CN109666106A - A kind of hydrogel composite material and preparation method thereof with near-infrared response temperature sensitive properties - Google Patents
A kind of hydrogel composite material and preparation method thereof with near-infrared response temperature sensitive properties Download PDFInfo
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- CN109666106A CN109666106A CN201811626543.9A CN201811626543A CN109666106A CN 109666106 A CN109666106 A CN 109666106A CN 201811626543 A CN201811626543 A CN 201811626543A CN 109666106 A CN109666106 A CN 109666106A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention belongs to functionalization gel complex material fields, specifically disclose a kind of hydrogel composite material with near-infrared response temperature sensitive properties, are mainly prepared from the following raw materials: polymerized monomer, poly-dopamine, nano-cellulose, crosslinking agent and initiator；The polymerized monomer is by 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester and oligomeric ethylene glycol methyl ether methyl methacrylate in molar ratio (50~100): (0~50) blendes together.There is hydrogel composite material prepared by the present invention excellent toughness and mechanical strength can be brought rapidly up and occur phase transition after carrying out near infrared light, can quickly restPose after removing illumination, and have excellent repeatability.Meanwhile the invention also discloses the preparation method of the hydrogel composite material, the preparation method has a simple process, and easily operated, reaction condition is mild.
Description
Technical field
The invention belongs to functionalization gel complex material fields, and in particular to one kind has near-infrared response temperature sensitive special
The hydrogel composite material and preparation method thereof of property.
Background technique
Hydrogel be by polymer by the one kind being physically or chemically crosslinked contain a large amount of water have it is three-dimensional netted
The soft material of structure, jellyfish, sea cucumber in nature, the muscle etc. of the mankind belong to the scope of hydrogel, and hydrogel exists
The numerous areas such as bionical, sensor, actuator, organizational project, medicament slow release, which have, to be widely applied.
Water-setting colloid material with intelligent response characteristic can be pierced by external environment such as light, thermal and magnetic, ionic strength etc.
Swash and changes gel structure and physical state variation.There is temperature sensitive polyisopropyl acrylamide (Poy (N- as most common
Isopropryl acrylamide), PNIPAM) hydrogel, when the environment temperature of hydrogel is more than its phase transition temperature (32 DEG C)
When, the hydrogen bond that polymer segment and hydrone are formed by partial destruction, dredge by the ball of string or spherical shape that segment becomes closely knit from unfolding state
Water base group is exposed, and hydrone can be also expelled from the gel network of collapsing, such hydrogel can occur in Macroscopic physical state
Volume contraction, therefore there is potential application in terms of actuator or medicament slow release.Compared to amides hydrogel, it is based on alkyloxy-ethers
Class (Oligo(ethylene glycol)) hydrogel due to its excellent biocompatibility and phase transition temperature adjustability and
It is concerned, however mechanical strength is low and can only be an important factor for restricting the application of such hydrogel by temperature-induced phase transformation.
Summary of the invention
The purpose of the present invention is to provide a kind of with good mechanical strength and has the near-infrared sound of photothermal conversion effect
The hydrogel composite material for answering temperature sensitive properties, providing corresponding preparation method is then another object of the present invention.
Based on above-mentioned purpose, the present invention adopts the following technical scheme:
A kind of hydrogel composite material with near-infrared response temperature sensitive properties, be mainly prepared from the following raw materials: polymerization is single
Body, poly-dopamine (PDA), nano-cellulose, crosslinking agent and initiator；The polymerized monomer is 2- methyl -2- acrylic acid -2(2-
Methoxy ethoxy) ethyl ester (MOE2MA) or 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester (MOE2) and oligomerization MA
The mixture of ethylene glycol monomethyl ether methyl methacrylate (OEGMA), 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester
(MOE2It MA is) (50~100): (0~50) with the molar ratio of oligomeric ethylene glycol methyl ether methyl methacrylate (OEGMA).
Further, the OEMGA is according to repetitive unit-(CH2CH2O)-different, molecular weight 300,475 or 950 g/
mol。
Further, the raw material further includes rate accelerating material, and the additive amount of the rate accelerating material is polymerized monomer gross mass
0.1%~0.4%.
Preferably, the poly-dopamine is the poly-dopamine nano particle of 50~500 nm, and the additive amount of poly-dopamine is
The 0.10%~0.60% of polymerized monomer gross mass；The additive amount of nano-cellulose is the 0.66%~2% of polymerized monomer gross mass, more
Add preferably, the additive amount of nano-cellulose is the 2% of polymerized monomer gross mass；The additive amount of crosslinking agent is the total matter of polymerized monomer
The 0.06%~0.16% of amount；The additive amount of the initiator is polymerized monomer gross mass 0.25%~0.80%.
Preferably, the poly-dopamine is the production that dopamine polymerize in ethanol/water/ammonium hydroxide in the mixed solvent autoxidation
Object.
Preferably, the nano-cellulose is Cellulose nanocrystal body and/or cellulose nano-fibrous.
Preferably, the Cellulose nanocrystal body obtains, with aqueous by microcrystalline cellulose through strong acid hydrolysis after dialysis purification
Suspension exists, and the concentration of Cellulose nanocrystal body is 2% in suspension, the diameter of Cellulose nanocrystal body in suspension
For 10~30 nm, length is 100~400 nm.
Preferably, it is described it is cellulose nano-fibrous by wood pulp after TEMPO oxidation reaction again through mechanical lapping and height
It is obtained after pressure homogeneous, with the presence of aqueous suspension liquid status, cellulose nano-fibrous concentration is 3% in suspension, fine in suspension
The diameter for tieing up plain nanofiber is 2~40 nm, and length is 0.5~2 um.
Cellulose nanocrystal body and it is cellulose nano-fibrous be aqueous suspension liquid status, the draw ratio with superelevation is high
It is added in composite material especially gel rubber material by Young's modulus and high-specific surface area and good biocompatibility on a small quantity
It can express excellent reinforcing effect.Prepared hydrogel carries out in water phase in the present invention, and two kinds of nano materials all have
Good dispersibility, prepared hydrogel material are demonstrated by good toughness and mechanical strength, with the increase of additive amount,
Reinforcing effect is more obvious, but after 2% of additive amount more than polymerized monomer quality, solution will appear the phenomenon that mutually separating, most
The hydrogel mechanical strength and toughness caused eventually is decreased obviously, therefore nano-cellulose additive amount should not be greater than 2%.
Preferably, the crosslinking agent is N, N- methylene-bisacrylamide or ethylene glycol dimethacrylate；It is described to draw
Hair agent is potassium peroxydisulfate (KPS), ammonium persulfate (APS) or ultraviolet initiator 2-Hydroxy-4 '-(2-
hydroxyethoxy)-2-methylpropiophenone(Irgacrue 2959)。
Preferably, the rate accelerating material is N, N ', N ', N '-tetramethylethylenediamine (TEMD).
The preparation method of the above-mentioned hydrogel composite material with near-infrared response temperature sensitive properties, including following step
It is rapid:
(1) polymerized monomer, poly-dopamine particle suspension liquid, nano-cellulose suspension, water, crosslinking are sequentially added into reaction tube
Agent, magnetic agitation and nitrogen are bubbled 5~10min,
(2) initiator is added, anoxybiotic sealing and standing 12 hours black hydrogels derived above are hydrogel at 0~10 DEG C
Composite material.
Further, in step (2), when initiator is added, while rate accelerating material is added, then anoxybiotic sealing and standing again.
Further, the poly-dopamine particle suspension liquid is made by following methods:
A, by ethyl alcohol, water and ammonium hydroxide 20:45:(1~3 by volume) it mixes, the concentration of the ammonium hydroxide is 24%~28%；
B, Dopamine hydrochloride is added in the mixed solvent obtained by step a, continues to be stirred to react 24 hours at 25 DEG C, whipping process
Guarantee that reaction liquid level and air are permanently connected to；The amount ratio of Dopamine hydrochloride and mixed solvent is (0.25~0.5) g:100mL；
C, the resulting reaction solution of step b is dialysed in bag filter, molecular cut off MWCO=50K~300K, dialysis to dialyzate
After conductivity is constant, the mass concentration of rotary evaporation to poly-dopamine is outstanding to get poly-dopamine particle until being 0.1%~0.15%
Supernatant liquid.
In this application, polymerized monomer realizes Raolical polymerizable under the action of initiator, forms chemical crosslinking net
Network；Simultaneously in the case where initiator agent introduces living radical, poly-dopamine functional group (amino, catechol etc.) is received
Rice cellulose surface hydroxyl also will form a small amount of living radical, causes monomer polymerization, obtains graft copolymer.
Further, poly-dopamine (PDA) is existed by Dopamine hydrochloride (3-Hydroxytyramine hydrochloride)
It is obtained after aoxidizing auto polymerization under mild alkaline conditions, since it had not only had strong adhesion but also is rich in various functional groups, the neighbour that PDA has
Benzenediol, amino isoreactivity group, can be anti-with the generation of the molecule containing amino or sulfydryl Michael addition reaction, schiff bases
It answers, or complexation reaction occurs with metal ion, to realize the functional modification of material.More importantly poly-dopamine
Molecular structure is close with the chemical structure of natural black pigment, has many excellent properties, such as good biocompatibility, also
Originality, fluorescent quenching property and photothermal conversion property etc..Poly-dopamine nano particle is by Dopamine hydrochloride used in the present invention
In weak base aqueous solution aoxidize auto polymerization obtain, diameter in 500 nm hereinafter, and nano particle diameter with ammonia concn increasing
It reduces greatly.Poly-dopamine nano granule suspension prepared by the application has good dispersibility at room temperature and stablizes
Property, but after drying or being freeze-dried, irreversible reunion occurs for nano particle, even with high-speed stirred or ultrasound
It is difficult effectively to disperse again, therefore, the dispersion liquid of poly-dopamine nano particle is concentrated by Rotary Evaporators first by the present invention
It to corresponding concentration, then is added directly into polymerization reaction system, so as to avoid the agglomeration traits of nano particle.Together
When ,-the OCH of the alkyloxy-ethers chain section surface in the polymerizate of poly-dopamine functional group and polymerized monomer2CH2Oxygen in group
Hydrogen bond is formed, physics crosslinking points are formed, the hydrogel composite material for assigning the application absorbs the characteristic of near-infrared.
Meanwhile diameter, height of the nano-cellulose (Cellulose nanocrystal body and cellulose nano-fibrous) with nanoscale
Draw ratio and surface hydroxyl abundant, thus not only can effectively be scattered in gel rubber system, but also can be by a plurality of polymer chain
Section interlinks to form physics crosslinking points by hydrogen bond action, and then forms stable physical cross-linked network, the physical crosslinking net
Network can be used as effective supplement of former chemical crosslinking network, the mechanical strength of hydrogel composite material be improved, when hydrogel composite wood
For material by external force (compression or stretching), which can discharge resulting stress by reversible fracture, thus
Assign the preferable toughness of hydrogel composite material.
In conclusion hydrogel composite material prepared by the present invention is a kind of advanced composite material (ACM), have excellent toughness and
Mechanical strength can be brought rapidly up and occur phase transition after carrying out near infrared light, remove after illumination can fast quick-recovery it is initial
State, and there is excellent repeatability, the hydrogel composite material is in organizational project, medicament slow release, sensor and actuator
Equal fields have potential application.Meanwhile preparation method process provided by the invention is simple, easily operated, reaction condition is mild.
Detailed description of the invention
Fig. 1 is PDA nano particle diameter distribution map prepared by embodiment 1 and embodiment 2；
Fig. 2 is state diagram of the hydrogel composite material before and after near infrared light prepared by embodiment 1；
Fig. 3 is that the Adhesion property of hydrogel composite material prepared by embodiment 1 tests photo；
Fig. 4 is that the anti-compression properties of hydrogel composite material prepared by embodiment 1 test photo.
Specific embodiment
To further understand the present invention, explanation is further explained to the present invention with attached drawing with reference to embodiments.
Embodiment 1
A kind of hydrogel composite material with near-infrared response temperature sensitive properties, is made: 2- methyl-of following weight raw material
2- acrylic acid -2(2- methoxy ethoxy) 3.0 g (0.016mol) of ethyl ester (MOE2MA), 1.0 g Cellulose nanocrystal bodies suspend
Liquid (quality of Cellulose nanocrystal body is the 0.66% of polymerized monomer quality), 9.0 g poly-dopamine nano granule suspensions are (outstanding
In supernatant liquid the quality of PDA be polymerized monomer quality 0.45%), 2.0 mg N,N methylene bis acrylamides (crosslinking agent) and 20
Mg ammonium persulfate (initiator), 10 mg N, N ', N ', N '-tetramethyl diethylamine (TEMD) is made.
The Cellulose nanocrystal body through strong acid hydrolysis, is obtained, with aqueous suspension by microcrystalline cellulose after dialysis purification
State exists, and the diameter of Cellulose nanocrystal body is 10~30 nm in Cellulose nanocrystal liquid suspension, and length is 100~400
Nm, mass concentration 2%.
The preparation method of above-mentioned hydrogel composite material, step are as follows:
A, poly-dopamine nano granule suspension preparation step:
A, take 80 mL dehydrated alcohols, 180 mL deionized waters be added after mixing 3.5 mL concentration be (24~28%) ammonium hydroxide simultaneously
Stirring 10 minutes；
B, the more Dopamine hydrochlorides of 1.0 g are added at one time in the mixed solvent, it is anti-in non-stirring under confined conditions at 25 DEG C
It answers 24 hours, guarantees that reaction solution can touch air in reaction carries out；
C, reaction solution is transferred to bag filter (molecular cut off=300K) after completion of the reaction, dialysed 48 hours in deionized water,
Period repeatedly changes water, and until conductivity of dialysate is constant, gained dialyzate, which is concentrated into concentration through Rotary Evaporators, is
0.15% and collect and obtain poly-dopamine nano granule suspension, be placed in (5 DEG C) of refrigerator save it is stand-by.Quantitative liquid is taken to pass through dynamic
State determination of light scattering nanoparticle fluid mechanics radius, freeze-dried measurement solid content carry out other characterizations, the result is shown in Figure 1.
B, free radical polymerization step::
(1) successively by 3.0 g(0.016 mmol) 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester, 9.0 g
(0.15%) poly-dopamine nano granule suspension, 1.0 g(2%) 2.0 mg of Cellulose nanocrystal liquid suspension and crosslinking agent
N, N- methylene-bisacrylamide are added sequentially in the reaction tube with magneton, and 300 revs/min of revolving speed, with nitrogen (0.3 mL/
Min it) is bubbled 10 minutes；
(2) 20 mg ammonium persulfates (APS) and 10 mg N, N ', N ' are sequentially added, after N '-tetramethyl diethylamine (TEMD)
Reaction tube anoxybiotic is sealed, is placed at 10 DEG C and stands 12 hours, obtain black hydrogel and be denoted as target product, be denoted as sample 1.
Embodiment 2
A kind of hydrogel composite material with near-infrared response temperature sensitive properties, is made: 2- methyl-of following weight raw material
2- acrylic acid -2(2- methoxy ethoxy) ethyl ester (MOE2MA) 2.5g(0.013mol), 2.5g Cellulose nanocrystal liquid suspension
(quality of Cellulose nanocrystal body is the 2.0% of polymerized monomer quality), 8.0 g poly-dopamine nano granule suspension (suspension
The quality of middle PDA is the 0.40% of polymerized monomer quality), 2.5 mg ethylene glycol dimethacrylates (crosslinking agent) and 20 mg
Ammonium persulfate (initiator), 10 mg N, N ', N ', N '-tetramethyl diethylamine (TEMD) is made.
The Cellulose nanocrystal body through strong acid hydrolysis, is obtained, with aqueous suspension by microcrystalline cellulose after dialysis purification
State exists, and the diameter of Cellulose nanocrystal body is 10~30 nm in Cellulose nanocrystal liquid suspension, and length is 100~400
Nm, mass concentration 2%.
The preparation method of above-mentioned hydrogel composite material, step are as follows:
A, poly-dopamine nano granule suspension preparation step:
A, take 80 mL dehydrated alcohols, 180 mL deionized waters be added after mixing 5.0 mL concentration be (24~28%) ammonium hydroxide simultaneously
Stirring 10 minutes；
B, the more Dopamine hydrochlorides of 1.0 g are added at one time in the mixed solvent, it is anti-in non-stirring under confined conditions at 25 DEG C
It answers 24 hours, guarantees that reaction solution can touch air in reaction carries out；
C, reaction solution is transferred to bag filter (molecular cut off=300K) after completion of the reaction, dialysed 48 hours in deionized water,
Period repeatedly changes water, and until conductivity of dialysate is constant, gained dialyzate is concentrated into a certain concentration through Rotary Evaporators
(0.12%) and collection obtains poly-dopamine nano granule suspension, is placed in (5 DEG C) of refrigerator and saves for use.Quantitative liquid is taken to pass through
Dynamic light scattering measures nanoparticle fluid mechanics radius, and freeze-dried measurement solid content carries out other characterizations, as a result sees figure
1。
B, free radical polymerization step:
(1) successively by 2.5 g(0.013 mmol) 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester, 8.0 g
(0.12%) poly-dopamine nano granule suspension, 1.5g(2%) 2.5 mg of Cellulose nanocrystal liquid suspension and crosslinking agent
Ethylene glycol dimethacrylate is added sequentially in the reaction tube with magneton, and 300 revs/min of revolving speed, with nitrogen (0.3 mL/
Min it) is bubbled 10 minutes；
(2) 20 mg ammonium persulfates (APS) and 10 mg N, N ', N ' are sequentially added, it will after N '-tetramethyl diethylamine (TEMD)
The sealing of reaction tube anoxybiotic, is placed at 10 DEG C and stands 12 hours, obtain black hydrogel and be denoted as target product, be denoted as sample 2.
Embodiment 3
A kind of hydrogel composite material with near-infrared response temperature sensitive properties, is made: 2.5g of following weight raw material
(0.013 mmol) 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester (MOE2MA), 0.9g(0.003 mol) oligomerization
Ethylene glycol monomethyl ether methyl methacrylate (Mw=300g/mol), the cellulose nano-fibrous suspension of 1.0g are (cellulose nano-fibrous
Quality be the 0.88% of polymerized monomer quality), (quality of PDA is M to 9.0 g poly-dopamine nano granule suspensions in suspension
The 0.40% of polymerized monomer quality), 2.5 mg ethylene glycol dimethacrylates (crosslinking agent) and 20 mg ammonium persulfates (cause
Agent), 10 mg N, N ', N ', N '-tetramethyl diethylamine (TEMD) is made.
It is described it is cellulose nano-fibrous by wood pulp after TEMPO oxidation reaction again through mechanical lapping and it is high-pressure homogeneous after
It obtains, with the presence of aqueous suspension liquid status, cellulose nano-fibrous diameter is 20~40 in cellulose nano-fibrous suspension
Nm, length are 0.5~2 um, mass concentration 3%.
The preparation method of above-mentioned hydrogel composite material, step are as follows:
A, poly-dopamine nano granule suspension preparation step is same as Example 1.
B, free radical polymerization step::
(1) successively by 2.5g(0.013 mmol) 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester (MOE2MA),
1.0g(0.003 mol) oligomeric ethylene glycol methyl ether methyl methacrylate (Mw=300g/mol), 9.0 g (0.15%) poly- DOPA
Amine nano granule suspension, 1.0g(2%) 2.5 mg ethylene glycol dimethyl of cellulose nano-fibrous suspension and crosslinking agent
Acrylate is added sequentially in the reaction tube with magneton, 600 revs/min of revolving speed, is bubbled 10 points with nitrogen (0.9 mL/min)
Clock；
(2) 20 mg ammonium persulfates (APS) and 10 mg N, N ', N ' are sequentially added, after N '-tetramethyl diethylamine (TEMD)
Reaction tube anoxybiotic is sealed, is placed at 10 DEG C and stands 12 hours, obtain black hydrogel and be denoted as target product, be denoted as sample 3.
Embodiment 4
A kind of hydrogel composite material with near-infrared response temperature sensitive properties, is made: 1.5g of following weight raw material
(0.008 mmol) 2- methyl -2- acrylic acid -2(2- methoxy ethoxy) ethyl ester (MOE2MA), 2.4g(0.008 mol) oligomerization
Ethylene glycol monomethyl ether methyl methacrylate (Mw=300g/mol), the cellulose nano-fibrous suspension of 1.0g are (cellulose nano-fibrous
Quality be the 0.77% of polymerized monomer quality), (quality of PDA is 3.0 g poly-dopamine nano granule suspensions in suspension
The 0.12% of polymerized monomer quality), 4.0g deionized water (guaranteeing that polymerized monomer has suitable concentration), 5.0 mg ethylene glycol two
Methacrylate (crosslinking agent) and 20 mg potassium peroxydisulfates (initiator), 10 mg N, N ', N ', N '-tetramethyl diethylamine
(TEMD) it is made.
The cellulose nano-fibrous suspension is the same as embodiment 3.
The preparation method of hydrogel composite material is the same as embodiment 3.
Embodiment 5
A kind of hydrogel composite material with near-infrared response temperature sensitive properties, is made: 2- methyl-of following weight raw material
2- acrylic acid -2(2- methoxy ethoxy) ethyl ester (MOE2MA) 3.0 g (0.016mol), 1.0 g Cellulose nanocrystal bodies suspend
(quality of Cellulose nanocrystal body is MOE to liquid2The 0.66% of MA mass), 12 g poly-dopamine nano granule suspension (suspension
The quality of middle PDA is MOE2The 0.6% of MA mass), 2.0 mg N,N methylene bis acrylamides (crosslinking agent) and 20 mg over cures
Sour ammonium (initiator), 10 mg N, N ', N ', N '-tetramethyl diethylamine (TEMD) is made.The Cellulose nanocrystal body suspends
Liquid is the same as embodiment 1.
The preparation method is the same as that of Example 1 for hydrogel composite material.
Comparative example 1
A kind of hydrogel composite material with near-infrared response temperature sensitive properties is: fine with the difference place of embodiment 3
The dosage for tieing up plain nanofiber suspension is 3.5g, and cellulose nano-fibrous quality is the 3% of polymerized monomer gross mass, remaining
Raw material type and dosage are same as Example 3.Preparation method is same as Example 3.
In the preparation process of hydrogel composite material, there is the phenomenon that mutually separating, adds due to cellulose nano-fibrous
Dosage is more, will lead to decreased solubility of the monomer in system, and phenomenon of phase separation occurs, can extreme influence monomer polymerization and
Cross-linking reaction between polymer segment, obtained hydrogel mechanical strength die down instead, and toughness is also poor, no practical application valence
Value.
Comparative example 2
A kind of hydrogel composite material with near-infrared response temperature sensitive properties is: fine with the difference place of embodiment 3
The dosage for tieing up plain nanofiber suspension is 0 g, remaining raw material type and dosage are same as Example 3.Preparation method and reality
It is identical to apply example 3.
It is not added with cellulose nano-fibrous, prepared hydrogel in the comparative example to be mainly made of chemical crosslinking, system
Middle to lack the cellulose nano-fibrous physical cross-linked network formed between polymerized segment, which can not when being squeezed
Effective dispersive stress, toughness are poor, it may occur that broken.
Phenetic analysis
(1) dynamic light scattering granularmetric analysis
PDA nano particle Hydrodynamic diameter (D h), it is measured by Nanotrac Wave dynamic light scattering.PDA nano particle
Test concentrations~0.02%, test temperature be 20 DEG C.
Attached drawing 1a and 1b are respectively partial size (diameter) distribution of PDA nano particle prepared by embodiment 1 and embodiment 2
Figure, by distribution map it can be seen that particle size dispersion is uniform, it is nanometer that Hydrodynamic diameter, which is respectively 256.6 nm and 452.0 nm,
Rank, the measured value are higher compared with actual value.
(2) the photic temperature-sensing property characterization of near-infrared
Hydrogel prepared by embodiment 1 is placed on plastic pallet, after near-infrared light irradiation 1 minute, removes near-infrared
Lamp.Attached drawing 2 shows state of the hydrogel respectively before irradiation, in irradiation and after irradiation.Hydrogel is homogeneous state, warp before irradiating
After near infrared light, on gel top since photo-thermal effect causes hydrogel that dehydration aggregation occurs, blushing is shown,
After removing near-infrared irradiation, hydrogel loses illumination energy and cools down rapidly water suction, is again restored to original state.
(3) Adhesion property is tested
Hydrogel composite material Adhesion property with higher prepared by the present invention, from figure 3, it can be seen that prepared by embodiment 1
Hydrogel composite material can easily be attached on nitrile rubber and skin surface.
(4) compression performance is tested
The mechanical strength of alcoxyl ethers hydrogel is lower, even if being easy to be destroyed by external force after molding, but cellulose nanometer is added
Crystal and it is cellulose nano-fibrous after, hydrogel shows good self-supporting and mechanical performance.As shown in figure 4, to reality
Apply hydrogel prepared by example 1 and carry out anti-compression properties test: compression speed is 50 mm/min, even if being compressed to original height
10% after, then remove pressure, gel restores rapidly, can finally return to original state, and shows good toughness.
Claims (10)
1. a kind of hydrogel composite material with near-infrared response temperature sensitive properties, which is characterized in that mainly by following original
Material is made: polymerized monomer, poly-dopamine, nano-cellulose, crosslinking agent and initiator；The polymerized monomer is by 2- methyl -2- third
Olefin(e) acid -2(2- methoxy ethoxy) ethyl ester and oligomeric ethylene glycol methyl ether methyl methacrylate in molar ratio (50~100): (0
~50) it blendes together.
2. the hydrogel composite material according to claim 1 with near-infrared response temperature sensitive properties, feature exist
In the raw material further includes rate accelerating material, and the additive amount of the rate accelerating material is the 0.1%~0.4% of polymerized monomer gross mass.
3. the hydrogel composite material according to claim 2 with near-infrared response temperature sensitive properties, feature exist
In the poly-dopamine is the poly-dopamine nano particle of 50~500 nm, and the additive amount of poly-dopamine is the total matter of polymerized monomer
The 0.10%~0.60% of amount；The additive amount of nano-cellulose is the 0.66%~2% of polymerized monomer gross mass；The additive amount of crosslinking agent
It is the 0.06%~0.16% of polymerized monomer gross mass；The additive amount of initiator is polymerized monomer gross mass 0.25%~0.80%.
4. the hydrogel composite material according to claim 3 with near-infrared response temperature sensitive properties, feature exist
In the poly-dopamine is the product that dopamine polymerize in ethanol/water/ammonium hydroxide in the mixed solvent autoxidation.
5. the hydrogel composite material according to claim 4 with near-infrared response temperature sensitive properties, feature exist
In, the nano-cellulose be Cellulose nanocrystal body and/or cellulose nano-fibrous.
6. the hydrogel composite material according to claim 3 with near-infrared response temperature sensitive properties, feature exist
In the crosslinking agent is N, N- methylene-bisacrylamide or ethylene glycol dimethacrylate；The initiator is persulfuric acid
Potassium, ammonium persulfate or photoinitiator.
7. the hydrogel composite material according to claim 4 with near-infrared response temperature sensitive properties, feature exist
In the rate accelerating material is N, N ', N ', N '-tetramethylethylenediamine.
8. the preparation of any hydrogel composite material with near-infrared response temperature sensitive properties of claim 1~7
Method, which comprises the following steps: sequentially add polymerized monomer into reaction tube, poly-dopamine particle suspension liquid, receive
After nitrogen is bubbled 5~10min under magnetic agitation, initiator is added, at 0~10 DEG C in rice cellulose suspension, water, crosslinking agent
Black hydrogel derived above is hydrogel composite material within anoxybiotic sealing and standing 12 hours.
9. the preparation side of the hydrogel composite material according to claim 8 with near-infrared response temperature sensitive properties
Method, which is characterized in that after initiator is added, add rate accelerating material, then anoxybiotic sealing and standing.
10. the preparation of the hydrogel composite material with near-infrared response temperature sensitive properties according to claim 8 or claim 9
Method, which is characterized in that the poly-dopamine particle suspension liquid is made by following methods:
A, by ethyl alcohol, water and ammonium hydroxide 20:45:(1~3 by volume) it mixes, the concentration of the ammonium hydroxide is 24%~28%；
B, Dopamine hydrochloride is added in the mixed solvent obtained by step a, continues to be stirred to react 24 hours at 25 DEG C, whipping process
Guarantee that reaction liquid level and air are permanently connected to；The amount ratio of Dopamine hydrochloride and mixed solvent is (0.25~0.5) g:100mL；
C, the resulting reaction solution of step b is dialysed in bag filter, molecular cut off MWCO=50K~300K, dialysis to dialyzate
After conductivity is constant, the mass concentration of rotary evaporation to poly-dopamine is outstanding to get poly-dopamine particle until being 0.1~0.15%
Supernatant liquid.
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| CN114456527A (en) * | 2022-02-08 | 2022-05-10 | 西北工业大学深圳研究院 | nanocellulose/g-C3N4/polyacrylamide composite hydrogel and preparation method and application thereof |
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