CN101704907A - Method for preparing acylation chitosan - Google Patents
Method for preparing acylation chitosan Download PDFInfo
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- CN101704907A CN101704907A CN200910213688A CN200910213688A CN101704907A CN 101704907 A CN101704907 A CN 101704907A CN 200910213688 A CN200910213688 A CN 200910213688A CN 200910213688 A CN200910213688 A CN 200910213688A CN 101704907 A CN101704907 A CN 101704907A
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Abstract
The invention discloses a method for preparing acylation chitosan, which comprises the following steps: (1) mixing a chitosan raw material with a polar inert solvent, heating the mixture, and performing suction filtration on the mixture; (2) mixing the filter residues after the suction filtration with the polar inert solvent, and adding fatty acyl halide and an organic catalyst into the mixture to perform acylation reaction with the chitosan; and (3) performing suction filtration, purification and drying to obtain the acylation chitosan. The method for preparing the acylation chitosan has simple and easy steps and mild reaction conditions, lowers the production cost and reduces the reaction toxicity and the difficulties for the post-treatment of a product. The acylation chitosan prepared by the method has non-degradable backbone chains and high purity, and improves the solubility of the chitosan.
Description
Technical field
The present invention relates to the polymer modification field, be specifically related to a kind of Preparation of Hydrophobing Acyl Chitosan method.
Background technology
Chitosan is the product of chitin deacetylate, is unique commercial alkaline polysaccharide.Chitosan reaches absorption of proteins with its favorable tissue consistency, biodegradability, germ resistance, make it obtain widely using, be regarded as 21st century one of the most promising material in industries such as chemical industry, environmental protection, food, printing and dyeing, medicine.But chitosan exists stronger intramolecularly and intermolecular hydrogen bonding, makes it have crystalline structure closely, thereby is insoluble in most of organic solvent, has limited chitosan and has used widely.Therefore; to chitosan carry out acidylate, etherificate, alkylation, sulfonation, carboxylated, and quaternised modified be current research focus to improve its solvability; can on repeating unit, introduce different groups by chemical modification; generate corresponding derivative; both can improve the solubility property of chitosan, can give the chitosan more function again.
Abroad the easy steps by freezing sodium hydroxide-sodium lauryl sulphate system has prepared successfully alkyl-CHITIN fiber.Alkylation has produced the alkyl halide compound of various different chain length and bulkiness, to the increase of the affinity of water or formic acid, produces owing to the part molecule crystallographic texture destroys during the increase of this affinity.Nucleus magnetic resonance studies show that the locational hydroxyl of C6 is better than the C3 position and is substituted, also prepared simultaneously alkyl-CHITIN fiber membrane.The improvement of this affine character, chitosan afterwards has good value in using.Also prepare chitosan multi-porous globule in addition, heavy metal has been had sequestering action, also can be used for the immobilized reactant of biomaterial.Prepared chitosan by iodate, halogenation and transplanted multipolymer, halogenation and iodinating method are mainly carried out the transformation of chitosan functional group.Wherein iodate mild condition, and can produce the precursor of various reactions, this reaction is easy to occur on the C6 position, also can be used for preparing the cation implantation multipolymer.Its reaction conditions carries out in room temperature and UV-light 308nm place, and the transformation of the various functional groups of chitosan is also comprised preparation hydroxyl chitosan.Present domestic be linking agent with formaldehyde and diacetyl oxide, having prepared with the chitosan is the chitosan gel rubber of parent, and its character is studied.
In Chemical Modifications of Chitosan, acylation modification is studied morely, and superfine as Liu is that reaction medium has prepared complete hydrophobic long-chain acylation chitosan derivative with pyridine and chloroform, but the used reagent toxicity of this method is big and reaction time consumption is longer; Kurita etc. locate chemical reaction technology by the chitosan of amido protecting-deaminizating protection and have prepared the O-acylation chitosan, have realized the orienting response of chitosan, but the reaction process complexity, have increased the difficulty of product postprocessing; Li Zhijun etc. are by with the methylsulfonic acid being medium and Preparation of Catalyst O, O-two dodecanoyl chitosan derivatives, but have the degraded of chitosan main chain in the reaction process; Vasnev etc. have prepared N in the homogeneous system of acetone and water, O-acylation chitosan derivative, but this reaction need be used the bigger trifluoracetic acid of toxicity, and must under nitrogen atmosphere protection, carry out.In a word, there is the agents useful for same costliness in these reactions, and toxicity is bigger, and complex process or reaction conditions be problem such as harshness comparatively.
Summary of the invention
The object of the invention is at the deficiencies in the prior art, and a kind of reaction conditions gentleness, simple Preparation of Hydrophobing Acyl Chitosan method are provided.
The object of the invention is achieved by the following technical programs:
A kind of Preparation of Hydrophobing Acyl Chitosan method comprises the steps:
(1) the chitosan raw material is mixed with polar aprotic solvent, heating, suction filtration;
(2) filter residue behind the suction filtration is mixed with polar aprotic solvent, add fatty carboxylic acid halides and organic catalyst, carry out acylation reaction with chitosan;
(3) after suction filtration, purifying, drying, obtain acylation chitosan.
Wherein, chitosan raw material described in the step (1) is different molecular weight and different deacetylation, and wherein, preferred deacetylation is 80 ~ 95%, the chitosan of molecular weight 20000 ~ 300000 is done raw material; Preferred 80 ℃ of described Heating temperature.
The preferred N of polar aprotic solvent described in step (1) and (2), dinethylformamide.
The molar weight ratio of fatty carboxylic acid halides and chitosan is 5: 1 ~ 1: 1 described in the step (2); The preferred C of fat carboxylic acid halides
8~ C
18The saturated fatty acyl chlorides, the preparation method of this saturated fatty acyl chlorides reacted 2 ~ 5 hours at 80 ℃ with lipid acid and sulfur oxychloride, the hydrogenchloride and the sulfur dioxide gas of unreacted sulfur oxychloride and production were removed in decompression after reaction was finished, what obtain is colourless to light yellow transparent liquid, is the saturated fatty acyl chlorides.
The pyridine of the preferred weakly alkaline organic reagent of organic catalyst described in the step (2).
Acylation reaction described in the step (2) is to carry out being added with under the condition of drying installation, and to prevent the hydrolysis of acyl chlorides, the acylation reaction time is preferably 6 ~ 48 hours, preferred 80 ~ 120 ℃ of temperature of reaction.
Purifying is a general procedure in this area described in the step (3), specifically be with filter residue place refluxed 2 ~ 5 hours under 80 ℃ of conditions of 95% alcohol after, suction filtration once more; Wherein, described pure preferred alcohol.
Acylation chitosan has the backbone structure similar with the chitosan raw material described in the step (3), the 2-amino and 3 in the molecule, and the 6-hydroxyl is partly or entirely replaced, and structure is as follows:
Wherein, R
1Be CH
3CO-or CH
3(CH
2)
mCO-; R
2Be H-or CH
3(CH
2)
mCO-; R
3Be H-or CH
3(CH
2)
mCO-.
Compared with prior art, the present invention has following beneficial effect:
Preparation of Hydrophobing Acyl Chitosan method steps of the present invention is simple, the reaction conditions gentleness, and the reagent that reaction is used is easy to get, and has reduced production cost; Reduce reaction process toxic production of by-products, reduced the difficulty of product postprocessing; Utilize the main chain of the acylation chitosan that present method prepares non-degradable, the purity height has improved the solubility property of chitosan.
Description of drawings
Fig. 1 is that molecular weight is 20000 the chitosan raw material and the infrared figure of palmitoylation chitosan, and wherein, a is the palmitoylation chitosan, and b is the chitosan raw material;
Fig. 2 is that molecular weight is 30000 the chitosan raw material and the infrared figure of palmitoylation chitosan, and wherein, a is the palmitoylation chitosan, and b is the chitosan raw material;
Fig. 3 is that molecular weight is 150000 the chitosan raw material and the infrared figure of palmitoylation chitosan, and wherein, a is the palmitoylation chitosan, and b is the chitosan raw material;
Fig. 4 is that molecular weight is 200000 the chitosan raw material and the infrared figure of palmitoylation chitosan, and wherein, a is the palmitoylation chitosan, and b is the chitosan raw material;
Fig. 5 is to be 30000 the chitosan raw material and the infrared figure of bay acylation chitosan with molecular weight, and wherein, a is the bay acylation chitosan, and b is the chitosan raw material;
Fig. 6 is that molecular weight is 80000 the chitosan raw material and the infrared figure of bay acylation chitosan, and wherein, a is the bay acylation chitosan, and b is the chitosan raw material;
Fig. 7 is to be 200000 the chitosan raw material and the infrared figure of decoyl chitosan product with molecular weight, and wherein, a is the decoyl chitosan, and b is the chitosan raw material;
Fig. 8 is that molecular weight is 300000 the chitosan raw material and the infrared figure of decoyl chitosan product, and wherein, a is the decoyl chitosan, and b is the chitosan raw material.
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any qualification to the present invention.
The preparation of embodiment 1 palmitoylation chitosan
1. the preparation of palmityl chloride
The 46g palmitinic acid places there-necked flask, add the 25ml thionyl chloride, take and reflux and device for absorbing tail gas, slowly being warming up to 60 ℃ of reaction for some time to systems under the agitation condition is the homogeneous liquid system, attemperation is 80 ℃ of reactions 2.5 hours, under reduced pressure, remove sulfurous gas and hydrogen chloride gas that unreacted thionyl chloride and reaction generate then, get light yellow transparent liquid 60ml.
2. the preparation of palmitoylation chitosan
Place the 100ml there-necked flask 2.1 take by weighing 2.015g chitosan (M=20000); add 40mlDMF; 80 ℃ of oil baths were stirred 3 hours; suction filtration is transferred to filter residue in the 250ml there-necked flask, adds 40ml DMF and 10ml pyridine again; the 10ml palmityl chloride is dissolved in disposable being added in the reaction system among the 20ml DMF; 120 ℃ of back flow reaction 13 hours, stopped reaction, suction filtration; filter residue is placed the 500ml flask; add 300ml 95% ethanol, refluxed 5 hours suction filtration under 80 ℃ of conditions; (70 ℃ of dry filter residues; 12 hours) get 1.638g, carry out the secondary acidylate with the gained filter residue as reactant then, the final product 1.215g that gets.Its respective shell glycan raw material and product infared spectrum such as Fig. 1.
Place the 250ml there-necked flask 2.2 take by weighing 2.012g chitosan (M=30000), add 40mlDMF, 80 ℃ of oil baths were stirred 2 hours, and suction filtration is scattered in filter residue among the 50ml DMF again, take and reflux and air dry-set, add the 10ml pyridine, the 10ml palmityl chloride is dissolved in 10ml DMF gets light yellow transparent liquid, disposable being added in the reaction system, 80 ℃ were reacted 17 hours, get the red-brown two-phase system, suction filtration is transferred to filter residue in the 1000ml flask, add 450ml 95% ethanol, refluxed under 80 ℃ of conditions 4 hours, suction filtration, filter residue was in 70 ℃ of dryings 12 hours, get 1.976g, its respective shell glycan raw material and product infared spectrum such as Fig. 2.
Place the 250ml there-necked flask 2.3 take by weighing 3.006g chitosan (M=150000), add 60mlDMF, 80 ℃ of oil baths were stirred 2 hours, and suction filtration is scattered in filter residue among the 60ml DMF again, take and reflux and air dry-set, add the 10ml pyridine, the 15ml palmityl chloride is dissolved in 30ml DMF gets light yellow transparent liquid, disposable being added in the reaction system, 120 ℃ were reacted 6 hours, get the red-brown two-phase system, suction filtration is transferred to filter residue in the 1000ml flask, add 450ml 95% ethanol, refluxed under 80 ℃ of conditions 3 hours, suction filtration, filter residue was in 70 ℃ of dryings 8 hours, get 6.267g, its respective shell glycan raw material and product infared spectrum such as Fig. 3.
Place the 250ml there-necked flask 2.4 take by weighing 2.006g chitosan (M=200000), add 40mlDMF, 80 ℃ of oil baths were stirred 2 hours, and suction filtration is scattered in filter residue among the 40ml DMF again, take and reflux and air dry-set, add the 10ml pyridine, the 10ml palmityl chloride is dissolved in 20ml DMF gets light yellow transparent liquid, disposable being added in the reaction system, 120 ℃ were reacted 8 hours, get the red-brown two-phase system, suction filtration is transferred to filter residue in the 1000ml flask, add 450ml 95% ethanol, refluxed under 80 ℃ of conditions 2 hours, suction filtration, filter residue was in 75 ℃ of dryings 24 hours, get 2.556g, its respective shell glycan raw material and product infared spectrum such as Fig. 4.
Embodiment 2 bay Preparation of Hydrophobing Acyl Chitosan
1. the preparation of lauroyl chloride
Take by weighing the 30.026g lauric acid and place the 250ml there-necked flask, add the 15ml sulfur oxychloride, take and reflux and device for absorbing tail gas, regulating oil bath temperature is 50 ℃ of reactions 30 minutes, make system become homogeneous liquid, attemperation is 80 ℃ of reactions 2.5 hours then, and the hydrogenchloride and the sulfur dioxide gas of unreacted sulfur oxychloride and generation were removed in decompression after reaction was finished, and got colourless transparent liquid 17ml.
2. bay Preparation of Hydrophobing Acyl Chitosan
Place the 250ml there-necked flask 2.1 take by weighing 1.052g chitosan (M=30000), add 20mlDMF, 80 ℃ of oil baths were stirred 2 hours, and suction filtration is scattered in filter residue among the 20ml DMF again, take and reflux and air dry-set, add the 5ml pyridine, the 6ml palmityl chloride is dissolved in 12ml DMF gets light colourless transparent liquid, disposable being added in the reaction system, 120 ℃ were reacted 16 hours, get the red-brown two-phase system, suction filtration is transferred to filter residue in the 250ml flask, add 150ml 95% ethanol, refluxed under 80 ℃ of conditions 2 hours, suction filtration, filter residue was in 70 ℃ of dryings 12 hours, get 1.039g, its product infared spectrum such as Fig. 5.
Place the 250ml there-necked flask 2.2 take by weighing 1.087g chitosan (M=80000), add 20mlDMF, 80 ℃ of oil baths were stirred 2 hours, and suction filtration is scattered in filter residue among the 20ml DMF again, take and reflux and air dry-set, add the 5ml pyridine, the 5ml palmityl chloride is dissolved in 10ml DMF gets light colourless transparent liquid, disposable being added in the reaction system, 120 ℃ were reacted 10 hours, get the red-brown two-phase system, suction filtration is transferred to filter residue in the 250ml flask, add 150ml 95% ethanol, refluxed under 80 ℃ of conditions 2 hours, suction filtration, filter residue was in 70 ℃ of dryings 12 hours, get 0.775g, its respective shell glycan raw material and product infared spectrum such as Fig. 6.
Embodiment 3 hot Preparation of Hydrophobing Acyl Chitosan
1. the preparation of capryl(yl)chloride
Measure the 20ml n-caprylic acid and place the 250ml there-necked flask, add the 17ml sulfur oxychloride, take and reflux and device for absorbing tail gas, 50 ℃ were reacted 30 minutes, attemperation is 80 ℃ of reactions 2.5 hours then, the hydrogenchloride and the sulfur dioxide gas of unreacted sulfur oxychloride and generation were removed in decompression after reaction was finished, and got colourless transparent liquid 23ml.
2. hot Preparation of Hydrophobing Acyl Chitosan
Place the 250ml there-necked flask 2.1 take by weighing 1.028g (M=200000), add 20ml DMF, 80 ℃ of oil baths were stirred 2 hours, and suction filtration is scattered in filter residue among the 20ml DMF again, take and reflux and air dry-set, add the 5ml pyridine, the 5ml capryl(yl)chloride is dissolved in 10ml DMF gets light yellow transparent liquid, disposable being added in the reaction system, 120 ℃ were reacted 10 hours, get the red-brown two-phase system, suction filtration is transferred to filter residue in the 250ml flask, add 150ml 95% ethanol, refluxed under 80 ℃ of conditions 2 hours, suction filtration, filter residue was in 70 ℃ of dryings 12 hours, get 0.552g, its product infared spectrum such as Fig. 7.
Place the 250ml there-necked flask 2.2 take by weighing 1.025g (M=300000), add 20ml DMF, 80 ℃ of oil baths were stirred 2 hours, and suction filtration is scattered in filter residue among the 20ml DMF again, take and reflux and air dry-set, add the 5ml pyridine, the 5ml capryl(yl)chloride is dissolved in 10ml DMF gets light yellow transparent liquid, disposable being added in the reaction system, 120 ℃ were reacted 24 hours, get the red-brown two-phase system, suction filtration is transferred to filter residue in the 250ml flask, add 150ml 95% ethanol, refluxed under 80 ℃ of conditions 3 hours, suction filtration, filter residue was in 70 ℃ of dryings 12 hours, get 0.193g, its respective shell glycan raw material and product infared spectrum such as Fig. 8.
From the contrast at the raw material peak of chitosan and acidylate after product peak as can be seen, though 2-amino with respect to 3, the 6-hydroxyl has stronger nucleophilicity because acyl chlorides is a kind of stronger acylating agent, can observe products therefrom mostly has 1740cm with respect to raw material
-1The appearance at ester carbonyl group peak, place, and 2920cm
-1, 2850cm
-1And 720cm
-1The appearance of the long-chain methylene radical absorption peak of place correspondence has also proved the generation of acylate.
Claims (10)
1. a Preparation of Hydrophobing Acyl Chitosan method is characterized in that described method comprises the steps:
(1) the chitosan raw material is mixed with polar aprotic solvent, heating, suction filtration;
(2) filter residue behind the suction filtration is mixed with polar aprotic solvent, add fatty carboxylic acid halides and organic catalyst, carry out acylation reaction with chitosan;
(3) after suction filtration, purifying, drying, obtain acylation chitosan.
2. Preparation of Hydrophobing Acyl Chitosan method according to claim 1, the deacetylation that it is characterized in that chitosan raw material described in the step (1) is 80 ~ 95%, molecular weight is 20000 ~ 300000.
3. Preparation of Hydrophobing Acyl Chitosan method according to claim 1 is characterized in that described polar aprotic solvent is N, dinethylformamide.
4. Preparation of Hydrophobing Acyl Chitosan method according to claim 1 is characterized in that the molar weight ratio of fatty carboxylic acid halides described in the step (2) and chitosan is 5: 1 ~ 1: 1.
5. according to claim 1 or 4 described Preparation of Hydrophobing Acyl Chitosan methods, it is characterized in that fatty carboxylic acid halides is C described in the step (2)
8~ C
18The saturated fatty acyl chlorides.
6. Preparation of Hydrophobing Acyl Chitosan method according to claim 5; the preparation method who it is characterized in that described saturated fatty acyl chlorides reacted 2 ~ 5 hours at 80 ℃ with lipid acid and sulfur oxychloride; the hydrogenchloride and the sulfur dioxide gas of unreacted sulfur oxychloride and production were removed in decompression after reaction was finished; must be colourless to light yellow transparent liquid, be the saturated fatty acyl chlorides.
7. Preparation of Hydrophobing Acyl Chitosan method according to claim 1 is characterized in that organic catalyst described in the step (2) is a weakly alkaline organic reagent pyridine.
8. Preparation of Hydrophobing Acyl Chitosan method according to claim 1 is characterized in that acylation reaction is carried out described in the step (2) under drying regime, the reaction times is 6 ~ 48 hours, and temperature of reaction is 80 ~ 120 ℃.
9. Preparation of Hydrophobing Acyl Chitosan method according to claim 1 is characterized in that the amino of the 2-in the acylation chitosan molecule described in the step (3) and 3, and the 6-hydroxyl is partly or entirely replaced, and structure is as follows:
Wherein, R
1Be CH
3CO-or CH
3(CH
2)
mCO-; R
2Be H-or CH
3(CH
2)
mCO-; R
3Be H-or CH
3(CH
2)
mCO-.
10. Preparation of Hydrophobing Acyl Chitosan method according to claim 1, it is characterized in that purifying described in the step (3) be with filter residue place refluxed 2 ~ 5 hours under 80 ℃ of conditions of 95% alcohol after, suction filtration once more.
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CN102351963A (en) * | 2011-10-25 | 2012-02-15 | 广东药学院 | Preparation method of galactosylated fatty acylchitosan |
CN102488932A (en) * | 2011-12-22 | 2012-06-13 | 哈尔滨工程大学 | Magnesium alloy support coated with acylated chitosan and polyester blend medicine coating |
CN104558243A (en) * | 2014-12-19 | 2015-04-29 | 浙江理工大学 | Preparation method and application of N-alkyl-O-acylated chitosan quaternary ammonium salt |
CN104878621A (en) * | 2015-06-05 | 2015-09-02 | 苏州大学 | Acid dye leveling agent |
CN107619446A (en) * | 2017-09-26 | 2018-01-23 | 西南石油大学 | A kind of preparation method of maleylation phthalyl chitosan |
CN108559009A (en) * | 2017-09-26 | 2018-09-21 | 西南石油大学 | A kind of preparation method of phthaloyl chitosan |
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2009
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102351963A (en) * | 2011-10-25 | 2012-02-15 | 广东药学院 | Preparation method of galactosylated fatty acylchitosan |
CN102488932A (en) * | 2011-12-22 | 2012-06-13 | 哈尔滨工程大学 | Magnesium alloy support coated with acylated chitosan and polyester blend medicine coating |
CN104558243A (en) * | 2014-12-19 | 2015-04-29 | 浙江理工大学 | Preparation method and application of N-alkyl-O-acylated chitosan quaternary ammonium salt |
CN104878621A (en) * | 2015-06-05 | 2015-09-02 | 苏州大学 | Acid dye leveling agent |
CN104878621B (en) * | 2015-06-05 | 2017-07-21 | 苏州大学 | A kind of acid dyes levelling agent |
CN107619446A (en) * | 2017-09-26 | 2018-01-23 | 西南石油大学 | A kind of preparation method of maleylation phthalyl chitosan |
CN108559009A (en) * | 2017-09-26 | 2018-09-21 | 西南石油大学 | A kind of preparation method of phthaloyl chitosan |
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Application publication date: 20100512 |