JP3476555B2 - Method for producing quaternary ammonium salt - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a quaternary ammonium salt. More specifically, the present invention relates to a method for producing a quaternary ammonium salt which is useful as a surfactant and as a soft base for fabrics, hair and the like.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
The quaternary ammonium salt used as a softening agent base for cloth and hair is produced by reacting a corresponding secondary or tertiary amine with a quaternizing agent. At that time, it was general to use an alcohol solvent such as isopropyl alcohol or ethanol in an amount of 15 to 25% by weight. Such an alcohol solvent has a low flash point and a risk of fire, has a unique odor and adversely affects the odor of products containing these bases, and is a softening active ingredient for cloth and hair. Since it does not work as such, there is a problem that extra cost is required for that. However, when such a solvent is not used, there is a problem that the quaternary ammonium salt has a high melting point and is difficult to handle.

Therefore, an object of the present invention is to carry out the quaternization reaction without using such a volatile alcohol solvent or by reducing the amount used as much as possible.
A quaternary ammonium salt which can be added during the grading reaction, lowers the melting point of the quaternary ammonium salt produced, and also has a flexibility-enhancing effect, and further has a higher flexibility-enhancing effect. Is to find a combination with.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific polyhydric alcohol ester is optimal for the above purpose, and completed the present invention. That is, in the present invention, a tertiary amine is reacted with a quaternizing agent to react in the presence of a polyhydric alcohol ester represented by the following general formula (I) in the step of producing a quaternary ammonium salt. The present invention provides a method for producing a quaternary ammonium salt characterized by the above.

[0005]

[Chemical 7]

[In the formula, G group: represents a residue obtained by removing all alcoholic hydroxyl groups from the starting polyhydric alcohol.

[0007]

[Chemical 8]

The carbon atom to which the hydroxyl group, which is removed from the polyhydric alcohol as the raw material, is bonded, represents a group bonded to the G group. Here, the A group represents an alkylene group having 2 to 4 carbon atoms, the R group represents a linear or branched alkyl group or alkenyl group having 7 to 23 carbon atoms, and m and n are 0 respectively.
Indicates a number from ~ 100. The m + n A's may be the same or different.

P, q, r and s: each represents a number of 0 or more, and p + q + r + s represents the total number of alcoholic hydroxyl groups of the starting polyhydric alcohol. However, p + q and r + s are 0
Not a number. The polyhydric alcohol ester represented by the general formula (I) used in the present invention is preferably at least one selected from the group consisting of the following (a), (b) and (c). (A) pentaerythritol fatty acid ester (however,
An ester having at least one hydroxyl group) and its alkylene oxide (provided that it is an alkylene oxide having 2 to 3 carbon atoms) adduct. (B) Glycerin / fatty acid ester (provided that it is an ester having at least one hydroxyl group) and its alkylene oxide (provided that it is an alkylene oxide having 2 to 3 carbon atoms) adduct. (C) Sorbitan / fatty acid ester (provided that it is an ester having at least one hydroxyl group) and its alkylene oxide (provided that it is an alkylene oxide having 2 to 3 carbon atoms) adduct. Among these polyhydric alcohol esters, especially glycerin / fatty acid ester (b) is an ester having at least one hydroxyl group and its alkylene oxide (which is an alkylene oxide having 2 to 3 carbon atoms). Addition products are preferable, and further, a reaction product of natural fats and oils, glycerin and alkylene oxide (where the reaction molar ratio of fats and oils, glycerin and alkylene oxide is 1: (0.1
5): (2 to 100)) is preferable.

The polyhydric alcohol ester represented by the general formula (I) used in the present invention can be synthesized, for example, by the following known synthetic methods (i) to (vi).

[0011]

[Chemical 9]

[In the formula, G, R, p, q, r and s: have the above-mentioned meanings. r ', s': 0 <(r '+ s') <(p + q + r + s)
Shows the number that satisfies. The synthesis method (i) is a method of esterifying a polyhydric alcohol with a fatty acid. The molar ratio of the polyhydric alcohol and the fatty acid used is such that the resulting polyhydric alcohol ester (I-1)
In, the hydroxyl groups are selected to remain. As the esterification condition, no catalyst may be used, but an acid catalyst such as sulfuric acid, hydrochloric acid or paratoluenesulfonic acid may be used. To give an example of the polyhydric alcohol used in this case,
Examples thereof include glycerin, erythritol, pentaerythritol, sorbitol, sorbitan, etc., and these may be used alone or as a mixture. Examples of fatty acids used in this case include, for example, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, or uncured or hardened tallow. (beef tallow,
Examples include fatty acids obtained from butter fat, etc.), palm oil, rapeseed oil, fish oil, etc., and these may be used alone or as a mixture.

[0013]

[Chemical 10]

[Wherein G, R, p, q, r, s, r'and s': have the above meanings. R ′: Indicates a residue obtained by removing a hydroxyl group from a monohydric alcohol or a polyhydric alcohol. The synthesis method (ii) is a method of transesterifying a polyhydric alcohol and a fatty acid ester. In the synthesis method (ii), NaOH, KOH, NaOCH ₃ , KOCH ₃ or the like is used as a reaction catalyst. Examples of the fatty acid ester used in the present synthesis method (ii) include, for example, the fatty acid methanol ester, ethanol ester, propanol ester, butanol ester, ethylene glycol ester, glycerin ester, erythritol ester, and pentaerythritol ester described in the synthesis method (i). , Xylitol ester, sorbitol ester, sorbitan ester, natural fats and oils and the like are used.

[0015]

[Chemical 11]

[In the formula, polyhydric alcohol ester (I-1): represents a polyhydric alcohol ester obtained by the synthetic method (i) or (ii). m, n: Indicates the above meaning. This synthetic method (iii) has 2 to 10 carbon atoms in the polyhydric alcohol ester (I-1) obtained by the synthetic method (i) or (ii).
4 is a method of adding an alkylene oxide of 4 to obtain a polyhydric alcohol ester (I-2). In this case, NaOH, KOH, NaOCH ₃ , KOCH ₃ or an alkali metal salt of fatty acid is used as a reaction catalyst. In this alkylene oxide addition reaction, the molar ratio of [alkylene oxide] / [polyhydric alcohol ester (I-1)] = 1 /
1 to 100/1 is preferable, and 1/1 to 50/1 is more preferable.

[0017]

[Chemical 12]

[In the formula, R and R ′ are as defined above. Polyhydric alcohol ester (I-2): The polyhydric alcohol ester (I-2) obtained by the synthetic method (iii) is shown. r ", s": Indicates a number that satisfies 0 <(r '+ s' + r "+ s") <(p + q + r + s). Here, r ', s', p, q, r, and s have the above-mentioned meanings. This synthetic method (iv) synthesizes the polyhydric alcohol ester (I-2) obtained by the synthetic method (iii) and the fatty acid or its ester used in the synthetic method (i) or (ii), respectively. This is a method of reacting under the same conditions as described in method (i) or (ii). In the polyhydric alcohol ester (I) obtained by such a method, unreacted polyhydric alcohol ester and fatty acid remain, and even if they are contained, they may be contained within a range not impairing the effects of the present invention.

[0019]

[Chemical 13]

[Wherein G, R, R ', p, q, r, s, r',
s', m and n have the above-mentioned meanings. In the present synthesis method (v), the molar ratio of the polyhydric alcohol and the fatty acid ester used is such that the polyhydric alcohol (I
In -2), hydroxyl groups are selected so that they remain.
The molar ratio of polyhydric alcohol and alkylene oxide is (alkylene oxide) / (polyhydric alcohol) = 1/1.
-100-100 / 1 is preferable and 5 / 1-50 / 1 is more preferable. The catalyst used in this synthetic method is a synthetic method (i
It may be the same as that used in ii).

[0021]

[Chemical 14]

[Wherein G, R, p, q, r, s, r ', s', m
And n have the above-mentioned meanings. In this synthesis method (vi), an alkylene oxide is added to a polyhydric alcohol (reaction conditions are in accordance with the conditions described in the synthesis method (iii)), and then esterification is performed with a fatty acid (reaction conditions are described in the synthesis method (i)). Method).

Examples of the polyhydric alcohol ester (I) obtained by the above synthetic methods (i) to (vi) include the following compounds, which may be used alone or as a mixture.

[0024]

[Chemical 15]

[0025]

[Chemical 16]

[Wherein R and A are as defined above. a, b, c, d, e, f: Shows the number of moles of alkylene oxide having 2 to 4 carbons added. Among the polyhydric alcohol esters represented by the above general formula (I) used in the present invention, in particular, a reaction product of natural fats and oils, glycerin and alkylene oxide (provided that the reaction molar ratio of fats and oils, glycerin and alkylene oxide is 1: (0.1-5) :( 2-100) is preferable, but the reaction product of this natural fat / oil, glycerin and alkylene oxide is produced, for example, as follows.

That is, it can be obtained by mixing natural fat and oil with glycerin, adding a basic catalyst, and gradually adding alkylene oxide to react. As the natural fats and oils, beef tallow, palm oil, palm kernel oil, coconut oil, or the like, or partially hardened oil or fully hardened oil thereof, or a mixture thereof can be used. As the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc., preferably ethylene oxide, propylene oxide, or a mixture thereof can be used. If a mixture of alkylene oxides is used, they can be reacted simultaneously or sequentially. As the basic catalyst, potassium hydroxide, sodium hydroxide, sodium methylate or the like can be used. The reaction temperature is 100 ° C to 200 ° C, preferably 140 ° C to 170 ° C.
The reaction molar ratio of natural oil / fat, glycerin and alkylene oxide is preferably 1: (0.1-5) :( 2-100), more preferably 1: (1-5) :( 10-100).

As the reaction mixture, those prepared by the following method may be used. That is, a fatty acid corresponding to natural fats and oils and glycerin may be mixed, esterification may be first performed, and then alkylene oxide may be added. Further, alkylene oxide may be added to glycerin and then esterified with a fatty acid corresponding to natural fats and oils.

The quaternary ammonium salt produced in the present invention may be of any type as long as it is produced from the corresponding tertiary amine, but is preferably one of the general formulas (II) and (III). , (IV) or (V).

[0030]

[Chemical 17]

(In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group or alkenyl group having 8 to 36 carbon atoms, and X represents a halogen or a group represented by CH ₃ SO _4. Show.)

[0032]

[Chemical 18]

[In the formula, R ³ and R ⁴ are the same or different and each represents a linear or branched alkyl or alkenyl group having 7 to 35 carbon atoms, and R ⁵ represents an alkyl group or hydroxyalkyl having 1 to 6 carbon atoms. Or a group represented by the formula: —CH ₂ CH ₂ OCOR ⁶ (R ⁶ represents a linear or branched alkyl or alkenyl group having 7 to 35 carbon atoms), X is halogen or CH ₃ SO _{3. The} group represented by ₄ is shown. ]

[0034]

[Chemical 19]

(In the formula, R ⁷ and R ⁸ are the same or different and are a linear or branched alkyl or alkenyl group having 7 to 35 carbon atoms, and R ⁹ is an alkyl group or hydroxyalkyl having 1 to 6 carbon atoms. And v and w are the same or different and are 2 to
X represents an integer of 6 or halogen or a group represented by CH ₃ SO ₄ . )

[0036]

[Chemical 20]

(In the formula, R ¹⁰ and R ¹¹ are the same or different and each represents a linear or branched alkyl or alkenyl group having 7 to 35 carbon atoms, and X represents a halogen or a group represented by CH ₃ SO _4. The compound represented by the general formula (III), (IV) or (V) is more preferable, and the compound represented by the general formula (IV) is further preferable. This is because the flexibility enhancing effect of the polyhydric alcohol ester represented by the general formula (I) is further increased. The ester bond of the polyhydric alcohol ester represented by the general formula (I) and the general formula (III), (IV) or (V)
It is considered that the effect of enhancing the flexibility of the polyhydric alcohol ester represented by the general formula (I) is increased by the interaction between the ester bond and the amide bond of the quaternary ammonium salt represented by.

The tertiary amine used as a raw material for the reaction of the present invention is the following general formula (II '), which is a raw material for producing the quaternary ammonium salt represented by the general formulas (II) to (V). ~
A tertiary amine represented by (V ′) may be mentioned.

[0039]

[Chemical 21]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ ,
R ⁹ , R ¹⁰ , R ¹¹ , v and w have the above-mentioned meanings. ) The quaternization reaction of the tertiary amine is carried out by mixing the polyhydric alcohol ester represented by the general formula (I) with the corresponding tertiary amine and adding a quaternizing agent. The mixing weight ratio of the polyhydric alcohol ester represented by formula (I) and the tertiary amine is preferably 1:99 to 99: 1, more preferably 50:50 to 10:90. If necessary, use an alcohol solvent such as isopropyl alcohol or ethanol in an amount of 0% with respect to all reaction products.
-20% may be added, but addition of more than this is not preferable for the purpose of the present invention. Examples of the quaternizing agent include chloromethane, bromomethane, iodomethane, dimethylsulfate and the like. Chloromethane and dimethylsulfate are preferred. The reaction temperature is 60 to 140 ° C, preferably 80 to 120 ° C.

[0041]

[Examples] The present invention will be described in more detail with reference to synthesis examples of polyhydric alcohol esters and Examples of the present invention.
The invention is not limited to these examples.

Synthesis Example 1 85.9 g of beef tallow was placed in an autoclave equipped with a stirrer and a thermometer.
Add 9.2 g of glycerin and 0.40 g of 85% potassium hydroxide,
It was dehydrated at 110 ° C. and 200 torr for 1 hour. Then, the inside of the system was closed, the temperature was raised to 160 ° C., and the reaction was carried out for 3 hours. Next, 105.6 g of ethylene oxide was added over 2 hours, followed by aging for 1 hour. After cooling, 0.36 g of acetic acid was added to neutralize the catalyst, and a reaction product of beef tallow, glycerin and ethylene oxide was obtained.

Synthetic Examples 2 to 6 Reactants of natural fats and oils, glycerin and alkylene oxide were obtained in the same manner as in Example 1 except for the conditions shown in Table 1.

[0044]

[Table 1]

Example 1 In an autoclave equipped with a stirrer and a thermometer, 146 g of the reaction product obtained in Synthesis Example 1 and N, N-di (hardened tallow alkyl) were used.
-N-Methylamine 535g was charged, and chloromethane 61g
After being pressed in, the mixture was heated to 90 ° C. When reacted at that temperature for 6 hours, N, N-di (hardened tallow alkyl) -N, N-dimethylammonium chloride was obtained.

Examples 2 to 4 Reactions were carried out under the conditions shown in Table 2 in the same manner as in Example 1 to obtain quaternary ammonium salts shown in Table 2.

Comparative Examples 1 to 4 Instead of the reaction products obtained in Synthesis Examples 1 to 3 used in Examples 1 to 4, the same amount of isopropyl alcohol was used to obtain quaternary ammonium salts in the same manner.

Table 2 shows the reaction conditions of Examples 1 to 4 and Comparative Examples 1 to 4, the structure of the obtained quaternary ammonium salt, and the evaluation results of the flexibility and odor of the quaternary ammonium salt.
Are summarized in. The flexibility and odor were evaluated by the following methods. <Flexibility and odor evaluation method> Preparation of quaternary ammonium salt dispersions The quaternary ammonium salt mixtures prepared in Examples and Comparative Examples were melted and added dropwise to water with stirring to give quaternary ammonium salts. A dispersion liquid having a concentration of 5% was prepared. Treatment method 2 kg of commercially available cotton towel, using a 30 liter washing machine,
After repeatedly washing with a commercially available detergent attack (registered trademark, manufactured by Kao Corporation) 5 times in 3.5 ° DH hard water, 25 ml of the above dispersion liquid was added, and the mixture was treated at 25 ° C. for 1 minute under stirring. Flexibility evaluation method After air-drying the cloth treated by the above method at room temperature, 25 ℃, 65% RH
It was left for 24 hours in a constant temperature and humidity chamber. The softness of these cloths was evaluated. For the evaluation, a pair of comparisons were carried out using the cloth treated with the quaternary ammonium salt of Comparative Example 1 as a control. The evaluation is expressed as follows. 4; considerably softer than the control 3; softer than the control 2; softer or slightly softer than the control 1; slightly softer than the control 0; softer than the control Odor evaluation method 5% dispersion prepared by the above method is nasal The odor was evaluated.
The evaluation is expressed as follows. X: Odor is not generated O: No offensive odor

[0049]

[Table 2]

As is clear from the results shown in Table 2, in all cases, the Examples are superior to the Comparative Examples in flexibility and odor. Further, it can be seen that in Examples 2, 3 and 4, especially in Example 3, the flexible performance is significantly improved.

Example 5 500 g of the reaction product obtained in Synthesis Example 4 and 630 g of beef tallow fatty acid diester of N-methyldiethanolamine were charged into a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, and heated to 70 ° C. to be dissolved. . 120 g of dimethylsulfate was added dropwise over 2 hours and aged at the same temperature for 3 hours to obtain the desired quaternary ammonium salt.

Examples 6 to 7 The reaction was carried out under the conditions shown in Table 3 in the same manner as in Example 5, and Table 3
A quaternary ammonium salt as shown in was obtained.

The reaction conditions of Examples 5 to 7, the structure of the obtained quaternary ammonium salt, and the flexibility and odor of this quaternary ammonium salt were evaluated in the same manner as in Example 1 and summarized in Table 3. Shown in.

[0054]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C07C 231/12 C07C 231/12 233/36 233/36 233/38 233/38 (72) Inventor Kazuhiko Okabe Spain 08021 Barcelona, Spain Calle Mariano Coobi 155,2-1 (56) Reference JP-A-2-91050 (JP, A) JP-A-54-48691 (JP, A) JP-A-6-157435 (JP, A) JP-A-5 −230001 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 209/12 C07C 211/62 C07C 213/02 C07C 219/06 C07C 219/08 C07C 231/12 C07C 233 / 36 C07C 233/38

Claims (6)

(57) [Claims] 1. A is reacted with a tertiary amine quaternizing agent, under
In the step of producing the quaternary ammonium salt represented by the general formulas (II) to (V), the reaction is performed in the presence of a polyhydric alcohol ester represented by the following general formula (I). Method for producing quaternary ammonium salt. [Chemical 1] [In the formula, G group: represents a residue obtained by removing all alcoholic hydroxyl groups from the starting polyhydric alcohol. [Chemical 2] Each of the carbon atoms to which the hydroxyl group removed from the raw polyhydric alcohol was bonded represents a group bonded to the G group.
Here, the A group represents an alkylene group having 2 to 4 carbon atoms, and R
The group represents a linear or branched alkyl group or alkenyl group having 7 to 23 carbon atoms, and m and n each represent a number of 0 to 100. The m + n A's may be the same or different. p, q, r and s: each represents a number of 0 or more, and p + q + r + s represents the total number of alcoholic hydroxyl groups in the raw material polyhydric alcohol. However,
p + q and r + s represent numbers that are not zero. ] [Chemical 3] (In the formula, R1 and R2 are the same or different and have 8 to 3 carbon atoms.
6 straight or branched chain alkyl or alkenyl groups
X is halogen or a group represented by CH3SO4
Show. ) [Chemical 4] [In the formula, R3 and R4 are the same or different and have 7 to 3 carbon atoms.
5 straight or branched chain alkyl or alkenyl groups
R5 is an alkyl group having 1 to 6 carbon atoms or a hydroxy group.
Sialkyl group or formula-CH2CH2OCOR6
(R6 is a linear or branched alkyl group having 7 to 35 carbon atoms.
Represents a phenyl group or an alkenyl group. ) Is a group represented by
A group represented by halogen or CH3SO4 is shown. ] [Chemical 5] (In the formula, R7 and R8 are the same or different and have 7 to 3 carbon atoms.
5 straight or branched chain alkyl or alkenyl groups
R9 is an alkyl group having 1 to 6 carbon atoms or a hydroxy group.
A cyalkyl group, where v and w are the same or different and are 2 to 6
An integer, X is represented by halogen or CH3SO4
Indicates a group. ) [Chemical 6] (In the formula, R10 and R11 are the same or different and have 7 carbon atoms.
~ 35 straight or branched chain alkyl group or alkene
Group, X is represented by halogen or CH3SO4
Indicates a group. ) 2. The production method according to claim 1, wherein the polyhydric alcohol ester represented by the general formula (I) is at least one selected from the group consisting of the following (a), (b) and (c). . (A) pentaerythritol fatty acid ester (however,
An ester having at least one hydroxyl group) and its alkylene oxide (provided that it is an alkylene oxide having 2 to 3 carbon atoms) adduct. (B) Glycerin / fatty acid ester (provided that it is an ester having at least one hydroxyl group) and its alkylene oxide (provided that it is an alkylene oxide having 2 to 3 carbon atoms) adduct. (C) Sorbitan / fatty acid ester (provided that it is an ester having at least one hydroxyl group) and its alkylene oxide (provided that it is an alkylene oxide having 2 to 3 carbon atoms) adduct. 3. The polyhydric alcohol ester represented by the general formula (I) is a glycerin / fatty acid ester (provided that it has at least one hydroxyl group) and its alkylene oxide (provided that it has 2 to 3 carbon atoms). The method according to claim 1, wherein the adduct is an alkylene oxide). 4. A polyhydric alcohol ester represented by the general formula (I) is a reaction product of natural fats and oils, glycerin and alkylene oxides (provided that the reaction molar ratio of fats and oils, glycerin and alkylene oxides is 1: (0.1 ~ 5): (2-10
It is 0)), The manufacturing method of Claim 1. 5. The mixing weight ratio of the polyhydric alcohol ester represented by formula (I) and the tertiary amine is 1:99 to.
The manufacturing method according to claim 1, wherein the ratio is 99: 1. 6. The quaternary ammonium salt has the formula (I)
The production method according to claim 1, which is a compound represented by V).