CN108192069A - A kind of selfreparing hydrogel based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond - Google Patents
A kind of selfreparing hydrogel based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the polyurethane selfreparing hydrogel based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond, the hydrogel is that organogel is obtained by the reaction in tetrahydrofuran by diisocyanate, polyethylene glycol, double selenium glycol, UPy bases chain extender and crosslinking agent trimethylolpropane, is obtained after then impregnating removing solvent and unreacted small molecule in deionized water.Dynamic characteristic and UPy Quadrupolar hydrogen bond fast fracture recombination characteristic of the hydrogel based on double selenium dynamic covalent bonds under visible ray photograph, it can be realized under mild visible ray photograph to damaging repeatable quick selfreparing, avoid destruction of the stronger outside stimulus of such as high temperature, ultraviolet lighting to material structure needed for traditional selfreparing.The hydrogel is polyurethane structural, using polyethylene glycol as hydrophily soft segment, has excellent biocompatibility and molecular structure designability, is well positioned to meet the needs of practical application, thus is had broad application prospects in bioengineered tissue field.
Description
Technical field
The present invention relates to a kind of preparation methods of selfreparing hydrogel, are based particularly on double selenium dynamic covalent bonds and hydrogen bond is total to
The preparation of the selfreparing polyurethane hydrogel of same-action.
Background technology
Hydrogel is a kind of with the high molecular material with tridimensional network being physically or chemically crosslinked, with water
For decentralized medium, a large amount of water can be absorbed and be swollen and keep the stabilization of its structure.As a kind of high water-keeping material of high water absorption, water-setting
Glue is obtained for and is widely applied in industrial or agricultural and bioengineered tissue field.But in practical applications, traditional hydrogel
Due to the independent or comprehensive function by external force, light, heat, chemistry, the micro-crack that its internal generation can be made to be difficult to detect and repair.
The extension and increase of these micro-cracks can reduce the mechanical performance of material, shorten its service life, brought sternly to the use of material
The hidden danger of weight.
Selfreparing hydrogel refers to that material has spontaneous healing ability to self-defect or damage, and this ability is
The one of organism big feature (Nature, 2001,409 (415) in nature:794-7.).According to whether additional renovation agent, is reviewed one's lessons by oneself
Intrinsical and foreign aid's type (Soft Matter, 2008,4 (3) can be divided into again:400-418.).Intrinsical self-repair material is reviewed one's lessons by oneself
Renaturation can be realized then by the intrinsic reversible chemical reaction of system, without additional renovation agent or catalyst, repeat and realize
The selfreparing of material, as the research emphasis of current selfreparing high molecular material.
If Chinese patent (CN104804115A) discloses a kind of preparation method of selfreparing hydrogel, it is with acryloyl
Base glycine amide is monomer, causes in the presence of initiator and is prepared.The patent claim this hydrogel have very strong stretching,
While compression can tear-proof, can realize thermoplasticity and the function of selfreparing at 50 DEG C~90 DEG C.But its selfreparing institute
It needs temperature higher, can not carry out at room temperature, and higher temperature can have an adverse effect to the structural behaviour of hydrogel, this limit
Its application range is made.
If Chinese patent (CN102643375A) discloses a kind of preparation method of selfreparing hydrogel, it is by N, N- bis-
Methyl acrylamide monomer, initiator potassium persulfate, accelerator N,N,N',N' tetramethylethylene diamine and graphene hydrogel exist
Initiated polymerization obtains at room temperature.The patent claims its simple for process, and reaction condition is mild, and the reaction time is short, and in body temperature
In the range of and near infrared light under show good self-healing performance.But N,N-DMAA toxicity is larger, should
There are potential security risks to environmental and biological materials for hydrogel.
Visible ray photograph is mild controllable, also easily obtains in practical applications, and radiation of visible light is for including protein
Most of bioactive substances inside will not all damage, therefore for hydrogel material, it is seen that photoresponse selfreparing is
A kind of ideal selfreparing mode.According to relevant report (AngewandteChemie International Edition in
English,2014, 53(26):6781-5.), the characteristic for having dynamic reversible under visible ray photograph of double selenium dynamic covalent bonds,
Selenium is also trace element necessary to human body.
Hydrogen bond is formed by the interaction of proton donor and proton acceptor, there is faster scission of link recombination ability,
Become most common non-covalent bond connection in supermolecule polymer.The intensity of single hydrogen bond is too small, therefore by introducing one
The Quadrupolar hydrogen bond effect that kind 2- urea -41H- pyrimidones (UPy) are formed, can effectively promote the mechanical property of materials and review one's lessons by oneself reactivation
Power.
Hydrogen bond and double selenium dynamic covalent bonds are all that can mildly realize material selfreparing under room temperature, and hydrogen bond energy is weaker
But self-repair efficiency is higher, and double selenium dynamic bond energy of covalent bond are relatively low compared with strong but self-repair efficiency.By double selenium dynamic covalent bonds and hydrogen
Both selfreparing mechanism of key combine, while introduce the polyglycol chain with fabulous hydrophily and biocompatibility
Section, prepares the selfreparing polyurethane hydrogel based on double selenium dynamic covalent bonds and hydrogen bond, can be real in the case where mild visible ray shines
Now to the quick selfreparing of damage, while there is good biocompatibility, these characteristics cause the hydrogel in biological tissue
Engineering field has broad application prospects.Currently based on double selenium dynamic covalent bonds and the coefficient visible ray of Quadrupolar hydrogen bond certainly
It repairs polyurethane hydrogel and there is no relevant report.
Invention content
Patent of the present invention is related to a kind of preparation of the selfreparing polyurethane hydrogel based on double selenium dynamic covalent bonds and hydrogen bond
The rapidly and efficiently selfreparing of damage can be achieved in method, the hydrogel material under mild visible light conditions.
For achieving the above object, it is somebody's turn to do the synthesis of the selfreparing hydrogel based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond
The quality proportioning of each component is as follows in raw material：
Double selenium glycol 20~30
2-Amino-2-methyl-1,3-propanediol 2~15
Trimethylolpropane 2~8
Methylcystein 2~10
Organic solvent 150~350
Polyethylene glycol 50~80
Diisocyanate 15~35
Dibutyl tin laurate 0.006~0.02
The selfreparing hydrogel is synthesized by following special process：
(1) at 90~130 DEG C, using rotating retorts vacuum degree under conditions of 0.09MPa to macromolecule binary
Alcohol is evaporated under reduced pressure 3~5 hours, to remove moisture removal；
(2) at 100~120 DEG C, a certain amount of methylcystein and di-isocyanate reaction 16~24 hours then add in
A certain amount of pentane generates precipitation in product, filters out sediment, after being cleaned with pentane 30~40 DEG C, 0.09~
Solvent evaporated under 0.08MPa obtains the methylcystein with isocyanate groups, i.e. UPy-NCO；
(3) at 25~35 DEG C, a certain amount of UPy-NCO is returned in organic solvent with 2-Amino-2-methyl-1,3-propanediol
Stream reaction 4~8 hours takes sediment fraction solvent evaporated under 30~40 DEG C, 0.09~0.08MPa after product centrifugation, obtains UPy
Base chain extender；
(4) a certain amount of macromolecule diol, diisocyanate, two bays are sequentially added in sequence in three-necked flask
Sour dibutyl tin is heated to 60~90 DEG C, reacts 3~6 hours；
(5) 50~60 DEG C are cooled to, adds in a certain amount of organic solvent viscosity reduction, adds a certain amount of UPy bases chain extender
Chain extension is carried out with double selenium glycol, the reaction was continued 6~8 hours, obtains the base polyurethane prepolymer for use as that end group is isocyanate group；
(6) 30~50 DEG C are cooled to, adds in a certain amount of trimethylolpropane, after being vigorously stirred, product is moved into mold,
And cured 8~12 hours in 50~80 DEG C of baking oven, it obtains the selfreparing based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond and gathers
Urethane gel；
(7) by gel at 0.09~0.08MPa, 40~60 DEG C solvent evaporated, and impregnate in deionized water 48~72
Hour, it changes a water within every 12 hours, to remove unreacted small molecule, obtains based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond
Selfreparing polyurethane hydrogel.
In above-mentioned preparation method, its number-average molecular weight of the polyethylene glycol used is 400g/mol, 750g/mol,
A kind of or combination in 1000 g/mol and 2000g/mol.
Preferably, the polyethylene glycol is any one or combination in PEG-750, PEG-1000.
Diisocyanate used be isophorone diisocyanate, toluene di-isocyanate(TDI), two isocyanide of diphenyl methane
One kind in acid esters, hexamethylene diisocyanate and its homologue.
Preferably, the diisocyanate is isophorone diisocyanate (IPDI) and hexa-methylene diisocyanate
Any one or combination in ester (HDI).
Organic solvent used is tetrahydrofuran, acetone, butanone, one kind in chloroform.
It is tetrahydrofuran and chloroform as the preferably described organic solvent.
Methylcystein used is -4 carboxyl -6- methylpyrimidines of 2- amino, 2- amino -4- carboxyls -5- (2- ethoxys) -6-
A kind of or combination in methylpyrimidine and 2- amino-4-hydroxy -6- methylpyrimidines.
Preferably, the methylpyrimidine is -4 carboxyl -6- first of 2- amino-4-hydroxy -6- methylpyrimidines and 2- amino
A kind of or combination in yl pyrimidines.
The advantage of the invention is that：
(1) the selfreparing hydrogel provided by the present invention based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond is based on double selenium keys
Visible ray dynamic reversible characteristic and hydrogen bond dynamic reversible characteristic, can be realized in the case where mild visible ray shines to damage
Quick selfreparing, and can still keep good mechanical performance after being repeated several times and repairing；
(2) the selfreparing hydrogel provided by the present invention based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond is based on mild
Under the conditions of can be achieved fracture-recombination double selenium dynamic covalent bonds and Quadrupolar hydrogen bond, avoid needed for traditional selfreparing as high temperature,
Destruction of the stronger outside stimulus such as ultraviolet lighting to material structure；
(3) the selfreparing hydrogel provided by the present invention based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond is polyurethane knot
Structure using polyethylene glycol as hydrophily soft segment, has excellent biocompatibility and molecular structure designability, is well positioned to meet
The needs of practical application, thus have broad application prospects in bioengineered tissue field.
Specific embodiment：
Embodiment one：At 110 DEG C, using rotating retorts vacuum degree under conditions of 0.09MPa to PEG-1000
Vacuum distillation 3 hours, to remove moisture removal；Into reaction vessel add in 0.47g 2- amino-4-hydroxy -6- methylpyrimidines with
0.86g IPDI react 16 hours at 120 DEG C, then add in the pentane of 20ml, precipitate product, recycle sand core funnel
Sediment is filtered out, and is cleaned three times with pentane, product utilization vacuum drying oven is toasted 2 hours under 40 DEG C, 0.09MPa and is evaporated
Solvent obtains methylcystein powder 1.65g, i.e. UPy-NCO with isocyanate groups；At 30 DEG C, 1.65g UPy-NCO with
0.78g 2-Amino-2-methyl-1,3-propanediol back flow reaction 5 hours in 30ml chloroforms, product centrifuge exist
After being centrifuged under 10000r/min, sediment fraction solvent evaporated under 40 DEG C, 0.09MPa is taken, obtains UPy base chain extenders 1.59g；
PEG-1000,4.47g IPDI that 10g has been dried are sequentially added in three-necked flask in sequence, is kept stirring and is heated to 50 DEG C,
Stirring adds in 0.021g dibutyl tin laurates after 30 minutes, is warming up to 80 DEG C and reacts 3 hours；60 DEG C are cooled to, is added in
100ml tetrahydrofuran viscosity reductions, then the bis- selenium glycol of 1.46g and 1.47gUPy base chain extenders are added in reaction vessel, the reaction was continued 7
A hour obtains the base polyurethane prepolymer for use as that end group is hydroxyl；40 DEG C are cooled to, it is acute that 0.67g trimethylolpropanes are added in product
It is strong to be stirred, and mixture is moved into mold, the cross-linking curing in baking oven at 60 DEG C by 12 hours；By the block of forming
Shape gel demoulds, and is placed in vacuum drying oven 40 DEG C, lower 6 hours of 0.09MPa, to remove solvent, puts later in deionized water
It impregnates, changes a water within every 12 hours, can obtain the selfreparing based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond after 48 hours gathers
Urethane hydrogel.
Embodiment two：At 100 DEG C, PEG-750 is subtracted under conditions of vacuum degree is 0.09MPa using rotating retorts
Pressure distillation 4 hours, to remove moisture removal；2- amino-4-hydroxy -6- the methylpyrimidines and 0.73g of 0.49g is added in into reaction vessel
IPDI reacts 16 hours at 120 DEG C, then adds in the pentane of 20ml, precipitate product, sand core funnel is recycled to filter out
Sediment, and cleaned three times with pentane, product utilization vacuum drying oven toasts 2 hours solvent evaporateds under 40 DEG C, 0.09MPa,
Obtain methylcystein powder 1.26g, i.e. UPy-NCO with isocyanate groups；At 30 DEG C, 1.26g UPy-NCO and 0.76g
2-Amino-2-methyl-1,3-propanediol back flow reaction 6 hours in 30ml chloroforms, product centrifuge is under 10000r/min
After centrifugation, sediment fraction solvent evaporated under 40 DEG C, 0.09MPa is taken, obtains UPy base chain extenders 1.22g；It is pressed in three-necked flask
It according to PEG-750,4.51g IPDI for sequentially sequentially adding 7.5g and having dried, is kept stirring and is heated to 50 DEG C, after stirring 30 minutes
0.02g dibutyl tin laurates are added in, 80 DEG C is warming up to and reacts 3 hours；50 DEG C are cooled to, adds in 90ml tetrahydrofurans drop
It is viscous, then the bis- selenium glycol of 1.19g and 1.22gUPy base chain extenders are added in reaction vessel, the reaction was continued 6 hours, obtains end group
Base polyurethane prepolymer for use as hydroxyl；30 DEG C are cooled to, 0.71g trimethylolpropanes are added in product and are vigorously stirred mixing, and will
Mixture is moved into mold, the cross-linking curing in baking oven at 70 DEG C by 9 hours；The blocky gel of forming is demoulded, is placed
It 50 DEG C in vacuum drying oven, 6 hours under 0.09MPa, to remove solvent, puts impregnate in deionized water later, change within every 12 hours
Water can obtain the selfreparing polyurethane hydrogel based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond after 72 hours.
Embodiment three：At 120 DEG C, using rotating retorts vacuum degree under conditions of 0.09MPa to PEG-1000
Vacuum distillation 3 hours, to remove moisture removal；Into reaction vessel add in 0.46g 2- amino-4-hydroxy -6- methylpyrimidines with
0.82g IPDI react 20 hours at 100 DEG C, then add in the pentane of 15ml, precipitate product, recycle sand core funnel
Sediment is filtered out, and is cleaned three times with pentane, product utilization vacuum drying oven is toasted 2 hours under 40 DEG C, 0.09MPa and is evaporated
Solvent obtains methylcystein powder 1.26g, i.e. UPy-NCO with isocyanate groups；At 30 DEG C, 1.26g UPy-NCO with
0.69g 2-Amino-2-methyl-1,3-propanediol back flow reaction 6 hours in 20ml chloroforms, product centrifuge is 10000
After being centrifuged under r/min, sediment fraction solvent evaporated under 40 DEG C, 0.09MPa is taken, obtains UPy base chain extenders 1.29g；At three mouthfuls
PEG-1000,2.21g IPDI that 5g has been dried are sequentially added in flask in sequence, is kept stirring and is heated to 50 DEG C, stirring 30
0.009g dibutyl tin laurates are added in after minute, 70 DEG C is warming up to and reacts 4 hours；60 DEG C are cooled to, adds in 50ml tetrahydrochysenes
Furans viscosity reduction, then the bis- selenium glycol of 1.25g and 1.03gUPy base chain extenders are added in reaction vessel, the reaction was continued 8 hours, obtains
To the base polyurethane prepolymer for use as that end group is hydroxyl；30 DEG C are cooled to, addition 0.33g trimethylolpropanes are vigorously stirred mixed in product
It closes, and mixture is moved into mold, the cross-linking curing in baking oven at 80 DEG C by 8 hours；The blocky gel of forming is taken off
Mould is placed in vacuum drying oven 60 DEG C, lower 6 hours of 0.09MPa, to remove solvent, puts impregnate in deionized water later, and every 12
Hour changes a water, and the selfreparing polyurethane water-setting based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond can be obtained after 72 hours
Glue.
Example IV：At 120 DEG C, PEG-750 is subtracted under conditions of vacuum degree is 0.09MPa using rotating retorts
Pressure distillation 2 hours, to remove moisture removal；2- amino-4-hydroxy -6- the methylpyrimidines and 0.89g of 0.61g is added in into reaction vessel
IPDI reacts 16 hours at 120 DEG C, then adds in the pentane of 25ml, precipitate product, sand core funnel is recycled to filter out
Sediment, and cleaned three times with pentane, product utilization vacuum drying oven toasts 3 hours solvent evaporateds under 50 DEG C, 0.09MPa,
Obtain methylcystein powder 1.31g, i.e. UPy-NCO with isocyanate groups；At 30 DEG C, 1.31g UPy-NCO and 0.67g
2-Amino-2-methyl-1,3-propanediol back flow reaction 6 hours in 30ml chloroforms, product centrifuge is under 10000 r/min
After centrifugation, sediment fraction solvent evaporated under 40 DEG C, 0.09MPa is taken, obtains UPy base chain extenders 1.39g；It is pressed in three-necked flask
It according to PEG-750,4.47g IPDI for sequentially sequentially adding 7.5g and having dried, is kept stirring and is heated to 50 DEG C, after stirring 30 minutes
0.023g dibutyl tin laurates are added in, 80 DEG C is warming up to and reacts 3 hours；60 DEG C are cooled to, adds in 90ml tetrahydrofurans drop
It is viscous, then the bis- selenium glycol of 1.57g and 1.23g UPy base chain extenders are added in reaction vessel, the reaction was continued 7 hours, is held
Base is the base polyurethane prepolymer for use as of hydroxyl；40 DEG C are cooled to, 0.65g trimethylolpropanes are added in product and are vigorously stirred mixing, and
Mixture is moved into mold, the cross-linking curing in baking oven at 60 DEG C by 12 hours；The blocky gel of forming is demoulded, is put
It puts in vacuum drying oven 50 DEG C, 6 hours under 0.09MPa, to remove solvent, puts impregnate in deionized water later, every 12 hours
A water is changed, the selfreparing polyurethane hydrogel based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond can be obtained after 56 hours.
Claims (2)
1. patent of the present invention is related to a kind of preparation method of the selfreparing polyurethane hydrogel based on double selenium dynamic covalent bonds, the water
Gel is to obtain base polyurethane prepolymer for use as by diisocyanate, polyethylene glycol, double selenium glycol and UPy base chain extender reactions, then
It adds in trimethylolpropane and is cross-linked into gel, and impregnate obtain in deionized water.The quality proportioning of its each component is as follows：
The selfreparing hydrogel is synthesized by following special process：
(1) at 90~130 DEG C, macromolecule diol is subtracted under conditions of vacuum degree is 0.09MPa using rotating retorts
Pressure distillation 3~5 hours, to remove moisture removal；
(2) at 100~120 DEG C, a certain amount of methylcystein and di-isocyanate reaction 16~24 hours then add in certain
Pentane is measured, precipitation is generated in product, sediment is filtered out, after being cleaned with pentane under 30~40 DEG C, 0.09~0.08MPa
Solvent evaporated obtains the methylcystein with isocyanate groups, i.e. UPy-NCO；
(3) at 25~35 DEG C, a certain amount of UPy-NCO flows back instead in organic solvent with 2-Amino-2-methyl-1,3-propanediol
It answers 4~8 hours, sediment fraction solvent evaporated under 30~40 DEG C, 0.09~0.08MPa is taken after product centrifugation, obtain the expansion of UPy bases
Chain agent；
(4) a certain amount of macromolecule diol, diisocyanate, tin dilaurate two are sequentially added in sequence in three-necked flask
Butyl tin is heated to 60~90 DEG C, reacts 3~6 hours；
(5) 50~60 DEG C are cooled to, adds in a certain amount of organic solvent viscosity reduction, adds a certain amount of UPy bases chain extender and double
Selenium glycol carries out chain extension, and the reaction was continued 6~8 hours, obtains the base polyurethane prepolymer for use as that end group is isocyanate group；
(6) 30~50 DEG C are cooled to, adds in a certain amount of trimethylolpropane, after being vigorously stirred, product is moved into mold, and
It is cured 8~12 hours in 50~80 DEG C of baking oven, obtains the selfreparing polyurethane based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond
Gel；
(7) by gel at 0.09~0.08MPa, 40~60 DEG C solvent evaporated, and impregnate in deionized water 48~72 hours,
It changes a water within every 12 hours, to remove unreacted small molecule, obtains the selfreparing based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond
Polyurethane hydrogel.
2. the preparation side of the selfreparing polyurethane hydrogel based on double selenium dynamic covalent bonds and Quadrupolar hydrogen bond according to right 1
Method, it is characterised in that the polyethylene glycol its number-average molecular weight for 400g/mol, 750g/mol, 1000g/mol and
A kind of or combination in 2000g/mol；The diisocyanate be isophorone diisocyanate, toluene diisocynate
One kind in ester, methyl diphenylene diisocyanate, hexamethylene diisocyanate and its homologue；Organic solvent used is
Tetrahydrofuran, acetone, butanone, a kind of or combination in chloroform；Methylcystein used is phonetic for -4 carboxyl -6- methyl of 2- amino
Pyridine, 2- amino -4- carboxyls -5- (2- ethoxys) -6- methylpyrimidines and one kind in 2- amino-4-hydroxy -6- methylpyrimidines or
A combination thereof.
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| CN113105607B (en) * | 2021-04-09 | 2022-04-22 | 青岛科技大学 | Self-repairing polyurethane cross-linked network containing UPy side chain, preparation method and application |
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