CN101367886A - Preparation method for reactive chitosan derivant - Google Patents
Preparation method for reactive chitosan derivant Download PDFInfo
- Publication number
- CN101367886A CN101367886A CNA2008102244912A CN200810224491A CN101367886A CN 101367886 A CN101367886 A CN 101367886A CN A2008102244912 A CNA2008102244912 A CN A2008102244912A CN 200810224491 A CN200810224491 A CN 200810224491A CN 101367886 A CN101367886 A CN 101367886A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- hours
- preparation
- reactive
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a preparation method of reactive chitosan derivatives, comprising adding chitosan in the mixture solution of organic amine and chloralkane or organic amine and acetone with the volume ratio of 1 to 3:1, stirring and placing for 48 hours at room temperature, cooling and stirring for 2 hours in ice bath at 5 DEG C below zero, dripping the chloralkane solution of 40 to 60wt% of unsaturated acyl chloride in the mixture solution within 2 to 4 hours, continuing to react for 6 hours at room temperature, wherein, the dripped long chain acyl chloride is 2 to 4 times of the mole number of the chitosan, obtaining the reactive chitosan derivative containing a double bond. The method of the invention realizes the solution of the chitosan derivative in organic solvents. The chitosan derivative can react and polymerize under ultraviolet light. The preparation method of reactive chitosan derivatives has the advantages of strong reaction process controllability, simple equipment and easy reaction process operation. The industrialization of products can be realized.
Description
Technical field
The present invention relates to a kind of reactive N, the preparation method of O-chitosan derivatives.Belong to the natural biological macromolecule material preparation area.
Background technology
Chitin is that the occurring in nature storage capacity is only second to cellulosic second largest natural biological polymer, and chitosan is the product of chitin behind the chemical treatment deacetylation, is a kind of environmentally friendly natural polymer.Chitosan has nontoxic antisepsis and anti-inflammation, excellent biological compatibility, advantage that biodegradability is strong, and simultaneously, chitosan has many excellent properties such as cancer resistance, hemostatic, enhancing immunity ability again.Therefore it has bigger using value at aspects such as food, makeup, wrapping material, textile printing and dyeing, oilfield treatments, agricultural application, especially can be used as burn dressing, tissue adhesion material, pharmaceutical carrier, enzyme inhibitors etc. in field of biomedical materials.
Chitosan is not dissolved in water and organic solvent, and this has greatly limited it in industrial application.For widening its range of application, researchist's research has been carried out the number of chemical modification to hydroxyl in the chitosan and amido, as etherificate, alkylation, esterification, sulfonation, carboxylated, quaternized etc., thereby obtained being dissolved in the chitosan derivatives of the aqueous solution and organic solvent.But the substitution value of the water-solubility chitosan derivative that obtains is lower, and need under acidic conditions, prepare, cause the degraded of chitosan in acidic solution easily, not only the molecular weight of the chitosan derivatives of feasible preparation reduces, and has changed original biological property; Reaction time is longer, the aftertreatment trouble.
Compare with the preparation method of water-solubility chitosan derivative, the preparation method of reactive chitosan derivant report both at home and abroad is less.People (J.Biomater.Sci.Polymer Edn such as Ramb Gupta, 2005 (4): 473-488) reported chitosan and glycidyl methacrylate ring-opening reaction preparation feedback chitosan derivatives under acidic conditions, people (Adv.Funct.Mater., 2007 (17): 2139-2150) reported chitosan and glycidyl methacrylate ring-opening reaction preparation feedback chitosan derivatives under catalytic condition such as Mary B.Chan-Park.But there is following shortcoming in above-mentioned preparation method: 1. the substitution value of the reactive chitosan derivant of preparing is very low, greatly about about 0.4; 2. preparation method's complexity needs catalyzer, and aftertreatment is purified and bothered, and has increased cost; 3. chitosan must be dissolved in the organic acid, causes degraded in the reaction process easily, makes the molecular weight of chitosan derivatives reduce; 4. the water-soluble and the organic solvent dissolution of the reactive chitosan derivant of preparing are relatively poor.
Summary of the invention
The object of the invention is at chitosan method of modifying cost in the prior art higher, complex process, and the product substitution value is low, the shortcoming that is easy to degrade provides a kind of cost low, and technology is simple, product substitution value height, and the difficult preparation method that the reactive chitosan derivant of degraded takes place.
The preparation method of a kind of reactive chitosan derivant provided by the present invention may further comprise the steps:
(1) chitosan is joined in the mixing solutions of organic amine that volume ratio is 1～3:1 and chloroparaffin or organic amine and acetone, stir under the room temperature and placed 48 hours;
(2) cooling and stirring 2 hours under-5 ℃ ice bath;
(3) the chloroparaffin solution of the unsaturated acyl chlorides of dropping 40～60wt%, the dropping time is 2～4 hours, the unsaturated acyl chlorides of dropping is 2～4 times of chitosan mole number;
(4) continue to react at normal temperatures 6 hours, the precipitation after the filtration is reactive chitosan derivant.
Chitosan in the above-mentioned steps (1) is a chitosan, and its deacetylation (DP) is 50～90%, and weight-average molecular weight is 3,000～1,000,000.
Above-mentioned organic amine is triethylamine, ethamine or aniline.
Chloroparaffin in above-mentioned steps (1) and (3) is methylene dichloride, trichloromethane, tetracol phenixin or ethylene dichloride.
Above-mentioned unsaturated acyl chlorides is methacrylic chloride or acrylate chloride.
The reactive chitosan derivant that the present invention prepares has following general structure (I), and substitution value is 1～3.8,
General formula (I)
In the formula, R is COCH=CH
2Or COCH=CHCH
3
The present invention introduces unsaturated acyl chlorides by amino on chitosan molecule and hydroxyl, obtains reactive chitosan derivant.Can control the substitution value of chitosan derivatives by adjusting reaction conditions, not only make outside its biocompatibility, the physiologically active, also successfully realize the polymerization of its derivative under ultraviolet lighting with natural polymer.
With 1wt% acetic acid solution dissolving 20wt% reactive chitosan derivant, add the 1wt% free radical photo-initiation again, at ultraviolet light intensity 30mw/m
2Condition under irradiation got final product initiated polymerization in 20 seconds.Radical initiator is 2-hydroxy-2-methyl-1-phenyl-acetone (1173), 1-[4-(2-hydroxyl hydroxyethyl)-phenyl]-2-hydroxy-2-methyl-1-propane (2959) or 1-hydroxyl-cyclohexyl-phenyl ketone (184).
Compared with prior art, the invention has the advantages that: the solid-liquid suspension method is carried out easily, the reaction process easy handling; The reaction process controllability is strong, and experimental installation is simple, and product can be realized industrialization; The unsaturated acyl chlorides of experimental raw is widely used in industry, and other organic solvents are recyclable utilization after experiment, has reduced production cost; Chitosan derivatives after the modification can be dissolved in the multiple organic solvent, especially can be dissolved in the ethanol, the substitution value of the chitosan derivatives after its modification can be controlled to be needed in the scope, and this has decided good application foundation for the biomedical applications pad of chitosan derivatives.
Embodiment
Embodiment 1
With 2.0g chitosan (DP=85%, Mw=100,000) joins in the solution of triethylamine that the 200mL volume ratio is 1:1 and trichloromethane, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 1.24g methacrylic chloride is dissolved in the 20mL trichloromethane, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 2 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of the precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 2
With 2.0g chitosan (DP=85%, Mw=100,000) joins in the solution of triethylamine that the 200mL volume ratio is 1:1 and methylene dichloride, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 2.2g acrylate chloride is dissolved in the 30mL methylene dichloride, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 3 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of the precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 3
With 2.0g chitosan (DP=85%, Mw=200,000) joins in the solution of ethamine that the 200mL volume ratio is 2:1 and methylene dichloride, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 1.5g acrylate chloride is dissolved in the 20mL methylene dichloride, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 3 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of the precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 4
With 2.0g chitosan (DP=50%, Mw=200,000) joins in the solution of ethamine that the 200mL volume ratio is 2:1 and tetracol phenixin, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 2.2g acrylate chloride is dissolved in the 25mL tetracol phenixin, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 3 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of the precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 5
With 2.0g chitosan (DP=50%, Mw=3,000) joins in the solution that the 200mL volume ratio is 2:1 triethylamine and methylene dichloride, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 1.2g methacrylic chloride is dissolved in the 15mL methylene dichloride stirs, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 2 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 6
With 2.0g chitosan (DP=90%, Mw=3,000) joins in the solution of ethamine that the 200mL volume ratio is 2:1 and methylene dichloride, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 2.3g methacrylic chloride is dissolved in the 30mL methylene dichloride, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 4 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of the precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 7
With 2.0g chitosan (DP=90%, Mw=1,000,000) joins in the solution of aniline that the 200mL volume ratio is 3:1 and trichloromethane, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 2.3g methacrylic chloride is dissolved in the 30mL trichloromethane, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 3 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 8
With 2.0g chitosan (DP=50%, Mw=1,000,000) joins in the solution of aniline that the 200mL volume ratio is 3:1 and trichloromethane, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 3.8g acrylate chloride is dissolved in the 40mL trichloromethane, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 4 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 9
With 2.0g chitosan (DP=85%, Mw=100,000) join in the solution of triethylamine that the 200mL volume ratio is 2:1 and acetone, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 2.2g acrylate chloride is dissolved in the 30mL acetone stirs, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 3 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 10
With 2.0g chitosan (DP=80%, Mw=60,000) joins in the solution of ethamine that the 200mL volume ratio is 2:1 and acetone, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 2.2g acrylate chloride is dissolved in the 30mL acetone, stirs, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 4 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of the precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 11
With 2.0g chitosan (DP=80%, Mw=1,000,000) joins in the solution of triethylamine that the 200mL volume ratio is 2:1 and ethylene dichloride, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 2.8g acrylate chloride is dissolved in the 30mL ethylene dichloride, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 3 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of precipitation after the filtration promptly obtain this reactive chitosan derivant.
Embodiment 12
With 2.0g chitosan (DP=85%, Mw=60,000) joins in the solution of ethamine that the 200mL volume ratio is 3:1 and tetracol phenixin, stir under the room temperature and placed 48 hours, cooling and stirring is 2 hours under-5 ℃ ice bath, the 3.0g methacrylic chloride is dissolved in the 30mL tetracol phenixin, stir, under-5 ℃ condition of ice bath, slowly be added drop-wise in the solution of chitosan, reacted 4 hours, continue to react at normal temperatures 6 hours, washing with acetone three times of the precipitation after the filtration promptly obtain this reactive chitosan derivant.
Claims (6)
1. the preparation method of a reactive chitosan derivant is characterized in that may further comprise the steps:
(1) chitosan is joined in the mixing solutions of organic amine that volume ratio is 1～3:1 and chloroparaffin or organic amine and acetone, stir under the room temperature and placed 48 hours;
(2) cooling and stirring 2 hours under-5 ℃ ice bath;
(3) the chloroparaffin solution of the unsaturated acyl chlorides of dropping 40～60wt% reacted 2～4 hours, and the unsaturated acyl chlorides of dropping is 2～4 times of chitosan mole number;
(4) continue to react at normal temperatures 6 hours, the precipitation after the filtration is reactive chitosan derivant.
2. preparation method according to claim 1 is characterized in that the chitosan described in the step (1) is a chitosan, and its deacetylation is 50～90%, and weight-average molecular weight is 3,000～1,000,000.
3. preparation method according to claim 1 is characterized in that described organic amine is triethylamine, ethamine or aniline.
4. preparation method according to claim 1 is characterized in that the chloroparaffin described in step (1) and (3) is methylene dichloride, trichloromethane, tetracol phenixin or ethylene dichloride.
5. preparation method according to claim 1 is characterized in that described unsaturated acyl chlorides is methacrylic chloride or acrylate chloride.
6. preparation method according to claim 1 is characterized in that the reactive chitosan derivant described in the step (4) has following general structure (I), and substitution value is 1～3.8,
General formula (I)
In the formula, R is COCH=CH
2Or COCH=CHCH
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102244912A CN101367886A (en) | 2008-10-17 | 2008-10-17 | Preparation method for reactive chitosan derivant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102244912A CN101367886A (en) | 2008-10-17 | 2008-10-17 | Preparation method for reactive chitosan derivant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101367886A true CN101367886A (en) | 2009-02-18 |
Family
ID=40411897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008102244912A Pending CN101367886A (en) | 2008-10-17 | 2008-10-17 | Preparation method for reactive chitosan derivant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101367886A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781375A (en) * | 2010-04-01 | 2010-07-21 | 北京化工大学常州先进材料研究院 | Preparation method of organic soluble photosensitive chitosan derivative |
| CN102382208A (en) * | 2011-11-17 | 2012-03-21 | 北京化工大学常州先进材料研究院 | Preparation method of photo-polymerizable chitosan derivative |
| CN106349406A (en) * | 2016-08-25 | 2017-01-25 | 浙江澳兴生物科技有限公司 | Preparation method of chitosan hydrochloride |
| CN108359142A (en) * | 2018-02-08 | 2018-08-03 | 湖州科博信息科技有限公司 | A kind of starch base degradable plastic |
| CN109575218A (en) * | 2018-11-14 | 2019-04-05 | 安徽明光中兴阳光新能源科技有限公司 | A kind of solar water container polyurethane inorganic flame-retardant thermal insulation material and preparation method thereof |
| CN109593177A (en) * | 2018-11-14 | 2019-04-09 | 安徽明光中兴阳光新能源科技有限公司 | A kind of solar water heater flame-retardant thermal insulation material and preparation method thereof |
-
2008
- 2008-10-17 CN CNA2008102244912A patent/CN101367886A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781375A (en) * | 2010-04-01 | 2010-07-21 | 北京化工大学常州先进材料研究院 | Preparation method of organic soluble photosensitive chitosan derivative |
| CN102382208A (en) * | 2011-11-17 | 2012-03-21 | 北京化工大学常州先进材料研究院 | Preparation method of photo-polymerizable chitosan derivative |
| CN106349406A (en) * | 2016-08-25 | 2017-01-25 | 浙江澳兴生物科技有限公司 | Preparation method of chitosan hydrochloride |
| CN108359142A (en) * | 2018-02-08 | 2018-08-03 | 湖州科博信息科技有限公司 | A kind of starch base degradable plastic |
| CN109575218A (en) * | 2018-11-14 | 2019-04-05 | 安徽明光中兴阳光新能源科技有限公司 | A kind of solar water container polyurethane inorganic flame-retardant thermal insulation material and preparation method thereof |
| CN109593177A (en) * | 2018-11-14 | 2019-04-09 | 安徽明光中兴阳光新能源科技有限公司 | A kind of solar water heater flame-retardant thermal insulation material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zainal et al. | Preparation of cellulose-based hydrogel: A review | |
| CN105622847B (en) | A kind of synthetic method of water soluble chitosan-based flocculant and its application | |
| CN108310460B (en) | Injectable high-strength temperature-sensitive modified chitin-based hydrogel and preparation method and application thereof | |
| de Castro et al. | Surface grafting of cellulose nanocrystals with natural antimicrobial rosin mixture using a green process | |
| CN107383236B (en) | Novel water-soluble natural polysaccharide antibacterial material and preparation method thereof | |
| de Britto et al. | Synthesis and mechanical properties of quaternary salts of chitosan-based films for food application | |
| CN101367886A (en) | Preparation method for reactive chitosan derivant | |
| CN103951764B (en) | A kind of homogeneous phase prepares the method for the hydroxypropyl modified chitin of low deacetylation | |
| CN110522948B (en) | Injectable hydrogel and preparation method and application thereof | |
| CN103965372B (en) | The preparation method of a kind of chitosan-gallic acid graft copolymer | |
| Hamcerencu et al. | Synthesis and characterization of new unsaturated esters of gellan gum | |
| Liu et al. | Preparation of chitosan-g-polylactide graft copolymers via self-catalysis of phthaloylchitosan and their complexation with DNA | |
| Xu et al. | A fast and dual crosslinking hydrogel based on vinyl ether sodium alginate | |
| CN103467760A (en) | Method for preparing high-strength chitosan/cellulose composite hydrogel film | |
| CN106995502B (en) | Bifunctional group modified chitosan derivative and preparation method thereof | |
| CN109867729B (en) | Photoresponse type galactomannan hydrogel and preparation method thereof | |
| WO2019052321A1 (en) | Water-soluble chitosan antimicrobial derivative and preparation method therefor | |
| CN104231112B (en) | A kind of synthetic method of CARB OXYMETHYL-CHITOSAN sulfation product | |
| Chen et al. | Photo-curable, double-crosslinked, in situ-forming hydrogels based on oxidized hydroxypropyl cellulose | |
| Bi et al. | Homogeneous modification of chitin and chitosan based on an alkali/urea soluble system and their applications in biomedical engineering | |
| JP4356289B2 (en) | Polysaccharide complex and method for producing the same | |
| Delgado-Rangel et al. | Deep eutectic solvent-assisted phase separation in chitosan solutions for the production of 3D monoliths and films with tailored porosities | |
| Budishevska et al. | Formation of three-dimensional polymer structures through radical and ionic reactions of peroxychitosan | |
| Feng et al. | Solubility, chain characterization, and derivatives of chitin | |
| CN101659710B (en) | Preparation method of reactive type water-solubility chitosan derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090218 |