JPH07242654A - Diallyl ester or dimethallyl ester compound - Google Patents
Diallyl ester or dimethallyl ester compoundInfo
- Publication number
- JPH07242654A JPH07242654A JP3594394A JP3594394A JPH07242654A JP H07242654 A JPH07242654 A JP H07242654A JP 3594394 A JP3594394 A JP 3594394A JP 3594394 A JP3594394 A JP 3594394A JP H07242654 A JPH07242654 A JP H07242654A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- ester
- formula
- tetraoxaspiro
- undecane
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、成形材料、積層材料、
電気絶縁材料、各種合成樹脂の架橋剤あるいは改質剤等
として使用される可撓性に優れたポリマーを与える新規
なジアリルエステルまたはジメタリルエステル化合物に
関するものである。The present invention relates to a molding material, a laminated material,
The present invention relates to a novel diallyl ester or dimethallyl ester compound which provides a highly flexible polymer used as an electrically insulating material, a crosslinking agent or a modifier for various synthetic resins, and the like.
【０００２】[0002]
【従来の技術】従来、アリル基をもった反応性モノマー
としては、ジアリルフタレート及び、トリアリルイソシ
アヌレートが知られている。しかし、これらのモノマー
を重合させ得られたポリマーは、一般的に耐熱性の点で
優れているが可撓性にとぼしく、成形材料として使用し
た場合、ヒビや割れを生じやすいという欠点を有してい
る。2. Description of the Related Art Conventionally, diallyl phthalate and triallyl isocyanurate are known as reactive monomers having an allyl group. However, the polymers obtained by polymerizing these monomers are generally excellent in heat resistance but poor in flexibility, and when used as a molding material, they have a drawback that cracks and cracks are likely to occur. ing.
【０００３】また、スピロアセタール環を有している反
応性アクリレートモノマーが提案されている（特開昭５
９−７８１９３号公報および特開昭６１−２６３９８１
号公報）。これらのモノマーを重合させ得られたポリマ
ーは、可撓性に優れている。しかしながら、これらの化
合物は、融点が１００℃以上であったり、粘度がかなり
高いなど取り扱いが悪く作業性に劣るという欠点を有し
ている。Further, a reactive acrylate monomer having a spiro acetal ring has been proposed (Japanese Patent Laid-Open No. Sho 5).
9-78193 and Japanese Patent Laid-Open No. 61-263981.
Issue). The polymer obtained by polymerizing these monomers has excellent flexibility. However, these compounds have the drawbacks of poor handling and poor workability such as a melting point of 100 ° C. or higher and a considerably high viscosity.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来の反応
性ビニルモノマーの問題点である作業性を改良し、可撓
性に優れたポリマーを与える反応性ビニルモノマーを得
ようとするものである。DISCLOSURE OF THE INVENTION The present invention is intended to improve the workability, which is a problem of conventional reactive vinyl monomers, and to obtain a reactive vinyl monomer which gives a polymer having excellent flexibility. is there.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、前
記問題点を解決した下記一般式[I]That is, the present invention provides the following general formula [I] which solves the above problems.
【０００６】[0006]
【化２】 （式中、Ｒは水素原子またはメチル基を示す）で示され
る、新規なジアリルエステルまたはジメタリルエステル
化合物を提供するものである。本発明のジアリルエステ
ルは流動性のよい液状であり、ジメタリルエステルは５
４〜５６℃の低融点固形物であり、取扱い易く、作業性
に優れ、これらを重合すると、スピロアセタール環を有
するところから可撓性に優れたポリマーを与える。[Chemical 2] The present invention provides a novel diallyl ester or dimethallyl ester compound represented by the formula (wherein R represents a hydrogen atom or a methyl group). The diallyl ester of the present invention is a liquid having good fluidity, and the dimethallyl ester is 5
It is a solid having a low melting point of 4 to 56 ° C., is easy to handle and is excellent in workability. When these are polymerized, a polymer having a spiro acetal ring and excellent in flexibility is provided.
【０００７】本発明の一般式[I]で表わされるジアリル
エステルまたはジメタリルエステルは、従来の公知の方
法で製造することが可能であり、例えば、入手容易な
３，９−ビス（２−カルボキシエチル）２，４，８，１
０−テトラオキサスピロ〔５，５〕ウンデカンと下記一
般式[II]The diallyl ester or dimethallyl ester represented by the general formula [I] of the present invention can be produced by a conventionally known method, for example, easily available 3,9-bis (2-carboxy). Ethyl) 2,4,8,1
0-Tetraoxaspiro [5,5] undecane and the following general formula [II]
【０００８】[0008]
【化３】 （式中、Ｒは前記と同じ、Ｘは水酸基またはハロゲン原
子を示す）で示されるアリルまたはメタリル化合物を有
機溶媒中で反応することにより、前記一般式[I] で示さ
れるジアリルエステルまたはジメタリルエステル化合物
を得ることができる。[Chemical 3] (Wherein R is the same as above, X is a hydroxyl group or a halogen atom) is reacted with an allyl or methallyl compound in an organic solvent to give a diallyl ester or dimetallyl represented by the general formula [I]. A ruster compound can be obtained.
【０００９】すなわち具体的には、上記ジカルボン酸１
モルに対し、一般式[II]で示されるアリルまたはメタリ
ル化合物を２〜１０モル用い、有機溶媒中、酸触媒また
は塩基性化合物の存在下、５０〜２００℃の温度範囲
で、１〜１０時間縮合反応を行なう。アリルまたはメタ
リル化合物としてはアリルアルコール、メタリルアルコ
ール、アリルクロライド、メタリルクロライド、アリル
フルオライド、メタリルフルオライド、アリルブロマイ
ド、メタリルブロマイド、アリルアイオダイド、メタリ
ルアイオダイド等が挙げられる。That is, specifically, the above dicarboxylic acid 1
2 to 10 mol of the allyl or methallyl compound represented by the general formula [II] is used in an organic solvent in the presence of an acid catalyst or a basic compound in a temperature range of 50 to 200 ° C. for 1 to 10 hours. Conduct a condensation reaction. Examples of the allyl or methallyl compound include allyl alcohol, methallyl alcohol, allyl chloride, methallyl chloride, allyl fluoride, methallyl fluoride, allyl bromide, methallyl bromide, allyl iodide and methallyl iodide.
【００１０】本反応に使用される酸触媒としては、硫
酸、無水硫酸、リン酸、ポリリン酸、メタリン酸、縮合
リン酸等の無機酸触媒、およびｐ−トルエンスルホン
酸、トリクロル酢酸、トリフルオロ酢酸、メタンスルホ
ン酸等の有機酸触媒が挙げられる。使用される量は、ジ
カルボン酸のカルボキシル基１当量に対して、０．００
０１〜１当量、好ましくは０．００１〜０．５当量であ
る。The acid catalyst used in this reaction includes inorganic acid catalysts such as sulfuric acid, sulfuric anhydride, phosphoric acid, polyphosphoric acid, metaphosphoric acid and condensed phosphoric acid, and p-toluenesulfonic acid, trichloroacetic acid, trifluoroacetic acid. , Organic acid catalysts such as methanesulfonic acid. The amount used is 0.00 based on 1 equivalent of the carboxyl group of the dicarboxylic acid.
It is 01 to 1 equivalent, preferably 0.001 to 0.5 equivalent.
【００１１】また、塩基性化合物としては、水酸化ナト
リウム、水酸化カリウム等のアルカリ金属水酸化物、炭
酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩、
ナトリウムメトキシド、ナトリウムエトキシド等のアル
カリ金属アルコラートが挙げられる。使用される量は、
ジカルボン酸のカルボキシル基１当量に対して、０．５
〜２当量、好ましくは１〜１．５当量である。As the basic compound, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate,
Examples thereof include alkali metal alcoholates such as sodium methoxide and sodium ethoxide. The amount used is
0.5 to 1 equivalent of carboxyl group of dicarboxylic acid
~ 2 equivalents, preferably 1-1.5 equivalents.
【００１２】また、有機溶媒としてベンゼン、トルエ
ン、キシレン、エチルベンゼン、キュメン、メシチレン
等の芳香族炭化水素、クロロホルム、１，２−ジクロル
エタン、クロルベンゼン、ジクロルベンゼン、クロルト
ルエン、１，１，２，２−テトラクロルエタン等のハロ
ゲン化炭化水素、ギ酸エチル、ギ酸−ｎ−ブチル、酢酸
エチル、酢酸−ｎ−ブチル、酢酸イソブチル等のエステ
ル、ジエチルエーテル、テトラヒドロフラン、１，４−
ジオキサン、エチレングリコール−モノ−メチルエーテ
ル、エチレングリコール−モノ−エチルエーテル、ジエ
チレングリコール−モノ−エチルエーテル等のエーテ
ル、アセトン、メチルエチルケトン、メチルイソブチル
ケトン、シクロヘキサノン等のケトン、及び、Ｎ，Ｎ−
ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミ
ド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシ
ド、ジグライム等の非プロトン性極性溶媒が挙げられ
る。As the organic solvent, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, 1,1,2, Halogenated hydrocarbons such as 2-tetrachloroethane, ethyl formate, esters of -n-butyl formate, ethyl acetate, -n-butyl acetate, isobutyl acetate, diethyl ether, tetrahydrofuran, 1,4-
Ethers such as dioxane, ethylene glycol-mono-methyl ether, ethylene glycol-mono-ethyl ether, diethylene glycol-mono-ethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and N, N-
Aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diglyme and the like can be mentioned.
【００１３】反応終了後、反応溶液を水で洗浄し、触媒
等を除去した後、前記反応溶媒を留去することにより、
目的のジアリルエステルまたはジメタリルエステル化合
物を収率よく得ることができる。After completion of the reaction, the reaction solution is washed with water to remove the catalyst and the like, and then the reaction solvent is distilled off,
The desired diallyl ester or dimethallyl ester compound can be obtained in good yield.
【００１４】[0014]
【実施例】以下、実施例により本発明の化合物の製造方
法をさらに詳しく説明する。 実施例１ 温度計、撹拌機及び水分離器の付いた５００ｍｌの四ツ
口フラスコに３，９−ビス（２−カルボキシエチル）
２，４，８，１０−テトラオキサスピロ〔５．５〕ウン
デカン３０．４ｇ（０．１モル）及びトルエン１５０
ｇ、アリルアルコール１７．４ｇ（０．３モル）、パラ
トルエンスルホン酸１．０ｇ（０．００５モル）を仕込
み、９５〜１２０℃で４時間エステル化反応を遂行し
た。この間に生成した水は、トルエンと共に系外に留去
させた。EXAMPLES The method for producing the compound of the present invention will be described in more detail with reference to the following examples. Example 1 3,9-Bis (2-carboxyethyl) in a 500 ml four necked flask equipped with a thermometer, stirrer and water separator.
2,4,8,10-Tetraoxaspiro [5.5] undecane 30.4 g (0.1 mol) and toluene 150
g, allyl alcohol 17.4 g (0.3 mol) and paratoluene sulfonic acid 1.0 g (0.005 mol) were charged, and an esterification reaction was carried out at 95 to 120 ° C. for 4 hours. The water generated during this time was distilled out of the system together with toluene.
【００１５】反応終了後、純水３００ｇで３回洗浄し、
トルエンを減圧下（１５０〜１０ｍｍＨｇ）、油浴中８
０〜１００℃の温度範囲で留去し、淡黄色透明液状の生
成物３８．３ｇを得た。（収率９９．７％）After completion of the reaction, the product was washed with 300 g of pure water three times,
Toluene under reduced pressure (150 to 10 mmHg) in an oil bath 8
The solvent was distilled off in the temperature range of 0 to 100 ° C to obtain 38.3 g of a pale yellow transparent liquid product. (Yield 99.7%)
【００１６】下記に示す1Ｈ−ＮＭＲのスペクトルデー
タより、得られた化合物が３，９−ビス（２−アリルオ
キシカルボニルエチル）２，４，８，１０−テトラオキ
サスピロ〔５．５〕ウンデカンであることが確認され
た。From the 1 H-NMR spectral data shown below, the obtained compound was found to be 3,9-bis (2-allyloxycarbonylethyl) 2,4,8,10-tetraoxaspiro [5.5] undecane. Was confirmed.
【００１７】[0017]
【化４】 １．９〜２．０ｐｐｍ ： ２．４〜２．６ｐｐｍ ： ３．２〜３．４ｐｐｍ ： ４．４〜４．６ｐｐｍ ： ５．２〜５．６ｐｐｍ ： ５．８〜６．０ｐｐｍ ： [Chemical 4] 1.9-2.0 ppm: 2.4-2.6 ppm: 3.2-3.4 ppm: 4.4-4.6 ppm: 5.2-5.6 ppm: 5.8-6.0 ppm:
【００１８】実施例２ 温度計、撹拌機を備えた５００ｍｌの四ツ口フラスコ内
に、３，９−ビス（２−カルボキシエチル）２，４，
８，１０−テトラオキサスピロ〔５．５〕ウンデカン３
０．４ｇ（０．１モル）メタリルクロライド２２．６ｇ
（０．２５モル）、炭酸ナトリウム２８ｇ（０．２モ
ル）及びＮ，Ｎ−ジメチルホルムアミド１８０ｇを仕込
み、１００〜１４５℃の温度範囲で４時間縮合反応させ
た。Example 2 3,9-bis (2-carboxyethyl) 2,4 was placed in a 500 ml four-necked flask equipped with a thermometer and a stirrer.
8,10-Tetraoxaspiro [5.5] undecane 3
0.4 g (0.1 mol) methallyl chloride 22.6 g
(0.25 mol), 28 g (0.2 mol) of sodium carbonate and 180 g of N, N-dimethylformamide were charged and the condensation reaction was carried out at a temperature range of 100 to 145 ° C. for 4 hours.
【００１９】反応終了後、副生した塩化ナトリウム及び
過剰の炭酸ナトリウムを濾別した反応溶液中から、Ｎ，
Ｎ−ジメチルホルムアミドを減圧下（１５０〜１０ｍｍ
Ｈｇ）、油浴中１００〜１３０℃の温度で留去した。
Ｎ，Ｎ−ジメチルホルムアミドを留去後、トルエン２０
０ｇを加えた後、純水２００ｇで２回洗浄し、減圧下
（１５０〜１０ｍｍＨｇ）、油浴中８０〜１００℃の温
度で留去し、固体淡黄色の生成物３９．８ｇを得た。
（収率９６．６％）このものの融点は、５４〜５６℃の
固形物であった。After completion of the reaction, N, N
N-dimethylformamide under reduced pressure (150-10 mm
Hg), distilled off in an oil bath at a temperature of 100-130 ° C.
After distilling off N, N-dimethylformamide, toluene 20
After adding 0 g, the product was washed twice with 200 g of pure water and distilled under reduced pressure (150 to 10 mmHg) in an oil bath at a temperature of 80 to 100 ° C to obtain 39.8 g of a solid pale yellow product.
(Yield 96.6%) This product had a melting point of 54 to 56 ° C. as a solid substance.
【００２０】下記に示す1Ｈ−ＮＭＲのスペクトルデー
タより、得られた化合物が３，９−ビス（２−メタリル
オキシカルボニルエチル）２，４，８，１０−テトラオ
キサスピロ〔５．５〕ウンデカンであることが確認され
た。From the 1 H-NMR spectrum data shown below, the obtained compound was 3,9-bis (2-methallyloxycarbonylethyl) 2,4,8,10-tetraoxaspiro [5.5]. It was confirmed to be undecane.
【００２１】[0021]
【化５】 １．６〜１．８ｐｐｍ ： １．９〜２．０ｐｐｍ ： ２．４〜２．６ｐｐｍ ： ３．２〜３．８ｐｐｍ ： ４．４〜４．６ｐｐｍ ： ４．８〜５．０ｐｐｍ ： [Chemical 5] 1.6-1.8 ppm: 1.9-2.0 ppm: 2.4-2.6 ppm: 3.2-3.8 ppm: 4.4-4.6 ppm: 4.8-5.0 ppm:
Claims (1)
れるジアリルエステルまたはジメタリルエステル化合物1. A compound represented by the general formula [I]: (Wherein R represents a hydrogen atom or a methyl group) or a diallyl ester or dimethallyl ester compound
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03594394A JP3577732B2 (en) | 1994-03-07 | 1994-03-07 | Diallyl ester or dimethallyl ester compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03594394A JP3577732B2 (en) | 1994-03-07 | 1994-03-07 | Diallyl ester or dimethallyl ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07242654A true JPH07242654A (en) | 1995-09-19 |
| JP3577732B2 JP3577732B2 (en) | 2004-10-13 |
Family
ID=12456089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03594394A Expired - Fee Related JP3577732B2 (en) | 1994-03-07 | 1994-03-07 | Diallyl ester or dimethallyl ester compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3577732B2 (en) |
-
1994
- 1994-03-07 JP JP03594394A patent/JP3577732B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3577732B2 (en) | 2004-10-13 |
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