JPS60166691A - Tetrasiloxanylpropyl methacrylate - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (a is 1-3). EXAMPLE:Bis(trimethylsiloxy)dimethylsiloxy-gamma-methacryloxypropylsil ane. USE:An improver for raising oxygen permeability, toughness, etc. of a polymer. Having improved reactivity. PREPARATION:For example, a gamma-methacryloxypropyltrialkoxysilane, dimethylchlorosilane, and trimethylchlorosilane (a is not 3) are preferably added to methanol, etc., and hydrolyzed in the presence of excess water at room temperature -50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel tetrasiloxanylpropyl methacrylate having a reactive hydrogen atom directly bonded to a silicon atom, and more specifically, as a modifier for various polymers. The present invention relates to tetrasiloxanylpropyl methacrylate which is useful and has a γ-methacryloxypropyl group bonded to the central silicon atom of a branched tetrasiloxane structure.

[Technical background of the invention and its problems] Tris(trimethylsiloxy)silylpropyl methacrylate represented by the following is a known compound.

Such a compound can undergo vinyl polymerization in the presence of a radical polymerization initiator due to the double bond of a methacryloxy group bonded via three carbon atoms from a silicon atom, and can also be used to perform vinyl polymerization in the presence of a radical polymerization initiator. lit typeface, e.g.
It is also possible to carry out copolymerization with alkyl (meth)acrylates such as methyl methacrylate. In particular, when the above monomers are used as modifiers in the synthesis of acrylic resins used as contact lens materials, the oxygen permeability of the hard and transparent acrylic resins is improved, which improves the performance when worn as contact lenses. It helps oxygen absorption in the cornea and can prevent corneal function from deteriorating due to lack of oxygen.

However, in order to copolymerize this tris(trimethylsiloxy)silylpropyl methacrylate with an acrylic monomer and to impart sufficient oxygen permeability to the contact lens, the monomer must be added to the quadrant. Copolymers have problems in that they have poor machinability during the production of Contact I lenses and also have poor lens toughness. On the other hand, in order to maintain hardness that can withstand machining during lens manufacturing, it is not possible to add a large amount of tris(trimethylsiloxy)silylpropyl methacrylate, and the amount added within this range is sufficient for oxygen permeability. Contact lens material is not available.

[Objective of the Invention] The object of the present invention is to provide a polymer that is useful as a modifier for various polymers, has high oxygen permeability, and has excellent toughness. Our objective is to provide excellent tetrasiloxanylpropyl methacrylate.

[Summary of the Invention] As a result of extensive research, the present inventors have discovered a siloxanyl monomer having a silicon functionality in which a reactive hydrogen atom is directly bonded to a silicon atom, and a vinyl double bond consisting of a methacryloxy group. This discovery led to the completion of the present invention.

That is, the tetrasiloxanylbropyrme of the present invention (wherein,
a represents an integer from 1 to 3. ).

In the following, the invention will be explained in more detail.

1-I having a reactive hydrogen atom represented by the general formula
- Examples of cycloxanylpropyl methacrylate include the following three types.

The tetrasiloxanylpropyl methacrylate of the present invention can be produced by, for example, cohydrating γ-methacryloxypropyltrialkoxysilane with dimethylchlorosilane and trimethylchlorosilane (however, in the case of (3), only dimethylchlorosilane) in the presence of water. It can be produced by decomposition and purification.

As the γ-methacryloxypropyltrialkoxysilane, it is preferable to use methoxysilane because it is easily available, has a low boiling point and thus is easy to purify, and has an appropriate hydrolysis rate.

Hydrolysis is preferably carried out in the presence of excess water at a temperature ranging from room temperature to 50°C, and in order to carry out the reaction in a homogeneous state, methanol, benzene, toluene, xylene, n-hexane, n- It is preferable to add a hydrocarbon solvent such as butane or cyclohexane. Among these, it is particularly preferable to use methanol.

Next, the acid generated by the hydrolysis is removed by a liquid separation operation, and the mixture is further neutralized using a saturated sodium bicarbonate solution or the like, and after 1 liquid separation, it is washed with a saturated saline solution, and liquid separation is performed. These operations are repeated as necessary. Next, it is possible to obtain the desired tetrasiloxanylpropyl methacrylate by drying using anhydrous sodium sulfate or the like and performing a purification operation such as vacuum distillation.

These tetrasiloxanylpropyl methacrylate-1.
Among them, tetrasiloxanylpropyl methacrylate shown in (3) above can be synthesized with good purity and yield because only a single chlorosilane is used for cohydrolysis.

[Effects of the Invention] Tetrasiloxanylpropyl methacrylate obtained by the present invention has excellent reactivity because it is a polysiloxane having a reactive hydrogen atom bonded to a silicon atom and a methacryloxy group. There is. Moreover, this monomer is useful as a modifier for various polymers by taking advantage of the reactivity of both the reactive hydrogen atom and the methacryloxy group.

[Examples of the Invention] The present invention will be explained in more detail with reference to Examples below. In the examples, all parts represent parts by weight.

50 parts of n-hexane, 50 parts of methanol and 100 parts of city water
82% of γ-methacryloxypropyltrimethoxysilane was placed in a flask with a reflux condenser, and while stirring vigorously.
143 parts of dimethylchlorosilane and 62 parts of dimethylchlorosilane at a reaction temperature of room temperature to
The mixture was added dropwise over 1 hour while maintaining the temperature within the range of 40°C. After completion of the dropwise addition, stirring was continued for an additional 2 hours while cooling to perform cohydrolysis.

After standing still, the organic layer was separated, 80 parts of saturated sodium bicarbonate solution was added to the organic layer, and the mixture was stirred for 5 minutes for neutralization, and the organic layer was separated. 100 parts of saturated brine was added to this organic layer, stirred for 5 minutes, washed, and then the organic layer was separated. After repeating this neutralization and washing operation again, it was dried using anhydrous sodium sulfate. This liquid was then distilled by fractional distillation to a boiling point of 112-113°C/0. I Tor
91.5 parts of the target product having r was obtained. The yield of this product was 68% based on the theoretical amount.

The specific gravity, refractive index, IR and 'H-NMR of the obtained compound were measured. The results are shown below. These values indicate that the obtained compound is the desired compound.

Specific gravity: d:5=0.942 Refractive index: n2°=1.418 ■R: Characteristic absorption 2200cm-1Si-H〇=10 1730cm-C-0- 1250cm-1Si-CI'H-NMR: δppm (cat4 Medium) 0.05
(24H1d, J=3H2) 5l-C! 1U30.
50 (2H, m) 5i-C: H21,88 (2H,
m) 5i-CH2-C tan 24.00 (2H, t)
0-CH2 4,65 (IH, n+) Si-■ 50 parts of n-hexane, 50 parts of methanol and 100 parts of city water
In the same manner as in Example 1, a mixture of 72 parts of γ-methacryloxypropyltrimethoxysilane trimethylchlorosilane and 125 parts of dimethylchlorosilane was added dropwise to perform hydrolysis.

The obtained organic layer was neutralized and washed in the same manner as in Example 1, and after liquid separation. Dry. This liquid was then distilled by fractional distillation to a boiling point of 108-109°C10, lTorr.
95.5 parts of the target product having the following were obtained. The yield of this product is
It was 71% of the theoretical amount.

The specific gravity, refractive index, IR and 'H-NMR of the obtained compound were measured. The results are shown below. These values indicate that the obtained compound is the desired product.

Specific gravity: d : 5 = 0.941 Refractive index: n n0 = 1 - 4 18IR: Characteristic absorption 2200c+w-ISi-■I11 1730cm -C-0- 1250cm-lSi-CH'H-NMR: δpp+s (in CGIa) 0 ,0
5 (18H, d, J=3Hz) Si-C! i3
0,50 (28, m) Si-CLI21,88
(2H, m) Sl-CH2-C! ! 2C! l! 3 1,85 (3H, s) -L-. -4.00 (2
H, t) 0-C:j424.65 (2H, m) 5
i-H 50 parts of n-hexane, 50 tfR of methanol and 1 part of city water
In the same manner as in Synthesis Example 1, a mixture of 74.5 parts of γ-methacryloxypropyltrimethoxysilane and 170 parts of dimethylchlorosilane, which had been mixed in advance, was added dropwise to 00 parts of the mixture, and hydrolysis was carried out.

The obtained organic layer was neutralized, washed, separated, and dried in the same manner as in Example 1. Next, this liquid was distilled by fractional distillation to obtain 82 parts of a target product having a boiling point of 103-104° C. 10 and an ITorr. The yield of this product was 81% based on the theoretical amount.

The specific gravity, refractive index, IR and 'H-NMR of the obtained compound were measured. The results are shown below. Moreover, the 1H-NMR spectrum of the obtained compound is shown in FIG. These values indicate that the obtained compound is the desired compound.

Specific gravity: ds 5 = 0.940 Refractive index: n-pan 0 = 1.41.7 ■R: Characteristic absorption 2200cm-ISi-H111 1730arm -C-0- 1 1250cm 5i-(J3'H-NMR: δppII( CC14) 0.05
(18H, d, J=31(z) 5i-CH30,5
0(2H,m) 5i-OH2 1,68(2H9m) 5i-CH2-G and.

4.00 (2H, t) 0-0H2 4,85 (3H, m) Si once 2

[Brief explanation of the drawing]

FIG. 1 is an 'H-NMR spectrum diagram of tris(dimethylsiloxy)silylpropyl methacrylate obtained in Example 3.

Claims (1)

[Claims] 1. Tetrasiloxanylpropyl methacrylate l/, characterized in that it is represented by the general formula: (wherein a represents an integer of 1 to 3)
-t. 2. The tetrasiloxanylpropyl methacrylate according to claim 1, wherein a is 3.