CN109364889A - A kind of preparation method and its usage of temperature-sensitive hydrogel - Google Patents
A kind of preparation method and its usage of temperature-sensitive hydrogel Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of temperature-sensitive hydrogel comprising following steps: preparing cellulose acetate nanofiber；The cellulose acetate nanofiber is carried out with lye deacetylated, obtained cellulose nano-fibrous；Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of cellulose nano-fibrous grafting is prepared using described；Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting is immersed in the mixed solution of frerrous chloride and iron chloride, ammonium hydroxide is added to be reacted, cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic anhydride)/Fe of grafting is obtained3O4Magnetic Nano fiber composite hydrogel, i.e., the described temperature-sensitive hydrogel.Compared with prior art, the present invention has following the utility model has the advantages that the present invention prepare cellulose nano-fibrous by Thermal inactive method, and simple process, yield height are very suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of temperature-sensitive hydrogel, belong to porous adsorbing material technical field.
Background technique
Heavy metal refers to that density is greater than 4.5m2The metallic element of/g, such as Cu, Ag, Cr, Pb metal.Heavy metal ion master
It to be discharged into water by Chemical Manufacture, fertilizer and pesticide, sanitary wastewater and mining etc., when the concentration of heavy metal ion in water is super
When crossing the self-purification capacity of water body, heavy metal pollution of water body is resulted in.With the fast development of industry and agricultural, a large amount of heavy metal
Discharge of wastewater, heavy metal pollution have become one of environmental pollution damage maximum.Heavy metal is not easy to be degraded under field conditions (factors), and
It is enriched in human body by food chain, domestic heavy metal water contamination accident takes place frequently nearly ten years, solves heavy metal pollution problem and carves
Do not allow to delay.Chemical method, such as chemical precipitation method, oxidation-reduction method are mainly passed through to the pollution of heavy metal at present；Bioanalysis, such as plant
Weight repairing method, biosorption process and bio-flocculation process；Physical method, such as partition method, ion-exchange and absorption method.Absorption method due to
The advantages that adsorbent abundance, cheap, large amount of adsorption, treatment effeciency are high, simple and easy to operate and without secondary pollution, it is wide
The general processing applied to effluent containing heavy metal ions.Common adsorbent comes with some shortcomings in terms of selectivity and recycling.
The adsorbent studied at present is attempted to combine a variety of adsorbent materials by physical doping or chemical connection process, utilizes each material
Structural advantage, preparation have high-adsorption-capacity, strong adaptability and the adsorbent material convenient for recycling.
Hydrogel is that a kind of hydrophilic polymer is intertwine with each other by being physically or chemically crosslinked, and forms three-dimensional net structure
Solid material, hole of the water as decentralized medium filling whole network structure.Hydrogel has three-dimensional net structure as one kind
High molecular material, had its unique advantages in terms of removing removing heavy metals.Progress in Intelligent Hydrogel to environmental stimuli (such as: temperature,
PH, ionic strength, electric field strength etc.), there is responsiveness, therefore using progress in Intelligent Hydrogel as adsorbent, it can be outer by changing
Boundary's environment regulates and controls hydrogel to the adsorption process of heavy metal ion, or according to the specific response of hydrogel to heavy metal ion
It is identified.
Natural polymer hydrogel has abundance, and inexpensive and good biocompatibility is widely used in hydrogel system
It is standby, but its stability is poor, therefore the modes such as natural polymer and the polymer blended or graft copolymerization of synthesis are often improved water-setting
Glue actual requirement.However most of natural polymer is powdered, blocky or membrane structure, porosity is low, specific surface area is small, connects
Branch is modified, however it remains the problems such as porosity is low, specific surface area is small, therefore it is low to the adsorption capacity of heavy metal ion.Why
The adsorption capacity that sample improves heavy metal ion becomes critical issue urgently to be solved.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and its usages of temperature-sensitive hydrogel.The present invention is by following
What technical solution was realized:
A kind of preparation method of temperature-sensitive hydrogel comprising following steps:
Prepare cellulose acetate nanofiber；
The cellulose acetate nanofiber is carried out with lye deacetylated, obtained cellulose nano-fibrous；
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the horse of cellulose nano-fibrous grafting is prepared using described
Carry out acid anhydrides) hydrogel；
By the cellulose nano-fibrous poly- (N of grafting-N-isopropylacrylamide-co- maleic anhydride) hydrogel is immersed in
In the mixed solution of frerrous chloride and iron chloride, ammonium hydroxide is added and is reacted, obtains cellulose nano-fibrous poly- (the N- isopropyl of grafting
Base acrylamide-co- maleic anhydride)/Fe3O4Magnetic Nano fiber composite hydrogel, i.e., the described temperature-sensitive hydrogel.
Preferably, the cellulose acetate nanofiber the preparation method comprises the following steps:
Cellulose acetate is dissolved in tetrahydrofuran and N, the in the mixed solvent of N '-dimethyl formamide obtains quenching liquid,
After the quenching liquid is quenched at -30~-15 DEG C, it is washed with distilled water and removes tetrahydrofuran and N, N '-dimethyl first
Amide, the cellulose acetate nanofiber being freeze-dried.
Preferably, in the quenching liquid, cellulose acetate, tetrahydrofuran and N, the weight of N '-dimethyl formamide
Measuring number is respectively 0.2~0.5 part, 1~3 part, 5~10 parts.
Preferably, the lye is the ethanol solution of NaOH, and wherein the concentration of NaOH is 0.1~0.2mol/L.
Preferably, cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) water of grafting
Gel the preparation method comprises the following steps:
By n-isopropyl acrylamide, maleic anhydride, N, N '-methylene-bisacrylamide is dissolved in nitric acid solution, obtains
To reaction solution A；
Ammonium ceric nitrate is dissolved in nitric acid solution, modified by vinyl silica and the cellulose Nanowire is added
Dimension, obtains reaction solution B；
Reaction solution A is added dropwise in reaction solution B by constant pressure funnel, after being reacted at 30~60 DEG C, according to
Secondary adopt is washed with distilled water, and using acetone Soxhlet extraction, filters, and obtains cellulose nano-fibrous poly- (the N- isopropyl propylene of grafting
Amide-co- maleic anhydride) hydrogel.
Preferably, in the reaction solution A: n-isopropyl acrylamide, maleic anhydride, N, N '-di-2-ethylhexylphosphine oxide third
The parts by weight of acrylamide are respectively 5~10 parts, 2~3 parts, 0.05~0.1 part；In the reaction solution B: ammonium ceric nitrate, fiber
Plain nanofiber, modified by vinyl silica parts by weight be respectively 1~3 part, 2~6 parts, 0.2~0.5 part.
Preferably, the modified by vinyl silica the preparation method comprises the following steps: by vinyltriethoxysilane
With silicon dioxde reaction, modified by vinyl silica is obtained.
Preferably, in the mixed solution of the frerrous chloride and iron chloride, mole of frerrous chloride and iron chloride
Than for 1:2；The concentration of the ammonium hydroxide is 1mol/L.
A kind of purposes of the temperature-sensitive hydrogel obtained by aforementioned preparation process in heavy metal ion adsorbed.
Preferably, the heavy metal ion is copper ion.
Mechanism of the invention is:
It is prepared by Thermal inactive method cellulose nano-fibrous.By free radical polymerization, by N- isopropyl third
In acrylamide and maleic anhydride to cellulose chain.It is compound will to have magnetic ferroso-ferric oxide finally by coprecipitation method
Onto hydrogel.
Using in n-isopropyl acrylamide amino and maleic anhydride hydrolysis after the coordination of the carboxyl that generates to copper ion
Chelating plays suction-operated.Using cellulose nano-fibrous high porosity and bigger serface, its adsorption capacity is improved.It utilizes
Fe on hydrogel3O4Magnetism, be conducive to hydrogel absorption after recycling.The addition of modified by vinyl silica
In order to improve the porosity of hydrogel, its swelling ratio and adsorption capacity are improved.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, n-isopropyl acrylamide and maleic anhydride are grafted on cellulose nano-fibrous with biocompatibility,
The volume size for reducing hydrogel increases specific surface area and porosity, and swelling ratio greatly improves, to improve copper ion
Adsorption capacity；
2, the addition of modified by vinyl silica forms discrete network pore structure, and porosity improves, swelling ratio
It improves, adsorption capacity also increases accordingly；
3, by Thermal inactive method prepare it is cellulose nano-fibrous, simple process, yield height, be very suitable for industry
Metaplasia produces.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Poly- (the Malaysia n-isopropyl acrylamide-co- of cellulose nano-fibrous grafting that in Fig. 1 present invention prepared by embodiment 1
Acid anhydrides)/Fe3O4Magnetic coupling hydrogel scanning electron microscope (SEM) photograph；
Poly- (the Malaysia n-isopropyl acrylamide-co- of cellulose nano-fibrous grafting that in Fig. 2 present invention prepared by embodiment 1
Acid anhydrides)/Fe3O4The relationship of magnetic coupling hydrogel temperature and swelling ratio；
Poly- (the Malaysia n-isopropyl acrylamide-co- of cellulose nano-fibrous grafting that in Fig. 3 present invention prepared by embodiment 1
Acid anhydrides)/Fe3O4The curve of adsorption kinetics of magnetic coupling hydrogel.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
1) cellulose nano-fibrous preparation
By 1g tetrahydrofuran and 10g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.3g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 3h at -20 DEG C.After
It takes out, is put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate Nanowire
Dimension；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.1mol/L for 24 hours, after be washed with distilled water, until
Cleaning solution pH value is 7.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
By 0.6g n-isopropyl acrylamide, 0.2g maleic anhydride, the dissolution of 0.008g N, N '-methylene-bisacrylamide
In 15mL 1mol/L nitric acid solution, reaction solution A is obtained；0.1g ammonium ceric nitrate is dissolved in 15mL 1mol/L nitric acid solution
In, it is added that 0.2g is cellulose nano-fibrous and 0.03g modified by vinyl silica, obtains reaction solution B；It is leaked by constant pressure addition
Bucket reaction solution A is added dropwise in reaction solution B, 50 DEG C of reaction temperature, reaction 4h, distillation water washing, using acetone Soxhlet extraction,
It filters, obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, be abbreviated as Cell-
G-P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.3g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 9h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4Scanning electron microscope (SEM) photograph such as Fig. 1 institute of magnetic Nano fiber composite hydrogel
Show, porous fibrous structure is presented in hydrogel, and fibre diameter is 178 ± 100nm, and the porosity and specific surface area of hydrogel are distinguished
For 93.8% and 24.4m2/ g, intensity of magnetization 0.022emu/g.Fig. 2 is Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetism is received
Rice fiber composite swelling behavior ratio varies with temperature curve, Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic Nano fiber is multiple
Heshui gel starts quick dehydration at 28 DEG C, and about 40 DEG C reach balance, and it is sensitive special good temperature nearby occur at 36.2 DEG C
Property.
The Cu for being 500mg/L by 50mL concentration2+Solution is added in conical flask, adjusts pH=7.0 with NaOH or HCl.It will
10mg hydrogel is added in above-mentioned solution, 25 DEG C, respectively water bath with thermostatic control concussion 10,20,50,100,200,300,400,500,
800, after 1200 and 1500min, supernatant liquor is taken to filter.Using Cu in Atomic Absorption Spectrometer measurement solution2+Concentration is calculated and is inhaled
Cu in attached solution2+Concentration, adsorption curve are as shown in Figure 3.In 0-300min, adsorbance is sharply increased with adsorption time,
300-500min adsorbance gradually eases up, and adsorption equilibrium is reached after 500min, fiber hydrogel is to Cu2+Saturated extent of adsorption reach
390.2mg/g。
Embodiment 2
1) cellulose nano-fibrous preparation
By 2g tetrahydrofuran and 8g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.2g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 2.5h at -25 DEG C.Terminate
After take out, be put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate nanometer
Fiber；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.15mol/L for 24 hours, after be washed with distilled water,
Until cleaning solution pH value is 7.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
By 0.4g n-isopropyl acrylamide, 0.28g maleic anhydride, the dissolution of 0.01g N, N '-methylene-bisacrylamide
In 15mL 1mol/L nitric acid solution, reaction solution A is obtained；0.3g ammonium ceric nitrate is dissolved in 15mL 1mol/L nitric acid solution
In, it is added that 0.3g is cellulose nano-fibrous and 0.04g modified by vinyl silica, obtains reaction solution B；It is leaked by constant pressure addition
Bucket reaction solution A is added dropwise in reaction solution B, 45 DEG C of reaction temperature, reaction 3h, distillation water washing, using acetone Soxhlet extraction,
It filters, obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, be abbreviated as Cell-
G-P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.3g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 6h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4In magnetic Nano fiber composite hydrogel fibre diameter be 170 ±
70nm, the porosity and specific surface area of hydrogel are respectively 91.8% and 26.1m2/ g, intensity of magnetization 0.024emu/g.
Cell-g-P(NIPAm-co-MA)/Fe3O4Magnetic Nano fiber composite hydrogel is to Cu2+Saturated extent of adsorption reach
410.1mg/g。
Embodiment 3
1) cellulose nano-fibrous preparation
By 3g tetrahydrofuran and 7g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.3g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 3h at -20 DEG C.After
It takes out, is put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate Nanowire
Dimension；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.15mol/L for 24 hours, after be washed with distilled water, directly
It is 7 to cleaning solution pH value.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
0.5g n-isopropyl acrylamide, 0.25g maleic anhydride, 0.008g N, N '-methylene-bisacrylamide is molten
Solution obtains reaction solution A in 15mL 1mol/L nitric acid solution；0.2g ammonium ceric nitrate is dissolved in 15mL 1mol/L nitric acid solution
In, it is added that 0.5g is cellulose nano-fibrous and 0.05g modified by vinyl silica, obtains reaction solution B；It is leaked by constant pressure addition
Bucket reaction solution A is added dropwise in reaction solution B, 40 DEG C of reaction temperature, reaction 3h, distillation water washing, using acetone Soxhlet extraction,
It filters, obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, be abbreviated as Cell-
G-P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.4g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 6h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4In magnetic Nano fiber composite hydrogel fibre diameter be 189 ±
90nm, the porosity and specific surface area of hydrogel are respectively 92.1% and 23.1m2/ g, intensity of magnetization 0.020emu/g.
Cell-g-P(NIPAm-co-MA)/Fe3O4Magnetic Nano fiber composite hydrogel is to Cu2+Saturated extent of adsorption reach
380.1mg/g。
Embodiment 4
1) cellulose nano-fibrous preparation
By 2g tetrahydrofuran and 8g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.45g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 3h at -15 DEG C.After
It takes out, is put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate Nanowire
Dimension；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.2mol/L for 24 hours, after be washed with distilled water, until
Cleaning solution pH value is 7.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
By 0.7g n-isopropyl acrylamide, 0.2g maleic anhydride, the dissolution of 0.005g N, N '-methylene-bisacrylamide
In 15mL 1mol/L nitric acid solution, reaction solution A is obtained；0.2g ammonium ceric nitrate is dissolved in 15mL1mol/L nitric acid solution,
It is added that 0.4g is cellulose nano-fibrous and 0.02g modified by vinyl silica, obtains reaction solution B；Pass through constant pressure funnel
Reaction solution A is added dropwise in reaction solution B, 40 DEG C of reaction temperature, reaction 4h distill water washing, using acetone Soxhlet extraction, pumping
Filter obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, is abbreviated as Cell-g-
P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.2g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 8h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4In magnetic Nano fiber composite hydrogel fibre diameter be 169 ±
80nm, the porosity and specific surface area of hydrogel are respectively 93.2% and 22.1m2/ g, intensity of magnetization 0.025emu/g.
Cell-g-P(NIPAm-co-MA)/Fe3O4Magnetic Nano fiber composite hydrogel is to Cu2+Saturated extent of adsorption reach
397.1mg/g。
Comparative example 1
Difference from Example 1 is: cellulose acetate is dissolved in tetrahydrofuran and N, N '-dimethyl first by step 1)
Amide in the mixed solvent prepares cellulose casting films using casting film-forming method afterwards.
Subsequent step is same as Example 1, finally obtains cellulose casting films and is grafted poly- (n-isopropyl acrylamide-co-
Maleic anhydride)/Fe3O4Magnetic coupling hydrogel.The porosity and specific surface area of the hydrogel are respectively 60.3% and 1.19m2/
g.It is compared to tunica fibrosa hydrogel, porosity and specific surface area reduce significantly.It is primarily due to no image of Buddha tunica fibrosa hydrogel one
Sample forms porous structure.Casting films hydrogel is to Cu2+Saturated extent of adsorption be 120.1m2/g。
Comparative example 2
Difference from Example 1 is: the additive amount that step 2) medium vinyl modifies silica is 0.It finally obtains
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic anhydride)/Fe of grafting3O4Magnetic coupling hydrogel.
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic anhydride)/Fe of grafting3O4Magnetic coupling hydrogel
Middle fibre diameter is 161 ± 55nm.Porosity and specific surface area are respectively 81.1% and 15.12m2/g.Fiber hydrogel is to Cu2+
Saturated extent of adsorption reach 267.78mg/g.It is to mention that the main purpose of modified by vinyl silica is added in reaction system
The porosity and specific surface area of high hydrogel, and further increase its heavy metal adsorption capacity.
Comparative example 3
Difference from Example 1 is: the additive amount of maleic anhydride is 0 in step 2).Finally obtain cellulose nanometer
Fibre grafting poly(N-isopropylacrylamide) hydrogel.Fibre diameter is 151 ± 78nm, the hole of hydrogel in the hydrogel
Rate and specific surface area are respectively 67.2% and 0.45m2/g.The hydrogel is to Cu2+Saturated extent of adsorption reach 110.6mg/g.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of preparation method of temperature-sensitive hydrogel, which comprises the steps of:
Prepare cellulose acetate nanofiber；
The cellulose acetate nanofiber is carried out with lye deacetylated, obtained cellulose nano-fibrous；
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic acid of cellulose nano-fibrous grafting is prepared using described
Acid anhydride) hydrogel；
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting is immersed in chlorination
In ferrous and iron chloride mixed solution, ammonium hydroxide is added and is reacted, obtains cellulose nano-fibrous poly- (the N- isopropyl third of grafting
Acrylamide-co- maleic anhydride)/Fe3O4Magnetic Nano fiber composite hydrogel, i.e., the described temperature-sensitive hydrogel.
2. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that the cellulose acetate Nanowire
Dimension the preparation method comprises the following steps:
Cellulose acetate is dissolved in tetrahydrofuran and N, the in the mixed solvent of N '-dimethyl formamide obtains quenching liquid, by institute
It states after quenching liquid quenched at -30~-15 DEG C, is washed with distilled water and removes tetrahydrofuran and N, N '-dimethyl formamide,
It is freeze-dried obtained cellulose acetate nanofiber.
3. the preparation method of temperature-sensitive hydrogel as claimed in claim 2, which is characterized in that in the quenching liquid, acetic acid is fine
Dimension element, tetrahydrofuran and N, the parts by weight of N '-dimethyl formamide are respectively 0.2~0.5 part, 1~3 part, 5~10 parts.
4. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that the lye is the ethyl alcohol of NaOH
Solution, wherein the concentration of NaOH is 0.1~0.2mol/L.
5. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that described cellulose nano-fibrous to connect
Poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of branch the preparation method comprises the following steps:
By n-isopropyl acrylamide, maleic anhydride, N, N '-methylene-bisacrylamide is dissolved in nitric acid solution, is obtained anti-
Answer liquid A；
Ammonium ceric nitrate is dissolved in nitric acid solution, modified by vinyl silica and described cellulose nano-fibrous is added, obtains
To reaction solution B；
Reaction solution A is added dropwise in reaction solution B by constant pressure funnel, after being reacted at 30~60 DEG C, is successively adopted
It is washed with distilled water, using acetone Soxhlet extraction, filters, obtain the cellulose nano-fibrous poly- (n-isopropyl acrylamide-of grafting
Co- maleic anhydride) hydrogel.
6. the preparation method of temperature-sensitive hydrogel as claimed in claim 5, which is characterized in that in the reaction solution A: N- isopropyl
Base acrylamide, maleic anhydride, N, the parts by weight of N '-methylene-bisacrylamide are respectively 5~10 parts, 2~3 parts, 0.05
~0.1 part；In the reaction solution B: ammonium ceric nitrate, cellulose nano-fibrous, modified by vinyl silica parts by weight point
It Wei not be 1~3 part, 2~6 parts, 0.2~0.5 part.
7. the preparation method of temperature-sensitive hydrogel as claimed in claim 5, which is characterized in that the modified by vinyl titanium dioxide
Silicon the preparation method comprises the following steps: by vinyltriethoxysilane and silicon dioxde reaction, obtain modified by vinyl silica.
8. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that the frerrous chloride and iron chloride
Mixed solution in, the molar ratio of frerrous chloride and iron chloride is 1:2；The concentration of the ammonium hydroxide is 1mol/L.
9. a kind of temperature-sensitive hydrogel that the preparation method as described in any one of claim 1~8 obtains is in heavy metal ion
Purposes in absorption.
10. purposes as claimed in claim 9, which is characterized in that the heavy metal ion is copper ion.
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