JPH0745446B2 - Method for purifying dialkylaminoethyl ester of acrylic acid or methacrylic acid - Google Patents
Method for purifying dialkylaminoethyl ester of acrylic acid or methacrylic acidInfo
- Publication number
- JPH0745446B2 JPH0745446B2 JP22211686A JP22211686A JPH0745446B2 JP H0745446 B2 JPH0745446 B2 JP H0745446B2 JP 22211686 A JP22211686 A JP 22211686A JP 22211686 A JP22211686 A JP 22211686A JP H0745446 B2 JPH0745446 B2 JP H0745446B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- acrylic acid
- meth
- dialkylaminoethyl
- methacrylic acid
- 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
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- 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） 本発明はアクリル酸ジアルキルアミノエチルエステルま
たはメタクリル酸ジアルキルアミノエチルエステル（以
下、（メタ）アクリル酸ジアルキルアミノエチルエステ
ルとする）の精製法に関するものである。詳しくは、こ
れら（メタ）アクリル酸ジアルキルアミノエチルエステ
ルを中和塩または四級塩とし、さらに重合して、高分子
量の良好な水溶性を有する重合体を得るのに適した（メ
タ）アクリル酸ジアルキルアミノエチルエステルの精製
法に関するものである。TECHNICAL FIELD The present invention relates to a method for purifying acrylic acid dialkylaminoethyl ester or methacrylic acid dialkylaminoethyl ester (hereinafter referred to as (meth) acrylic acid dialkylaminoethyl ester). Is. Specifically, these (meth) acrylic acid dialkylaminoethyl esters are suitable as neutralizing salts or quaternary salts and are further polymerized to obtain a polymer having a high molecular weight and good water solubility. The present invention relates to a method for purifying dialkylaminoethyl ester.
（メタ）アクリル酸ジアルキルアミノエチルエステル
は、塩酸、硫酸などの鉱酸で中和するか、塩化メチル、
ジメチル硫酸などのアルキル化剤と反応せしめることに
より中和塩または四級塩とし、この中和塩または四級塩
の単独重合、あるいはアクリルアミド等の共重合体は、
カチオン系高分子凝集剤、繊維処理剤、紙加工剤等とし
て広く用いられている。(Meth) acrylic acid dialkylaminoethyl ester can be neutralized with a mineral acid such as hydrochloric acid or sulfuric acid, or methyl chloride,
A neutralization salt or quaternary salt is obtained by reacting with an alkylating agent such as dimethylsulfate, and the neutralization salt or quaternary salt is homopolymerized or a copolymer such as acrylamide is
It is widely used as a cationic polymer flocculant, fiber treatment agent, paper processing agent and the like.
（従来の技術） 凝集剤として使用するためには、高分子量でしかも水溶
性が良好であることが望ましい。ところが（メタ）アク
リル酸ジアルキルアミノエチルエステルに含まれる不純
物は、重合の際、連鎖移動剤として作用し得られる重合
体の分子量を低下させたり、架橋剤となって重合体の水
溶液を低下させる原因となる。（メタ）アクリル酸ジア
ルキルアミノエチルエステルの精製は、一般に減圧蒸留
により行われる。(Prior Art) In order to use it as a flocculant, it is desirable that it has a high molecular weight and good water solubility. However, the impurities contained in the (meth) acrylic acid dialkylaminoethyl ester may act as a chain transfer agent during the polymerization to reduce the molecular weight of the obtained polymer, or become a cross-linking agent to reduce the aqueous solution of the polymer. Becomes The purification of (meth) acrylic acid dialkylaminoethyl ester is generally performed by vacuum distillation.
また、中和して水溶性の塩とした後、水不溶性の非極性
溶剤と接触させて不純物を抽出する方法も知られてい
る。Also known is a method of neutralizing the water-soluble salt and then contacting it with a water-insoluble non-polar solvent to extract impurities.
（発明が解決しようとする問題点） しかし、（メタ）アクリル酸ジアルキルアミノエチルエ
ステルと不純物の沸点は近く、不純物を蒸留のみで精度
良く分離するには、多くの蒸留段数及び還流比を必要と
する。しかし、（メタ）アクリル酸ジアルキルアミノエ
チルエステルは重合しやすい化合物であり、厳しい蒸留
条件で長時間蒸留操作を行うことは、系内での重合物の
析出、蒸留収率の低下等を引き起こし、工業的には好ま
しくない。また（メタ）アクリル酸ジアルキルアミノエ
チルエステルを中和塩として水に不溶性の非極性溶剤と
接触させて不純物を抽出除去する方法は、抽出効率が悪
く、また、使用した多量の溶剤の回収が必要で、製造工
程が煩雑となる。(Problems to be Solved by the Invention) However, the boiling points of the (meth) acrylic acid dialkylaminoethyl ester and the impurities are close to each other, and a large number of distillation stages and a high reflux ratio are required to accurately separate the impurities only by distillation. To do. However, (meth) acrylic acid dialkylaminoethyl ester is a compound that is easily polymerized, and performing a long-time distillation operation under severe distillation conditions causes precipitation of a polymer in the system, a decrease in distillation yield, and the like. Not industrially preferable. Also, the method of extracting and removing impurities by contacting (meth) acrylic acid dialkylaminoethyl ester as a neutralizing salt with a water-insoluble non-polar solvent has poor extraction efficiency and requires the recovery of a large amount of the used solvent. Therefore, the manufacturing process becomes complicated.
（問題を解決するための手段） 本発明者らは、前述の精製法の欠点を解決し、高分子量
でかつ水溶性が良好な重合体を製造するに適した、（メ
タ）アクリル酸ジアルキルアミノエチルエステルの精製
法について鋭意検討した結果、（メタ）アクリル酸ジア
ルキルアミノエチルエステルの精製に際し、活性炭で処
理することにより品質良好な（メタ）アクリル酸ジアル
キルアミノエチルエステルが得られることを見出し、本
発明を完成するに至った。(Means for Solving the Problem) The inventors of the present invention have solved the drawbacks of the above-described purification method and are suitable for producing a polymer having a high molecular weight and good water solubility, and a dialkylamino (meth) acrylate. As a result of diligent studies on the purification method of ethyl ester, it was found that good quality (meth) acrylic acid dialkylaminoethyl ester can be obtained by treating with activated carbon when purifying (meth) acrylic acid dialkylaminoethyl ester. The invention was completed.
すなわち、本発明は、一般式 （式中、R1は水素原子またはメチル基、R2及びR3は炭素
数１〜２のアルキル基を示す）で表される（メタ）アク
リル酸ジアルキルアミノエチルエステルの精製に際し、
活性炭で処理することを特徴とする（メタ）アクリル酸
ジアルキルアミノエチルエステルの精製法に関する。That is, the present invention has the general formula (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 and R 3 represent an alkyl group having 1 to 2 carbon atoms) In the purification of the (meth) acrylic acid dialkylaminoethyl ester,
It relates to a method for purifying (meth) acrylic acid dialkylaminoethyl ester, which is characterized in that it is treated with activated carbon.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明の方法により精製される（メタ）アクリル酸ジア
ルキルアミノエチルエステルは、一般式 （式中、R1は水素原子またはメチル基、R2及びR3は炭素
数１〜２のアルキル基を示す）で表される（メタ）アク
リル酸ジアルキルアミノエチルエステルであり、具体的
には、アクリル酸ジメチルアミノエチル、メタクリル酸
ジメチルアミノエチル、アクリル酸ジエチルアミノエチ
ル、メタクリル酸ジエチルアミノエチルなどが挙げられ
る。これら（メタ）アクリル酸ジアルキルアミノエチル
エステルの合成は、一般に（メタ）アクリル酸のジアル
キルアミノアルコールによるエステル化、あるいは（メ
タ）アクリル酸の低級アルキルエステルとジアルキルア
ミノアルコールのエステル交換反応により行われる。前
記のごとく合成した（メタ）アクリル酸ジアルキルアミ
ノエチルエステル含有液は、低沸点成分を除去した後、
通常、まず、減圧蒸留により精製する。蒸留は通常の方
法により行うことが可能である。例えば、理論段数４〜
20段の蒸留塔を用いて、還流比0.1〜４程度の連続また
は回分蒸留により行う。減圧蒸留により得られる（メ
タ）アクリル酸ジアルキルアミノエチルエステルの純度
は、一般に97.0〜99.9％で、含まれる主な不純物は（メ
タ）アクリル酸、（メタ）アクリル酸の低級アルキルエ
ステル、ジアルキルアミノアルコール及び（メタ）アク
リル酸エステル類の不飽和結合部へアルコール類が付加
した化合物などである。その他にも数種類の微量の不純
物が含まれる。次に不純物を含有する前記の純度97.0〜
99.9％の（メタ）アクリル酸ジアルキルアミノエチルエ
ステルを活性炭で処理する。活性炭処理の方法には、活
性炭を充填した塔に処理液を流す連続法、または処理液
に活性炭を添加して処理した後、活性炭を濾過、遠心分
離等により分離除去する回分法がある。本発明の方法で
はいずれの方法も用いることができる。使用する活性炭
は、市販の種々のものがそのまま使用可能である。The (meth) acrylic acid dialkylaminoethyl ester purified by the method of the present invention has the general formula (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 and R 3 represent an alkyl group having 1 to 2 carbon atoms), and is a (meth) acrylic acid dialkylaminoethyl ester, and specifically, , Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and the like. These (meth) acrylic acid dialkylaminoethyl esters are generally synthesized by esterification of (meth) acrylic acid with a dialkylamino alcohol or transesterification reaction of a lower alkyl ester of (meth) acrylic acid with a dialkylamino alcohol. The (meth) acrylic acid dialkylaminoethyl ester-containing liquid synthesized as described above, after removing low-boiling components,
Usually, first, purification is carried out by vacuum distillation. Distillation can be performed by a usual method. For example, theoretical plate number 4 ~
It is carried out by continuous or batch distillation with a reflux ratio of about 0.1 to 4 using a 20-stage distillation column. The purity of (meth) acrylic acid dialkylaminoethyl ester obtained by vacuum distillation is generally 97.0 to 99.9%, and the main impurities contained are (meth) acrylic acid, lower alkyl ester of (meth) acrylic acid, and dialkylamino alcohol. And compounds in which alcohols are added to the unsaturated bond of (meth) acrylic acid esters. In addition, several kinds of trace impurities are contained. Next, the above-mentioned purity containing impurities 97.0-
99.9% (meth) acrylic acid dialkylaminoethyl ester is treated with activated carbon. As a method of treating activated carbon, there are a continuous method in which a treated solution is caused to flow through a column filled with activated carbon, or a batch method in which activated carbon is added to the treated solution for treatment and then the activated carbon is separated and removed by filtration, centrifugation or the like. Either method can be used in the method of the present invention. As the activated carbon used, various commercially available products can be used as they are.
活性炭の使用量は、（メタ）アクリル酸ジアルキルアミ
ノエチルエステルの0.1〜５重量％が好ましい。処理温
度は、（メタ）アクリル酸ジアルキルアミノエチルエス
テルの凝固点から沸点まで可能であるが、エステルの安
定性を考慮すると０〜100℃の範囲が好ましい。活性炭
により除去される不純物の知見については明らかではな
いが、極く微量のエチレングリコールメタクリレート等
のジビニル化合物が含まれており、これらの除去効果が
考えられる。The amount of activated carbon used is preferably 0.1 to 5% by weight of (meth) acrylic acid dialkylaminoethyl ester. The treatment temperature can be from the freezing point to the boiling point of the (meth) acrylic acid dialkylaminoethyl ester, but it is preferably in the range of 0 to 100 ° C. in consideration of the stability of the ester. Although the knowledge of impurities removed by activated carbon is not clear, a very small amount of divinyl compounds such as ethylene glycol methacrylate is contained, and the effect of removing these is considered.
（実施例） 以下、実施例により本発明の方法を具体的に説明する。(Examples) Hereinafter, the method of the present invention will be specifically described with reference to Examples.
実施例１ （合成及び蒸留） 攪拌機、温度計及び理論段数10段の分留塔を備えた内容
積１のフラスコに、ジメチルアミノエタノール178g、
メタクリル酸メチル600g、ナトリウムメトキシド3.0g、
重合禁止剤としてフェノチアジン1.5gを仕込み、圧力30
0mmHgで攪拌しながら加熱還流した。生成するメタノー
ルをメタノール−メタクリル酸メチル共沸混合物として
留去して反応を進めた。６時間で反応は終了し、過剰に
仕込んだメタクリル酸メチルを留去後、さらに圧力5mmH
g、分留塔塔頂温度56〜58℃でメタクリル酸ジメチルア
ミノエチルエステルを留去させた。得られたメタクリル
酸ジメチルアミノエチルエステルは280gで純度は99.2％
であった。Example 1 (Synthesis and Distillation) In a flask having an internal volume of 1 equipped with a stirrer, a thermometer, and a fractionation column having 10 theoretical plates, 178 g of dimethylaminoethanol,
600 g of methyl methacrylate, 3.0 g of sodium methoxide,
Charge 1.5g of phenothiazine as a polymerization inhibitor, pressure 30
The mixture was heated to reflux with stirring at 0 mmHg. The produced methanol was distilled off as a methanol-methyl methacrylate azeotrope to proceed the reaction. The reaction was completed in 6 hours, and after excess methyl methacrylate was distilled off, the pressure was further increased to 5 mmH.
g, Methacrylic acid dimethylaminoethyl ester was distilled off at a distillation column tower top temperature of 56 to 58 ° C. The obtained methacrylic acid dimethylaminoethyl ester is 280 g and the purity is 99.2%.
Met.
（活性炭処理） 上記のメタクリル酸ジメチルアミノエチルエステルに、
粉状活性炭（ツルミコール PC）5.6gを加え、室温にて3
0分間攪拌した後、活性炭を減圧濾過により分離した。
得られたメタクリル酸ジメチルアミノエチルエステルは
272gで純度は99.4％であった。(Activated carbon treatment) The above-mentioned methacrylic acid dimethylaminoethyl ester,
Add 5.6 g of powdered activated carbon (Tsurumi Coal PC) and stir at room temperature for 3
After stirring for 0 minutes, activated carbon was separated by vacuum filtration.
The obtained methacrylic acid dimethylaminoethyl ester is
At 272 g, the purity was 99.4%.
（四級化及び重合） １ガラス製耐圧四ツ口フラスコに、前記の如く活性炭
処理したメタクリル酸ジメチルアミノエチルエステル22
0g、水73gを仕込み、30℃で塩化メチルを吹き込みなが
ら、圧力1kg/cm2・Ｇで５時間反応させた。反応終了
後、過剰に吹き込んだ塩化メチルを除去して四級アンモ
ニウム塩水溶液を得た。この四級アンモニウム塩水溶液
250gをアクリルアミド360gと通常の方法により共重合さ
せた。得られた重合体は、乾燥、粉砕して粒状とした。
重合体の0.1重量％水溶液は、溶解性良好で不溶性のゲ
ルは認められなかった。また、その粘度は230cps（１重
量％水溶液、食塩1.1重量％添加、25℃にてＢ型粘度計
で測定）と十分な高分子量の重合体であった。(Quaternization and Polymerization) 1 In a glass pressure-resistant four-necked flask, methacrylic acid dimethylaminoethyl ester 22 treated with activated carbon as described above was used.
0 g and 73 g of water were charged, and the reaction was carried out at a pressure of 1 kg / cm 2 · G for 5 hours while blowing methyl chloride at 30 ° C. After completion of the reaction, excessively blown methyl chloride was removed to obtain an aqueous quaternary ammonium salt solution. This quaternary ammonium salt solution
250 g was copolymerized with 360 g of acrylamide by the usual method. The obtained polymer was dried and pulverized into particles.
A 0.1 wt% aqueous solution of the polymer had good solubility and no insoluble gel was observed. Further, its viscosity was 230 cps (1% by weight aqueous solution, 1.1% by weight of sodium chloride added, measured by a B-type viscometer at 25 ° C.) and a sufficiently high molecular weight polymer.
比較例 実施例１と同様の合成及び蒸留を行い、活性炭処理を行
わず実施例１と同様に四級化及び重合を行った。得られ
た重合体は水に対して不溶性であった。Comparative Example The same synthesis and distillation as in Example 1 were carried out, and quaternization and polymerization were carried out in the same manner as in Example 1 without treatment with activated carbon. The obtained polymer was insoluble in water.
実施例２ （活性炭処理） 実施例１と同様の方法で合成及び蒸留を行い、純度99.2
％のメタクリル酸ジメチルアミノエチルエステルを得
た。内径20mm、長さ500mmのガラス管に粒状活性炭（ツ
ルミコール GL-30）を充填し前記メタクリル酸ジメチル
アミノエチルエステルを流速6m/Hrで流した。処理後の
メタクリル酸ジメチルアミノエチルエステルの純度は9
9.4％であった。Example 2 (Treatment with activated carbon) Synthesis and distillation were carried out in the same manner as in Example 1, and the purity was 99.2.
% Methacrylic acid dimethylaminoethyl ester was obtained. A glass tube having an inner diameter of 20 mm and a length of 500 mm was filled with granular activated carbon (Tsurumi Coal GL-30), and the methacrylic acid dimethylaminoethyl ester was flown at a flow rate of 6 m / Hr. The purity of methacrylic acid dimethylaminoethyl ester after treatment is 9
It was 9.4%.
（四級化及び重合） 前記の如く得られたメタクリル酸ジメチルアミノエチル
エステルを、実施例１と同様の方法で四級化及び重合を
行った。得られた重合体の0.1重量％水溶液は、溶解性
良好で不溶性のゲルは認められなかった。また、その粘
度は235cps（実施例１と同様の方法で測定）と、十分な
高分子量の重合体であった。(Quaternization and Polymerization) The methacrylic acid dimethylaminoethyl ester obtained as described above was subjected to quaternization and polymerization in the same manner as in Example 1. The 0.1 wt% aqueous solution of the obtained polymer had good solubility and no insoluble gel was observed. The viscosity was 235 cps (measured by the same method as in Example 1), which was a sufficiently high molecular weight polymer.
（発明の効果） 本発明の方法により精製したメタクリル酸ジメチルアミ
ノエチルエステルは、カチオン系高分子凝集剤、繊維処
理剤、紙加工剤等の用途に好適な品質のものであった。(Effect of the Invention) The methacrylic acid dimethylaminoethyl ester purified by the method of the present invention was of a quality suitable for use as a cationic polymer flocculant, a fiber treating agent, a paper treating agent and the like.
Claims (1)
数１〜２のアルキル基を示す）で表されるアクリル酸ジ
アルキルアミノエチルエステルまたはメタクリル酸ジア
ルキルアミノエチルエステルの精製に際し、活性炭で処
理することを特徴とするアクリル酸ジアルキルアミノエ
チルエステルまたはメタクリル酸ジアルキルアミノエチ
ルエステルの精製法。1. A general formula (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 and R 3 represent an alkyl group having 1 to 2 carbon atoms) when purifying acrylic acid dialkylaminoethyl ester or methacrylic acid dialkylaminoethyl ester A method for purifying acrylic acid dialkylaminoethyl ester or methacrylic acid dialkylaminoethyl ester, which comprises treating with activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22211686A JPH0745446B2 (en) | 1986-09-22 | 1986-09-22 | Method for purifying dialkylaminoethyl ester of acrylic acid or methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22211686A JPH0745446B2 (en) | 1986-09-22 | 1986-09-22 | Method for purifying dialkylaminoethyl ester of acrylic acid or methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6379858A JPS6379858A (en) | 1988-04-09 |
| JPH0745446B2 true JPH0745446B2 (en) | 1995-05-17 |
Family
ID=16777402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22211686A Expired - Lifetime JPH0745446B2 (en) | 1986-09-22 | 1986-09-22 | Method for purifying dialkylaminoethyl ester of acrylic acid or methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745446B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01230610A (en) * | 1988-03-11 | 1989-09-14 | Kohjin Co Ltd | Cationic polymer |
| JP2006028080A (en) * | 2004-07-15 | 2006-02-02 | Osaka Organic Chem Ind Ltd | Method of purifying (meth)acrylic ester |
-
1986
- 1986-09-22 JP JP22211686A patent/JPH0745446B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6379858A (en) | 1988-04-09 |
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