JPH0477467A - New sulfur-containing aromatic acrylate - Google Patents
New sulfur-containing aromatic acrylateInfo
- Publication number
- JPH0477467A JPH0477467A JP18937990A JP18937990A JPH0477467A JP H0477467 A JPH0477467 A JP H0477467A JP 18937990 A JP18937990 A JP 18937990A JP 18937990 A JP18937990 A JP 18937990A JP H0477467 A JPH0477467 A JP H0477467A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- hexane
- refractive index
- raw materials
- added
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 7
- 125000003118 aryl group Chemical group 0.000 title claims description 7
- 239000011593 sulfur Substances 0.000 title claims description 7
- 229910052717 sulfur Inorganic materials 0.000 title claims description 7
- 239000000126 substance Substances 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 17
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000004386 diacrylate group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- -1 aromatic acrylates Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、高屈折率を有する樹脂の原料として有用な新
規な含硫芳香族アクリレートに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel sulfur-containing aromatic acrylate useful as a raw material for a resin having a high refractive index.
Ｃ従来の技術〕
エチレングリコールジアクリレート、ジエチレングリコ
ールジメタクリレートは、ポリアクリレートやポリメタ
クリレート樹脂の改質、すなわち架橋に利用されている
。C. Prior Art Ethylene glycol diacrylate and diethylene glycol dimethacrylate are used for modifying, that is, crosslinking, polyacrylate and polymethacrylate resins.
本発明者らは、アクリル樹脂やメタクリル樹脂をレンズ
用などの光学部品用の樹脂として利用することを研究し
ている。The present inventors have been researching the use of acrylic resins and methacrylic resins as resins for optical components such as lenses.
公知の（メタ）アクリル系千ツマ−であるエチレングリ
コールジアクリレートやジエチレングリコールジメタク
リレートを原料とした場合、得られる樹脂の屈折率は１
．５０程度である。これに対して、本出願人は、先番こ
高屈折率を存する含ｇ（メタ）アクリレート系モノマー
として、特開昭６３３１６７６６や６３−１８８６６０
を提案した。しかしながら、これらの含硫アクリレート
モノマーから得られる樹脂の屈折率は最大１．６５程度
であり、さらなる改良が望まれていた。When using ethylene glycol diacrylate or diethylene glycol dimethacrylate, which are known (meth)acrylic resins, as raw materials, the refractive index of the resulting resin is 1.
．． It is about 50. On the other hand, the present applicant has previously proposed JP-A-63316766 and JP-A No. 63-188666 as a g-containing (meth)acrylate monomer having a high refractive index.
proposed. However, the refractive index of resins obtained from these sulfur-containing acrylate monomers is about 1.65 at most, and further improvement has been desired.
［課題を解決するための手段］
本発明者らは、高い屈折率を存する樹脂を得るため、含
硫二官能性モノマーの研究を鋭意行い、その結果、含硫
芳香族アクリレートを用いることによりこの目的を達成
し得ることを見いだし本発明に至った。[Means for Solving the Problems] In order to obtain a resin with a high refractive index, the present inventors conducted extensive research on sulfur-containing bifunctional monomers, and as a result, by using sulfur-containing aromatic acrylates, this The inventors have discovered that the object can be achieved and have developed the present invention.
すなわち、本発明は高屈折率を有する樹脂の原料として
有用な新規な式（Ｉ）で表される含硫芳香族アクリレー
トを提供するものである。That is, the present invention provides a novel sulfur-containing aromatic acrylate represented by formula (I) that is useful as a raw material for resins having a high refractive index.
本発明の合鏡芳香族アクリレートは、４，４゛−チオビ
ス−ベンゼンチオールを溶媒、例えばアセトン、ヘキサ
ン、トルエン、クロロホルム等のような原料類との反応
性を有しない溶媒中で、−１０〜２０°Ｃの温度で、原
料１モルに対して２〜５モルのピリジンまたは水酸化ナ
トリウムの存在下、２〜２．５モルのβ−クロロプロピ
オニルクロライドを反応させ、さらに−１０〜２０°Ｃ
で２〜２．５モルのトリエチルアミンを加え、反応終了
後、この反応液に水を加えた後、炭化水素類、特にｎ−
ヘキサンを抽出溶剤として抽出を行うことにより得るこ
とができる。The synthetic aromatic acrylate of the present invention can be prepared by mixing 4,4'-thiobis-benzenethiol in a solvent such as acetone, hexane, toluene, chloroform, etc., which has no reactivity with the raw materials. At a temperature of 20°C, 2 to 2.5 mol of β-chloropropionyl chloride is reacted with 1 mol of raw materials in the presence of 2 to 5 mol of pyridine or sodium hydroxide, and further at -10 to 20°C.
Add 2 to 2.5 moles of triethylamine, and after the reaction is complete, water is added to the reaction solution, and hydrocarbons, especially n-
It can be obtained by extraction using hexane as an extraction solvent.
本発明の合鏡芳香族アクリレートは、単独またはジエチ
レングリコールジアクリレートやエチレングリコールジ
アクリレート等の不飽和カルボン酸エステルとともに加
熱重合させることにより、従来のジエチレングリコール
ジアクリレートやエチレングリコールジアクリレートを
用いた樹脂に比べ、高い屈折率を有する合鏡アクリル樹
脂を得ることができる。さらに、本発明の合鏡芳香族ア
クリレートと三官能以上のポリチオール類を反応させる
ことにより、高い屈折率を有するポリスルフィド系樹脂
を得ることができ、光学部品用に有効である。The synthetic aromatic acrylate of the present invention can be thermally polymerized alone or together with unsaturated carboxylic acid esters such as diethylene glycol diacrylate or ethylene glycol diacrylate, thereby making it more effective than resins using conventional diethylene glycol diacrylate or ethylene glycol diacrylate. , a synthetic acrylic resin with a high refractive index can be obtained. Furthermore, by reacting the mirror aromatic acrylate of the present invention with trifunctional or higher functional polythiols, a polysulfide resin having a high refractive index can be obtained, which is effective for optical parts.
以下、実施例を示すが、実施例中の部は重量部を示す。 Examples will be shown below, and parts in the examples indicate parts by weight.
実施例１
クロロホルム２００部に、４．４’−チオビスーヘンゼ
ンチオール２５．０部（０，１０モル）をン容解し、か
き混ぜながらピリジン３１．６部（０，４０モル）を全
量加えた。このとき内容液を１０°Ｃに保つため冷却し
た。Example 1 In 200 parts of chloroform, 25.0 parts (0.10 mol) of 4,4'-thiobisuhensenthiol was dissolved, and while stirring, 31.6 parts (0.40 mol) of pyridine was added in total. Ta. At this time, the content liquid was cooled to maintain it at 10°C.
次に、内容液を１０°Ｃに保ちながら、β−クロロプロ
ピオニルクロライド２６．７部（０，２１モル）を−時
間かけて滴下した。反応終了後、撹拌を続けながら、３
部量％重ソウ水ｍＷ４．２００部を加えて、クロロホル
ム溶液層を分液した。これを三回繰り返した後、水２０
０部を加えて水洗した。このクロロホルム溶液層を３６
〜３８“Ｃで濃縮して、結晶を得た。Next, while maintaining the content at 10°C, 26.7 parts (0.21 mol) of β-chloropropionyl chloride was added dropwise over an hour. After the reaction is complete, while continuing to stir,
4.200 parts of sodium chloride water (mW) was added to separate the chloroform solution layer. After repeating this three times, water 20
0 parts was added and washed with water. This chloroform solution layer was
Concentration at ~38"C gave crystals.
次に、この結晶２２．０部（０，０５モル）をアセトン
１００部に溶解し、内容液を１０°Ｃに保ち、トリエチ
ルアミン１１．４部（０，１１モル）をかき混ぜながら
一時間かけて滴下した０反応終了後、攪拌を続けなから
ｎ−へキサン６００部と水４００部を加え、ｎ〜へ牛サ
ン溶液層を分液した。これをミロ繰り返した後、ｎ−ヘ
キサン層を３０°Ｃで濃縮した後、再結晶化を行い、針
状結晶の目的物４，４゛−ジメルヵプトジフェニルスル
フィドジアクリレー目５．２部を得た。Next, 22.0 parts (0.05 mol) of these crystals were dissolved in 100 parts of acetone, the content was kept at 10°C, and 11.4 parts (0.11 mol) of triethylamine was added with stirring for 1 hour. After the completion of the dropwise reaction, 600 parts of n-hexane and 400 parts of water were added while stirring, and the beef san solution layer was separated into n-hexane. After repeating this several times, the n-hexane layer was concentrated at 30°C and recrystallized to obtain the desired needle-like crystals 4,4゛-dimercapto diphenyl sulfide diacrylate 5.2 I got the department.
元素分析値（Ｃ＋Ｊ＋ａＯｚＳ３として）Ｈ３
測定値（％） ６０．０４ ４．１２ ２６．２
７計算値（％） ６０．３１ ３．９４ ２６．
８３部ＭＲ（δｃ＋＋ｃＬ３）
δ＝５．７９ （ｍ、 ２Ｈ，−ＣＪＬ＝）６．４２
（ｍ、 ４Ｈ，Ｃｆ１ｚ＝−）融点 ５２〜５３°Ｃ
参考例１
４．４゛−ジメルカプトジフェニルスルフィドジアクリ
レート５０部およびラウロイルパーオキサイド０．１０
部を混合し、均一とした液をガラスモールドとエチレン
−酢酸ビニル共重合体からなるガスケットで構成された
モールド型中に注入した。次いで、最初３０°Ｃで重合
を開始し、６時間後に７０’Ｃになるように徐々に温度
を上昇させた。更に、８０℃で二間接重合した後、ガス
ケットおよびモールドから重合体を取り出した。重合体
は、更に９０″Ｃで二間接重合した。この重合体は、屈
折率１．７１であり無色透明で加工性も良好であった。Elemental analysis value (as C+J+aOzS3) H3 Measured value (%) 60.04 4.12 26.2
7 Calculated value (%) 60.31 3.94 26.
83 parts MR (δc++cL3) δ=5.79 (m, 2H, -CJL=)6.42
(m, 4H, Cf1z=-) Melting point 52-53°C Reference example 1 50 parts of 4.4゛-dimercapto diphenyl sulfide diacrylate and 0.10 parts of lauroyl peroxide
The mixture was mixed and the homogeneous solution was poured into a mold consisting of a glass mold and a gasket made of ethylene-vinyl acetate copolymer. Next, polymerization was initially started at 30°C, and the temperature was gradually raised to 70'C after 6 hours. Further, after double indirect polymerization at 80° C., the polymer was taken out from the gasket and mold. The polymer was further subjected to double indirect polymerization at 90''C. This polymer had a refractive index of 1.71, was colorless and transparent, and had good processability.
参考例２
４．４゛−ジメルカプトジフェニルスルフィドジアクリ
レート３０部および１，２−ビス〔（２−メルカブトエ
チル）千オ〕３−メルカプトプロパン１４．４部を混合
し、均一とした液をガラスモールドとエチレン−酢酸ビ
ニル共重合体からなるガスヶ・７トで構成されたモール
ド型中に注入した。次いで、最初３０’Ｃで重合を開始
し、６時間後に７０°Ｃになるように徐々に温度を上昇
させた。更に、８０°Ｃで二間接重合した後ガスケット
およびモールドから重合体を取り出した。重合体は、更
に９０°Ｃで二間接重合した。この重合体は、屈折率１
．６９であり無色透明で加工性も良好であった。Reference Example 2 30 parts of 4.4'-dimercapto diphenyl sulfide diacrylate and 14.4 parts of 1,2-bis[(2-mercaptoethyl)1,000]3-mercaptopropane were mixed and a homogeneous solution was prepared. The mixture was poured into a mold consisting of a glass mold and a gas container made of ethylene-vinyl acetate copolymer. Next, polymerization was initially started at 30'C, and the temperature was gradually raised to 70C after 6 hours. Further, after double indirect polymerization at 80°C, the polymer was taken out from the gasket and mold. The polymer was further double-indirectly polymerized at 90°C. This polymer has a refractive index of 1
．． 69, it was colorless and transparent and had good workability.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
式、化学式、表等があります▼（ I ）1) Sulfur-containing aromatic acrylate represented by formula (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18937990A JPH0477467A (en) | 1990-07-19 | 1990-07-19 | New sulfur-containing aromatic acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18937990A JPH0477467A (en) | 1990-07-19 | 1990-07-19 | New sulfur-containing aromatic acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0477467A true JPH0477467A (en) | 1992-03-11 |
Family
ID=16240333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18937990A Pending JPH0477467A (en) | 1990-07-19 | 1990-07-19 | New sulfur-containing aromatic acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0477467A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7491441B2 (en) * | 2004-12-30 | 2009-02-17 | 3M Innovative Properties Company | High refractive index, durable hard coats |
| CN109651612A (en) * | 2018-12-13 | 2019-04-19 | 江南大学 | A kind of preparation method of sulfur-bearing high refractive index optical resin |
-
1990
- 1990-07-19 JP JP18937990A patent/JPH0477467A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7491441B2 (en) * | 2004-12-30 | 2009-02-17 | 3M Innovative Properties Company | High refractive index, durable hard coats |
| CN109651612A (en) * | 2018-12-13 | 2019-04-19 | 江南大学 | A kind of preparation method of sulfur-bearing high refractive index optical resin |
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