CN107442086B - A kind of adsorbent material and its preparation method and application causing shape memory function with water - Google Patents

A kind of adsorbent material and its preparation method and application causing shape memory function with water Download PDF

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CN107442086B
CN107442086B CN201710742976.XA CN201710742976A CN107442086B CN 107442086 B CN107442086 B CN 107442086B CN 201710742976 A CN201710742976 A CN 201710742976A CN 107442086 B CN107442086 B CN 107442086B
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shape memory
memory function
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water
adsorbent material
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CN107442086A (en
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张敏
黄学芳
李成涛
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a kind of adsorbent material and its preparation method and application for causing shape memory function with water, which is to carry out adsorbent material made from physical crosslinking gelation using the tape casting in water solution system；Wherein, porous water solution system is made by 10~20 parts of functional polymer materials containing amido functional group, 10~20 parts containing polyhydroxy/carboxyl/amino water-soluble high molecular polymer, 0.5~10 part of microorganism, 0.01~10 part of nutrient solution by mass fraction.The preparation method is easy to operate, at low cost, raw material is easy to get, prepared material not only has excellent absorption property, and non-stimulated quick response can be realized in deionized water at normal temperature, the excellent mechanical performance of the material and shape memory function are imparted, and this performance goes out certain recyclability.

Description

A kind of adsorbent material and its preparation method and application causing shape memory function with water
Technical field
The invention belongs to shape memory polymer composite material technical fields, and in particular to there is one kind water to cause shape memory Adsorbent material of function and its preparation method and application.
Background technique
Shape memory high molecule material is a kind of novel intelligent macromolecule material responded to extraneous environmental stimulus. The material under certain condition (such as ultraviolet irradiation state), is endowed certain shape under external influence；When external condition is sent out When changing, it can correspondingly change shape and be fixed.If external environment changes again in a particular manner, it Reversibly restore to starting form, the circulation for " remember primary state → fixed deformation state → recovery primary state " to complete, This property of polymer is known as memory effect.Environmental stimuli can be passed through after implementing deformation to shape memory polymer material (such as heat, light, power, electricity, magnetic, chemistry) makes it be returned to the state before deformation, and this unique performance has evoked grinding for people Study carefully interest.In recent years, researcher constantly can make shape-memory material a variety of driving methods that deformation occurs replys in exploration, and take Obtained good research achievement.However, although at present shape-memory polymer driving method oneself realize diversification (as heat, light, Electricity, magnetic etc.), but corresponding research also seldom expands to this convenient, efficient, quick, the potential stimulation mode of tool of pure water.
ToshisadaTakahashi etc. is the study found that the polyurethane containing low molecular weight soft segment shows good shape Shape memory performance, and the Tg of shape memory polyurethane is usually at 10~50 DEG C；Cyclic tension experiments have shown that, with cyclic tension time Several and tensile stress increase, sample residual stress increase, and deformation recovery stress is reduced；DMA experiments have shown that, the poly- ammonia of shape memory The shape-memory properties of ester should be attributed to the molecular motion of amorphous soft segment.
Bin Yan etc. has studied influence of the moisture to polymer Tg value, it is found that the intrusion meeting failure mode memory of aqueous vapor is poly- Hydrogen bond in urethane between N-H key and C=O key, so that it is decreased obviously Tg value, and this process is that heating is reversible, 120 DEG C when can all remove the effect of water.This moisture being partly absorbed is divided into two parts again: free state water and bonding state water.Wherein Free state water is to the Tg of polymer and is uniaxially stretched performance and has little effect, and bonding state water to Tg and is uniaxially stretched performance and has It significantly affects, it can be considered that this is a kind of water cause shape-memory polymer.
Many research shape memory high molecule materials all utilize solvent method to synthesize at present, have used in synthesis process a large amount of Organic solvent, but being increasingly enhanced and security for all countries, the establishment of environmental regulation and increasingly strengthen, tradition with people's environmental consciousness The application of solvent type high molecular material is increasingly restricted, and water-soluble high-molecular material has the advantages such as environmental protection, energy conservation, because This has obtained extensive concern.But shape-memory material still has some shortcomings and defect at present, mainly: recovery of shape power Small, lesser stress (< 4MPa) can make it lose shape memory function, and recovery rate is slower, and mechanical strength and chemistry are durable Property it is not ideal enough, recovery of shape temperature is inaccurate, and processing conditions is stringenter, remembers without amphicheirality and comprehensive property etc.；With General-purpose plastics is compared, and higher cost, processing performance are poor, realizes that unitized difficulty need to be captured at present.Therefore optimization shape The shape-memory properties of shape memory polymer, reduce cost, improve its comprehensive performance, are the hairs of shape-memory polymer research from now on The key point of exhibition.
Summary of the invention
It is an object of the invention to propose it is a kind of with water cause shape memory function adsorbent material and preparation method thereof and Using using the functional polymer material containing amido functional group and another containing polyhydroxy/carboxyl/amino water-soluble high score The mutual synergistic effect of sub- polymer is blended the composite material for being formed and having memory function, which has excellent water-fast Property and higher elongation at break.The composite material that microorganism prepares natural environmental-protective is introduced simultaneously, and raw material has source wide, economical It is easy to get, the composite material of preparation has the characteristics that nontoxic, easy mineralising, degradable.And the composite material of synthesis can be utilized Contained in amino, carboxyl, the functional groups such as hydroxyl carry out absorption dyestuff and heavy metal ion.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of the adsorbent material with shape memory function, includes the following steps:
1) by 10~40 parts of functional polymer materials containing amido functional group, 10~25 parts containing polyhydroxy/carboxyl/ Amino polymer is dissolved in water, and at 20 DEG C~80 DEG C, is stirred to react, and shape memory function matrices of composite material A is obtained；
2) 0.5~10 part of mass fraction of microorganism, 0.01~10 part of nutrient solution are mixed, is stirred at 20 DEG C~50 DEG C Uniformly, microbiological culture media B is obtained；
3) temperature of shape memory function matrices of composite material A is reduced to 20 DEG C~50 DEG C, microbiological culture media is added B is stirred evenly at 20 DEG C~50 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is formed by physical crosslinking Method obtains porous gel matrix C；
4) porous gel matrix C thaw after freeze-day with constant temperature to get to shape memory function adsorbent material.
As a further improvement of the present invention, described is polyvinyl alcohol containing polyhydroxy/carboxyl/amino polymer, gathers Acrylic acid and its copolymer, cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch, hydroxyethyl cellulose, water-soluble first One or more mixtures of shell element, gelatin.
As a further improvement of the present invention, the functional polymer material containing amido functional group is polyacrylamide One of amine, polyetheramine, poly- phthalein amine, polyethyleneimine, aqueous polyurethane, polyurethane elastomer, polyvinylpyrrolidone or A variety of mixtures.
As a further improvement of the present invention, the microorganism be lactic acid bacteria, Escherichia coli, butyric, bacillus, One of saccharomycete, lactobacillus, Bifidobacterium, actinomyces, chlorella or a variety of Mixed Microbes.
As a further improvement of the present invention, the nutrient solution is beef extract, peptone, sodium chloride, calcium carbonate, phosphoric acid Salt, magnesium sulfate, sodium nitrate, potassium nitrate, glucose, calcium citrate, citric acid, salt, sodium bicarbonate, starch, brewer's wort, distilled water One of or a variety of combinations.
As a further improvement of the present invention, in step 1), mixing speed is 40~400r/min, and stirring 0.1~12 is small When.
As a further improvement of the present invention, in step 3), physical crosslinking forming method is circulating frozen-freezing process, very One of empty seasoning, mechanical stirring, ultraviolet lighting, heating, microwave radiation or a variety of combinations.
As a further improvement of the present invention, in step 4), freeze-day with constant temperature is permanent in 25~45 DEG C of vacuum oven Temperature dry 4~36 hours.
A kind of adsorbent material as made from the preparation method with shape memory function, material shape in 2min Shape memory is replied completely, and shape recovery rate reaches 85%~98%；Elongation at break after the material impregnates in deionized water Increase 2~4 times.
A kind of biodegradable plastic film as made from the preparation method is applied in absorption dyestuff, can biology drop For adsorbing dyestuff after solution plastic film water absorption and swelling, dyestuff includes: methyl orange, methylene blue, crystal violet, peacock green, alkalinity Magenta, bismarck brown, acid orange, weak acid orange R one or two kinds of mixtures.
Compared with the existing technology, the invention has the following advantages:
The present invention is using the functional polymer material containing amido functional group and contains polyhydroxy/carboxyl/amino water-soluble High molecular polymer by way of physical blending, while introducing microorganism preparation with shape memory function in the composite The adsorbent material of energy；The adsorbent material has amino, hydroxyl mostly, and carboxyl isoreactivity functional group is easy through ligand complex, quiet The modes such as Electro Sorb adsorb heavy metal ion and toxic dye, in addition suction of the introducing of microorganism to heavy metal and toxic dye Attached performance increases significantly, and mineralization occurs under the action of microorganism, peomotes its degradation；Entirely Preparation process all carries out in aqueous solution, nontoxic, natural environmental-protective, and the introducing of microorganism is on material structure without influencing simultaneously And significantly improve its absorption property, degradation property etc..The composite material has excellent water resistance and higher elongation at break. The composite material for preparing natural environmental-protective it is an object of the invention to introduce microorganism simultaneously, raw material have source wide, economical and easily available, The composite material of preparation has the characteristics that nontoxic, easy mineralising, degradable.
There is excellent shape memory function in the composite material that the present invention synthesizes, can be replied in 2min completely, and shape Shape response rate reaches 85~98%, has excellent water resistance and higher elongation at break；Contained amino, carboxyl, hydroxyl Ji Deng functional group carries out absorption dyestuff and heavy metal ion.
Detailed description of the invention
Fig. 1 is porous gel matrix SEM figure；
Fig. 2 is that the adsorbent material SEM of shape memory function schemes.
Specific embodiment
A kind of preparation method for the adsorbent material that shape memory function is caused with water of the present invention, comprising the following steps:
1) preparation of shape memory function matrices of composite material: contain amido functional group for 10~40 parts by mass fraction Functional polymer material, 10~25 parts containing polyhydroxy/carboxyl/amino water-soluble high molecular polymer be dissolved in 10~ In 1000 water, and at 20 DEG C~80 DEG C, mixing speed is 40~400r/min, blending and stirring 0.1~12 hour, obtains shape Memory function matrices of composite material A；
2) culture of microorganism base: 0.5~10 part of microorganism, the mixing of 0.01~10 part of nutrient solution, 20 DEG C~50 It DEG C stirs evenly, obtains microbiological culture media B；Microorganism be lactic acid bacteria, Escherichia coli, butyric, bacillus, saccharomycete, One of lactobacillus, Bifidobacterium, actinomyces, chlorella or a variety of Mixed Microbes；Nutrient solution is beef extract, peptone, chlorination Sodium, calcium carbonate, phosphate, magnesium sulfate, sodium nitrate, potassium nitrate, glucose, calcium citrate, citric acid, salt, sodium bicarbonate, shallow lake One of powder, brewer's wort, distilled water or a variety of combinations.
3) preparation of porous gel matrix: above-mentioned obtained matrix A temperature is reduced to 20 DEG C~50 DEG C, micro- life is added Object culture medium B is stirred evenly at 20 DEG C~50 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in -50 DEG C Circulating frozen thaws for several times in ultralow temperature incubator, obtains porous gel matrix C；
4) porous gel matrix C defrosting is placed on 4~36 hours of freeze-day with constant temperature in 25~45 DEG C of vacuum oven, i.e., Obtain the adsorbent material with shape memory function.
Below with reference to specific case study on implementation, preparation method of the invention is described further.
Embodiment 1:
A kind of preparation method of the adsorbent material with shape memory function, includes the following steps:
1) preparation of shape memory function matrices of composite material: by mass fraction by 10 parts of polyethyleneimines, 10 parts poly- Vinyl alcohol is dissolved in 100 parts of deionized water；At 80 DEG C, mixing speed 400r/min blending and stirring 12 hours, is obtained Shape memory function matrices of composite material A；
2) culture of microorganism base: 0.5 part of bacillus, the mixing of 0.01 part of peptone stir evenly at 50 DEG C, obtain To microbiological culture media B；
3) preparation of porous gel matrix: above-mentioned obtained matrix A temperature is reduced to 20 DEG C, microculture is added Base B is stirred evenly at 20 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in micro-wave oven and carries out spoke It penetrates, obtains porous gel matrix C；
4) porous gel matrix C is placed in 45 DEG C of air dry oven 4 hours of forced air drying to get to having shape note Recall the adsorbent material of function.
Comparative example 1:
1) preparation of shape memory function matrices of composite material: by mass fraction by 10 parts of polyethyleneimines, 10 parts poly- Vinyl alcohol is dissolved in 100 parts of deionized water；At 80 DEG C, mixing speed 400r/min blending and stirring 12 hours, is obtained Shape memory function matrices of composite material A；
2) preparation of porous gel matrix: being reduced to 20 DEG C for above-mentioned obtained matrix A temperature, stirs at 20 DEG C equal It is even, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in micro-wave oven and is radiated, obtain porous gel matrix C；
3) porous gel matrix C is placed in 45 DEG C of air dry oven 4 hours of forced air drying to get to having shape note Recall the adsorbent material of function.
Embodiment 2:
A kind of preparation method of the adsorbent material with shape memory function, includes the following steps:
1) preparation of shape memory function matrices of composite material: by mass fraction by 20 parts of polyurethane elastomers, 20 parts Polyvinylpyrrolidone, 20 parts of cellulose dissolutions are in 1000 parts of deionized water；At 20 DEG C, mixing speed 40r/min, Blending and stirring 0.1 hour, obtain shape memory function matrices of composite material A；
2) culture of microorganism base: 10 parts of bacillus, the mixing of 10 parts of beef extract stir evenly at 20 DEG C, obtain Microbiological culture media B；
3) preparation of porous gel matrix: above-mentioned obtained matrix A temperature is risen to 50 DEG C, microbiological culture media is added B is stirred evenly at 50 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in ultraviolet light and irradiates, obtain Porous gel matrix C；
4) porous gel matrix C defrosting is placed in 25 DEG C of vacuum oven 36 hours of freeze-day with constant temperature to get to tool There is the adsorbent material of shape memory function.
Comparative example 2:
1) preparation of shape memory function matrices of composite material: by mass fraction by 20 parts of polyacrylic acid, 20 parts of poly- second Alkene pyrrolidone, 20 parts of cellulose dissolutions are in 1000 parts of deionized water；At 20 DEG C, mixing speed 40r/min is blended Stirring 0.1 hour, obtains shape memory function matrices of composite material A；
2) preparation of porous gel matrix: rising to 50 DEG C for above-mentioned obtained matrix A temperature, stirs at 50 DEG C equal It is even, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in ultraviolet light and irradiates, obtain porous gel matrix C；
3) porous gel matrix C defrosting is placed in 25 DEG C of vacuum oven 36 hours of freeze-day with constant temperature to get to tool There is the adsorbent material of shape memory function.
Embodiment 3:
A kind of preparation method of the adsorbent material with shape memory function, includes the following steps:
1) preparation of shape memory function matrices of composite material: mass fraction is pressed by 15 parts of aqueous polyurethanes, 15 parts of poly- second Enol is dissolved in 100 parts of deionized water；At 80 DEG C, mixing speed 200r/min blending and stirring 8 hours, obtains shape Shape memory function matrices of composite material A；
2) culture of microorganism base: 5 parts of saccharomycete, the mixing of 5 parts of glucose stir evenly at 30 DEG C, obtain micro- life Object culture medium B；
3) preparation of porous gel matrix: above-mentioned obtained matrix A temperature is reduced to 30 DEG C, microculture is added Base B is stirred evenly at 30 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in circulating frozen at -50 DEG C It thaws for several times, obtains porous gel matrix C；
4) porous gel matrix C defrosting is placed in 30 DEG C of vacuum oven 20 hours of freeze-day with constant temperature to get to tool There is the adsorbent material of shape memory function.
The microscopic appearance of embodiment 3 is observed by SEM, as shown in figures 1 and 2.Fig. 1 is the porous gel matrix in embodiment, It observes that hole configurations is relatively more uniform closely knit in figure, there are a large amount of microorganisms to be uniformly adhered to its surface around hole wall, this table Bright microorganism is successfully supported on prepared composite material；Fig. 2 is the shape memory function composite material in embodiment Cross-section morphology observation figure, by observing in figure, microorganism is closely embedded in the material.This is because passing through hydroxyl Reversible change can occur under certain condition for base, the network structure that the molecule hydrogen bond action between amino is built, this structure, After i.e. gel-in-matrix passes through centainly processing, the network structure of gel-in-matrix becomes closely, and passes through after water immersion, this network Structure can be restored again again, make it have excellent water phase and answer shape memory function.The material has unique performance, increases It is functional, and environmentally protective, nonhazardous, so that it has potential application in the fields such as biological medicine and food.
Comparative example 3:
1) preparation of shape memory function matrices of composite material: mass fraction is pressed by 10 parts of aqueous polyurethanes, 20 parts of poly- second Enol is dissolved in 100 parts of deionized water；At 80 DEG C, mixing speed 200r/min blending and stirring 8 hours, obtains shape Shape memory function matrices of composite material A；
2) preparation of porous gel matrix: being reduced to 30 DEG C for above-mentioned obtained matrix A temperature, by mixed liquor using stream The method of prolonging is poured into polyfluortetraethylene plate, is placed in circulating frozen at -50 DEG C and is thawed for several times, obtains porous gel matrix C；
3) porous gel matrix C defrosting is placed in 30 DEG C of vacuum oven 20 hours of freeze-day with constant temperature to get to tool There is the adsorbent material of shape memory function.
Embodiment 4:
A kind of preparation method of the adsorbent material with shape memory function, includes the following steps:
1) preparation of shape memory function matrices of composite material: mass fraction is pressed by 20 parts of aqueous polyurethanes, 10 parts of poly- second Enol, 10 parts of carboxymethyl celluloses are dissolved in 110 parts of deionized water；At 50 DEG C, mixing speed 200r/min is blended Stirring 0.1 hour, obtains shape memory function matrices of composite material A；
2) culture of microorganism base: 10 parts of bacillus, the mixing of 0.01 part of brewer's wort stir evenly at 30 DEG C, obtain To microbiological culture media B；
3) preparation of porous gel matrix: above-mentioned obtained matrix A temperature is reduced to 30 DEG C, microculture is added Base B is stirred evenly at 30 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in micro-wave oven and carries out spoke It penetrates, obtains porous gel matrix C；
4) porous gel matrix C is placed in 45 DEG C of vacuum oven 4 hours of freeze-day with constant temperature to get to having shape The adsorbent material of memory function.
Comparative example 4:
1) preparation of shape memory function matrices of composite material: mass fraction is pressed by 20 parts of aqueous polyurethanes, 10 parts of poly- second Enol, 10 parts of carboxymethyl celluloses are dissolved in 110 parts of deionized water；At 50 DEG C, mixing speed 200r/min is blended Stirring 0.1 hour, obtains shape memory function matrices of composite material A；
2) preparation of porous gel matrix: being reduced to 30 DEG C for above-mentioned obtained matrix A temperature, stirs at 30 DEG C equal It is even, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in micro-wave oven and is radiated, obtain porous gel matrix C；
3) porous gel matrix C is placed in 45 DEG C of vacuum oven 4 hours of freeze-day with constant temperature to get to having shape The adsorbent material of memory function.
Embodiment 5:
A kind of preparation method of the adsorbent material with shape memory function, includes the following steps:
1) preparation of shape memory function matrices of composite material: mass fraction is pressed by 20 parts of polyacrylamides, 15 parts of poly- second Enol, 10 parts of starch dissolutions are in 1000 parts of deionized water；At 20 DEG C, mixing speed 400r/min, blending and stirring 8 is small When, obtain shape memory function matrices of composite material A；
2) culture of microorganism base: 0.01 part of chlorella, the mixing of 10 parts of phosphate stir evenly at 20 DEG C, obtain Microbiological culture media B；
3) preparation of the adsorbent material of shape memory function: above-mentioned obtained matrix A temperature is reduced to 20 DEG C, is added Microbiological culture media B is stirred evenly at 20 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in 45 DEG C Vacuum oven in 36 hours of freeze-day with constant temperature to get to shape memory function adsorbent material.
Comparative example 5；
1) preparation of shape memory function matrices of composite material: mass fraction is pressed by 20 parts of polyacrylamides, 15 parts of poly- second At 20 DEG C, mixing speed 400r/min blending and stirring 8 hours, obtains shape memory function composite wood for enol, 10 parts of starch Expect matrix A；
2) preparation of the adsorbent material of shape memory function: above-mentioned obtained matrix A temperature is reduced to 20 DEG C, is added Microbiological culture media B is stirred evenly at 20 DEG C, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in 45 DEG C Vacuum oven in 36 hours of freeze-day with constant temperature to get to shape memory function adsorbent material.
Examples 1 to 4 and the obtained sample of comparative example 1~4 test such as 1 institute of table the adsorption capacity of toxic dye Show.
Table 1
After the obtained sample of Examples 1 to 4 impregnates 2min in water, mechanical performance is tested such as compared with before immersion Shown in table 2.
Table 2
The obtained sample of Examples 1 to 5 mid labels at a distance of about 20mm 2 graticules, accurately measure its spacing L0.After being placed in self-control stretching clamp, sample is stretched at room temperature, extensibility should reach 100%, in a stretched state measurement mark Line spacing L1, unclamp the static 3min of fixture until shape no longer reply, again measure graticule spacing L2, it is in by the sample after stretching Two graticule spacing L of measurement are taken out in deionized water needed for free state is placed in deformation recovery, after 2min3, the shape of sample is solid Determine rate S calculation method to see formula (1), the shape recovery rate R calculation method of sample is shown in formula (2):
S=(L2-L0)/(L1-L0) (1)
R=(L2-L3)/(L2-L0) (2)
Examples 1 to 5 obtained sample shape fixed rate S and shape recovery rate R is as shown in table 3.
Table 3
Project Shape fixed rate S (%) Shape recovery rate R (%)
Embodiment 1 61% 92%
Embodiment 2 58% 89%
Embodiment 3 43% 87%
Embodiment 4 69% 96%
Embodiment 5 67% 91%
In short, a kind of adsorbent material with shape memory function of the present invention, which is in water solution system Adsorbent material made from physical crosslinking gelation is carried out using the tape casting；Wherein, porous water solution system is by mass fraction by 10 ~20 parts of functional polymer materials containing amido functional group, 10~20 parts contain polyhydroxy/carboxyl/amino water-soluble high score Sub- polymer, 0.5~10 part of microorganism, 0.01~10 part of nutrient solution are made；Contain polyhydroxy/carboxyl/amino water-soluble High molecular polymer is added in 10~1000 parts of deionized water by 0.1~20 part of high molecular polymer and is made.Benefit of the invention With the functional polymer material containing amido functional group and containing between polyhydroxy/carboxyl/amino water-soluble high molecular polymer Good compatibility forms matrix with mutually synergistic effect composite, while introducing a small amount of microorganism and being prepared for one kind with shape The adsorbent material of shape memory function.The preparation method is easy to operate, at low cost, raw material is easy to get, and prepared material not only has Excellent absorption property, and non-stimulated quick response can be realized in deionized water at normal temperature, it is excellent to impart the material Different mechanical performance and shape memory function, and this performance goes out certain recyclability.
The composite material has excellent adsorption function, wherein to dyestuff (such as methyl orange, methylene blue, crystal violet, peacock The dyestuffs such as green, basic fuchsin, bismarck brown, acid orange, weak acid orange R) adsorption rate can reach 94% or so.It is at normal temperature Can be achieved non-stimulated quick response, quick response can be realized in immersion in deionized water, can in 2min shape memory It replys completely, shape recovery rate reaches 85%~98%.
The material becomes milky from transparence in 30s in deionized water, and mineralization occurs.In deionized water Its elasticity and suppleness obviously increase after immersion, and elongation at break increases 2~4 times.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention Protection scope in.

Claims (7)

1. a kind of preparation method of the adsorbent material with shape memory function, which comprises the steps of:
1) by 10~40 parts of functional polymer materials containing amido functional group, 10~25 parts contain polyhydroxy/carboxyl/amino Polymer is dissolved in water, and at 20 DEG C~80 DEG C, is stirred to react, and shape memory function matrices of composite material A is obtained；
2) 0.5~10 part of mass fraction of microorganism, 0.01~10 part of nutrient solution are mixed, it is equal in 20 DEG C~50 DEG C stirrings It is even, obtain microbiological culture media B；
3) temperature of shape memory function matrices of composite material A is reduced to 20 DEG C~50 DEG C, microbiological culture media B, In is added 20 DEG C~50 DEG C stir evenly, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, by being physical crosslinking forming method, Obtain porous gel matrix C；
4) porous gel matrix C thaw after freeze-day with constant temperature to get to shape memory function adsorbent material；
Described is polyvinyl alcohol, polyacrylic acid and its copolymer, cellulose, hydroxypropyl containing polyhydroxy/carboxyl/amino polymer One or more mixing of base cellulose, carboxymethyl cellulose, starch, hydroxyethyl cellulose, water-soluble chitosan, gelatin Object；
The functional polymer material containing amido functional group is polyacrylamide, polyetheramine, poly- phthalein amine, polyethyleneimine One of amine, aqueous polyurethane, polyurethane elastomer, polyvinylpyrrolidone or a variety of mixtures；
The microorganism is lactic acid bacteria, Escherichia coli, butyric, bacillus, saccharomycete, lactobacillus, Bifidobacterium, unwrapping wire One of bacterium, chlorella or a variety of Mixed Microbes.
2. the preparation method of the adsorbent material according to claim 1 with shape memory function, it is characterised in that: described Nutrient solution be beef extract, peptone, sodium chloride, calcium carbonate, phosphate, magnesium sulfate, sodium nitrate, potassium nitrate, glucose, lemon One of sour calcium, citric acid, sodium bicarbonate, starch, brewer's wort, distilled water or a variety of combinations.
3. the preparation method of the adsorbent material according to claim 1 with shape memory function, it is characterised in that: step 1) in, mixing speed is 40~400r/min, is stirred 0.1~12 hour.
4. the preparation method of the adsorbent material according to claim 1 with shape memory function, it is characterised in that: step 3) in, physical crosslinking forming method is circulating frozen-freezing process, boulton process, mechanical stirring, ultraviolet lighting, heating, microwave One of radiation or a variety of combinations.
5. the preparation method of the adsorbent material according to claim 1 with shape memory function, it is characterised in that: step 4) in, freeze-day with constant temperature be in 25~45 DEG C of vacuum oven 4~36 hours of freeze-day with constant temperature.
6. with the adsorption material of shape memory function made from a kind of preparation method as described in claim 1 to 5 any one Material, it is characterised in that: material shape memory in 2min is replied completely, and shape recovery rate reaches 85%~98%；The material Elongation at break increases 2~4 times after impregnating in deionized water.
7. with the adsorption material of shape memory function made from a kind of preparation method as described in claim 1 to 5 any one Material is applied in absorption dyestuff, it is characterised in that: for adsorbing dyestuff after adsorbent material water absorption and swelling, dyestuff include: methyl orange, Methylene blue, crystal violet, peacock green, basic fuchsin, bismarck brown, acid orange, weak acid orange R one or two kinds of mixtures.
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