JPS6320242B2 - - Google Patents
Info
- Publication number
- JPS6320242B2 JPS6320242B2 JP9028780A JP9028780A JPS6320242B2 JP S6320242 B2 JPS6320242 B2 JP S6320242B2 JP 9028780 A JP9028780 A JP 9028780A JP 9028780 A JP9028780 A JP 9028780A JP S6320242 B2 JPS6320242 B2 JP S6320242B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- ethyl cellulose
- dispersion medium
- polymerization
- mixture
- 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
Links
- 239000001856 Ethyl cellulose Substances 0.000 claims description 37
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 37
- 229920001249 ethyl cellulose Polymers 0.000 claims description 37
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002612 dispersion medium Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 3
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- -1 halogen ion Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- SSZXAJUPVKMUJH-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate;hydrochloride Chemical compound Cl.CN(C)CCOC(=O)C=C SSZXAJUPVKMUJH-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CRGOPMLUWCMMCK-UHFFFAOYSA-M benzyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)CC1=CC=CC=C1 CRGOPMLUWCMMCK-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- BJZJDEOGMBZSLE-UHFFFAOYSA-N cyclohexane;hydrate Chemical compound O.C1CCCCC1 BJZJDEOGMBZSLE-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical class C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ZJKSNDSFYBPOFZ-UHFFFAOYSA-M ethyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CC[N+](C)(C)CCOC(=O)C(C)=C ZJKSNDSFYBPOFZ-UHFFFAOYSA-M 0.000 description 1
- QUUVXPUXYIWGHA-UHFFFAOYSA-M ethyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CC[N+](C)(C)CCOC(=O)C(C)=C QUUVXPUXYIWGHA-UHFFFAOYSA-M 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XLRLRFILSCUPFG-UHFFFAOYSA-M triethyl(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CCOC(=O)C=C XLRLRFILSCUPFG-UHFFFAOYSA-M 0.000 description 1
- 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 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
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は重合混合物からのエチルセルロースの
回収法に関するものであり、詳しくは、ジアルキ
ルアミノアルキル（メタ）アクリレートの中和塩
及び／又は４級化物（以下、DAAと言う）を含
有するモノマーを重合して得た混合物から分散剤
として使用したエチルセルロースを回収する方法
に関するものである。
DAAを含有するモノマーを重合して得た水溶
性ポリマーは例えば、凝集剤として広く利用され
ている。この水溶性ポリマーの製造法として、
DAA含有モノマーを炭化水素系分散媒―水―分
散剤の混合物中で、触媒の存在下、懸濁重合する
方法が知られている。近年、この重合において、
均一なビーズ状のポリマーを得るために、分散剤
としてエチルセルロースを使用し、油中水型で懸
濁重合を行なう方法が提案されている。この方法
は得られるポリマーがビーズ状であるためポリマ
ーの製造面からは好ましい方法であるが、重合後
の分散媒よりエチルセルロースを分離回収する操
作が難しかつた。すなわち、エチルセルロースは
水には溶解しないので、通常、重合後のポリマー
を分離したのちの母液に水を加え、この混合物を
加熱処理し分散媒を留出除去するとともにエチル
セルロースを水中に析出させる方法が考えられる
が、この方法ではエチルセルロースは水中に良好
に分散せず、粘着性を帯び撹拌槽の内面に付着す
る欠点がある。そのため、エチルセルロースの回
収率が低下するのみならず、装置内面に付着した
エチルセルロースの洗浄操作が面倒であつた。
本発明者等は上記実情に鑑み、エチルセルロー
スを分散剤として使用し、DAA含有モノマーの
重合を行なつた場合の重合混合物よりエチルセル
ロースを効率的に回収する方法につき種種検討し
た結果、ある特定の方法で重合後の母液を処理す
ることにより、本発明の目的が達成されることを
知り本発明を完成した。
すなわち、本発明の要旨は、DAA単独、又は
該モノマーと共重合可能なモノマーとの混物を炭
化水素系分散媒―水―分散剤よりなる混合物中で
触媒の存在下、油中水型にて懸濁重合するに際
し、分散媒として水の沸点よりも低い沸点を有す
る化合物を使用し、しかも、分散剤としてエチル
セルロースを使用する方法において、重合後の混
合物より生成ポリマーを別したのちの母液を、
前記分散媒が沸騰する温度以上に加熱保持された
水中に撹拌下、供給することにより、分散媒を留
去して回収するとともに、エチルセルロースを水
中に析出させ、次いで、エチルセルロースを別
することを特徴とする重合混合物からのエチルセ
ルロースの回収法に存する。
以下、本発明を詳細に説明する。
本発明で対象となるDAAは下記一般式（）
（式中、R1は水素原子またはメチル基、R2及
びR3は炭素数１〜４の直鎖または分岐アルキル
基を示し、R2およびR3は同一のものでもよく、
R4は水素原子、炭素数１〜８の直鎖状あるいは
分岐アルキル基、炭素数１〜４のヒドロキシ置換
アルキル基またはベンジル基を示す。Ｙは炭素数
２〜４のアルキレンまたはヒドロキシ置換アルキ
レン基を示す。XはCl，Brなどのハロゲンイ
オン、硫酸イオン、硝酸イオン、リン酸イオン、
カルボン酸イオン、スルホン酸イオン、炭素数１
〜８のアルキル基を有するアルキル硫酸イオンな
どを示す。）
で代表される化合物である。たとえば、ジメチ
ルアミノエチルアクリレート、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、ジブチルアミノエチルアクリレート、ジブチ
ルアミノエチルメタクリレートなどと塩酸、硫
酸、硝酸、リン酸、酢酸、プロピオン酸、ベンゼ
ンスルホン酸などの酸との中和塩およびβ―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、β―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エート、β―
メタクリロイルオキシエチルジメチルエチルアン
モニウムブロマイド、β―メタクリロイルオキシ
エチルジメチルエチルアンモニウムモノエチルサ
ルフエート、β―メタクリロイルオキシエチルジ
メチルベンジルアンモニウムクロライド、β―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、β―アクリロイルオキシエチルトリ
エチルアンモニウムブロマイド、２―ヒドロキシ
―３――メタクリロイルオキシプロピルトリメチ
ルアンモニウムクロライドなどの４級化物が挙げ
られる。
本発明の対象となるカチオン性高分子量水溶性
ポリマーは、一般式（）で示される化合物の単
独、または一般式（）で示される化合物と共重
合可能なモノマー、例えば、アクリルアミド、メ
タクリルアミド、ビニルピリジン中和塩または４
級化物、ジメチルジアリルアンモニウム化合物な
どとの共重合体が挙げられる。この共重合体の場
合には、通常、DAAの含有量は５モル％以上、
好ましくは10モル％以上である。
本発明で使用する分散媒は水の沸点よりも低い
沸点を有する炭化水素であり、特に、水と共沸す
る化合物が好ましい。通常、DAA含有モノマー
の重合は常圧で行なうのであり、分散媒は常圧で
液状であることが必要であり、例えば、炭化水素
の沸点又は水との共沸点が40〜100℃の範囲のも
のが選ばれる。これらの具体例としては例えば、
シクロヘキサン、シクロペンタン、メチルシクロ
ヘキサンなどの脂環式炭化水素、ベンゼン、トル
エン、キシレン、クロルベンゼン、トリクロルエ
チレン、１，２―ジクロルエタン、などの芳香族
又は脂肪族炭化水素等の炭化水素が挙げられる。
これらの分散媒は通常、モノマーに対して１〜10
重量倍、好ましくは１〜５重量倍が使用される。
本発明の分散剤であるエチルセルロースの使用
量はモノマーに対して0.1〜７重量％、好ましく
は0.3〜３重量％であり、この使用量があまり少
ない場合には、得られるポリマーが塊状となり均
一なビーズ状とはならず、また、あまり多い場合
には、ポリマーの乾燥時にポリマー粒子同志が固
結し易く、更に、製品ポリマーの水への溶解性が
低下するので好ましくない。
本発明での重合は通常、分散媒と分散剤を反応
器に仕込み、別に調整したモノマー水溶液及び触
媒を添加し混合撹拌することにより分散媒―水―
分散剤の懸濁状態を形成させ重合を行なうことが
できる。この際のモノマー水溶液の濃度は通常、
10〜80重量％、好ましくは40〜80重量％である。
撹拌状態は理想的には分散が良好に行なわれ、し
かも、分散粒子が大きい方が好ましい。
触媒としては通常、過硫酸アンモニウム、過硫
酸カリウム、過酸化水素などの過酸化物、２，
2′―アゾビス―２―アミジノプロパン塩酸塩、
４，4′―アゾビス―４―シアノペンタノイツクア
シツドなどのアゾ化合物等の公知の水溶性触媒が
挙げられる。また、過酸化物の場合には、メタ重
亜硫酸ソーダ、亜硫酸ソーダ、塩化第１鉄などの
還元剤と併用しレドツクス系触媒として使用する
こともできる。これら触媒の使用量は通常、モノ
マーに対し10〜3000ppm程度である。
重合温度は使用するモノマーの種類により多少
異なるが、通常、35℃〜混合物の沸点までの温度
であり、好ましくは40〜70℃である。
重合後の混合物は過により生成したビーズ状
ポリマーを分離し、分離したポリマーは常法に従
つて洗浄、乾燥して回収される。一方、母液は炭
化水素系分散媒を主体とし、エチルセルロースが
溶解されているので、これらの回収工程に送られ
る。
本発明では母液を分散媒の沸騰温度以上に加熱
保持された水中に撹拌下、供給することにより、
分散媒を留出除去し、エチルセルロースを水中に
析出させる。この処理は通常、蒸留装置を備えた
撹拌槽に供給する母液に対して３〜20重量倍、好
ましくは４〜10重量倍の水を仕込み、分散媒が沸
騰する温度以上に加熱したのち、この水中に母液
を徐々に滴下することにより実施される。この処
理中は水の温度を分散媒の沸騰温度以上に保持す
ることが必要であり、途中で水の温度が低下する
と析出するエチルセルロースが粘着性を有するの
で好ましくない。
次いで、水中に析出したエチルセルロースは
過により回収する。回収したエチルセルロースは
必要に応じて、例えば、0.1〜1.0重量％の苛性ア
ルカリ水溶液にて洗浄したのち、次の重合反応の
分散剤として使用することができる。
以上、本発明によれば、分散剤として使用した
エチルセルロースの回収に際し、エチルセルロー
スが粘着性を帯びて装置の内面に付着することも
ないので、エチルセルロースの回収率も高く、ま
た、装置の洗浄操作も簡単である。
次に、本発明を実施例により更に詳細に説明す
るが、本発明はその要旨を超えない限り以下の実
施例に限定されるものではない。
実施例
〔重合工程〕
温度調節装置、撹拌機及びモノマー供給口を有
する１密閉型反応器にシクロヘキサン（水との
共沸点69℃）375ｇ（モノマーに対して1.25wt倍）
及びエチルセルロース（ハーキユレス社製、商品
名Ｔ−100）1.87ｇ（モノマーに対して0.62wt％）
を仕込み、系内をN2ガスで脱気し、50℃に加熱
したのち、250r.p.mの撹拌下、これに、予めN2
ガスで脱気したジメチルアミノエチルアクリレー
ト塩酸塩131.9ｇ及びアクリルアミド67.6ｇと２，
2′―アゾビス―２―アミジノプロパン塩酸塩0.3
ｇを含有する66wt％水溶液を60分間かけて徐々
に滴下混合したのち、30分間撹拌を続けた。な
お、この際の温度は50〜55℃の範囲であつた。
重合終了後の混合物を過し、ビーズ状ポリマ
ー295ｇ及び母液325ｇを得た。
〔エチルセルロースの回収工程〕
加熱装置及び上部に蒸留装置を有する0.5の
撹拌槽に水150ｇを仕込み85℃に加熱したのち、
同温度に保持して250r.p.mの撹拌下、上記で得た
母液を0.3時間かけて徐々に滴下し、上部よりシ
クロヘキサン―水の共沸物を留出させ、また、エ
チルセルロースを水中に析出させた。
このようにして得たエチルセルロースを過
し、乾燥したのち、回収したエチルセルロースの
回収率を計算し第１表に示す結果を得た。
比較例
実施例において、エチルセルロースの回収を母
液と室温の水150ｇとを予め混合したのち、常温
から69℃（水とシクロヘキサンの共沸点）まで加
熱し、母液中のシクロヘキサンの全量が留出する
まで0.3時間蒸留を行ない、水中にエチルセルロ
ースを析出させた。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering ethylcellulose from a polymerization mixture, and specifically relates to a neutralized salt and/or quaternized product of dialkylaminoalkyl (meth)acrylate (hereinafter referred to as DAA). The present invention relates to a method for recovering ethylcellulose used as a dispersant from a mixture obtained by polymerizing monomers containing ethyl cellulose. Water-soluble polymers obtained by polymerizing monomers containing DAA are widely used, for example, as flocculants. As a method for producing this water-soluble polymer,
A method is known in which a DAA-containing monomer is suspension polymerized in a mixture of a hydrocarbon dispersion medium, water, and a dispersant in the presence of a catalyst. In recent years, in this polymerization,
In order to obtain uniform bead-shaped polymers, a method has been proposed in which ethyl cellulose is used as a dispersant and suspension polymerization is carried out in a water-in-oil type. Although this method is preferable from the viewpoint of polymer production because the resulting polymer is bead-shaped, it is difficult to separate and recover ethyl cellulose from the dispersion medium after polymerization. In other words, since ethylcellulose does not dissolve in water, the usual method is to separate the polymer after polymerization, add water to the mother liquor, heat the mixture, distill off the dispersion medium, and precipitate ethylcellulose in water. However, this method has the drawback that ethylcellulose does not disperse well in water, becomes sticky and adheres to the inner surface of the stirring tank. As a result, not only the recovery rate of ethyl cellulose was reduced, but also the cleaning operation of ethyl cellulose adhering to the inner surface of the apparatus was troublesome. In view of the above circumstances, the present inventors have investigated various methods for efficiently recovering ethyl cellulose from a polymerization mixture when a DAA-containing monomer is polymerized using ethyl cellulose as a dispersant, and have found a certain method. The present invention was completed based on the knowledge that the object of the present invention can be achieved by treating the mother liquor after polymerization. That is, the gist of the present invention is to convert DAA alone or a mixture of the monomer and a copolymerizable monomer into a water-in-oil type in the presence of a catalyst in a mixture consisting of a hydrocarbon dispersion medium, water, and a dispersant. When carrying out suspension polymerization, a compound having a boiling point lower than the boiling point of water is used as a dispersion medium, and in addition, in a method in which ethyl cellulose is used as a dispersant, the mother liquor after separating the produced polymer from the mixture after polymerization is used. ,
The method is characterized in that the dispersion medium is supplied under stirring into water that is heated to a boiling temperature or higher, thereby distilling off and recovering the dispersion medium, precipitating ethyl cellulose in the water, and then separating the ethyl cellulose. A method for recovering ethylcellulose from a polymerization mixture. The present invention will be explained in detail below. The DAA targeted by the present invention has the following general formula () (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are a straight chain or branched alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 may be the same,
R 4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a hydroxy-substituted alkyl group having 1 to 4 carbon atoms, or a benzyl group. Y represents an alkylene group having 2 to 4 carbon atoms or a hydroxy-substituted alkylene group. X is a halogen ion such as Cl, Br, sulfate ion, nitrate ion, phosphate ion,
Carboxylate ion, sulfonate ion, carbon number 1
Indicates an alkyl sulfate ion having ~8 alkyl groups. ) is a compound represented by. For example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dibutylaminoethyl acrylate, dibutylaminoethyl methacrylate, etc. and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, propionic acid, benzenesulfonic acid, etc. Neutralized salts with acids and β-methacryloyloxyethyltrimethylammonium chloride, β-methacryloyloxyethyltrimethylammonium methylsulfate, β-
Methacryloyloxyethyldimethylethylammonium bromide, β-methacryloyloxyethyldimethylethylammonium monoethyl sulfate, β-methacryloyloxyethyldimethylbenzylammonium chloride, β-acryloyloxyethyltrimethylammonium chloride, β-acryloyloxyethyltriethylammonium bromide, 2 Examples include quaternized products such as -hydroxy-3-methacryloyloxypropyltrimethylammonium chloride. The cationic high molecular weight water-soluble polymer that is the subject of the present invention is a monomer copolymerizable with the compound represented by the general formula () alone or with the compound represented by the general formula (), such as acrylamide, methacrylamide, vinyl Pyridine neutralized salt or 4
and copolymers with dimethyl diallylammonium compounds and the like. In the case of this copolymer, the content of DAA is usually 5 mol% or more,
Preferably it is 10 mol% or more. The dispersion medium used in the present invention is a hydrocarbon having a boiling point lower than that of water, and compounds that are azeotropic with water are particularly preferred. Generally, polymerization of DAA-containing monomers is carried out at normal pressure, and the dispersion medium must be liquid at normal pressure. Things are chosen. Specific examples of these include,
Hydrocarbons include alicyclic hydrocarbons such as cyclohexane, cyclopentane, and methylcyclohexane, and aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, trichloroethylene, and 1,2-dichloroethane.
These dispersion media usually have a ratio of 1 to 10
times by weight, preferably 1 to 5 times by weight are used. The amount of ethyl cellulose used as a dispersant of the present invention is 0.1 to 7% by weight, preferably 0.3 to 3% by weight based on the monomer. If this amount is too small, the resulting polymer will become lumpy and not uniform. They do not form beads, and if the amount is too large, the polymer particles tend to solidify together when the polymer is dried, and furthermore, the solubility of the product polymer in water decreases, which is not preferable. Polymerization in the present invention is usually carried out by charging a dispersion medium and a dispersant into a reactor, adding a separately prepared monomer aqueous solution and a catalyst, and mixing and stirring.
Polymerization can be carried out by forming a suspended state of the dispersant. The concentration of the monomer aqueous solution at this time is usually
10 to 80% by weight, preferably 40 to 80% by weight.
Ideally, the stirring state is such that good dispersion is achieved and the dispersed particles are large. The catalyst is usually a peroxide such as ammonium persulfate, potassium persulfate, hydrogen peroxide, etc.
2′-azobis-2-amidinopropane hydrochloride,
Known water-soluble catalysts such as azo compounds such as 4,4'-azobis-4-cyanopentanoic acid may be used. In the case of peroxides, they can also be used as redox catalysts in combination with reducing agents such as sodium metabisulfite, sodium sulfite, and ferrous chloride. The amount of these catalysts used is usually about 10 to 3000 ppm based on the monomer. The polymerization temperature varies somewhat depending on the type of monomer used, but is usually from 35°C to the boiling point of the mixture, preferably from 40 to 70°C. After the polymerization, the mixture is filtered to separate the generated bead-like polymer, and the separated polymer is washed and dried in a conventional manner and recovered. On the other hand, since the mother liquor is mainly composed of a hydrocarbon dispersion medium and has ethyl cellulose dissolved therein, it is sent to these recovery steps. In the present invention, by supplying the mother liquor to water heated and maintained above the boiling temperature of the dispersion medium while stirring,
The dispersion medium is removed by distillation, and ethyl cellulose is precipitated in water. This treatment is usually carried out by charging water in an amount of 3 to 20 times, preferably 4 to 10 times the weight of the mother liquor to be supplied to a stirring tank equipped with a distillation device, and heating it above the boiling temperature of the dispersion medium. It is carried out by gradually dropping the mother liquor into water. During this treatment, it is necessary to maintain the temperature of the water above the boiling temperature of the dispersion medium, and if the temperature of the water drops during this treatment, the precipitated ethyl cellulose will become sticky, which is not preferable. Next, the ethylcellulose precipitated in the water is recovered by filtration. The recovered ethylcellulose can be washed with, for example, a 0.1 to 1.0% by weight aqueous caustic solution, if necessary, and then used as a dispersant in the next polymerization reaction. As described above, according to the present invention, when recovering ethyl cellulose used as a dispersant, the ethyl cellulose does not become sticky and adhere to the inner surface of the device, so the recovery rate of ethyl cellulose is high, and the cleaning operation of the device is also simplified. It's easy. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Example [Polymerization step] 375 g of cyclohexane (azeotropic point with water: 69°C) (1.25 wt times the monomer) was placed in a closed reactor equipped with a temperature control device, a stirrer, and a monomer supply port.
and ethyl cellulose (manufactured by Hercules, trade name T-100) 1.87g (0.62wt% based on monomer)
The system was degassed with N 2 gas, heated to 50°C, and then N 2 gas was added to this in advance while stirring at 250 rpm.
131.9 g of dimethylaminoethyl acrylate hydrochloride and 67.6 g of acrylamide degassed,
2'-azobis-2-amidinopropane hydrochloride 0.3
After a 66 wt % aqueous solution containing g was gradually mixed dropwise over 60 minutes, stirring was continued for 30 minutes. Note that the temperature at this time was in the range of 50 to 55°C. After the polymerization was completed, the mixture was filtered to obtain 295 g of bead-like polymer and 325 g of mother liquor. [Ethylcellulose recovery process] 150g of water was placed in a 0.5 stirring tank equipped with a heating device and a distillation device on the top, and heated to 85℃.
While maintaining the same temperature and stirring at 250 rpm, the mother liquor obtained above was gradually added dropwise over 0.3 hours to distill the cyclohexane-water azeotrope from the upper part, and to precipitate ethyl cellulose in the water. Ta. After the ethyl cellulose thus obtained was filtered and dried, the recovery rate of the recovered ethyl cellulose was calculated and the results shown in Table 1 were obtained. Comparative Example In the example, ethyl cellulose was collected by pre-mixing the mother liquor with 150 g of water at room temperature, then heating from room temperature to 69°C (azeotropic point of water and cyclohexane) until the entire amount of cyclohexane in the mother liquor was distilled out. Distillation was performed for 0.3 hours to precipitate ethyl cellulose in water. 【table】
Claims (1)
ートの中和塩及び／又は４級化物モノマー単独、
又は該モノマーと共重合可能なモノマーとの混合
物を炭化水素系分散媒―水―分散剤よりなる混合
物中で触媒の存在下、油中水型にて懸濁重合する
に際し、分散媒として水の沸点よりも低い沸点を
有する化合物を使用し、しかも、分散剤としてエ
チルセルロースを使用する方法において、重合後
の混合物より生成ポリマーを別したのちの母液
を、前記分散媒が沸騰する温度以上に加熱保持さ
れた水中に撹拌下、供給することにより、分散媒
を留去して回収するとともに、エチルセルロース
を水中に析出させ、次いで、析出したエチルセル
ロースを別することを特徴とする重合混合物か
らのエチルセルロースの回収法。1 Neutralized salt of dialkylaminoalkyl (meth)acrylate and/or quaternized monomer alone,
Alternatively, when a mixture of the monomer and a copolymerizable monomer is subjected to suspension polymerization in a water-in-oil type in the presence of a catalyst in a mixture consisting of a hydrocarbon dispersion medium, water, and a dispersant, water is used as the dispersion medium. In a method in which a compound having a boiling point lower than the boiling point is used and ethyl cellulose is used as a dispersant, the mother liquor after separating the produced polymer from the mixture after polymerization is heated and held at a temperature higher than the temperature at which the dispersion medium boils. Recovery of ethyl cellulose from a polymerization mixture, characterized in that the dispersion medium is distilled off and recovered by supplying the ethyl cellulose into water under stirring, and the ethyl cellulose is precipitated in the water, and then the precipitated ethyl cellulose is separated. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9028780A JPS5716008A (en) | 1980-07-02 | 1980-07-02 | Recovery of ethylcellulose from polymerization mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9028780A JPS5716008A (en) | 1980-07-02 | 1980-07-02 | Recovery of ethylcellulose from polymerization mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5716008A JPS5716008A (en) | 1982-01-27 |
| JPS6320242B2 true JPS6320242B2 (en) | 1988-04-27 |
Family
ID=13994304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9028780A Granted JPS5716008A (en) | 1980-07-02 | 1980-07-02 | Recovery of ethylcellulose from polymerization mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5716008A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6127711A (en) * | 1984-07-06 | 1986-02-07 | Sumitomo Rubber Ind Ltd | Tire identification barcode ticket and tire dentification method |
| JPH0523892Y2 (en) * | 1989-05-29 | 1993-06-17 |
-
1980
- 1980-07-02 JP JP9028780A patent/JPS5716008A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5716008A (en) | 1982-01-27 |
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