JPH078837B2 - Method for producing allyl ester - Google Patents
Method for producing allyl esterInfo
- Publication number
- JPH078837B2 JPH078837B2 JP62322946A JP32294687A JPH078837B2 JP H078837 B2 JPH078837 B2 JP H078837B2 JP 62322946 A JP62322946 A JP 62322946A JP 32294687 A JP32294687 A JP 32294687A JP H078837 B2 JPH078837 B2 JP H078837B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- allyl
- allyl alcohol
- catalyst
- ester
- 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.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は芳香族多塩基酸、例えばテレフタル酸、イソフ
タル酸、トリメリット酸、ピロメリット酸等のアルキル
エステルとアリルアルコールまたはメタリルアルコール
とのエステル交換反応により対応するアリルまたはメタ
リル〔以下（メタ）アリルと称す〕エステル類を合成す
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to aromatic polybasic acids such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and other alkyl esters with allyl alcohol or methallyl alcohol. The present invention relates to a method for synthesizing corresponding allyl or methallyl [hereinafter referred to as (meth) allyl] esters by a transesterification reaction.
本発明の目的化合物である芳香族多塩基酸の（メタ）ア
リルエステル類は反応性の高いモノマーである。各種架
橋剤として用いられるほか、そのもの自身の重合物も、
電気特性、寸法安定性、耐熱性、耐候性、耐薬品性、機
械的特性に優れ各種成形品、積層板、化粧板等に広く使
用できる。また近年、優れた光学特性を持つこともわか
り、光学材料としても使用されつつある。The (meth) allyl esters of aromatic polybasic acids, which are the target compounds of the present invention, are highly reactive monomers. In addition to being used as various crosslinking agents,
It has excellent electrical properties, dimensional stability, heat resistance, weather resistance, chemical resistance, and mechanical properties, and can be widely used for various molded products, laminated boards, decorative boards, etc. Further, in recent years, it has been found that it has excellent optical characteristics, and it is being used as an optical material.
［従来技術と問題点］ 従来この種のエステルの合成法としては、 １）カルボン酸クロライドとアルコールを原料とする合
成法。[Prior Art and Problems] Conventionally, as a synthetic method of this kind of ester, 1) a synthetic method using carboxylic acid chloride and alcohol as raw materials.
２）カルボン酸のアルカリ塩とアルキルハライドを原料
とする合成法。2) A synthetic method using an alkali salt of carboxylic acid and an alkyl halide as raw materials.
３）カルボン酸とアルコールを原料とする合成法。3) A synthetic method using carboxylic acid and alcohol as raw materials.
４）カルボン酸のアルキルエステルとアルコールを原料
とする合成法。4) A synthetic method using an alkyl ester of carboxylic acid and an alcohol as raw materials.
等が知られていた。Etc were known.
しかし、これらの方法を本発明に関係する化合物の合成
に用いようとした場合には、１）の方法は原料の酸クロ
ライドが高価であるという致命的欠点がある。However, when these methods are used for the synthesis of the compounds related to the present invention, the method 1) has a fatal disadvantage that the acid chloride as a raw material is expensive.
２）の方法を適用した場合には、アルキルハライドが加
水分解されてアリルアルコールになる副反応がかなりの
割合で起こり、原料と副生物との分離回収等の操作が複
雑になる上に、コストもかかる。When the method of 2) is applied, a considerable amount of side reaction occurs in which the alkyl halide is hydrolyzed to form allyl alcohol, which complicates operations such as separation and recovery of the raw material and by-products, and also reduces the cost. Also takes.
３）の方法では、一般に芳香族多塩基酸の溶解度が（メ
タ）アリルアルコールに対して極めて低く、円滑に反応
を進行させることが困難な上に、通常用いられる酸触媒
に対して（メタ）アリルアルコールが安定でなく、ジ
（メタ）アリルエーテルを副生するという欠点がある。In the method 3), generally, the solubility of the aromatic polybasic acid is extremely low in (meth) allyl alcohol, and it is difficult to smoothly proceed the reaction. Allyl alcohol is not stable and has a drawback that di (meth) allyl ether is by-produced.
４）の方法については、特開昭48-28444、48-97833、48
-99136、48-103536、49-1531、56-71045等の方法が知ら
れているが、これらはいずれも高価な亜鉛またはマンガ
ンのβ−ジケトン錯体や有機スズ化合物を触媒として使
用しなければならない。For the method 4), see JP-A-48-28444, 48-97833, 48
-99136, 48-103536, 49-1531, 56-71045, etc. are known, but all of them must use expensive zinc or manganese β-diketone complex or organotin compound as a catalyst. .
本発明者らは特開昭62-12747にアルカリ金属の炭酸塩ま
たは炭酸水素塩を用いる方法を出願したが、この方法で
は触媒は安価な化合物を用い、収率は高いものの、反応
液に着色がみられ、特に光学材料として使用する場合に
は問題が残った。また、この触媒を用いると副反応とし
て芳香族多塩基酸とアルカリ金属の塩が生成してしま
い、芳香族多塩基酸として、ジメチルイソフタレートを
用いた場合には、反応終了後、アリルアルコールを除去
すると、この塩により反応液がゲル状になってしまい、
分離に多大な労力を要するという問題がある。The inventors of the present invention filed a method using an alkali metal carbonate or hydrogen carbonate in JP-A-62-12747. In this method, an inexpensive compound is used as a catalyst, and although the yield is high, the reaction liquid is colored. However, the problem remained especially when used as an optical material. When this catalyst is used, a salt of an aromatic polybasic acid and an alkali metal is produced as a side reaction, and when dimethylisophthalate is used as the aromatic polybasic acid, allyl alcohol is added after the reaction is completed. When removed, this salt causes the reaction solution to gel,
There is a problem that a great deal of labor is required for separation.
また、これらの触媒は、一般に水分により失活してしま
うので、原料のアリルアルコールの水分を極力減らす必
要があった。Further, since these catalysts are generally deactivated by water, it is necessary to reduce the water content of the raw material allyl alcohol as much as possible.
［発明が解決しようとする問題点］ 本発明では上記のような従来技術の欠点を考慮し、芳香
族多塩基酸のアルキルエステルと（メタ）アリルアルコ
ールを反応させて、芳香族多塩基酸の（メタ）アリルエ
ステルを得るに際して、工業的に有利に生産できて、着
色等の品質面での問題を起こさず、水分等の不純物の共
存にも影響を受けにくい方法を開発することである。[Problems to be Solved by the Invention] In the present invention, in consideration of the above-mentioned drawbacks of the conventional techniques, an alkyl ester of an aromatic polybasic acid is reacted with a (meth) allyl alcohol to produce an aromatic polybasic acid. To obtain a (meth) allyl ester, it is necessary to develop a method that can be industrially advantageously produced, does not cause quality problems such as coloring, and is not easily affected by the coexistence of impurities such as water.
［問題を解決するための手段］ そこで本発明者らは、これらの問題を解決すべく研究を
重ねた結果、アルカリ土類金属の水酸化物または酸化物
が、このエステル交換反応に対して、従来知られている
触媒よりも非常に優れていることを見いだした。[Means for Solving Problems] Therefore, as a result of repeated studies to solve these problems, the present inventors have found that the hydroxide or oxide of an alkaline earth metal is associated with this transesterification reaction. It has been found to be very superior to previously known catalysts.
つまり、従来知られている触媒よりも、アリルアルコー
ル中に含まれる水分の反応に与える影響が低く、また、
反応中の着色もほとんどない上に、極めて高い活性およ
び選択性を有する。That is, the effect of water contained in allyl alcohol on the reaction is lower than that of a conventionally known catalyst,
There is almost no coloration during the reaction, and it has extremely high activity and selectivity.
この反応は芳香族多塩基酸のポリアルキルエステルと
（メタ）アリルアルコールを、アルカリ土類金属の水酸
化物または酸化物を触媒としててエステル交換反応を行
い対応する（メタ）アリルエステルを合成する反応であ
る。In this reaction, a polyalkyl ester of an aromatic polybasic acid and a (meth) allyl alcohol are subjected to transesterification using a hydroxide or oxide of an alkaline earth metal as a catalyst to synthesize a corresponding (meth) allyl ester. It is a reaction.
原料の芳香族多塩基酸のポリアルキルエステルのアルキ
ル基としては、アリルアルコールよりも低沸点のアルコ
ールを生成するものが望ましく、このようなものとして
はC4以下のアルキル基であり、具体的には、メチル、エ
チル、イソプロピル、ｔ−ブチル基であり特にメチル基
が工業的にみて好ましい。As the alkyl group of the polyalkyl ester of the aromatic polybasic acid of the raw material, it is desirable that an alkyl group having a boiling point lower than that of allyl alcohol is produced, and such an alkyl group having C 4 or less, specifically, Is a methyl group, an ethyl group, an isopropyl group, and a t-butyl group, and a methyl group is particularly preferable from an industrial viewpoint.
触媒として用いるアルカリ土類金属の水酸化物、酸化物
としては具体的には、水酸化カルシウム、水酸化マグネ
シウム、水酸化バリウム、酸化カルシウム、酸化マグネ
シウムであるが、特に水酸化カルシウム、酸化カルシウ
ムが性能的にみて好ましい。Specific examples of the hydroxides and oxides of alkaline earth metals used as catalysts include calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium oxide, and magnesium oxide, but calcium hydroxide and calcium oxide are particularly preferable. It is preferable in terms of performance.
反応の形態としては芳香族多塩基酸エステルと（メタ）
アリルアルコールを触媒の存在下に加熱するという方法
をとる。反応温度は30から200℃、好ましくは50〜150℃
の範囲から選ばれ、常圧または加圧下、または必要に応
じて減圧下で、不活性ガス雰囲気で行われることが望ま
しい。さらに、反応を効率的に行うためには、生成する
アルコールを反応系外に速やかに留出させたほうがよ
い。The reaction forms include aromatic polybasic acid ester and (meth)
The method of heating allyl alcohol in the presence of a catalyst is adopted. Reaction temperature is 30 to 200 ° C, preferably 50 to 150 ° C
It is desirable to carry out in an inert gas atmosphere under normal pressure or under pressure, or under reduced pressure if necessary. Further, in order to carry out the reaction efficiently, it is preferable that the produced alcohol be promptly distilled out of the reaction system.
（メタ）アリルアルコールの使用量としては、原料エス
テルに対して理論量は最低限必要であり、反応速度、平
衡等を考慮すれば、更に過剰モル使用したほうがよい。
しかし、（メタ）アリルアルコールをあまりに大過剰用
いても、その過剰量に見合う効果が出ないので経済的に
好ましくない。よって通常（メタ）アリルアルコールは
原料エステルの理論量に対して、1.2〜10倍モルより好
ましくは1.5〜４倍モル程度を使用する。その際の仕込
方法としては反応の最初に仕込んでもよいし、反応途中
に順次加えて入ってもよい。As for the amount of (meth) allyl alcohol used, the theoretical amount is the minimum necessary with respect to the raw material ester, and in consideration of the reaction rate, equilibrium and the like, it is better to use an excessive molar amount.
However, even if the (meth) allyl alcohol is used in an excessively large amount, the effect corresponding to the excessive amount is not obtained, which is not economically preferable. Therefore, usually (meth) allyl alcohol is used in an amount of 1.2 to 10 times, preferably 1.5 to 4 times the molar amount of the starting ester. As the charging method at that time, the charging may be carried out at the beginning of the reaction or may be sequentially added during the reaction.
触媒の使用量としては、原料エステルに対して0.1wt％
〜5wt％、好ましくは0.5wt％〜3wt％程度である。この
場合も、少なすぎる場合には反応速度が遅くなるし、多
い場合にはその量に見合う効果が得られないばかりか、
副反応のためにかえって収率が低下してしまう場合すら
ある。The amount of catalyst used is 0.1 wt% with respect to the raw material ester.
It is about 5 wt%, preferably about 0.5 wt% to 3 wt%. Also in this case, if the amount is too small, the reaction speed becomes slow, and if the amount is too large, not only the effect corresponding to the amount cannot be obtained,
In some cases, the yield may decrease due to side reactions.
本反応系で生成した芳香族多塩基酸のアリルエステルの
単離法としては、反応時の着色が少ないために、（メ
タ）アリルアルコールを留出後、濾過等の適当な手段で
触媒を分離後、酸洗浄、アルカリ洗浄するだけで、製品
として得ることが出来るという大きな特徴を有する。As a method for isolating the allyl ester of aromatic polybasic acid produced in this reaction system, since the (meth) allyl alcohol is distilled off, the catalyst is separated by an appropriate means such as filtration, because the coloration during the reaction is small. After that, it has a great feature that it can be obtained as a product only by performing acid cleaning and alkali cleaning.
無論、蒸留等の適当な手段で精製すれば、更に高品質な
製品が得られることはいうまでもない。Needless to say, a higher quality product can be obtained by purifying by an appropriate means such as distillation.
以下に実施例をあげて説明する。Examples will be described below.
［実施例］ 実施例１ ジメチルイソフタレート（以下DMIと略記）100g、アリ
ルアルコール120g、水酸化カルシウム2gを温度計、精留
塔のついた300ml三ツ口フラスコに仕込み、120℃に調節
した油浴により加熱して反応を行った。反応の進行とと
もに、生成してくるメタノールを精留塔から留出させて
18時間反応を行った。反応終了後、ガスクロマトグラフ
ィー（以下GCと略）分析によりDMIに対し、95.8％のジ
アリルイソフタレートが生成していることを確認した。
この後系内に残っているアリルアルコールを減圧下に留
去し、濾過により触媒を除いた。濾液はほぼ無色透明で
あり、APHA数は５であった。[Examples] Example 1 100 g of dimethyl isophthalate (hereinafter abbreviated as DMI), 120 g of allyl alcohol, and 2 g of calcium hydroxide were placed in a 300 ml three-necked flask equipped with a thermometer and a rectification column, and an oil bath adjusted to 120 ° C was used. The reaction was carried out by heating. As the reaction progresses, the generated methanol is distilled from the rectification column.
The reaction was performed for 18 hours. After completion of the reaction, it was confirmed by gas chromatography (hereinafter abbreviated as GC) analysis that 95.8% of diallyl isophthalate was produced with respect to DMI.
After this, allyl alcohol remaining in the system was distilled off under reduced pressure, and the catalyst was removed by filtration. The filtrate was almost colorless and transparent, and the APHA number was 5.
この濾液を直接減圧蒸留して、沸点140℃〜142℃（0.2m
mHg）の無色透明なジアリルイソフタレート115.4g（収
率91％）を得た。This filtrate is directly distilled under reduced pressure to give a boiling point of 140 ℃ -142 ℃ (0.2m
As a result, 115.4 g (yield 91%) of colorless and transparent diallyl isophthalate (mHg) was obtained.
実施例２ 実施例１の水酸化カルシウムに代え、種々のアルカリ土
類金属の水酸化物、酸化物で反応を行った。触媒と反応
時間、GC収率を表−１に示す。Example 2 Instead of the calcium hydroxide used in Example 1, various alkaline earth metal hydroxides and oxides were used for the reaction. Table 1 shows the catalyst, reaction time, and GC yield.
実施例３ DMI10.0g、メタリルアルコール14.86g、水酸化カルシウ
ム0.3gを温度計、精留塔のついた50mlの三ツ口フラスコ
に仕込み、130℃に調節した油浴により加熱し反応を行
った。反応の進行とともに、生成してくるメタノールを
精留塔から留出させて18時間反応を行った。反応終了
後、GC分析によりDMIに対し、92.6％のジメタリルイソ
フタレートが生成していることを確認した。 Example 3 10.0 g of DMI, 14.86 g of methallyl alcohol and 0.3 g of calcium hydroxide were placed in a 50 ml three-necked flask equipped with a thermometer and a rectification column, and the reaction was carried out by heating in an oil bath adjusted to 130 ° C. With the progress of the reaction, the produced methanol was distilled off from the rectification column and the reaction was carried out for 18 hours. After the reaction was completed, it was confirmed by GC analysis that 92.6% of dimethallyl isophthalate was produced based on DMI.
実施例４ 実施例３のDMIの代わりに種々の芳香族カルボン酸のア
ルキルエステルで反応を行った。原料と反応時間、GCま
たは液体クロマトグラフィー（以下LCと略）での収率を
表−２に示す。Example 4 Instead of the DMI of Example 3, the reaction was carried out with alkyl esters of various aromatic carboxylic acids. Table 2 shows the raw materials, the reaction time, and the yield by GC or liquid chromatography (hereinafter abbreviated as LC).
比較例 従来のエステル交換反応の触媒と比較するために、DMI1
00g、アリルアルコール120g、表−３の触媒を実施例１
と同じ反応装置に仕込み、120℃に調節した油浴で加熱
して反応を行った。表−３に結果を示す。 Comparative Example To compare with a conventional transesterification catalyst, DMI1
00g, allyl alcohol 120g, the catalyst of Table-3 in Example 1
It was charged in the same reaction apparatus as above and heated in an oil bath adjusted to 120 ° C. to carry out the reaction. The results are shown in Table-3.
この表よりK2CO3，Ti(OEt)4,NaOMeは水分による失活が
起こり易く、また反応中の着色が著しい。 From this table, K 2 CO 3 , Ti (OEt) 4 , and NaOMe are easily deactivated by water, and coloring during the reaction is remarkable.
また、炭酸カリウムの場合、反応終了後にアリルアルコ
ールを留去すると、反応系全体がゲル状になった。In the case of potassium carbonate, when allyl alcohol was distilled off after the reaction was completed, the whole reaction system became gel.
［効果］ 本発明によれば、芳香族多塩基酸のアリルエステルを反
応中の着色がなく、経済的な方法で合成することが出来
る。[Effect] According to the present invention, an allyl ester of an aromatic polybasic acid can be synthesized by an economical method without coloring during the reaction.
Claims (3)
ルアルコールまたはメタリルアルコールとを反応させて
芳香族多塩基酸のアリルエステルを合成する際に、エス
テル交換反応の触媒としてアルカリ土類金属の水酸化物
または酸化物を用いる方法。1. When an alkyl ester of an aromatic polybasic acid is reacted with allyl alcohol or methallyl alcohol to synthesize an allyl ester of an aromatic polybasic acid, an alkaline earth metal catalyst is used as a catalyst for the transesterification reaction. A method using a hydroxide or an oxide.
カルシウム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 hydroxide of alkaline earth metal is calcium hydroxide.
ートである特許請求の範囲第１項記載の方法。3. The method according to claim 1, wherein the aromatic polybasic acid is dimethyl isophthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322946A JPH078837B2 (en) | 1987-12-22 | 1987-12-22 | Method for producing allyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322946A JPH078837B2 (en) | 1987-12-22 | 1987-12-22 | Method for producing allyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01165549A JPH01165549A (en) | 1989-06-29 |
| JPH078837B2 true JPH078837B2 (en) | 1995-02-01 |
Family
ID=18149401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62322946A Expired - Lifetime JPH078837B2 (en) | 1987-12-22 | 1987-12-22 | Method for producing allyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH078837B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911986A (en) * | 2018-07-24 | 2018-11-30 | 寿光诺盟化工有限公司 | A kind of preparation method of diallyl isophthalate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0425450A (en) * | 1990-05-21 | 1992-01-29 | Showa Denko Kk | Copper-clad laminated sheet |
| JP5530606B2 (en) * | 2008-07-10 | 2014-06-25 | 国立大学法人 東京大学 | Method for producing triphenylene carboxylic acid ester |
-
1987
- 1987-12-22 JP JP62322946A patent/JPH078837B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911986A (en) * | 2018-07-24 | 2018-11-30 | 寿光诺盟化工有限公司 | A kind of preparation method of diallyl isophthalate |
| CN108911986B (en) * | 2018-07-24 | 2021-02-26 | 寿光诺盟化工有限公司 | Preparation method of diallyl isophthalate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01165549A (en) | 1989-06-29 |
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