KR20020088328A - The method of preparing alkylpolygluco side - Google Patents

Abstract

The present invention relates to a method for preparing alkyl polyglucozide by reacting glucose with alcohol using an organic solvent and an acid as a catalyst.

In particular, in the present invention, by introducing a low-boiling solvent and glass beads into the reaction, the excessive amount of alcohol corresponding to the equivalent ratio of 2-7 times the glucose was used to reduce the production and suppress the viscosity of the conventional polyglucose. It can reduce the recovery cost of unreacted alcohol by reducing it to less than 2 equivalents, and maximize the reaction area by using glass beads, which can greatly increase the reaction yield of alkyl polyglucozide. The present invention relates to a method for producing alkylpolyglucoside using low boiling point solvent and glass beads that can be prevented from discoloration caused by high temperature reaction because it can be reacted at a relatively low temperature.

Description

The manufacturing method of alkyl polyglucozide {THE METHOD OF PREPARING ALKYLPOLYGLUCO SIDE}

The present invention relates to a method for producing alkyl polyglucozide, which has been spotlighted as an additive for detergents and cosmetics with good biodegradability and little toxicity. The production of alkyl polyglucozide using alcohols, low boiling solvents and glass beads reacting with glucose The method is characterized in that an alkyl polyglucozide having a low DP value can be obtained without using an alcohol that reacts with glucose in an excessive amount as in the prior art, and thus it is possible to save the cost of removing the unreacted alcohol and lower boiling point. It is easy to recover the solvent by using a solvent and reacts at a relatively low temperature so that the color of the alkylpolyglucozide reactant does not discolor and alkyl polyglucozide can be obtained by maximizing the reaction area by adding glass beads to the reactants. Can be called have.

As the prior art,

The method for the preparation of alkylpolyglucosides has been produced by companies such as Henkel and Horizon since it was first introduced by Emill Fisher, and the general structure of alkylpolyglucosides is shown in (I).

H- (G) _DP -OR (I)

Where G is glucozide, R is carbon group in alcohol which undergoes acetal reaction with glucozide, and DP is the degree of polymerization.

The most widely known industrial manufacturing method is fisher glycosidation method, which is obtained by reacting glucose with a large amount of alcohol under acid catalysis and neutralizing it by vacuum-reducing the unreacted alcohol according to US Pat. No. 3,839,318, corn, wheat, Starch extracted from palm oil is first reacted with butanol having a short carbon length, and then butylglucoid is formed as an intermediate. Alkylpolyglucozide is reacted by reacting a long carbon (C ₁ -C ₃₀ ) alcohol under an acid catalyst. The indirect method obtained is introduced in US Pat. No. 3,547,828, and the advantages and disadvantages of these methods are that the direct method has a low equipment cost but a high raw material cost, and the indirect method has a large equipment cost.

By-products formed during the production of alkyl polyglucosides include polyglucose, ether, and colored impurities. Factors controlling them include temperature, pressure, reaction time, and catalyst. To increase the viscosity may cause a precipitate, and if the reaction temperature is too high, discoloration may cause a problem as a surfactant of consumer goods, which may be a color problem, so you must find suitable reaction conditions.

Catalysts used to prepare alkylpolyglucosidides include sulfuric acid, hydrochloric acid, phosphoric acid, BF ₃ , PTSA (paratoluene sulfonic acid), alkyl as described in US Pat. Nos. 4,223,129,4,393,203, 4,393,203, German Patents 3,723,826, 3,842,541, 3,900,590 In addition to benzenesulfonic acid, alkylsulfonic acid, dinonylnaphthalenesulfonic acid, and the like, there are various kinds, and the most widely used is PTSA (paratoluene sulfonic acid).

After the reaction, the neutralizing agent is usually used a lot of NaOH, MgO, and in addition to the alcoholate of alkali and earth alkali metals introduced in US Patent 4,713,447.

As a method of removing the unreacted alcohol after the completion of the alkylpolyglucoside reaction, as described in US Pat. No. 4,889,925, a thin film distilation is used at 150-180 ° C., and the degree of polymerization DP is 1.2-1.7. The method for obtaining the obtained alkyl polyglucozide was introduced.

In addition, a method of solvent extraction is introduced in US Patent 3,547,828 and European Patent 92,355. In addition, a method for removing unreacted fatty alcohol is disclosed in French Patent A2017240, German Patent A13001064, European Patent EP-B10092876, A10531647, B10493, and the like. It is introduced.

In addition, according to European Patent 132,043, when a catalyst is used to inhibit the production of polyglucose, bluetoluene sulfonic acid (PTSA) or benzene sulfonic acid instead of sulfuric acid is used as a catalyst, the amount of polyglucose is generated when the reaction ratio of alcohol and glucose is 2: 1. In the European Patent 449,866, the reaction rate of alcohol and glucose can be reduced from 5: 1 to 2% polyglucose by using a new catalyst with a hydrophobic group added to sulfuric acid. It introduces.

In addition, European Patent B10437460 introduced various combinations of synthetic processes, and a method of removing odors of alkyl polyglucozide using steam was introduced in German Patent C2 4312559, and a method of obtaining a low polymerization degree was disclosed in German Patent A1 4414696. Introducing.

In order to increase the yield of polyalkylpolyglucosides and to suppress the production of alkylpolyglucosids in the conventional method of producing alkylpolyglucosides, the amount of alcohol used at least 2-7 times is minimized by the equivalent ratio of glucose so that the alcohol after the reaction The removal cost can be greatly reduced, and the solvent having a low boiling point can be reacted at a relatively low reaction temperature (80-100 ° C.), thereby preventing discoloration of the alkylpolyglucozide, thereby increasing the merchandise and allowing the glass beads to be reacted with the glass. It is an object of the present invention to provide a method for producing an alkylpolyglucoside that can increase the product yield while maximizing the reaction area by adding glass bead).

The present invention is a method for producing an alkylpolyglucoside by solving the problems occurring in the conventional method for producing an alkylpolyglucoside and improving the conventional method,

First, the fatty acid alcohol 1-1.8 equivalent ratio relative to glucose 1 equivalent ratio low boiling point solvent is 0.5-3 times the weight of glucose, the catalyst is a sulfonic acid-based acid in the molar ratio of glucose 5 mol%, glass beads 0.5 to the weight of the glucose After adding -5 times, stirring while maintaining the reaction temperature of 80-100 ℃ and circulating the low-boiling solvent while continuing to remove the water generated by the reaction for 7-8 hours to complete the reaction and neutralized with a neutralizing agent and then remove the low-boiling solvent It can be said to be a method for producing an alkyl polyglucozide represented by the following <II> formula.

R in the formula (II) has a carbon length of about 1 to 30, Ra, Rb, Rc, Rd is hydrogen or C ₁ -C _{30 is} composed of linear, branched, saturated or unsaturated form, DP ( Degree of polymerization) represents the number of glucose units bound to one molecule of alcohol, and the value of DP represents a degree of polymerization of 1-5.

Here, when the amount of use of the low boiling point solvent is increased in the range of use of alcohol, the circulating process is possible even in the range of the minimum amount of use of the low boiling point solvent, but when it is used below, problems occur in the circulation process and the range of use of the low boiling point solvent is used. The above use does not affect the reaction, but will be disadvantageous in the recovery process after the reaction,

In addition, the amount of glass beads used is at least 0.5 g / w weight ratio, and the reaction rate is remarkable, and the reaction rate is gradually increased.

As the fatty acid alcohol used in the above method, nucleic acid, heptan, octane, etc. may be used, and as the low boiling point solvent, nucleic acid, heptan, octane, etc. may be used, and the boiling point is relatively low boiling point such as hexane 68.742 ° C, heptan 98.428 ° C, octane 125.6 ° C, etc. Have

As the catalyst, sulfonic acid-based acids include ortho and para. Meta-toluene sulfonic acid, sulfuric acid and the like can be used.

Glass bead can be used with JHM 60 (BINEX), and its particle size can be used from 0.5mm to 10mm, and caustic soda, magnesium oxide, caustic, etc. are used as neutralizing agent.

In particular, the use of glass beads is not the core technology of the present invention, and the yield of alkylpolyglucoside is extremely low, the amount of polyglucose produced is high, and the degree of polymerization is high, so it cannot be used as a detergent or cosmetic additive.

The most suitable degree of polymerization suitable for the purpose of the invention can be said to be in the range of 1.2-1.7 median.

In order to clarify the technical configuration of the present invention and to examine the effects, comparative examples and examples were given.

Comparative Example

In a round flask equipped with a reflux device and a thermometer, 90 parts of glucose was added, 65 parts of octanol was added, 0.5 parts of para-toluene sulfonic acid was added as a catalyst, and glass bead JHM 60 was not added, and the solvent was stirred using a nucleic acid. The nucleic acid was circulated while stirring at about 100 ° C. for 12 hours, but 36 g of polyglucozide having a degree of polymerization (DP) of 55 was obtained.

Preparation Example 1

90 parts of glucose is added into a round flask equipped with a reflux device and a thermometer, 65 parts of octanol is added, 0.5 parts of para-toluene sulfonic acid is added as a catalyst, 90 parts of glass bead JHM is added, and the solvent is stirred at 90 ° by using a nucleic acid. After raising the temperature to 7 ℃ and circulating the nucleic acid while stirring for about 7 hours to remove the water and neutralized by adding 5 parts of magnesium oxide, and distilled the nucleic acid used as a solvent to form an alkyl polyglucozide of the formula (II) (DP = 1.7 88 g was obtained.

Preparation Example 2

In a round flask equipped with a reflux device and a thermometer, 90 parts of glucose, 80 parts of decanol, 0.5 parts of para-toluene sulfonic acid are added as a catalyst, 90 parts of glass beads JHM are added, and the solvent is stirred using a nucleic acid and heated to 90 °. After raising to ℃ and circulating the nucleic acid while stirring for about 8 hours to remove water, neutralize by adding 2 parts of potassium hydroxide and distilling the nucleic acid used as a solvent to give the alkyl polyglucozide of the form of formula (II) (DP = 2.5 ) 93 g was obtained.

Preparation Example 3

In a round flask equipped with a reflux device and a thermometer, 90 parts of glucose is added, 90 parts of dodecanol is added, 0.5 parts of para-toluene sulfonic acid is added as a catalyst, 90 parts of glass bead JHM is added, and the solvent is stirred using a nucleic acid. After raising the temperature to 8 ℃ and removing the water while circulating the nucleic acid while stirring for about 8 hours, neutralized by adding 5 parts of magnesium oxide and distilling the nucleic acid used as a solvent to give the alkyl polyglucozide of the form of formula (II) (DP = 3.7 ) 86 g was obtained.

Preparation Example 4

Put 90 parts of glucose in a round flask equipped with a reflux device and a thermometer, add 80 parts of decanol, add 0.5 parts of para-toluene sulfonic acid as a catalyst, use haptan as a solvent, and add 90 parts of JHM to glass beads. After raising the temperature to 8 ℃, circulating the nucleic acid while circulating for 8 hours to remove water, neutralize 4 parts of sodium hydroxide and distill the Heptop used as a solvent to give the alkyl polyglucozide of the formula (II) (DP = 4.2 80 g was obtained.

Preparation Example 5

In a round flask equipped with a reflux device and a thermometer, 90 parts of glucose was added, 70 parts of octanol was added, 0.5 parts of sulfuric acid was added as a catalyst, 90 parts of glass beads JHM were added, and the solvent was heated to 90 ° C. while stirring using a nucleic acid. After removing the water while circulating the nucleic acid while stirring for about 7 hours, neutralized by adding 5 parts of magnesium oxide, and distilled the nucleic acid used as a solvent to obtain 70 g of alkyl polyglucozide (DP = 3.8). .

Compared with the above comparative example and the embodiment of the present invention, in the comparative example, the input amount of the raw material is the same as the example, but the yield of alkylpolyglucozide is greatly reduced in terms of yield, and the polymerization degree is also represented by DP 55, which is actually used as a detergent or cosmetic additive. Can't.

According to the present invention, since glucose and alcohol are reacted in an equivalent ratio using a low boiling point solvent and beads, it is more economical than the conventional method using a large amount of alcohol, and the used solvent can be easily recovered and reused, and there is no need to remove unreacted alcohol. Since the reaction temperature is low to solve the problem of discoloration in the existing method it is possible to easily prepare the alkyl polyglucozide.

Claims (1)

The fatty acid alcohol is 1-1.8 equivalent weight, 0.5-3 times the weight ratio of the low boiling solvent, 0.5 mmol% the molar ratio of the acid of sulfonic acid, and 0.5-5 times the weight ratio of the glass beads. Stirring while maintaining and circulating a low boiling point solvent for 7-8 hours to complete the reaction to neutralize with a neutralizing agent and then to remove the low boiling point solvent of the following formula (II). R in general formula (II) has a carbon length of 1 to 30, and Ra, Rb, Rc and Rd are branched or linear structures of saturated or unsaturated form composed of hydrogen or C ₁ -C ₃₀ , and of DP The value has a value of 1-5.