JPH02258819A - New polymerizable monomer - Google Patents

Abstract

PURPOSE:To obtain a polymerizable monomer, having a specific structural formula and capable of readily (co)polymerizing alone or with an olefinic double bond-containing polymerizable monomer and providing transparent cured products having high heat resistance and refractive index and low water absorptivity. CONSTITUTION:A 4,4'-bis[omega-(meth)acryloyl(polyoxyalkylene)thio]phenyl sulfide compound, expressed by formula II (R1 is H or methyl) and obtained by, e.g. adding a substituted or unsubstituted alkylene oxide to 4,4'-dimercaptophenyl sulfide, and subjecting the resultant dihydric alcohol expressed by formula I (R2 is H or methyl; m and n are 1-5) to esterifying reaction with (meth)acrylic acid, etc. The above-mentioned compound is then (co)polymerized alone or with an olefinic double bond-containing polymerizable monomer, such as methyl (meth)acrylate, to afford cured products suitable as optical materials, etc.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention can produce a transparent cured product with high heat resistance, low water absorption, and high refractive index. A novel difunctional polymerizable monomer, more particularly an optical material. 4,4゛-bis[ω-(
meth)acryloyl(polyoxyalkylene)thioJ phenyl sulfide. [Conventional technology J Conventionally, polystyrene resins, polymethyl methacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate polymers, etc. have been used as organic optical materials, and these are lightweight, safe, and easy to process. The demand for it has been increasing in recent years due to its excellent dyeability. However, in the case of conventional organic optical materials 1, such as polymethyl methacrylate resins, their resin properties are high hygroscopicity, and as a result of moisture absorption, the shape and refractive index are likely to change, making them unstable as optical materials. Furthermore, polystyrene resins and polycarbonate resins have drawbacks such as optical birefringence, generation of light, and decrease in transparency due to aging. Furthermore, the polymer of diethylene glycol diallyl carbonate has a low refractive index (refractive index = 1.499), so it has many applications as an optical material! There was 1111 nearby. Various resins for optical materials have been proposed to overcome these drawbacks. Examples of these include, for example, Japanese Unexamined Patent Publication No. 5
No. 7-28115, No. 57-28116, No. 59-184210, and No. 60-7314. 60-179406, 60-217301, 60-186514, 60-1663
Publication No. 07, Publication No. 60-103301, Publication No. 60-1
No. 24607, No. 62-232414, No. 6
2-2359 old publication, 62-267316 publication,
Publications No. 63-15811 and No. 63-46213. Publication No. 63-72707 can be mentioned. However, the cured products obtained by these prior art techniques have advantages and disadvantages as optical materials, such as optical non-uniformity, significant weathering coloring, and lack of one-dimensional stability, and are not necessarily satisfactory materials. There wasn't.

[Problems to be Solved by the Invention] The purpose of the present invention is to overcome the drawbacks of conventional resins for optical materials, and to make the resin suitable not only for optical materials but also for coating agents, sealants, paints, adhesives, and adhesives. It can also be used as a mold material or a photosensitive resin material. The object of the present invention is to provide a novel polymerizable monomer suitable for producing a well-balanced cured product having various physical properties such as optical uniformity, low water absorption, and heat resistance. [Means for Solving the Problems 1] The present invention was able to provide a novel polymerizable monomer that can achieve the above objects. That is, 1 the present invention is a compound represented by the general formula (N (wherein R6 and R* each independently represent hydrogen or a methyl group, and m and n each independently represent an integer from 1 to 5). °-bis[ω-(meth)acryloyl(polyoxyalkylene)thio phenyl sulfide compound. The compound represented by the general formula (1) according to the present invention can be synthesized by various methods, but specific examples thereof are as follows. Examples are as follows.In addition, in the following method, the synthesis reaction conditions can be generally those in similar known reaction techniques. (i) Dihydric alcohol represented by the following - generation (II) A method of esterifying with (meth)acrylic acid (in the present invention, acrylic acid and/or methacrylic acid)...-(II) (wherein R8 represents hydrogen or a methyl group) m and n represent integers of 1 to 5; (ii) A method of transesterifying a dihydric alcohol represented by the above-mentioned generation (II) and a lower alkyl ester of C meth)acrylic acid. (iii) A method of reacting a dihydric alcohol represented by the above-mentioned generation (II) with a chloride of (meth)acrylic acid in the presence of a base. It is generally obtained by adding a substituted or unsubstituted alkylene oxide to 4.4°-dimercaptophenyl sulfide, or by addition-condensing a substituted or unsubstituted alkylene carbonate to 4.4°-dimercaptophenyl sulfide. Therefore, according to this method, the value of m or n in the -generation (TI) compound depends on the reaction molar ratio of the 4,4°-dimercaptophenyl sulfide used with the substituted or unsubstituted alkylene oxide. Alternatively, it is determined by the reaction molar ratio of 4,4'-dimercaptophenyl sulfide and substituted or unsubstituted fullkylene carbonate.The substituted or unsubstituted alkylene oxide used in synthesizing these polyoxyalkylene compounds is as follows: Ethylene oxide or propylene oxide is used. Ethylene carbonate or propylene carbonate is used as the substituted or unsubstituted alkylene carbonate. ) Acryloyl (polyoxyalkylene) thio phenyl sulfide is a colorless and transparent compound with an extremely high refractive index that is liquid at room temperature and has high polymerization activity. It can be mixed with various polymerizable monomers having a double bond and polymerized using an ordinary radical polymerization initiator.Moreover, the obtained cured product has a high refractive index and is colorless and transparent. Moreover, since it has a low water absorption rate, it is a suitable material for optical marking materials, as well as paints, adhesives, coating agents, casting materials, etc. Copolymerization that can be used with the compound represented by general formula (I) Polymerizable @mers with possible olefinic double bonds may be monofunctional or polyfunctional.
There is no particular restriction as long as it is compatible with the bis[ω-(meth)acryloyl(polyoxyalkylene)thioJ phenyl sulfide compound, and a polymerizable monomer having a copolymerizable olefinic double bond It is also possible to use a mixture of two or more types, and there is no limit to the mixing ratio (any ratio can be selected).As a polymerizable monomer having such an olefinic double bond, Examples include unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and their derivatives, unsaturated dibasic acids and their derivatives, cyanide vinyl compounds such as (meth)acrylonitrile, etc. Unsaturated fatty acid esters include , methyl (meth)acrylate, ethyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, (iso)bornyl (meth)acrylate ) acrylate, alkyl (meth)acrylate such as adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, l-naphthyl (meth)acrylate, fluorophenyl (meth)acrylate, chlorophenyl (meth)acrylate, bromo Acrylic acid aromatic esters such as phenyl (meth)acrylate, tribromophenyl (meth)acrylate, methoxyphenyl (meth)acrylate, cyanophenyl (meth)acrylate, biphenyl (meth)acrylate, bromobenzyl (meth)acrylate, fluoromethyl Haloalkyl (meth)acrylates such as (meth)acrylate, chloromethyl (meth)acrylate, bromoethyl (meth)acrylate, trichloromethyl (meth)acrylate. 2-Hydroxyethyl (meth)acrylate, (meth)acrylate.
In addition to polyethylene glycol acrylate esters, there are (meth)acrylic esters such as glycidyl (meth)acrylate and alkylamino (meth)acrylate. In addition, α-i! such as α-fluoroacrylic acid ester, a-cyanoacrylic acid ester, etc. Converted acrylic acid ester. Examples of aromatic vinyl compounds include styrene or α-
There are α-substituted styrenes such as methylstyrene, a-ethylstyrene, and α-chlorostyrene, and nuclear-substituted styrenes such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene. Examples of unsaturated fatty acids and derivatives thereof include (meth)acrylamide, N,N-dimethyl(meth)acrylamide,
N,N-diethyl (meth) such as methanoacrylamide
Examples include acrylamides and (meth)acrylic acid. As the unsaturated dibasic acid and its derivatives, N-methylmaleimide. N-substituted maleimides such as N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, maleic acid, maleic anhydride There are acids, fumaric acid, etc. In addition to the above-mentioned monofunctional vinyl monomers, examples of polymerizable monomers having an olefinic double bond that can be mixed with the compound represented by formula (I) include crosslinkable polyfunctional monomers. Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,
Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tribrobylene glycol di(meth)acrylate, 1.3-
Butylene glycol di(meth)acrylate, 1.4-
Butane diol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexane diol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neobentyl glycol ester Di(meth)acrylate, : 4 ligoester di(meth)acrylate, polybutadiene di(meth)acrylate, 2.2-bis(4
-(meth)acryloyloxyphenyl)propane, 2
．． 2-bis(4-(ω-(meth)acryloyloxyboIJnidoxinphenyl)propane, 2.2-bis(4
-(ω-(meth)acryloyloxybo-17ethoxinedibromophenyl)propane, 2,2-bis(4-(ω
- di(meth)acrylates such as (meth)acryloyloxypolypropoxy)phenyl)propane, bis(4-(ω-(meth)acryloyloxypolyethoxy)ph, I-nyl)methane, diallyl phthalate, diallyl isophthalate, Difunctional crosslinking monomers such as diallyl terephthalate, divinylbenzene, N,N'-m-phenylenebismaleimide, trimethylolethane tri(
meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)
Acrylates 2 Trifunctional cross-linking agents such as tri(meth)allyl isocyanurate, triallyl trimellitate, diallyl chlorendate, tetrafunctional fruit-based agents such as pentaerythritol tetra(meth)acrylate etc. As the radical polymerization initiator used during curing, any radical polymerization initiator can be used as long as it can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays. Examples of radical polymerization initiators that can be used in polymerization using heat, microwaves, and infrared rays include azo compounds such as 2.2°-azobisisobutyronitrile and 2゜2゛-azobisisovaleronitrile, and methyl ethyl ketone. peroxide, ketone peroxides such as methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 0-
Diacyl peroxides such as methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2.4.4-trimethylpentyl-2-
Hydroperoxide, diisopropyl benzene peroxide, cumene hydroperoxide, t-butyl peroxide and other hydroperoxides, dicumyl peroxide, di-butyl cumyl peroxide, di-save til peroxide, tris- dialkyl peroxides such as (butylperoxy)triazine, peroxyketals such as 1.1-di-butylperoxycyclohexone, 2.2-di(t-butylperoxy)butane, etc. t-
Butyl peroxy bivalate, t-butyl peroxy-
2-ethyl hequinanoate, t-butyl peroxy isobutyrate, di-t-butyl peroxy hexahydroterephthalate, di-butyl peroxy azelate,
Alkyl peresters such as di-butylperoxy-3,5,5-trimethylhexanoate, 1-butylperoxyacetate, t-butylperoxybenzoate, di-butylperoxytrimethyladipate, diisobrobylperoxy Dicarbonate, G5eC-
Examples include bar carbonates such as butyl peroxydicarbonate and t-butylperoxyisopropyl carbonate. Examples of radical polymerization initiators that can be used in polymerization using ultraviolet light include acetophenone. 2.2-dimethoxy-2-phenylacetophenone, 2
．． 2-jethoxyacetophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-
Hydroxy-2-methylpropyphenone, 4.4°-bis(diethylamino)benzophenone, benzophenone, methyl(0-benzoyl)benzoate, l-phenyl 1.2-propanedione-2-(0-ethoxycarbonyl)oxime, l -phenyl-1,2-propanedione-2-(0-benzoyl)oxime, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl,
Benzyl dimethyl ketal, benzyl dimethyl ketal, carbonyl compounds such as diacetyl, methylanthraquinone, chloroanthraquinone, chlorothioxanthone,
Examples include anthraquinone or dioxanthone derivatives such as 2-methylthioxanthone and 2-isopropylthioxanthone, and sulfur compounds such as diphenyl disulfide and dithiocarbamate. The amount of the radical polymerization initiator used cannot be determined unconditionally as it varies depending on the type of radical polymerization initiator, the type of monomer charged, and the composition ratio, but it is usually 0.001 to 20 mol% based on the 7-mer component. range, preferably 0.01
-10 mol% range. If the amount of radical polymerization initiator used is less than o, ooi mol%, one polymerization takes a long time,
Moreover, if the amount used exceeds 20 mol %, it is not only uneconomical but also undesirable because it may cause foaming during polymerization or the molecular weight of the cured product obtained by pentapolymerization will become extremely small. The polymerizable monomer of the present invention may be directly polymerized and cured, or depending on the purpose, it can be prepolymerized and then polymerized and cured to adjust the viscosity or reduce the shrinkage rate during polymerization. . 【fruit! Example M] Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples. Of course, the scope of the present invention is not limited by these Examples. (Example 1) 50.0g of 4.4゛-bis(2-hydroxyethylthio)phenyl sulfide, which is a dihydric alcohol, was added together with 300rr+42 benzene, a thermometer, a Dimroth cooler, a stirring blade, and a water collector. The mixture was poured into a triple-separable flask (500 mg) and dissolved therein.Acrylic acid, p-4 toluenesulfonic acid, and hydroquinone were added to this solution, and the mixture was heated under reflux for 10 hours. A 1N aqueous sodium hydroxide solution was added to the obtained reaction solution for extraction, and washing with water was repeated until the solution became neutral. Anhydrous magnesium sulfate was added to the washed organic solution to dry it, and the solvent was removed under reduced pressure to obtain a crude product. This crude product was purified using silica gel column chromatography (distillation solvent: hexane/ethyl acetate = 7/3) to obtain the desired 4,4゛-bis(2-acryloyloxyethylthio)phenyl sulfide. . The obtained 4,4゛-bis(2-acryloyloxyethylthio) phenyl sulfide was a colorless and transparent oily liquid (boiling point: >200℃ gelation) at room temperature.The elemental analysis values of this compound are as follows. show. Refractive index No = 1, 6291 (3L type refractometer manufactured by Kinsei Seisakusho, measurement temperature: 25°C) Elemental analysis C*mHz*04S s = 446.59 total W
(a C: 59.17% H: 4.97%
S 2 21.36%': i: am c 2 59
．． 02% + (: 5.13% S +
21.81% Furthermore, the obtained 4,4°-bis(2-
The IR spectrum of acryloyloxyethylthio) phenyl sulfide is shown in Figure 1, and the 'r(-NMR spectrum is shown in Figure 2).The fR spectrum is
The 'H-NMR spectra were measured using a 7.270-50 photo spectrometer, and the internal p! JEOL J as a quasi-A
Measurement was performed using a NM-PMX 60 (60 MHz) NMR measuring device. (Example 2) A dihydric alcohol, 4.4°-bis(ω-hydroxypolyoxypropylthio)phenyl sulfide (formula (
In II), R1=-CH,, n=m=2)50.
0g was put into a three-way adjustable flask (500 mβ) equipped with a thermometer, a Dimroth condenser, a stirring blade, and a dropping funnel, together with 300 ml of methylene chloride, and dissolved. Further, 940 mg of triethylamine was added to this solution and cooled to 0 to 5°C. While keeping the temperature of the reaction solution at 0 to 5°C, methacrylic acid chloride 2, which had been purified by distillation in advance, was
After 1 drop of 2.8 g was gradually dropped from the dropping funnel, stirring was continued for about 31 LV at room temperature, and 1N aqueous sodium hydroxide solution was added to the reaction solution for extraction.
Washing with water was repeated until the mixture became neutral. Anhydrous magnesium sulfate was added to the washed organic solution to dry it, and the solvent was removed under reduced pressure to obtain a crude product. This crude product was purified using silica gel column chromatography (distillation solvent: hexane/ethyl acetate = 7/3) to obtain the desired colorless transparent liquid 4.4°-bis(ω-methacryloylpolyoxypropylthio). Phenyl sulfide (R,= in formula (I)
-CHa, 11°=-CHs, n=m=2) was obtained. The refractive index, elemental analysis value, and each spectral data value of the obtained target object are shown below. Refractive index N, = 1.5960 (3L type refractometer manufactured by Kinsei Seisakusho, measurement temperature: 25°C) Elemental analysis C, aH, □0, S, = 618.86
Calculated value C: 62.11% Eye 1: [1,84
% S: 15.54% Actual value C: 62.02%
H: 6.75% S: 15.8:1 R:
νcm +740 <ester carbonyl] 1590 and 1490 (phenyl)i>1180 (
ether), 810 (phenyl out-of-plane bending)'H-NMR
, δ (CDC1,) 7.23 (8H, s), 6.0 δ (2) 1. m)5.
64 (2H, m), 4.6~3.8 (1
0H, m) 3.28 (2) 1. m) 1.98 (611, d, J = 2Hz) 1.26 (6)
1. d, J = 7Jlz) 1.25 (6H, d
, J=7Hz) (Example 3) It is a dihydric alcohol. 4.4j4 instead of 4'-bis(2-hydroxyethylthio)phenyl sulfide
°-bis(ω-hydroxypolyoxyethylthio)phenyl sulfide (in formula (II), R1=-f
, n=m=2) was used in the same manner as in Example 1 to obtain the target product 4°4°-bis(ω-methacryloyloxypolyoxyethylthio)phenyl sulfide (formula (
In I), R1=-H, R*=-H, n=m=2
) was obtained. The refractive index, elemental analysis value, and each spectral data value of the obtained target object are shown below. Refractive index N o ” 1.6075 (31. type refractometer manufactured by Kinsei Seisakusho, dll + constant temperature = 25
°C) Elemental analysis CggHsao, S3 = 53
4.70 calculated value C: 58.40 pieces H: 5.65
% S: 17.99% Actual value C+ 511.43
% II: 5.51% S: 17J5%IR Niji cm 17:10 (ester carbonyl) +590 and 1480 (phenyl nucleus) +160 (ether), 810 (phenyl out-of-plane bending angle)' H-NMR
: δ (CDC1,) 7.28 (8H, s) 6.44 (2H, dd, J=2.17Hz) 6.13 (
2H, dd, J=11.17Hz) 5.80 (2H, d
d, J=2. I IHz) 4.53 (411,t, J=
6Hz) 4.20(41(,t,,J=6Hz)4.13(41
-1,t,J=6Hz)3゜34(4H,t,J=6H
z) (Example 4) It is a dihydric alcohol. 4.4'-bis(ω-hydroxypolyoxypropylthio)phenyl sulfide (formula (
II), R□=-CHs, n=m
= 2 > instead of 4.4°-bis(ω-hydroxypolyoxyethylthio]phenyl sulfide (formula (
Using the same method as in Example 2, except that R2 = -11, n = m = 4) was used for the target object 4.4゛-
Bis(ω-methacryloyloxypolyoxyethylthio)phenyl sulfide (in formula (1), R4=-C
11, Rx=-H, n=m=4) was obtained. The refractive index, elemental analysis value, and each spectral data value of the obtained target object are shown below. Refraction: 4N o = 1.5871 (3L type refractometer manufactured by Kinsei Rakusakusho, measurement temperature: 25°C) Elemental analysis C3°H5°O, S 3 =738. 'J7
Calculated value C: 58.51% H: 6.82$
S + 13.02% actual value C: 5L44% H:
6-59% S: 13. :13%I R: sic
m-' 1735 (ester carbonyl) 1580 and 1490 (phenyl nucleus) 1160 (ether), 810 (phenyl out-of-plane bending) II -N
M R・δ (CDCI,)7.25 (8Il,
s), ll+, IO(2H,m)5.62
(2H, m) 4.51 (4fl, t, j=611Z) 4.1
8 (24F1.br t, J=61-1z)3
, :11 (4H,t, J=61(z)1.99(
6H, d, J = 21-1z) (Reference Example 1) In Example 1, 20 g of 4,4°-bis(2-acnoloyloxyethylthio)phenyl sulfide was added as a radical polymerization initiator. 2゜Dissolve 20mg of azobis(2,4-dimethylvaleronitrile) and add 0.2m
mx20mmx20mm glass cell and 2.0mmx
Pour each into a 75 mmφ glass mold, and
After heating at 10°C for 10 hours, it was heated to 80°C at a temperature increase rate of 10°C/hr to deharden it, and then heated and hardened at 100°C for 1 hour. The obtained resin is colorless and transparent, and has the physical properties shown below as f1.
I was there. Tg 150℃ (manufactured by Orientic Co., Ltd., Shiobibron DDV-
II-E P type) Moisture absorption rate 0.2% (ASTM D-570-59'r
) (23°C, 24h immersion) Refractive index N o ” = 1. (i56 (3LP manufactured by Kinsei Seisakusho!: U refractometer, measurement - degree: 25°C) (Reference example 2) 4 obtained in Example 3 , 4゛-bis(ω-methacryloyloxypolyoxyethylthio)phenyl sulfide (
In formula (1), 11, = −[−1. Rm = -14, n = m = 2 ] 35 g
50 mg of 2.2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator was dissolved in 50 g of a curable composition consisting of 15 g of methyl methacrylate and a 5 cm x 5 cm x 0.3 cm glass mold and a 0.2 mm x 50 mm x 20 mm glass. Each was poured into a cell and heated at 35° C. for 10 hours under a nitrogen stream, then demolded by heating to 80° C. at a rate of 10° C./h, and further heat-cured at 100° C. for 1 hour. (The resulting resin was colorless and transparent, and the physical properties were measured in the same manner as in Reference Example 1, and the results were as shown below.
II-E P type) Moisture absorption rate 0.22% (ASTM Low 570-59T
) (23°C, 241+ immersion) Refractive index N o ” = 1.588 (3L type refractometer manufactured by Kinsei Seisakusho, measurement temperature: 25°C)

[Brief explanation of drawings]

FIG. 1 is an IR spectrum diagram of the compound obtained in Example 1, and FIG. 2 is an IR spectrum diagram of the compound obtained in Example 1 c′+! ! FIG. 2 is a 'H-NMR spectrum diagram of the compound obtained.

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (In the formula, R_1 and R_2 each independently represent hydrogen or a methyl group, and m and n each independently represent an integer from 1 to 5.) 4,4'-bis[ω-(meta) Acryloyl (polyoxyalkylene) thio] phenyl sulfide compound.