JPH0359062B2 - - Google Patents
Info
- Publication number
- JPH0359062B2 JPH0359062B2 JP26544087A JP26544087A JPH0359062B2 JP H0359062 B2 JPH0359062 B2 JP H0359062B2 JP 26544087 A JP26544087 A JP 26544087A JP 26544087 A JP26544087 A JP 26544087A JP H0359062 B2 JPH0359062 B2 JP H0359062B2
- Authority
- JP
- Japan
- Prior art keywords
- resins
- present
- spectrum
- refractive index
- optical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 mercaptoethylthio Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Eyeglasses (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
＜産業上の利用分野＞
本発明は下記一般式（）で示される光学用プ
ラスチツク原料として有用な新規チオールカルボ
ン酸エステルに関する。
（Ｘは、ＯまたはＳを示し、ｎは２または３を示
す。）
＜従来の技術＞
無機光学レンズに替る素材として、透明性合成
樹脂よりなる高屈折率レンズ用樹脂はその軽量性
や耐衝撃性・成型加工性・染色性が良好なことか
ら、プラスチツクレンズ原料として適用分野を拡
大しつつある。
従来、プラスチツクレンズ材料として用いられ
ている樹脂としては、ジエチレングリコールビス
アリルカーボネート樹脂、ポリメチルメタクリレ
ート、ポリカーボネートが一般に用いられている
が、ジエチレングリコールビスアリルカーボネー
ト樹脂およびポリメチルメタクリレートは屈折率
が1.49〜1.50と小さいため、これらの樹脂をプラ
スチツクレンズに成型すると、無機光学ガラスレ
ンズに比較して、中心厚、コバ厚および曲率が大
きくなる欠点があつた。また、ポリカーボネート
は屈折率は1.58〜1.59と高いが成型時に複屈折が
生じやすく光学的均一性において欠点があつた。
また、ビニルナフタレンやビニルカルバゾール
は高屈折率な樹脂を与えるが、得られる樹脂は分
散が大きい、着色が著しい等光学用プラスチツク
レンズ用樹脂として満足できるものではなかつ
た。
＜発明が解決しようとする問題点＞
以上説明したように、従来の光学用プラスチツ
ク材料は種々の欠点を有しており改善が望まれて
いる。そこで本発明の目的も光学用プラスチツク
材料として有用な高屈折率で透明性の優れた樹脂
を与える単量体を提供することにある。
＜問題点を解決するための手段＞
本発明者らは、上記目的を達成するために、検
討を重ねた結果本発明に至つた。すなわち、本発
明は文献未載の下記一般式（）で示される新規
チオールカルボン酸エステルを提供するものであ
る。
（Ｘは、ＯまたはＳを示し、ｎは２または３を示
す。）
本発明化合物は次式（）に示したようにジチ
オール誘導体とメタクリル酸誘導体とを反応させ
ることによつて製造できる。
（但し、式中ＸはＯまたはＳを、ｎは２または３
を示し、ＹはCl、Br、OHまたはC1〜C4のアルコ
キシ基を示す。）
＜発明の効果＞
本発明によつて提供される前記一般式（）で
示される新規なチオールカルボン酸エステルは、
それぞれ自体で重合させるか、または各種のオレ
フイン性二重結合を有する化合物と共重合させる
ことによつてポリマーやオリゴマーを得ることが
できる。そして、本発明の新規化合物を主成分と
する樹脂は高屈折率で透明性に優れ、しかも三次
元架橋体であるので、切削、研磨等の加工性が良
好であり、光学用プラスチツクとして好適であ
る。また、これらのポリマーやオリゴマーは、金
属やガラスとの密着性の向上剤としても用いるこ
とができる。
＜実施例＞
以下、本発明を実施例により具体的に説明す
る。
実施例 １
撹拌機、温度計、ジムロート型冷却管及び滴下
漏斗を備えた容量500mlのガラス製フラスコにト
リオクチルメチルアルモニウムクロライド2.44
ｇ、フエノチアジン0.19ｇ及びクロロホルム219
ｇを仕込んだ。内温を10℃以下に保ちながら、別
途調整しておいた１，２−ビス−（２−メルカプ
トエトキシ）エタン22.0ｇと7.5重量％水酸化カ
リウム水溶液319ｇとを混合した液とメタクル酸
クロライド30.3ｇとを別々の滴下漏斗より同時に
20分間で滴下した。
滴下終了後、更に同温度で30分間撹拌を続けた
後、反応溶液を二層分液した。クロロホルム層を
５重量％水酸化カリウム水溶液、水の順に洗浄し
た後、無水硫酸ナトリウムで乾燥した。クロロホ
ルムを留去することによりチオールカルボン酸エ
ステル１34.3ｇ（収率89.3％）を得た。
このものは更にシリカゲルカラムクロマトグラ
フイーによつて精製した。この新規物質は、元素
分析、質量分析スペクトルおよび赤外線吸収スペ
クトルの特性吸収より構造決定した。その結果を
表−１に示した。更に、赤外線吸収スペクトルを
第１図に 1H−NMRスペクトルを第２図に、
13C−NMRスペクトルを第３図に示した。
実施例 ２
実施例１と同様な方法で、ビス−２−（２−メ
ルカプトエトキシ）エチルエーテルとメタクリル
酸クロライドとから新規物質２を製造した。収率
は84.0％であつた。この新規物質は更にシリカゲ
ルカラムクロマトグラフイーにより精製したの
ち、元素分析、質量分析スペクトルおよび赤外線
吸収スペクトルの特性吸収より構造決定した。そ
の結果を表−１に示した。
実施例 ３
実施例１と同様な方法で１，２−ビス−（２−
メルカプトエチルチオ）エタンとメタクリル酸ク
ロライドとから新規物質３を製造した。収率は
88.7％であつた。この新規物質は更にシリカゲル
カラムクロマトグラフイーにより精製したのち元
素分析、質量分析スペクトルおよび赤外線吸収ス
ペクトルの特性吸収より構造決定した。その結果
を表−１に示した。
実施例 ４
実施例１と同様な方法でビス−２−（２−メル
カプトエチルチオ）エチルスルフイドとメタクリ
ル酸クロライドとから新規物質４を製造した。収
率は82.5％であつた。この新規物質は更にシリカ
ゲルカラムクロマトグラフイーにより精製したの
ち元素分析、質量分析スペクトルおよび赤外線吸
収スペクトルの特性吸収より構造決定した。その
結果を表−１に示した。
【表】DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel thiol carboxylic acid ester represented by the following general formula () and useful as a raw material for optical plastics. (X represents O or S, and n represents 2 or 3.) <Prior art> As a material to replace inorganic optical lenses, high refractive index lens resins made of transparent synthetic resins are lightweight and durable. Due to its good impact resistance, moldability, and dyeability, its application as a raw material for plastic lenses is expanding. Conventionally, diethylene glycol bisallyl carbonate resin, polymethyl methacrylate, and polycarbonate are generally used as resins for plastic lens materials, but diethylene glycol bisallyl carbonate resin and polymethyl methacrylate have a refractive index of 1.49 to 1.50. Because of their small size, when these resins are molded into plastic lenses, they have the disadvantage that the center thickness, edge thickness, and curvature are larger than inorganic optical glass lenses. Furthermore, although polycarbonate has a high refractive index of 1.58 to 1.59, it tends to cause birefringence during molding and has a drawback in terms of optical uniformity. Furthermore, although vinylnaphthalene and vinyl carbazole provide resins with high refractive index, the resulting resins have large dispersion and significant coloration, and are not satisfactory as resins for optical plastic lenses. <Problems to be Solved by the Invention> As explained above, conventional optical plastic materials have various drawbacks, and improvements are desired. Therefore, it is an object of the present invention to provide a monomer that provides a resin with a high refractive index and excellent transparency that is useful as an optical plastic material. <Means for Solving the Problems> In order to achieve the above object, the present inventors have conducted repeated studies and have arrived at the present invention. That is, the present invention provides a novel thiol carboxylic acid ester represented by the following general formula (), which has not been described in any literature. (X represents O or S, and n represents 2 or 3.) The compound of the present invention can be produced by reacting a dithiol derivative and a methacrylic acid derivative as shown in the following formula (). (However, in the formula, X is O or S, and n is 2 or 3.
and Y represents Cl, Br, OH or a C1 to C4 alkoxy group. ) <Effects of the Invention> The novel thiol carboxylic acid ester represented by the general formula () provided by the present invention is
Polymers and oligomers can be obtained by polymerizing each by itself or by copolymerizing with compounds having various olefinic double bonds. The resin containing the new compound of the present invention as a main component has a high refractive index and excellent transparency, and since it is a three-dimensional crosslinked product, it has good processability in cutting, polishing, etc., and is suitable as an optical plastic. be. Furthermore, these polymers and oligomers can also be used as adhesion improvers with metals and glass. <Examples> Hereinafter, the present invention will be specifically explained using examples. Example 1 In a 500 ml glass flask equipped with a stirrer, thermometer, Dimroth condenser and addition funnel, 2.44 g of trioctylmethylalmonium chloride was added.
g, phenothiazine 0.19 g and chloroform 219
I prepared g. While keeping the internal temperature below 10°C, a mixture of 22.0 g of 1,2-bis-(2-mercaptoethoxy)ethane and 319 g of a 7.5% by weight aqueous potassium hydroxide solution, which had been prepared separately, was mixed with 30.3 g of methacrylic acid chloride. g and at the same time from separate dropping funnels.
It was added dropwise over 20 minutes. After the dropwise addition was completed, stirring was continued for an additional 30 minutes at the same temperature, and then the reaction solution was separated into two layers. The chloroform layer was washed with a 5% by weight aqueous potassium hydroxide solution and then with water, and then dried over anhydrous sodium sulfate. By distilling off the chloroform, 134.3 g (yield: 89.3%) of thiol carboxylic acid ester was obtained. This product was further purified by silica gel column chromatography. The structure of this new substance was determined by elemental analysis, mass spectrometry spectrum, and characteristic absorption in infrared absorption spectrum. The results are shown in Table-1. Furthermore, the infrared absorption spectrum is shown in Figure 1, the 1 H-NMR spectrum is shown in Figure 2,
The 13 C-NMR spectrum is shown in Figure 3. Example 2 In the same manner as in Example 1, novel substance 2 was produced from bis-2-(2-mercaptoethoxy)ethyl ether and methacrylic acid chloride. The yield was 84.0%. This new substance was further purified by silica gel column chromatography, and its structure was determined by elemental analysis, mass spectrometry spectrum, and characteristic absorption in infrared absorption spectrum. The results are shown in Table-1. Example 3 1,2-bis-(2-
New substance 3 was prepared from mercaptoethylthio)ethane and methacrylic acid chloride. The yield is
It was 88.7%. This new substance was further purified by silica gel column chromatography, and its structure was determined by elemental analysis, mass spectrometry spectrum, and characteristic absorption in infrared absorption spectrum. The results are shown in Table-1. Example 4 New substance 4 was produced from bis-2-(2-mercaptoethylthio)ethyl sulfide and methacrylic acid chloride in the same manner as in Example 1. The yield was 82.5%. This new substance was further purified by silica gel column chromatography, and its structure was determined by elemental analysis, mass spectrometry spectrum, and characteristic absorption in infrared absorption spectrum. The results are shown in Table-1. 【table】
第１図は実施例１で得られた新規物質１の
TMS基準に従つた重クロロホルム溶媒における
1H−NMRスペクトル図である。第２図は実施例
１で得られた新規物質１のTMS基準に従つた重
クロロホルム溶媒における 13C−NMRスペクト
ル図である。第３図は実施例１で得られた新規物
質１のNaCl板上における赤外線吸収スペクトル
図である。
Figure 1 shows the new substance 1 obtained in Example 1.
in deuterated chloroform solvent according to TMS standards.
FIG. 1 is a 1 H-NMR spectrum diagram. FIG. 2 is a 13 C-NMR spectrum diagram of novel substance 1 obtained in Example 1 in deuterated chloroform solvent according to TMS standards. FIG. 3 is an infrared absorption spectrum diagram of the novel substance 1 obtained in Example 1 on a NaCl plate.
Claims (1)
ルボン酸エステル。 （Ｘは、ＯまたはＳを示し、ｎは２または３を示
す。）[Claims] 1. A novel thiol carboxylic acid ester represented by the following general formula (). (X represents O or S, and n represents 2 or 3.)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26544087A JPH01110666A (en) | 1987-10-22 | 1987-10-22 | Novel thiolcarboxylic acid ester |
| US07/135,045 US4810812A (en) | 1986-12-26 | 1987-12-18 | Thiolcarboxylic acid esters |
| EP87311203A EP0273661B1 (en) | 1986-12-26 | 1987-12-18 | Thiolcarboxylic acid esters |
| AT87311203T ATE54909T1 (en) | 1986-12-26 | 1987-12-18 | ESTERS OF THIOLCARBOXYLIC ACIDS. |
| DE8787311203T DE3763968D1 (en) | 1986-12-26 | 1987-12-18 | ESTER OF THIOL CARBOXYL ACIDS. |
| AU82869/87A AU593416B2 (en) | 1986-12-26 | 1987-12-21 | Thiolcarboxylic acid esters |
| AU82945/87A AU603404B2 (en) | 1986-12-26 | 1987-12-22 | Resin having high refractive index, process for producing said resin and optical materials composed of said resin |
| CA000555242A CA1267909A (en) | 1986-12-26 | 1987-12-23 | Thiolcarboxylic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26544087A JPH01110666A (en) | 1987-10-22 | 1987-10-22 | Novel thiolcarboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01110666A JPH01110666A (en) | 1989-04-27 |
| JPH0359062B2 true JPH0359062B2 (en) | 1991-09-09 |
Family
ID=17417181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26544087A Granted JPH01110666A (en) | 1986-12-26 | 1987-10-22 | Novel thiolcarboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01110666A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2030797A1 (en) | 2007-08-25 | 2009-03-04 | Mondi Business Paper Services AG | Optically and thermally writeable nano coating |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2546887B2 (en) * | 1989-02-07 | 1996-10-23 | 株式会社トクヤマ | Thiocarboxylic acid ester compound and method for producing the same |
| DE4234253A1 (en) * | 1992-10-10 | 1994-04-14 | Roehm Gmbh | Monomers for highly refractive plastics |
| JP3556027B2 (en) * | 1995-11-09 | 2004-08-18 | 三井化学株式会社 | Sulfur-containing (meth) acrylate compounds and uses thereof |
| KR20020062712A (en) * | 2002-06-29 | 2002-07-29 | 김상균 | Plastic vessel wrapped with a paper cover and paper cover for a glass cup |
| KR101626472B1 (en) | 2011-09-05 | 2016-06-01 | 닛산 가가쿠 고교 가부시키 가이샤 | Resin composition |
-
1987
- 1987-10-22 JP JP26544087A patent/JPH01110666A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2030797A1 (en) | 2007-08-25 | 2009-03-04 | Mondi Business Paper Services AG | Optically and thermally writeable nano coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01110666A (en) | 1989-04-27 |
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