CN1995072A - Oil soluble chitose derivative and its preparation method - Google Patents
Oil soluble chitose derivative and its preparation method Download PDFInfo
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- CN1995072A CN1995072A CN 200610147656 CN200610147656A CN1995072A CN 1995072 A CN1995072 A CN 1995072A CN 200610147656 CN200610147656 CN 200610147656 CN 200610147656 A CN200610147656 A CN 200610147656A CN 1995072 A CN1995072 A CN 1995072A
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Abstract
The invention discloses an oil chitose derivant and making method, which is reacted by chitose, ortho-phthalic anhydride, diacid and diacid anhydride. The invention possesses self-catalyzing property as intermediate without catalyst, which can react with large monomer with hydroxyl group to obtain grafted copolymer synthesized by a series of chitose and macromolecule.
Description
Technical field
The present invention relates to derivative of a kind of natural high moleculer eompound and preparation method thereof, particularly a kind of oil soluble chitosan derivative and preparation method thereof.
Background technology
The a large amount of free amine groups that exist in the chitosan make it become occurring in nature positively charged biopolymer few in number, and this unique texture has been given its unique biological activity, make it become a kind of biomaterial with broad prospect of application.But a large amount of amino and hydroxyl interact and bring in the chitosan molecule and intermolecular intensive hydrogen bond action, molecular chain is closely arranged the formation crystallizing field, make the anti-swollen of chitosan, poorly soluble, can only be dissolved in the diluted acid aqueous solution and the special halogen-containing organic solvent, limit the widespread use of these natural resource of chitosan greatly.Phthaloyl chitosan (phthaloylchitosan is called for short PHCS) is a kind of important chitosan derivatives.It has good solubility in the strong polar organic solvent such as dinethylformamide, methyl-sulphoxide, pyridine, and shows typical lyotropic liquid crystalline at N.In addition, thus its N phlhalimide base can be easy to be sloughed the free amine group that recovers chitosan.Based on these advantages, the phthaloyl chitosan can carry out the selective derivatization reaction of multiple chitosan as a kind of important intermediate.
The graft modification of chitosan more and more is subject to people's attention.By graft reaction, can be incorporated on the chitosan main chain having molecular chain of different nature as required, in conjunction with the new material of excellent properties acquisition of natural polymer and synthetic macromolecule.Introduce two keys and obtain the PHCSMA intermediate on the hydroxyl of phthaloyl chitosan, its deliquescent improvement helps the carrying out of graft reaction on the one hand; On the other hand, deprotection recovery easily was amino again after graft reaction was finished.This graft reaction route can keep the free amine group of chitosan in graft product, not only comprised the synthetic macromolecule side chain but also the natural polymer of glycosaminoglycan main chain is arranged and the material of synthetic macromolecule.
U.S. Pat .Pat 4619995 and 3911098 discloses, and introduces the group of hydroxyl or carboxyl on the chitosan repeating unit, the preparation water-soluble chitosan.But they react under the highly basic condition mostly, are accompanied by the chitosan molecule chain break in reaction process, and these reactions are many simultaneously carries out in isopropanol solvent, and cost is higher relatively.Chinese patent 98126756.4 discloses, and on the repeating unit of chitosan, with the substitution reaction of hydroxyl and carboxyl, derivative has water-soluble, and higher limiting viscosity is arranged in the low-carbon alcohol solution at sodium hydroxide under 20-80 ℃ the temperature.Chinese patent 200410019960.9 discloses, and a kind of oil soluble O-chitosan derivatives and preparation and application are starting material with the chitosan, and the derivative of the last replacement of 6-OH of chitosan ring carbon that synthesizes is an O-9-octadecanoic acid chitosan.This product not only can be used for the treatment of obesity but also can be used for fat prevention.Have the Nantural non-toxic fat-reducing effect, human body is had no side effect.
Summary of the invention
The object of the invention provides a kind of oil soluble chitosan derivative, and it can be dissolved in organic solvents such as N, dinethylformamide, has the autocatalysis performance; Can be used as intermediate, need not catalyzer can with hydroxyl big monomer reaction, obtain the graft copolymer of a series of chitosans and synthetic macromolecule.
The chemical structural formula of a kind of oil soluble chitosan derivative of the present invention is as follows:
Wherein R is C
2-C
4Alkyl, n is 1000-3000.
The preparation method of a kind of oil soluble chitosan derivative of the present invention is as follows, below all represents with mass parts:
(1) chitosan and the 3-15 part Tetra hydro Phthalic anhydride with 1-5 part adds exsiccant 50-250 part N, in the dinethylformamide, at 120-130 ℃, under the nitrogen atmosphere stirring reaction 5-6 hour, after reaction finishes, through frozen water precipitation, suction filtration, the ethanol extracting and purifying obtains the phthaloyl chitosan in 40 ℃ of following vacuum-dryings again;
(2) phthaloyl chitosan of 1-5 part and the diprotic acid or the dibasic acid anhydride of 3-45 part are added exsiccant 50-250 part N; in the dinethylformamide; under nitrogen atmosphere, be warmed up to 100-120 ℃ of stirring reaction 12-24 hour; after reaction finishes; precipitate through frozen water; suction filtration, the ethanol extracting and purifying obtains oil soluble chitosan derivative in 40 ℃ of following vacuum-dryings again.
The diprotic acid that the present invention uses is hexanodioic acid or succsinic acid.
The dibasic acid anhydride that the present invention uses is succinyl oxide or maleic anhydride.
The molecular weight of the chitosan that the present invention uses is 5 * 10
3-8 * 10
5
The preparation feedback equation of a kind of oil soluble chitosan derivative of the present invention is as follows:
A kind of oil soluble chitosan derivative of the present invention, owing on amino, introduced Tetra hydro Phthalic anhydride, on hydroxyl, introduced diprotic acid, destroyed the hydrogen bond of chitosan, made derivative can be dissolved in N fully, in the organic solvents such as dinethylformamide, and chitosan itself is insoluble to organic solvent, by hydrogen bond or the absorption of ion-conductance negativity, has the autocatalysis performance, can with hydroxyl big monomer reaction, obtain multiple graft copolymer.Need not catalyzer in the preparation process, product postprocessing is simple.
Description of drawings
Curve a among Fig. 1 is the infrared spectrum of chitosan.
Curve b among Fig. 1 is the infrared spectrum of phthaloyl chitosan.
Fig. 2 is O-succsinic acid-N-phthalyl chitosan
13The C-NMR spectrogram.
Fig. 3 is the infrared spectrum of O-hexanodioic acid-N-phthalyl chitosan.
Fig. 4 is the graft copolymer of O-succsinic acid-N-phthalyl chitosan and polycaprolactone
1The H-NMR spectrogram.
Embodiment
The invention will be further described below in conjunction with embodiment.
The molecular weight of the chitosan that the chitosan that the present invention adopts is to use is 7.57 * 10
5, purchase in Zhejiang Yuhuan marine organisms company limited.
Embodiment 1
(1) the 5g chitosan is added 250gN, in the dinethylformamide solution, be stirred to dissolving fully; add the 13.8g Tetra hydro Phthalic anhydride again, reaction is 15 hours about 125 ℃, the frozen water precipitation; ethanol extracting and purifying, vacuum-drying obtain 8g phthaloyl chitosan.Curve a among Fig. 1 is the infrared spectrum of chitosan, and the curve b among Fig. 1 is the infrared spectrum of phthaloyl chitosan.Comparative analysis as can be seen, in the infrared spectrum of phthaloyl chitosan on the chitosan C=0 vibration of the amino acid amides that forms through the phthaloyl reaction at 1712cm
-1Strong absorption peak has appearred, and because the formation of imide structure, adjacent two carbonyls interact and make it split into two peaks, and one of them appears at the more about 1777cm of high frequency
-1Near.
(2) 5g phthaloyl chitosan is added 250gN, in the dinethylformamide solution, be stirred to dissolving fully; the succinyl oxide that adds 4g again, 110 ℃ of reactions 15 hours, the frozen water precipitation; ethanol extracting and purifying, vacuum-drying obtain 6g O-succsinic acid-N-phthalyl chitosan.Fig. 2 is O-succsinic acid-N-phthalyl chitosan
13The C-NMR spectrogram is the mesomethylene carbon of succsinic acid at the peak of 25-35ppm, and 160-165ppm is a carbonyl carbon, and 120-140ppm is an aromatic ring, and 57-100ppm is the skeleton carbon of chitosan.
Embodiment 2
5g phthaloyl chitosan is added 250gN, in the dinethylformamide solution, be stirred to dissolving fully; add the 5g hexanodioic acid again, 100 ℃ of reactions 12 hours, the frozen water precipitation; extracting, vacuum-drying obtains 6.2g O-hexanodioic acid-N-phthalyl chitosan.Fig. 3 is the infrared spectrum of O-hexanodioic acid-N-phthalyl chitosan.The amino C=O that reacts the acid amides of formation through phthaloyl vibrates at 1712cm on the chitosan
-1Strong absorption peak has appearred, and because the formation of imide structure, adjacent two carbonyls interact and make it split into two peaks, and one of them appears at the more about 1777cm of high frequency
-1Near, the methylene radical in the hexanodioic acid is at 2800-3000cm
-1Near absorption peak appears.
Embodiment 3
Add 100mLN with making 1g O-succsinic acid-N-phthalyl chitosan and polycaprolactone among the embodiment 1, in the dinethylformamide solution, add 4mL toluene.Under nitrogen atmosphere, about 15 hours of 100 ℃ of stirring reactions of temperature of reaction.Product is through precipitate and separate, and removes unreacted polycaprolactone in 24 hours with the acetone extracting, and vacuum-drying obtains chitose graft copolymer.Fig. 4 is chitosan and polycaprolactone graft copolymer
1H-NMR spectrogram, the chemistry of the proton of the methylene radical of Succinic Acid are 4, and the methylene radical of polycaprolactone is respectively 1,2,3,5, and the chemical shift of Tetra hydro Phthalic anhydride phenyl ring methylene radical is 6.
Claims (2)
1. oil soluble chitosan derivative is characterized in that chemical structural formula is as follows:
Wherein R is C
2-C
4Alkyl, n is 1000-3000.
2. the preparation method of a kind of oil soluble chitosan derivative as claimed in claim 1 is characterized in that the preparation method is as follows, below all represents with mass parts:
(1) chitosan and the 3-15 part Tetra hydro Phthalic anhydride with 1-5 part adds exsiccant 50-250 part N, in the dinethylformamide solution, at 120-130 ℃, under the nitrogen atmosphere stirring reaction 5-6 hour, after reaction finished, product precipitated through frozen water, suction filtration, use the ethanol extracting and purifying, obtain the phthaloyl chitosan in 40 ℃ of following vacuum-dryings; Wherein the molecular weight of chitosan is 5 * 10
3-8 * 10
5
(2) phthaloyl chitosan of 1-5 part and the diprotic acid or the dibasic acid anhydride of 3-45 part are added exsiccant 50-250 part N, in the dinethylformamide solution, under nitrogen atmosphere, be warmed up to 100-120 ℃ of stirring reaction 12-24 hour, after reaction finishes, product precipitates through frozen water, suction filtration is used the ethanol extracting and purifying, obtains oil soluble chitosan derivative in 40 ℃ of following vacuum-dryings again; Wherein diprotic acid is succsinic acid or hexanodioic acid; Dibasic acid anhydride is succinyl oxide or maleic anhydride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285002B (en) * | 2008-05-06 | 2011-08-24 | 中国科学技术大学 | Process for separating bio-oil via solvent with high boiling point |
| 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 |
-
2006
- 2006-12-21 CN CN 200610147656 patent/CN1995072A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285002B (en) * | 2008-05-06 | 2011-08-24 | 中国科学技术大学 | Process for separating bio-oil via solvent with high boiling point |
| 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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Open date: 20070711 |