CN1218967C - Quaternised chitosan resin and chitosan-carried boron hydrogen anion reductant and its making method - Google Patents
Quaternised chitosan resin and chitosan-carried boron hydrogen anion reductant and its making method Download PDFInfo
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- CN1218967C CN1218967C CN 200310111451 CN200310111451A CN1218967C CN 1218967 C CN1218967 C CN 1218967C CN 200310111451 CN200310111451 CN 200310111451 CN 200310111451 A CN200310111451 A CN 200310111451A CN 1218967 C CN1218967 C CN 1218967C
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- chitosan
- resin
- epoxypropyl
- boron hydride
- hydride ion
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Abstract
The present invention discloses a boron hydride ion reducing agent which is supported by quaternary ammonium chitosan resin and chitosan. The structural formula is the upper formula, wherein R is methyl or ethyl, X is chlorine, bromine or BH4; the weight average molecular weight is from 30*10<4> to 50*10 <4>. Firstly, chitosan microspheres are prepared by a reverse-phase suspension method. Then, amino is protected by aldehyde. Finally, the crosslinked chitosan resin is prepared by a crosslinking agent, and the crosslinked chitosan resin and epoxypropyl trialkyl ammonium salt react to be synthesized into quaternary ammonium resin. Compared with the present chitosan resin, the swelling property of the resin is little affected by acidity basicity of the treated solution, and the resin has good adsorbing effect on cations of heavy metals and anions of acid radicals. The resin can be used in a packing way, and has the antibacterial function; the resin can be used as separating material, and has application prospect in the preparation fields of foods, medicine processing, water treatment and high molecule reagents. The quaternary ammonium chitosan resin is used as an intermediate body, the quaternary ammonium chitosan resin and potassium borohydride solution can further react to prepare a boron hydride ion reducing agent which is supported by the chitosan. The reducing agent can also be applied to the reduction fields of carbonyl compounds and oligosaccharide.
Description
Technical field
The present invention relates to a kind of n-trimethyl chitosan chloride resin and chitosan and prop up the boron hydride ion reductive agent and the method for making thereof of carrying.
Background technology
Now, fossil resources such as oil, coal reduce day by day, and the nondegradation synthesized polymer material is serious day by day to the pollution that human ecological environment causes.So the huge natural renewable resource of potentiality to be exploited just become the effective way of releasing the pressure.Chitin and its acetyl product chitosan that takes off are that occurring in nature output is only second to cellulosic natural polysaccharide.Chitosan itself has been used to do parting material, but its loss easily in the aqueous solution, and be easy to generate high post pressure, reduce separation efficiency; The swelling property of chitosan resin is influenced greatly by the Property of Acid and Alkali of Solution of handling, and be unfavorable for adorning post and use, and under alkaline condition, very weak to anionic adsorptive power.
Summary of the invention
The present invention is exactly in order to address the above problem, provide a kind of n-trimethyl chitosan chloride resin and chitosan to prop up the boron hydride ion reductive agent and the method for making thereof of carrying, the swelling property of this resin is subjected to the Property of Acid and Alkali of Solution of handling to influence little, heavy metal cation and acid radical anion all there are good adsorption effect, can adorn post and use.
Technical scheme provided by the invention is: a kind of n-trimethyl chitosan chloride resin, its structural formula is
R is methyl or ethyl in the formula, and X is a chlorine or bromine, and weight-average molecular weight is 30 * 10
4To 50 * 10
4A kind of chitosan props up its structural formula of boron hydride ion reductive agent that carries
R is methyl or ethyl in the formula, and X is a chlorine or bromine, and weight-average molecular weight is 30 * 10
4To 50 * 10
4
The present invention also provides the preparation method of above-mentioned resin, and this resin adopts inverse suspension method preparation chitosan microball earlier, protects amido with aldehyde then, re-uses linking agent and makes crosslinked chitosan resin; The gained crosslinked chitosan resin is suspended in water, obtain required n-trimethyl chitosan chloride resin in 50～90 ℃ of reactions with the epoxypropyl trimethyl-ammonium halide.With gained n-trimethyl chitosan chloride resin is that intermediate further makes chitosan with POTASSIUM BOROHYDRIDE (or sodium borohydride) solution reaction and props up the boron hydride ion reductive agent that carries.
Above-mentioned epoxypropyl trialkyl ammonium salts is the epoxypropyl trimethylammonium chloride ammonium, epoxypropyl triethyl ammonium chloride, the mixture of one or both in the epoxypropyl trimethylammonium bromide etc.
Gained resin of the present invention has strong basicity and weakly alkaline resin simultaneously, its swelling property is subjected to the Property of Acid and Alkali of Solution of handling to influence little, heavy metal cation and acid radical anion all there is good adsorption effect, also can be used for removing the protein impurities in the water-soluble polysaccharide, as remove protein contained in the chitoanase catalytic hydrolysis.The present invention can be used as the preparation field that parting material is used for food, medical processing, water treatment and polymer reactant, can adorn post and use.This resin is harmless, has anti-microbial effect again.With this n-trimethyl chitosan chloride resin is that the chitosan that intermediate makes props up the boron hydride ion reductive agent that carries, except that purposes with above n-trimethyl chitosan chloride resin, also can be applicable to the reduction field of carbonyl compound and oligosaccharides, as fragrant carbonyl compound can be reduced to corresponding alcohol, with end group reduction of chitosan etc.
Description of drawings
The n-trimethyl chitosan chloride resin (a) that Fig. 1 makes for the present invention and the infrared spectra of crosslinked chitosan resin (b);
Fig. 2 is the breakthrough experiment of Cr (VI) in crosslinked chitosan resin (▲) and quaternised chitosan resin (●).
Embodiment
Embodiment 1:30 gram chitosan is dissolved in and is made into 5% chitosan solution in 2% the acetum, adds 2 gram polyoxyethylene glycol PEG2000 then.After the PEG dissolving, 500mL paraffin oil and 3mL Span80 add as the oil phase dispersion medium.Behind the vigorous stirring 1h, add 150ml 40% formaldehyde solution under the room temperature.Continue to stir in the mixed solution of 10% sodium hydroxide/ethyl alcohol (volume ratio is 1: 1) of pouring 3000ml after 2 hours into, stir 2h gently after, filter, use sherwood oil successively, washing with alcohol makes ball.These chitosan balls are suspended in the sodium hydroxide solution of 0.067mol/L of 1500ml; add linking agent epoxy chloropropane 6.3 grams then; temperature control stirred 3 hours for 45 ℃; filter; washing is placed on to stir among the 0.5mol/L HCl spends the night, and removes protecting group, filters; washing obtains crosslinked chitosan resin.This crosslinked chitosan resin (0.1mol-NH
2) be suspended in the 400mL distilled water, after epoxypropyl trimethylammonium chloride ammonium (1.0mol) added, 60 ℃ of reactions of temperature control 24h filtered, and washing obtains the n-trimethyl chitosan chloride resin.The exchange capacity of this resin is 2.13mol Cl
-/ gram dried resin, quaternized substitution value is approximately 0.6.This n-trimethyl chitosan chloride resin infrared spectra has shown a new absorption peak 1483cm
-1Appearance, that is the methyl peak of ammonium salt, sees accompanying drawing 1.
Embodiment 2: with above-mentioned crosslinked chitosan resin (0.1mol-NH
2) be suspended in the 400mL distilled water, after epoxypropyl triethyl ammonium chloride (1.0mol) added, 80 ℃ of reactions of temperature control 16 hours were filtered, and washing obtains the n-trimethyl chitosan chloride resin.Its quaternized substitution value is approximately 0.7.
Embodiment 3: with above-mentioned crosslinked chitosan resin (0.05mol-NH
2) be suspended in the 100mL distilled water, after epoxypropyl trimethylammonium bromide (1.0mol) added, 70 ℃ of reactions of temperature control 24 hours were filtered, and washing obtains the n-trimethyl chitosan chloride resin.Its quaternized substitution value is approximately 0.7.
Embodiment 4: wet quaternized chitosan resin 100 grams immerse in the 1.0mol/L sodium hydroxide solution of 200ml among the embodiment 1, stir 1 hour, filter washing then.Resin is adorned post, and the solution of potassium borohydride of the 0.5mol/L of 200ml by resin, changes resin into BH with the speed of 1ml/min then
4 -Form.The resin that the generates residual POTASSIUM BOROHYDRIDE of distilled water washes clean.Further wash portioned product vacuum-drying then successively with ethanol, ether.The resin Infrared spectroscopy of preparation shows that a new absorption peak is at 2292cm
-1Near the appearance is the characteristic peak of B-H.By measuring the releasing hydrogen gas amount, convert its BH to
4 -Amount, recording resin capacity is 1.92mmol BH
4 -/ g dried resin.
In the foregoing description 1 preparation the n-trimethyl chitosan chloride resin in pH is 2.5 to 11.5 scopes, swelling capacity is 26 to 19, and accordingly not n-trimethyl chitosan chloride resin swelling degree be 40 to 5.This quaternized resin is to the K of 10.0mg Cr/L
2Cr
2O
7The breakthrough point of solution is every gram dried resin 3200ml, and the chromium of the at first effusive 3000mL aqueous solution (VI) concentration meets drinking water standard less than 10ppb, sees accompanying drawing 2.
The boron hydride ion reductive agent of preparation can arrive corresponding alcohol by reducing carbonyl compound in the foregoing description 3, and has some selectivity.
Claims (5)
1. n-trimethyl chitosan chloride resin, its structural formula is
R is methyl or ethyl in the formula, and X is a chlorine or bromine, and weight-average molecular weight is 30 * 10
4To 50 * 10
4
2. chitosan props up the boron hydride ion reductive agent that carries, and its structural formula is
R is methyl or ethyl in the formula, and X is a chlorine or bromine, and weight-average molecular weight is 30 * 10
4To 50 * 10
4
3. the method for making of the described n-trimethyl chitosan chloride resin of claim 1 is characterized in that: prepare chitosan microball with inverse suspension method, protect amido with formaldehyde then, re-use the epoxy chloropropane linking agent and prepare crosslinked chitosan resin; The gained crosslinked chitosan resin is suspended in water, obtain required n-trimethyl chitosan chloride resin in 50～90 ℃ of reactions with epoxypropyl trialkyl ammonium halide.
4. method for making according to claim 3 is characterized in that: epoxypropyl trialkyl ammonium halide is that epoxypropyl trimethylammonium chloride ammonium, epoxypropyl triethyl ammonium chloride are or/and the epoxypropyl trimethylammonium bromide.
5. the described chitosan of claim 2 props up the method for making of the boron hydride ion reductive agent that carries, it is characterized in that: with the described n-trimethyl chitosan chloride resin of claim 1 is intermediate, makes chitosan with POTASSIUM BOROHYDRIDE or sodium borohydride solution reaction and props up the boron hydride ion reductive agent that carries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310111451 CN1218967C (en) | 2003-11-25 | 2003-11-25 | Quaternised chitosan resin and chitosan-carried boron hydrogen anion reductant and its making method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310111451 CN1218967C (en) | 2003-11-25 | 2003-11-25 | Quaternised chitosan resin and chitosan-carried boron hydrogen anion reductant and its making method |
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| Publication Number | Publication Date |
|---|---|
| CN1544480A CN1544480A (en) | 2004-11-10 |
| CN1218967C true CN1218967C (en) | 2005-09-14 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100487000C (en) * | 2005-09-02 | 2009-05-13 | 中国科学院海洋研究所 | Carboxymethyl chitosan quaternary ammonium salt and its preparation method |
| FI20055503A0 (en) * | 2005-09-20 | 2005-09-20 | Fennopharma Oy | New quaternized polymers |
| CN102382206B (en) * | 2010-08-30 | 2014-10-01 | 华东理工大学 | Chitooligosaccharide quaternary ammonium salt and preparation method thereof |
| CN105622780B (en) * | 2016-03-15 | 2017-11-28 | 武汉大学 | A kind of homogeneous preparation method of quaternized chitin |
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2003
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