JPH0632904A - Fluorosiloxane compound - Google Patents

Abstract

PURPOSE:To obtain a siloxane monomer capable of giving a polymer which has good wettability with water and is satisfactory in antifouling property, gas permeability, pliability, and optical clarity by forming a molecular structure which has at least 1 fluorinated substituent having a hydroxy group. CONSTITUTION:This compound is a hydroxylated fluorosiloxane monomer represented by the formula, wherein X is a substituent having a radical- polymerizable unsaturated group; Y is the same as R<9> or X; (n) is 0-500; (m) is 1-500; R<3> and R<4> each is a 1-10C (halo)alkyl or trimethylsiloxy, provided that they may be the same or different; R<5> is a fluorinated substituent having at least 1 hydroxy group; and R<1>, R<2>, R<6>, R<7>, R<8>, and R<9> each is a fluorinated substituent which has at least 1 hydroxy group and may be identical with or different from R<5>, a 1-10C (halo)alkyl, or trimethylsiloxy, provided that they may be the same or different.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel siloxane compound. More specifically, it relates to a hydrophilic fluorine-containing siloxane monomer which gives a polymer excellent in water wettability, gas permeability, flexibility, and stain resistance.

[0002]

2. Description of the Related Art Conventionally, polysiloxane compounds, as represented by dimethyl silicone compounds, have been utilized by taking advantage of unique functions such as heat resistance, chemical stability, electrical insulation, flexibility, lubricity, and water repellent property. It is industrially widely used alone or for modifying other materials. For example, polydimethylsiloxane having a 3-methacryloxypropyl group at both ends, which is a polymerizable siloxane compound, is used for modifying various polymers such as acrylic polymer and polystyrene by utilizing its polymerizability. Further, since siloxane polymers have high gas permeability, they are also used as gas selective permeable membranes, and because they have little effect on living bodies, they are widely used as biomaterials and medical materials. For example, taking advantage of its excellent oxygen permeability, flexibility, and optical transparency,
Application to contact lenses is also being considered, and many patents have been proposed (for example, Japanese Patent Publication No. 62-36046).
JP-A-63-29741, JP-A-63-
85719, and Japanese Patent Laid-Open No. 2-188717).
However, in contact lens materials, wetting by tear fluid is essential, so improving the hydrophilicity of hydrophobic siloxane polymers is a major issue, and attempts to introduce hydrophilic substituents into polysiloxane side chains (For example, JP-B-62-29776 and JP-A-50-108881). On the other hand, in the field of contact lens materials and coating materials, attempts have been made to introduce a fluorine substituent into a siloxane compound to improve the stain resistance, heat resistance and weather resistance of the siloxane compound (for example, Japanese Patent Publication No. 75558, JP 62-38.
419, JP-A-62-296118, JP-A-1-308419, and JP-A-2-304093).

[0003]

However, when a siloxane compound having a fluorine-substituted group is used on the cornea of the eye like a contact lens, it is not sufficient in terms of stain resistance. It has a strong hydrophobicity and is likely to cause tear repellency, which is a problem as a contact lens material. Therefore, an object of the present invention is to solve the above-mentioned drawbacks, that is, to provide a novel siloxane polymer and a raw material thereof which have good water wettability, and further satisfactory stain resistance, gas permeability, flexibility and optical transparency. It is intended to provide a certain monomer.

[0004]

[Means for solving the problems] As a result of various studies,
That a siloxane compound having a hydroxyl group-containing fluorine-containing substituent in which a hydroxyl group which is a hydrophilic functional group and a fluorine substituent which is a hydrophobic substituent are in close proximity to each other in the same substituent is extremely useful for solving the above problems The inventors have found the present invention and have reached the present invention. That is, the present invention provides a hydroxyl group-containing fluorine-containing siloxane monomer represented by the following formula (1).

[0005]

[Chemical 2]

(In the formula (1), X can be radically polymerized.
Is a substituent having a functional unsaturated group, and Y is R⁹Or X
Indicates. n is 0 to 500, m is 1 to 500,
R³, R ^FourIs an alkyl group having 1 to 10 carbon atoms, carbon
Halogenated alkyl group consisting of the numbers 1 to 10 and trimer
A group selected from tilsiloxy groups, which may be the same or different.
May be. R^FiveHas at least one hydroxyl group attached
It is a fluorine-containing substituent. R¹, R², R⁶, R⁷,
R⁸, R⁹Is R^FiveMay be different or the same as
Fluorine-containing substituent in which at least one is bonded, carbon number
1-10 alkyl group, 1-10 carbon atoms
From halogenated alkyl and trimethylsiloxy groups
It is a selected group and may be the same or different. ) In the present invention, the monomer represented by the formula (1) contains a hydroxyl group.
It is sufficient if at least one fluorine-containing substituent is bonded.
Yes. The hydroxyl group-containing fluorine-containing substituents referred to here are hydroxyl groups and
And fluorine are bonded together in the same substituent
It may be a structure. If a preferred substituent is shown, S
The substituent except the linking group with the i atom is replaced by "-C_aF_b
(OH)_cH_{2a + 1-bc}, "A is 2 to 7, b
Is 2 to 9 and c is 1 to 3;
-O- between carbon-carbon bonds of the fluorine-containing substituent containing an acid group,
-OCO-, -COO-, -CO-
You can go out. Obtained from a monomer having a substituent of this structure
The polymer obtained has a good balance between water wettability and stain resistance,
Good gas permeability, contact lenses, intraocular lenses, etc.
It is useful as an ophthalmic lens material. Also contains hydroxyl groups
In the fluorine-containing substituent, the carbon atom to which the hydroxyl group is directly bonded is
Chemically when a fluorine atom or an oxygen atom is bound
Unstable and not suitable for practical use.

The reason why the polymer obtained from the monomer having a hydroxyl group-containing fluorine-containing substituent disclosed in the present invention exhibits excellent stain resistance is not clear, but a hydrophilic hydroxyl group and a hydrophobic fluorine atom are It is a substituent having opposite properties, and the presence of these two kinds of substituents in close proximity to each other makes it possible to obtain a hydrophilic substance,
It is considered that the interaction with both hydrophobic substances is small, and it is considered that proteins, lipids, etc., which are the causative substances of stains, are unlikely to adhere to the material surface.

An example of the fluorine-containing substituent having a hydroxyl group is "--CH ₂ CH (OH) CH ₂ OCF ₂ CF _{2
H "," - CH 2 CH} (OH) CF 3 "," - CH 2 C
_{H (OH) CH 2 OCH 2} CF 3 "," - CH 2 C (O
_{H) (CF 3) 2 "} ," - CH 2 CH (OH) CH 2 O
_{CH (CF 3) 2 ",} " - CH 2 CH (OH) CH 2 O
_{CH 2 CF 2 CF 3 ",} " - CH 2 CH (OH) CH 2
_{OCH 2 CF 2 CF 2 CH 2} OH "," - CH 2 CH
(OH) CH ₂ OOCCH ₂ C (OH) (CF ₃ ) CH
_{3 "," - CF (CF} 3) CH 2 OH "," - CH 2 C
_{H (OH) CH 2 OCF 2} CH 3 "," - CH 2 CH
_{(OH) CH 2 OCF (CF} 3) CF 2 H "," - CH
₂ CH (OH) CH ₂ (CF ₂ ) ₄ F ″ and the like. These hydroxyl group-containing fluorine-containing substituents may be directly bonded to a Si atom, or may be bonded to a Si atom via a linking group. The linking group that can be used is an alkylene group having 1 to 10 carbon atoms and is —COO—, —OCO—, or — between carbon-carbon bonds or between a fluorine-containing substituent containing a hydroxyl group.
CO-, -O-, -OCONH-, -NHCOO-,-
It may have a CONH-, -NHCO-, or -NHCONH- bond. However, the Si atom is directly bonded to the hydrocarbon group having 1 or more carbon atoms.

In addition to the fluorine-containing substituent containing a hydroxyl group, the substituent bonded to the Si atom is selected from an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms and a trimethylsiloxy group. Groups, which may be the same or different. Preferred is an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, and particularly preferred is a methyl group. A small substituent such as a methyl group is highly flexible in the siloxane chain and has good gas permeability. The length of the siloxane chain of the monomer represented by the formula (1) is preferably from 1 to 1000 in terms of the number of Si atoms. More preferably 10-40
It is 0. Siloxane monomers in this range are useful because they give polymers having good flexibility and gas permeability and have good compatibility with other copolymerizable monomers.

The formula (1) shows a structural formula as if the siloxane moiety linked to the hydroxyl group-containing fluorine-containing substituent and the siloxane moiety bound to the other substituent are bonded in a block manner. In the field of siloxane chemistry, it is believed that the arrangement of siloxane moieties is a structure in which they are randomly bonded, and formula (1) also means a random structure.

One example of the radically polymerizable unsaturated group represented by the formula (1) is vinyl group, allyl group, acrylate group, methacrylate group, acrylamide group, methacrylamide group, fumarate group, maleate group. , Mesaconate group, styryl group and the like,
An acrylate group and a methacrylate group are preferable from the viewpoint of ease of polymerization. Further, radically polymerizable unsaturated groups and Si
There may be other linking groups between the atoms, and preferred examples thereof are groups having an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group or a phenylene group,
Further, in this linking group, between a carbon-carbon bond or between an unsaturated group, -COO-, -OCO-, -CO-, -O.
-, -OCONH-, -NHCOO-, -CONH-,
The -NHCO- and -NHCONH- bonds may be sandwiched. Further, the hydrogen of the hydrocarbon of the linking group is further halogen,
Although it may be substituted with an alkyl group or a hydroxyl group, it is preferable that at least a hydrocarbon group having 1 or more carbon atoms is bonded to the Si atom from the viewpoint of chemical stability.

Various methods for synthesizing the fluorine-containing siloxane monomer having a hydroxyl group disclosed in the present invention are conceivable, and the following methods are given as examples. That is, a cyclic siloxane having a hydroxyl group-containing fluorine-containing substituent and a disiloxane having a radical-polymerizable unsaturated group are subjected to ring opening using an acid catalyst such as sulfuric acid or acid clay or an alkali catalyst such as sodium hydroxide or cesium hydroxide. Polymerize. At that time, an alkyl group-substituted cyclic siloxane may be used in combination depending on the case, and the degree of polymerization and the introduction ratio of the hydroxyl group-containing fluorine-containing substituent may be changed by changing the charging ratio of each cyclic siloxane and disiloxane. can get.
Further, a living polymerization method can be used in the ring-opening polymerization. With this living polymerization method, a method having a small variation in the degree of polymerization can be obtained, and a polymerizable unsaturated group can be introduced only at one end. Polymerization is carried out by adding lithium trimethylsilanolate or sodium trimethylsilanolate as a polymerization catalyst to a cyclic siloxane having an alkyl group-substituted cyclic siloxane and a hydroxyl group-containing fluorine-containing substituent, and a chlorosilane having a radically polymerizable unsaturated group as a terminating agent. To use.

To give an example of a method for synthesizing a cyclic siloxane having a hydroxyl group-containing fluorine-containing substituent to be used in ring-opening polymerization, a hydroxyl group-containing fluorine-containing unsaturated compound and chloroplatinic acid are added to a cyclic siloxane having a hydrosilyl group. There is a method utilizing a so-called hydrosilylation reaction in which an addition reaction is performed as a catalyst. It is known that active hydrogen of a hydroxyl group causes a dehydrogenation reaction by a side reaction during the reaction between the hydrosilyl compound and a hydroxyl group-containing unsaturated compound, and in order to suppress this side reaction, a hydroxyl group is previously converted to a trimethylsilyl group, It is necessary to protect with an acetyl group, an acetal group or the like, or to add a buffer agent (for example, US Pat. No. 3,907,851, JP-A No. 62-195389). Of course, if the side reaction product can be easily separated, the reaction may be performed as it is. At this time, a commercially available compound can be used as the fluorine-containing unsaturated compound having a hydroxyl group, but it may be necessary to synthesize it in some cases. To give an example of the synthetic method, 1,1,1-trifluoro-
Fluorine-containing epoxy compounds such as 2,3-epoxypropane and 2-hydroperfluoroethylglycidyl ether, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, unsaturated alcohols such as allyl alcohol, and unsaturated amines such as allylamine. How to react. Reaction of fluorine-containing alcohols such as hexafluoroisopropanol and trifluoroethanol, fluorine-containing amines such as pentafluoropropylamine, or fluorine-containing carboxylic acids such as trifluoroacetic acid with unsaturated epoxy compounds such as glycidyl methacrylate. Four four four
-Fluorine-containing hydroxycarboxylic acid such as trifluoro-3-hydroxy-3-methylbutyric acid and 4,4,4-trifluoro-3-hydroxy-3- (trifluoromethyl) butyric acid and allyl glycidyl ether With unsaturated epoxy compounds or unsaturated alcohols such as allyl alcohol and 2-hydroxyethyl methacrylate. The reaction of an unsaturated alcohol such as allyl glyceryl ether or glyceryl methacrylate with a fluorine-containing unsaturated compound such as perfluoroethylene, perfluoropropylene or vinylidene fluoride can be used.

As another route of the synthesis method of the cyclic siloxane having a hydroxyl group-containing fluorine-containing substituent, an unsaturated compound having a reactive group such as a carboxylic acid, a hydroxyl group, an amino group and an epoxy group, which has been mentioned above, is hydrosilylated. Thus, it is possible to add the compound to the cyclic siloxane having a hydrosilyl group in advance and then introduce the compound having a fluorine substituent and a hydroxyl group.

To describe another method for synthesizing a fluorine-containing siloxane monomer having a hydroxyl group, first, a cyclic siloxane having a hydrosilyl group and a disiloxane having a radically polymerizable unsaturated group, and optionally an alkyl group-substituted Cyclic siloxane is added and the ring-opening polymerization is carried out by an acid catalyst, an alkali catalyst or a living polymerization method to obtain a siloxanyl monomer having a hydrosilyl group. Next, there is a method of introducing a hydroxyl group-containing fluorine-containing substituent by using a hydrosilylation reaction. At that time, a fluorine-containing unsaturated compound containing a hydroxyl group may be added by a hydrosilylation reaction, or an unsaturated compound having a reactive group such as a carboxylic acid, a hydroxyl group, an amino group or an epoxy group may be added by a hydrosilylation reaction. A compound having a post-fluorine substituent or a hydroxyl group may be introduced.

The hydroxyl group-containing fluorine-containing siloxane monomer of the present invention is polymerized alone or in combination with another radically polymerizable monomer by using a radical polymerization initiator to obtain a polymer. Examples of radical polymerization initiators used include peroxides such as benzoyl peroxide and t-butyl peroxide, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, and benzoin ethyl ether. Photosensitizers such as benzyl dimethyl ketal and α, α′-diethoxyacetophenone can also be used.

As the monomer copolymerizable with the hydrophilic group-containing fluorine-containing siloxane monomer of the present invention, any monomer can be used so long as it can be radically polymerized, but one example is an acrylate such as methyl methacrylate or butyl acrylate. And aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl esters such as vinyl acetate, and the like. Further, a fluorine-containing monomer such as fluoroalkyl acrylate or a siloxane-containing monomer such as siloxanyl acrylate, 2-hydroxyethyl methacrylate, dimethyl acrylamide or N.
-It has good compatibility with hydrophilic monomers such as vinylpyrrolidone and can be copolymerized.

[0018]

The present invention will be described in detail below with reference to Examples.
The invention is in no way limited to these examples. In addition, the oxygen permeability coefficient described in the examples was measured at 35 ° C. by a gas permeability measuring device (Rika Seiki Industry Co., Ltd. model K-315N-02) based on the pressure method.

The contact angle with water was measured by a contact angle meter (CA-A type manufactured by Kyowa Interface Science Co., Ltd.) based on the underwater bubble method.

[0020]

[Reference Example 1] 430 of 2-hydroperfluoroethyl glycidyl ether was added to a 2 liter separable flask equipped with a stirrer, a thermometer, a gas introduction tube, a cooling tube and a dropping funnel.
g, potassium hydroxide 30 g, hydroquinone 4.3
g and added 431 methacrylic acid under a nitrogen gas atmosphere.
g was dropped. After the dropping, the mixture was reacted at 80 ° C. for 8 hours. After allowing to cool, 800 ml of chloroform was added to the reaction product and filtered. The filtrate was washed with 1N-sodium hydroxide and then with saturated brine until the aqueous layer became neutral, the chloroform layer was separated, and then dehydrated with 200 g of anhydrous magnesium sulfate. Chloroform was distilled off under reduced pressure and then vacuum distilled. A transparent viscous liquid having a boiling point of 93 ° C./1 mmHg and a yield of 230 g was obtained. When the product was analyzed by infrared absorption spectrum and nuclear magnetic resonance spectrum, the product was 3- (1,1,2,2-tetrafluoroethoxy) -2-hydroxypropyl methacrylate represented by the following formula. Was confirmed.

[0021]

[Chemical 3]

[0022]

Reference Example 2 3- (1, 1, 2, 2 obtained in Reference Example 1
-Tetrafluoroethoxy) -2-hydroxypropylmethacrylate, 92 g, 10 mg of chloroplatinic acid hexahydrate dissolved in 1 ml of 2-propanol, and 6 of toluene.
00 ml was placed in a 1 l separable flask equipped with a stirrer, a thermometer, and a distillation tube, heated under stirring, and 150 ml of a mixture of toluene, 2-propanol and water was distilled off by azeotropic distillation. After cooling, 100 g of heptamethylcyclotetrasiloxane was added to the flask, the distillation tube was replaced with a reflux condenser, and heating was performed again. The reaction was carried out under reflux for 2 hours, and it was confirmed by gas chromatography that there were almost no starting materials. After cooling the mixture, the precipitate was filtered and toluene was distilled off from the filtrate under reduced pressure. When the residual liquid was distilled under a vacuum using a Kugelrohr type distiller, a fraction of 140 to 160 ° C /
104 g of a transparent viscous liquid was obtained at 0.05 mmHg. The product was analyzed by infrared absorption spectrum and nuclear magnetic resonance spectrum and found to have no SiH absorption and no absorption derived from an unsaturated group. The product was a cyclic siloxane derivative having a hydroxyl group-containing fluorine-containing substituent represented by the following formula. It was confirmed that

[0023]

[Chemical 4]

[0024]

Example 1 60 g of the cyclic siloxane derivative obtained in Reference Example 2 and 33 g of octamethylcyclotetrasiloxane were obtained.
g, 1,3-bis (3-methacryloxypropyl)-
Add 1,1,3,3-tetramethyldisiloxane to 7.2
g, chloroform 100 g, sulfuric acid 0.6 g with a stirrer,
Add to a 300 ml flask with a drying tube and mix at room temperature for 9
Stir for 0 hours. Next, 1 g of sodium hydrogen carbonate dissolved in 50 ml of water was added to the mixture to neutralize it, and the reaction was stopped. The resulting mixture was mixed with 100 ml of saturated saline 4 times.
After washing twice, the chloroform layer was separated, anhydrous magnesium sulfate was added, dried and filtered. Chloroform was removed from the filtrate under reduced pressure, and the residual liquid was washed 3 times with 100 g of 10% hydrous methanol. The water-containing methanol-insoluble portion was separated, 100 g of 100% methanol was added and filtered, and then the filtrate was heated to 50 ° C. under a vacuum of 1 mmHg to remove the volatile portion. The remaining liquid was a transparent viscous liquid, and 32 g was obtained. When this liquid was analyzed by gel permeation chromatography, it was found that there were almost no low molecular weight substances such as raw materials, and the polymer had a number average molecular weight of 5,100 in terms of polystyrene. Further, it was analyzed by infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum ( ¹ H-NMR), and it was confirmed to be a siloxane monomer having a hydroxyl group-containing fluorine-containing substituent having the following structure.

Characteristic absorption by IR analysis (measured on a KBr plate) is 3475 cm ^-1 (-OH), 2965 cm.
_{^{-1 (-CH 3), 1740cm -1}} (= C (CH 3) C =
O), 1725 cm ^-1 (-CH (CH ₃ ) C = O), 1
260 cm ⁻¹ (Si—CH ₃ ), 1095 cm ⁻¹ and 1025 cm ⁻¹ (Si—O—Si), 800 cm ⁻¹ (S
i-CH _3).

[0026]¹H-NMR analysis (CDCl₃Measured in
And CHCl₃The data (δ) is shown. 0.05
ppm (s) (SiCH₃), 0.5 ppm (t) (S
iCH ₂C-), 1.2 ppm (d) (-C (CH₃)
-) 1.7 ppm (m) (SiCCH₂C-), 1.
9ppm (s) (= CCH₃) 5.6 and 6.1p
pm (CH₂= C), 5.7 ppm (t) (CF₂CF
₂H).

[0027]

[Chemical 5]

[0028]

Example 2 The cyclic siloxane derivative obtained in Reference Example 2 was used
0 g, 0.63 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 50 g of chloroform and 0.5 g of trifluoromethylsulfonic acid were placed in a 200 ml flask equipped with a stirrer and a drying tube. Charge, 10 at room temperature
Stir for hours. Next, the mixture was neutralized with sodium hydrogen carbonate and then purified in the same manner as in Example 3. 25 g of a clear viscous liquid was obtained. This liquid was subjected to gel permeation chromatography, infrared absorption spectrum (I
R) and nuclear magnetic resonance spectrum ( ¹ H-NMR), and it was confirmed that the siloxane monomer had a hydroxyl group-containing fluorine-containing substituent having the following structure.

Characteristic absorption in IR analysis (measured on a KBr plate) is 3475 cm ^-1 (-OH), 2965 cm.
_{^{-1 (-CH 3), 1725cm -1}} (-CH (CH 3) C
^{= O), 1595cm -1 (CH} 2 = CH -), 1260
_{^{cm -1 (Si-CH 3)}} , 1095cm -1 and 102
5 cm ^-1 (Si-O-Si), 800 cm ^-1 (Si-C
H _3).

[0030]¹H-NMR analysis (CDCl₃Measured in
And CHCl₃The data (δ) is 0.05 ppm
(S) (SiCH₃), 0.5 ppm (t) (SiCH
₂C-), 1.2 ppm (d) (-C (CH₃) −),
1.7 ppm (m) (SiCCH₂C-), 5.9 pp
m (CH₂= C-), 5.7 ppm (t) (CF₂CF
₂H).

[0031]

[Chemical 6]

[0032]

Reference Example 3 In Reference Example 2, 3- (1,1,2,2-
3-perfluorobutyl-2-instead of tetrafluoroethoxy) -2-hydroxypropylmethacrylate
When 50 g of hydroxypropyl acrylate was used and 4 mg of chloroplatinic acid hexahydrate was reacted with 40 g of heptamethylcyclotetrasiloxane, 42 g of the product was obtained.
Was obtained. When analyzed by infrared absorption spectrum and nuclear magnetic resonance spectrum, it was confirmed that this product was a cyclic siloxane derivative having a hydroxyl group-containing fluorine-containing substituent represented by the following formula.

[0033]

[Chemical 7]

[0034]

[Reference Example 4] 1,3-bis (3-hydroxypropyl)
-1,1,3,3-tetramethyldisiloxane 50
g, 0.5 g of dibutyltin dilaurylate and 150 ml of dried acetone were charged into a 500 ml flask equipped with a stirrer, a drying tube and a dropping funnel, and 62 g of 2- (methacryloxy) ethyl isocyanate was added to dry hexane 10
The solution dissolved in 0 ml was added dropwise at room temperature. Next, the dropping funnel was replaced with a reflux condenser, and the mixture was heated under reflux for 3 hours. Next, after cooling, 10 g of water was added, and the mixture was further stirred for 30 minutes. The obtained liquid is dried over anhydrous sodium sulfate,
Filtered. After removing hexane from the filtrate under reduced pressure, 106 g of a transparent liquid was obtained by vacuum distillation. The product was analyzed by infrared absorption spectrum and nuclear magnetic resonance spectrum,
It was confirmed to be a disiloxane having the following structure.

[0035]

[Chemical 8]

[0036]

Example 3 Cyclic siloxane derivative 50 obtained in Reference Example 3
g, 0.89 g of the disiloxane obtained in Reference Example 4 and 50 g of chloroform were reacted in the same manner as in Example 2 and purified to obtain 21 g of a transparent viscous liquid. This liquid was subjected to gel permeation chromatography, infrared absorption spectrum (IR), nuclear magnetic resonance spectrum ( ¹ H-NM
It was confirmed by R) that the siloxane monomer has a hydroxyl group-containing fluorine-containing substituent having the following structure.

Characteristic absorption in IR analysis (measured on KBr plate)
Income is 3470 cm^-1(-OH), 2965 cm^-1(-
CH₃), 1740 cm^-1(= C (CH₃) C = O),
1725 cm^-1(-CH₂C = O and NHC = O),
1260 cm^-1(Si-CH ₃) 1095 cm^-1And
1025 cm^-1(Si-O-Si), 800 cm
^-1(Si-CH₃).

¹ H-NMR analysis (measured in CDCl ₃ , based on CHCl ₃ ) data (δ) are shown. 0.05
ppm (s) (SiCH ₃ ), 0.5 ppm (t) (S
_{iCH 2 C -), 1.2ppm (} d) (- C (CH 3)
-), 1.7ppm (m) ( SiCCH 2 C -), 1.
9ppm (s) (= C ( CH 3) -), 4.0ppm
_{(Q) (COOCH 2 CN -} ), 4.2ppm (t)
(COOCCH ₂ N-), 5.6 and 6.1 ppm
(CH ₂ = C).

[0039]

[Chemical 9]

[0040]

[Reference Example 5] Tetramethylcyclotetrasiloxane was added to 5
0 g, 62 g of octamethylcyclotetrasiloxane,
And 41.6 g of the disiloxane obtained in Reference Example 4,
1.0 g of sulfuric acid was charged into a 500 ml flask equipped with a stirrer and a drying tube, and stirred at room temperature for 20 hours. Next, 4 g of sodium hydrogen carbonate was added and stirred, and after the foaming had subsided, 200 ml of hexane was added and dried over anhydrous magnesium sulfate. After filtration, the filtrate was treated under reduced pressure and hexane was distilled off. Furthermore, when the residual cyclic siloxane was removed by heating under a high vacuum of 0.05 mmHg, about 100 g of a transparent liquid was obtained. This liquid was analyzed by gel permeation chromatography, infrared absorption spectrum and nuclear magnetic resonance spectrum, and was confirmed to be silicon hydride polydimethylsiloxane having the following structure.

[0041]

[Chemical 10]

[0042]

Reference Example 6 In the same manner as in Reference Example 1, 50 g of allyl glycidyl ether, 3 g of potassium hydroxide and 0.5 g of hydroquinone were charged into a flask, 74 g of hexafluoroisopropanol was added dropwise, and the mixture was heated and stirred under reflux. After the product was separated after the reaction, a fraction in the range of 80 ° C. to 100 ° C. was taken out at 1 mmHg with a Kugelrohr distiller. Yield 105g. It was confirmed by infrared absorption spectrum and nuclear magnetic resonance spectrum that it was 3- (hexafluoroisopropoxy) -2-hydroxypropyl allyl ether.

Next, 12.7 g of trimethylchlorosilane, 19 g of hexamethylsilazane, and 200 ml of dried diethyl ether were charged into a 500 ml flask equipped with a stirrer, a drying tube, a reflux condenser, and a dropping funnel, and the mixture was obtained with stirring. 3- (hexafluoroisopropoxy)-
100 g of 2-hydroxypropyl allyl ether was added dropwise. After completion of dropping, the mixture was heated under reflux for 1 hour and then left to cool. The formed white precipitate of ammonium chloride was filtered off, and diethyl ether was removed under reduced pressure. Vacuum distillation was carried out to obtain 120 g of a transparent liquid. From the analysis of infrared absorption spectrum, there is no absorption due to the hydroxyl group, and 3- (hexafluoroisopropoxy)-
It was confirmed to be 2- (trimethylsiloxy) propyl allyl ether.

[0044]

[Example 4] 500 m equipped with a stirrer, a thermometer, and a distillation tube
In a 1-liter separable flask, 300 ml of hexane and 0.1 g of 1% 2-propanol solution of chloroplatinic acid hexahydrate were charged and heated to distill off about 50 ml of hexane.
After cooling, 100 g of the hydroxyl-protected allyl ether obtained in Reference Example 6 and 40 g of silicon hydride polydimethylsiloxane having a methacrylate group at both ends obtained in Reference Example 5 were added. Replace the distillation tube with a reflux device,
The mixture was heated under reflux for 2 hours. It was confirmed from the infrared absorption spectrum that the absorption of silicon hydride (2175 cm ⁻¹ ) was gone. Hexane was removed under reduced pressure. Next, the residual liquid was charged into a 500 ml flask equipped with a reflux condenser, 300 ml of acetone and 20 g of water were added, and the mixture was heated under reflux for 3 hours for hydrolysis to remove the trimethylsilyl group as a protective group for the hydroxyl group. After distilling off acetone under reduced pressure, the residue was washed with methanol containing 10% water to remove low-molecular compounds.
Yield 53g. The obtained product was analyzed by gel permeation chromatography, infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum ( ¹ H-NMR), and a siloxane monomer having a hydroxyl group-containing fluorine-containing substituent having the following structure was analyzed. I confirmed that there is.

Characteristic absorption by IR analysis (measured on a KBr plate) is 3470 cm ^-1 (-OH), 2960 cm.
_{^{-1 (-CH 3), 1740cm -1}} (= C (CH 3) C =
O), 1730 cm ^-1 (NHC = O), 1260 cm ^-1
_{(Si-CH 3), 1090cm} -1 and 1025cm
^-1 (Si-O-Si), 800 cm ^-1 (Si-C
H _3).

¹ H-NMR analysis (measured in CDCl ₃ , based on CHCl ₃ ) data (δ) are shown. 0.05
ppm (s) (SiCH ₃ ), 0.5 ppm (t) (S
_{iCH 2 C -), 1.2ppm (} d) (- C (CH 3)
-), 1.7ppm (m) ( SiCCH 2 C -), 1.
9 ppm (s) (= C (CH ₃ )) 4.0 ppm
(Q) (COOCH ₂ CN-), 4.3 ppm (m)
(OCH (CF ₃ ) ₂ ), 5.6 and 6.1 ppm
(CH ₂ = C).

[0047]

[Chemical 11]

[0048]

[Reference Example 7] Siloxane monomer 1 obtained in Example 1
0.1 g of photosensitizer benzyl dimethyl ketal is added to 0 g.
In addition, the solution was uniformly dissolved and then replaced with nitrogen. When this mixed solution was poured into a mold sandwiched between two quartz glass plates and irradiated with an ultra-high pressure mercury lamp for 1 hour, the thickness was about 0.3 m.
A transparent elastic film of m was obtained. The film was washed with ethanol and then dried to examine the oxygen permeability. As a result, the oxygen permeability coefficient was 100 × 10 ^-11 ml.
It showed a high value of cm / (cm ² · sec · mmHg), and it was found that the obtained polymer had excellent oxygen permeability. Moreover, when the contact angle with water was measured to see the water wettability, it showed a small value of 52 degrees, and it was found that the water wettability was also good.

[0049]

The hydroxyl group-containing fluorine-containing siloxane monomer of the present invention is a novel compound, and is excellent in water wettability and stain resistance by homopolymerization or copolymerization, gas permeability, flexibility, and optical transparency. Which gives a polymer having good properties,
It is useful as a medical material, especially as an ophthalmic lens material.

Claims (1)

[Claims] 1. A structure represented by the following formula (1):
A fluorine-containing siloxane monomer containing a hydroxyl group. [Chemical 1](In the formula (1), X is a radically polymerizable unsaturated group.
Is a substituent having Y and R is R⁹Or X is shown. n is
0-500, m is 1-500, R³, R ^FourIs carbon
An alkyl group consisting of 1 to 10 carbon atoms consisting of 1 to 10
Halogenated alkyl group and trimethylsiloxy group
It is a group selected from the above and may be the same or different. R
^FiveIs fluorine-containing substitution in which at least one hydroxyl group is bonded
It is a base. R¹, R², R⁶, R⁷, R⁸, R⁹Is R^Five
At least one hydroxyl group which may be the same as or different from
Fluorine-containing substituent bonded, consisting of 1 to 10 carbon atoms
Alkyl group, halogenated alkyl having 1 to 10 carbon atoms
A group selected from the group
And may be the same or different. )