CN104387609B - A kind of preparation method of cellulose porous adsorbing material - Google Patents

A kind of preparation method of cellulose porous adsorbing material Download PDF

Info

Publication number
CN104387609B
CN104387609B CN201410664910.XA CN201410664910A CN104387609B CN 104387609 B CN104387609 B CN 104387609B CN 201410664910 A CN201410664910 A CN 201410664910A CN 104387609 B CN104387609 B CN 104387609B
Authority
CN
China
Prior art keywords
cellulose
adsorbing material
preparation
porous adsorbing
urea
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410664910.XA
Other languages
Chinese (zh)
Other versions
CN104387609A (en
Inventor
刘鹤
黄旭娟
王爱婷
商士斌
宋杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemical Industry of Forest Products of CAF
Original Assignee
Institute of Chemical Industry of Forest Products of CAF
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Industry of Forest Products of CAF filed Critical Institute of Chemical Industry of Forest Products of CAF
Priority to CN201410664910.XA priority Critical patent/CN104387609B/en
Publication of CN104387609A publication Critical patent/CN104387609A/en
Application granted granted Critical
Publication of CN104387609B publication Critical patent/CN104387609B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

A kind of preparation method of cellulose porous adsorbing material
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.
CN201410664910.XA 2014-11-18 2014-11-18 A kind of preparation method of cellulose porous adsorbing material Active CN104387609B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410664910.XA CN104387609B (en) 2014-11-18 2014-11-18 A kind of preparation method of cellulose porous adsorbing material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410664910.XA CN104387609B (en) 2014-11-18 2014-11-18 A kind of preparation method of cellulose porous adsorbing material

Publications (2)

Publication Number Publication Date
CN104387609A CN104387609A (en) 2015-03-04
CN104387609B true CN104387609B (en) 2018-06-01

Family

ID=52605578

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410664910.XA Active CN104387609B (en) 2014-11-18 2014-11-18 A kind of preparation method of cellulose porous adsorbing material

Country Status (1)

Country Link
CN (1) CN104387609B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP3572435B1 (en) 2017-01-23 2022-03-09 Panasonic Intellectual Property Management Co., Ltd. Method for producing polymer film
EP3382095A1 (en) * 2017-03-30 2018-10-03 Borregaard AS Microfibrillated cellulose foams
RU2019135202A (en) * 2017-04-05 2021-05-05 Джелесис ЭлЭлСи IMPROVED SUPERABORATIVE MATERIALS AND METHODS FOR THEIR PRODUCTION
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
CN109517082B (en) * 2017-09-18 2021-04-13 中国石油化工股份有限公司 Non-long linear chain alkyl hydrophobically modified hydroxyethyl guar gum thickener and preparation method thereof
CN108084460A (en) * 2017-11-15 2018-05-29 深圳大学 A kind of cellulose/black phosphorus quantum dot composite hydrogel and preparation method thereof
CN108530840A (en) * 2018-04-24 2018-09-14 常州思宇知识产权运营有限公司 A kind of preparation method of transparent heat insulation diaphragm
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1482143A (en) * 2003-07-25 2004-03-17 武汉大学 Method for preparing hydroxypropyl cellulose
CN101445609A (en) * 2008-11-14 2009-06-03 武汉大学 Hydroscopic cellulose hydrogel and preparation method thereof
CN102553545A (en) * 2012-03-16 2012-07-11 川渝中烟工业有限责任公司 Cellulose composite microsphere and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003901834A0 (en) * 2003-04-17 2003-05-01 Clearcoll Pty Ltd Cross-linked polysaccharide compositions
WO2012146031A1 (en) * 2011-04-26 2012-11-01 北京爱美客生物科技有限公司 Composite gel of hyaluronic acid and hydroxypropyl methylcellulose and production method therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1482143A (en) * 2003-07-25 2004-03-17 武汉大学 Method for preparing hydroxypropyl cellulose
CN101445609A (en) * 2008-11-14 2009-06-03 武汉大学 Hydroscopic cellulose hydrogel and preparation method thereof
CN102553545A (en) * 2012-03-16 2012-07-11 川渝中烟工业有限责任公司 Cellulose composite microsphere and preparation method thereof

Also Published As

Publication number Publication date
CN104387609A (en) 2015-03-04

Similar Documents

Publication Publication Date Title
CN104387609B (en) A kind of preparation method of cellulose porous adsorbing material
CN102417606B (en) Preparation method of chitin aerogel
CN104448396A (en) Chemical and physical crosslinking based dual-network cellulose gel system material
CN102492163A (en) Preparation method of high-hydrophobicity cellulose membrane
CN104386684A (en) Preparation method of graphene and graphene
CN103950915B (en) A kind of carbon nanobelts of high-specific surface area and preparation method thereof
CN104118863B (en) A kind of ionic liquid activation rice husk prepares the method for porous carbon material for supercapacitor
CN107082894A (en) A kind of double-network hydrogel adsorbent and preparation method thereof and it is used as the application of heavy metal absorbent
CN103937023A (en) Preparation method of light calcium-alginate-base sponge body functional material
CN112724266A (en) Preparation method of lithium carboxymethyl cellulose for lithium battery
Ding et al. Light weight, mechanically strong and biocompatible α-chitin aerogels from different aqueous alkali hydroxide/urea solutions
CN106866741A (en) A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr)
CN102432912A (en) Preparation method of cellulose/metal oxide composite aerogel
Hao et al. Dialdehyde xylan-based sustainable, stable, and catalytic liquid metal nano-inks
CN102877376B (en) A kind of acetate fiber paper
CN110917825B (en) Composite aerogel moisture absorption material and preparation method and application thereof
CN109134944A (en) A kind of porous small ball and its application with different chemical functional groups
CN115124757A (en) Cellulose-based aerogel small ball capable of efficiently removing chromium, and preparation method and application thereof
Chen et al. A robust polyethyleneimine-based supramolecular hydrogel towards uranium adsorption and deposition
CN109232993A (en) A kind of preparation method of cellulose/micrometer fibers element long filament porous small ball
CN106188436B (en) A kind of cationic polyacrylamide remaining and filling assistant agent and preparation method thereof
CN109244327A (en) The preparation method of lithium ion battery composite separation membrane
CN114907592A (en) Method for efficiently preparing chitin membrane material
Zhang et al. Effects of different lignins on absorption properties and pore structure of polyacrylic acid resin
Zhang et al. Regenerated lignocellulose beads prepared with wheat straw

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant