CN106009458A - Novel pineapple peel residue cellulose-g-acrylic acid-kaolin-cuttlefish ink hydrogel and preparation method and application thereof - Google Patents
Novel pineapple peel residue cellulose-g-acrylic acid-kaolin-cuttlefish ink hydrogel and preparation method and application thereof Download PDFInfo
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- CN106009458A CN106009458A CN201610453926.5A CN201610453926A CN106009458A CN 106009458 A CN106009458 A CN 106009458A CN 201610453926 A CN201610453926 A CN 201610453926A CN 106009458 A CN106009458 A CN 106009458A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The invention discloses novel pineapple peel residue cellulose-g-acrylic acid-kaolin-cuttlefish ink hydrogel and a preparation method and application thereof. The preparation method comprises the steps that pineapple peel residues are taken as raw materials to be cleaned, dried, smashed, bleached and treated through alkali liquor, and then pineapple peel residue cellulose is obtained; the pineapple peel residue cellulose is stirred to be dissolved in ionic liquid through heating, and grafting modification is conducted by taking ammonium persulfate as an initiator, taking N,N-methylene bisacrylamide as a cross-linking agent and taking acrylic acid as a monomer; kaolin and cuttlefish ink are added, after reacting is completed, a product is cooled to room temperature and soaked and washed by adding distilled water, freeze drying is conducted, and then the hydrogel is obtained. According to the novel pineapple peel residue cellulose-g-acrylic acid-kaolin-cuttlefish ink hydrogel, the adopted raw materials are rich in source, convenient and easy to obtain and good in economy; the technology that the pineapple peel residue cellulose is modified and then prepared into the hydrogel is simple and short in reaction time, the thermal stability of the hydrogel can be improved through the cuttlefish ink and the kaolin, and the obtained hydrogel has a good application prospect in the fields of waste water treatment and adsorption materials.
Description
Technical field
The invention belongs to the technical field of composite aquogel, be specifically related to a kind of pineapple bran cellulose-g-acrylic acid/height
Ridge soil/Ink sepiellae seu sepiae novel hydrogels and preparation method and application.
Background technology
Fructus Ananadis comosi (Ananas comosus) it is the tropical fruit (tree) of a kind of aboundresources, unique flavor, it is deeply loved by the public,
The main place of production concentrates on China, Thailand, Brazil, Mexico, Philippine and Malaysia etc., and whole world annual production is about 1600-
19000000 tons, the annual production in China is about more than 200 ten thousand tons.Fructus Ananadis comosi mostly as eating raw, or be processed into pineapple tin,
Fruit jam, salad, cocktail adjuvant etc., and the extraction raw material as bromelain.In Fructus Ananadis comosi product processing, Fructus Ananadis comosi
Skin slag occupies the 30-42% of Fructus Ananadis comosi processing refuse, abandons usually used as processing byproduct, also results in while polluting environment
The wasting of resources.Therefore, how to make full use of and process the pineapple bran high-valued and environmental conservation tool to promoting pineapple industry
Significant.Research finds, pineapple bran is mainly made up of cellulose, hemicellulose, lignin and pectin, wherein cellulose
Dry weight content reaches 22%, and making full use of these celluloses is the high-valued important point of penetration of pineapple bran, but at present for spinach
The research of trailing plants skin slag cellulose higher value application is relatively fewer.
Cellulose prepares raw material as a kind of natural hydrogel, compares other synthetic polymer and has more preferable biofacies
Capacitive, degradability and avirulence.
Kaolin (kaolin) belongs to hydrophilic clay of laminar silicate mineral material, has specific surface area big, inexpensive easily
The feature obtained, preferably can be polymerized with organic monomer, adsorb various ion and impurity from surrounding medium.
Ink sepiellae seu sepiae (sepia ink) is mainly made up of melanin and proteoglycan, and wherein melanin can active adsorption Cu2 +、Fe3+、Pb2+And Cd2+Etc. heavy metal ion, and Ink sepiellae seu sepiae is generally discarded in fish market.
The multicomponent system that hydrogel is made up of with water hydrophilic polymer three-dimensional network, it can absorb and keep big
But amount moisture is water insoluble.Due to hydrophilic, biocompatibility, permeability and high moisture expansivity that hydrogel is excellent, make water-setting
Glue obtains extensive concern in fields such as sewage disposal, packaging for foodstuff, medical material, sensor and drug releases.
Therefore, research material, Kaolin and Ink sepiellae seu sepiae based on pineapple bran cellulose prepares as additive
Novel hydrogels is significant.
Summary of the invention
The primary and foremost purpose of the present invention is that providing a kind of prepares with pineapple bran cellulose, Kaolin and Ink sepiellae seu sepiae for raw material
Hydrogel and preparation method thereof.
Another object of the present invention is to provide the application conduct of the hydrogel prepared by above-mentioned preparation method
Adsorbent is applied in the treatment of waste water.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels, specifically include with
Lower step:
(1) preparation of pineapple bran cellulose
Pull an oar, be dried, pulverize, sieve after fresh pineapple skin slag is cleaned, obtain pineapple bran dry powder, take pineapple bran dry powder with
Distilled water mixes, and collects filtering residue and carry out bleaching after heating in water bath, then filters, washs, obtains pineapple bran fibre after drying
Dimension element crude product, carries out base extraction by pineapple bran coarse product of cellulose, then filters, washs, is dried, sieves, obtain pineapple peel
Slag cellulose (Pineapple peel cellulose, PPC)；
(2) preparation of Ink sepiellae seu sepiae
Will fresh sepiellae seu sepiae dissect after take out ink sac, separate extrusion prepared Chinese ink, soak in distilled water, be then centrifuged for, be dried, grind,
Sieve and obtain Ink sepiellae seu sepiae (sepia ink)；
(3) preparation of described hydrogel
Pineapple bran cellulose is mixed with ionic liquid, heats while stirring, make pineapple bran cellulose dissolution uniform,
Adding initiator after cooling, continue stirring, addition acrylic acid, cross-linking agent carry out graft modification, are subsequently adding Kaolin and sepiellae seu sepiae
Ink continues stirring and reacts, and after cooling, distilled water immersion washing, removes unreacted material and ionic liquid, after lyophilization
Obtain pineapple bran cellulose aquagel (PPCH), the most described hydrogel.
Further, in step (1), described pineapple bran is dried after cleaning and is dried 24-36h at 50-60 DEG C；Described
Pulverizing and use crusher for Chinese herbal medicine, crossing grit number is 80-100 mesh.
Further, in step (1), described pineapple bran and distilled water mixed proportion are 1:(20-25) g/mL；Described water
The temperature of bath heating is 70-80 DEG C, and the time of heating in water bath is 2-3h.
Further, described in step (1), bleaching is: the sodium chlorite solution with mass fraction as 7.5-8.0% is
Bleach, solid-liquid ratio is 1:(15-20) g/mL, with hydrochloric acid solution regulation solution ph as 3.8-4.0, under the conditions of 70-80 DEG C
Bleaching 2-4h.
Further, described in step (1) bleaching after washing, be dried: described washing refers to first be washed with distilled water to
Neutrality, washs 3-5 time with the ethanol solution that volume fraction is 95% the most again；Described be dried air-dry 2-3h for room temperature after, then at
18-20h it is dried at 50-60 DEG C.
Further, described in step (1), base extraction is: the sodium hydroxide solution with mass fraction as 10-12% is as alkali
Liquid, solid-liquid ratio is 1:(15-20) g/mL, stirring reaction 10-12h under room temperature, speed of agitator is 300-500rpm.
Further, described in step (1), washing, drying condition after base extraction are consistent with after bleaching, mistake
Grit number is 80-100 mesh.
Further, in step (2), described fresh sepiellae seu sepiae is tiger spot sepiellae seu sepiae；Described soak time is 16-20h, solid-liquid ratio
For 1:(20-30) g/mL, soaking temperature is 4-8 DEG C.
Further, described in step (2), centrifugal rotational speed is 4000-5000r/min, and centrifugation time is 20-30min.
Further, in step (2), described dry time temperature be 50-60 DEG C, drying time is 16-20h；Described mistake
The mesh number of sieve is 80-100 mesh.
Further, ionic liquid described in step (3) is [BMIm] Cl(chlorination 1-butyl-3-Methylimidazole .), Fructus Ananadis comosi
Skin slag cellulose and the ratio with ionic liquid are 1:(40-50) g/g.
Further, described in step (3), after mixing, the heating-up temperature of agitating heating is 80-100 DEG C, and heat time heating time is 3-
5h, speed of agitator is 300-500rpm.
Further, in step (3), described initiator is Ammonium persulfate., and consumption is pineapple bran cellulose and propylene
The 1.5-2.5% of acid gross mass；Described cross-linking agent is N,N methylene bis acrylamide, and consumption is pineapple bran cellulose and third
Olefin(e) acid gross mass 0.5-1.0%；Described acrylic acid degree of neutralization is that 60-80%(adjusts with the sodium hydroxide solution that mass fraction is 40%
Joint), consumption is (4-6) with the ratio of pineapple bran cellulose quality: 1.
Further, in step (3), the chilling temperature before described addition initiator is 50-60 DEG C；Described continuation stirring
Time is 10-20min；The reaction temperature of described graft modification is 60-80 DEG C, and the response time is 1-2h, and speed of agitator is 300-
500rpm。
Further, in step (3), the reaction temperature after described addition Ink sepiellae seu sepiae and Kaolin is 60-80 DEG C, during reaction
Between be 1-3h, speed of agitator is 300-500rpm；Described kaolinic addition with the ratio of pineapple bran cellulose quality is
(1-4):10；The addition of described Ink sepiellae seu sepiae is (2-6) with the ratio of pineapple bran cellulose quality: 10.
Further, in step (3), described addition Kaolin and Ink sepiellae seu sepiae carry out reacted cooling and refer to be cooled to room
Temperature；The washing of described distilled water immersion refers to that the every 8-12h of continuous 4d changes first water.
Further, lyophilization described in step (3) is-(55-60) DEG C dry 36-40h.
Pineapple bran cellulose-g-acrylic acid/novel the water-setting of Kaolin/Ink sepiellae seu sepiae prepared by above-mentioned preparation method
Glue.
Described pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels processes and adsorption material at waste water
Application in material field.
Compared with prior art, the invention have the benefit that
(1) present invention prepares the cellulose origin of hydrogel in agricultural production garbage pineapple bran, and material is rich and easy to get, and adopts
Using ion liquid dissolving cellulose, reaction condition is gentle, and ecological, environmental protective meets the feature of Green Chemistry.
(2) present invention pineapple bran cellulose is carried out acrylic graft-modified while prepare hydrogel, technique is grasped
Making simple, equipment requirements is low；Graft acrylic acid makes hydrogel have pH response and good swelling behavior, enriches this water-setting
The application of glue.
(3) present invention utilizes Kaolin and Ink sepiellae seu sepiae to improve the application performance of pineapple bran cellulose aquagel, Kaolin
Cheap, adsorbable all kinds of ions and impurity；And Ink sepiellae seu sepiae is generally discarded in fish market, but can active adsorption weight
Metal；These characteristics the hydrogel of preparation can be made to have sewage disposal in terms of using value.
Accompanying drawing explanation
Fig. 1 is hydrogel (PPCH-1) and pineapple bran cellulose (PPC), Ink sepiellae seu sepiae, the Kaolin of embodiment 1 preparation
FT-IR collection of illustrative plates；
Fig. 2 is hydrogel (PPCH-2) and the XRD diffracting spectrum of pineapple bran cellulose (PPC) of embodiment 2 preparation；
Fig. 3 is hydrogel (PPCH-3) and the TG curve chart of pineapple bran cellulose (PPC) of embodiment 3 preparation；
Fig. 4 a is the SEM figure of hydrogel PPCH-4 in embodiment 4；
Fig. 4 b is the SEM figure of pineapple bran cellulose PPC in embodiment 4；
Fig. 5 be embodiment 1 ~ 4 preparation hydrogel (PPCH-1, PPCH-2, PPCH-3 and PPCH-4) swelling behavior and to Asia
First indigo plant absorbability.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described and describes, but embodiments of the present invention do not limit
In this.
Embodiment 1
(1) pineapple bran is pulled an oar after over cleaning, 50 DEG C of dry 36h, sieves now in 80, obtain pineapple peel ground-slag after smashing；
(2) pineapple peel ground-slag mixes with distilled water, and solid-liquid ratio is 1:20g/mL, 70 DEG C of heating in water bath 2h, collects filtering residue after filtration
Carry out bleaching.With sodium chlorite solution that mass fraction is 7.5% as bleach, solid-liquid ratio is 1:15g/mL, with 4mol/L
Hydrochloric acid solution regulation solution ph be 3.8,70 DEG C of bleaching 2h；
(3) insoluble matter bleaching after is collected by filtration, molten with the ethanol that volume fraction is 95% again after distilled water wash to neutrality
Liquid washs 3 times, and room temperature air-dries 2h, is dried 18h and obtains pineapple bran coarse product of cellulose at 50 DEG C；
(4) pineapple bran coarse product of cellulose being mixed with the sodium hydroxide solution that mass fraction is 10%, solid-liquid ratio is 1:15g/
ML, stirring reaction 10h under room temperature, speed of agitator is 300rpm, and filtering residue is collected by filtration, and uses volume after distilled water wash to neutrality again
Mark be 95% ethanol solution wash 3 times, room temperature air-dries 2h, at 50 DEG C be dried 18h, 80 mesh that sieve obtain pineapple bran fiber
Element；
(5) Ink sepiellae seu sepiae preparation technology: take out ink sac after being dissected by fresh tiger spot sepiellae seu sepiae, separates extrusion prepared Chinese ink, at 4 DEG C, solid-liquid ratio
Soaking 20h, 4000r/min under the conditions of 1:20g/mL in distilled water and be centrifuged 20min, precipitate is dried 16h under the conditions of 50 DEG C,
Cross 80 mesh sieves after grinding and obtain Ink sepiellae seu sepiae；
(6) 0.2g pineapple bran cellulose adds 8g ionic liquid [BMIm] Cl, and 80 DEG C of heated and stirred 5h, speed of agitator is
300rpm, adds initiator ammonium persulfate 0.015g after being cooled to 50 DEG C, continue stirring 10min, and adding degree of neutralization is the third of 60%
Olefin(e) acid 0.8g, cross-linking agent N,N methylene bis acrylamide 0.005g, 60 DEG C of stirring reaction 1h, speed of agitator is 300rpm, so
Rear addition 0.02g Kaolin and 0.04g Ink sepiellae seu sepiae, continue stirring 1h at 60 DEG C, and speed of agitator is 300rpm, after having reacted
Liquid to be mixed adds distilled water immersion 4d, every 8h after being cooled to room temperature and changes distilled water, then carries out lyophilization, lyophilization
Temperature be-55 DEG C, drying time is 36h, obtains hydrogel PPCH-1.
Fig. 1 is hydrogel (PPCH-1) and pineapple bran cellulose (PPC), Ink sepiellae seu sepiae, the Kaolin of embodiment 1 preparation
FT-IR collection of illustrative plates.3400cm in PPCH-1 and PPC-1The characteristic absorption peak that peak is-OH of left and right, 1400cm-1The peak of left and right is
C-H bending vibration absworption peak, 1053cm-1For C-O-C stretching vibration absworption peak, these are all the characteristic absorption of native cellulose
Peak.1088cm in Kaolin-1And 907cm-1For Si-O stretching vibration absworption peak, 792cm-1And 564cm-1It is respectively Si-O-Al to stretch
Contracting vibration and Si-O-Al bending vibration absworption peak.In Ink sepiellae seu sepiae 3224,1578,1368cm-1It is respectively O-H and N-H stretching vibration
Absworption peak, COO-ionization and C=O double bond absorption peak and C-N stretching vibration absworption peak, these are all melanic in Ink sepiellae seu sepiae
Characteristic absorption peak.Compared with PPC, PPCH-1 is at 1720cm-1New absworption peak occurs, for C=O stretching vibration absworption peak, this be by
Cause in pineapple bran cellulose graft acrylic acid.3400cm in PPC-1Absworption peak broadens, and this may be with the addition of Ink sepiellae seu sepiae
Relevant.565cm in PPCH-1-1For Si-O-Al bending vibration absworption peak, this causes due to kaolinic embedding.
Embodiment 2
(1) pineapple bran is pulled an oar after over cleaning, 55 DEG C of dry 24h, sieves now in 100, obtain pineapple peel ground-slag after smashing；
(2) pineapple peel ground-slag mixes with distilled water, and solid-liquid ratio is 1:25g/mL, 75 DEG C of heating in water bath 3h, collects filtering residue after filtration
Carry out bleaching.With sodium chlorite solution that mass fraction is 8.0% as bleach, solid-liquid ratio is 1:20g/mL, with 4mol/L
Hydrochloric acid solution regulation solution ph be 3.9,75 DEG C of bleaching 3h；
(3) insoluble matter bleaching after is collected by filtration, molten with the ethanol that volume fraction is 95% again after distilled water wash to neutrality
Liquid washs 4 times, and room temperature air-dries 3h, is dried 20h and obtains pineapple bran coarse product of cellulose at 55 DEG C；
(4) pineapple bran coarse product of cellulose being mixed with the sodium hydroxide solution that mass fraction is 10%, solid-liquid ratio is 1:20g/
ML, stirring reaction 12h under room temperature, speed of agitator is 400rpm, and filtering residue is collected by filtration, and uses volume after distilled water wash to neutrality again
Mark be 95% ethanol solution wash 3 times, room temperature air-dries 3h, 55 DEG C of dry 18h, and 100 mesh that sieve obtain pineapple bran fiber
Element；
(5) Ink sepiellae seu sepiae preparation technology: take out ink sac after being dissected by fresh tiger spot sepiellae seu sepiae, separates extrusion prepared Chinese ink, at 5 DEG C, solid-liquid ratio
In distilled water, soak 18h, 4500r/min under the conditions of 1:25g/mL be centrifuged 25min, be dried 18h under the conditions of being deposited in 55 DEG C, grind
Cross 100 mesh sieves after mill and obtain Ink sepiellae seu sepiae；
(6) 0.2g pineapple bran cellulose adds 9g ionic liquid [BMIm] Cl, and 90 DEG C of heated and stirred 4h, speed of agitator is
400rpm, adds initiator ammonium persulfate 0.024g after being cooled to 55 DEG C, continue stirring 15min, and adding degree of neutralization is the third of 70%
Olefin(e) acid 1.0g, cross-linking agent N,N methylene bis acrylamide 0.0096g, 60 DEG C of stirring reaction 3h, speed of agitator is 400rpm, so
Rear addition 0.05g Kaolin and 0.04g Ink sepiellae seu sepiae, continue stirring 1.5h at 70 DEG C, and speed of agitator is 400rpm, and reaction completes
Rear liquid to be mixed adds distilled water immersion 4 d, every 8 h and changes first water, then carry out lyophilization after being cooled to room temperature,
Cryodesiccated temperature is-58 DEG C, and drying time is 38h, obtains hydrogel PPCH-2.
Fig. 2 is the XRD diffraction spectrogram of the hydrogel PPCH-2 in embodiment 2 and pineapple bran cellulose PPC.PPC exists
21.8 ° have the last one diffraction maximum, and at 15.3 ° and 34.6 °, the intensity of diffraction maximum is more weak, and this is pineapple bran cellulose self crystallization
Formed.And in hydrogel PPCH-2, in PPC, the intensity of original diffraction maximum all dies down, spreading out at 15.3 ° and 34.6 °
Penetrating peak almost to disappear, occur in that new more weak diffraction maximum simultaneously at 26.4 °, these all show that pineapple bran cellulose is changing
Property and hydrogel preparation process in, original crystal structure be destroyed, degree of crystallinity is decreased obviously.
Embodiment 3
(1) pineapple bran is pulled an oar after over cleaning, 55 DEG C of dry 30h, sieves now in 100, obtain pineapple peel ground-slag after smashing；
(2) pineapple peel ground-slag mixes with distilled water, and solid-liquid ratio is 1:20g/mL, 80 DEG C of heating in water bath 3 h, collects filtering residue after filtration
Carry out bleaching.With sodium chlorite solution that mass fraction is 7.5% as bleach, solid-liquid ratio is 1:20g/mL, with 4mol/L
Hydrochloric acid solution regulation solution ph be 3.9,80 DEG C of bleaching 3h；
(3) insoluble matter bleaching after is collected by filtration, molten with the ethanol that volume fraction is 95% again after distilled water wash to neutrality
Liquid washs 5 times, and room temperature air-dries 3h, and 55 DEG C of dry 18h obtain pineapple bran coarse product of cellulose；
(4) pineapple bran coarse product of cellulose being mixed with the sodium hydroxide solution that mass fraction is 10%, solid-liquid ratio is 1:15g/
ML, stirring reaction 10h under room temperature, speed of agitator is 500rpm, and filtering residue is collected by filtration, and uses volume after distilled water wash to neutrality again
Mark be 95% ethanol solution wash 3 times, room temperature air-dries 3h, 55 DEG C of dry 20h, and 80 mesh that sieve obtain pineapple bran cellulose；
(5) Ink sepiellae seu sepiae preparation technology: take out ink sac after being dissected by fresh tiger spot sepiellae seu sepiae, separates extrusion prepared Chinese ink, at 8 DEG C, solid-liquid ratio
In distilled water, soak 20h, 5000r/min under the conditions of 1:20g/mL be centrifuged 20min, be dried 16h under the conditions of being deposited in 60 DEG C, grind
Cross 100 mesh sieves after mill and obtain Ink sepiellae seu sepiae；
(6) 0.2g pineapple bran cellulose adds 10g ionic liquid [BMIm] Cl, and 100 DEG C of heated and stirred 3h, speed of agitator is
500rpm, adds initiator ammonium persulfate 0.035g after being cooled to 60 DEG C, continue stirring 20min, and adding degree of neutralization is the third of 80%
Olefin(e) acid 1.2g, cross-linking agent N,N methylene bis acrylamide 0.014g, 60 DEG C of stirring reaction 3h, speed of agitator is 400rpm, so
Rear addition 0.05g Kaolin and 0.08 g Ink sepiellae seu sepiae, continue stirring 1h at 80 DEG C, and speed of agitator is 500rpm, and reaction completes
Rear liquid to be mixed adds distilled water immersion 4d, every 8h after being cooled to room temperature and changes first water, then carries out lyophilization, cold
The dry temperature of lyophilizing is-60 DEG C, and drying time is 40h, obtains hydrogel PPCH-3.
Fig. 3 is hydrogel PPCH-3 and the TG curve chart of pineapple bran cellulose PPC in embodiment 3.Can be seen by Fig. 3
Going out, the initial decomposition temperature of hydrogel PPCH-3 is lower than PPC, illustrates that pineapple bran is cellulose modified and hydrogel preparation process
In, it being destroyed with intermolecular hydrogen bonding in pineapple bran cellulosic molecule, heat stability reduces.But PPC has higher compared with PPCH-3
Weight-loss ratio, when temperature reaches 500 DEG C, PPC weight-loss ratio is about 80%, and the weight-loss ratio of PPCH-3 is only 60%, and hydrogel is described
The palliating degradation degree of PPCH-3 is relatively low.
Embodiment 4
(1) pineapple bran is pulled an oar after over cleaning, 60 DEG C of dry 24h, sieves now in 80, obtain pineapple peel ground-slag after smashing；
(2) pineapple peel ground-slag mixes with distilled water, and solid-liquid ratio is 1:20g/mL, 80 DEG C of heating in water bath 2h, collects filtering residue after filtration
Carry out bleaching.With sodium chlorite solution that mass fraction is 7.5% as bleach, solid-liquid ratio is 1:15g/mL, with 4mol/L
Hydrochloric acid solution regulation solution ph be 4.0,75 DEG C of bleaching 4h；
(3) insoluble matter bleaching after is collected by filtration, molten with the ethanol that volume fraction is 95% again after distilled water wash to neutrality
Liquid washs 3 times, and room temperature air-dries 3h, and 60 DEG C of dry 18h obtain pineapple bran coarse product of cellulose；
(4) pineapple bran coarse product of cellulose being mixed with the sodium hydroxide solution that mass fraction is 10%, solid-liquid ratio is 1:20g/
ML, stirring reaction 12h under room temperature, speed of agitator is 400rpm, and filtering residue is collected by filtration, and uses volume after distilled water wash to neutrality again
Mark be 95% ethanol solution wash 3 times, room temperature air-dries 3h, at 55 DEG C be dried 18h, 100 mesh that sieve obtain pineapple bran fiber
Element；
(5) Ink sepiellae seu sepiae preparation technology: take out ink sac after being dissected by fresh tiger spot sepiellae seu sepiae, separates extrusion prepared Chinese ink, at 4 DEG C, solid-liquid ratio
In distilled water, soak 18h, 4500r/min under the conditions of 1:30g/mL be centrifuged 30min, be dried 20h under the conditions of being deposited in 50 DEG C, grind
Cross 100 mesh sieves after mill and obtain Ink sepiellae seu sepiae；
(6) 0.2g pineapple bran cellulose adds 8g ionic liquid [BMIm] Cl, and 90 DEG C of heated and stirred 3h, speed of agitator is
400rpm, adds initiator ammonium persulfate 0.025g after being cooled to 60 DEG C, continue stirring 15min, and adding degree of neutralization is the third of 70%
Olefin(e) acid 0.8g, cross-linking agent N,N methylene bis acrylamide 0.005g, 80 DEG C of stirring reaction 2h, speed of agitator is 300rpm, so
Rear addition 0.08g Kaolin and 0.04g Ink sepiellae seu sepiae, continue stirring 2h at 60 DEG C, and speed of agitator is 500rpm, after having reacted
Liquid to be mixed adds distilled water immersion 4d, every 8h after being cooled to room temperature and changes first water, then carries out lyophilization, freezing
The temperature being dried is-55 DEG C, and drying time is 36h, obtains hydrogel PPCH-4.
Fig. 4 a is the SEM figure of hydrogel PPCH-4 in embodiment 4, and Fig. 4 b is pineapple bran cellulose PPC in embodiment 4
SEM schemes.As can be seen from Figure, the original club shaped structure of Fig. 4 a pineapple bran cellulose was being prepared through modified and hydrogel
Cheng Hou, Fig. 4 b hydrogel PPCH-4 obtained is layered planar structure, the more particulate material of its surface distributed, for Ink sepiellae seu sepiae and
Kaolinic mixture, shows that Ink sepiellae seu sepiae and Kaolin have been evenly distributed in hydrogel.
Embodiment 5
The hydrogel utilizing embodiment 1 ~ 4 to prepare studies its swellability and the absorbability to methylene blue.
Accurately weigh the hydrogel that 25mg embodiment 1 ~ 4 prepares, be respectively placed in the beaker equipped with 100mL distilled water,
After the most swelling 24h, taking out hydrogel, filter paper blots hydrogel and shows moisture, weighs the quality after swelling behavior, meter
Calculation obtains swelling ratio；
Accurately weighing the hydrogel that 25mg embodiment 1 ~ 4 prepares, immersing 40mL concentration respectively is the methylene blue solution of 100mg/L
In, after absorption at room temperature 72h, take out hydrogel, measure the concentration of Methylene Blue in Solution solution, be calculated hydrogel to Asia
The absorbability of methyl blue；
The swellability of hydrogel that test obtains and to the absorbability of methylene blue as shown in Figure 5.As shown in Figure 5, hydrogel
Swelling Capacity in PPCH-1, PPCH-2, PPCH-3 and PPCH-4 at room temperature distilled water is respectively 25.41,22.14,24.91
And 24.16g/g, swelling behavior is preferable, wherein a little higher than other 3 kinds of the Swelling Capacity of PPCH-1.Methylene blue adsorption number experiment knot
Fruit shows, hydrogel PPCH-1, PPCH-2, PPCH-3 and PPCH-4 all have preferable absorbability to methylene blue, wherein
A little higher than other 3 kinds of PPCH-1, adsorbance is 153.85mg/g, and it is relevant that this has more preferable swelling behavior with PPCH-1, shows
The type hydrogel has good absorption property to the cationic dyes in waste water, can be applicable to the absorption during waste water processes
Agent.
Above-described embodiment is only for illustrating the example of the present invention, but the present invention is not limited to appeal embodiment.For
In the ken that those of ordinary skill in the field are possessed, any repaiied make within the spirit and principles in the present invention
Change, be equal to replacement and improvement etc., be regarded as the protection domain of the invention.
Claims (10)
1. a preparation method for pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels, its feature exists
In, specifically include following steps:
(1) preparation of pineapple bran cellulose: pull an oar after fresh pineapple skin slag is cleaned, be dried, pulverize, sieve, obtain Fructus Ananadis comosi
Skin slag dry powder, takes pineapple bran dry powder and mixes with distilled water, collects filtering residue and carry out bleaching after heating in water bath, then filter,
Washing, be dried to obtain pineapple bran coarse product of cellulose, then through base extraction, filter, wash, be dried, sieve, obtain pineapple peel
Slag cellulose；
(2) preparation of Ink sepiellae seu sepiae: take out ink sac after being dissected by fresh sepiellae seu sepiae, separates extrusion prepared Chinese ink, soaks, then in distilled water
Be centrifuged, be dried, grind, sieving obtains Ink sepiellae seu sepiae；
(3) preparation of described hydrogel: pineapple bran cellulose is mixed with ionic liquid, heats while stirring, make spinach
Trailing plants skin slag cellulose dissolution is uniform, adds initiator after cooling, continues stirring, and addition acrylic acid, cross-linking agent carry out graft modification,
Being subsequently adding Kaolin and Ink sepiellae seu sepiae continues stirring and reacts, distilled water immersion washing after cooling, lyophilization obtains described
Hydrogel.
A kind of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels the most according to claim 1
Preparation method, it is characterised in that in step (1), the ratio that described pineapple bran mixes with distilled water is 1:(20-25) g/mL；
The temperature of described heating in water bath is 70-80 DEG C, and the time of heating in water bath is 2-3h.
A kind of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels the most according to claim 1
Preparation method, it is characterised in that in step (1), described bleaching is that the sodium chlorite with mass fraction as 7.5-8.0% is molten
Liquid is bleach, and solid-liquid ratio is 1:(15-20) g/mL, with hydrochloric acid solution regulation pH as 3.8-4.0, at 70-80 DEG C of bleaching
2-4h；Described base extraction be the sodium hydroxide solution with mass fraction as 10-12% as alkali liquor, solid-liquid ratio is 1:(15-20) g/
ML, stirs 10-12h under room temperature.
A kind of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels the most according to claim 1
Preparation method, it is characterised in that in step (2), described fresh sepiellae seu sepiae is tiger spot sepiellae seu sepiae；The time of described immersion is 16-20h,
Solid-liquid ratio is 1:(20-30) g/mL, soaking temperature is 4-8 DEG C.
A kind of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels the most according to claim 1
Preparation method, it is characterised in that in step (3), described ionic liquid is chlorination 1-butyl-3-Methylimidazole., and pineapple bran is fine
Dimension element is 1:(40-50 with the ratio of ionic liquid) g/g；The described heating-up temperature heated while stirring is 80-100 DEG C, heating
Time is 3-5h.
A kind of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels the most according to claim 1
Preparation method, it is characterised in that in step (3), described initiator is Ammonium persulfate., and consumption is pineapple bran cellulose and third
The 1.5-2.5% of olefin(e) acid gross mass；Described cross-linking agent is N,N methylene bis acrylamide, consumption be pineapple bran cellulose and
Acrylic acid gross mass 0.5-1.0%；Described acrylic acid degree of neutralization is 60-80%, consumption and the ratio of pineapple bran cellulose quality
Example is (4-6): 1.
A kind of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels the most according to claim 1
Preparation method, it is characterised in that in step (3), the chilling temperature before described addition initiator is 50-60 DEG C；Described continuation stirs
The time mixed is 10-20min；The reaction temperature of described graft modification is 60-80 DEG C, and the response time is 1-2h.
A kind of pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels the most according to claim 1
Preparation method, it is characterised in that in step (3), add the reaction temperature after Kaolin and Ink sepiellae seu sepiae and be 60-80 DEG C, during reaction
Between be 1-3h；The ratio of the addition of described Kaolin and Ink sepiellae seu sepiae and pineapple bran cellulose quality is respectively (1-4): 10 and
(2-6):10；Described lyophilization is-(55-60) DEG C dry 36-40h.
9. pineapple bran cellulose-g-acrylic acid/kaolinite that a kind is obtained by the preparation method described in any one of claim 1-9
Soil/Ink sepiellae seu sepiae novel hydrogels.
10. pineapple bran cellulose-g-acrylic acid/Kaolin/Ink sepiellae seu sepiae novel hydrogels described in claim 9 processes at waste water
With the application in adsorbing material field.
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| CN109457472A (en) * | 2018-10-22 | 2019-03-12 | 武汉轻工大学 | A kind of cellulose nano-fibrous hydrogel and preparation method thereof |
| CN110790873A (en) * | 2019-11-13 | 2020-02-14 | 赵沐辰 | Self-floating photo-thermal conversion hydrogel material and preparation method and application thereof |
| CN111548441A (en) * | 2020-06-17 | 2020-08-18 | 自然资源部第三海洋研究所 | Ink melanin nanoparticle composite gel and preparation method thereof |
| CN111978566A (en) * | 2020-08-15 | 2020-11-24 | 重庆市蚕业科学技术研究院 | Preparation method of mulberry twig cellulose-based hydrogel |
| CN112263510A (en) * | 2020-10-16 | 2021-01-26 | 宁波保税区华萌生物科技有限公司 | Preparation method of facial mask |
| CN112920332A (en) * | 2021-03-18 | 2021-06-08 | 河南工程学院 | Method for preparing green hydrogel by crosslinking of various wastes |
| CN114702697A (en) * | 2022-04-26 | 2022-07-05 | 中国林业科学研究院林产化学工业研究所 | Hemicellulose-based hydrogel based on eutectic solvent and preparation method and application thereof |
| CN114752078A (en) * | 2022-04-26 | 2022-07-15 | 西北农林科技大学 | Hydrogel adsorbent of cellulose grafted polyacrylic acid and bentonite, and preparation method and application thereof |
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| CN109457472A (en) * | 2018-10-22 | 2019-03-12 | 武汉轻工大学 | A kind of cellulose nano-fibrous hydrogel and preparation method thereof |
| CN110790873B (en) * | 2019-11-13 | 2022-07-15 | 赵沐辰 | Self-floating photo-thermal conversion hydrogel material and preparation method and application thereof |
| CN110790873A (en) * | 2019-11-13 | 2020-02-14 | 赵沐辰 | Self-floating photo-thermal conversion hydrogel material and preparation method and application thereof |
| CN111548441A (en) * | 2020-06-17 | 2020-08-18 | 自然资源部第三海洋研究所 | Ink melanin nanoparticle composite gel and preparation method thereof |
| CN111548441B (en) * | 2020-06-17 | 2022-04-29 | 自然资源部第三海洋研究所 | Ink melanin nanoparticle composite gel and preparation method thereof |
| CN111978566A (en) * | 2020-08-15 | 2020-11-24 | 重庆市蚕业科学技术研究院 | Preparation method of mulberry twig cellulose-based hydrogel |
| CN112263510A (en) * | 2020-10-16 | 2021-01-26 | 宁波保税区华萌生物科技有限公司 | Preparation method of facial mask |
| CN112263510B (en) * | 2020-10-16 | 2023-08-18 | 宁波保税区华萌生物科技有限公司 | Preparation method of facial mask |
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