JPS5849337A - Preparation of unsaturated monocarboxylic acid isobornyl ester - Google Patents
Preparation of unsaturated monocarboxylic acid isobornyl esterInfo
- Publication number
- JPS5849337A JPS5849337A JP14801481A JP14801481A JPS5849337A JP S5849337 A JPS5849337 A JP S5849337A JP 14801481 A JP14801481 A JP 14801481A JP 14801481 A JP14801481 A JP 14801481A JP S5849337 A JPS5849337 A JP S5849337A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated monocarboxylic
- monocarboxylic acid
- cation exchange
- exchange resin
- acidic cation
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、カンフエンと不飽和モノカルボン酸を強酸性
陽イオン交換樹脂を触媒として反応させ不飽和モノカル
ボン酸イソボルニルエステルを製造する方法に関する・
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing unsaturated monocarboxylic acid isobornyl ester by reacting camphene and unsaturated monocarboxylic acid using a strongly acidic cation exchange resin as a catalyst.
.
不飽和モノカルボン酸イソボルニルエステルは反応性モ
ノマー、ゴムやプラスチヅク類の可塑剤として有用な化
合物であるが、中でもカンフエンとアクリル酸又はメタ
クリル酸の付加反応物でゐろイソボルニルアクリレート
又はイソボルニルメタクリレートは、印刷用ＵＶインキ
や光硬化型、塗料のバインダーとして優秀な化合物であ
る。Unsaturated monocarboxylic acid isobornyl ester is a reactive monomer and a compound useful as a plasticizer for rubber and plastics. Bornyl methacrylate is an excellent compound as a binder for UV printing inks, photocurable types, and paints.
これまでにカンフエンと不飽和モノカルボン酸を反応さ
せて不飽和モノカルボン酸イソボルニルエステルを製造
する方法に関する特許や文献類は殆ント無＜、唯−米国
特許徊→命−岡 においてＢＦ８ を触媒として、カン
フエンとアクリル酸又ハメタクリル酸を反応させる製造
例があるのみである。しかし、この方法によると収率が
低く、又ＢＦ８ を用いるために装置の腐食対策や触媒
分離が煩雑になるという欠点があり工業的には好ましい
方法であるとは言えない。 ゛
本発明は、このような製造工程におけろ問題を解消する
とともに、高収率で本発明に係る化合物を製造する新規
な方法を提供するものである。Until now, there are almost no patents or documents related to the method of producing unsaturated monocarboxylic acid isobornyl ester by reacting camphene with unsaturated monocarboxylic acid. There is only a production example in which camphene is reacted with acrylic acid or methacrylic acid as a catalyst. However, this method has the drawbacks of low yield and the use of BF8, which makes it complicated to take measures against corrosion of the equipment and to separate the catalyst, so it cannot be said to be an industrially preferred method. The present invention solves these problems in the production process and provides a new method for producing the compound according to the present invention in high yield.
本発明の製造方法を詳しく述べると、カンフエンと不飽
和モノカルボン酸及び、少量の重合禁止剤を混合し、こ
の混合溶液に対し００５重量％以上、好ましくは０５重
量％以上の強酸性陽イオン交換樹脂を添加し、０〜１０
０℃、好ましくは１０〜６０℃でかき混ぜ反応を行う。To describe the production method of the present invention in detail, camphene, an unsaturated monocarboxylic acid, and a small amount of a polymerization inhibitor are mixed, and the mixed solution is subjected to strong acidic cation exchange in an amount of 0.05% by weight or more, preferably 0.5% by weight or more. Add resin, 0-10
The stirring reaction is carried out at 0°C, preferably from 10 to 60°C.
反応終了後触媒を分離し、更に蒸留を行うと本化合物が
得られる。あ・、いは、強酸性陽イオン交換樹脂を反応
管に充填し反応管の温度を０〜１００℃、−好ましくは
１０〜６０℃に保ちながら前記混合溶液を反応管中を通
過させることにより反応を行ってもよい。更にこの反応
物は前記と同様に処理することにより本化合物が得られ
る。これらの方法はいづれも収率は原料であるカンフエ
ンと不飽和モノカルボン酸の混合物に対して８５〜９０
重量％であった。After the reaction is completed, the catalyst is separated and further distilled to obtain the present compound. Ah, by filling a reaction tube with a strongly acidic cation exchange resin and passing the mixed solution through the reaction tube while maintaining the temperature of the reaction tube at 0 to 100°C, preferably 10 to 60°C. A reaction may also be carried out. Furthermore, this compound can be obtained by treating this reaction product in the same manner as described above. In all of these methods, the yield is 85 to 90% based on the raw material mixture of camphene and unsaturated monocarboxylic acid.
% by weight.
ヒ
前記の混合溶液ｉ触媒をかき混ぜる方法の反応の場合、
反応液と触媒の分離は触媒濾過器を用いるか、あるいは
反応終了後静置し、触媒を沈降させ上澄液を回収する方
法を用いてもよいが、いずれも操作としては簡単である
。In the case of the reaction using the method of stirring the mixed solution i catalyst described above,
The reaction solution and catalyst may be separated by using a catalyst filter, or by allowing the reaction to stand after the completion of the reaction, allowing the catalyst to settle, and recovering the supernatant, both of which are easy to operate.
又、強酸性陽イオン交換樹脂は反復して使用することが
可能であり経済的に極めて好ましい触媒である。In addition, strongly acidic cation exchange resins can be used repeatedly and are economically very preferable catalysts.
本発明における反応は前記のような無溶媒下でもまた適
当な溶媒を用いて行ってもよい。用い得る溶媒としては
ｎ−ヘキサン、シクロヘキサン等ノ飽和炭化水素、ベン
ゼン、トルエン、キシレン等の芳香族系炭化水素等があ
る。The reaction in the present invention may be carried out without a solvent as described above, or may be carried out using a suitable solvent. Examples of solvents that can be used include saturated hydrocarbons such as n-hexane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene.
本発明で用いる強酸性陽イオン交換樹脂は、スルホン酸
型（Ｒ−８０８Ｈ）のイオン交換樹脂が適表
当で、市販のものとしては、ＲＯｈｍ＆Ｈａ幻社製のア
ンバーリスト１５や三菱化成工業■製のダイヤイオンＨ
ＰＫ等がある。The strongly acidic cation exchange resin used in the present invention is suitably a sulfonic acid type (R-808H) ion exchange resin, and commercially available ones include Amberlyst 15 manufactured by ROhm & Ha Gensha and manufactured by Mitsubishi Chemical Corporation. Diamond Aeon H
There are PK etc.
前記製造方法において添加する重合禁止剤としては、ハ
イドロキノン、ハイドロキノンモノメチルエーテル、ｔ
−ブチルカテコール等がある。The polymerization inhibitors added in the production method include hydroquinone, hydroquinone monomethyl ether, t
-Butylcatechol, etc.
次に実施例によって本発明を更に具体的に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
かき混ぜ機、温度計、冷却管を付し′た反応容器６ζ、
カンフエン（自社製）８００？、アクリル酸（市販品）
１５９ｇとハイドロキノンＱ５ｆを入れよく混合し、こ
れに強酸性陽イオン交換樹脂（ＲＯＩＩＩＩＩｌＨａａ
ｓ社製アンバーリスト１５）２８ｆを入れ、３５〜４０
℃で５時間かき混ぜた後、触媒をガラス濾過器で炉別し
、反応油は減圧下蒸留を行い未反応物と高沸点物を除去
し、イソボルニルアクリレート（８８〜ｂ
このもののガスクロマトグラフィー純度は９４％（他の
６％はカンフエン異性体のアクリレート）であった。Example 1 Reaction vessel 6ζ equipped with a stirrer, thermometer, and cooling pipe,
Can Huen (made in-house) 800? , acrylic acid (commercially available)
Add 159g of hydroquinone Q5f and mix well, add strongly acidic cation exchange resin (ROIIIIIIHaa
Insert Amberlist 15) 28f made by S company, 35~40
After stirring at ℃ for 5 hours, the catalyst was filtered using a glass filter, and the reaction oil was distilled under reduced pressure to remove unreacted substances and high-boiling substances. The purity was 94% (the other 6% was camphene isomer acrylate).
実施例２ 実施例１と同様の装置に、カンフエン８００ｆ。Example 2 Camphuen 800f was added to the same apparatus as in Example 1.
メタクリル酸（市販品）１９０ｆとハイドロキノンＱ５
ｆを入れよく混合し、これに強酸性陽イオン交換樹脂（
実施例１と同品）２４．５ｆを入れ、以下実施例１と同
様に操作し、イソボルニルメタクリレート（８０〜ｂ
得た。このもののガスクロマトグラフィー純度は９８％
であった。Methacrylic acid (commercially available) 190f and hydroquinone Q5
Add f and mix well, add strongly acidic cation exchange resin (
24.5f (same product as in Example 1) was added and the following operations were carried out in the same manner as in Example 1 to obtain isobornyl methacrylate (80-b).The gas chromatography purity of this product was 98%.
Met.
実施例８
滴下ロート、温水加熱循環装置を付した内径１７ｍ１長
さ５００ｍｍのガラス管に、強酸性陽イオン交換樹脂（
三菱化成工業■製タイヤイ４ンＨＰＫンを４ＱＱｍｍの
長さに充填した反応管に、カンフエン８００ｆ、アクリ
ル酸１５９ ｆ 、ハイドロキノンα５ｆの混合溶液を
、３０〜３５亡で１．５〜２ ｍｌ／ｍ ｉ ｎの速度
で滴下した。得られた反応液）Ｊ、実施例１と同様に処
理し、イソボルニルアクリレート（８３〜ｌ１２℃／’
７ ｒｒｍＨｔの留分）８９０９が得られ、ガスクロマ
トグラフィー純度は９８％であった。Example 8 A strongly acidic cation exchange resin (
A mixed solution of camphene 800f, acrylic acid 159f, and hydroquinone α5f was added at 1.5 to 2 ml/m over a period of 30 to 35 minutes to a reaction tube filled with tire i4in HPK manufactured by Mitsubishi Chemical Corporation to a length of 4QQmm. It was dropped at a rate of i n. The obtained reaction solution) J was treated in the same manner as in Example 1, and was treated with isobornyl acrylate (83-112°C/'
A fraction of 7 rrmHt) 8909 was obtained, with gas chromatography purity of 98%.
★施例４
実施例８と同様の装置に、Ｒｏｈｍ ＆ Ｈａａｓ社製
アンバーリスト１５を充填し、カンフエン８００２、メ
タクリル酸１９（１，ハイドロキノンα５ｆの混合溶液
を実−施例８と同一の条件で滴下、更に処理し、イソボ
ルニルメタクリレート４２５ｆが得られガスクロマトグ
ラフィー純度は９４％であった。★Example 4 The same apparatus as in Example 8 was filled with Amberlyst 15 manufactured by Rohm & Haas, and a mixed solution of camphene 8002, methacrylic acid 19 (1, and hydroquinone α5f) was added under the same conditions as in Example 8. After dropping and further treatment, isobornyl methacrylate 425f was obtained with gas chromatography purity of 94%.
特許出願人 安原油脂工業株式会社
手続補正書（方式）
昭和５７年２月 １日
特貯庁長官殿 昭和５７ζ２月２ｔｌ ａｍｌ
、事件の表示
昭和５６年特許願第１４８０１４号
２ 発明の名称
不飽和モノカルボン酸イソボルニルエステルの製造方法
ａ 補正をする者
事件との関係 特許出願人
４、補正命令の日付
発送日 昭和５７年１月２６日
＆ 補正の対象
明細書の「発明の名称」の欄
６ 補正の内容
明細書の発明の名称「−イソポルエステル−」を「−イ
ソポルニルエステルー」と訂正する。Patent Applicant Anxiety Oil and Fat Industries Co., Ltd. Procedural Amendment (Method) February 1, 1980 To the Commissioner of the Special Savings Agency February 1982 2tl aml
, Indication of the case 1982 Patent Application No. 148014 2 Title of the invention Process for producing unsaturated monocarboxylic acid isobornyl ester a Person making the amendment Relationship to the case Patent applicant 4 Date of amendment order Date of dispatch 1982 January 26, 2015 & Column 6 of "Title of the Invention" in the Specification Subject to Amendment: The title of the invention "-Isopolester-" in the Specification of Contents of the Amendment is corrected to "-Isopolnylester-".
Claims (2)
陽イオン交換樹脂を触媒として反応させる事を特徴とす
る不飽和モノカルボン酸イソボルニルエステルの製造方
法。(1) A method for producing an unsaturated monocarboxylic acid isobornyl ester, which comprises reacting camphene and an unsaturated monocarboxylic acid using a strongly acidic cation exchange resin as a catalyst.
クリル酸である特許請求の範囲第（１）項記載の方法。(2) The method according to claim (1), wherein the unsaturated monocarboxylic acid is acrylic acid or methacrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14801481A JPS5849337A (en) | 1981-09-17 | 1981-09-17 | Preparation of unsaturated monocarboxylic acid isobornyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14801481A JPS5849337A (en) | 1981-09-17 | 1981-09-17 | Preparation of unsaturated monocarboxylic acid isobornyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5849337A true JPS5849337A (en) | 1983-03-23 |
Family
ID=15443172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14801481A Pending JPS5849337A (en) | 1981-09-17 | 1981-09-17 | Preparation of unsaturated monocarboxylic acid isobornyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5849337A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0624566A1 (en) * | 1993-05-13 | 1994-11-17 | Röhm Gmbh | Process for the preparation of isobornyle (meth)acrylate |
| EP0686620A1 (en) * | 1994-06-06 | 1995-12-13 | Hoechst Aktiengesellschaft | Process for the continuous production of terpene esters |
| EP0718271A1 (en) * | 1994-12-22 | 1996-06-26 | Elf Atochem S.A. | Process for the preparation of isobornyle (meth)acrylate |
| JP2006069944A (en) * | 2004-09-01 | 2006-03-16 | Osaka Organic Chem Ind Ltd | Method for manufacturing isobornyl (meth)acrylate |
| JP2009149559A (en) * | 2007-12-20 | 2009-07-09 | Mitsubishi Rayon Co Ltd | Camphene composition, method of preparing the same, and isobornyl (meth)acrylate preparation method |
-
1981
- 1981-09-17 JP JP14801481A patent/JPS5849337A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0624566A1 (en) * | 1993-05-13 | 1994-11-17 | Röhm Gmbh | Process for the preparation of isobornyle (meth)acrylate |
| EP0686620A1 (en) * | 1994-06-06 | 1995-12-13 | Hoechst Aktiengesellschaft | Process for the continuous production of terpene esters |
| EP0718271A1 (en) * | 1994-12-22 | 1996-06-26 | Elf Atochem S.A. | Process for the preparation of isobornyle (meth)acrylate |
| FR2728564A1 (en) * | 1994-12-22 | 1996-06-28 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF ISOBORNYL (METH) ACRYLATE |
| JPH0920719A (en) * | 1994-12-22 | 1997-01-21 | Elf Atochem Sa | Method for synthesizing isobornyl (meth)acrylate |
| JP2006069944A (en) * | 2004-09-01 | 2006-03-16 | Osaka Organic Chem Ind Ltd | Method for manufacturing isobornyl (meth)acrylate |
| JP2009149559A (en) * | 2007-12-20 | 2009-07-09 | Mitsubishi Rayon Co Ltd | Camphene composition, method of preparing the same, and isobornyl (meth)acrylate preparation method |
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