CN105884969B - A kind of double-bang firecracker is answered and adjustable intelligent aqueous gel of respondent behavior and preparation method thereof - Google Patents
A kind of double-bang firecracker is answered and adjustable intelligent aqueous gel of respondent behavior and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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Abstract
The invention belongs to technical field of function materials, specially a kind of double-bang firecracker is answered and adjustable intelligent aqueous gel of respondent behavior and preparation method thereof.The present invention removes two chalcogen compound powder of transition metal by natural polymer water phase ultrasound, the nanoscale twins of two chalcogen compound of transition metal of polymer non-covalent bond modification are obtained, temperature sensitive monomer and other comonomers is added and one step of crosslinking agent prepares the composite hydrogel of two chalcogen compound nanoscale twins.The plural gel excellent in mechanical performance, at the same have near infrared light response and temperature-responsive double response characteristics, and respondent behavior may customize it is adjustable.Raw material involved in the present invention is the nontoxic reagents such as natural polymer, solvent for use is water, preparation process green non-pollution, it is easy to operate, production cost is low, it is expected to realize large-scale industrial production, obtained intelligent aqueous gel has multiple functions, has the potentiality prepared on a large scale and wide commercial application prospect.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of double-bang firecracker is answered and the adjustable intelligence of respondent behavior
Hydrogel and preparation method thereof.
Background technology
In recent years, intellectual material is closely related with bionical and information due to its unique response and feedback function,
Cause the great attention of countries in the world government and a variety of subject scientists.People can be compound by MOLECULE DESIGN and multiple material
Method make material that there are the Premium Features that are assigned of biology:Such as self-reparing capability, understanding and distinguishing ability, stimuli responsive
With environment adaptability to changes etc..In the intellectual material field developed at present, intelligent macromolecule hydrogel material therein, due to it
High degree of water amount is often good with human body environment's compatibility, more causes the interest of the numerous researchers in countries in the world.Common
Environmental stimulus factor such as temperature and light stimulus under, these intelligent aqueous gel self properties that can generate significant response can be therewith
It changes, therefore people can be designed that a series of chemical energy-mechanical energy, interior energy-chemical energy-mechanical energy, luminous energy-chemistry
The multiple kinds of energies reforming unit such as energy-mechanical energy, in wearable smart machine, artificial haptic system, artificial-muscle and drug release
The fields such as system have important application prospect.But often its mechanical property is poor, rings for existing intelligent aqueous gel material at present
It answers that behavior is single, not good etc. enough factors of biocompatibility, greatly limits its practical application.Therefore, it develops with excellent
Mechanical property, respondent behavior may customize intelligent aqueous gel that is adjustable, having superior bio compatibility, it will have extensive quotient
Industry application prospect.
In intelligent macromolecule hydrogel material, relatively conventional intelligent response behavior is thermal response and photoresponse, especially
With reference to photothermal response reagent and temperature sensitive high molecular material, the material of photo-thermal and temperature double-response can be prepared, utilizes luminous energy-interior
Can-chemical transformation of energy, position and the behavior of remote control gel can be realized, before having greatly application in terms of the smart machine
Scape.It has been reported that recently（《Nanometer bulletin》Nano Lett. 2013, 13, 2826 − 2830）It is set by anisotropic structure
Meter, is prepared for the plural gel of redox graphene and elastin, can be deformed by the light-operated gel of near-infrared, but
It is that wherein redox graphene prepares complex, the cost of material used is higher and complex process, is unfavorable for extensive
Commercially produce application.2014《It is micro-nano》It also has been reported that on magazine and is polymerize using ferroferric oxide nano granules with temperature sensitive
Object is compound, is prepared for the intelligent aqueous gel of multiple response（Small 2014, 10, 2796–2800）, can realize remote control
The position of gel, but the respondent behavior of intelligent aqueous gel is generally all fairly simple at present, is difficult to realize more complicated gel
Motor behavior.In addition, required photothermal response agent such as gold nano grain, graphite in many light-operated intelligent hydrogel materials
Alkene, carbon nanotube, ferroferric oxide nano granules etc., all there are preparation process is complicated, production cost is higher, biocompatibility still
The problems such as disputable, is unfavorable for being commercialized production application, and the mechanical property of macromolecule hydrogel network is poor, difficult
To realize compound movement.
We are concerned about other than the photothermal response reagent widely studied above, and two chalcogen compound of transition metal also has
There is a stronger near-infrared absorption ability, 2013《German applied chemistry》（Angew. Chem. 2013, 125, 4254 –
4258）It is reported that two chalcogen compound of transition metal is also probably a kind of potential photothermal reagent, and have
There is good biocompatibility, preparation method is simple, can realize that water phase processes, and is expected to realize industrialized production and application.
And 2014 have research（Advanced Functional Materials, 25, 2980-2991.）It points out, in gel net
The sheet layer materials such as lithium diatomaceous earth are further introduced into network, the mechanical property of gel can be further improved；Pass through two-layer gel structure
Design is also easier to realize the intelligent response behavior of gel.
It is chalcogenide that the present invention dexterously removes transition metal two using the aqueous solution of natural polymer, that is, carboxyl chitosan
Close object, obtained nanoscale twins have good dispersibility in water, by with lithium diatomaceous earth and temperature sensitive high-molecular gel network
It is compound, by two step gelation reactions, anisotropic bilayer hydrogel material in a kind of structure is devised, wherein one layer has
Photo-thermal and temperature-responsive feature, layer of gel network only have swelling behavior, therefore under near infrared light photograph or heating condition,
Anisotropic volume contraction/swelling variation can occur for gel, realize luminous energy-interior energy-machinery transformation of energy, obtain a kind of biology
The good double-response intelligent gel rubber material of compatibility, and by changing comonomer ratio, the response of gel can be adjusted
Temperature realizes that the respondent behavior of gel is adjusted, and is expected to be applied in intellectual material field.And due to being adopted in preparation process
Medium is natural polymer aqueous solution, is not related to any organic solvent in preparation process wherein, therefore preparation process is easy
Green pollution-free, preparation condition relative loose, before being suitble to high-volume, large-scale production and having extensive commercial application
Scape.
Invention content
The purpose of the present invention is to provide a kind of double-bang firecracker should and the adjustable intelligent aqueous gel of respondent behavior and its preparation
Method.
Double-bang firecracker proposed by the present invention is answered and the preparation method of the adjustable intelligent aqueous gel of respondent behavior, is to pass through green
Water phase remove to obtain two chalcogen compound nanoscale twins of transition metal, then being prepared by two step gelation reactions, there is temperature to ring
The double-response intelligent gel rubber material that should be responded near infrared light.The specific steps are：
（1）0.1 ~ 1 g transition metal, two chalcogen compound powder and 0.05 ~ 5 g carboxyl chitosans are dispersed in 250
In mL water, 3 ~ 48 h of ultrasound；
（2）Aqueous solution after ultrasound stands or by the way that supernatant is collected by centrifugation to get to the non-covalent work of carboxyl chitosan
With the nanoscale twins aqueous solution of two chalcogen compound of transition metal of modification；
（3）In step（2）Added in prepared nanoscale twins aqueous solution temperature sensitive monomer, copolyamide monomer, lithium diatomaceous earth,
Crosslinking agent N, N- methylene-bisacrylamide, initiator and accelerating agent, nitrogen is protected at room temperature in rectangle Teflon mold
It is reacted 1-24 hours in shield（It is preferred that it reacts 15-24 hours）, the individual layer for obtaining two chalcogen compound nanoscale twins of transition metal answers
Close gel；Wherein, mass fraction of the monomer in nanoscale twins aqueous solution is 5 ~ 20 %, temperature sensitive monomer monomer of polyamide together
Molar ratio is 0.3 ~ 10, and the content of lithium diatomaceous earth is 0.5 ~ 3%, N of content of monomer, and the amount of N- methylene-bisacrylamides is monomer
0.38 ~ 30 % of content, the amount of initiator are 0.1 ~ 1 % of content of monomer, and the mass ratio of accelerating agent and initiator is 0.1-1；
（4）The chitosan aqueous solution, lithium diatomaceous earth, crosslinking of amide monomer are added on molded individual layer plural gel upper strata again
Agent, initiator and accelerating agent react 1-24 hours in nitrogen protection at room temperature（It is preferred that it reacts 15-24 hours）, finally obtain one
Kind two-layer compound gel, the double-response intelligent gel rubber material as responded with temperature-responsive and near infrared light.Wherein, carboxylation
Chitosan concentration is consistent with carboxyl chitosan concentration in first layer hydrogel, the mass fraction of amide monomer in aqueous solution for 5 ~
20%, the content of lithium diatomaceous earth is 0.5 ~ 4%, N, and the amount of N- methylene-bisacrylamides is 0.38 ~ 30 % of content of monomer, initiator
Amount be content of monomer 0.1 ~ 1 %, the mass ratio of accelerating agent and initiator is 0.1-1.
In the present invention, the temperature sensitive monomer can be n-isopropyl acrylamide (NIPAM), N- caprolactams
(VCL), one kind in oligomeric ethylene glycol methyl ether methacrylate (OEGMA) or wherein several mixtures.
In the present invention, the initiator is ammonium persulfate etc..
In the present invention, two chalcogen compound of transition metal is molybdenum disulfide, two selenizing molybdenums, tungsten disulfide, two selenizings
One kind or wherein several mixtures in tungsten.
In the present invention, the copolyamide monomer is dimethacrylamide etc..
In the present invention, the accelerating agent is tetramethylethylenediamine etc..
Multi-functional plural gel prepared by the method for the present invention is to remove two chalcogen of transition metal by environmentally protective water phase
Compound nano lamella adds temperature sensitive monomer and further prepares three-dimensional plural gel, prepared Intelligent Composite gel tool
There are reversible temperature-responsive, near infrared light response characteristic, have broad application prospects.
Operating process of the present invention is convenient, and with short production cycle, preparation condition is simple, and production cost is relatively low, is easy to batch metaplasia
Production；And universality is strong, and the preparation method of the plural gel is simple, has excellent performance and has both multiple functions, has wide
Industrial applications prospect.
Description of the drawings
The transmission electron microscope picture of molybdenum disulfide nano sheet layer that Fig. 1 are prepared using the stripping of carboxyl chitosan aqueous solution
Piece.
Fig. 2 Intelligent Composites gel responds the differential scanning calorimetric curve of temperature.
The temperature-responsive behavior of Fig. 3 Intelligent Composite gels.
The near infrared light respondent behavior of Fig. 4 Intelligent Composite gels.
Specific embodiment
The present invention is further described by the following examples, a kind of double-bang firecracker is prepared by the synthesis in water of green
Should and the adjustable intelligent aqueous gel of respondent behavior.However, the embodiment is merely possible to provide explanation rather than limits this
Invention.
Embodiment 1
1 g molybdenum disulfide powders and 5 g carboxyl chitosan powder are dispersed in 250 mL water, 8 h of ultrasound, ultrasound
Nanoscale twins water of the supernatant to get the molybdenum disulfide modified to carboxyl chitosan noncovalent interaction is collected by centrifugation in aqueous solution afterwards
Solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 1 g n-isopropyl acrylamide monomers, 0.3 g dimethyl propylenes
Acrylamide monomer, 0.2 g lithium diatomaceous earths, 0.005 g crosslinking agents N, N- methylene-bisacrylamide and 0.012 g initiator over cures
Sour ammonium, 0.006 g tetramethylethylenediamines, is poured into Teflon mould after mixing, anti-in nitrogen protection at room temperature
It answers 24 hours, obtains the individual layer plural gel of two chalcogen compound nanometer sheet of transition metal；Again 1.5 g dimethyl are added on upper strata
Acrylamide monomer, 0.1 g carboxyl chitosans, 0.2 g lithium diatomaceous earths, 0.005 g crosslinking agents N, N- methylene-bisacrylamide
With 0.012 g initiator ammonium persulfates, 0.006 g tetramethylethylenediamines are dissolved in 5 mL water, anti-in nitrogen protection at room temperature
To get to a kind of double-response intelligent aqueous gel material responded with temperature-responsive and near infrared light after answering 24 hours.
It will be noted from fig. 1 that the molybdenum disulfide nano sheet layer that stripping obtains is relatively thin, and it is observed that nanoscale twins
Outer rim have one layer of unbodied polymer overmold object, therefore this nanoscale twins by polymer wrapped can be well dispersed in
In water.
Change temperature sensitive monomer monomer of polyamide ratio together as can be seen from Figure 2, molybdenum disulfide compound water congealing can be adjusted
The response temperature of glue, 2:1 and 3:1 represents the molar ratio of temperature sensitive monomer monomer of polyamide together.
As can be seen from Figure 3 intelligent aqueous gel can be with responsive movement in 70 degree of hot water, and can reply at room temperature.
As can be seen from Figure 4 intelligent aqueous gel is in 808 nm, 5 W cm-2Near infrared light shine under can with responsive movement, and
And have recorded the relationship of bending curvature, temperature change and light application time.
Embodiment 2
0.1 g tungsten disulphide powders and 0.05 g carboxyl chitosan powder are dispersed in 250 mL water, ultrasound 48
H, ultrasound after aqueous solution nanometer of the supernatant to get the tungsten disulfide modified to carboxyl chitosan noncovalent interaction is collected by centrifugation
Lamella aqueous solution.It takes prepared 5 mL of nanoscale twins aqueous solution, adds in 0.06 g n-isopropyl acrylamide monomers, 0.19
G dimethacrylamide monomers, 0.025 g lithium diatomaceous earths, 0.0125 g crosslinking agents N, N- methylene-bisacrylamide and
0.00025 g initiator ammonium persulfates, 0.00025 g tetramethylethylenediamines, are poured into Teflon mould after mixing,
It is reacted 1 hour in nitrogen protection at room temperature, obtains the individual layer plural gel of two chalcogen compound nanometer sheet of transition metal；Exist again
Upper strata adds in 0.25 g dimethacrylamide monomers, 0.001 g carboxyl chitosans, 0.025 g lithium diatomaceous earths, 0.0125 g friendships
Connection agent N, N- methylene-bisacrylamide and 0.00025 g initiator ammonium persulfates, 0.00025 g tetramethylethylenediamines are dissolved in 5
In mL water, to get to a kind of pair responded with temperature-responsive and near infrared light after react 1 hour in nitrogen protection at room temperature
Intelligent aqueous gel material is responded again.
Embodiment 3
0.5 g, bis- selenizing molybdenum powders and 2.5 g carboxyl chitosan powder are dispersed in 250 mL water, ultrasound 10
H, ultrasound after aqueous solution supernatant is collected by centrifugation to get the nanometer of two selenizing molybdenums modified to carboxyl chitosan noncovalent interaction
Lamella aqueous solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 0.5 g oligomeric ethylene glycol methyl ether methacrylates
Monomer, 0.5 g dimethacrylamide monomers, 0.02 g lithium diatomaceous earths, 0.3 g crosslinking agents N, N- methylene-bisacrylamide and
0.01 g initiator ammonium persulfates, 0.001 g tetramethylethylenediamines, are poured into Teflon mould, after mixing in room
It is reacted 24 hours in the lower nitrogen protection of temperature, obtains the individual layer plural gel of two chalcogen compound nanometer sheet of transition metal；Again upper
Layer adds in 1 g dimethacrylamide monomers, 0.05 g carboxyl chitosans, 0.02 g lithium diatomaceous earths, 0.3 g crosslinking agents N, N- Asias
Bisacrylamide and 0.01 g initiator ammonium persulfates, 0.001 g tetramethylethylenediamines are dissolved in 5 mL water, in room temperature
To get to a kind of double-response intelligent water with temperature-responsive and near infrared light response after react 24 hours in the protection of lower nitrogen
Gel rubber material.
Embodiment 4
1 g, bis- selenizing tungsten powders and 5 g carboxyl chitosan powder are dispersed in 250 mL water, 3 h of ultrasound, ultrasound
Supernatant is collected by centrifugation to get the nanoscale twins water of two selenizing molybdenums modified to carboxyl chitosan noncovalent interaction in aqueous solution afterwards
Solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 0.5 g n-isopropyl acrylamide monomers, 0.05 g diformazans
Base acrylamide monomer, 0.01 g lithium diatomaceous earths, 0.05 g crosslinking agents N, N- methylene-bisacrylamide and 0.005 g initiators
Ammonium persulfate, 0.0025 g tetramethylethylenediamines, is poured into Teflon mould after mixing, and nitrogen is protected at room temperature
Middle reaction 10 hours, obtains the individual layer plural gel of two chalcogen compound nanometer sheet of transition metal；Again 0.55 g is added on upper strata
Dimethacrylamide monomers, 0.1 g carboxyl chitosans, 0.01 g lithium diatomaceous earths, 0.05 g crosslinking agents N, N- di-2-ethylhexylphosphine oxide third
Acrylamide and 0.005 g initiator ammonium persulfates, 0.0025 g tetramethylethylenediamines are dissolved in 5 mL water, at room temperature nitrogen
To get to a kind of double-response intelligent aqueous gel material responded with temperature-responsive and near infrared light after being reacted 10 hours in protection
Material.
Embodiment 5
1 g molybdenum disulfide powders and 5 g carboxyl chitosan powder are dispersed in 250 mL water, 8 h of ultrasound, ultrasound
Nanoscale twins water of the supernatant to get the molybdenum disulfide modified to carboxyl chitosan noncovalent interaction is collected by centrifugation in aqueous solution afterwards
Solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 0.68 g n-isopropyl acrylamide monomers, 0.2 g diformazans
Base acrylamide monomer, 0.1 g carboxyl chitosans, 0.2 g lithium diatomaceous earths, 0.05 g crosslinking agents N, N- methylene-bisacrylamide
With 0.005 g initiator ammonium persulfates, 0.0025 g tetramethylethylenediamines are poured into Teflon mould after mixing,
It is reacted 24 hours in nitrogen protection at room temperature, obtains the individual layer plural gel of two chalcogen compound nanometer sheet of transition metal；Again
0.88 g dimethacrylamide monomers, 0.2 g lithium diatomaceous earths, 0.05 g crosslinking agents N, N- methylene bisacrylamide are added on upper strata
Amide and 0.005 g initiator ammonium persulfates, 0.0025 g tetramethylethylenediamines are dissolved in 5 mL water, and nitrogen is protected at room temperature
To get to a kind of double-response intelligent aqueous gel material responded with temperature-responsive and near infrared light after being reacted 24 hours in shield
Material.
Embodiment 6
1 g molybdenum disulfide powders and 5 g carboxyl chitosan powder are dispersed in 250 mL water, 8 h of ultrasound, ultrasound
Nanoscale twins water of the supernatant to get the molybdenum disulfide modified to carboxyl chitosan noncovalent interaction is collected by centrifugation in aqueous solution afterwards
Solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 0.68 g n-isopropyl acrylamide monomers, 0.3 g diformazans
Base acrylamide monomer, 0.2 g lithium diatomaceous earths, 0.05 g crosslinking agents N, N- methylene-bisacrylamide and 0.005 g initiator mistakes
Ammonium sulfate, 0.0025 g tetramethylethylenediamines, is poured into Teflon mould after mixing, at room temperature in nitrogen protection
Reaction 24 hours, obtains the individual layer plural gel of two chalcogen compound nanometer sheet of transition metal；Again 0.98 g bis- is added on upper strata
Methyl acrylamide monomer, 0.1 g carboxyl chitosans, 0.2 g lithium diatomaceous earths, 0.05 g crosslinking agents N, N- methylene bisacrylamide acyl
Amine and 0.005 g initiator ammonium persulfates, 0.0025 g tetramethylethylenediamines are dissolved in 5 mL water, and nitrogen is protected at room temperature
To get to a kind of double-response intelligent aqueous gel material responded with temperature-responsive and near infrared light after middle reaction 24 hours.
Embodiment 7
1 g molybdenum disulfide powders and 5 g carboxyl chitosan powder are dispersed in 250 mL water, 8 h of ultrasound, ultrasound
Nanoscale twins water of the supernatant to get the molybdenum disulfide modified to carboxyl chitosan noncovalent interaction is collected by centrifugation in aqueous solution afterwards
Solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 0.5 g n-isopropyl acrylamide monomers, 0.2 g lithium algaes
Soil, 0.05 g crosslinking agents N, N- methylene-bisacrylamide and 0.005 g initiator ammonium persulfates, 0.0025 g tetramethyls second two
Amine is poured into Teflon mould after mixing, is reacted 24 hours in nitrogen protection at room temperature, is obtained transition metal two
The individual layer plural gel of chalcogen compound nanometer sheet；Again 0.5 g dimethacrylamide monomers, 0.1 g carboxylations are added on upper strata
Chitosan, 0.2 g lithium diatomaceous earths, 0.05 g crosslinking agents N, N- methylene-bisacrylamide and 0.005 g initiator ammonium persulfates,
0.0025 g tetramethylethylenediamines are dissolved in 5 mL water, to get to a kind of tool after being reacted 24 hours in nitrogen protection at room temperature
There is the double-response intelligent aqueous gel material of temperature-responsive and near infrared light response.
Embodiment 8
1 g molybdenum disulfide powders and 5 g carboxyl chitosan powder are dispersed in 250 mL water, 8 h of ultrasound, ultrasound
Nanoscale twins water of the supernatant to get the molybdenum disulfide modified to carboxyl chitosan noncovalent interaction is collected by centrifugation in aqueous solution afterwards
Solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 0.9 g n-isopropyl acrylamide monomers, 0.4 g dimethyl
Acrylamide monomer, 0.2 g lithium diatomaceous earths, 0.005 g crosslinking agents N, N- methylene-bisacrylamide and 0.012 g initiator mistakes
Ammonium sulfate, 0.006 g tetramethylethylenediamines, is poured into Teflon mould after mixing, at room temperature in nitrogen protection
Reaction 24 hours, obtains the individual layer plural gel of two chalcogen compound nanometer sheet of transition metal；Again 1.5 g diformazans are added on upper strata
Base acrylamide monomer, 0.1 g carboxyl chitosans, 0.2 g lithium diatomaceous earths, 0.005 g crosslinking agents N, N- methylene bisacrylamide acyl
Amine and 0.012 g initiator ammonium persulfates, 0.006 g tetramethylethylenediamines are dissolved in 5 mL water, at room temperature in nitrogen protection
To get to a kind of double-response intelligent aqueous gel material responded with temperature-responsive and near infrared light after reaction 24 hours.
Embodiment 9
1 g molybdenum disulfide powders and 5 g carboxyl chitosan powder are dispersed in 250 mL water, 8 h of ultrasound, ultrasound
Nanoscale twins water of the supernatant to get the molybdenum disulfide modified to carboxyl chitosan noncovalent interaction is collected by centrifugation in aqueous solution afterwards
Solution.Prepared 5 mL of nanoscale twins aqueous solution is taken, adds in 1.5 g n-isopropyl acrylamide monomers, 0.2 g lithium algaes
Soil, 0.005 g crosslinking agents N, N- methylene-bisacrylamide and 0.012 g initiator ammonium persulfates, 0.006 g tetramethyls second two
Amine is poured into Teflon mould after mixing, is reacted 24 hours in nitrogen protection at room temperature, is obtained transition metal two
The individual layer plural gel of chalcogen compound nanometer sheet；Again 1.5 g dimethacrylamide monomers, 0.1 g carboxylations are added on upper strata
Chitosan, 0.2 g lithium diatomaceous earths, 0.005 g crosslinking agents N, N- methylene-bisacrylamide and 0.012 g initiator ammonium persulfates,
0.006 g tetramethylethylenediamines are dissolved in 5 mL water, to get to a kind of tool after being reacted 24 hours in nitrogen protection at room temperature
There is the double-response intelligent aqueous gel material of temperature-responsive and near infrared light response.
Claims (7)
1. a kind of double-bang firecracker is answered and the preparation method of the adjustable intelligent aqueous gel of respondent behavior, it is characterised in that specific steps
For：
（1）0.1 ~ 1 g transition metal, two chalcogen compound powder and 0.05 ~ 5 g carboxyl chitosans are dispersed in 250 mL water
In, 3 ~ 48 h of ultrasound；
（2）Aqueous solution after ultrasound stands or is repaiied by the way that supernatant is collected by centrifugation to get to carboxyl chitosan noncovalent interaction
The nanoscale twins aqueous solution of two chalcogen compound of transition metal of decorations；
（3）In step（2）Temperature sensitive monomer, copolyamide monomer, lithium diatomaceous earth, crosslinking are added in prepared nanoscale twins aqueous solution
Agent N, N- methylene-bisacrylamide, initiator and accelerating agent, during nitrogen is protected at room temperature in rectangle Teflon mold
Reaction 1-24 hours, obtains the individual layer plural gel of two chalcogen compound nanoscale twins of transition metal；Wherein, monomer is in nanometer sheet
Mass fraction in layer aqueous solution is 5 ~ 20 %, and the molar ratio of temperature sensitive monomer monomer of polyamide together is 0.3 ~ 10, lithium diatomaceous earth
Content is 0.5 ~ 4%, N of content of monomer, and the amount of N- methylene-bisacrylamides is 0.38 ~ 30 % of content of monomer, initiator
Measure 0.1 ~ 1 % for content of monomer, the mass ratio of accelerating agent and initiator is 0.1-1；
（4）The chitosan aqueous solution, lithium diatomaceous earth, crosslinking of copolyamide monomer are added on molded individual layer plural gel upper strata again
Agent, initiator and accelerating agent react 1-24 hours in nitrogen protection, finally obtain a kind of two-layer compound gel, as at room temperature
The double-response intelligent gel rubber material responded with temperature-responsive and near infrared light；Wherein, carboxyl chitosan concentration and first layer
Carboxyl chitosan concentration is consistent in hydrogel, and the mass fraction of amide monomer in aqueous solution is 5 ~ 20%, and the content of lithium diatomaceous earth is
Content of monomer 0.5 ~ 3%, N, the amount of N- methylene-bisacrylamides are 0.38 ~ 30 % of content of monomer, and the amount of initiator is monomer
The mass ratio of 0.1 ~ 1 % of content, accelerating agent and initiator is 0.1-1.
2. preparation method according to claim 1, it is characterised in that two chalcogen compound of transition metal is curing
Molybdenum, two selenizing molybdenums, tungsten disulfide, one kind in two tungsten selenides or wherein several mixtures.
3. preparation method according to claim 1, it is characterised in that the temperature sensitive monomer for n-isopropyl acrylamide,
N- caprolactams, one kind in oligomeric ethylene glycol methyl ether methacrylate or wherein several mixtures.
4. preparation method according to claim 1, which is characterized in that step（3）With（4）In, the copolyamide list
Body is dimethacrylamide.
5. preparation method according to claim 1, it is characterised in that the initiator is ammonium persulfate.
6. preparation method according to claim 1, it is characterised in that the accelerating agent is tetramethylethylenediamine.
7. the two chalcogen compound nanoscale twins of transition metal obtained as the preparation method described in one of claim 1-6 are compound
The double-response intelligent aqueous gel material that object is temperature-responsive and near infrared light responds.
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| CN106913872A (en) * | 2017-04-17 | 2017-07-04 | 山东省医学科学院药物研究所 | Adriamycin and NO donor nano composite materials and preparation method thereof |
| CN108034073B (en) * | 2017-12-06 | 2021-04-06 | 北京服装学院 | Intelligently-changed particles and preparation method thereof |
| CN109897314B (en) * | 2019-02-20 | 2021-06-08 | 南京邮电大学 | Near-infrared light-initiated self-healing polyvinyl alcohol-molybdenum disulfide composite hydrogel and preparation method and testing method thereof |
| CN110983472B (en) * | 2019-11-05 | 2021-11-02 | 东华大学 | Rapid-response nano composite hydrogel fiber driver and preparation method thereof |
| CN111184917B (en) * | 2020-02-27 | 2021-09-28 | 福州大学 | Temperature-sensitive collagen-based hydrogel loaded with bioactive polypeptide and preparation method thereof |
| CN111253535B (en) * | 2020-03-23 | 2022-11-08 | 合肥工业大学 | Preparation method of novel photoinduced self-repairing nano composite hydrogel |
| CN113651919A (en) * | 2021-08-30 | 2021-11-16 | 上海应用技术大学 | Cold-resistant solar-driven photothermal effect hydrogel electrolyte and preparation and application thereof |
| CN114166681A (en) * | 2021-11-12 | 2022-03-11 | 常州大学 | QCM humidity sensor based on high polymer/inorganic composite sensitive material and preparation method thereof |
| CN115160488A (en) * | 2022-07-13 | 2022-10-11 | 常州工学院 | Preparation method of azopyridine-containing multiple-response intelligent hydrogel |
| CN117126430B (en) * | 2023-10-27 | 2023-12-26 | 涿州市柯林电子产品有限公司 | Cold gel with circulating heat dissipation function and preparation process thereof |
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