SU1520067A1 - Method of producing carboxymethyl ether hisotan - Google Patents

Abstract

The invention relates to the chemistry and technology of polysaccharide derivatives, specifically to the preparation of chitosan esters, and can be used in medicine, food and chemical industries. The invention allows to simplify the process of obtaining water-soluble chitosan carboxymethyl ester (exclude the re-precipitation, incorporation, blocking of amino groups and their release, reducing the consumption of alkylating reagent, acetic acid, caustic soda, etc.). Chitosan is treated with monochloroacetic acid in isopropanol medium at a mass ratio of chitosan: monochloroacetic acid: isopropanol 1: (0.6-1.1) :( 6-12) for 0.5-1.0 h at 21-35 ° C, then a 30-45% aqueous solution of sodium hydroxide is introduced into the reaction mixture at a weight ratio of monochloroacetic acid: sodium hydroxide 1: (0.83-1.0) and the treatment is continued for 1.5-2.0 hours at 70 -80 ° C. In order to increase the solubility of the target product, the introduction of monochloroacetic acid can be carried out in two steps: first, 0.3-0.6 wt.h. on 1 wt.h. chitosan, then before adding caustic soda - the rest. 2 tab.

Description

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The invention relates to the chemistry and technology of polysaccharide derivatives, in particular, to methods for producing chitosan esters containing carboxyl and amino groups and which are alkali- and acid-soluble polyampholytes that can be used in medicine, food and chemical industries.

The purpose of the method is to simplify the process, reduce the consumption of reagents and increase the solubility of the target product.

Example 1 To 1.0 ma.h. chitoo-zaia (moisture 10%, a solution of 0.7 masvCh of monochloroacetic acid (MCA) in 6.0 mAcOH of isopropacol is added and the mixture is stirred for 1 h at 21 ° C. Then 2.4 m is added to the reaction medium. 33% sodium hydroxide and stirring is continued for 1.5 hours at 80 ° C. At the end, the product is filtered, dissolved in 20 ml of a 0.1 N HC1 solution, and the solution is dialyzed to remove inorganic impurities.

but

the precipitated product is filtered off, centrifuged and dried. The obtained chitosan carboxymethyl ether (CMH) as an internal salt is analyzed for ionic chlorine content and solubility. The degree of substitution (C3) for the carmoxymethyl groups is calculated by the amounts

li pimer 8 "The process is carried out analogously to example 6. When activated, the mass ratio of the components is 1.0: 0.3: 6, O, temperature 23 ° C, duration 0.5 hours. When sodium is washed after the condition 0.7 mach.h.

Mortar Acid-Base Conductometric Extraction Based on Associated Hydrogen Chloride

PRI mme R 2. The process is carried out analogously to example 1. The mass ratio of chitosan, MCAA and isopropanol with activation is 1.0: 1.1: 12.0, the temperature, the treatment time is 0.5 hours. The amount of added my solution of NaOH in the subsequent processing of 2.3 masoCh. Processing is continued for 2 h at

Example 3: Mass ratio of chitosan, MCAA and isopropanol with activation 1.0: 0.6: 10.0, treatment temperature, duration 0.9 hours. The amount of 30% NaOH solution added during subsequent processing is 1 May 8, h Processing continued for 1.5 hours at.

Example 4 "The mass ratio of chitosan, MHUK and isopropanol when activated is 1.0: 0.3: 10.0, treatment temperature is 22 ° C, duration is 0.9 hours. The amount of MCAA added during the subsequent treatment is 0.3 mass%, 30% NaOH solution is added in the amount of 1.8 May, h. Processing time 1.5 hours, temperature

Example 5, Implementation Process 15

20

25

thirty

35

40

MHUK and 2.7 May, h. 37% NaOH solution, Duration 1.5 hours, temperature 75 ° С,

Example 9, The process is carried out analogously to example B, but after activation carried out according to example 8, 0.7 May is added, h. and

2.2maech, 45% NaOH solution, treatment time 2.0 h.

Example 10 (with extreme parameters), the process is carried out analogously to example 6, the mass ratio of the components when activated is 1.0: 0.3: 6.0, the temperature, the processing time is 0.3 hours. May, h, MHUK and 1.8 May, h, 30% NaOH solution, after a long time processing 1.5 hours, temperature 80 ° С,

Example 11 (with exorbitant values of the parameters), Process is analogous to example I, Mass ratio of hitbzan, MCAA and isopropanol with activation 1.0: 1.2: 12, O, temperature, processing time 0.5 h The amount of the added 26% NaOH solution with the following treatment was 4.2 May, h, the treatment time at 68 ° С

2.3h,

are eluted as in Example 4, but the duration is 0.5 h.

EXAMPLE 6 The process is carried out analogously to Example 2, but the introduction of the MCAA is carried out fractionally. When activated, the mass ratio of the components is 1.0: 0.6: 6.0, the duration is 0.6 hours. The number of MCAA and NaOH added during the subsequent processing in the form of a 45% aqueous solution is 0.5 mash, and 3, May 2, h, respectively, the processing time is 2.0 h,,

EXAMPLE 7 The process is carried out analogously to Example 6. When activated, the mass ratio of chitosan.

40

45

50

2.3h,

PRI imper 12 (with transcendental values, parameters), the process is similar to example 6, when activated, the ratio of components is 1.0: 0.3: 6.0, temperature, processing time is 1.5 hours. post-treatment add 0.3 May, h. MHUK, 30% of the caustic soda shed in ca. 1.8 May, h.

Example 13 (with exorbitant values of the parameters), the process is analogous to example 6, the mass ratio of the components upon activation is 1.0: 0.2: 6.0, the temperature is 35 ° C, the duration of treatment

 with g-f V X Ch. Ch, .4DH ACh A

MCAA and isopropanol 1.0: 0.3: 7.0, temp. 5 h. For post-treatment, dopture, duration 0.5 h. For post-treatment add 0.7 May, h o MCAA and 2 , 7 May „h.

0.5 mCoCh of MJUK and 0.2 May, h, 25% aqueous solution of NaOH, and a treatment time of 1.4 h.

37% aqueous solution of caustic soda. Duration 2,0 h, temperature.

li p i mep 8 "The process is carried out analogously to example 6. When activated, the mass ratio of the components is 1.0: 0.3: 6, O, temperature is 23 ° C, duration is 0.5 h. During the subsequent processing, 0 is added, 7 ma.ch.

five

0

five

0

five

0

five

0

MHUK and 2.7 May, h. 37% NaOH solution, Duration 1.5 hours, temperature 75 ° С,

Example 9, The process is carried out analogously to example B, but after activation carried out according to example 8, 0.7 May is added, h. and

2.2maech, 45% NaOH solution, treatment time 2.0 h.

Example 10 (with extreme parameters), the process is carried out analogously to example 6, the mass ratio of the components when activated is 1.0: 0.3: 6.0, the temperature, the processing time is 0.3 hours, 0 is added to the subsequent processing May 3, h, MHUK and 1.8 May, h, 30% NaOH solution, after a long time processing 1.5 hours, temperature 80 ° С,

Example 11 (with exorbitant values of the parameters), Process is analogous to example I, Mass ratio of hitbzan, MCAA and isopropanol with activation 1.0: 1.2: 12, O, temperature, duration of treatment 0.5 h. The amount of the added 26% NaOH solution with the following treatment was 4.2 May, h, the treatment time at 68 ° С

2.3h,

PRI imper 12 (with transcendental values, parameters), the process is similar to example 6, when activated, the ratio of components is 1.0: 0.3: 6.0, temperature, processing time is 1.5 hours. post-treatment add 0.3 May, h. MHUK, 30% of the caustic soda shed in ca. 1.8 May, h.

Example 13 (with exorbitant values of the parameters), the process is analogous to example 6, the mass ratio of the components upon activation is 1.0: 0.2: 6.0, the temperature is 35 ° C, the duration of treatment

with g-f V X Ch. Ch, .4DH ACh A

0.5 mCoCh of MJUK and 0.2 May, h, 25% aqueous NaOH solution, and the treatment time 1.4 h.

e p 14 (modified by Example 4

the sequence of treatment with an alkylating agent and caustic soda, for comparison with example 2). By May 1.0, h, chitosan is added on May 20, h. aqueous NaOH solution of 43% NaOH and it is stirred for 0.5 h at. At the end of the treatment, the chitosan is filtered off from excess sodium hydroxide in order to produce a chitosan: caustic soda ratio of 1: 1 to produce a weight ratio. Then, 1.1, MHAA is added to the pressed chitosan at 12 May, h, isopropanol and mixed together for a period of 2 h at 15 ° C, Isolation of the product of example 1,

Example 15 (with modified processing condition). The treatment; chitosan was carried out on 20 May, h, 20% aqueous NaOH solution for 1 h at 21 ° C. Chitosan was squeezed out until the chitosan: sodium hydroxide ratio, 1: 0.6, was added to the ochatoma chitosan; P, May 6, h, MCA in 6.0 maSoC, isopropipoprophyl alcohol, the process is continued at so С for 1.5 h,

PRI me R 16 (according to the known epo poo), Chitosan is pre-rotated in a 2% solution in the ukeuenoy kyolot, neutralized with caustic soda, neutralized with water from eols and dispersed in water,

By May, h, (calculated for each | substance), chitosan is added about, 65 May, h, salicylic aldehyde and stirred at

3 hours. At the end of the finish, the ealidnide-hitosac (CAX) is filtered off, washed on the filter with water (20.0 mash.), Alcohol (20.0 May, h), acetone (20.0 wt.), And isopropanol. (May 20.0, h). Then SAX wring out up to 5 times

By 1.1 May, h, NaOH at 30 May, h. isopropanol is added with pressed CAH. and stirred for 0.6 h, then 3.2 May is added, h, Na-aols of monochloro-cyanotel and continue to stir at 80 ° C for 2 h. After the end of the reaction, the product is filtered and purified from alkaline primeey by dialysis of the solution or by washing until neutral,

To remove the salicylidene protection, the resulting product is dissolved in 40 May, h, 50% aqueous solution of uvyeloin and aldehyde. To get 1520067

about 5

0 5

0

five

to 5

0 5

Neither counter-anionic or anti-oxidative water-soluble forms of the product are treated with 100 May, h, 0.1 N solutions of eolian kielota or caustic soda, respectively,

Characteristics of the product are given in Table 1

I Example 17 (by a known method), Carried out analogously to Example 16, but instead of using isopropanol, use of isopropanol and keylol 1: 1 (V / V) and Na-eoli of monochloro-kueloi 6.4 MasvCH,

The invention allows to simplify the process of obtaining CMH due to the exclusion of the stages of re-precipitation, blocking of the amino group and their release, as well as to reduce the consumption of alkylating reagent from 3.2-6.4 to 1.1 May, h, chitosan and reagents (ukeuena). acid, caustic soda, water, etalicyl aldehyde, epirt, isopropanol), used in the isolated stages. The invention allows to increase the heat of the target product with an euphoric injection of monochloro-kuenoi kieloty for its replacement rate,

Claims (1)

Table 2 shows the characteristics of the obtained samples and data on their eorbational capacity. Invention Formula 1, The method for producing chitosan carboxymethyl ester by its alkylation in the presence of caustic soda in isopropanol, characterized in that, in order to simplify the process and shorten the reagent, as an alkylating reagent, use monochloroxy-nicotho, while first - the treatment of chitosan with a monochloride cyanotic acid in an isopropanol chain at a Maes chitosan: monochloroacetic acid: isopropanol ratio of 1: 0.6-1.1: 6-12 for 0.5-1.0 h at 21- 35 ° C, then 30-45% is introduced into the reaction mixture odny solution of sodium hydroxide at a weight ratio of monochloroacetic acid: sodium hydroxide of 1.0: 0,83-1,0 and processing is continued for 1.5-2.0 hours at 70-80 ° C .: 2, Method of pop, 1, differing from that by the fact that, in order to increase the reliability of the target product. the introduction of monochloracetic acid is carried out in two steps; first, 0.3-0.6 wt. parts are introduced. on 1 ma.ch. 21 1.0 NaOH Merserig atsi 4E% NaOH solution Chideam redeposition 6.0 and protection of amino groups salicylic action aldehyde 1: 0.7: 0.6: 6.0 1.5 70 0.80 Chitoean: NaMXyK: NaOH: : isopropanol: xylene 1: 3.2: 1.1: 30.0: 0.00 2.0800.61 chitosan, then the rest of monochloroacetic acid is added before the addition of caustic soda. Table 0.90 incomplete Incomplete Table2