CN103554372B - The preparation method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel - Google Patents
The preparation method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel Download PDFInfo
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Abstract
The invention discloses a kind of method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel, hemp stalk core part after air-dry is got the raw materials ready through shearing, Mierocrystalline cellulose extraction, making beating pre-treatment are carried out to stalk core, then adopt piperidines nitroxide radical/co-oxidation system method to carry out selective oxidation to the pretreated Mierocrystalline cellulose of making beating, obtain nano oxidized Mierocrystalline cellulose; Meanwhile, adopt aqueous solution polymerization method to carry out graft copolymerization to pretreated stalk core cellulose, obtain dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body; Then immerse in nano oxidized cellulose aqueous solution, obtain industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel; Obtained industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel has UCST characteristic, and Volume-phase transition temperature is within the scope of 35 ~ 50 DEG C; Fix at medicine controlled release carrier, organizational project, organized enzyme, the many aspects such as chemical conversion element play good application prospect.
Description
Technical field
The present invention relates to a kind of Technology 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 be made up of high molecular three-dimensional network and water
[1].According to the response condition that hydrogel stimulates to external world, conventional hydrogels and intelligent aqueous gel capable can be divided into.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 in the embedding etc. of the Co ntrolled release system of chemical converter, memory cell switch, sensor, medicine, artificial muscle, chemical storage device, molecular separation system, organized enzyme
[3], thus 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 receives extensive concern and the further investigation of multiple Application Areas gradually due to the phase in version behavior of uniqueness.As a member of Thermo-sensitive water-keeping material, LCST(Low Critical Solution Temperature) macromolecular chain can be there is at relatively high temperatures and assemble and shrink, swelling capacity sharply be declined, and when low temperature, imbibition swelling behavior occurs in type resin
[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 cause the great interest of people, research about LCST type water-keeping material emerges in an endless stream, and all obtains detailed probing into and developing from aspects such as Theory and applications.In addition, contrary with LCST shaped material, UCST(Upper Critical Solution Temperature) type hydrogel has a high Kraft point, lower than the gel generation volumetric shrinkage of swollen during this temperature, be in and release water state, higher than then swollen once again during this temperature, be in water suction state.Compared with LCST type, the correlative study of UCST type water-keeping material focuses mostly in the synthesis family macromolecule field of non-renewable recycle, such as, and for, the degradable natural polymer of product renewable for raw material, Mierocrystalline cellulose, 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 comparatively large, and so, in numerous floristics, selection is applicable to the underlying issue that the cellulosic material of UCST type hydrogel is the application.
Industrial hemp is the Hemp Varieties that tetrahydrocannabinol (THC) content meets the EU criteria (THC<0.3%) extensively adopted in the world
[6].Industrial hemp does not have drugs utility value, its objective is the output improving fiber, seed or oil to greatest extent, improves its quality, and therefore this kind of hemp mainly carries 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]), play an important role in the extensive fiber production such as weaving, papermaking, natural-fiber composite material; And the fiber of stalk core segment is because the limitation of its length is (greatly about about 0.5mm
[8]) application in multiple 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 be hemp stalk core as the one in plant material, 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, prove that industrial hemp stalk core can be used as the initial feed of Cellulose functional materials from feed composition.
Prepare functional type temperature-sensitive hydrogel not harsh to the length requirement of raw fibre, so under the research of cellulose-based UCST type temperature-sensitive hydrogel remains 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, the road of stalk core fibre high value added utilization can also be expanded.
Reference
[1] Yan Youwang. progress in Intelligent Hydrogel [J]. chemistry teaching, 2009, (10): 74-76.
[2] Liu Xiaohua, Wang Xiaogong, Liu Deshan. the progress [J] of progress in Intelligent Hydrogel structure and Response Mechanism. chemistry circular, 2000, (10): 1-6.
[3] Zhao Yuqiang, Zhang Zhibin, Liu Ning etc. the application [J] of intelligent aqueous gel capable. modern chemical industry, 2007,27(3): 66-69.
[4] Yang Jie, Huo Danqun etc. the progress [J] of Thermo-sensitive PNIPAAm porous aquagel preparation method. 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. the feature of industrial hemp new variety " cloud fiber crops No. 1 " and cultivation technique [J]. 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. the reviews and prospects [J] of world industry hemp stalk pulp and paper industry study and practice. 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 not having 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 up to now is substantially still in space state.Therefore, the invention provides a kind of preparation method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel, the method utilize aboundresources and comparatively weak " cloud fiber crops No. 1 " the stalk core of 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 carries out shearing and to get the raw materials ready process after air-dry;
2. Glacial acetic acid/hydrogen peroxide method is adopted to carry out Mierocrystalline cellulose extraction to the stalk core of getting the raw materials ready qualified;
3. mechanical hollander is adopted to pull an oar pre-treatment to stalk core cellulose;
4. employing piperidines nitroxide radical/being total to oxygen system carries out C to pretreated stalk core cellulose
6the selective oxidation of position hydroxyl, oxidation products is by solid-liquid separation, and liquid portion dehydrated alcohol carries out precipitating, centrifugation and washing, lyophilize, obtains nano oxidized Mierocrystalline cellulose;
5. adopt aqueous solution polymerization method to carry out graft copolymerization to pretreated stalk core cellulose, namely select ammonium persulphate as initiator, with N, N
'-methylene-bisacrylamide is linking agent, select dimethyl diallyl ammonium chloride to come as cationic monomer simultaneously, precipitating, washing, lyophilize are carried out to multipolymer dehydrated alcohol, obtains 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 gel no longer imbibition, obtain UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL and independently fill mixture, lyophilize is carried out to mixture, sealing, obtains industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel finished product.
The preparation method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel 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 process, wherein the moisture of air-dry raw material is different according to different areas Various Seasonal atmospheric moisture difference, general moisture control is in the scope of 7 ~ 20%, 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, hydrogen peroxide and Glacial acetic acid mixed solution is added in stalk core raw material, after temperature 60 ~ 100 DEG C process 12 ~ 48h, sample is taken out after mixing, deionization cleaning is to neutral, air-dry drying, obtain industrial hemp stalk core cellulose, for subsequent use, wherein the mass percent concentration of over dry stalk core raw material in mixed solution is 8 ~ 15%, hydrogen peroxide and Glacial acetic acid mixed solution to be mass percent concentration be 30 ~ 35% hydrogen peroxide and Glacial acetic acid obtain for the ratio of 3:1 ~ 1:3 mix by volume;
3. in order to improve cellulosic reactivity worth, adopt QB/T-1463-1992 standard method, PFI hollander is utilized to carry out making beating pre-treatment to industrial hemp stalk core cellulose, and the real time measure of this kind of slurry pulping degree is carried out with Xiao Baier beating degree determinator, 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. nano oxidized Mierocrystalline cellulose process is prepared as follows: add in over dry stalk core cellulose after the pre-treatment containing 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 after stirring 30 ~ 60min at 30 ~ 60 DEG C, 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, solid-liquid separation is carried out with the filter membrane that aperture is 0.02 ~ 0.10 μm, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, explanation precipitating is complete, centrifugal 10 ~ 20min with absolute ethanol washing and under 7000 ~ 15000rpm, repeatedly after 3 ~ 5 times, lyophilize process, until material complete drying, obtains nano oxidized Mierocrystalline cellulose,
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 DEG C, reaction times is 2.0 ~ 15.0h, and over dry stalk core cellulose quality controls 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, precipitating is carried out repeatedly to fritter synthetics with dehydrated alcohol, washs to pH6 ~ 8, lyophilize, obtain dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel;
6. dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel being immersed in mass percent concentration is in the nano oxidized cellulose aqueous solution of 0.1 ~ 5.0%, until gel no longer imbibition, lyophilize is carried out to mixture, sealing, obtain UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL mixture, i.e. industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel of the present invention.
The invention has the beneficial effects as follows: using agricultural wastes---industrial hemp stalk core is as cellulose origin, portion of cellulose crystallizing field can be destroyed well by machinery making beating mode, increase the quantity of activity hydroxy, improve subsequent reactions ability, prepare negatively charged ion nanoscale Mierocrystalline cellulose and positively charged ion dimethyl diallyl ammonium chloride Mierocrystalline cellulose network polymer respectively, independently fill formation by electrostatic attraction and Hyarogen-bonding and there is UCST temperature sensitive type cellulose base mixture hydrogel.Cellulose family natural polymer temperature-sensitive hydrogel has the general character of synthesis high score subclass hydrogel, can fix, plays good application prospect in chemical conversion element etc. at medicine controlled release carrier, organizational project, organized enzyme.Meanwhile, cellulose base temperature-sensitive hydrogel also possess hypotoxicity, good biocompatibility, to advantages such as environment sensitive and cheap prices, be novel, the green intelligent material of a class of mainstream development now; The cellulosic functionalization of hemp stalk core that is embodied as of this cellulose base temperature sensing material develops proposition feasible scheme, also for the extension of industrial hemp industrial chain and expansion provide new development space, meanwhile, compensate for the vacancy of natural polymer subbase UCST type temperature sensing material research.
Obtain industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel by the method and have UCST characteristic, Volume-phase transition temperature is within the scope of 35 ~ 50 DEG C; More than this Volume-phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and Equilibrium swelling ratio is larger; Upper and lower in Volume-phase transition temperature, product have good swelling/shrinkage; Can fix at medicine controlled release carrier, organizational project, organized enzyme, the many aspects such as chemical conversion element play good application prospect.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but scope is not limited to described content.
Embodiment 1: the preparation method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel, 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, for subsequent use.
(2) extraction of stalk core cellulose
Hydrogen peroxide and Glacial acetic acid mixed solution is adopted to carry out the process of extraction Mierocrystalline cellulose to qualified stalk core, wherein to be 30% hydrogen peroxide obtain hydrogen peroxide and Glacial acetic acid mixed solution for the ratio of 1:3 mix with Glacial acetic acid to mass percent concentration by volume, the mass percent concentration of stalk core raw material in mixed solution is 8%, then at 60 DEG C, 48h is processed, after completion of the reaction, material cleans to neutrality and air-dry drying through deionization, obtains stalk core cellulose.
Concrete operations are: take the air-dry stalk core of 21.5g (because feed moisture content is 7%, so over dry stalk core is 20g), put into digester, the Glacial acetic acid mixed solution pouring 30% hydrogen peroxide of corresponding 57.1ml and 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 the dry raw material of removal system apoplexy, is amount of liquid 228.5g; Because hydrogen peroxide and Glacial acetic acid volume ratio are 1:3, the amount of 30% hydrogen peroxide of 57.1ml and the Glacial acetic acid of 171.4ml can be obtained; Calculate for simplifying, setting fluid density is 1g/cm
3.), sealing, design temperature is 60 DEG C of process 48h, reacts complete, and material cleans to neutrality and air-dry drying through deionization, obtains stalk core cellulose.
(3) stalk core cellulose making beating pre-treatment
Adopt QB/T-1463-1992 standard method, PFI hollander is utilized to carry out making beating pre-treatment to " cloud fiber crops No. 1 " stalk core cellulose, and carry out the real time measure of this kind of slurry pulping degree with Xiao Baier beating degree determinator, until the beating degree of " cloud fiber crops No. 1 " stalk core cellulose is 35
°sR, for subsequent use.
(4) nano oxidized Mierocrystalline cellulose preparation
Utilize mechanical agitation methods, by pretreated for 10g bone dry fiber element and the 4-acetylaminohydroxyphenylarsonic acid 2 containing 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, after then stirring 30min at 30 DEG C, the mass percent concentration adding 5mmol is 8% chlorine bleach liquor, carries out selective oxidation reaction 12h.
After oxidizing reaction, solid-liquid separation is carried out with the filter membrane that aperture is 0.10um, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, explanation precipitating is complete, after each centrifugal 10min of 7000rpm repeatedly absolute ethanol washing 3 times, lyophilize process, until material complete drying, obtains nano oxidized Mierocrystalline cellulose.
(5) preparation of dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body
The pretreated bone dry fiber element of 10g and 10g dimethyldiallylammonchloride chloride monomer is added in three mouthfuls of reaction flasks that reflux condensing tube, mechanical stirrer are housed; add the abundant solubilizing reaction monomer of a certain amount of deionized water; 0.05g ammonium persulphate and 0.05gN, N is added after fully being stirred in the water bath with thermostatic control of 30 DEG C by fibrous suspension in bottle under nitrogen protection
,-methylene-bisacrylamide, adds deionized water simultaneously, makes reaction solution cumulative volume be 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 the nano oxidized cellulose aqueous solution of 0.1% that above-mentioned dried dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in mass percent concentration, wait until 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 base temperature-sensitivcomposite composite hydrogel.
(7) proterties of stalk core cellulose base UCST temperature-sensitive hydrogel
Gel sample is placed in respectively the deionized water of differing temps, take out after band gel swelling balance and wipe surperficial moisture away, weigh, 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.
Have UCST characteristic by the dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL composite aquogel of above-mentioned reaction gained, Volume-phase transition temperature is 42 DEG C; When 45 DEG C, 50 DEG C and 55 DEG C, the Equilibrium swelling ratio of plural gel is respectively 96g/g, 129g/g and 193g/g, and the time reaching Equilibrium swelling ratio is respectively 83min, 62min and 45min, illustrates more than this Volume-phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and Equilibrium swelling ratio is larger.Temperature drops to 35 DEG C by 45 DEG C, and the Equilibrium swelling ratio of composite aquogel drops to 11g/g by 96g/g, illustrates in Volume-phase transition temperature upper and lower, product have good swelling/shrinkage.
embodiment 2:industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel 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, for subsequent use.
(2) extraction of stalk core cellulose
Hydrogen peroxide and Glacial acetic acid mixed solution is adopted to carry out the process of extraction Mierocrystalline cellulose to qualified stalk core, the ratio that wherein mass percent concentration is 35% hydrogen peroxide is 3:1 with the volume ratio of Glacial acetic acid mixes obtained 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 DEG C, 12h is processed, after completion of the reaction, material cleans to neutrality and air-dry drying through deionization, obtains stalk core cellulose.
Concrete operations are: take the air-dry stalk core of 25.0g (because feed moisture content is 20%, so over dry stalk core is 20g), put into digester, the Glacial acetic acid mixed solution pouring 35% hydrogen peroxide of corresponding 81.2ml and 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 the dry raw material of removal system apoplexy, is amount of liquid 108.3g; Because hydrogen peroxide and Glacial acetic acid volume ratio are 3:1, the amount of 30% hydrogen peroxide of 81.2ml and the Glacial acetic acid of 27.1ml can be obtained; Calculate for simplifying, setting fluid density is 1g/cm
3.), sealing, design temperature is 100 DEG C of process 12h, reacts complete, and material cleans to neutrality and air-dry drying through deionization, obtains stalk core cellulose.
(3) stalk core cellulose making beating pre-treatment
Adopt QB/T-1463-1992 standard method, PFI hollander is utilized to carry out making beating pre-treatment to " cloud fiber crops No. 1 " stalk core cellulose, and carry out the real time measure of this kind of slurry pulping degree with Xiao Baier beating degree determinator, until the beating degree of " cloud fiber crops No. 1 " stalk core cellulose is 90
°sR, for subsequent use.
(4) nano oxidized Mierocrystalline cellulose preparation
Utilize mechanical agitation methods, by pretreated for 10g bone dry fiber element and the 4-acetylaminohydroxyphenylarsonic acid 2 containing 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, after then stirring 60min at 60 DEG C, the mass percent concentration adding 60mmol is 12% chlorine bleach liquor, carries out selective oxidation reaction 240h;
After oxidizing reaction, solid-liquid separation is carried out with the filter membrane that aperture is 0.02um, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, explanation precipitating is complete, after each centrifugal 20min of 15000rpm repeatedly absolute ethanol washing 5 times, lyophilize process, 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 that 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.0.25g ammonium persulphate and 2g N, N is added after fully being stirred in the water bath with thermostatic control of 80 DEG C by fibrous suspension in bottle under nitrogen protection
,-methylene-bisacrylamide, adds deionized water simultaneously, makes reaction solution cumulative volume be 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 the nano oxidized cellulose aqueous solution of 5.0% that above-mentioned dried dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in mass percent concentration, wait until 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 base temperature-sensitivcomposite composite hydrogel.
(7) proterties of stalk core cellulose base UCST temperature-sensitive hydrogel
Gel sample is placed in respectively the deionized water of differing temps, takes out after band gel swelling balance and wipe surperficial moisture away, weighing.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.
Have UCST characteristic by the dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL composite aquogel of above-mentioned reaction gained, Volume-phase transition temperature is 47 DEG C; When 50 DEG C, 55 DEG C and 60 DEG C, the Equilibrium swelling ratio of plural gel is respectively 306g/g, 488g/g and 556g/g, and the time reaching Equilibrium swelling ratio is respectively 72min, 67min and 45min, illustrates more than this Volume-phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and Equilibrium swelling ratio is larger.Temperature drops to 35 DEG C by 50 DEG C, and the Equilibrium swelling ratio of composite aquogel drops to 49g/g by 306g/g, illustrates in Volume-phase transition temperature upper and lower, product have good swelling/shrinkage.
embodiment 3:industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel 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, for subsequent use.
(2) extraction of stalk core cellulose
Hydrogen peroxide and Glacial acetic acid mixed solution is adopted to carry out the process of extraction Mierocrystalline cellulose to qualified stalk core, the ratio that wherein mass percent concentration is 32% hydrogen peroxide is 1:1 with the volume ratio of Glacial acetic acid mixes obtained 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 DEG C, 36h is processed, after completion of the reaction, material cleans to neutrality and air-dry drying through deionization, obtains stalk core cellulose.
Concrete operations are: take the air-dry stalk core of 20.0g (because feed moisture content is 10%, so over dry stalk core is 20g), put into digester, the Glacial acetic acid mixed solution pouring 32% hydrogen peroxide of corresponding 90ml and 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 the dry raw material of removal system apoplexy, is amount of liquid 180g; Because hydrogen peroxide and Glacial acetic acid volume ratio are 1:1, the amount of 30% hydrogen peroxide of 90ml and the Glacial acetic acid of 90ml can be obtained; Calculate for simplifying, setting fluid density is 1g/cm
3.), sealing, design temperature is 80 DEG C of process 36h, reacts complete, and material cleans to neutrality and air-dry drying through deionization, obtains stalk core cellulose.
(3) stalk core cellulose making beating pre-treatment
Adopt QB/T-1463-1992 standard method, PFI hollander is utilized to carry out making beating pre-treatment to " cloud fiber crops No. 1 " stalk core cellulose, and carry out the real time measure of this kind of slurry pulping degree with Xiao Baier beating degree determinator, until the beating degree of " cloud fiber crops No. 1 " stalk core cellulose is 80
°sR, for subsequent use.
(4) nano oxidized Mierocrystalline cellulose preparation
Utilize mechanical agitation methods, by pretreated for 10g bone dry fiber element and the 4-acetylaminohydroxyphenylarsonic acid 2 containing 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, after then stirring 40min at 45 DEG C, add 10% chlorine bleach liquor of 30mmol, carry out selective oxidation reaction 120h;
After oxidizing reaction, solid-liquid separation is carried out with the filter membrane that aperture is 0.05um, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, explanation precipitating is complete, after each centrifugal 15min of 10000rpm repeatedly absolute ethanol washing 4 times, lyophilize process, until material complete drying, obtains nano oxidized Mierocrystalline cellulose.
(5) preparation of dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body
The pretreated bone dry fiber element of 10g and 50g dimethyl diallyl ammonium chloride is added in three mouthfuls of reaction flasks that reflux condensing tube, mechanical stirrer are housed; add the abundant solubilizing reaction monomer of a certain amount of deionized water; 0.15g ammonium persulphate and 0.50gN, N is added after fully being stirred in the water bath with thermostatic control of 50 DEG C by fibrous suspension in bottle under nitrogen protection
,-methylene-bisacrylamide, adds deionized water simultaneously, makes reaction solution cumulative volume be 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 the nano oxidized cellulose aqueous solution of 3.0% that above-mentioned dried dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel is immersed in mass percent concentration, wait until 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 base temperature-sensitivcomposite composite hydrogel.
(7) proterties of stalk core cellulose base UCST temperature-sensitive hydrogel
Gel sample is placed in respectively the deionized water of differing temps, takes out after band gel swelling balance and wipe surperficial moisture away, weighing.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.
Have UCST characteristic by the dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL composite aquogel of above-mentioned reaction gained, Volume-phase transition temperature is 38 DEG C; When 40 DEG C, 45 DEG C and 55 DEG C, the Equilibrium swelling ratio of plural gel is respectively 277g/g, 334g/g and 508g/g, and the time reaching Equilibrium swelling ratio is respectively 50min, 43min and 30min, illustrates more than this Volume-phase transition temperature, when temperature is higher, it is shorter that composite aquogel reaches the swelling equilibrium time, and Equilibrium swelling ratio is larger.Temperature drops to 30 DEG C by 40 DEG C, and the Equilibrium swelling ratio of composite aquogel drops to 20g/g by 277g/g, illustrates in Volume-phase transition temperature upper and lower, product have good swelling/shrinkage.
Claims (2)
1. a preparation method for industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel, is characterized in that carrying out as follows:
1. industrial hemp stalk core segment carries out shearing and gets the raw materials ready after air-dry drying, and raw material adopts Glacial acetic acid/hydrogen peroxide method to extract stalk core cellulose, then utilizes mechanical hollander to carry out making beating pre-treatment to Mierocrystalline cellulose;
2. piperidines nitroxide radical/co-oxidation system method is adopted 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 dehydrated alcohol carries out precipitating, centrifugation and washing, lyophilize, obtains nano oxidized Mierocrystalline cellulose;
3. adopt aqueous solution polymerization method to carry out graft copolymerization to pretreated stalk core cellulose, namely select ammonium persulphate as initiator, with N, N
'-methylene-bisacrylamide is linking agent, select dimethyl diallyl ammonium chloride to come as cationic monomer simultaneously, precipitating, washing, lyophilize are carried out to multipolymer dehydrated alcohol, obtains 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 gel no longer imbibition, obtain UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL self-assembly composite aquogel, lyophilize is carried out to plural gel, sealing, obtains industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel.
2. the preparation method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel according to claim 1, is characterized in that concrete operations are as follows:
1. the industrial hemp stalk core after air-dry process is carried out shearing to get the raw materials ready, system grows 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, hydrogen peroxide and Glacial acetic acid mixed solution is added in stalk core raw material, after temperature 60 ~ 100 DEG C process 12 ~ 48h, sample is taken out after mixing, washed with de-ionized water is to neutral, dry, obtain industrial hemp stalk core cellulose, for subsequent use, wherein the mass percent concentration of over dry stalk core raw material in mixed solution is 8 ~ 15%, hydrogen peroxide and Glacial acetic acid mixed solution to be mass percent concentration be 30 ~ 35% hydrogen peroxide and Glacial acetic acid obtain for the ratio of 3:1 ~ 1:3 mix by volume;
3. industrial hemp stalk core cellulose utilizes mechanical beating method to carry out pre-treatment, adopt QB/T-1463-1992 standard method, industrial hemp stalk core cellulose is pulled an oar, and the real time measure of slurry pulping degree is carried out with beating degree determinator, wherein pre-treatment degree is the beating degree of stalk core cellulose is 35 ~ 90
°sR;
4. add containing 4-acetylaminohydroxyphenylarsonic acid 2 in stalk core cellulose after the pre-treatment, 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, deionized water consumption is 80ml:1g ~ 150ml:1g with the ratio of over dry stalk core cellulose, then after stirring 30 ~ 60min at 30 ~ 60 DEG C, adding mass percent concentration is the chlorine bleach liquor of 8% ~ 12%, its consumption is 0.5mmol:1g ~ 6.0mmol:1g with the ratio of over dry stalk core cellulose, after carrying out selective oxidation reaction 12 ~ 240h, solid-liquid separation is carried out with the filter membrane that aperture is 0.02 ~ 0.10 μm, liquid portion pours dehydrated alcohol into until white emulsion state appears in transparent liquid, centrifugal 10 ~ 20min with absolute ethanol washing and under 7000 ~ 15000rpm, repeatedly after 3 ~ 5 times, lyophilize process is until material complete drying, obtain nano oxidized Mierocrystalline cellulose,
5. step 3. pretreated stalk core cellulose obtain dimethyl diallyl ammonium chloride Mierocrystalline cellulose network body by aqueous solution graft copolymerization, be 1:1 ~ 10:1 by dimethyldiallylammonchloride chloride monomer and over dry stalk core cellulose mass ratio, 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, temperature of reaction 30 ~ 80 DEG C, 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, graft copolymerization is carried out under logical nitrogen condition, after completion of the reaction, network body gel is cut into small pieces, precipitating is carried out repeatedly to fritter synthetics with dehydrated alcohol, washs to pH6 ~ 8, lyophilize, obtains dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel;
6. dimethyl diallyl ammonium chloride Mierocrystalline cellulose network soma gel being immersed in mass percent concentration is in the nano oxidized cellulose aqueous solution of 0.1 ~ 5.0%, until gel no longer imbibition, lyophilize is carried out to mixture, sealing, obtains UCST temperature sensitive type dimethyl diallyl ammonium chloride cellulose/nanometer SURGICEL mixture.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102587138A (en) * | 2011-12-19 | 2012-07-18 | 陕西科技大学 | Temperature-sensitive antibacterial finishing agent as well as preparation method and use method thereof |
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| CN102587138A (en) * | 2011-12-19 | 2012-07-18 | 陕西科技大学 | Temperature-sensitive antibacterial finishing agent as well as preparation method and use method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 9759. * |
| Influence of TEMPO-Mediated Oxidation on Properties of Hemp Fibers;Jovana Milanovic, et al.;《Industrial & Engineering Chemistry Research》;20120702;第51卷(第29期);9750-9759 * |
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