KR101616836B1 - Polydentate cationic surfactant having multi-hydrophilic and multi-hydrophobic groups, method for efficient preparation of thereof and fabric softener composition containing thereof - Google Patents

Abstract

상기 폴리덴테이트형 양이온 계면활성제는 특정한 촉매를 사용하지 않아 촉매를 제거하는 과정이 필요 없으며 상온에 감압이나 가압 과정 없이 반응을 진행함으로서, 경쟁력 있고 환경 친화적인 방법으로 양이온 계면활성제를 제조하면서, 높은 수율을 나타낼 수 있다.The present invention relates to a polydentate-type cationic surfactant having a large number of hydrophilic groups and hydrophobic groups, an efficient process for producing the same, and a fabric softener composition containing the same, and more particularly to a polydentate-type cationic surfactant represented by the general formula do.
[Chemical Formula 1]

The polydentate type cationic surfactant does not require a catalyst to remove the catalyst without using a specific catalyst. Since the reaction proceeds without decompression or pressurization at room temperature, the cationic surfactant is produced in a competitive and environmentally friendly manner, Yield.

Description

TECHNICAL FIELD [0001] The present invention relates to a polydentate-type cationic surfactant having a plurality of hydrophilic groups and hydrophobic groups, a method for producing the same, and a fabric softening agent composition containing the same. thereof}

The present invention relates to a polydentate-type cationic surfactant having a large number of hydrophilic groups and hydrophobic groups, a method for producing the same, and a fabric softening agent composition containing the same.

Generally, a surfactant has one hydrophilic group and one hydrophobic group in one molecule. When the number of carbon atoms in the alkyl chain, which is a hydrophobic group, is increased in order to improve the micelle formation ability, the surfactant having such a structure has a structural limitation on the performance improvement, such as a decrease in solubility in water, Studies on active agents are underway.

In recent years, studies have been conducted on gemini surfactants having two hydrophilic groups and two hydrophobic chains in one molecule to enhance such properties. International Patents 00-27795, 02-30957, U.S. Pat. No. 2,069,652, and U.S. Patent 2008/0058279 disclose various studies on gemini surfactants. In addition, Korean Patent Publication No. 2010-0090133 discloses a method for producing a gemini surfactant which has two hydrophobic groups, two hydrophilic groups and a polar group, and has high solubility in water, excellent conditioning effect and biodegradability.

 However, in this case, there is a problem that a gemini surfactant should be prepared at a relatively high temperature of 90 ° C or higher.

Further, Korean Patent Publication No. 2006-0111181 discloses a surfactant having a plurality of hydrophilic groups and hydrophobic groups by introducing spiculisporic acid into glycerin or a glycerin fatty acid ester derivative. In this case, the esterification reaction proceeds A high-temperature, low-pressure process is required.

On the other hand, when there are many cations in one molecule such as a gemini type cationic surfactant, they easily bind to a form capable of dispersing with the residual detergent after washing, and a stable emulsion having a small emulsion size is formed. Also, the antistatic property and effective concentration are increased, the solubility in water is excellent, and the biodegradability is also increased. When there are many alkyl chains which are hydrophobic, the vesicles are well formed to increase the flexibility. In addition, when used as a fabric softener, it can serve as a functional carrier such as long lasting fragrance.

 Accordingly, in the case of a polydentate-type cationic surfactant in which a plurality of hydrophilic groups and a plurality of hydrophobic groups exist together in one molecule as compared with a gemini-type cationic surfactant having two hydrophilic groups and two hydrophobic groups in one molecule, Can be expected. Therefore, even if only a small amount is used, high performance is exhibited and flexibility, antistatic property, functional carrier and the like can be played. In addition, water solubility is increased and biodegradability is excellent, so that it can serve as an environmentally friendly surfactant.

Accordingly, there have been many studies on the production of polydentate type cationic surfactants having these advantages. Korean Patent Publication No. 2012-0000833 discloses a method for producing a cationic surfactant of the gemini pendant type. In the present invention, an alkyl glycidyl ether is condensed with N, N-dimethylpropylenediamine to obtain an intermediate {(N1, N1-bis- (3-alkoxy-2-hydroxypropyl) -N3, N3- - propylene diamine: DMAPA) and reacted with dimethyl sulfate to introduce two hydrophilic groups and a hydrophobic group.

Accordingly, the present inventors have developed a novel structure of a polydentate type cationic surfactant using the above-mentioned intermediate. The inventors of the present invention invented a method for producing a cationic surfactant in a competitive and environmentally friendly manner by eliminating the need for catalyst removal without using a specific catalyst and proceeding the reaction without decompression or pressurization at room temperature.

International Patent No. 00-27795 International Patent No. 02-30957 US Patent 2011/0269652 U.S. Patent No. 2008/0058279 Domestic patent 2010-0090133 Domestic Patent 2006-0111181

It is an object of the present invention to provide a polydentate-type cationic surfactant having a large number of hydrophilic groups and hydrophobic groups, a method for efficiently producing the same, and a fabric softener composition containing the same.

In order to achieve the above object,

There is provided a polydentate-type cationic surfactant represented by the following formula (1).

[Chemical Formula 1]

는 중성이며, R²가 C_1-5의 직쇄 또는 측쇄의 알킬일 경우

는 양이온이다.
In Formula 1, R ¹ is a C _8-24 alkenyl in which the alkyl, or one or more double bonds in the straight-chain or branched C _8-24 Al a straight or branched, R ² is absent, or C _1-5 X is halogen and Y is absent or methylsulfate. Here, when R ² is a member, Y is a member, and when R ² is a member

Is neutral and R < ² > is a straight or branched alkyl of C < _1-5 >

Is a cation.

The present invention also relates to a process for producing a compound represented by the formula (1)

(Step 1) of reacting the compound represented by the formula (2) with 1.5 to 2.5 equivalents of the compound represented by the formula (2) and 1 equivalent of the compound represented by the formula (3) to obtain the compound represented by the formula And a manufacturing method thereof.

[Reaction Scheme 1]

In the above Reaction Scheme 1, the straight or branched alkyl of R ¹ C _8-24 , or C _8-24 linear or branched alkenyl having at least one double bond, X is halogen, Is contained in the polymeric cationic surface active agent represented by the general formula (1).

Furthermore, the present invention relates to a process for producing a compound represented by the following formula 2,

A process for preparing a polymeric cationic surfactant according to claim 1, which comprises reacting 1 equivalent of a compound represented by the formula (1A) with 1.5 to 2.5 equivalents of a compound represented by the formula (4) to obtain a compound represented by the formula (1B) Of the present invention.

[Reaction Scheme 2]

In the above Reaction Scheme 2, R ¹ is straight or branched alkyl of C _8-24 , or straight or branched alkenyl of C _8-24 having at least one double bond, R ² is absent or C _1-5 And X is a halogen. The polydentate-type cationic surfactant represented by the formula (1B) is included in the polymeric cationic surfactant represented by the formula (1).

The present invention also relates to a polydentate-type cationic surfactant represented by the following formula (1A); And a polydentate-type cationic surfactant represented by the following formula (1B).

≪ EMI ID =

≪ RTI ID = 0.0 &

In the general formula 1A and 1B, R ¹ is a C _8-24 alkenyl in which the alkyl, or one or more double bonds in the straight-chain or branched C _8-24 Al a straight or branched, R ² is absent, or C _{1 -5} < / RTI > linear or branched alkyl, and X is halogen.

Further, the present invention relates to a polymeric cationic surfactant represented by the above formula (1A); And a polydentate-type cationic surfactant represented by the formula (1B). The present invention also provides an antistatic agent composition comprising at least one member selected from the group consisting of

The novel polydentate-type cationic surfactant having a large number of hydrophilic groups and hydrophobic groups according to the present invention, an efficient method for producing the same, and a fabric softening agent composition containing the same, wherein the polydentate-type cationic surfactant does not use a specific catalyst No catalyst removal process was required and the reaction proceeded at room temperature without decompression or pressurization, resulting in high yields while producing cationic surfactants in a competitive and environmentally friendly manner.

Furthermore, the present invention is superior in flexibility and antistatic property to the polyadentate-type cationic surfactants prepared in the present invention, as compared with the cationic surfactants conventionally used as the fabric softener or fabric softener composition. In addition, when they are mixed according to the length of the alkyl chain, they have excellent performance in that they exhibit good absorbency in use as a fabric softener and antistatic agent.

Hereinafter, the present invention will be described in detail.

The present invention, in order to achieve the above object,

There is provided a polydentate-type cationic surfactant represented by the following formula (1).

[Chemical Formula 1]

는 중성이며, R²가 C_1-5의 직쇄 또는 측쇄의 알킬일 경우

는 양이온이다.
In Formula 1, R ¹ is a C _8-24 alkenyl in which the alkyl, or one or more double bonds in the straight-chain or branched C _8-24 Al a straight or branched, R ² is absent, or C _1-5 X is halogen and Y is absent or methylsulfate. Here, when R ² is a member, Y is a member, and when R ² is a member

Is neutral and R < ² > is a straight or branched alkyl of C < _1-5 >

Is a cation.

The polydentate-type cationic surfactant represented by the formula (1) is a polydentate-type cationic surfactant characterized by being a polydentate-type cationic surfactant represented by the following formula (1A) or (1B).

≪ EMI ID =

≪ RTI ID = 0.0 &

Hereinafter, the cationic surfactant according to the present invention will be described in detail.

The present invention is directed to cationic surfactants having four hydrophilic groups (including two quaternary ammonium cations) and four hydrophobic groups.

In general, a surfactant having a long chain of hydrophobic groups or a plurality of hydrophobic groups has a problem in that the physical properties are excellent but the solubility in water is poor.

However, in the case of having a plurality of hydrophobic groups and a plurality of hydrophobic groups in one molecule, only one hydrophilic group of two or more hydrophilic groups forms a complex with opposite charge ions, and the other hydrophilic groups are arranged in the water phase to increase solubility in water. Therefore, it has better surface activity than single chain surfactants and exhibits excellent performance such as low critical micelle concentration (CMC), excellent foamability, high surface tension lowering ability, and low kraft point. In particular, it forms a very stable bay sicle and has a very good solubility in water, so that a high interface property can be obtained even with a small amount of use.

The present invention has an advantage that it has a large number of hydrophilic groups and has an increased solubility in water and excellent antistatic property, and a large number of cations are easily combined with a form capable of dispersing with the residual detergent after washing.

 In addition, it contains many hydrophobic groups to increase the flexibility of the beacles, and also serves as a functional carrier such as long lasting fragrance when used as a fabric softener. The cationic surfactant having a large number of hydrophilic groups and a large number of hydrophobic groups manufactured by the present invention exhibits high performance even with a small amount of use due to such a synergistic effect and can serve as a flexible, antistatic, excellent biodegradable and functional carrier have.

Preferably, R1 is a linear or branched C16-20 alkyl, or a linear or branched C16-20 alkenyl having at least one double bond, and X is a cationic surfactant, which is chlorine (Cl).

More preferably N1, N3-bis (3- (bis (3-octadecyloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy-N1, N1, N3, N3-tetramethylpropane- (3-octadecyloxy-2-hydroxypropyl) methylammonium) propyl) -2-hydroxy-1,3- -N1, N1, N3, N3-tetramethylpropane-1,3-diammonium dichloride bismethyl sulfate (hereinafter, Example 5).

As a result of evaluating the physical properties of the cationic surfactant according to the present invention, the physical properties of solubility, flexibility, chargeability and water absorbability are improved as compared with the conventional surfactants, and when they are mixed at a constant mixing ratio, (See Experimental Example 1). ≪ tb >< TABLE >

The present invention also relates to a process for producing a compound represented by the formula (1)

(Step 1) of reacting the compound represented by the formula (2) with 1.5 to 2.5 equivalents of the compound represented by the formula (2) and 1 equivalent of the compound represented by the formula (3) to obtain the compound represented by the formula And a manufacturing method thereof.

[Reaction Scheme 1]

In the above Reaction Scheme 1, the straight or branched alkyl of R ¹ C _8-24 , or C _8-24 linear or branched alkenyl having at least one double bond, X is halogen, Is contained in the polymeric cationic surface active agent represented by the general formula (1).

Hereinafter, a method for producing the polydentate-type cationic surfactant according to the present invention will be described in more detail.

In the present invention, an alkyl glycidyl ether is condensed with N, N-dimethylpropylenediamine to obtain N1, N1-bis- (3-alkoxy-2-hydroxypropyl) -N3, N3- (DMAPA, hereinafter referred to as Formula 2) was synthesized. In this DMA, it is possible to use a substance having 8 to 24 carbon atoms, which does not contain an unsaturated group, one, or two or more of which are saturated, or which contains a straight chain or a side chain.

In the present invention, epichlorohydrin was used as a linking group. Since the epichlorohydrin has a structure in which a halogen element having excellent reactivity and an epoxide ring are present together, there are two reaction sites capable of reacting. Since both of the reaction sites of epichlorohydrin have excellent reactivity with the tertiary amine, 2 moles of DMAPA reacts with the reaction sites at both ends of 1 mole of epichlorohydrin, respectively, so that epichlorohydrin Hydrin acts as a linkage and is synthesized into a structure with four hydrophilic groups (two quaternary ammonium ions) and four hydrophobic groups in one molecule.

 N3-bis (3- (bis (3 (meth) acrylate), which is a cationic surfactant having four hydrophilic groups (including two quaternary ammonium cations) and four hydrophobic groups through the condensation reaction of DMAPA and epichlorohydrin, N1, N3, N3-tetramethylpropane-1,3-diammonium dichloride (hereinafter referred to as Formula 1A) was obtained in a yield of 90% 99.9%.

  Generally, when a cationic surfactant is prepared through a condensation reaction, the reaction proceeds at a high temperature or a decompression and a pressurization process are added, and an additional process for removing the catalyst using the catalyst is required.

In the present invention, the reaction can proceed at a relatively low temperature by condensation reaction using epichlorohydrin. On the other hand, even if the reaction is carried out at a low temperature, the conversion efficiency is high and the reaction efficiency is high. Further, since the catalyst is not used, the purification process is simple since no additional process is required, and it is an effective reaction method that can solve the resource waste and environmental pollution problem in the use of the cationic surfactant.

As described above, in the reaction of DMAPA with epichlorohydrin to prepare a cationic surfactant, the reaction temperature is preferably 60 to 70 ° C. and the reaction time is preferably 6 to 10 hours. The reaction time is terminated when DMAPA and epichlorohydrin remain below 1% on the gas chromatogram, and the time is approx. 8 hours.

When the solvent is not used or the solvent is used, the reaction may be carried out in the presence of a solvent selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and isopentanol Or more can be further used.

Preferably, isopropanol is used as the solvent.

If the solvent is not used, the reaction proceeds, but in this case, a fever may occur and epichlorohydrin should be slowly added dropwise. In addition, the use of isopropanol can prevent the generation of heat and further improve the yield in that side reactions may occur.

At this time, the amount of isopropanol used is preferably 25% by weight in the final product. This is because it is necessary to remove isopropanol in order to obtain a pure cationic surfactant. Therefore, when the amount is too large, it may take a lot of time and cost in the removal step.

The solvent is preferably used in an amount of 10 to 40 parts by weight based on 100 parts by weight of the compound represented by the formula (1A) as the final product. More preferably 25 parts by weight.

Furthermore, the present invention relates to a process for producing a compound represented by the following formula 2,

A process for preparing a polymeric cationic surfactant according to claim 1, which comprises reacting 1 equivalent of a compound represented by the formula (1A) with 1.5 to 2.5 equivalents of a compound represented by the formula (4) to obtain a compound represented by the formula (1B) Of the present invention.

[Reaction Scheme 2]

In the above Reaction Scheme 2, R ¹ is straight or branched alkyl of C _8-24 , or straight or branched alkenyl of C _8-24 having at least one double bond, R ² is absent or C _1-5 And X is a halogen. The polydentate-type cationic surfactant represented by the formula (1B) is included in the polymeric cationic surfactant represented by the formula (1).

Hereinafter, a method for producing the polydentate-type cationic surfactant according to the present invention will be described in detail.

(3-alkoxy-2-hydroxypropyl) methylammonium) propyl) - (3-alkoxy-2-hydroxypropyl) methylammonium salt having four quaternary ammonium salts and four hydrophobic groups, quaternized with dimethyl sulfate. 2-hydroxy-N1, N1, N3, N3-tetramethylpropane-1,3-diammonium dichloride A bismethyl sulfate compound (hereinafter referred to as the formula 1B) is prepared at a yield of 90 to 99.9%.

In preparing the cationic surfactant, the reaction temperature is preferably 60 to 70 ° C. and the reaction time is preferably 6 to 10 hours. The reaction time is terminated when the DMAPA and epichlorohydrin remain below 1% on the gas chromatogram and the time is preferably about 8 hours.

When the solvent is not used or the solvent is used, the reaction may be carried out in the presence of a solvent selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and isopentanol Or more can be further used.

Preferably, isopropanol is used as the solvent.

If the solvent is not used, the reaction proceeds, but in this case, a fever may occur and epichlorohydrin should be slowly added dropwise. In addition, the use of isopropanol can prevent the generation of heat and further improve the yield in that side reactions may occur.

At this time, the amount of isopropanol used is preferably 25% by weight in the final product. This is because it is necessary to remove isopropanol in order to obtain a pure cationic surfactant. Therefore, when the amount is too large, it may take a lot of time and cost in the removal step.

The solvent is preferably used in an amount of 10 to 40 parts by weight based on 100 parts by weight of the compound represented by the formula (1A) as the final product. More preferably 25 parts by weight.

The present invention also relates to a polydentate-type cationic surfactant represented by the following formula (1A); And a polydentate-type cationic surfactant represented by the following formula (1B).

≪ EMI ID =

≪ RTI ID = 0.0 &

In the general formula 1A and 1B, R ¹ is a C _8-24 alkenyl in which the alkyl, or one or more double bonds in the straight-chain or branched C _8-24 Al a straight or branched, R ² is absent, or C _{1 -5} < / RTI > linear or branched alkyl, and X is halogen.

Hereinafter, the fabric softener composition according to the present invention will be described in detail.

In the fabric softener composition according to the present invention, the polydentate-type cationic surfactants represented by the above-mentioned general formulas (1A) and (1B) may be used alone or in combination of compounds having different carbon chain lengths of the substituent R ¹ .

Alone, preferably in the above formula (1A) or (1B), R ¹ is a straight-chain or branched C _16-20 alkyl, or a linear or branched C _16-20 alkenyl having at least one double bond and X is chlorine Cl) is a cationic surfactant.

More preferably, it is the cationic surfactant of Example 2 or 5.

The mixture is preferably a cationic surfactant in which the ratio of Example 2: Example 4 is 50:50.

More preferably, in the fabric softener composition according to the present invention,

15-25 parts by weight of a compound wherein the substituent R < ¹ > is straight chain alkyl of C < ₁₂ > in the polydentate type cationic surfactant represented by the above formula (1A);

35-45 parts by weight of a compound wherein the substituent R < ¹ > is straight chain alkyl of C < ₁₈ > in the polydentate-type cationic surfactant represented by the above formula (1A); And

And 35 to 45 parts by weight of a compound in which the substituent R ¹ is C ₁₈ linear alkyl in the polydentate-type cationic surfactant represented by Formula 1B may be used in combination.

20 parts by weight of Example 1; 40 parts by weight of Example 2; And 40 parts by weight of Example 5 are mixed and used (see Experimental Example 1).

In addition, the fabric softener composition according to the present invention may further contain a nonionic surfactant as an emulsifier to the extent that the object of the present invention is not impaired. The non-ionic surfactants include C _10-20 polyoxyethylene ( _2-50 moles) alkyl-alkenyl ethers or polyoxyethylene (2-50 moles) -alkyl phenyl ethers (2-50 moles); C _10-20 polyoxyethylene ( _2-50 moles) alkyl-alkenyl esters or polyoxyethylene (2-50 moles) alkyl-hydroxy fatty acid esters; Sorbitan fatty acid alkyl esters and their ethylene oxide (15 to 40 mol) adducts, polyoxyethylene (1 to 30 mol) alkyl-alkenyl amides; Polyoxyethylene (1 to 50 mol) alkyl-alkenylamines, glyceryl monoalkyl-alkenyl esters; Ethylene oxide adduct of hydrogenated castor oil (2 to 50 mol); Alkylamine oxides; Or amidopropylamine oxide. These surfactants may be used alone or in a mixture of two or more. The content of the nonionic surfactant is preferably 0.1 to 30% by weight with respect to the cationic surfactant of the present invention.

Further, the fabric softener composition according to the present invention may contain a dispersion stabilizer. Examples of the dispersion stabilizer include at least one selected from the group consisting of C _1-7 lower alcohols, C _12-20 higher alcohols, polyethylene glycols having a molecular weight of 400 to 20000, magnesium chloride, sodium chloride, calcium chloride and sodium nitrate Can be used. The content of the dispersion stabilizer is preferably 0.1 to 30% by weight based on the total weight of the cationic surfactant of Formula 1 according to the present invention.

In addition, a small amount of fragrance, preservative, bactericide, fluorescent whitening agent, dye, antioxidant, antifoaming agent and the like which are generally used as additives for the fabric softener can be added to the fiber composition within a range not affecting the stability of the product.

Further, the present invention relates to a polydentate-type cationic surfactant represented by the following formula (1A); And a polydentate-type cationic surfactant represented by the following general formula (1B): < EMI ID = 1.0 >

≪ EMI ID =

≪ RTI ID = 0.0 &

In the general formula 1A and 1B, R ¹ is a C _8-24 alkenyl in which the alkyl, or one or more double bonds in the straight-chain or branched C _8-24 Al a straight or branched, R ² is absent, or C _{1 -5} < / RTI > linear or branched alkyl, and X is halogen.

Hereinafter, the antistatic agent composition according to the present invention will be described in detail.

In the antistatic agent composition according to the present invention, the polydentate-type cationic surfactants represented by the above-mentioned general formulas (1A) and (1B) may be used alone or in combination with a compound having a different carbon chain length of the substituent R ¹ .

Alone, preferably in the above formula (1A) or (1B), R ¹ is a straight-chain or branched C _16-20 alkyl, or a linear or branched C _16-20 alkenyl having at least one double bond and X is chlorine Cl) is a cationic surfactant.

More preferably, it is the cationic surfactant of Example 2 or 5.

The mixture is preferably a cationic surfactant in which the ratio of Example 2: Example 4 is 50:50.

More preferably, in the antistatic agent composition according to the present invention,

15-25 parts by weight of a compound wherein the substituent R < ¹ > is straight chain alkyl of C < ₁₂ > in the polydentate type cationic surfactant represented by the above formula (1A);

35-45 parts by weight of a compound wherein the substituent R < ¹ > is straight chain alkyl of C < ₁₈ > in the polydentate-type cationic surfactant represented by the above formula (1A); And

And 35 to 45 parts by weight of a compound in which the substituent R ¹ is C ₁₈ linear alkyl in the polydentate-type cationic surfactant represented by Formula 1B may be used in combination.

20 parts by weight of Example 1; 40 parts by weight of Example 2; And 40 parts by weight of Example 5 are mixed and used (see Experimental Example 1)

Hereinafter, the present invention will be described in detail with reference to Production Examples, Examples and Experimental Examples.

However, the following Production Examples and Examples are illustrative of the present invention, and the content of the present invention is not limited by the following Production Examples and Examples.

Preparation Example 1: Preparation of N 1, N 3 -bis (3- (bis (3-dodecyloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy- N 1, N 1, N 3, N 3 -tetra Bis (3-dodecyloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy-N1, N1, N3, N3-tetramethylpropan- 1,3-diammonium dichloride

(3-dodecyloxy-2-hydroxypropyl) -N3, N3-dimethyl-1, 3-dodecyloxy-2-hydroxypropyl) -polysiloxane manufactured by National Patent Application No. 2012-0000833 at room temperature in a reactor equipped with a stirrer, a thermometer and a condenser. 93.91 g (0.16 mol) of 3-propylenediamine and 34.8 g of isopropanol were charged and stirred. 8.34 g of hydrochloric acid was slowly added dropwise thereto. After stirring for 10 to 20 minutes, 7.41 g (0.08 mol) of epichlorohydrin was slowly added dropwise using a dropping funnel. After completion of dropwise addition, the mixture was stirred at 60 to 70 DEG C for about 8 hours. Thin film chromatography and gas chromatography were used to confirm the progress of the reaction. After completion of the reaction, the reaction was concentrated to obtain 95.71 g of the compound represented by Preparation Example 1 (yield: 95.71%). The reaction structure was confirmed by nuclear magnetic resonance (NMR) and infrared spectroscopy (IR).

IR result

OH stretching 3345.43 cm ^-1 ; CH stretching 2925.48, 2854.79 cm < ^{-1 &} gt ;; CH bending 1465.80 cm ^-1 ; CN stretching 1118.71 cm ^-1

proton NMR results

? 0.86 to 0.90: t, 12H (-C H ₃ ); 1.13 to 1.26: m, 72H (-C H ₂ -); 1.55-1.66: m, 8H (-C H ₂ -CH ₂ -O-); 2.37 to 2.78: m, 16H (-C H ₂ -CH ₂ -N ⁺ -, -C H ₂ -N-); ^{3.30: s, 8H (-N +} (C H 3) 2); 3.24 to 3.78: m, 24H (-C H ₂ -OC H ₂ -, -C H ₂ -N ⁺ -); 3.82~3.85: m, 4H (-N- CH 2 -C H OH-CH 2 -N + -); 4.05-4.12: m, 2H (-N ⁺ -CH ₂ -C H OH-CH ₂ -N ⁺ -)

Preparation Example 2: Preparation of N1, N3-bis (3- (bis (3-octadecyloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy-N1, N1, N3, Bis (3-octadecyloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy-N1, N1, N3, N3-tetramethylpropan- 1,3-diammonium dichloride

The synthesis of the above compound was carried out in the same manner as in Example 1. However, instead of N1, N1-bis- (3-octadecyloxy-2-hydroxypropyl) -N3, N3-dimethyl-1,3-propylenediamine in place of N1, N1- -Hydroxypropyl) -N3, N3-dimethyl-1,3-propylenediamine, 129.97 g of the compound represented by the above Preparation Example 2 (yield: 99.09%) was prepared. The reaction structure was confirmed by NMR and IR.

IR result

OH stretching 3398.46 cm ^-1 ; CH stretching 2918.56, 2850.29 cm ^-1 ; CH bending 1468.39 cm ^-1 ; CN stretching 1125.18 cm ^-1

NMR results

? 0.86 to 0.90: t, 12H (-C H ₃ ); 1.13 to 1.26: m, 120H (-C H ₂ -); 1.55-1.66: m, 8H (-C H ₂ -CH ₂ -O-); 2.37 to 2.78: m, 16H (-C H ₂ -CH ₂ -N ⁺ -, -C H ₂ -N-); ^{3.30: s, 8H (-N +} (C H 3) 2); 3.24 to 3.78: m, 24H (-C H ₂ -OC H ₂ -, -C H ₂ -N ⁺ -); 3.82~3.85: m, 4H (-N- CH 2 -C H OH-CH 2 -N + -); 4.05-4.12: m, 2H (-N ⁺ -CH ₂ -C H OH-CH ₂ -N ⁺ -)

Preparation Example 3: Preparation of N1, N3-bis (3- (bis (3-octadec-9-ynyloxy-2- hydroxypropyl) amino) propyl) -2- N3-bis (3- (bis (3-octadec-9-yloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy-N1, N1-tetramethylpropane-1,3-diammonium dichloride , N3, N3-tetramethylpropan-1,3-diammonium dichloride)

The synthesis of the above compound was carried out in the same manner as in Example 1. Instead, N1, N1-bis- (3-octadec-9-ynyl) propylenediamine was used in place of N1, N1-bis- (3-dodecyloxy- Oxy-2-hydroxypropyl) -N3, N3-dimethyl-1,3-propylenediamine, 129.24 g of the compound represented by the above-mentioned Preparation Example 3 (yield: 99.02%) was prepared. The reaction structure was confirmed by NMR and IR.

IR result

OH stretching 3349.73 cm ^-1 ; CH stretching 2926.86, 2855.24 cm ^-1 ; CH bending 1464.64 cm ^-1 ; CN stretching 1121.35 cm ^-1

NMR results

? 0.86 to 0.90: t, 12H (-C H ₃ ); 1.13 to 1.26: m, 88H (-C H ₂ -); 1.55-1.66: m, 8H (-C H ₂ -CH ₂ -O-); 1.98 to 2.02: m, 16H (-C H ₂ -CH = CH-); 2.37 to 2.78: m, 16H (-C H ₂ -CH ₂ -N ⁺ -, -C H ₂ -N-); ^{3.30: s, 8H (-N +} (C H 3) 2); 3.24 to 3.78: m, 24H (-C H ₂ -OC H ₂ -, -C H ₂ -N ⁺ -); 3.82~3.85: m, 4H (-N- CH 2 -C H OH-CH 2 -N + -); 4.05-4.12: m, 2H (-N ⁺ -CH ₂ -C H OH-CH ₂ -N ⁺ -); 5.33-5.36: m, 8H (-C H = C H- )

Preparation Example 4: Preparation of N1, N3-bis (3- (bis (3-dodecyloxy-2-hydroxypropyl) methylammonium) propyl) -2-hydroxy-N1, N1, N3, Bis (3-dodecyloxy-2-hydroxypropyl) methylammonium) propyl) -2-hydroxy-N1, N1, N3, N3 -tetramethylpropan-1,3-diammonium dichloride bismethylsulfate)

97.9 g (0.075 mol) of the compound of Preparation Example 1 and 38.9 g of isopropanol were added to a reactor equipped with a stirrer, a thermometer and a condenser at room temperature and stirred at 30 to 35 ° C. 18.9 g (0.15 mol) of dimethyl sulfate was slowly dropped thereinto using a dropping funnel. After completion of dropwise addition, the mixture was stirred at 60 to 70 DEG C for about 8 hours. The progress of the reaction was confirmed by thin layer chromatography and gas chromatography. After completion of the reaction, the reaction mixture was concentrated to obtain 113.86 g of the compound represented by Preparation Example 4 (yield: 96.00%). The reaction structure was confirmed by NMR and IR.

IR result

OH stretching 3381.46 cm ^-1 ; CH stretching 2925.81, 2854.74 cm ^-1 ; CH bending 1465.04 cm ^-1 ; CN stretching 1120.68 cm ^-1

NMR results

? 0.86 to 0.90: t, 12H (-C H ₃ ); 1.13 to 1.26: m, 72H (-C H ₂ -); 1.55-1.66: m, 8H (-C H ₂ -CH ₂ -O-); ^{3.30: s, 12H (-N +} (C H 3) 2); 3.32 to 3.48: m, 36H (-C H ₂ -OC H ₂ -, -C H ₂ -N ⁺ -); 3.72: s, 6H (-SOC H 3); 4.05~4.12: m, 5H (-C H OH-CH 2 -N + -)

Preparation Example 5: Preparation of N1, N3-bis (3- (bis (3-octadecyloxy-2-hydroxypropyl) methylammonium) propyl) -2- Bis (3-octadecyloxy-2-hydroxypropyl) methylammonium) propyl) -2-hydroxy-N1, N1, N3, N3-tetramethylpropan-1,3-diammonium dichloride bismethylsulfate)

The synthesis of the compound was carried out in the same manner as in Example 4. However, when N1, N3-bis (3- (bis (3-dodecyloxy-2-hydroxypropyl) amino) propyl) -2- N3-bis (3- (bis (3-octadecyloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy-N1, N1, N3, N3-tetramethyl Propane-1,3-diammonium dichloride, 135.94 g of the title compound (yield: 95.81%) was prepared. The reaction structure was confirmed by NMR and IR.

IR result

OH stretching 3366.68 cm ^-1 ; CH stretching 2924.73, 2854.70 cm < ^{-1 &} gt ;; CH bending 1466.71 cm ^-1 ; CN stretching 1117.39 cm ^-1

NMR results

? 0.86 to 0.90: t, 12H (-C H ₃ ); 1.13 to 1.26: m, 120H (-C H ₂ -); 1.55-1.66 m, 8H (-C H ₂ -CH ₂ -O-) 3.30 s, 12H (-N ⁺ (C H ₃ ) ₂ ) 3.32-3.48 m, 36H (-C H ₂ -OC H ^{_{2 -, -C H 2 -N +}} -) 3.72: s, 6H (-SOC H 3) 4.05~4.12: m, 5H (-C H OH-CH 2 -N + -)

Preparation Example 6: Preparation of N1, N3-bis (3- (bis (3-octadec-9-ynyloxy-2- hydroxypropyl) methylammonium) propyl) -2- , N3-tetramethylpropane-1,3-diammonium dichloride bismethyl sulfate (N1, N3-bis (3- (bis (3-octadec-9-yloxy-2-hydroxypropyl) methylammonium) propyl) -N1, N1, N3, N3-tetramethylpropan-1,3-diammonium dichloride bismethylsulfate)

The synthesis of the compound was carried out in the same manner as in Example 4. However, when N1, N3-bis (3- (bis (3-dodecyloxy-2-hydroxypropyl) amino) propyl) -2- (3-octadec-9-ynyloxy-2-hydroxypropyl) amino) propyl) -2-hydroxy-N1, N1, N3, N3 -Tetramethylpropane-1,3-diammonium dichloride, 137.19 g of the compound represented by Production Example 6 (yield: 97.11%) was prepared. The reaction structure was confirmed by NMR and IR.

IR result

OH stretching 3414.77 cm ^-1 ; CH stretching 2918.59, 2850.46 cm ^-1 ; CH bending 1468.88 cm ^-1 ; CN stretching 1124.16 cm ^-1

NMR results

? 0.86 to 0.90: t, 12H (-C H ₃ ); 1.13 to 1.26: m, 88H (-C H ₂ -); 1.55-1.66: m, 8H (-C H ₂ -CH ₂ -O-); ^{3.30: s, 12H (-N +} (C H 3) 2); 3.32 to 3.48: m, 36H (-C H ₂ -OC H ₂ -, -C H ₂ -N ⁺ -); 3.72: s, 6H (-SOC H 3); 4.05~4.12: m, 5H (-C H OH-CH 2 -N + -); 5.33-5.36: m, 8H (-C H = C H- )

Comparative Preparation Example 1 A cationic surfactant (ester-quat)

Triethylene amine (1.254 mol), oleic acid (0.535 mol), stearic acid (1.035 mol) and p-toluenesulfonic acid (0.35 mmol) were mixed. The inside of the reactor was put into a nitrogen atmosphere, and the mixture was stirred at 140 ° C for 3 hours, then heated to 145 ° C and stirred for 12 hours. After completion of the reaction, the reaction temperature was lowered to 80 ° C, isopropanol (149.2 g) was added, and after cooling to 55 ° C, dimethyl sulfate (1.15 mol) was slowly added dropwise. The mixed solution was stirred at 60 ° C for 6 hours to terminate the reaction, and then purified to yield the desired compound in the form of a pale yellow solid.

≪ Comparative Production Example 2 > The imidazoline type cationic surfactant

Diethylene triamine (0.5 mol) was slowly added to oleic acid (0.3 mol) and stearic acid (0.65 mol) heated to 80-90 占 폚. The reaction temperature was 150-160 占 폚 and stirred for 3 hours. Next, the reaction was further continued at 160-170 ° C under a vacuum of 0.5-1 mmHg for 3 hours. When the reaction was completed, the temperature was lowered to 50 ° C, dimethylsulfate (0.6 mol) was added, The reaction was carried out for 6 hours to prepare the target compound .

Example 1: Use of the surfactant according to the present invention alone

100 parts by weight of the surfactant prepared in Preparation Example 1 was used.

Example 2: Use of surfactant according to the present invention alone

100 parts by weight of the surfactant prepared in Preparation Example 2 was used.

≪ Example 3 > The use of the surfactant according to the present invention alone

100 parts by weight of the surfactant prepared in Preparation Example 3 was used.

≪ Example 4 > The use of the surfactant according to the present invention alone

100 parts by weight of the surfactant prepared in Preparation Example 4 was used.

Example 5: Use of surfactant according to the present invention alone

100 parts by weight of the surfactant prepared in Preparation Example 5 was used.

Example 6: Use of the surfactant according to the present invention alone

100 parts by weight of the surfactant prepared in Preparation Example 6 was used.

Example 7 Mixed use of the surfactant according to the present invention

30 parts by weight of the surfactant prepared in Preparation Example 2 and 70 parts by weight of the surfactant prepared in Preparation Example 4 were mixed and used.

≪ Example 8 > Mixed use of surfactant according to the present invention

50 parts by weight of the surfactant prepared in Preparation Example 2 and 50 parts by weight of the surfactant prepared in Preparation Example 4 were mixed and used.

Example 9: Mixed use of the surfactant according to the present invention

70 parts by weight of the surfactant prepared in Preparation Example 2 and 30 parts by weight of the surfactant prepared in Preparation Example 4 were mixed and used.

≪ Example 10 > Mixed use of the surfactant according to the present invention

20 parts by weight of the surfactant prepared in Preparation Example 1, 40 parts by weight of the surfactant prepared in Preparation Example 2 and 40 parts by weight of the surfactant prepared in Preparation Example 5 were used.

≪ Example 11 > Mixed use of the surfactant according to the present invention

40 parts by weight of the surfactant prepared in Preparation Example 2, 20 parts by weight of the surfactant prepared in Preparation Example 3 and 40 parts by weight of the surfactant prepared in Preparation Example 5 were used.

Example 12: Mixed use of the surfactant according to the present invention

40 parts by weight of the surfactant prepared in Preparation Example 2, 20 parts by weight of the surfactant prepared in Preparation Example 4 and 40 parts by weight of the surfactant prepared in Preparation Example 5 were mixed and used.

≪ Example 13 > Mixed use of the surfactant according to the present invention

40 parts by weight of the surfactant prepared in Preparation Example 2, 40 parts by weight of the surfactant prepared in Preparation Example 5 and 20 parts by weight of the surfactant prepared in Preparation Example 6 were used.

≪ Comparative Example 1 > Conventional use of a conventional surfactant

100 parts by weight of the surfactant prepared in Comparative Preparation Example 1 was used.

≪ Comparative Example 2 > Conventional use of a conventional surfactant

100 parts by weight of the surfactant prepared in Comparative Preparation Example 2 was used.

≪ Comparative Example 3 > Mixed use of surfactant according to the prior art and the present invention

40 parts by weight of the surfactant prepared in Preparation Example 2, 40 parts by weight of the surfactant prepared in Preparation Example 5 and 20 parts by weight of the surfactant prepared in Comparative Preparation Example 1 were used.

≪ Comparative Example 4 > Mixed use of surfactant according to the prior art and the present invention

40 parts by weight of the surfactant prepared in Preparation Example 2, 40 parts by weight of the surfactant prepared in Preparation Example 5 and 20 parts by weight of the surfactant prepared in Comparative Preparation Example 2 were used.

<Experimental Example 1> Evaluation of physical properties of the surfactant according to the present invention

In order to examine the physical properties of the surfactant according to the present invention, the flexibility, chargeability and water absorption of the cationic surfactants of Examples 1 to 5 and Comparative Examples 1 to 13 were measured.

1. Flexible force measurement

1 or 3% by weight of a surfactant aqueous solution sample was prepared and the amount of adsorption to gold and oxidized silica gel was measured using Quartz Crystal Microbalance (Q-Sense E4; Q-Sense). At this time, the higher the adsorption amount, the higher the flexibility.

2. Antistatic measurement

A 0.25% by weight aqueous surfactant solution was prepared and padded to cotton and PET (polyester), dried at 105 ° C for 2 minutes, treated at 160 ° C for 2 hours, and treated at 180 ° C for 30 seconds After that, the treated cloth was maintained at a relative humidity of 60% for 24 hours, and resistance was measured with an insulation resistance tester (Supermeghmmeter). At this time, the lower the resistance value, the better the antistatic property.

3. Absorption measurement

After the sample was prepared in the same manner as the above antistatic property measurement, the time of absorption by using the dropping dropping method was measured. The shorter the time of absorption, the better the absorbency.

[Table 1]

As shown in Table 1, when the polydentate type cationic surfactants according to the present invention were each used alone (Examples 1 to 6), when conventional cationic surfactants were used (Comparative Examples 1 and 2) It is found that the flexibility, charging property, and absorbability are improved by about 3 to 12 times as much as that of the nonwoven fabric.

Flexibility and antistatic properties showed the best results when the number of alkyl groups was 18 (Example 2 and Example 5).

On the other hand, when the surfactant according to the present invention was used in combination (Examples 7 to 13), it exhibited significantly superior flexibility, chargeability, and absorbency than the case of using alone (Examples 1 to 6).

It was found that Example 8 obtained by mixing Example 2 and Example 4 prepared in the present invention at a weight ratio of 50:50 was found to have the most excellent flexibility and antistatic property.

In the case of the water absorbent, the best results were obtained in the case of Example 1 in which the alkyl length was short, and in the case of Example 8 in which the softening power and the antistatic property were excellent, the water absorbency was relatively poor.

Considering both flexibility and antistatic property and absorbency, the longer the alkyl chain, the better the flexibility and chargeability, while the water absorption is somewhat poor. However, it is mixed with the cationic surfactant including the chain having short alkyl chain or medium unsaturated group It is good to do.

On the other hand, in the present invention, the most excellent properties were shown in Example 1, Production Example 2, and Production Example 5, which were mixed at a weight ratio of 20:40:40 (Example 10).

Compared with the cationic surfactants used in conventional fabric softener or fabric softener compositions, the polydentate cationic surfactants prepared according to the present invention have excellent flexibility and antistatic properties, When they are mixed together, they have good absorbency and can be used as a fabric softener and an antistatic agent having excellent performance.

Claims (10)

delete delete delete delete 15 to 25 parts by weight of a compound wherein the substituent R &lt; ¹ &gt; is straight chain alkyl of C &lt; ₁₂ &gt; in the polydentate type cationic surfactant represented by the following formula (1A);
35 to 45 parts by weight of a compound in which the substituent R &lt; ¹ &gt; is straight chain alkyl of C &lt; ₁₈ &gt; in the polythanate type cationic surfactant represented by the following formula (1A); And
And 35 to 45 parts by weight of a compound in which the substituent R ¹ is C ₁₈ straight-chain alkyl in the poly (indole type) cationic surfactant represented by the following formula (1B):
&Lt; EMI ID =

(In the formula (1A)
R ¹ is C ₁₂ or C ₁₈ linear alkyl;
X is halogen;

&Lt; RTI ID = 0.0 &

(In the above formula (1B)
R &lt; ¹ &gt; is straight chain alkyl of C &lt; ₁₈ &gt;;
R ² is C _1-5 linear or branched alkyl;
And X is halogen.
delete delete 15 to 25 parts by weight of a compound wherein the substituent R &lt; ¹ &gt; is straight chain alkyl of C &lt; ₁₂ &gt; in the polydentate-type cationic surfactant represented by the following formula (1A);
35 to 45 parts by weight of a compound in which the substituent R &lt; ¹ &gt; is straight chain alkyl of C &lt; ₁₈ &gt; in the polythanate type cationic surfactant represented by the following formula (1A); And
And 35 to 45 parts by weight of a compound wherein R ¹ is C ₁₈ straight chain alkyl in the polydentate type cationic surfactant represented by the following formula (1B):
&Lt; EMI ID =

(In the formula (1A)
R ¹ is C ₁₂ or C ₁₈ linear alkyl;
X is halogen;

&Lt; RTI ID = 0.0 &

(In the above formula (1B)
R &lt; ¹ &gt; is straight chain alkyl of C &lt; ₁₈ &gt;;
R ² is C _1-5 linear or branched alkyl;
And X is halogen. delete delete