JPS6048955A - Purification of neutralized salt of dialkylaminoethyl (meth)acrylate or its quaternary salt - Google Patents
Purification of neutralized salt of dialkylaminoethyl (meth)acrylate or its quaternary saltInfo
- Publication number
- JPS6048955A JPS6048955A JP15636683A JP15636683A JPS6048955A JP S6048955 A JPS6048955 A JP S6048955A JP 15636683 A JP15636683 A JP 15636683A JP 15636683 A JP15636683 A JP 15636683A JP S6048955 A JPS6048955 A JP S6048955A
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- meth
- dialkylaminoethyl
- salt
- aqueous solution
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 150000003839 salts Chemical class 0.000 title claims abstract description 20
- 238000000746 purification Methods 0.000 title claims description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 abstract description 8
- 150000001412 amines Chemical class 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- -1 halogen ion Chemical class 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229920006158 high molecular weight polymer Polymers 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 21
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229940050176 methyl chloride Drugs 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical class CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical class CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical class CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- DSHKXOXFCMCZQH-UHFFFAOYSA-N [Cl-].C(C)C([NH+](C)C)CC Chemical compound [Cl-].C(C)C([NH+](C)C)CC DSHKXOXFCMCZQH-UHFFFAOYSA-N 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UZDXAQLLVAUBQD-UHFFFAOYSA-N ethyl prop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C=C UZDXAQLLVAUBQD-UHFFFAOYSA-N 0.000 description 1
- UMSGVWVBUHUHEH-UHFFFAOYSA-M ethyl(trimethyl)azanium;bromide Chemical compound [Br-].CC[N+](C)(C)C UMSGVWVBUHUHEH-UHFFFAOYSA-M 0.000 description 1
- VFRQEVIIBMUKCQ-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical class [Cl-].CC[N+](C)(C)CCOC(=O)C=C VFRQEVIIBMUKCQ-UHFFFAOYSA-M 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- UZLGVMYVDYNSCS-UHFFFAOYSA-M methyl sulfate;trimethyl(2-prop-2-enoyloxyethyl)azanium Chemical compound COS([O-])(=O)=O.C[N+](C)(C)CCOC(=O)C=C UZLGVMYVDYNSCS-UHFFFAOYSA-M 0.000 description 1
- IHBKAGRPNRKYAO-UHFFFAOYSA-M methyl sulfate;trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound COS([O-])(=O)=O.CC(=C)C(=O)OCC[N+](C)(C)C IHBKAGRPNRKYAO-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- XDFFVDDBWQREAJ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCOC(=O)C=C XDFFVDDBWQREAJ-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
リレートの中和塩あるいはその４級塩の精製法に係るも
のである。詳しくはこれらジアルキルアミンエチル（メ
タ）アクリレートの中和塩あるいはその４級塩を重合し
て溶解性良好な高分子量重合体を得るのに適したジアル
キルアミノエチル（メタ）アクリレートの中和塩あるい
はその４級塩の精製法に係るものである。但しく）内の
メタはメタアクリレートを含むことを示す。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for purifying a neutralized salt of rylate or a quaternary salt thereof. In detail, neutralized salts of dialkylaminoethyl (meth)acrylates or their quaternary salts suitable for obtaining high molecular weight polymers with good solubility by polymerizing these neutralized salts of dialkylamine ethyl (meth)acrylates or their quaternary salts. This relates to a method for purifying quaternary salts. However, "Meta" in ) indicates that it contains methacrylate.
本発明におけるジアルキルアミンエチル（メタ）アクリ
レートの中和塩あるいはその４級塩（以下アクリレート
類と称する）は２次の一般式（Ｉ）ルキル基、Ｒ４は水
素原子、炭素数１〜２のアルキル基またはベンジル基を
示す。ＸｏはＣＩ、Ｂｒなどのハロゲンイオン、硫酸イ
オン、炭素数１〜２のアルキル基を有するアルキル硫酸
イオンなどが挙げられる。）
で代表される化合物である。In the present invention, the neutralized salt of dialkylamine ethyl (meth)acrylate or its quaternary salt (hereinafter referred to as acrylates) has the following general formula (I): alkyl group, R4 is a hydrogen atom, and alkyl group having 1 to 2 carbon atoms. group or benzyl group. Examples of Xo include halogen ions such as CI and Br, sulfate ions, and alkyl sulfate ions having an alkyl group having 1 to 2 carbon atoms. ) is a compound represented by.
たトエば、ジメチルアミンエチルアクリレート。Also, dimethylamine ethyl acrylate.
ジメチルアミノエチルメタクリレート、ジエチルアミノ
エチルアクリレート、ジエチルアミノエチルメタクリレ
ートなどと塩酸、硫酸などの酸との中和塩およびアクリ
ロイルオ中ジエチルトリメチルアンモニウムクロライド
、メタクリロイルオキシエチルトリメチルアンモニウム
クロライド、アクリロイルオキシエチルトリメチルアン
モニウムブロマイド、メタクリロイルオキシエチルトリ
メチルアンモニウムブロマイド、アクリロイルオキシエ
チルトリメチルアンモニウムメチルサルフェート、メタ
クリロイルオキシエチルトリメチルアンモニウムメチル
サルフェート、アクリロイルオキシエチルジメチルエチ
ルアンモニウムクロライ塩化合物が挙げられる。Neutralized salts of dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc. with acids such as hydrochloric acid and sulfuric acid, and diethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium bromide, methacryloyloxy Examples include ethyltrimethylammonium bromide, acryloyloxyethyltrimethylammonium methylsulfate, methacryloyloxyethyltrimethylammonium methylsulfate, and acryloyloxyethyldimethylethylammonium chloride salt compounds.
アクリレート類はジアルキルアミノエチル（メタ）アク
リレートを塩酸、硫酸などの鉱酸にて中和するか、塩化
メチル、ジメチル硫酸のようなアルキル化剤と反応せし
めることにより製造することが出来る。このようにして
得られたアクリレート類の単独重合体あるいはアクリル
アミドなどとの共重合体はカチオン性高分子電解質とし
て種々の用途に使用されており、特に高分子量重合体は
水性懸濁物の＃集あるいは、各釉汚泥の脱水に対して優
れた効果を有している。Acrylates can be produced by neutralizing dialkylaminoethyl (meth)acrylate with a mineral acid such as hydrochloric acid or sulfuric acid, or by reacting it with an alkylating agent such as methyl chloride or dimethyl sulfate. Homopolymers of acrylates or copolymers with acrylamide, etc., obtained in this way are used for various purposes as cationic polymer electrolytes, and high molecular weight polymers in particular are used for collection of aqueous suspensions. Alternatively, it has an excellent effect on dewatering each glazed sludge.
凝集剤あるいは脱水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。In order to use it as a flocculant or dehydrating agent, it is desirable to have a high molecular weight and good water solubility.
ところがアクリレート類中に含まれる微量不純物は重合
中に連鎖移動剤として作用し分子量を低下させたり、あ
るいは架橋剤として作用し、得られる重合体の溶解性を
低下させる原因となってい１８７１６記載の方法あるい
は特開５２−４８６２０記載の方法がある。前者は、ア
クＩＪＬ／−ト類中に含まれる不純物がアクリレート類
を製造する際の原料であるジメチルアミノアルキル（メ
タ）アクリレート中に含有される不純物によるものとし
て、アクリレート類を水に対する溶解性が１０チ以下の
有機溶剤で処理している。また後者は分子量の低下済解
性の低下を起こす原因はアクリレート類中の油溶性不純
物に由来するとしてアクリレート類を水不溶性非極性溶
媒で処理している。However, trace impurities contained in acrylates act as a chain transfer agent during polymerization and reduce the molecular weight, or act as a crosslinking agent and cause a decrease in the solubility of the resulting polymer. Alternatively, there is a method described in JP-A-52-48620. The former is based on the assumption that the impurities contained in acrylates are due to impurities contained in dimethylaminoalkyl (meth)acrylate, which is a raw material for producing acrylates, and the solubility of acrylates in water is Treated with less than 10% organic solvent. In the latter method, the acrylates are treated with a water-insoluble non-polar solvent because the cause of the decrease in molecular weight and deterioration in solubility is derived from oil-soluble impurities in the acrylates.
出効来が悪く、また抽出効果を上げるためには多量の有
機溶媒を使用することが必要となり、溶媒の回収、製造
工程の煩雑化９作業環境の面で問題が多い。The extraction efficiency is poor, and in order to improve the extraction effect, it is necessary to use a large amount of organic solvent, which causes many problems in terms of solvent recovery, complicating the manufacturing process, and the working environment.
以上のことから１本発明者らは、高分子量でし−たり、
前記のような欠点がない精製法について鋭意研究した結
果１重合体の分子量の低下あるいは溶解性の低下を引き
起こす原因が、ジアルキルアミノエチル（メタ）アクリ
レートの中和塩あるいはその４級塩製造の際の原料であ
るジアルキルアミノエチル（メタ）アクリレート中に含
有される不純物のみによるものでなく、ジアルキルアミ
ノエチル（メタ）アクリレートの中和塩あるいはその４
級塩の製造の際に発生する物質により大きく影響される
ことを見い出し本発明に到達した。Based on the above, the present inventors have determined that high molecular weight
As a result of intensive research on purification methods that do not have the above-mentioned drawbacks, we found that the cause of the decrease in the molecular weight or solubility of the single polymer was during the production of neutralized salt of dialkylaminoethyl (meth)acrylate or its quaternary salt. This is not only due to impurities contained in dialkylaminoethyl (meth)acrylate, which is the raw material for dialkylaminoethyl (meth)acrylate;
The present invention was achieved based on the discovery that this is greatly affected by the substances generated during the production of grade salts.
すなわち本発明は、高分子量でしかも溶解性の良好な重
合体を製造するに適した一般式（１）であられされるア
クリレート類を得る目的で、アクリレート類水溶液をイ
オン交換樹脂で処理することを特徴とする上記アクリレ
ート類の精製法である。That is, the present invention involves treating an aqueous solution of acrylates with an ion exchange resin in order to obtain acrylates represented by the general formula (1) suitable for producing polymers with high molecular weight and good solubility. This is a characterized method for purifying the above acrylates.
ジアルキルアミノエチル（メタ）アクリレート塩はジア
ルキルアミノエチル（メタ）アクリレートを水溶媒おる
いは有機溶媒の存在下で塩化メチル等の４級化剤と反応
せしめることによって行われるが、経済的な面からは水
溶媒中で行われる。Dialkylaminoethyl (meth)acrylate salt is produced by reacting dialkylaminoethyl (meth)acrylate with a quaternizing agent such as methyl chloride in the presence of an aqueous solvent or an organic solvent, but from an economical point of view is carried out in an aqueous medium.
しかしジアルキルアミノエチル（メタ）アクリレートは
非常に加水分解を受けやすいため、水ｍ媒中で行わ１％
るアクリレート類の製造中ジアルキルアミノエチル（メ
タ）アクリレートの加水分解を完全に抑えることは不可
能であり、製造して得られるアクリレート類水溶、液中
には加水分解による遊離酸、遊離酸忙対応する遊離アミ
ンあるいは未反応のジアルキルアミノエチル（メタ）ア
クリレート（遊離アミン）が含有されることになる。However, dialkylaminoethyl (meth)acrylate is very susceptible to hydrolysis, so it was carried out at 1% in water medium.
It is impossible to completely suppress the hydrolysis of dialkylaminoethyl (meth)acrylate during the production of acrylates, and the resulting aqueous acrylate solution contains free acid due to hydrolysis and free acid production. free amine or unreacted dialkylaminoethyl (meth)acrylate (free amine).
一般にカチオン性重合体の製造方法としては。Generally, as a method for producing cationic polymers.
水溶ｇ重合、沈澱重合、懸濁重合などの種々の方の含量
の多いものを重合しても高分子量の重合体は得がたく、
また得られた重合体は水不溶物の多いものとなる。It is difficult to obtain a polymer with a high molecular weight even if polymerization is performed using various methods such as aqueous polymerization, precipitation polymerization, and suspension polymerization, which have a higher content.
Moreover, the obtained polymer contains many water-insoluble substances.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明はアクリレート類水溶液をイオン交換樹脂で処理
することにより実施さｎるが、その方法は攪拌機を備え
付けた容器にアクリレート類水溶液を仕込み２次いでイ
オン交換樹脂を加え一定時間攪拌しその後払い出し濾過
する方法、あるいはイオン交換樹脂を充填１７た塔にア
クリレート類水溶液を通して行う方法などがある。The present invention is carried out by treating an aqueous solution of acrylates with an ion exchange resin, and the method involves charging the aqueous solution of acrylates into a container equipped with a stirrer, then adding the ion exchange resin, stirring for a certain period of time, and then discharging and filtering. Alternatively, there is a method in which an aqueous acrylate solution is passed through a column filled with an ion exchange resin.
イオン交換樹脂としては強酸性あるいは弱酸性の陽イオ
ン交換樹脂１強塩基性あるいは弱塩基性の陰イオン交換
樹脂などがあるがイオン交換樹脂の選択は処理されるア
クリレート類水溶液中に含有される不純物の種類により
適宜選択される。また陽イオン交換樹脂で処理した後陰
イオン交換樹アクリレート類水溶液中のアクリレート類
の濃度についても特に制限されるものではなく、Ｍ造さ
れた濃度のアクリレート類水溶液をそのまま処理するこ
とが出来る。本方法では結晶が析出しない範囲なら高濃
度の水溶液でも容易にその処理が可能なことも設備面、
生産性の面から有利な方法である。Ion exchange resins include strongly acidic or weakly acidic cation exchange resins, strongly basic or weakly basic anion exchange resins, etc., but the selection of the ion exchange resin depends on impurities contained in the acrylate aqueous solution to be treated. It is selected as appropriate depending on the type. Further, the concentration of acrylates in the anion exchange resin acrylate aqueous solution after treatment with the cation exchange resin is not particularly limited, and the acrylate aqueous solution having the concentration M can be treated as it is. In terms of equipment, this method can easily handle even highly concentrated aqueous solutions as long as crystals do not precipitate.
This is an advantageous method in terms of productivity.
処理温度、処理時間についても特に制限されるものでは
ないが温度についてけ逆常２０〜４０℃が好ましく、あ
まり高い温度ではアクリレート類の重合等の面で好まし
くない。時間については数時間で目的が達せられるが適
宜その時間を延長してもさしつかえない。The treatment temperature and treatment time are not particularly limited either, but a temperature of 20 to 40° C. is preferable, and too high a temperature is not preferable in terms of polymerization of acrylates. As for time, the goal can be achieved within a few hours, but it is okay to extend that time as appropriate.
本発明方法によってアクリレート類水溶液中の遊離酸、
遊離アミンが除去され、更にはその他の不純物も付随的
に除去さｎる。その結果本発明方法で処理したアクリレ
ート類水溶液を重合して得゛次に本発明を実施例により
具体的に説明するが本発明はその要旨を超えない限り以
下の実施例によって制約されるものではない。Free acid in an aqueous solution of acrylates by the method of the present invention,
Free amines are removed and other impurities are also concomitantly removed. As a result, the aqueous acrylate solution treated by the method of the present invention was polymerized.Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited by the following Examples unless the gist of the present invention is exceeded. do not have.
実施例 １
１ｔガラス製オートクレーブにジメチルアミノエチルア
クリレ−）２０（ｌと水６６．７ｆを仕込み更に重合禁
止剤としてハイドロキノンモノメチルエーテルをジメチ
ルアミノエチルアクリレートに対して１５００ ｐｐｍ
＋を加え８０℃でメチルクロライドを攪拌下吹き込み８
時間反応させた。反応後オートクレーブの残圧を放出し
、更にエアーバブリングにより過剰のメチルクロライド
を除去しアクリロイルオキシエチルトリメチルアンモニ
ウムクロライド・水溶液８Ｂ２．ｌｆを得た。得られた
第４級アンモニウム垣水溶液について未反応ジメチルア
ミノエチルアクリレート、加水分解によって生成したア
クリル酸等を電位差滴定法、高速液水”溶液中の遊離ア
ミン（未反応ジメチルアミノエチルアクリレート、加水
分解により生成したジメチルアミノエチルアルコール等
の合計）含量は１゜１０％、加水分解（（より生成した
アクリル酸含量は０．５５重を係であった。Example 1 In a 1-ton glass autoclave, 20 (l) of dimethylaminoethyl acrylate and 66.7 f of water were charged, and hydroquinone monomethyl ether was added as a polymerization inhibitor at 1500 ppm based on dimethylaminoethyl acrylate.
Add + and blow in methyl chloride at 80℃ with stirring 8
Allowed time to react. After the reaction, the residual pressure in the autoclave was released, and excess methyl chloride was removed by air bubbling, and acryloyloxyethyltrimethylammonium chloride aqueous solution 8B2. I got lf. From the obtained quaternary ammonium aqueous solution, unreacted dimethylaminoethyl acrylate, acrylic acid generated by hydrolysis, etc. were determined by potentiometric titration, and free amine (unreacted dimethylaminoethyl acrylate, generated by hydrolysis) in the high-performance liquid water solution was measured. The total content of dimethylaminoethyl alcohol etc. produced was 1.10%, and the content of acrylic acid produced by hydrolysis was 0.55%.
この第４級アンモニウム塩水溶液１ｏｏｆに強酸性陽イ
オン交換ｍＨｒｉ （ＤＯＷＩＤＸ −５０Ｗ−Ｘ４）
ＩＯ−を加え室温で２時間激しく攪拌後、イオン交換樹
脂を炉別除去した。この処理液に強塩基性イオン交換樹
脂（アンバーライ）ＩＲＯ−８４）１０−を加え室温２
時間攪拌後、イオン交換樹脂を炉別した。Strongly acidic cation exchange mHri (DOWIDX-50W-X4) was applied to 1oof of this quaternary ammonium salt aqueous solution.
After adding IO- and stirring vigorously for 2 hours at room temperature, the ion exchange resin was removed in a furnace. A strongly basic ion exchange resin (Amberly) IRO-84) 10- was added to this treatment solution at room temperature 2.
After stirring for an hour, the ion exchange resin was separated from the furnace.
処理終了後の液に含有される遊離アミンは０．０６チ、
アクリル酸は０．０２係であった。The amount of free amine contained in the solution after treatment is 0.06
Acrylic acid had a coefficient of 0.02.
前述の方法で精製したアクリロイルオキシエチルトリメ
チルアンモニウムクロライド水溶液８０り、アクリルア
ミド８１．７ｆおよび水’７９．７ｆを５００ ｍｌ四
つロフラスコに入れ３０゛Ｃに保ちながまたので内容物
を取り出しアセトンにより脱水。Put 80ml of the aqueous solution of acryloyloxyethyltrimethylammonium chloride purified by the above method, 81.7f of acrylamide, and 79.7f of water into a 500ml four-necked flask and keep it at 30°C, then remove the contents and dehydrate with acetone. .
更に粉砕乾燥後収率９重合度（粘度）、溶解性を測定し
た。収率は重量により１重合度（粘度）はポリマーを１
係濃度に：ｌＮ−ＮａＣｌ溶解しＢ型粘度計により２５
℃で測定、１また溶解性はポリマー１０２をｌＮ−Ｎａ
Ｃｌ溶液中で２時間攪拌溶解後１００メツシー金網で濾
過し金網に残るゲルを肉眼判定することにより比較した
。その結果収率９９．２係、粘度１４・００ｃｐでゲル
状物はなく完全溶解しく１１）
た。Furthermore, the yield after pulverization and drying, degree of polymerization (viscosity), and solubility were measured. The yield is 1 polymerization degree (viscosity) by weight.
To the relevant concentration: 1N-NaCl was dissolved and measured with a B-type viscometer at 25
Measured at °C, 1 and solubility of polymer 102 in lN-Na
After stirring and dissolving in a Cl solution for 2 hours, it was filtered through a 100 mesh wire mesh, and the gel remaining on the wire mesh was visually evaluated for comparison. As a result, the yield was 99.2%, the viscosity was 14.00 cp, and there was no gel-like substance, indicating complete dissolution11).
実施例２〜４及び比較例１
実施例１で４・級化して得られた卯、４・級アンモニウ
ム塩水溶液を強酸性イオン交換樹脂（Ｄ ＯＷ ＥＸ
−５０Ｗ−Ｘ ４・） ｌ Ｏｍｌのみ（実施例２）、
騒塩基性陰イオン交１実樹脂（アンバーライｌ−Ｉ １
１． Ａ−４１０）５ｍ、！＝ （ｒ）ＯＷＥＸ−５０
Ｗ−Ｘ４）５ｍｌ（実施例８）９弱塩基性陰イオン交換
樹脂（アンバーライトＩｆもＡ ６８） １０ｍｌと（
ＤＯＷで処理した。また処理して得られた第４１級アン
−ｅニウム塩水溶液を実施例１と同様の方法で重合した
。Examples 2 to 4 and Comparative Example 1 The rabbit, quaternary ammonium salt aqueous solution obtained by quaternizing in Example 1 was treated with a strongly acidic ion exchange resin (DOW EX
-50W-X 4・) l Oml only (Example 2),
Noisy base anion exchange 1 real resin (Amberly I-I 1
1. A-410) 5m,! = (r)OWEX-50
W-X4) 5 ml (Example 8) 9 Weakly basic anion exchange resin (Amberlite If also A 68) 10 ml and (
Processed with DOW. Further, the 41st class an-e nium salt aqueous solution obtained by the treatment was polymerized in the same manner as in Example 1.
その結果を表−１に示す。また比較例１として精製処理
を施こさなかった場合の結果も合せて表−１に示す。The results are shown in Table-1. Table 1 also shows the results of Comparative Example 1 in which no purification treatment was performed.
（１２） 表−１ （１８） (12) Table-1 (18)
Claims (1)
塩あるいはその４級アンモニウム塩水溶液をイオン交換
樹脂で処理することを特徴とする上記ジアルキルアミノ
エチル（メタ）アクリレートの酸中和塩あるいはその４
級アンモニウム塩の精製法。The above-mentioned acid neutralized salt of dialkylaminoethyl (meth)acrylate or its fourth form, characterized in that the acid neutralized salt of dialkylaminoethyl (meth)acrylate or its quaternary ammonium salt aqueous solution is treated with an ion exchange resin.
Purification method for grade ammonium salts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15636683A JPS6048955A (en) | 1983-08-29 | 1983-08-29 | Purification of neutralized salt of dialkylaminoethyl (meth)acrylate or its quaternary salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15636683A JPS6048955A (en) | 1983-08-29 | 1983-08-29 | Purification of neutralized salt of dialkylaminoethyl (meth)acrylate or its quaternary salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6048955A true JPS6048955A (en) | 1985-03-16 |
Family
ID=15626177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15636683A Pending JPS6048955A (en) | 1983-08-29 | 1983-08-29 | Purification of neutralized salt of dialkylaminoethyl (meth)acrylate or its quaternary salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6048955A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02237967A (en) * | 1989-03-13 | 1990-09-20 | Toagosei Chem Ind Co Ltd | Production of tertiary ammonium salt of dialkylaminoalkyl acrylate |
-
1983
- 1983-08-29 JP JP15636683A patent/JPS6048955A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02237967A (en) * | 1989-03-13 | 1990-09-20 | Toagosei Chem Ind Co Ltd | Production of tertiary ammonium salt of dialkylaminoalkyl acrylate |
| JP2697093B2 (en) * | 1989-03-13 | 1998-01-14 | 東亞合成株式会社 | Method for producing neutralized salt of dialkylaminoalkyl acrylate |
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