CN102617753A - Inexpensive simple separation and purification method for quaternized chitosan - Google Patents
Inexpensive simple separation and purification method for quaternized chitosan Download PDFInfo
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- CN102617753A CN102617753A CN2011104583994A CN201110458399A CN102617753A CN 102617753 A CN102617753 A CN 102617753A CN 2011104583994 A CN2011104583994 A CN 2011104583994A CN 201110458399 A CN201110458399 A CN 201110458399A CN 102617753 A CN102617753 A CN 102617753A
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Abstract
The invention discloses an inexpensive simple separation and purification method for quaternized chitosan. The method comprises the following steps: dispersing the raw material chitosan (abbreviated as CTS) with a deacetylation degree of more than 60% and a molecular weight of more than 5 KDa in water; adjusting a pH value of an obtained mixture to 3 to 6 with dilute acetic acid until chitosan completely dissolves; heating a system; dissolving 2,3-epoxypropyltrimethyl ammonium chloride in water and slowly adding an obtained solution into the system by using a peristaltic pump; carrying out a thermostatic reaction after feeding is finished; and diluting a reaction solution with 10 times volume of water after discharging and successively treating the diluted reaction solution with a pp cotton filtration system and an ultrafiltration membrane system so as to obtain an aqueous solution (concentrate) product of quaternized chitosan (HTCC) with high purity. The separation and purification method provided in the invention does not use any organic solvent, can obtain a product with high purity, has the advantages of high yield, low cost and reduction in consumption of energy and is more convenient for practical application.
Description
Technical field
The present invention relates to the separating and purifying method of the easy n-trimethyl chitosan chloride of a kind of low cost (HTCC).
Background technology
Preparation and separation method that a lot of chitosan quaternary ammonium salts have been arranged at present; But these methods have a lot of defectives; Mainly contain following some: one, in production or the last handling process, with an organic solvent, not only cost is high during suitability for industrialized production; And industrial accident very easily takes place, simultaneously also bigger to environment damage.Two, chitosan will through and anticipating, be dissolved in the weak acid earlier after, separating out with alkali precipitation, simultaneously the pH of reaction medium is also higher; Three, productive rate is very low, and cost is high.The preparation technology who the present invention is directed to chitosan quaternary ammonium salt improves, and adopts ultrafiltration membrane technique to separate the purification aftertreatment simultaneously, has avoided the problems referred to above, reaches environmental protection and economic aim cheaply.
Summary of the invention
The object of the present invention is to provide the separating and purifying method of the easy n-trimethyl chitosan chloride of a kind of low cost (english abbreviation is HTCC).Do not use any organic solvent in the separating and purifying method of the present invention, can obtain highly purified product, and productive rate is expensive low, reduce the consumption of the energy, and more convenient practical application.
In order to achieve the above object, technical scheme of the present invention is:
The separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost is easy comprises the steps: to adopt deacetylation＞60%, and the raw materials of chitosan of molecular weight＞5KDa (english abbreviation is CTS) is dispersed in the water; After regulating pH 3-6 and dissolve fully with dilute acetic acid to chitosan; With 2,3-epoxypropyl trimethylammonium chloride ammonium was dissolved in the water, utilizes peristaltic pump slowly to be added in the system after system heated up; Behind reinforced the finishing, isothermal reaction; After the discharging,, handle with cotton filtering system of pp and ultrafiltration membrane system successively, can obtain the aqueous solution (liquid concentrator) product of highly purified n-trimethyl chitosan chloride (HTCC) with the water dilute reaction solution of 10 times of amounts.
The weight ratio of described chitosan and water is 1: 50.
Described dilute acetic acid employing concentration is 10% dilute acetic acid adjusting pH value.
Described system intensification scope is: 30-90 ℃.
Described 2, the mol ratio of the add-on of 3-epoxypropyl trimethylammonium chloride ammonium and chitosan is: 2: 1-8: 1.
Described 2,3-epoxypropyl trimethylammonium chloride ammonium adopts peristaltic pump, slowly to be added in the system in the time at 30min-180min.
The described isothermal reaction time is 12-24h.
Described separating and purifying method is with the water dilute reaction solution of 10 times of amounts, successively with cotton filtering system of pp and ultrafiltration membrane system processing (being commercially available treatment system) after the discharging; Described ultrafiltration membrane system is handled the filter membrane that adopts molecular weight cut-off 3000.
Below be chitosan and 2, the reaction of 3-epoxypropyl trimethylammonium chloride ammonium obtains the reaction equation of n-trimethyl chitosan chloride:
The invention has the beneficial effects as follows: chitosan is a kind of naturally occurring alkaline kation polysaccharide; Have good biological activity, biocompatibility, biodegradability and antibiotic, anticorrosion, hemostasis and promote specific function such as wound healing, but poorly soluble its range of application that limited of chitosan.The present invention is directed to this shortcoming; Carry out quaternised modified to chitosan; The chitosan quaternary ammonium salt that obtains not only has the character of typical quaternary ammonium salt; Like antibacterial bacteriostatic property and moisture absorbability and moisture retentivity, and kept performances such as the original good film-forming properties of chitosan, flocculence, biocompatibility and biological degradation, made it potential using value arranged in functional high molecule material, Treatment of Industrial Water, textiles processing and other fields.In addition, because the quaternary ammonium group in the chitosan quaternary ammonium salt is connected on the linear polymeric skeleton, this makes it can be used as the load etc. that carrier is used for medicine, auxiliary agent, biomaterial again, has widened its range of application.Therefore separating and purifying method of the present invention has following advantage:
1) produces and separate purification process, do not use any organic solvent.
2) raw materials of chitosan directly is dispersed in the aqueous systems.
3) after chitosan dissolves with dilute acetic acid, do not re-use sodium hydroxide adjustment pH value.
4) 2, slowly reinforced after 3-epoxypropyl trimethylammonium chloride ammonium is dissolved in the water with peristaltic pump, can reduce decomposition, help the raising of productive rate.
5) post-processing stages adopts earlier the cotton filtering system of PP to go out a spot of solid particulate and insolubles, and filtrating dilution back adopts ultrafiltration membrane system to handle (molecular weight cut-off 3000), can obtain highly purified product.
6) ultrafiltration membrane system has concentrating function, and product can highly purified aqueous solution form provide, and helps reducing cost, and reduces the consumption of the energy, and more convenient practical application.The solid phase prod pure like need can adopt lyophilize or spray-dired method to obtain.
Description of drawings
Fig. 1 is chitosan CTS of the present invention and n-trimethyl chitosan chloride HTCC infrared spectrogram;
Fig. 2 is the hydrogen spectrogram of CTS of the present invention in 1% deuterated salt acid solution;
Fig. 3 for HTCC of the present invention at 1% deuterium for the hydrogen spectrogram in the water.
Embodiment
The separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost of the present invention is easy; It is characterized in that comprising the steps: to adopt deacetylation＞60%; The raw materials of chitosan of molecular weight＞5KDa is dispersed in the water, and wherein the weight ratio of chitosan and water is 1: 50; Regulate pH 3-6 with dilute acetic acid then and dissolve fully to chitosan, described dilute acetic acid employing concentration is 10% dilute acetic acid adjusting pH value.Then after system intensification 30-90 ℃ with 2,3-epoxypropyl trimethylammonium chloride ammonium is dissolved in the water, 2, the mol ratio of the add-on of 3-epoxypropyl trimethylammonium chloride ammonium and chitosan is: 2: 1-8: 1; And utilize in the peristaltic pump 30min-180min time slowly with 2,3-epoxypropyl trimethylammonium chloride ammonium is added in the system, behind reinforced the finishing, and isothermal reaction 12-24h; Discharging then after the water dilution with 10 times of amounts, adopts cotton filtering system of pp and ultrafiltration membrane system to handle successively.Described ultrafiltration membrane system is handled the filter membrane that adopts molecular weight cut-off 3000.Can obtain the aqueous solution (liquid concentrator) product of highly purified n-trimethyl chitosan chloride (HTCC).The liquid concentrator that takes a morsel obtains solid phase prod after the lyophilize, characterize.
The structural characterization of chitosan quaternary ammonium salt: solid sample is used the KBr compressing tablet behind 45 ℃ of vacuum-drying 48h, measures with the NEXUS-470 Fourier transformation infrared spectrometer, obtains infrared spectrogram.Fig. 1 is chitosan CTS and n-trimethyl chitosan chloride HTCC infrared spectrogram.Contrast finds that on the HTCC spectral line, the characteristic peak that 1596 places characterize N-H disappears, and explains to replace mainly to occur in-NH
2On, there is sign-CH at 1481 places simultaneously
3The characteristic peak of C-H, explain and successfully introduced quaternary ammonium group.Chitosan is dissolved in 1% the deuterated salt acid, and HTCC is dissolved in deuterium in the water, carries out the proton nmr spectra test through the INOVA-600 nuclear magnetic resonance spectrometer under the 313K.CTS and HTCC are carried out nmr analysis, obtain CTS as shown in Figure 2 hydrogen spectrogram in 1% deuterated salt acid solution; Fig. 3 be HTCC at 1% deuterium for the hydrogen spectrogram in the water; Comprehensive above infrared and nuclear magnetic spectrum can draw the chitosan that product has quaternary ammonium salt structure.
The mensuration of quaternized degree:
Preparation cl ions standard (1.00mg/L NaCL standardized solution; 10.00mg/L NaCL standardized solution; 100.00mg/L the NaCL standardized solution) and sample solution (15mg/L); Concentration with cl ions in the thunder magnetic PXSJ-226 type ionometer working sample solution converses chloride ion content X% in the sample then, can calculate substitution value DS%=161*X%/(35.5-152.5*X%) according to formula.The actual computation value is 0.62.
Quaternised substitution value can calculate according to the nuclear-magnetism integration, quaternized substitution value=9 [N (CH
3)
3]/5 ([H3+H4+H5+H6+H6 ']).[N (CH in the formula
3)
3] be N (CH
3)
3Corresponding peak area, [H3+H4+H5+H6+H6 '] be the peak area sum of H3, H4, H5, H6, H6 ' correspondence.Calculating quaternized substitution value according to integration is 0.65.The quaternized substitution value basically identical that obtains with ion determination and nuclear-magnetism integration.
Claims (8)
1. the separating and purifying method of the n-trimethyl chitosan chloride that a low cost is easy is characterized in that comprising the steps: to adopt deacetylation＞60%, and the raw materials of chitosan of molecular weight＞5KDa is dispersed in the water; After regulating pH 3-6 and dissolve fully with dilute acetic acid to chitosan; With 2,3-epoxypropyl trimethylammonium chloride ammonium was dissolved in the water, utilizes peristaltic pump slowly to be added in the system after system heated up; Behind reinforced the finishing, isothermal reaction; With the water dilute reaction solution of 10 times of amounts, separate purification with the cotton filtering system of pp with ultrafiltration membrane system successively after the discharging; Can obtain the aqueous products of highly purified n-trimethyl chitosan chloride.
2. the separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost as claimed in claim 1 is easy is characterized in that: the weight ratio of described chitosan and water is 1: 50.
3. the separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost as claimed in claim 1 is easy is characterized in that: described dilute acetic acid employing concentration is 10% dilute acetic acid adjusting pH value.
4. the separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost as claimed in claim 1 is easy is characterized in that described system intensification scope is: 30-90 ℃.
5. the separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost as claimed in claim 1 is easy is characterized in that: described 2, the mol ratio of the add-on of 3-epoxypropyl trimethylammonium chloride ammonium and chitosan is: 2: 1-8: 1.
6. the separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost as claimed in claim 1 is easy is characterized in that: described 2,3-epoxypropyl trimethylammonium chloride ammonium adopts peristaltic pump, slowly to be added in the system in the time at 30min-180min.
7. the separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost as claimed in claim 1 is easy is characterized in that: the described isothermal reaction time is 12-24h.
8. the separating and purifying method of the n-trimethyl chitosan chloride that a kind of low cost as claimed in claim 1 is easy; It is characterized in that: after the discharging with the water dilute reaction solution of 10 times of amounts; Separate purification with the cotton filtering system of pp with ultrafiltration membrane system successively, described ultrafiltration membrane system is handled the filter membrane that adopts molecular weight cut-off 3000.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418283A (en) * | 2017-09-11 | 2017-12-01 | 浙江理工大学 | Environmental-friendputty putty powder that a kind of high-strength antibacterial is water-fast and preparation method thereof |
| CN107496176A (en) * | 2016-06-14 | 2017-12-22 | 哈尔滨盈聚生物科技有限公司 | A kind of safe and efficient antibacterial wet tissue and preparation method thereof |
| CN107496206A (en) * | 2016-06-14 | 2017-12-22 | 中国科学院理化技术研究所 | A kind of chitosan derivatives base children special-purpose non-water hand cleanser and preparation method thereof |
| CN109293796A (en) * | 2018-09-11 | 2019-02-01 | 北京华城新创环境科技有限公司 | A kind of preparation method and applications of n-trimethyl chitosan chloride |
| CN114634665A (en) * | 2022-03-02 | 2022-06-17 | 国家电投集团氢能科技发展有限公司 | Vinyl polymer/modified polyhydroxy polymer composites and uses thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798393A (en) * | 2009-02-10 | 2010-08-11 | 同济大学 | Method for producing a quaternary ammonium chitosan/polyving akohol membrane |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798393A (en) * | 2009-02-10 | 2010-08-11 | 同济大学 | Method for producing a quaternary ammonium chitosan/polyving akohol membrane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107496176A (en) * | 2016-06-14 | 2017-12-22 | 哈尔滨盈聚生物科技有限公司 | A kind of safe and efficient antibacterial wet tissue and preparation method thereof |
| CN107496206A (en) * | 2016-06-14 | 2017-12-22 | 中国科学院理化技术研究所 | A kind of chitosan derivatives base children special-purpose non-water hand cleanser and preparation method thereof |
| CN107418283A (en) * | 2017-09-11 | 2017-12-01 | 浙江理工大学 | Environmental-friendputty putty powder that a kind of high-strength antibacterial is water-fast and preparation method thereof |
| CN109293796A (en) * | 2018-09-11 | 2019-02-01 | 北京华城新创环境科技有限公司 | A kind of preparation method and applications of n-trimethyl chitosan chloride |
| CN114634665A (en) * | 2022-03-02 | 2022-06-17 | 国家电投集团氢能科技发展有限公司 | Vinyl polymer/modified polyhydroxy polymer composites and uses thereof |
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Application publication date: 20120801 |