JPH078830B2 - Purification method of acrylate or methacrylate - Google Patents
Purification method of acrylate or methacrylateInfo
- Publication number
- JPH078830B2 JPH078830B2 JP1158384A JP15838489A JPH078830B2 JP H078830 B2 JPH078830 B2 JP H078830B2 JP 1158384 A JP1158384 A JP 1158384A JP 15838489 A JP15838489 A JP 15838489A JP H078830 B2 JPH078830 B2 JP H078830B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- mercaptan
- meth
- copper
- compound
- 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 - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は微量のメルカプタンを含有する（メタ）アクリ
レートの精製法に関する。即ち、微量のメルカプタン系
化合物例えばｎ−ブチルメルカプタン、ｔ−ブチルメル
カプタン、ｎ−オクチルメルカプタン等を不純物として
含む（メタ）アクリレートを鉛化合物及び／又は銅化合
物で処理することにより、該不純物を殆んど系内から除
去することのできる（メタ）アクリレートの精製法に関
する。TECHNICAL FIELD The present invention relates to a method for purifying (meth) acrylate containing a trace amount of mercaptan. That is, by treating a (meth) acrylate containing a trace amount of a mercaptan compound such as n-butyl mercaptan, t-butyl mercaptan, n-octyl mercaptan as an impurity with a lead compound and / or a copper compound, most of the impurities are removed. The present invention relates to a method for purifying (meth) acrylate that can be removed from the system.
（メタ）アクリレートを過酸化物又はアゾ系化合物を重
合開始剤として重合させ、連鎖移動剤としてメルカプタ
ン系化合物を使用し、重合後、残存モノマーを脱揮回収
すると、回収されたモノマー中にメルカプタンが含まれ
ることになる。メルカプタンは極微量存在しても特有の
臭気を発するため、回収したモノマーは、このままでは
通常、再利用が困難である。また、これらメルカプタン
は抽出、蒸留等により完全に除去することが困難であ
る。従つて簡便かつ効果的な不純物としてのメルカプタ
ンの除去法の開発が望まれていた。The (meth) acrylate is polymerized with a peroxide or an azo compound as a polymerization initiator, the mercaptan compound is used as a chain transfer agent, and after the polymerization, the residual monomer is volatilized and recovered, and mercaptan is contained in the recovered monomer. Will be included. Since mercaptan emits a peculiar odor even if it is present in an extremely small amount, it is usually difficult to reuse the recovered monomer as it is. Further, it is difficult to completely remove these mercaptans by extraction, distillation and the like. Therefore, development of a simple and effective method for removing mercaptan as an impurity has been desired.
本発明は、微量のメルカプタンを含有する（メタ）アク
リレートを鉛化合物及び／又は銅化合物で処理すること
を特徴とする（メタ）アクリレートの精製法である。The present invention is a method for purifying (meth) acrylate, which comprises treating a (meth) acrylate containing a trace amount of mercaptan with a lead compound and / or a copper compound.
本発明においては、処理液を蒸留して、精製（メタ）ア
クリレートを取得することが好ましい。In the present invention, it is preferable to distill the treatment liquid to obtain purified (meth) acrylate.
本発明に用いられる鉛化合物としては、例えば四酸化三
鉛、酸化鉛、二酸化鉛、及びこれらの混合物等が挙げら
れる。四酸化三鉛が好ましい。Examples of the lead compound used in the present invention include trilead tetraoxide, lead oxide, lead dioxide, and a mixture thereof. Trilead tetroxide is preferred.
また銅化合物としては、例えば蟻酸銅、酢酸銅、くえん
酸銅、オレイン酸銅、ナフテン酸銅等を含むカルボン酸
銅（II）塩特にC2〜C19のカルボン酸銅（II）塩が好ま
しい。そのほか例えば硫酸銅、塩化銅等の無機の銅塩、
銅（II）アセチルアセトナート等の錯化合物及びこれら
の混合物も挙げられる。また、これら鉛及び銅化合物
は、それぞれ単独で使用しても、また併用しても効果を
発揮する。As the copper compound, for example, copper carboxylate (II) salts containing copper formate, copper acetate, copper citrate, copper oleate, copper naphthenate, etc., particularly C 2 to C 19 carboxylate copper (II) salts are preferable. . In addition, for example, copper sulfate, inorganic copper salts such as copper chloride,
Complex compounds such as copper (II) acetylacetonate and mixtures thereof may also be mentioned. In addition, these lead and copper compounds are effective when used alone or in combination.
本発明の（メタ）アクリレートとしては、メチルアクリ
レート、エチルーアクリレート、プロピルアクリレー
ト、ブチルアクリレート、メチルメタクリレート、エチ
ルメタクリレート、プロピルメタクリレート、ブチルメ
タクリレート及びこれらの混合物等が挙げられる。Examples of the (meth) acrylate of the present invention include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and mixtures thereof.
（メタ）アクリレートに含有されるメルカプタンとして
は、炭素数１〜８のアルキルメルカプタン例えばメチル
メルカプタン、エチルメルカプタン、プロピルメルカプ
タン、ブチルメルカプタン、オクチルメルカプタン及び
これらの混合物が挙げられる。これらは主に（メタ）ア
クリレートの重合の際に、連鎖移動剤として添加された
化合物である。Examples of the mercaptan contained in the (meth) acrylate include alkyl mercaptans having 1 to 8 carbon atoms, such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, and mixtures thereof. These are compounds added as a chain transfer agent mainly during the polymerization of (meth) acrylate.
本発明を実施するに際しては、微量のメルカプタンを含
有する（メタ）アクリレートに鉛及び／又は銅化合物を
添加し、必要に応じ加熱しながら、好ましくは攪拌しな
がら、一定時間保持する。In carrying out the present invention, a lead and / or copper compound is added to (meth) acrylate containing a trace amount of mercaptan, and if necessary, heated and preferably stirred for a certain period of time.
鉛及び／又は銅化合物は、（メタ）アクリレート中に不
純物として含まれているメルカプタン１重量部当り、鉛
及び／又は銅として0.05〜５重量部の鉛及び／又は銅化
合物になるように添加するのが好ましい。処理温度は０
〜60℃好ましくは室温ないし40℃の範囲であり、処理時
間は１ないし数時間が好ましい。The lead and / or copper compound is added so as to be 0.05 to 5 parts by weight of lead and / or copper compound per 1 part by weight of mercaptan contained as an impurity in the (meth) acrylate. Is preferred. Processing temperature is 0
-60 ° C, preferably room temperature to 40 ° C, and the treatment time is preferably 1 to several hours.
こうして処理することにより、不純物として含まれてい
たメルカプタン類を完全に除去することができ、（メ
タ）アクリレートは何らの影響を受けない。By this treatment, mercaptans contained as impurities can be completely removed and the (meth) acrylate is not affected at all.
こうして得られた処理液を好ましくは重合防止剤を添加
して蒸留処理を行うことによりメルカプタンをまつたく
含有しない高純度の（メタ）アクリレートを取得するこ
とが可能となる。It is possible to obtain a high-purity (meth) acrylate containing no mercaptan by distilling the thus obtained treatment liquid, preferably by adding a polymerization inhibitor.
実施例１ 撹拌機及びクーラーを付した300mlの三ツ口フラスコに
ｎ−ブチルメルカプタンを1400ppm含むメタクリル酸メ
チル200gを入れ、鉛化合物として四酸化三鉛0.6gを加
え、25℃の恒温槽にその三ツ口フラスコを浸漬し、300
〜400rpmで攪拌する。Example 1 200 g of methyl methacrylate containing 1400 ppm of n-butyl mercaptan was placed in a 300 ml three-necked flask equipped with a stirrer and a cooler, 0.6 g of trilead tetroxide was added as a lead compound, and the three-necked flask was placed in a thermostat at 25 ° C. Dip, 300
Stir at ~ 400 rpm.
２時間後、重合防止剤としてジフエニル−ｐ−フエニレ
ンジアミンを500ppm添加し、リービツヒの冷却管を付
し、恒温槽温度を60℃に昇温し、減圧下（180mmHg）メ
タクリル酸メチルを蒸留する。約98％留出した留出液に
ついて、水素炎型ガスクロマトグラフ法でｎ−ブチルメ
ルカプタンを定量した結果、定量限界（10ppm）以下で
あつた。After 2 hours, add 500ppm of diphenyl-p-phenylenediamine as a polymerization inhibitor, attach a Liebig cooling tube, raise the temperature of the constant temperature bath to 60 ° C, and distill methyl methacrylate under reduced pressure (180mmHg). . The amount of n-butyl mercaptan in the distillate obtained by distilling out about 98% was determined by hydrogen flame gas chromatography, and the result was below the limit of quantification (10 ppm).
実施例２ 実施例１において四酸化三鉛の代りに、ナフテン酸銅0.
8gを用い、その他は同様に処理した結果、蒸留液中には
ｎ−ブチルメルカプタンは検出されなかつた。Example 2 Instead of trilead tetroxide in Example 1, copper naphthenate 0.
As a result of using 8 g and the same treatment as above, n-butyl mercaptan was not detected in the distillate.
実施例３ 実施例１において四酸化三鉛を0.6gから0.2gに代え、更
にナフテン酸銅を0.4g加え、その他は同様に処理した結
果、蒸留液中にはｎ−ブチルメルカプタンは検出されな
かつた。Example 3 In Example 1, the amount of trilead tetroxide was changed from 0.6 g to 0.2 g, copper naphthenate was further added to 0.4 g, and the same treatment was carried out with respect to others, and as a result, n-butyl mercaptan was not detected. It was
実施例４〜11 下記表に示す鉛化合物及び銅化合物を用い、それぞれの
（メタ）アクリル酸エステルに加え、実施例１と同様に
処理した。得られた（メタ）アクリル酸エステル中のメ
ルカプタンの定量結果を併せて表中に示す。Examples 4 to 11 Using the lead compounds and copper compounds shown in the table below, the compounds were added to the respective (meth) acrylic acid esters and treated in the same manner as in Example 1. The quantitative results of mercaptan in the obtained (meth) acrylic acid ester are also shown in the table.
Claims (2)
クリレートを鉛化合物及び／又は銅化合物で処理するこ
とを特徴とする（メタ）アクリレートの精製法。1. A method for purifying (meth) acrylate, which comprises treating a (meth) acrylate containing a trace amount of mercaptan with a lead compound and / or a copper compound.
クリレートを鉛化合物及び／又は銅化合物で処理したの
ち、処理液を蒸溜して、精製（メタ）アクリレートを取
得することを特徴とする（メタ）アクリレートの精製
法。2. A method of treating a (meth) acrylate containing a trace amount of mercaptan with a lead compound and / or a copper compound, and distilling the treatment liquid to obtain a purified (meth) acrylate (meth). ) Acrylate purification method.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1158384A JPH078830B2 (en) | 1989-06-22 | 1989-06-22 | Purification method of acrylate or methacrylate |
| DE1990601099 DE69001099T2 (en) | 1989-06-22 | 1990-06-14 | METHOD FOR REMOVING MERCAPTANS. |
| EP19900401660 EP0404643B1 (en) | 1989-06-22 | 1990-06-14 | Method for removing mercaptans |
| CA 2019488 CA2019488A1 (en) | 1989-06-22 | 1990-06-21 | Method for removing mercaptans |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1158384A JPH078830B2 (en) | 1989-06-22 | 1989-06-22 | Purification method of acrylate or methacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0324035A JPH0324035A (en) | 1991-02-01 |
| JPH078830B2 true JPH078830B2 (en) | 1995-02-01 |
Family
ID=15670543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1158384A Expired - Fee Related JPH078830B2 (en) | 1989-06-22 | 1989-06-22 | Purification method of acrylate or methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH078830B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01143168A (en) * | 1987-11-27 | 1989-06-05 | Yamaichi Electric Mfg Co Ltd | Contact mechanism in socket for electric part |
| JP3076782B2 (en) * | 1997-12-01 | 2000-08-14 | 山一電機株式会社 | IC socket |
| JP2895039B1 (en) | 1998-02-02 | 1999-05-24 | 山一電機株式会社 | IC socket |
| JP7604701B1 (en) * | 2024-05-10 | 2024-12-23 | 住友化学株式会社 | Method for producing methyl methacrylate, composition, polymer, cured product, and molded product |
-
1989
- 1989-06-22 JP JP1158384A patent/JPH078830B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0324035A (en) | 1991-02-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090201 Year of fee payment: 14 |
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| LAPS | Cancellation because of no payment of annual fees |