JPH0311025A - Fluorine-containing alicyclic alcohol compound, derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing alicyclic alcohol prepared by grafting 2-30C fluorine-substituted hydrocarbon group containing at least three fluorine atoms to an alicyclic alcohol shown by formula I (R<1> is H or OH; x and y are 0-30 integer; m is 0-10 integer; n is 1-12 integer; m+n=1-22) and a fluorine- containing alicyclic (meth)acrylic acid ester prepared by grafting 1-30C fluorine- substituted hydrocarbon group containing at least three fluorine atoms to a compound shown by formula II (R<2> is H, OH or group shown by formula III; R<3> is H or CH3). EXAMPLE:1-Hexafluoropropyl-1,3-cyclohexanediol. USE:A comonomer for oxygen permeable polymer, useful for contact lens. PREPARATION:A compound shown by formula I is reacted with a fluorine- containing olefin (e.g. CF2=CFCH3) in the presence of a radical generating agent (e.g. isobutyryl peroxide) at 50-200 deg.C for 0.2-5 hours to give the title compound.

Description

[Detailed Description of the Invention] The present invention relates to a novel fluorine-containing alicyclic alcohol, its (meth)acrylic acid ester derivative, and a method for producing the same. In particular, fluorine-containing alicyclic alcohols that are useful as raw materials for producing comonomers for copolymers constituting oxygen permeable materials such as contact lenses, and fluorine-containing alicyclic alcohols derived from these fluorine-containing alicyclic alcohols. ,
The present invention relates to (meth)acrylic acid ester derivatives useful as comonomers for medical oxygen permeable materials, particularly polymers constituting oxygen permeable materials such as contact lenses, and methods for producing them.

BACKGROUND OF THE INVENTION Materials for contact lenses must have excellent optical properties, chemical properties, physical properties, and the like, as well as excellent oxygen permeability.

Conventionally, polymethyl methacrylate and various methacrylate ester copolymers have been widely used as materials for such contact lenses, but these materials are required to further improve oxygen permeability. There is.

Therefore, in order to improve the oxygen permeability of methacrylic ester polymers, for example, Japanese Patent Publication No. 5233502 proposed a siliconized methacrylic ester polymer in which a siloxane bond was introduced into the methacrylic ester molecules. JP-A-57-51705, JP-A-Sho 6
Contact lenses using oxygen-permeable polymers mainly composed of cellulose acetate butyrate and fluorine-containing methacrylic acid ester polymers have been proposed in Japanese Patent No. 1-111308 and the like.

The present invention was made to obtain an oxygen permeable material for medical use, particularly a material with extremely excellent oxygen permeability for contact lenses, etc., and which also has excellent stain resistance and wearability. It is. That is, the present invention provides a fluorine-containing alicyclic alcohol useful as a raw material for producing a comonomer for a novel medical oxygen-permeable copolymer, a novel medical oxygen-permeable copolymer, It is particularly useful as a comonomer for copolymers useful as materials for contact lenses, etc.
The present invention aims to provide meth)acrylic acid ester derivatives and methods for producing them.

First, according to the present invention, the general formula (1) % formula % ) () (wherein R1 represents a hydrogen atom or a hydroxyl group, and X and y are each an integer of 0 to 30, m is an integer from 0 to 10, n is 1
Indicates an integer of −12, and m + n is 1 to 22. ) At least one fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is grafted to the carbon atom of the alicyclic alcohol represented by () per molecule of the alicyclic alcohol. A fluorine-containing alicyclic alcohol is provided.

Examples of the alicyclic alcohol represented by the above general formula (1) include cyclopropylmethanol, cyclobutanol, cyclopencune-1,3-diol, cyclopentylmethanol, cyclopentanol, 3-cyclopentyl-1-propatol, and cyclohexyl. methanol,
Cyclohexane-1゜6-simethanol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexanol, 4-cyclohexyl-1-butanol, cyclohexylethyl carbinol ,■-cyclohexyl-
2-ethanol, cyclohebutane-1,2-diol,
cyclohebutylmethanol, cycloheptatool, cyclooctane-1,2-diol, cyclooctane-1,
Examples include 4-diol and cyclooctatool.

The fluorine-containing alicyclic alcohol according to the present invention is such an alicyclic alcohol that one molecule of a fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms per carbon forming the alicyclic alcohol. At least one graft is attached to each.

The fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having a fluorine atom is preferably a fluorine-substituted saturated alkyl group or a fluorine-substituted cycloalkyl group which may have a condensed ring or a bridged ring.

Therefore, as a specific example, for example, -CFICFHCF
! , -CFtCFHCJs--CFICFHCoF1,
-CPgCFHCiFts, -CFtCFHCl, F*
I-, -CFzCFHCFtH, -CFtCFH (Ch
)J.

-CFzCFH(CFz)4H1-CF, CFH(CF
ri, H, -CFtCF)l(cpz)1N, -CFI
CFH(Ch), H, -CFzCFH(Ch)J.

-CFzCFH (CFri +.H, -CHzCHzCF
s, -CHzCHzCJs, CHgCHg(Ch)! ,
-CFtCFHCFtC(CFi)s, -ChCFl-
Examples include fluorine-substituted saturated alkyl groups such as ICFtCH(C*Fs)z, and the like.

Among the above, particularly preferred are alkyl groups having 2 to 20 carbon atoms and having at least three fluorine atoms.

In the fluorine-containing alicyclic alcohol according to the present invention, the above-described fluorine-substituted hydrocarbon group is graft-bonded to a carbon atom in the saturated hydrocarbon chain of the alicyclic alcohol represented by the general formula (1). The grafting ratio of this fluorine-substituted hydrocarbon group is at least 1 or more, preferably 1 to 4, per molecule of alicyclic alcohol. Therefore, the fluorine-containing alicyclic alcohol according to the present invention has a The molecule usually has 3 to 120, preferably 3 to 60 fluorine atoms.

When a plurality of fluorine-substituted hydrocarbon groups are graft-bonded to the fluorine-containing alicyclic alcohol according to the present invention, these fluorine-substituted hydrocarbon groups are usually graft-bonded to different carbon atoms.

Therefore, as specific examples of the novel fluorine-containing alicyclic alcohol according to the present invention, for example, CF, CIPCen:OgF, CHFCFff"kai'C'
:t(ASP(CFZ), H, etc.).

According to the present invention, the fluorine-containing alicyclic alcohol represented by the general formula (1) is represented by the general formula (1).
) (1) (In the formula, R1 represents a hydrogen atom or a hydroxyl group, X and y are each an integer of 0 to 30, m is an integer of 0 to 1O, and n is 1
Indicates an integer of ~12, and m + n is 1-22. ) can be obtained by reacting an alicyclic alcohol represented by the following with a fluorine-containing olefin in the presence of a radical generator.

The above-mentioned fluorine-containing olefins include, for example, CF2/CFC)13,
Ch=CFCtHCFz"CFCJ*, CF!=CF
C&I (13, CF,=CF-C1@H!I,CF!=
CFCF! , CFt=CFCFzH, CFz=CPCC
Ft)tH.

CF,・CF(CFri4B, CFt・CF(CFri&
H, CF2・CF (CFri? H-Ch=CF(CFz)
JSCP!・CF(CFt)J, Ch・CF(Ch)
+. H1CHz=CHCFs, C1h=CHCzFs,
CHz=cH(CFz) bH.

CF, CFCFzC(CFs)s, CFtt=CFC
hCH(CtFs)t, CPzgCF-CF=CFt
1 etc. can be mentioned.

The reaction between the fluorine-containing olefin and the alicyclic alcohol is preferably carried out in a solvent in the presence of a radical generator. Although the radical generator is not particularly limited, it usually includes, for example, isobutyryl peroxide, 1-hexyl peroxyneohexanoate, 2,4-dichlorobenzoyl peroxide, octanoyl peroxide, and cumyl peroxide. Luperoxyoff [・
ate, m-) lylver oxide, benzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl cumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, etc. can be mentioned.

Such radical generators are usually present in the reaction mixture.
0.1 ms+ol/] to 10 mol/j! , preferably in the range of 10'5nol/l to 1 mol/l.

As the reaction solvent, aromatic hydrocarbons and halogenated aromatic hydrocarbons, particularly chlorinated or fluorinated alkyl aromatic hydrocarbons, are preferably used. For example, benzene, xylene, toluene, chlorobenzene, dichlorobenzene, pencitrifluoride, chloropencitrifluoride,
Xylene hexafluoride, etc. are used.

The reaction between the alicyclic alcohol and the fluorine-containing olefin is usually carried out at a temperature of 20 to 300°C, preferably 50 to 200°C.
It is usually carried out at a temperature in the range of 0.2 to 5 hours.

After the reaction is completed, the unreacted fluorinated olefin and the solvent are separated and removed from the resulting reaction mixture under reduced pressure to obtain the fluorinated alicyclic alcohol of the present invention, and if necessary, distillation is performed. It can be purified by

Further, according to the present invention, the general formula (n) 3 QC-C=CI+□ is shown, R3 is a hydrogen atom or a methyl group 1, X and y are each an integer of 0 to 30, and m is 0 to
An integer of 10, n is an integer of 1-12, and m+n is an integer of 1 to 12.
It is 22. ) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by A fluorine-containing alicyclic (meth)acrylic acid ester having at least one graft bond per molecule is provided.

According to the present invention, the fluorine-containing alicyclic (meth)acrylic ester according to the present invention has the general formula <r> (II) (wherein R2 is a hydrogen atom, a hydroxyl group, or a group (r)) (wherein, R1 represents a hydrogen atom or a hydroxyl group, X and y are each an integer of 0 to 30, m is an integer of θ to IO, and n is 1
Indicates an integer of ~12, and m+n is 1-22. ) At least one fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is grafted to the carbon atom of the alicyclic alcohol represented by () per molecule of the alicyclic alcohol. It can be obtained by reacting a fluorine-containing alicyclic alcohol with (meth)acrylic acid or (meth)acrylic acid halide in a solvent in the presence of a basic compound.

As the (meth)acrylic acid halide, (meth)acrylic acid chloride is preferably used.

Both inorganic and organic bases can be used as the basic compound, and examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. , alkali metal carbonates and hydrogen carbonates such as potassium hydrogen carbonate are used. Further, as the organic base, an amine compound is preferable, and for example, triethylamine, methyldiethylamine, triisopropylamine, pyridine, etc. are used.

As the reaction solvent, hydrocarbons, ketones, ethers and the like are preferably used, such as hexane, pentane, benzene, toluene, cyclohexane, acetone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran and the like.

The (meth)acrylic acid esterification reaction of the alicyclic fluorine-containing alcohol is usually carried out at a temperature of 0 to 150°C, preferably 10 to 80°C. The reaction time is usually
It is about 0.2 to 50 hours.

After completion of the reaction, excess or unreacted (meth)acrylic acid halide remaining in the reaction mixture is decomposed using an alcohol such as methanol as necessary, and solid matter is filtered.
By concentrating the filtrate and removing the unreacted basic compound with the solvent and the (meth)acrylic acid ester by-produced in the above decomposition operation, for example by distilling it off, the fluorine-containing alicyclic (
meth)acrylic acid esters can be obtained.

Therefore, as a specific example of the fluorine-containing (meth)acrylic ester represented by the general formula (■) according to the present invention,
For example, 1h 1 C) 13 CI+CHs, etc. can be mentioned.

The fluorine-containing (meth)acrylic acid ester according to the present invention obtained as described above has, for example, the general formula (I[r) I (III) (wherein R4 represents a hydrogen atom or a methyl group, and X' is C
H3 x2 each represents an independent knee (0-5i) r-CI3 total 3 L CHs p represents an integer of 1 to 5, q represents an integer of 1 to 3, and r represents an integer of 02. ) and a siloxanyl (meth)acrylate monomer represented by the general formula (IV) S C)lz=c-COOR' (IV) (wherein, R1 represents a hydrogen atom or a methyl group, and R6 represents a hydrogen atom or By copolymerizing with a (meth)acrylic acid ester monomer represented by (representing an alkyl group having 1 to 14 carbon atoms or a fluorine-substituted alkyl group), it has excellent oxygen permeability, and therefore, for example, hard contact. A copolymer useful as a medical oxygen permeable material such as a lens can be obtained.

Siloxane (meth) represented by the general formula (III) above
As the acrylate monomer, for example, CH2= CI
IGOOCHg-5i (O5i (CHs) ko1゜(
:, Hs CH mushroom-CC00CHtCHt-5i [053(Ct
Hs) x) sCHz=C)ICOOCHzCHzC
Il□(:Hg-3i [O5i (Czllt) 3
) 3 etc. can be mentioned. These may be used alone or as a mixture of two or more.

In addition, examples of the (meth)acrylic acid ester monomer represented by the general formula (IV) include acrylic acid,
Methacrylic acid, methyl acrylate, ethyl acrylate,
In addition to (meth)acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, and octyl methacrylate, CHl CHt=CCOOCHzC)lzcFHch, CHl CHz=CCOOCHzCHt(CFz)scF+, C
H.

CIl□= CC00C) ItCH! CCFt) v
ch, CHl (CIl□=CCOO=CC00C1lzCH++CFz
, Ctl.

CHz=CCOO(JIzChCFHCh, CHl CHz=CCOOCR1CF(Ch)CFHCF(CF
the law of nature! , C.I.

CIl□= CC00C(C1(3) ICF zcF
Examples include H(CF z) bH. These (meth)acrylic acid ester monomers may also be used alone or as a mixture of two or more.

In the polymer obtained by copolymerizing these monomer components with the fluorine-containing (meth)acrylic acid ester monomer according to the present invention, the fluorine-containing (meth)acrylic acid ester monomer component according to the present invention contains 1 to 90% by weight. %, preferably in the range of 2 to 60% by weight, it has particularly excellent oxygen permeability and biocompatibility, and is useful as a material for hard contact lenses.

The fluorine-containing alicyclic alcohol according to the present invention can be used as a raw material for producing comonomers for medical oxygen permeable materials, particularly copolymers constituting oxygen permeable materials such as contact lenses. The (meth)acrylic acid ester derivative of the present invention derived from such a fluorine-containing alicyclic alcohol is useful for use in medical oxygen permeable materials, particularly copolymers constituting oxygen permeable materials such as contact lenses. It is useful as a comonomer for

The present invention also provides a method for producing such fluorine-containing alicyclic alcohol and (meth)acrylic acid ester derivatives.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 (Production of l-hexafluoropropyl-113-cyclohexanediol) 65 g of cyclohexane-1,3-diol 3.5 g of di-t-butyl peroxide as a radical generator, I
250 ml of chlorobenzene as an agent with an internal volume of 500 m
1 in a stainless steel autoclave, then
110 g of hexafluoropropylene was press-fitted into the flask, the flask was sealed, and the flask was reacted at 120° C. for 7 hours with stirring.

After the reaction is complete, the contents of the autoclave are cooled to room temperature,
After slowly purging the gas inside, the autoclave was opened and the reaction mixture was taken out.

After concentrating the reaction mixture under reduced pressure and distilling off the solvent,
Extraction with diethyl ether and washing of this extract with water were repeated.

The ether layer was then concentrated to isolate a crude product with a purity of 96% (by gas chromatography).

Furthermore, this was subjected to vacuum distillation to obtain 135 g of 1-hexafluoropropyl-1,3-cyclohexanediol represented by the following formula with a purity of 99% (as determined by gas chromatography). The infrared absorption spectrum is shown in FIG.

The yield based on hexafluoropropylene was 69%, and the yield based on cyclohexane-1,3-diol was 90%.

y C-F 1200cm-' GC-MS analysis El ex/e=266, 416 (weak)
(M”)'3C-NMR (solvent CDCh, reference value 77,
Oppm (C”DCI) Boiling point 121-128℃73
~4 Dragon Hg elemental analysis C11F Actual value 38.9 4.1 44. f Calculated value 40.6 4.5 42.9 (The calculated value is
Calculated value for 1:1 adduct of cyclohexane-1,3-diol and hexafluoropropylene. ) Infrared absorption spectrum yo-1 (3600cm-' (sL 3350c
m-' (s, br,).

νC-[12920cm+-' (s), 2850
cm-'δC-81440cm-' Attributed peak number of each peak (1) (8) Chemical shift (δppra) 74.59.76.01 (divided into 8 each) h, ~Cr #2O-30Hz 34.43 .34.65.37.81.38.2666
．． 89.67.12.67.30.67.3127.6
5.27.87.28.25.28.6514.42.
14.78.18.60.1B, 7829.30.29
．． 50.30.2.32.1117.2. hq~C?
#25BHz.

b*~Ct #19.5)1z 82.96. Jya~Cm #196) 1z.

JF9. Jyt~Cs #26Hz(9)
121.2. JH~Cq#282Hz.

JFll~C9# 25.8H2 From the above analysis results, the reaction product is 1 shown by the following formula.
, 3-bis(hexafluoropropyl)-1,3-cyclohexanediol.

(Production of 1-hexafluoropropyl-1-cyclohexanol-3-methacrylate) Next, 1j? A volumetric flask was charged with 77 g of the above 1-hexafluoropropyl-1,3-cyclohexanediol, 90 g of methacrylic acid chloride, and 300 ml of tetrahydrofuran, and while cooling in a water bath under a nitrogen atmosphere, 105 g of triethylamine was added over a period of 2 hours. dropwise at 40°C.
The mixture was reacted for 3 hours with stirring.

After the reaction was completed, methanol was added dropwise to the resulting reaction mixture to decompose excess methacrylic acid chloride, and then
The reaction mixture was filtered. The resulting filtrate was concentrated under reduced pressure to obtain the crude product. Ether was added to this, filtered again, and the ether was distilled off from the filtrate under reduced pressure to obtain a purity of 97.
92 g of 1-hexafluoropropyl-1-cyclohexanol-3-methacrylate expressed in % (by gas chromatography) was obtained.

Elemental analysis actual value 45.8 Calculated value 46.7 Infrared absorption spectrum O-H3550cm+-' HP 4.6 33.6 4.8 34.1 V C-H2950cm-', 2870c+w-
'νC=0 1720cm-'νC=C1640c+w-' vC-F 1200cm-' GC-MS analysis El m/e=334 (M”) 13C-NMR (solvent cocis, standard value?7.Oppm (C”DC) Attribution peak number of each peak (1) Chemical shift (δppm) 75.63 (split into 4 lines), 74.0 (split into 5 lines) JF?~, C1kq20-30Hz 30.8.30.6.34. 2.35.169.2.6
9.6.69.7.70.225.3-29.0 15.0.15.11.1B, 3.18.60 (6)
28.0-30.6(7) 11
7.6. bv~ct#258Hz.

(8) 83.28. JFI~CI''-
196Hz.

Jtq, Jr? ~Ca#27Hz (9) 123.0. Jvq〜Cq″q
28211z.

JF, ~C9″q 26Hz (10) 125.27 (11) 136.5 (12) 17.6-18.0 (13)
166.91 Example 2 1.6-cyclohexanediol 41 g, hexafluoropropylene 49 g 1 benzoyl peroxide 4.0
65 g of a fluorine-containing alicyclic alcohol represented by 100 was obtained in the same manner as in Example 1 using 100 el of chlorobenzene as a solvent.

Boiling point 130~b Elemental analysis C) I P Actual value 38.9 4.3 44.2 Calculated value 40.6 4.5 42.9 Infrared absorption spectrum vo-H3600cm-', 3350cm-'C-
8 2920cm-', 2860c+a-'C-F
1200 cm-' GC-MS analysis El m/e=266 (M") Example 3 20 g of 1.3-cyclobentanediol, CF as a fluorinated olefin!"CF(Ch)J 66 g, di-t-
Using 2.0 g of butyl peroxide and 100 ml of toluene as a solvent, 130
The reaction was carried out at ℃ for 9 hours, and the following formula % formula % Infrared absorption spectrum
C-F 1200 cm-' GC-MS analysis El i+/e-498 (M") Example 4 100 g of 1.6-cyclohexane dimetatool.

Using 120 g of hexafluoropropylene and 2.0 g of di[-butyl peroxide, a reaction was carried out at 135°C for 10 hours without a solvent in the same manner as in Example 1. 72 g of alcohol was obtained. 45 g of fluorine-containing alicyclic alcohol was obtained.

Boiling point 152-b Elemental analysis CHP Actual value 45.6 4.9 36.9 Calculated value 44.9 5,4 38.8 Infrared absorption spectrum 0-8 3350cm-'C-H2910c+a-', 2850cm-C
-F 1180ca+-' GC-MS analysis EI s/e-294 (M") Example 5 70 g of cyclooctyl methanol 90 g of hexafluoropropylene, 4.0 g of di-t-butyl peroxide
using 100ml of chlorobenzene as a solvent,
In the same manner as in Example 1, the reaction was carried out at 130° C. for 8 hours to obtain 48 g of a fluorine-containing alicyclic alcohol represented by the following formula.

Boiling point 102~b Elemental analysis tlF Actual value 48.4 5,8 40.6 Calculated value 49.3 6,2 39.0 Infrared absorption spectrum ShiO-H3400cm-' ShiC-8 2935cm-', 2860cm-'
C-F 1200 cm-' GC-MS analysis 81 Kaku/e-292 (M") Example 6 In Example 1, 54 g of the fluorine-containing alicyclic alcohol obtained in Example 2, 72 g of methacrylic acid chloride, and In the same manner as in Example 1 using 84 g of triethylamine, 58 g of a methacrylic acid ester derivative represented by the following formula was obtained in the same manner as in Example 1 using 21 g of the following formula and 32 g of pyridine.

Elemental analysis CHF Actual value 47.1 4.7 33.4 Calculated value 46.7 4,8 34.1 Infrared absorption spectrum 0-11 3300cm-'C-H2930cm-', 2850cm-'V C
=0 1700cm-' y C=C1620cm-' C-F 1200cm-' GC-MS analysis El s/e"334 (M") Example 7゜In Example 1, 40 g of basic alicyclic alcohol and 45 g of acrylic acid ester derivative represented by acrylic acid chloride were obtained.

Elemental analysis C) IP Actual value 34.9 2.4 53.7 Calculated value 35.7 2,4 53.0 Infrared absorption spectrum v O-83350cm-' J/ C-H2950cm-', 2870cm-
'νG=0 1710cm-'νC=C1638cm-' C-F 1200cm-' GC-MS analysis El s/e-538 (M Example 8 In Example 1, the fluorine-containing fat obtained in Example 4 In the following formula Example 1, using 19 g of cyclic alcohol, 21 g of methacrylic acid chloride, and 24 g of triethylamine, 20 g of the fluorine-containing alicyclic alcohol obtained in Example 5, and methacrylic acid chloride Using 21 g and 30 g of triethylamine, 25 g of a methacrylic acid ester derivative represented by the following formula was obtained in the same manner as in Example 1.

The infrared absorption spectrum is shown in Figure 2.

Elemental analysis HF 5.5 25.7 5.6 26.5 Actual value 53.8 Calculated value 53.0 Infrared absorption spectrum C-11 2930cm-', 2850cm-'j
'C=0 1720 cm-'νC=C1635ca+-' C-F 1180 cm-' GC-MS analysis El s/e=430 (27 g of methacrylic acid ester ta'J shown in Example 9 was obtained.

Elemental analysis 11 F 5.9 32.4 6.1 31.7 Actual value 54.1 Calculated value 53.3 Infrared absorption spectrum p C-H2935ca+-', 2860cm-'
νC・0 1720cm-'νC=C1640cm-' C-F 1200cm-' GC-MS analysis t! I m/e=360 (M”) Application Example 1 The fluorine-containing alicyclic (meth)acrylic acid ester obtained in Examples 1 and 6 to 9 was converted into the following siloxanyl methacrylate.
) (SiMA) L CH2= C-C00(CHz) 5-5i [O5i
(CHs) sl 3 and methyl methacrylate (HMA
) in a polymerization kettle. The obtained copolymer was formed into a film having a thickness of 220 to 250 μm. For these films, the oxygen permeability coefficient CDK value x l
Q-11cc (STP) cm/cm"-sec-1
llHg) was measured using a Seikaken Ni film oxygen permeability meter. The results are shown in Table 1.

Comparative Example 1 Siloxanyl methacrylate (SiMA), methyl methacrylate, and ethylene glycol dimethacrylate (I
I! GDM) to form a film in the same manner as above, and its oxygen permeability coefficient was measured using a Seikaken film oxygen permeability meter. The results are shown in Table 1.

Table 1 Application examples SiMA/MMA/I SiMA/MMA/6 SiMA/MMA/7 SiMA/MMA/8 90/4015 50.6 90/4015 48.5 90/4015 43.2 90/4015 51.8 Comparison Example SiMA/MMA/BGDM 90/401
5 32.0 (Note) 1) The numbers indicate the example numbers in which they were produced to indicate the fluorine-containing alicyclic (meth)acrylic esters used.

2) Weight%

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of an example of a fluorine-containing alicyclic alcohol according to the present invention, and FIG. 2 shows an infrared absorption spectrum of an example of a fluorine-containing (meth)acrylic ester according to the present invention.

Claims (4)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents a hydrogen atom or a hydroxyl group, x and y
are each an integer of 0 to 30, m is an integer of 0 to 10, n is an integer of 1 to 12, and m+n is 1 to 22. ) At least one fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is grafted to the carbon atom of the alicyclic alcohol represented by () per molecule of the alicyclic alcohol. A fluorine-containing alicyclic alcohol characterized by: (2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R^2 is a hydrogen atom, hydroxyl group, or group ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^ 3 represents a hydrogen atom or a methyl group, and x and y are each 0 to 3
m is an integer of 0 to 10, n is an integer of 1 to 12, and m+n is 1 to 22. ) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by A fluorine-containing alicyclic (meth)acrylic acid ester characterized by having at least one graft bond per molecule. (3) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents a hydrogen atom or a hydroxyl group, x and y
are each an integer of 0 to 30, m is an integer of 0 to 10, n is an integer of 1 to 12, and m+n is 1 to 22. ) At least one fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is grafted to the carbon atom of the alicyclic alcohol represented by () per molecule of the alicyclic alcohol. The method for producing a fluorine-containing alicyclic alcohol is characterized in that the alicyclic alcohol represented by the above general formula (I) is reacted with a fluorine-containing olefin in the presence of a radical generator. Production method. (4) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R^2 is a hydrogen atom, hydroxyl group, or group ▲There are mathematical formulas, chemical formulas, tables, etc.▼, 3 represents a hydrogen atom or a methyl group, and x and y are each 0 to 3
m is an integer of 0 to 10, n is an integer of 1 to 12, and m+n is 1 to 22. ) A fluorine-substituted hydrocarbon group having at least three fluorine atoms and having 1 to 30 carbon atoms is added to the saturated carbon atom of the alicyclic (meth)acrylic ester represented by In the method for producing a fluorine-containing alicyclic (meth)acrylic acid ester having at least one graft bond per molecule, there are general formulas (I)▲mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, R ^1 represents a hydrogen atom or a hydroxyl group, x and y
are each an integer of 0 to 30, m is an integer of 0 to 10, n is an integer of 1 to 12, and m+n is 1 to 22. ) At least one fluorine-substituted hydrocarbon group having 2 to 30 carbon atoms and having at least three fluorine atoms is grafted to the carbon atom of the alicyclic alcohol represented by () per molecule of the alicyclic alcohol. A method for producing an alicyclic (meth)acrylic acid ester, which comprises reacting a fluorine-containing alicyclic alcohol with (meth)acrylic acid or (meth)acrylic acid halide in a solvent in the presence of a basic compound. .