JPS6318936B2 - - Google Patents
Info
- Publication number
- JPS6318936B2 JPS6318936B2 JP56012124A JP1212481A JPS6318936B2 JP S6318936 B2 JPS6318936 B2 JP S6318936B2 JP 56012124 A JP56012124 A JP 56012124A JP 1212481 A JP1212481 A JP 1212481A JP S6318936 B2 JPS6318936 B2 JP S6318936B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- group
- carbon atoms
- polymerization
- quaternary ammonium
- 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
- 239000000178 monomer Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000001302 tertiary amino group Chemical group 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000005956 quaternization reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 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 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 229940050176 methyl chloride Drugs 0.000 description 6
- 150000003839 salts Chemical group 0.000 description 6
- -1 diethylamino-2 -Hydroxypropyl Chemical group 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 4
- 229940073608 benzyl chloride Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 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 description 1
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- ZNJOCVLVYVOUGB-UHFFFAOYSA-N 1-iodooctadecane Chemical compound CCCCCCCCCCCCCCCCCCI ZNJOCVLVYVOUGB-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-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
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical group O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は第四級アンモニウム塩の製造法に関す
るものである。さらに詳しくは第四級アンモニウ
ム基を有するビニルモノマーの製造法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing quaternary ammonium salts. More specifically, the present invention relates to a method for producing a vinyl monomer having a quaternary ammonium group.
第四級アンモニウム塩を有するビニルモノマー
は単独重含、他のモノマーとの共重合または他の
基材へのグラフト重合などによつて陽イオン性、
導電性、水溶性、接着性などの機能をもつポリマ
ーを容易に与えるため、多くの分野で使用されて
いる。 Vinyl monomers containing quaternary ammonium salts can be made cationic by monopolymerization, copolymerization with other monomers, or graft polymerization onto other base materials.
It is used in many fields because it easily provides polymers with functions such as conductivity, water solubility, and adhesive properties.
第四級アンモニウム基を有するビニルモノマー
は通常は第三級アミノ基を有するビニルモノマー
を四級化剤と反応させて得られる。第三級アミン
の四級化剤との反応はメンシユトキン反応と通称
され、通常は第三級アミンの水溶液に四級化剤を
添加して反応が行なわれる。 Vinyl monomers having quaternary ammonium groups are usually obtained by reacting vinyl monomers having tertiary amino groups with a quaternizing agent. The reaction of a tertiary amine with a quaternizing agent is commonly called the Menshutkin reaction, and the reaction is usually carried out by adding the quaternizing agent to an aqueous solution of the tertiary amine.
しかしながら後述するような一般式(1)で示され
る第三級アミノ基含有不飽和酸エステルや不飽和
酸アミドの場合、該ビニルモノマーのエステル基
またはアミド基が極めて加水分解を受け易いため
反応中に相当する不飽和酸（アクリル酸またはメ
タクリル酸）が多量副生する結果を招くことが多
かつた。この様な不飽和酸は四級化物の品質の著
しい低下を招くのみならず第三級アミノ基含有ビ
ニルモノマーおよびその第四級アンモニウム塩の
重合を促進する傾向があり、四級化反応中に予期
せざる重合を惹起する原因となることが多かつ
た。 However, in the case of unsaturated acid esters or unsaturated acid amides containing a tertiary amino group represented by the general formula (1) as described later, the ester group or amide group of the vinyl monomer is extremely susceptible to hydrolysis, so that during the reaction This often resulted in large amounts of unsaturated acids (acrylic acid or methacrylic acid) being produced as by-products. Such unsaturated acids not only cause a significant deterioration in the quality of the quaternized product, but also tend to promote the polymerization of the tertiary amino group-containing vinyl monomer and its quaternary ammonium salt, and may cause problems during the quaternization reaction. This often caused unexpected polymerization.
この様な問題点を解決するため従来から行われ
ている方策の一つは、室温以下の低温で四級化反
応を行うことである。しかしこの場合には加水分
解速度自体は大巾に低下するが同時に四級化反応
速度も著しく低下するため、反応終了までに極め
て長時間を要し、工業的には好適な方法とは言え
なかつた。 One of the measures conventionally used to solve such problems is to carry out the quaternization reaction at a low temperature below room temperature. However, in this case, the hydrolysis rate itself is greatly reduced, but at the same time, the quaternization reaction rate is also significantly reduced, so it takes an extremely long time to complete the reaction, and it is not an industrially suitable method. Ta.
本発明者らはこの様な現状に鑑み一般式(1)で示
される第三級ビニルモノマーの四級化方法を鋭意
研究した結果、高品質の四級化物を迅速に且つ反
応中の重合トラブルなく得る方法を見出し本発明
に到つた。すなわち本発明は一般式
（式中R1はＨまたはCH3；R2，R3はそれぞれ
独立に炭素数１〜４のアルキル基、または炭素数
２〜４のヒドロキシアルキル基；ＡはＯ（酸素原
子）またはNH、Ｂは炭素数１〜４のアルキレン
基または炭素数２〜４のヒドロキシアルキレン基
である。）で示される第三級アミノ基を有するビ
ニルモノマーを四級化剤と反応させて該モノマー
の第四級アンモニウム塩を製造する方法におい
て、反応と並行して水を断続的または連続的に添
加しながら反応を行うことを特徴とする第四級ア
ンモニウム塩の製造法である。 In view of the current situation, the present inventors have conducted intensive research on a method for quaternizing the tertiary vinyl monomer represented by the general formula (1), and have found that they can rapidly produce high-quality quaternized products and eliminate polymerization problems during the reaction. The present invention was achieved by finding a method to obtain the above-mentioned results. That is, the present invention is based on the general formula (In the formula, R 1 is H or CH 3 ; R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms; A is O (oxygen atom) or NH, B is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms.) A vinyl monomer having a tertiary amino group represented by This is a method for producing a quaternary ammonium salt, which is characterized in that the reaction is carried out while adding water intermittently or continuously in parallel with the reaction.
一般式(1)において、R2，R3はそれぞれ炭素数
１〜４のアルキル基または炭素数２〜４のヒドロ
キシアルキル基である。炭素数１〜４のアルキル
基としては、メチル基、エチル基、ｎ−もしくは
iso−プロピル基、およびブチル基をあげること
ができる。炭素数２〜４のヒドロキシアルキル基
としては−CH2CH2OH，−CH2CH2CH2OHおよ
び−CH2CH（CH2OH）CH3をあげることができ
る。Ｂは炭素数１〜４のアルキレン基または炭素
数２〜４のヒドロキシアルキレン基である。該ア
ルキレン基としては−CH2CH2−，−
CH2CH2CH2−，−CH2CHCH3−があげられ、該
ヒドロキシアルキレン基としては−CH2CH
（OH）CH2−があげられる。 In general formula (1), R 2 and R 3 are each an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms, methyl group, ethyl group, n- or
Examples include iso-propyl group and butyl group. Examples of the hydroxyalkyl group having 2 to 4 carbon atoms include -CH2CH2OH , -CH2CH2CH2OH and -CH2CH ( CH2OH ) CH3 . B is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms. The alkylene group is -CH 2 CH 2 -, -
CH 2 CH 2 CH 2 −, −CH 2 CHCH 3 − are mentioned, and the hydroxyalkylene group is −CH 2 CH
(OH) CH2- is mentioned.
一般式(1)で示されるモノマーとしては具体的に
は下記のモノマーがあげられる。 Specific examples of the monomer represented by the general formula (1) include the following monomers.
(A) 第三級アミノ基含有（メタ）アクリレート
(a) ジアルキルアミノアルキル（メタ）アクリ
レート
ジメチルアミノエチル（メタ）アクリレー
ト、ジエチルアミノエチル（メタ）アクリレ
ートなど
(b) ジアキルアミノヒドロキシアルキル（メ
タ）アクリレート
ジメチルアミノ−２−ヒドロキシプロピル
（メタ）アクリレート、ジエチルアミノ−２
−ヒドロキシプロピル（メタ）アクリレート
など
上記および以下において（メタ）アクリレート
とはアクリレートおよび／またはメタアクリレー
トという。(A) Tertiary amino group-containing (meth)acrylates (a) Dialkylaminoalkyl (meth)acrylates Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. (b) Diacylaminohydroxyalkyl (meth)acrylates Dimethylamino-2-hydroxypropyl (meth)acrylate, diethylamino-2
-Hydroxypropyl (meth)acrylate, etc. In the above and below, (meth)acrylate is referred to as acrylate and/or methacrylate.
(B) 第三級アミノ基含有（メタ）アクリルアミド
(a) ジアルキルアミノアルキル（メタ）アクリ
ルアミド
ジメチルアミノエチル（メタ）アクリルア
ミド、ジエチルアミノプロピル（メタ）アク
リルアミドなど
(b) ジアルキルアミノヒドロキミアルキル（メ
タ）アクリルアミド
ジメチルアミノ−２−ヒドロキシプロピル
（メタ）アクリルアミド、ジエチルアミノ−
２−ヒドロキシプロピル（メタ）アクリルア
ミドなど
上記および以下において（メタ）アクリルアミ
ドとはアクリルアミドおよび／またはメタアクリ
ルアミドをいう。(B) Tertiary amino group-containing (meth)acrylamides (a) Dialkylaminoalkyl (meth)acrylamide Dimethylaminoethyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, etc. (b) Dialkylaminohydroxyalkyl (meth)acrylamide Dimethylamino-2-hydroxypropyl (meth)acrylamide, diethylamino-
2-Hydroxypropyl (meth)acrylamide, etc. In the above and below, (meth)acrylamide refers to acrylamide and/or methacrylamide.
本発明は、これらのモノマー中で四級化剤によ
る副反応（加水分解、重合など）がもつともおこ
り易い第三級アミノ基含有（メタ）アクリレート
の場合にとくに有効であり好ましい。 The present invention is particularly effective and preferred in the case of tertiary amino group-containing (meth)acrylates, which are susceptible to side reactions (hydrolysis, polymerization, etc.) due to quaternizing agents among these monomers.
本発明における四級化剤は公知のものを選ぶこ
とができ、たとえばアルキルハライド（メチルク
ロライド、メチルアイオダイド、ブチルクロライ
ド、オクチルブロマイド、ラウリルブロマイド、
ステアリルアイオダイドなど）、アラルキルハラ
イド（ベンジルクロライド、Ｐ−メチルベンジル
クロライド、Ｐ−オクチルベンジルクロライド、
フエネチルブロマイドなど）、アルキル硫酸（ジ
メチル硫酸、ジエチル硫酸など）、およびスルホ
ン酸エステル（Ｐ−トルエンスルホン酸メチルな
ど）があげられる。これらの中で工業的観点から
メチルクロライド、ベンジルクロライドおよびジ
メチル硫酸が好ましい。 The quaternizing agent used in the present invention can be selected from known ones, such as alkyl halides (methyl chloride, methyl iodide, butyl chloride, octyl bromide, lauryl bromide,
stearyl iodide, etc.), aralkyl halides (benzyl chloride, P-methylbenzyl chloride, P-octylbenzyl chloride,
phenethyl bromide, etc.), alkyl sulfates (dimethyl sulfate, diethyl sulfate, etc.), and sulfonic acid esters (methyl P-toluenesulfonate, etc.). Among these, methyl chloride, benzyl chloride and dimethyl sulfate are preferred from an industrial standpoint.
本発明における四級化反応は、反応と並行して
水を断続的または連続的にモノマーに添加しなが
ら行う。四級化反応にさいし、四級化剤は反応開
始前に反応槽内の第三級アミノ基を有するビニル
モノマーに加えておいてもよく、反応と並行して
添加していつてもよいが、反応の暴走を防ぐため
反応と並行して添加する方法が好ましい。 The quaternization reaction in the present invention is carried out while adding water intermittently or continuously to the monomer in parallel with the reaction. In the quaternization reaction, the quaternization agent may be added to the vinyl monomer having a tertiary amino group in the reaction tank before the start of the reaction, or may be added in parallel with the reaction. In order to prevent the reaction from running out of control, it is preferable to add it in parallel with the reaction.
四級化剤を反応と並行して添加する方法をとる
場合、四級化剤と水とは並行して加えてもよく、
交互に加えてもよい。またそれぞれを連続的に加
えてもよく、断続的に加えてもよい。添加の方法
はとくに限定なく常圧で滴下する方法、加圧下に
圧入する（吹込む）方法などがあげられる。 When using a method of adding the quaternizing agent in parallel with the reaction, the quaternizing agent and water may be added in parallel,
They may be added alternately. Moreover, each may be added continuously or intermittently. The method of addition is not particularly limited, and examples include a method of dropping it under normal pressure and a method of injecting it under pressure (blowing).
その他の四級化反応の条件は公知の範囲でとく
に限定なく選び得るが、以下の条件は本特許にと
くに有効でありこれらの条件で実施することが好
ましい。すなわち四級化温度は10〜60℃が好まし
く20〜40℃がさらに好ましい。四級化剤の使用量
は三級アミンモノマーのアミノ基１モルに対して
1.00〜1.20モルが好ましく、1.01〜1.10モルがさ
らに好ましい。水の量は一般式(1)で示される第三
級アミノ基を有するビニルモノマーの第四級アン
モニウム塩（四級塩モノマー）の濃度に関係し、
四級化反応終了時の四級塩モノマーの濃度は四級
化時の加水分解を押えるためできるだけ高い方が
好ましいが、高すぎると四級化反応速度が遅くな
ること、四級化中の重合が起り易くなること等の
理由で通常は50〜90重量％、好ましくは70〜85重
量％である。 Although other conditions for the quaternization reaction can be selected without particular limitation within a known range, the following conditions are particularly effective for this patent, and it is preferable to carry out the reaction under these conditions. That is, the quaternization temperature is preferably 10 to 60°C, more preferably 20 to 40°C. The amount of quaternizing agent used is per mole of amino group of tertiary amine monomer.
1.00 to 1.20 mol is preferable, and 1.01 to 1.10 mol is more preferable. The amount of water is related to the concentration of the quaternary ammonium salt (quaternary salt monomer) of the vinyl monomer having a tertiary amino group represented by the general formula (1),
The concentration of the quaternary salt monomer at the end of the quaternization reaction is preferably as high as possible in order to suppress hydrolysis during quaternization, but if it is too high, the quaternization reaction rate will be slow and polymerization during quaternization will be reduced. The content is usually 50 to 90% by weight, preferably 70 to 85% by weight, for the reason that this tends to occur.
また、四級化剤を反応と並行して添加する場合
はその添加速度は一般に系中の未反応四級化剤量
が未反応モノマーおよびこれから生成する四級塩
モノマーの合計モル数に対して通常20モル％以
下、好ましくは10モル％以下にするのが好まし
い。 In addition, when adding a quaternizing agent in parallel with the reaction, the rate of addition is generally determined based on the amount of unreacted quaternizing agent in the system relative to the total number of moles of unreacted monomers and quaternary salt monomers to be produced. It is usually 20 mol% or less, preferably 10 mol% or less.
本発明によつて得られる四級塩モノマーは反応
終了時点では四級塩の水溶液となつているがこの
ものを必要に応じてさらに希釈または濃縮しても
よい。また四級塩モノマー水溶液は必要に応じて
更にイオン交換樹脂や活性炭による処理、溶剤抽
出等により精製することができる。さらにハイド
ロキノンモノメチルエーテル、ターシヤリブチル
カテコール、ニトロソベンゼン、バラフエニレン
ジアミン、フエノチアジン、ジエチルヒドロキシ
ルアミンなど公知の重合禁止剤、EDTA、ポリ
リン酸、ニトリロトリ酢酸などの公知のキレート
剤、およびPH調整剤などの添加剤を四級化反応前
または反応後加えてもよい。 The quaternary salt monomer obtained by the present invention is an aqueous solution of the quaternary salt at the end of the reaction, but this solution may be further diluted or concentrated as necessary. Further, the quaternary salt monomer aqueous solution can be further purified by treatment with an ion exchange resin or activated carbon, solvent extraction, etc., if necessary. In addition, known polymerization inhibitors such as hydroquinone monomethyl ether, tertiary butylcatechol, nitrosobenzene, paraphenyl diamine, phenothiazine, and diethylhydroxylamine, known chelating agents such as EDTA, polyphosphoric acid, and nitrilotriacetic acid, and PH regulators, etc. Additives may be added before or after the quaternization reaction.
本発明の第四級アンモニウム塩ビニルモノマー
は単独でまたはこの第四級アンモニウム塩ビニル
モノマ以外の他のビニルモノマーとともに公知の
（共）重合方法によつて（共）重合体にすること
ができる。（共）重合体を製造する際使用できる
第四級アンモニウム塩以外の他のビニルモノマー
としては、特開昭54−102388号公報に記載の単量
体たとえば親水性の非イオン性ビニル単量体、親
水性の他のカチオン性ビニル単量体、親水性のア
ニオン性ビニル単量体および油溶性のビニル単量
体があげられる。 The quaternary ammonium salt vinyl monomer of the present invention can be made into a (co)polymer alone or together with other vinyl monomers other than the quaternary ammonium salt vinyl monomer by a known (co)polymerization method. Other vinyl monomers other than the quaternary ammonium salt that can be used in producing the (co)polymer include the monomers described in JP-A-54-102388, such as hydrophilic nonionic vinyl monomers. , other hydrophilic cationic vinyl monomers, hydrophilic anionic vinyl monomers, and oil-soluble vinyl monomers.
本発明により安定化されたモノマーは通常の方
法により重合可能である。たとえばラジカル重合
開始剤、紫外線、放射線などを使用する方法で行
うことができる。これらのうち水溶性の過硫酸塩
（過硫酸ナトリウム、過硫酸アンモニウムなど）、
アゾ化合物（アゾビスイソブチロニトリル、アゾ
ビスジメチルワレロニトリルなど）などのラジカ
ル重合開始剤を用いる方法が好ましい。 The monomers stabilized according to the invention can be polymerized by conventional methods. For example, it can be carried out by a method using a radical polymerization initiator, ultraviolet rays, radiation, or the like. Among these, water-soluble persulfates (sodium persulfate, ammonium persulfate, etc.),
A method using a radical polymerization initiator such as an azo compound (azobisisobutyronitrile, azobisdimethylvaleronitrile, etc.) is preferred.
また重合は公知の方法、たとえば水溶液重合、
乳化重合、懸濁重合、沈澱重合などの方法により
行うことができる。水溶液重合の場合にはたとえ
ば単量体を水溶液（単量体濃度はたとえば10〜90
重量％）とし、系内を不活性ガスで置換したの
ち、ラジカル重合開始剤を加え、通常０〜80℃程
度で数時間重合することにより行うことができ
る。乳化重合の場合は、たとえば特開昭50−
102388号公報に記載の方法により行うことができ
る。 The polymerization can be carried out using known methods such as aqueous solution polymerization,
It can be carried out by methods such as emulsion polymerization, suspension polymerization, and precipitation polymerization. In the case of aqueous solution polymerization, for example, monomers are added to an aqueous solution (monomer concentration is, for example, 10 to 90
After replacing the system with an inert gas, a radical polymerization initiator is added, and polymerization is carried out usually at about 0 to 80° C. for several hours. In the case of emulsion polymerization, for example,
This can be carried out by the method described in Japanese Patent No. 102388.
本発明により一般式(1)で示されるモノマーの四
級化に際する加水分解、重合等の不都合な副反応
が効果的に抑止でき、不飽和酸、重合物等の不純
物含有量の極めて低い高品質の第四級アンモニウ
ム塩モノマーの工業的製造が可能となつた。これ
は水を反応と並行して添加しながら四級化を行う
ことにより初めて達成できたものであり従来より
公知の方法では為し得なかつたものである。 According to the present invention, disadvantageous side reactions such as hydrolysis and polymerization during quaternization of the monomer represented by general formula (1) can be effectively suppressed, and the content of impurities such as unsaturated acids and polymers is extremely low. Industrial production of high quality quaternary ammonium salt monomers has become possible. This was achieved for the first time by performing quaternization while adding water in parallel with the reaction, and could not be achieved by conventionally known methods.
本発明によつて得られた第四級アンモニウム塩
モノマーは繊維処理剤、高分子疑豊剤、製紙用薬
剤、接着剤等に用いられる機能性ポリマーの原料
モノマーとして極めて有用性が高い。 The quaternary ammonium salt monomer obtained by the present invention is extremely useful as a raw material monomer for functional polymers used in fiber treatment agents, polymer enrichment agents, paper-making agents, adhesives, and the like.
以下実施例を以て本発明をさらに説明するが、
本発明はこれに限定されるものではない。 The present invention will be further explained below with reference to Examples.
The present invention is not limited to this.
実施例 １
撹拌機、温度計、滴下ロート（２個）およびサ
ンプリング管を備えた２ガラスコルベンに、ジ
メチルアミノエチルメタクリレート628ｇ（４モ
ル）を仕込み、滴下ロートの一方に水300ｇ、他
方にベンジルクロライド512ｇ（4.05モル）を仕
込んだ。コルベン内の液温を25℃に調整し撹拌し
ながら水とベンジルクロライドを同時に滴下開始
し、それぞれ４時間で全量を添加した。この後更
に１時間熟成して濃度79％の第四級アンモニウム
塩水溶液1475ｇを得た。この間液温は外部冷却に
より25±５℃に保つた。第四級アンモニウム塩の
収率はアミン価から計算して99.8％、メタクリル
酸の副生量は使用したジメチルアミノエチルメタ
クリレートに対して0.05モル％にすぎなかつた。
また四級化反応中の重合も認めなかつた。Example 1 628 g (4 moles) of dimethylaminoethyl methacrylate was placed in a two-glass kolben equipped with a stirrer, a thermometer, two dropping funnels, and a sampling tube, and 300 g of water was placed in one of the dropping funnels and benzyl chloride was placed in the other. 512g (4.05mol) was charged. The temperature of the liquid in the colben was adjusted to 25°C, and while stirring, water and benzyl chloride were simultaneously added dropwise, and the entire amount was added over 4 hours. Thereafter, the mixture was further aged for 1 hour to obtain 1475 g of a quaternary ammonium salt aqueous solution having a concentration of 79%. During this time, the liquid temperature was maintained at 25±5°C by external cooling. The yield of the quaternary ammonium salt was calculated from the amine value to be 99.8%, and the amount of methacrylic acid by-produced was only 0.05 mol% based on the dimethylaminoethyl methacrylate used.
Further, no polymerization was observed during the quaternization reaction.
比較例 １
実施例１で水を反応中に滴下する代りにあらか
じめ反応前に全量コルベン内に加えた点を除き他
は全く同様の条件で四級化を行つた。この場合に
はジメチルアミノエチルメタクリレートが四級化
中に加水分解し、最終的には第四級アンモニウム
塩の収率は96・０％、メタクリル酸の副生量は使
用したジメチルアミノエチルメタクリレートに対
して1.9％に達していた。また反応液はわずかに
増粘しており0.4％のポリマーを含有していた。Comparative Example 1 Quaternization was carried out under exactly the same conditions as in Example 1, except that instead of adding water dropwise during the reaction, the entire amount was added to the kolben before the reaction. In this case, dimethylaminoethyl methacrylate is hydrolyzed during quaternization, and the final yield of quaternary ammonium salt is 96.0%, and the amount of methacrylic acid by-product is equal to the amount of dimethylaminoethyl methacrylate used. In comparison, it reached 1.9%. Additionally, the reaction solution had slightly increased viscosity and contained 0.4% polymer.
実施例２ （四級化剤と水を断続的に添加する
例）
撹拌機、温度計、滴下ロート（２個）およびサ
ンプリング管を備えた1.5リツトルのガラスオー
トクレーブにモノマーとしてジメチルアミノエチ
ルメタクリレート471ｇ（３モル）を仕込み、滴
下ロートの一方に水156ｇ、他方にメチルクロラ
イド153ｇ（3.03モル）を仕込んだ。オートクレ
ーブ内の液温を20〜25℃に調整し撹拌しながらメ
チルクロライドと水を５回に分けて断続的に添加
した。この場合、添加は最初メチルクロライド30
ｇと水30ｇを30分かけて行いその後30分間熟成し
た。更に同じ方法により断続的にメチルクロライ
ドと水を添加してゆき５回目に残り全部を投入し
た後、３時間熟成して濃度80％の第四級アンモニ
ウム塩水溶液780ｇを得た。第四級アンモニウム
塩の収率は、アミン価から計算して99.5％、メタ
クリル酸の副生量は使用したジメチルアミノエチ
ルメタクリレートに対し0.09モル％であつた。ま
たこの場合実施例１と同じく反応中は重合は認め
られなつかた。Example 2 (Example of intermittent addition of quaternizing agent and water) 471 g of dimethylaminoethyl methacrylate as a monomer ( One side of the dropping funnel was charged with 156 g of water, and the other was charged with 153 g (3.03 moles) of methyl chloride. The liquid temperature in the autoclave was adjusted to 20 to 25°C, and methyl chloride and water were added intermittently in five portions while stirring. In this case, the addition is initially methyl chloride 30
g and 30 g of water over 30 minutes, and then aged for 30 minutes. Further, in the same manner, methyl chloride and water were added intermittently, and after the fifth addition, the remaining mixture was added and aged for 3 hours to obtain 780 g of a quaternary ammonium salt aqueous solution with a concentration of 80%. The yield of the quaternary ammonium salt was calculated from the amine value to be 99.5%, and the amount of methacrylic acid by-produced was 0.09 mol% based on the dimethylaminoethyl methacrylate used. In this case, as in Example 1, no polymerization was observed during the reaction.
実施例３ （四級化剤と水を別添する例）
実施例２のガラスオートクレーブにモノマーと
してジメチアミノエチルアクリレート429ｇ（３
モル）を仕込み、滴下ロートの一方に水146ｇ、
他方にメチルクロライド153ｇ（3.03モル）を仕
込んだ。オートクレーブ内の液温を20℃に調整し
撹拌しながらメチルクロライドを２時間で全量添
加した。この後水を連続的に２時間かけて全量滴
下した。水の添加終了後、液温を常に20±２℃に
保つて15時間熟成し、濃度80％の第四級アンモニ
ウム塩水溶液725ｇを得た。第四級アンモニウム
塩の収率は、アミン価から計算して99.5％、アク
リル酸の副生量は使用したジメチルアミノエチル
アクリレートに対し0.12モル％であつた。この場
合も反応中に重合は認められなつかた。Example 3 (Example of adding quaternizing agent and water separately) 429 g of dimethyaminoethyl acrylate (3
mol), add 146g of water to one side of the dropping funnel,
On the other side, 153 g (3.03 mol) of methyl chloride was charged. The liquid temperature in the autoclave was adjusted to 20°C, and the entire amount of methyl chloride was added in 2 hours while stirring. After that, the entire amount of water was continuously added dropwise over 2 hours. After the addition of water, the solution was aged for 15 hours while keeping the temperature at 20±2° C. to obtain 725 g of a quaternary ammonium salt aqueous solution with a concentration of 80%. The yield of the quaternary ammonium salt was calculated from the amine value to be 99.5%, and the amount of acrylic acid by-produced was 0.12 mol% based on the dimethylaminoethyl acrylate used. In this case as well, no polymerization was observed during the reaction.
Claims (1)
れ独立に炭素数１〜４のアルキル基、または炭素
数２〜４のヒドロキシアルキル基；ＡはＯ（酸素
原子）またはNH、Ｂは炭素数１〜４のアルキレ
ン基または炭素数２〜４のヒドロキシアルキレン
基である。）で示される第三級アミノ基を有する
ビニルモノマーに四級化剤を加えて反応させて該
モノマーの第四級アンモニウム塩を製造する方法
において、反応と並行して水を断続的または連続
的に添加しながら反応を行うことを特徴とする第
四級アンモニウム塩の製造法。 ２ 第三級アミノ基を有するビニルモノマーに四
級化剤の添加と並行して水を断続的または連続的
に添加する特許請求の範囲第１項記載の製造法。[Claims] 1. General formula (In the formula, R 1 is H or CH 3 ; R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms; A is O (oxygen atom) or NH , B is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms. A method for producing a quaternary ammonium salt, characterized in that the reaction is carried out while adding water intermittently or continuously in parallel with the reaction. 2. The production method according to claim 1, wherein water is added intermittently or continuously to the vinyl monomer having a tertiary amino group in parallel with the addition of the quaternizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1212481A JPS57126452A (en) | 1981-01-28 | 1981-01-28 | Preparation of quaternary ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1212481A JPS57126452A (en) | 1981-01-28 | 1981-01-28 | Preparation of quaternary ammonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57126452A JPS57126452A (en) | 1982-08-06 |
| JPS6318936B2 true JPS6318936B2 (en) | 1988-04-20 |
Family
ID=11796785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1212481A Granted JPS57126452A (en) | 1981-01-28 | 1981-01-28 | Preparation of quaternary ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57126452A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4745214A (en) * | 1986-06-20 | 1988-05-17 | Norsolor | Process for the preparation of an aqueous solution of unsaturated quaternary ammonium salts |
| NL193088C (en) * | 1988-02-11 | 1998-10-05 | Norsolor Sa | Process for the preparation of aqueous solutions of unsaturated quaternary ammonium salts. |
| US5639840A (en) * | 1995-01-26 | 1997-06-17 | Indiana University Foundation | Fluoride ion releasing dental materials |
| KR100491098B1 (en) * | 1997-10-15 | 2005-09-26 | 삼성정밀화학 주식회사 | Method for preparing high purity methacrylate quaternary ammonium salt |
| JP4967292B2 (en) * | 2005-03-07 | 2012-07-04 | 住友ベークライト株式会社 | Composition, ion conductive electrolyte obtained therefrom, and secondary battery using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231017A (en) * | 1975-09-03 | 1977-03-09 | Mitsubishi Chem Ind Ltd | Quaternizing process |
| JPS55127351A (en) * | 1979-03-27 | 1980-10-02 | Toagosei Chem Ind Co Ltd | Preparation of quaternary ammonium salt monomer |
-
1981
- 1981-01-28 JP JP1212481A patent/JPS57126452A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231017A (en) * | 1975-09-03 | 1977-03-09 | Mitsubishi Chem Ind Ltd | Quaternizing process |
| JPS55127351A (en) * | 1979-03-27 | 1980-10-02 | Toagosei Chem Ind Co Ltd | Preparation of quaternary ammonium salt monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57126452A (en) | 1982-08-06 |
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