CN104387609B - A kind of preparation method of cellulose porous adsorbing material - Google Patents
A kind of preparation method of cellulose porous adsorbing material Download PDFInfo
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Abstract
The invention discloses a kind of novel preparation method of cellulose porous adsorbing material, cellulosic material is dissolved in NaOH/ urea/H by this method2In O dicyandiamide solutions, cellulose solution is formed, then reaction is crosslinked with diglycidyl ether, cellulose porous adsorbing material is obtained through washing drying process after purification.Compared with prior art, the outstanding advantages of this method include：It is crosslinked in alkali system, good stability, the good, surfacing of elasticity, the fibrination Porous materials that integrity degree is high, density is low, large specific surface area, water absorbing properties are high has been made.
Description
Technical field
The invention belongs to the synthesis fields of material, and in particular to a kind of preparation method of cellulose porous adsorbing material.
Background technology
High-molecular porous sorbing material has good absorption property, is used widely in numerous areas.Traditional
The chemical composition of polymer adsorbing material is the petroleum chemicals such as polyurethane, polystyrene.With the storage of fossil resources on earth
Amount is increasingly reduced, raising of the mankind to environmental protection and Consciousness of Sustainable Development, using reproducible biomass resource as raw material, peace
Entirely, biomass-based porous adsorbing material is efficiently produced as research hotspot.
Cellulose is one of biomass resource most abundant in the world, and has good physical and chemical performance, after discarding
It is degradable, it substitutes traditional petroleum chemicals using cellulose and has been taken seriously to produce new material.However, there is knot in cellulose
Crystalline region, this so that cellulose is difficult to be dissolved in general organic solvent, hinders its potential application study.Cellulose dissolution is existed
In specific solvent, thus it is possible to vary the original accumulation shape of cellulosic molecule improves the accessibility of fibrin reaction, makes cellulose
It is easy to chemical modification, prepares tencel cellulosic material.
The common solvent of cellulose has copper ammon solution, N-methylmorpholine-N- oxides, lithium chloride/dimethyl acetamide body
System, ionic liquid etc., there are respective advantage and disadvantage for these solvents.Sodium hydroxide/urea/aqueous solvent is developed in recent years
A kind of new method (patent CN101037479B) of more green dissolving cellulose, sodium hydroxide and cellulose in solution system
Reaction generation alkali cellulose, so as to further be dissolved in sodium hydroxide/urea/aqueous solvent.Using sodium hydroxide/urine
Element/aqueous solvent, patent CN102875836B disclose a kind of preparation method of cellulose sponge, and this method is molten by cellulose
In sodium hydroxide/urea/aqueous solvent, the cellulose solution of preparation is placed in mold, through regeneration, frozen dried, is obtained
A series of density are 0.129~0.387g/cm3, average pore size is the cellulose foam material of 78~3600nm；Patent
CN102504327B discloses a kind of side for preparing cellulose sponge for raw material using sisal hemp hemp wastes chaff and numb head discarded object
Cellulosic material is dissolved in sodium hydroxide/urea/aqueous solvent, using sodium sulphate as pore former, in sulfuric acid and sodium sulphate by method
It is regenerated in mixing bath, prepares cellulose sponge.Above-mentioned cellulose foam material is all to utilize to destroy cellulose, sodium hydroxide and urine
The inclusion compound that plain three is formed, makes secondary formation hydrogen bond between cellulosic molecule, passes through intermolecular hydrogen bonding and intermolecular force
It is secondary to be piled into fibrination Porous materials, there are the defects of stability is poor, matter is hard, and also need in preparation process to use pore former
Wait auxiliary agents.
The content of the invention
In order to overcome in the prior art the defects of cellulose foam material matter is hard, stability is poor, preparation is complicated, the present invention carries
For a kind of preparation method of cellulose porous adsorbing material.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
A kind of preparation method of cellulose porous adsorbing material, including following steps connected in order：
(1), cellulosic material is dissolved in NaOH/ urea/H2In O dicyandiamide solutions, mass percent concentration is prepared as 3%
~12% cellulose solution；
(2), diglycidyl ether will be added in the cellulose solution obtained by step (1), in 0~80 DEG C of reaction temperature condition
0.1~20h of lower reaction, obtains cellulose crosslinked product；
(3), the cellulose crosslinked product obtained by step (2) in dilute acid soln is regenerated, obtains cellulose aquagel；
(4), the cellulose aquagel obtained by step (3) with deionized water is washed and purified, being adjusted to mass concentration is
After 0.5%~3.5% hydrogel, cellulose porous adsorbing material is obtained through drying process.
Applicant it has been investigated that, crosslinking agent is added in cellulose solution, is made by chemical reaction between cellulosic molecule
The effect of crosslinking forms cellulose gel, can not only improve the stability and reappearance of cellulosic molecule aggregation, moreover it is possible to
Flexible or rigid group is enough introduced by crosslinking agent, improves the performance of fibrination Porous materials；The application has broken Traditional Thinking,
Be crosslinked in alkali system, be made good stability, the good, surfacing of elasticity, integrity degree is high, density is low, large specific surface area, suction
Aqueous fibrination Porous materials that can be high.
The application reaction mechanism is as follows：
Cellulosic material described in step (1) is timber, cotton, cotton linter, wheat straw, straw, reed, fiber crops or mulberry skin
One or both of cellulose any of the above compares mixture；The scope of the cellulosic degree of polymerization DP is 100~2000.So
It not only ensure that the cheap and easy to get of raw material, but also further ensure the stability and flexibility of products obtained therefrom.
Diglycidyl ether described in step (2) is ethylene glycol diglycidylether, 1,4- butanediol 2-glycidyls
Ether, 1,6 hexanediol diglycidylether, polyethylene glycol diepoxide for example methyl ether, neopentylglycol diglycidyl ether or 1,3-
One or both of resorcinol diglycidyl ether any of the above scalemic thereof.So further ensure products obtained therefrom
Elasticity, profile pattern, low-density and high-hydroscopicity energy.
The quality dosage of diglycidyl ether described in step (2) is 1~20 times of cellulosic material quality.So into
One step ensure that the elasticity of products obtained therefrom.
Dilute acid soln described in step (3) is the one or two of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or dilute solution of acetic acid
The mixed solution of any of the above ratio；Wherein, the concentration of diluted acid is 0~1mol/L.This further ensures that products obtained therefroms
Specific surface area and average pore size.
Regenerated temperature described in step (3) is 20~70 DEG C, and the recovery time is 20~90min.So further really
The elasticity of products obtained therefrom is protected.
Drying described in step (4) is freeze-drying and supercritical CO2Any one in drying means.So into one
Step ensures the quality of products obtained therefrom.
It is preferred that the density of the cellulose sorbing material is 0.0139~0.105g/cm3, specific surface area for 100~
280m2/ g, 8~60nm of average pore size, Water absorption are 20~50 times.
It is preferred that NaOH/ urea/H in step (1)2In O dicyandiamide solutions, NaOH/ urea/H2The mass ratio of tri- kinds of substances of O is
(6~11%)：(7~14%)：(78~85%), first by NaOH/ urea/H before cellulosic material dissolving2O dicyandiamide solutions are pre-
It is cooled to -6~-14 DEG C, the dissolution time of cellulosic material is 0.5~3h.
The unmentioned technology of the present invention is the prior art.
The present invention is using native cellulose as raw material, with cheap, environmentally protective sodium hydroxide/urea/aqueous solvent body
It is for cellulose solvent, using diglycidyl ether as crosslinking agent, cellulose is made to be sent out in sodium hydroxide/urea/aqueous solvent
Raw cross-linked gelization reaction, purified drying process prepare cellulose porous adsorbing material, need not add pore former etc. in the process
Auxiliary agent；The surfacing of gained cellulose porous adsorbing material, integrity degree are high, with good stability, relatively low density, larger
Specific surface area and higher water absorbing properties；Gained cellulose porous adsorbing material is because of its function admirable, easy to use, nontoxic nothing
It is pollution, safety and environmental protection, environmental-friendly, so as to extensive use.
Description of the drawings
Fig. 1 is the XRD diagram of cellulose porous adsorbing material obtained by embodiment 1 and comparative example.
Fig. 2 is the thermal multigraph of cellulose porous adsorbing material obtained by embodiment 1 and comparative example.
In figure, cellulose refers to cellulosic material, and regenerated cellulose refers to cellulose sponge product obtained by comparative example, fibrination
Porous materials refer to 1 gained cellulose porous adsorbing material of embodiment.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Implement one
It is NaOH/ urea/H by 100g mass ratioes2O=7.5/13/79.5 dicyandiamide solutions are cooled to -8 DEG C in advance, weigh 7g crystallites
Cellulose (degree of polymerization DP is 180) is added to stirring and dissolving 2h in dicyandiamide solution, obtains cellulose solution, measures 30g crosslinking agents
Neopentylglycol diglycidyl ether is added drop-wise in above-mentioned system, 80 DEG C of reaction 0.5h to gel.By the cellulose crosslinked gel of gained
It pours into the sulfuric acid solution of 0.5mol/L to neutralize and regenerates 30min at 30 DEG C, washed and purified with deionized water, the fast quickly cooling in liquid nitrogen
Freeze, it is freeze-dried, obtain cellulose porous adsorbing material.Its density is 0.0152g/cm3, specific surface area 135m2/ g is put down
Equal aperture is 30nm, and Water absorption 40 can recover deformation after compression.
As seen from Figure 1：The characteristic peak of cellulosic material is appeared at the peak position that the angle of diffraction is 16 °, 22 ° and 34 °, performance
Go out typical cellulose Ⅰ type crystalline texture；The crystalline structure of regenerated cellulose substantially changes, near 12 ° of low angles only
There is 1 peak crystallization, be two diffraction maximums between 20~22 °, cellulose Ⅱ type crystal form knot is changed by cellulose Ⅰ type crystalline structure
Structure；Fibrination Porous materials are there are a wider diffraction maximum between 20~22 °, and overall diffraction intensity significantly declines, and is in
Amorphous structure.
As seen from Figure 2：The heat decomposition temperature of fibrination Porous materials is higher than the heat decomposition temperature of regenerated cellulose, heat
Stability is better than the thermal stability of regenerated cellulose.
Implement two
It is NaOH/ urea/H by 100g mass ratioes2O=9/10/81 dicyandiamide solutions are cooled to -14 DEG C in advance, weigh 6g cotton linters
Cellulose (degree of polymerization DP is 1000) and 5 grams of dragon spruce pulp celluloses (degree of polymerization DP is 500) be added in dicyandiamide solution stir it is molten
2.5h is solved, obtains cellulose solution.It measures 60g crosslinking agent 1,4-butanediol diglycidyl ether to be added drop-wise in above-mentioned system, 40
DEG C reaction 2.5h is to gel.Cellulose crosslinked gel is poured into deionized water and regenerates 60min at 40 DEG C, is washed with deionized water
Purifying, the snap frozen in liquid nitrogen is freeze-dried, obtains cellulose porous adsorbing material.Its density is 0.0243g/cm3,
Specific surface area is 250m2/ g, average pore size 10nm, Water absorption 32 can recover deformation after compression.
Implement three
It is NaOH/ urea/H by 100g mass ratioes2O=10/8/82 dicyandiamide solutions are cooled to -10 DEG C in advance, weigh 4g wood pulps
Cellulose (degree of polymerization DP is 1130) is added to stirring and dissolving 1.5h in dicyandiamide solution, obtains cellulose solution.Measure 10g crosslinkings
Agent 1,6- hexanediol diglycidyl ethers are added drop-wise in above-mentioned system, 60 DEG C of reaction 1.5h to gel.By cellulose crosslinked gel
Pour into the acetic acid of 0.2mol/L and the HNO of 0.1mol/L3It is neutralized in mixed solution at 40 DEG C and regenerates 40min, washed with deionization
Purifying is washed, the snap frozen in liquid nitrogen is freeze-dried, obtains cellulose porous adsorbing material.Its density is 0.0358g/
cm3, specific surface area 210m2/ g, average pore size 50nm, Water absorption 36 can recover deformation after compression.
Implement four
It is NaOH/ urea/H by 100g mass ratioes2O=6/14/80 dicyandiamide solutions are cooled to -12 DEG C in advance, weigh 9g paper pulp fibre
Dimension element (degree of polymerization DP is 710) is added to stirring and dissolving 1h in dicyandiamide solution, obtains cellulose solution.20g crosslinking agents 1 are measured,
3- resorcinol diglycidyl ethers are added drop-wise to 30g polyethylene glycol diepoxide for example methyl ether mixtures in above-mentioned system, 30 DEG C
6h is reacted to gel.Cellulose crosslinked gel is poured into the phosphoric acid solution of 0.4mol/L to neutralize and regenerate 80min at 30 DEG C, to go
Ion water washing purifies, with supercritical CO2It is dry, obtain cellulose porous adsorbing material.Its density is 0.0140g/cm3, compare table
Area is 180m2/ g, average pore size 40nm, Water absorption 48 can recover deformation after compression.
Comparative example
102875836 B of patent CN disclose a kind of controllable cellulose foam material preparation method of form density and its
Product, method are as follows：Prepare NaOH/ urea/H of 400g2O solution, wherein NaOH/ urea/H2O=7/12/81wt%, precooling
To -12 DEG C, the cellulose of 5wt% is added in immediately, and 1h is stirred by ultrasonic, obtains cellulose solution.By obtained cellulose solution
It is placed in mold, is handled in 70 DEG C of baking oven for 24 hours, after cellulose solution gelation, be placed in distilled water and impregnate, until system
PH=7.Neutral fibre hydrogel is placed in 50 DEG C of vacuum drying oven dry 8h, it is quick that it is carried out in liquid nitrogen to low temperature
After freezing, then 2 days dry, final acquisition cellulose sponge product is placed in -50 DEG C of freeze drier.Its density is
0.209g/cm3, specific surface area 45m2/ g, average pore size 415nm, Water absorption 10, non-recoverable deformation after compression.
The performance table of 1 each products obtained therefrom of table
Test method：
The thermodynamic property of the fibrination Porous materials sample using thermogravimetric analysis (Netzsch TG209F1Iris types,
Netzsch companies, Germany) it studies, test condition is：Temperature range is 20 DEG C~700 DEG C, and heating rate is 10 DEG C/min, is carried
Gas is high pure nitrogen, gas flow 60mL/min.From attached drawing 2 it can be seen that fibrination Porous materials are more first than regenerated cellulose
Beginning decomposition temperature is high, and thermal stability is good.
The density measurement method of the fibrination Porous materials：By the fibrination Porous materials electronics day after freeze-drying
It is flat to weigh, and with vernier caliper measure the sizes of regular shape fibrination Porous materials (each size surveys three data, takes it flat
Average), it calculates volume and then acquires density.By table 1 it will be evident that each embodiment cellulose of the application and 2-glycidyl
The density of the fibrination Porous materials prepared after ether reaction is well below the density of the regenerated cellulose obtained by comparative example.
The specific surface area of the fibrination Porous materials and the test method of average pore size：By the porous material of the cellulose of preparation
After material deaerates 12 hours at a certain temperature, nitrogen adsorption-detachment assays, selection are carried out with reference to GB/T19587-2004 methods
Full-automatic specific surface area and Physisorption Analyzer (ASAP2020M types, Micromeritics Instrument Corp. U.S.A) specific surface area and average hole
Footpath analyzer.Analysis specific surface area and average pore size are calculated using BET methods.
The water absorbing properties test method of the fibrination Porous materials：Dry fibrination Porous materials are weighed (m1) after
It immerses in the beaker equipped with distilled water, absorbs water to sample constant weight (m at room temperature2) after, Water absorption (Q) is counted according to formula 1-1
It calculates.The Water absorption of each porous material is surveyed 5 times, is averaged as final Water absorption.
Formula 1-1
Fibrination Porous materials obtained by each embodiment of the application are softer flexible, on transverse direction and longitudinal direction direction after stress
It deforms upon, the deformation that power cancels rear fibrination Porous materials transverse direction and longitudinal direction restores to the original state.
Claims (7)
1. a kind of preparation method of cellulose porous adsorbing material, it is characterised in that：Including following steps connected in order：
（1）, cellulosic material is dissolved in NaOH/ urea/H2In O dicyandiamide solutions, it is fine for 3% ~ 12% to prepare mass percent concentration
The plain solution of dimension, the scope of cellulosic degree of polymerization DP is 100 ~ 2000；
（2）, by step（1）Diglycidyl ether is added in the cellulose solution of gained, it is anti-under the conditions of 0 ~ 80 DEG C of reaction temperature
0.1 ~ 20h is answered, obtains cellulose crosslinked product, the quality dosage of diglycidyl ether is 1 ~ 20 times of cellulosic material quality；
（3）, by step（2）The cellulose crosslinked product of gained regenerates in dilute acid soln, obtains cellulose aquagel；
（4）, by step（3）The cellulose aquagel of gained is washed with deionized water and purified, be adjusted to mass concentration for 0.5% ~
After 3.5% hydrogel, cellulose porous adsorbing material is obtained through drying process；
The density of the cellulose sorbing material is 0.0139 ~ 0.105 g/cm3, specific surface area is 100 ~ 280m2/ g, average hole
Footpath is 8 ~ 60nm, and Water absorption is 32 ~ 50 times.
2. the preparation method of cellulose porous adsorbing material as claimed in claim 1, it is characterised in that：Step（1）Middle institute
The cellulosic material stated is one kind or two in the cellulose of timber, cotton, cotton linter, wheat straw, straw, reed, fiber crops or mulberry skin
Kind any of the above compares mixture.
3. the preparation method of the cellulose porous adsorbing material as described in claims 1 or 2, it is characterised in that：Step（2）In
The diglycidyl ether is 1,4- butanediol diglycidyl ethers, 1,6 hexanediol diglycidylether, polyethylene glycol two
It is more than one or both of oxiranylmethyl ether, neopentylglycol diglycidyl ether or 1,3- resorcinol diglycidyl ethers
Arbitrary proportion mixture.
4. the preparation method of the cellulose porous adsorbing material as described in claims 1 or 2, it is characterised in that：Step（3）In
The dilute acid soln is the mixing of one or more kinds of arbitrary proportions of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or dilute solution of acetic acid
Solution；Wherein, the concentration of diluted acid is 0 ~ 1mol/L.
5. the preparation method of the cellulose porous adsorbing material as described in claims 1 or 2, it is characterised in that：Step（3）In
The regenerated temperature is 20 ~ 70 DEG C, and the recovery time is 20 ~ 90min.
6. the preparation method of the cellulose porous adsorbing material as described in claims 1 or 2, it is characterised in that：Step（4）In
The drying is freeze-drying or supercritical CO2It is dry.
7. the preparation method of the cellulose porous adsorbing material as described in claims 1 or 2, it is characterised in that：Step（1）In
NaOH/ urea/H2In O dicyandiamide solutions, NaOH/ urea/H2The mass ratio of tri- kinds of substances of O is（6~11%）：（7~14%）：（78~
85%）, first by NaOH/ urea/H before cellulosic material dissolving2O dicyandiamide solutions are cooled to -6 ~ -14 DEG C in advance, cellulosic material it is molten
The solution time is 0.5 ~ 3h.
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| CN105457604B (en) * | 2015-11-30 | 2018-02-09 | 同济大学 | A kind of preparation method of the sorbing material based on natural polysaccharide |
| CN106009031B (en) * | 2016-07-15 | 2018-10-12 | 东北林业大学 | A method of improving the mechanical strength of cellulose aerogels |
| CN105950186A (en) * | 2016-07-21 | 2016-09-21 | 蒋黔湘 | Water retention soil stabilizer for mountain slope greening and preparation technology thereof |
| US9828725B1 (en) * | 2016-11-16 | 2017-11-28 | Rayonier Performance Fibers, Llc | Specialty pulp with high intrinsic viscosity |
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| EP3382095A1 (en) * | 2017-03-30 | 2018-10-03 | Borregaard AS | Microfibrillated cellulose foams |
| CA3058740A1 (en) * | 2017-04-05 | 2018-10-11 | Gelesis, Llc | Improved superabsorbent materials and methods of production thereof |
| CN107602766A (en) * | 2017-09-06 | 2018-01-19 | 中国林业科学研究院林产化学工业研究所 | Cellulose base water imbibition gel and preparation method thereof |
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| CN108587634A (en) * | 2018-08-06 | 2018-09-28 | 吉林建筑大学 | The production method of stalk powder and hydroxypropyl methyl cellulose composite water absorbing water-retaining agent |
| CN109232993A (en) * | 2018-08-28 | 2019-01-18 | 安徽聚欣新材料科技有限公司 | A kind of preparation method of cellulose/micrometer fibers element long filament porous small ball |
| CN109433162B (en) * | 2018-11-29 | 2022-02-18 | 广西科技师范学院 | Preparation method of cellulose/graphene oxide/magnetic titanium dioxide efficient environment-friendly adsorption aerogel |
| CN112759787A (en) * | 2020-12-30 | 2021-05-07 | 鹤山市绿湖生物能源有限公司 | Preparation method of thick-wall regenerated cellulose sponge |
| CN116059976A (en) * | 2021-10-29 | 2023-05-05 | 中国船舶重工集团公司第七一八研究所 | Solid acid material and preparation method thereof |
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