KR101918074B1 - Manufacturing method of saccharides system surfactant - Google Patents

Abstract

The present invention relates to a method for producing a sugar-based surfactant. More specifically, the present invention provides a method for producing a sugar-based surfactant, which is excellent in solubility in water, physico-chemical properties such as bubble power, It is possible to provide a production method capable of mass production.

Description

[0001] Manufacturing method of saccharides system surfactant [0002]

The present invention relates to a method for producing a sugar-based surfactant, and a method for producing a sugar-based nonionic surfactant having excellent biodegradability and solubility in water.

Surfactants are compounds that have both a hydrophilic group and a lipophilic group in a molecule, and they exist in natural systems or are made by synthesis, and their kinds are more than several hundred kinds. Surfactants have the functions of emulsifying, solubilizing, dispersing, cleaning, wetting, bubbling, antistatic, and sterilizing. They are used in detergents, fibers, cosmetics, medicines, foods, paints, pesticides, paper, mining, lubricants, , Rubber, plastics, petroleum extraction, and soil regeneration. In particular, household and industrial detergents used for hygiene and cleaning purposes contain a surfactant as a main component and play a key role in cleaning. However, surfactants that are commonly used throughout the industry are synthetic interfacial surfactants, and as a result, they are reported to cause environmental pollution and pollution problems. Accordingly, development of surfactants having higher stability and biodegradability is required.

In the process of petroleum fermentation research that has been carried out since the late 1960s, it has been known that a specific microorganism having hydrocarbon magnetization absorbs hydrocarbons in the cells to produce a large amount of surfactant. It is very attractive to decompose hydrocarbons as a substrate and produce a surfactant as a metabolite. However, it is difficult to purify the final product due to the discoloration, deodorization and high purity of the final product due to the microbial reaction. And complicated subsequent processes must be accompanied for the recovery and removal of microorganisms after the reaction.

As a method for solving the problems of the above-mentioned microorganism-based surfactant and its preparation method, studies on glycolipids, acyl peptides, phospholipids, fatty acids, sugar surfactants and their production methods have been extensively studied However, amidation and esterification reactions, which are reactions between fatty acids and amines in the prior art, require a large amount of unreacted fats after the reaction or a large amount of unreacted amines depending on temperature conditions, And the problem of difficulty in complete removal of impurities even though refined was not solved.

The Applicant has repeatedly conducted research on surfactants having high stability and excellent biodegradability. As a result, it has been found that a sugar-based surfactant prepared from an ethylene glycol-based compound having a sugar compound and a specific alkyl group at the terminal thereof is subjected to reaction with a specific acid catalyst Can be produced in a very simple manner at a high reaction yield. As a result, the present invention has been completed.

DISCLOSURE OF THE INVENTION An object of the present invention is to solve the problems in the conventional method of producing a surfactant having high stability and excellent biodegradability. When an ethylene glycol compound having a specific alkyl group as a terminal is reacted under a sulfonic acid-containing organic acid catalyst, And also to provide a method for producing a nonionic sugar surfactant with a high reaction yield.

It is still another object of the present invention to provide a sugar-based nonionic surfactant having a low temperature or a high-temperature cloud point and exhibiting excellent solubility, particularly a very low irritant property to the human body and having excellent interfacial properties, It is a way to do that.

To this end, the method for preparing a sugar-based surfactant according to the present invention comprises reacting a sugar compound with 3.0 to 5.0 moles of an ethylene oxide-based compound per mole of the sugar compound to prepare a nonionic surfactant represented by the following formula .

[Chemical Formula 1]

[Chemical Formula 1]

Sugar is a glycosyl group of a monosaccharide or polysaccharide;

R < ₁ > is (C6-C20) alkyl or (C6-C20) alkenyl;

n is an integer of 1 to 5]

According to an embodiment of the present invention, the above step may be performed by adjusting the reaction pressure (T _press ) and the reaction temperature (T _temp ) to produce a nonionic surfactant at a dramatically improved reaction yield . Particularly, when the following reaction conditions are satisfied, it is possible to minimize reaction byproducts and to produce nonionic surfactants with high reactivity, which is preferred in the present invention.

1 ≤ T _press ≤ 50 mmHg

100 ≤ T _temp ≤ 150 ° C

According to one embodiment of the present invention, the step may be carried out under an acid catalyst. The acid catalyst is not limited, but is preferably selected from acetic acid, phosphoric acid, boric acid, sulfuric acid, hydrochloric acid, nitric acid, benzoic acid, salicylic acid, p- toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and naphthalenesulfonic acid Lt; / RTI >

According to an embodiment of the present invention, Sugar of the nonionic surfactant represented by Formula 1 may be selected from glucose, galactose, arabinose, mannose, threose, sucrose, tagatose, trehalose, fructose, have.

Further, according to an embodiment of the present invention, the method may further include a neutralization step using a base after the step.

According to the present invention, not only is mass production possible in a very economical manner, but also minimizes the residual of unreacted materials with high reactivity and does not require a complicated reaction process. In addition, since the used solvent can be reused by vacuum distillation, environmental pollution is small.

In addition, the sugar-based surfactant prepared therefrom has a large number of hydroxyl groups and thus has excellent physico-chemical properties such as bubble power, washing power and biodegradability as well as solubility in water, It can be used as an alternative to an active agent and is expected to be applied in a wide range of fields such as cosmetics, soaps, detergents, and shampoos, which are in contact with the human body because of low irritation to the human body.

The production method of the sugar-based surfactant according to the present invention will be described below. However, unless otherwise defined in the technical terms and scientific terms used herein, it is to be understood that those skilled in the art In the following description, well-known functions and constructions that may unnecessarily obscure the gist of the present invention will not be described.

The present invention provides a nonionic production method comprising the step of reacting a sugar compound with 3.0 to 5.0 moles of an ethylene glycol compound per mole of the sugar compound to prepare a nonionic surfactant represented by the following formula .

[Chemical Formula 1]

[Chemical Formula 1]

Sugar is a glycosyl group of a monosaccharide or polysaccharide;

R < ₁ > is (C6-C20) alkyl or (C6-C20) alkenyl;

n is an integer of 1 to 5]

According to one embodiment of the present invention, when the ethylene glycol compound is used in an amount of 3.0 to 5.0 moles per mole of the sugar compound, the reason is unknown, but it is confirmed that the effect is remarkably improved in reaction yield and product selectivity Respectively. In particular, when 4.0 to 5.0 moles is used, a sugar type nonionic surfactant can be obtained at a reaction yield of 90% or more, which is more preferable, but is not limited thereto.

According to the present invention, the reaction of the above step is carried out under an acid catalyst. However, it has been confirmed that the use of a specific acid catalyst has a synergistic effect in the above-mentioned effects. The acid catalyst used in the present invention is not limited as long as it is an acid catalyst used in the art. However, the acid catalyst may be acetic acid, phosphoric acid, boric acid, sulfuric acid, hydrochloric acid, nitric acid, benzoic acid, salicylic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid, and the like. At this time, when one or more acid catalysts selected from p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and naphthalenesulfonic acid and the like are included, reaction by-products are minimized with remarkably enhanced activity under the reaction conditions described above In the present invention.

The reaction step between the sugar compound and the ethylene glycol compound described in the present invention is hereinafter referred to as a " saccharification reaction step " so as to be distinguished from the additional reaction step.

&Quot; Alkyl " as used in the present invention means a linear or branched hydrocarbon, and " alkenyl " means a linear or branched hydrocarbon having at least one double bond. In addition, when the ethylene glycol-based compound according to the present invention is a hydrocarbon having a carbon number of 6 or more, it is preferred that it is a hydrocarbon having a straight chain form, because it has excellent foamability, stability of bubbles and cleaning power, and is included as an aspect of the present invention. Of course.

Also, according to one embodiment of the present invention, the ethylene glycol-based compound has a large number of by-products due to side reactions or unreacted reactions when the alkyl or alkenyl group having more than 12 carbon atoms is present under the reaction conditions according to the present invention, There is a problem that a bubble force is remarkably lowered. However, it is preferable to have a hydrocarbon having a carbon number of 6 to 12, but since the viscosity is low even when used at a high concentration without causing a decrease in solubility in water, More preferably a branched alkyl or branched alkenyl having 6 to 12 carbon atoms. The ethylene glycol compound having a branched alkyl or alkenyl group having 6 to 12 carbon atoms exhibits faster reactivity and a higher reaction yield due to the combination with a sulfonic acid-containing organic acid catalyst, which is preferred in the present invention.

According to an embodiment of the present invention, the sugar compound may be one selected from glucose, galactose, arabinose, mannose, threose, sucrose, tagatose, trehalose, fructose, gulose, galactose, May be one selected from glucose, galactose, arabinose, mannose, and treose, but is not limited thereto. At this time, the saccharide compound may be partially protected with an acyl group or the like in order to introduce an ethylene glycol compound at a desired position, and the acyl may be (C1-C6) alkylcarbonyl or benzoyl , Preferably acetyl, but is not limited thereto.

The ethylene glycol compound may be selected from the group consisting of soybean oil, palm oil, linseed oil, sesame oil, safflower oil, corn oil, palm oil, sesame oil, castor oil, coconut oil, olive oil, jojoba oil, cottonseed oil, vegetable oils such as oiticica, coconut milk, peanut oil, sunflower seed oil, rice bran oil, camellia oil, avocado oil, macadamia nut oil and perilla oil; And saturated or unsaturated alcohols derived from animal oils such as lanolin. In this case, the ethyleneglycol compound derived from vegetable or animal oil, which is a saturated or unsaturated alcohol, may be a single substance or a mixed substance. In case of a mixed substance, the nonionic surfactant prepared therefrom may have better interfacial properties, But is not limited thereto.

A specific example of the ethylene glycol-based compound according to an embodiment of the present invention may include a compound represented by the following formula (2).

(2)

In Formula 2,

R < ₁ > is (C6-C20) alkyl or (C6-C20) alkenyl;

n is an integer of 1 to 5]

The saccharification reaction step according to an embodiment of the present invention is preferable because the reaction pressure (T _press ) and the reaction temperature (T _temp ) satisfy the following reaction conditions and can exhibit a synergistic effect on the reaction yield.

1 ≤ T _press ≤ 50 mmHg

100 ≤ T _temp ≤ 150 ° C

According to an embodiment of the present invention, in the saccharification step, if the reaction pressure is 20 to 50 mmHg and the reaction temperature is 110 to 140 ° C, the end product can be obtained with high selectivity, no.

The saccharification step according to an embodiment of the present invention may be performed under an acid catalyst. The acid catalyst is not limited as long as it can initiate the glycation reaction according to the present invention. Non-limiting examples of the acid catalyst include acetic acid, phosphoric acid, boric acid, sulfuric acid, hydrochloric acid, nitric acid, benzoic acid, salicylic acid, p- , Methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid, and one or more selected from p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and naphthalenesulfonic acid, In the case of containing two or more acid catalysts, it is surprisingly more preferable in terms of minimizing reaction byproducts with improved reactivity, and in particular, in the ethylene glycol compound having the above-mentioned specific branched alkyl or alkenyl at the terminal, The invention overrides.

According to one embodiment of the present invention, a saccharide-based surfactant capable of producing a saccharide-based surfactant in a high yield by a simple reaction process, which can be applied to a mass production process and realizes the above- .

According to an embodiment of the present invention, the saccharification step may be performed by dissolving or melting the sugar compound directly in the ethylene glycol compound without using an additional reaction solvent. At this time, the unreacted ethylene glycol compound can be easily removed under vacuum distillation after the saccharification step. At this time, the production method according to the present invention does not involve any reaction solvent capable of inducing stimulation.

The method may further include a step of removing the unreacted sugar compound not participating in the reaction after the saccharification step. This may be a step of recrystallizing the unreacted dissolved or melted sugar compound at a room temperature (20 캜) to 80 캜, and then filtering it. The step of removing the unreacted sugar compound may be performed after the saccharification step or after the neutralization step described later.

According to an embodiment of the present invention, the method may further include a neutralization step using a base after the saccharification step or the unreacted sugar compound removal step. At this time, by performing the neutralization step, it is possible to reduce specific odor that may occur in the final product and effectively suppress the problems such as discoloration due to external environment such as heat, light, moisture, etc., . At this time, in the neutralization step, the base may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, sodium carbonate and magnesium oxide, though not limited thereto.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are illustrative of the present invention but are not limited thereto.

The solubility, foaming power, biodegradability and irritability of the sugar surfactant prepared by the method described below were evaluated in the following Tables 1 and 2 by performing the following method.

1. Evaluation of solubility

The permeability of the saccharide-based surfactant prepared in Example 1 was measured using a TurbiScane LAb (Leanontech, pulse infrared light source; 880 nm). The transmittance was scanned at 37 ° C for 72 hours every 6 hours in the longitudinal direction of the sample solution, and the post-scattered (transmitted) light (135 °) was measured by the sample solution. A 5 wt% aqueous solution of commercial polyoxyethylene (1) palm oil fatty acid monoethanolamide (trade name: Norfox DGCA, Norman, Fox & Co.) was used as a control substance. Relative permeability was measured based on its permeability (1.0) And the higher the relative value, the higher the solubility.

2. Evaluation of bubble power

19 g of water was added to 6 g of the sugar surfactant prepared in Example 1 to prepare a 3 wt% sample solution having a solid content of 3 wt%. After dropping 0.05 g of the artificial sebum solution, the rotation of the rotor was stopped by using a SITA R-2000 bubble analyzer (condition: rotated at 800 rpm / min 15 times (once for 20 seconds)), and then the height of the bubbles was measured. The mean value was obtained after repeated iteration.

3. Evaluation of biodegradability

OECD 301D Closed Bottle Test (OECD 301D Closed Bottle Test, test for 28 days to determine whether biodegradation is possible by 60% or more within two weeks from the start of decomposition of the sample) The final biodegradability of the saccharide surfactant (5 wt% in water) prepared in Example 1 was evaluated. When the final biodegradability was more than 60%, it was judged that the biodegradability was excellent. As a control substance, 5 wt% aqueous solution of polyoxyethylene (1) palm oil fatty acid monoethanolamide (trade name: Norfox DGCA, Norman, Fox & Were used.

4. Evaluation of Irritability

And the HET-CAM method (Hen's Egg Chorioallantoic Membrane). A 5 wt% aqueous solution of commercial polyoxyethylene (1) palm oil fatty acid monoethanolamide (trade name: Norfox DGCA, Norman, Fox & Co) and a sugar surfactant prepared in Example 1 (5 wt% in water) 8: 2, 6: 4, 4: 6, 2: 8, 0:10 by weight to evaluate their irritancy. The criteria for evaluation were unstimulated (0), light stimulus (1), moderate irritation (2), erythema with edema (3) It was evaluated as strong erythema accompanied by (4).

(Example 1)

(4 moles) of 2- (3-ethylhexyloxy) ethanol was charged into a 1 L flask equipped with a stirrer, a thermometer and a distiller equipped with a condenser, and 180.16 g (1 mole) Toluenesulfonic acid (1.05 g) was added and heated to 115 ° C. The reaction is allowed to proceed for 4 hours while maintaining the internal pressure at 20 mmHg. After the reaction was completed, the reactor was heated to about 80 ° C., and 0.15 g of MgO 2 - was added to neutralize it, followed by filtering to remove unreacted materials. Thereafter, ethoxylate ethylhexyl alcohol charged at an excess amount of 5 mmHg at 130 캜 was removed by applying vacuum to obtain a saccharide surfactant (yield of 330.42.36 g = 90.47%).

Structural analysis (NMR) data of the saccharide-based surfactant prepared by the above method are as follows (see FIGS. 1 and 2).

1H-NMR (400 MHz, CD 3 OD): δ 3.42 (1H), 3.51 (1H), 3.75 (1H), 4.89 (1H), 3.81 (1H), 3.78 (1H), 3.48 (1H), 2.36 ( (2H), 0.94 (6H), 1.22 (2H), 1.20 (2H)

13 C-NMR (400 MHz, CD ₃ OD):? 10.5 (-CH ₂ -CH ₃ ), 12.1 (-CH ₂ -CH ₃ ), 21.9 (-CH ₂ -CH ₂ -CH ₃ ) _{-CH 2 -CH 3), 30.5 (} -CH 2 -CH (-CH 2) -CH 2), 30.8 (-CH-CH 2 -CH 2 -), 40.2 (-CH-CH 2 -CH 2 -) _{, 61.1 (-CH 2 -OH),} 61.5 (-O-CH-CH 2 -), 70.8 (-O-CH 2 -CH 2 -), 70.9 (-O-CH 2 -CH 2 -), 71.8 ( HO-CH-CH-), 72.8 (HO-CH-CH-), 79.0 (-O-CH-CH-), 79.1 (HO-CH-CH-), 100.2 (-O-CH-CH-).

(Example 2-6)

The reaction was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1 below to obtain a sugar-based surfactant.

In addition, the solubility, foaming power and biodegradability of the sugar surfactant prepared by the above method were evaluated by the method in Example 1 and shown in Tables 1 and 2 below.

(Example 7)

Except that 873.32 g (4 mole) of 2- (2- (3-ethylhexyloxy) ethoxy) ethanol was used in place of 697.12 g (4 mole) of 2- (3-ethylhexyloxy) Was subjected to a reaction in the same manner as in Example 1 to obtain a sugar-based surfactant.

1H-NMR (400 MHz, CD 3 OD): δ 3.42 (1H), 3.51 (1H), 3.80 (1H), 5.11 (1H), 3.83 (1H), 3.76 (1H), 3.48 (1H), 2.20 ( (2H), 1.18 (2H), 0.98 (6H), 1.34 (2H)

In addition, the solubility, foaming power and biodegradability of the sugar surfactant prepared by the above method were evaluated by the method in Example 1 and shown in Tables 1 and 2 below.

(Example 8)

(4 moles) of 2- (2-2- (3-ethylhexyloxy) ethoxy) ethoxy) ethanol instead of 697.12 g (4 moles) of 2- (3- ethylhexyloxy) The reaction was carried out in the same manner as in Example 1 to obtain a saccharide-type surfactant.

1H-NMR (400 MHz, CD 3 OD): δ 3.40 (1H), 3.49 (1H), 3.37 (1H), 5.03 (1H), 3.76 (1H), 3.79 (1H), 3.54 (1H), 2.19 ( 2H), 1.33 (2H), 0.96 (6H), 1.43 (2H)

In addition, the solubility, foaming power and biodegradability of the sugar surfactant prepared by the above method were evaluated by the method in Example 1 and shown in Tables 1 and 2 below.

(Example 9)

The reaction was carried out in the same manner as in Example 1 except that 2.5 ml of sulfuric acid was used instead of 1.05 g of p-Toluenesulfonic acid in Example 1 to obtain a saccharide-type surfactant.

In addition, the solubility, foaming power and biodegradability of the sugar surfactant prepared by the above method were evaluated by the method in Example 1 and shown in Tables 1 and 2 below.

(Comparative Example 1-6)

The reaction was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1 below to obtain a sugar-based surfactant.

In addition, the solubility, foaming power and biodegradability of the sugar surfactant prepared by the above method were evaluated by the method in Example 1 and shown in Tables 1 and 2 below.

As can be seen from Table 1, according to the present invention, it was confirmed that when a specific acid catalyst was used, it was possible to realize a remarkably improved effect on the reaction yield. In addition, in the reaction condition according to the present invention, It was confirmed that the reaction yield was up to 414% or higher at the time of preparation (Example 5 vs. Comparative Example 1).

As can be seen from Tables 2 and 3, according to the present invention, not only high solubility in water but also bubble power equal to or higher than that of a conventional surfactant can be realized and high cleaning power can be provided. In addition, it is possible to provide a nonionic surfactant which is low in irritation to the human body and is excellent in biodegradability, at the same time minimizes the residual of unreacted materials with high reactivity, and also has the above- Can be provided in a more competitive and environmentally friendly manner.

Claims (7)

Under a temperature condition of 110 to 140 DEG C and a pressure condition of 20 to 50 mmHg,
And reacting the saccharide compound with 3.0 to 5.0 moles of an ethylene oxide compound per mole of the saccharide compound to prepare a nonionic surfactant represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (1)
Sugar is a glycosyl group of a monosaccharide or polysaccharide;
R < ₁ > is (C6-C20) alkyl or (C6-C20) alkenyl;
n is an integer of 1 to 5] delete The method according to claim 1,
Wherein said step is carried out under an acid catalyst. The method of claim 3,
The acid catalyst may be at least one nonionic surfactant selected from the group consisting of acetic acid, phosphoric acid, boric acid, sulfuric acid, hydrochloric acid, nitric acid, benzoic acid, salicylic acid, p- toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and naphthalenesulfonic acid Gt; The method according to claim 1,
Wherein the sugar is glucose, galactose, arabinose, mannose, treose, sucrose, tagatose, trehalose, fructose, gulose or galactose. The method according to claim 1,
Wherein the neutralization step further comprises a neutralization step with a base after the step
A method for producing a surfactant. The method according to claim 6,
Wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, sodium carbonate and magnesium oxide.