JP3563474B2 - Novel quaternary ammonium salt and method for producing the same - Google Patents

Description

【０００６】
（式中、Ｒ^１、Ｒ^２及びＲ^３は同一又は異なって炭素数１〜４のアルキル基又はヒドロキシアルキル基、Ｒ^４及びＲ^５は同一又は異なって水酸基で置換されていてもよい炭素数８〜３６の直鎖又は分岐のアルキル基又はアルケニル基、Ａ は炭素数２〜３の直鎖又は分岐のアルキレン基、Ｘ は陰イオン基、ｎ は１〜６の整数、ｍ はアルキレンオキサイドの平均付加モル数を示す０〜２０の数である。）
以下、本発明を詳細に説明する。
【０００７】
本発明の一般式（１） で表される第４級アンモニウム塩において、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ炭素数１〜４のアルキル基又はヒドロキシアルキル基を示すが、具体的にはメチル、エチル、プロピル、ブチル、ヒドロキシエチル基等が挙げられ、好ましくはメチル、エチル、ヒドロキシエチル基、更に好ましくはメチル基である。
また、Ｒ^４及びＲ^５はそれぞれ水酸基で置換されていてもよい炭素数８〜３６の直鎖又は分岐のアルキル基又はアルケニル基を示すが、具体的にはデシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、ヒドロキシオクタデシル、ドコシル等の基が挙げられ、好ましくは炭素数１２〜２２の直鎖アルキル基、更に好ましくはオクタデシル、ヘキサデシル基及びこれらの混合物、更に特に好ましくはオクタデシル基である。又、Ｒ^４とＲ^５が同一のものが好ましい。
【０００８】
また、Ａ は炭素数２〜３の直鎖又は分岐のアルキレン基を示すが、好ましくは
【０００９】
【化９】

【００１０】
更に好ましくはエチレン基である。ｍ はアルキレンオキサイドの平均付加モル数を示す０〜２０の数であるが、好ましくは０〜１０、更に好ましくは０である。ｎ は１〜６の整数を示すが、好ましくは１〜３、更に好ましくは１である。Ｘ は陰イオン基を示すが、好ましくはハロゲン原子、サルフェート、炭素数１〜４の水酸基で置換されていてもよいカルボキシレート又は炭素数１〜４のアルキルサルフェート、更に好ましくはＣｌ又はＣＨ_３ＳＯ_４である。
【００１１】
一般式（１） で表される第４級アンモニウム塩としては、例えば次のようなものが挙げられる。
【００１２】
【化１０】

【００１３】
上記の一般式（１） で表される本発明の第４級アンモニウム塩（以下第４級アンモニウム塩（１） と略記する）は、次の製造方法１及び２により製造することができる。
＜製造方法１＞
一般式（２）
【００１４】
【化１１】

【００１５】
（式中、Ｒ^４， Ｒ^５， Ａ 及びｍ は前記と同じ意味を示す。）
で表されるグリセロール体と、一般式（３）
Ｙ−（ＣＨ_２）_ｎ−ＣＯＯＲ^６ （３）
（式中、Ｒ^６は水素原子又は炭素数１〜４のアルキル基、Ｙ はハロゲン原子、ｎ は前記と同じ意味を示す。）
で表される化合物を反応させてエステル化を行い、一般式（４）
【００１６】
【化１２】

【００１７】
（式中、Ｒ^４， Ｒ^５， Ａ， Ｙ， ｎ 及びｍ は前記と同じ意味を示す。）
で表されるハロエステルを得、更に、このハロエステルと一般式（５）
【００１８】
【化１３】

【００１９】
（式中、Ｒ^１， Ｒ^２及びＲ^３は前記と同じ意味を示す。）
で表される第３級アミンとを反応させ、更に必要に応じて塩交換を行い、第４級アンモニウム塩（１） を得る方法。
【００２０】
＜製造方法２＞
前記一般式（４） で表されるハロエステルと、一般式（６）
【００２１】
【化１４】

【００２２】
（式中、Ｒ^１及びＲ^２は前記と同じ意味を示す。）
で表される第２級アミンとを反応させ、一般式（７）
【００２３】
【化１５】

【００２４】
（式中、Ｒ^１， Ｒ^２， Ｒ^４， Ｒ^５， Ａ， ｎ及びｍ は前記と同じ意味を示す。）
で表されるアミノエステルを得、さらに一般式（８）
Ｒ^３Ｘ （８）
（式中、Ｒ^３及びＸ は前記と同じ意味を示す。）
で表される４級化剤を反応させ、更に必要に応じて塩交換を行い、第４級アンモニウム塩（１） を得る方法。
【００２５】
以下、第４級アンモニウム塩（１） の製造方法の詳細を説明する。
製造方法１においては、まず、一般式（２）で表されるグリセロール体に対し０．９〜２．０ 倍モル、好ましくは１．０ 〜１．５ 倍モルの一般式（３） で表される化合物を用いて、７０〜２００ ℃、好ましくは １００〜１５０ ℃の温度で、必要であれば触媒を用い１〜２０時間かけてエステル化を行い一般式（４） で表されるハロエステルを得る。
【００２６】
ここで用いられる一般式（２） で表されるグリセロール体としては、１，３ −ジオクタデカノキシ−２−プロパノール、１−オクタデカノキシ−３−ヘキサデカノキシ−２−プロパノール、１−ドデカノキシ−３−ドコサノキシ−２−プロパノール等や、これらのエチレンオキサイド付加物、プロピレンオキサイド付加物及びこれらの混合物が挙げられる。
【００２７】
また一般式（３） で表される化合物としてはモノクロロ酢酸、モノクロロ酪酸、モノクロロヘキサン酸及びこれらのメチルエステル、エチルエステル等が挙げられる。エステル化に用いる触媒としてはｐ−トルエンスルホン酸、硫酸等の酸触媒が挙げられる。
【００２８】
次に、上記のようにして得られた一般式（４） で表されるハロエステルと、このハロエステルに対し０．９ 〜５．０倍モル、好ましくは０．９５〜２．０ 倍モルの一般式（５）で表される第３級アミンとを、３０〜１２０ ℃、好ましくは４０〜７０℃の温度で、必要であれば溶媒を用いて０．１ 〜１０時間かけて４級化を行い、更に必要に応じて塩交換を行い、第４級アンモニウム塩（１） を得ることができる。
【００２９】
ここで用いられる一般式（５） で表される第３級アミンとしては、トリメチルアミン、トリエチルアミン、トリプロピルアミン、 Ｎ−メチルジエタノールアミン、Ｎ，Ｎ −ジメチルエタノールアミン、トリエタノールアミン、Ｎ，Ｎ −ジメチル−２−ヒドロキシプロピルアミン、Ｎ，Ｎ −ジメチルブチルアミン、Ｎ，Ｎ −ジエチルメチルアミン、Ｎ，Ｎ −ジメチルイソプロピルアミン、 Ｎ−メチルジブチルアミン等が挙げられ、溶媒としてはメタノール、エタノール、イソプロピルアルコール、アセトン等が挙げられる。
【００３０】
製造方法２においては、まず製造方法１と同様にして得られた一般式（４） で表されるハロエステルと、このハロエステルに対し０．９ 〜５．０ 倍モル、好ましくは０．９５〜２．０ 倍モルの一般式（６） で表される第２級アミンとを、０〜９００ ℃、好ましくは３０〜７００ ℃の温度で、必要であれば水溶媒を用いて１〜２０時間かけてアミノ化反応を行い、一般式（７） で表されるアミノエステルを得る。次いで、この一般式（７） で表されるアミノエステルに対し０．８ 〜２．０ 倍モル、好ましくは０．９５〜１．５ 倍モルの一般式（８） で表される４級化剤を用いて、７０〜１２０ ℃で０．５ 〜１０時間かけて無溶媒あるいは溶媒中で４級化を行えば反応が終結し、その後、常法に従い後処理を行い、さらに必要ならば、イオン交換樹脂等を用いて塩交換を行えば、必要な対イオンを有する第４級アンモニウム塩（１） を得ることができる。
【００３１】
ここで用いられる一般式（６） で表される第２級アミンとしては、ジメチルアミン、 Ｎ−エチルメチルアミン、ジエチルアミン、 Ｎ−メチルイソプロピルアミン、 Ｎ−エチルイソプロピルアミン、 Ｎ−メチルブチルアミン、ジイソプロピルアミン、ジプロピルアミン、 Ｎ−エチルブチルアミン、 Ｎ−メチルエタノールアミン、ジエタノールアミン、 Ｎ−メチル−２−ヒドロキシプロピルアミン、ジ−（２−ヒドロキシプロピル）アミン等が挙げられ、一般式（８） で表される４級化剤としては、メチルクロライド等の低級アルキルハライド、ジメチル硫酸等のジ低級アルキル硫酸等が挙げられる。４級化反応の溶媒としては水、メタノール、エタノール、イソプロピルアルコール、アセトン等が挙げられる。
【００３２】
本発明の第４級アンモニウム塩（１） は赤外線吸収スペクトル、核磁気共鳴スペクトルでその構造を確認することができる。
本発明の第４級アンモニウム塩（１） は新規な界面活性剤であり、繊維に対して優れた柔軟性を付与でき、生分解性の優れた柔軟基剤として有用である。また毛髪に対しても優れた柔軟性と平滑性を付与でき、毛髪化粧料であるヘアリンス、ヘアトリートメント等にも応用することができる。
【００３３】
【実施例】
以下に実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００３４】
実施例１
攪拌機、温度計、冷却管の付いた４つ口フラスコに１，３ −ジオクタデカノキシ−２−プロパノール １７７．６ｇとモノクロロ酢酸３８ｇを入れ １４０℃まで昇温した。生成する水を留去しながらそのままの温度で７時間反応させた後、水洗により過剰のモノクロロ酢酸を除去し対応するクロロ酢酸エステルを ２００ｇ得た。
次に、攪拌機、温度計の付いたオートクレーブに上記クロロ酢酸エステル １５０ｇ、トリメチルアミン１６ｇ、イソプロピルアルコール４０ｇを入れ６０℃で４時間反応させた。反応後、アセトンによる晶析を行い、乾燥後、白色粉末の目的物 １５０ｇを得た。
ＮＭＲスペクトル、ＩＲスペクトルから以下の構造を確認した。
【００３５】
【化１６】

【００３６】
【化１７】

【００３７】
・ＩＲスペクトル（ＫＢｒ 錠剤）
１７５２ｃｍ^−１、１２０９ｃｍ^−１、１１２８ｃｍ^−１
実施例２
攪拌機、温度計、冷却管の付いた４つ口フラスコに１，３ −ジオクタデカノキシ−２−プロパノール １７７．６ｇとモノクロロ酪酸４６ｇを入れ １４０℃まで昇温した。生成する水を留去しながらそのままの温度で７時間反応させた後、水洗により過剰のモノクロロ酢酸を除去し対応するクロロ酪酸エステルを ２１０ｇ得た。
次に、攪拌機、温度計の付いたオートクレーブに上記クロロ酪酸エステル １５０ｇ、トリメチルアミン１５ｇ、イソプロピルアルコール４０ｇを入れ８０℃で４時間反応させた。反応後、アセトンによる晶析を行い、乾燥後、白色粉末の目的物 １５０ｇを得た。
ＮＭＲスペクトル、ＩＲスペクトルから以下の構造を確認した。
【００３８】
【化１８】

【００３９】
【化１９】

【００４０】
・ＩＲスペクトル（ＫＢｒ 錠剤）
１７５０ｃｍ^−１、１２０５ｃｍ^−１、１１３３ｃｍ^−１
実施例３
攪拌機、温度計、冷却管の付いた４つ口フラスコに１，３ −ジオクタデカノキシ−２−プロパノール １７７．６ｇとモノクロロヘキサン酸４５ｇを入れ １４０℃まで昇温した。生成する水を留去しながらそのままの温度で７時間反応させ対応するクロロヘキサン酸エステルを ２２０ｇ得た。
次に、攪拌機、温度計の付いたオートクレーブに上記クロロヘキサン酸エステル １５０ｇ、トリメチルアミン１４ｇ、エタノール６０ｇを入れ８０℃で４時間反応させた。反応後、アセトンによる晶析を行い、乾燥後、白色粉末の目的物 １５０ｇを得た。
ＮＭＲスペクトル、ＩＲスペクトルから以下の構造を確認した。
【００４１】
【化２０】

【００４２】
【化２１】

【００４３】
・ＩＲスペクトル（ＫＢｒ 錠剤）
１７５６ｃｍ^−１、１２１３ｃｍ^−１、１１２９ｃｍ^−１
実施例４
攪拌機、温度計、冷却管の付いた４つ口フラスコに、実施例１と同様の方法で得たクロロ酢酸エステル １６７ｇ、５０％ジメチルアミン水溶液５６ｇ、イオン交換水９０ｇを入れ５０℃まで昇温した。そのままの温度で１２時間攪拌した後、水洗により過剰のジメチルアミンを除去し対応するアミノエステルを １６５ｇ得た。
次に、攪拌機、温度計の付いたオートクレーブに上記アミノエステル １２０ｇ、メチルクロライド１２ｇ、アセトン８０ｇを入れ、９０℃で６時間反応させた。反応後、アセトンによる晶析を行い、乾燥後、白色粉末の目的物 １００ｇを得た。
ＮＭＲスペクトル、ＩＲスペクトルから実施例１で合成したものと同一構造の以下の構造を確認した。
【００４４】
【化２２】

【００４５】
実施例５
攪拌機、温度計、冷却管の付いた４つ口フラスコに、１，３ −ジオクタデカノキシ−２−プロパノールのエチレンオキサイド５モル付加物（水酸基価６９（ＫＯＨｍｇ／ｇ））２４３．６ ｇとモノクロロ酢酸３８ｇを入れ、 １４０℃まで昇温した。生成する水を留去しながらそのままの温度で７時間反応させた後、水洗により過剰のモノクロロ酢酸を除去し対応するクロロ酢酸エステルを ２７０ｇ得た。
次に、攪拌機、温度計の付いたオートクレーブに上記クロロ酢酸エステル１５０ ｇ、トリメチルアミン１３ｇ、イソプロピルアルコール４０ｇを入れ６０℃で４時間反応させた。反応後、アセトンによる晶析を行い、乾燥後、淡黄色ゲル状の目的物 １２０ｇを得た。
ＮＭＲスペクトル、ＩＲスペクトルから以下の構造を確認した。
【００４６】
【化２３】

【００４７】
【化２４】

【００４８】
・ＩＲスペクトル（ＫＢｒ 錠剤）
１７４８ｃｍ^−１、１２０６ｃｍ^−１、１１１７ｃｍ^−１ [0001]
[Industrial applications]
The present invention relates to a novel quaternary ammonium salt and a method for producing the same, and more particularly, it can impart excellent flexibility to fibers, and can impart excellent flexibility and smoothness to hair, The present invention relates to a quaternary ammonium salt having good biodegradability and a method for producing the same.
[0002]
Problems to be solved by the prior art and the invention
At present, most of the products marketed as fabric softeners or hair treatment agents are quaternary compounds having two long-chain alkyl groups in one molecule such as di (hardened tallowalkyl) dimethylammonium chloride. A composition comprising a quaternary ammonium salt.
However, the quaternary ammonium salt has a problem in that, when the residue after treatment is released into nature such as a river, the quaternary ammonium salt accumulates without being substantially biodegraded. Methyl bis [hardened tallow alkanoyloxyethyl] 2-hydroxyethylammonium methylsulfate and dimethylbis [alkanoyloxyethyl] ammonium chloride are marketed as improved products, and these are compared with the above quaternary ammonium salts. Although biodegradability has been improved, it cannot be said that the base material is sufficiently satisfactory in flexibility and environmental safety.
[0003]
Accordingly, an object of the present invention is to provide a quaternary ammonium salt which is excellent in flexibility and suitable as a flexible base having good biodegradability.
[0004]
[Means for Solving the Problems]
Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a novel quaternary ammonium salt that is optimal for the above purpose, and have completed the present invention.
That is, the present invention provides a novel quaternary ammonium salt represented by the general formula (1) and a method for producing the same.
[0005]
Embedded image

[0006]
(Wherein, R ¹ , R ² and R ³ are the same or different and are an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are the same or different and may have the same A linear or branched alkyl or alkenyl group of 8 to 36, A is a linear or branched alkylene group having 2 to 3 carbon atoms, X is an anionic group, n is an integer of 1 to 6, m is an alkylene oxide It is a number from 0 to 20 indicating the average number of moles added.)
Hereinafter, the present invention will be described in detail.
[0007]
In the quaternary ammonium salt represented by the general formula (1) of the present invention, R ¹ , R ² and R ³ each represent an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. , Ethyl, propyl, butyl, hydroxyethyl groups, etc., preferably methyl, ethyl, hydroxyethyl groups, and more preferably methyl groups.
R ⁴ and R ⁵ each represent a linear or branched alkyl or alkenyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, and specifically, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl , Hydroxyoctadecyl, docosyl and the like, preferably a straight-chain alkyl group having 12 to 22 carbon atoms, more preferably an octadecyl, hexadecyl group and a mixture thereof, and particularly preferably an octadecyl group. Further, it is preferable that R ⁴ and R ⁵ are the same.
[0008]
A represents a linear or branched alkylene group having 2 to 3 carbon atoms, preferably
Embedded image

[0010]
More preferably, it is an ethylene group. m is a number of 0 to 20 indicating the average number of added moles of the alkylene oxide, preferably 0 to 10, and more preferably 0. n represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1. X represents an anionic group, preferably a halogen atom, a sulfate, a carboxylate which may be substituted with a hydroxyl group having 1 to 4 carbon atoms or an alkyl sulfate having 1 to 4 carbon atoms, more preferably Cl or CH ₃ SO ₄ .
[0011]
Examples of the quaternary ammonium salt represented by the general formula (1) include the following.
[0012]
Embedded image

[0013]
The quaternary ammonium salt of the present invention represented by the above general formula (1) (hereinafter abbreviated as quaternary ammonium salt (1)) can be produced by the following production methods 1 and 2.
<Production method 1>
General formula (2)
[0014]
Embedded image

[0015]
(In the formula, R ⁴ , R ⁵ , A and m have the same meaning as described above.)
A glycerol compound represented by the general formula (3)
^{_{Y- (CH 2) n -COOR 6}} (3)
(In the formula, R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a halogen atom, and n has the same meaning as described above.)
The esterification is carried out by reacting the compound represented by the general formula (4).
[0016]
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[0017]
(Wherein, R ⁴ , R ⁵ , A, Y, n and m have the same meaning as described above.)
And further obtained by combining the haloester represented by the general formula (5)
[0018]
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[0019]
(In the formula, R ¹ , R ² and R ³ have the same meaning as described above.)
A quaternary ammonium salt (1) is obtained by reacting with a tertiary amine represented by the formula (1), and further performing salt exchange if necessary.
[0020]
<Production method 2>
A haloester represented by the general formula (4);
[0021]
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[0022]
(In the formula, R ¹ and R ² have the same meaning as described above.)
With a secondary amine represented by the general formula (7)
[0023]
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[0024]
(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , A, n and m have the same meanings as described above.)
To obtain an amino ester represented by the general formula (8)
R ³ X (8)
(In the formula, R ³ and X have the same meaning as described above.)
A quaternary ammonium salt (1) is obtained by reacting a quaternizing agent represented by the formula (1), and further performing salt exchange as needed.
[0025]
Hereinafter, the method for producing the quaternary ammonium salt (1) will be described in detail.
In the production method 1, first, the glycerol compound represented by the general formula (2) is represented by the general formula (3) in a molar amount of 0.9 to 2.0 times, preferably 1.0 to 1.5 times. The compound is subjected to esterification at a temperature of 70 to 200 ° C., preferably 100 to 150 ° C. for 1 to 20 hours using a catalyst, if necessary, to obtain a haloester represented by the general formula (4). To get.
[0026]
Examples of the glycerol compound represented by the general formula (2) used herein include 1,3-dioctadecoxy-2-propanol, 1-octadecanoloxy-3-hexadecanoloxy-2-propanol, and 1-dodecanoxy-3-propanol. Docosanoxy-2-propanol and the like, ethylene oxide adduct thereof, propylene oxide adduct thereof, and a mixture thereof.
[0027]
Examples of the compound represented by the general formula (3) include monochloroacetic acid, monochlorobutyric acid, monochlorohexanoic acid, and methyl esters and ethyl esters thereof. Examples of the catalyst used for the esterification include an acid catalyst such as p-toluenesulfonic acid and sulfuric acid.
[0028]
Next, the haloester represented by the general formula (4) obtained as described above and 0.9 to 5.0 times, preferably 0.95 to 2.0 times, the mole of this haloester. With a tertiary amine represented by the general formula (5) at a temperature of 30 to 120 ° C., preferably 40 to 70 ° C., using a solvent, if necessary, for 0.1 to 10 hours. The quaternary ammonium salt (1) can be obtained by carrying out salt conversion, if necessary.
[0029]
The tertiary amine represented by the general formula (5) used herein includes trimethylamine, triethylamine, tripropylamine, N-methyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, N, N-dimethyl -2-hydroxypropylamine, N, N-dimethylbutylamine, N, N-diethylmethylamine, N, N-dimethylisopropylamine, N-methyldibutylamine, etc., and the solvent is methanol, ethanol, isopropyl alcohol, or the like. Acetone and the like can be mentioned.
[0030]
In the production method 2, first, a haloester represented by the general formula (4) obtained in the same manner as the production method 1, and 0.9 to 5.0 moles, preferably 0.95 mol, of the haloester are used. The secondary amine represented by the general formula (6) is added to the solution at a temperature of 0 to 900 ° C., preferably 30 to 700 ° C., and, if necessary, using an aqueous solvent at a temperature of 1 to 20 times. The amination reaction is performed for a long time to obtain an amino ester represented by the general formula (7). Next, the quaternization represented by the general formula (8) is 0.8 to 2.0 times, preferably 0.95 to 1.5 times the mol of the amino ester represented by the general formula (7). The reaction is terminated by performing quaternization without a solvent or in a solvent at 70 to 120 ° C. for 0.5 to 10 hours using the agent, followed by post-treatment according to a conventional method. If salt exchange is performed using an ion exchange resin or the like, a quaternary ammonium salt (1) having a necessary counter ion can be obtained.
[0031]
The secondary amine represented by the general formula (6) used herein includes dimethylamine, N-ethylmethylamine, diethylamine, N-methylisopropylamine, N-ethylisopropylamine, N-methylbutylamine, diisopropylamine , Dipropylamine, N-ethylbutylamine, N-methylethanolamine, diethanolamine, N-methyl-2-hydroxypropylamine, di- (2-hydroxypropyl) amine and the like, and are represented by the general formula (8). Examples of the quaternizing agent include lower alkyl halides such as methyl chloride and di-lower alkyl sulfates such as dimethyl sulfate. Examples of the solvent for the quaternization reaction include water, methanol, ethanol, isopropyl alcohol, and acetone.
[0032]
The structure of the quaternary ammonium salt (1) of the present invention can be confirmed by an infrared absorption spectrum and a nuclear magnetic resonance spectrum.
The quaternary ammonium salt (1) of the present invention is a novel surfactant, can impart excellent flexibility to fibers, and is useful as a soft base having excellent biodegradability. In addition, it can impart excellent flexibility and smoothness to hair, and can be applied to hair rinses, hair treatments and the like, which are hair cosmetics.
[0033]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0034]
Example 1
177.6 g of 1,3-dioctadecanoxy-2-propanol and 38 g of monochloroacetic acid were placed in a four-necked flask equipped with a stirrer, a thermometer, and a condenser, and the temperature was raised to 140 ° C. After reacting at the same temperature for 7 hours while distilling off generated water, excess monochloroacetic acid was removed by washing with water to obtain 200 g of a corresponding chloroacetic acid ester.
Next, 150 g of the above-mentioned chloroacetic acid ester, 16 g of trimethylamine and 40 g of isopropyl alcohol were put into an autoclave equipped with a stirrer and a thermometer, and reacted at 60 ° C. for 4 hours. After the reaction, crystallization with acetone was performed, and after drying, 150 g of the target substance as a white powder was obtained.
The following structures were confirmed from the NMR spectrum and the IR spectrum.
[0035]
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[0036]
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[0037]
・ IR spectrum (KBr tablet)
1752 cm ^-1 , 1209 cm ^-1 , 1128 cm ^-1
Example 2
177.6 g of 1,3-dioctadecanoxy-2-propanol and 46 g of monochlorobutyric acid were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser, and the temperature was raised to 140 ° C. After reacting at the same temperature for 7 hours while distilling off generated water, excess monochloroacetic acid was removed by washing with water to obtain 210 g of the corresponding chlorobutyrate.
Next, 150 g of the above-mentioned chlorobutyrate, 15 g of trimethylamine and 40 g of isopropyl alcohol were put into an autoclave equipped with a stirrer and a thermometer and reacted at 80 ° C. for 4 hours. After the reaction, crystallization with acetone was performed, and after drying, 150 g of the target substance as a white powder was obtained.
The following structures were confirmed from the NMR spectrum and the IR spectrum.
[0038]
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[0039]
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[0040]
・ IR spectrum (KBr tablet)
^{1750cm -1,} 1205cm ^-1, 1133cm ^-1
Example 3
177.6 g of 1,3-dioctadecanoxy-2-propanol and 45 g of monochlorohexanoic acid were placed in a four-necked flask equipped with a stirrer, a thermometer, and a condenser, and the temperature was raised to 140 ° C. The reaction was carried out at the same temperature for 7 hours while distilling off generated water to obtain 220 g of the corresponding chlorohexanoic acid ester.
Next, 150 g of the above-mentioned chlorohexanoic acid ester, 14 g of trimethylamine and 60 g of ethanol were placed in an autoclave equipped with a stirrer and a thermometer and reacted at 80 ° C. for 4 hours. After the reaction, crystallization with acetone was performed, and after drying, 150 g of the target substance as a white powder was obtained.
The following structures were confirmed from the NMR spectrum and the IR spectrum.
[0041]
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[0042]
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[0043]
・ IR spectrum (KBr tablet)
1756 cm ^-1 , 1213 cm ^-1 , 1129 cm ^-1
Example 4
In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, 167 g of the chloroacetate ester obtained in the same manner as in Example 1, 56 g of a 50% aqueous dimethylamine solution, and 90 g of ion-exchanged water were charged, and the temperature was raised to 50 ° C. . After stirring at the same temperature for 12 hours, excess dimethylamine was removed by washing with water to obtain 165 g of the corresponding amino ester.
Next, 120 g of the above amino ester, 12 g of methyl chloride and 80 g of acetone were placed in an autoclave equipped with a stirrer and a thermometer, and reacted at 90 ° C. for 6 hours. After the reaction, crystallization was performed with acetone, and after drying, 100 g of the target substance as a white powder was obtained.
The following structure having the same structure as that synthesized in Example 1 was confirmed from the NMR spectrum and the IR spectrum.
[0044]
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[0045]
Example 5
In a four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 243.6 g of a 5-mol addition product of 1,3-dioctadecoxy-2-propanol with ethylene oxide (hydroxyl value 69 (KOH mg / g)) And 38 g of monochloroacetic acid were added, and the temperature was raised to 140 ° C. After reacting at the same temperature for 7 hours while distilling off generated water, excess monochloroacetic acid was removed by washing with water to obtain 270 g of the corresponding chloroacetic acid ester.
Next, 150 g of the above-mentioned chloroacetic acid ester, 13 g of trimethylamine and 40 g of isopropyl alcohol were put into an autoclave equipped with a stirrer and a thermometer, and reacted at 60 ° C. for 4 hours. After the reaction, crystallization was carried out with acetone, and after drying, 120 g of the target product was obtained as a pale yellow gel.
The following structures were confirmed from the NMR spectrum and the IR spectrum.
[0046]
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[0047]
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[0048]
・ IR spectrum (KBr tablet)
1748 cm ^-1 , 1206 cm ^-1 , 1117 cm ^-1

Claims (5)

A novel quaternary ammonium salt represented by the general formula (1).

(Wherein, R ¹ , R ² and R ³ are the same or different and are an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are the same or different and may have the same A linear or branched alkyl or alkenyl group of 8 to 36, A is a linear or branched alkylene group having 2 to 3 carbon atoms, X is an anionic group, n is an integer of 1 to 6, m is an alkylene oxide It is a number from 0 to 20 indicating the average number of moles added.) In the general formula (1), R ¹ , R ² and R ³ are a methyl group, an ethyl group or a hydroxyethyl group, R ⁴ and R ⁵ are a linear alkyl group having 12 to 22 carbon atoms, and A is

X is a halogen atom, a sulfate, a carboxylate which may be substituted with a hydroxyl group having 1 to 4 carbon atoms or an alkyl sulfate having 1 to 4 carbon atoms, n is 1 to 3, and m is 0 to 10. Quaternary ammonium salts. In the general formula (1), R ¹ , R ² and R ³ are a methyl group, R ⁴ and R ⁵ are an octadecyl group, a hexadecyl group or a mixed group thereof, A is an ethylene group, X is Cl or CH ₃ SO ₄ , The quaternary ammonium salt according to claim 1, wherein n is 1 and m is 0. General formula (2)

(In the formula, R ⁴ , R ⁵ , A and m have the same meaning as described above.)
A glycerol compound represented by the general formula (3)
^{_{Y- (CH 2) n -COOR 6}} (3)
(In the formula, R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a halogen atom, and n has the same meaning as described above.)
The esterification is carried out by reacting the compound represented by the general formula (4).

(Wherein, R ⁴ , R ⁵ , A, Y, n and m have the same meaning as described above.)
And further obtained by combining the haloester represented by the general formula (5)

(In the formula, R ¹ , R ² and R ³ have the same meaning as described above.)
The method for producing a quaternary ammonium salt according to claim 1, wherein the reaction is carried out with a tertiary amine represented by the following formula: A haloester represented by the general formula (4);

(In the formula, R ¹ and R ² have the same meaning as described above.)
With a secondary amine represented by the general formula (7)

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , A, n and m have the same meanings as described above.)
To obtain an amino ester represented by the general formula (8)
R ³ X (8)
(In the formula, R ³ and X have the same meaning as described above.)
The method for producing a quaternary ammonium salt according to claim 1, wherein a quaternizing agent represented by the following formula is reacted.