KR20150141081A - Method for preparing of alkyl poly glycosides - Google Patents

Abstract

The present invention relates to a method of manufacturing higher alkyl polyglycosides, and more specifically, to a method of manufacturing higher alkyl polyglycosides having a light yellow color or no color corresponding to APHA color 2-3, and having little color change with excellent colors and with no discoloration even after a long period of storage. The method makes higher alcohol with 8 or more carbon atoms react with glucose under an acid catalyst atmosphere, wherein the reaction is performed after a dispersant is added, under a vacuum condition of 300-600 mmHG at 100-120°C; and neutralization, dilution, pH adjustment, and discoloration, etc. are progressed after the reaction.

Description

METHOD FOR PREPARING OF ALKYL POLY GLYCOSIDES [0002]

The present invention relates to a process for producing a high alkylpolyglycoside, and more particularly, to a process for producing a high alkylpolyglycoside, which is improved in manufacturing process and method, And a method for producing the polyglycoside.

The higher alkylpolyglycosides are nonionic ones, which are ethylene oxide adducts, and are more resistant to skin and eye irritation than the sulfonate or phosphoric acid anionic surfactants (also referred to as 'anionic surfactants'). And is an environmentally friendly surfactant having excellent mildness and excellent biodegradability to the skin.

The method for preparing such an environmentally-favorable alkylpolyglycoside includes Fisher, which is prepared by performing a secondary reaction in which glucose and a lower alcohol are subjected to a primary reaction in the presence of an acid catalyst and then an ester exchange reaction with a higher alcohol, There is a way.

However, such a Fischer process has a disadvantage in that it takes a long reaction time and the mixing ratio of glucose and alcohol is constant, and a device for recovering and purifying lower alcohol is required and a complicated process is required.

In addition, in US Pat. No. 3,598,865, which is similar to the above-mentioned Fisher method, low-alkylpolyglycoside is produced by firstly reacting glucose glucose and butanol with glucose in the presence of a sulfuric acid catalyst as a mineral acid catalyst Proposes a method for producing a high-alkylpolyglucoside by adding a high-grade alcohol in a second step to exchange glycosylation,

U.S. Patent No. 3,707,535 describes the preparation of lower alkylpolyglycosides by using lower alcohols such as methanol, ethanol or propanol, followed by exchange glucosylation with higher alcohols to produce higher alkylpolyglycosides .

However, these methods also require a complicated device for recovering the lower alcohol, which is a factor for raising the equipment cost of the machine. In addition, 50 to 10 times lower alcohol than glucose is used. The use of methanol, ethanol, It is difficult to remove water, and therefore, there is a drawback in that water must be removed using a solvent.

That is, water can be removed by adding a solvent such as toluene, benzene, or a nucleic acid. At this time, however, glycols having a high boiling point are disadvantageously difficult to remove.

Further, a method of producing a high-alkylpolyglucoside by reacting glucose which is not soluble in higher alcohol with glucose in the presence of a reaction solvent of dimethyl formamide or dimethyl sulfoxide, .

However, dimethylformamide or dimethylsulfoxide used in this method has a very high boiling point, and there is a drawback that there is a considerable difficulty in the removal thereof.

In addition, Austrian Patent No. 135333 proposes a process for producing an alkylpolyglycoside by acetobromoglycosination in the presence of a base, followed by exchange acetalization with a higher alcohol in the presence of leucic acid, There is a drawback that the process is difficult.

In addition, an alkylpolyglycoside is prepared by directly reacting glucose with an excess alcohol in the presence of a catalytic acid, or using a solvent, or a primary reaction with a lower alcohol or glycol as a reactant, Various methods including a method of introducing information are introduced in patent documents and non-patent documents.

Accordingly, in the present invention, in the production of alkylpolyglycoside, which is a nonionic environmentally friendly surfactant, it is possible to improve the problem of difficulty in recovery of alcohol due to a complicated system or mechanism of process or high viscosity, I would like to propose a recipe.

On the other hand, in Korean Patent Laid-Open No. 10-2005-0106676, there is disclosed a process for producing a polylactic acid by a) reacting an aliphatic alcohol with glucose under an acid catalyst; b) neutralizing the reaction product of step a) with a neutralizing agent, dissolving the neutralized product in water and ethyl alcohol mixture to measure pH; c) distilling the unreacted aliphatic alcohol in the neutralized product of step b) to concentrate the alkyl polyglycoside; d) diluting the concentrated alkyl polyglycoside concentrate of step c); And e) bleaching by adding a base and a peroxide to the diluted alkyl polyglycoside of step d), and then producing alkylpolyglycoside having excellent color and transparency. The present invention has a technical difference.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing a high alkylpolyglycoside for producing an improved alkylpolyglycoside.

The present invention relates to a process for producing an alkylpolyglycoside, which is a nonionic environmentally friendly surfactant, in which a complex system or mechanism of the process or a high viscosity is used to improve the difficulty in recovery of alcohol, Another object is to provide a method for producing a polyglycoside.

It is another object of the present invention to provide a method for producing a high alkylpolyglycoside which is capable of exhibiting the advantage that the change of color is small, the color is excellent, and the color is not discolored even in storage for a long time through improvement of the manufacturing process and method.

Particularly, the present invention enables the reaction to be smoothly performed by uniformly dispersing glucose insoluble in alcohol using a surfactant dispersant in the course of the reaction, improving the flowability in the recovery process of the alcohol and lowering the viscosity thereof, And the resultant decolorized product in the decolorization process is a high quality high alkylpolyglycoside having a colorless or pale yellow color corresponding to 2 to 3 of Apha Color The present invention provides a method for producing a high alkylpolyglycoside.

(A) reacting a higher fatty alcohol having 8 to 22 carbon atoms with glucose in the presence of an acid catalyst, and adding the glucose to the higher fatty alcohol in the presence of an acid catalyst, Adding and dispersing a dispersing agent for uniform dispersion treatment; (B) neutralizing the result of step (A) by adding a neutralizing agent; (C) distilling the resultant product in the step (B) in a vacuum atmosphere to recover and remove excess fatty alcohol remaining unreacted to produce an alkyl polyglycol seed; (D) adding water to the resultant of step (C) to dilute the resultant; (E) adding a pH adjusting agent to the result of step (D) to adjust pH to alkaline; (F) adding a decolorant to the result of step (E) to decolorize the resultant; And a control unit.

The step (A) may be carried out at a reaction temperature of 100 to 120 ° C and a vacuum of 300 to 600 mmHg.

Here, the step (C) may be carried out at a temperature of 120 to 180 ° C and a vacuum of 0.01 to 1 mmHg.

The step (F) may be performed at a temperature of 60 to 80 ° C for 60 to 90 minutes.

Here, the higher fatty alcohol having 8 to 22 carbon atoms and glucose may be added in a mixing ratio of 1: 3.5 to 1: 5 by weight or volume.

Here, the higher fatty alcohol having 8 to 22 carbon atoms may be any one selected from octyl alcohol, decyl alcohol, myristyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, hexadecyl alcohol and stearyl alcohol Or a mixed alcohol in which two or more kinds are mixed can be used.

Here, the acid catalyst may be any one selected from the group consisting of hydrochloric acid, phthalic acid, paratoluenesulfonic acid, malic acid, phosphorous acid, formic acid, and boric acid.

Here, it is preferable to use polyoxyethylene lauryl ether as the dispersing agent.

Here, the dispersant may be any one selected from the group consisting of 40-50 moles adduct of lauryl alcohol ethylene oxide, 40-50 moles adduct of nonylphenol ethylene oxide, and 40-50 moles adduct of cetyl alcohol ethylene oxide.

Here, caustic soda may be used as the neutralizing agent and the pH adjusting agent.

Here, the decoloring agent may be hydrogen peroxide.

Here, the decolorizing agent is a composition in which sodium silicate is added to hydrogen peroxide, and can be used in a blending ratio of 1: 1 by weight or volume.

According to the present invention, it is possible to produce a high-alkylpolyglycolic seed through the organic bonding process, and in particular, it can exhibit the advantage that the color change is small and the color is excellent and the product is not discolored even in long-term storage, Can be produced with high quality.

The present invention can smoothly proceed the reaction between the higher fatty alcohol and the glucose, improve the flowability and lower the viscosity, and can easily recover the alcohol, and the final product can be classified into Apha Color High-quality, high-alkylpolyglycoside having colorless to light yellow corresponding to 2 to 3 can be produced.

The present invention relates to a process for producing an alkylpolyglycoside which is a nonionic environmentally friendly surfactant and which has difficulties in recovery of alcohol due to a complicated system or mechanism or high viscosity in the process, can do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic block flow diagram illustrating a process for preparing a high alkyl polyglycoside according to an embodiment of the present invention. FIG.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.

As shown in FIG. 1, the method for producing a high alkylpolyglycoside according to the present invention includes a reaction step S10, a neutralization step S20, an alkylpolyglycolide generation step S30, a dilution step S40, A step S50, and a decolorizing step S60.

The reaction step ( S10 )

The reaction step is a step for introducing a high fatty alcohol having 8 to 22 carbon atoms and glucose into a reactor having a stirrer, adding an acid catalyst and reacting in the presence of an acid catalyst, So that the reaction proceeds smoothly.

At this time, the reaction is preferably carried out at a reaction temperature of 100 to 120 ° C. and a vacuum of 300 to 600 mmHg, and it is preferable to proceed while removing water generated during the reaction between the high-density fatty alcohol and glucose.

If the reaction temperature is less than 100 ° C., the reaction takes a long time and the yield is decreased. When the reaction temperature exceeds 120 ° C., the glucose, which is a reactant, is charged and the color may be deformed do.

In addition, the range of the vacuum degree takes into consideration the reaction according to the formation of the pressure in the reactor, and when it is out of the above range, the reaction does not occur or the yield of the reaction decreases.

More specifically, when the reaction temperature is in the range of 100 to 110 ° C, the degree of vacuum is preferably in the range of 400 to 600 mmHg. When the reaction temperature is in the range of 110 to 120 ° C, the degree of vacuum is in the range of 300 to 500 mmHg .

The high fatty alcohol having 8 to 22 carbon atoms and glucose are preferably added at a mixing ratio of 1: 3.5 to 1: 5 by weight or volume so as to increase the reaction yield.

Here, the higher fatty alcohol having 8 to 22 carbon atoms may be any one selected from octyl alcohol, decyl alcohol, myristyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, hexadecyl alcohol and stearyl alcohol Or a mixed alcohol in which two or more kinds are mixed can be used.

The acid catalyst may be any one selected from the group consisting of hydrochloric acid, phthalic acid, paratoluenesulfonic acid, malic acid, phosphorous acid, formic acid, and boric acid, or a mixture of two or more thereof.

The dispersant is used for uniformly dispersing glucose in a high-fat fatty alcohol when it is reacted with a high-fat fatty alcohol, and it is preferable to use a polyoxyethylene lauryl ether .

It is preferable that the dispersant contains any one of 40-50 moles adduct of lauryl alcohol ethylene oxide, 40-50 moles adduct of nonylphenol ethylene oxide and 40-50 moles adduct of cetyl alcohol ethylene oxide .

Neutralization phase S20 )

The neutralization step is a step for neutralizing the result of the reaction step (S10) by adding a neutralizing agent, and it is preferable to use caustic soda as the neutralizing agent.

In this case, the neutralizing agent is preferably a caustic soda solution diluted by adding caustic soda to water, and water and caustic soda are added in a weight ratio of 1: 0.2 to 1: 1 in order to improve the efficiency of neutralization treatment and reduce skin irritation. : 0.3 is preferably used.

Here, distilled water can be used as water.

Alkyl polyglycol seed  Generation step ( S30 )

The step of producing alkylpolyglycolide is a step for producing an alkylpolyglycolide by recovering and removing excess fatty alcohol remaining unreacted by distillation in a vacuum atmosphere to the finished product through the neutralization step (S20) It is preferable that the residual concentration of the remaining fatty alcohol in the solution is maintained at 0 to 1%.

At this time, in the step of producing the alkyl polyglycolide, it is preferable to carry out the reaction under the temperature condition of 120-180 ° C and the vacuum condition of 0.01-1 mmHG.

If the temperature is lower than 120 ° C., the recovery of excess fatty alcohol may take a long time and the recovery may be deteriorated. If the temperature is higher than 180 ° C., the flowability for recovering excess fatty alcohol may be lowered, And the like.

In addition, the range of the degree of vacuum is intended to promote the production of alkyl polyglycol seeds and increase the recovery rate for excess fatty alcohol.

That is, the temperature condition and the vacuum condition can remove excess fatty alcohol in a short time and can remove the residual concentration of the fatty alcohol to 1% or less quickly, and improve the flowability according to the recovery of the fatty alcohol Biodegradability can be maintained, viscosity can be lowered, and simple and easy recovery can be achieved.

Dilution step ( S40 )

In the diluting step, water is added to the resulting product by the alkylpolyglycolic acid producing step (S30) to dilute the resulting alkylpolyglycolic acid so as to maintain the concentration of 40 to 60% desirable.

At this time, it is more preferable to adjust the concentration to 50%.

Here, distilled water can be used as water.

pH Adjustment phase ( S50 )

The pH adjusting step is a step of adjusting the pH to alkaline by adding a pH adjusting agent to the result of the completion of the diluting step (S40) so that the alkylpolyglycolide formed is dissolved in water and the skin irritation etc. can be lowered It is preferable to adjust the pH to 10 to 11.

As the pH adjusting agent, caustic soda is preferably used, and powdery or liquid phase can be selectively used.

Discoloration phase ( S60 )

The decolorization step may be performed for 60 to 90 minutes at a temperature of 60 to 80 DEG C by decolorizing the result of the pH adjustment step (S50).

When the temperature is less than 60 ° C, the time required for the decoloring treatment is long and the decolorization is not achieved properly. When the temperature exceeds 80 ° C, the decolorization efficiency is lowered, such as lowering the color transparency.

At this time, it is more preferable to maintain the temperature condition at 65 to 75 캜.

As the decoloring agent, it is preferable to use hydrogen peroxide. In order to allow the hydrogen peroxide to exhibit a stable function as a decolorizing agent, sodium silicate may be added to hydrogen peroxide.

Here, in the case of adding sodium silicate to hydrogen peroxide, it is preferable to form the mixture at a mixing ratio of 1: 1 by weight or volume.

Therefore, in the present invention, a high-alkylpolyglycolic seed can be produced through the steps of forming the organic bonding relationship from step S10 to step S60. In particular, But also a high quality high alkylpolyglycolic acid having colorless to light yellow can be produced.

Hereinafter, the present invention will be described in more detail with reference to specific embodiments.

270 g of a mixed alcohol obtained by mixing octyl alcohol and decyl alcohol in a weight or volume ratio (4.5: 5.5), 1.2 g of an aqueous acid as an acid catalyst, 3.8 g of polyoxyethylene oxide, and 65 g of glucose were added in a primary composition, Heating is carried out at a reaction temperature of 102 to 110 ° C and the reaction is maintained for 1 hour and 50 minutes under a vacuum maintained at 400 to 600 mmHg, and water generated under reduced pressure is removed.

At this time, the reactor is equipped with a stirrer, a thermometer and a pressure gauge, and an apparatus for removing alcohol and water is connected.

After confirming the reaction state, 45 g of glucose is added in a second order, and the mixture is stirred for 2 hours under the same reaction temperature and vacuum as described above, and water generated under reduced pressure is removed.

After the reaction was completed, 0.34 g of caustic soda was neutralized by adding a caustic soda solution diluted in 1.5 g of distilled water, and the excess fatty alcohol remaining after the unreacted reaction was distilled at a temperature of 120 to 150 ° C and a high vacuum of 1 mmHG And recovered and removed by processing.

As a result, 157 g of an alkyl polyglycoside, which is a pale yellow product of a transparent body, was obtained. Properties of the obtained alkyl polyglycoside product are as follows.

(Product property)

Alkylpolyglycoside: 99% or more

Glucose: not more than 0.3%

Residual alcohol: Not more than 0.6%

Hydroxyl value: 605

Next, distilled water was added to the alkylpolyglycoside product to dilute it. The concentration was adjusted to 50%, and 0.9 g of caustic soda was added to adjust the pH to 10 to 11. Thereafter, 2.5 g of hydrogen peroxide (30 to 35% 2.5 g of sodium silicate (2%) was added as a hydrogen peroxide stabilizer and decolorized at a temperature of 65 to 75 ° C for 1 hour to 1 hour and 30 minutes.

This resulted in the production of an improved high alkylpolyglycoside and a very light yellow final product with a grade of APHA Color 2-3.

270 g of decyl alcohol, 3.8 g of polyoxyethylene lauryl ether, 65 g of glucose and 1.2 g of acid catalyst were added to the reactor, and the inside of the reactor was heated at a reaction temperature of 102 to 110 DEG C and a degree of vacuum of 400 to 600 mmHg Under the maintained condition, the reaction is allowed to proceed for 1 hour and 40 minutes, and the water produced under reduced pressure is removed.

At this time, the reactor is equipped with a stirrer, a thermometer and a pressure gauge, and an apparatus for removing alcohol and water is connected.

In this case, the reaction proceeds to a colorless or pale yellow transparent liquid. After the end point of the reaction is confirmed, 40 g of glucose is further added and the mixture is stirred for 1 hour and 50 minutes under the same temperature conditions and vacuum conditions as described above. Water to be removed.

After the reaction was completed, 0.34 g of caustic soda was neutralized by adding a caustic soda solution diluted in 1.5 g of distilled water, and the excess fatty alcohol remaining after the unreacted reaction was distilled at a temperature of 120 to 150 ° C and a high vacuum of 1 mmHG And recovered and removed by processing.

As a result, 159 g of decyl polyglycoside as a pale yellow product having a degree of polymerization of 1.6 was obtained. The characteristics of the obtained decyl polyglycoside product are as follows.

(Product property)

Decyl polyglycoside: 99% or more

Glucose: not more than 0.3%

Decyl alcohol: Not more than 0.6%

Hydroxyl value: 625

Then, distilled water was added to the decyl polyglycoside product to dilute it. The concentration was adjusted to 50%, and 0.9 g of caustic soda was added to adjust the pH to 10 to 11. Thereafter, 2.5 g of hydrogen peroxide (30 to 35% 2.5 g of sodium silicate (2%) was added as a hydrogen peroxide stabilizer and decolorized at a temperature of 65 to 75 ° C for 1 hour to 1 hour and 30 minutes.

This resulted in a very light yellow final product with a rating of APHA Color 2-3.

In the reactor, 270 g of mixed alcohol obtained by mixing lauryl alcohol and mystic alcohol, 1.2 g of oxalic acid as an acid catalyst, 3.8 g of polyoxyethylene lauryl ether and 40 g of glucose were added, and the inside of the reactor was heated to a reaction temperature of 110 to 116 캜 And the vacuum degree is maintained at 300 to 400 mmHg for 1 hour and 30 minutes, and the water produced under reduced pressure is removed.

At this time, the reactor is equipped with a stirrer, a thermometer and a pressure gauge, and an apparatus for removing alcohol and water is connected.

In this case, the reaction proceeds to a colorless or light yellow transparent liquid. After confirming the end point of the reaction, 25 g of glucose is further added, and the mixture is stirred for 50 minutes under the same temperature conditions and vacuum conditions as described above. .

After the reaction is completed, 0.34 g of caustic soda is neutralized by adding a caustic soda solution diluted in 1.5 g of distilled water, and excess fatty alcohol remaining by unreacted reaction is maintained at a temperature of 120 to 160 ° C. and a vacuum of 1 mmHg or less And is recovered by distillation under one condition.

As a result, 96 g of alkylpolyglycoside as a pale yellow product was obtained. The properties of the alkylpolyglycoside product obtained at this time are as follows.

(Product property)

Alkylpolyglycoside: 99% or more

Glucose: not more than 0.3%

Residual alcohol: Not more than 0.6%

Hydroxyl value: 650

Next, distilled water was added to the alkylpolyglycoside product to dilute it. The concentration was adjusted to 50%, and 0.9 g of caustic soda was added to adjust the pH to 10 to 11. Thereafter, 2.5 g of hydrogen peroxide (30 to 35% 2.5 g of sodium silicate (2%) was added as a hydrogen peroxide stabilizer and decolorized at a temperature of 65 to 75 ° C for 1 hour to 1 hour and 30 minutes.

This resulted in a very light yellow final product with a rating of APHA Color 2-3.

Accordingly, as can be seen from these Examples, the present invention can smoothly proceed the reaction between the higher fatty alcohol and glucose, improve the flowability and lower the viscosity, thereby facilitating the recovery of alcohol, High quality alkylpolyglycosides having a colorless or pale yellow color corresponding to 2 to 3 of Apha Color (gradation of hue of color) can be produced on the resultant.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative, Substitution can be made, which will be within the technical scope of the present invention.

S10: reaction step
S20: neutralization step
S30: Production step of alkylpolyglycolide
S40: Dilution step
S50: pH adjustment step
S60: decolorization step

Claims (12)

(A) reacting a high-fat fatty alcohol having 8 to 22 carbon atoms with glucose in the presence of an acid catalyst, and adding a dispersant for uniformly dispersing glucose to the high-fat fatty alcohol;
(B) neutralizing the result of step (A) by adding a neutralizing agent;
(C) distilling the resultant product in the step (B) in a vacuum atmosphere to recover and remove excess fatty alcohol remaining unreacted to produce an alkyl polyglycol seed;
(D) adding water to the resultant of step (C) to dilute the resultant;
(E) adding a pH adjusting agent to the result of step (D) to adjust pH to alkaline;
(F) adding a decolorant to the result of step (E) to decolorize the resultant; ≪ / RTI > wherein the method comprises the steps of: The method according to claim 1,
Wherein the step (A) is carried out at a reaction temperature of 100 to 120 ° C and a vacuum of 300 to 600 mmHg. The method according to claim 1,
Wherein the step (C) is carried out at a temperature of 120 to 180 ° C. and a vacuum of 0.01 to 1 mmHg. The method according to claim 1,
Wherein the step (F) is carried out at a temperature of 60 to 80 ° C for 60 to 90 minutes. The method according to claim 1,
Wherein the high fatty alcohol having 8 to 22 carbon atoms and glucose are added at a mixing ratio of 1: 3.5 to 1: 5 by weight or volume. The method according to claim 1,
The higher fatty alcohol having 8 to 22 carbon atoms may be any one selected from octyl alcohol, decyl alcohol, myristyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, hexadecyl alcohol and stearyl alcohol, Wherein the mixed alcohol is a mixture of at least two kinds of alcohols. The method according to claim 1,
Wherein the acid catalyst is one selected from the group consisting of hydrochloric acid, phthalic acid, paratoluenesulfonic acid, malic acid, phosphorous acid, formic acid, and boric acid. The method according to claim 1,
Wherein the dispersing agent is a polyoxyethylene lauryl ether. ≪ RTI ID = 0.0 > 8. < / RTI > The method according to claim 1 or 8,
Wherein the dispersant is at least one selected from the group consisting of 40-50 molar adduct of lauryl alcohol ethylene oxide, 40-50 molar adduct of nonylphenol ethylene oxide, and 40-50 molar adduct of cetyl alcohol ethylene oxide. ≪ / RTI > The method according to claim 1,
Wherein the neutralizing agent and the pH adjuster are caustic soda. The method according to claim 1,
Wherein the decolorizing agent is hydrogen peroxide. The method according to claim 1,
Wherein the decolorizing agent is added with hydrogen peroxide and sodium silicate, and the decolorizing agent is used in a blending ratio of 1: 1 by weight or volume.

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