CN101735486A - carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material and preparation method thereof - Google Patents
carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material and a preparation method thereof. The carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material basically comprises a carboxymethyl chitosan quaternary ammonium salt and rectorite and is formed by inserting the carboxymethyl chitosan quaternary ammonium salt into natural calcium-based rectorite layers, wherein the layer spacing of the rectorite after layer insertion is 2.58 to 3.27 nanometers. The preparation method comprises: dripping solution, at a certain concentration, of the carboxymethyl chitosan quaternary ammonium salt into suspension of the rectorite at two times under conditions of a temperature of 70 to 80 DEG C and stirring; and performing freeze drying to obtain the carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material. The nano composite material combines the structures and physical and chemical properties of organic and inorganic materials, has improved stability and can be desirably used in various fields such as antibacterial biological materials, daily chemical products and waste water treatment.
Description
Technical field
The invention belongs to field of nanometer technology, be specifically related to carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material and preparation method thereof.
Background technology
Amphiphilic polymers is meant the superpolymer that includes negatively charged ion and cation group on macromolecular skeleton simultaneously, it has and the similar structure of biopolymers such as protein, nucleic acid, have higher biological fitness, it has caused people's extensive concern at biomedicine, makeup, pharmacology, agricultural and biological technical field.
Chitosan is that a kind of source is abundant, has multiple bioactive natural polymer.Be widely used in various fields such as drug loading and sustained release, antibacterial biological material, daily chemical product, wastewater treatments, studies show that, the carboxymethyl chitosan quaternary ammonium salt of on the chitosan molecule chain, introducing carboxymethyl and quaternary ammonium salt group simultaneously and obtaining, compare with single chitosan, chitosan quaternary ammonium salt and cm-chitosan, better controlled release drug, remove free radical, flocculation Cd (II) and Cr (VI) ion, and stronger moisture-absorbing moisture-keeping and anti-microbial property are arranged.But similar with most of biomacromolecules, it is difficult to industrialization owing to be subjected to the restriction of poor heat resistance.
Summary of the invention
The present invention overcomes the shortcoming of prior art, and a kind of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material and preparation method thereof is provided, and the preparation method of matrix material of the present invention is the solution intercalation method, and this method is simple and effective, pollution-free, workable.Clay and carboxymethyl chitosan quaternary ammonium salt that resistance toheat is good are compound, can not only improve the thermostability of carboxymethyl chitosan quaternary ammonium salt, can also make material have the coupling advantage of nano composite polymer/laminated silicate material, have a wide range of applications.
A kind of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material basic composition is carboxymethyl chitosan quaternary ammonium salt and rectorite leng, and wherein carboxymethyl chitosan quaternary ammonium salt accounts for 33.3～80% weight, and rectorite leng accounts for 20～66.7% weight.
The interlamellar spacing of rectorite leng is at 2.58～3.27nm in described carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material.
The weight-average molecular weight of described carboxymethyl chitosan quaternary ammonium salt is 3.5 * 10
5～4.1 * 10
5, degree of substitution by carboxymethyl is 50～70%, the quaternary ammonium salt substitution value is 75～90%.
Described rectorite leng is unmodified natural calcium base rectorite leng.
A kind of preparation method of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material specifically comprises the steps:
(1) rectorite leng is dispersed in the suspension that forms 1～2g/ml in the water, swelling 18～36h,
(2) be heated to 70～80 ℃, when stirring the carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise to react 1～2d in the suspension after, keep 70～80 ℃ and whipped state, drip carboxymethyl chitosan quaternary ammonium salt reactant aqueous solution 1～2d again, adding the total amount of carboxymethyl chitosan quaternary ammonium salt and the weight ratio of rectorite leng is 1: 2～4: 1;
(3) lyophilize promptly gets carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material.
The weight-average molecular weight of described carboxymethyl chitosan quaternary ammonium salt is 3.5 * 10
5～4.1 * 10
5, degree of substitution by carboxymethyl is 50～70%, the quaternary ammonium salt substitution value is 75～90%.
Described rectorite leng is unmodified natural calcium base rectorite leng.
The weight of the carboxymethyl chitosan quaternary ammonium salt that adds is less than the weight of the carboxymethyl chitosan quaternary ammonium salt of back adding earlier.
The quality volumetric concentration of the carboxymethyl chitosan quaternary ammonium salt aqueous solution that adds is 0.1～0.25g/ml earlier; The carboxymethyl chitosan quaternary ammonium salt aqueous solution that the back adds the quality volumetric concentration be 0.5～1g/ml.
The application of a kind of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material in antibacterial biological material, daily chemical product and field of waste water treatment.
The present invention is with respect to advantage and beneficial effect that prior art had:
Owing to carboxymethyl chitosan quaternary ammonium salt is to introduce the water-soluble bisexual copolymer that carboxymethyl and quaternary ammonium salt generate on the chitosan molecule chain simultaneously, it has the performance more excellent than independent chitosan, cm-chitosan and chitosan quaternary ammonium salt, but the same with most of biomacromolecules, its thermostability is relatively poor.And that rectorite leng has is well more thermally-stabilised, it can strengthen high molecular resistance toheat, therefore carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material provided by the invention can have than the better resistance toheat of single carboxymethyl chitosan quaternary ammonium salt, can widen the application of carboxymethyl chitosan quaternary ammonium salt in antibacterial biological material, daily chemical product and field of waste water treatment.
The intercalation method of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material provided by the invention does not need rectorite leng is carried out modification, directly utilize the positive ion on the carboxymethyl chitosan quaternary ammonium salt and the sodium ion of rectorite leng interlayer to exchange, and the shearing force that rely on to stir is inserted into the silicate lamella with macromolecular chain and lamella is strutted, make clay reach the homodisperse of nanoscale, form matrix material.In addition, the present invention adopts and adds carboxymethyl chitosan quaternary ammonium salt at twice, earlier with carboxymethyl chitosan quaternary ammonium salt dilute solution and rectorite leng reaction, the polarity of rectorite leng interlayer microenvironment is changed, become lipophilicity from wetting ability, surface energy reduces, and more helps the carboxymethyl chitosan quaternary ammonium salt strong solution intercalation of back and forms nano composite material. and method provided by the invention has simple and effective, pollution-free, workable advantage.
Embodiment
Among the present invention, the method that the Sun Liping that the preparation of carboxymethyl chitosan quaternary ammonium salt has been reported according to prior art etc. provides obtains (Liping Sun, Yumin Du, Lihong Fan, Xiao Chen, Jianhong Yang, Preparation, characterization andantimicrobial activity of quaternized carboxymethyl chitosan and application as pulp-cap.Polymer, 2006,47 (6): 1796-1804).
Embodiment 1:
The preparation of carboxymethyl chitosan quaternary ammonium salt:
(weight-average molecular weight is 4.2 * 10 with the 1g chitosan
5, deacetylation is 92%, Zhejiang Yuhuan marine biochemistry company limited) be added in the 1.5ml 50%NaOH solution fully alkalization after ,-20 ℃ of placements are spent the night.Naturally after thawing under the room temperature, add the 10mL Virahol successively, by chitosan: the Mono Chloro Acetic Acid mol ratio is slowly to drip chloroacetic acid solution at 1: 6, behind the room temperature reaction 4h, regulates pH to neutral with Glacial acetic acid.Obtain the carboxymethyl chitose product after dialysis and the separation and purification.The cm-chitosan for preparing is placed there-necked flask, add Virahol, stir, heat up.According to chitosan and 2, the ratio of 3-epoxypropyl trimethylammonium chloride ammonium mole is adding 2 in 1: 7, and 3-epoxypropyl trimethylammonium chloride ammonium solution reacts for some time down at 80 ℃.With acetone separation purification carboxymethyl chitosan quaternary ammonium salt product, dialysis is to there not being Cl
-Ion, lyophilize.The weight-average molecular weight of the carboxymethyl chitosan quaternary ammonium salt that obtains is 4.1 * 10
5, degree of substitution by carboxymethyl is 70%, the quaternary ammonium salt substitution value is 75%.
The preparation of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material:
0.2g natural calcium base rectorite leng (Hubei Mingliu Leituoshi Stone Science ﹠ Technology Co. Ltd.) is made the aqeous suspension of 1g/ml, behind the swelling 18h, be heated to 80 ℃ while stirring, the carboxymethyl chitosan quaternary ammonium salt aqueous solution that 0.05g 0.1g/ml is prepared is added drop-wise in the rectorite leng aqeous suspension then, behind the reaction 2d, again the 0.05g 0.5g/ml carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise in the reacted solution, continue to stir 2d, lyophilize promptly gets carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material.The shared total weight percent of each component of this matrix material is respectively carboxymethyl chitosan quaternary ammonium salt 33.3%, rectorite leng 66.7%, the interlamellar spacing 2.58nm of the rectorite leng in the matrix material.The resistance toheat of matrix material of the present invention is better than single carboxymethyl chitosan quaternary ammonium salt, just begin to decompose at 276.9 ℃, just decomposed for 35.9% (single carboxymethyl chitosan quaternary ammonium salt decomposition temperature has just decomposed 73.6% at 256.1 ℃ during to 600 ℃) during to 600 ℃.
Embodiment 2:
The preparation of carboxymethyl chitosan quaternary ammonium salt:
(weight-average molecular weight is 3.9 * 10 with the 1g chitosan
5, deacetylation is 92%, Zhejiang Yuhuan marine biochemistry company limited) be added in the 1.5ml 45%NaOH solution fully alkalization after ,-20 ℃ of placements are spent the night.Naturally after thawing under the room temperature, add the 10mL Virahol successively, by chitosan: the Mono Chloro Acetic Acid mol ratio is slowly to drip chloroacetic acid solution at 1: 6, behind the room temperature reaction 4h, regulates pH to neutral with Glacial acetic acid.Obtain the carboxymethyl chitose product after dialysis and the separation and purification.The cm-chitosan for preparing is placed there-necked flask, add Virahol, stir, heat up.According to chitosan and 2, the ratio of 3-epoxypropyl trimethylammonium chloride ammonium mole is adding 2 in 1: 9, and 3-epoxypropyl trimethylammonium chloride ammonium solution reacts for some time down at 80 ℃.With acetone separation purification carboxymethyl chitosan quaternary ammonium salt product, dialysis is to there not being Cl
-Ion, lyophilize.The carboxymethyl chitosan quaternary ammonium salt weight-average molecular weight that obtains is 3.8 * 10
5, degree of substitution by carboxymethyl is 65%, the quaternary ammonium salt substitution value is 85%.
The preparation of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material:
0.2g natural calcium base rectorite leng (Hubei Mingliu Leituoshi Stone Science ﹠ Technology Co. Ltd.) is made the aqeous suspension of 1.5g/ml, behind the swelling 24h, stirring also is heated to 75 ℃, then the 0.05g 0.15g/ml carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise in the rectorite leng aqeous suspension, behind the reaction 1.5d, again the 0.15g 0.75g/ml carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise in the solution of reaction, continue to stir 1d, lyophilize promptly gets carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material.The shared total weight percent of each component of this matrix material is respectively carboxymethyl chitosan quaternary ammonium salt 50%, rectorite leng 50%.The interlamellar spacing of the rectorite leng in the material is 2.82nm.The resistance toheat of matrix material of the present invention is better than single carboxymethyl chitosan quaternary ammonium salt, just begin to decompose at 272.3 ℃, just decomposed for 44.2% (single carboxymethyl chitosan quaternary ammonium salt decomposition temperature has just decomposed 73.6% at 256.1 ℃ during to 600 ℃) during to 600 ℃
Embodiment 3:
The preparation of carboxymethyl chitosan quaternary ammonium salt:
(weight-average molecular weight is 3.6 * 10 with the 1g chitosan
5, deacetylation is 92%, Zhejiang Yuhuan marine biochemistry company limited) be added in the 1.5ml 30%NaOH solution fully alkalization after ,-20 ℃ of placements are spent the night.Naturally after thawing under the room temperature, add the 10mL Virahol successively, by chitosan: the Mono Chloro Acetic Acid mol ratio is slowly to drip chloroacetic acid solution at 1: 6, behind the room temperature reaction 4h, regulates pH to neutral with Glacial acetic acid.Obtain the carboxymethyl chitose product after dialysis and the separation and purification.The cm-chitosan for preparing is placed there-necked flask, add Virahol, stir, heat up.According to chitosan and 2, the ratio of 3-epoxypropyl trimethylammonium chloride ammonium mole is adding 2 in 1: 10, and 3-epoxypropyl trimethylammonium chloride ammonium solution reacts for some time down at 80 ℃.With acetone separation purification carboxymethyl chitosan quaternary ammonium salt product, dialysis is to there not being Cl
-Ion, lyophilize.The carboxymethyl chitosan quaternary ammonium salt weight-average molecular weight that obtains is 3.5 * 10
5, degree of substitution by carboxymethyl is 50%, the quaternary ammonium salt substitution value is 90%.
The preparation of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material:
0.2g natural calcium base rectorite leng (Hubei Mingliu Leituoshi Stone Science ﹠ Technology Co. Ltd.) is made the aqeous suspension of 1.5g/ml, after the swelling 24, stirring also is heated to 75 ℃, then the 0.1g 0.2g/ml carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise in the rectorite leng aqeous suspension, behind the reaction 1.5d, again the 0.3g 0.75g/ml carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise in the solution of reaction, continue to stir 1.5d, lyophilize promptly gets carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material.The shared total weight percent of each component of this matrix material is respectively carboxymethyl chitosan quaternary ammonium salt 66.7%, rectorite leng 33.3%.The interlamellar spacing of the rectorite leng in the material is 3.27nm.The resistance toheat of matrix material of the present invention is better than single carboxymethyl chitosan quaternary ammonium salt, just begin to decompose at 264.5 ℃, just decomposed for 64.9% (single carboxymethyl chitosan quaternary ammonium salt decomposition temperature has just decomposed 73.6% at 256.1 ℃ during to 600 ℃) during to 600 ℃
Embodiment 4:
The preparation of carboxymethyl chitosan quaternary ammonium salt:
(weight-average molecular weight is 3.9 * 10 with the 1g chitosan
5, deacetylation is 92%, Zhejiang Yuhuan marine biochemistry company limited) be added in the 1.5ml 50%NaOH solution fully alkalization after ,-20 ℃ of placements are spent the night.Naturally after thawing under the room temperature, add the 10mL Virahol successively, by chitosan: the Mono Chloro Acetic Acid mol ratio is slowly to drip chloroacetic acid solution at 1: 6, behind the room temperature reaction 4h, regulates pH to neutral with Glacial acetic acid.Obtain the carboxymethyl chitose product after dialysis and the separation and purification.The cm-chitosan for preparing is placed there-necked flask, add Virahol, stir, heat up.According to chitosan and 2, the ratio of 3-epoxypropyl trimethylammonium chloride ammonium mole is adding 2 in 1: 8, and 3-epoxypropyl trimethylammonium chloride ammonium solution reacts for some time down at 80 ℃.With acetone separation purification carboxymethyl chitosan quaternary ammonium salt product, dialysis is to there not being Cl
-Ion, lyophilize.The carboxymethyl chitosan quaternary ammonium salt weight-average molecular weight that obtains is 3.8 * 10
5, degree of substitution by carboxymethyl is 70%, the quaternary ammonium salt substitution value is 80%.
The preparation of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material:
0.2g natural calcium base rectorite leng (Hubei Mingliu Leituoshi Stone Science ﹠ Technology Co. Ltd.) is made the aqeous suspension of 2g/ml, behind the swelling 36h, stirring also is heated to 70 ℃, then the 0.2g 0.25g/ml carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise in the rectorite leng aqeous suspension, behind the reaction 1d, the 0.6g 1g/ml carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise in the solution of reaction again, continues to stir 2d, lyophilize promptly gets carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material.The shared total weight percent of each component of this matrix material is respectively carboxymethyl chitosan quaternary ammonium salt 80%, rectorite leng 20%.The interlamellar spacing of the rectorite leng in the matrix material of the present invention is 2.72nm.The resistance toheat of this material is better than single carboxymethyl chitosan quaternary ammonium salt, just begins to decompose at 261.6 ℃, just decomposes for 68.9% (single carboxymethyl chitosan quaternary ammonium salt decomposition temperature has just decomposed 73.6% at 256.1 ℃ during to 600 ℃) during to 600 ℃.
Single chitosan is because stable on heating problem has limited its application in fields such as antibacterial biological material, daily chemical product, wastewater treatments, carboxymethyl chitosan quaternary ammonium salt/the rectorite nano composite material of the present invention that obtains by embodiment 1-4, better than single carboxymethyl chitosan quaternary ammonium salt aspect resistance toheat, stability improves, can better application in various fields such as antibacterial biological material, daily chemical product, wastewater treatments.
Claims (10)
1. a carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material is characterized in that basic composition is carboxymethyl chitosan quaternary ammonium salt and rectorite leng, and wherein carboxymethyl chitosan quaternary ammonium salt accounts for 33.3～80% weight, and rectorite leng accounts for 20～66.7% weight.
2. carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material according to claim 1, the interlamellar spacing that it is characterized in that rectorite leng in described carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material is at 2.58～3.27nm.
3. carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material according to claim 1, the weight-average molecular weight that it is characterized in that described carboxymethyl chitosan quaternary ammonium salt is 3.5 * 10
5～4.1 * 10
5, degree of substitution by carboxymethyl is 50～70%, the quaternary ammonium salt substitution value is 75～90%.
4. carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material according to claim 1 is characterized in that: described rectorite leng is unmodified natural calcium base rectorite leng.
5. the preparation method of the described carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material of claim 1 is characterized in that specifically comprising the steps:
(1) rectorite leng is dispersed in the suspension that forms 1～2g/ml in the water, swelling 18～36h,
(2) be heated to 70～80 ℃, when stirring the carboxymethyl chitosan quaternary ammonium salt aqueous solution is added drop-wise to react 1～2d in the suspension after, keep 70～80 ℃ and whipped state, drip carboxymethyl chitosan quaternary ammonium salt reactant aqueous solution 1～2d again, adding the total amount of carboxymethyl chitosan quaternary ammonium salt and the weight ratio of rectorite leng is 1: 2～4: 1;
(3) lyophilize promptly gets carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material.
6. carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material according to claim 1, the weight-average molecular weight that it is characterized in that described carboxymethyl chitosan quaternary ammonium salt is 3.5 * 10
5～4.1 * 10
5, degree of substitution by carboxymethyl is 50～70%, the quaternary ammonium salt substitution value is 75～90%.
7. carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material according to claim 1 is characterized in that described rectorite leng is unmodified natural calcium base rectorite leng.
8. carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material according to claim 1 is characterized in that the weight of the carboxymethyl chitosan quaternary ammonium salt that elder generation adds is less than the weight of the carboxymethyl chitosan quaternary ammonium salt of back adding.
9. carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material according to claim 1 is characterized in that the quality volumetric concentration of the carboxymethyl chitosan quaternary ammonium salt aqueous solution of adding is 0.1～0.25g/ml earlier; The carboxymethyl chitosan quaternary ammonium salt aqueous solution that the back adds the quality volumetric concentration be 0.5～1g/ml.
10. the application of the described a kind of carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material of claim 1 in antibacterial biological material, daily chemical product and field of waste water treatment.
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Application publication date: 20100616 Assignee: Jiujiang hi tech Pharmaceutical Technology Co., Ltd. Assignor: South China University of Technology Contract record no.: 2013440000532 Denomination of invention: carboxymethyl chitosan quaternary ammonium salt/rectorite nano composite material and preparation method thereof Granted publication date: 20120509 License type: Exclusive License Record date: 20131205 |
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