CN110194877A - A kind of Nanometer composite hydrogel and its preparation method and application - Google Patents
A kind of Nanometer composite hydrogel and its preparation method and application Download PDFInfo
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- CN110194877A CN110194877A CN201910212220.3A CN201910212220A CN110194877A CN 110194877 A CN110194877 A CN 110194877A CN 201910212220 A CN201910212220 A CN 201910212220A CN 110194877 A CN110194877 A CN 110194877A
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Abstract
The present invention devises a kind of novel multifunctional nano composite hydrogel, has syringeability, self-healing property, good mechanical strength, irritative response and adhesiveness.Presoma is used as by using the polymer (PGMA) containing glycol and the polymer (PAPBA-stat-PDMA) containing phenyl boric acid, and the nanoparticle (rGO@PDA) of a certain amount of poly-dopamine coating decoration is added, prepare multifunctional nano composite hydrogel.In alkaline environment, hydrogel network can easily be realized by the interaction of the polymer containing phenyl boric acid/polymer containing glycol.Compared with the straight polymer hydrogel of the nanoparticle (rGO@PDA) without poly-dopamine coating decoration, the storage modulus (G') of gained Nanometer composite hydrogel is significantly improved, and the Nanometer composite hydrogel has adhesiveness.
Description
Technical field
The present invention relates to a kind of hydrogels, and in particular to one kind has pH response, selfreparing, tack, injectable nanometer
Composite hydrogel and its preparation method and application belongs to bio-medical material preparation field.
Background technique
The three-dimensional net structure that hydrogel is made of hydrophilic polymer chains.It is in physics, chemistry, biology and high biological
It is with a wide range of applications in terms of compatible drug release.Although hydrogel has many advantages, there are still some defects.
If mechanical strength is low, bad mechanical property, single performance, stability difference etc..These defects limit hydrogel in every field
Using.For these reasons, researcher designs and develops novel hydrogels to overcome hydrogel defect, while assigning water-setting
The some unique properties of glue.With the raising of hydrogel mechanical property, it has been proposed that many strategies for preparing hydrogel, including
Dual network structure, nanocomposite and Supramolecular Network.Wherein, the nanometer with non-covalent or covalent fixed nano particle is multiple
Heshui gel is received more and more attention due to its simple and effective characteristic.By by nano particle and polymer network knot
Conjunction prepares nanocomposite hydrogel, and the polymer network is as nano particle such as carbon-based nano particle (carbon nanotube, graphite
Alkene, C60), polymer nano granules (polymer nano granules, hyperbranched nano particle), inorganic/ceramic nanoparticles (silicic acid
Salt, calcium phosphate), metal/metal oxide nano particle (gold, silver, ferroso-ferric oxide).
Although the physical property of polymer network is improved, nano particle due to being added to functionalized nano-particles
Physics filler is served as in polymer network, and is not covalently bonded in resulting materials in most of researchs.We are logical
The covalent cross-linking crossed between polymer and nano particle shifts mechanical force in cross-linked network to increase mechanical strength and toughness.Stone
Black alkene is two dimension (2D) single layer of sp2 hydbridized carbon atoms, has excellent electricity, mechanical and thermal property.Geim is same with his
Thing had found graphene in 2004 and obtains Nobel Prize in physics.Since graphene discovery, the research of graphene by
Gradually from photoconductive material in electronics, photoelectric device and solar battery, drug conveying and heterogeneity in organizational project and answer
With middle increase.However, original graphite alkene is substantially water contact angle hydrophobic and with 95-100 °.In order to enhance stone
The dispersion effect of black alkene can handle graphene film with strong oxidizer to obtain graphite oxide (GO).GO can be with hydrophilic polymer
It interacts to form the network of physics or covalent cross-linking.
Dopamine belongs to a kind of catecholamine with good biocompatibility.It can be with spontaneous polymerization at poly-dopamine
(PDA), adhesive coating is formed in various matrix, this is by viscous protein matter spy's sexual enlightenment in marine mussel.Using more
Bar amine reducing agent enables us to the graphene hydrogel for preparing functionalization in a mild condition, this is more time-consuming than what is be previously reported
Hydrothermal method is more flexible.In view of the reproducibility of dopamine, auto polymerization and strongly adherent energy, the electronation oxidation of PDA cladding
Graphene (rGO@PDA) is successfully prepared in this work by one-step method.
Summary of the invention
For the problems such as composite hydrogel mechanical strength is not high, toughness is insufficient in the prior art, the present invention passes through polymer
Covalent cross-linking between nano particle shifts mechanical force in cross-linked network to increase mechanical strength and toughness.Present invention design
A kind of novel multifunctional nano composite hydrogel, has a syringeability, self-healing property, good mechanical strength, and irritation is anti-
Should and adhesiveness.By using the polymer (PGMA) containing glycol and the polymer (PAPBA-stat- containing phenyl boric acid
PDMA it) is used as presoma, and adds the nanoparticle (rGO@PDA) of a certain amount of poly-dopamine coating decoration, is prepared multi-functional
Nanometer composite hydrogel.In alkaline environment, hydrogel can easily be realized by the interaction of PBA/ glycol complex
Network.Compared with the straight polymer hydrogel of the nanoparticle (rGO@PDA) without poly-dopamine coating decoration, gained nanometer is multiple
Storage modulus (G') significant raising of Heshui gel, and the Nanometer composite hydrogel has adhesiveness.
The purpose of the present invention is to provide a kind of Nanometer composite hydrogels, by synthesizing two kinds of polymer: containing phenyl boric acid
Polymer, the polymer containing glycol, in addition nanoparticle: the nanoparticle of poly-dopamine coating decoration；Benzene boron will be contained
The polymer of acid, the nanoparticle of the polymer containing glycol and poly-dopamine coating decoration are dissolved in alkaline aqueous solution respectively,
By being blended two kinds of polymer and nanoparticle to obtain gel, for field of biomedical materials provide it is a kind of have pH response,
Selfreparing, tack, injectable Nanometer composite hydrogel.The Nanometer composite hydrogel can cross be applied to drug controlled release,
The fields such as organizational project.
The first embodiment provided according to the present invention, provides a kind of Nanometer composite hydrogel.
A kind of Nanometer composite hydrogel, the Nanometer composite hydrogel pass through following reaction: boronate passes through with glycol group
The nanoparticle that borate dynamic is covalently cross-linked, is coated using poly-dopamine is prepared as reinforcing agent.
In the present invention, which is blended preparation by two kinds of polymer and nanoparticle and obtains；Its
In: two kinds of polymer is the polymer containing phenyl boric acid, the polymer containing glycol, and the nanoparticle is poly-dopamine cladding
The nanoparticle of modification.
Preferably, the polymer containing phenyl boric acid is the polymer containing hydrophilic unit.
Preferably, the hydrophilic unit is N,N-DMAA, n-vinyl pyrrolidone, acrylic acid, third
One of acrylamide, n-isopropyl acrylamide are a variety of.
Preferably, the polymer containing glycol is to contain 1,2- glycol or 1, the polymer of 3- glycol.Preferably
One of polyethylene glycol, polyvinyl alcohol, polyglycerolmethacrylate are a variety of.
Preferably, the nanoparticle is one of carbon nanotube, graphene, nano silica, nanoclay
Or it is a variety of.
Second of the embodiment provided according to the present invention, provides a kind of preparation method of Nanometer composite hydrogel.
A kind of preparation method of Nanometer composite hydrogel prepares Nanometer composite hydrogel described in the first embodiment
Method, method includes the following steps:
(1) synthesis of the polymer containing phenyl boric acid: the substance containing phenyl boric acid is dissolved in solvent, and chain-transferring agent is added
And initiator, it is reacted, obtains the polymer containing phenyl boric acid；
(2) synthesis of the polymer containing glycol: will contain 1,2- glycol or 1, and the substance of 3- glycol is dissolved in solvent, adds
Enter chain-transferring agent and initiator, reacted, obtains the polymer containing glycol；
(3) synthesis of the nanoparticle of poly-dopamine coating decoration: dispersing nanoparticle in buffer solution, is added more
Bar amine is stirred to react a period of time, isolates solid, obtain the nanoparticle of poly-dopamine coating decoration；
(4) preparation of Nanometer composite hydrogel: the nanoparticle dissolution for the poly-dopamine coating decoration that step (3) is obtained
In dispersion liquid, adjustment pH value is alkalinity, and the polymer containing glycol that step (2) obtain then is added, is labeled as mixture
I；The polymer containing phenyl boric acid that step (1) obtains is dissolved in alkaline solution, mixtures II is labeled as；By mixture I with
Mixtures II mixing, is stirred to react, obtains Nanometer composite hydrogel.
Preferably, step (1) specifically: in the reactor, the substance containing phenyl boric acid is (described containing phenyl boric acid
Substance is the substance containing hydrophilic unit；Wherein: the hydrophilic unit is N, N- dimethylacrylamide, N- ethenyl pyrrolidone
One of ketone, acrylic acid, acrylamide, n-isopropyl acrylamide are a variety of) being dissolved in solvent, (solvent is preferably DMF and H2O
Mixed solvent, more preferably DMF and H2The in the mixed solvent of O, DMF and H2The volume ratio of O is 1-100:1) in, chain is added
Transfer agent (preferably EMP) and initiator (preferably AIBN), the oxygen being discharged in reactor (are preferably blasted into reactor
Then nitrogen seals reactor), isothermal reaction (preferably uses oil bath constant temperature, the temperature of reaction is 40-100 DEG C, and the reaction time is
0.5-6h), stop reaction (preferably using the sudden cold stopping reaction of liquid nitrogen), dilution (is preferably diluted using DMF), and sedimentation (is preferably adopted
Settled with ether), obtain the polymer containing phenyl boric acid.
Preferably, the degree of polymerization of the polymer containing phenyl boric acid is 20-1000, preferably 40-600, more preferably 50-
500；The mass ratio of substance and solvent containing phenyl boric acid is 1:1-50, preferably 1:2-30, more preferably 1:3-20；Chain tra nsfer
The molar ratio of agent and initiator is 1-50:1, preferably 2-30:1, more preferably 3-20:1.
Preferably, step (2) specifically: in the reactor, 1,2- glycol or 1 will be contained, the substance of 3- glycol is (described
Substance containing 1,2- glycol or 1,3- glycol is preferably one of ethylene glycol, vinyl alcohol, glyceral methacrylate or more
Kind), chain-transferring agent (preferably EMP) and initiator (preferably AIBN) be dissolved in solvent (preferably DMF), in discharge reactor
Oxygen (preferably blasted into reactor nitrogen and then seal reactor), isothermal reaction (preferably uses oil bath constant temperature, reaction
Temperature be 40-100 DEG C, reaction time 1-24h), stop reaction (preferably using sudden cold the stoppings reaction of liquid nitrogen), dilution is (excellent
Choosing is diluted using DMF), sedimentation (is preferably settled using ether), and it is dry (preferably using vacuum drying), it obtains poly- containing glycol
Close object.
Preferably, the degree of polymerization of the polymer containing glycol is 20-1000, preferably 40-600, more preferably 50-
500；Contain 1,2- glycol or 1, the substance of 3- glycol and the mass ratio of solvent are 1:1-50, preferably 1:2-30, more preferably
1:3-20；The molar ratio of chain-transferring agent and initiator is 1-50:1, preferably 2-30:1, more preferably 3-20:1.
Preferably, step (3) specifically: by nanoparticle, (nanoparticle is carbon nanotube, graphene, nanometer
One of silica, nanoclay are a variety of) being scattered in alkaline solution, (alkaline solution preferably uses Tris-HCl molten
Liquid more preferably uses 0.001-0.1M, pH for the Tris-HCl solution of 8-10) in, dopamine solution is then added and (preferably adopts
With Dopamine hydrochloride), it is stirred to react and (preferably uses and be stirred at room temperature, mixing time 1-48h, preferably 2-24h), isolate solid
(preferably using separation is filtered, described filter is filtered body using organic film, more preferably uses aperture for the organic film of 100-500nm
Filter), washing (preferably uses ethanol washing), filters and (is preferably filtered using organic film, more preferably use aperture for 100-
The organic film of 500nm filters), it is dry (preferably using vacuum drying), obtain the nanoparticle of poly-dopamine coating decoration.
Preferably, nanoparticle is dispersed in alkaline solution, the concentration of nanoparticle is 0.1-5mg/mL, preferably
0.3-3mg/mL；After dopamine solution is added, concentration of the dopamine solution in alkaline solution is 0.1-5mg/mL, preferably
0.5-3mg/mL。
Preferably, step (4) specifically: the nanoparticle dissolution for the poly-dopamine coating decoration for obtaining step (3)
In dispersion liquid (the preferably aqueous solution of sodium hydroxide), adjustment pH value is alkalinity, and step (2) acquisition is then added contains two
The polymer of alcohol is labeled as mixture I；The polymer containing phenyl boric acid that step (1) obtains is dissolved in alkaline solution (preferably
The aqueous solution of sodium hydroxide) in, it is labeled as mixtures II；Mixture I is mixed with mixtures II, is stirred to react, obtains nanometer
Composite hydrogel.
Preferably, the content of the nanoparticle of poly-dopamine coating decoration is 0.1-5% in mixture I, contain glycol
Polymer content be 1-20%；Mixtures II, the content of the polymer containing phenyl boric acid are 1-20%；Mixture I and mixed
The mixed volume ratio for closing object II is 0.1-10:1, preferably 0.5-5:1, more preferably 1-2:1.
Preferably, the substance containing phenyl boric acid is acrylamido phenyl boric acid and the different acrylamido of N- in step (1)
The molar ratio of the mixture of phenyl boric acid, acrylamido phenyl boric acid and the different acrylamido phenyl boric acid of N- is 1:0.1-20, preferably
For 1:0.2-10.The polymer containing phenyl boric acid is the different acrylamido phenyl boric acid copolymerization of acrylamido phenyl boric acid-N-
Object.
Preferably, containing 1,2- glycol or 1 described in step (2), the substance of 3- glycol is glycidyl acrylate.
The polymer containing glycol is polyglycidyl acrylate.
Preferably, nanoparticle described in step (3) is graphene oxide.
The third embodiment provided according to the present invention, provides a kind of purposes of Nanometer composite hydrogel.
The side according to Nanometer composite hydrogel described in the first embodiment or according to second of embodiment
The purposes of the Nanometer composite hydrogel of method preparation, is used for bio-medical material, organizational project for the nanocomposite hydrogel
Material.
In the present invention, polymerization reaction is carried out by the substance containing phenyl boric acid first, synthesizes the polymerization containing phenyl boric acid
Object；Polymerization reaction is carried out by the substance (preferably use and contain 1,2- glycol or 1, the substance of 3- glycol) containing glycol, is closed
At the polymer containing glycol；Nanoparticle is subjected to coating decoration by dopamine, dopamine carries out certainly on nanoparticle
Polymerization reaction forms the nanoparticle of poly-dopamine cladding；Then by the polymer containing phenyl boric acid, contain the substance of glycol
It is polymerize under alkaline environment with the nanoparticle of poly-dopamine coating decoration；Hydrogen in alkaline environment, under alkaline environment
Oxygen radical ion, so that the polymer containing phenyl boric acid has negative electrical charge, contains phenyl boric acid in conjunction with the polymer containing phenyl boric acid
Polymer react with the substance containing glycol forming borate dynamic covalent bond；And then form gel；It is poly- simultaneously more
The catechol group of the nanoparticle surface of bar amine coating decoration can also be combined into borate dynamic covalent bond with boric acid, so that
The nanoparticle of poly-dopamine coating decoration is also integrated on gel, finally obtains Nanometer composite hydrogel of the invention.
In the present invention, the polymer containing phenyl boric acid and the polymer containing glycol and the dopamine containing glycol coat
Nanoparticle by borate dynamic Covalent bonding together so that two kinds of polymer and nanoparticle form an overall structure,
Nanometer composite hydrogel as of the invention.
In the present invention, the borate dynamic covalent cross-linking network formed by the hydroxyl of the boronate of phenyl boric acid and glycol
The hydrogel of formation makes hydrogel have pH responsiveness, self-repairability, can infuse due to borate dynamic covalent bond inherent characteristic
Penetrating property.Simultaneously because having catechol group in the nanoparticle of poly-dopamine coating decoration, make hydrogel that there is tack.Cause
This, Nanometer composite hydrogel is fully established on the basis of borate dynamic covalent bond, forms nano combined water-setting of the invention
Glue.
In the present invention, the molar ratio of change phenyl boric acid and glycol group, i.e. PAPBA-stat-PDMA solution can be passed through
With the crosslink density and mechanical property of PGMA solution blending proportion adjustment hydrogel, while addition rGO@PDA also can change
The mechanical property of content adjusting Nanometer composite hydrogel.
In the present invention, the boric acid base group on the polymer architecture containing phenyl boric acid is with the polymer containing glycol and containing youngster
The nanoparticle of the poly-dopamine cladding of tea phenolic group group is bonded by borate to be closed, and Nanometer composite hydrogel is formed.Of the invention
In the structure of Nanometer composite hydrogel, the polymer containing phenyl boric acid forms cross-linked network structure bone with the polymer containing glycol
The nanoparticle of frame, poly-dopamine cladding is embedded in centre, so that both containing boron in the structure of entire Nanometer composite hydrogel
Acid esters dynamic covalent bond, the catechol group for also containing dopamine, so that Nanometer composite hydrogel prepared by the present invention
With pH responsiveness, self-repairability, syringeability and tack.
The Nanometer composite hydrogel that the present invention obtains forms cross-linked network skeleton by borate dynamic covalent bond, meanwhile,
Since the nanoparticle of poly-dopamine coating decoration being integrated in the cross-linked network skeleton, so that the Nanometer composite hydrogel
Mechanical strength significantly improves, and the storage modulus (G') of gained Nanometer composite hydrogel significantly improves.
Compared with prior art, technical solution of the present invention has following advantageous effects:
1, Nanometer composite hydrogel provided by the invention, it is covalently cross-linked with phenyl boric acid-glycol dynamic, assign receiving for preparation
Rice composite hydrogel has pH responsiveness, self-repairability, syringeability；
2, the catechol group of dopamine is passed through nanoparticle by the nanoparticle of poly-dopamine coating decoration by the present invention
The interaction of son and polymer, is integrated on hydrogel, so that the Nanometer composite hydrogel of preparation has tack；
3, the present invention can adjust preparation by adjusting the molar ratio of polymer containing phenyl boric acid and the polymer containing glycol
Nanometer composite hydrogel crosslink density and mechanical property；
4, the present invention can add the content of rGO@PDA by adjusting, and adjust the mechanics of the Nanometer composite hydrogel of preparation
Performance.
Detailed description of the invention
Fig. 1 is the forming process schematic diagram of Nanometer composite hydrogel of the present invention.
Fig. 2 is the reaction equation of polymer of the present invention preparation containing phenyl boric acid.
Fig. 3 is the reaction equation of polymer of the present invention preparation containing glycol.
The nuclear-magnetism that Fig. 4 is PGMA of the present invention and PAPBA-stat-PDMA characterizes；
Wherein: the nuclear-magnetism that figure A is PGMA characterizes, and the nuclear-magnetism that figure B is PAPBA-stat-PDMA characterizes, and figure c is PGMA middle-end
Base-CH2The partial enlargement of nuclear-magnetism figure, figure f are end group-CH in PAPBA-stat-PDMA3The partial enlargement of nuclear-magnetism figure.
Fig. 5 is PGMA of the present invention (A) and the GPC characterization of PAPBA-stat-PDMA.
Fig. 6 is the AEM of GO and rGO@PDA of the present invention, TEM, Raman spectrum and thermal weight loss characterization；
Wherein: the AFM that figure A is GO is characterized；Scheme the AFM that B is rGO@PDA to characterize；Scheme the TEM that C is GO to characterize；Scheming D is
The TEM of rGO@PDA is characterized；Scheme the Raman Characterization that E is GO and rGO@PDA；Scheme the thermal weight loss that F is GO and rGO@PDA to characterize.
Fig. 7 is that the rheology of Nanometer composite hydrogel of the present invention characterizes schematic diagram.
Fig. 8 is the polymer content of Nanometer composite hydrogel of the invention and the SEM figure after freeze-drying；
Scheming A is the SEM figure after sample S1 freeze-drying；Scheming B is the SEM figure after sample S2 freeze-drying；Figure C is sample S3
SEM figure after freeze-drying；Scheming D is the SEM figure after sample S4 freeze-drying；Scheming E is the SEM figure after sample S5 freeze-drying.
Comparative sample S1 and S2 illustrate under conditions of total polymer content is certain, change polymer P GMA and PAPBA-stat-PDMA
Proportion can change the size of modulus (G) and crosslink density aperture of polymer, and S3, S4, S5 are added not on the basis of S1
With the rGO@PDA of content, with the increase of rGO@PDA content, the mechanical property (G) of Nanometer composite hydrogel increases, still
The increase of rGO@PDA content can hinder the crosslinking of polymer chain, and so as to cause becoming larger for crosslinking aperture, this can be from freeze-drying sample
SEM scheme prove.
Fig. 9 is the self-repairability effect picture of Nanometer composite hydrogel of the invention.
Figure 10 is the syringeability figure of Nanometer composite hydrogel of the invention；
Wherein: figure B is the scanning of sample S4 stress-strain；Figure C is sample S4 oscillation frequency sweep；Figure D is sample S4 viscosity
With the relationship of shear rate；Figure E is sample S4 injectable schematic diagram.
Figure 11 is the pH responsiveness figure of Nanometer composite hydrogel of the invention；
Specific detection process is that gel disappears after a certain amount of hydrochloric acid is added in Nanometer composite hydrogel, is then added certain
Gel is re-formed after the sodium hydroxide of amount, the transformation of gel-sol is realized by acid adding plus alkali.
Figure 12 is the cementability effect picture of Nanometer composite hydrogel of the invention；
Wherein: A is to be bonded two aluminium flakes with Nanometer composite hydrogel；Scheme B be with Nanometer composite hydrogel be bonded aluminium flake and
Sheet glass；Scheme C and is bonded two sheet glass with Nanometer composite hydrogel.
Specific embodiment
Technical solution of the present invention is illustrated below, the claimed range of the present invention include but is not limited to
Lower embodiment.(each raw material is marketable material, and no specified otherwise purity is the pure grade of analysis)
The embodiment provided according to the present invention provides a kind of Nanometer composite hydrogel.
A kind of Nanometer composite hydrogel, the Nanometer composite hydrogel pass through following reaction: boronate and hydroxyl pass through boric acid
The nanoparticle that ester dynamic is covalently cross-linked, is coated using poly-dopamine is prepared as reinforcing agent.
In the present invention, which is blended preparation by two kinds of polymer and nanoparticle and obtains；Its
In: two kinds of polymer is the polymer containing phenyl boric acid, the polymer containing glycol, and the nanoparticle is poly-dopamine cladding
The nanoparticle of modification.
Preferably, the polymer containing phenyl boric acid is the polymer containing hydrophilic unit.
Preferably, the hydrophilic unit is N,N-DMAA, n-vinyl pyrrolidone, acrylic acid, third
One of acrylamide, n-isopropyl acrylamide are a variety of.
Preferably, the polymer containing glycol is to contain 1,2- glycol or 1, the polymer of 3- glycol.Preferably
One of polyethylene glycol, polyvinyl alcohol, polyglycerolmethacrylate are a variety of.
Preferably, the nanoparticle is one of carbon nanotube, graphene, nano silica, nanoclay
Or it is a variety of.
Embodiment 1
A kind of preparation method of Nanometer composite hydrogel prepares Nanometer composite hydrogel described in the first embodiment
Method, method includes the following steps:
(1) synthesis of the polymer containing phenyl boric acid: the substance containing phenyl boric acid is dissolved in solvent, and chain-transferring agent is added
And initiator, it is reacted, obtains the polymer containing phenyl boric acid；
(2) synthesis of the polymer containing glycol: will contain 1,2- glycol or 1, and the substance of 3- glycol is dissolved in solvent, adds
Enter chain-transferring agent and initiator, reacted, obtains the polymer containing glycol；
(3) synthesis of the nanoparticle of poly-dopamine coating decoration: dispersing nanoparticle in buffer solution, is added more
Bar amine is stirred to react a period of time, isolates solid, obtain the nanoparticle of poly-dopamine coating decoration；
(4) preparation of Nanometer composite hydrogel: the nanoparticle dissolution for the poly-dopamine coating decoration that step (3) is obtained
In dispersion liquid, adjustment pH value is alkalinity, and the polymer containing glycol that step (2) obtain then is added, is labeled as mixture
I；The polymer containing phenyl boric acid that step (1) obtains is dissolved in alkaline solution, mixtures II is labeled as；By mixture I with
Mixtures II mixing, is stirred to react, obtains Nanometer composite hydrogel.
Embodiment 2
There is one kind pH to respond, self-repairability, the preparation method of the Nanometer composite hydrogel of tack and syringeability, should
Method the following steps are included:
(1) synthesis of the polymer containing phenyl boric acid: by APBA and GMA monomer, DMF and H2The mixed solvent of O, chain tra nsfer
Agent EMP and initiator A IBN is added in round-bottomed flask, seals round-bottomed flask after drum nitrogen deoxygenation, the isothermal reaction in oil bath pan,
The sudden cold stopping reaction of liquid nitrogen, is settled after being diluted with solvent DMF with ether after a period of time, and vacuum is dry at room temperature for obtained product
It is dry；
(2) synthesis of the polymer containing glycol: by GMA monomer, chain-transferring agent EMP, initiator A IBN and solvent DMF add
Enter in round-bottomed flask, seal round-bottomed flask after drum nitrogen deoxygenation, the isothermal reaction in oil bath pan, liquid nitrogen is sudden after a period of time cold stops
It only reacts, is settled after being diluted with solvent DMF with ether, obtained product is dried in vacuo at room temperature；
(3) synthesis of the nanoparticle of poly-dopamine coating decoration: by GO ultrasonic disperse in Tris-HCl buffer solution
(pH=8.5,0.01M) is added dopamine (DA) and is stirred at room temperature, stop reaction after a period of time, filter, and collection is obtained by filtration
Solid, freeze-drying, obtain black blocks of solid be rGO PDA；
(4) preparation of Nanometer composite hydrogel: PAPBA-stat-PDMA is dissolved in alkaline water, and PGMA is dissolved in alkalinity
In rGO@PDA dispersion liquid, two kinds of solution are blended according to the ratio of 1:1, Nanometer composite hydrogel can be obtained in gentle agitation.
Embodiment 3
There is one kind pH to respond, self-repairability, the preparation method of the Nanometer composite hydrogel of tack and syringeability, should
Method the following steps are included:
(1) PAPBA-stat-PDMA is synthesized: by 90mg EMP (0.4mmol RAFT group), DMA (3.172g, 32mmol),
APBA (1.528g, 8mmol), AIBN (6.56mg, 0.04mmol), 19mL fresh DMF and 1mLH2O is added to dry round-bottomed flask；
Nitrogen is blasted, the oxygen in reactor is discharged, flask is sealed, is then immersed in 70 DEG C of oil bath；After 2 hours, pass through liquid nitrogen
Terminate polymerization reaction；After being cooled to room temperature, polymer is diluted with DMF；Polymer is precipitated in anhydrous ether, is contained
The polymer of phenyl boric acid；
(2) PGMA is synthesized: by 45.0mg EMP (0.2mmol RAFT group), GMA (3.2g, 20mmol), AIBN
(3.28mg, 0.02mmol), the fresh DMF of 16mL are fitted into dry round-bottomed flask；Nitrogen is blasted, the oxygen in reactor is discharged
Gas seals flask, is then immersed in 70 DEG C of oil bath；After 3 hours, polymerization reaction is terminated by liquid nitrogen.After being cooled to room temperature,
Polymer is diluted with DMF；Polymer is precipitated in anhydrous ether；Products therefrom is dried in vacuo at room temperature；Contained
There is the polymer of glycol；
(3) GO the preparation of rGO@PDA: is prepared by oxidation of natural graphite powder according to improved Hummers method；GO exists
It is ultrasonically treated 1 hour under Tris-HCl buffer (pH=8.5,0.01mol/L)；Then dopamine is added into the suspension
It (2mg/ml) and is stirred at room temperature 4 hours；Then suspension is filtered；Filter cake is washed with water unreacted more to remove for several times
Bar amine；Finally, being filtered with ethanol washing black solid and using organic film；Products therefrom is dry under freeze-drying；It obtains
The nanoparticle of poly-dopamine coating decoration；
(4) it is water-soluble that PAPBA-stat-PDMA prepared by step (1) preparation of Nanometer composite hydrogel: is added to NaOH
In liquid (pH=12.5), and accelerate dissolution in the case where ultrasonic wave acts on formed PAPBA-stat-PDMA aqueous solution (solution it is final
10) pH is equal to；The PAPBA-stat-PDMA aqueous solution of formation is known as mixture I；By the PGMA and step of step (2) preparation
(3) the rGO@PDA prepared is dispersed in NaOH aqueous solution (pH=10), which is known as mixtures II；It will mix at room temperature
It closes object I and mixtures II to mix according to the ratio that volume ratio is 1.5:1, and quickly forms gel under mild agitation, received
Rice composite hydrogel.
Embodiment 4
There is one kind pH to respond, self-repairability, the preparation method of the Nanometer composite hydrogel of tack and syringeability, should
Method the following steps are included:
(1) PAPBA-stat-PDMA is synthesized: by 120mg EMP (0.4mmol RAFT group), DMA (4.758g,
48mmol), APBA (3.056g, 16mmol), AIBN (9.84mg, 0.06mmol), the fresh DMF and 20mL H of 320mL2O is added
To dry round-bottomed flask；Nitrogen is blasted, the oxygen in reactor is discharged, flask is sealed, is then immersed in 60 DEG C of oil bath；4 is small
Shi Hou terminates polymerization reaction by liquid nitrogen；After being cooled to room temperature, polymer is diluted with DMF；By polymer in anhydrous ether
Precipitating, obtains the polymer containing phenyl boric acid；The degree of polymerization for detecting the polymer containing phenyl boric acid is 68, and phenyl boric acid content is about
18%.Structure is PAPBA12-stat-PDMA56, molecular weight 7800, PDI 1.09.
(2) PGMA is synthesized: by 67.5mg EMP (0.3mmol RAFT group), GMA (6.4g, 40mmol), AIBN
(4.92mg, 0.03mmol), the fresh DMF of 300mL are fitted into dry round-bottomed flask；Nitrogen is blasted, the oxygen in reactor is discharged
Gas seals flask, is then immersed in 60 DEG C of oil bath；After 12 hours, polymerization reaction is terminated by liquid nitrogen.It is cooled to room temperature
Afterwards, polymer is diluted with DMF；Polymer is precipitated in anhydrous ether；Products therefrom is dried in vacuo at room temperature；It obtains
Polymer containing glycol；The degree of polymerization for detecting the polymer containing glycol is 170, and molecular weight 27000g/mol, PDI are
1.30。
(3) GO the preparation of rGO@PDA: is prepared by oxidation of natural graphite powder according to improved Hummers method；GO exists
It is ultrasonically treated 3 hours under Tris-HCl buffer (pH=9,0.05mol/L), concentration of the GO in Tris-HCl buffer is
3mg/mL；Then dopamine (concentration of the dopamine in Tris-HCl buffer is 3.5mg/ml) is added into the suspension simultaneously
It is stirred at room temperature 4 hours；Then aperture is used to filter for the organic film of 300nm；Filter cake is washed with water for several times to remove not
The dopamine of reaction；Finally, being filtered with ethanol washing black solid and using organic film；Products therefrom is done under freeze-drying
It is dry；Obtain the nanoparticle of poly-dopamine coating decoration；
(4) it is water-soluble that PAPBA-stat-PDMA prepared by step (1) preparation of Nanometer composite hydrogel: is added to NaOH
In liquid (pH=12), and accelerate dissolution to form the PAPBA-stat-PDMA aqueous solution (final pH of solution in the case where ultrasonic wave acts on
Equal to 10)；The PAPBA-stat-PDMA aqueous solution of formation is known as mixture I；By the PGMA and step (3) of step (2) preparation
The rGO@PDA of preparation is dispersed in NaOH aqueous solution (pH=10), which is known as mixtures II；At room temperature by mixture
I and mixtures II are mixed according to the ratio that volume ratio is 2:1, and quickly form gel under mild agitation, are obtained nano combined
Hydrogel.
Embodiment 5
Embodiment 4 is repeated, only substitutes APBA, the middle poly- second of step (2) with Methacrylamide phenyl boric acid in step (1)
Glycol substitutes polyglycerolmethacrylate, substitutes graphene oxide with nano silica in step (3).
Embodiment 6
Embodiment 4 is repeated, the amount that APBA is only added is 4.584g, 24mmol；The amount that DMA is added is 6.8g,
42.5mmol；The degree of polymerization for detecting the polymer containing phenyl boric acid is 86, and phenyl boric acid content is about 29%.Structure is PAPBA25-
Stat-PDMA61, molecular weight 14500, PDI 1.07.
Embodiment 7
Embodiment 4 is repeated, the amount that GMA is only added is 9.6g, 60mmol；Detect the degree of polymerization of the polymer containing glycol
It is 251, molecular weight 40000g/mol, PDI 1.37.
Embodiment 8
Embodiment 4 is repeated, only mixture I and mixtures II are mixed according to the ratio that volume ratio is 3:1 in step (4).
Can by freeze-drying water Nanometer composite hydrogel SEM figure in pore size judge crosslink density.Gel in SEM
The more big then crosslink density in aperture is smaller in network, and aperture is smaller, illustrates that crosslink density is bigger.Because crosslinking is boric acid ester bond
It is formed, boric acid ester bond is more, then two kinds of polymer chain is then crosslinked about close, and the gap (aperture) that centre is not crosslinked just is got over certainly
It is small closeer.How to find out from SEM figure of the invention it is prepared by the present invention it is nano combined say gel have preferable crosslink density.
By it is prepared by the present invention it is nano combined say gel carry out rheology characterization test:
Mechanical property is the most simple and direct with storage modulus (G ') in rheometer test, and storage modulus is indicated in general literature
(G ').G " indicates loss modulus in figure.
The mechanical property of hydrogel is generally indicated with the modulus in rheometer test.As a result as shown in fig. 7, from test result
As can be seen that adding 0.25% rGO@PDA on the basis of sample S1, storage modulus (G ') increases to from 5.5KPa
39.8KPa increases about 6.3 times, adds 0.50% rGO@PDA, and storage modulus (G ') increases to from 5.5KPa, 60.3KPa,
About 10 times are increased, this shows that the Nanometer composite hydrogel for adding certain content rGO@PDA can significantly improve hydrogel
Mechanical property.Certainly, when rGO@PDA content increases to 0.75% from 0.5%, for storage modulus (G ') there is no increasing, this may
It is that excessive rGO@PDA is likely difficult to disperse, hinders the crosslinking of polymer, cause hydrogel crosslink density too low, lead to water
Gel mechanics reduced performance.Nanometer composite hydrogel prepared by the present invention has biggish storage modulus (G '), has excellent
Mechanical property.
Claims (10)
1. a kind of Nanometer composite hydrogel, which passes through following reaction: boric acid base group passes through with glycol group
The nanoparticle that borate dynamic is covalently cross-linked, is coated using poly-dopamine is prepared as reinforcing agent.
2. Nanometer composite hydrogel according to claim 1, it is characterised in that: the Nanometer composite hydrogel is poly- by two kinds
It closes object and nanoparticle is blended preparation and obtains；Wherein: two kinds of polymer is respectively the polymer containing phenyl boric acid, contains glycol
Polymer, the nanoparticle be poly-dopamine coating decoration nanoparticle.
3. Nanometer composite hydrogel according to claim 2, it is characterised in that: the polymer containing phenyl boric acid be containing
There is the polymer of hydrophilic unit；Preferably, the hydrophilic unit is N,N-DMAA, N- ethenyl pyrrolidone
One of ketone, acrylic acid, acrylamide, n-isopropyl acrylamide are a variety of；And/or
The polymer containing glycol is the polymer containing 1,2- glycol or 1,3- glycol；Preferably polyethylene glycol, poly- second
One of enol, polyglycerolmethacrylate are a variety of；And/or
The nanoparticle is one of carbon nanotube, graphene, nano silica, nanoclay or a variety of.
4. Nanometer composite hydrogel described in any one of a kind of preparation method of Nanometer composite hydrogel or preparation claim 1-3
Method, method includes the following steps:
(1) synthesis of the polymer containing phenyl boric acid: the substance containing phenyl boric acid is dissolved in solvent, and chain-transferring agent is added and draws
Agent is sent out, is reacted, obtains the polymer containing phenyl boric acid；
(2) synthesis of the polymer containing glycol: will contain 1,2- glycol or 1, and the substance of 3- glycol is dissolved in solvent, and chain is added
Transfer agent and initiator, are reacted, and the polymer containing glycol is obtained；
(3) synthesis of the nanoparticle of poly-dopamine coating decoration: dispersing nanoparticle in buffer solution, and DOPA is added
Amine is stirred to react a period of time, isolates solid, obtain the nanoparticle of poly-dopamine coating decoration；
(4) preparation of Nanometer composite hydrogel: the nanoparticle dissolution for the poly-dopamine coating decoration that step (3) is obtained in point
In dispersion liquid, adjustment pH value is alkalinity, and the polymer containing glycol that step (2) obtain then is added, is labeled as mixture I；It will
The polymer containing phenyl boric acid that step (1) obtains is dissolved in alkaline solution, is labeled as mixtures II；By mixture I with mix
Object II mixing, is stirred to react, obtains Nanometer composite hydrogel.
5. according to the method described in claim 4, it is characterized by: step (1) specifically: in the reactor, benzene boron will be contained
(substance containing phenyl boric acid is the substance containing hydrophilic unit to the substance of acid；Wherein: the hydrophilic unit is N, N- diformazan
One of base acrylamide, n-vinyl pyrrolidone, acrylic acid, acrylamide, n-isopropyl acrylamide are a variety of) it is molten
In solvent, (solvent is preferably DMF and H2The mixed solvent of O, more preferably DMF and H2The in the mixed solvent of O, DMF and H2O's
Volume ratio is 1-100:1) in, chain-transferring agent (preferably EMP) and initiator (preferably AIBN) is added, is discharged in reactor
Oxygen (preferably blasts nitrogen into reactor and then seals reactor), isothermal reaction (oil bath constant temperature is preferably used, reaction
Temperature is 40-100 DEG C, reaction time 0.5-6h), stop reaction (preferably using the sudden cold stopping reaction of liquid nitrogen), dilution is (preferably
Diluted using DMF), sedimentation (is preferably settled using ether), and the polymer containing phenyl boric acid is obtained；
Preferably, the degree of polymerization of the polymer containing phenyl boric acid is 20-1000, preferably 40-600, more preferably 50-500；
The mass ratio of substance and solvent containing phenyl boric acid is 1:1-50, preferably 1:2-30, more preferably 1:3-20；Chain-transferring agent and
The molar ratio of initiator is 1-50:1, preferably 2-30:1, more preferably 3-20:1.
6. method according to claim 4 or 5, it is characterised in that: step (2) specifically: in the reactor, 1 will be contained,
(substance containing 1,2- glycol or 1,3- glycol is preferably ethylene glycol, vinyl alcohol, first to the substance of 2- glycol or 1,3- glycol
One of base glycerol acrylate is a variety of), chain-transferring agent (preferably EMP) and initiator (preferably AIBN) be dissolved in solvent
In (preferably DMF), the oxygen (preferably blast nitrogen into reactor and then seal reactor) being discharged in reactor, constant temperature
Reaction (preferably uses oil bath constant temperature, the temperature of reaction is 40-100 DEG C, reaction time 1-24h), stops reaction and (preferably uses
The sudden cold stopping reaction of liquid nitrogen), dilution (is preferably diluted using DMF), and sedimentation (is preferably settled using ether), and drying (preferably uses
Vacuum drying), obtain the polymer containing glycol；
Preferably, the degree of polymerization of the polymer containing glycol is 20-1000, preferably 40-600, more preferably 50-500；Contain
There are 1,2- glycol or 1, the substance of 3- glycol and the mass ratio of solvent are 1:1-50, preferably 1:2-30, more preferably 1:3-20；
The molar ratio of chain-transferring agent and initiator is 1-50:1, preferably 2-30:1, more preferably 3-20:1.
7. the method according to any one of claim 4-6, it is characterised in that: step (3) specifically: by nanoparticle
(nanoparticle is one of carbon nanotube, graphene, nano silica, nanoclay or a variety of) is scattered in alkalinity
(alkaline solution preferably uses Tris-HCl solution to solution, more preferably uses 0.001-0.1M, pH for the Tris- of 8-10
HCl solution) in, dopamine solution (preferably using Dopamine hydrochloride) is then added, be stirred to react (it preferably uses and is stirred at room temperature,
Mixing time is 1-48h, preferably 2-24h), isolating solid, (preferably using separation is filtered, described filter is taken out using organic film
Filter more preferably uses aperture to filter for the organic film of 100-500nm), washing (preferably uses ethanol washing), and suction filtration (is preferably adopted
Filtered with organic film, aperture more preferably used to filter for the organic film of 100-500nm), it is dry (preferably using vacuum drying), it obtains
To the nanoparticle of poly-dopamine coating decoration；
Preferably, nanoparticle is dispersed in alkaline solution, the concentration of nanoparticle is 0.1-5mg/mL, preferably 0.3-
3mg/mL；After dopamine solution is added, concentration of the dopamine solution in alkaline solution is 0.1-5mg/mL, preferably 0.5-
3mg/mL。
8. the method according to any one of claim 4-7, it is characterised in that: step (4) specifically: obtain step (3)
The nanoparticle dissolution of the poly-dopamine coating decoration arrived adjusts pH value in dispersion liquid (the preferably aqueous solution of sodium hydroxide)
For alkalinity, the polymer containing glycol that step (2) obtain then is added, is labeled as mixture I；Contain what step (1) obtained
There is the polymer of phenyl boric acid to be dissolved in alkaline solution (the preferably aqueous solution of sodium hydroxide), is labeled as mixtures II；It will mixing
Object I is mixed with mixtures II, is stirred to react, and Nanometer composite hydrogel is obtained；
Preferably, the content of the nanoparticle of poly-dopamine coating decoration is 0.1-5% in mixture I, it is poly- containing glycol
The content for closing object is 1-20%；Mixtures II, the content of the polymer containing phenyl boric acid are 1-20%；Mixture I and mixture
The mixed volume ratio of II is 0.1-10:1, preferably 0.5-5:1, more preferably 1-2:1.
9. the method according to any one of claim 4-8, it is characterised in that: the substance containing phenyl boric acid in step (1)
For the mixture of acrylamido phenyl boric acid and the different acrylamido phenyl boric acid of N-, acrylamido phenyl boric acid and the different acryloyl of N-
The molar ratio of amido phenyl boric acid is 1:0.1-20, preferably 1:0.2-10；The polymer containing phenyl boric acid is acrylamide
The different acrylamido phenyl boric acid copolymer of base phenyl boric acid-N-；And/or
Contain 1,2- glycol or 1 described in step (2), the substance of 3- glycol is glycidyl acrylate, described to contain glycol
Polymer be polyglycidyl acrylate；And/or
Nanoparticle described in step (3) is graphene oxide.
10. Nanometer composite hydrogel according to any one of claim 1-3 is square according to any one of claim 4-9
The purposes of the Nanometer composite hydrogel of method preparation, is used for bio-medical material, organizational project for the nanocomposite hydrogel
Material.
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