CN107442086A - A kind of sorbing material that shape memory function is caused with water and its preparation method and application - Google Patents

A kind of sorbing material that shape memory function is caused with water and its preparation method and application Download PDF

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CN107442086A
CN107442086A CN201710742976.XA CN201710742976A CN107442086A CN 107442086 A CN107442086 A CN 107442086A CN 201710742976 A CN201710742976 A CN 201710742976A CN 107442086 A CN107442086 A CN 107442086A
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shape memory
memory function
preparation
sorbing material
water
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CN107442086B (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 sorbing material that shape memory function is caused with water and its preparation method and application, the sorbing material is to carry out sorbing material made from physical crosslinking gelation using the tape casting in water solution system；Wherein, porous water solution system is made 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 by 10~20 parts of functional high molecule materials containing amido functional group, 10~20 parts.The preparation method is simple to operate, cost is low, raw material is easy to get, prepared material not only has excellent absorption property, and non-stimulated quick response can be achieved in deionized water at normal temperatures, the excellent mechanical performance of the material and shape memory function are imparted, and this performance goes out certain recyclability.

Description

A kind of sorbing material that shape memory function is caused with water and its preparation method and application
Technical field
The invention belongs to shape memory polymer composite material technical field, and in particular to there is one kind water to cause shape memory Sorbing material of function and its preparation method and application.
Background technology
Shape memory high molecule material is a kind of new 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 During changing, it can correspondingly change shape and be fixed.If external environment condition changes again in a particular manner, it Reversibly recover to starting form, so as to complete the circulation of " remember primary state → fixed deformation state → recovery primary state ", This property of polymer is referred to as memory effect.It can pass through environmental stimuli after implementing deformation to shape memory polymer material (such as heat, light, power, electricity, magnetic, chemistry) makes its state being returned to before deformation, and this unique performance has evoked grinding for people Study carefully interest.In recent years, researcher constantly can make shape-memory material deform upon a variety of type of drive of reply in exploration, and take Obtained good achievement in research.However, although at present shape-memory polymer type of drive oneself realize variation (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.
The researchs such as ToshisadaTakahashi find that the polyurethane containing low molecule amount soft segment shows good shape Shape memory performance, and the Tg of shape memory polyurethane is generally at 10~50 DEG C；Cyclic tension experiment shows, with cyclic tension The increase of number and tensile stress, the increase of sample residual stress, deformation recovery stress are reduced；DMA, which is tested, to be shown, 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. have 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 keys and C=O keys, so that Tg values are decreased obviously, 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 has little to no effect to the Tg and uniaxial tension performance of polymer, and bonding state water has to Tg and uniaxial tension performance Significantly affect, it can be considered that this, which is a kind of water, causes shape-memory polymer.
Many research shape memory high molecule materials are all synthesized using solvent method at present, have been used in building-up process substantial amounts of Organic solvent, but with people's environmental consciousness increasingly enhancing and security for all countries, the establishment of environmental regulation and increasingly strengthen, tradition The application of solvent-borne type high polymer 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 It is small, less stress (<It can 4MPa) be set to lose shape memory function, recovery rate is slower, and mechanical strength and chemistry are durable Property it is not ideal enough, recovery of shape temperature is not accurate enough, and processing conditions is stricter, remembers without amphicheirality and comprehensive property etc.；With General-purpose plastics is compared, and cost is higher, processing characteristics is 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 combination property, are the hairs of shape-memory polymer research from now on The key point of exhibition.
The content of the invention
It is an object of the invention to propose it is a kind of with water cause shape memory function sorbing material and preparation method thereof and Using containing polyhydroxy/carboxyl/amino water-soluble high score with another using the functional high molecule material containing amido functional group The mutual synergy of sub- polymer is blended to form the composite with memory function, and the composite has excellent water-fast Property and higher elongation at break.The composite that microorganism prepares natural environmental-protective is introduced simultaneously, and raw material has source wide, economical It is easy to get, the composite of preparation has the characteristics of nontoxic, easy mineralising, degradable.And the composite of synthesis can be utilized In contained amino, carboxyl, the functional group such as hydroxyl carries out adsorbing dyestuff and heavy metal ion.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of preparation method of the sorbing material with shape memory function, comprises the following steps：
1) by 10~40 parts of functional high molecule 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, stirring reaction, obtains shape memory function matrices of composite material A；
2) microorganism of 0.5~10 part of mass fraction, 0.01~10 part of nutrient solution are mixed, in 20 DEG C~50 DEG C stirrings Uniformly, microbiological culture media B is obtained；
3) shape memory function matrices of composite material A temperature is reduced to 20 DEG C~50 DEG C, adds microbiological culture media B, stirred at 20 DEG C~50 DEG C, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, be molded by being physical crosslinking Method, obtain porous gel matrix C；
4) freeze-day with constant temperature after porous gel matrix C thaws, that is, obtain the sorbing material with shape memory function.
As a further improvement on 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 Shell element, one or more mixtures of gelatin.
As a further improvement on the present invention, the functional high molecule material containing amido functional group is polyacrylamide Amine, polyetheramine, poly- phthalein amine, polyethyleneimine, aqueous polyurethane, polyurethane elastomer, one kind in polyvinylpyrrolidone or A variety of mixtures.
As a further improvement on the present invention, described microorganism be lactic acid bacteria, Escherichia coli, butyric, bacillus, One or more Mixed Microbes in saccharomycete, lactobacillus, Bifidobacterium, actinomyces, chlorella.
As a further improvement on the present invention, described 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 acid carbonate, starch, brewer's wort, distilled water In one or more combinations.
As a further improvement on the present invention, in step 1), mixing speed is 40~400r/min, and stirring 0.1~12 is small When.
As a further improvement on the present invention, in step 3), physical crosslinking forming method is circulating frozen-freezing process, very One or more combinations in empty seasoning, mechanical agitation, ultraviolet lighting, heating, microwave radiation.
As a further improvement on the present invention, in step 4), freeze-day with constant temperature is permanent in 25~45 DEG C of vacuum drying chamber Temperature dries 4~36 hours.
A kind of sorbing material as made from described 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 soaks in deionized water 2~4 times of increase.
A kind of biodegradable plastic film as made from described preparation method is applied in dyestuff is adsorbed, and biological can be dropped It is used to adsorb dyestuff after solution plastic sheeting water absorption and swelling, dyestuff includes：Methyl orange, methylene blue, crystal violet, peacock green, alkalescence Magenta, bismarck brown, acid orange, weak acid orange R one or two kinds of mixtures.
Relative to prior art, the invention has the advantages that：
The present invention is using the functional high molecule material containing amido functional group and contains polyhydroxy/carboxyl/amino water-soluble High molecular polymer, by way of physical blending, while the preparation of introducing microorganism has shape memory work(in the composite The sorbing material of energy；The sorbing material has amino mostly, hydroxyl, and carboxyl isoreactivity functional group is quiet easily by ligand complex The modes such as Electro Sorb adsorb heavy metal ion and toxic dye, in addition the introducing heavy metal of microorganism and the suction of toxic dye Attached performance increases significantly, and mineralization occurs in the presence of microorganism, helps lend some impetus to its degradation；Entirely Preparation process is all carried out in aqueous, nontoxic, natural environmental-protective, and the introducing of microorganism is on material structure without influenceing simultaneously And significantly improve its absorption property, degradation property etc..The composite has excellent water resistance and higher elongation at break. It is an object of the invention to introduce the composite that microorganism prepares natural environmental-protective simultaneously, raw material has that source is wide, economical and easily available, The composite of preparation has the characteristics of nontoxic, easy mineralising, degradable.
There is excellent shape memory function in the composite 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 groups carry out adsorbing dyestuff and heavy metal ion.
Brief description of the drawings
Fig. 1 schemes for porous gel matrix SEM；
Fig. 2 is that the sorbing material SEM of shape memory function schemes.
Embodiment
A kind of preparation method of the sorbing material with water cause shape memory function of the present invention, comprises the following steps：
1) preparation of shape memory function matrices of composite material：Contain amido functional group by 10~40 parts by mass fraction Functional high molecule 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 DEG C stir, obtain microbiological culture media B；Microorganism be lactic acid bacteria, Escherichia coli, butyric, bacillus, saccharomycete, One or more Mixed Microbes in lactobacillus, Bifidobacterium, actinomyces, chlorella；Nutrient solution is beef extract, peptone, chlorination Sodium, calcium carbonate, phosphate, magnesium sulfate, sodium nitrate, potassium nitrate, glucose, calcium citrate, citric acid, salt, sodium acid carbonate, shallow lake One or more combinations in powder, brewer's wort, distilled water.
3) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is reduced to 20 DEG C~50 DEG C, adds micro- life Thing culture medium B, stirred at 20 DEG C~50 DEG C, 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 is placed in 4~36 hours of freeze-day with constant temperature in 25~45 DEG C of vacuum drying chamber after thawing, i.e., Obtain the sorbing material with shape memory function.
With reference to specific case study on implementation, the preparation method of the present invention is described further.
Embodiment 1：
A kind of preparation method of the sorbing material with shape memory function, comprises 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, obtain 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 at 50 DEG C, obtain To microbiological culture media B；
3) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is reduced to 20 DEG C, adds microculture Base B, stirred at 20 DEG C, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in micro-wave oven and carries out spoke Penetrate, obtain porous gel matrix C；
4) porous gel matrix C is placed in 4 hours of forced air drying in 45 DEG C of air dry oven, that is, obtains with shape note Recall the sorbing 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, obtain Shape memory function matrices of composite material A；
2) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is reduced to 20 DEG C, stirred 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 4 hours of forced air drying in 45 DEG C of air dry oven, that is, obtains with shape note Recall the sorbing material of function.
Embodiment 2：
A kind of preparation method of the sorbing material with shape memory function, comprises 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 at 20 DEG C, obtain Microbiological culture media B；
3) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is risen to 50 DEG C, adds microbiological culture media B, stirred at 50 DEG C, 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 is placed in 36 hours of freeze-day with constant temperature in 25 DEG C of vacuum drying chamber after thawing, that is, is had There is the sorbing 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, blending Stirring 0.1 hour, obtains shape memory function matrices of composite material A；
2) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is risen to 50 DEG C, stirred 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, obtains porous gel matrix C；
3) porous gel matrix C is placed in 36 hours of freeze-day with constant temperature in 25 DEG C of vacuum drying chamber after thawing, that is, is had There is the sorbing material of shape memory function.
Embodiment 3：
A kind of preparation method of the sorbing material with shape memory function, comprises the following steps：
1) preparation of shape memory function matrices of composite material：By mass fraction 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, shape is obtained 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 at 30 DEG C, obtain micro- life Thing culture medium B；
3) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is reduced to 30 DEG C, adds microculture Base B, stirred at 30 DEG C, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in circulating frozen at -50 DEG C Thaw for several times, obtain porous gel matrix C；
4) porous gel matrix C is placed in 20 hours of freeze-day with constant temperature in 30 DEG C of vacuum drying chamber after thawing, that is, is had There is the sorbing material of shape memory function.
The microscopic appearance of embodiment 3, such as Fig. 1, shown in 2 are observed by SEM.Fig. 1 is the porous gel matrix in embodiment, Observe that pore space structure is relatively more uniform closely knit, there are a large amount of microorganisms to be uniformly adhered to its surface, this table around hole wall in figure Bright microorganism is successfully supported on prepared composite；Fig. 2 is the shape memory function composite in embodiment Cross-section morphology observation figure, by being observed in figure, microorganism is closely embedded among the material.This is due to pass 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, I.e. gel-in-matrix by necessarily handling after, the network structure of gel-in-matrix becomes close, and pass through water immersion after, this network Structure can be recovered again again, make it have excellent aqueous phase and answer shape memory function.The material has unique performance, adds Its feature, and green, nonhazardous so that it has potential application value in the field such as biological medicine and food.
Comparative example 3：
1) preparation of shape memory function matrices of composite material：By mass fraction 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, shape is obtained Shape memory function matrices of composite material A；
2) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is reduced to 30 DEG C, 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 is placed in 20 hours of freeze-day with constant temperature in 30 DEG C of vacuum drying chamber after thawing, that is, is had There is the sorbing material of shape memory function.
Embodiment 4：
A kind of preparation method of the sorbing material with shape memory function, comprises the following steps：
1) preparation of shape memory function matrices of composite material：By mass fraction 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, blending 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 at 30 DEG C, obtain To microbiological culture media B；
3) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is reduced to 30 DEG C, adds microculture Base B, stirred at 30 DEG C, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in micro-wave oven and carries out spoke Penetrate, obtain porous gel matrix C；
4) porous gel matrix C is placed in 4 hours of freeze-day with constant temperature in 45 DEG C of vacuum drying chamber, that is, obtained with shape The sorbing material of memory function.
Comparative example 4：
1) preparation of shape memory function matrices of composite material：By mass fraction 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, blending Stirring 0.1 hour, obtains shape memory function matrices of composite material A；
2) preparation of porous gel matrix：Above-mentioned resulting matrix A temperature is reduced to 30 DEG C, stirred 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 4 hours of freeze-day with constant temperature in 45 DEG C of vacuum drying chamber, that is, obtained with shape The sorbing material of memory function.
Embodiment 5：
A kind of preparation method of the sorbing material with shape memory function, comprises the following steps：
1) preparation of shape memory function matrices of composite material：By mass fraction 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 at 20 DEG C, obtain Microbiological culture media B；
3) preparation of the sorbing material of shape memory function：Above-mentioned resulting matrix A temperature is reduced to 20 DEG C, added Microbiological culture media B, stirred at 20 DEG C, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in 45 DEG C Vacuum drying chamber in 36 hours of freeze-day with constant temperature, that is, obtain the sorbing material with shape memory function.
Comparative example 5；
1) preparation of shape memory function matrices of composite material：By mass fraction by 20 parts of polyacrylamides, 15 parts of poly- second Enol, 10 parts of starch mixing speed 400r/min, blending and stirring 8 hours, obtain shape memory function composite wood at 20 DEG C Expect matrix A；
2) preparation of the sorbing material of shape memory function：Above-mentioned resulting matrix A temperature is reduced to 20 DEG C, added Microbiological culture media B, stirred at 20 DEG C, mixed liquor is poured into polyfluortetraethylene plate using the tape casting, is placed in 45 DEG C Vacuum drying chamber in 36 hours of freeze-day with constant temperature, that is, obtain the sorbing material with shape memory function.
Sample obtained by embodiment 1~4 and comparative example 1~4 is tested such as the institute of table 1 adsorption capacity of toxic dye Show.
Table 1
After sample obtained by embodiment 1~4 soaks 2min in water, its mechanical performance is tested such as compared with before immersion Shown in table 2.
Table 2
The mid labels of sample obtained by embodiment 1~5 accurately determine its spacing at a distance of about 20mm 2 graticules L0.After being placed in self-control stretching clamp, sample is stretched at room temperature, its extensibility should reach 100%, in a stretched state measure mark Line spacing L1, the static 3min of fixture is unclamped until shape is no longer replied, and determines graticule spacing L again2, it is in by the sample after stretching Free state is placed in the deionized water needed for deformation recovery, and two graticule spacing L of measure are taken out after 2min3, the shape of sample consolidates Determine rate S computational methods and see formula (1), the shape recovery rate R computational methods of sample are shown in formula (2)：
S=(L2-L0)/(L1-L0) (1)
R=(L2-L3)/(L2-L0) (2)
Sample shape fixed rate S and shape recovery rate R obtained by embodiment 1~5 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 a word, a kind of sorbing material with shape memory function of the present invention, the sorbing material is in water solution system Sorbing material made from physical crosslinking gelation is carried out using the tape casting；Wherein, porous water solution system presses mass fraction by 10 ~20 parts of functional high molecule 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.Profit of the invention With the functional high molecule material containing amido functional group and containing between polyhydroxy/carboxyl/amino water-soluble high molecular polymer Good compatibility and mutually synergy composite form matrix, while introduce a small amount of microorganism and be prepared for a kind of having shape The sorbing material of shape memory function.The preparation method is simple to operate, cost is low, raw material is easy to get, and prepared material not only has Excellent absorption property, and non-stimulated quick response can be achieved in deionized water at normal temperatures, it is excellent to impart the material Different mechanical performance and shape memory function, and this performance goes out certain recyclability.
The composite 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 temperatures Non-stimulated quick response can be achieved, quick response can be achieved in immersion in deionized water, can in 2min shape memory Reply completely, shape recovery rate reaches 85%~98%.
The material is changed into milky in 30s from transparence in deionized water, and mineralization occurs.In deionized water Its elasticity and suppleness substantially increase after immersion, and elongation at break increases 2~4 times.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention Protection domain in.

Claims (10)

1. a kind of preparation method of the sorbing material with shape memory function, it is characterised in that comprise the following steps：
1) 10~40 parts of functional high molecule materials containing amido functional group, 10~25 parts are contained into polyhydroxy/carboxyl/amino Polymer is dissolved in water, and at 20 DEG C~80 DEG C, stirring reaction, obtains shape memory function matrices of composite material A；
2) microorganism of 0.5~10 part of mass fraction, 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) shape memory function matrices of composite material A temperature is reduced to 20 DEG C~50 DEG C, adds microbiological culture media B, 20 DEG C~50 DEG C are stirred, and mixed liquor is poured into polyfluortetraethylene plate using the tape casting, by being physical crosslinking forming method, Obtain porous gel matrix C；
4) freeze-day with constant temperature after porous gel matrix C thaws, that is, obtain the sorbing material with shape memory function.
2. the preparation method of the sorbing material according to claim 1 with shape memory function, it is characterised in that：It is described Containing polyhydroxy/carboxyl/amino polymer be polyvinyl alcohol, polyacrylic acid and its copolymer, cellulose, hydroxy propyl cellulose Element, carboxymethyl cellulose, starch, hydroxyethyl cellulose, water-soluble chitosan, one or more mixtures of gelatin.
3. the preparation method of the sorbing material according to claim 1 with shape memory function, it is characterised in that：It is described The functional high molecule material containing amido functional group be polyacrylamide, it is polyetheramine, poly- phthalein amine, polyethyleneimine, water-based poly- One or more mixtures in urethane, polyurethane elastomer, polyvinylpyrrolidone.
4. the preparation method of the sorbing material according to claim 1 with shape memory function, it is characterised in that：It is described Microorganism for lactic acid bacteria, Escherichia coli, butyric, bacillus, saccharomycete, lactobacillus, Bifidobacterium, actinomyces, bead One or more Mixed Microbes in algae.
5. the preparation method of the sorbing material according to claim 1 with shape memory function, it is characterised in that：It is described Nutrient solution for beef extract, peptone, sodium chloride, calcium carbonate, phosphate, magnesium sulfate, sodium nitrate, potassium nitrate, glucose, lemon One or more combinations in sour calcium, citric acid, salt, sodium acid carbonate, starch, brewer's wort, distilled water.
6. the preparation method of the sorbing 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.
7. the preparation method of the sorbing 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 agitation, ultraviolet lighting, heating, microwave One or more combinations in radiation.
8. the preparation method of the sorbing 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 drying chamber 4~36 hours of freeze-day with constant temperature.
9. there is the adsorption material of shape memory function made from a kind of preparation method as described in claim 1 to 8 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 soaking in deionized water.
10. biodegradable plastic film made from a kind of preparation method as described in claim 1 to 8 any one is adsorbing Applied in dyestuff, it is characterised in that：It is used to adsorb dyestuff after biodegradable plastic film water absorption and swelling, dyestuff includes：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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