JPH0834768A - New dimethacrylate - Google Patents
New dimethacrylateInfo
- Publication number
- JPH0834768A JPH0834768A JP19230194A JP19230194A JPH0834768A JP H0834768 A JPH0834768 A JP H0834768A JP 19230194 A JP19230194 A JP 19230194A JP 19230194 A JP19230194 A JP 19230194A JP H0834768 A JPH0834768 A JP H0834768A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- dimethacrylate
- bis
- represented
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規有用なジメタクリ
レートに関する。FIELD OF THE INVENTION The present invention relates to a new and useful dimethacrylate.
【０００２】[0002]
【従来の技術】従来、式１で表わされるフルオレン骨格
と硫黄原子を含有したジメタクリレートは知られていな
い。2. Description of the Related Art Hitherto, a dimethacrylate containing a fluorene skeleton represented by the formula 1 and a sulfur atom has not been known.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、高耐熱性、
高屈折率の樹脂とし得る、重合性、共重合性、架橋性に
富んだ新規なジメタクリレートを提供する。The present invention has a high heat resistance,
Disclosed is a novel dimethacrylate that is a resin having a high refractive index and is highly polymerizable, copolymerizable, and crosslinkable.
【０００４】[0004]
【課題を解決するための手段】本発明は、次式The present invention has the following formula:
【化２】 で表わされる新規なジメタクリレートにある。Embedded image It is a novel dimethacrylate represented by.
【０００５】本発明の上記式で表わされるジメタクリレ
ートは、フルオレン骨格を有するため、これを用いて重
合すると一般の脂肪族メタクリレートと比較して高耐熱
性の樹脂とすることができる。また、硫黄原子が１分子
に２個あり高屈折率である。この化合物は、１分子中に
重合性のメタクリレート基を２個有しており、単独で、
あるいは他の重合性化合物と共重合させて物理的、化学
的特性を制御し有用な耐熱性高分子やレンズ材料等に好
適な高屈折率高分子材料を得ることができる。Since the dimethacrylate represented by the above formula of the present invention has a fluorene skeleton, it can be made into a resin having high heat resistance as compared with general aliphatic methacrylate by polymerizing using this. In addition, there are two sulfur atoms in one molecule, which has a high refractive index. This compound has two polymerizable methacrylate groups in one molecule.
Alternatively, a high refractive index polymer material suitable for use as a heat resistant polymer or a lens material, which is useful for controlling physical and chemical properties by copolymerizing with another polymerizable compound, can be obtained.
【０００６】次に、前記式１で表わされる新規なジメタ
クリレートの製造例を記述するが、この方法のみに限定
されるものではない。Next, a production example of the novel dimethacrylate represented by the above formula 1 will be described, but the method is not limited to this method.
【０００７】まず、次の式２First, the following equation 2
【化３】 で表わされるジオールを、市販の９−フルオレノンと２
−メルカプトエタノールから合成する。この合成は、
Ｍ．Ｓ．Ｎｅｗｍａｎ，Ｗ．Ｂ．Ｌｕｔｚ，Ｊ．Ａｍ．
Ｃｈｅｍ．Ｓｏｃ．，７８，２４６９（１９５６）に開
示されている方法により容易にできる。次に、得られた
式２で表わされるジオールを以下に掲げた式３，式４お
よび式５の化合物の何れかと反応させて本発明の新規な
ジメタクリレートを合成する。Embedded image The diol represented by
-Synthesized from mercaptoethanol. This composition
M. S. Newman, W.C. B. Lutz, J .; Am.
Chem. Soc. , 78 , 2469 (1956). Next, the obtained diol represented by the formula 2 is reacted with any of the compounds of the formulas 3, 4 and 5 listed below to synthesize the novel dimethacrylate of the present invention.
【０００８】[0008]
【化４】 [Chemical 4]
【０００９】[0009]
【化５】 Embedded image
【００１０】[0010]
【化６】 [Chemical 6]
【００１１】式２のジオールと式３で表わされるメタク
リル酸との反応は、トルエン、ヘキサンやシクロヘキサ
ンなどの脱水溶媒中で硫酸、メタンスルホン酸、ｐ−ト
ルエンスルホン酸や強酸性イオン交換樹脂などの触媒を
用い脱水エステル化し、本発明のジメタクリレートを得
ることができる。The reaction between the diol of the formula 2 and the methacrylic acid represented by the formula 3 is carried out by using sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or a strongly acidic ion exchange resin in a dehydrating solvent such as toluene, hexane or cyclohexane. The dimethacrylate of the present invention can be obtained by dehydration esterification using a catalyst.
【００１２】また、式２のジオールと式４で表わされる
アルキルメタクリレートとをチタンテトラブトキシドに
代表されるチタン化合物やジブチルスズオキシドに代表
されるスズ化合物や一般のプロトン酸などのエステル交
換触媒を適当に選ぶことによって本発明のジメタクリレ
ートが得られる。Further, a transesterification catalyst such as a titanium compound typified by titanium tetrabutoxide, a tin compound typified by dibutyltin oxide, or a general protic acid is used as the diol of the formula 2 and the alkyl methacrylate represented by the formula 4 is suitable. By selection, the dimethacrylate of the present invention is obtained.
【００１３】上記の式４で表わされるアルキルメタクリ
レートのアルキル基としては、炭素数４以下のものが留
出除去と言う点から好ましく、最も好ましいのはメチル
基である。炭素数が４以上となると脱離するアルコール
の沸点が高くなり反応工程上不利である。さらにアルキ
ルメタクリレートのコストの面を考慮するとメチルメタ
クリレートが好ましい。As the alkyl group of the alkyl methacrylate represented by the above formula 4, those having 4 or less carbon atoms are preferable from the viewpoint of distillative removal, and the most preferable is the methyl group. If the carbon number is 4 or more, the boiling point of the alcohol to be eliminated becomes high, which is disadvantageous in the reaction process. Further, methyl methacrylate is preferable in consideration of the cost of alkyl methacrylate.
【００１４】さらに、式２のジオールと式５で表わされ
るメタクリル酸ハロゲン化物（一般的には塩化物が用い
られる）を、ジオールを溶解させるクロロホルム、ジク
ロロメタンなどの不活性な汎用溶剤中で、脱酸剤として
ピリジンやトリエチルアミンなどの第３級アミンを使用
し、温和な条件下で反応させることによって、本発明の
ジメタクリレートが得られる。Further, the diol of the formula 2 and the methacrylic acid halide represented by the formula 5 (generally chloride) are removed in an inert general-purpose solvent such as chloroform or dichloromethane which dissolves the diol. The dimethacrylate of the present invention can be obtained by using a tertiary amine such as pyridine or triethylamine as an acid agent and reacting under a mild condition.
【００１５】[0015]
【発明の効果】本発明のジメタクリレートは、重合性を
有し、単独で重合又は他の共重合性化合物と共重合し、
高耐熱性、高屈折率の樹脂とすることができる。INDUSTRIAL APPLICABILITY The dimethacrylate of the present invention has polymerizability, and is polymerized alone or copolymerized with another copolymerizable compound,
A resin having high heat resistance and high refractive index can be used.
【００１６】[0016]
９，９−ビス（２−メタクリロイルオキシエチルチオ）
フルオレンの合成 ９−フルオレノンと２−メルカプトエタノールから前記
した方法により合成した式２で表わされるフルオレノン
−ビス−２−ヒドロキシエチルメルカプトール１２ｇ
（０．０３７７モル）を、脱水ジクロロメタン４００ｍ
ｌに溶解し、脱水ピリジン１６ｇ（０．２０２モル）を
加え、窒素雰囲気下室温で撹拌した。9,9-bis (2-methacryloyloxyethylthio)
Synthesis of fluorene 12 g of fluorenone-bis-2-hydroxyethylmercaptor represented by formula 2 synthesized from 9-fluorenone and 2-mercaptoethanol by the method described above.
(0.0377 mol) was added to 400 m of dehydrated dichloromethane
16 g (0.202 mol) of dehydrated pyridine was added, and the mixture was stirred at room temperature under a nitrogen atmosphere.
【００１７】これにメタクリル酸クロリド８．８７ｇ
（０．０８４８モル）とジクロロメタン２０ｍｌの混合
液を、１８〜２２℃に反応液温を制御しながら１５分か
けて滴下した。滴下終了後、さらに２時間室温で撹拌を
続け、分液ロートに反応液を取り、５％の重曹水で洗浄
した。さらに、５％の苛性ソーダ水溶液及び水で洗浄し
た。次いでジクロロメタン層を無水硫酸マグネシウムで
乾燥後、ジクロロメタンを留去して淡黄色のオイル状粗
製物１９．５３ｇを得た。Methacrylic acid chloride 8.87 g
A mixed solution of (0.0848 mol) and 20 ml of dichloromethane was added dropwise over 15 minutes while controlling the temperature of the reaction solution at 18 to 22 ° C. After completion of dropping, stirring was continued at room temperature for additional 2 hours, the reaction solution was taken in a separating funnel and washed with 5% aqueous sodium hydrogen carbonate. Further, it was washed with a 5% aqueous sodium hydroxide solution and water. Then, the dichloromethane layer was dried over anhydrous magnesium sulfate, and then dichloromethane was distilled off to obtain 19.53 g of a pale yellow oily crude product.
【００１８】得られた粗製物をシリカゲルカラムクロマ
ト（留出液トルエン）により精製し、目的の式１で表わ
される９，９−ビス（２−メタクリロイルオキシエチル
チオ）フルオレンを１２．１７ｇ（０．０２６８モル、
収率７１％）をオイル状の液状物として得た。以下にそ
の分析同定のデータを示す。The resulting crude product was purified by silica gel column chromatography (distillate toluene) to obtain 12.17 g (0.10%) of the target 9,9-bis (2-methacryloyloxyethylthio) fluorene represented by the formula 1. 0268 mol,
Yield 71%) was obtained as an oily liquid. The data of the analysis and identification are shown below.
【００１９】［元素分析値］ Ｃ25Ｈ26Ｏ4 Ｓ2 ＝４５
４．６３として 計算値；Ｃ：６６．０４％ Ｈ：５．７８％ Ｏ：１
４．１０％ Ｓ：１４．１０％ 実測値；Ｃ：６５．６％ Ｈ：５．８％ Ｏ：１
４．１％ Ｓ：１４．０％[Elemental analysis value] C 25 H 26 O 4 S 2 = 45
Calculated as 4.63; C: 66.04% H: 5.78% O: 1
4.10% S: 14.10% Found: C: 65.6% H: 5.8% O: 1
4.1% S: 14.0%
【００２０】［ 1Ｈ−ＮＭＲスペクトル］ＣＤＣｌ3
（内部標準ＴＭＳ）1 Ｈ−ＮＭＲスペクトルを図１に示す。 δH １．８７（６Ｈ，ｓ，−ＣＨ3 ） δH ２．５４（４Ｈ，ｔ，Ｓ−ＣＨ2 ） δH ３．９１（４Ｈ，ｔ，Ｏ−ＣＨ2 ） δH ５．５２（２Ｈ，ｔ，ＨＣ＝） δH ６．０３（２Ｈ，ｓ，ＨＣ＝） δH ７．３６〜７．４３（４Ｈ，ｍ，フルオレン環） δH ７．６９〜７．７２（４Ｈ，ｍ，フルオレン環）[ 1 H-NMR spectrum] CDCl 3
(Internal standard TMS) 1 H-NMR spectrum is shown in FIG. 1. δ H 1.87 (6H, s, -CH 3 ) δ H 2.54 (4H, t, S-CH 2 ) δ H 3.91 (4H, t, O-CH 2 ) δ H 5.52 ( 2H, t, HC =) δ H 6.03 (2H, s, HC =) δ H 7.36~7.43 (4H, m, fluorene ring) δ H 7.69~7.72 (4H, m , Fluorene ring)
【００２１】［13Ｃ−ＮＭＲスペクトル］ＣＤＣｌ3
（内部標準ＴＭＳ）13 Ｃ−ＮＭＲスペクトルを図２に示す。 δC １８．２３５（−ＣＨ3 ） δC １３５．９６９（＝Ｃ−ＣＨ3 ） δC ３０．１３１（Ｓ−ＣＨ2 ） δC １２５．８０５（＝ＣＨ2 ） δC ６１．７５９（Ｓ−Ｃ−Ｓ） δC １６６．８４２（Ｃ＝Ｏ） δC ６２．９７０（Ｏ−ＣＨ2 ） δC １２０，３５６，１２４，７９６，１２８，３２０，１２９，１３５ １３８，８９１，１４６，４６１（フルオレン環）[ 13 C-NMR spectrum] CDCl 3
(Internal standard TMS) 13 C-NMR spectrum is shown in FIG. 2. δ C 18.235 (-CH 3) δ C 135.969 (= C-CH 3) δ C 30.131 (S-CH 2) δ C 125.805 (= CH 2) δ C 61.759 (S -C-S) δ C 166.842 ( C = O) δ C 62.970 (O-CH 2) δ C 120,356,124,796,128,320,129,135 138,891,146,461 (Fluorene ring)
【００２２】［赤外吸収スペクトル］（ＫＢｒ錠剤法） 赤外吸収スペクトルを図３に示す。 １７２０ｃｍ-1（エステルカルボニル） １４５０ｃｍ-1（芳香環）[Infrared absorption spectrum] (KBr tablet method) The infrared absorption spectrum is shown in FIG. 1720 cm -1 (ester carbonyl) 1450 cm -1 (aromatic ring)
【００２３】［屈折率］ ｎD ：１．５９４８（１５℃）[Refractive index] n D : 1.5948 (15 ° C.)
【図面の簡単な説明】[Brief description of drawings]
【図１】実施例で得られた化合物の 1Ｈ−ＮＭＲスペク
トル図である。FIG. 1 is a 1 H-NMR spectrum diagram of the compounds obtained in Examples.
【図２】実施例で得られた化合物の13Ｃ−ＮＭＲスペク
トル図である。FIG. 2 is a 13 C-NMR spectrum diagram of the compounds obtained in Examples.
【図３】実施例で得られた化合物の赤外吸収スペクトル
図である。FIG. 3 is an infrared absorption spectrum chart of the compounds obtained in Examples.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19230194A JPH0834768A (en) | 1994-07-25 | 1994-07-25 | New dimethacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19230194A JPH0834768A (en) | 1994-07-25 | 1994-07-25 | New dimethacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0834768A true JPH0834768A (en) | 1996-02-06 |
Family
ID=16289005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19230194A Pending JPH0834768A (en) | 1994-07-25 | 1994-07-25 | New dimethacrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0834768A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100588819B1 (en) * | 1998-07-13 | 2006-06-13 | 도레이 가부시끼가이샤 | Curable and foamable polyolefinic resin composition, cured foam of polyolefinic resin and method for producing it |
| WO2006073755A1 (en) * | 2004-12-30 | 2006-07-13 | 3M Innovative Properties Company | High refractive index monomers for optical applications |
| DE102005003303A1 (en) * | 2005-01-24 | 2006-07-27 | Röhm GmbH & Co. KG | New thio(meth)acrylate, obtained by reacting methyl thioacrylic acid compound(s) with thiol compounds, useful preparing transparent plastics, which are useful as optical lenses or glass panes |
| US7264872B2 (en) | 2004-12-30 | 2007-09-04 | 3M Innovative Properties Company | Durable high index nanocomposites for AR coatings |
| US7491441B2 (en) | 2004-12-30 | 2009-02-17 | 3M Innovative Properties Company | High refractive index, durable hard coats |
| US7981986B2 (en) | 2008-04-29 | 2011-07-19 | 3M Innovative Properties Company | Optical films comprising fluorenol (meth)acrylate monomer |
| JP2011168526A (en) * | 2010-02-18 | 2011-09-01 | Tokyo Institute Of Technology | Novel (meth)acrylate compound and manufacturing method of the same |
| JP2013213030A (en) * | 2012-03-09 | 2013-10-17 | Osaka Gas Chem Kk | Polycarboxylic acid having florene skeleton and method for producing the same |
| CN105001751A (en) * | 2015-08-07 | 2015-10-28 | 天津大学 | Paint for improving damp heat resistance of precise metal film resistor and preparation method of paint |
| JP2018028010A (en) * | 2016-08-17 | 2018-02-22 | Jsr株式会社 | Polymer and method for producing the same |
-
1994
- 1994-07-25 JP JP19230194A patent/JPH0834768A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100588819B1 (en) * | 1998-07-13 | 2006-06-13 | 도레이 가부시끼가이샤 | Curable and foamable polyolefinic resin composition, cured foam of polyolefinic resin and method for producing it |
| WO2006073755A1 (en) * | 2004-12-30 | 2006-07-13 | 3M Innovative Properties Company | High refractive index monomers for optical applications |
| US7264872B2 (en) | 2004-12-30 | 2007-09-04 | 3M Innovative Properties Company | Durable high index nanocomposites for AR coatings |
| US7297810B2 (en) | 2004-12-30 | 2007-11-20 | 3M Innovative Properties Company | High refractive index monomers for optical applications |
| US7491441B2 (en) | 2004-12-30 | 2009-02-17 | 3M Innovative Properties Company | High refractive index, durable hard coats |
| DE102005003303A1 (en) * | 2005-01-24 | 2006-07-27 | Röhm GmbH & Co. KG | New thio(meth)acrylate, obtained by reacting methyl thioacrylic acid compound(s) with thiol compounds, useful preparing transparent plastics, which are useful as optical lenses or glass panes |
| US7981986B2 (en) | 2008-04-29 | 2011-07-19 | 3M Innovative Properties Company | Optical films comprising fluorenol (meth)acrylate monomer |
| JP2011168526A (en) * | 2010-02-18 | 2011-09-01 | Tokyo Institute Of Technology | Novel (meth)acrylate compound and manufacturing method of the same |
| JP2013213030A (en) * | 2012-03-09 | 2013-10-17 | Osaka Gas Chem Kk | Polycarboxylic acid having florene skeleton and method for producing the same |
| CN105001751A (en) * | 2015-08-07 | 2015-10-28 | 天津大学 | Paint for improving damp heat resistance of precise metal film resistor and preparation method of paint |
| JP2018028010A (en) * | 2016-08-17 | 2018-02-22 | Jsr株式会社 | Polymer and method for producing the same |
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