JP2893940B2 - Sulfur-containing acrylic oligomer composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a sulfur-containing acrylic oligomer. The oligomer provides a cured product that is lightweight, has a high refractive index, is excellent in heat resistance and impact resistance, and is suitable for use in plastic lenses.

[Conventional technology]

As a resin that gives a high refractive index plastic lens,
Various diacrylate or dimethacrylate compounds are known. For example, a bromine-containing bisphenol skeleton (JP-A-59-184210, JP-A-59-193915) and a sulfur-containing aromatic skeleton (JP-A-60-26010, JP-A-62-10610)
-195357) show optical characteristics excellent in balance between high refractive index and high Abbe number.

However, these compounds form a highly crosslinked product by radical polymerization, and exhibit excellent properties such as heat resistance and abrasiveness, but give an extremely brittle cured product. As a method of improving this defect, a method of copolymerizing a monofunctional vinyl monomer is generally mentioned. However, there is much room for improvement because heat resistance is lowered.

As a method for solving the problems caused by curing shrinkage of these compounds, a method using an oligomer composition (Japanese Patent Application Laid-Open No. 1-254655) is known. Sex is not enough.

[Summary of the Invention]

(Problems to be Solved by the Invention) An object of the present invention is to solve the above-mentioned problems and to provide a resin for a lens which is lightweight, has a high refractive index, and is excellent in transparency, heat resistance and impact resistance. Things.

(Means for Solving the Problems) The present invention provides a sulfur-containing acrylic oligomer composition represented by the following formula (I).

Wherein R ₁ is H or CH ₃ , R ₂ , R ₃ is an alkylene group having 1 to 12 carbon atoms, or an oxydialkylene group having 2 to 12 carbon atoms, and R ₄ is CH ₂ CH ₂ S ₁ CH ₂ A CH ₂ — group (where l is an integer of 1 to 10), X represents Cl, Br, I, m is an integer of 0 to 4,
n is a non-zero number of 10 or less, which indicates the average degree of oligomerization. The oligomer composition of the present invention has the following general formula Wherein each symbol is as defined above. ] And a monomer of the following general formula which is chain-extended with a group for enhancing impact resistance Wherein each symbol is as defined above, and n ′ is an integer of 1 or more. And an average degree of oligomerization of 10 or less, preferably 5 or less, more preferably 0.1 or less.
-1.

If the average degree of oligomerization n is too small, the impact resistance is not improved, and the improvement by oligomerization is not remarkable. On the other hand, if n is too large, handling becomes extremely difficult due to an increase in viscosity accompanying the increase in molecular weight.

In the oligomer represented by the formula (I), R ₂ , R ₃
As the alkylene group represented by, for example, methylene,
Examples include ethylene, butylene, hexylene, and octylene groups. Among these, a group having 4 or less carbon atoms is preferable.

Examples of the oxydialkylene group include oxydimethylene, methyleneoxyethylene, methylenebisoxyethylene, and oxydipropylene group. Among them, those having 2 to 6 carbon atoms are preferable, and those having 4 carbon atoms are preferable.
Are more preferred.

R ₄ is a group represented by CH ₂ CH ₂ S ₁ CH ₂ CH ₂ —
It is an integer of 10, preferably 1-3.

The oligomer composition of the present invention is described in the above-mentioned JP-A-1-254655.
The diol oligomer obtained from a dihalogen compound, a dimercaptan compound, and a hydroxyl group-containing mercaptan compound by a method similar to the method described in Japanese Patent Application Laid-Open Publication No. H11-15095 is converted to a (meth) acrylic ester.

In particular, [Wherein, R ₁ , R ₂ , R ₃ , R ₄ , X, m and n represent the same meaning as in the above formula (I). Y is chlorine, a hydroxyl group, a (meth) acryloyl residue, or an alkoxy group. Synthesis of Terminal Dihalogen Oligomers A dihalogen compound represented by the above formula (II) and a dimethylcaptan compound represented by the above formula (III) are converted into ((II)
/ (III) (molar ratio)> 1), a known method (for example,
By reacting according to Shunsuke Murahashi et al., Synthetic Polymer IV, p. 356), dihalogen-terminated oligomer (IV) can be obtained.

Examples of the dihalogen compound represented by the formula (II) include α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α '-Dibromo-p-xylene, α, α',
2,3,5,6-hexachloro-p-xylene, α, α ', 2,3,
5,6-hexabromo-p-xylene, p-bis (β-chloroethyl) benzene, m-bis (β-chloroethyl)
Benzene, o-bis (β-chloroethyl) benzene, p
-Bis (β-chloroethyl) tetrachlorobenzene, p
-Bis (β-bromoethyl) tetrabromobenzene, p
-(6-chlorohexyl) benzene, p-bis (10-chlorooctyl) benzene and the like are exemplified.

Examples of the dimercaptan compound having a group represented by CH ₂ CH ₂ S ₁ CH ₂ CH ₂ — of formula (III) include di (mercaptoethyl) sulfide, 1,2-di (2-mercaptoethylthio) ethane, Di (mercaptoethylthioethyl)
Sulfide and the like.

The reaction between the dihalogen compound and the dimercaptan compound is carried out according to a desired value of the average n value of the oligomer.
The dimercaptan compound is compounded in an amount of 0.09 (corresponding to n = 0.1) to 0.91 (corresponding to n = 10) mol, preferably 0.09 to 0.5 (corresponding to n = 1) mol per mol of the dihalogen compound. Let react.

As a solvent in this reaction, for example, water or a halogen-based solvent such as alcohols, ketones, methylene chloride, and chloroform alone or mixed with water
Use 500-1000 ml. The reaction temperature is from 50 ° C to 100 ° C, preferably from 70 ° C to 90 ° C. As the neutralizing agent, a metal salt such as potassium carbonate or sodium hydroxide is used in an amount equal to or larger than the used dimercaptan compound.

In this reaction, first, a dimercaptan compound and a metal salt may be reacted in a solvent to separately synthesize a dimercaptan metal salt, and then reacted with a dihalogen compound.

After the reaction, the solvent is distilled off, washed with water and dried,
A terminal dihalogen oligomer is obtained. The composition of the obtained terminal dihalogen oligomer and the total number of moles are determined by the mixing ratio of the dihalogen compound and the dimercaptan compound, and can be confirmed by a liquid chromatograph or a molecular weight distribution analyzer.

Synthesis of Terminal Diol Organomer The obtained terminal dihalogen oligomer and the above-mentioned formula (V)
A hydroxyl group-containing mercaptan compound represented by the following formula (I) can be prepared by a known method (for example, Organic Sulfur Compounds, N. Kharasch. Vol. 1, 11).
(P. 97-111, U.S. Pat. No. 3,824,293) to give the terminal diol oligomer represented by the formula (VI). Examples of the hydroxyl group-containing mercaptan compound include, for example, 2-mercaptoethanol, 3-mercaptopropanol, 2-mercapto-1-methylethanol, 2-hydroxy-2′-mercaptoethyl ether, 2-hydroxy-2′-mercaptoethylsulfide, Triethylene glycol mercaptan, 6-mercaptohexanol and the like.

The reaction is carried out using a hydroxyl group-containing mercaptan compound in a molar ratio of 2 times or a slight excess with respect to the terminal dihalogen oligomer. As the solvent, the same solvent as the solvent for the synthesis reaction of the terminal dihalogen oligomer is used. The reaction temperature is 50 ° C to 110 ° C, preferably 70 ° C to 90 ° C.
Do with. As the neutralizing agent, a metal salt such as potassium carbonate, sodium hydroxide or the like is used in a half or excess molar ratio with respect to the hydroxyl group-containing mercaptan compound used.

In this reaction, the above-mentioned metal salt is used to neutralize the generated hydrochloric acid. After reacting the hydroxyl-containing mercaptan compound with these metal salts in a solvent to separately synthesize the hydroxyl-containing mercaptan metal salt, You may make it react with a dihalogen oligomer. After the reaction, the solvent is distilled off, washed with water, and dried to obtain a terminal diol oligomer represented by the above formula (VI).

This method can also be carried out without isolating the terminal dihalogen oligomer obtained by the above method. In this case, an appropriate amount of a hydroxyl group-containing mercaptan compound and a metal salt are added to the system in which the dihalogen compound and the dimercaptan compound have been reacted, and reacted. The metal salt may be added in an amount required for the reaction with the hydroxyl group-containing mercaptan compound at the time of the reaction between the dihalogen compound and the dimeric captan compound.
It is also possible to blend a dimercaptan compound and a hydroxyl group-containing mercaptan compound so that the average n value of the oligomer becomes a desired value, and obtain a terminal diol oligomer compound by one-step reaction.

The composition of the obtained terminal diol oligomer, the total number of moles, and the like can be confirmed by liquid chromatography or a molecular weight distribution analyzer.

Synthesis of sulfur-containing acrylic oligomer The sulfur-containing acrylic oligomer composition of the present invention can be obtained by reacting the terminal diol oligomer obtained as described above with the acylating agent represented by the above formula (VII). As the acylating agent, for example, carboxylic acid such as (meth) acrylic acid, (meth) acrylic acid chloride, (meth) methyl acrylate, (meth) acrylic anhydride, carboxylic acid halide, carboxylic acid ester, or And a carboxylic anhydride.

Here, (meth) acryl is used to mean both methacryl and acryl.

When a carboxylic acid is used as the acylating agent, a catalyst such as sulfuric acid,
Mineral products such as hydrochloric acid, aromatic sulfonic acids such as p-toluenesulfonic acid are used in an amount of 0.01 to 0.5 mol, and methacrylic acid and / or acrylic acid are used in an amount of 2 to 6 mol, preferably 2 to 3 mol. 500 to 1000 ml of toluene, etc.
The resulting water is removed from the system by azeotropic distillation. The reaction temperature is 60 ° C to 120 ° C, preferably 80 ° C to 1 ° C.
Perform at 10 ° C.

When a carboxylic acid ester is used as the acylating agent, as a catalyst, an organic metal complex such as titanium butoxide and potassium butoxide is used in an amount of 0.01 to 0.5 mol, for example,
Methyl methacrylate is 2 to 10 mol, preferably 4 to 6 mol.
React using 1000 ml. The reaction is carried out at a temperature of 60 to 120 ° C, preferably 80 to 110 ° C, and the formed alcohol is removed from the system by azeotropic distillation.

When a carboxylic anhydride is used as the acylating agent, the reaction can be carried out in the same manner as in the case of the carboxylic acid ester. The carboxylic acid generated is removed at the stage of post-treatment.

When an acid halide is used as the acylating agent,
The reaction is carried out using a nitrogen-containing organic base such as triethylamine, tributylamine, diisopropylamine, pyridine or the like as a catalyst in an amount of 2 to 6 mol, preferably 2 to 3 mol. The reaction is performed by mixing a diol oligomer with a nitrogen-containing organic base at -10 ° C to + 50 ° C, preferably at -10 ° C.
Keep at ~ 30 ° C and add the acid halide dropwise. For the above reaction, for example, a ketone-based solvent such as acetone and methyl ethyl ketone, a chlorine-based solvent such as chloroform and dichloromethane, and an ether-based solvent such as tetrahydrofuran and dioxane are preferably used.

After completion of the reaction, the reaction solution was washed with dilute hydrochloric acid, a dilute aqueous alkali solution, and water, and when a solvent was used, the solvent was distilled off.
The sulfur-containing (meth) acrylic oligomer composition of the present invention can be obtained. Incidentally, the n value of the oligomer composition is:
It can be adjusted by adding a monomer or blending oligomers having different n values.

The sulfur-containing (meth) acrylic oligomer composition of the present invention has a high refractive index of 1.60 or more, and is transparent, optically uniform, and excellent in impact resistance by being subjected to a polymerization reaction using a radical initiator. Give things. Further, it can be copolymerized with another radical polymerizable monomer. Examples of the radical polymerizable monomer include, for example, styrene, vinyltoluene, methoxystyrene, chlorostyrene, divinylbenzene, vinyl acetate, vinyl compounds such as vinyl chloride, methyl methacrylate, phenyl acrylate, chlorophenyl methacrylate, benzyl methacrylate, and 2-hydroxyethyl. (Meth) acrylic compounds such as methacrylate, glycidyl methacrylate, trimethylolpropane triacrylate, epoxy acrylate, diethylene glycol bisallyl carbonate, diallyl phthalate, diallyl epoxy succinate,
And allyl compounds such as allylphenylsilane and diallyldimethylsilane.

Further, the radical initiator used in the polymerization is not particularly limited, and a general initiator can be used. For example,
Peroxides such as benzoyl peroxide, diisopropyl peroxycarbonate, tertiary butyl peroxyisopropyl carbonate, ditertiary butyl peroxide, azo compounds such as azobisisobutyronitrile, benzophenone, benzoin, benzoin ethyl ether,
Photosensitizers such as benzyl, acetophenone, anthracene, α-chloromethylnaphthalene, 1-hydroxycyclohexylphenylketone, benzyldimethylketal, and p-toluyldiphenylphosphine oxide; and sulfur compounds such as diphenylsulfide and thiocarbamate.

〔Example〕

In order to better explain the present invention below, specifically,
1 shows an embodiment of the present invention. The parts in the examples are parts by weight.

Production Example 1 10 equipped with a stirrer, thermometer, dropping funnel, and cooling tube
In a 00 ml four-necked flask, 100 parts of α, α'-dichloro-p-xylene, di (mercaptoethyl) sulfide 29
Parts, potassium carbonate 170 parts, and methyl ethyl ketone 500
Then, the temperature of the solution was raised to 82 to 83 ° C. while stirring, and reflux was performed for 3 hours. Then, with stirring,
After 75 parts of mercaptoethanol was added dropwise, the mixture was refluxed for 3 hours. After the reaction, the solvent was distilled off, washed with water, and dried with hot air to obtain a sulfur-containing terminal diol oligomer represented by the following formula.

The product is a white powdery solid and the yield is 138 parts (94
%)Met. From the results of high performance liquid chromatography and the like, the average n value of the oligomer was 0.50.

Production Examples 2 to 7 In the same manner as in Production Example 1 with the composition shown in Table (1),
A sulfur-containing terminal diol oligomer was obtained. The results are shown in Table (1).

Example 1 In a 1000 ml four-necked flask equipped with a stirrer, a thermometer, and a separator equipped with a condenser, 138 parts of the sulfur-containing terminal diol oligomer obtained in Production Example 1, 264 parts of methyl methacrylate, polymerization inhibition 0.2 parts of p-methoxyphenol and 2 parts of N, N-diethylhydroxylamine as an agent and 150 parts of toluene as a solvent were charged, and the reaction system was stirred for 8 hours.
After the temperature was raised to 0 ° C, transesterification was performed by adding a titanium butoxide portion. The produced methanol was removed out of the system by azeotropic distillation with methyl methacrylate. Next, the reaction solution was transferred to a separating funnel, 300 parts of toluene was added, and the mixture was washed with dilute hydrochloric acid and a dilute alkali aqueous solution, and then washed with water until neutral. This was dehydrated with anhydrous magnesium sulfate, filtered, and the solvent toluene was distilled off under reduced pressure to obtain a sulfur-containing dimethacrylate oligomer represented by the following formula.
The product is a clear, colorless liquid with a yield of 165 parts (88%).
Met.

The average n value of the oligomer composition was 0.5.

Example 2 A sulfur-containing dimethacrylate oligomer represented by the following formula was prepared in the same manner as in Example 1, except that 138 parts of the terminal diol oligomer obtained in Production Example 2 was used instead of 138 parts of the terminal diol oligomer in Example 1. I got

The product was a clear, colorless liquid with a yield of 153 parts (88
%)Met. The average n value in the oligomer was 1.0
Met.

Example 3 A sulfur-containing dimethacrylate oligomer represented by the following formula was obtained in the same manner as in Example 1, except that 146 parts of the terminal diol oligomer obtained in Production Example 3 was used.

The product was a clear, colorless liquid with a yield of 166 parts (82
%)Met. The average n value in the oligomer was 0.3
Met.

Example 4 A sulfur-containing dimethacrylate oligomer represented by the following formula was obtained in the same manner as in Example 1 except that 153 parts of the terminal diol oligomer obtained in Production Example 4 was used.

The product is a clear, colorless liquid with a yield of 179 parts (85
%)Met. The average n value in the oligomer was 0.3
Met.

Example 5 A sulfur-containing dimethacrylate oligomer represented by the following formula was obtained in the same manner as in Example 1, except that 138 parts of the terminal diol oligomer obtained in Production Example 5 was used.

The product is a clear, colorless liquid with a yield of 170 parts (91
%)Met. The average n value of the oligomer composition was 0.5.

Example 6 The procedure of Example 1 was repeated except for using 119 parts of the terminal diol oligomer obtained in Production Example 6, to obtain a sulfur-containing dimethacrylate oligomer represented by the following formula.

The product is a clear, colorless liquid with a yield of 125 parts (82
%)Met. The average n value of the oligomer composition was 0.2.

Example 7 A sulfur-containing dimethacrylate oligomer represented by the following formula was obtained in the same manner as in Example 1, except that 175 parts of the terminal diol oligomer obtained in Production Example 7 was used.

The product is a clear and colorless liquid with a yield of 176 parts (76
%)Met. The average n value in the oligomer was 0.3
%Met.

Example 8 217 parts of the sulfur-containing dimethacrylate obtained in Example 2 and 132 parts of p-bis (β-methacryloyloxyethylthio) xylene represented by the following formula were mixed, and the average n value of the oligomer was 0.5. A colorless transparent liquid was obtained.

Application Example 1 Sulfur-containing acrylic oligomer 10 obtained in Example 1
The mixture obtained by adding 0 parts and 0.5 parts of benzoyl peroxide was poured into a mold composed of a silicone rubber spacer and two glass plates.
The polymerization was carried out by raising the temperature over 2 hours. The cured product taken out of the mold had no optical distortion and had good light transmittance and hardness.

Application Examples 2 to 8 The sulfur-containing dimethacrylate oligomers obtained in Examples 2 to 8 were polymerized and cured in the same manner as in Application Example 1. All the obtained cured products have no optical distortion,
Both translucency and hardness were good.

Comparative Example 1 Sulfur-containing acrylic oligomer 10 obtained in Example 1
Polymerization and curing were carried out in the same manner as in Application Example 1, except that 100 parts by weight of p-bis (β-methacryloyloxyethylthio) xylylene was used instead of 0 parts by weight.

Comparative Example 2 A sulfur-containing dimethacrylate oligomer represented by the following formula was synthesized according to JP-A-1-254655, and 100 parts by weight of the oligomer was replaced with 100 parts by weight of the sulfur-containing acrylic oligomer obtained in Example 1. Polymerization and curing were carried out in the same manner as in Application Example 1 except that was used.

Table 2 shows the specific gravity, refractive index, Abbe number, and results of the falling ball test of the cured products obtained in Application Examples 1 to 8 and Comparative Examples 1 and 2.

In the ball drop test, a steel ball of 16 g was naturally dropped from a height of 127 cm to a hardened product having a thickness of 2 mm based on the FDA standard.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁶ identification code FI G03F 7/027 511 G03F 7/027 511 (58) Field surveyed (Int.Cl. ⁶ , DB name) C07C 323/00 C08G 75 / 00 C08F 299/00 C08F 20/00 REGISTRY (STN) CA (STN)

Claims (1)

(57) [Claims] 1. A sulfur-containing acrylic oligomer composition represented by the following formula: Wherein R ₁ is H or CH ₃ , R ₂ , R ₃ is an alkylene group having 1 to 12 carbon atoms, or an oxydialkylene group having 2 to 12 carbon atoms, and R ₄ is CH ₂ CH ₂ S ₁ CH ₂ A CH ₂ — group (where l is an integer of 1 to 10), X represents Cl, Br, I, m is an integer of 0 to 4,
n is a non-zero number of 10 or less, which indicates the average degree of oligomerization. ]