JPH02160757A - Production of sulfobetaine - Google Patents
Production of sulfobetaineInfo
- Publication number
- JPH02160757A JPH02160757A JP31445188A JP31445188A JPH02160757A JP H02160757 A JPH02160757 A JP H02160757A JP 31445188 A JP31445188 A JP 31445188A JP 31445188 A JP31445188 A JP 31445188A JP H02160757 A JPH02160757 A JP H02160757A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- reaction
- sulfobetaine
- alkali
- alcohol
- 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
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229940117986 sulfobetaine Drugs 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 4
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 4
- -1 haloalkyl sulfonate Chemical compound 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical group 0.000 abstract description 3
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 239000003599 detergent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000012467 final product Substances 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 description 2
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical compound CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 description 1
- OQFSYHWITGFERZ-UHFFFAOYSA-N 2-bromoethanesulfonic acid Chemical compound OS(=O)(=O)CCBr OQFSYHWITGFERZ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、洗浄剤及び起泡剤として浸れたスルホベタイ
ンを、高い反応率で得る製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a process for producing impregnated sulfobetaine as a detergent and foaming agent with a high conversion rate.
［従来の技術及びその課題］
スルホベタインの製造に関し９０％以上の高い反応率を
得るため、アルコール又はアルコール水混合溶媒を用い
３級アミンをハロアルキルスルホン酸より２倍モル以上
の過剰量使われる方法が既に知られている（特開昭５０
−３６４２１号公報）。[Prior art and its problems] In order to obtain a high reaction rate of 90% or more regarding the production of sulfobetaine, a method in which alcohol or an alcohol-water mixed solvent is used and a tertiary amine is used in an excess amount of 2 times or more mole or more than haloalkylsulfonic acid. is already known (Japanese Unexamined Patent Application Publication No. 1973)
-36421 publication).
しかしこの方法に於いては高反応率でスルホベタインを
得るために、高温、加圧下で反応を行なう必要があり、
更にアミンのモル比が高いため反応後アミンを抽出除去
する必要があるなど装置的、経済的、及び工業的に問題
がある。However, in this method, in order to obtain sulfobetaine at a high reaction rate, it is necessary to conduct the reaction at high temperature and under pressure.
Furthermore, since the molar ratio of amine is high, it is necessary to extract and remove the amine after the reaction, which poses problems in terms of equipment, economy, and industry.
また水溶媒系でアルカリを反応促進剤として用い高反応
率を得る方法も知られている（特公昭６１−１６２６９
号公報）。この方法は、系内の水分蟲度を３０〜５０％
に調整し、ハロアルキルスルホン酸塩を長鎖アルキル第
３級アミン１モル当たり１．１−１．５モル使用し、更
にカセイアルカリを長鎖アルキル第３級アミン！モル当
たり０゜１１〜０．２５モルの範囲で添加することによ
り高い反応率でスルホベタインを得る。しかしこの方法
では高反応率でスルホベタインを得るために、反応系を
高濃度（固型分５０〜７０％）に保つ必要があり、その
結果有効分が高いため冷却後は高粘度となり取り扱い上
困難な面を有する。It is also known to obtain a high reaction rate using an alkali as a reaction accelerator in an aqueous solvent system (Japanese Patent Publication No. 61-16269
Publication No.). This method reduces the moisture content in the system by 30-50%.
The haloalkyl sulfonate was adjusted to 1.1-1.5 mol per mol of the long-chain alkyl tertiary amine, and the caustic alkali was added to the long-chain alkyl tertiary amine! By adding in a range of 0.11 to 0.25 mol per mol, sulfobetaine can be obtained at a high reaction rate. However, in this method, in order to obtain sulfobetaine with a high reaction rate, it is necessary to maintain the reaction system at a high concentration (solid content 50-70%). It has some difficult aspects.
そこで本発明者らは、製品として取り扱いが容易でしか
も高反応率のスルホベタインを容易に得る方法を鋭意検
討した結果、アルコールを反応促進剤として用い且つ反
応時系内のｐＨを一定に保つことにより所望の目的を達
成出来ることを見い出し本発明を完成した。Therefore, the present inventors have conducted intensive studies on a method for easily obtaining sulfobetaine that is easy to handle as a product and has a high reaction rate.As a result, the present inventors have found that they use alcohol as a reaction accelerator and keep the pH constant during the reaction time. The present invention has been completed by discovering that the desired object can be achieved by the following methods.
すなわち本発明は、一般式（Ｉ）で表される３級アミン
（式中の飢は炭素数８〜２８のアルキル基又はアルケニ
ル基、Ｒ１及びＲ１はそれぞれ独立して炭素数１〜３の
アルキル基又はヒドロキシアルキル基を表す）と、一般
式（Ｉｆ）
Ｘ Ｒ４ＳＯａＭ （Ｕ）（式中のＲ４
は炭素数２〜４のアルキレン基又はヒドロキシアルキレ
ン基、Ｘはハロゲン原子及びＭはアルカリ金属を表す）
で表されるハロアルキルスルホン酸塩とを反応させて一
般式（ＩＩＩ）で表わされるスルホベタインを製造する
方法においてＲ″３
（式中のＲｌ−Ｒ４は前記と同じ意味を表す）炭素数Ｉ
〜４のアルコールを全仕込み量に対し２〜２０重量％の
範囲で添加し、且つ反応系の１％ｌ）Ｈを６〜８に保つ
様にアルカリを連続又は断続的に添加することを特徴と
するスルホベタインの製造方法を提供する。That is, the present invention provides a tertiary amine represented by the general formula (I) (wherein is an alkyl group or alkenyl group having 8 to 28 carbon atoms, and R1 and R1 are each independently an alkyl group having 1 to 3 carbon atoms). or a hydroxyalkyl group), and the general formula (If)
is an alkylene group or hydroxyalkylene group having 2 to 4 carbon atoms, X is a halogen atom, and M is an alkali metal)
In the method for producing sulfobetaine represented by general formula (III) by reacting with a haloalkyl sulfonate represented by
-4 alcohol is added in the range of 2 to 20% by weight based on the total amount charged, and an alkali is added continuously or intermittently so as to maintain 1% H of the reaction system at 6 to 8. Provided is a method for producing sulfobetaine.
本発明方法で用いる原料に於いて、前記一般式（Ｉ）の
長鎖アルキル第３級アミンは、Ｒ１が炭素数８〜２８好
ましくはｌＯ〜２２の直鎖状又は分岐状のいずれで６良
いアルキル若しくはアルケニル基、例えばデシル基、ラ
ウリル基、トリデシル基、ミリスチル基、パルミチル基
、ステアリル基、ベヘニル基、オレイル基及びイソステ
アリル基等であり、Ｒ１及びＲ１がそれぞれ独立して炭
素数１〜３のアルキル基若しくはヒドロキシアルキル基
、例えばメチル基、エチル基、プロピル基、イソプロピ
ル基、２−ヒドロキシエチル基及び２−ヒドロキシプロ
ピル基等であるアミンである。In the raw material used in the method of the present invention, the long-chain alkyl tertiary amine of the general formula (I) may be linear or branched, with R1 having 8 to 28 carbon atoms, preferably 10 to 22 carbon atoms. An alkyl or alkenyl group, such as a decyl group, lauryl group, tridecyl group, myristyl group, palmityl group, stearyl group, behenyl group, oleyl group, isostearyl group, etc., and R1 and R1 each independently have 1 to 3 carbon atoms. or hydroxyalkyl groups such as methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl and 2-hydroxypropyl groups.
もう一方の原料である一般式（ＩＩ）のハロアルキルス
ルホン酸塩としては、Ｒ４が炭素数２〜４のアルキレン
基又はヒドロキシアルキレン基、Ｘがハロゲン原子及び
Ｍがアルカリ金属であるもの、例えば３−ブロモ−２−
ヒドロキシプロパンスルホン酸、３−クロロ−２−ヒド
ロキシプロパンスルホン酸ソーダ、３−ブロモ−２−ヒ
ドロキシスルホン酸カリウム及びβ−ブロモエタンスル
ホン酸ソーダなどである。The other raw material, the haloalkylsulfonate of general formula (II), is one in which R4 is an alkylene group or hydroxyalkylene group having 2 to 4 carbon atoms, X is a halogen atom, and M is an alkali metal, such as 3- Bromo-2-
These include hydroxypropanesulfonic acid, sodium 3-chloro-2-hydroxypropanesulfonate, potassium 3-bromo-2-hydroxysulfonate, and sodium β-bromoethanesulfonate.
又、本発明において反応促進剤として使用するアルコー
ルは、炭素数１〜４のアルコール、例えばエタノール、
イソプロピルアルコール、１，３−ブタンジオール、ｌ
、４−ブタンジオール、プロピレングリコール、エチレ
ングリコール及びジエヂレングリコール等が挙げられる
が特に好ましくは、エタノール及びイソプロピルアルコ
ールが使用される。Further, the alcohol used as a reaction accelerator in the present invention is an alcohol having 1 to 4 carbon atoms, such as ethanol,
Isopropyl alcohol, 1,3-butanediol, l
, 4-butanediol, propylene glycol, ethylene glycol, and diethlene glycol, but particularly preferably ethanol and isopropyl alcohol are used.
更に、本発明に於いて使用するアルカリとしては、水酸
化ナトリウム、水酸化カリウム、炭酸ソーダ、炭酸カリ
、重炭酸ソーダ及び重炭酸カリ等を挙げることができる
。Further, examples of the alkali used in the present invention include sodium hydroxide, potassium hydroxide, soda carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
上記各成分の混合比としては、該ハロアルキルスルホン
酸塩は、該長鎖アルキル第３級アミン１モル当たり１．
１〜２．０モル、好ましくは１．１〜１．５モルの割合
で用いることが必要である。As for the mixing ratio of each of the above components, the haloalkyl sulfonate is 1.0% per mole of the long-chain alkyl tertiary amine.
It is necessary to use it in a proportion of 1 to 2.0 mol, preferably 1.1 to 1.5 mol.
１．１モルより少ないと反応率が低下し、又２．０モル
より多すぎると未反応のハロアルキルスルホン酸塩及び
その加水分解物の含有量が多くなり、且つ反応率はこれ
以上モル比を上げてもほとんど変化せずコスト的に不利
となり好ましくない。If it is less than 1.1 mol, the reaction rate will decrease, and if it is more than 2.0 mol, the content of unreacted haloalkyl sulfonate and its hydrolyzate will increase, and if the molar ratio is more than 2.0 mol, the reaction rate will decrease. Even if it is increased, there is almost no change, which is disadvantageous in terms of cost, which is not desirable.
アルコールについては、全仕込み量に対し重量％で２〜
２０％、好ましくは３〜ｌＯ％で加えられる。２％以下
であると充分な反応促進効果が認められず好ましくない
。また２０％以上使用しても反応促進効果は上がらずコ
スト的に不利となり、またアルコールには消泡作用があ
るので多量の使用は配合系では好ましくない。Regarding alcohol, it is 2 to 2% by weight based on the total amount of preparation.
It is added at 20%, preferably 3-10%. If it is less than 2%, a sufficient reaction promoting effect will not be observed, which is not preferable. Further, even if it is used in an amount of 20% or more, the reaction promoting effect will not be improved and it will be disadvantageous in terms of cost.Also, since alcohol has an antifoaming effect, it is not preferable to use a large amount in a compounding system.
更にアルカリについては、該長鎖アルキル第３級アミン
１モルに対し０．１０〜０．４０モル、好ましくは０．
１５〜０．４０モル使用される。０゜１０モル以下であ
ると充分な反応性が得られず、また０、４０モルよりも
多いとハロアルキルスルホン酸の加水分解が起こって好
ましくない。Further, regarding the alkali, 0.10 to 0.40 mol, preferably 0.10 to 0.40 mol, preferably 0.1 to 0.40 mol, per 1 mol of the long-chain alkyl tertiary amine.
15 to 0.40 mol is used. If it is less than 0.10 moles, sufficient reactivity cannot be obtained, and if it is more than 0.40 moles, hydrolysis of the haloalkylsulfonic acid will occur, which is undesirable.
反応については、ハロアルキルスルホン酸塩にアルコー
ルを加えた後、長鎖アルキル第３級アミンを滴下する。For the reaction, alcohol is added to the haloalkyl sulfonate and then a long chain alkyl tertiary amine is added dropwise.
滴下終了後、反応温度が５０℃以上、好ましくは８０〜
１００℃で２〜１５時間熟成を行ない、この間上記のよ
うな方法でアルカリを添加して目的物のスルホベタイン
溶液を得る。After the dropwise addition is completed, the reaction temperature is 50°C or higher, preferably 80°C or higher.
Aging is carried out at 100° C. for 2 to 15 hours, and during this time an alkali is added in the manner described above to obtain a sulfobetaine solution, which is the desired product.
尚、反応温度が５０℃未満だと反応が遅くなり好ましく
なく、又１００℃を越えると着色原因となり好ましくな
い。If the reaction temperature is less than 50°C, the reaction will be slow, which is undesirable, and if it exceeds 100°C, it will cause coloring, which is undesirable.
アルカリ添加は、系内のｐ Ｉ−１を一定に保つことが
重要であり連続的に少量づつ仕込んでも断続的に仕込ん
でも問題ない。しかし、−度に反応系に仕込みｐｌ−１
を請求範囲外で反応する方法あるいは反応終了後ｐＨを
調整する方法では高反応率を得ることが堆しい。仕込み
速度は特に限定しない。When adding alkali, it is important to keep the p I-1 in the system constant, and there is no problem whether the alkali is added continuously in small amounts or intermittently. However, when charged to the reaction system at -1
It is difficult to obtain a high reaction rate with a method in which the reaction is performed outside the claimed range or a method in which the pH is adjusted after the reaction is completed. The preparation speed is not particularly limited.
またアルカリ濃度も特に限定しないがこのアルカリ量と
反応時間を考慮し決定すれば良い。この仕込み時間が短
いと一度に仕込む方法と同じでｐＨが範囲外となり高反
応率の達成は望めない。またアルカリの仕込みは系内の
ｐＨが一定になる様に仕込めば形態は特に問題にしない
例えば粉体、スラリーでも水溶液状態でも良い。特に好
ましくはアルカリ水溶液を２〜６時間連続的に少量づつ
仕込む方法が望ましい。Further, the alkali concentration is not particularly limited, but may be determined by considering the alkali amount and reaction time. If this charging time is short, the pH will be out of range and a high reaction rate cannot be expected, as is the case with the method of charging all at once. Further, the form of the alkali does not particularly matter as long as it is charged so that the pH within the system is constant, for example, it may be in the form of a powder, slurry, or aqueous solution. Particularly preferred is a method in which the alkaline aqueous solution is continuously introduced in small amounts for 2 to 6 hours.
［発明の効果］
本発明の方法により、未反応アミンを殆んど含まず且つ
製品の粘度が低く取り扱いが容易なスルホベタインを高
反応率で得ることができる。又本発明の方法は、反応系
が常圧であるため重設端、例えば加圧反応設備を使用す
ることなくスルホベタインを合成できる。[Effects of the Invention] According to the method of the present invention, sulfobetaine that contains almost no unreacted amine, has a low viscosity product, and is easy to handle can be obtained at a high reaction rate. Furthermore, in the method of the present invention, since the reaction system is at normal pressure, sulfobetaine can be synthesized without using a heavy equipment such as pressurized reaction equipment.
［実施例］
次に実施例により本発明を更に詳細に説明するが本発明
はこれら実施例に限定されるものではない。[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
撹拌機、冷却管、滴下漏斗、温度計を付した４つロフラ
スコに、水２８１．１ｇ、重亜硫酸ソーダ１３０．０ｙ
（Ｉ，２５モル）を仕込み７０℃まで昇温した。次にエ
ビクロロヒドリン１１５．６９（Ｉ。Example 1 281.1 g of water and 130.0 y of sodium bisulfite were placed in a four-bottle flask equipped with a stirrer, condenser, dropping funnel, and thermometer.
(I, 25 mol) was charged and the temperature was raised to 70°C. Next, shrimp chlorohydrin 115.69 (I.
２５モル）を約１時間かけて滴下した。この時発熱が起
こるが系内の温度を７０〜８０８Ｃにコントロールした
。滴下終了後８０〜９０°Ｃで約１時間熟成ヲ行ない、
３−クロロ−２−ヒドロキシプロパンスルポン酸ソーダ
を得た。次にエタノールを５０９加え、更にジメチルラ
ウリルアミン２＋７４ｙ（Ｉ，０モル）をこの温度で約
１時間かけて滴下した。滴下終了後９０℃で熟成を始め
た。熟成を開始して１時間後（Ｉ％ｐＩＫは７．５であ
った）より、４％水酸化ナトリウム水溶液２００＠（０
，２モル）を５時間かけて連続的に滴下した（滴下中の
反応系内の１％ｐｔ（は７．８〜７．３であった）。滴
下終了後更に４時間熟成を行った。冷却後ラウリルジメ
チルアンモニオヒドロキシスルホベタインの約３０％溶
液を得た。最終製品のＩ％ｐ Ｉ−（は７．２であった
。抽出アミン分の分析よりアミンに対する反応率は９９
％であり、またエタノール含量はガスクロマトグラフィ
ー分析より５％であった。25 mol) was added dropwise over about 1 hour. At this time, heat generation occurred, but the temperature in the system was controlled at 70 to 808C. After dropping, ripen at 80-90°C for about 1 hour.
Sodium 3-chloro-2-hydroxypropanesulfonate was obtained. Next, 509 g of ethanol was added, and further dimethyllaurylamine 2+74y (I, 0 mol) was added dropwise at this temperature over about 1 hour. After completion of the dropwise addition, ripening was started at 90°C. One hour after starting the ripening (I% pIK was 7.5), a 4% aqueous sodium hydroxide solution 200 @ (0
, 2 mol) was continuously added dropwise over a period of 5 hours (1% pt (in the reaction system during dropping was 7.8 to 7.3). After the completion of the dropping, aging was further carried out for 4 hours. After cooling, an approximately 30% solution of lauryldimethylammoniohydroxysulfobetaine was obtained. The I%p I-( of the final product was 7.2. From the analysis of the extracted amine content, the reaction rate for amine was 99%.
%, and the ethanol content was 5% by gas chromatography analysis.
比較例１
実施例１でエタノールを添加せずその量だけ水分を増や
した点以外は実施例１と全く同じ様に反応を行った。最
終製品の反応率は８５％であった。Comparative Example 1 The reaction was carried out in exactly the same manner as in Example 1, except that ethanol was not added and water was increased by the same amount. The reaction rate of the final product was 85%.
比較例２
実施例１で水酸化ナトリウムの添加を熟成開始１時間後
に一度に加えた（その時の１％ｐＨは９゜３であった）
点以外は実施例１と同様に行なった。Comparative Example 2 In Example 1, sodium hydroxide was added all at once 1 hour after the start of ripening (1% pH at that time was 9°3).
The same procedure as in Example 1 was carried out except for this point.
最終製品の反応率は８８％であり、１％ｐＨは７゜４、
エタノール含ｍは５％であった。The reaction rate of the final product was 88%, and the 1% pH was 7°4.
The ethanol content was 5%.
比較例３
実施例Ｉで水酸化ナトリウムを添加せず又最終製品の有
効分が３０％になる様に水分含量を上げた点以外は、実
施例１と全く同様に反応を行なった。この反応中の１％
ｐＨ変化は、７．４から最終で３．５になった。最終製
品での反応率は８０％であった。Comparative Example 3 The reaction was carried out in exactly the same manner as in Example 1, except that sodium hydroxide was not added in Example I and the water content was increased so that the effective content of the final product was 30%. 1% in this reaction
The pH change was from 7.4 to 3.5 final. The reaction rate in the final product was 80%.
実施例２
実施例Ｉで水酸化ナトリウム水溶液の代わりに８％重曹
水溶液３１５９（０，３モル）を用い有効分が約３０％
になる様に水分量を調整した点以外は実施例１と同様の
反応を行った。尚、重曹水溶液の滴下時間は５時間で滴
下後熟成を５時間行った。Example 2 In Example I, an 8% sodium bicarbonate aqueous solution 3159 (0.3 mol) was used instead of the sodium hydroxide aqueous solution, and the effective content was about 30%.
The same reaction as in Example 1 was carried out except that the water content was adjusted so that the following reaction occurred. The aqueous sodium bicarbonate solution was added dropwise for 5 hours, and then aged for 5 hours.
１％ｐＨは、重曹水溶液滴下前が７．４、滴下中が７．
９〜７．６及び最終製品が７．４であった。また最終製
品での反応率は９７％でエタノール含量は５％であった
。The 1% pH was 7.4 before dropping the sodium bicarbonate aqueous solution and 7.4 during dropping.
9-7.6 and the final product was 7.4. The reaction rate in the final product was 97% and the ethanol content was 5%.
実施例３
実施例１でジメチルラウリルアミンの代わりにジメチル
ステアリルアミンを用い、エタノールの代わりにイソプ
ロピルアルコールを１０重量％になる様に加え、更に最
終製品に於いてステアリルジメチルアンモニオヒドロキ
シスルホベタインの約３０％溶液になる様に水分量を減
量した点以外は実施例１と同様に反応を行なった。１％
ｐＨは、水酸化ナトリウム水溶液滴下前が７，５、滴下
中が７．８〜７．３、最終製品が７．３であった。また
最終製品での反応率は９７％であった。Example 3 In Example 1, dimethylstearylamine was used in place of dimethyllaurylamine, and isopropyl alcohol was added in place of ethanol to give a concentration of 10% by weight. Furthermore, in the final product, approximately 1% of stearyldimethylammoniohydroxysulfobetaine was added. The reaction was carried out in the same manner as in Example 1, except that the water content was reduced to a 30% solution. 1%
The pH was 7.5 before dropping the aqueous sodium hydroxide solution, 7.8 to 7.3 during dropping, and 7.3 in the final product. The reaction rate in the final product was 97%.
Claims (1)
ケニル基、Ｒ＿２及びＲ＿３はそれぞれ独立して炭素数
１〜３のアルキル基又はヒドロキシアルキル基を表す）
と、一般式（II） Ｘ−Ｒ＿４−ＳＯ＿３Ｍ（II） （式中のＲ＿４は炭素数２〜４のアルキレン基又はヒド
ロキシアルキレン基、Ｘはハロゲン原子及びＭはアルカ
リ金属を表す）で表されるハロアルキルスルホン酸塩と
を反応させて一般式（III）で表わされるスルホベタイ
ンを製造する方法において、▲数式、化学式、表等があ
ります▼（III） （式中のＲ＿１〜Ｒ＿４は前記と同じ意味を表す）炭素
数１〜４のアルコールを全仕込み量に対し２〜２０重量
％の範囲で添加し、且つ反応系の１％ｐＨを６〜８に保
つ様にアルカリを連続又は断続的に添加することを特徴
とするスルホベタインの製造方法。[Claims] 1. Tertiary amine represented by general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (R_1 in the formula is an alkyl group or alkenyl group having 8 to 28 carbon atoms , R_2 and R_3 each independently represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms)
and is represented by the general formula (II) In the method for producing sulfobetaine represented by the general formula (III) by reacting it with a haloalkyl sulfonate, there are ▲numerical formulas, chemical formulas, tables, etc.▼(III) (R_1 to R_4 in the formula have the same meanings as above) ) Alcohol having 1 to 4 carbon atoms is added in the range of 2 to 20% by weight based on the total amount charged, and an alkali is added continuously or intermittently to maintain the pH of the reaction system at 6 to 8. A method for producing sulfobetaine, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31445188A JPH02160757A (en) | 1988-12-13 | 1988-12-13 | Production of sulfobetaine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31445188A JPH02160757A (en) | 1988-12-13 | 1988-12-13 | Production of sulfobetaine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02160757A true JPH02160757A (en) | 1990-06-20 |
Family
ID=18053516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31445188A Pending JPH02160757A (en) | 1988-12-13 | 1988-12-13 | Production of sulfobetaine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02160757A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920014A (en) * | 1987-02-27 | 1990-04-24 | Sumitomo Metal Mining Co., Ltd. | Zirconia film and process for preparing it |
| CN102964277A (en) * | 2012-12-17 | 2013-03-13 | 江南大学 | Preparation method of N,N-dimethyl-N-fatty alcohol polyethenoxy ether-base sulfopropyl lycine |
| WO2019140038A1 (en) | 2018-01-12 | 2019-07-18 | Eastman Chemical Company | Branched trialkylamine precursors, intermediates, products made therefrom and processes of manufacture |
-
1988
- 1988-12-13 JP JP31445188A patent/JPH02160757A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920014A (en) * | 1987-02-27 | 1990-04-24 | Sumitomo Metal Mining Co., Ltd. | Zirconia film and process for preparing it |
| CN102964277A (en) * | 2012-12-17 | 2013-03-13 | 江南大学 | Preparation method of N,N-dimethyl-N-fatty alcohol polyethenoxy ether-base sulfopropyl lycine |
| WO2019140038A1 (en) | 2018-01-12 | 2019-07-18 | Eastman Chemical Company | Branched trialkylamine precursors, intermediates, products made therefrom and processes of manufacture |
| US10640452B2 (en) | 2018-01-12 | 2020-05-05 | Eastman Chemical Company | Branched trialkyl quaternary ammonium compounds |
| US10961180B2 (en) | 2018-01-12 | 2021-03-30 | Eastman Chemical Company | Branched trialkyl amine oxides |
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