CN101633711A - Temperature-sensitive hydrogel containing adamantyl and preparation method and application thereof - Google Patents
Temperature-sensitive hydrogel containing adamantyl and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a temperature-sensitive hydrogel containing adamantyl and a preparation method and an application thereof. The preparation method comprises the following steps: adopting organic solvent to dissolve crosslinking agent and monomer which is composed with N-isopropylacrylamide and at least one hydrophobic monomer with adamantyl, then adding initiator to react at 55-85 DEG C for 6-24h under the protection of inert gas, then treating by using distilled water and obtaining the temperature-sensitive hydrogel containing adamantly. The temperature-sensitive hydrogel containing adamantly has excellent properties such as higher mechanical strength and fast deswelling dynamics and easily controllable mechanical strength and temperature response performance, and overcomes the problem that the temperature-sensitive hydrogel provided by the prior art does not have good comprehensive performance. The temperature-sensitive hydrogel containing adamantly can be widely used in fields such as drug delivery, material separation, biosensors, switching valves, reaction control, biomedical material and the like.
Description
Technical field
The present invention relates to a kind of temperature-sensitive hydrogel, particularly a kind of temperature-sensitive hydrogel that contains adamantyl and preparation method thereof and application.
Background technology
Poly N-isopropyl acrylamide (PNIPAM) is a kind of typical temperature-sensitive hydrogel.It exists a minimum critical solution temperature or volume phase transition temperature (LCST) in the aqueous solution, thereby the PNIPAM hydrogel can the small variation of perception outside temperature and violent contraction or expansion takes place for volume that unexpected generation suction or dehydration make self near this LCST.The variation of this volume is discontinuous.Utilize this special thermal stimulus response characteristic, the PNIPAM hydrogel has obtained using widely aspect a lot, as Separation ﹠ Purification, the chemical reaction control that is used as material in chemical industry; On biomedicine, be used for the immobilization of controlled delivery of pharmaceutical agents release, enzyme; On mechanical industry, be used for making memory temperature-sensitive switch, transmitter etc.Therefore the PNIPAM hydrogel becomes present research focus.But traditional method synthetic PNIPAM hydrogel exists generally that physical strength is relatively poor, temperature response speed reaches shortcomings such as LCST is non-adjustable more slowly, thereby has limited its practical application in more areas greatly.
In different application places, people wish to obtain suitable LCST, the swelling hydrogel of certain physical strength when always.In recent years, the researchist is at the problem that improves PNIPAM hydrogel over-all properties, carried out number of research projects, some achievements in research have been obtained: (Zhang Xianzheng such as Zhang Xianzheng, Zhuo Renxi. the preparation and the performance study of responsive poly-(N-N-isopropylacrylamide-co-acrylamide) hydrogel of fast temperature, SCI, 2000,21:1309～1311) synthesized poly-(N-N-isopropylacrylamide/acrylamide) hydrogel, compare with traditional PNIPAM hydrogel, it goes swelling rate faster, but the mechanical strength behind this swelling behavior acutely descends; People such as Liu Qiang in 2004 (Liu Qiang. the preparation and the performance study of hydrophobically modified poly N-isopropyl acrylamide hydrogel, Sichuan University's master thesis 2004) respectively with hydrophobic monomer methyl acrylate (MA), ethyl propenoate (EA), butyl acrylate (BA) and dodecyl acrylate (DA) adopt free radical micellar aqueous solution polymerization process to prepare the PNIPAM hydrogel of a series of hydrophobically modifieds with N-N-isopropylacrylamide (NIPAM) copolymerization, result of study shows, in the PNIPAM hydrogel, introduce a spot of MA, EA, esters of acrylic acid such as BA and DA structural unit can improve the temperature sensitivity and the mechanical strength of hydrogel, but the effect of its raising weakens with the growth of alkyl chain in the acrylate, and can not effectively regulate and control the LCST of gel, be not very remarkable to the raising of hydrogel over-all properties; (Xiaomei Ma such as MaXM, Xiaobin Huang, Lu Zhu, Xi ' an Zhao and XiaozhenTang, Influence of ethyl methacrylate content on the volume-phase transitionof temperature-sensitive poly[(N-isopropylacrylamide)-and co-(ethyl methacrylate)] microgels, Polym Int 2005,54:83-89) adopt Jia Jibingxisuanyizhi and a kind of novel microgel of NIPAM copolymerization, test shows, can regulate and control the volume phase transition temperature of microgel by the content that changes Jia Jibingxisuanyizhi, but the efficient of regulation and control is not high, and the swelling ratio of gained gel descends.
In a word, prior art promptly has quick response and has higher mechanical strength again providing, and also there is very big deficiency in the hydrogel aspect of the adjustable again good combination property of LCST.
Summary of the invention
Primary and foremost purpose of the present invention be to overcome can not have quick response in the prior art simultaneously, the weak point of physical strength and the volume phase transition temperature temperature-sensitive hydrogel that is easy to regulate and control preferably, provide a kind of physical strength and temperature response performance all to be easy to, physical strength is higher and the temperature-sensitive hydrogel that contains adamantyl of quick response.
Another object of the present invention is to provide the preparation method of described temperature-sensitive hydrogel.
A further object of the present invention is to provide the application of described temperature-sensitive hydrogel.
Purpose of the present invention is achieved through the following technical solutions: a kind of temperature-sensitive hydrogel that contains adamantyl, comprise monomer and linking agent, and wherein monomer is made up of N-N-isopropylacrylamide and at least a hydrophobic monomer that contains adamantyl;
The described hydrophobic monomer that contains adamantyl has following structural formula:
R
0Be hydrogen or methyl;
R
1, R
2And R
3Be respectively the alkyl that is independently selected from hydrogen or 1～3 carbon atom.
Preferred 10: 1～100: 1 of the mass ratio of N-N-isopropylacrylamide and the hydrophobic monomer that contains adamantyl in the described monomer; Preferred mass ratio is 20: 1～100: 1
Described linking agent is N, at least a in N '-methylene-bisacrylamide (BIS), dimethacrylate glycol ether ester (DEGDMA) or the Ethylene glycol dimethacrylate (EGDMA);
The consumption of described linking agent preferably is equivalent to 2～8% of monomer mass; Preferred consumption is 2～5% of a monomer mass;
The described preparation method who contains the temperature-sensitive hydrogel of adamantyl comprises following steps:
With adding initiator behind organic solvent dissolution monomer and the linking agent again, under the protection of rare gas element,, then handle then with distilled water in 55～85 ℃ of reactions 6～24 hours, obtain containing the temperature-sensitive hydrogel of adamantyl.
Described rare gas element is preferably nitrogen;
Preferred 10: 1～100: 1 of the mass ratio of N-N-isopropylacrylamide and the hydrophobic monomer that contains adamantyl in the described monomer; Preferred mass ratio is 20: 1～100: 1;
Described linking agent is N, at least a in N '-methylene-bisacrylamide (BIS), dimethacrylate glycol ether ester (DEGDMA) or the Ethylene glycol dimethacrylate (EGDMA);
The consumption of described linking agent is preferably and is equivalent to 2～8% of monomer mass; Preferred consumption is 2～5% of a monomer mass;
Described initiator is at least a in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or the dilauroyl peroxide;
The consumption of described initiator is preferably and is equivalent to 0.5～2% of monomer and linking agent quality summation;
The concentration of the solute that described monomer, linking agent and initiator form is 0.1～0.3g/ml, and solvent is described organic solvent;
Described organic solvent is dehydrated alcohol, tetrahydrofuran (THF), trichloromethane, 1,4-dioxane, benzene, toluene or N, at least a in N '-dimethyl formamide.
Described distilled water is treated to the described temperature-sensitive hydrogel that contains adamantyl of distilled water immersion, and the time is 1～7 day, during change water temperature, make described temperature-sensitive hydrogel carry out swelling and go the swollen circular treatment;
Described swelling with go the preferred following condition of swollen circular treatment: the swollen temperature is to be lower than 5～15 ℃ of corresponding gel volume phase transition temperature, go the swollen temperature to be higher than 5～15 ℃ of corresponding gel volume phase transition temperature, swelling is carried out 3 times at least with going the swollen circulation.
The described temperature-sensitive hydrogel that contains adamantyl can be widely used in fields such as the separating of the conveying of medicine and controllable release, material, biosensor, switch-valve, chemical reaction control and biological medicine material.
The present invention has following advantage and effect with respect to prior art:
(1) temperature-sensitive hydrogel that contains adamantyl provided by the invention has higher physical strength, and physical strength increases along with the increase of the hydrophobic monomer that contains adamantyl content in hydrogel, as 2.5% the hydrogel that feeds intake for monomer NIPAM of the hydrophobic monomer mole addition that contains adamantyl, its modulus of compression just increases to 50kPa (as shown in Figure 3) by 1kPa.
(2) temperature-sensitive hydrogel provided by the invention is fast to the speed of response of temperature, has to remove swelling behavior fast, can lose 93% water (as shown in Figure 1) in 5min.
(3) size, the speed of response speed and the height of volume phase transition temperature of the prepared temperature-sensitive hydrogel physical strength of the present invention can directly be controlled by regulating monomeric proportioning, operate very easy.
Description of drawings
Fig. 1 be the prepared temperature-sensitive hydrogel of embodiment 1～3 and comparative example in 40 ℃ hot water, surveyed respectively remove swelling kinetic curve figure.
Fig. 2 is the compressive stress strain curve figure of the temperature-sensitive hydrogel of embodiment 1～3 and comparative example's preparation.
Fig. 3 is the modulus of compression of temperature-sensitive hydrogel of embodiment 1～3 and comparative example preparation and the graph of relation of monomer ratio.
Fig. 4 is the DSC graphic representation of the temperature-sensitive hydrogel of embodiment 1～3 and comparative example's preparation.
Fig. 5 is the LCST of temperature-sensitive hydrogel hydrogel of embodiment 1～3 and comparative example preparation and the graph of relation of monomer ratio.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1:
Take by weighing hydrophobic monomer methacrylic acid diamantane ester (AdMA, R in structure such as the general formula
0=CH
3, R
1=H, R
2=H, R
3=H) 0.01g in a little reaction flask, add 1g N-N-isopropylacrylamide (NIPAM) and 30mg N again, N '-methylene-bisacrylamide, add 7ml 1 then, 4-dioxane, vibration add initiator Diisopropyl azodicarboxylate 12.5mg after treating that solid all dissolves, again through vacuumize-inflated with nitrogen 4 times circulation after tube sealing, reaction flask put into 75 ℃ oil bath and reacts 10h.Obtain water white gel and use distilled water immersion 5 days, with 20 ℃ distilled water immersion 24h, the distilled water of putting into 40 ℃ again allows it shrink naturally, changes water then earlier, so remain in the room temperature distilled water after the circulation four times and soak, obtain containing the temperature-sensitive hydrogel AdMA1 of adamantyl.
Embodiment 2:
Contain the preparation of the temperature sensitive property copolymer aquagel AdMA3 of adamantyl, the feed ratio that has only hydrophobic monomer AdMA and NIPAM is 3%, and other raw material feed ratio and reactions steps obtain containing the temperature-sensitive hydrogel AdMA3 of adamantyl with embodiment 1.
Embodiment 3:
Contain the preparation of the temperature sensitive property copolymer aquagel AdMA5 of adamantyl, the feed ratio that has only hydrophobic monomer AdMA and NIPAM is 5%, and other raw material feed ratio and reactions steps obtain containing the temperature-sensitive hydrogel AdMA5 of adamantyl with embodiment 1.
Embodiment 4:
Take by weighing hydrophobic monomer vinylformic acid 3-methyl isophthalic acid-diamantane ester (R in structure such as the general formula
0=H, R
1=CH
3, R
2=H, R
3=H) 0.03g in a little reaction flask, add 1g NIPAM and 62mgN again, N '-methylene-bisacrylamide, add the 10ml trichloromethane then, after vibration treats that solid all dissolves, add initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) 21mg, again through vacuumize-3 circulations of inflated with nitrogen after tube sealing, reaction flask put into 55 ℃ oil bath and reacts 24h.Obtain water white gel and use distilled water immersion 1 day, with 20 ℃ distilled water immersion 5h, the distilled water of putting into 35 ℃ again allows it shrink naturally, changes water then earlier, so remain in the room temperature distilled water after the circulation four times and soak, obtain containing the temperature-sensitive hydrogel of adamantyl.
The LCST of gained hydrogel is 27 ℃, has higher physical strength and the ultrafast swelling behavior that goes.
Embodiment 5:
Take by weighing hydrophobic monomer methacrylic acid 3,5-dimethyl-1-diamantane ester (R in structure such as the general formula
0=CH
3, R
1=CH
3, R
2=CH
3, R
3=H) 0.1g in a little reaction flask, add 1g NIPAM and 22mg N again, N '-methylene-bisacrylamide, add the 6ml tetrahydrofuran (THF) then, after vibration treats that solid all dissolves, add initiator benzoyl peroxide 16.8mg, again through vacuumize-4 circulations of inflated with nitrogen after tube sealing, reaction flask put into 60 ℃ oil bath and reacts 20h.Obtain water white gel and use distilled water immersion 7 days, with 15 ℃ distilled water immersion 24h, the distilled water of putting into 30 ℃ again allows it shrink naturally, changes water then earlier, so remain in the room temperature distilled water after the circulation five times and soak, obtain containing the temperature-sensitive hydrogel of adamantyl.
The LCST of gained temperature-sensitive hydrogel is 22 ℃, has very high physical strength and removes swelling behavior faster.
Embodiment 6:
Take by weighing hydrophobic monomer vinylformic acid 3,5,7-trimethylammonium-1-diamantane ester (R in structure such as the general formula
0=H, R
1=CH
3, R
2=CH
3, R
3=CH
3) 0.06g is in a little reaction flask, add 1g NIPAM and 53mg dimethacrylate glycol ether ester again, add the 8.5ml dehydrated alcohol then, after vibration treats that solid all dissolves, add initiator Diisopropyl azodicarboxylate 11mg, again through vacuumize-inflated with nitrogen 3 times circulation after tube sealing, reaction flask put into 70 ℃ oil bath and reacts 15h.Obtain water white gel and use distilled water immersion 4 days, with 20 ℃ distilled water immersion 12h, the distilled water of putting into 30 ℃ again allows it shrink naturally, changes water then earlier, so remain in the room temperature distilled water after the circulation five times and soak, obtain containing the temperature-sensitive hydrogel of adamantyl.
The LCST of gained temperature-sensitive hydrogel is 24 ℃, has the swelling behavior that goes of very high physical strength and acceleration.
Embodiment 7:
Take by weighing hydrophobic monomer methacrylic acid 3,5-diethyl-1-diamantane ester (R in structure such as the general formula
0=CH
3, R
1=CH
2CH
3, R
2=CH
2CH
3, R
3=H) 0.08g in a little reaction flask, add 1gNIPAM and 43mg Ethylene glycol dimethacrylate again, add 4.5ml benzene then, after vibration treats that solid all dissolves, add initiator dilauroyl peroxide 9mg, again through vacuumize-inflated with nitrogen 3 times circulation after tube sealing, reaction flask put into 75 ℃ oil bath and reacts 10h.Obtain water white gel and use distilled water immersion 6 days, with 15 ℃ distilled water immersion 24h, the distilled water of putting into 30 ℃ again allows it shrink naturally, changes water then earlier, so remain in the room temperature distilled water after the circulation five times and soak, obtain containing the temperature-sensitive hydrogel of adamantyl.
The LCST of gained temperature-sensitive hydrogel is 20 ℃, has very high physical strength and removes swelling behavior faster.
Embodiment 8:
Take by weighing hydrophobic monomer methacrylic acid 3,5-di-isopropyl-1-diamantane ester (R in structure such as the general formula
0=CH
3, R
1=CH (CH
3)
2, R
2=CH (CH
3)
2, R
3=H) 0.04g in a little reaction flask, add 1g NIPAM and 83mg N again, N '-methylene-bisacrylamide, add 6ml toluene then, after vibration treats that solid all dissolves, add initiator benzoyl peroxide 6.4mg, again through vacuumize-4 circulations of inflated with nitrogen after tube sealing, reaction flask put into 80 ℃ oil bath and reacts 8h.Obtain water white gel and use distilled water immersion 3 days, with 20 ℃ distilled water immersion 12h, the distilled water of putting into 35 ℃ again allows it shrink naturally, changes water then earlier, so remain in the room temperature distilled water after the circulation four times and soak, obtain containing the temperature-sensitive hydrogel of adamantyl.
The LCST of gained temperature-sensitive hydrogel is 26 ℃, has high physical strength and removes swelling behavior fast.
Embodiment 9:
Take by weighing hydrophobic monomer vinylformic acid 1-diamantane ester (R in structure such as the general formula
0=H, R
1=H, R
2=H, R
3=H) 0.02g in a little reaction flask, add 1g NIPAM and 25mg dimethacrylate glycol ether ester again, add 3.5ml N then, N '-dimethyl formamide, after vibration treats that solid all dissolves, add initiator Diisopropyl azodicarboxylate 12.6mg, again through vacuumize-5 circulations of inflated with nitrogen after tube sealing, reaction flask put into 85 ℃ oil bath and reacts 6h.Obtain water white gel and use distilled water immersion 2 days, with 25 ℃ distilled water immersion 6h, the distilled water of putting into 35 ℃ again allows it shrink naturally, changes water then earlier, so remain in the room temperature distilled water after the circulation five times and soak, obtain containing the temperature-sensitive hydrogel of adamantyl.
The LCST of gained temperature-sensitive hydrogel is 30 ℃, has the swelling behavior that goes of higher physical strength and acceleration.
Comparative example and contrast effect:
What the comparative example prepared is the temperature-sensitive hydrogel for preparing with the hydrophobic monomer that does not contain adamantyl, the preparation method is the same with the temperature-sensitive hydrogel preparation method who contains adamantyl, concrete preparation process is as follows: take by weighing 1g NIPAM in a little reaction flask, add 0.03g N again, N '-methylene-bisacrylamide, add 7ml 1 then, the 4-dioxane, after vibration treats that solid all dissolves, add initiator Diisopropyl azodicarboxylate 0.0123g, again through vacuumize-inflated with nitrogen 4 times circulation after tube sealing, reaction flask put into 75 ℃ oil bath and reacts 10h.Obtain water white gel with distilled water immersion 5 days, with 25 ℃ distilled water immersion 24h, the distilled water of putting into 40 ℃ again allows it shrink naturally, changes water then earlier, so circulates to remain in the room temperature distilled water after four times to soak.Can obtain the temperature sensitive property of comparative sample homopolymer hydrogel PNIPAM.
Temperature-sensitive hydrogel AdMA1, AdMA3 and the AdMA5 of the adamantyl that embodiment 1～3 is prepared, the temperature-sensitive hydrogel PNIPAM that does not contain adamantyl for preparing with the comparative example carries out performance test:
Go the swelling dynamic test: above-mentioned four kinds of hydrogels are transferred to rapidly after 5 ℃ are issued to swelling equilibrium in 40 ℃ the hot water, hydrogel can shrink dehydration and went swelling this moment.Quality at the time point determining hydrogel of each setting no longer changes until its quality.Earlier wipe the moisture that the surface is taken out of away during mensuration with moistening filter paper.At last the weight data that obtains is carried out normalized, the water retention rate (WR) that is the solvent swelling state of gel or gel transforms by following calculating and obtains between 0 and 1: WR=(weight of the weight-xerogel of t moment gel)/(weight of the weight-xerogel of swelling equilibrium state gel).Make hydrogel WR～t relation curve, promptly get hydrogel 40 ℃ remove swelling (contraction) kinetic curve, as shown in Figure 1.In Fig. 1, the temperature-sensitive hydrogel that contains adamantyl all has than the temperature-sensitive hydrogel that does not contain adamantyl and removes swelling rate faster, in 5min, lose 80% water as AdMA1, AdMA3 loses 93% water in 5min, AdMA5 loses 88% water in 5min, and the PNIPAM that does not contain adamantyl just loses 66% water in 20min.Experimental result shows, adds the swelling rate that goes that the hydrophobic monomer that contains adamantyl can quicken hydrogel, and in certain content range, contains many more that the hydrophobic monomer of adamantyl adds, and the effect of this acceleration is obvious more.So method provided by the invention can be improved the speed of response of temperature-sensitive hydrogel, that quickens gel goes swelling kinetics.
The compression Experiments of Machanics of hydrogel: adopt U.S. Brookfield CT3 type matter structure instrument that hydrogel is carried out stress under compression-strain testing, sample is cut into unified cylindrical, in 25 ℃ water bath with thermostatic control, reach swelling equilibrium before the test, the size of sample is also measured when swelling equilibrium, set deformation quantity 20% and be the compression terminal point, test speed is 0.5mm/s, and the cross-sectional area that stress under compression is pressed before the sample deformation calculates, and the result who obtains as shown in Figure 2.The difference of the temperature-sensitive hydrogel that contains adamantyl that embodiment 1～3 prepares only is to contain the hydrophobic monomer content difference of adamantyl, the amount that contains the hydrophobic monomer of adamantyl among AdMA1, AdMA3 and the AdMA5 increases successively, as can be seen from Figure 2, the mechanical strength of AdMA1, AdMA3 and AdMA5 also is to increase successively in the temperature-sensitive hydrogel, means that the mechanical strength of hydrogel increases gradually with the increase of the hydrophobic monomer content that contains adamantyl.
The modulus of compression of each hydrogel of being tried to achieve through linear match by the stress-strain curve of each hydrogel of Fig. 2 is mapped to the monomeric charge proportioning, the relation that obtains the modulus of compression of hydrogel and monomer ratio as shown in Figure 3, the modulus of compression of copolymer aquagel almost linear increase as can be known with the increase of the hydrophobic monomer feed ratio that contains adamantyl, both relations can be expressed by a linear equation, so method provided by the invention can obtain suitable high-intensity hydrogel easily.
The measurement of the LCST of hydrogel: to above-mentioned four kinds of hydrogel sample, allow it through fully carrying out dsc analysis after the swelling, the intensification scope is 0 ℃～40 ℃, and stops 2min at 0 ℃, and temperature rise rate is 2 ℃/min, dry nitrogen atmosphere, flow rate 50ml/min.The gained result as shown in Figure 4, the LCST of hydrogel PNIPAM, AdMA1, AdMA3 and AdMA5 is followed successively by 31 ℃, 30 ℃, 28 ℃ and 26 ℃, as seen, the volume phase transition temperature LCST of hydrogel significantly reduces with the increase of the hydrophobic monomer content that contains adamantyl.
Tested the volume phase transition temperature of each gel of gained maps to the monomeric charge proportioning by DSC, obtain a proximate linear relation as shown in Figure 5, the available straight line equation of the relation of the volume phase transition temperature of gel and monomeric charge ratio is described as can be known, and the collinear slope is-1, so method provided by the invention can be regulated the volume phase transition temperature of gained copolymer aquagel efficiently by the content that adjusting contains the hydrophobic monomer of adamantyl.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1, a kind of temperature-sensitive hydrogel that contains adamantyl comprises monomer and linking agent, it is characterized in that, described monomer is made up of N-N-isopropylacrylamide and at least a hydrophobic monomer that contains adamantyl;
The described hydrophobic monomer that contains adamantyl has following structural formula:
R
0Be hydrogen or methyl;
R
1Alkyl for hydrogen or 1～3 carbon atom;
R
2Alkyl for hydrogen or 1～3 carbon atom;
R
3Alkyl for hydrogen or 1～3 carbon atom.
2, according to the described temperature-sensitive hydrogel that contains adamantyl of claim 1, it is characterized in that:
The N-N-isopropylacrylamide is 10: 1～100: 1 with the mass ratio that contains the hydrophobic monomer of adamantyl in the described monomer;
The consumption of described linking agent is 2～8% of a monomer mass.
3, according to claim 1 or the 2 described temperature-sensitive hydrogels that contain adamantyl, it is characterized in that:
Described linking agent is N, at least a in N '-methylene-bisacrylamide, dimethacrylate glycol ether ester or the Ethylene glycol dimethacrylate.
4, according to the described preparation method who contains the temperature-sensitive hydrogel of adamantyl of claim 1, it is characterized in that, comprise following steps:
With adding initiator behind organic solvent dissolution monomer and the linking agent again, under the protection of rare gas element,, then handle then with distilled water in 55～85 ℃ of reactions 6～24 hours, obtain containing the temperature-sensitive hydrogel of adamantyl.
5, according to the described preparation method who contains the temperature-sensitive hydrogel of adamantyl of claim 4, it is characterized in that: described rare gas element is a nitrogen.
6, according to the described preparation method who contains the temperature-sensitive hydrogel of adamantyl of claim 4, it is characterized in that: described distilled water is treated to the described temperature-sensitive hydrogel that contains adamantyl of distilled water immersion, time is 1～7 day, during described temperature-sensitive hydrogel is carried out swelling and goes the swollen circular treatment.
7, according to the described preparation method who contains the temperature-sensitive hydrogel of adamantyl of claim 6, it is characterized in that: described swelling is as follows with the condition of going the swollen circular treatment: the swollen temperature is to be lower than 5～15 ℃ of corresponding gel volume phase transition temperature, go the swollen temperature to be higher than 5～15 ℃ of corresponding gel volume phase transition temperature, swelling is carried out 3 times at least with going the swollen circulation.
8, according to the described preparation method who contains the temperature-sensitive hydrogel of adamantyl of claim 4, it is characterized in that:
The N-N-isopropylacrylamide is 10: 1～100: 1 with the mass ratio that contains the hydrophobic monomer of adamantyl in the described monomer;
The consumption of described linking agent is 2～8% of a monomer mass;
The consumption of described initiator is 0.5～2% of monomer and a linking agent quality summation;
The concentration of the solute that described monomer, linking agent and initiator form is 0.1～0.3g/ml, and solvent is described organic solvent.
9, each described preparation method who contains the temperature-sensitive hydrogel of adamantyl of claim 4～8 is characterized in that:
Described linking agent is N, at least a in N '-methylene-bisacrylamide, dimethacrylate glycol ether ester or the Ethylene glycol dimethacrylate.
Described initiator is at least a in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or the dilauroyl peroxide;
Described organic solvent is dehydrated alcohol, tetrahydrofuran (THF), trichloromethane, 1,4-dioxane, benzene, toluene or N, at least a in N '-dimethyl formamide.
10, claim 1 or the 2 described temperature-sensitive hydrogels that contain adamantyl are applied to following field: the conveying of medicine and controllable release; The separation of material; Biosensor; Switch-valve; Chemical reaction control and biological medicine material.
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| CN102432774A (en) * | 2011-09-01 | 2012-05-02 | 中科院广州化学有限公司 | Biodegradable temperature response hydrogel and preparation method thereof |
| CN102432774B (en) * | 2011-09-01 | 2013-03-20 | 中科院广州化学有限公司 | Biodegradable temperature response hydrogel and preparation method thereof |
| CN103554356A (en) * | 2013-10-25 | 2014-02-05 | 东南大学 | Preparation method and application method of hydrogel for intelligent temperature control |
| CN104098746A (en) * | 2014-07-02 | 2014-10-15 | 西南石油大学 | Adamantyl contained hydrophobic association zwitter-ion starch and preparation method thereof |
| CN104098746B (en) * | 2014-07-02 | 2017-01-25 | 西南石油大学 | Adamantyl contained hydrophobic association zwitter-ion starch and preparation method thereof |
| CN107033281A (en) * | 2017-05-05 | 2017-08-11 | 南开大学 | Excellent fluorescence hydrogel of a kind of swelling behavior and preparation method thereof |
| CN107033281B (en) * | 2017-05-05 | 2019-01-15 | 南开大学 | A kind of fluorescence hydrogel and preparation method thereof that swelling behavior is excellent |
| CN109438723A (en) * | 2018-12-29 | 2019-03-08 | 广东工业大学 | Supramolecular materials, temperature-sensitive hydrogel and preparation method thereof |
| CN109694479A (en) * | 2018-12-29 | 2019-04-30 | 广东工业大学 | A kind of supramolecular materials and Subjective and Objective Self-Assembled and preparation method thereof |
| CN109851694A (en) * | 2018-12-29 | 2019-06-07 | 广东工业大学 | A kind of supramolecular materials and a kind of selfreparing hydrogel |
| CN109851694B (en) * | 2018-12-29 | 2021-01-26 | 广东工业大学 | Supramolecular material and self-repairing hydrogel |
| CN109438723B (en) * | 2018-12-29 | 2021-05-11 | 广东工业大学 | Supramolecular material, temperature-sensitive hydrogel and preparation method thereof |
| CN109694479B (en) * | 2018-12-29 | 2021-05-28 | 广东工业大学 | Supermolecular material and host-guest self-assembly hydrogel and preparation method thereof |
| CN112940290A (en) * | 2021-02-05 | 2021-06-11 | 广东工业大学 | Double-network self-repairing hydrogel and preparation method thereof |
| CN112961375A (en) * | 2021-02-05 | 2021-06-15 | 广东工业大学 | Chitosan-based self-repairing hydrogel and preparation method thereof |
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