') 1640. 1620° refractive index: nzs 1.3420° Mass m/e 470 (M”),
426°169, 131. 1)9. 69. 5?
.

Example 8 Synthesis of poly(IH,LH-perfluorooctyloxyethyl vinyl ether)+CIIICH+ 0CHzCHxOCHtCJ+s LH obtained by the method of Example 7 under an argon stream.

IH-perfluorooctyloxyethyl vinyl ether 1). The 0 ml solution was cooled to -20°C, 5 μl of trifluoroboron ethyl ether (1 mo 1%) was added, and the mixture was stirred at the same temperature for 24 hours. Triethylamine 0.2rnl
was added to stop the reaction, and the solvent was distilled off. The residue was washed with hexane and tetrahydrofuran to obtain 1.42 g (yield 75.5%) of poly(1) (LH-perfluorooctyloxyethyl vinyl ether) as a colorless oil.

Elemental analysis (%): Calculated value as (C+zHeF+sO□): C. 3 Q. 65 i H. 1.
93.

Actual value: C. 3 0.92; H, 2.18.

NMR (CF*C I CFC In CDC
In).

(ppm): 1.52 ~ 2.04 (2H
), 3.37-4.22 (7H).

I R (cm-') (ne a L)29
50, 2900, 1460. 1360.

1220, 1) 50, 960.　880.

840, 810, 735.

Intrinsic viscosity (BTB 30℃) [η)-0.10 2 d l/g.

Thermal properties Tg: -60℃. Tm; Tdeg: 100°C.

Refractive index: n ``o' 1 , 3 6 0 5 - contact angle 1to, 28°C), θ-104' Example 9 2- (II (, IH, 5H-perfluoropentanyloxy) Synthesis of ethyl vinyl ether Cl1z ” C.I.
'1OCHtCHtCICHI□= Cll0CII
tcHtOcHyo-tCFzηCFJIH, IH, 5H
-Perfluoropentanol 2.32g (10mmo
+), tetra-n-butylammonium sulfate 1.6
98 g (5 mmol) and 10 ml of 40% aqueous sodium hydroxide solution were mixed and stirred at room temperature for 30 minutes.
Next, add 10 ml of 2-chloroethyl vinyl ether,
The reaction mixture was stirred at room temperature for 40 hours, diluted with 30 ml of water, and extracted with dichloromethane. Wash the extract with water,
It was dried with anhydrous magnesium sulfate. Thereafter, 2-(LH, IH,
2.58 g (yield: 85.4%) of 5H-perfluoropentanyloxy)ethyl vinyl ether was obtained.

Elemental analysis (%): c, H,. F@0° Calculated value: C, 35, 77, H, 3, 34 Actual value; C, 3
5,90,H,3,21gMR(+)pm) <CD
CI *) 3.77-4.37 (6H), 3.90
(2H), 5.20°6.08. 6.93
(IH), 6.30-6.66 (IH).

IR(ca-') 1640. 1620° refractive index:
n ”t,' 1-3680Mass m/e
302 (M”), 259°145, 9
5. 69. 57. 45° Example 10 Synthesis of poly (IH, IH, 5H-perfluoropentyloxyethyl vinyl ether) Hx-CB 0CHtCHtOCHtfCFt'? xCFJ 1,000GHz
CII → - QC) IICH! 0CHI (Ch) *CF2H LH, IH obtained in Example 9 under argon flow.

5H-perfluoropentyloxyethyl vinyl ether 1.934 g (6,4 mmo +) of trif c+
N17. The Oml solution was cooled to -18°C, 8 μl (1 mo 1%) of boron trifluoride ethyl ether was added, and the mixture was stirred at the same temperature for 24 hours. The reaction was stopped by adding 0.2 ml of triethylamine, and the solvent was distilled off. The residue was washed with hexane and a pale yellow oily PoU (LH,IH,5H-
perfluoropentyloxyethyl vinyl ether) 1
．． 85 g (95.7% adult insects) was obtained.

Elemental analysis <9'6): (CwH+oFsOi)-7 Calculated value FC, 35, 7? , H, 3, 34 actual measurements (1
c, 36.19. H,3,32gMR(CFtC
I CFC+z-coc 12).

(ppm) 1.51-2.03 (2H).

3.44-4.12 (7H), 5.88-6.
26 (LH).

TR (cm-') (neat)2950. 290
0°1460, 1285. 1) 70°1) 30.975, 900. 805°755° Molecule it (Boristi L/7 conversion) Mn-16600 Thermal properties TgH -71℃, TmH Tdeg; 126℃ Refractive index: n ”o l -3863 Contact angle (H,0
, 28°C), θ-82″Example 1) Synthesis of 2-(II(IH,1)1(-perfluoroundecanyloxy)ethyl vinyl ether CI+!
= (JIOCHtC)IICIC)1z-C1)0
C) ItCHgOcHt-I Ch one; Cp, 1) 1H
, IH, IIH-perfluoroundecanol 4.28
g (8.06 mmol), 2-chloroethyl vinyl ether 8 ml, tetra-n-butylammonium sulfate 543.2 oyr (1.6 mmol) and 40
% sodium hydroxide aqueous solution and heated to 60°C.
The mixture was stirred for 24 hours. After cooling, 30 ml of water was added to the mixture, and the mixture was extracted with dichloromethane. Wash the extract with water,
It was dried with anhydrous magnesium sulfate.

Then, by distillation, the boiling point was 92 to 94℃, 10.45mmH.
3.16 g (yield: 65.2%) of 2-(IH,IH,IIH-perfluoroundecanyloxy)ethyl vinyl ether was obtained.

Elemental analysis (%): C+ s Hlo F t. 0
□Calculated value: C, 29,91,H, 1,67 Actual value: C,
29,92,H,1,85NMR (ppm) (CDC1
3): 3.80-4.39 (6rH, 3,92(
2H), 5.19°6.07. 6.93 (L
H), 6.33-6.68 (LH).

IR (am-'> 1640. 1620° refractive index:
n341.3392 Mass m10 602 (M”),
558°131, 100. 69. 57゜Example 12 Synthesis of poly (1) (, IH, IIH-perfluoroundecanyloxyethyl vinyl ether) CH,=CH +1) (JzCIIJCHz1CF2, Cr'2H+
CHtCIl+ 0CHzCHtOcn ICh+*CFJ Under argon flow, 1) 1゜lH obtained in Example 1), 1)) 1-perfluoroundecanyloxyethyl vinyl ether 2
．． 409 g (4, Ommo I) of Triflon 1)
．． Cool the 0 ml solution to -20°C, add 10 μl (2 mo 1%) of boron trifluoride ethyl ether, and stir at the same temperature.
Stirred for 4 hours. After adding 0.2 ml of triethylamine to stop the reaction, insoluble matter was filtered, and the solvent was distilled off.
Colorless powder poly (I H, I H, 1) H-perfluoroundecanyloxyethyl vinyl ether)2.
40 g (yield 99.6%) was obtained.

Elemental analysis (%): Calculated value as (C+sH+.F2°08): C, 29,91, H, 1,67° Actual value:
C,29,71,H,1,61°NMR (CFICI
CFCI□-CD CI t) (ppm) 1.52-2
．． 03 (2H).

3648-4.12 (7H), 5.78-6.12 (
IH).

IR (c+a-') (KB'r) 2950.2900°1400.1320.1205°1) 50, 960. 910. 830゜Patent viscosity (
BTB 30°C] [η) -0,064 dl/g Molecule f (polystyrene H,) Mn-32000 Thermal property 'ji Tg; -, Tm; 70°C.

Tdeg; 108°C Refractive index 203D'==1.3392 Contact angle (H, o, 28°C) 2 θ=96' Example 13 Synthesis of 2-(2,2,2-)lifluoroethoxy)ethyl vinyl ether CHz=C1lOCIIzClhCI CHt=Cll0CIIzCHzOClltCF2.2.21 Lifluoroethanol 1.0 g (l Om
mol), 339.5 N (1 mmo +) of tetra-n-butylammonium hydrogen sulfate, and 10 ml of 40% aqueous sodium hydroxide solution were mixed and stirred at room temperature for 30 minutes. Next, 10 ml of 2-chloroethyl vinyl ether was added, and 60 The mixture was stirred at ℃ for 20 hours. After cooling, the reaction solution was diluted with water and extracted with dichloromethane. The extract was washed with water and dried over anhydrous magnesium sulfate. Thereafter, 0.51 g (yield: 30%) of 2-(2,2,2-trifluoroethoxy)ethyl vinyl ether having a boiling point of 1) 5°C was obtained by distillation.

NMR (ppm) (CDC1z): 3.87 (2H)
.

3.57-4.37 (6H), 6.33-6.67 (
IH).

Mass m/e 170 (M”), 126°8
3.57.47゜Example 14 Synthesis of poly (IH, IH, 2H, 2H-perfluorodecanyloxyethyl vinyl ether) CIlt =
C1) 0CHzClbOC81CI□C@F+knock---1--
-→ -4CH, CH→-0CR2CII! 0CH2C
II, C, + Fl? IH, IH, 2H, 2H-perfluorodecanyloxyethyl vinyl ether 1.068
g (2,0 mmol) and t-butyl peroxide 72+
y (0.08 mmol) was placed in a polymerization tube, the tube was degassed and sealed by a conventional method, and then stirred at 135° C. for 29 hours. The reaction solution was washed with tetrahydrofuran, and a pale yellow oily poly(IH)
, IH, 2H, 2H-perfluorodecanyloxyethyl vinyl ether) 0.48 g (yield 44.9%) was obtained.

NMR (CFICI CFC1, -CDC1)) (pp
m) 1.51-2.06 (2H) 2.26-2.58
(2H), 3.27-4.00 (7H) 2950, 2900°1430°1200°970, 870°I R(am-') (ne at)1725,
1460°1370, 1240 1) 50, 1005°825° Intrinsic viscosity [BTB 30°C] [η) =0.023 a l/g Thermal properties Tg; -, Tm; 14°C.

Tdeg; 127°C Refractive index: n”= 1.3651 Procedural amendment 1985 l/month 2nd day Director General of the Patent Office Yoshi 1) Moon Yi 1, Indication of case Patent Application No. 39525 1988 2, Invention Name of fluoroalkoxyethyl vinyl ether and its polymer 3, relationship to the amended party case Patent applicant

Claims (2)

[Claims] (1) General formula CH_2=CHOCH_2CH_2OCHR^1R^2
A fluoroalkoxyethyl vinyl ether represented by (wherein R^1 is a hydrogen atom, a lower alkyl group or a lower polyfluoroalkyl group, and R^2 is a polyfluoroalkyl group). (2) It consists of a repeating unit represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. A certain fluoroalkoxyethyl vinyl ether polymer (wherein R^1 is a hydrogen atom,
lower alkyl group or lower polyfluoroalkyl group,
R^2 is a polyfluoroalkyl group. ).