CN107321318A - A kind of preparation method of N phthalic acids substitution chitosan oligosaccharide sorbing material and its derivative - Google Patents
A kind of preparation method of N phthalic acids substitution chitosan oligosaccharide sorbing material and its derivative Download PDFInfo
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- CN107321318A CN107321318A CN201710567907.XA CN201710567907A CN107321318A CN 107321318 A CN107321318 A CN 107321318A CN 201710567907 A CN201710567907 A CN 201710567907A CN 107321318 A CN107321318 A CN 107321318A
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- chitosan oligosaccharide
- phthalic acids
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- sorbing material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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Abstract
The invention discloses the preparation method of a kind of N phthalic acids substitution chitosan oligosaccharide sorbing material and its derivative.Chitosan oligosaccharide and phthalic anhydride are mixed according to a certain percentage, under the protection of inert gas, organic solvent dissolving is added, reaction is stirred at reflux at a certain temperature, after reaction terminates, post processing obtains the chitosan oligosaccharide product that part is replaced by N phthalic acids；Again under the protection of inert gas, a certain proportion of maleic anhydride is added in reaction solution, reaction is stirred at reflux at a certain temperature, after reaction terminates, post processing obtains the chitosan oligosaccharide derivative that part is replaced by N phthalic acids.The present invention prepares reaction and uses single bath process, and raw material used is few, and technique is simple, improves the dissolubility of product, adds its application.
Description
Technical field
The invention belongs to chitosan oligosaccharide derivant material preparation field, more particularly to a kind of N- phthalic acids substitution chitosan oligosaccharide
The preparation method of sorbing material and its derivative.
Background technology
With phthalic anhydride N- acylation reactions occur for chitosan oligosaccharide, and the amino in chitosan oligosaccharide molecule can be protected
Shield, significantly improves its dissolubility in organic solvent.At the same time it can also continue to enter N- phthalic acids substitution chitosan oligosaccharide
Row reaction, synthesizes a series of derivatives.Numerous chitosan oligosaccharide derivatives have been synthesized, and for sorbing material.Its Literature report
The phthalic acid substitution chitosan oligosaccharide and its derivative in road mainly have N- substitutions and O- to replace two kinds of forms.
The content of the invention
In order to solve problem present in background technology, taken it is an object of the invention to provide a kind of shell N- phthalic acids
For the preparation method of chitosan oligosaccharide sorbing material and its derivative.The present invention can be prepared into by being controlled to reaction condition
The chitosan oligosaccharide sorbing material replaced to only N-, it has very wide application prospect in terms of gas absorption.
Based on above-mentioned purpose, the present invention is adopted the following technical scheme that：
Chitosan oligosaccharide and phthalic anhydride are mixed according to a certain percentage, under the protection of inert gas, added organic molten
Agent is dissolved, and 8~10h of reaction is stirred at reflux at a certain temperature, after reaction terminates, and post processing obtains part by N- phthalic acids
Substituted chitosan oligosaccharide product.
Further, after the back flow reaction terminates, then under the protection of inert gas, one is added in reaction solution
The maleic anhydride of certainty ratio, is stirred at reflux 8~10h of reaction at a certain temperature, after reaction terminates, and post processing obtains part by N-
The chitosan oligosaccharide derivative of phthalic acid substitution.
The specific reaction equation that chitosan oligosaccharide derivative is made by two-step reaction in the present invention is as follows：
The ratio between described chitosan oligosaccharide and the amount of material of phthalic anhydride are 1:1~3, the consumption of the organic solvent makes
It is 0.03g~0.09g/mL to obtain the mass content of chitosan oligosaccharide in organic solvent.
The ratio between the maleic anhydride of the addition and the amount of material of chitosan oligosaccharide are 1~4:1；
Described organic solvent is the mixing of N,N-dimethylformamide or N,N-dimethylformamide and deionized water
Solution, and if mixed solution, the volume ratio of DMF and deionized water is 19:1.
Reaction terminates the post-processing approach of the rear reaction solution：Frozen water precipitation is added, precipitation is centrifugally separating to obtain,
Precipitation is washed with deionized, and finally vacuum drying obtains product.
The reaction temperature of the back flow reaction is 80~120 DEG C.
The ratio between described chitosan oligosaccharide and the amount of material of phthalic anhydride are 1:1~3, the consumption of the organic solvent makes
It is 0.03g~0.09g/mL to obtain the mass content of chitosan oligosaccharide in organic solvent.
The ratio between the maleic anhydride of the addition and the amount of material of chitosan oligosaccharide are 1~4:1；
Described organic solvent is the mixing of N,N-dimethylformamide or N,N-dimethylformamide and deionized water
Solution, and if mixed solution, the volume ratio of DMF and deionized water is 19:1.
Reaction terminates the post-processing approach of the rear reaction solution：Frozen water precipitation is added, precipitation is centrifugally separating to obtain,
Precipitation is washed with deionized, and finally vacuum drying obtains product.
The reaction temperature of the back flow reaction is 80~120 DEG C, and the reaction time is 8~10h.
The beneficial effects of the invention are as follows：
1st, the preparation reaction of chitosan oligosaccharide derivant material of the present invention uses single bath process, and raw material used is few, and technique is simple；
2nd, the dissolubility of chitosan oligosaccharide derivative of the present invention is significantly improved, so as to add its application.
Brief description of the drawings
Fig. 1 be the N- phthalic acids substitution chitosan oligosaccharide sorbing material that synthesizes in Example 1 and Example 2 of the present invention and its
The FT-IR collection of illustrative plates of derivative.
Embodiment
The present invention is specifically described below by embodiment, is served only for that the present invention is further described, no
It is understood that for limiting the scope of the present invention, the technician in the field can be according to the content of foregoing invention to the present invention
Some nonessential modifications and adaptations are made, are thought within protection scope of the present invention.
Embodiments of the invention are as follows：
Embodiment 1：
A kind of N- phthalic acids replace the preparation method of chitosan oligosaccharide sorbing material, comprise the following steps：Weigh about 6.71g
Chitosan oligosaccharide (0.04mol or so) and about 7.95g phthalic anhydrides (0.06mol or so) are added in 250mL three-neck flasks
The anhydrous DMFs of 100mL, lead to Ar protections, the magnetic agitation at 100 DEG C until chitosan oligosaccharide is completely dissolved；Afterwards,
Reacted at 120 DEG C, reaction is terminated after reaction 9h：Product is transferred in beaker, adding frozen water precipitates product,
Centrifuged 10 minutes under 2000rpm rotating speeds, obtained precipitation is washed three times with 250mL deionized waters, be put into 40 DEG C of vacuum bakings
Dried in case to constant weight, that is, obtain N- phthalic acids substitution chitosan oligosaccharide sorbing material.
Replace chitosan oligosaccharide sorbing material to be placed in agate mortar about 2mgN- phthalic acids, add KBr and grind together,
After tabletting 1min, infrared test is carried out on infrared tester, the infrared spectrum of sample is shown in Fig. 1 (a).As seen from the figure, original shell
It is due in 1662cm in oligosaccharides-1Representative-the NH at place3The peak of group N-H key stretching vibrations is vanished from sight, and 1598cm-1Place
The peak for representing N-H keys stretching vibration in amide group is still present.In addition, 1770 and 1710cm-1The peak at place is phthalic acid
The peak of the stretching vibration of upper phenyl ring skeleton.It can confirm that N- phthalic acids replace chitosan oligosaccharide to synthesize successfully by FT-IR collection of illustrative plates,
Product can be dissolved in DMSO.
Embodiment 2：
About 3.10g N- phthalic acids substitution chitosan oligosaccharide (0.01mol or so) peace treaty is weighed from the product of embodiment 1
1.01g maleic anhydrides (about 0.01mol or so), react 9h at 90 DEG C；After reaction terminates, product is transferred in beaker, added
Frozen water precipitates product, is centrifuged 10 minutes under 2000rpm rotating speeds, obtained precipitation washs three with 250mL deionized waters
It is secondary, it is put into 40 DEG C of vacuum drying ovens and dries to constant weight, that is, obtains N- phthalic acids substitution chitosan oligosaccharide derivative sorbing material.
Replace chitosan oligosaccharide derivative sorbing material to be placed in agate mortar about 2mg N- phthalic acids, add KBr mono-
Rise after grinding, tabletting 1min, infrared test is carried out on infrared tester, the infrared spectrum of sample is shown in Fig. 1 (b).As seen from the figure,
In 1641cm-1Place occurs in that the stretching vibration peak of C=C in maleic anhydride.N- phthalic acids can confirm that by FT-IR collection of illustrative plates
Substitution chitosan oligosaccharide derivative is synthesized successfully, and product can be dissolved in DMSO.
Embodiment 3：
About 3.10gN- phthalic acids substitution chitosan oligosaccharide (0.01mol or so) peace treaty is weighed from the product of embodiment 1
1.98g maleic anhydrides (about 0.02mol or so), react 9h at 90 DEG C；After reaction terminates, product is transferred in beaker, added
Frozen water precipitates product, is centrifuged 10 minutes under 2000rpm rotating speeds, obtained precipitation washs three with 250mL deionized waters
It is secondary, it is put into 40 DEG C of vacuum drying ovens and dries to constant weight, that is, obtains N- phthalic acids substitution chitosan oligosaccharide derivative sorbing material, production
Thing can be dissolved in DMSO.
Embodiment 4：
About 3.10gN- phthalic acids substitution chitosan oligosaccharide (0.01mol or so) peace treaty is weighed from the product of embodiment 1
2.95g maleic anhydrides (about 0.03mol or so), react 9h at 90 DEG C；After reaction terminates, product is transferred in beaker, added
Frozen water precipitates product, is centrifuged 10 minutes under 2000rpm rotating speeds, obtained precipitation washs three with 250mL deionized waters
It is secondary, it is put into 40 DEG C of vacuum drying ovens and dries to constant weight, that is, obtains N- phthalic acids substitution chitosan oligosaccharide derivative sorbing material, production
Thing can be dissolved in DMSO.
Claims (7)
1. a kind of N- phthalic acids replace the preparation method of chitosan oligosaccharide sorbing material, it is characterised in that comprise the following steps：Will
Chitosan oligosaccharide and phthalic anhydride are mixed according to a certain percentage, under the protection of inert gas, organic solvent dissolving are added, one
Determine to be stirred at reflux 8~10h of reaction at temperature, after reaction terminates, post processing obtains the shell widow that part is replaced by N- phthalic acids
Sugared product.
2. a kind of preparation side of the derivative of N- phthalic acids substitution chitosan oligosaccharide sorbing material according to claim 1
Method, it is characterised in that：Further, after the back flow reaction terminates, then under the protection of inert gas, in reaction solution
A certain proportion of maleic anhydride is added, 8~10h of reaction is stirred at reflux at a certain temperature, after reaction terminates, obtaining portion is post-processed
Divide the chitosan oligosaccharide derivative replaced by N- phthalic acids.
3. a kind of N- phthalic acids according to claim 1 replace the preparation method of chitosan oligosaccharide sorbing material, its feature
It is：The ratio between described chitosan oligosaccharide and the amount of material of phthalic anhydride are 1:1~3, the consumption of the organic solvent causes
The mass content of chitosan oligosaccharide in organic solvent is 0.03g~0.09g/mL.
4. a kind of N- phthalic acids according to claim 1 replace the preparation method of chitosan oligosaccharide sorbing material, its feature
It is：The ratio between the maleic anhydride of the addition and the amount of material of chitosan oligosaccharide are 1~4:1.
5. a kind of N- phthalic acids according to claim 1 replace the preparation method of chitosan oligosaccharide sorbing material, its feature
It is：Described organic solvent is molten for the mixing of N,N-dimethylformamide or N,N-dimethylformamide and deionized water
Liquid, and if mixed solution, the volume ratio of DMF and deionized water is 19:1.
6. a kind of system of N- phthalic acids substitution chitosan oligosaccharide sorbing material according to claim 1 or 2 or derivatives thereof
Preparation Method, it is characterised in that：Reaction terminates the post-processing approach of the rear reaction solution：Add frozen water precipitation, centrifugation point
From being precipitated, precipitation is washed with deionized, and finally vacuum drying obtains product.
7. a kind of system of N- phthalic acids substitution chitosan oligosaccharide sorbing material according to claim 1 or 2 or derivatives thereof
Preparation Method, it is characterised in that：The reaction temperature of the back flow reaction is 80~120 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710567907.XA CN107321318A (en) | 2017-07-12 | 2017-07-12 | A kind of preparation method of N phthalic acids substitution chitosan oligosaccharide sorbing material and its derivative |
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| CN201710567907.XA CN107321318A (en) | 2017-07-12 | 2017-07-12 | A kind of preparation method of N phthalic acids substitution chitosan oligosaccharide sorbing material and its derivative |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857649A (en) * | 2010-03-18 | 2010-10-13 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material |
| CN102241883A (en) * | 2010-09-25 | 2011-11-16 | 深圳市科聚新材料有限公司 | Antimicrobial polyamide material and preparation method thereof |
| CN103254599A (en) * | 2013-05-31 | 2013-08-21 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide modified biodegradable composite |
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2017
- 2017-07-12 CN CN201710567907.XA patent/CN107321318A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857649A (en) * | 2010-03-18 | 2010-10-13 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material |
| CN102241883A (en) * | 2010-09-25 | 2011-11-16 | 深圳市科聚新材料有限公司 | Antimicrobial polyamide material and preparation method thereof |
| CN103254599A (en) * | 2013-05-31 | 2013-08-21 | 沈阳工业大学 | Method for preparing chitosan oligosaccharide modified biodegradable composite |
Non-Patent Citations (1)
| Title |
|---|
| 王俊骅: "壳寡糖的化学改性及其对氨和苯酚吸附性能的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
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