CN104086785A - Method for preparing composite hydrogel through modifying bamboo shoot leftovers and application of composite hydrogel - Google Patents
Method for preparing composite hydrogel through modifying bamboo shoot leftovers and application of composite hydrogel Download PDFInfo
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- CN104086785A CN104086785A CN201410281083.6A CN201410281083A CN104086785A CN 104086785 A CN104086785 A CN 104086785A CN 201410281083 A CN201410281083 A CN 201410281083A CN 104086785 A CN104086785 A CN 104086785A
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Abstract
The invention provides a method for preparing composite hydrogel through modifying bamboo shoot leftovers and an application of the composite hydrogel. An adsorption material is prepared by the steps of extracting cellulose from the bamboo shoot leftovers, then modifying by sodium chloroacetate, carrying out epoxy chloropropane cross-linking, followed by carrying out inverse suspension polymerization, and finally carrying out freeze drying. The prepared hydrogel beads are used as a bio-adsorbent, methylene blue is used as a dye model molecule, an adsorption effect on methylene blue is studied, and a theoretical foundation is laid for adsorption and sustained release of the hydrogel. The novel composite hydrogel prepared by utilizing the bamboo shoot processing waste leftovers is rich in raw material sources and low in cost, can achieve waste utilization, and promotes recycling economy; and the prepared hydrogel can be applied to adsorption of dye wastewater and adsorption and sustained release of a model drug, reduces pollution of bamboo shoot leftover arbitrarily discarding on the environment, and can play a certain role in promoting green development of ecological resources.
Description
Technical field
The present invention relates to method and the application thereof of composite aquogel, be specifically related to a kind of bamboo shoots tankage be carried out to method and the application thereof that composite aquogel is prepared in modification.
Background technology
Bamboo shoots (Bamboo shoot) are a kind of aboundresources, the edible plants that output is higher.Bamboo shoots unique bud stem that expands that to be bamboos have in early days of growth, its matter is tender delicious, contains abundant essential amino acid, mineral element, VITAMIN and the fibre composition that is difficult to be digested by human body etc., is a kind of natural food materials of nutritive value that have.Because the plantation of forest land bamboo shoots in recent years is constantly applied, since 2010,5,000,000-6,000,000 tons, every annual output bamboo shoots, except 40% marketing fresh, all the other are all for the processing of can bamboo shoot and dried bamboo shoots.
In bamboo shoots for make the bamboo shoot meat of the bamboo shoot products such as Bamboo shoots, dry bamboo shoot only account for whole bamboo shoot body compared with small part, take moso bamboo shoot as example, its bamboo shoot meat accounts for 28%, all the other are the tankage such as bamboo shoot head and bamboo shoot shell, it is because rough wearing fiber composition is up to 72%, therefore in the course of processing, be discarded, and in these tankage that not yet effectively utilize, nutrition and health care composition is also lower comparatively speaking, is not processed to food.So, in the course of processing of bamboo shoots processing, all can produce a large amount of processing wastes---tankage, if it is bad that these by products are processed, will cause the wasting of resources and environmental pollution, will have a negative impact to people's production, life and health, and cause the waste of biomass resource.So, the research of the recycling of processing waste is just seemed to extremely important.Therefore, the utilisation technology of research bamboo shoots processing waste just has possibility.
Along with the day by day worry of people to petroleum resources exhaustion, by renewable natural agricultural-forestry biomass, replace petroleum resources, synthesis of natural macromolecular material has obtained increasing concern.Processing of farm products waste is renewable resources inexhaustible on the earth, and these natural polymers have various structures and functional group, is easy to chemistry and physical modification, has the features such as biological degradability and biological safety simultaneously.Therefore, asparagus tankage skin slag in processing of farm products is carried out to modification, and synthesis of natural macromolecule hydrogel material, for curbing environmental pollution, medicine controls and discharge, for the processing treatment of asparagus tankage has provided certain terms of settlement, significant to a certain extent.
The invention provides a kind of novel by the cellulose modified method of preparing composite aquogel of bamboo shoots, take that to discard bamboo shoots tankage slag be main raw material, through to extracting bamboo shoots Mierocrystalline cellulose after the bleaching of bamboo shoots, alkalinisation treatment, then the bamboo shoots Mierocrystalline cellulose extracting is carried out to carboxymethyl-modification.For independent carboxymethylation bamboo shoots Mierocrystalline cellulose, form the less-than-ideal problem of water-setting colloid structure feature, by adding kappa-carrageenan, improve the texture characteristic of hydrogel.Finally, by via Inverse-Phase Suspension Polymerization, pass through regulating rotary rotor speed, rotor and reactor diameter ratio, whiteruss volume is prepared hydrogel beads, after lyophilize using it as a kind of biological adsorption agent, due to this hydrogel, contain the negative charge groups such as a large amount of carboxymethyls and thionyl, the theory of adsorbing mutually according to positive and negative charge is studied its absorption property to model cationic dyestuff methylene blue.
Summary of the invention
The present invention is devoted to by bamboo shoots tankage are carried out to modification, provide a kind of bamboo shoots tankage are carried out to method and the application thereof that composite aquogel is prepared in modification, this sorbent material be take bamboo shoots tankage as main raw material, add kappa-carrageenan and improve hydrogel texture characteristic, by itself and sodium chloroacetate, in Virahol, carry out modification, epoxy chloropropane is cross-linked, the hydrogel beads finally making by via Inverse-Phase Suspension Polymerization.
A kind ofly bamboo shoots are carried out to modification prepare hydrogel beads as the method for biological adsorption agent, described composite aquogel is extracted after Mierocrystalline cellulose by bamboo shoots tankage that with sodium chloroacetate, to carry out carrying out after modification epoxy chloropropane crosslinked, inverse suspension polymerization, finally carries out lyophilize and forms afterwards, and concrete steps are:
(1) bamboo shoots tankage are through washing, oven drying 12-16h, and drying temperature is 70-80 ℃ or dries in the sun, the shape that is cut into small pieces after dry, is convenient to pulverize, and pulverizes 80 mesh sieves afterwards through pulverizer, obtains bamboo shoots ground-slag end standby;
(2) bamboo shoots tankage ground-slag end adds distilled water according to material quality than the ratio of 1:20-1:25, under 65-80 ℃ of condition, complete and process 2h-2.5h passivation bamboo shoots active enzyme, use afterwards the Glacial acetic acid regulator solution pH of massfraction 10%-15% at 3.8-4.0, after adjusting, add Textone to carry out bleaching, under 75-80 ℃ of condition, carry out bleaching, to remove the xylogen in bamboo shoots tankage;
(3) after bleaching, insoluble flocculent substance in filtering solution, and it is colourless to filtrate with distilled water wash, last functional quality mark 85%-95% ethanol carries out alcohol wash, finally in 50-70 ℃ of baking oven, carry out drying treatment 16-20h, obtain pre-treatment bamboo shoots fiber; Be denoted as PBSC (Pretreatment Bamboo Shoot Cellulose)
(4) dry pre-treatment bamboo shoots fiber is later pulverized, cross 80 mesh sieves, according to solid-liquid ratio 1:15-1:20 (g/ml), join potassium hydroxide aqueous solution and stir alkalization 12h-20h, the object of alkalinisation treatment is in order to remove the hemicellulose in PBSC, and reaction finishes the PBSC that rear taking-up was processed, washing, put into baking oven and process 16-20h at 50-70 ℃, after dry, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC (Bamboo Sheet Cellulose);
(5) bamboo shoots Mierocrystalline cellulose after the de-hemicellulose being dried after processing is pulverized, after pulverizing, crossed 80 mesh sieves;
(6) modified technique is as follows: after accurately weighing the de-hemicellulose of 10-12g, bamboo shoots Mierocrystalline cellulose adds in reactor, add afterwards distilled water and Virahol, then after adding the massfraction of 80-100ul to be 30%-35% hydrogen peroxide, shake up, after shaking up, adding massfraction is 40%-50%NaOH solution 16-20ml, carry out alkalinisation treatment, alkalization time is 2-3h, makes 2 on basic all fibres element molecule, 4, the hydroxyl of 6 can activate, and alkalizes complete, and bamboo shoots Mierocrystalline cellulose obtains alkalizing;
(7) the modification stage, in reactor, add sodium chloroacetate solution, start gradient increased temperature etherificate, reaction solution under magnetic agitation condition in room temperature treatment 30-50min, be transferred to afterwards shaking table and carry out 40-45 ℃ of shaking water bath 30-40min, carry out afterwards 55-60 ℃ of shaking water bath 30-40min, then carry out 75-80 ℃ of pyroprocessing 80-90min;
(8) recover after completion of the reaction room temperature, again adding 6ml massfraction is that 50%NaOH solution carries out double alkalisation, and alkalization time is 30min, carries out secondary etherificate after alkalization, and etherificate concrete technology is with consistent in temperature parameter same (7);
(9) after treating etherificate, supernatant discarded after cool to room temperature, after the spherical dope of lower floor is cooling, pouring 300-500ml methyl alcohol into processes, shaking table room temperature concussion 30-40min, wash away unreacted component and other impurity wherein, after stratification, outwell upper strata alcohol liquid, again add after 300-500ml methyl alcohol after concussion after standing over night with Glacial acetic acid be adjusted to stir after neutral after the standing upper strata alcohol liquid of outwelling, carrying out ethanol washes, after cleaning, filter out ethanol, dry sediment at 45-50 ℃, obtain modification carboxymethylation bamboo shoots Mierocrystalline cellulose afterwards, be denoted as MBSC (Modified Bamboo Sheet Cellulose),
(10) after BSC is carried out to carboxymethyl-modification, need to prepare MBSC/ kappa-carrageenan composite aquogel pearl by inverse suspension crosslinking method, first, carboxymethylation bamboo shoots Mierocrystalline cellulose/kappa-carrageenan composite solution 50-60ml after the modification of preparation 0.05-0.07 (g/ml), wherein the carboxymethylation bamboo shoots Mierocrystalline cellulose after modification and the mass ratio of kappa-carrageenan are 8:2-7:3, add again afterwards 2.5g-3g sodium hydroxide to carry out alkalinisation treatment and 6-10ml epoxy chloropropane (ECH) is cross-linked, after it stirs in magnetic agitation, carried out ultrasonic deaeration processing, ultrasonic power is 200W, ultrasonic time 2min, obtain mixture glue,
(11) after ultrasonic, 25ml-30ml mixture glue is splashed into rapidly just in the whiteruss of magnetic stirrer, and in dropping process, magnetic stirring apparatus keeps 1000-1200rpm to prevent glue automatic bonding in whiteruss, after stable, regulating magnetic stirring apparatus rotating speed is 700-800rpm;
(12) at room temperature, under 700-800rpm, with constant speed, stir, after reaction 36-48h, recovering liquid paraffin, obtain hydrogel, use deionized water and 85-95% ethanol respectively the hydrogel of preparing to be washed, remove complete linking agent and the reaction raw materials of unreacted;
(13) hydrogel of preparing is put into-20 ℃ of refrigerator freezing 12-16h, put on Freeze Drying Equipment and carry out vacuum freezedrying, obtain described modification bamboo shoots Mierocrystalline cellulose composite aquogel.Obtaining its diameter is 2-3mm, water white transparency, and particle size distribution range is also very narrow, is the MBSC/ kappa-carrageenan composite aquogel pearl of spheroidal particle, i.e. composite aquogel completely.
In above-mentioned method, bamboo shoots tankage described in step (1) refer to the more waste that is unfavorable for processing of aging fiber that bamboo shoots work in-process abandons, and are that the rear portion bamboo shoot root of bamboo shoots divides; Resulting bamboo shoots tankage slag powder diameter is 0.1-0.6mm.
In above-mentioned method, in step (2), the mass ratio of described bamboo shoots powder and Textone is 1:1-1:0.8, and bleaching time is 2-3h.
In above-mentioned method, in step (4), the mass percent concentration of described potassium hydroxide aqueous solution is 10%-15%.
In above-mentioned method, in step (4), the concrete grammar of described washing is: make to be successively washed with distilled water to filtrate pH for neutral, use afterwards 95% ethanol and dehydrated alcohol respectively to wash 1 time.
In above-mentioned method, in step (6), in described reactor, should be provided with magnetic stirring apparatus and thermostatically heating rocking equipment.
In above-mentioned method, in step (6), in reaction system, the mass ratio of distilled water and Virahol is 1:8.5-1:10.
In above-mentioned method, the mass ratio of alkalization bamboo shoots Mierocrystalline cellulose and sodium chloroacetate is 1:1.2-1:1.4 in step (7), sodium chloroacetate before adding reaction system, 1:1 predissolve in dehydrated alcohol in mass ratio.
In above-mentioned method, in step (9), the mode of washing of described washing with alcohol is: use successively 75%, 85%, 95% ethanol to wash 3 times modified product.
In above-mentioned method, described in step (11), in reactor, the length of magnetic agitation rotor accounts for the 75%-80% of reactor bottom diameter; Whiteruss accounts for the 45%-55% of reactor volume.
A kind ofly bamboo shoots tankage are carried out to modification prepare composite aquogel and be applied to absorption or the Thermosensitive Material Used for Controlled Releasing of Medicine of cationic dyestuff molecule as sorbing material.
Sorbent material of the present invention compared with prior art has following feature:
(1) sorbent material of the present invention main raw material used is discarded bamboo shoots tankage slag, and source is abundant, cheap, and sorbent material is to dye molecule high adsorption capacity, and absorption property is stable;
(2) bamboo shoots Mierocrystalline cellulose only needs carboxymethylation one step modification, and modified technique is fairly simple;
(3) modification bamboo shoots Mierocrystalline cellulose is prepared in hydrogel process and is added appropriate carrageenin, and the matter structure of the composite aquogel of preparing is improved;
(4) bamboo shoots Mierocrystalline cellulose, through after modification, is introduced carboxyl by carboxymethylation, and in the aqueous solution, on hydrogel, carboxyl ionizes, and produces the carboxylic ions of electronegative property, and cationic dyestuff is had to good adsorption effect;
(5) hydrogel that prepared by the present invention can be for the absorption of cationic dyestuff, and described cationic dyestuff refers to that in the aqueous solution group is with the dyestuff of positive charge, as: methylene blue, cationic red G etc.;
(6) take methylene blue as drug model, similar to some medicines because of molecular structure, can select its absorption of studying described hydrogel and slowly-releasing behavior, for this hydrogel provides certain theoretical basis as Thermosensitive Material Used for Controlled Releasing of Medicine.
(7) composite aquogel of the present invention adopts via Inverse-Phase Suspension Polymerization moulding, the hydrogel beads good looking appearance of formation, and size distribution homogeneous, specific surface area is large, and the oil phase liquid paraffin body using can be repeatedly used, and reduces cost and pollution.
(8) reaction conditions is gentle, uses green non-pollution NaOH system to carry out hydrogel preparation, and operational path is simple, is easy to industrialization operation.
Accompanying drawing explanation
MBSC and MBSC-CMC/CN-GEL FTIR spectrogram in Fig. 1 embodiment 1;
Fig. 2 embodiment 2 Methylene Blue starting point concentrations affect modification bamboo shoots Mierocrystalline cellulose composite aquogel adsorptive power;
In Fig. 3 embodiment 3, initial pH affects modification bamboo shoots Mierocrystalline cellulose composite aquogel adsorptive power.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described and description:
Embodiment 1:
(1) bamboo shoots tankage, through after washing, be dried after 12h in 70 ℃, the shape that is cut into small pieces, and pulverizer was pulverized 80 mesh sieves, obtained bamboo shoots ground-slag last, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots tankage ground-slag end adds distilled water according to the ratio of material-water ratio (mass ratio) 1:20, under 70 ℃ of conditions, complete and process 2h passivation bamboo shoots active enzyme, the Glacial acetic acid regulator solution pH that is 10% with massfraction is afterwards 3.8, after adjusting, add Textone to carry out bleaching 2h, the mass ratio of the add-on of Textone and bamboo shoots tankage powder is 1:1, under 80 ℃ of conditions, carries out bleaching, to remove the xylogen in bamboo shoots tankage;
(3) after bleaching, insoluble flocculent substance in filtering solution, and it is colourless to filtrate with distilled water wash, last functional quality mark 90% ethanol carries out alcohol wash, finally in 60 ℃ of baking ovens, carry out drying treatment 20h, obtain pre-treatment bamboo shoots fiber, be denoted as PBSC (Pretreatment Bamboo Shoot Cellulose).Pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, and to be carried out at massfraction be the 16h that alkalizes in 10% potassium hydroxide solution, wherein the amount ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1:15 (g/ml), it is neutral after alkalization, with distilled water, washing to filtrate, then use after 95% washing with alcohol, dry 16h at 50 ℃, obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose, be denoted as BSC (Bamboo Shoot Cellulose).
(4) after dried de-hemicellulose, after the pulverizing of bamboo shoots Mierocrystalline cellulose, cross 80 mesh sieves and carry out carboxymethyl-modification, modified condition is as follows: 10g bamboo shoots Mierocrystalline cellulose is added in 200ml aqueous isopropanol, in aqueous isopropanol, the mass ratio of distilled water and Virahol is in 1:9,30% hydrogen peroxide, the 50%NaOH solution 16ml that add successively again 80ul, 2h alkalinisation treatment.
(5) alkalize completely, add 50% sodium chloroacetate solution 14ml gradient increased temperature etherificate.Reaction conditions: room temperature 30min, shaking water bath 30min at 45 ℃, shaking water bath 30min at 60 ℃, processes 80min for last 75 ℃.
(6) treat that it recovers room temperature, again add the 50%NaOH of 6ml to carry out double alkalisation 30min, carry out secondary temperature elevation etherificate, etherificate parameter is with etherificate is consistent for the first time.
(7) after etherificate, supernatant discarded, add 300ml methyl alcohol room temperature concussion 30min, after filter liquor, again add after 300ml methyl alcohol standing over night after concussion, with Glacial acetic acid regulate sample liquid be stir after neutral after standing supernatant discarded, use successively 75%, 85%, 95% ethanolic soln successively precipitation to be cleaned 3 times, after cleaning, filter out ethanol, dry at 50 ℃, obtain the carboxymethylation bamboo shoots Mierocrystalline cellulose after modification.
(8) the carboxymethylation bamboo shoots Mierocrystalline cellulose/carrageenin composite solution 50ml after the modification of preparation 0.07 (g/ml), wherein the carboxymethylation bamboo shoots Mierocrystalline cellulose after modification and the mass ratio of carrageenin are 7:3, add again afterwards 2.5g sodium hydroxide to carry out alkalinisation treatment and 8ml epoxy chloropropane (ECH) is cross-linked, after it stirs in magnetic agitation, 200W ultrasonic degas is processed 2min, obtains mixture glue.
(9) use dropper that 25ml mixture glue is splashed into rapidly just in stirred liq paraffin, dropping process keeps magnetic agitation 1000rpm, after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, in reactor, the length of magnetic agitation rotor accounts for 75% of reactor bottom diameter, and whiteruss accounts for 50% of reactor volume.
(10) reactant is after whiteruss reaction 36h, reclaim the whiteruss in beaker, use deionized water and 95% ethanol to wash the hydrogel of preparing, can obtain its diameter probably in 2.4mm left and right, water white transparency, particle size distribution range is also very narrow, is spheroidal particle carboxymethyl bamboo shoots Mierocrystalline cellulose/carrageenin composite aquogel pearl completely.
(11) will prepare described hydrogel beads and put into-20 ℃ of refrigerators and carry out freezing 12h, 12h is processed in lyophilize afterwards, obtains described composite aquogel.
Getting the carboxymethylation bamboo shoots Mierocrystalline cellulose of preparing in appropriate embodiment 1 (is denoted as: MBSC) (be denoted as: MBSC-CMC/CN-GEL with carboxymethylation bamboo shoots Mierocrystalline cellulose composite aquogel, wherein CN refers to kappa-carrageenan), with KBr (spectroscopically pure) compressing tablet, then use FT-IR infrared spectra (Bruker Vector33, German) in 4000-400cm
-1under scan, can obtain sample F T-IR spectrogram, as shown in Fig. 1 in accompanying drawing explanation.
By Fig. 1, analyzed, in MBSC, find at 1416cm
-1and 1602cm
-1the absorption peak of position is mainly because carboxyl carries out symmetry and asymmetric vibrations cause, at 1060cm
-1place is the distinctive flexible shock absorbing of acetal radical peak, and these are the distinctive groups of carboxymethyl, proves that carboxymethyl is successfully connected on bamboo shoots Mierocrystalline cellulose and can finds at 1377cm in MBSC-CMC/CN-GEL
-1, 1323cm
-1and 1246cm
-1there is new peak in place, they are due to form under the crosslinked action of epoxy chloropropane-CH-O-CH-of MBSC ehter bond stretching peak, this proof modification bamboo shoots carboxymethyl cellulose and epoxy chloropropane generation crosslinking reaction.In addition, at 847cm
-1the new peak that place occurs is-the flexible vibrations of C-O-S-, and this proves in described composite aquogel carrageenin composition, and composite aquogel preparation is successful.
Embodiment 2:
(1) bamboo shoots tankage, through after washing, be dried after 16h in 80 ℃, the shape that is cut into small pieces, and pulverizer was pulverized 80 mesh sieves, obtained bamboo shoots ground-slag last, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots tankage ground-slag end adds distilled water according to the ratio of material-water ratio (mass ratio) 1:25, under 65 ℃ of conditions, complete and process 2.5h passivation bamboo shoots active enzyme, the Glacial acetic acid regulator solution pH that is 10% with massfraction is afterwards 4.0, after adjusting, add Textone to carry out bleaching 2h, the mass ratio of the add-on of Textone and bamboo shoots tankage powder is 0.9:1, under 80 ℃ of conditions, carries out bleaching, to remove the xylogen in bamboo shoots tankage.
(3) after bleaching, insoluble flocculent substance in filtering solution, and it is colourless to filtrate with distilled water wash, finally functional quality mark 90% ethanol carries out alcohol wash, finally in 50 ℃ of baking ovens, carries out drying treatment 20h, obtains pre-treatment bamboo shoots fiber.Pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, and to be carried out at massfraction be the 18h that alkalizes in 10% potassium hydroxide solution, wherein the solid-liquid ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1:15 (g/ml), it is neutral after alkalization, with distilled water, washing to filtrate, then use after 95% washing with alcohol, dry 16h at 50 ℃, obtains bamboo shoots Mierocrystalline cellulose after de-hemicellulose.
(4) after dried de-hemicellulose, bamboo shoots Mierocrystalline cellulose carries out carboxymethyl-modification processing according to method in embodiment 1 after pulverizing, and finally obtains modification carboxymethylation bamboo shoots Mierocrystalline cellulose afterwards.
(5) the carboxymethylation bamboo shoots Mierocrystalline cellulose/carrageenin composite solution 50ml after the modification of preparation 0.07 (g/ml), wherein the carboxymethylation bamboo shoots Mierocrystalline cellulose after modification and the mass ratio of carrageenin are 7:3, add again afterwards 3g sodium hydroxide to carry out alkalinisation treatment and 10ml epoxy chloropropane (ECH) is cross-linked, after it stirs in magnetic agitation, 200W ultrasonic degas is processed 2min, obtains mixture glue.
(6) use dropper that 25ml mixture glue is splashed into rapidly just in stirred liq paraffin, dropping process keeps magnetic agitation 1000rpm, after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, and in reactor, the length of magnetic agitation rotor accounts for 75% of reactor bottom diameter; Whiteruss accounts for 50% of reactor volume.
(7) reactant is after whiteruss reaction 36h, reclaim the whiteruss in beaker, use deionized water and 95% ethanol to wash the hydrogel of preparing, can obtain its diameter probably in 2.4mm left and right, water white transparency, particle size distribution range is also very narrow, is spheroidal particle carboxymethyl bamboo shoots Mierocrystalline cellulose/carrageenin composite aquogel pearl completely.
(8) will prepare described hydrogel beads and put into-20 ℃ of refrigerators and carry out freezing 12h, 12h is processed in lyophilize afterwards, obtains described composite aquogel.
The neutral methylene blue solution of configuration different concns, then pipettes different concns methylene blue solution 25ml in clear bottle with transfer pipet, and concussion 30s mediates.Then in each serum bottle, pour accurate load weighted 0.03g lyophilize hydrogel into, standing 5d.
By loading capacity calculation formula:
and R
m=(1-C
t/ C
0described hydrogel adsorptive power and adsorption efficiency are calculated in) * 100, and wherein Q is loading capacity, and unit is mg/g; R
mfor adsorption efficiency; C
0, Ct is in initial time and t simulation strength of solution constantly; V is simulation liquor capacity, and unit is ml; M is adsorbent mass g.
Methylene blue starting point concentration on described hydrogel adsorptive power impact as shown in Figure 2.
As seen from Figure 2, increase along with methylene blue solution starting point concentration, bamboo shoots carboxymethyl cellulose/carrageenin composite aquogel is ever-increasing to its adsorptive power, but adsorption efficiency is declining, the loading capacity that is 1200mg/L place at starting point concentration can reach 665.43mg/g, and adsorption efficiency reaches 55.48%.It is mainly because have a large amount of carboxylic acid ions above bamboo shoots carboxymethyl cellulose after modification that composite aquogel has so large adsorptive power to methylene blue, together with the entrained negative charge of the sulfate ion on carrageenin, cationic dyestuff is had to very strong adsorptive power causes.
Embodiment 3:
(1) bamboo shoots tankage, through after washing, be dried after 16h in 75 ℃, the shape that is cut into small pieces, and pulverizer was pulverized 80 mesh sieves, obtained bamboo shoots ground-slag last, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots tankage ground-slag end adds distilled water according to the ratio of material-water ratio 1:20, under 70 ℃ of conditions, complete and process 2h passivation bamboo shoots active enzyme, use afterwards 10% Glacial acetic acid regulator solution pH 3.8, after adjusting, add Textone to carry out bleaching 3h, the mass ratio of the add-on of Textone and bamboo shoots tankage powder is 1:1, under 80 ℃ of conditions, carries out bleaching, to remove the xylogen in bamboo shoots tankage.
(3) after bleaching, insoluble flocculent substance in filtering solution, and it is colourless to filtrate with distilled water wash, finally functional quality mark 95% ethanol carries out alcohol wash, finally in 50 ℃ of baking ovens, carries out drying treatment 20h, obtains pre-treatment bamboo shoots fiber.Pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, and to be carried out at massfraction be the 18h that alkalizes in 10% potassium hydroxide solution, wherein the solid-liquid ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1:15 (g/ml), it is neutral after alkalization, with distilled water, washing to filtrate, then use after 95% washing with alcohol, dry 16h at 50 ℃, obtains bamboo shoots Mierocrystalline cellulose after de-hemicellulose.
(4) after dried de-hemicellulose, bamboo shoots Mierocrystalline cellulose carries out carboxymethyl-modification processing according to method in embodiment 1 after pulverizing, and finally obtains modification carboxymethylation bamboo shoots Mierocrystalline cellulose afterwards.
(5) the carboxymethylation bamboo shoots Mierocrystalline cellulose/carrageenin composite solution 50ml after the modification of preparation 0.06 (g/ml), wherein the carboxymethylation bamboo shoots Mierocrystalline cellulose after modification and the mass ratio of carrageenin are 7:3, add again afterwards 2.5g sodium hydroxide to carry out alkalinisation treatment and 10ml epoxy chloropropane (ECH) is cross-linked, after it stirs in magnetic agitation, ultrasonic degas is processed, and obtains mixture glue.
(6) use dropper that mixture glue is splashed into rapidly just in stirred liq paraffin, dropping process keeps magnetic agitation 1200rpm, after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, and in reactor, the length of magnetic agitation rotor accounts for 80% of reactor bottom diameter; Whiteruss accounts for 55% of reactor volume.
(6) reactant, after whiteruss reaction 36h, is used deionized water and 95% ethanol to wash the hydrogel of preparing, and can obtain spheroidal particle carboxymethyl bamboo shoots Mierocrystalline cellulose/carrageenin composite aquogel pearl.
(7) will prepare described hydrogel beads and put into-20 ℃ of refrigerators and carry out freezing 12h, 12h is processed in lyophilize afterwards, obtains described composite aquogel.
Configure the methylene blue solution of different pH values, then with transfer pipet, pipette different concns methylene blue solution 25ml in small beaker.Then in each small beaker, pour accurate load weighted 0.025g lyophilize hydrogel into, standing 5d.
By loading capacity calculation formula:
and R
m=(1-C
t/ C
0described hydrogel adsorptive power and adsorption efficiency are evaluated in) * 100, and wherein Q is loading capacity, and unit is mg/g; R
mfor adsorption efficiency; C
0, Ct is in initial time and t simulation strength of solution constantly; V is simulation liquor capacity, and unit is ml; M is adsorbent mass g.
Methylene blue starting point concentration on described hydrogel adsorptive power impact as shown in Figure 2.
As seen from Figure 3, increase along with solution initial pH value, bamboo shoots carboxymethyl cellulose/carrageenin composite aquogel is ever-increasing to methylene blue adsorption number ability, adsorption efficiency is also increasing, the loading capacity that is 9.0 places at initial pH can reach 408.73mg/g, and adsorption efficiency reaches 82.87%.
Embodiment 4:
(1) bamboo shoots tankage, through after washing, be dried after 12h in 80 ℃, the shape that is cut into small pieces, and pulverizer was pulverized 80 mesh sieves, obtained bamboo shoots ground-slag last, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots tankage ground-slag end adds distilled water according to the ratio of material-water ratio (mass ratio) 1:20, under 75 ℃ of conditions, complete and process 2h passivation bamboo shoots active enzyme, the Glacial acetic acid regulator solution pH that is 10% with massfraction is afterwards 4.0, after adjusting, add Textone to carry out bleaching 3h, the mass ratio of the add-on of Textone and bamboo shoots tankage powder is 1:1, under 80 ℃ of conditions, carries out bleaching, to remove the xylogen in bamboo shoots tankage.
(3) after bleaching, filter insoluble flocculent substance, and it is colourless to filtrate with distilled water wash, finally functional quality mark is that 90% ethanol carries out alcohol wash, finally in 50 ℃ of baking ovens, carries out drying treatment 18h, obtains pre-treatment bamboo shoots fiber.Pre-treatment bamboo shoots Mierocrystalline cellulose was pulverized 80 mesh sieves, and to be carried out at massfraction be the 18h that alkalizes in 10% potassium hydroxide solution, wherein the solid-liquid ratio of pre-treatment bamboo shoots Mierocrystalline cellulose and potassium hydroxide aqueous solution is 1:15 (g/ml), it is neutral after alkalization, with distilled water, washing to filtrate, then use after 95% washing with alcohol, dry 16h at 50 ℃, obtains bamboo shoots Mierocrystalline cellulose after de-hemicellulose.
(4) after dried de-hemicellulose, bamboo shoots Mierocrystalline cellulose carries out carboxymethyl-modification processing according to method in embodiment 1 after pulverizing, and finally obtains modification carboxymethylation bamboo shoots Mierocrystalline cellulose afterwards.
(5) the carboxymethylation bamboo shoots Mierocrystalline cellulose/carrageenin composite solution 50ml after the modification of preparation 0.06 (g/ml), wherein the carboxymethylation bamboo shoots Mierocrystalline cellulose after modification and the mass ratio of carrageenin are 7:3, add again afterwards 2.5g sodium hydroxide to carry out alkalinisation treatment and 10ml epoxy chloropropane (ECH) is cross-linked, after it stirs in magnetic agitation, 200W ultrasonic degas is processed 2min, obtains mixture glue.
(6) use dropper that 25ml mixture glue is splashed into rapidly just in stirred liq paraffin, dropping process keeps magnetic agitation 1000rpm, after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, and in reactor, the length of magnetic agitation rotor accounts for 80% of reactor bottom diameter; Whiteruss accounts for 50% of reactor volume.
(7) reactant, after whiteruss reaction 48h, is used deionized water and 95% ethanol to wash the hydrogel of preparing, and can obtain spheroidal particle carboxymethyl bamboo shoots Mierocrystalline cellulose/carrageenin composite aquogel.
(8) will prepare described hydrogel beads and put into-20 ℃ of refrigerators and carry out freezing 12h, 12h is processed in lyophilize afterwards, obtains described composite aquogel.
Configuration concentration is that the methylene blue solution of 50mg/L is in beaker, then to adding in beaker described in accurate load weighted 0.300g hydrogel in this beaker, standing 72h, described hydrogel can draw by the calculation of capacity formula of step (10) in embodiment 2 absorption of methylene blue.By calculating at methylene blue starting point concentration, be under 50mg/L condition, the loading capacity of described hydrogel is 166.65mg/g, and adsorption efficiency is 99.94%.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.All any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in the protection domain of the claims in the present invention.
Claims (10)
1. one kind is carried out by bamboo shoots tankage the method that composite aquogel is prepared in modification, it is characterized in that, described composite aquogel carries out after modification with sodium chloroacetate after extracting Mierocrystalline cellulose by bamboo shoots tankage, carry out again epoxy chloropropane crosslinked, inverse suspension polymerization afterwards, finally carry out lyophilize and form, concrete steps are:
(1) bamboo shoots tankage are through washing, oven drying 12-16h, and drying temperature is 70-80 ℃ or dries in the sun, the shape that is cut into small pieces after dry, pulverized 80 mesh sieves through pulverizer afterwards, obtained bamboo shoots ground-slag end standby;
(2) bamboo shoots tankage ground-slag end adds distilled water according to material quality than the ratio of 1:20-1:25, under 65-80 ℃ of condition, complete and process 2h-2.5h passivation bamboo shoots active enzyme, use afterwards the Glacial acetic acid regulator solution pH of massfraction 10%-15% at 3.8-4.0, after adjusting, add Textone to carry out bleaching, under 75-80 ℃ of condition, carry out bleaching, to remove the xylogen in bamboo shoots tankage;
(3) after bleaching, filtering solution, get insoluble flocculent substance, and it is colourless to be washed with distilled water to filtrate, and last functional quality mark 85%-95% ethanol carries out alcohol wash, finally in 50-70 ℃ of baking oven, carries out drying treatment 16-20h, obtains pre-treatment bamboo shoots fiber;
(4) dry pre-treatment bamboo shoots fiber is later pulverized, cross 80 mesh sieves, according to solid-liquid ratio 1:15-1:20 g/ml, join potassium hydroxide aqueous solution and stir alkalization 12h-20h, washing, put into baking oven and process 16-20h at 50-70 ℃, dry obtain bamboo shoots Mierocrystalline cellulose after de-hemicellulose;
(5) bamboo shoots Mierocrystalline cellulose after dry de-hemicellulose is pulverized, after pulverizing, crossed 80 mesh sieves;
(6) modified technique is as follows: accurately weigh bamboo shoots Mierocrystalline cellulose after the de-hemicellulose that 10-12g step (5) obtains, add in reactor, add afterwards distilled water and Virahol, after adding again the massfraction of 80-100ul to be 30%-35% hydrogen peroxide, shake up, after shaking up, adding massfraction is 40%-50%NaOH solution 16-20ml, carries out alkalinisation treatment, alkalization time is 2-3h, and bamboo shoots Mierocrystalline cellulose obtains alkalizing;
(7) the modification stage, in alkalization bamboo shoots Mierocrystalline cellulose, add sodium chloroacetate solution, start gradient increased temperature etherificate, reaction solution under magnetic agitation condition in room temperature treatment 30-50min, be transferred to afterwards shaking table and carry out 40-45 ℃ of shaking water bath 30-40min, carry out afterwards 55-60 ℃ of shaking water bath 30-40min, then carry out 75-80 ℃ of pyroprocessing 80-90min;
(8) recover after completion of the reaction room temperature, again adding 6ml massfraction is that 50%NaOH solution carries out double alkalisation, and alkalization time is 30min, carries out secondary etherificate after alkalization, and etherificate concrete technology is with consistent in temperature parameter same (7);
(9) after treating etherificate, supernatant discarded after cool to room temperature, after the spherical dope of lower floor is cooling, pouring 300-500ml methyl alcohol into processes, shaking table room temperature concussion 30-40min, after stratification, outwell upper strata alcohol liquid, again add after 300-500ml methyl alcohol after concussion after standing over night with Glacial acetic acid be adjusted to stir after neutral after the standing upper strata alcohol liquid of outwelling, carry out washing with alcohol, after cleaning, filter out ethanol, dry sediment at 45-50 ℃, obtains modification carboxymethylation bamboo shoots Mierocrystalline cellulose afterwards;
(10) prepare the technique of modification bamboo shoots Mierocrystalline cellulose/kappa-carrageenan composite aquogel pearl: the carboxymethylation bamboo shoots Mierocrystalline cellulose/kappa-carrageenan composite solution 50-60ml after modification preparation 0.05-0.07(g/ml), wherein the carboxymethylation bamboo shoots Mierocrystalline cellulose after modification and the mass ratio of kappa-carrageenan are 8:2-7:3, add again afterwards 2.5g-3g sodium hydroxide to carry out alkalinisation treatment and 6-10ml epoxy chloropropane (ECH) is cross-linked, after it stirs in magnetic agitation, carried out ultrasonic deaeration processing, obtained mixture glue;
(11) after ultrasonic, 25ml-30ml mixture glue is splashed into rapidly just in the reactor that whiteruss is housed of magnetic stirrer, and in dropping process, magnetic stirring apparatus keeps 1000-1200rpm to prevent glue automatic bonding in whiteruss, after stable, regulating magnetic stirring apparatus rotating speed is 700-800rpm;
(12) at room temperature, under 700-800rpm, with constant speed, stir, after reaction 36-48h, recovering liquid paraffin, obtain hydrogel, use deionized water and 85-95% ethanol respectively the hydrogel of preparing to be washed, remove complete linking agent and the reaction raw materials of unreacted;
(13) hydrogel of preparing is put into refrigerator freezing 12-16h, put into and on Freeze Drying Equipment, carry out vacuum freezedrying, obtain described modification bamboo shoots Mierocrystalline cellulose composite aquogel, obtaining its diameter is 2-3mm, water white modification bamboo shoots Mierocrystalline cellulose/kappa-carrageenan composite aquogel pearl, i.e. composite aquogel.
2. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, bamboo shoots tankage described in step (1) refer to the more waste that is unfavorable for processing of aging fiber that bamboo shoots work in-process abandons, and are that the rear portion bamboo shoot root of bamboo shoots divides; Resulting bamboo shoots tankage slag powder diameter is 0.1-0.6mm.
3. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, in step (2), the mass ratio of described bamboo shoots powder and Textone is 1:1-1:0.8, and bleaching time is 2-3h.
4. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, in step (4), the mass percent concentration of described potassium hydroxide aqueous solution is 10%-15%.
5. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, in step (4), the concrete grammar of described washing is: make to be successively washed with distilled water to filtrate pH for neutral, use afterwards 95% ethanol and dehydrated alcohol respectively to wash 1 time.
6. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, in step (6), in described reactor, should be provided with magnetic stirring apparatus and thermostatically heating rocking equipment; In reaction system, the mass ratio of distilled water and Virahol is 1:8.5-1:10.
7. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, in step (7), the mass ratio of alkalization bamboo shoots Mierocrystalline cellulose and sodium chloroacetate is 1:1.2-1:1.4, sodium chloroacetate before adding reaction system, 1:1 predissolve in dehydrated alcohol in mass ratio.
8. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, in step (9), the mode of washing of described washing with alcohol is: use successively 75%, 85%, 95% ethanol to wash 3 times modified product.
9. according to claim 1 bamboo shoots tankage are carried out to the method that composite aquogel is prepared in modification, it is characterized in that, described in step (11), in reactor, the length of magnetic agitation rotor accounts for the 75%-80% of reactor bottom diameter; Whiteruss accounts for the 45%-55% of reactor volume.
10. the composite aquogel that described in claim 1-9, preparation method prepares is applied in the absorption or Thermosensitive Material Used for Controlled Releasing of Medicine of cationic dyestuff molecule as sorbing material.
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