CN103965403A - Novel method for grafting chitosan onto 2-acrylamido-2-methylpropanesulfonic acid (AMPS) - Google Patents
Novel method for grafting chitosan onto 2-acrylamido-2-methylpropanesulfonic acid (AMPS) Download PDFInfo
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- CN103965403A CN103965403A CN201310026592.XA CN201310026592A CN103965403A CN 103965403 A CN103965403 A CN 103965403A CN 201310026592 A CN201310026592 A CN 201310026592A CN 103965403 A CN103965403 A CN 103965403A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a novel preparation method for a chitosan graft copolymer, which belongs to the field of modification technology for natural polymers. According to the method, chitosan is used as a raw material, amino acid hydrochloride ionic liquid is used as a reaction solvent, AMPS is used as a monomer, ceric ammonium nitrate is used as an initiator, benzoquinone is used as a polymerization inhibitor, a reaction is carried out at 50 to 60 DEG C in a water bath for 2.5 to 3.5 h, and then separation and purification and vacuum drying are successively carried out so as to obtain a chitosan/AMPS graft copolymer. The graft copolymer is cross-linking-state gel, has a grafting ratio of 180%, is hard to dissolve under acidic, neutral and alkaline conditions and has certain swelling properties. The chitosan/AMPS graft copolymer prepared by using the method has the characteristics of simple process, short reaction time, a high grafting ratio, easily controllable reaction conditions, no addition of organic solvents, etc. and has wide application prospects in fields like medicine and environmental protection.
Description
Technical field
The invention belongs to natural high molecular substance technical field, specifically belong to a kind of ionic liquid green reaction solvent that relies on and carry out novel method prepared by chitosan graft copolymerization.
Background technology
Chitosan is the N-deacetylation product of chitin, has the features such as good biocompatibility, nontoxicity and biodegradability, and at food, medicine, many fields such as water treatment obtain extensive concern.In actual applications, often by various monomer-grafted to its surface, thus broadened application scope.But by monomer-grafted when the macromolecule surface, the homopolymer often producing due to monomer homopolymerization has affected the raising of percentage of grafting, even can be too many and cannot make graft reaction proceed due to homopolymer.How in chitosan graft process, improving or stoping monomer homopolymerization, improve percentage of grafting is an important problem.At present, the graft modification of chitosan extensively adopts traditional method,, under the reaction system of chitosan and diluted acid or chitosan and organic solvent composition, carry out graft reaction, but most of method consumption quantity of solvent is large, complex steps, and organic solvent is volatile;
Ionic liquid (ionic liquids) is called again ionic liquid at room temperature (room temperature ionic liquids), it is the liquid being comprised of ion completely, being the salt being in a liquid state under near room temperature, also referred to as low temperature molten salt, is the environmentally friendly solvent newly rising in recent years.Traditional organic solvent is compared with ionogen, have advantages of a series of outstanding: (1) has non-volatile characteristic, almost there is no vapour pressure, therefore they can be used in high vacuum system, have simultaneously odorless, the feature such as do not fire, can be used as eco-friendly solvent, reduce the problem of environmental pollution producing because of volatilization; (2) there is wider equilibrium temperature scope, even when higher than 200 ℃, there is very good thermostability; (3) have good solubility energy, by adjustable its solvability to inorganics, water, organism and polymkeric substance of the design of its zwitterion, and its acidity also can regulate; (4) be easy to and other separating substances, can recycle; (5) there is good chemical stability and wider electrochemical window.At present, be widely used in chemosynthesis, biocatalysis, the matrix material field such as synthetic synthetic, nano material even.In recent years, investigator utilizes ionic liquid for dissolution with solvents Mierocrystalline cellulose both at home and abroad, finds that it can be dissolved in ionic liquid, and ionic liquid can also recycling simultaneously.Because chitosan and Mierocrystalline cellulose have similar structure, theoretically, ionic liquid that can dissolving cellulos also can dissolve chitosan;
[0004] about chitosan, in ionic liquid, be dissolved with at present certain report, but in ionic liquid, carry out chitin modified report also seldom.Chinese patent CN200710043563.9 has openly reported take preparation and the application of the cellulose blending fibre that ionic liquid is solvent; Chinese patent CN200810228127.3 has openly reported a kind of method of hydrolyzing chitosan and chitin; Chinese patent CN200810013967.8 has openly reported a kind of method of cleanly preparing acylchitosan; Akihiko Takegawa etc. are at Carbohydrate Polymers(2010,79:85-90) on reported employing bromination 1-allyl group-3-Methylimidazole and two kinds of ionic liquids of chlorination 1-butyl-3-Methylimidazole, prepared chitin/cellulose gel film.Liang Sheng exists. polymer material science and engineering (2010,26(2): 70-72), reported and synthesized a series of amino acid ion liquids, and adopt its aqueous solution to dissolve chitosan, respectively the chitosan before and after dissolving is characterized, result shows not find in dissolution process chitosan derivative.
Summary of the invention
Object of the present invention is the means that adopt a kind of Green Chemistry, carries out the graft modification of chitosan and acrylamide group methyl propanesulfonic acid (AMPS) in ionic liquid, obtains target product.Efficiency of the present invention is high, and process is simply controlled, can meet production requirement;
A kind of novel method of preparing Graft Copolymer Ofa Crylamide Onto Chitosan ylmethyl propanesulfonic acid of the present invention, comprises the following steps:
(1) to adding mass concentration in chitosan, be 1% amino acid salts hydrochlorate ionic liquid, after dissolving to chitosan, sealed storage, obtains uniform solution, standby;
(2) under nitrogen protection, add initiator ceric ammonium nitrate, stir 0.06% the stopper benzoquinone who once adds monomer mass per-cent after 15min, and chitosan mass 3.5-4.5 AMPS monomer doubly, be warming up to 50-60 ℃, reaction 2.5-3.5h, is cooled to room temperature;
(3) with the dehydrated alcohol of 3 times of volumes, make graft product Precipitation, throw out is used washing with alcohol 3～5 times again, and 40 ℃ of vacuum-dryings, to constant weight, obtain chitose graft copolymer pressed powder;
Described deacetylating degree of chitosan ﹥ 90%, graft copolymer is crosslinking condition gel, and product percentage of grafting can reach 180%, and under acid, neutrality, alkaline condition, equal indissoluble, has certain swelling behavior.Described ionic liquid solution is the aqueous solution of ionic liquid.Ionic liquid is comprised of zwitterion, is to take the glycine ionic liquid that chlorion is negatively charged ion, and ionic liquid is aobvious acid.The described material modified aspects such as makeup, pharmaceutical carrier, water treatment absorbent and flocculation agent that can be used for;
Provided by the inventionly take ionic liquid as solvent, carry out chitosan graft modification and compared with prior art there is following advantage:
(1) modifying process of the present invention has overcome the shortcomings such as conventional solvent is volatile, seriously polluted, etching apparatus, is a kind of more green method of modifying; (2) product that this process obtains is directly cross-linking copolymer, has certain water suction and absorption property.(3) preparation process provided by the invention is simple, mild condition, and the reaction times is short, and substitution value is high, does not produce pollutent, is a kind of environmentally friendly preparation technology;
Embodiment
By specific examples, further illustrate the method that the present invention describes below, but be not limited to these examples of implementation;
Embodiment 1
In three mouthfuls of reaction flasks with whipping appts, it is in 1% glycine ionic liquid aqueous solution that 1g chitosan powder is dissolved in to 100ml concentration, is stirred to chitosan and dissolves completely, airtight, and room temperature is placed and spent the night, standby; Under nitrogen protection, add initiator ceric ammonium nitrate, stir 0.06% the stopper benzoquinone who once adds monomer mass per-cent after 15min, and the AMPS monomer of 4 times of chitosan masses, being warming up to 60 ℃, reaction 2.5h, is cooled to room temperature; With the dehydrated alcohol of 3 times of volumes, make graft product Precipitation, throw out is used washing with alcohol 3～5 times again, and 40 ℃ of vacuum-dryings, to constant weight, obtain chitose graft copolymer pressed powder, and recording its percentage of grafting is 180%.Products therefrom finds through Infrared spectroscopy, and graft copolymer infrared spectra is except having retained the charateristic avsorption band (3440cm of chitosan
-1) outside, at 1039 cm
-1appearance-the SO of place
2charateristic avsorption band, this shows that graft copolymerization has occurred for chitosan and AMPS;
Embodiment 2
In three mouthfuls of reaction flasks with whipping appts, it is in 1% glycine ionic liquid aqueous solution that 1g chitosan powder is dissolved in to 100ml concentration, is stirred to chitosan and dissolves completely, airtight, and room temperature is placed and spent the night, standby; Under nitrogen protection, add initiator ceric ammonium nitrate, stir 0.06% the stopper benzoquinone who once adds monomer mass per-cent after 15min, and the AMPS monomer of 4 times of chitosan masses, being warming up to 60 ℃, reaction 3h, is cooled to room temperature; With the dehydrated alcohol of 3 times of volumes, make graft product Precipitation, throw out is used washing with alcohol 3～5 times again, and 40 ℃ of vacuum-dryings, to constant weight, obtain chitose graft copolymer pressed powder, and recording its percentage of grafting is 113%;
Embodiment 3
In three mouthfuls of reaction flasks with whipping appts, it is in 1% glycine ionic liquid aqueous solution that 1g chitosan powder is dissolved in to 100ml concentration, is stirred to chitosan and dissolves completely, airtight, and room temperature is placed and spent the night, standby; Under nitrogen protection, add initiator ceric ammonium nitrate, stir 0.06% the stopper benzoquinone who once adds monomer mass per-cent after 15min, and the AMPS monomer of 3.5 times of chitosan masses, being warming up to 60 ℃, reaction 2.5h, is cooled to room temperature; With the dehydrated alcohol of 3 times of volumes, make graft product Precipitation, throw out is used washing with alcohol 3～5 times again, and 40 ℃ of vacuum-dryings, to constant weight, obtain chitose graft copolymer pressed powder, and recording its percentage of grafting is 102%;
Embodiment 4
In three mouthfuls of reaction flasks with whipping appts, it is in 1% glycine ionic liquid aqueous solution that 1g chitosan powder is dissolved in to 100ml concentration, is stirred to chitosan and dissolves completely, airtight, and room temperature is placed and spent the night, standby; Under nitrogen protection, add initiator ceric ammonium nitrate, stir 0.06% the stopper benzoquinone who once adds monomer mass per-cent after 15min, and the AMPS monomer of 4 times of chitosan masses, being warming up to 50 ℃, reaction 2.5h, is cooled to room temperature; With the dehydrated alcohol of 3 times of volumes, make graft product Precipitation, throw out is used washing with alcohol 3～5 times again, and 40 ℃ of vacuum-dryings, to constant weight, obtain chitose graft copolymer pressed powder, and recording its percentage of grafting is 135%.
Figure of description explanation
Fig. 1 is the infrared spectrogram of chitosan; Fig. 2 is the infrared spectrogram of the new grafting of chitosan/AMPS.
Claims (3)
1. a method of preparing chitosan/AMPS, is characterized in that comprising the following steps:
(1) to adding mass concentration in chitosan, be 1% amino acid salts hydrochlorate ionic liquid, after dissolving to chitosan, sealed storage, obtains uniform solution, standby;
(2) under nitrogen protection, add initiator ceric ammonium nitrate, stir 0.06% the stopper benzoquinone who once adds monomer mass per-cent after 15min, and chitosan mass 3.5-4.5 AMPS monomer doubly, be warming up to 50-60 ℃, reaction 2.5-3.5h, is cooled to room temperature;
(3) with the dehydrated alcohol of 3 times of volumes, make graft product Precipitation, throw out is used washing with alcohol 3～5 times again, and 40 ℃ of vacuum-dryings, to constant weight, obtain chitose graft copolymer pressed powder;
According to right 1, require a kind of described method of preparing chitosan/AMPS, it is characterized in that: described deacetylating degree of chitosan ﹥ 90%.
2. according to right 1, require a kind of described method of preparing chitosan/AMPS, it is characterized in that: graft copolymer is crosslinking condition gel, product percentage of grafting can reach 180%, and under acid, neutrality, alkaline condition, equal indissoluble, has certain swelling behavior.
3. according to right 1, require a kind of described method of preparing chitosan/AMPS, it is characterized in that: described ionic liquid solution is for take the glycine ionic liquid that chlorion is negatively charged ion.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785227A (en) * | 2015-04-30 | 2015-07-22 | 南京大学 | Chitosan-grafting amino acid magnetic composite microsphere as well as preparation method and application |
| CN107519845A (en) * | 2017-10-18 | 2017-12-29 | 福州大学 | A kind of ion liquid modified cross-linked porous chitosan absorbent and its preparation and application |
| WO2018028058A1 (en) * | 2016-08-08 | 2018-02-15 | 江南大学 | Preparation method for surface functionalized drug-loaded eluting microspheres |
| CN108264610A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of chitosan flocculant and its preparation method and application |
| CN108264612A (en) * | 2018-02-25 | 2018-07-10 | 温岭汉德高分子科技有限公司 | A kind of preparation method of chitosan-poly- 2- acrylamide-2-methylpro panesulfonic acid sodium copolymers for monocrystalline silicon making herbs into wool |
| CN108360072A (en) * | 2018-02-25 | 2018-08-03 | 温岭汉德高分子科技有限公司 | A kind of monocrystalline silicon flocking additive based on the poly- 2- acrylamide-2-methylpro panesulfonic acids sodium copolymer of chitosan- |
| CN108360071A (en) * | 2018-02-25 | 2018-08-03 | 温岭汉德高分子科技有限公司 | A kind of etching method of antiradar reflectivity monocrystalline silicon piece |
| CN109400814A (en) * | 2018-11-02 | 2019-03-01 | 重庆工商大学 | A kind of preparation method of the chitosan-based flocculant of anion |
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2013
- 2013-01-24 CN CN201310026592.XA patent/CN103965403A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785227A (en) * | 2015-04-30 | 2015-07-22 | 南京大学 | Chitosan-grafting amino acid magnetic composite microsphere as well as preparation method and application |
| WO2018028058A1 (en) * | 2016-08-08 | 2018-02-15 | 江南大学 | Preparation method for surface functionalized drug-loaded eluting microspheres |
| CN108264610A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of chitosan flocculant and its preparation method and application |
| CN107519845A (en) * | 2017-10-18 | 2017-12-29 | 福州大学 | A kind of ion liquid modified cross-linked porous chitosan absorbent and its preparation and application |
| CN107519845B (en) * | 2017-10-18 | 2019-09-13 | 福州大学 | A kind of ion liquid modified cross-linked porous chitosan absorbent and its preparation and application |
| CN108264612A (en) * | 2018-02-25 | 2018-07-10 | 温岭汉德高分子科技有限公司 | A kind of preparation method of chitosan-poly- 2- acrylamide-2-methylpro panesulfonic acid sodium copolymers for monocrystalline silicon making herbs into wool |
| CN108360072A (en) * | 2018-02-25 | 2018-08-03 | 温岭汉德高分子科技有限公司 | A kind of monocrystalline silicon flocking additive based on the poly- 2- acrylamide-2-methylpro panesulfonic acids sodium copolymer of chitosan- |
| CN108360071A (en) * | 2018-02-25 | 2018-08-03 | 温岭汉德高分子科技有限公司 | A kind of etching method of antiradar reflectivity monocrystalline silicon piece |
| CN108264612B (en) * | 2018-02-25 | 2020-10-09 | 温岭汉德高分子科技有限公司 | Preparation method of chitosan-poly (2-acrylamide-2-methylpropanesulfonic acid) sodium sulfonate copolymer for monocrystalline silicon texturing |
| CN109400814A (en) * | 2018-11-02 | 2019-03-01 | 重庆工商大学 | A kind of preparation method of the chitosan-based flocculant of anion |
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Application publication date: 20140806 |