CN103554372A - Preparation method of industrial hemp stalk core cellulose based temperature-sensitive composite hydrogel - Google Patents
Preparation method of industrial hemp stalk core cellulose based temperature-sensitive composite hydrogel Download PDFInfo
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- UJVWPZIWWKDJNH-UHFFFAOYSA-N (4-acetamido-2-hydroxyphenyl)arsonic acid Chemical compound CC(=O)NC1=CC=C([As](O)(O)=O)C(O)=C1 UJVWPZIWWKDJNH-UHFFFAOYSA-N 0.000 claims description 7
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 7
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Abstract
The invention discloses a preparation method of an industrial hemp stalk core cellulose based temperature-sensitive composite hydrogel. The preparation method comprises the steps of: preparing the raw material by cutting the hemp stalk core part which is air-dried previously, performing cellulose extraction and pulping pretreatment on the stalk core, and then carrying out selective oxidization of the cellulose which is subjected to the pulping pretreatment previously by the method of a piperidine oxynitride free radical/cooxidation system to obtain nano oxidized cellulose; simultaneously, carrying out a grafting copolymerization reaction of the pretreated stalk core cellulose by an aqueous solution polymerization method to obtain a dimethyl diallyl ammonium chloride cellulose network body; next, dipping the dimethyl diallyl ammonium chloride cellulose network body into the aqueous solution of the nano oxidized cellulose to obtain the industrial hemp stalk core cellulose based temperature-sensitive composite hydrogel. The obtained industrial hemp stalk core cellulose based temperature-sensitive composite hydrogel has UCST (Upper Critical Solution Temperature) characteristic; the volume phase transition temperature of the industrial hemp stalk core cellulose based temperature-sensitive composite hydrogel is controlled within the range from 35 to 50 DEG C; the industrial hemp stalk core cellulose based temperature-sensitive composite hydrogel has bright application prospect in a plurality aspects such as drug controlled-release carriers, tissue engineering, active enzyme immobilization and chemical conversion elements.
Description
Technical field
The present invention relates to a kind of Technology of utilizing industrial hemp stalk core cellulose to manufacture temperature sensitive hydrogel, belong to natural macromolecular material technical field.
Background technology
Hydrogel is wetting ability but water-fast polymkeric substance, the multicomponent system being comprised of high molecular three-dimensional network and water
[1].The response condition stimulating to external world according to hydrogel, can be divided into traditional hydrogel and intelligent aqueous gel capable.Intelligent aqueous gel capable is that a class stimulates the hydrogel that can produce responsive response to external world
[2].Typical external stimulus has temperature, pH value, solvent, salt concn, optical, electrical field, chemical substance etc.Due to the potential application of progress in Intelligent Hydrogel at the aspects such as embedding of the control delivery systme of chemical transformation device, memory cell switch, sensor, medicine, artificial muscle, chemical storage device, molecular separation system, organized enzyme
[3], thereby the research of intelligent aqueous gel capable has been become to a large focus of functional polymer research field.
Wherein Thermo-sensitive water-keeping material has been subject to extensive concern and the further investigation of a plurality of Application Areass gradually due to the changing behavior mutually of uniqueness.As a member of Thermo-sensitive water-keeping material, LCST(Low Critical Solution Temperature) can there is macromolecular chain and assemble and shrink in type resin under comparatively high temps, swelling capacity sharply declined, and when low temperature, imbibition swelling behavior occurs
[4].From people such as Tanaka in 1984
[5]since finding that poly N-isopropyl acrylamide (PNIPAAm) hydrogel has the temperature sensitive phenomenon of low-temperature phase transition temperature, all kinds of LCST type water-keeping materials that PNIPAAm is relevant have caused the great interest of people, research about LCST type water-keeping material emerges in an endless stream, and from aspects such as theoretical and application, has all obtained detailed probing into and developing.In addition, contrary with LCST shaped material, UCST(Upper Critical Solution Temperature) type hydrogel has a high Kraft point, the gel generation volumetric shrinkage of swollen during lower than this temperature, in releasing water state, swollen once again during higher than this temperature, in water suction state.Compare with LCST type, the correlative study of UCST type water-keeping material focuses mostly in the synthetic family macromolecule field of non-renewable recycle, and for, the degradable natural polymer of product renewable for raw material, Mierocrystalline cellulose for example, the application report in such temperature-sensitive hydrogel is but relatively less.
In the category of natural macromolecule modification research, Mierocrystalline cellulose is mainly derived from plant material, occurring in nature plant of a great variety, the stock number of each kind of plant is not quite similar, in every class plant, contained cellulose amount is different, Mierocrystalline cellulose microtexture in every kind of plant raw material and structure also differ larger, and so, the cellulosic material of selecting to be applicable to UCST type hydrogel in numerous floristics is the application's a underlying issue.
Industrial hemp is the Hemp Varieties that tetrahydrocannabinol (THC) content meets the European Union's standard (THC<0.3%) extensively adopting in the world
[6].Industrial hemp does not have drugs utility value, its objective is the output that improves to greatest extent fiber, seed or oil, improve its quality, so this kind of hemp is mainly to carry out directive breeding for paper-making industry, textile industry and oil plant industry
[7].Industrial hemp comprises two kinds of different pieces: bast and stalk core.The fiber of bast part is because the advantage of its length is (within the scope of 10-20mm
[8]), in the extensive fiber production such as weaving, papermaking, natural-fiber composite material, play an important role; And the fiber of stalk core segment is because the limitation of its length is (greatly about 0.5mm left and right
[8]) application in a plurality of production such as papermaking, weaving is greatly limited, high value added utilization rate is low, is now mainly used in pulp mill or heat energy is reclaimed in family expenses burning.But undeniable to be hemp stalk core as in plant material a kind of, it has the identical point of other plant raw material chemical constitution, and its content of cellulose is 46.8%
[9], be one of main constituent of stalk core, from feed composition, prove that industrial hemp stalk core can be used as the initial feed of Mierocrystalline cellulose functional materials.
Prepare functional type temperature-sensitive hydrogel not harsh to the length requirement of raw fibre, so the research at cellulose-based UCST type temperature-sensitive hydrogel remains under the prerequisite of blank out, by industrial hemp stalk core for the preparation of such functional materials, not only make natural resource be utilized effectively, can also expand the road of stalk core fibre high value added utilization.
Reference
[1] Yan Youwang. progress in Intelligent Hydrogel [J]. chemistry teaching, 2009, (10): 74-76.
[2] Liu Xiaohua, Wang Xiaogong, Liu Deshan. the progress of progress in Intelligent Hydrogel structure and Response Mechanism [J]. chemistry circular, 2000, (10): 1-6.
[3] Zhao Yuqiang, Zhang Zhibin, Liu Ning etc. the application of intelligent aqueous gel capable [J]. modern chemical industry, 2007,27(3): 66-69.
[4] Yang Jie, Huo Danqun etc. Thermo-sensitive PNIPAAm porous aquagel preparation method's progress [J]. material Leader, 2010,24(9): 62-70.
[5]?Hirokawa?Y,?Tanaka?T.?Volume?phase-transition?in?a?nonionic?gel?[J].?J?Chem?Phys,?1984,?81(12):?6379-6380.
[6] Yang Ming, Guo Hongyan, Hu Xueli etc. feature and the cultivation technique [J] of industrial hemp new variety " cloud fiber crops No. 1 ". Crop Diseases in Yunnan science and technology, 2003(6): 21-23.
[7] Zhang Yunxiong. the new trend [J] of external industrial hemp research and product development. world agriculture, 2003, (9): 37-40.
[8] Gao Xin, Chen Keli. world industry is the reviews and prospects [J] with research with the application of hemp stalk pulp and paper industry. southwestern papermaking, 2006,35(6): 7-12.
[9] Zhang Heng, Gao Xin, Chen Keli. the pulpability [J] of " cloud fiber crops No. " hemp. paper and papermaking, 2012,31(9): 14-18.
Summary of the invention
Owing to there is no the basis of associated fiber element class natural polymer UCST type temperature-sensitive hydrogel development technique, the utilization of industrial hemp stalk core intelligent material is substantially still in space state up to now.Therefore, the invention provides a kind of preparation method of industrial hemp stalk core cellulose Ji Wenmin composite aquogel, the method utilizes comparatively weak " cloud fiber crops No. 1 " the stalk core of aboundresources and deep development as Mierocrystalline cellulose initial feed, prepare the cellulose base hydrogel product with the temperature sensitive effect of UCST type, open the cellulosic value segment of infant industry hemp stalk core, this green recyclable materials of industrial hemp is more widely used.
Realize the process technology scheme that the object of the invention takes as follows:
1. " cloud fiber crops No. 1 " industrial hemp stalk core is sheared the processing of getting the raw materials ready after air-dry;
2. adopt Glacial acetic acid/hydrogen peroxide method to carry out Mierocrystalline cellulose extraction to the stalk core of getting the raw materials ready qualified;
3. adopt mechanical hollander to the stalk core cellulose pre-treatment of pulling an oar;
4. adopt piperidines oxynitride free radical/common oxygen system to carry out C to pretreated stalk core cellulose
6the selective oxidation of position hydroxyl, oxidation products is by solid-liquid separation, and liquid portion carries out precipitating, centrifugation and washing with dehydrated alcohol, and lyophilize obtains nano oxidized Mierocrystalline cellulose;
5. adopt aqueous solution polymerization method to carry out graft copolymerization to pretreated stalk core cellulose, select ammonium persulphate as initiator, with N, N
'-methylene-bisacrylamide is linking agent, select dimethyl diallyl ammonium chloride to complete as cationic monomer simultaneously, multipolymer is carried out to precipitating, washing, lyophilize with dehydrated alcohol, obtain dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel;
6. dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in certain density nano oxidized cellulose aqueous solution, until no longer imbibition of gel, obtain UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL and independently fill mixture, mixture is carried out to lyophilize, sealing, obtains industrial hemp stalk core cellulose Ji Wenmin composite aquogel finished product.
The preparation method of industrial hemp stalk core cellulose Ji Wenmin composite aquogel of the present invention, concrete operations are as follows:
1. the melting process of industrial hemp stalk core raw material: stalk core is after air-dry processing, wherein the moisture of air-dry raw material is different and different according to different areas Various Seasonal atmospheric moisture, general moisture control is in 7～20% scope, air-dry thing is cut and is grown into 10～40mm, wide is 1～3mm, and thickness has raw material itself to determine;
2. stalk core raw material adopts hydrogen peroxide/ice acetic acid method to extract the Mierocrystalline cellulose of raw material, in stalk core raw material, add hydrogen peroxide and Glacial acetic acid mixed solution, after mixing, after processing 12～48h, 60～100 ℃ of temperature take out sample, deionization cleans to neutral, air-dry dry, obtain industrial hemp stalk core cellulose, standby, wherein the mass percent concentration of over dry stalk core raw material in mixed solution is 8～15%, and hydrogen peroxide and Glacial acetic acid mixed solution are that mass percent concentration is that 30～35% hydrogen peroxide mixes and makes for the ratio of 3:1～1:3 by volume with Glacial acetic acid;
3. in order to improve cellulosic reactivity worth, adopt QB/T-1463-1992 standard method, utilize PFI hollander to the pre-treatment of pulling an oar of industrial hemp stalk core cellulose, and with Xiao Baier beating degree determinator, carry out the real time measure of this kind of slurry pulping degree, pre-treatment degree is that the beating degree of " cloud fiber crops No. 1 " stalk core cellulose is 35～90
°within the scope of SR;
4. prepare nano oxidized Mierocrystalline cellulose process as follows: in pretreated over dry stalk core cellulose, add and contain 4-acetylaminohydroxyphenylarsonic acid 2, 2, 6, the deionized water of 6-tetramethyl piperidine-1-nitroxyl free radical and Textone, 4-acetylaminohydroxyphenylarsonic acid 2, 2, 6, 6-tetramethyl piperidine-1-nitroxyl free radical is 0.15mmol:1g～1.00mmol:1g with the ratio of over dry stalk core cellulose, Textone is 5.0mmol:1g～30.0mmol:1g with the ratio of over dry stalk core cellulose, deionization consumption is 80ml:1g～150ml:1g with the ratio of over dry stalk core cellulose, then at 30～60 ℃, stir after 30～60min, adding mass percent concentration is 8%～12% chlorine bleach liquor, its consumption is 0.5mmol:1g～6.0mmol:1g with the ratio of over dry stalk core cellulose, carry out selective oxidation reaction 12～240h, after oxidizing reaction, with the filter membrane that aperture is 0.02～0.10 μ m, carry out solid-liquid separation, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, illustrate that precipitating is complete, with absolute ethanol washing and under 7000～15000rpm centrifugal 10～20min, after 3～5 times, lyophilize processing is until material complete drying obtains nano oxidized Mierocrystalline cellulose repeatedly,
5. dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel preparation course is: dimethyldiallylammonchloride chloride monomer consumption and pretreated over dry stalk core cellulose mass ratio are 1:1～10:1, and initiator ammonium persulfate consumption and over dry stalk core cellulose mass ratio are 0.005:1～0.025:1; Linking agent N, N
,-methylene-bisacrylamide consumption and dimethyldiallylammonchloride chloride monomer mass ratio are 0.005:1～0.02:1, temperature of reaction is 30～80 ℃, reaction times is 2.0～15.0h, and over dry stalk core cellulose quality is controlled in the scope of 1g:100ml～1g:200ml with the ratio of reaction liquid cumulative volume; Whole graft copolymerization carries out in logical nitrogen situation; After completion of the reaction, network body gel is cut into the fritter of 1.00～2.00cm * 1.00～2.00cm * 0.10～1.00cm, with dehydrated alcohol, fritter synthetics is carried out repeatedly precipitating, washed to pH6～8, lyophilize, obtains dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel;
6. dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in to mass percent concentration and is in 0.1～5.0% nano oxidized cellulose aqueous solution, until no longer imbibition of gel, mixture is carried out to lyophilize, sealing, obtain UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL mixture, i.e. industrial hemp stalk core cellulose Ji Wenmin composite aquogel of the present invention.
The invention has the beneficial effects as follows: using that agricultural wastes---industrial hemp stalk core is originated as Mierocrystalline cellulose, by the machinery mode of pulling an oar, can destroy well part Mierocrystalline cellulose crystallizing field, increase the quantity of activity hydroxy, improve subsequent reactions ability, prepare respectively negatively charged ion nano level SURGICEL and positively charged ion dimethyl diallyl ammonium chloride Mierocrystalline cellulose network polymer, by electrostatic attraction and Hyarogen-bonding, independently fill formation and there is UCST temperature sensitive type cellulose base mixture hydrogel.Cellulose family natural polymer temperature-sensitive hydrogel has the general character of synthetic high score subclass hydrogel, can fix at medicine controlled release carrier, organizational project, organized enzyme, the aspect such as chemical conversion element brings into play good application prospect.Meanwhile, cellulose base temperature-sensitive hydrogel also possesses hypotoxicity, good biocompatibility, to environment sensitive and the cheap advantages such as price, is novel, the green intelligent material of a class of mainstream development now; The cellulosic functionalization exploitation of hemp stalk core that is embodied as of this cellulose base temperature sensing material proposes a feasible scheme, also extension and the expansion for industrial hemp industrial chain provides new development space, meanwhile, made up the vacancy of natural polymer subbase UCST type temperature sensing material research.
By the method, make industrial hemp stalk core cellulose Ji Wenmin composite aquogel and have UCST characteristic, volume phase transition temperature is within the scope of 35～50 ℃; At this, more than volume phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and equilibrium swelling degree is larger; Upper and lower at volume phase transition temperature, product has good swelling/shrinkage; Can fix at medicine controlled release carrier, organizational project, organized enzyme, the many aspects such as chemical conversion element bring into play good application prospect.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1: the preparation method of industrial hemp stalk core cellulose Ji Wenmin composite aquogel, and concrete operations are as follows:
(1) melting process of " cloud fiber crops No. 1 " stalk core
Stalk core is 7% through air-dry processing controls moisture content, and air-dry thing is cut and grown into 10mm, and wide is 1mm, and thickness has raw material itself and determines, standby.
(2) extraction of stalk core cellulose
Adopting hydrogen peroxide and Glacial acetic acid mixed solution to extract Mierocrystalline cellulose to qualified stalk core processes, wherein mass percent concentration is that 30% hydrogen peroxide mixes and makes hydrogen peroxide and Glacial acetic acid mixed solution for the ratio of 1:3 by volume with Glacial acetic acid, the mass percent concentration of stalk core raw material in mixed solution is 8%, then at 60 ℃, process 48h, after completion of the reaction, material cleans to neutral and air-dry dry through deionization, obtains stalk core cellulose.
Concrete operations are: take the air-dry stalk core of 21.5g (because raw material water content is 7%, so over dry stalk core is 20g), put into digester, pouring 30% hydrogen peroxide of corresponding 57.1ml and the Glacial acetic acid mixed solution of 171.4ml into (is wherein 8% because reaction system slurry is dense, so the total liquid of reaction system and amount of solid are 20g/8%=250g, the weight 21.5g of air-dry raw material in removal system, is amount of liquid 228.5g; Because hydrogen peroxide and Glacial acetic acid volume ratio are 1:3, can obtain the amount of 30% hydrogen peroxide of 57.1ml and the Glacial acetic acid of 171.4ml; For simplifying, calculate, set fluid density and be 1g/cm
3.), sealing, design temperature is 60 ℃ and processes 48h, reacts complete, material cleans to neutrality air-dry dry through deionization, obtains stalk core cellulose.
(3) stalk core cellulose making beating pre-treatment
Adopt QB/T-1463-1992 standard method, utilize PFI hollander to the pre-treatment of pulling an oar of " cloud fiber crops No. 1 " stalk core cellulose, and with Xiao Baier beating degree determinator, carry out the real time measure of this kind of slurry pulping degree, until the beating degree of " cloud fiber crops No. 1 " stalk core cellulose is 35
°sR, standby.
(4) nano oxidized Mierocrystalline cellulose preparation
Utilize mechanical stirring method, by the pretreated bone dry fiber element of 10g and the 4-acetylaminohydroxyphenylarsonic acid 2 that contains 1.5mmol, 2,6, the deionized water of the Textone of 6-tetramethyl piperidine-1-nitroxyl free radical and 50mmol mixes, and wherein the consumption of deionization consumption is 800ml, then at 30 ℃, stirs after 30min, the mass percent concentration that adds 5mmol is 8% chlorine bleach liquor, carries out selective oxidation reaction 12h.
After oxidizing reaction, the filter membrane that is 0.10um with aperture carries out solid-liquid separation, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, illustrate that precipitating is complete, by the each centrifugal 10min of 7000rpm repeatedly after absolute ethanol washing 3 times, lyophilize processing is until material complete drying obtains nano oxidized Mierocrystalline cellulose.
(5) preparation of dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body
In being housed, three mouthfuls of reaction flasks of reflux condensing tube, mechanical stirrer add the pretreated bone dry fiber element of 10g and 10g dimethyldiallylammonchloride chloride monomer; add the abundant solubilizing reaction monomer of a certain amount of deionized water; after fibrous suspension in bottle fully being stirred in the water bath with thermostatic control of 30 ℃ under nitrogen protection, add 0.05g ammonium persulphate and 0.05gN, N
,-methylene-bisacrylamide adds deionized water simultaneously, and making reaction solution cumulative volume is 1000ml, reaction 2h;
After graft copolymerization, network body gel is cut into the fritter of 1.00cm * 1.00cm * 0.10cm, with dehydrated alcohol to fritter synthetics repeatedly precipitating, wash to pH6, lyophilize, obtains dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel.
(6) preparation of stalk core cellulose base UCST temperature-sensitive hydrogel
It is in 0.1% nano oxidized cellulose aqueous solution that above-mentioned dried dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in to mass percent concentration, wait for to gel no longer after imbibition, mixture carries out lyophilize, sealing, obtain finished product---UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL mixture, i.e. industrial hemp stalk core cellulose Ji Wenmin composite aquogel.
(7) proterties of stalk core cellulose base UCST temperature-sensitive hydrogel
Gel sample is placed in respectively to the deionized water of differing temps, with taking out and wipe away surperficial moisture after gel swelling balance, weighs, swelling capacity (Swelling Ratio, SR) is:
SR=(m
s-m
d)/?m
d
In formula: m
sfor the quality after gel swelling balance, g; m
dfor the quality of gel dry state, g.
Dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL composite aquogel by above-mentioned reaction gained has UCST characteristic, and volume phase transition temperature is 42 ℃; When 45 ℃, 50 ℃ and 55 ℃, the equilibrium swelling degree of plural gel is respectively 96g/g, 129g/g and 193g/g, and the time that reaches equilibrium swelling degree is respectively 83min, 62min and 45min, illustrate at this more than volume phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and equilibrium swelling degree is larger.Temperature drops to 35 ℃ by 45 ℃, and the equilibrium swelling degree of composite aquogel drops to 11g/g by 96g/g, illustrates at volume phase transition temperature up and down, and product has good swelling/shrinkage.
embodiment 2:industrial hemp stalk core cellulose Ji Wenmin composite aquogel preparation method, concrete operations are as follows:
(1) melting process of " cloud fiber crops No. 1 " stalk core
Stalk core is 20% through air-dry processing controls moisture content, and air-dry thing is cut and grown into 40mm, and wide is 3mm, and thickness has raw material itself and determines, standby.
(2) extraction of stalk core cellulose
Adopting hydrogen peroxide and Glacial acetic acid mixed solution to extract Mierocrystalline cellulose to qualified stalk core processes, the ratio that wherein mass percent concentration be 35% hydrogen peroxide is 3:1 with the volume ratio of Glacial acetic acid is mixed and is made hydrogen peroxide and Glacial acetic acid mixed solution, the mass percent concentration of stalk core raw material in treatment solution is 15%, then at 100 ℃, process 12h, after completion of the reaction, material cleans to neutral and air-dry dry through deionization, obtains stalk core cellulose.
Concrete operations are: take the air-dry stalk core of 25.0g (because raw material water content is 20%, so over dry stalk core is 20g), put into digester, pouring 35% hydrogen peroxide of corresponding 81.2ml and the Glacial acetic acid mixed solution of 27.1ml into (is wherein 15% because reaction system slurry is dense, so the total liquid of reaction system and amount of solid are 20g/15%=133.3g, the weight 25.0g of air-dry raw material in removal system, is amount of liquid 108.3g; Because hydrogen peroxide and Glacial acetic acid volume ratio are 3:1, can obtain the amount of 30% hydrogen peroxide of 81.2ml and the Glacial acetic acid of 27.1ml; For simplifying, calculate, set fluid density and be 1g/cm
3.), sealing, design temperature is 100 ℃ and processes 12h, reacts complete, material cleans to neutrality air-dry dry through deionization, obtains stalk core cellulose.
(3) stalk core cellulose making beating pre-treatment
Adopt QB/T-1463-1992 standard method, utilize PFI hollander to the pre-treatment of pulling an oar of " cloud fiber crops No. 1 " stalk core cellulose, and with Xiao Baier beating degree determinator, carry out the real time measure of this kind of slurry pulping degree, until the beating degree of " cloud fiber crops No. 1 " stalk core cellulose is 90
°sR, standby.
(4) nano oxidized Mierocrystalline cellulose preparation
Utilize mechanical stirring method, by the pretreated bone dry fiber element of 10g and the 4-acetylaminohydroxyphenylarsonic acid 2 that contains 10mmol, 2,6, the deionized water of the Textone of 6-tetramethyl piperidine-1-nitroxyl free radical and 300mmol mixes, and wherein the consumption of deionization consumption is 1500ml, then at 60 ℃, stirs after 60min, the mass percent concentration that adds 60mmol is 12% chlorine bleach liquor, carries out selective oxidation reaction 240h;
After oxidizing reaction, the filter membrane that is 0.02um with aperture carries out solid-liquid separation, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, illustrate that precipitating is complete, by the each centrifugal 20min of 15000rpm repeatedly after absolute ethanol washing 5 times, lyophilize processing is until material complete drying obtains nano oxidized cellulose finished product.
(5) preparation of dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body
In three mouthfuls of reaction flasks of reflux condensing tube, mechanical stirrer are housed, add the pretreated bone dry fiber element of 10g and 100g dimethyl diallyl ammonium chloride, add the abundant solubilizing reaction monomer of a certain amount of deionized water.After fibrous suspension in bottle fully being stirred in the water bath with thermostatic control of 80 ℃ under nitrogen protection, add 0.25g ammonium persulphate and 2g N, N
,-methylene-bisacrylamide adds deionized water simultaneously, and making reaction solution cumulative volume is 2000ml, reaction 15h.
After graft copolymerization, network body gel is cut into the fritter of 2.00cm*2.00cm*1.00cm, with dehydrated alcohol to fritter synthetics repeatedly precipitating, wash to pH8, lyophilize, obtains dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel.
(6) realization of stalk core cellulose base UCST temperature-sensitive hydrogel
It is in 5.0% nano oxidized cellulose aqueous solution that above-mentioned dried dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in to mass percent concentration, wait for to gel no longer after imbibition, mixture carries out lyophilize, sealing, obtain finished product---UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL mixture, i.e. industrial hemp stalk core cellulose Ji Wenmin composite aquogel.
(7) proterties of stalk core cellulose base UCST temperature-sensitive hydrogel
Gel sample is placed in respectively to the deionized water of differing temps, with taking out and wipe away surperficial moisture after gel swelling balance, weighs.Swelling capacity (Swelling Ratio, SR) is:
SR=(m
s-m
d)/?m
d
In formula: m
sfor the quality after gel swelling balance, g; m
dfor the quality of gel dry state, g.
Dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL composite aquogel by above-mentioned reaction gained has UCST characteristic, and volume phase transition temperature is 47 ℃; When 50 ℃, 55 ℃ and 60 ℃, the equilibrium swelling degree of plural gel is respectively 306g/g, 488g/g and 556g/g, and the time that reaches equilibrium swelling degree is respectively 72min, 67min and 45min, illustrate at this more than volume phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and equilibrium swelling degree is larger.Temperature drops to 35 ℃ by 50 ℃, and the equilibrium swelling degree of composite aquogel drops to 49g/g by 306g/g, illustrates at volume phase transition temperature up and down, and product has good swelling/shrinkage.
embodiment 3:industrial hemp stalk core cellulose Ji Wenmin composite aquogel preparation method, concrete operations are as follows:
(1) melting process of " cloud fiber crops No. 1 " stalk core
Stalk core is 10% through air-dry processing controls moisture content, and air-dry thing is cut and grown into 20mm, and wide is 2mm, and thickness has raw material itself and determines, standby.
(2) extraction of stalk core cellulose
Adopting hydrogen peroxide and Glacial acetic acid mixed solution to extract Mierocrystalline cellulose to qualified stalk core processes, the ratio that wherein mass percent concentration be 32% hydrogen peroxide is 1:1 with the volume ratio of Glacial acetic acid is mixed and is made hydrogen peroxide and Glacial acetic acid mixed solution, the mass percent concentration of stalk core raw material in treatment solution is 10%, then at 80 ℃, process 36h, after completion of the reaction, material cleans to neutral and air-dry dry through deionization, obtains stalk core cellulose.
Concrete operations are: take the air-dry stalk core of 20.0g (because raw material water content is 10%, so over dry stalk core is 20g), put into digester, pouring 32% hydrogen peroxide of corresponding 90ml and the Glacial acetic acid mixed solution of 90ml into (is wherein 10% because reaction system slurry is dense, so the total liquid of reaction system and amount of solid are 20g/10%=200g, the weight 20.0g of air-dry raw material in removal system, is amount of liquid 180g; Because hydrogen peroxide and Glacial acetic acid volume ratio are 1:1, can obtain the amount of 30% hydrogen peroxide of 90ml and the Glacial acetic acid of 90ml; For simplifying, calculate, set fluid density and be 1g/cm
3.), sealing, design temperature is 80 ℃ and processes 36h, reacts complete, material cleans to neutrality air-dry dry through deionization, obtains stalk core cellulose.
(3) stalk core cellulose making beating pre-treatment
Adopt QB/T-1463-1992 standard method, utilize PFI hollander to the pre-treatment of pulling an oar of " cloud fiber crops No. 1 " stalk core cellulose, and with Xiao Baier beating degree determinator, carry out the real time measure of this kind of slurry pulping degree, until the beating degree of " cloud fiber crops No. 1 " stalk core cellulose is 80
°sR, standby.
(4) nano oxidized Mierocrystalline cellulose preparation
Utilize mechanical stirring method, by the pretreated bone dry fiber element of 10g and the 4-acetylaminohydroxyphenylarsonic acid 2 that contains 5.5mmol, 2,6, the deionized water of the Textone of 6-tetramethyl piperidine-1-nitroxyl free radical and 200mmol mixes, and wherein the consumption of deionization consumption is 1000ml, then at 45 ℃, stirs after 40min, 10% chlorine bleach liquor who adds 30mmol, carries out selective oxidation reaction 120h;
After oxidizing reaction, the filter membrane that is 0.05um with aperture carries out solid-liquid separation, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, illustrate that precipitating is complete, by the each centrifugal 15min of 10000rpm repeatedly after absolute ethanol washing 4 times, lyophilize processing is until material complete drying obtains nano oxidized Mierocrystalline cellulose.
(5) preparation of dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body
In being housed, three mouthfuls of reaction flasks of reflux condensing tube, mechanical stirrer add the pretreated bone dry fiber element of 10g and 50g dimethyl diallyl ammonium chloride; add the abundant solubilizing reaction monomer of a certain amount of deionized water; after fibrous suspension in bottle fully being stirred in the water bath with thermostatic control of 50 ℃ under nitrogen protection, add 0.15g ammonium persulphate and 0.50gN, N
,-methylene-bisacrylamide adds deionized water simultaneously, and making reaction solution cumulative volume is 1500ml, reaction 8h;
After graft copolymerization, network body gel is cut into the fritter of 1.50cm * 1.50cm * 0.50cm, with dehydrated alcohol to fritter synthetics repeatedly precipitating, wash to Ph7, lyophilize, obtains dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel.
(6) realization of stalk core cellulose base UCST temperature-sensitive hydrogel
It is in 3.0% nano oxidized cellulose aqueous solution that above-mentioned dried dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in to mass percent concentration, wait for to gel no longer after imbibition, mixture carries out lyophilize, sealing, obtain finished product---UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL mixture, i.e. industrial hemp stalk core cellulose Ji Wenmin composite aquogel.
(7) proterties of stalk core cellulose base UCST temperature-sensitive hydrogel
Gel sample is placed in respectively to the deionized water of differing temps, with taking out and wipe away surperficial moisture after gel swelling balance, weighs.Swelling capacity (Swelling Ratio, SR) is:
SR=(m
s-m
d)/?m
d
In formula: m
sfor the quality after gel swelling balance, g; m
dfor the quality of gel dry state, g.
Dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL composite aquogel by above-mentioned reaction gained has UCST characteristic, and volume phase transition temperature is 38 ℃; When 40 ℃, 45 ℃ and 55 ℃, the equilibrium swelling degree of plural gel is respectively 277g/g, 334g/g and 508g/g, and the time that reaches equilibrium swelling degree is respectively 50min, 43min and 30min, illustrate at this more than volume phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and equilibrium swelling degree is larger.Temperature drops to 30 ℃ by 40 ℃, and the equilibrium swelling degree of composite aquogel drops to 20g/g by 277g/g, illustrates at volume phase transition temperature up and down, and product has good swelling/shrinkage.
Claims (2)
1. a preparation method for industrial hemp stalk core cellulose Ji Wenmin composite aquogel, is characterized in that carrying out as follows:
1. industrial hemp stalk core segment is got the raw materials ready through air-dry shearing after dry, and raw material adopts Glacial acetic acid/hydrogen peroxide method extraction stalk core cellulose, then utilizes mechanical hollander to the Mierocrystalline cellulose pre-treatment of pulling an oar;
2. adopt piperidines oxynitride free radical/co-oxidation system method to carry out C to pretreated stalk core cellulose
6the selective oxidation of position hydroxyl, oxidation products is by solid-liquid separation, and liquid portion carries out precipitating, centrifugation and washing with dehydrated alcohol, and lyophilize obtains nano oxidized Mierocrystalline cellulose;
3. adopt aqueous solution polymerization method to carry out graft copolymerization to pretreated stalk core cellulose, select ammonium persulphate as initiator, with N, N
'-methylene-bisacrylamide is linking agent, select dimethyl diallyl ammonium chloride to complete as cationic monomer simultaneously, multipolymer is carried out to precipitating, washing, lyophilize with dehydrated alcohol, obtain dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel;
4. dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in nano oxidized cellulose aqueous solution, until no longer imbibition of gel, obtain UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL and independently fill composite aquogel, plural gel is carried out to lyophilize, sealing, obtains industrial hemp stalk core cellulose Ji Wenmin composite aquogel.
2. the preparation method of industrial hemp stalk core cellulose Ji Wenmin composite aquogel according to claim 1, is characterized in that concrete operations are as follows:
1. the industrial hemp stalk core after air-dry processing is sheared and got the raw materials ready, system is grown into 10～40mm, and wide is the raw material of 1～3mm;
2. stalk core raw material adopts hydrogen peroxide/ice acetic acid method to extract the Mierocrystalline cellulose of raw material, in stalk core raw material, add hydrogen peroxide and Glacial acetic acid mixed solution, after mixing, after processing 12～48h, 60～100 ℃ of temperature take out sample, deionization cleans to neutral, dry, obtain industrial hemp stalk core cellulose, standby, wherein the mass percent concentration of over dry stalk core raw material in mixed solution is 8～15%, and hydrogen peroxide and Glacial acetic acid mixed solution are that mass percent concentration is that 30～35% hydrogen peroxide mixes and makes for the ratio of 3:1～1:3 by volume with Glacial acetic acid;
3. industrial hemp stalk core cellulose utilization machinery beating method carries out pre-treatment, adopt QB/T-1463-1992 standard method, industrial hemp stalk core cellulose is pulled an oar, and with beating degree determinator, carry out the real time measure of slurry pulping degree, the beating degree that wherein pre-treatment degree is stalk core cellulose is 35～90
°sR;
4. in pretreated over dry stalk core cellulose, add and contain 4-acetylaminohydroxyphenylarsonic acid 2, 2, 6, the deionized water of 6-tetramethyl piperidine-1-nitroxyl free radical and Textone, 4-acetylaminohydroxyphenylarsonic acid 2, 2, 6, 6-tetramethyl piperidine-1-nitroxyl free radical is 0.15mmol:1g～1.00mmol:1g with the ratio of over dry stalk core cellulose, Textone is 5.0mmol:1g～30.0mmol:1g with the ratio of over dry stalk core cellulose, deionization consumption is 80ml:1g～150ml:1g with the ratio of over dry stalk core cellulose, then at 30～60 ℃, stir after 30～60min, the chlorine bleach liquor that interpolation mass percent concentration is 8%～12%, its consumption is 0.5mmol:1g～6.0mmol:1g with the ratio of over dry stalk core cellulose, carry out after selective oxidation reaction 12～240h, with the filter membrane that aperture is 0.02～0.10 μ m, carry out solid-liquid separation, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, with absolute ethanol washing and under 7000～15000rpm centrifugal 10～20min, repeatedly after 3～5 times, lyophilize processing is until material complete drying, obtain nano oxidized Mierocrystalline cellulose,
5. step 3. pretreated over dry stalk core cellulose by aqueous solution graft copolymerization, make dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body, by dimethyldiallylammonchloride chloride monomer and over dry stalk core cellulose mass ratio, be 1:1～10:1, initiator ammonium persulfate and over dry stalk core cellulose mass ratio are 0.005:1～0.025:1, linking agent N, N
,-methylene-bisacrylamide and dimethyldiallylammonchloride chloride monomer mass ratio are 0.005:1～0.02:1,30～80 ℃ of temperature of reaction, reaction times is 2.0～15.0h, over dry stalk core cellulose quality is 1g:100ml～1g:200ml with the ratio of reaction liquid cumulative volume, under logical nitrogen condition, carry out graft copolymerization, after completion of the reaction, network body gel is cut into small pieces, with dehydrated alcohol, fritter synthetics is carried out repeatedly precipitating, washed to pH6～8, lyophilize, obtains dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel;
6. dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in to mass percent concentration and is in 0.1～5.0% nano oxidized cellulose aqueous solution, until no longer imbibition of gel, mixture is carried out to lyophilize, sealing, obtains UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL mixture.
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| CN104387618A (en) * | 2014-10-30 | 2015-03-04 | 昆明理工大学 | Preparation method of maize leaf holocellulose derivative blended gel |
| CN104387617A (en) * | 2014-10-30 | 2015-03-04 | 昆明理工大学 | Preparation method of corn stalk modified cellulose gel |
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| CN106832346A (en) * | 2017-02-17 | 2017-06-13 | 南通苏源化纤有限公司 | Novel type of sucrose oxycellulose base temperature-sensitive hydrogel |
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