CN102863543B - Water-soluble cationic cellulose material and preparation method thereof - Google Patents
Water-soluble cationic cellulose material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble cationic cellulose material and a preparation method of the water-soluble cationic cellulose material. The method comprises the following steps of: taking high-purity alpha-cellulose as raw material, dissolving by a certain solvent, carrying out milder quaternization or tertiary amination on hydroxyl of cellulose by proper primary alkyl halide, acid halide, anhydride or epoxy compound with tertiary amine or quaternary ammonium structure under the condition of the existence of different catalysts to obtain cellulose derivatives with even cationization; and washing, dialyzing and drying, so that the pure cationic cellulose material can be obtained, and the complete water-soluble effect can be achieved.
Description
Technical field
The present invention relates to a kind of cellulose materials, especially a kind of Water-soluble cationic cellulose material and method for making thereof.
Background technology
Mierocrystalline cellulose is the natural macromolecular material that occurring in nature content enriches the most, is that the natural polymer be formed by connecting by β-1-4-glycosidic link by β-D-Glucopyranose gathers polysaccharide.Each glucose unit on cellulose macromolecule there are three hydroxyls, one of them primary hydroxyl, two secondary hydroxyls.By carrying out etherificate or esterification to these three hydroxyls, cellulosic derivative can be obtained.
Cation macromolecular is a kind of very important polyelectrolyte material, widely as sterilant, fine surface promoting agent, polymeric flocculant, moisture adsorbent and wetting Agent for Printing Inks etc., wherein what is more important cation macromolecular plays important role in genetically engineered research, and cation macromolecular can be used for coated DNA macromole.The cation macromolecular mainly polymine (PEI) of the coated DNA molecular of current widespread use, but, the gene transfection rate of the polymine of small-molecular-weight is low, although the polymine transfection efficiency of macromolecule is higher, but cytotoxicity is very large, limit its application in genetically engineered.
Cationic cellulose is the one of derivatived cellulose, according to the change of molecular weight of its raw material, can obtain the cationic cellulose of different molecular weight rank, little of 3KDa, greatly to 1000KDa.Simultaneously due to the compound with regular structure of cellulosic molecule, various excellent property, its cationic derivative is expected to replace the transgenic line that PEI becomes a new generation.
But, current production cationic cellulose method used mainly uses cationic etherifying agent (3-chloro-2-hydroxypropyl-trimethyl ammonium chloride) to carry out etherificate to Mierocrystalline cellulose, due to cellulosic poorly soluble, be difficult to carry out even etherificate to Mierocrystalline cellulose, major part product is all to cellulose surface etherificate, cause etherificate uneven, cationization degree is not high, poorly water-soluble.
Summary of the invention
The present invention is directed to the defect that prior art exists, provide a kind of water-soluble cationic cellulosic preparation method.This method is, with certain solvent by fibrolysis, to carry out etherificate and/or esterification to reach under homogeneous phase condition to Mierocrystalline cellulose.
Another object of the present invention is to the cationic cellulose providing aforesaid method obtained.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
A preparation method for Water-soluble cationic cellulose material, comprises the steps:
A. get the cellulose materials that alpha-cellulose content is not less than 98%, be dissolved in non-protonic solvent;
B. reaction process chooses any one in following four kinds of methods:
I. under agitation, add catalyzer, add uncle's haloalkane of band tertiary amine structure after reaction 10 ~ 30min again, react 1 ~ 15 hour; PH value is adjusted to 6 ~ 8, under agitation, adds alkylating reagent, react 1 ~ 8 hour;
Ii. under agitation, add Tosyl chloride and acid binding agent, react 0.5 ~ 3 hour, then add catalyzer and the mixture of the alcohol of band tertiary amine structure, react 1 ~ 15 hour; PH value is adjusted to 6 ~ 8, under agitation, adds alkylating reagent, react 1 ~ 8 hour;
Iii. under agitation, add the epoxy compounds of catalyzer, band quaternary ammonium structure, react 1 ~ 18 hour;
Iv. under agitation, catalyzer is added, and the acid anhydrides of the carboxylic acid halides of band quaternary ammonium structure and/or band quaternary ammonium structure, react 1 ~ 10 hour;
Alkylating reagent described in I, II be in active uncle haloalkane, methyl-sulfate and methylcarbonate any one or two or more;
C. take out reactant, with precipitation agent, cationic cellulose is precipitated out from reaction soln, filter, wash with clean-out system; Then with semi-permeable membranes dialysis 1 ~ 5 day;
D. evaporate the solvent of dialysis, collect solid-state cationic cellulose; In vacuum drying oven, 40-80 DEG C of dry 3-10 hour, namely obtains cationic cellulose materials.
Preferably, uncle's haloalkane of described band tertiary amine structure is:
The alcohol of described band tertiary amine structure is:
The epoxy compounds of described band quaternary ammonium structure is:
The carboxylic acid halides of described band quaternary ammonium structure and the acid anhydrides of band quaternary ammonium structure are respectively:
Wherein, X is Cl, Br or I, and R is the alkyl chain of 0 ~ 4 carbon atom, R
1, R
2, R
3be the alkyl of 1 ~ 3 carbon atom, R
4for the alkyl of H or 1 ~ 3 carbon atom;
Preferably, the amount of substance of glucose unit in the Mierocrystalline cellulose of described cellulose materials is defined as 1, then
B(i.) in, the amount of substance of uncle's haloalkane of band tertiary amine structure is 0.4 ~ 2.5, and the amount of substance of described catalyzer is 0.6 ~ 3;
B(II .) amount of substance of toluene sulfonyl chloride is 0.6 ~ 3, the amount of substance of catalyzer is 0.8 ~ 4, the amount of substance of the alcohol of band tertiary amine structure is 0.4 ~ 2.5;
B(III .) amount of substance of the epoxy compounds of band quaternary ammonium structure is 0.4 ~ 2.5, the amount of substance of catalyzer is 0.8 ~ 4;
B(IV .) amount of substance of the carboxylic acid halides of band quaternary ammonium structure is 0 ~ 2, the amount of substance of the acid anhydrides of band quaternary ammonium structure is 0 ~ 2, and the amount of substance of catalyzer is 0.8 ~ 4.
Preferably, described b(i.), b(ii.), b(III .), b(IV .) whole reaction carries out under nitrogen protection.
Preferably, described non-protonic solvent is N,N-dimethylacetamide/lithium chloride (DMAc/LiCl) solution, ionic liquid or cupriethylene diamine solution.
Preferably, described ionic liquid is the ammonium salt that imidazole salts, pyridinium salt and steric bulk are large.
Preferably, b(i.), b(ii.) described in catalyzer be the amalgam solution of the alkali metal simple substance (lithium, sodium, potassium, rubidium, caesium) of the first main group, the alkaline-earth metal simple substance (calcium, strontium, barium) of the second main group, the hydride of alkali-metal hydride, alkaline-earth metal, alkali-metal alcoholate, the alcoholate of alkaline-earth metal, alkali-metal amide, the amide of alkaline-earth metal, alkali-metal amalgam solution, alkaline-earth metal;
B(iii.) catalyzer described in is one or more in the vitriol oil, Glacial acetic acid, dry hydrogen chloride gas, boron trifluoride, concentrated nitric acid, concentrated hydrochloric acid, aluminum chloride, iron trichloride, trifluoroacetic acid and trichoroacetic acid(TCA);
B(iv.) catalyzer described in be triethylamine, Trimethylamine 99, pyridine, pyrroles and piperidines one or more;
B(ii.) described acid binding agent be triethylamine, Trimethylamine 99, pyridine, pyrroles and piperidines one or more.
Preferably, described active uncle's haloalkane is one or more in iodate short chain alkanes, chlorallylene, allyl bromide 98, benzyl chloride and bromotoluene;
Described precipitation agent is one or more in acetonitrile, ethanol, methyl alcohol, acetone, butanone, acetic acid and formic acid;
Described washing composition is alcohol solution, the ketone aqueous solution of volume fraction 95%, the acetonitrile solution of volume fraction 95% of volume fraction 95%.
Hydroxyl substitution value on the glucose unit of cationic cellulose materials prepared by aforesaid method is between 1.2 ~ 3.
Beneficial effect of the present invention: compared with prior art, after the present invention makes cellulose dissolution in a solvent, cellulosic crystallization is completely destroyed, under relatively mild reaction conditions, efficiently cationization is carried out to the hydroxyl of Mierocrystalline cellulose glucose unit, replaced evenly.Obtained cationic cellulose materials can be completely water-soluble, and substitution value is controlled.
Accompanying drawing explanation
The cationic cellulose of Fig. 1 prepared by embodiment 2 is dissolved in D
2o is at 100MHz
13the nmr spectrum of C NMR.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
Get 1g Microcrystalline Cellulose in the there-necked flask of 500mL, add N,N-dimethylacetamide/lithium chloride (mass volume ratio of DMAc/LiCl is 0.1g/ml) solution 200mL, under nitrogen protection, be warming up to 120 DEG C, motor machine stirs lower 10 hours, dissolves; Be down to room temperature, add 0.9gNaH, after 10 minutes, be warming up to 55 DEG C, measure 8mLN, N-dimethyl-2-chloroethyl amine, in constant pressure funnel, drips in 15 minutes, reacts 5 hours; Drip Glacial acetic acid, make pH value be adjusted to 7, drip 1mL methyl-sulfate, react 5 hours; Reaction solution is transferred in the beaker of 1000mL, add the dehydrated alcohol of reaction solution 3 times of volumes, leave standstill 3 hours, supernatant liquid is transferred in returnable bottle, suction filtration, with the ethanolic soln washing filter residue three times of 95%, then by the dissolution of solid that obtains in deionized water, be transferred in dialysis tubing, dialyse 3 days with deionized water; Revolve and evaporate water, collect solid; 60 DEG C of vacuum-drying 4 hours.The cationic cellulose that the present embodiment obtains can be completely water-soluble.
Embodiment 2
Get 7g degreasing cotton fiber element, 80g chlorination-1-butyl-3 methylimidazole salt is in 250mL there-necked flask, and at 100 DEG C, motor machine stirs 24 hours; Be cooled to room temperature, under nitrogen protection, 8gNaH, after 10 minutes, is warming up to 55 DEG C, measures 45mL N, and N-dimethyl-2-chloroethyl amine, in constant pressure funnel, drips in 30 minutes, reacts 5 hours; Drip Glacial acetic acid, adjust ph, to 6, is warming up to 75 DEG C, drips 15mL methyl-sulfate, reacts 5 hours; Reaction solution is transferred in the beaker of 1000mL, adds the acetonitrile of 3 times of volumes, leaves standstill 3 hours, supernatant liquid is transferred in returnable bottle, suction filtration, the acetonitrile solution washing filter residue with 95% three times, again by the dissolution of solid that obtains in deionized water, be transferred in dialysis tubing, dialyse 3 days with deionized water; Revolve and evaporate water, collect solid; 80 DEG C of vacuum-drying 3 hours.The cationic cellulose that the present embodiment obtains can be completely water-soluble, and its general structure is as follows:
wherein, R be H or
wherein, δ=42.80 ~ 42.91ppm is the chemical shift of No. 9 carbon atoms in R, δ=48.00 ~ 52.00ppm is the chemical shift of 7, No. 8 carbon atoms in R, δ=53.10 ~ 61.00ppm is the chemical shift of 3, No. 4 carbon atoms in Mierocrystalline cellulose, δ=63.82ppm is the chemical shift of No. 6 carbon atoms in Mierocrystalline cellulose, δ=70.00 ~ 80.00ppm is the chemical shift of 2,3,4, No. 5 carbon atoms in Mierocrystalline cellulose, δ=80.87ppm is the chemical shift of No. 4 carbon atoms in Mierocrystalline cellulose, and δ=101.41ppm is the chemical shift of No. 1 carbon atom in Mierocrystalline cellulose.
Embodiment 3
Get 5g Microcrystalline Cellulose in the there-necked flask of 500mL, add N,N-dimethylacetamide/lithium chloride (mass volume ratio of DMAc/LiCl is 0.1g/ml) solution 200mL, under nitrogen protection, be warming up to 120 DEG C, motor machine stirs lower 10 hours, dissolves; Be down to room temperature, add 20mL triethylamine, in two hours, add 56.72g Tosyl chloride (TsCl), after 10 minutes, be warming up to 55 DEG C; Measure 10mLN, N-dimethyl-2 hydroxy ethylamine, in 50mL tool plug Erlenmeyer flask, takes 3gNaH in Erlenmeyer flask, shakes up; Transfer to rapidly in the constant pressure funnel of reactor, drip in 15 minutes, react 5 hours; Drip Glacial acetic acid, make pH value be adjusted to 7, drip 5mL methyl-sulfate, react 5 hours; Reaction solution is transferred in the beaker of 1000mL, adds the methyl alcohol of 3 times of volumes, leaves standstill 3 hours, supernatant liquid is transferred in returnable bottle, suction filtration, the methanol solution washing filter residue with 95% three times, again by the dissolution of solid that obtains in deionized water, be transferred in dialysis tubing, dialyse 4 days with deionized water; Revolve and evaporate water, collect solid; 70 DEG C of vacuum-drying 5 hours.The cationic cellulose that the present embodiment obtains can be completely water-soluble.
Embodiment 4
Get 10g degreasing cotton fiber element, 100g chlorination-1-butyl-3 methylimidazole salt is in 500mL there-necked flask, and at 100 DEG C, motor machine stirs 24 hours; Be cooled to room temperature, under nitrogen protection, under continuous stirring, add the 3mL vitriol oil, after 5 minutes, add 35g 2,3-epoxypropyltrimethylchloride chloride, react 8 hours, be warming up to 75 DEG C, react 5 hours; Reaction solution is transferred in the beaker of 1000mL, adds the acetonitrile of 3 times of volumes, leaves standstill 3 hours, supernatant liquid is transferred in returnable bottle, suction filtration, the acetonitrile solution washing filter residue with 95% three times, again by the dissolution of solid that obtains in deionized water, be transferred in dialysis tubing, dialyse 3 days with deionized water; Revolve and evaporate water, collect solid; 80 DEG C of vacuum-drying 3 hours.The cationic cellulose that the present embodiment obtains can be completely water-soluble.
Embodiment 5
Get 10g Microcrystalline Cellulose in the there-necked flask of 1000mL, add N,N-dimethylacetamide/lithium chloride (mass volume ratio of DMAc/LiCl is 0.1g/ml) solution 400mL, under nitrogen protection, be warming up to 120 DEG C, motor machine stirs lower 10 hours, dissolves; Be down to room temperature, add 20mL pyridine, add 52g in two hours to chloroformyl phenyl trimethicone ammonium chloride, after 1 hour, be warming up to 55 DEG C; Reaction solution is transferred in the beaker of 2000mL, adds the ethanol of 3 times of volumes, leaves standstill 3 hours, supernatant liquid is transferred in returnable bottle, suction filtration, the ethanolic soln washing filter residue with 95% three times, again by the dissolution of solid that obtains in deionized water, be transferred in dialysis tubing, dialyse 5 days with deionized water; Revolve and evaporate water, collect solid; 60 DEG C of vacuum-drying 6 hours.The cationic cellulose that the present embodiment obtains can be completely water-soluble.
Embodiment 6
Get 20g degreasing cotton fiber element in the there-necked flask of 1000mL, add 300g chlorination-1-butyl-3 methylimidazole salt, under nitrogen protection, be warming up to 100 DEG C, motor machine stirs lower 24 hours, dissolves; Be down to room temperature, add 15g sodium ethylate, after 10 minutes, be warming up to 55 DEG C, get 90g to chloromethyl xylidine, be dissolved in 300mL ether, be transferred in constant pressure funnel, drip in 1 hour, react 5 hours; Drip Glacial acetic acid, make pH value be adjusted to 7, drip 10mL methyl-sulfate, react 5 hours; Reaction solution is transferred in the beaker of 1000mL, adds the acetonitrile of 3 times of volumes, leaves standstill 3 hours, supernatant liquid is transferred in returnable bottle, suction filtration, the acetonitrile solution washing filter residue with 95% three times, again by the dissolution of solid that obtains in deionized water, be transferred in dialysis tubing, dialyse 2 days with deionized water; Revolve and evaporate water, collect solid; 50 DEG C of vacuum-drying 8 hours.The cationic cellulose that the present embodiment obtains can be completely water-soluble.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. a preparation method for Water-soluble cationic cellulose material, is characterized in that, comprises the steps:
A. get the cellulose materials that alpha-cellulose content is not less than 98%, be dissolved in non-protonic solvent;
B. reaction process chooses any one in following four kinds of methods:
I. under agitation, add catalyzer, add uncle's haloalkane of band tertiary amine structure after reaction 10 ~ 30min again, react 1 ~ 15 hour; PH value is adjusted to 6 ~ 8, under agitation, adds alkylating reagent, react 1 ~ 8 hour;
Ii. under agitation, add Tosyl chloride and acid binding agent, react 0.5 ~ 3 hour, then add catalyzer and the mixture of the alcohol of band tertiary amine structure, react 1 ~ 15 hour; PH value is adjusted to 6 ~ 8, under agitation, adds alkylating reagent, react 1 ~ 8 hour;
Iii. under agitation, catalyzer is added, and the acid anhydrides of the carboxylic acid halides of band quaternary ammonium structure and/or band quaternary ammonium structure, react 1 ~ 10 hour;
Alkylating reagent described in I, II be in active uncle haloalkane, methyl-sulfate and methylcarbonate any one or two or more;
C. take out reactant, with precipitation agent, cationic cellulose is precipitated out from reaction soln, filter, wash with clean-out system; Then with semi-permeable membranes dialysis 1 ~ 5 day;
D. evaporate the solvent of dialysis, collect solid-state cationic cellulose; In vacuum drying oven, 40-80 DEG C of dry 3-10 hour, namely obtains cationic cellulose materials;
Uncle's haloalkane of described band tertiary amine structure is:
The alcohol of described band tertiary amine structure is:
The carboxylic acid halides of described band quaternary ammonium structure and the acid anhydrides of band quaternary ammonium structure are respectively:
Wherein, X is Cl, Br or I, and R is the alkyl chain of 0 ~ 4 carbon atom, R
1, R
2it is the alkyl of 1 ~ 3 carbon atom;
B (i.), catalyzer described in b (ii.) are the amalgam solution of the hydride of lithium, sodium, potassium, rubidium, caesium, calcium, strontium, barium, alkali-metal hydride or alkaline-earth metal, alkali-metal alcoholate, the alcoholate of alkaline-earth metal, alkali-metal amide, the amide of alkaline-earth metal, alkali-metal amalgam solution, alkaline-earth metal;
Catalyzer described in b (iii.) be triethylamine, Trimethylamine 99, pyridine, pyrroles and piperidines one or more;
B (ii.) described acid binding agent be triethylamine, Trimethylamine 99, pyridine, pyrroles and piperidines one or more.
2. preparation method according to claim 1, is characterized in that, the amount of substance of glucose unit in the Mierocrystalline cellulose of described cellulose materials is defined as 1, then
In b (i.), the amount of substance of uncle's haloalkane of band tertiary amine structure is 0.4 ~ 2.5, and the amount of substance of described catalyzer is 0.6 ~ 3;
The amount of substance of b (II .) toluene sulfonyl chloride is 0.6 ~ 3, and the amount of substance of catalyzer is 0.8 ~ 4, the amount of substance of the alcohol of band tertiary amine structure is 0.4 ~ 2.5;
B (III .) is with the amount of substance of the carboxylic acid halides of quaternary ammonium structure to be 0 ~ 2, and the amount of substance of the acid anhydrides of band quaternary ammonium structure is 0 ~ 2, and the amount of substance of catalyzer is 0.8 ~ 4.
3. preparation method according to claim 1 and 2, is characterized in that, described b (i.), b (ii.), b (III .) whole reaction are carried out under nitrogen protection.
4. preparation method according to claim 1 and 2, is characterized in that, described non-protonic solvent is N,N-dimethylacetamide/lithium chloride solution, ionic liquid or cupriethylene diamine solution.
5. preparation method according to claim 4, is characterized in that, described ionic liquid is the ammonium salt that imidazole salts, pyridinium salt and steric bulk are large.
6. preparation method according to claim 1 and 2, is characterized in that, described active uncle's haloalkane is one or more in chlorallylene, allyl bromide 98, benzyl chloride and bromotoluene;
Described precipitation agent is one or more in acetonitrile, ethanol, methyl alcohol, acetone, butanone, acetic acid and formic acid;
Described washing composition is alcohol solution, the ketone aqueous solution of volume fraction 95%, the acetonitrile solution of volume fraction 95% of volume fraction 95%.
7. the cationic cellulose materials that described in claim 1 ~ 6 any one prepared by method.
8. cationic cellulose materials according to claim 7, is characterized in that, the hydroxyl substitution value on the glucose unit of described cationic cellulose is between 1.2 ~ 3.
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| CN103394292A (en) * | 2013-06-23 | 2013-11-20 | 中国石油大学(华东) | Method for preparing selective air semi-permeable membrane |
| CN105085688B (en) * | 2015-03-19 | 2018-03-16 | 北京林业大学 | The preparation method of water-soluble cellulose and the water-soluble cellulose prepared by this method |
| CN110240977B (en) * | 2019-06-28 | 2020-11-10 | 天津市博仁易洁物业服务有限公司 | Multifunctional cleaning agent and preparation method thereof |
| CN114031769B (en) * | 2021-11-29 | 2024-03-26 | 广州市慧科高新材料科技有限公司 | Quaternary ammonium salt leveling agent, preparation method thereof, electroplating solution containing quaternary ammonium salt leveling agent and electroplating method |
| CN114737200B (en) * | 2022-04-20 | 2024-05-28 | 国家纳米科学中心 | Dechlorination and corrosion inhibition method for iron articles |
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| DE19742165A1 (en) * | 1997-09-24 | 1999-04-01 | Cellcat Gmbh | Process for the production of cellulose particles |
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