JPH0617083A - Ampholytic surface active compound - Google Patents

Ampholytic surface active compound

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Publication number
JPH0617083A
JPH0617083A JP4192711A JP19271192A JPH0617083A JP H0617083 A JPH0617083 A JP H0617083A JP 4192711 A JP4192711 A JP 4192711A JP 19271192 A JP19271192 A JP 19271192A JP H0617083 A JPH0617083 A JP H0617083A
Authority
JP
Japan
Prior art keywords
mol
alcohol
compound
group
active compound
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.)
Granted
Application number
JP4192711A
Other languages
Japanese (ja)
Other versions
JP3047145B2 (en
Inventor
Yoshinobu Nakamura
好伸 中村
Kenichi Tomihara
賢一 富原
Yuji Kimura
雄二 木村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toho Chemical Industry Co Ltd
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Toho Chemical Industry Co Ltd
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Filing date
Publication date
Application filed by Toho Chemical Industry Co Ltd filed Critical Toho Chemical Industry Co Ltd
Priority to JP4192711A priority Critical patent/JP3047145B2/en
Publication of JPH0617083A publication Critical patent/JPH0617083A/en
Application granted granted Critical
Publication of JP3047145B2 publication Critical patent/JP3047145B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To obtain an ampholitic surface active compound whose lipophilicity and hydrophilicity can be adjusted in accordance with purposes, by forming a constitution having both an alkylene oxide group and a betaine group as the hydrophilic groups. CONSTITUTION:The compound is represented by the formula, wherein R is 8-24C alkyl or alkenyl; R' is an ethylene and/or propylene group; R'' is 5C or lower alkyl; n is an integer of 1 to 50; and M is a monovalent alkali metal. Since the compound does not contain sodium chloride, etc., it is less corrosive to metal than an ampholytic surfactant obtained from a tertiary amine by using monochloroacetic acid and an alkali and containing sodium chloride, etc. It also has good compatibility with other substances and good solubility in water, whether acidic, neutral or alkaline, and in an alcohol, exhibits an excellent ability to reduce surface tension, and is also excellent in foaming ability and its persistence.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は新規な両性界面活性化合
物及びその製法に関するものである。近時両性界面活性
剤は広汎なｐＨ領域で界面活性を有し、しかもアニオ
ン、カチオン、非イオンのいずれのタイプの界面活性剤
とも相溶性を有することから各産業分野で広く利用され
るに至っている。本発明者等はかかる両性界面活性剤の
有用性に着目し鋭意新規な両性界面活性剤の研究を行な
った結果本発明に到達したものである。FIELD OF THE INVENTION The present invention relates to a novel amphoteric surface active compound and a process for producing the same. Recently, amphoteric surfactants have surface activity in a wide range of pH, and are compatible with any type of anionic, cationic, and nonionic surfactants, and thus have been widely used in various industrial fields. There is. The present inventors have arrived at the present invention as a result of earnestly researching novel amphoteric surfactants while paying attention to the usefulness of such amphoteric surfactants.

【０００２】[0002]

【従来の技術】従来、両性界面活性剤は親油性及び親水
性を目的に応じて調整することが困難であり、アルキル
基によってその度合いは決定されてしまう欠点があっ
た。2. Description of the Related Art Conventionally, it has been difficult to adjust the lipophilicity and hydrophilicity of an amphoteric surfactant according to the purpose, and the degree thereof is determined by the alkyl group.

【０００３】[0003]

【発明が解決しようとする課題】本発明は親水基として
アルキレンオキサイド基及びベタイン基を有するため、
目的に応じて親油性及び親水性が調整できるものであ
る。The present invention has an alkylene oxide group and a betaine group as hydrophilic groups,
The lipophilicity and hydrophilicity can be adjusted according to the purpose.

【０００４】[0004]

【課題を解決するための手段】本発明は一般式 (但し、Ｒは炭素数８〜２４ののアルキル基、アルケニ
ル基、Ｒ’はエチレン及び又はプロピレン、ｎは１〜５
０の整数、Ｒ”は炭素数５以下のアルキル基、Ｍは一価
のアルカリ金属である。)で表わされる新規な両性界面
活性剤を提案するものである。The present invention has the general formula (However, R is an alkyl group having 8 to 24 carbon atoms, an alkenyl group, R'is ethylene and / or propylene, and n is 1 to 5
An integer of 0, R "is an alkyl group having 5 or less carbon atoms, and M is a monovalent alkali metal."

【０００５】本発明の両性界面活性剤の合成法を反応式
で示すと下記の通りである。 (１） ＲＯＨ＋ｎ(Ｒ'Ｏ) → ＲＯ(Ｒ'Ｏ)ｎＨ (２） ＲＯ(Ｒ'Ｏ)ｎＨ＋ＳＯＸ2 → Ｒ(ＯＲ')ｎＸ
＋ＳＯ2＋ＨＸ (３） Ｒ(ＯＲ')ｎＸ＋Ｈ2ＮＲ"＋ＭＯＨ → Ｒ(ＯＲ')ｎＮＨＲ” ＋ ＭＸ ＋ Ｈ2Ｏ (但し、Ｒ、Ｒ'、Ｒ"およびｎは前記と同様、Ｒ1は炭素
数５以下のアルキル基、Ｘはハロゲン原子、Ｍは一価の
アルカリ金属である。)The synthetic method of the amphoteric surfactant of the present invention is shown by the reaction formula as follows. (1) ROH + n (R'O) → RO (R'O) nH (2) RO (R'O) nH + SOX 2 → R (OR ') nX
+ SO 2 + HX (3) R (OR ') nX + H 2 NR "+ MOH → R (OR') nNHR" + MX + H 2 O (However, R, R ′, R ″ and n are the same as above, R 1 is an alkyl group having 5 or less carbon atoms, X is a halogen atom, and M is a monovalent alkali metal.)

【０００６】反応(１)は炭素数８〜２４の高級アルコー
ル、例えばオクタノール、デカノール、ラウリルアルコ
ール、ミリスチルアルコール、セチルアルコール、ステ
アリルアルコール、ベヘニルアルコール、オレイルアル
コール、炭素数１１〜１５のオキソ法混合アルコール、
炭素数１２のセカンダリーアルコール、トリデシルアル
コール等の高級アルコール１モルに公知の方法でエチレ
ンオキサイド又は／及びプロピレンオキサイドを１〜５
０モル付加させるものであるが、経済性及び有用性の面
からはラウリルアルコール、ミリスチルアルコール、オ
レイルアルコール、トリデシルアルコール、炭素数１１
〜１５のオキソ法混合アルコール１モルにエチレンオキ
サイドを２〜１０モル付加させたものが好ましい。又、
プロピレンオキサイドのみの付加物は有用性が無い。The reaction (1) is a higher alcohol having 8 to 24 carbon atoms, for example, octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, oxo process mixed alcohol having 11 to 15 carbon atoms,
1 to 5 of ethylene oxide or / and propylene oxide is added to 1 mol of a higher alcohol such as a secondary alcohol having 12 carbon atoms or tridecyl alcohol by a known method.
Although 0 mol is added, from the viewpoint of economy and usefulness, lauryl alcohol, myristyl alcohol, oleyl alcohol, tridecyl alcohol, carbon number 11
It is preferable to add 2 to 10 mol of ethylene oxide to 1 mol of the oxo-method mixed alcohol of -15. or,
Adducts of propylene oxide alone have no utility.

【０００７】反応(２)はかくして得られた高級アルコー
ルアルキレンオキサイド付加物１モルにチオニルハライ
ド又は無水塩酸１モルを常圧又は加圧下４０〜１４０℃
で反応せしめる。In the reaction (2), 1 mol of thionyl halide or anhydrous hydrochloric acid is added to 1 mol of the higher alcohol alkylene oxide adduct thus obtained at 40 to 140 ° C. under normal pressure or pressure.
To react.

【０００８】反応(３)は反応(２)で得られた末端ハロゲ
ン化１モルにモノアルキルアミン例えばメチルアミン、
プロピルアミン、ブチルアミン好ましくはメチルアミン
１モルを常圧もしくは加圧下、望ましくは加圧下で８０
〜１８０℃で反応させ、次いで１００℃以下でアルカリ
例えば苛性カリ、苛性ソーダ１モルの水溶液を加え副生
する水及び塩を除去する。In the reaction (3), 1 mol of the terminal halogenated product obtained in the reaction (2) is added to a monoalkylamine such as methylamine,
Propylamine, butylamine, preferably 1 mol of methylamine is used under normal pressure or pressure, preferably 80% under pressure.
The reaction is carried out at .about.180.degree. C., and then an aqueous solution of alkali such as caustic potash and 1 mol of caustic soda is added at 100.degree.

【０００９】反応(４)及び(５)はかくして得られた三級
アミン化合物１モルにアクリル酸エステル例えばアクリ
ル酸メチル、アクリル酸エチル、アクリル酸プロピル、
アクリル酸ブチル、経済的には、好ましくはアクリル酸
メチルを７０〜１５０℃にて反応させ、次いで苛性ソー
ダ、苛性カリ等のアルカリ水溶液を１００℃以下で加え
加水分解し、カルボン酸塩型両性界面活性剤として得
る。反応(５)で得られた本発明の両性界面活性剤は場合
により脱水濾過を行なうことによって精製品が得られ
る。In the reactions (4) and (5), 1 mol of the thus obtained tertiary amine compound is added to an acrylic ester such as methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, economically, preferably methyl acrylate is reacted at 70 to 150 ° C., and then alkaline aqueous solution of caustic soda, caustic potash, etc. is added at 100 ° C. or lower to hydrolyze, and a carboxylate-type amphoteric surfactant is added. Get as. The amphoteric surfactant of the present invention obtained in the reaction (5) can be optionally purified by dehydration filtration to obtain a purified product.

【００１０】本発明の両性界面活性剤はその精製品を得
るとき、何れもＩＲ吸収スペクトルで２９３０、２８７
０、１６４０、１６００、１４７０、１２７０、１１１
０カイザーに吸収が認められる。本発明の両性界面活性
剤は洗浄剤、浸透剤、乳化剤、分散剤、発泡剤、湿潤剤
及び帯電防止剤などに使用される。特に本発明の化合物
は食塩などを含まないため、三級アミンにモノクロル酢
酸とアルカリを使用して得られる食塩などを含む両性界
面活性剤と比較して金属の腐食が少なく、他の物質との
相溶性も良好である。The amphoteric surfactants of the present invention have IR absorption spectra of 2930 and 287 when obtaining their purified products.
0, 1640, 1600, 1470, 1270, 111
Absorption is observed at 0 Kaiser. The amphoteric surfactant of the present invention is used as a detergent, a penetrant, an emulsifier, a dispersant, a foaming agent, a wetting agent, an antistatic agent and the like. In particular, since the compound of the present invention does not contain salt, etc., it is less corrosive to metals as compared with an amphoteric surfactant containing salt etc. obtained by using monochloroacetic acid and an alkali as a tertiary amine, and is less likely to react with other substances. The compatibility is also good.

【００１１】[0011]

【実施例】以下に本発明の実施例を示す。EXAMPLES Examples of the present invention will be shown below.

【実施例１】ラウリルアルコール１モルにエチレンオキ
サイドを５モル付加したポリ(５)オキシエチレンラウリ
ルエーテル１モル、４０６ｇを四ツ口コルベンに採り、
ジメチルフォルムアマイド６ｇを加え、７０℃に昇温し
た後、撹拌しながら塩化チオニル１モル１１９ｇを徐々
に３０分を要して滴下し、後同温度で８時間撹拌した。
その後１４０℃に昇温しＮ2ガスを導入し、ジメチルフ
ォルムアマイドを溜去し、常温で淡黄色液状、ＯＨＶ：
０.６、Ｃｌ分６.３％のラウリルポリ(６)オキシエチレ
ンクロライド１モル４６８.５ｇを得た。次いでラウリ
ルポリ(６)オキシエチレンクロライド１モル４６８.５
ｇをオートクレーブに採り、メチルアミン１モル、３１
ｇを加え、１２０℃に昇温し４時間反応させた後冷却
し、四ツ口コルベンに移し６０℃で苛性ソーダ４０％水
溶液１００ｇを加え、脱水濾過し常温で淡黄色液状、ア
ミン価 のＮ−ラウリルポリ(５)オキシエチレンＮ
−メチルアミン４７０ｇを得た。Example 1 1 mol of poly (5) oxyethylene lauryl ether prepared by adding 5 mol of ethylene oxide to 1 mol of lauryl alcohol, and 406 g of the compound were placed in a four-necked Korben.
After 6 g of dimethylformamide was added and the temperature was raised to 70 ° C., 119 g of 1 mol of thionyl chloride was slowly added dropwise over 30 minutes with stirring, and then the mixture was stirred at the same temperature for 8 hours.
Then, the temperature was raised to 140 ° C., N 2 gas was introduced, dimethylformamide was distilled off, and a pale yellow liquid at room temperature, OHV:
Thus, 468.5 g of 1 mol of lauryl poly (6) oxyethylene chloride having a Cl content of 0.6% and a Cl content of 6.3% was obtained. Then lauryl poly (6) oxyethylene chloride 1 mol 468.5
g in an autoclave, 1 mol of methylamine, 31
g, heated to 120 ° C., reacted for 4 hours, cooled, transferred to a four-necked Kolben, added 100 g of 40% aqueous solution of caustic soda at 60 ° C., dehydrated and filtered, and then subjected to dehydration filtration at room temperature to give a pale yellow liquid and amine value of N- Lauryl poly (5) oxyethylene N
-470 g of methylamine are obtained.

【００１２】更にこのアミン化合物０.５モル２３５ｇ
を四ッ口コルベンに採り１２０℃でアクリル酸メチル
０.５モル８６ｇを徐々に２時間を要して滴下し、その
後８時間同温度で反応を行なった。次に７０℃に冷却
し、水４８０ｇ、５０％苛性ソーダ４０ｇを加え、同温
度で１０時間反応させ、その後８０〜９０℃に昇温しＮ
2ガスを導入して脱メタノールを行い、常温で淡黄色液
状の水分４０.１％、ｐＨ(１％)８.８のＮ−ラウリルポ
リ(５)オキシエチレンＮ−メチルＮ−エチルカルボン酸
ナトリウム８３１ｇを得た。本品はＮ：０.８６％、Ｎ
ａ：３.５１％であった。本品については後記のテスト
に供した。Furthermore, 0.5 mol of this amine compound, 235 g
Was taken into a four-necked Kolben, and 86 g of 0.5 mol of methyl acrylate was gradually added dropwise at 120 ° C. over 2 hours, and then the reaction was carried out at the same temperature for 8 hours. Next, it was cooled to 70 ° C., 480 g of water and 40 g of 50% caustic soda were added, and the reaction was carried out at the same temperature for 10 hours, and then the temperature was raised to 80 to 90 ° C.
Introducing 2 gases to remove methanol, light yellow liquid water at room temperature 40.1%, pH (1%) 8.8 N-lauryl poly (5) oxyethylene N-methyl N-ethylcarboxylate sodium 831 g Got This product is N: 0.86%, N
a: It was 3.51%. This product was subjected to the test described below.

【００１３】[0013]

【実施例２】ミリスチルアルコール１モルにプロピレン
オキサイドを２モル、エチレンオキサイドを５モル付加
したポリ(２)オキシプロピレンポリオキシ(５)エチレン
ミリスチルエーテル１モル、５４４ｇを四ツ口コルベン
に採り、ジメチルフォルムアマイド６ｇを加え、７０℃
に昇温した後、撹拌しながら塩化チオニル１モル１１９
ｇを徐々に３０分を要して滴下し、後同温度で８時間撹
拌した。その後１４０℃に昇温し、ジメチルフォルムア
マイドを溜去し、常温で淡黄色液状、ＯＨＶ：０.２、
Ｃｌ：１１.７％のミリスチルポリ(２)オキシプロピレ
ンポリ(５)オキシエチレンクロライド５６２.５ｇを得
た。次いで冷却し、７０℃にてエチルアミン４５ｇを加
え同温度で１０時間反応させ、アミン価が０となり反応
終了を確認し、５０℃に冷却し、苛性ソーダ４０％水溶
液２４１ｇを加え、減圧下７０℃にて脱水濾過し、水分
０.０４％、アミン価８８.３のＮ−ミリスチルポリ(２)
オキシプロピレンポリ(５)オキシエチレンＮ−メチルア
ミン５７０ｇを得た。Example 2 1 mol of myristyl alcohol, 2 mol of propylene oxide and 5 mol of ethylene oxide were added to poly (2) oxypropylene polyoxy (5) ethylene myristyl ether 1 mol, 544 g was taken in a four-necked Kolben, and dimethyl was added. Add 6 g of Form Amide, 70 ℃
After the temperature was raised to 1, the mixture was stirred with 1 mol of thionyl chloride 119
g was gradually added dropwise over 30 minutes, and then the mixture was stirred at the same temperature for 8 hours. Then, the temperature was raised to 140 ° C., dimethylformamide was distilled off, and a pale yellow liquid at room temperature, OHV: 0.2,
562.5 g of myristyl poly (2) oxypropylene poly (5) oxyethylene chloride with Cl: 11.7% was obtained. Then, cool and add ethylamine (45 g) at 70 ° C. and react at the same temperature for 10 hours, confirm the completion of the reaction when the amine value becomes 0, cool to 50 ° C., add 241 g of 40% aqueous solution of caustic soda, and reduce the pressure to 70 ° C. After dehydration filtration, N-myristyl poly (2) having a water content of 0.04% and an amine value of 88.3.
570 g of oxypropylene poly (5) oxyethylene N-methylamine was obtained.

【００１４】更にこのアミン化合物０.５モル２８５ｇ
を四ツ口コルベンに採り、１２０℃でアクリル酸エチル
０.５モル５０ｇを徐々に２時間を要して滴下し、その
後８時間同温度で反応を行った。次に７０℃に冷却し、
イソプロピルアルコール６０ｇ及び５０％苛性ソーダ４
０ｇを加え、同温度で１０時間加水分解を行った後窒素
ガスを導入し徐々に昇温し最終的に１１０℃迄昇温し、
脱水、脱溶剤を行った後濾過し、常温で淡黄褐色液状、
水分：０.０４％、Ｎ：２.１０％、Ｎａ：３.４６％、
ｐＨ(１％)：８.６のＮ−ミリスチルポリ(２)オキシプ
ロピレンポリ(５)オキシエチレンＮ−メチルＮ−エチル
カルボン酸ナトリウム３２８ｇを得た。本品については
後記のテストに供した。Furthermore, 0.5 mol of this amine compound 285 g
Was taken in a four-necked Kolben, and 0.5 mol of 50 g of ethyl acrylate was gradually added dropwise at 120 ° C. over 2 hours, and then the reaction was carried out at the same temperature for 8 hours. Then cool to 70 ° C,
Isopropyl alcohol 60g and 50% caustic soda 4
0 g was added, hydrolysis was carried out at the same temperature for 10 hours, nitrogen gas was introduced, and the temperature was gradually raised to finally 110 ° C.,
After dehydration and desolvation, it is filtered to give a pale yellowish brown liquid at room temperature.
Moisture: 0.04%, N: 2.10%, Na: 3.46%,
There was obtained 328 g of sodium N-myristyl poly (2) oxypropylene poly (5) oxyethylene N-methyl N-ethylcarboxylate having a pH (1%) of 8.6. This product was subjected to the test described below.

【００１５】[0015]

【実施例３〜１８】実施例２と同様に表１の如く実施例
３〜１５を合成した。表−２に合成物の分析値を示し
た。これらについては後記のテストに供する。実施例で
得られた合成物の溶解性と界面活性について表−３に示
す。表−３の通り実施例１〜１８の合成物はいずれも優
れた界面活性剤である。Examples 3 to 18 Examples 3 to 15 were synthesized as shown in Table 1 in the same manner as in Example 2. Table 2 shows the analytical values of the synthetic products. These will be used in the tests described below. Table 3 shows the solubility and surface activity of the compounds obtained in the examples. As shown in Table 3, the compounds of Examples 1 to 18 are all excellent surfactants.

【００１６】 ＊１：日産化学社製、＊２：三菱油化社製、＊３：日本
触媒社製、＊４：丸善石油化学社製[0016] * 1: Nissan Chemical Co., Ltd. * 2: Mitsubishi Petrochemical Co., Ltd. * 3: Nippon Shokubai Co., Ltd. * 4: Maruzen Petrochemical Co., Ltd.

【００１７】 [0017]

【００１８】 [0018]

【００１９】実施例２、３、１１、１３、１７、１８に
ついての起泡力テストの結果を表−４に示す。 測定法：ロスマイルス法、温度４０℃、濃度０.２５％ 表−４：起泡力試験結果 実施例Ｎｏ． 直後泡高 ｍｍ １分後泡高 ｍｍ ２ ２１５ ２１０ ３ ２１８ ２０８ １１ ２０５ １９８ １３ ２１０ ２０４ １７ ２１２ ２０８ １８ １８８ １８０The results of the foaming power test for Examples 2, 3, 11, 13, 17, and 18 are shown in Table 4. Measurement method: Loss Miles method, temperature 40 ° C., concentration 0.25% Table-4: Foaming power test results Example No. Immediately after foam height mm 1 minute after foam height mm 2 215 210 3 218 208 11 205 205 198 13 210 210 204 17 212 212 208 18 188 180

【００２０】[0020]

【発明の効果】実施例に見るように本発明による両性界
面活性剤は酸性、中性、アルカリ性を問わず水、アルコ
ールによく溶解し、優れた表面張力低下能も示してお
り、起泡力とその持続性も優れた結果を示した。As can be seen from the examples, the amphoteric surfactant according to the present invention dissolves well in water or alcohol regardless of acidity, neutrality or alkalinity, and has an excellent ability to reduce surface tension. And its sustainability also showed excellent results.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 (但しＲは炭素数８〜２４のアルキル基、アルケニル
基、Ｒ’はエチレン又は／及びプロピレン基、ｎは１〜
５０の整数、Ｒ”は炭素数５以下のアルキル基、Ｍは一
価のアルカリ金属である。)で表わされることを特徴と
する両性界面活性化合物。1. (However, R is an alkyl group having 8 to 24 carbon atoms, an alkenyl group, R'is an ethylene or / and a propylene group, and n is 1 to
An amphoteric surface-active compound represented by an integer of 50, R ″ is an alkyl group having 5 or less carbon atoms, and M is a monovalent alkali metal.
JP4192711A 1992-06-29 1992-06-29 Amphoteric surfactant compound Expired - Fee Related JP3047145B2 (en)

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JP4192711A JP3047145B2 (en) 1992-06-29 1992-06-29 Amphoteric surfactant compound

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JPH0617083A true JPH0617083A (en) 1994-01-25
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