KR20020085016A - Purification method for crude 3-chloro-2-hydroxypropyl trimethyl ammonium chloride - Google Patents

Abstract

PURPOSE: A method for purifying crude 3-chloro-2-hydroxypropyltrimethylammonium chloride is provided to remove glycidyl trimethylammonium hydrochloride contained in the compound which induces yellowing, effectively and simply without using a molecular sieve or an active carbon. CONSTITUTION: The method comprises the step of adding an acid to 3-chloro-2-hydroxypropyltrimethylammonium chloride containing glycidyl trimethylammonium hydrochloride to adjust the pH to be 2-8, thereby removing the unreacted glycidyl trimethylammonium hydrochloride. Preferably the acid is selected from the group consisting of HCl, H2SO4, H3PO4 and acetic acid.

Description

Purification method for crude 3-chloro-2-hydroxyfurophylltrimethylammonium chloride {Purification method for crude 3-chloro-2-hydroxypropyl trimethyl ammonium chloride}

The present invention relates to a process for the purification of crude 3-chloro-2-hydroxyfurophylltrimethylammonium chloride.

Specifically, in the method for purifying crude 3-chloro-2-hydroxyfurophylltrimethylammonium chloride containing an alkyl quaternary ammonium salt such as glycidyltrimethylammonium chloride, crude 3-chloro-2-hydroxyfurofill Addition of acid to trimethylammonium chloride to maintain the pH of the aqueous solution at 2-8 to remove crude 3-chloro-2-hydroxyfurophiltrimethylammonium chloride. It relates to a purification method.

3-Chloro-2-hydroxyfurophylltrimethylammonium chloride is a highly reactive substance that reacts with starch or cellulose to produce cationic polysaccharides or to change synthetic polymers to be electrically positively charged. It is used as a cationic ionizer. In particular, cationic starch, which has been starched using 3-chloro-2-hydroxyfurophiltrimethylammonium chloride, is used as an important raw material for the papermaking process and is an important active intermediate in the manufacture of paper, textiles, water treatment chemicals, and cosmetics. chemical intermedate).

3-Chloro-2-hydroxyfurophylltrimethylammonium chloride is prepared by reacting trimethylamine or trimethylammonium hydrochloride with epichlorohydrin in an aqueous solution or an organic solvent (USP 2,876,217, USP 3,135,788, USP 4,450,295, USP 5,494,452).

US Pat. No. 2,876,217 discloses a method for preparing 3-chloro-2-hydroxyfurophyltrimethylammonium chloride by reacting epihalohydrin with tertiary amine or a salt thereof in an aqueous solution, and the resulting side reactant Phosphorus 1,3-dichloro-furopanol-2 was removed by solvent extraction or vacuum distillation. Since 1,3-dichloro-furopanol-2 has a property of causing crosslinking with starch, its content should not exceed 50 ppm.

As such, the main contents of the existing patents refer only to a method for removing 1,3-dichloro-furopanol-2, which is an optimized reaction condition for synthesis or a side reaction organic material. However, when an excessive amount of trimethylammonium hydrochloride in the raw material is used, by-products such as 1-3-dichloro-furopanol-2 are not produced, but an alkyl quaternary ammonium salt such as glycidyltrimethylammonium chloride is used. It is produced as a byproduct. This yellows the product, degrading the quality of the product, causing dissatisfaction from the user, affecting the color of the final product, and maintaining the APHA value of 20 or less, which is usually a color standard. In the colorimetric analysis, there are several units indicating strength and weakness of color intensity, and one of them is "APHA".

APHA (APHA Color Scale) is a color measurement method adopted by the American Public Health Association, and the measurement method is defined in ASTM D-1209.

Conventionally, the alkyl quaternary ammonium salt is purified by adsorption using a molecular sieve or activated carbon.

It is an object of the present invention to react trimethylammonium hydrochloride [(CH ₃ ) ₃ N.HCl] with epichlorohydrin [CH ₂ OCH CH ₂ Cl] in an aqueous solution to form 3-chloro-hydroxyfurophyltrimethylammonium chloride [Cl]. ^- (CH ₃ ) ₃ N ⁺ -CH ₂ CHOH CH ₂ Cl] Elimination of alkyl quaternary ammonium salts such as by-product glycidyltrimethylammonium chloride [CH ₂ OCH CH ₂ ON (CH) ₃ Cl] The present invention provides a method for preparing a colorless, odorless and transparent 3-chloro-hydroxyfurophylltrimethylammonium chloride having no odor and having a chromaticity of 10 or less APHA value.

The present invention provides a simple and economical method for the treatment of alkyl quaternary ammonium salts, such as glycidyltrimethylammonium chloride, contained in crude 3-chloro-2-hydroxyfurophiltrimethylammonium chloride, 3-chloro-2-hydroxyfurofill. A method for purification by conversion to trimethylammonium chloride. When glycidyltrimethylammonium chloride is reacted with hydrochloric acid, glycidyltrimethylammonium chloride is converted into 3-chloro-2-hydroxyfurofiltrimethylchloride. The method of the present invention can also be used to purify crude 3-halo-2-hydroxyfurophylltrialkylammonium halide prepared by reacting trialkylammoniumhydrohalide and epihalohydrin in an aqueous solution.

3-halo-2-hydroxyfurophylltrialkylammonium halide is an amine compound and epi selected from trimethylamine, triethylamine, tripropylamine, dimethylstearylamine, dimethylmonoisopropylamine, tri-N-butylamine, etc. It is prepared by reacting epihalohydrin such as chlorohydrin, epibromohydrin and epiiodhydrin.

Hereinafter, the configuration of the present invention will be briefly described.

Epichlorohydrin was slowly added dropwise to the 59% aqueous solution of trimethylammonium hydrochloride at 5 to 30 ° C. for 4 to 12 hours while maintaining the reaction temperature not to exceed 5 to 30 ° C.

After the dropwise addition of epichlorohydrin, ripening at 40 ° C. for 1-3 hours yields crude 3-chloro-2-hydroxyfurophylltrimethylammonium chloride in a yield of about 80-98%. During the recovery process through reduced pressure distillation, steam distillation, etc., it causes yellowing, and the transparency of the product greatly decreases the APHA value to 30 ~ 100. Hydrochloric acid with a concentration of 1% to 35% was added to this solution at 10 ~ 60 ℃ to adjust the hydrogen ion concentration (pH) of the solution to 2.0 ~ 6.9. A yellow aqueous solution of 3-chloro-2-hydroxyfurofiltrimethylammonium chloride was prepared. The transparency of APHA values 1-29 is shown. In addition, through the above operation, alkyl quaternary ammonium salts such as glycidyltrimethylammonium chloride as a by-product of the reaction are completely converted into 3-chloro-2-hydroxyfurophyltrimethylammonium chloride, so that they do not exist in the product.

The present invention utilizes an acid such as HCl from an aqueous solution of 3-chloro-2-hydroxyfurophyltrimethylammonium chloride having an APHA value of 30 to 50 to increase transparency in a very simple and economical manner, and to use an alkyl quaternary ammonium salt (glycidyltrimethyl Ammonium halide) is converted into 3-chloro-2-hydroxyfurophiltrimethylammonium chloride by the following examples. The chromaticity measurement (transparency, APHA value) of each item was used a spectrophotometer.

Example 1

HCl (35% aqueous solution) was added to 1 kg of a 68% 3-chloro-2-hydroxyfurophyltrimethylammonium chloride solution containing 2% glycidyltrimethylammonium chloride with an APHA value of 500 and a pH of 8 to bring the hydrogen ion concentration to 6. After the composition was stirred at 40 ° C. for 30 minutes and then chromaticity was measured. Spectrophotometer was used for color analysis, and glycidyltrimethylammonium chloride concentration was analyzed using a titration method. The results are shown in Table 1 below.

division pH Chromaticity (APHA value) Glycidyltrimethylammonium chloride content (%) sample 8 50 2.0% Example 1 6 20 Not detected

Examples 2-4

Except for using sulfuric acid (Example 2), phosphoric acid (Example 3), acetic acid (Example 4) instead of HCl, the same method as in Example 1 was carried out in the same manner as the color and glycidyltrimethylammonium chloride Was measured and the results are shown in Table 2 below.

division pH Mountain type Chromaticity (APHA value) Glycidyltrimethylammonium chloride content (%) Example 2 5 H ₂ SO ₄ 15 Not detected Example 3 4 Phosphoric Acid 10 Not detected Example 4 3 Acetic acid 10 Not detected

In the conventional patent literature, the purification technique is hardly mentioned or when the chromaticity is removed with a general adsorbent (such as activated carbon), the cost increases and the process is very complicated.

The following Comparative Examples 1 to 4 are chromaticity and results during activated carbon treatment.

Comparative Examples 1 to 4

0.5 g, 1.0 g, 3.0 g, and 10.0 g of industrial powdered activated carbon were added to 1 kg of an aqueous 68% 3-chloro-2-hydroxyfurophylltrimethylammonium chloride solution having a chromaticity APHA of 500, and the mixture was stirred at 30 ° C. for 1 hour and filtered. The result of chromaticity analysis of the sample which came out is shown in the following table.

division Activated carbon Chromaticity (APHA value) Glycidyltrimethylammonium chloride (%) sample 0.5g 100 2.0% Example 1 1.0 g 50 2.0% Example 2 3.0 g 35 2.0% Example 3 5.0 g 16 2.0% Example 4 10.0 g 9 2.0%

From the above results, the chromatic solution of 3-chloro-2-hydroxyfurophylltrimethylammonium chloride with APHA value of 50 was reduced to HCl by a very simple method, and the epoxidized quaternary salt (glycidyltrimethylammonium chloride) was totally 3 Chloro-2-hydroxyfurophiltrimethylammonium chloride could be converted.

Purification method of the present invention is a crude 3-chloro-3-hydride containing glycidyltrimethylammonium chloride in a very simple method without a separate purification process compared to the conventional purification method using a molecular sieve (molecular seive) and activated carbon It has the effect of being able to refine | purify oxyfurofil trimethylammonium chloride to APHA value 10 or less.

Claims (2)

In the purification method of crude 3-chloro-2-hydroxyfurophylltrimethylammonium chloride containing glycidyltrimethylammonium chloride, an aqueous solution is added by adding an acid to the crude 3-chloro-2-hydroxyfurophiltrimethylammonium chloride. Purification of crude 3-chloro-2-hydroxyfurophiltrimethylammonium chloride by removing the glycidyltrimethylammonium chloride in crude 3-chloro-2-hydroxyfurophylltrimethylammonium chloride by maintaining the pH of 2-8 . The process for purifying crude 3-chloro-2-hydroxyfurophyltrimethylammonium chloride according to claim 1, wherein the acid is selected from hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid.