CN108059693A - A kind of preparation method of the temperature sensitive type physical hydrogel of multiple hydrogen bonding enhancing - Google Patents
A kind of preparation method of the temperature sensitive type physical hydrogel of multiple hydrogen bonding enhancing Download PDFInfo
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Abstract
The present invention relates to enviromental sensitive hydrogel fields, it is desirable to provide a kind of preparation method of the temperature sensitive type physical hydrogel of multiple hydrogen bonding enhancing.Including：By 2 urea groups, 4 [1H] methacrylic acid pyrimidone, acrylic acid and octadecyl acrylate random copolymer is prepared in the method for free radical solution polymerization, copolymer is dissolved in organic solvent, then under conditions of 70 90 DEG C solvent is made to volatilize, obtains glued membrane；Then glued membrane is impregnated into 10~15h with deionized water, when reaching swelling equilibrium, obtains Thermo-sensitive supramolecular hydrogel.The present invention is poured using solution and prepared with the method for solvent volatilization, simple and practicable, and exploitativeness is high.Quadrupolar hydrogen bond based on UPy constructs supermolecule polymer, and Quadrupolar hydrogen bond active force is strong, can promote the crystallization of alkyl side chain, so as to regulate and control the mechanical performance of hydrogel.The supramolecular hydrogel of multiple hydrogen bonding enhancing of the present invention can assign hydrogel shape memory characteristic to temperature and ion-sensitive.
Description
Technical field
It is more particularly to a kind of that there is excellent mechanical properties and shape memory the present invention relates to enviromental sensitive hydrogel field
The preparation method of the supramolecular hydrogel of performance.
Background technology
Hydrogel is a kind of three-dimensional network high molecular material that can keep definite shape, has high-moisture percentage, shows
Good biocompatibility.It is different according to the crosslinking points of hydrogel network, two class of chemical gel and physical gel can be classified as.
Under the action of chemical cross-linking agent, three dimensional network mainly is cross-linked by covalent bond effect by chemical gel for polymer molecular chain
Network, mechanical performance is usually higher, but environmental sensitivity is relatively poor, limits its application range.And physical gel is mainly
It is cross-linked to form by non-covalent bond effect, chemical cross-linking agent is not related in preparation process, it is environmentally friendly；And crosslinked action is usual
It is reversible so that gel has good environment-responsive.But since non-covalent bond effect power is weak, physical gel mechanical strength
It is usually relatively low.In order to prepare high intensity physical hydrogel, domestic and foreign scholars have done numerous studies, have usually been introduced not in hydrogel
Same energy dissipation mechanism, such as hydrophobic effect, hydrogen bond, metal coordination, host-guest interaction etc..
By hydrophilic monomer and hydrophobic monomer copolymerization or by chemically reacting, introducing hydrophobic grouping can on macromolecular main chain
Obtain amphipathic copolymer.Due to simultaneously contain hydrophilic and hydrophobic grouping, under the driving of entropy, hydrophobic grouping can occur aggregation and
Association, during a certain concentration, macromolecular is cross-linked to form three-dimensional net structure i.e. hydrogel in water.But non-covalent bond is more covalent
Key stability is poor, therefore the simple hydrogel creep-resistant property by hydrophobic effect preparation is poor, gel when external environment changes
Structure easily changes, and loses primary characteristic.
The content of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of simple, multiple hydrogen bonding and increase
The preparation method of strong Thermo-sensitive supramolecular hydrogel.
To solve technical problem, solution of the invention is：
A kind of amphipathic copolymer of multiple hydrogen bonding enhancing is provided, which is by 2- urea groups -4 [1H]-metering system
What sour pyrimidone (UPyMA), acrylic acid (AA) and octadecyl acrylate (SA) were prepared in the method for free radical solution polymerization
Random copolymer；Entitled poly- (the 2- urea groups -4 [1H]-methacrylic acid pyrimidone-co- octadecyl acrylates-co- of copolymer
Acrylic acid) [P (UPyMA-co-SA-co-AA)], concrete structure formula is：
In formula, x represents mole percent (f of -4 [1H]-pyrimidone (UPy) group of 2- urea groups in the copolymerUPy),
Between 0~8mol%；Y represents mole percent (f of the octadecyl acrylate unit in the copolymerSA), be 0~
Between 25mol%.
Invention further provides the preparation method of the copolymer, including step：
(1) by 2- urea groups -4 [1H]-methacrylic acid pyrimidone (UPyMA) monomer, octadecyl acrylate (SA) monomer and
Initiator is added in into dry reactor, normal-temperature vacuum drying 0.5h, argon gas protection；
(2) acrylic acid (AA) monomer is dissolved in organic solvent, with bubbling argon 0.5h；Then previous reaction device is added to
In, it is stirred to react 10h under the conditions of 60 DEG C；After reaction, suitable organic solvent diluting is added in reaction system, added
Dichloromethane filters the solid to precipitate, is dried to obtain copolymer；
When the reaction of step (2) starts, 2- urea groups -4 [1H]-methacrylic acid pyrimidone (UPyMA) monomer accounts for monomer
Mole percent (the f of total amountUPy) it is 0~8mol%, octadecyl acrylate (SA) monomer accounts for the mole percent of monomer total amount
(fUPy) it is 0~25mol%；Initiator accounts for the 1% of monomer gross mass；The organic solvent and dichloromethane added in after reaction
Alkane, volume ratio 1: 6.
In the present invention, the initiator is azodiisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide.
The method that the temperature sensitive type physical hydrogel of multiple hydrogen bonding enhancing is prepared the present invention also provides the utilization copolymer,
It is that the copolymer is dissolved in organic solvent, under conditions of 70-90 DEG C solvent is made to volatilize, obtain glued membrane；Then by glue
Film impregnates 10~15h with deionized water, to get the Thermo-sensitive supermolecule water enhanced to multiple hydrogen bonding when reaching swelling equilibrium
Gel.
In the present invention, the organic solvent is arbitrary in dimethyl sulfoxide (DMSO), dimethylformamide or dimethyl acetamide
One or more of mixtures.
Inventive principle describes：
The present invention is enhanced using the multiple hydrogen bonding that the synergistic effect and additive effect preparation property of a variety of non-covalent bonds are stablized
Temperature sensitive type physics supramolecular hydrogel.2- urea groups -4 [1H]-pyrimidone (UPy) group be it is a kind of with self-identifying effect four
Deuterium bond system has height-oriented property and dynamic reversibility, its own has higher binding constant.UPy groups are introduced
In amphipathic copolymer aquagel, it is made to be cooperateed with hydrophobic effect, the hydrophobic microcell of alkyl side chain formation is protected by hydrogen bond, into
And promote the crystallization of alkyl side chain, it can further improve the mechanical performance of gel.In addition, when the temperature increases, hydrogen bond generation can
Inverse property is broken, and three-dimensional network dissociates, this can assign hydrogel material environmental sensitivity, shape memory, self-repairability etc.
Excellent performance.
Compared with prior art, the present invention has the following advantages：
(1) the Thermo-sensitive supramolecular hydrogel of multiple hydrogen bonding enhancing of the present invention is poured using solution volatilizees with solvent
Method prepare, simple and practicable, exploitativeness is high.
(2) Quadrupolar hydrogen bond the present invention is based on UPy constructs supermolecule polymer, and Quadrupolar hydrogen bond active force is strong, can promote alkane
The crystallization of base side chain, so as to regulate and control the mechanical performance of hydrogel.
(3) supramolecular hydrogel of multiple hydrogen bonding enhancing of the present invention can assign water-setting to temperature and ion-sensitive
Glue shape memory characteristic.
Description of the drawings
Fig. 1 is the mechanical performance contrast curve of the physical hydrogel of embodiment 2,3 and comparative example 1.
Fig. 2 is the mechanical performance contrast curve of the physical hydrogel of embodiment 2,5 and comparative example 2.
Fig. 3 is sensitivity curves figure of the physical hydrogel to temperature of embodiment 2.
Fig. 4 is sensitivity curves figure of the physical hydrogel to pH value of embodiment 2.
Fig. 5 is the Shape memory behavior schematic diagram of the physical hydrogel of embodiment 1.
Specific embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.The following examples can make
The present invention, but do not limit the invention in any way is more fully understood in professional and technical personnel.
Reagent used herein and drug are as follows：2- amino-4-hydroxy -6- methylpyrimidines (MIS, 99%), methyl-prop
Olefin(e) acid isocyano group ethyl ester (ICEMA, 98%), nuclear magnetic resonance test deuterated reagent used are purchased from J＆K companies.Acrylic acid 18
Ester (SA) is purchased from J＆K companies, is recrystallized using preceding in absolute ethyl alcohol.Acrylic acid (AA) is purchased from the limited public affairs of traditional Chinese medicines chemical reagent
Department.
The structural formula of 2- urea groups -4 [1H] of the present invention-methacrylic acid pyrimidone (UPyMA) is：
Method described in UPyMA reference literatures (Long T E etc., Macromolecules 2003,36,1083-1088)
It prepares, is as follows：2- amino-4-hydroxy -6- methylpyrimidines (4.0g) are added in into 150mL three-necked flasks, 45 DEG C
Under vacuumize 1h, argon filling gas shielded.20mL dimethyl sulfoxide (DMSO)s are added in into flask with syringe, 155 DEG C is gradually heating to, makes MIS
Dissolving.Then 5.5g isocyanatoethyls are added in reactor, wherein isocyanatoethyl mole
Number is 1.1 times of 2- amino-4-hydroxy -6- methylpyrimidine molal quantitys, after being stirred to react 0.5h, is cooled to room temperature, and terminates reaction.
Reactant is added in into 400mL acetone and is precipitated, filters, is repeated twice.White powder product finally is put into 30 DEG C of vacuum to dry
Drying is for 24 hours, spare in case.
1st, the preparation of P (UPyMA-co-SA-co-AA) random copolymer
P (UPyMA-co-SA-co-AA) random copolymer is prepared using the method for free radical solution polymerization, and one typical
Example (embodiment 1 i.e. in table 1) is prepared to be described as follows：
The molar content of UPy is designed as 4mol%, the molar content of SA is the P (UPyMA-co-SA-co-AA) of 4mol%
The preparation process of random copolymer is as follows：By the initiator of 1.24g UPyMA, 1.43g SA and certain mass, two isobutyl of azo
Nitrile (1% of monomer gross mass) is added in into dry reactor, normal-temperature vacuum drying 0.5h, argon gas protection.By 7.33g AA
Monomer is dissolved in 50mL dimethyl sulfoxide (DMSO)s, is added in after bubbling argon 0.5h in reactor.By reaction mixture under the conditions of 60 DEG C
It is stirred to react 10h.After reaction, 20mL dimethyl sulfoxide (DMSO)s are added in reaction system, then reaction mixture is added in 6 times two
In the dichloromethane of methyl sulfoxide, the solid to precipitate is filtered, is dried to obtain polymer.Mole of the UPy and SA of polymer
Content is by nuclear magnetic resonance hydrogen spectruming determining.
P (UPyMA-co-SA-co-AA) random copolymer used in the present invention is prepared in other embodiments, each
Preparation condition and chemical composition be listed in Table 1 below.
Table 1：The preparation condition and chemical composition of P (UPyMA-co-SA-co-AA)
Note：In polymer code name US-x-y, US represents UPy and SA units respectively, and wherein x represents the mole percent of UPy
fUPy, the mole percent f of y expressions SASA.For convenience, marked with the mole percent of UPyMA in initial reactant and SA
Sample.In synthesis, the initiator used in each embodiment is respectively azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN)
Or dibenzoyl peroxide (BPO), organic solvent are dimethyl sulfoxide (DMSO), dimethylformamide or dimethyl acetamide.It reacted
Controlling reaction temperature is 60 DEG C in journey, reaction time 10h.
NMR is tested：Polymer is tested using nuclear magnetic resonance (Bruker companies, 400MHz)1H NMR spectras, and then
Calculate its number-average molecular weight (Mn).Test temperature is room temperature, and solvent is deuterated dimethyl sulfoxide, and chemical shift (δ) is by solvent peak
Correction.Based on methylene hydrogen formant methine hydrogen formant, the SA in nuclear magnetic spectrum on UPy pyrimidine rings adjacent with ester group with
The area ratio at AA terminal carboxyl group proton resonances peak calculates the mole percent of UPy and SA in polymer.
2nd, the preparation of P (UPyMA-co-SA-co-AA) physical gel film
Examples 1 to 5
Reference literature (Geng YH etc., Polymer 2016,100,60-68) method of the present invention, is prepared for gel film.
In Examples 1 to 5, P (UPyMA-co-SA-co-AA) random copolymer is dissolved in dimethyl sulfoxide (DMSO), and makes polymer molten
The concentration of liquid is 0.15g/mL.It is cast in around on the fixed glass plate of silica gel plate, solvent is made under the conditions of 70-90 DEG C
Volatilization, then immerses glued membrane in a large amount of deionized waters, impregnates 10~15h, reaches swelling equilibrium to get to multiple hydrogen bonding
The Thermo-sensitive supramolecular hydrogel of enhancing.Table 2 represents the preparation condition of Thermo-sensitive supermolecular gel film.
Table 2：The preparation condition of P (UPyMA-co-SA-co-AA) physical gel film
In comparative example 1,2, using identical method, the physical gel of US-0-4 and US-4-0 random copolymers is prepared for
Film.
The quality swelling ratio and water cut test of gel：The gel sample of swelling equilibrium is taken, surface water is wiped with blotting paper
It weighs after point, is denoted as ms.Then gel sample is freeze-dried to constant weight, weight is denoted as m at this time0.Quality swelling ratio S=ms/
m0, moisture content wg=(ms-m0)/ms=S-1/S.
Thermal performance test：It is tested using DSC, nitrogen atmosphere.Sample is warming up to 70 DEG C with 2 DEG C/min from 10 DEG C, and herein
Temperature elder generation constant temperature 2min is to eliminate thermal history.Then 10 DEG C, then the rate liter with 2 DEG C/min are cooled to the rate of 2 DEG C/min
Crystallization and melting behavior of the temperature to 70 DEG C of determination samples.The Thermal Parameter of polymer is calculated from DSC heating-cooling curves, such as
Fusing point (Tm)。
Measuring mechanical property：Uniaxial tensile test is carried out to sample using cupping machine, test temperature is 24 ± 1 DEG C.
Test bars use the dumbbell shaped of standard, total length 50.0mm, and the width of cross section is 4.0mm, span 20.0mm, thickness
About 0.3mm.Test bars after cutting place 48h at room temperature, to eliminate the internal stress of batten.Each sample at least uses
5 battens carry out parallel testing, finally take result of its average value as sample mechanical performance.Gel is obtained from stress strain curve
Tensile strength, Young's modulus and elongation at break.
Temperature-responsive：A diameter of 1cm, the gel sample that thickness is 0.5mm are put into the sample bottle equipped with deionized water
In, sample bottle is then placed in water bath with thermostatic control, heats up and in each test temperature point constant temperature 30min, gel sample is made to reach molten
Then swollen balance surveys its diameter.The volume change of gel is represented by volume sweell(ing) rate：qv=(d/d0)3, wherein d0Distinguish with d
Represent gel in room temperature (25 DEG C) and the diameter of test temperature point.
PH responses：By a diameter of 1cm, thickness is that the gel sample of 0.5mm is put into the sample equipped with different pH value
In bottle, and 5h is kept under room temperature (25 DEG C) so that gel sample reaches swelling equilibrium, then surveys its diameter.The volume of gel
Variation is represented by volume sweell(ing) rate：qv=(d/d0)3, wherein d0Represent gel under pH=7 and other pH value respectively with d
Diameter.
The Shape memory behavior of Ion response：The gel strip batten that thickness is about 0.7mm is converted into Z-shaped,
The CaCl of 1mol/L2Solution impregnates 5h and is fixed as temporary shapes 1；Then batten is converted into " L " shape, is placed in the FeCl of 0.5mol/L3
Batten is fixed as temporary shapes 2 by 0.5h in solution, this can find that batten becomes brown color from white in the process.It is first during reply
First the batten of brown color is placed in the ascorbic acid solution of 0.3g/mL, batten is recovered by " L " shape to Z-shaped, then batten is put
In the EDTA2Na solution of 0.1mol/L so that batten recovers to original state.
Table 3 is the Thermal Parameter and machine of P (UPyMA-co-SA-co-AA) gel in Examples 1 to 5 and comparative example 1~2
Tool performance.
As shown in Table 3, the physical gel of comparative example 1~4 and comparative example 1, the molar content of UPy remain
4mol%, 1 gel US-4-0 of comparative example are highly swollen in water, and intensity is relatively low, it is impossible to form good gel film, machine
Tool performance cannot test.This is mainly due to SA hydrophobic monomers are free of in 1 gel network of comparative example, crosslinking points are by tetra- heavy hydrogen of UPy
Key is formed, and as the network structure of gel, AA hydrophilic units content is high, is swollen hydrogel height.When the molar content of SA is from 0
When increasing to 2mol%, the moisture content of gel is reduced by 98% to 64%.Hereafter with the increase of SA molar contents, gel contains
Water rate is held essentially constant.This is because with the raising of SA contents, hydrophobic part content increases in the copolymer of synthesis, gel
Moisture content reduce.The physical gel of comparative example 2,5 and comparative example 2, when the molar content of UPy increases to 4mol% from 0
When, the moisture content of gel is reduced to 51% by 84%.With further improving for UPy molar contents, the moisture content of gel is basic
It remains unchanged.This may be because in polymerization system after introducing UPy, and the Quadrupolar hydrogen bond that UPy is formed improves physical gel net
The crosslink density of network, and with the raising of UPy contents, Quadrupolar hydrogen bond effect reaches saturation state.
Further the hot property of gel is analyzed.As can be known from Table 3, comparative example 1 and 1 gel of embodiment are heating up
Do not occur melting peak in the process, the former be because not containing crystallizable SA side chains, the latter be due to SA molar contents too
It is low, so that it cannot form sufficient crystalline domains.In embodiment 2~4, with SA molar contents fSAIncrease, gel
Melting peak becomes strong, fusing point increase, this is because SA side chain ordered arrangements form more complete crystalline domains, temperature raises,
Crystalline domains melt.The hot property of the physical gel of comparative example 2,5 and comparative example 2, when SA molar contents remain unchanged,
With the increase of UPy molar contents, the melting peak intensity of gel increases, and is moved to high temperature direction, this illustrates that the introducing of UPy increases
Hydrophobic interaction between big SA side chains improves the crystallizing power of SA side chains, so as to increase hydrophobic region in gel
Melting enthalpy.
It was found from from table 2 and Fig. 1, since 1 gel of comparative example cannot form a film, mechanical performance is not tested.By reality
Example 1~4 is applied to understand, when SA molar contents increase to 25mol% from 2mol%, the fracture strength of gel from 0.75 improve to
1.87MPa, Young's modulus are improved from 0.14 to 5.68MPa, and elongation at break is reduced to 60.3% from 725.2%.This is because
The hydrophobic microcell that SA side chains are formed increases gel cross-linkage density, therefore the intensity increase of gel, toughness reduce.Comparative example
2nd, 5 and comparative example 2 physical gel, when the molar content of UPy increases to 8mol% from 0, the fracture strength and Young of gel
Modulus is respectively increased from 0.3 and 0.07MPa to 4.6 and 10.0MPa respectively, and elongation at break is reduced to from 450.3%
220.1%.Show that the introducing of UPy Quadrupolar hydrogen bond groups increases the crosslink density of gel network, improve the machinery of gel
Intensity, Young's modulus.
P (UPyMA-co-SA-co-AA) physical gel shows the sensibility to temperature and pH.Fig. 3 is 2 physics of embodiment
Hydrogel is to the sensibility of temperature.When temperature is more than 45 DEG C, as temperature raises, gel volume increase, this is mainly due to
The melting in SA crystallizable side chains area.When temperature is more than 70 DEG C, gel volume dramatically increases, and this is mainly due to UPy Quadrupolar hydrogen bonds
Fracture.Fig. 4 is sensitivity curves figure of 2 physical gel of embodiment to pH value.When pH value is less than 10, gel volume is almost protected
It holds constant.Continue to increase with pH value, gel volume increases.When pH value is more than 13, gel complete swelling.This is because work as
When pH is more than some critical value, carboxylic acid group deprotonation, the osmotic pressure inside gel increases, so as to destroy the hydrophobic of SA side chains
Effect and the hydrogen bond action of UPy, are swollen gel.
By carboxyl and the coordination of different metal ions, have studied P (UPyMA-co-SA-co-AA) hydrogels to from
The dual-shaped memory behavior of son response.As shown in Figure 5, the physical gel of embodiment 1 is immersed into CaCl2In solution, gel net
Carboxylic acid group and Ca in network2+Metal coordination is formed, temporary shapes 1 (Z-shaped) can be fixed as.Equally, hydrogel is put
In FeCl3When in solution, due to Fe3+With the coordination of carboxylic acid group, hydrogel is fixed to temporary shapes 2 (" L " shape).When
When hydrogel after fixation is placed in in ascorbic acid solution, since ascorbic acid has strong reproducibility, Fe3+It is reduced
For Fe2+, hydrogel becomes green from brown color, and hydrogel returns back to temporary shapes 1 (Z-shaped).Hydrogel is placed in again
In EDTA2Na solution, EDTA2Na can make Ca2+With carboxylic acid group decomplexing so that hydrogel returns back to original state, table
Reveal the response to ion.
Finally it should be noted that listed above is only specific embodiments of the present invention.It is clear that the invention is not restricted to
Above example can also have many variations.Those of ordinary skill in the art can directly lead from present disclosure
All deformations for going out or associating, are considered as protection scope of the present invention.
Claims (6)
1. a kind of amphipathic copolymer of multiple hydrogen bonding enhancing, which is characterized in that the copolymer is by 2- urea groups -4 [1H]-methyl
The random copolymer that acrylic acid pyrimidone, acrylic acid and octadecyl acrylate are prepared in the method for free radical solution polymerization；
Entitled poly- (2- urea groups -4 [1H]-methacrylic acid pyrimidone-co- octadecyl acrylate-co- the acrylic acid) [P of copolymer
(UPyMA-co-SA-co-AA)], concrete structure formula is：
In formula, x represents mole percent f of -4 [the 1H]-pyrimidine ketone groups of 2- urea groups in the copolymerUPy, it is 0~8mol%
Between；Y represents mole percent f of the octadecyl acrylate unit in the copolymerSA, between 0~25mol%.
2. the preparation method of copolymer described in claim 1, which is characterized in that including step：
(1) 2- urea groups -4 [1H]-methacrylic acid pyrimidine one monomers, octadecyl acrylate monomer and initiator is added in drying
Reactor in, normal-temperature vacuum drying 0.5h, argon gas protection；
(2) acrylic monomers is dissolved in organic solvent, with bubbling argon 0.5h；Then add in previous reaction device, at 60 DEG C
Under the conditions of be stirred to react 10h；After reaction, suitable organic solvent diluting is added in into reaction system, then adds in dichloro
Methane filters the solid to precipitate, is dried to obtain copolymer；
When the reaction of step (2) starts, 2- urea groups -4 [1H]-methacrylic acid pyrimidine one monomers account for moles the hundred of monomer total amount
Fraction fUPyFor 0~8mol%, octadecyl acrylate monomer accounts for the mole percent f of monomer total amountUPyFor 0~25mol%；Trigger
Agent accounts for the 1% of monomer gross mass；The organic solvent and dichloromethane added in after reaction, volume ratio 1: 6.
3. according to the method described in claim 2, it is characterized in that, the initiator is azodiisobutyronitrile, two different heptan of azo
Nitrile or dibenzoyl peroxide.
4. according to the method described in claim 2, it is characterized in that, the organic solvent is dimethyl sulfoxide (DMSO), dimethyl formyl
Amine or dimethyl acetamide.
5. a kind of method for the temperature sensitive type physical hydrogel that multiple hydrogen bonding enhancing is prepared using copolymer described in claim 1,
It is characterized in that, is that the copolymer is dissolved in organic solvent, then under conditions of 70-90 DEG C solvent is made to volatilize, obtained
Glued membrane；Then glued membrane is impregnated into 10~15h with deionized water, to get enhancing to multiple hydrogen bonding when reaching swelling equilibrium
Thermo-sensitive supramolecular hydrogel.
6. according to the method described in claim 5, it is characterized in that, the organic solvent is dimethyl sulfoxide (DMSO), dimethyl formyl
Any one or a few mixture in amine or dimethyl acetamide.
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| CN110423337A (en) * | 2019-07-08 | 2019-11-08 | 浙江大学衢州研究院 | A kind of Thermo-sensitive supermolecule polymer and preparation method thereof of multiple hydrogen bonding regulation |
| WO2020134385A1 (en) * | 2018-12-28 | 2020-07-02 | 华南理工大学 | Temperature-sensitive polymer, synthesis method thereof, and temperature-sensitive injectable hydrogel |
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| CN111848990A (en) * | 2020-07-02 | 2020-10-30 | 浙江大学衢州研究院 | Preparation method of bidirectional shape memory elastomer constructed based on self-nucleation effect |
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| CN112169013A (en) * | 2019-07-05 | 2021-01-05 | 香港城市大学 | Particle stacking type biological adhesive and preparation and application thereof |
| CN112625190A (en) * | 2020-12-24 | 2021-04-09 | 陕西师范大学 | temperature/pH double-sensitive amphiphilic co-network gel and preparation method thereof |
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| CN114395071A (en) * | 2022-02-21 | 2022-04-26 | 西北工业大学 | High-transparency, adhesive and self-healing hydrogel film and preparation method thereof |
| CN114716601A (en) * | 2022-03-16 | 2022-07-08 | 华南理工大学 | Hydrogel adhesive based on hyperbranched polymer and preparation method and application thereof |
| CN114957535A (en) * | 2022-06-16 | 2022-08-30 | 西安石油大学 | Adhesive gel with adjustable interface binding force and preparation method and application thereof |
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| CN109180965A (en) * | 2018-09-04 | 2019-01-11 | 中南大学 | A kind of hydrogel and preparation method thereof of multiple physical crosslinking |
| WO2020134385A1 (en) * | 2018-12-28 | 2020-07-02 | 华南理工大学 | Temperature-sensitive polymer, synthesis method thereof, and temperature-sensitive injectable hydrogel |
| CN112169013A (en) * | 2019-07-05 | 2021-01-05 | 香港城市大学 | Particle stacking type biological adhesive and preparation and application thereof |
| CN112169013B (en) * | 2019-07-05 | 2022-07-29 | 香港城市大学 | Particle stacking type biological adhesive as well as preparation and application thereof |
| CN110423337B (en) * | 2019-07-08 | 2022-06-07 | 浙江大学衢州研究院 | Temperature-sensitive supramolecular polymer regulated and controlled by multiple hydrogen bonds and preparation method thereof |
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| CN111848990B (en) * | 2020-07-02 | 2023-03-21 | 浙江大学衢州研究院 | Preparation method of bidirectional shape memory elastomer constructed based on self-nucleation effect |
| CN111978894A (en) * | 2020-08-31 | 2020-11-24 | 浙江海泰新材料有限公司 | Adhesive based on multiple hydrogen bond effects and preparation method thereof |
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| CN114142034A (en) * | 2021-10-29 | 2022-03-04 | 西安交通大学 | Negative self-healing adhesive and preparation method and application thereof |
| CN114249858A (en) * | 2022-01-18 | 2022-03-29 | 江南大学 | Visual polymer thermometer with temperature memory function and preparation method thereof |
| CN114395071A (en) * | 2022-02-21 | 2022-04-26 | 西北工业大学 | High-transparency, adhesive and self-healing hydrogel film and preparation method thereof |
| CN114395071B (en) * | 2022-02-21 | 2023-01-03 | 西北工业大学 | High-transparency, adhesive and self-healing hydrogel film and preparation method thereof |
| CN114716601A (en) * | 2022-03-16 | 2022-07-08 | 华南理工大学 | Hydrogel adhesive based on hyperbranched polymer and preparation method and application thereof |
| CN114716601B (en) * | 2022-03-16 | 2023-01-06 | 华南理工大学 | Hydrogel adhesive based on hyperbranched polymer and preparation method and application thereof |
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