CN1294152C - Hydrophobically modified succinylated chitosan derivative and its prepn process - Google Patents
Hydrophobically modified succinylated chitosan derivative and its prepn process Download PDFInfo
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- CN1294152C CN1294152C CNB2005100425318A CN200510042531A CN1294152C CN 1294152 C CN1294152 C CN 1294152C CN B2005100425318 A CNB2005100425318 A CN B2005100425318A CN 200510042531 A CN200510042531 A CN 200510042531A CN 1294152 C CN1294152 C CN 1294152C
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- chitosan
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- preparation
- succinylated
- hydrophobically modified
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Abstract
The present invention relates to a modified hydrophobic succinyl chitosan derivative and a preparation method thereof, which belongs to the field of biologic and medical macromolecular materials. The general formula of the chitosan derivative is disclosed in the specification, wherein R1 is H or COCH3; R2 and R3 are respectively COCH2CH2COO and (CH2)mCH3 or CH2CHOHCH2O(CH2)mCH3; m is from 3 to 17. The preparation method comprises: firstly, chitosan and succinic anhydride carry out reaction under acid condition so as to obtain water soluble succinyl chitosan; then, the water soluble succinyl chitosan and the alkyl glycerol triglycidyl ether or alkyl halide of a long chain alkane derivative carry out reaction under the alkali condition so as to obtain the modified hydrophobic succinyl chitosan derivative. Through the method of the present invention, an amphipathic chitosan derivative with favorable surface activity and emulsifying property can be obtained, which provides multifunctional raw materials with good quality and low price for fields, such as cosmetics, medicines, foods, etc.
Description
(1) technical field
The present invention relates to succinylated chitosan derivative of a kind of hydrophobically modified and preparation method thereof, belong to biology and medical macromolecular materials technical field.
(2) background technology
Chitin is that occurring in nature output is only second to cellulosic second largest renewable resources, have non-stimulated, no sensitization, no haemolysis, no mutagenesis, in addition can natural degradation, thereby have favorable tissue consistency and a security, have a lot of special physiological functions in addition, be described as " the 6th key element of life ".Be used widely in recent years.
Yet the solvent that chitin itself is water insoluble and general, deacetylation also only are dissolved in acidic solution after becoming chitosan, have limited its application.For widening its range of application, can utilize the active group in its molecule to carry out chemical modification, improve solubility property, give new function, improve using value.Wherein the acylations modification obtains people's attention.As succinylated chitosan cancer cells had selectivity; can be used as the carrier of targeted drug; open report is seen people such as Ka Miyama; N-succinylated chitosan and glycol-chitosan are to normal and carry the biological characteristics that mouse showed of tumour; biomedical wall bulletin; 1999; 22 (2): 179 (Kamiyama K; et al.Biodisposition characteristics ofN-succinyl-chitosan and glycol-chitosan in normal and tumor-bearing mice[J] .Biol PharmBull; 1999; 179) and people such as Kato 22 (2):; the N-succinylated chitosan is as the high molecular evaluation of the long-term circulation of whole body; biomaterial; 2000; 21:1579 (Karo Y; et al.Evaluation of N-succinyl-chitosan as asystemic long-circulating polymer[J] .Biomaterials; 2000; 21:1579); succinylated chitosan also has very strong moisture-absorbing moisture-keeping effect; referring to the preparation method of CN98126756 (applying date 1999.8.18) water-solubility chitosan derivative and the preparation of CN 98110568 (applying date 2000.5.24) chitosan derivative cosmetic humectant.
Yet in actual use, often have some insoluble composition, the derivative of simple hydrophilic modifying is difficult to reach solubilising emulsive effect.
(3) summary of the invention
The present invention is directed to chitosan poorly water-soluble in the prior art, do not have shortcomings such as solubilising emulsifying capacity, a kind of succinylated chitosan derivative and preparation method thereof of hydrophobically modified of good water solubility is provided.
The present invention is by introducing hydrophilic group and hydrophobic group, the amphipathy macromolecule that obtains having the polymeric surface active agent performance on chitosan molecule.Make it except that the biocompatibility with natural polymer, physiologically active, also have the premium properties of polymeric surface active agent, have green, environmental protection, multi-functional characteristics, the raw material of super quality and competitive price is provided for makeup, medicine and other fields.
The succinylated chitosan derivative of hydrophobically modified of the present invention, general formula is as follows:
Wherein n is 20-2000, R
1Be H/COCH
3, deacetylation is 60-100%, R
2, R
3One of be COCH2CH2COO-, another is (CH
2)
mCH
3Or CH
2CHOHCH
2O (CH
2)
mCH
3, m=3～17.
The succinylated chitosan derivative preparation method of hydrophobically modified of the present invention is as follows:
At first with the acetic acid/methanol mixed solution of chitosan; reacted 3-12 hour in 20-60 ℃ with succinic anhydride; the mol ratio of chitosan unit and Succinic anhydried is 1: 0.4-1.4; product fully soaks dehydration by ethanol; precipitation, filtration; filter cake is used aqueous ethanol and washing with acetone respectively, and vacuum-drying obtains water-soluble succinylated chitosan.Succinylated chitosan with above-mentioned preparation alkalizes with alkaline Virahol then; add the long chain alkane derivative; chitosan unit and long chain alkane derivative mol ratio are 1: 1-10; 30-80 ℃ was reacted 3-24 hour; be chilled to room temperature,, filter with acetic acid or hydrochloric acid neutralization; use aqueous ethanol and washing with acetone successively, drying.Then product is dissolved in water, through dialysis back concentrating under reduced pressure, again with acetone precipitation, obtain pure product through vacuum-drying.
Described chitosan is a chitosan, and deacetylation is 60-100%, and molecular weight is 5,000～500,000.
Described long chain alkane derivative is alkyl glycidyl ether or haloalkane, and the alkane chain length is 4～18.
The abovementioned alkyl glycidyl ether is selected from butylglycidyl ether or lauryl diglycidyl ether, perhaps by other alkyl glycidyl ether of epoxy chloropropane and alkyl alcohol prepared in reaction, the preparation method is with reference to openly speciallyying permit the clear 56-63974 of communique and openly speciallyying permit the clear 54-115307 of communique.
The acetic acid of above-mentioned chitosan/methanol mixed solution is that chitosan is dissolved as the solution of 1-3% (w/v) with the acetum of weight percent 1-3%, adds equal-volume methyl alcohol again.
Above-mentioned alkaline aqueous isopropanol is that 0.5-3% (w/v) KOH is scattered in Virahol, weight percent 2-6% succinylated chitosan is scattered in the alkaline aqueous isopropanol alkalizes then.
The present invention is by preferred method of modifying, on chitosan molecule, introduce hydrophilic group and hydrophobic group, synthesize novel amphipathic derivatives, except that premium properties with original natural polymer, the character that also has tensio-active agent, can reduce the surface tension of solution, have characteristics such as emulsifying property, lyotropy.
Excellent results compared with prior art of the present invention is to obtain a kind of good water solubility, have the amphipathic chitose derivative of carboxyl, amido, chain alkyl concurrently, the characteristic of the existing polyamphoteric electrolyte of this product, the surface of good activity is arranged again, the biocompatibility of existing natural polymer, the characteristic of high-molecular surface active is arranged again, and the preparation method is simple and easy to do, good product quality.Can provide raw material multi-functional, of high quality and at a reasonable price for fields such as makeup, medicine, food.
(4) embodiment
Embodiment 1: the succinylated chitosan derivative of hydrophobically modified can be expressed as:
R wherein
1Be H/COCH
3, deacetylation is 90%, R
2, R
3Be respectively COCH
2CH
2COO
-Or CH
2CHOHCH
2O (CH
2)
3CH
3
The preparation method is as follows:
With 2% acetate dissolution of 0.5g chitosan with 25ml, and then add 25ml methyl alcohol, the back that stirs adds 30 ℃ of reactions of 0.5g Succinic anhydried 5h.Product fully soaks dehydration by ethanol, uses aqueous ethanol then, washing with acetone final vacuum drying.The succinylated chitosan of above-mentioned preparation was scattered in behind the 15ml aqueous isopropanol of 0.15gKOH alkalization 4 hours, and got the 3.3g butylglycidyl ether and dropwise be added in the flask with the dividing potential drop dropping funnel.The reflux condensation mode reaction was chilled to room temperature after 20 hours in 55 ℃ of water-baths.Be chilled to room temperature,, use aqueous ethanol and washing with acetone successively, drying with acetic acid neutralization, filtration.Then product is dissolved in water, through dialysis back concentrating under reduced pressure, again with acetone precipitation, obtain pure product through vacuum-drying.Butylglycidyl ether is selected from Shanghai Resin Factory.
Embodiment 2:
The succinylated chitosan derivative general formula of the hydrophobically modified of present embodiment such as embodiment 1, different is that deacetylation is 80%, R
2, R
3Be respectively COCH
2CH
2COO
-Or CH
2CHOHCH
2O (CH
2)
11CH
3
The preparation method is as follows:
With the 2% acetum dissolving of 6g chitosan with 250ml, and then add 250ml methyl alcohol, the back that stirs adds 35 ℃ of reactions of 100g Succinic anhydried 3h.Product fully soaks dehydration by ethanol, uses aqueous ethanol then, washing with acetone final vacuum drying.The succinylated chitosan of above-mentioned preparation was scattered in behind the 200ml aqueous isopropanol of 1%KOH alkalization 5 hours, and got the 15g lauryl diglycidyl ether and dropwise be added in the flask with the dividing potential drop dropping funnel.Reaction was chilled to room temperature after 24 hours in 60 ℃ of water-baths.With acetic acid neutralization, filtration, use aqueous ethanol and washing with acetone successively, drying.Then product is dissolved in water, through dialysis back concentrating under reduced pressure, again with acetone precipitation, obtain pure product through vacuum-drying.Lauryl diglycidyl ether is selected from Shanghai Resin Factory.
Embodiment 3:
The succinylated chitosan derivative of the hydrophobically modified of present embodiment such as embodiment 1, different is that deacetylation is 75%, R
2, R
3Be respectively COCH
2CH
2COO
-Or (CH
2)
7CH
3
The preparation method is as follows: with 2% acetate dissolution of 0.5g chitosan with 25ml, and then add 25ml methyl alcohol, the back that stirs adds 25 ℃ of reactions of 0.5g Succinic anhydried 5h.Product fully soaks dehydration by ethanol, uses aqueous ethanol then, washing with acetone final vacuum drying.Alkalization was got the 2.9g bromooctane and dropwise is added in the flask with the dividing potential drop dropping funnel more than 4 hours after the succinylated chitosan of above-mentioned preparation being scattered in the 15ml aqueous isopropanol of 0.1gKOH.Reaction was chilled to room temperature after 5 hours in 60 ℃ of water-baths.With acetic acid neutralization, filtration, use aqueous ethanol and washing with acetone successively, drying.Then product is dissolved in water, through dialysis back concentrating under reduced pressure, again with acetone precipitation, obtain pure product through vacuum-drying.Above-mentioned bromooctane is selected from Jiangsu dragon production of sperm refinement factory.
Embodiment 4:
The succinylated chitosan derivative of the hydrophobically modified of present embodiment such as embodiment 1, different is that deacetylation is 70%, R
2, R
3Be respectively COCH
2CH
2COO
-Or (CH
2)
9CH
3
The preparation method is as follows: with the 2% acetum dissolving of 6g chitosan with 250ml, and then add 250ml methyl alcohol, the back that stirs adds 35 ℃ of reactions of 100g Succinic anhydried 3h.Product fully soaks dehydration by ethanol, uses aqueous ethanol then, washing with acetone final vacuum drying.The succinylated chitosan of above-mentioned preparation was scattered in behind the 1500ml aqueous isopropanol of 1gKOH alkalization 5 hours, and got the 28g bromo-decane and dropwise be added in the flask with the dividing potential drop dropping funnel.Reaction was chilled to room temperature after 6 hours in 65 ℃ of water-baths.With acetic acid neutralization, filtration, use aqueous ethanol and washing with acetone successively, drying.Then product is dissolved in water, through dialysis back concentrating under reduced pressure, again with acetone precipitation, obtain pure product through vacuum-drying.Above-mentioned bromo-decane is selected from Jiangsu dragon production of sperm refinement factory.
Claims (6)
1. the succinylated chitosan derivative of hydrophobically modified is characterized in that, general formula is as follows:
Wherein n is 20-2000, R
1Be H/COCH
3, deacetylation is 60-100%, R
2, R
3One of be COCH
2CH
2COO
-, another is (CH
2)
mCH
3Or CH
2CHOHCH
2O (CH
2)
mCH
3, m=3～17.
2. the succinylated chitosan derivative preparation method of the described hydrophobically modified of claim 1, step is as follows:
At first with the acetic acid/methanol mixed solution of chitosan, reacted 3-12 hour in 20-60 ℃ with Succinic anhydried, the mol ratio of chitosan unit and Succinic anhydried is 1: 0.4-1.4, product fully soaks dehydration by ethanol, precipitation, filtration, filter cake is used aqueous ethanol and washing with acetone respectively, and vacuum-drying obtains water-soluble succinylated chitosan;
Succinylated chitosan with above-mentioned preparation alkalizes with alkaline Virahol then, add the long chain alkane derivative, described long chain alkane derivative is alkyl glycidyl ether or haloalkane, the alkane chain length is 4～18, and chitosan unit and long chain alkane derivative mol ratio are 1: 1-10, and 30-80 ℃ was reacted 3-24 hour, be chilled to room temperature, neutralize, filter with acetic acid or hydrochloric acid, use aqueous ethanol and washing with acetone successively, drying;
At last above-mentioned product is dissolved in water,, uses acetone precipitation again, obtain pure product through vacuum-drying through dialysis back concentrating under reduced pressure.
3. the preparation method of the succinylated chitosan derivative of hydrophobically modified as claimed in claim 2 is characterized in that described chitosan is a chitosan, and deacetylation is 60-100%, and molecular weight is 5,000～500,000.
4. the preparation method of the succinylated chitosan derivative of hydrophobically modified as claimed in claim 2; acetic acid/methanol mixed the solution that it is characterized in that described chitosan is that chitosan is dissolved as the solution of 1-3%w/v with the acetum of weight percent 1-3%, adds equal-volume methyl alcohol again.
5. the preparation method of the succinylated chitosan derivative of hydrophobically modified as claimed in claim 2; it is characterized in that described alkyl glycidyl ether is selected from butylglycidyl ether or lauryl diglycidyl ether, perhaps other alkyl glycidyl ether by epoxy chloropropane and alkyl alcohol prepared in reaction.
6. the preparation method of the succinylated chitosan derivative of hydrophobically modified as claimed in claim 2; it is characterized in that described alkaline aqueous isopropanol is scattered in Virahol for 0.5-3%w/v KOH, weight percent 2-6% succinylated chitosan is scattered in the alkaline aqueous isopropanol alkalizes then.
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|---|---|---|---|
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| CN1294152C true CN1294152C (en) | 2007-01-10 |
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| CN102408497B (en) * | 2011-07-22 | 2013-07-31 | 华南农业大学 | Pesticide-carrying nano micellar solution as well as preparation method and application thereof |
| CN103483469A (en) * | 2013-09-26 | 2014-01-01 | 上海大学 | Preparation method for water-soluble chitosan |
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| CN106832058B (en) * | 2017-03-07 | 2019-06-07 | 陕西科技大学 | A kind of O- succinic acid Chitosan Schiff-base and preparation method thereof |
| CN110713556A (en) * | 2019-10-15 | 2020-01-21 | 浙江海洋大学 | Method for preparing carboxymethyl chitosan by using Antarctic krill shells |
| CN112321748B (en) * | 2020-11-16 | 2022-11-22 | 齐鲁工业大学 | Biological macromolecule, preparation method thereof and application thereof in membrane material |
| CN114014954B (en) * | 2021-11-08 | 2022-10-04 | 华邦特西诺采新材料股份有限公司 | Hydrophobic decorative base paper and preparation method thereof |
| CN115595347B (en) * | 2022-11-03 | 2023-06-06 | 广州增城潮徽生物技术有限公司 | Chitin derivative and preparation method and application thereof |
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| JPH02107601A (en) * | 1988-10-15 | 1990-04-19 | Kawaken Fine Chem Co Ltd | Novel chitosan compound, production thereof and use as humectant |
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| WO2002064698A1 (en) * | 2001-02-13 | 2002-08-22 | Venture Innovations, Inc. | Viscosified aqueous chitosan-containing well drilling and servicing fluids |
| CN1542022A (en) * | 2003-11-04 | 2004-11-03 | 武汉大学 | Carboxybutyryl chitosan sulfuric ester and preparation method and use thereof |
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2005
- 2005-03-02 CN CNB2005100425318A patent/CN1294152C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02107601A (en) * | 1988-10-15 | 1990-04-19 | Kawaken Fine Chem Co Ltd | Novel chitosan compound, production thereof and use as humectant |
| JPH08157501A (en) * | 1994-12-12 | 1996-06-18 | Katakura Chitsukarin Kk | N-carboxyacylchitosan and its production |
| JPH08183710A (en) * | 1994-12-28 | 1996-07-16 | Sansho Seiyaku Co Ltd | Skin preparation for external use containing amino sugar derivative |
| RU2144040C1 (en) * | 1998-04-07 | 2000-01-10 | Всероссийский научно-исследовательский и технологический институт биологической промышленности | Chitosan succinate salt production method |
| WO2002064698A1 (en) * | 2001-02-13 | 2002-08-22 | Venture Innovations, Inc. | Viscosified aqueous chitosan-containing well drilling and servicing fluids |
| CN1542022A (en) * | 2003-11-04 | 2004-11-03 | 武汉大学 | Carboxybutyryl chitosan sulfuric ester and preparation method and use thereof |
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| CN1673235A (en) | 2005-09-28 |
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