CN104558243A - Preparation method and application of N-alkyl-O-acylated chitosan quaternary ammonium salt - Google Patents
Preparation method and application of N-alkyl-O-acylated chitosan quaternary ammonium salt Download PDFInfo
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- CN104558243A CN104558243A CN201410796223.3A CN201410796223A CN104558243A CN 104558243 A CN104558243 A CN 104558243A CN 201410796223 A CN201410796223 A CN 201410796223A CN 104558243 A CN104558243 A CN 104558243A
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- ammonium salt
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Abstract
The invention discloses a preparation method of an N-alkyl-O-acylated chitosan quaternary ammonium salt and application of the N-alkyl-O-acylated chitosan quaternary ammonium salt in dyeing wastewater treatment. The preparation method comprises the following steps: introducing an alkyl acyl group to the O position of N,N-dimethyl chitosan, introducing an alkyl chain to the N position, and quaternizing to obtain the chitosan quaternary ammonium salt. When being added into the dyeing wastewater, the chitosan quaternary ammonium salt can be self-assembled to the high-cation-density nanoparticles on the surface, and dyes in the water body are removed by adsorption. The chitosan quaternary ammonium salt has better adsorption capacity than the commercial polyaluminum chloride which is industrially used on a large scale at present.
Description
Technical field
The present invention relates to a kind of N-alkyl-O-shellglycan quaternary ammonium salt preparation method and application, belong to producing high-molecular condensation material field.
Background technology
Dyeing is the industry that textile industry water consumption is larger, but the dyeing waste water produced is the main aspect causing environmental pollution.Dyeing waste water, due to its high chroma, high COD, the feature such as organic principle is complicated, microbial degradation degree is low, becomes one of difficult industrial wastewater that current environmental protection industry generally acknowledges.The adsorbent of high efficiency, low cost is subject to extensive concern, and the cationic polysaccharide shitosan that wherein occurring in nature is unique is more and more subject to people's attention.
Shitosan wide material sources, containing amino and hydroxyl on its strand, have good biocompatibility, excellent adsorptivity and chelation.It is by electrostatic interaction adsorpting anion dye molecule, also by complexing Adsorption of Heavy Metal Ions.But because hydrogen bond action between chitosan molecule is comparatively strong, strand is rigidity, can only be dissolved in acidic aqueous solution.But the most pH of dyeing waste water is alkalescent, cannot directly use shitosan to process.Therefore chemical modification is carried out to shitosan, prepare chitosan quaternary ammonium salt, improve that it is water-soluble, promote its application in treatment of dyeing wastewater.But the cation degree of the linear chitosan quaternary ammonium salt of routine is on the low side, cause its adsorption capacity not enough, flocculate is suspended state.
Summary of the invention
A kind of N-alkyl-O-shellglycan quaternary ammonium salt preparation method and application are the object of the present invention is to provide; chitosan quaternary ammonium salt of the present invention is put in dyeing waste water; it can carry out the nano particle that self assembly obtains surperficial high-cation density, removes the dyestuff in water body by suction-operated.The adsorption capacity of chitosan quaternary ammonium salt prepared by the present invention is better than the commodity aluminium polychloride of current industrial extensive use.
For achieving the above object, technical scheme of the present invention is:
A preparation method for N-alkyl-O-shellglycan quaternary ammonium salt, comprises the following steps:
1) shitosan is prepared N with formolite reaction in formic acid environment, N-dimethyl shitosan;
2) N, N-dimethyl shitosan and lauryl sodium sulfate are prepared compound by electrostatic interaction in weakly acidic solution; Compound is dissolved in dimethyl sulfoxide (DMSO), slow dropping alkyl acyl chloride, be warmed up to 40 DEG C ~ 80 DEG C reaction 3 ~ 24h, reaction terminates rear tris solution and precipitates, and removes lauryl sodium sulfate, is collected by precipitated product high speed centrifugation, wash with acetone, vacuum drying, to constant weight, obtains N, N-dimethyl-O-shellglycan;
3) by N, N-dimethyl-O-alkyl chitosan is dissolved in 1-METHYLPYRROLIDONE, drip halogenated alkane, be warmed up to 40 DEG C of reaction 3 ~ 24h, reaction terminates rear acetone and precipitates, and collected by centrifugation, with absolute ethanol washing, vacuum drying is to constant weight, and dialysis postlyophilization obtains N-alkyl-O-shellglycan quaternary ammonium salt;
Wherein said N-alkyl-O-shellglycan quaternary ammonium salt has following structure:
Wherein R1 is the alkyl chain of C3 ~ C18, and R2 is the alkyl chain of C1 ~ C12; The molecular weight of described N-alkyl-O-shellglycan quaternary ammonium salt is 2.0 × 10
4~ 1.0 × 10
5, n is 100 ~ 600 natural numbers.
Described step 1) in shitosan be deacetylation be 90%, viscosity average molecular weigh is 5.0 × 10
4shitosan; Shitosan is 1:(3 ~ 10 with the molal weight ratio of formaldehyde).
Described step 2) in the pH of weakly acidic solution be 4.5 ~ 6.8; N, N-dimethyl shitosan is 1:(1 ~ 5 with the molal weight ratio of lauryl sodium sulfate); N, N-dimethyl shitosan is 1:(1 ~ 10 with the molal weight ratio of alkyl acyl chloride); Alkyl acyl chloride adopts the straight or branched alkyl acyl chloride of C3 ~ C18.
Described step 3) in the molal weight of N, N-dimethyl shitosan and halogenated alkane than being 1:(1 ~ 10).Described step 3) in halogenated alkane adopt the straight or branched halogenated alkane of C1 ~ C12.
A kind of application of N-alkyl-O-shellglycan quaternary ammonium salt; the process being mainly used in dyeing waste water of N-alkyl-O-shellglycan quaternary ammonium salt prepared by method according to claim 1; N-alkyl-O-shellglycan the quaternary ammonium salt prepared is put in dyeing waste water; it can carry out the nano particle that self assembly obtains surperficial high-cation density, removes the dyestuff in water body by suction-operated.
Described N-alkyl-O-shellglycan quaternary ammonium salt self assembly can obtain nano particle in aqueous, and the particle diameter of particle is 10 ~ 200nm.
The invention has the beneficial effects as follows: the preparation method of N-alkyl-O-shellglycan quaternary ammonium salt of the present invention and application thereof; at N; the O position acyl groupization of N dimethyl shitosan introduces alkyl chain; again quaternized process is carried out to shitosan N position and improve water-soluble in neutral or weakly alkaline solution of shitosan; give chitosan quaternary ammonium salt self-assembly property in aqueous; the nanoparticle surface cation obtained is intensive, effectively improves it to the treatment effeciency of dyeing waste water.The adsorption capacity of chitosan quaternary ammonium salt prepared by the present invention is better than the commodity aluminium polychloride of current industrial extensive use.
Accompanying drawing explanation
Fig. 1 is the absorption dynamic curve of aluminium polychloride in the own acylation chitosan of N-propyl group-O-prepared of embodiment 2 and embodiment 6; Wherein 1 is the own acylation chitosan of N-propyl group-O-prepared by embodiment 2, and 2 is aluminium polychloride.
Detailed description of the invention
Embodiment 1
A kind of N-alkyl-O-shellglycan quaternary ammonium salt of the present embodiment, its preparation method is as follows: in single port flask, 1) add 300ml water, the formalin of 30ml37% and 30ml formic acid, then adding 10g viscosity average molecular weigh is 5.0 × 10
4, deacetylation is the shitosan of 90%, is warming up to 80 DEG C of reaction 24h, is deposited in acetone soln and obtains N, N-dimethyl shitosan.2) get 5g N, N-dimethyl shitosan and 8g lauryl sodium sulfate act on and obtain water-insoluble compound, filtering drying in weakly acidic solution.Get 3g compound and 3g caproyl chloride, 40 DEG C of reaction 8h, reactant liquor is deposited in Pehanorm solution, the own acylation chitosan of collecting precipitation thing N, N-dimethyl-O-.3) get 1gN, the own acylation chitosan of N-dimethyl-O-, is dissolved in 1-METHYLPYRROLIDONE; add 0.8g N-Propyl Bromide, 40 DEG C of reaction 6h, reactant liquor is deposited in acetone soln; repeatedly, vacuum drying obtains the own acylation chitosan of N-propyl group-O-to absolute ethanol washing.Pass through nuclear magnetic resonance
1it is 3.3% that H measures caproyl substitution value in chitosan quaternary ammonium salt, and season ammonification degree is 1.9%.
Embodiment 2
A kind of N-alkyl-O-shellglycan quaternary ammonium salt of the present embodiment, its preparation method is as follows: in single port flask, 1) add 300ml water, the formalin of 15ml 37% and 20ml formic acid, then adding 10g viscosity average molecular weigh is 5.0 × 10
4, deacetylation is the shitosan of 90%, is warming up to 80 DEG C of reaction 24h, is deposited in acetone soln and obtains N, N-dimethyl shitosan.2) get 5g N, N-dimethyl shitosan and 35g lauryl sodium sulfate act on and obtain water-insoluble compound, filtering drying in weakly acidic solution.Get 3g compound and 10g caproyl chloride, 40 DEG C of reaction 12h, reactant liquor is deposited in Pehanorm solution, the own acylation chitosan of collecting precipitation thing N, N-dimethyl-O-.3) get 1gN, the own acylation chitosan of N-dimethyl-O-, is dissolved in 1-METHYLPYRROLIDONE, adds 4g N-Propyl Bromide, and 40 DEG C of reaction 12h, reactant liquor is deposited in acetone soln, and repeatedly, vacuum drying obtains the own acylation chitosan of N-propyl group-O-to absolute ethanol washing.Pass through nuclear magnetic resonance
1it is 8.3% that H measures caproyl substitution value in chitosan quaternary ammonium salt, and season ammonification degree is 7.6%.
Embodiment 3
A kind of N-alkyl-O-shellglycan quaternary ammonium salt of the present embodiment, its preparation method is as follows: in single port flask, 1) add 300ml water, the formalin of 20ml 37% and 20ml formic acid, then adding 10g viscosity average molecular weigh is 5.0 × 10
4, deacetylation is the shitosan of 90%, is warming up to 80 DEG C of reaction 24h, is deposited in acetone soln and obtains N, N-dimethyl shitosan.2) get 5g N, N-dimethyl shitosan and 10g lauryl sodium sulfate act on and obtain water-insoluble compound, filtering drying in weakly acidic solution.Get 3g compound and 20g caproyl chloride, 40 DEG C of reaction 24h, reactant liquor is deposited in Pehanorm solution, the own acylation chitosan of collecting precipitation thing N, N-dimethyl-O-.3) get 1gN, the own acylation chitosan of N-dimethyl-O-, is dissolved in 1-METHYLPYRROLIDONE, adds 8g N-Propyl Bromide, and 40 DEG C of reaction 24h, reactant liquor is deposited in acetone soln, and repeatedly, vacuum drying obtains the own acylation chitosan of N-propyl group-O-to absolute ethanol washing.Pass through nuclear magnetic resonance
1it is 13.3% that H measures caproyl substitution value in chitosan quaternary ammonium salt, and season ammonification degree is 13.9%.
Embodiment 4
A kind of N-alkyl-O-shellglycan quaternary ammonium salt of the present embodiment, its preparation method is as follows: in single port flask, 1) add 300ml water, the formalin of 40ml 37% and 40ml formic acid, then adding 10g viscosity average molecular weigh is 5.0 × 10
4, deacetylation is the shitosan of 90%, is warming up to 80 DEG C of reaction 24h, is deposited in acetone soln and obtains N, N-dimethyl shitosan.2) get 5g N, N-dimethyl shitosan and 20g lauryl sodium sulfate act on and obtain water-insoluble compound, filtering drying in weakly acidic solution.Get 3g compound and 15g lauroyl chloride, 40 DEG C of reaction 24h, reactant liquor is deposited in Pehanorm solution, collecting precipitation thing N, N-dimethyl-O-bay acylation chitosan.3) get 1gN, the own acylation chitosan of N-dimethyl-O-, is dissolved in 1-METHYLPYRROLIDONE; add 5g iodomethane, 40 DEG C of reaction 3h, reactant liquor is deposited in acetone soln; repeatedly, vacuum drying obtains N-propyl group-O-bay acylation chitosan to absolute ethanol washing.Pass through nuclear magnetic resonance
1it is 9.3% that H measures lauryl substitution value in chitosan quaternary ammonium salt, and season ammonification degree is 5.8%.
Embodiment 5
A kind of N-alkyl-O-shellglycan quaternary ammonium salt of the present embodiment, its preparation method is as follows: in single port flask, 1) add 300ml water, the formalin of 50ml 37% and 50ml formic acid, then adding 10g viscosity average molecular weigh is 5.0 × 10
4, deacetylation is the shitosan of 90%, is warming up to 80 DEG C of reaction 24h, is deposited in acetone soln and obtains N, N-dimethyl shitosan.2) get 5g N, N-dimethyl shitosan and 30g lauryl sodium sulfate act on and obtain water-insoluble compound, filtering drying in weakly acidic solution.Get 3g compound and 5g propionyl chloride, 40 DEG C of reaction 3h, reactant liquor is deposited in Pehanorm solution, collecting precipitation thing N, N-dimethyl-O-bay acylation chitosan.3) get 1gN, the own acylation chitosan of N-dimethyl-O-, is dissolved in 1-METHYLPYRROLIDONE; add 10g bromo-dodecane, 40 DEG C of anti-24h, reactant liquor is deposited in acetone soln; repeatedly, vacuum drying obtains N-propyl group-O-bay acylation chitosan to absolute ethanol washing.Pass through nuclear magnetic resonance
1it is 6.6% that H measures lauryl substitution value in chitosan quaternary ammonium salt, and season ammonification degree is 4.3%.
Embodiment 6
Application Example
The present embodiment selects the preparation-obtained chitosan quaternary ammonium salt of embodiment 2 and commercial goods aluminium polychloride, and concentration is 25mg/L, studies its adsorption dynamics adsorption kinetics to Wastewater Dyes.The chitosan quaternary ammonium salt that embodiment 2 obtains is self-assembled into nano particle in aqueous, and its particle diameter is about 60nm.Dyestuff selected by the present embodiment is active blue 19.Wherein the initial concentration of dyestuff is 100mg/L.Observe change in time, chitosan quaternary ammonium salt and aluminium polychloride to the change of the adsorbance of dyestuff, as shown in Figure 1.As we can see from the figure, the chitosan quaternary ammonium salt that embodiment 2 obtains has stronger adsorption capacity, is better than commercial goods aluminium polychloride.Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; other are any do not run counter to Spirit Essence of the present invention and principle under the change, modification, combination etc. carried out be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (6)
1. a N-alkyl-O-shellglycan quaternary ammonium salt preparation method, is characterized in that comprising the following steps:
1) shitosan is prepared N with formolite reaction in formic acid environment, N-dimethyl shitosan;
2) N, N-dimethyl shitosan and lauryl sodium sulfate are prepared compound by electrostatic interaction in weakly acidic solution; Compound is dissolved in dimethyl sulfoxide (DMSO), slow dropping alkyl acyl chloride, be warmed up to 40 DEG C ~ 80 DEG C reaction 3 ~ 24h, reaction terminates rear tris solution and precipitates, and removes lauryl sodium sulfate, is collected by precipitated product high speed centrifugation, wash with acetone, vacuum drying, to constant weight, obtains N, N-dimethyl-O-shellglycan;
3) by N, N-dimethyl-O-alkyl chitosan is dissolved in 1-METHYLPYRROLIDONE, drip halogenated alkane, be warmed up to 40 DEG C of reaction 3 ~ 24h, reaction terminates rear acetone and precipitates, and collected by centrifugation, with absolute ethanol washing, vacuum drying is to constant weight, and dialysis postlyophilization obtains N-alkyl-O-shellglycan quaternary ammonium salt;
Wherein said N-alkyl-O-shellglycan quaternary ammonium salt has following structure:
Wherein R1 is the alkyl chain of C3 ~ C18, and R2 is the alkyl chain of C1 ~ C12; The molecular weight of described N-alkyl-O-shellglycan quaternary ammonium salt is 2.0 × 10
4~ 1.0 × 10
5, n is 100 ~ 600 natural numbers.
2. a kind of N-alkyl-O-shellglycan quaternary ammonium salt preparation method as claimed in claim 1, is characterized in that: described step 1) in shitosan be deacetylation be 90%, viscosity average molecular weigh is 5.0 × 10
4shitosan; Shitosan is 1:(3 ~ 10 with the molal weight ratio of formaldehyde).
3. a kind of N-alkyl-O-shellglycan quaternary ammonium salt preparation method as claimed in claim 1, is characterized in that: described step 2) in the pH of weakly acidic solution be 4.5 ~ 6.8; N, N-dimethyl shitosan is 1:(1 ~ 5 with the molal weight ratio of lauryl sodium sulfate); N, N-dimethyl shitosan is 1:(1 ~ 10 with the molal weight ratio of alkyl acyl chloride); Alkyl acyl chloride adopts the straight or branched alkyl acyl chloride of C3 ~ C18.
4. a kind of N-alkyl-O-shellglycan quaternary ammonium salt preparation method as claimed in claim 1, is characterized in that: described step 3) in the molal weight of N, N-dimethyl shitosan and halogenated alkane than being 1:(1 ~ 10); Halogenated alkane adopts the straight or branched halogenated alkane of C1 ~ C12.
5. the application of a N-alkyl-O-shellglycan quaternary ammonium salt; it is characterized in that: the process being mainly used in dyeing waste water of N-alkyl-O-shellglycan quaternary ammonium salt prepared by method according to claim 1; N-alkyl-O-shellglycan the quaternary ammonium salt prepared is put in dyeing waste water; it can carry out the nano particle that self assembly obtains surperficial high-cation density, removes the dyestuff in water body by suction-operated.
6. the application of a kind of N-alkyl-O-shellglycan quaternary ammonium salt as claimed in claim 5, is characterized in that: described N-alkyl-O-shellglycan quaternary ammonium salt self assembly can obtain nano particle in aqueous, and the particle diameter of particle is 10 ~ 200nm.
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| CN111659353A (en) * | 2020-05-26 | 2020-09-15 | 广西大学 | Preparation method of in-situ quaternized magnetic chitosan microspheres |
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| CN109487552A (en) * | 2018-10-28 | 2019-03-19 | 青岛大学 | A method of removing cationic superfine pigment from dyeing waste-water |
| CN111659353A (en) * | 2020-05-26 | 2020-09-15 | 广西大学 | Preparation method of in-situ quaternized magnetic chitosan microspheres |
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Denomination of invention: Preparation and application of n-alkyl-o-acylated chitosan quaternary ammonium salt Effective date of registration: 20210704 Granted publication date: 20170405 Pledgee: Haining Chengxin Financing Guarantee Co., Ltd Pledgor: Zhejiang Lvyu Textile Technology Co.,Ltd. Registration number: Y2021330000796 |