CN104892871B - A kind of hydrogel with self-repair function and preparation method thereof - Google Patents
A kind of hydrogel with self-repair function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of hydrogel with self-repair function and preparation method thereof, described hydrogel is hydrophobic units urea groups pyrimidone polyethylene glycol urea groups pyrimidone hydrophobic units polymer.Its preparation is synthetic intermediate Br PEG Br first and Quadrupolar hydrogen bond unit intermediate UPyMA, then obtains subject polymer with the hydrophobic monomer copolymerization such as the methacrylate of butyl acrylate, styrene or 3~10 carbon.The hydrogel water-retaining property is strong, by adjusting the ratio of the hydrophobe segment in polymer, or changes the species of hydrophobic monomer, can prepare wide variety, performance more preferably hydrogel improves application.
Description
Technical field
The present invention relates to self-repair material field, a kind of hydrogel with self-repair function and its preparation are specifically related to
Method.
Background technology
In recent years, the hydrogel with self-repair function was prepared by synthesizing the supermolecule polymer of hydrogen bonds, and was to grind
Study carefully an important directions of self-repair material.Due to the presence of multiple hydrogen bonding unit in polymer, polymeric inner formation one
Reversible cross-linked structure, it can dissociate and recombinate under the stimulation of external environment, so as to realize the purpose of selfreparing.
Hydrogel can absorb substantial amounts of water and expand, with good water retention, and it has to biological tissue certain similar
Property, biocompatibility is good, therefore is widely used in the fields such as building, food, biomedicine.
Most of hydrogel all haves the shortcomings that more crisp, limits its application, therefore preparing with high water absorption
While the hydrogel of performance, it is also desirable to which it can remain good mechanical property and elastic-restoring force.Mingyu Guo et al.
(Mingyu Guo, J.Am.Chem.Soc.2014,136,6969-6977) utilizes the copolymerization system of polyethylene glycol and urea groups pyrimidone
For a kind of parents' hydrogel is gone out, shadow of the crosslink density to mechanical properties of polymer is have studied by adjusting the chain length of polyethylene glycol
Ring, finally prepared a kind of with high intensity, the supramolecular hydrogel of elastic recovery power.Roxanne E.Kieltyka etc.
People (Roxanne E.Kieltyka, J.Am.Chem.Soc.2013,135,11159-11164) be prepared for respectively simple function group with
The UPy-PEG copolymers of difunctional, when the UPy-PEG copolymers that simple function group is mixed into a small amount of difunctional UPy-PEG
In, in the synergy of two kinds of copolymers, prepare excellent performance and stable supramolecular hydrogel.Its key is
Two kinds of copolymers are in the basic conditions due to intermolecular electrostatic repulsion so that the state that blend formation one interts mutually,
After peracid treatment, the UPy-PEG of difunctional will make polymer form stable cross-linked structure as crosslinking agent.
However, the hydrogen bond unit of above-mentioned hydrogel is on the main chain of polymer, with the increase of peg molecule chain,
The crosslink density of polymer reduces, and the intensity of hydrogel can also be decreased, therefore improves water-retaining property and intensity at the same time
Spatially there is a definite limitation.
The content of the invention
It is contemplated that overcoming the deficiency of prior art containing what multiple hydrogen bonding was acted on to there is self-repair function there is provided a kind of
Hydrogel and preparation method thereof.
Described hydrogel is polyethylene glycol-urea groups pyrimidone-hydrophobic units polymer, specifically hydrophobic units-urea groups
Pyrimidone-polyethylene glycol-urea groups pyrimidone-hydrophobic units, is designated as compound C, its chemical structural formula is as follows：
Wherein R is hydrophobic units, the specifically different butyl polyacrylate of the degree of polymerization, polystyrene, polymethylacrylic acid
The hydrophobic monomers such as ester polymerize the hydrophobic segment to be formed；X, y value are 1~30；The molecular weight of polyethylene glycol (PEG) be 200~
10000g/mol.Polyethylene glycol is hydrophilic section, and the hydrophobe of hydrogel can be adjusted by the degree of polymerization for adjusting polyethylene glycol and R
Ratio.
The synthetic route of the polymer is as follows：
1. intermediate PEG-Br (being designated as compound A) synthesis：
2. the synthesis of Quadrupolar hydrogen bond unit intermediate (being designated as compound B)：
3. target compound C synthesis：
The preparation method of the polymer, comprises the following steps：
1) compound A synthesis：
A certain amount of polyethylene glycol (PEG) and triethylamine are dissolved in anhydrous dichloromethane, it is slow under condition of ice bath
The 2- bromine isobutyl acylbromides for being dissolved in solvent 1 are added dropwise, stir, after question response terminates, concentrated by rotary evaporation, suction filtration is repeated several times, three second are removed
Amine hydrochlorate, then with precipitating reagent 1, compound A is produced after drying.
2) compound B synthesis：
A certain amount of different pyrimidine of 6- methyl (MIC) is dissolved in solvent 2, methacrylic acid is added dropwise after after MIC dissolvings in heating
Normal temperature water cooling is used after ethyl isocyanate (IEM), stirring, completion of dropping, until separating out white precipitate, is washed with solvent 3, gained
Solid solvent 4 dissolves, suction filtration, removes after insoluble matter, rotates filtrate, and vacuum drying produces compound B.
3) compound C synthesis：
Take a certain amount of compound A, compound B and hydrophobic monomer to be dissolved in solvent 5, add a small amount of cuprous bromide and pentamethyl two
Ethene triamine (PMDETA), continuous freeze thawing degassing, temperature reaction, question response is precipitated 2~3 times after terminating with precipitating reagent 2, and vacuum is done
It is dry, produce compound C.
In step 1) in, described PEG molecular weight can be 200~10000g/mol, the PEG and 2- bromine isobutyl acylbromides
Mol ratio can be 1：(1~5), the addition of the triethylamine can be by mass percentage the 5%~20% of reaction gross mass；
The reaction condition can react 8~36h at 20~120 DEG C；The solvent 1 can be some hydrophobic solvents, such as dichloromethane, chlorine
It is imitative, n-hexane, ether etc.；The precipitating reagent 1 can be：Methanol, n-hexane etc..
In step 2) in, the mol ratio of the different pyrimidine of 6- methyl (MIC) and isocyanatoethyl methacrylate (IEM) can
For 1：(0.5~2)；It is described vacuumize after be filled with argon gas protection and can continuously vacuumize rear applying argon gas and circulate 3~5 times；The heating
Condition can be heated at 80~200 DEG C；The solvent 2 can be dimethyl sulfoxide (DMSO)；The solvent 3 can be acetone, methanol etc.；It is described
Washed with solvent washable 2~3 times；The solvent 4 can be dichloromethane, chloroform etc.；The condition of the drying can be under vacuo
30 DEG C~45 DEG C dry 8-20h.
In step 3) in, the hydrophobic monomer can be the methacrylate of styrene, butyl acrylate and 3~10 carbon
Deng；The solvent 5 can be dichloromethane, chloroform etc.；Compound A, compound B, the mol ratio of hydrophobic monomer can be 1：(10~
50)：(55~85)；The addition of the cuprous bromide and PMDETA is the 5%~15% of the reactant gross mass.The company
Continuous freeze thawing degassing can be 3~5 times；The reaction condition can react 8~72h at 30~160 DEG C；The precipitating reagent 2 can be first
Alcohol, n-hexane, ether etc.；The condition of the drying can be in 30 DEG C~45 DEG C dry 8-20h of vacuum.
Advantages of the present invention is as follows：
1. polyethylene glycol (PEG) is a kind of compound with good hydrophilic performance, melting temperature is between 40~50 DEG C, profit
The hydrogel prepared with polyethylene glycol, gelation can be just produced easily under mild conditions, and with good shape
Memory function, can be applied in biomedicine field；Quadrupolar hydrogen bond effect between urea groups pyrimidone (UPy) unit, is allowed to
Dimer is easily formed, critically important effect is played for the cross-linked structure for forming stable；With the mode of polymerization by multiple hydrogen bonding
Unit is introduced into aquogel system, can increase the quantity of multiple hydrogen bonding, is passed through hydrogen bond action and is formed more stable water-setting
Glue；Hydrogen bond unit is located at the side chain of polymer, and the influence of the change of molecular weight polyethylene glycol to crosslink density is smaller.
2. introducing hydrophobic units in polymer, long hydrophobic segment is assembled in water, reversible crosslink point is served as, in certain journey
The intensity of hydrogel is improved on degree；Hydrogen bond unit can be coated on polymeric inner, destruction of the reduction water to hydrogen bond by hydrophobic segment
Degree；Polymer hydrophobic unit can be butyl polyacrylate, polystyrene, polymethyl methacrylate etc., and raw material selection is abundant,
The hydrogel for the wide variety that can be prepared；, can by changing the degree of polymerization of hydrophilic unit and hydrophobic units in polymer
The different hydrogel of performance is prepared, has very big excellent to improving the water-retaining property of hydrogel, mechanical strength, stability and application
Gesture.
The present invention is described in further detail below in conjunction with drawings and Examples；But one kind of the present invention has selfreparing
Hydrogel of function and preparation method thereof is not limited to embodiment.
Brief description of the drawings
Fig. 1 be embodiment 1 in compound A hydrogen nuclear magnetic resonance (1HNMR) spectrogram.Abscissa is chemical shift in figure
(ppm)；
Fig. 2 be embodiment 1 in compound C hydrogen nuclear magnetic resonance (1HNMR) spectrogram.Abscissa is chemical shift in figure
(ppm)。
Embodiment
Embodiment 1
The synthesis of step 1, compound A
First, 10g PEG and 2.2g triethylamines are added in 100mL round-bottomed flasks, are dissolved with 60mL dichloromethane, ice bath
It is cooled to 0 DEG C.Then it will be slowly added dropwise into round-bottomed flask, stirred with the 3.68g 2- bromine isobutyl acylbromides of 5mL dchloromethanes
Mix, normal-temperature reaction 24h after completion of dropping, after reaction terminates, concentration of reaction solution, suction filtration removes the triethylamine hydrochloride separated out, instead
It is multiple then to be precipitated 2~3 times with ether twice, 40 DEG C of dry 12h under vacuo after suction filtration, product is brown solid.This implementation
PEG molecular weight used is 2000g/mol in example.
Compound A hydrogen nuclear magnetic resonance (1HNMR) spectrogram is as shown in figure 1, δ~3.75ppm is the peak of methylene on PEG, δ
~1.45ppm is the peak of methyl on isobutyryl.
The synthesis of step 2, compound B
1.5g MIC are added in 100mL round-bottomed flasks, 6mL dmso solutions are used, oil bath heating is treated to 140 DEG C
After MIC dissolvings, oil bath is removed, 1.84mLIEM is instilled rapidly, stirred, normal temperature water cooling is used after completion of dropping, until separating out white
Precipitation, is washed 2~3 times with acetone, methanol respectively, uses chloroform dissolved solid, and suction filtration is removed after insoluble matter, suction filtration under vacuo
40 DEG C of dry 12h, product is white solid.
The synthesis of step 3, compound C
0.2g compound A, 0.56g compounds B, 1.136g butyl acrylate, 0.056g are added in 50mL round-bottomed flasks
Cuprous bromide and 0.144gPMDETA, are dissolved with 6mL chloroforms, and continuous freeze thawing deaerates 3~5 times, and except deoxidation and water, inflated with nitrogen is protected
Shield, 60 DEG C of stirring reaction 24h.Question response is precipitated three times after terminating with n-hexane, and 40 DEG C of dry 12h are under vacuo after suction filtration
Can, product is white solid.
Compound C hydrogen nuclear magnetic resonance (1HNMR) spectrogram is as shown in Fig. 2 tri- peaks of δ~10ppm to 13ppm are on UPy
The peak of Hydrogen Proton on amino, δ~6.0ppm is the proton peak on MIC rings, and δ~3.8ppm is the matter for the methylene being connected with ester group
Sub- peak, δ~3.75ppm is the proton peak of methylene on PEG, and δ~2.5ppm is the proton peak of methyl on MIC, and δ~1.0ppm is extremely
2.0ppm is the proton peak on main chain.
Embodiment 2
Step 1, compound A synthesis in embodiment 1 with reference to being synthesized, and wherein PEG molecular weight is 4000g/mol.
Step 2, compound B synthesis be the same as Example 1.
Step 3, compound C synthesis are with reference to embodiment 1, and wherein compound A consumption is 0.4g.
Embodiment 3
Step 1, compound A synthesis in embodiment 1 with reference to being synthesized, and wherein PEG molecular weight is 6000g/mol.
Step 2, compound B synthesis be the same as Example 1.
Step 3, compound C synthesis are with reference to embodiment 1, and wherein compound A consumption is 0.62g.
Embodiment 4
Step 1, compound A synthesis in embodiment 1 with reference to being synthesized, and wherein PEG molecular weight is 8000g/mol.
Step 2, compound B synthesis be the same as Example 1.
Step 3, compound C synthesis are with reference to embodiment 1, and wherein compound A consumption is 0.8g.
Embodiment 5：
Step 1 and step 2, the synthesis of compound A, B respectively refer to carry out in embodiment 1.
The synthesis of step 3, compound C
0.2g compound A, 0.84g compounds B, 1.278g butyl acrylate, 0.056g are added in 50mL round-bottomed flasks
Cuprous bromide and 0.144g PMDETA, are dissolved with 6mL chloroforms, and continuous freeze thawing deaerates 3~5 times, and except deoxidation and water, inflated with nitrogen is protected
Shield, 30 DEG C of stirring reaction 72h.Question response is precipitated three times after terminating with n-hexane, and 40 DEG C of dry 12h are under vacuo after suction filtration
Can, product is white solid.
Embodiment 6：
Step 1 and step 2, the synthesis of compound A, B respectively refer to carry out in embodiment 1.
The synthesis of step 3, compound C
0.2g compound A, 0.84g compounds B, 0.833g styrene, 0.056g brominations are added in 50mL round-bottomed flasks
Cuprous and 0.144gPMDETA, is dissolved with 6mL chloroforms, and continuous freeze thawing deaerates 3~5 times, except deoxidation and water, nitrogen charging gas shielded, 110
DEG C stirring reaction 36h.Question response is precipitated three times after terminating with n-hexane, 40 DEG C of dry 12h, product under vacuo after suction filtration
For white solid.
Embodiment 7：
Step 1 and step 2, the synthesis of compound A, B respectively refer to carry out in embodiment 1.
The synthesis of step 3, compound C
Added in 50mL round-bottomed flasks 0.2g compound A, 0.84g compounds B, 0.588g methacrylates,
0.056g cuprous bromides and 0.144g PMDETA, are dissolved with 6mL chloroforms, and continuous freeze thawing deaerates 3~5 times, except deoxidation and water, are filled
Nitrogen is protected, 160 DEG C of stirring reaction 8h.Question response is precipitated three times after terminating with n-hexane, 40 DEG C of dryings under vacuo after suction filtration
12h, product is white solid.
Above-described embodiment is only used for further illustrating a kind of hydrogel and its preparation with self-repair function of the present invention
Method, but the invention is not limited in embodiment, it is any that every technical spirit according to the present invention is made to above example
Simple modification, equivalent variations and modification, each fall within the protection domain of technical solution of the present invention.
Claims (9)
1. a kind of hydrogel with self-repair function, it is characterised in that the hydrogel is polyethylene glycol-urea groups pyrimidone-dredge
Water unit polymer, chemical structural formula is：
Wherein R be hydrophobic monomer polymerized segment formation hydrophobic units, the hydrophobic monomer be butyl acrylate, styrene or
Methacrylate；X, y value are 1~30；The molecular weight of polyethylene glycol is 200~10000g/mol.
2. a kind of preparation method of hydrogel as claimed in claim 1, it is characterised in that comprise the following steps：
1) polyethylene glycol and triethylamine are dissolved in dichloromethane, add 2- bromine isobutyl acylbromide solution, in reaction at 20~120 DEG C
8~36h, filter cake is taken out in concentration, dry PEG-Br intermediates, and its chemical structural formula is
2) 6- methylisocytosines are dissolved in organic solvent, add isocyanatoethyl methacrylate, the precipitation of precipitation is washed
Filtering, dry Quadrupolar hydrogen bond unit intermediate after washing, its chemical structural formula is
3) the PEG-Br intermediates, Quadrupolar hydrogen bond unit intermediate and hydrophobic monomer are dissolved in organic solvent, add bromination
Cuprous and pentamethyl-diethylenetriamine, continuous freeze thawing degassing, in reacting 8~72h at 30~160 DEG C, institute is obtained after precipitation, drying
State the hydrogel of polyethylene glycol-urea groups pyrimidone-hydrophobic monomer polymer；Wherein in PEG-Br intermediates, Quadrupolar hydrogen bond unit
The mol ratio of mesosome and hydrophobic monomer is 1：10~50：55~85.
3. preparation method according to claim 2, it is characterised in that：Step 1) in, the triethylamine account for polyethylene glycol and
The 5%~20% of triethylamine gross mass.
4. preparation method according to claim 2, it is characterised in that：Step 1) in, the 2- bromine isobutyl acylbromides solution is
It is dissolved in what is formed in hydrophobic solvent by 2- bromine isobutyl acylbromides, the hydrophobic solvent is dichloromethane, chloroform, n-hexane or ether；
The mol ratio of the polyethylene glycol and 2- bromine isobutyl acylbromides is 1:1~5.
5. preparation method according to claim 2, it is characterised in that：Step 2) in, the 6- methylisocytosines and first
The mol ratio of base acrylic acid ethyl isocyanate is 1：0.5~2.
6. preparation method according to claim 2, it is characterised in that：Step 2) in, the 6- methylisocytosines be in
It is dissolved at 80~200 DEG C in dimethyl sulfoxide (DMSO).
7. preparation method according to claim 2, it is characterised in that：Step 3) in, the cuprous bromide and pentamethyl two
The addition of ethene triamine is the 5%~15% of the reactant gross mass.
8. preparation method according to claim 2, it is characterised in that：Step 1) and 3) in, the precipitating reagent of the precipitation is
Methanol, n-hexane or ether.
9. preparation method according to claim 2, it is characterised in that：Step 1) in 3), the drying is in vacuum 30
DEG C~45 DEG C at dry 8-20h.
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