WO2011099810A2 - Method for preparing a cationic surfactant - Google Patents

Abstract

The present invention relates to a method for preparing a cationic surfactant containing a compound of chemical formula 1, wherein the method comprises performing esterification on monomeric acid and triethanolamine or methyl dimethylamine, and quaternizing thus-obtained product using dimethyl sulfate or methyl chloride. The cationic surfactant prepared by the method of the present invention uses reaction by-products, thus enabling the re-use of resources and accomplishing economic advantages, and achieving improved low temperature stability and chromatic stability, thus can be valuably used in softeners, hair care products and the like.

Description

 【Specification】

 [Name of invention]

 Method for preparing cationic surfactant

Technical Field

 The present invention relates to a method for preparing a cationic surfactant having excellent phase stability, dispersibility and discoloration stability.

Background Art

 Although dimethyl dialkyl ammonium chloride (DDAC) has conventionally been used as a cationic surfactant for softening fibers or hair or providing industrial softness and antistatic function, biodegradability Low usage is gradually decreasing. Accordingly, studies are being actively conducted to prepare cationic surfactants using various derivatives of quaternary ammonium salts having functional groups that can be decomposed such as esters or amides in alkyl groups.

Representatively, WO 94/07978 discloses softeners and hair care products prepared using quaternized cationic surfactants derived from triethanolamine, and WO 93/23510. Discloses concentrated fiber softeners and biodegradable fiber softener compositions prepared using cationic surfactants having ester linkages to two hydrophobic groups, and WO 92/15745 discloses imidazolines or imidas. Disclosed is a concentrated fabric softener composition prepared using a sleepy ester, a linear fatty alcohol ethoxylate, a polydialkylsiloxane, or the like. In addition, International Patent Publication No. WO 94/14935 discloses a concentrated fiber soft dispersant comprising a quaternary ammonium compound prepared using triethanolamine and fatty acids, and International Patent Publication No. WO 94/13772 discloses A highly concentrated fibrous softener prepared using a small amount of a quaternary ammonium compound comprising an ester group and a nonionic dispersant is disclosed.

 However, the fatty acids used in the preparation of the compounds for the preparation of cationic surfactants are fatty acids of oils extracted from palm, palm oil, tallow, etc. As the demand of biodiesel spreads, the price of fatty acids increases. Accordingly, there is a demand for fatty acid raw materials that can be cheaper and recycle resources.

 On the other hand, dimer acid represented by the following formula (A) is mainly used to improve the color brightness or stability of the ink using a polyamide resin, such as epoxy, flexo ink, gravure ink, as a main raw material of polyamide. Dimer acid is also applied to the production of coatings, adhesives, castings, or laminating agents made from polyesters, epoxy resins, etc., and other petroleum products additives, surfactants, plasticizers, hydraulic agents, linoleum, rubber additives, pesticides, It is also used as a raw material for foamed plastics.

 [Formula A]

 cm

 (CHirJs

、어 I

Er

COOH

The dimer acid may be prepared by reacting fatty acids mainly composed of unsaturated fatty acids of oleic acid and linoleic acid such as soybean oil and oil, and in this process, monomeric acid and trimeric acid which are not formed as dimer acid are produced as by-products. Accordingly, the present inventors, by the transesterification reaction and quaternization using the monomer acid produced as a by-product during the production process of the dimer acid, the phase stability, dispersibility and discoloration stability due to isostearic acid and isooleic acid contained in the monomer acid It was found that good compounds can be prepared and used to prepare cationic surfactants to complete the present invention.

[Start of invention]

 Accordingly, it is an object of the present invention to provide a method for producing a cationic surfactant excellent in phase stability, dispersibility and discoloration stability. In order to achieve the above object, the present invention

 1) transesterification of amine or triethanolamine with monomeric acid and methyldiethane, which are by-products generated during the production of dimer acid; And

 2) cationic surfactant comprising a compound of formula 1, comprising quaternizing the product obtained in step 1) with a quaternizing agent selected from the group consisting of dimethyl sulfate, methyl chloride and diethyl sulfate Providing a method for preparing the agent:

 [Formula 1]

R-GH ₃ + 入

 In the above formula,

Ri, R ₂ , and R ₃ are each independently CH ₃ , —CH ₂ CH ₂ OH or —CH ₂ CH ₂ 0a R _4, wherein R ₄ is omega-6 (ω-6) to omega-12 ( a fatty acid group of d2-22 derived from a monomeric acid including isostearic acid and isooleic acid having a methyl group branched at a carbon position of ω-12);

X is halogen, CH ₃ S0 ₄ or C ₂ H ₆ S0 ₄ . Best Embodiment of the Invention

 The present invention provides a method for preparing a cationic surfactant comprising a compound of formula (I):

[Formula 1]

 In the above formula,

Ri, R ₂ , and R ₃ are independently of each other CH ₃ , —CH ₂ CH ₂ OH or —CH ₂ CH ₂ 0a) R _4, wherein R ₄ is omega-6 (ω-6) to omega-12 (ω- the fatty acid group of ₂₂ to 12) in the carbon position of the methyl group attached to the isostearic acid and isophthalic acid-derived monomer containing oleic acid of ₁₂ C;

X is halogen, CH ₃ S0 ₄ or C ₂ H ₆ S0 ₄ . The process of the present invention comprises the steps of: 1) transesterifying monomeric acid and methyldiethanolamine or triethanolamine; And 2) quaternizing the product obtained in step 1) with a quaternizing agent selected from the group consisting of dimethyl sulfate, methyl chloride and diethyl sulfate.

 Preparation process of the cationic surfactant comprising the compound of Formula 1 according to the present invention is transesterification reaction using monomeric acid and methyl diethanolamine or triethanolamine (step 1); And quaternization reaction (step 2) using a quaternizing agent selected from the group consisting of dimethylsulfate, methylchloride and diethylsulfate.

 Specifically, in step 1) of the present invention, the monomeric acid may be transesterified using methyldiethanolamine or triethanolamine.

The monomeric acid may be a by-product generated during the preparation of dimer acid, and specifically, Douglas A. Burg et al, Journal of the American Oil Chemists' Society (JAOCS), Vol 68, no. 8, p.6 (X)], reacting the dimer acid from about 60% to 80% depending on the reaction conditions by reacting the reaction under a temperature and a high pressure of about 25 CTC using soybean oil or oil. And about 20% to 40% of monomeric acid and trimeric acid may be obtained as a by-product. The dimer acid and trimeric acid may be purified to obtain a monomeric acid. The monomeric acid thus produced may be a fatty acid having a unique isoalkyl structure such as palmitic acid, stearic acid, oleic acid, linoleic acid, and isostearic acid and isooleic acid. And as a main component, a compound of dimer acid, cyclic or aromatic structure may be common depending on the distillation method.

 In general, isostearic acid represents a structure in which a methyl group is branched at a carbon position of omega-2 (ω-2) represented by the following formula (2). Most isostearic acids on the market also have this structure. However, isostearic acid contained in the monomeric acid used in the present invention is represented by the following general formula (3), which is not an end of the carbon chain, that is, omega-6 (ω-6) to omega-12 (α) -12) ( For example, the structure in which a methyl group is branched at the carbon position of omega-9 carbon position) is shown.

 The monomeric acid of the present invention is characterized by containing such isostearic acid and isooleic acid in an amount of 1% by weight or more, preferably 7 to 60% by weight based on the total amount of monomeric acid.

상기 이소스테아린산의 녹는점은 o°c 이하로서， 일반 스테아린산의 녹는점 이 5(rc 이상인 것과 비교하여 우수한 물성을 갖고 있지만， 고가의 가격 때문에 경 제성 이 없었다. 하지 만， 본 발명에서는 다이머산의 부산물로 존재하는 모노머산을 이용함으로써 상기 모노머산에 함유되어 있는 이소스테아린산을 활용할 수 있으므로， 물성 이 우수하면서도 가격 경 쟁력 이 있고， 또한 자원을 재활용할 수 있는 양이온성 계면활성제를 제조할 수 있다. [Formula 2]

The melting point of isostearic acid is below o ° c, and the melting point of general stearic acid is 5 (rc or more). However, the melting point of isostearic acid does not have economic properties due to the high price. By using the monomeric acid present as a by-product, it is possible to utilize the isostearic acid contained in the monomeric acid, thereby preparing a cationic surfactant having excellent physical properties and competitive price and recyclable resources.

 The transesterification reaction is used to react monomeric acid, methyldiethanolamine or triethanolamine without solvent, and may be performed at a reaction temperature of 160 to 20 CTC for a reaction time of 2 to 8 hours. The monomer acid is preferably used in the amount of 1.5 to 2.2 equivalents of methyl diethan based on amine or triethanolamine. When the amount of the monomeric acid is less than 1.5 equivalents, the monoester content is increased, and when the amount of the monomer acid is more than 2.2 equivalents, the amount of the triester is increased, thereby deteriorating physical properties and performance.

 In step 2) of the present invention, the product obtained after the transesterification in step 1) is quaternized with a quaternizing agent selected from the group consisting of dimethyl sulfate, methyl chloride and diethyl sulfate in a reaction mixture. The compound of 1 can be prepared. Quaternization reactions can use conventional methods.

 The quaternized reaction mixture is ethanol (ethyl alcohol), propyl alcohol, hexylene glycol, butyl alcohol, isopropyl alcohol, ethylene glycol as ethylene glycol. ), Glycerine, propylene glycol, propylene glycol, polyethylene glycol, and one or more of two or more common primary, secondary, tertiary or polyhydric alcohols selected from the group consisting of Combined solvents may be used, the amount of which is preferably used in the range of 5 to 40% by weight of the total amount of the semi-agar.

The quaternization agent used in the quaternization reaction is methyldiethanolamine of step 1) Or 0.9 to 1.0 equivalent based on triethanolamine.

The reaction temperature of the quaternized reaction reaction is 40 to 80 ^° C, reaction time is preferably performed for 3 to 7 hours.

 As such, by using the method of the present invention, cationic surfactants having superior phase stability, dispersibility, and discoloration stability can be easily prepared, and the cationic surfactants prepared as described above can be recycled because of the use of byproducts. It is economical and can be usefully used in the manufacture of softeners and hair care products. Hereinafter, the present invention will be described in more detail with reference to Examples, which are only intended to help understanding the structure and operation of the present invention, and the scope of the present invention is not limited to these Examples. Example 1

 Monomeric acids were prepared using soybean oil according to the method described in Douglas A. Burg et al, Journal of the American Oil Chemists' S c / ey (JAOCS), Vol 68, no. 8, p. 60C>.

In a four-necked flask equipped with a mechanical stirrer, thermometer, condenser, and distillation unit, under nitrogen atmosphere, 584 g of soybean oil-derived monomeric acid and 198 g of triethane amine were added under nitrogen atmosphere, and the water produced during reaction was removed at 19 CTC at atmospheric pressure. The reaction was performed for 6 hours. After the reaction, the mountain was less than two. After reacting the reaction product, 145 g of isopropyl alcohol (IPA) was added thereto as a reaction solvent, and 149 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature at 55 ^° C or lower. After completion of the dropwise reaction, reaction was carried out at 55 ^° C. for 5 hours, and the reaction was terminated to obtain l, 007 g of reaction product. Example 2 Monomer acids were prepared using eul oil according to the method described in Douglas A. Burg et al, Journal of the American Oil Chemists' 5 c / ey (JAOCS), Vol 68, no. 8, p. 600.

With mechanical stirrer, thermometer, Hung accumulation (condenser) and the distillation apparatus was installed four-necked In an oil derived from a monomer acid 578g of a nitrogen atmosphere in a flask and triethanolamine 198g and removing the water produced during banung to 190 ^° C at normal pressure 6 The reaction was performed during the time. After the reaction, the mountain was less than two. After reacting the reaction product, 145 g of isopropyl alcohol (IPA) was added thereto as a reaction solvent, and dimethyl sulfate U9g was slowly added dropwise while maintaining it ^at 55 ^° C or lower. After the dropwise addition, the reaction was allowed to proceed at 55 ^° C. for 5 hours, and the reaction was terminated to obtain l, 002 g of the reaction product. Comparative Example 1

In a four-necked flask equipped with a mechanical stirrer, thermometer, condenser, and distillation apparatus, 300 g of stearic acid (from Palm Oleo), 284 g of elein acid (from Palm to Leo) and 198 g of triethanolamine under nitrogen atmosphere The reaction was carried out for 5 hours while removing the water generated during reaction at 19 CTC at atmospheric pressure. After the reaction, the mountain was less than 2.4. After reacting the reaction product, 145 g of isopropyl alcohol (IPA) was added thereto as a reaction solvent, and 150 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature at 55 ^° C. or lower. After completion of the dropwise reaction, the reaction was carried out at 55 ^° C. for 5 hours, and the reaction was terminated to obtain l, 002 g of the reaction product. Comparative Example 2

In a four-necked flask equipped with a mechanical stirrer, a thermometer, a condenser, and a distillation apparatus, 580 g of oleic acid and 198 g of triethanolamine were added under a nitrogen atmosphere, and reaction was carried out for 6 hours while removing the water produced in the reaction at 19 CTC at atmospheric pressure. After the reaction, the mountain was less than two. Reaction products 넁 After quenching, 145 g of isopropyl alcohol (IPA) was added as a reaction solvent, and 149 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature at 55 ^° C. or lower. After completion of the dropwise reaction, the reaction was performed at 55 ^° C. for 5 hours to terminate the reaction, thereby obtaining 998 g of the reaction product. Experimental Example 1

In order to compare the quality of Examples 1 and 2, and Comparative Examples 1 and 2, the color stability and dispersion stability were measured and the results are shown in Table 1 below. The color stability was measured by Gardner numerical values after 1 month storage at 50 ^° C. under the initial color using a Rovibond Colorimeter, and the dispersion stability of Examples 1 and 2, And 10% of the products of Comparative Examples 1 and 2 were visually observed by stirring for 10 minutes at 90 rpm at 90 ^° C. in water at 60 ^° C. and at 800 rpm in a stirrer-type mixer.

 Table 1

상기 표 1에서 나타난 바와 같이 , 실시 예 1 및 2는 안정한 분산 안정성을 유지하고， 5(rc의 가혹 조건에서 1개월 동안 유지되어도 초기 색상을 유지하는 반면， 비교예 1 및 2는 가혹 조건에 따른 변색이 심하게 발생하고， 상이 분리되는 등 분산 안정성도 낮음을 알 수 있었다. 이상에서 본 발명은 특정 실시 태양과 관련지어 설명되 었으나， 첨부한 청구범위에 의해 정해지는 본 발명의 범주내에서 당해 분야의 숙련자는 본 발명을 다양하게 변형 및 변화시 킬 수 있다.

As shown in Table 1, Examples 1 and 2 maintain a stable dispersion stability, 5 (maintaining the initial color even if maintained for 1 month in the harsh conditions of rc, while Comparative Examples 1 and 2 according to the harsh conditions It was found that the dispersing stability was also low, such as severe discoloration, phase separation, etc. The present invention has been described above in connection with specific embodiments, but within the scope of the present invention as defined by the appended claims. Those skilled in the art can make various modifications and variations to the present invention.

Claims

Claims Claim 1 1) transesterification of amine or triethanolamine with monomeric acid and methyldiethane, which are by-products generated during the production of dimer acid; And 2) quaternizing the product obtained in step 1) with a quaternization agent selected from the group consisting of dimethyl sulfate, methyl chloride and diethyl sulfate. Method of Preparation of Surfactant: [Formula 1]

 Where Ri, R ₂ , and R ₃ are each independently CH ₃ , —CH ₂ CH ₂ OH or —CH ₂ CH ₂ (XX ⁾ R _4, wherein R ₄ is omega-6 (ω-6) to omega -12 of the acid-derived monomers containing isostearic acid and isopropyl oleate attached to the methyl group of the carbon position of the _{(ω-12) C 12 -} 22 fatty acid group, and the; X is halogen, CH ₃ S0 ₄ or C ₂ H ₆ S0 ₄ . [Claim 2]  The method of claim 1,  The monomeric acid contains 1 wt% or more of isostearic acid and isooleic acid having a methyl group at a carbon position of omega-6 (ω-6) to omega-12 (ω-12) based on the total amount of monomeric acid. Characterized in that the preparation method of the cationic surfactant. [Claim 3] The method of claim 2, The monomeric acid is 7 to 60% by weight based on the total amount of isostearic acid and isooleic acid monomer monomer having a methyl group at a carbon position of omega-6 (ω-6) to omega-12 (ο) -12). A method for producing a cationic surfactant, characterized in that it contains. [Claim 4]  The method of claim 1,  In step 1), the monomeric acid is used in an amount of 1.5 to 2.2 equivalents based on methyldiethanolamine or triethanolamine.