JPH02193962A - Production of 4,4'-bis(4-methacryloylthiophenyl)sulfide - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as paint, adhesive, etc., and also useful for the synthesis of a transparent resin having high refractive index in high yield by reacting a metal salt of 4,4'-dimercaptodiphenyl sulfide with methacryloyl halide. CONSTITUTION:The objective compound of formula is produced by using a metal salt of 4,4'-dimercaptodiphenyl sulfide as a raw material and reacting the material with a methacryloyl halide. The 4,4'-dimercaptodiphenyl sulfide metal salt used as a raw material is produced by dissolving 4,4'-bis(methacryloylthio)diphenyl sulfide in a solvent such as sufficiently dehydrated diethyl ether or ethylene glycol dimethyl ether, adding 2-20mol of an alkali metal (e.g. sodium) or an alkali metal hydride compound (e.g. lithium hydride) to the solution based on 1 mol of 4,4'-dimercaptodiphenyl sulfide to reduce the raw material and removing the solvent from the reaction mixture.

Description

[Detailed Description of the Invention] <Industrial Application/Field> The present invention comprises 4. The present invention relates to a method for producing 4'-bis(4-methacryloylthiophenyl) sulfide in high yield. 4 obtained by the iai method of the present invention,
4'-Bis(4-methacryloylthiophenyl) sulfide is a colorless solid with a low melting point and has excellent compatibility with other polymerizable monomers, and is used as a vulcanizing agent for paints, adhesives, and rubber. , casting materials, photosensitive resins, ion exchange resins, etc., as well as its homopolymerized cured products or other copolymerizable products with 4,4'-bis(4-methacryloylthiophenyl) sulfide. The copolymerized cured product with the polymerizable monomer has low hygroscopicity and a high refractive index, so it is a polymerizable monomer suitable for producing a high refractive index transparent resin.

Prior art> Regarding the production method of carboxylic acid thiol esters,
Generally, a method of reacting thiols with acid halides [
R.B. Baker E.E. Raid (R,B
, Baker and Bi, E., Ra1d).

Journal of the American Chemical Society (J, ^a, Chew, Soc,), 51
．． 1589 (1929)] and a method of reacting thiols with a-anhydride [F.
E.S.I.D. (F, L Wenzel, E, E,
Re1d), Journal of American
Chemical Society (J, Am, Chew,
Soc, ), L9.1089 (1937)] is known. It is also known that in these methods, the reaction proceeds more easily by using an alkali metal salt of a thiol instead of a thiol, or by using a base catalyst such as pyridine [E. E,
E, Ra1d), “Organic Chemistry of Private Sulfur (Organic
Che+n1stry of Bivalent 5
ulfer).

Volume 1, Chemical Publishing Company New 1
York (Chemical Publishing
Company.

New York), (1958)], On the other hand, there are not many reports regarding the production method of unsaturated carboxylic acid thiol esters because the addition reaction of thiols to double bonds occurs extremely easily. T, Iwa+aoto et-al
), Synthesis, 134
(1982), reaction of unsaturated carboxylic acids with thiols using polyphosphorate esters, H.G.
Liu et al. (H, J.

Liu at al), Canadian Journal
Of Chemistry (Can, J, Chew,)
Reaction of unsaturated carboxylic acids with thiols via phenyl dichlorophosphate, T. Cohen et al., 58.2645 (1980).
al) Tetrahedron Letters (Tetrahe)
drone Lett, ), L2.4319 (197
8) The reaction between an unsaturated carboxylic acid and a thiol via boron trithiophenoxide is known. but,
All of these methods are reports on methods for producing unsaturated carboxylic acid thiol esters with no or extremely low thermal polymerizability, and thiol esters of methacrylic acid and acrylic acid with extremely high thermal polymerizability. Regarding the manufacturing method of
S, Marvel et al), Journal of
Polymer Science (J, Polym, Sci,
), 19.59 (1958), a method for producing acrylic acid thiol ester by deodorizing and unreacting 2,3-dibromopropionic acid thiol ester, and M.M.
(M, M, ni oton et al), Zhur, 0bs
hchei Khim, ), 2U, 475 (19
58) and G. Sumrell et al.
tal), Journal of the American Chemical Society (J, As, Chem, So
c, ), u, 2509 (+958) There is only a report on a method for producing by reacting (meth)acryloyl halide with an alkali metal salt of thiols.
However, these production methods are limited to monofunctional (meth)acrylic acid thiol esters, and there have been no reports on methods for producing bifunctional methacrylic acid thiol esters.

<Problems to be Solved by the Invention> The object of the present invention is to provide coatings, adhesives, rubber vulcanizing agents, casting materials, photosensitive resins, which have excellent compatibility and are extremely easy to handle in practical applications such as monopolymerization. 4. Not only can it be applied to industrial fields such as ion exchange resins, but it is also extremely useful as a raw material for high refractive index transparent resins. An object of the present invention is to provide a method for producing 4''-bis(4-methacryloylthiophenyl) sulfide in high yield.

<Means for solving am> According to the present invention, 4,4-bis(
A method for producing 4-methacryloylthiophenyl) sulfide is provided.

That is, 5 the present invention provides 4,4'-bis(4-methacryloylthiophenyl) sulfide represented by formula (I), which is characterized by reacting a metal salt of bis(4-mercaptophenyl) sulfide with methacryloyl halide. Relating to a manufacturing method.

The method for producing 4,4'-bis(4-methacryloylthiophenyl) sulfide will be specifically described below.

The 4,4'-bis(4-methacryloylthiophenyl) sulfide of the present invention is bis(4-mercabutophenyl)
It is produced at a high yield by gradually dropping methacryloyl halide into an aqueous solution of a sulfide metal salt.

The metal group group of bis(4-mercaptophenyl) sulfide used in the present invention can be prepared in advance to form a 4,4'-
It may be used for the production of bis(4-methacryloylthiophenyl) sulfide, or directly in the reaction vessel.
However, the latter method is generally preferred because the manufacturing process is simple. The metal salt of bis(4-mercaptophenyl) sulfide used is preferably an alkali metal salt of bis(4-mercaptophenyl) sulfide.

When preparing the alkali metal salt of bis(4-mercaptophenyl) sulfide in advance, bis(4-mercaptophenyl) sulfide is mixed with sufficiently dried diethyl ether, ethylene glycol dimethyl ether,
After dissolving in an ether solvent such as tetrahydrofuran or an aromatic hydrocarbon solvent with a relatively low boiling point such as benzene or toluene, alkali metals such as sodium, potassium, and lithium, sodium hydride, lithium hydride, etc. are added to this solution. I
It can be made @. The isolated alkali metal salt of bis(4-mercaptophenyl) sulfide can be prepared by dissolving it in an alkaline aqueous solution containing an alkali metal hydroxide compound such as sodium hydroxide or potassium hydroxide. -methacryloylthiophenyl) sulfide.

The amount of water used in this case is not particularly limited as long as it can completely dissolve the alkali metal salt of bis(4-mercaptophenyl) sulfide, and generally the alkali metal salt of bis(4-mercaptophenyl) sulfide The range is from 1 part by weight to 10 parts by weight. In addition, in this case) the amount of the alkali metal hydroxide compound used is bis(4-mercaptophenyl) sulfide 1
0.0 per mole. 1 to 18 moles of I! rg, more preferably in the range of 1 mol to 13 mol. The amount of alkali metal hydroxide compound used is 0. If it is less than 1 mole, the reaction between the methacryloyl halide and the alkali metal salt of bis(4-mercaptophenyl) sulfide, which is added later, will not proceed efficiently and by-products will be produced, which is undesirable. If the amount of the metal compound used is more than 18 moles, it is uneconomical and undesirable.

When preparing an alkali metal salt of bis(4-mercaptophenyl) sulfide directly in a reaction vessel, add 1 ml of water, such as sodium hydroxide or potassium hydroxide, to water that has been sufficiently purged with nitrogen to remove dissolved oxygen. A homogeneous aqueous solution can be prepared by dissolving the alkali metal oxide compound, adding bis(4-mercaptophenyl) sulfide to this solution under a nitrogen stream, and heating if necessary. The amount of alkali metal hydroxide compound used in this case is
The amount is in the range of 2 mol to 20 mol, more preferably in the range of 3 mol to 15 mol, per 1 mol of bis(4-mercaptophenyl) sulfide. If the amount of the alkali metal hydroxide compound used is less than 2 moles, the reaction between the methacryloyl halide and the alkali metal salt of bis(4-mercaptophenyl) sulfide, which is added later, will not proceed efficiently and by-products will be produced. Furthermore, if the amount of the alkali metal hydroxide compound used is more than 20 moles, it is uneconomical and undesirable. Also, the amount of water used in this preparation method.

An amount in which the m degree of the alkali metal hydroxide compound to be used with respect to water ranges from 2 M% to 40% by weight.

More preferably, the amount is in the range of 5% to 30% by weight. It is not economical when the amount of water used is so large that the concentration of the alkali metal hydroxide compound in water is less than 2% by weight, and the amount of water used is so large that the concentration of the alkali metal hydroxide compound in water exceeds 40% by weight. If it is less than
This is not preferable because the alkali metal salt of the bis(4-mercaptophenyl) sulfide produced precipitates, resulting in a heterogeneous reaction.

A methacryloyl halide such as methacryloyl chloride or methacryloyl bromide is gradually added dropwise to the aqueous solution of the alkali metal salt of bis(4-mercaptophenyl) sulfide prepared as above under a nitrogen stream. By that, 4,4
'-Bis(4-methacryloylthiophenyl) sulfide! Ji is built.

The amount of methacryloyl halide used in the i11 production method of the present invention is in the range of 2 to 8 moles per mole of bis(4-mercaptophenyl) sulfide;
More preferably, it is in the range of 2.01 mol to 5 mol.

When the amount of methacryloyl halide used is less than 2 moles, a part of the mercapto group of bis(4-mercaptophenyl) sulfide remains unreacted with methacryloyl halide, and the 4,4'-bis(4 −
This is not preferred because it causes gelation of (methacryloylthiophenyl) sulfide. Also.

If the amount of methacryloyl halide used is more than 8 moles, it is not economical and is therefore not preferred.

What is the reaction temperature between metal salt of bis(4-mercaptophenyl) sulfide and methacryloyl halide?

-10°C to 50°C, more preferably 0°C to 4°C
If the reaction temperature is lower than 110°C, which is in the range of 0°C, it is not preferable because the alkali metal salt of bis(4-mercaptophenyl) sulfide often precipitates from the reaction solution, and the reaction temperature is lower than 110°C. If it is higher than this, 4,4'-bis(4-methacryloylthiophenyl) sulfide, which is often produced in the reaction system, is thermally polymerized and gelled, which is not preferable.

4,4I bis(4-
(methacryloylthiophenyl) sulfide is a colorless solid with a low melting point (8 points: 6L, 0°C to 61.5°C) at room temperature, and can be isolated by heating above the melting point using a common radical polymerization initiator. Not only can it be polymerized, but it can also be mixed and copolymerized with other polymerizable In polymers that can be copolymerized with 4,4'-bis(4-methacryloylthiophenyl) sulfide.

Other polymerizable monomers copolymerizable with 4.4'-bis(4-methacryloylthiophenyl) sulfide include:
4. There is no particular restriction as long as it is compatible with 4'-bis(4-methacryloylthiophenyl) sulfide, and it may be monofunctional or polyfunctional. Also,
Other polymerizable monomers copolymerizable with 4,4'-bis(4-methacryloylthiophenyl) sulfide can also be used as a mixture of diN or higher compounds. 4,4
There is no particular restriction on the mixing ratio of other polymerizable monomers that can be copolymerized with '-bis(4-methacryloylthiophenyl) sulfide, and any ratio can be selected. Examples of such polymerizable monomers include unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and their derivatives, unsaturated dibasic acids and their derivatives, and vinyl cyanide compounds such as (meth)acrylonitrile. Other examples include polyfunctional mercapto compounds such as pentaerythritol tetrathioglycolate.

What is the radical polymerization initiator used during curing?

Use of any commonly used radical polymerization initiator, such as 2゜2'-azobisisobutyronitrile or benzoyl peroxide, as long as it can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays. is also possible.

<Examples> Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples.

Example 1 In a 2,000-meter four-hole flask equipped with a stirrer, a thermometer, a Dimroth condenser, and an isobaric crushing funnel, under a nitrogen stream, 1,200 meters of distilled water that had sufficiently removed dissolved aS by blowing nitrogen day and night was added. Pour 1 then sodium hydroxide 287.6
After dissolving 150 g (0.6 mol) of bis(4-mercaptophenyl) sulfide, the mixture was heated at 110°C for about 2 hours to form a homogeneous aqueous solution.
Next, while cooling this aqueous solution to 0°C to 5°C, 188°2 g of methacryloyl chloride (1,
After one drop of 8 mol) was gradually added dropwise, the mixture was further stirred at room temperature for 4 hours, and the resulting solid was collected by filtration, and then the solid was repeatedly washed with distilled water until the filtrate became neutral. The obtained solid was vacuum dried at room temperature to remove water, and then dissolved in acetone (11). Approximately 50 g of magnesium sulfate was added to this solution, stirred, and filtered. The solvent of the resulting solution was removed under reduced pressure to obtain crude 4,4'-bis(
4-methacryloylthiophenyl) sulfide was obtained.

This [4,4'-bis(4-methacryloylthiophenyl) sulfide was added to 4.49 methanol, and 40
Dissolved by heating at ℃, recrystallized by cooling day and night, and filtering and drying the obtained crystals to obtain colorless needle-like crystals of 4,4''-bis(4-methacryloylthiophenyl) sulfide 12.
6g was obtained. Furthermore, from the remaining recrystallization mother liquor, crude 4,4'-
By taking bis(4-methacryloylthiophenyl) sulfide and repeating recrystallization in the same manner, 4
．． 48 g of 4'-bis(4-methacryloylthiophenyl) sulfide was obtained. The yield of 4,4'-bis(4-methacryloylthiophenyl) sulfide obtained was 75%.
Met.

The analysis results for determining the structure of the obtained compound are shown below.

Melting point 61.0℃~61.5℃ Elemental analysis C (%) H (%) S (%) Calculated value
62. 14 4. 69 24. 88 actual measurement value
62. 51 4. 11 24. 53 Furthermore,
The 'H-NMR (solvent CG lm, internal standard TMS) spectrum of the obtained compound is shown in Figure 1, and the IR
The absorption and absorption spectrum surface diagram is shown in Figure 2.

The 'H-NMR spectrum diagram is newly manufactured by Hitachi.
Measured using an R-24B spectrometer (60 MHz), IR absorption spectra shown in the same figure, newly manufactured by Hitachi,
Measurement was performed using a 270-50 IR spectrophotometer.

Examples 2-4 Amount of bis(4-mercaptophenyl) sulfide used,
4 and 4 were prepared in the same manner as in Example 1, except that the type and amount of methacryloyl halide, the type and amount of alkali metal hydroxide compound, and the amount of water used were changed as shown in Table 1. ''-bis(4-methacryloylthiophenyl) sulfide was produced. The results are shown in Table 1.

(Margins below) Example 5 tt! which has been sufficiently heated and dried in advance! 4'1! Dry purified tetrahydrofuran 500ml was placed in a fourth flask equipped with a Dimroth type condenser, a thermometer, and an isobaric dropping funnel, and Dobis(4-mercaptophenyl) was added to the flask with a nitrogen stream.
150 g (0.6 mol) of sulfide are dissolved and then 27.0 g of sodium metal is dissolved in this solution. 6 g (1.2 mol) were added portionwise.

After confirming that the metallic sodium is completely consumed,
Tetrahydrofuran was distilled off to obtain bis(4), a yellow solid.
-Mercaptophenyl) sulfide sodium salt was obtained.

To the obtained sodium salt of bis(4-mercaptophenyl) sulfide, which is a yellow solid, were added 1000 g of distilled water, which had been thoroughly blown with nitrogen to remove dissolved Pa cords, and 96 g (2.4 mol) of sodium hydroxide. Then, while cooling this aqueous solution to 0°C to 5°C, 1 methacryloyl chloride was added through an isobaric dropping funnel.
After 0 dropwise addition of 88.2 g (1.8 mol), the mixture was further stirred at room temperature for 4 hours and 11 fl, the solid produced was collected by filtration, and the mixture was repeatedly added with distilled water until the filtrate became neutral. Washed. The obtained solid was vacuum dried at room temperature to remove water, and then dissolved in 1 part acetone. About 50 g of magnesium sulfate was added to this solution, stirred, and filtered. The solvent of the resulting solution was removed under reduced pressure to obtain crude 4,4'-bis(4-methacryloylthiophenyl) sulfide. This crude 4,4'-bis(4-methacryloylthiophenyl) sulfide was recrystallized in the same manner as in Example 1 to obtain colorless needle-like crystals.
, 155 g (yield: 66.8%) of 4'-bis(4-methacryloylthiophenyl) sulfide was obtained.

The IR spectrum and H-NMR spectrum of the obtained 4,4'-bis(4-methacryloylthiophenyl) sulfide are the same as those of the 4,4'-bis(4-methacryloylthiophenyl) sulfide obtained in Example 1. The spectrum was completely consistent with the 'H-NMR spectrum.

Examples 6 to 8 As the alkali metal compound used in the preparation of the alkali metal salt of bis(4-mercaptophenyl) sulfide, sodium hydride was used in Example 6, potassium hydride was used in Example 7, and potassium hydride was used in Example 7. 8 uses metallic lithium,
In addition, 4,4'-
Bis(4-methacryloylthiophenyl) sulfide was produced. The results are shown in Table 2.

(Left below) Reference Example To 10 g of 4,4'-bis(4-methacryloylthiophenyl) sulfide obtained in Example 1.

As a radical polymerization initiator: 1. 10 mg of 1-bis(t-butylperoxy)-3,3,5-1-limethylcyclohexane was added and dissolved by heating at 65°C. Add this to a 0.2mm x 20mm x 20mm glass cell and 2
．． Each was poured into a 0 mm x 75 mmφ glass mold, heated at 70°C for 5 hours, and then heated to 100°C at a temperature increase rate of 3°C/hr to 1!5! Mold,
Furthermore, it was heat-cured at 150° C. for 2 hours. The obtained cured product was colorless and transparent, and had the physical properties shown below.

"rg 150°C (Orientic Co., Ltd., Rheopybron DDV-n-EP type) Moisture absorption rate 0.25% (ASTM D570-(23
'C, 24 hour immersion) 59T) Refractive index N61+
=1. 689 (Shimadzu Corporation, 3L type refractometer) <Effects of the invention> According to the manufacturing method of the present invention + 4. 4'-bis(4-
methacryloylthiophenyl) sulfide in high yield.
can be built. In addition, 4,4'-bis(4-methacryloylthiophenyl) sulfide obtained by the production method of the present invention is a colorless needle crystal that is solid at room temperature, and is not compatible with other polymerizable monomers. Due to its excellent properties, it is used in paints, adhesives, rubber vulcanizing agents, casting materials, photosensitive resins,
Not only is it applicable to industrial fields such as ion exchange resins, but also its homopolymerized cured products or 4,4-
The copolymerized cured product of bis(4-methacryloylthiophenyl) sulfide and other copolymerizable monomers has low hygroscopicity, and its high refractive index can be used to create a high refractive index transparent resin. It is a useful polymerizable monomer that can be applied.

[Brief explanation of the drawing]

FIG. 1 is an 'H-NMR spectrum diagram of the compound obtained in Example 1, and FIG. 2 is an IR absorption spectrum diagram of the compound obtained in Example 1.

Claims (1)

[Claims] Formula (I) characterized by reacting a metal salt of bis(4-mercaptophenyl) sulfide with methacryloyl halide ▲There are numerical formulas, chemical formulas, tables, etc.▼ 4 represented by (I) , 4'-bis(4-methacryloylthiophenyl) sulfide.