RU2590982C1 - Method of producing granules of cross-linked chitosan - Google Patents

Method of producing granules of cross-linked chitosan Download PDF

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Publication number
RU2590982C1
RU2590982C1 RU2015125829/15A RU2015125829A RU2590982C1 RU 2590982 C1 RU2590982 C1 RU 2590982C1 RU 2015125829/15 A RU2015125829/15 A RU 2015125829/15A RU 2015125829 A RU2015125829 A RU 2015125829A RU 2590982 C1 RU2590982 C1 RU 2590982C1
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Russia
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granules
chitosan
hydrochloric acid
method
glutaraldehyde
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RU2015125829/15A
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Russian (ru)
Inventor
Александр Викторович Пестов
Светлана Юрьевна Братская
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Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук
Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук
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Application filed by Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук, Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук filed Critical Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук
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Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to polymer materials and specifically to a method of producing granules of cross-linked chitosan, which involves cross-linking chitosan with glutaric aldehyde using hydrochloric acid solution containing glutaric aldehyde, with molar ratio of chitosan:hydrochloric acid:glutaric aldehyde, equal to 1:(0.5-1.0):(0.1-1.0), and then extrusion moulding gel in form of threads, which are mechanically cut into granules and dried at temperature 40-70 °C for 1-2 hours.
EFFECT: invention provides decrease in method of amounts of acid, glutaric aldehyde and precipitation agents, enables to obtain chitosan granules of controlled size.
1 cl, 6 ex

Description

The invention relates to the field of polymeric materials, and in particular to methods for producing granular forms of chitosan and its derivatives, which can be used as ion-exchange resins for the extraction of metal and non-metal ions from aqueous solutions and as carriers of metal-containing catalysts for organic reactions.

A known method of producing granules of non-crosslinked chitosan by precipitating a polymer by dripping from a citric acid solution into an aqueous solution of sodium hydroxide (WO 2011124380). The use of an aqueous-organic solvent (J. Appl. Polym. Sci. 103 (2007) 211-217) or an aqueous solution of sodium tripolyphosphate (Chem. Eng. J., 210 (2012) 590-596) is described as a precipitant. The disadvantages of the method include the need to use a precipitator of inorganic or organic nature and a dropping device, which, in turn, requires a dilute solution of the polymer. The size of the formed spherical granules when using a precipitant is determined by the diameter of the nozzle, which creates a limitation on the minimum size of the obtained granules and limits the possibility of their use.

A known method of producing granules of crosslinked chitosan (Desalination and Water Treatment 52 (2014) 7733-7742) by initially preparing an emulsion of an acetic acid diluted solution of chitosan in paraffin containing Tween 80 surfactants and polyethylene glycol 2000, with vigorous stirring of the mixture, followed by treatment of the emulsion with water formaldehyde solution and precipitant - 5% aqueous-ethanol NaOH solution. Then the granules are washed with petroleum ether, dispersed in an aqueous solution of sodium hydroxide, treated with epichlorohydrin and washed successively with water, a solution of hydrochloric acid and a solution of NaOH. The granules are dried in vacuum for 24 hours to constant weight. The disadvantages of the method include the need to use organic compounds in large quantities for the preparation of the emulsion and the subsequent cleaning of the granules from paraffin, precipitant in an aqueous-ethanol solution, a mixing device and numerous washing operations of the granules. The distribution of the formed spherical granules according to the particle size with this method is irreproducible and the spread is large, which limits the possibility of using granules.

A known method for producing granules of crosslinked chitosan (Can. J. Chem. Eng., 89 (2011) 833-843) is a prototype based on the initial preparation of a 3% solution of chitosan in acetic acid with a molar ratio of chitosan: acetic acid of 1: 4, followed by sprinkling it in an aqueous solution of NaOH. Then the granules are washed with water to remove residual NaOH and dried in air. After that, the granules are dispersed in an aqueous solution of glutaraldehyde at a molar ratio of chitosan: glutaraldehyde 1: 1, incubated for 24 hours, washed with water, filtered and dried in air.

The disadvantages of the method include the need to use a large amount of acetic acid and glutaraldehyde, a dilute solution of chitosan, which entails the uneconomical use of solvent and reagents. In turn, this causes technological inconvenience, because equipment is used inefficiently due to the large volumes of solvent and reagents. In addition, in this method it is necessary to use an inorganic precipitant, a spray device, for the operation of which it is necessary to use a dilute polymer solution and numerous granule washing operations. The distribution of the formed spherical granules by particle size with this method is irreproducible and significantly large, which limits the possibility of using granules.

The objective of the invention is to obtain granules of cross-linked chitosan and its derivatives in a simple and effective way using minimal amounts of acid, glutaraldehyde and precipitating substances.

The problem is solved in that in the method for producing granules of crosslinked chitosan, including the step of forming granules and crosslinking the polymer with glutaraldehyde in an acidic solution, the polymer is first crosslinked using a solution of hydrochloric acid containing glutaraldehyde at a molar ratio of chitosan: hydrochloric acid: glutar aldehyde 1: (0.5-1.0) :( 0.1-1.0), and then the gel is extruded into filaments, they are mechanically cut into granules and dried at a temperature of 40-70 ° C for 1- 2 hours. The preparation of an aqueous polymer gel is carried out by mixing it with a solution of hydrochloric acid containing glutaraldehyde as a crosslinking agent. Extrusion molding of the gel is carried out by passing it through a tube made of a synthetic polymer. The mechanical cutting of the obtained thread is carried out using a metal knife. Recommended conditions for the production of granules of crosslinked chitosan and its derivatives are established experimentally, and are also determined by the ideas about the process described below. For the preparation of granules, it is necessary to use a 3-6% aqueous polymer gel. A lower polymer concentration leads to excessive water consumption. A high polymer concentration will not allow extrusion to form the gel in the form of threads. The use of a molar ratio of chitosan: hydrochloric acid above 1: 1 leads to the destruction of the polymer and to excessive consumption of acid. The use of a molar ratio of chitosan: hydrochloric acid below 1: 0.5 is ineffective due to insufficient swelling and dissolution of the polymer, which also will not allow the gel to be extruded into filaments. The use of a molar ratio of chitosan: glutaraldehyde above 1: 1 will not allow the gel to be extruded into filaments and is an excessive consumption of aldehyde. The use of a molar ratio of chitosan: glutaraldehyde below 1: 0.1 is ineffective due to insufficient crosslinking of the polymer. Carrying out drying at a temperature of less than 40 ° C does not provide the formation of a crosslinked structure of the granules, and at temperatures above 70 ° C, polymer and granules are destroyed. Conducting drying for less than 1 hour is not enough to completely dry the granules, and more than 2 hours is impractical due to the cessation of their further drying.

The proposed method can be obtained granules of not only cross-linked chitosan, but also its derivatives: N-2- (2-pyridyl) ethylchitosan, N-2- (4-pyridyl) ethylchitosan and N- (4-imidazolyl) methylchitosan.

The preparation of crosslinked chitosan, N-2- (2-pyridyl) ethylchitosan, N-2- (4-pyridyl) ethylchitosan and N- (4-imidazolyl) methylchitosan granules is illustrated by the following examples:

Example 1

2 g of chitosan is dissolved in 40 ml of a hydrochloric acid solution containing 0.3% glutaraldehyde (molar ratio of chitosan: hydrochloric acid: glutaraldehyde 1: 1: 0.1). The resulting gel was extruded from a polyvinyl chloride tube with simultaneous cutting and dried for 1 hour at 70 ° C. Get the granules of the same shape with a particle size of 1 mm

Example 2

2 g of chitosan is dissolved in 62 ml of a hydrochloric acid solution containing 0.6% glutaraldehyde (molar ratio of chitosan: hydrochloric acid: glutaraldehyde 1: 0.5: 0.2). The resulting gel was extruded from a polyvinyl chloride tube with simultaneous cutting and dried for 2 hours at 50 ° C. Get granules of the same shape with a particle size of 0.5 mm

Example 3

2 g of chitosan is dissolved in 40 ml of a hydrochloric acid solution containing 1.2% glutaraldehyde (molar ratio of chitosan: hydrochloric acid: glutaraldehyde 1: 0.7: 0.4). The resulting gel was extruded from a polyvinyl chloride tube with simultaneous cutting and dried for 2 hours at 50 ° C. Get granules of the same shape with a particle size of 0.2 mm

Example 4

2 g of N-2- (2-pyridyl) ethylchitosan is dissolved in 31 ml of a hydrochloric acid solution containing 1.8% glutaraldehyde (molar ratio of N-2- (2-pyridyl) ethylchitosan: hydrochloric acid: glutaraldehyde 1: 1: one). The resulting gel was extruded from a polyvinyl chloride tube with simultaneous cutting and dried for 1 hour at 70 ° C. Get the granules of the same shape with a particle size of 1 mm

Example 5

2 g of N-2- (4-pyridyl) ethylchitosan is dissolved in 40 ml of a hydrochloric acid solution containing 1.8% glutaraldehyde (molar ratio of N-2- (4-pyridyl) ethylchitosan: hydrochloric acid: glutaraldehyde 1: 1: one). The resulting gel was extruded from a polyvinyl chloride tube with simultaneous cutting and dried for 1 hour at 70 ° C. Get granules of the same shape with a particle size of 0.2 mm

Example 6

2 g of N- (4-imidazolyl) methylchitosan is dissolved in 50 ml of hydrochloric acid containing 1.8% glutaraldehyde (molar ratio of N- (4-imidazolyl) methylchitosan: hydrochloric acid: glutaraldehyde 1: 1: 1). The resulting gel was extruded from a polyvinyl chloride tube with simultaneous cutting and dried for 2 hours at 50 ° C. Get granules of the same shape with a particle size of 0.5 mm

The granulation method is simple to implement, it uses commercially available compounds, eliminates the use of non-crosslinking inorganic and organic compounds and an excessive amount of solvents, both in the granulation process and in the process of product isolation, does not require mixing and complex dropping devices or spraying devices. The starting material for granulation has a gel consistency, which ensures the convenience of its experimental use and increase the efficiency of the equipment used, since it consumes less reagents and solvent. The method allows to form granules of both chitosan and its derivatives. The granules obtained by the present method have a cylindrical shape, which provides a larger surface area of the particles compared to spherical granules. This allows reproducibly forming granules of a controlled size depending on their subsequent use. A significant advantage of the proposed method for producing granules is the simplicity and manufacturability of the process of producing granules with fewer stages in contrast to the known methods. The inventive method allows to obtain granules on any industrial extrusion equipment without additional improvements. Granules can be used in their intended form as a sorbent of metal ions, and also as a carrier in hybrid organo-inorganic catalytic systems.

Claims (1)

  1. A method of producing granules of crosslinked chitosan, comprising the step of forming granules and crosslinking the polymer with glutaraldehyde in an acidic solution, characterized in that the polymer is first crosslinked using a hydrochloric acid solution containing glutaraldehyde with a molar ratio of chitosan: hydrochloric acid: glutaraldehyde 1 (0.5-1.0) :( 0.1-1.0), and then the gel is extruded into filaments, they are mechanically cut into granules and dried at a temperature of 40-70 ° C for 1-2 hours.
RU2015125829/15A 2015-06-29 2015-06-29 Method of producing granules of cross-linked chitosan RU2590982C1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2657506C1 (en) * 2017-09-25 2018-06-14 Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" (ИГХТУ) Method of extracting heavy metal ions from aqueous solutions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2094117C1 (en) * 1996-07-23 1997-10-27 Акционерное общество закрытого типа "Фосфосорб" Sorbent and method for its production
RU2172325C2 (en) * 1997-12-18 2001-08-20 Маев Сергей Петрович Method of preparing chitosan-base substance for food and pharmaceutical industry
US6752938B2 (en) * 2001-10-13 2004-06-22 Invigor Biotechnology Co., Ltd. Method of preparing microsphere composite of collagen and bioceramic powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2094117C1 (en) * 1996-07-23 1997-10-27 Акционерное общество закрытого типа "Фосфосорб" Sorbent and method for its production
RU2172325C2 (en) * 1997-12-18 2001-08-20 Маев Сергей Петрович Method of preparing chitosan-base substance for food and pharmaceutical industry
US6752938B2 (en) * 2001-10-13 2004-06-22 Invigor Biotechnology Co., Ltd. Method of preparing microsphere composite of collagen and bioceramic powder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Петрова Ю.С. Физико-химические свойства и аналитическое применение сульфоэтилированного хитозана для определения меди и серебра / Автореферат диссертации на соискание ученой степени кандидата химических наук / 2014, 24 с.. KC Ofokansi et al. Formulation and Evaluation of Glutaraldehyde-Crosslinked. Chitosan Microparticles for the Delivery of Ibuprofen / Tropical Journal of Pharmaceutical Research February, 2013, Vol.12, N1, pages 19-25. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2657506C1 (en) * 2017-09-25 2018-06-14 Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" (ИГХТУ) Method of extracting heavy metal ions from aqueous solutions

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