Method for preparing water-soluble derivatives of chitosan

FIELD: chemical technology of natural compounds.

SUBSTANCE: invention describes a method for preparing water-soluble derivatives of chitosan. Method involves treatment of chitosan with acid medium up to its swelling wherein vapor medium water-acid is used as acid medium. Treatment of chitosan is carried out with vapor of monobasic acid aqueous solution taken among the group including hydrochloric acid, formic acid and acetic acid. Method allows simplifying technology in preparing water-soluble derivatives of chitosan.

EFFECT: improved preparing method.

4 cl, 1 tbl, 9 ex

 

The invention relates to chemical technology, in particular to methods for water-soluble chitosan (HTZ), and can be used in research practice, medicine, biology, cosmetic and food industry, agriculture, as well as solving a number of environmental problems: effective treatment of drinking and industrial water.

It is known that HTZ - natural polysaccharide possesses a number of useful physico-chemical and biological properties. This unique polymer with unlimited reproducible raw materials non-toxic, biocompatible, shows high complexing and sorption activity of ions of metals and organic molecules and is considered a promising material for making films and fibers with valuable properties [Modern perspectives in the study of chitin and chitosan: proceedings of the seventh international, proc. M: VNIRO. 2003. 452 S.].

From practice it is known that the source of Khartsyzsk pipe, derived from crustacean shell chemical and enzymatic methods, soluble in aqueous solutions of monobasic inorganic and organic acids. It is established that its molecular weightquite high and reaches values up to 1000 Da. The solubility of Khartsyzsk pipe in water depends on the degree of deacetylation (DM) and. N is scimolecular high BOD≥70 mole.% samples are easily dissolved in water. Therefore, water-soluble forms HTZ receive, through the destruction and/or chemical transformations of the original HTZ [Chitin and chitosan: synthesis, properties, application. M.: Nauka. 2002. 368 S.].

It is known that water-soluble derivatives of Khartsyzsk pipe are formed by N - and O-acylation [Loubaki E., Sicsic, S., Le Goffic f //Eur. polym. j. 1989. V.25. No. 6. P.379-384], quaternization of nitrogen with subsequent translation Quaternary policeware in the salt form [nud'ga L.A., Plisko E.A., S.N. Danilov. //Joh. 1973. T. No. 12. S-2760], graft polymerization [Chung J-E.,] Chung B-O., Chung B-K. //Kongop Hwahak. 1994. V.5. No. 3. R-536], synthesis of branched polysaccharides based on HTZ [Yalpani, M., Hall, L.D. //Macromolec. 1984. V.17. No. 3. R-281].

In addition to these processes for the dissolution of Khartsyzsk pipe in water are water-soluble compositions based on it [RF Patent №2144768, IPC And 01 N 43/16, a 01 N 63/00; RF Patent №2127056, IPC a 01 N 63/00], and also on the basis of Khartsyzsk pipe, modified (meth)acrylates [Mochalova AU, Izvozchikova V.A., Smirnova L.A., Semikov UD Synthesis and properties of water-soluble compositions based on chitosan modified with (meth)acrylates. Proc. Dokl. 3herUserassist. Of late, proc. M.: Moscow state University. 2004. T.1. S].

In addition, it is known that highly soluble in water, salt HTZ with odnoosnovny inorganic and monocarbonate acids [Muzarelli R.A.A. //Chitin. Oxford: Pergamon Press. 1977]. Although the literature dealing with the re are only a few data on the dependence of their solubility in water from the method of selection of samples from aqueous solution: the process of evaporation of water or by planting an organic precipitant, followed by drying in vacuum at room the temperature to constant weight. Found that planted acetic acid HTZ is not dissolved in water [Wasnew VA, Tarasov AI, Markov GD //polymer sciense ser. Conn. 2003. TB. No. 10. S-1792].

Thus, to date the problem remains the insolubility of macromolecular Khartsyzsk pipe in the water. This circumstance limits the expansion of the application area and complicates the processing.

Known methods of destruction HTZ enzymatic complex with chitinolytic activity of microbiological origin. Producers enzymatic complexes are Streptomyces kurssanovii [RF patent №2073016. IPC 08 In 37/08], Trichoderma reesei [Ilyin A.V., Tkachev, J.V., Varlamov V.P. //go active. biochem. and microbiol. 2002. V.38. No. 2. P.132-135], Serratia marcescens, Bacillus subtilis [Ilyin A.V., Varlamov V.P., Melent'ev A.P. //go active. biochem. and microbiol. 2001. V.37. No. 2, p.160-163]. Obtained by using the process of low-molecularwater-soluble Khartsyzsk pipe plant used in medicine as antiviral and anticancer drug and, as a carrier of biologically active compounds.

The disadvantage of this method is the complexity, the multi-stage process, the need for observance of a temperature mode and the use of different buffer systems and organic reagents. In addition, the product is ineffective when clear the e water.

A method of obtaining water-soluble succinate sodium salt of Khartsyzsk pipe, comprising the following steps: dissolution of Khartsyzsk pipe in 1%aqueous solution of acetic acid; the allocation of Khartsyzsk pipe from solution as a result of processing an alkaline agent to a pH of 6.9 and 7.5; the production of fine suspension HTZ; activation of Khartsyzsk pipe in water suspension shear cavitation effects or mechanical fields; the interaction of activated HTZ with powdered succinic anhydride with a particle size less than 100 microns; neutralizing the mixture with alkali solution; the selection of the target product by using spray or freeze drying [RF Patent №2144040, IPC 08 In 37/08, And 61 To 31/722].

The main disadvantage of this method is a multi-stage, the need for activation of Khartsyzsk pipe that extends and complicates the process.

A method of obtaining water-soluble forms of Khartsyzsk pipe, comprising preparing a homogeneous solution of Khartsyzsk pipe, its allocation by processing walochnik agent to a pH of 6.9 and 7.5, the amorphization of the polymer in the form of the aqueous suspension in cavitation or mechanical fields with shear effects, the interaction of the suspension with inorganic, organic acids or their anhydrides and isolation of the target product from solution in demineralized water using spray or freeze drying. If this is m use HTZ molefractions composition according to DM at a fixed molar ratio of amine groups of all factions HTZ and acid or anhydride of an organic acid [RF Patent №2215749, IPC 08 In 37/08, And 61 To 31/722, And 23 L 1/056].

The disadvantage of this method is the complexity, multi-stage, using aggressive environments, the need for strict control over the modes of dissolution, sedimentation, filtration and destruction.

Closest to the present invention is a method of obtaining water-soluble derivatives of Khartsyzsk pipe, including swelling onkodispansere (particle sizes) fraction of Khartsyzsk pipe plant in a highly polar solvent in an acidic environment; the treatment, if necessary, a chemical reagent (salt-forming, destruction or allermuir) in heterogeneous environments and the subsequent allocation of derivative HTZ [RF Patent №2099351, IPC 08 In 37/08].

The disadvantage of this method is the complexity of the process, a multi-stage, and use of, in addition to acids and other chemicals.

The objective of the proposed solutions is to simplify the technology of water-soluble derivatives of Khartsyzsk pipe.

The problem is solved in that in the method of obtaining water-soluble derivatives of Khartsyzsk pipe, including processing HTZ acidic environment to its swelling, according to the proposed solution processing HTZ lead pairs solution of monobasic acid.

As monobasic the acid may be used hydrochloric (HCl) or formic (HCOOH) or acetic acid (CH 3COOH), this processing is conducted to the point of vapor absorption HTZ at least 80±5 wt.%, 120±5 wt.%, 180±5 wt.% respectively.

The method is as follows. The sample powder (granules) Khartsyzsk pipe is maintained in a vapor solution of monobasic acid in a sealed vessel filled 1/25 part of the acid solution of fixed concentration (Cto). The amount absorbed by the polymer vapor was determined by the gravimetric method by weighing the sample before and after swelling in water vapor - salt (acetic or formic acid on an analytical balance (precision weighing was ±0.0001 g). The process of swelling characterized by the degree of absorption of vapors α=(m-m0)/m0·100%, where m and m0- mass dry and swollen sample HTZ. When calculating and account humidity (10-11%) source HTZ. Water vapor and vapor of acetic acid (96%) and in pairs of a 5%solution of hydrochloric acid polymer partially swells and value α reaches the equilibrium value. In pairs, formic acid, hydrochloric acid and aqueous solutions of acetic acid, formic acid and hydrochloric (except 5%solution) value α does not reach the equilibrium value even after 30 days of treatment of chitosan.

The minimum value of the degree of absorption of water vapor-acid (α), providing a solubility of the polymer in water, d is I each different acid concentrations to>0 to 38% for HCl, and 100% for HCOOH, up to 96% for CH3COOH also determined experimentally selected from a range of α 59 wt.% up to 110 wt.% for water vapor - HCl, up to 550 wt.% for water vapor - HCOOH, up to 510 wt.% for water vapor - CH3COOH and is hydrochloric acid solution of 80 wt.%, for formic acid, 120 wt.% and for solution of acetic acid - 180 wt.%.

When selecting the temperature of the swelling of the range 4-98°With best results obtained at a temperature of 20±5°C.

The following examples illustrate the present invention. Conditions modification of chitosan and characterization of its aqueous solutions are presented in the table.

Example 1. The hinge 0.15 g HTZDa and SD=83 mole.% soak in water vapor at t=19°C for 240 hours. Swollen HTZ not soluble in water.

Example 2. The hinge 0.15 g HTZD and SD=83 mole.% stand in pairs of 4% acetic acid at t=18°With over 173 hours. Swollen HTZ completely soluble in water.

Example 3. Analogously to example 2, HTZ stand in pairs 20% acetic acid at t=20°for 142,3 hours.

Example 4. Analogously to example 2, HTZ stand in pairs 96% acetic acid at t=22°With over 148,5 hours.

Example 5. Analogously to example 2, a sample of 0.1 g of Khartsyzsk pipe stand in pairs of 4% formic acid p and t=25° C for 144 hours.

Example 6. Analogously to example 5, HTZ stand in pairs 10% formic acid at t=21°With within 24 hours.

Example 7. Analogously to example 5, HTZ stand in pairs 100% formic acid at t=20°With within 24 hours.

Example 8. Analogously to example 2, HTZ stand in pairs 5% hydrochloric acid at t=20°for 315,5 hours.

Example 9. Analogously to example 2, HTZ stand in pairs 20% hydrochloric acid at t=18°for 292,5 hours.

Example 10. Analogously to example 2, HTZ stand in pairs 38% hydrochloric acid at t=20°C for 160 hours.

The table shows that the modified polymer pairs (with different degree of swelling), apparently, is a polymer in salt form and dissolved in water. Complete dissolution of the polymer was controlled visually, methods of dry residue and photojournalisme.

Thus, the proposed method allows to obtain water-soluble forms of Khartsyzsk pipe, simple, environmentally friendly, because it is conducted in a closed system, and economically viable, because modifications HTZ is only one reagent is a monobasic acid.

1. The method of obtaining water-soluble derivatives of chitosan, including the processing of chitosan acidic environment to its swelling, characterized in that the as the acidic environment of the use of steam environment water acid, and the processing of chitosan are pairs aqueous solution of monobasic acid selected from the group comprising hydrochloric acid, formic acid and acetic acid.

2. The method according to claim 1, characterized in that as the monobasic acid is chosen hydrochloric acid, and the treatment is carried out to the point of vapor absorption by not less than chitosan (80±5) wt.%.

3. The method according to claim 1, characterized in that as the monobasic acid is chosen formic acid, and the treatment is carried out to the point of vapor absorption chitosan at least (120±5) wt.%.

4. The method according to claim 1, characterized in that as the monobasic acid is chosen acetic acid, and the treatment is carried out to the point of vapor absorption chitosan at least (180±5) wt.%.



 

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