JPH04169565A - Alkenyl-or alkyl-succinic acid anhydride derivative containing sulfo, amido and carboxyl group in one molecule, salt thereof and production thereof - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I or II (R is 8-30C alkenyl or 8-30C alkyl.; R' is H, 1-4C saturated or unsaturated hydrocarbon group) and salts thereof. USE:A low irritative surfactant excellent in surface activity, mild to the skin and the mucous membrane and protective for hair. Since the substances, in addition thereto, are excellent in hygroscopicity, they are useful as a humectant. PREPARATION:A compound of formula III is reacted with a compound of formula IV in the presence of a solvent selected from an alcohol, an ester, a ketone, a glycol ester, a cyclic ether and a glycol diether or without using a solvent, thus obtaining the objective compound of formula I or II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel alkenyl or alkyl succinic anhydride derivatives and salts thereof, which are mildly irritating and have excellent surface activity, and a method for producing the same.

[Conventional technology]

Conventionally, alkyl sulfates (AS), alkyl ether sulfates (AES), α-olefin sulfonates (AO5), etc. have been used as surfactant base materials for shampoos, body shampoos, lotions, etc., but recently A mild cleaning agent that not only has foaming and cleaning properties, but also has a natural texture and conditioning effect, is less irritating to the skin and hair, and does not irritate the skin or damage the hair even when used repeatedly. The demand for In connection with this, N-acyl amino acid type surfactants, sulfosuccinate type surfactants, N-acyl taurine type surfactants, etc. have come to be used.

[Problem to be solved by the invention]

However, although N-acylamino acid surfactants have a mild effect with little irritation to the skin, they have insufficient surface activity, a decrease in foaming properties under weak acids, and the presence of divalent or higher metal salts. If it exists, it becomes insoluble in water, resulting in insufficient hard water resistance, and also has the drawbacks of bad odor and color.

Although sulfosuccinate type surfactants are hypoallergenic and stable under weak acidity, they have the disadvantage of being susceptible to hydrolysis.

N-acyl taurine type surfactants are hypoallergenic and have good hard water resistance, acid resistance, and alkali resistance, but they have the disadvantages of slightly inferior foaming properties, and are very expensive and not common. have.

Furthermore, although the above surfactants are less irritating than conventionally used anionic surfactants, they are still insufficient, and there is a need for surfactants that are even less irritating and have higher surfactant ability. It is being

[Means to solve the problem]

The present inventors have conducted extensive research on surfactants that have excellent surfactant ability, have mild effects on the skin and hair, are not subject to any restrictions in use, and are also economically viable. The present inventors have discovered that acid anhydrides and aminoethane sulfonic acids easily react and are bonded through amide bonds, leading to the completion of the present invention.

That is, the present invention provides novel alkenyl or alkyl succinic anhydride derivatives and salts thereof represented by the following general formulas (I) and (II) useful as low irritation surfactants, and a method for producing the same. It is something.

CH, Co○H (wherein R represents an alkyl group or alkenyl group having 8 to 30 carbon atoms, and R represents hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms) of the present invention Compound (I
) and (Il[) are produced, for example, by the following reaction.

R-CHCOR'' CH,C○ (m) (IV) R' R-CHCONCH,CH,SO,Na...
・-・ (II) CH, CC00 HR-CHCOO Base-1 → -CH, C0NCH, CH, SO, Na
-(V)■R.

as well as R.

RC: HCONCH, CH, So, Na...(
VI) CH, COOM (in the formula, R and R″ have the above-mentioned meanings, and M represents a base such as an alkali metal, ammonium, hydroxyammonium having a hydroxyalkyl group having 2 to 3 carbon atoms, or lower alkylammonium) ) The starting material, the compound represented by formula (m), can be obtained, for example, by subjecting an α-olefin and maleic anhydride to an ene reaction in an inert gas atmosphere using a known method. When octadecene is used, dodecenylsuccinic anhydride is obtained, and when octadecene is used, octadecenylsuccinic anhydride is obtained.Furthermore, alkenylsuccinic anhydride as described above is hydrogenated by a known method. By using alkyl succinic anhydride, the hue and odor can be improved.

That is, dodecenylsuccinic anhydride can be obtained by hydrogenating dodecenylsuccinic anhydride, and octadecylsuccinic anhydride can be obtained by hydrogenating off-davcenylsuccinic anhydride.

Further, the compound represented by formula (IV) can be obtained, for example, by reacting sodium oxyethanesulfonate with an alkylamine. That is, when methylamine is used as an alkylamine, sodium N-methylsulfoethylamine (sodium methyltaurate) is obtained, and when n-butylamine is used, sodium n-butyltaurate is obtained.

In general, R in these compounds has 12 to 1 carbon atoms.
6 is preferably an alkyl group or an alkenyl group, and R'' is preferably a compound of hydrogen or a methyl group.

The compound of the present invention is produced from these raw materials by either a non-solvent method or a solvent method as described below.

In the non-solvent method, the raw materials Compound (III) is a liquid and Compound (IV) is a powder, but the target product can be obtained by solid-liquid reaction without using a reaction solvent.

In this case, the reactant changes into powder through a very high viscosity region during the reaction. Therefore, stirring is not possible using the stirring method used in ordinary reactors, and a high-viscosity stirring device such as a kneader is required.

That is, compound (III) or compound (rV
), and while kneading the mixture, compound (rV) or compound (m) is added dropwise. Although it is possible to carry out the method of simultaneous charging, it is preferable to drop one of the raw materials in order to increase the reaction rate.
More preferred is a method in which the compound (m) is added dropwise to the mixture.

More specifically, the compound (rV) is charged into a kneader and heated to 70 to 120°C. Compound (m) is gradually added dropwise so as to uniformly contact the solution. Dripping time is 1-2
Time is enough. As the reaction progresses, the viscosity increases, and when the reaction rate exceeds 60%, it becomes block-like, and if stirring is continued, it becomes powder-like.

By stirring for 6 to 7 hours, compounds (1) and (II) of the present invention can be obtained with a reaction rate of 90% or more.

When the compound of the present invention is used as a cleaning agent, 90%
There is no problem with this reaction rate.

On the other hand, in the solvent method, compound (N) is dispersed in a solvent and heated to 70 to 120'C, and compound (III) is added dropwise, or conversely, compound (m) is dissolved in a solvent and heated to 70 to 120'C.
It is obtained by heating to 120° C. and adding compound (IV) dropwise to react. The dropwise addition time is required to be 2 hours or more, preferably 3 hours or more, and the reaction time including the preparation time after the dropwise addition is 5 hours or more, preferably 7 hours or more. Since the compound of the present invention is insoluble or poorly soluble in solvents and the reaction is carried out in a dispersed state, it is preferable to carry out the reaction so that the amount of the reactant is 35% or less, preferably 30% or less.

The solvents used in this reaction include alcohols, esters, ketones, glycol ethers, cyclic ethers, and glycol diethers because lipophilic solvents such as aliphatic or aromatic solvents have poor affinity with the reaction products. Hydrophilic solvents such as the like are preferred, and alkylene glycol dialkyl ethers having no polar group are preferred.

After the reaction is completed, the solvent is removed from the reaction product by a known method such as drying under reduced pressure, and the compounds (I) and (I[) of the present invention are obtained.
is obtained. However, due to the possibility of post-treatment and even trace amounts of solvent remaining, a non-solvent method is more preferable as a manufacturing method. (I) and (I[) are easily soluble in water, and known bases or their aqueous solutions It is neutralized by, and its salt is guided.

In this case, the bases used are potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium hydroxide,
Examples include inorganic bases such as ammonia, lower alkylamines such as monoalkylamines, dialkylamines, and trialkylamines, and alkanolamines such as monoethanolamine, jetanolamine, and triethanolamine. Alkanolamines are preferred.

[Effect]

Compounds (1) and (If) of the present invention and their salts have excellent surface activity, are hypoallergenic, have mild effects on the skin and hair, and also have excellent acid resistance, alkali resistance, and hard water resistance. The reason for this is thought to be as follows.

As is clear from the structure of the compound of the present invention, -CO
Since it has an N bond and a 1000H group and an amino acid skeleton, it has a mild effect on the skin and hair, and has a hair effect. Furthermore, not only this amino acid skeleton -
Since it has an S○3H group, it has improved hard water resistance compared to an amino acid type surfactant that only has a -〇〇H group. On the other hand, −
It is a sulfosuccinic acid type with a COOH group, -So, and Na groups, and is hypoallergenic and stable even on the weakly acidic side, and does not have an ester bond, so it does not undergo hydrolysis and is resistant to acids and alkalis. Excellent.

Furthermore, when used in combination with a quaternary nitrogen-containing water-soluble polymer, sulfosuccinic acid forms a complex salt with these polymers, and this complex salt easily precipitates on the hair surface and has a high affinity with the hair, so it is adsorbed to the hair. It also has the ability to easily apply hair shine and condition the hair.

〔effect〕

Compounds (1) and (II) and their salts of the present invention are hypoallergenic and have excellent surfactant ability, have mild effects on the skin and mucous membranes, and have a protective effect on hair. Furthermore, it has excellent hygroscopicity and is useful as a humectant.

Therefore, it is suitably used in daily shampoos, body shampoos, hair and skin cleansers for infants, kitchen cleansers for housewives who tend to get rough hands, lotions, moisturizers, and the like.

Furthermore, the effect is maintained not only when using tap water but also when using water with high hardness such as ground water, hot spring water, sea water, etc.

〔Example〕

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

[Example 1] 182 g of sodium N-methyl taurate was charged into an IQ kneader equipped with a thermometer and heated to 90°C. To this, 30% of n-hexadecenylsuccinic anhydride was added under a nitrogen stream.
0 g was added dropwise over 2 hours.

During the reaction, the reaction product became block-like after about 1 hour.

After the dropwise addition, stirring was continued for another 5 hours while maintaining the temperature at 90°C. In this way, 478 gr of a reactant was obtained. 6 The result of analysis of the obtained reactant by liquid chromatography showed that the reaction rate was 9.
It was 2%.

The reaction products separated by liquid chromatography were as follows, and were confirmed to be (11) and (H1) of the following formula.

The analytical values were as follows.

・Saponification value: 113.8 (theory @ 116.1) ・Double weight % as a result of elemental analysis (C!, Theoretical value as H4, O, N S Na is shown in parentheses) C: 57. 2 (57,4), H: 8.0 (8,3)
, ○: 20.2 (20,0), N: 2.9 (2,
9), S: 6°8 (6,7), Na: 4.7 (
4,7) Judgment result of infrared absorption spectrum Absorption of acid anhydride of n-hexadecenylsuccinic anhydride (
1865 cm-“) disappears, and the 1CO produced as a result of the reaction
61720 cm-' corresponding to OH group and 10ON group,
Absorption at 1650 cm-' appeared.

OH, (CH,), CH=C:H-CH, -CHC:
OOHζ CH, C0NCH, CH, So, Na CH.

・・・・・・・・・(I,) CH.

CH, (CH,)0. CH=CH-CH, -CHCoN
CH, CH, So, NaCH, C0OH (H1) The obtained reaction product was dissolved in water to a concentration of 50%, and further added with triethanolamine to adjust the pH to 7.0. Finally, water was added to adjust the solid content to 40% to obtain an aqueous salt solution.

[Example 2] 206 g of sodium N-methyl taurate was charged into an IQ kneader equipped with a temperature needle and heated to 110°C. This was added with n-tetradecenylsuccinic anhydride 2 under a nitrogen stream.
94 g was added dropwise over 1 hour. After dropping for another 5 hours, 1
Stirring was continued at 10°C. In this way, 482 gr of powdered reactant was obtained. Analysis of the obtained reaction product by liquid chromatography showed that the reaction rate was 95%.

The properties of the reaction product separated by liquid chromatography are as follows, and this compound has the following formulas (■,) and (■
, ) was confirmed.

The analytical values were as follows.

・Saponification value: 119.1 (theoretical value 123.2) ・Double weight% as a result of elemental analysis (Theoretical values as C□H,, O, N5Na are shown in parentheses) C: 55.4 (55 , 4), H: 8.2 (8, 4)
, O: 21.3 (21,1), N: 3.1 (3,1
), S: 7°0 (7,0), Na: 5.0 (5
, 0)・Judgment result of infrared absorption spectrum Absorption of acid anhydride of n-tetradecenylsuccinic anhydride (
1865 cm-') disappears, and the 1CO produced as a result of the reaction
172゜cm-' corresponding to OH group and 100N group,
Absorption at 1650 cm-' appeared.

CH, (CH,), CH=CH-CH, -CHCOO
HCH, GONCH, CH, SO, NaCH.

・・・・・・(1,) CH.

CH, (CH,), CH=CH-CH, -CHCoN
CH, CH, SO, NaCH, COOH (■,) In the same manner as in Example 1, an aqueous solution of triethanolamine salt (solid content 40%, pH = 7.3) was obtained.

[Example 3] 216 g of sodium N-methyl taurate was charged into an IQ kneader equipped with a thermometer and heated to 90°C. To this, 324 g of n-hexadecylsuccinic anhydride was added under a nitrogen stream.
was added dropwise over 3 hours. After the dropwise addition, stirring was continued at 90° C. for 5 hours. In this way, 530 gr of powdered reactant
I got it. Analysis of the obtained reaction product by liquid chromatography showed that the reaction rate was 93%.

The properties of the reaction product separated by liquid chromatography are as follows, and this compound has the following formulas (1,) and (n
, ) was confirmed.

The analysis values were as follows: Saponification value: 127.7 (theoretical value 131.1) Judgment results of infrared absorption spectrum Elemental analysis results: wt% (C,, H, 40, N5Na The theoretical value is shown in parentheses.) C: 56.8 (56,9), H: 9.1 (9,1)
, O: 19.9 (19,8), N: 2.9 (2,9
), S: 6°6 (6,6), Na: 4.7 (4
, 7)・Determination results of infrared absorption spectrum Absorption of acid anhydride of n-hexadecylsuccinic anhydride (1
865cm'-') disappeared, and 1720cm-', 16 corresponding to the 1000H group and -CON group produced as a result of the reaction.
Absorption at 50 cm-' appeared.

CH, (CH,) □, CH, -CH-CHC0OHCH
, -CON-CH, CH, So, Na...
(I,) and CH, (CH,), 4CH-CH-CON-CH,CH
, So, NaCH, C○○H ・・・・・−・ (■3) An aqueous solution of triethanolamine salt (solid content 40%, pH = 7.0) was obtained in the same manner as in Example 1. .

[Example 4] Diethylene glycol dimethyl ether 60 was added to a 2Ω four-eye flask equipped with a condenser, thermometer, and stirrer.
0g and 108g of sodium N-methyltaurate were added and heated to 100°C. While stirring thoroughly, 133g of n-dodecenylsuccinic anhydride was added over a period of 5 hours.
I completed another 2 hours of cram school. After the reaction, drying was performed under reduced pressure at 80° C. or lower to obtain 234 gr of a reaction product. Analysis of the obtained reaction product by liquid chromatography showed that the reaction rate was 88%.

The properties of the reaction product separated by liquid chromatography are as follows, and this compound has the following formulas (I4) and (■
4).

The analytical values were as follows.

・Saponification value: 127.7 (theoretical value 131.1) ・Double weight% as a result of elemental analysis (Theoretical value as C,, H, 40, N5Na is shown in parentheses) C: 53.4 ( 53,3), H2 8
．． 0(8,0), O: 22°4(22,5),
N: 3.3 (3,3), S: 7.5 (7,5)
.

Na: 5.4 (5,4) ・Infrared absorption spectrum judgment result Absorption of acid anhydride of n-dodecenylsuccinic anhydride (18
65cm-”) disappeared, and the 1000H produced as a result of the reaction
1720cm-', 1650 corresponding to the group and 100N group
cm-” absorption appeared.

CH, (CH,), CH=CHCH, CHCOOH■ CH,C0NCH2CH,5o3Na CH.

・・・・・・・・・(I4) as well as CH.

CH, (CH,), CH=CHCH, CHCONCH,
CH, So, NaCH, COOH (Il,) In the same manner as in Example 1, an aqueous solution of triethanolamine salt (solid content 40%, pH = 7.2) was obtained.

Patent applicant: Toho Chemical Industry Co., Ltd.

Claims (2)

[Claims] (1) The following formulas (I) and/or (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R represents an alkenyl group or an alkyl group having 8 to 30 carbon atoms, and R' is hydrogen or a carbon number of 1 to 4.) alkenyl or alkyl succinic anhydride derivatives containing a sulfone group, an amide group, or a carboxyl group in one molecule represented by (representing a saturated or unsaturated hydrocarbon group) and salts thereof. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents an alkenyl or alkyl group having 8 to 30 carbon atoms) Alkenyl succinic anhydride and general formula ▲ Numerical formula, chemical formula , tables, etc. ▼ (R' represents hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms) Sodium alkyl or alkenyl taurate is combined with alcohols, esters, ketones, General formulas obtained by reaction in the presence or absence of a solvent selected from glycol ethers, cyclic ethers, and glycol diethers▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R represents an alkenyl group or an alkyl group having 8 to 30 carbon atoms, and R' is hydrogen or a carbon number of 1 to 30. alkyl or alkenyl succinic anhydride derivatives represented by (4) representing a saturated or unsaturated hydrocarbon group; A method for producing an alkenyl or alkyl succinic anhydride derivative containing a sulfone group, an amide group, or a carboxyl group in one molecule and a salt thereof, which is obtained by neutralizing with a basic compound selected from the following.