JPS63162667A - Novel brominated sulfur-containing methacrylic ester - Google Patents
Novel brominated sulfur-containing methacrylic esterInfo
- Publication number
- JPS63162667A JPS63162667A JP30833586A JP30833586A JPS63162667A JP S63162667 A JPS63162667 A JP S63162667A JP 30833586 A JP30833586 A JP 30833586A JP 30833586 A JP30833586 A JP 30833586A JP S63162667 A JPS63162667 A JP S63162667A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- sulfur
- compound
- expressed
- optical plastic
- 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.)
- Pending
Links
- 150000003463 sulfur Chemical class 0.000 title claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 title 1
- 239000000126 substance Substances 0.000 claims description 6
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 brominated sulfur methacrylate ester Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- UHHUIHRNUYPDSK-UHFFFAOYSA-N 2-methylprop-2-enoic acid sulfane Chemical class S.CC(=C)C(O)=O.CC(=C)C(O)=O UHHUIHRNUYPDSK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 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 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は下記式（１）で示される光学用プラスチック原
料として有用な新規な臭素化合イオウメタクリル酸エス
テルに関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel brominated sulfur methacrylate ester represented by the following formula (1) and useful as a raw material for optical plastics.
〈従来の技術〉
近年、無機光学材料に替る素材として、透明性合成樹脂
よりなる高屈折率樹脂は、その軽量性、耐衝撃性、成型
加工性、染色性が良好なことから光学用プラスチック材
料として適用分野を拡大しつつある。<Conventional technology> In recent years, high refractive index resins made of transparent synthetic resins have been used as optical plastic materials as an alternative to inorganic optical materials due to their light weight, impact resistance, moldability, and dyeability. The field of application is expanding as a result.
しかし、従来の光学用プラスチック材料として用いられ
ているジエチレングリコールビスアリルカーボネート樹
脂は屈折率が１．４９〜１．５０と低いため、これから
得られる樹脂を、例えば眼鏡用レンズにすると無機光学
レンズに比較して中心厚、コバ厚が大きくなる欠点があ
った。However, diethylene glycol bisallyl carbonate resin, which is used as a conventional optical plastic material, has a low refractive index of 1.49 to 1.50, so if the resin obtained from this resin is used to make lenses for eyeglasses, for example, it will be compared to inorganic optical lenses. However, there was a drawback that the center thickness and edge thickness became large.
〈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ック材料は
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ッ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。<Problems to be Solved by the Invention> As explained above, conventional optical plastic materials have various drawbacks, and improvements are desired. Therefore, an object of the present invention is to provide a monomer that provides a resin with a high refractive index and excellent transparency that is useful as an optical plastic material.
〈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、検肘を重ね
た結果本発明に至った。すなわち、本発明は下記式〇）
で示される新規な臭素化合イオウメルメタクリレートを
提供するものである。<Means for Solving the Problems> In order to achieve the above object, the present inventors conducted repeated elbow tests and arrived at the present invention. That is, the present invention is based on the following formula 〇)
The present invention provides a novel brominated sulfur methacrylate represented by:
本発明化合物（１）は、ジシクロペンタジェンと２−メ
ルカプトエタノールの反応物を臭素化し、メタクリル酸
訪導体と反応させるととくよって製造できる。（下記式
（ＩＩ）、ｌ）参照）（ＸＦｉＩ（またはアルカリ金属
を示す。）〈発明の効果〉
本発明によって提供される前記式（１）で示される新規
なメタクリル酸エステルは、それ自体で重合させるか、
ま九は各種のオレフィン性二重結合を有する化合物と共
重合させることによって、側鎖に臭素、イオウ原子を含
む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
明性に優れているので光学用プラスチックとして好適で
ある。The compound (1) of the present invention can be produced by brominating a reaction product of dicyclopentadiene and 2-mercaptoethanol and reacting it with a methacrylic acid visiting conductor. (See formula (II), l) below) (XFiI (or represents an alkali metal)) <Effects of the Invention> The novel methacrylic acid ester represented by the above formula (1) provided by the present invention is itself polymerize or
By copolymerizing Maku with various compounds having olefinic double bonds, polymers and oligomers containing bromine and sulfur atoms in side chains can be obtained. and,
The resin containing the novel compound of the present invention as a main component has a high refractive index and excellent transparency, and is therefore suitable as an optical plastic.
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や樹脂の難燃化剤としても用いるこ
とができる。Moreover, these polymers and oligomers can also be used as adhesion improvers with metals and glass, and flame retardants for resins.
〈実施例〉 以下、本発明を実施例により具体的に説明する。<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.
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５００ｄのガラス製フラスコにジシクロペンタ
ジェン１００．９を予め仕込んでおいた。内温を１０℃
以下に保ち、系内を撹拌しながら、２−メルカプトエタ
ノール５９．１．Ｆを３０分間で滴下した。滴下終了後
、内温が２５℃になるまで加温し、更に２時間同温度で
撹拌を続は反応した。この反応生成物４５． ＯＮとク
ロロホルム３５０３１／を撹拌機、温度計、ジムロート
型冷却管及び滴下漏斗を備えた容量５００ｄのガラス製
フラスコに仕込み、室温下で撹拌を続けながら臭素６８
．４Ｊ’を２時間で滴下した。滴下終了後、１時間撹拌
を続けた後、反応溶液を亜硫酸水素す） ＩＪウム水溶
液にあけ、クロロホルム層を水酸化ナトリウム水溶液、
水の順で洗浄し、得られたクロロホルム層を無水硫酸ナ
トリウムで乾燥した。クロロホルムを留去し、得られた
反応生成物をシリカゲルカラムクロマトグラフィーにょ
夛精製した。Example 1 A glass flask with a capacity of 500 d equipped with a stirrer, a thermometer, a Dimroth type condenser, and a dropping funnel was charged with 100.9 g of dicyclopentadiene in advance. Internal temperature 10℃
While stirring the system, 2-mercaptoethanol 59.1. F was added dropwise over 30 minutes. After the dropwise addition was completed, the mixture was heated until the internal temperature reached 25°C, and the mixture was stirred at the same temperature for an additional 2 hours to continue the reaction. This reaction product 45. ON and chloroform 35031 were placed in a 500 d glass flask equipped with a stirrer, a thermometer, a Dimroth condenser, and a dropping funnel, and bromine 68 was added while stirring at room temperature.
．． 4J' was added dropwise over 2 hours. After the addition was completed, stirring was continued for 1 hour, the reaction solution was poured into an aqueous solution of hydrogen sulfite, and the chloroform layer was poured into an aqueous solution of sodium hydroxide,
The chloroform layer obtained was washed successively with water and dried over anhydrous sodium sulfate. Chloroform was distilled off, and the resulting reaction product was purified by silica gel column chromatography.
収量ｓｓ、ｏＩＩ（収率７０．２％）。Yield ss, oII (yield 70.2%).
次に、この反応生成物６５．ＯＩＩ、メタクリル酸カリ
ウム１８．６Ｆ、ジメチルスルホキシド４００ｍ１およ
びフェノチアジンｏ、 ｏ ｓ ＩＩを、撹拌機、温度
計、ジムロート型冷却器を備えた容量５００ｍＪのガラ
ス製フラスコに仕込んだ。次いで、撹拌しなから内温１
０〜１５℃で５時間反応させた。反応溶液を５００ｄの
水にあけ、ジエチルエーテル３００ｍ＋／で３回抽出し
た。エーテル層を水で充分洗浄した後、無水硫酸ナトリ
ウムで乾燥した。エーテルを留去し、得られた反応生成
物をシリカゲルカラムクロマトグラフィーにより精製し
前記式（１）の新規臭素化含イオウメタクリル敵エステ
ルを得た。収量４３．９Ｎ（収率６６．７％）。Next, this reaction product 65. OII, 18.6 F potassium methacrylate, 400 ml of dimethyl sulfoxide, and phenothiazine o, o s II were charged into a 500 mJ capacity glass flask equipped with a stirrer, thermometer, and Dimroth type condenser. Then, without stirring, the internal temperature
It was made to react at 0-15 degreeC for 5 hours. The reaction solution was poured into 500 ml of water and extracted three times with 300 ml of diethyl ether. The ether layer was thoroughly washed with water and then dried over anhydrous sodium sulfate. The ether was distilled off, and the resulting reaction product was purified by silica gel column chromatography to obtain a novel brominated sulfur-containing methacrylate ester of formula (1). Yield: 43.9N (yield: 66.7%).
次に得られたこの新規物質の構造決定のための分析結果
を示す。Next, we will show the analysis results for determining the structure of this new substance.
０沸 点 １９５〜１９６℃／ １．５〜２．０ ｍｉ
（ｇ０元素分析値
Ｃ（％） Ｈ（％） Ｓ（％）Ｂｒ（％）理論値 ４
３．８６ ５．０６ ７．３１ ３６．４７分析値 ４
３．６１ ５．２０ ７．４４ ３６．２８なおこの
新規物質のＩＨ−ＮＭＲスペクトルを第１図に、ｌａｃ
−ＮＭＲスペクトル図を第２図に、赤外線吸収スペクト
ルを第３図に示す。0 boiling point 195~196℃/1.5~2.0 mi
(g0 elemental analysis value C (%) H (%) S (%) Br (%) theoretical value 4
3.86 5.06 7.31 36.47 Analysis value 4
3.61 5.20 7.44 36.28 The IH-NMR spectrum of this new substance is shown in Figure 1.
-NMR spectrum diagram is shown in Fig. 2, and infrared absorption spectrum is shown in Fig. 3.
第１図は実施例１で得られた新規物質のＴＭＳ基準に従
った重クロロホルム溶媒におけるｔＨ−ＮＭＲスペクト
ル図である。
第１図は実施例１で得られた新規物質のＴＭＳ基準に従
った重クロロホルム溶媒におけるＩＩＣ−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のＮａＣ１板上に
おける赤外線吸収スペクトル図である。FIG. 1 is a tH-NMR spectrum diagram of the new substance obtained in Example 1 in deuterated chloroform solvent according to TMS standards. FIG. 1 is an IIC-NMR spectrum diagram of the new substance obtained in Example 1 in deuterated chloroform solvent according to TMS standards. FIG. 3 is an infrared absorption spectrum diagram of the new substance obtained in Example 1 on a NaCl plate.
Claims (1)
酸エステル。 ▲数式、化学式、表等があります▼(1) A novel brominated sulfur-containing methacrylic acid ester represented by the following formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30833586A JPS63162667A (en) | 1986-12-26 | 1986-12-26 | Novel brominated sulfur-containing methacrylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30833586A JPS63162667A (en) | 1986-12-26 | 1986-12-26 | Novel brominated sulfur-containing methacrylic ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63162667A true JPS63162667A (en) | 1988-07-06 |
Family
ID=17979819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30833586A Pending JPS63162667A (en) | 1986-12-26 | 1986-12-26 | Novel brominated sulfur-containing methacrylic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63162667A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659649A (en) * | 2012-04-17 | 2012-09-12 | 黑龙江省科学院大庆分院 | Method for synthesis of polyfunctional dicyclopentadienyl ether |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4377707A (en) * | 1981-12-17 | 1983-03-22 | The Dow Chemical Company | Halogenated (meth) acrylate compounds |
-
1986
- 1986-12-26 JP JP30833586A patent/JPS63162667A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4377707A (en) * | 1981-12-17 | 1983-03-22 | The Dow Chemical Company | Halogenated (meth) acrylate compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659649A (en) * | 2012-04-17 | 2012-09-12 | 黑龙江省科学院大庆分院 | Method for synthesis of polyfunctional dicyclopentadienyl ether |
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