CN101245113B - Hemicellulose group ion exchange resin and preparation method thereof - Google Patents
Hemicellulose group ion exchange resin and preparation method thereof Download PDFInfo
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- CN101245113B CN101245113B CN2007101503722A CN200710150372A CN101245113B CN 101245113 B CN101245113 B CN 101245113B CN 2007101503722 A CN2007101503722 A CN 2007101503722A CN 200710150372 A CN200710150372 A CN 200710150372A CN 101245113 B CN101245113 B CN 101245113B
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Abstract
The invention relates to a preparation method for hemicellulose-based ion exchange resin, pertaining to the field of integrated resources. A hemicellulose-based resin matrix is prepared by crosslinking reaction between hemicellulose and polyhydroxylated compound; and the hemicellulose-based ion exchange resin is prepared by chemical reaction of carrying out functionalization on the hemicellulose-based resin matrix.
Description
Technical field
The invention belongs to the comprehensive utilization of resources field, particularly relate to a kind of method for preparing hemicellulose group ion exchange resin from hemicellulose.
Background technology
Along with Nonrenewable resources total amounts such as oil, coal reduce day by day, transforming acquisition novel material, the high heating value energy, industrial chemicals and medicine by the agriculture and forestry organic waste material renewable resources is just becoming a kind of new development trend, and the hemicellulose modification becomes an important branch in the agriculture and forestry organic waste material renewable resources utilization research.The content of hemicellulose in plant resources occupies the 2nd, is only second to Mierocrystalline cellulose, accounts for the 1/4-1/3 of plant resources greatly.Hemicellulose is present in parts such as the stem, seed, shell of plant in a large number, hemicellulose level also can be different in different floristics, for example: its amount accounts for 10%～15% of cell walls dry weight in softwood tree, accounted for 18%～23% in the deciduous tree, accounted for 20%～25% in the grass.The novel material that this high relatively hemicellulose level makes them can be used as industrial copolymer replaces environmentally harmful petroleum chemicals.
Hemicellulose is one of main chemical composition of plant fiber material.They are different from Mierocrystalline cellulose, only have the D-glucosyl group to form the unimodality of the homogeneous glycan of linear chain structure mutually with the 1-4 connecting mode.Hemicellulose can become the homogeneous glycan also can become non-homogeneous glycan, it can also be connected into the various glycan of the mutually different multiple structure of structure with different connecting modes by different monosaccharide groups, and is defined as removing the material that the alkali soluble behind the pectin substance is separated.According to different ratios and different substituents, hemicellulose is made up of the different sugar unit, and they are low-molecular-weight branched chain polymers, and its polymerization degree is generally 80～200.These sugar are D one wood sugar, L-arabinose, glucose, semi-lactosi, D one seminose, glucuronic acid, 4-methyl one glucuronic acid, galacturonic acid and a spot of rhamnosyl, Fucose and the monomethylated neutral sugar of different O.These structural units are not the glycan that is made of a kind of homogeneous a kind of structural unit generally when constituting hemicellulose, but the heterogeneity glycan that constitutes by 2-4 kind structural unit.Though hemicellulose is distributed widely in the plant because the limitation of complexity of structure they application in industry.For example, hemicellulose has the unique chemical structure, such as several dissimilar monose (mixed polysaccharide) of branch, amorphous composition and dissimilar functional group'ss (for example OH base, ethanoyl, carboxyl, methoxyl group etc.).Compare with Mierocrystalline cellulose and starch, these dissimilar glycan have different chemical conducts, and these also will limit their utilization.Yet these shortcomings can overcome by modification, as: oxidation, hydrolysis, reduction, etherificate, esterification and crosslinking reaction are finished.Therefore, the characteristic of hemicellulose modification and new polymers becomes the important component part of hemicellulose research.
The half-and-half cellulosic research of scientist is morning relatively, but mainly based on selective extraction technology and structure determination research.In nearest 50 years, half-and-half cellulosic research is less.Up to the nineties in 20th century, along with the rapid minimizing of world's area of woods and the raising of timber price, started for the first time the climax that research and development utilizes agriculture and forestry organic waste material, particularly to the research of hemicellulose aspect.For example, need carry out quaternised modified to hemicellulose in order to improve the water-soluble of hemicellulose and to give characteristics such as hemicellulose positive polarity.Most typical quaternized cationoid reagent is a 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.Cationoid reagent forms earlier epoxide under alkaline condition, again with the hemicellulose molecule in hydroxyl on the sugar unit react, form the positively charged ion hemicellulose.Quaternised hemicellulose can be used as the making beating auxiliary agent, not only helps to save beating energy consumption, can also increase the tear strength of the organic dissolving pulp of bleaching dragon spruce, can also be applied in the papermaking as flocculation agent, retention aid etc.
Ion exchange resin is the macromolecular material that a class has ion exchanging function.It can exchange ion of itself and the jack per line ion in the solution in solution.By the difference of cation exchange groups character, ion exchange resin can be divided into Zeo-karb and anionite-exchange resin two classes.Zeo-karb mostly contains sulfonic group (SO
3H), carboxyl (COOH) or phenylol (C
6H
4Acidic-group such as OH), hydrogen ion wherein can exchange with solution metal ion or other positively charged ions.For example the superpolymer of vinylbenzene and divinylbenzene is handled through sulfonation and is obtained storng-acid cation exchange resin, but its structural formula simple table is shown R-SO
3H, on behalf of resin matrix anionite-exchange resin, R contain quaternary amine base [N (CH in the formula
3)
3OH], amido (NH
2) or imido grpup (basic group such as NR ' H).They can generate the OH-ion in water, can play exchange interaction with various negatively charged ion, and having many uses of ion exchange resin is mainly used in and separates and purification.For example be used for water softening and produce deionized water, reclaim trade effluent metal, separate rare metal and precious metal, separate and purification microbiotic etc.
How to pass through focus and the difficult point problem that the simple approach synthetic ion-exchange resin is current functional high molecule material research from renewable resources.
The present invention utilizes the greater activity group in the hemicellulose structural unit that it is carried out chemically crosslinked, preparation ion exchange resin.
Summary of the invention
The invention provides a kind of hemicellulose group ion exchange resin and method thereof.
The technological line that adopts is that hemicellulose and polyol are prepared the hemicellulose group resin matrix by crosslinking reaction, and by chemical reaction the hemicellulose group resin matrix is carried out functionalization and prepare hemicellulose group ion exchange resin.
The polymerization degree of hemicellulose is between 10-100.Polyol is any one in polyvinyl alcohol, chitosan, dextran, the gelatin.The molecular weight of polyvinyl alcohol, chitosan, dextran is 6000-20000.
The preparation of hemicellulose group ion exchange resin comprises the steps:
The preparation of 1 hemicellulose group resin matrix:
In 2～30% the hemicellulose aqueous solution, add the aqueous solution of a certain amount of polyol, stir.Regulate mixing solutions pH=2～4 with hydrochloric acid, add a certain amount of cross-linking agent aqueous solution.An amount of span-80 is dissolved in the organic phase, under agitation adds in the above-mentioned mixed aqueous solution, at 60-65 ℃ of reaction 2～6h.With reacting liquid filtering, washing, drying, as the hemicellulose group resin matrix.
Linking agent be formaldehyde, oxalic dialdehyde, in the suceinic aldehyde, glutaraldehyde any one; Organic phase is any one in kerosene or the whiteruss.
Material proportion in the preparation process of described hemicellulose group resin matrix is:
Hemicellulose: polyol: linking agent is 100: 1-30: 4-20, m/m;
Span-80: organic phase=1-50: 1000, m/v;
The functionalization process of 2 hemicellulose group resin matrixs:
2.1 the preparation of carboxylated hemicellulose ion exchange resin:
The hemicellulose group resin matrix is fully soaked in water, stir the acetone soln that drips carboxylated reagent down in mixed system slowly, behind the reaction 4-8h, filter, use acetone and water washing successively, drying obtains carboxylated hemicellulose ion exchange resin;
2.2 the preparation of quaternary ammoniated hemicellulose ion exchange resin:
The hemicellulose group resin matrix is distributed in the mixed solution of ethanol and water, adds NaOH, etherifying reagent successively, react 2-4h down at 50-60 ℃, be cooled to room temperature, hydrochloric acid is neutralized to pH=6, uses washing with alcohol, filter, dry air obtains quaternary ammoniated hemicellulose ion exchange resin.
In the preparation process of 2.1 carboxylated hemicellulose ion exchange resin, used carboxylated reagent is any one of succinyl oxide or maleic anhydride, and used material proportion is: the hemicellulose group resin matrix: carboxylated reagent is 100: 1～30, m/m;
In the preparation process of 2.2 quaternary ammoniated hemicellulose ion exchange resin, etherifying reagent is any one of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or epoxypropyl trimethylammonium chloride ammonium, used material proportion is: hemicellulose group resin matrix: etherifying reagent: NaOH is 100: 1～40: 0.5～4, m/m.
Embodiment
In order further to understand content of the present invention, characteristics, with specific embodiment the present invention is described below, but they do not impose any restrictions to the present invention.
The preparation of embodiment 1 hemicellulose group resin matrix:
In the hemicellulose aqueous solution of 100ml 10%, add the chitosan aqueous solution of 20ml 10%, stir.Regulate mixing solutions pH=3 with hydrochloric acid, add the glyoxal water solution of 20ml 5%.The 1g span-80 is dissolved in the 200ml kerosene, under agitation adds in the above-mentioned mixed aqueous solution, at 65 ℃ of reaction 3h.With reacting liquid filtering, washing, drying, as the hemicellulose group resin matrix.
The preparation of embodiment 2 hemicellulose group resin matrixs:
In the hemicellulose aqueous solution of 100ml 8%, add the polyvinyl alcohol water solution of 20ml 12%, stir.Regulate mixing solutions pH=3 with hydrochloric acid, add the glyoxal water solution of 20ml 6%.The 1g span-80 is dissolved in the 200ml whiteruss, under agitation adds in the above-mentioned mixed aqueous solution, at 65 ℃ of reaction 3h.With reacting liquid filtering, washing, drying, as the hemicellulose group resin matrix.
The preparation of embodiment 3 carboxylated hemicellulose ion exchange resin:
10g hemicellulose group resin matrix is fully soaked in 200ml water, stir the acetone soln that in mixed system, drips the 30ml4% succinyl oxide down slowly, behind the reaction 6h, use 160ml acetone and 200ml water washing successively, drying obtains carboxylated hemicellulose ion exchange resin.
Embodiment 4: the preparation of carboxylated hemicellulose ion exchange resin:
10g hemicellulose group resin matrix is fully soaked in 200ml water, stir the acetone soln that in mixed system, drips the 30ml5% maleic anhydride down slowly, behind the reaction 6h, use 200ml acetone and 200ml water washing successively, drying obtains carboxylated hemicellulose ion exchange resin.
Embodiment 5: the preparation of quaternary ammoniated hemicellulose ion exchange resin:
10g hemicellulose group resin matrix is distributed in the mixed solution of 100ml ethanol and 40ml water, add 0.2g NaOH, 1g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride successively, react 3h down at 55 ℃, be cooled to room temperature, hydrochloric acid is neutralized to pH=6, uses the 60ml washing with alcohol, filters, dry air obtains quaternary ammoniated hemicellulose ion exchange resin.
Embodiment 6: the preparation of quaternary ammoniated hemicellulose ion exchange resin:
10g hemicellulose group resin matrix is distributed in the mixed solution of 100ml ethanol and 40ml water, add 0.2g NaOH, 1.2g epoxypropyl trimethylammonium chloride ammonium successively, react 3h down at 55 ℃, be cooled to room temperature, hydrochloric acid is neutralized to pH=6, uses the 60ml washing with alcohol, filters, dry air obtains quaternary ammoniated hemicellulose ion exchange resin.
Claims (6)
1. the preparation method of a hemicellulose group ion exchange resin, the polyol that it is characterized in that hemicellulose and other non-hemicelluloses prepares the hemicellulose group resin matrix by crosslinking reaction, and by chemical reaction the hemicellulose group resin matrix is carried out functionalization and prepare hemicellulose group ion exchange resin;
The functionalization process of described hemicellulose group resin matrix comprises following preparation process:
1.1 the preparation of carboxylated hemicellulose ion exchange resin:
The hemicellulose group resin matrix is fully soaked in water, stir the acetone soln that drips carboxylated reagent down in mixed system slowly, behind the reaction 4-8h, filter, use acetone and water washing successively, drying obtains carboxylated hemicellulose ion exchange resin;
1.2 the preparation of quaternary ammoniated hemicellulose ion exchange resin:
The hemicellulose group resin matrix is distributed in the mixed solution of ethanol and water, adds NaOH, etherifying reagent successively, react 2-4h down at 50-60 ℃, be cooled to room temperature, hydrochloric acid is neutralized to pH=6, uses washing with alcohol, filter, dry air obtains quaternary ammoniated hemicellulose ion exchange resin.
2. according to the preparation method of the described hemicellulose group ion exchange resin of claim 1, the polymerization degree that it is characterized in that described hemicellulose is between 10-100.
3. according to the preparation method of the described hemicellulose group ion exchange resin of claim 1, the polyol that it is characterized in that described other non-hemicelluloses is any one of polyvinyl alcohol, chitosan.
4. according to the preparation method of the described hemicellulose group ion exchange resin of claim 3, the molecular weight that it is characterized in that described polyvinyl alcohol, chitosan is 6000-20000.
5. according to the preparation method of the described hemicellulose group ion exchange resin of claim 1, it is characterized in that the preparation of hemicellulose group resin matrix, comprise following preparation process:
5.1 in the hemicellulose aqueous solution of 100ml 10%, the chitosan aqueous solution that adds 20ml 10%, stir, regulate mixing solutions pH=3 with hydrochloric acid, add the glyoxal water solution of 20ml 5%, the 1g span-80 is dissolved in the 200ml kerosene, under agitation add in the above-mentioned mixed aqueous solution, at 65 ℃ of reaction 3h, with reacting liquid filtering, washing, drying, as the hemicellulose group resin matrix;
5.2 in the hemicellulose aqueous solution of 100ml 8%, the polyvinyl alcohol water solution that adds 20ml 12%, stir, regulate mixing solutions pH=3 with hydrochloric acid, add the glyoxal water solution of 20ml 6%, the 1g span-80 is dissolved in the 200ml whiteruss, under agitation add in the above-mentioned mixed aqueous solution, at 65 ℃ of reaction 3h, with reacting liquid filtering, washing, drying, as the hemicellulose group resin matrix.
6. according to the preparation method of the described hemicellulose group ion exchange resin of claim 1, it is characterized in that material proportion is:
In the preparation of 1.1 carboxylated hemicellulose ion exchange resin, used carboxylated reagent is any one of succinyl oxide or maleic anhydride; The hemicellulose group resin matrix: carboxylated reagent is 100: 1～30, m/m;
In the preparation of 1.2 quaternary ammoniated hemicellulose ion exchange resin, used etherifying reagent is any one of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or epoxypropyl trimethylammonium chloride ammonium, hemicellulose group resin matrix: etherifying reagent: NaOH is 100: 1～40: 0.5～4, g/g.
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| CN102875692B (en) * | 2012-10-30 | 2014-07-30 | 桂林理工大学 | Preparation method of cross-linked amphoteric bagasse xylan |
| CN107266630A (en) * | 2017-06-28 | 2017-10-20 | 常州万博金属构件厂 | A kind of preparation method of cellulose base water-absorbing resin |
| CN109181270B (en) * | 2018-07-02 | 2020-11-27 | 仲恺农业工程学院 | Super-absorbent hemicellulose aerogel and preparation method thereof |
| CN109225358B (en) * | 2018-08-03 | 2021-06-01 | 闽江学院 | Hydrophilic fiber-hydrogel composite anion exchange resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346708A (en) * | 2001-11-05 | 2002-05-01 | 南京大学环境学院 | Process for synthesizing weakly alkaline anionic exchange resin with double functions and superhigh cross-linking |
| US20040173533A1 (en) * | 2001-07-24 | 2004-09-09 | Farone William A. | Separation of xylose and glucose |
| CN1765505A (en) * | 2004-10-28 | 2006-05-03 | 中国石油化工股份有限公司 | Method for preparing fluorin-containing composite strong acid ion exchange resin |
| CN1973973A (en) * | 2006-11-17 | 2007-06-06 | 天津工业大学 | Hybric organic resin film and its prepn process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040173533A1 (en) * | 2001-07-24 | 2004-09-09 | Farone William A. | Separation of xylose and glucose |
| CN1346708A (en) * | 2001-11-05 | 2002-05-01 | 南京大学环境学院 | Process for synthesizing weakly alkaline anionic exchange resin with double functions and superhigh cross-linking |
| CN1765505A (en) * | 2004-10-28 | 2006-05-03 | 中国石油化工股份有限公司 | Method for preparing fluorin-containing composite strong acid ion exchange resin |
| CN1973973A (en) * | 2006-11-17 | 2007-06-06 | 天津工业大学 | Hybric organic resin film and its prepn process |
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