KR20060075836A - Production of alkylene oxide adduct using the additive - Google Patents

Abstract

The present invention relates to a method for producing an alkylene oxide adduct using an additive. More specifically, additives such as crown ether, alcohol ethoxylate monomethyl ether, PEG-DME (dimethyl ether), etc., to the base catalyst in the synthesis of the alkylene oxide nonionic surfactant The present invention relates to a method for preparing an alkylene oxide adduct having a narrow addition mole distribution and having a very low content of by-product PEG (polyethylene glycol).

Excipients * Alkylene oxide * Crown ether * PEG-DME

Description

Production method of alkylene oxide adduct using additives {Production of alkylene oxide adduct using the additive}

1 is a graph showing the adduct distribution of Example 3 and Comparative Examples 1 and 2. FIG.

The present invention relates to a method for producing an alkylene oxide adduct using an additive. More specifically, additives such as crown ether, alcohol ethoxylate monomethyl ether, PEG-DME (dimethyl ether), etc., to the base catalyst in the synthesis of the alkylene oxide nonionic surfactant The present invention relates to a method for preparing an alkylene oxide adduct having a narrow addition mole distribution and having a very low content of by-product PEG (polyethylene glycol).

In terms of environmental protection, the importance of nonionic surfactants, which are widely used as laundry detergents, dishwasher detergents, industrial detergents, and emulsifiers, is increasing. Generally, nonionic surfactants are prepared by adding ethylene oxide / propylene oxide to lipophilic compounds. The current trend of the nonionic surfactant industry is the tendency that the ethylene oxide / propylene oxide adduct products with a wide distribution of ethylene oxide / propylene oxide are gradually maximizing the distribution of adducts, and the active ingredient is shifting to an adduct product having a narrow distribution showing the maximum constituent distribution. to be.

Ethylene oxide / propylene oxide adducts with narrow addition water distribution have excellent detergency and foaming ability, excellent surface tension properties and increased solubility in water, reduction of specific odor through minimization of unreacted substances, and Excellent application properties such as improved stability and the possibility of high concentration of the product. In addition, ethylene oxide / propylene oxide adducts having a narrow addition water distribution can minimize side reactions such as 1,4-dioxane in sulfuration reactions, excellent foaming and penetrating ability, high viscosity increasing effect, and excellent powder to calcium soap. It is known to exhibit acid and hypoallergenic properties to the skin. Accordingly, in the nonionic surfactant industry, development of new ethylene oxide / propylene oxide adducts, which are characterized by a narrow adduct distribution, has been accelerated, and it is very important to secure a reaction technology capable of commercially manufacturing them.

As a conventional technique of narrow range ethoxylation (NRE), a method using various metal catalysts has been proposed. The specific techniques are summarized as follows.

U. S. Patent No. 4,886, 817 and U. S. Patent No. 4, 835, 321 have proposed a catalyst system based on calcium. In addition, US Pat. No. 5,817,488 discloses an alkoxylation reaction of a fatty acid ester with a substance treated with an alkali metal hydroxide, such as potassium hydroxide or sodium hydroxide, in order to improve the product distribution characteristics of the catalyst system heat-treated with a mixed metal or hydroxidetalite. It describes about the method to use. U.S. Patent No. 5,326,891 describes a catalytic material that enhances the dispersibility of a solid catalyst material to a reactant by treating hydrotalcite with a carboxylic acid compound to impart hydrophobicity. U. S. Patent No. 5,220, 077 describes a technique for preparing an addition compound having a narrow distribution using an alkoxide compound or alkoxide compound catalyst material containing Ca, Sr, Ti, and the like. Japanese Patent Laid-Open No. 2000-61304 discloses a catalytic material using Mg, Al, and other third component metals.

However, the above-described techniques using various metal catalysts not only require expensive catalyst synthesis costs, but also cause different activities of the alkoxy addition reaction depending on the reaction rate of the catalyst, the distribution of adducts, the degree of byproduct formation, and the like. In particular, a large amount of cost is consumed to remove catalyst residues present in the product, thereby increasing the price of the product and inefficiency of the process operation. In addition, the high content of PEG (polyethylene glycol) produced by catalytic side reactions in the product often adversely affects product properties.

Therefore, the present inventors have studied to obtain a product of excellent physical properties while solving the above problems, as a result of the synthesis of the alkylene oxide-based nonionic surfactants in the existing base catalysts (crown ether, alcohol ethoxylate mono When the additives such as methyl ether (alcohol ethoxylate monomethyl ether) and PEG-DME (dimethyl ether) are added, it has been found that alkylene oxide adducts having a narrow addition mole distribution can be efficiently produced.

Accordingly, an object of the present invention is to provide a method for producing an alkylene oxide adduct having a narrow addition mole distribution using a additive and having a very low content of polyethylene glycol (PEG) as a by-product.

In order to achieve the above object, the production method of the alkylene oxide adduct of the present invention is a conventional ether catalyst in the crown ether (crown ether), alcohol ethoxylate monomethyl ether (alcohol ethoxylate monomethyl ether), or PEG-DME ( dimethyl ether) is added to prepare an alkylene oxide adduct having a narrow addition mole distribution.

Hereinafter, the present invention will be described in more detail.

The present invention is used in alkoxy addition reactions such as fatty alcohols, fatty acid esters, fatty amines, etc., which are raw materials of nonionic surfactants, and thus, crown ethers and alcohol ethoxylates which can control the addition number distribution in a narrow range. The present invention relates to a method for preparing an alkylene oxide adduct using additives such as alcohol ethoxylate monoethyl ether and PEG-DME (dimethyl ether).

Additives used in the present invention include crown ether, alcohol ethoxylate monomethyl ether, PEG-DME (dimethyl ether) and the like.

Specific examples of the crown ether include 18-crown-6-ether, 12-crown-4-ether, 15-crown-5-ether and the like, and the most preferred example is 18-crown-6-ether. .

Specific examples of the alcohol ethoxylate monomethyl ether include monomethoxy polyoxyethylene lauryl ether, monoethoxy polyoxyethylene lauryl ether, Monobutoxy polyoxyethylene lauryl ether.

The content of the additive is It is preferable to add in 1 to 30% of the molar ratio of the product, and more preferably in 2 to 15% in terms of physical properties of the product.

The method for producing an alkylene oxide adduct using the additive of the present invention is a post-treatment by significantly reducing the content of PEG (polyethylene glycol) produced by the side reaction in the reaction step while using the existing process without the need for a separate catalyst manufacturing process No process or the like is required.

The additive of the present invention is used in the alkoxy addition reaction of reactants such as fatty alcohols, fatty amines, fatty acid esters and fatty acids with alkylene oxides such as ethylene oxide or propylene oxide in combination with a base catalyst and alkylene having a narrow addition mole distribution. Oxide adducts are prepared.

The production method of the present invention is described in more detail below.

First, a material selected from fatty alcohols, fatty amines, fatty acid esters, fatty acids, and the like as raw materials is introduced into the reactor, and the base catalyst and the additives are added at about 40 to 50 ° C. At this time, the additive is to be added in 1 ~ 30% of the molar ratio of the product. After the addition is completed, the temperature is raised while stirring to maintain the temperature of about 100 ~ 110 ℃. Next, to remove the water in the reactor by performing a vacuum at 100 ~ 110 ℃ to remove the water. At this time, the vacuum is about 10mmHg, time is about 30 minutes ~ 1 hour. After removing water, adjust the pressure to atmospheric pressure using nitrogen in the reactor, and then increase the temperature to 150 ~ 180 ° C. After raising the temperature, ethylene oxide or propylene oxide gas is added. At this time, the amount of ethylene oxide or propylene oxide used varies depending on the type of the desired surfactant, but is used in 1 ~ 30 mol per 1 mol (mol) of the raw material, the input pressure is about 4 ~ 5k / G. After the addition, the temperature and stirring are maintained for about 30 minutes to 1 hour to remove ethylene oxide or propylene oxide gas in the reactor. Next, after the reactor temperature is lowered to about 80 ~ 100 ℃ neutralized with acetic acid and the like to prepare a final product.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only to these examples.

[Examples 1-3]

200 g of lauryl alcohol as a raw material was added to the reactor, and KOH and 18-crown-6-ether were added at 50 ° C. at 1, 5, and 10 ratios of the catalyst, respectively. After the addition was completed, the temperature was raised while stirring to maintain the temperature of about 100 ℃, and then in order to remove the moisture in the reactor by vacuum at 100 ℃ 10mmHg for 30 minutes to remove the moisture. After removing water, adjust the pressure to atmospheric pressure using nitrogen in the reactor, and then raise the temperature again to 180 ° C. Then, 136 g of ethylene oxide was added at 4k / G. Supplied. After the end of the supply to maintain the temperature and stirring for about 30 minutes to remove the ethylene oxide or propylene oxide gas in the reactor, the reactor temperature was lowered to about 80 ℃ and neutralized with acetic acid to prepare the products Examples 1-3 It was.

Next, the distribution of the product and the distribution of the unreacted alcohol were measured using gas chromatographie (initial temperature; 100 ° C, elevated temperature; 350 ° C, carrier gas; helium), and the results are shown in Table 1 and FIG. 1. Shown in

EXAMPLES 4-6

Examples 4 to 6 were prepared in the same manner as in Examples 1 to 3, except that PEG-DME (dimethyl ether) (Mw 500) was added as an additive at 1, 5, and 10 ratios of the catalyst. The results are shown in Table 1 below.

Comparative Example 1

Comparative Example 1 was prepared by a conventional method using KOH, which is a conventional base catalyst. The results are shown in Table 1 and FIG. 1.

Comparative Example 2

Comparative Example 2 was prepared by a conventional method using a catalyst using a Mg-Al-based metal mixture as a conventional NRE catalyst. The results are shown in Table 1 and FIG. 1.

catalyst Catalyst content (ppm) Additive Type Additive / Catalyst Ratio Unreacted alcohol (wt%) By-product (wt%) Peak (mol%) Example 1 KOH 800 18-crown-6-ether One 14.3 Less than 1 15.5 Example 2 KOH 800 18-crown-6-ether 5 15.3 1.5 15.5 Example 3 KOH 800 18-crown-6-ether 10 15.2 3 16 Example 4 KOH 800 PEG-DME One 16.6 Less than 1 15.2 Example 5 KOH 800 PEG-DME 5 15.8 3 15.5 Example 6 KOH 800 PEG-DME 10 15.1 6 15.6 Comparative Example 1 KOH 800 - - 22 Less than 1 14.5 Comparative Example 2 NRE catalyst 3000 - - 13 8-15 20.5

In the case of the conventional production method without using the additive in the results of Table 1 and Figure 1 (Comparative Example 1) is about 22% by weight of the unreacted alcohol, about 6 to 7 compared to Examples 1 to 6 using the additive It was higher than%. Therefore, in the case of Comparative Example 1, a post-process for removing unreacted alcohol causing skin irritation is necessary.

In addition, in the case of using a conventional NRE catalyst (Comparative Example 2), the content of unreacted alcohol is significantly lower than that of Comparative Example 1 and shows a high degree of distribution of peaks. Since it must be removed, it is very unsuitable to use as a real product.

On the other hand, Examples 1 to 6 according to the present invention showed a lower content of unreacted alcohol than Comparative Example 1, the PEG content as a by-product shows a much lower level than the case of Comparative Example 2. Therefore, when using Examples 1 to 6 of the present invention as an actual product, it is possible to produce a product at a level that does not require a post-process, and in particular, it can be applied to an existing process as it is, and an expensive catalyst manufacturing cost is not incurred. have.

As described above, the present invention is to add the additive to the existing catalyst in the preparation of the nonionic surfactant to reduce the physical properties due to by-products in the alkoxy addition reaction while using the existing process without the need for a separate catalyst manufacturing process It is possible to provide a method for producing an alkylene oxide adduct having a narrow addition mole distribution that can be prevented and a very low content of byproduct PEG.

Claims (3)

In the method for producing an alkylene oxide adduct using a base catalyst, In the base catalyst, an additive selected from the group consisting of crown ether, alcohol ethoxylate monomethyl ether, and PEG-DME (dimethyl ether) is 1 to 30% of the molar ratio of the product. In addition, a method for producing an alkylene oxide adduct, characterized in that the alkoxy addition reaction is carried out. The method of claim 1, wherein the crown ether is selected from the group consisting of 18-crown-6-ether, 12-crown-4-ether, and 15-crown-5-ether. . According to claim 1, wherein the alcohol ethoxylate monomethyl ether is monomethoxy polyoxyethylene lauryl ether (monomethoxy polyoxyethylene lauryl ether), monoethoxy polyoxyethylene lauryl ether (monoethoxy ploloxyethylene lauryl ether), and mono- Method for producing an alkylene oxide adduct comprising the one selected from the group consisting of methoxy polyoxyethylene lauryl ether (monobutoxy polyoxyethylene lauryl ether).

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