JP2774362B2 - Siloxane compound having di (meth) acryloxyalkyl group - Google Patents

Description

The present invention relates to novel organofunctional siloxane compounds,
More specifically, the present invention relates to a siloxane compound having a di (meth) acryloxyalkyl group, which is useful as a cross-linking agent for a highly oxygen-permeable contact lens material.

[Technical background of the invention and its problems]

Conventionally, among crosslinking agents for high oxygen permeable contact lens materials, those containing a siloxane segment include 1,3-
Bis (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane and α, ω-bis (3-methacryloxypropyl) -polydimethylsiloxane (average degree of polymerization 2 or more) are known. .

However, the former compound has a disadvantage that the siloxane segment is too short and oxygen permeability is not sufficient.
On the other hand, the latter compound improves the oxygen permeability by increasing the average degree of polymerization, that is, the siloxane segment. On the other hand, the hardness of the contact lens finally obtained by introducing a long siloxane segment into the main chain skeleton is improved. There is a new disadvantage that is reduced.

[Object of the Invention] Therefore, a cross-linking agent which is excellent in oxygen permeability and does not cause a decrease in hardness has been desired. An object of the present invention is to provide a novel siloxane compound having a di (meth) acryloxyalkyl group, which is useful as a crosslinking agent for a high oxygen permeable contact lens material.

[Configuration of the invention]

That is, the present invention has a general formula (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group and may be the same or different from each other And n represents an integer of 1 to 3.) is a siloxane compound having a di (meth) acryloxyalkyl group.

In the compound (I) of the present invention, R ¹ is a hydrogen atom or a methyl group. When the compound (I) is used as a cross-linking agent for a contact lens material, R ¹ is methyl in consideration of biocompatibility. Preferably, the group is

In the compound (I) of the present invention, R ² , R ³ , R ⁴ and R ⁵
Is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different. R ² , R ³ ,
R ⁴ and R ⁵ are, for example, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. A cycloalkyl group such as cyclopentyl group or cyclohexyl group; an aralkyl group such as 2-phenylethyl group or 2-phenylpropyl group; an aryl group such as phenyl group or tolyl group; an alkenyl group such as vinyl group or allyl group. Groups; and one of these
A chloromethyl group, a chlorophenyl group, a 3,3,3-trifluoropropyl group in which a hydrogen atom bonded to a carbon atom of a divalent hydrocarbon group is partially substituted with a halogen atom, an amine group, a cyano group, or the like; Examples thereof include substituted hydrocarbon groups such as an aminoethyl group and a 2-cyanoethyl group. Among them, one having 1 carbon atom is preferred because of easy availability and synthesis of raw materials.
Saturated hydrocarbon groups or 3,3,3-trifluoropropyl groups are preferred, and a methyl group is particularly preferred from the viewpoint of biocompatibility.

In the compound (I) of the present invention, n is an integer of 1 to 3. However, when the compound (I) is used as a crosslinking agent for a contact lens material, n is taken into consideration in consideration of oxygen permeability.
Is preferably 3.

An example of the method for producing the compound (I) of the present invention is described below.

The compound (I) of the present invention can be produced by the following general formula: Wherein R ¹ , R ² and n are the same as those described above, and a methoxysilane having a di (meth) acryloxypropyl group represented by the general formula: (Wherein, R ³ , R ⁴ and R ⁵ are the same as described above). This chemical reaction formula is shown as a reaction formula (1).

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are the same as described above) In the compound (I) of the present invention, the di (meth) acryloxypropyl group used as a raw material is The methoxysilane (II) is, for example, disclosed in Japanese Patent Application No. Hei.
It can be synthesized by the method described in 331040.

In the compound (I) of the present invention, triorganochlorosilane (III) used as a raw material is a known substance. Examples of the triorganochlorosilane (III) include trimethylchlorosilane, dimethylchlorosilane, ethyldimethylchlorosilane, triethylchlorosilane,
Examples include phenyldimethylchlorosilane and 3,3,3-trifluoropropyldimethylchlorosilane. Among these, trimethylchlorosilane is particularly preferable in terms of availability, reactivity, and the like.

In the cohydrolysis reaction of the reaction formula (1), di (meth)
Methoxysilane having an acryloxypropyl group (I
The proportions of I), triorganochlorosilane (III) and water are not particularly limited. However, 1.5 mol or more, 5.0 mol or more per 1 mol of methoxy group of methoxysilane (II) having di (meth) acryloxypropyl group.
It is preferred to use less than the mole of triorganochlorosilane (III) for the reaction. If it is less than 1.5 mol, the reaction selectivity of the desired compound (I) is low, and even if it is used in an amount of 5.0 mol or more, there is no effect of the addition, and it is economically disadvantageous. On the other hand, the amount of water used is 20% by weight or more based on the total amount of methoxysilane (II) having di (meth) acryloxypropyl group and triorganochlorosilane (III).
It is preferred that the content be less than 00% by weight. If it is less than 20% by weight, the reaction is slow, and a good yield cannot be increased in a short time. Even if it is more than 500% by weight, there is no particular effect of adding, and it is disadvantageous in terms of pot yield.

In the cohydrolysis reaction of the reaction formula (I), an organic solvent is not essential, but if used, alcohols such as methyl alcohol and ethyl alcohol; ketones such as acetone; hexane and heptane Aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclohexane; ethers such as diethyl ether; benzene;
Aromatic hydrocarbons such as toluene, xylene; and 1,
Halogenated hydrocarbons such as 2-dichloroethane are preferred. These organic solvents may be used alone or as a mixture of two or more. The amount of the organic solvent used is not particularly limited, but should be in the range of 10 to 500% by weight based on the total amount of methoxysilane (II) having di (meth) acryloxypropyl group and triorganochlorosilane (III). Is preferred.

In this reaction, water and an organic solvent as needed were charged into a reaction vessel, and a mixed solution comprising methoxysilane (II) having a di (meth) acryloxypropyl group and triorganochlorosilane (III) was added dropwise thereto. It is preferable from the viewpoint of reaction control to carry out the reaction by a reaction method. The reaction temperature is preferably in the range of 0 to 80 ° C, more preferably 0 to 50 ° C.
It is in the range of ° C. The reaction time depends on the reaction conditions such as the temperature, the molar ratio of the raw materials, the reaction scale, etc., but usually 0.5 to 10 hours is sufficient. The pressure during the reaction is not particularly limited,
Usually, it is carried out at normal pressure.

The compound (I) of the present invention can be isolated and purified from the reaction mixture thus obtained by a method generally used in the field of synthetic organic chemistry. For example, after the reaction, liquid separation, neutralization, and drying are performed, and further, low-boiling components are removed by distillation under reduced pressure to obtain compound (I).

[Effect of the Invention] The compound (I) of the present invention has a plurality of siloxane segments and two radically polymerizable (meth) acryloxyalkyl groups in the molecule, and further comprises methyl methacrylate,
-When copolymerized with a methacrylic group-containing monomer such as methacryloxypropyltris (trimethylsiloxy) silane, the structure is such that the siloxane segment is introduced as a side chain instead of a main chain, so that high oxygen permeability and appropriate hardness are obtained. Is useful as a crosslinking agent for contact lenses requiring In addition, it is also useful as a raw material for silicone modification of organic materials utilizing the polymerization reactivity of carbon-carbon double bonds such as polystyrene, polyacrylamide, and polyacrylonitrile.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples. The scope of the present invention is not limited only to the following examples.

Example 1 A flask having an internal volume of 1 equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser, and an ice bath was charged with 100 g of n-hexane.
100 g of methyl alcohol and 100 g of water were charged, stirring was started, and the solution was cooled to about 5 ° C.

To this, a mixed solution consisting of 34.6 g (0.10 mol) of 2-methacryloxymethyl-3-methacryloxypropyltrimethoxysilane and 97.7 g (0.90 mol) of trimethylchlorosilane was adjusted to a temperature of 5 to 15 ° C. from a dropping funnel. The mixture was added dropwise over 1 hour while appropriately cooling with an ice bath. After completion of the dropwise addition, the mixture was stirred at 25 to 30 ° C. for 3 hours, and it was confirmed by gas chromatography analysis that the peak of 2-methacryloxymethyl-3-methacryloxypropyltrimethoxysilane had completely disappeared.

Next, the organic layer of the reaction solution was separated by a separating funnel, washed well with water until neutral, and dried over anhydrous sodium sulfate. After drying, the Glauber's salt is separated by filtration.
Under a condition of 45 ° C. and a degree of reduced pressure of 1 Torr, a low boiling fraction was removed over 2 hours. As a result, a colorless transparent liquid 2
-Methacryloxymethyl-3-methacryloxypropyl tris (trimethylsiloxy) silane 48.8 g was obtained. This is 94.0% based on the starting material 2-methacryloxymethyl-3-methacryloxypropyltrimethoxysilane.
Was the yield.

The results of gas chromatography analysis, infrared absorption spectrum analysis and ¹ H nuclear magnetic resonance absorption analysis of this product were as described below, and it was confirmed that the product had the molecular structure represented by the following formula.

・ Gas chromatography analysis: 95.0% ・ Infrared absorption spectrum analysis (liquid film method): Wave number (cm ^-1 ) Attribution 2950 C-H 1715 C = O 1635 C = C 1100-1010 Si-O-Si ¹ H nuclear magnetic resonance absorption analysis (90 MHz, in CDCl ₃ ): position chemical shift δ (ppm) integrated intensity multiplicity a 6.2 2Hsb 5.6 2Hsc 2.0 6Hsd 3.9 to 4.1 4Hde 1.8 to 2.2 1Hm f 0.4 ~ 0.6 2H dg -0.029H s

Claims (1)

(57) [Claims] (1) General formula (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group and may be the same or different from each other And n represents an integer of 1 to 3.) A siloxane compound having a di (meth) acryloxyalkyl group.