CN106832310B - A kind of degradable selfreparing hydrogel and the preparation method and application thereof - Google Patents

A kind of degradable selfreparing hydrogel and the preparation method and application thereof Download PDF

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CN106832310B
CN106832310B CN201710052876.4A CN201710052876A CN106832310B CN 106832310 B CN106832310 B CN 106832310B CN 201710052876 A CN201710052876 A CN 201710052876A CN 106832310 B CN106832310 B CN 106832310B
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degradable
acrylic acid
hydrazide
aldehyde radical
hydrogel
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CN106832310A (en
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秦江雷
王雪蒙
李旭
安恒
刘晓玉
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Hebei University
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Abstract

The present invention provides a kind of degradable selfreparing hydrogels and the preparation method and application thereof, the degradable selfreparing hydrogel reacts aldehyde radical phenol ester copolymer with more hydrazide-based compounds by dimethylacrylamide-acrylic acid in aqueous solution, dimethylacrylamide-the acrylic acid includes that repetitive unit A and repetitive unit B, the repetitive unit A account for the 25~98% of copolymer gross mass to aldehyde radical phenol ester copolymer.Degradable selfreparing hydrogel of the invention is based on biocompatible polymer polydimethylacrylamiin, the more hydrazide-based compounds of biocompatibility are crosslinking agent, it is with good stability, it is safe and non-toxic, ensure the application performance of its biocompatibility and biomedicine field.Importantly, hydrogel of the invention can degrade under the conditions of alkalescent (pH is 8.0~8.5) as mild as a dove, and the degradation condition is that life science can bear and realize.

Description

A kind of degradable selfreparing hydrogel and the preparation method and application thereof
Technical field
The present invention relates to a kind of hydrogels and the preparation method and application thereof, and in particular to a kind of degradable selfreparing water-setting Glue and the preparation method and application thereof.
Background technique
Hydrogel is the high molecular material with three-dimensional net structure for absorbing large quantity of moisture, and property is soft, and can Keep certain shape.Selfreparing hydrogel is hydrogel after by environmental damage with self-healing capability, and it is repaired Multiple process close to life entity self-regeneration, not only in bioscience and engineering field (such as man-made organ, organizational project and drug Controlled release etc.) there is boundless application prospect, it is expected to the secret for helping the mankind to open life entity self-regeneration. Therefore, the extensive concern of scientific circles can have been caused with the hydrogel of self-regeneration.
Although not having currently, existing selfreparing hydrogel can be automatically repaired damage when by external injury Standby degradability, after having exercised its own function, the residual of cross-linked structure will bring environmental problem, and be used for biological medicine The selfreparing hydrogel in field is more likely to cause potential side effect because of the residual of cross-linked structure.Therefore, cross-linked structure It is degraded into for technical problem urgently to be resolved in hydrogel research process.
Existing a variety of degradable structures in the prior art, including biodegradable polycaprolactone and polylactic acid, can be with Degradable reversible chemical key etc. under the cystine linkage and acidity or strong alkaline condition of deoxidization, degradation.But it is biodegradable Polyester is not used to prepare hydrogel material, and the degradation condition of other degradable structures is more harsh, cannot be mild weak It degrades under alkaline condition, therefore these degrading textures are can not to be applied to life science at all.It can as it can be seen that developing one kind The hydrogel degraded in a mild condition is very important.
Summary of the invention
An object of the present invention is just to provide a kind of degradable selfreparing hydrogel, to solve existing selfreparing water-setting Glue is difficult to the problem of degrading.
The second object of the present invention is just to provide a kind of preparation method of degradable selfreparing hydrogel, to prepare energy Enough self-regenerations and the hydrogel that can be degraded in a mild condition.
The third object of the present invention be just to provide a kind of degradable selfreparing hydrogel man-made organ, drug loading with Application in controlled release field.
An object of the present invention is achieved in that a kind of degradable selfreparing hydrogel, and the hydrogel is by diformazan Base acrylamide and acrylic acid reacts aldehyde radical phenol ester copolymer with more hydrazide-based compounds in aqueous solution, and described two Methacrylamide-acrylic acid includes repetitive unit A and repetitive unit B to aldehyde radical phenol ester copolymer, and the repetitive unit A is accounted for The 25~98% of copolymer gross mass, more hydrazide-based compounds refer to the compound of at least hydrazides group containing there are two,
In formula, R is H or C1~5Alkyl.
Preferably, the R is H or methyl, and the repetitive unit A accounts for the 50~95% of copolymer gross mass.
Preferably, more hydrazide-based compounds are monomeric compound, there are two the polymer or band of end hydrazides group for band There are two the polymer rolled into a ball with upside hydrazide group；It is highly preferred that more hydrazide-based compounds are to adipic dihydrazide, double sulphur dipropyls Hydrazides, band are there are two the polyethylene glycol of hydrazide group or with there are two the poly(N-isopropylacrylamide) of hydrazide group.
Degradable selfreparing hydrogel of the invention is raw based on biocompatible polymer polydimethylacrylamiin The more hydrazide-based compounds of object compatibility be crosslinking agent, it is with good stability, it is safe and non-toxic, ensured its biocompatibility and The application performance of biomedicine field.The preparation of hydrogel of the invention and self-repair procedure do not need any extraneous catalyst, Get rid of the dependence to catalyst.Importantly, hydrogel of the invention can (pH be in alkalescent as mild as a dove 8.0~8.5) it degrades under the conditions of, and the degradation condition is that life science can bear and realize, to solve existing The problem of selfreparing hydrogel brings potential side effect to life entity and damages to environment because of cross-linked structure residual.
The second object of the present invention is to what is be achieved: a kind of preparation method of degradable selfreparing hydrogel, including Following steps: dimethylacrylamide-acrylic acid is soluble in water to aldehyde radical phenol ester copolymer, more hydrazide group chemical combination are added Object is stood after completely dissolution to get degradable selfreparing hydrogel is arrived；Wherein, the dimethylacrylamide-acrylic acid pair Aldehyde radical phenol ester copolymer includes repetitive unit A and repetitive unit B, the repetitive unit A account for copolymer gross mass 25~ 98%, preferably 50~95%,
In formula, R is H or C1~5Alkyl, preferably H or methyl, more preferably H.
The specific steps of the method for the present invention are as follows:
A. be copolymerized: acrylic acid para hydroxybenzene phenol ester type compound shown in dimethylacrylamide and formula I is made in initiator It under, carries out in a solvent free-radical polymerized, obtains dimethylacrylamide-acrylic acid to aldehyde radical phenol ester copolymer, wherein Dimethylacrylamide and acrylic acid are 1/3~50: 1 to the mass ratio of aldehyde radical phenol ester type compound,
In formula, R is H or C1~5Alkyl, preferably H or methyl, more preferably H；
B. gelation: dimethylacrylamide-acrylic acid is soluble in water to aldehyde radical phenol ester copolymer, more hydrazides are added Based compound, sufficiently dissolution stand to arrive degradable selfreparing hydrogel after mixing.
The more specific step of the method for the present invention are as follows:
A, be copolymerized: by parts by weight 100 parts of dimethylacrylamide and 2~300 parts of (preferably 5~100 parts) third Olefin(e) acid is dissolved in solvent aldehyde radical phenol ester type compound, carries out free-radical polymerized (preferably controllable free-radical polymerisation), reaction Temperature is 30~120 DEG C (preferably 60~100 DEG C), and the reaction time is 2~for 24 hours (preferably 12~for 24 hours), after polymerization, Precipitating reagent is added into reaction solution, precipitating removes residual monomer, obtains dimethylacrylamide-acrylic acid and is copolymerized to aldehyde radical phenol ester Object；
B, gelation, gained dimethylacrylamide-acrylic acid is soluble in water to aldehyde radical phenol ester copolymer, it is added more Hydrazide-based compound simultaneously makes it dissolve, and stands after mixing, obtains degradability selfreparing hydrogel.
In the methods of the invention, the solvent in the step a is that n,N-Dimethylformamide, dioxane or dimethyl are sub- Any one in sulfone, copolymerization process can be active free radical polymerization, be also possible to general radical polymerization.
In the methods of the invention, more hydrazide-based compounds in the step b are monomeric compound, there are two hold hydrazides for band The polymer of group or polymer with more than two side hydrazides groups；Preferably, more hydrazide-based compounds are to oneself Two hydrazides, double sulphur dipropyl hydrazides, band are there are two the polyethylene glycol of hydrazide group or with there are two poly- (the N- isopropyl propylene of hydrazide group Amide).
In the methods of the invention, dimethylacrylamide-acrylic acid in the step b to aldehyde radical phenol ester copolymer with The quality sum of more hydrazide-based compounds accounts for the 5~20% of hydrogel gross mass.
The method of the present invention passes through dimethylacrylamide and acrylic acid first and obtains to aldehyde radical phenol esters copolymer compound Random copolymer, then reacted with more hydrazide-based compounds, the selfreparing hydrogel that can be degraded under weak basic condition is obtained, and lead to The mass ratio for preparing two kinds of monomers of copolymer is crossed, to realize the content control to two kinds of repetitive units in copolymer, to guarantee Gained hydrogel has excellent temperate condition degradability and self-repairability simultaneously.The preparation process of the method for the present invention is simple, behaviour Facilitate, is suitble to promote and apply.
Degradability selfreparing hydrogel provided by the invention can be applied to man-made organ, drug loading and controlled release And the fields such as disposable sanitary articles.
Detailed description of the invention
Fig. 1 be acrylic acid to aldehyde radical phenol ester and dimethylacrylamide-acrylic acid to the red of aldehyde radical phenol ester copolymer Outer spectrogram.Wherein, a is infrared spectrum of the acrylic acid to aldehyde radical phenol ester, and b is dimethylacrylamide-acrylic acid to aldehyde radical benzene The infrared spectrum of phenolic ester copolymer.
Fig. 2 is acrylic acid to aldehyde radical phenol ester and dimethylacrylamide-acrylic acid to the core of aldehyde radical phenol ester copolymer Magnetic spectrum figure.Wherein, solvent for use CDCl3。
Fig. 3 is the selfreparing effect picture of 1 gained hydrogel of embodiment.
Fig. 4 is 1 gained hydrogel of embodiment in NaHCO3Degradation process schematic diagram in aqueous solution.
Specific embodiment
The embodiment of the invention discloses the selfreparing hydrogels that one kind can degrade under weak basic condition, by dimethyl propylene Acrylamide-acrylic acid is not necessarily to add any catalyst in aqueous solution to aldehyde radical phenol ester copolymer and more hydrazide-based compounds In the case of react, wherein dimethylacrylamide-acrylic acid includes repetitive unit A and again to aldehyde radical phenol ester copolymer Multiple unit B, the repetitive unit A account for the 25~98% of copolymer gross mass, preferably 50~95%.
In formula, R is H or C1~5Alkyl, preferably H or methyl.
The embodiment of the invention also discloses the preparation methods of degradability selfreparing hydrogel, comprising the following steps:
A, be copolymerized, by parts by weight 100 parts of dimethylacrylamide and 2~300 parts of (preferably 5~100 parts) third Olefin(e) acid is dissolved in solvent aldehyde radical phenol ester type compound, carries out free-radical polymerized (preferably active free radical polymerization), reaction Temperature is 30~120 DEG C (preferably 60~100 DEG C), and the reaction time is 2~for 24 hours (preferably 12~for 24 hours), after polymerization, Precipitating reagent is added into reaction solution, precipitating removes residual monomer, obtains dimethylacrylamide-acrylic acid and is copolymerized to aldehyde radical phenol ester Object.Wherein, used solvent is any one in n,N-Dimethylformamide, dioxane or dimethyl sulfoxide, solvent Dosage be 120~1000 parts.
B, gelation, gained dimethylacrylamide-acrylic acid is soluble in water to aldehyde radical phenol ester copolymer, according to total Deionized water is added in solid content 5~20%, and more hydrazide-based compounds are added and dissolve it sufficiently, stood after mixing Night obtains degradable selfreparing hydrogel；More hydrazide-based compounds used are monomeric compound, there are two hold hydrazides group for band Polymer or polymer with more than two side hydrazides groups, preferably adipic dihydrazide, double sulphur dipropyl hydrazides, there are two bands There are two the poly(N-isopropylacrylamide) of end hydrazide group for the polyethylene glycol or band of hydrazide group.
The present invention is further explained combined with specific embodiments below, and in following embodiment, what is be not described in detail is various Process and method are conventional methods as known in the art, what agents useful for same did not indicated source and specification be commercially available analysis it is pure or Chemistry is pure.
Acrylic acid in following embodiment is prepared aldehyde radical phenol ester type compound as follows: first will be right Hydroxy benzaldehyde is dissolved in dry organic solvent, such as methylene chloride, tetrahydrofuran, acetone, and excessive alkali is then added and is used in combination Excessive acryloyl chloride or methacrylic chloride are added dropwise after ice-water bath is 30 minutes cooling, and stirs for 24 hours.Product through extracting, (methyl) acrylic acid is obtained to aldehyde radical phenol ester after silica gel column separating purification and vacuum drying, and reaction equation is as follows:
R is H or methyl in formula.
Embodiment 1
Copolymerization: by 20g dimethylacrylamide, 1g acrylic acid to aldehyde radical phenol ester, 25mg azodiisobutyronitrile (AIBN) It is dissolved in 50mL dioxane, and adds it to 100mg DDMAT chain-transferring agent (i.e. dodecyl trithiocarbonate) In the reaction flask of 100mL, it is warming up to 60 DEG C of progress Reversible Addition Fragmentation Chain Transfer in removing system after oxygen under magnetic stirring Free radical polymerization, reaction time are that for 24 hours, after reaction, reaction system is cooling, twice with petroleum ether precipitation, removing is not anti- The monomer answered is dried in vacuo to obtain white powder, and as dimethylacrylamide-acrylic acid is to aldehyde radical phenol ester copolymer, weighing Monomer conversion and average molecular weight are calculated, repeating unit of copolymer dimethylacrylamide and repetitive unit acrylic acid are to aldehyde The mass ratio of base phenol ester is about 20: 1.
Gelation: the above-mentioned copolymer of 0.6g is dissolved in 15g water, and 0.9g band is added, and there are two the polyethylene glycol of end hydrazide group (H2NHNCO-PEG-CONHNH2, the molecular weight of PEG is that 10118), sufficiently dissolution after mixing, is stood, can be obtained can drop The selfreparing hydrogel of solution, as shown in Figure 3a.
Infrared detection is carried out to aldehyde radical phenol ester copolymer to gained dimethylacrylamide-acrylic acid and nuclear-magnetism characterizes, As a result as depicted in figs. 1 and 2.
Infrared spectrum as shown in Figure 1 can be seen that in spectrogram of the monomeric acrylic to aldehyde radical phenol ester in 1744cm-1 And 1700cm-1Locate there are two carbonyl absorption peak, and the 1757cm contained in copolymer-1And 1700cm-1Place two peaks exactly by Monomeric acrylic is to aldehyde radical phenol ester, wherein since double bond is consumed, so the absorption peak of ester carbonyl group is to high wave number direction Movement has occurred；1645cm-1For the absorption peak of the corresponding C=O of dimethylformamide structural unit, dimethyl allene is thus demonstrated Copolymeric structure of the amide-acrylic acid to aldehyde radical phenol ester.
Nuclear magnetic spectrogram shown in Fig. 2 can be seen that in addition to double bond, and acrylic acid is both present in altogether the peak on aldehyde radical phenol ester In polymers, it was demonstrated that two monomers are copolymerized.The molar ratio and weight ratio of two kinds of repetitive units are found out by comparing peak area ratio, The result shows that its weight ratio is close with feed ratio, illustrate that phenolic ester structure is more stable in the course of the polymerization process, copolymerization has obtained mesh Mark product.
Self-reparing capability test is carried out to gained hydrogel, as shown in figure 3, gained hydrogel is cut into (such as Fig. 3 b), Selfreparing (such as Fig. 3 c) can be realized interior for 24 hours, and even if will not rupture (such as along incision under the action of adding tractive force outside Fig. 3 d).
Shown in Fig. 4 is the NaHCO that gained hydrogel is 2% in mass concentration3Degradation in aqueous solution at room temperature Journey schematic diagram, originally hydrogel has some strength, can support own wt (such as Fig. 4 a), and NaHCO is added3After solution, solution Be absorbed and show brown (such as Fig. 4 b), and be gradually degraded to thick liquid (such as Fig. 4 c) after 15 days, and at any time into One step extends, and mobility improves, and selfreparing hydrogel is degradable.PH value can be measured in degradation process in due course, guarantee system is weak Alkaline environment guarantees that pH is maintained between 8~8.5.
Embodiment 2
Copolymerization: by 10g dimethylacrylamide, 1g acrylic acid to aldehyde radical phenol ester, 15mg azodiisobutyronitrile (AIBN) It is dissolved in 30mL dioxane, and is added it in the reaction flask of 100mL with 50mg DDMAT chain-transferring agent, in removing system It is warming up to 80 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations after oxygen under magnetic stirring, reaction time 20h, instead It is after answering, reaction system is cooling, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo to obtain white powder, As dimethylacrylamide-acrylic acid is to aldehyde radical phenol ester copolymer, and weighing calculates monomer conversion and average molecular weight, altogether Repetitive unit dimethylacrylamide and repetitive unit acrylic acid are about 10: 1 to the mass ratio of aldehyde radical phenol ester in polymers.
Gelation: the above-mentioned copolymer of 1.7g is dissolved in 18g water, and adding 0.1g band, there are two two propionyl of double sulphur of end hydrazide group Hydrazine, sufficiently dissolution after mixing, stand, degradable selfreparing hydrogel can be obtained.
Embodiment 3
Copolymerization: by 20g dimethylacrylamide, 3g methacrylic acid to aldehyde radical phenol ester, 25mg azodiisobutyronitrile (AIBN) it is dissolved in 50mL dioxane, and is added it in the reaction flask of 200mL with 100mg DDMAT chain-transferring agent, removed It goes in system to be warming up to 75 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations, reaction time after oxygen under magnetic stirring It is after reaction, reaction system is cooling for 18h, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo To aldehyde radical phenol ester copolymer, weighing calculates monomer conversion and is averaged for white powder, as dimethylacrylamide-acrylic acid The mass ratio of molecular weight, repeating unit of copolymer dimethylacrylamide and repetitive unit methacrylic acid to aldehyde radical phenol ester About 7: 1.
Gelation: the above-mentioned copolymer of 2.1g is dissolved in 18g water, be added 0.6g band there are two end hydrazide group poly- (N- is different Propylacrylamide), sufficiently dissolution after mixing, stands, degradable selfreparing hydrogel can be obtained.
Embodiment 4
Copolymerization: by 10g dimethylacrylamide, 10g acrylic acid to aldehyde radical phenol ester, 30mg azodiisobutyronitrile (AIBN) It is dissolved in 45mL dioxane, and is added it in the reaction flask of 100mL with 200mg DDMAT chain-transferring agent, remove system Be warming up to 60 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations after interior oxygen under magnetic stirring, the reaction time be for 24 hours, After reaction, reaction system is cooling, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo to obtain white powder End, as dimethylacrylamide-acrylic acid calculate monomer conversion and mean molecule to aldehyde radical phenol ester copolymer, weighing Amount, repeating unit of copolymer dimethylacrylamide and repetitive unit acrylic acid are about 1: 1 to the mass ratio of aldehyde radical phenol ester.
Gelation: the above-mentioned copolymer of 1.4g is dissolved in 18g water, and 0.4g band is added, and there are two the polyethylene glycol of end hydrazide group (molecular weight of PEG is 2300), sufficiently dissolution after mixing, stand 20min, degradable selfreparing water-setting can be obtained Glue.
Embodiment 5
Copolymerization: by 25g dimethylacrylamide, 5g acrylic acid to aldehyde radical phenol ester, 30mg azodiisobutyronitrile (AIBN) It is dissolved in 70mL dioxane, and is added it in the reaction flask of 250mL with 150mg DDMAT chain-transferring agent, remove system It is warming up to 70 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations after interior oxygen under magnetic stirring, reaction time 17h, After reaction, reaction system is cooling, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo to obtain white powder End, as dimethylacrylamide-acrylic acid calculate monomer conversion and mean molecule to aldehyde radical phenol ester copolymer, weighing Amount, repeating unit of copolymer dimethylacrylamide and repetitive unit acrylic acid are about 5: 1 to the mass ratio of aldehyde radical phenol ester.
Gelation: the above-mentioned copolymer of 0.9g is dissolved in 18g water, and 1.8g band is added, and there are two the polyethylene glycol of end hydrazide group (molecular weight of PEG is 4000), sufficiently dissolution after mixing, stand, degradable selfreparing hydrogel can be obtained.
Embodiment 6
Copolymerization: by 10g dimethylacrylamide, 5g acrylic acid to aldehyde radical phenol ester, 25mg azodiisobutyronitrile (AIBN) It is dissolved in 30mL dioxane, and is added it in the reaction flask of 100mL with 40mg DDMAT chain-transferring agent, in removing system It is warming up to 65 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations after oxygen under magnetic stirring, reaction time 18h, instead It is after answering, reaction system is cooling, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo to obtain white powder, As dimethylacrylamide-acrylic acid is to aldehyde radical phenol ester copolymer, and weighing calculates monomer conversion and average molecular weight, altogether Repetitive unit dimethylacrylamide and repetitive unit acrylic acid are about 2: 1 to the mass ratio of aldehyde radical phenol ester in polymers.
Gelation: the above-mentioned copolymer of 1.55g is dissolved in 18g water, and 0.25g is added to adipic dihydrazide, sufficiently dissolution mixing After uniformly, stands, degradable selfreparing hydrogel can be obtained.
Embodiment 7
Copolymerization: by 4g dimethylacrylamide, 5g acrylic acid to aldehyde radical phenol ester, 10mg azodiisobutyronitrile (AIBN) and 20mg DDMAT chain-transferring agent is dissolved in 20mL dioxane, and is added it in the reaction flask of 100mL, oxygen in removing system 70 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations, reaction time 16h, reaction are warming up to after gas under magnetic stirring After, reaction system is cooling, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo to obtain white powder, i.e., It is dimethylacrylamide-acrylic acid to aldehyde radical phenol ester copolymer, weighing calculates monomer conversion and average molecular weight, copolymerization Repetitive unit dimethylacrylamide and repetitive unit acrylic acid are about 0.8: 1 to the mass ratio of aldehyde radical phenol ester in object.
Gelation: the above-mentioned copolymer of 0.3g is dissolved in 18g water, and 3.3g band is added, and there are two the polyethylene glycol of end hydrazide group (molecular weight of PEG is 10118), sufficiently dissolution after mixing, stand, degradable selfreparing hydrogel can be obtained.
Embodiment 8
Copolymerization: by 30g dimethylacrylamide, 0.6g acrylic acid to aldehyde radical phenol ester, 25mg azodiisobutyronitrile (AIBN) it is dissolved in 50mL dioxane, and is added it in the reaction flask of 200mL with 150mg DDMAT chain-transferring agent, removed It goes in system to be warming up to 60 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations, reaction time after oxygen under magnetic stirring For 24 hours, after reaction, by reaction system cooling, twice with petroleum ether precipitation, to remove unreacted monomer, being dried in vacuo To aldehyde radical phenol ester copolymer, weighing calculates monomer conversion and is averaged for white powder, as dimethylacrylamide-acrylic acid Molecular weight, repeating unit of copolymer dimethylacrylamide are about with mass ratio of the repetitive unit acrylic acid to aldehyde radical phenol ester 50∶1。
Gelation: the above-mentioned copolymer of 1g is dissolved in 18g water, and 0.8g band is added, and there are two poly- (the N- isopropyls of end hydrazide group Base acrylamide), sufficiently dissolution after mixing, stands, degradable selfreparing hydrogel can be obtained.
Embodiment 9
Copolymerization: by 8g dimethylacrylamide, 1g methacrylic acid to aldehyde radical phenol ester, 15mg azodiisobutyronitrile (AIBN) it is dissolved in 25mL dioxane, and is added it in the reaction flask of 100mL with 20mg DDMAT chain-transferring agent, removed It is warming up to 70 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations in system after oxygen under magnetic stirring, the reaction time is 16h, it is after reaction, reaction system is cooling, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo white To aldehyde radical phenol ester copolymer, weighing calculates monomer conversion peace for color powder, as dimethylacrylamide-methacrylic acid The quality of average molecular weight, repeating unit of copolymer dimethylacrylamide and repetitive unit methacrylic acid to aldehyde radical phenol ester Than being about 8: 1.
Gelation: the above-mentioned copolymer of 1.6g is dissolved in 18g water, and 2.0g band is added, and there are two the polyethylene glycol of end hydrazide group (molecular weight of PEG is 4000), sufficiently dissolution after mixing, stand, degradability selfreparing hydrogel can be obtained.
Embodiment 10
Copolymerization: by 25g dimethylacrylamide, 75g acrylic acid to aldehyde radical phenol ester, 100mg azodiisobutyronitrile (AIBN) it is dissolved in 100mL dioxane, and is added it in the reaction flask of 250mL with 1g DDMAT chain-transferring agent, removed It is warming up to 70 DEG C of progress reversible addition-fragmentation chain transfer free radical polymerizations in system after oxygen under magnetic stirring, the reaction time is 17h, it is after reaction, reaction system is cooling, twice with petroleum ether precipitation, unreacted monomer is removed, is dried in vacuo white Color powder, as dimethylacrylamide-acrylic acid calculate monomer conversion and average mark to aldehyde radical phenol ester copolymer, weighing Son amount, repeating unit of copolymer dimethylacrylamide and repetitive unit acrylic acid are about 1 to the mass ratio of aldehyde radical phenol ester: 3。
Gelation: the above-mentioned copolymer of 1g is dissolved in 18g water, and 3.5g band is added, and there are two the polyethylene glycol of end hydrazide group (molecular weight of PEG is 4000), sufficiently dissolution after mixing, stand 20min, degradable selfreparing water-setting can be obtained Glue.
Embodiment 11: selfreparing experiment.
2~10 products therefrom of embodiment is subjected to selfreparing experiment, the specific steps are as follows: by obtained hydrogel along intermediate It cuts in half, then joint-cutting alignment is put together, situation is repaired in observation afterwards for 24 hours, and is stretched with tweezers along joint-cutting vertical direction Whether verifying gel is repaired.The result shows that: prepared hydrogel can realize selfreparing interior for 24 hours, and even if in outer plus traction Under the action of power, it will not be ruptured along incision.
Embodiment 12: degradability experiment.
2~10 gained hydrogel of embodiment is placed in small sample bottle, the NaCO that mass concentration is 2% is added3Aqueous solution is seen Examine degradation situation, the results showed that prepared hydrogel can be degraded to liquid in 15 days.NaHCO3And NaCO3It is common Food additives, therefore the substance with biohazardous will not be generated in the degradation process of selfreparing hydrogel, guaranteed Its safety used and biocompatibility.The above selfreparing hydrogel can also degrade in triethylamine, and because alkali The enhancing of property, can be degraded to liquid for 24 hours.

Claims (9)

1. a kind of degradable selfreparing hydrogel, characterized in that the hydrogel is by dimethylacrylamide-acrylic acid to aldehyde radical Phenol ester copolymer reacts in aqueous solution with more hydrazide-based compounds, and dimethylacrylamide-acrylic acid is to aldehyde radical benzene The quality sum of phenolic ester copolymer and more hydrazide-based compounds accounts for the 5~20% of hydrogel gross mass, the dimethyl allene acyl Amine-acrylic acid includes that repetitive unit A and repetitive unit B, the repetitive unit A account for the total matter of copolymer to aldehyde radical phenol ester copolymer The 25~98% of amount,
In formula, R is H or C1~5Alkyl.
2. degradable selfreparing hydrogel according to claim 1, characterized in that the R is H or methyl.
3. degradable selfreparing hydrogel according to claim 1, characterized in that more hydrazide-based compounds are single Body compound is the end hydrazides group with there are two or the polymer of more than two sides hydrazides group.
4. degradable selfreparing hydrogel according to claim 1, characterized in that more hydrazide-based compounds are pair Adipic dihydrazide, double sulphur dipropyl hydrazides, band are there are two the polyethylene glycol of hydrazide group or with there are two poly- (the N- isopropyls third of hydrazide group Acrylamide).
5. a kind of preparation method of degradable selfreparing hydrogel, characterized in that the following steps are included: by dimethyl allene acyl Amine-acrylic acid is soluble in water to aldehyde radical phenol ester copolymer, and more hydrazide-based compounds are added, and is stood after completely dissolution to get arriving Degradable selfreparing hydrogel, dimethylacrylamide-acrylic acid is to aldehyde radical phenol ester copolymer and more hydrazide-based compounds Quality sum account for the 5~20% of hydrogel gross mass；Wherein, the dimethylacrylamide-acrylic acid is to aldehyde radical phenol ester Copolymer includes that repetitive unit A and repetitive unit B, the repetitive unit A account for the 25~98% of copolymer gross mass,
In formula, R is H or C1~5Alkyl.
6. the preparation method of degradable selfreparing hydrogel according to claim 5, characterized in that the dimethyl propylene Acrylamide-acrylic acid is passed through aldehyde radical phenol ester copolymer as dimethylacrylamide free-radical polymerized with compound shown in formula I And obtain, in formula, R is H or C1~5Alkyl,
7. the preparation method of degradable selfreparing hydrogel according to claim 5, which is characterized in that more hydrazides Based compound is monomeric compound or is that there are two end hydrazides group or the polymer of more than two sides hydrazides group for band.
8. the preparation method of degradable selfreparing hydrogel according to claim 5, which is characterized in that more hydrazides Based compound is to adipic dihydrazide, double sulphur dipropyl hydrazides, band there are two the polyethylene glycol of hydrazide group or with there are two hydrazide groups Poly(N-isopropylacrylamide).
9. degradable selfreparing hydrogel described in claim 1 is in microbial administration, man-made organ and drug controlled release Application.
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