CN109705372A - A kind of supramolecular materials and hydrogel and preparation method thereof - Google Patents
A kind of supramolecular materials and hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of supramolecular chemistry more particularly to a kind of supramolecular materials and hydrogel and preparation method thereof.Including the first construction unit, secondary building units, third construction unit and the 4th construction unit, first construction unit has one structure of formula, the secondary building units have two structure of formula, the third construction unit has three structure of formula, 4th construction unit has five structure of formula four or/and formula, and first construction unit, secondary building units, third construction unit are based on adamantane-cyclodextrin Subjective and Objective self assembly with the 4th construction unit and connect to form supramolecular materials.The present invention also provides a kind of hydrogel, the hydrogel that the present invention obtains solves the technological deficiency that its structure existing for existing hydrogel is mixed and disorderly, can not regulate and control, and Crack Self big for macroscopic view needs manually to be bonded.
Description
Technical field
The invention belongs to the technical field of supramolecular chemistry more particularly to a kind of supramolecular materials and hydrogel and its preparations
Method.
Background technique
Self-healing is can automatic self-healing after the most basic characteristic of organism, for example skin and skeletal injury.Hydrogel
It is usually soft and flexible, there is very high water content, these characteristics keep hydrogel quite similar with mechanics of biological tissue, because
This, by reasonably designing the self-repair function that hydrogel material can also be made to realize similar organism.With self-healing function
Hydrogel can be automatically repaired the material area damage due to caused by extreme external condition (as large deformation or external force are destroyed)
Hurt, impaired gel is made to restore its shape and function, thus extend the working life and stability in use of gel rubber material, optimization warp
Ji benefit, realizes intelligence, high efficiency and environmental-friendlyization of soft material.The world today, Smart self-repairing material are a Men Xin
The Comprehensive Science of rise.Currently, the hydrogel with self-repair function has become newly as a kind of novel intelligent soft material
One of research hotspot of Material Field.
Supramolecular hydrogel based on Subjective and Objective self assembly is a kind of important self-repair material.Osaka, Japan university
Harada professor team is devised in advance using the Subjective and Objective self assembly effect of beta-cyclodextrin (β-CD) and adamantane (Ad) from group
Two kinds of vinyl monomers of dress, then obtain a kind of hydrogel of selfreparing by free radical polymerization, what which cut
Section can bond (Kakuta T., Takashima Y., Nakahata M., Otsubo at once after being bonded to each other together
M.,Yamaguchi H.,Harada A.,Adv.Mater.2013,25(20):2849-2853.)。
However for the selfreparing hydrogel of prior art preparation, preparation method is uncontrollable, and gel network structure is inadequate
It is regular and flexibly adjustable.In addition, only the section of incision is fit together manually for reported selfreparing hydrogel
Afterwards, under certain condition just it is observed that selfreparing, it is, only working as material internal generates small crackle, polymer divides
Selfreparing just may be implemented in the case where capable of contacting with each other during free diffusing moves in subchain section.And for biggish
When crack contacts self-repair material section two sides not, generally requires that section both ends fit together manually, otherwise just can not
Complete selfreparing.
Summary of the invention
In view of this, it is adjustable and there is temperature sensitivity the purpose of the present invention is disclosing a kind of compound with regular structure, and it is not necessarily to
The hydrogel of the big Crack Self of macroscopic view is realized in artificial fitting.
The present invention provides a kind of supramolecular materials, including the first construction unit, secondary building units, third construction unit
With the 4th construction unit；
Wherein, the first construction unit has one structure of formula:
Wherein, R1It is selected from One or both of, L1 is
The secondary building units have two structure of formula:
Wherein, R2It is selected from One or both of, L2 is
The third construction unit has three structure of formula:
Wherein, R4It is selected fromOne or both of；
4th construction unit includes five structure of four structure of formula or/and formula:
Wherein, X is selected from Br or N3；R3Choosing
From
Wherein, X is selected from Br or N3；R3It is selected fromOne or both of；
First construction unit, secondary building units, third construction unit and the 4th construction unit are based on adamantane-ring
Dextrin Subjective and Objective self assembly connects to form supramolecular materials.
Connect it should be noted that formula one, formula two, formula three and four structure of formula are based on adamantane-cyclodextrin Subjective and Objective self assembly
It connects to form supramolecular materials, is also possible to formula one, formula two, formula three and five structure of formula and is based on adamantane-cyclodextrin Subjective and Objective from group
Load connects to form supramolecular materials, is also possible to formula one, formula two, formula three, formula four and formula five and is based on adamantane-cyclodextrin host and guest
Body self assembly connects to form supramolecular materials.
It is furthermore preferred that X is Br or N in formula four3；R3For
Preferably, in formula four, X Br；R3For
It is furthermore preferred that X is Br or N in formula five3；R3For
Preferably, in formula five, x Br；R3For
Preferably, in formula four and formula five, it is describedContain alpha-cyclodextrin, beta-cyclodextrin group or γ-ring paste
Smart group.
It is furthermore preferred that in formula four and formula five, it is describedContain beta-cyclodextrin group.
Preferably, the y is the integer of 50-100 in formula one；In formula two, the z is the integer of 50-100；Formula three
In, the w is the integer of 50-100；In polymer shown in polymer shown in formula four or/and formula five, the m is 50-100
Integer；The n is the integer of 0.5-10.
Preferably, the formula one the preparation method comprises the following steps: formula six and formula seven are carried out click-reaction, or by formula six and formula eight
Click-reaction is carried out, formula one is made, wherein the specific structure of formula six, formula seven and formula eight is as follows:
Wherein, L1 is
One (R of formula1It is selected fromOne or both of, L1 is) preparation road
Line is as follows:
Specifically, the preparation method of formula one is using ethylene glycol or adamantane glycol as raw material:
(L1 is formula one), using ethylene glycol as starting material method particularly includes: ethylene glycol and the bromo- isobutyl acylbromide of 2-
It carries out nucleophilic substitution and obtains two-way ATRP initiator, ATRP initiator causes n-isopropyl acrylamide (NIPAM) polymerization
Afterwards, both arms Thermo-sensitive linear polymer is obtained.Then formula six will be obtained after the processing of both arms Thermo-sensitive linear polymer nitrine, most
Afterwards, it reacts to obtain formula one by the way that formula six is carried out click chemistry with seven compound of formula, wherein R1ForBy by formula
Six, which carry out click chemistry with eight compound of formula, reacts to obtain formula one, wherein R1For
(L1 is formula one), using adamantane glycol as starting material method particularly includes: adamantane glycol and 2- are bromo-
Isobutyl acylbromide carries out nucleophilic substitution and obtains two-way ATRP initiator, and ATRP initiator causes n-isopropyl acrylamide
(NIPAM) after polymerizeing, both arms Thermo-sensitive linear polymer is obtained.Then it will be obtained after the processing of both arms Thermo-sensitive linear polymer nitrine
To formula six, finally, reacting to obtain formula one by the way that formula six is carried out click chemistry with seven compound of formula, wherein R1ForL1
ForIt reacts to obtain formula one by the way that formula six is carried out click chemistry with eight compound of formula, wherein R1ForL1 is
It should be noted that formula is first is that using ATRP and click chemistry technology, design and synthesis have various topological structures
It is reacted using ethylene glycol or adamantane glycol as two functional group A TRP initiator of Material synthesis using ATRP with the polymer of function
Linear temperature sensing polymer is made, after Azide, is reacted using click chemistry and is connected in the end of temperature sensing polymer chain
The tool for containing cyclodextrin residue or adamantane residue in end is made by the Cyclodextrin groups or adamantane group of alkynyl
There is the formula one of temperature-sensing property.
It should be noted that click chemistry is a kind of new method of a large amount of compounds of rapid synthesis, mainly pass through junior unit
Splicing, the combinatorial chemistry reaction based on carbon-heteroatom bond (C-X-C) synthesis, Formulas I of the invention mainly passes through copper (I)
The one alkynes cycloaddition (CuAAC) of nitrine of catalysis is reacted, and generating end in the end Azide of the polymer of both arms has azido
Both arms polymer carries out click chemistry reaction by the alkynes of low molecular weight based on this and prepares formula one.
Preferably, the formula two the preparation method comprises the following steps: formula nine and formula seven are carried out click-reaction, or by formula nine and formula eight
Click-reaction is carried out, formula two is made, wherein the specific structure of formula nine, formula seven and formula eight is as follows:
Wherein, L2 is
Specifically, the preparation method of formula two, with pentaerythrite or 1,3,5,7- tetrahydroxy adamantanes are raw material, wherein formula
Two, R2It is selected fromOne or both of, L2 isReaction route such as
Under:
Wherein, (L2 is formula two), using pentaerythrite as starting material method particularly includes: will by pentaerythrite and
The bromo- isobutyl acylbromide of 2- prepares pentaerythrite base tetrabromo ATRP initiator, then by pentaerythrite base tetrabromo ATRP by esterification
Initiator and n-isopropyl acrylamide (NIPAM) carry out ATRP polymerization, and four arm star Thermo-sensitives polymerization of the end with bromine is made
Object, then the bromine of the four arm star temperature sensing polymer ends by end with bromine is substituted by nitrine (- N3) after, obtain nine (L2 of formula
For), formula nine and formula seven (or formula nine and formula eight) carry out click-reaction, and obtaining formula two, (L2 is), wherein it clicks anti-
It should be that (L2 is by formula nine): formula seven (or formula eight): ligand PMDETA: catalyst cuprous bromide presses 1:(4~6): (4~
8): the molar ratio of (4~8) is reacted, and then crosses neutral alumina column, then dialyse, obtained product precipitates in ice ether
Dry after filtering, obtaining formula two, (L2 is), wherein if adding type seven in click-reaction, the R of formula two2For containing cyclodextrin
Residue, L2 isIf adding type eight in click-reaction, the R of formula two2For the residue containing adamantane, L2 is
Wherein, (L2 is formula two), it is starting material with 1,3,5,7- tetrahydroxy adamantane method particularly includes: will
Adamantyl tetrabromo ATRP initiator is prepared by esterification by 1,3,5,7- tetrahydroxy adamantane and 2- bromo- isobutyl acylbromide,
Adamantyl tetrabromo ATRP initiator and n-isopropyl acrylamide (NIPAM) are subjected to ATRP polymerization again, end is made with bromine
Four arm star temperature sensing polymers, then the bromine of the end of the four arm star temperature sensing polymers by end with bromine is substituted by nitrine
(-N3) after, obtaining formula nine, (L2 is), formula nine and formula seven (or formula nine and formula eight) are carried out click-reaction and obtain formula two
(L2 is), wherein click-reaction are as follows: (L2 is by formula nine): formula seven (or formula eight): ligand PMDETA: urge
Agent cuprous bromide is by 1:(4~6): (4~8): the molar ratio of (4~8) is reacted, rear to cross neutral alumina column, then is dialysed,
Obtained product is precipitated in ice ether dry after filtering, obtaining formula two, (L2 is), wherein if adding in click-reaction
Add formula seven, then the R of formula two2For the residue containing cyclodextrin, L2 isIf eight compound of adding type, the R of formula two2Containing for
The residue of adamantane, L2 are
It should be noted that formula is second is that using ATRP and click chemistry technology, design and synthesis have various topological structures
With the polymer of function, with pentaerythrite or 1,3,5,7- tetrahydroxy adamantanes are Material synthesis four-functional group ATRP initiation
Linear temperature sensing polymer is made using ATRP reaction in agent, after Azide, is polymerize using click chemistry reaction in Thermo-sensitive
The end of object chain, which is connected, contains cyclodextrin or Buddha's warrior attendant by the obtained end of Cyclodextrin groups or adamantane group of alkynyl
The formula two with temperature-sensing property of alkane.
It should be noted that click chemistry is a kind of new method of a large amount of compounds of rapid synthesis, mainly pass through junior unit
Splicing, by carbon-heteroatom bond (C-X-C) synthesis based on combinatorial chemistry reaction, formula two of the invention mainly pass through copper (I)
The one alkynes cycloaddition (CuAAC) of nitrine of catalysis is reacted, and generating end in the end Azide of the polymer of four arms has azido
Four arm polymer carry out click chemistry reaction by the alkynes of low molecular weight based on this and prepare formula two.
Preferably, the formula three the preparation method comprises the following steps: formula ten and formula six are carried out click-reaction, or by formula five and formula seven
Click-reaction is carried out, formula three is made, wherein the specific structure of formula five, formula six and formula seven is as follows:
Specifically, three (R of formula4It is selected fromOne or both of) preparation method with double seasons
Penta tetrol is raw material, and preparation route is as follows:
Specifically, formula three is prepared the preparation method is as follows: passing through esterification by dipentaerythritol and 2- bromine isobutyl acylbromide
Dipentaerythritol base hexabromo ATRP initiator, by dipentaerythritol base hexabromo ATRP initiator and n-isopropyl acrylamide
(NIPAM) it carries out ATRP polymerization and six arm star temperature sensing polymers of the end with bromine is made.Then six arm star Thermo-sensitives are gathered
The bromine for closing object end is substituted by nitrine (- N3) after, obtain formula ten.It is obtained finally, formula ten is carried out click-reaction with seven compound of formula
To formula three, wherein R1ForFormula ten and eight compound of formula are subjected to click-reaction and obtain formula three, wherein R1For
It should be noted that formula is third is that using ATRP and click chemistry technology, design and synthesis have various topological structures
It is reacted using ATRP using dipentaerythritol as Material synthesis six functional groups ATRP initiator with the polymer of function and is made linear
Temperature sensing polymer is reacted using click chemistry and is connected in the end of temperature sensing polymer chain by alkynyl after Azide
What the Cyclodextrin groups or adamantane group of change were made that end contains cyclodextrin residue or adamantane residue has temperature sensitive spy
The formula three of property.
It should be noted that click chemistry is a kind of new method of a large amount of compounds of rapid synthesis, mainly pass through junior unit
Splicing, the combinatorial chemistry reaction based on carbon-heteroatom bond (C-X-C) synthesis, Formulas I of the invention mainly passes through copper (I)
The one alkynes cycloaddition (CuAAC) of nitrine of catalysis is reacted, and generating end in the end Azide of the polymer of six arms has azido
Six arm polymer carry out click chemistry reaction by the alkynes of low molecular weight based on this and prepare formula three.
Wherein, preferably, the formula seven the preparation method comprises the following steps:
By beta-cyclodextrin and tolysulfonyl imidazoles are molten react a period of time in aqueous solution after, then to add sodium hydroxide molten
The reaction was continued for liquid, after reaction be added dropwise acid solution adjust pH to neutrality after crystallisation by cooling, and then will crystallization after solid product with
Propargylamine reacts to obtain formula seven.
Specifically, the formula seven the preparation method comprises the following steps: by tolysulfonyl imidazoles, beta cyclodextrin is sufficiently mixed in water
After even, be added sodium hydroxide solution, the reaction was continued, to be filtered to remove insoluble matter after reaction, and be added hydrochloric acid adjust PH to
Neutrality will filter after neutral products crystallisation by cooling 8-16h, and acetone washing crude product is used after being washed with deionized water；Deionization is used again
Twice, vacuum drying obtains white solid (being denoted as OTs-CD) to water heating recrystallization；By OTs-CD and propargylamine, in inert gas
Protection under, be protected from light, obtain the crude product of formula seven.For example following chemical equations of the preparation process of formula seven:
Wherein, the crude product of formula seven can be precipitated in acetone with after the mixed liquor dilution of first alcohol and water, is repeated this step
Rapid repeatedly to filter to obtain product, seven purity of formula is 95%.
Wherein, it is 42-60% that the preparation method of formula seven, which obtains the yield of formula seven,.
Wherein, in the preparation method of above formula seven, in terms of mass parts, tolysulfonyl imidazoles is 1 part, beta cyclodextrin 2-4
Part, sodium hydroxide solution be 5-6 part (mass fraction of sodium hydroxide solution is 20%), the concentration of hydrochloric acid be 1-3mol/L,
OTs-CD is 1 part, and propargylamine is 2-3 parts.
Wherein, tolysulfonyl imidazoles, beta cyclodextrin and water mixing, reaction time are 4-6 hours；Sodium hydroxide is added
Solution, incorporation time 25min-35min；Then crystallisation by cooling is carried out, cooling temperature is 4 DEG C；It is vacuum drying after crystallization
Time is 48h；Inert gas is nitrogen；The condition that OTs-CD and propargylamine are protected from light is 50 DEG C and is protected from light 72-96h.
Preferably, the formula eight the preparation method comprises the following steps:
Adamantanecarboxylic acid is added in methylene chloride (DCM), under condition of ice bath, by oxalyl chloride after methylene chloride dilutes
The mixed liquor that adamantanecarboxylic acid and methylene chloride is added is reacted；Solvent and extra oxalyl chloride are screwed out, pale yellow colored solid is obtained
Body 1- adamantane formyl chloride.Again by triethylamine, 1- adamantane formyl chloride, anhydrous ether, propargyl alcohol hybrid reaction, reaction terminates
Afterwards, it is filtered to remove insoluble matter, successively uses hydrochloric acid solution, NaHCO3Three times with deionized water washing, anhydrous magnesium sulfate is then used
Removing magnesium sulfate is dried, filtered, is rotated, neutral alumina column is crossed, obtains formula eight, eight property of formula is colorless viscous shape liquid.Formula
For example following chemical equations of eight preparation process:
Wherein, in the preparation method of above formula eight, in terms of molar part, adamantanecarboxylic acid is 1 molar part, oxalyl chloride 1-
1.5 molar parts, 1- adamantane formyl chloride are 1 molar part, triethylamine is 1.2 molar parts, propargyl alcohol is that 1.2 molar parts, hydrochloric acid are molten
The mass fraction of liquid is 10%, NaHCO3Mass fraction be 5%.
Wherein, the diluted oxalyl chloride of methylene chloride is that adamantanecarboxylic acid and methylene chloride is added by constant pressure funnel
In mixed liquor.
Wherein, the time that oxalyl chloride and adamantanecarboxylic acid are reacted is 12-16h.
Wherein, triethylamine, 1- adamantane formyl chloride and anhydrous ether are added in reaction flask, after propargyl alcohol is dissolved in anhydrous ether
It is added in reaction flask by constant pressure funnel, the reaction was continued 24-48h after being added dropwise.
Wherein, the anhydrous magnesium sulfate dry time is 6-12h.
The formula four the preparation method comprises the following steps: formula 11, formula 12 and formula 13 are reacted to obtain, the X of the formula four
For Br, R3ForWherein, the specific structure of the formula 11, the formula 12 and the formula 13 is as follows:
The formula five the preparation method comprises the following steps: formula 11, formula 12 and formula 14 are reacted to obtain, the X of the formula five
For Br, R3ForWherein, the specific structure of the formula 11, the formula 12 and the formula 14 is as follows:
Preferably, formula 11, formula 15 and formula 13 are reacted to obtain, the X of the formula four is Br, R3ForWherein, the specific structure of the formula 11, the formula 15 and the formula 13 is as follows:
The formula five the preparation method comprises the following steps: formula 11, formula 15 and formula 14 are reacted to obtain, the X of the formula five
For Br, R3For
Wherein, the specific structure of the formula 11, the formula 15 and the formula 14 is as follows:
It should be noted that the formula one, the formula two, the formula three, the formula four and the formula are fifth is that pass through atom
Transferring free-radical polymerization ATRP reacts to obtain, and is to draw with halogenated alkyl hydrocarbon (R-X) using low-valent transition metals halide as catalyst
Agent is sent out, electronic donor compound is ligand.The polymeric reaction condition is simple mildly, resulting polymers molecular weight distribution is relatively narrow.
It should be noted that the formula 15 the preparation method comprises the following steps: mono- 6- ethylenediamine-cyclodextrin and acryloyl chloride carry out
Reaction obtains.
The present invention also provides a kind of hydrogel, preparation method the following steps are included:
First construction unit, the secondary building units, the third construction unit and the described 4th are constructed into list
Member and water mixing, pass through first construction unit, the secondary building units, the third construction unit and the 4th structure
Adamantane-cyclodextrin the Subjective and Objective for building unit dissolves mixing under the conditions of 4-20 DEG C and carries out self assembly, is heated at 35-50 DEG C
Form hydrogel, wherein first construction unit has one structure of formula, and the secondary building units have two structure of formula, institute
Third construction unit is stated with three structure of formula, the 4th construction unit includes shown in polymer shown in formula four or/and formula five
Polymer.
It connects to form water-setting it should be noted that formula one, formula two are based on adamantane-cyclodextrin Subjective and Objective self assembly with water
Glue, is also possible to formula one, formula three and water are based on adamantane-cyclodextrin Subjective and Objective self assembly and connect to form hydrogel, can also be with
It is that formula two, formula three and water are based on adamantane-cyclodextrin Subjective and Objective self assembly and connect to form hydrogel, is also possible to formula one, formula
Two, formula three connects to form hydrogel with water based on adamantane-cyclodextrin Subjective and Objective self assembly.The present invention utilizes Subjective and Objective self assembly
Effect, carries out Subjective and Objective for the first construction unit and secondary building units in aqueous solution and is self-assembly of hydrogel, pass through survey
Examination and observation show that the hydrogel has Thermo-sensitive and self-healing properties, and the collaboration function by playing Thermo-sensitive and selfreparing
The big Crack Self for not having to be bonded manually can may be implemented.
Wherein, the preparation method of the hydrogel, comprising the following steps: under cryogenic, construct list for described first
First, the described secondary building units, the third construction unit and the 4th construction unit and water dissolution, after static a few hours
Hydrogel is formed under the promotion of mild heat；It can also be prepared by following steps: by first construction unit, described
Two construction units, the third construction unit and the 4th construction unit dissolve in tetrahydrofuran, then in water after dialysis
Obtain hydrogel.
Preferably, the Volume-phase transition temperature of the hydrogel is 20-35 DEG C.
Preferably, the sum of mole of the formula one, the formula two and the formula three, with rubbing for the 4th construction unit
You are than being 1:(0.1-10).
Preferably, what the formula one, the formula two, the formula three and the 4th construction unit mixed in aqueous solution
Mass concentration is 5-25wt%.
The invention regard formula one, formula two and formula three as " crosslinking agent ", and side chain is contained adamantane or/and ring is pasted
The polymer (formula four or/and formula five) of smart group forms hydrogel by way of Subjective and Objective self assembly, due to the end of formula one
Containing there are two cyclodextrin or/and adamantane group, since the end of formula two contains there are four cyclodextrin or/and adamantane group, by
The end of Yu Shisan contains there are six cyclodextrin or/and adamantane group, easily on the side chain of formula four or/and formula five adamantane or
Person's Cyclodextrin groups carry out Subjective and Objective assembling.Therefore, the present invention is constructed by the first construction unit, secondary building units, third
Unit and the 4th construction unit are physical crosslinking based on adamantane-cyclodextrin Subjective and Objective self assembly supermolecule and form gel net
Network can due to being uniformly distributed the physical crosslinking point of the Subjective and Objective self assembly based on adamantane and cyclodextrin in gel network
It first to be disconnected when being destroyed by external force, and can be re-assemblied together when section both ends contact with each other, to assign this hair
The excellent self-repair function of bright hydrogel.In addition, present invention utilizes formula one, formula two and formulas three and secondary building units to have
Temperature sensitive characteristic, the expansion or contraction of volume occur for the variation that can respond temperature, after hydrogel generates big crackle, by wet
The volume expansion of hydrogel may be implemented to reduce crack spacing in profit and reduction temperature, therefore, can pass through this hair of temperature remote control
The big crack spacing of bright hydrogel, to realize the selfreparing of the big crackle of the macroscopic view for not having to be bonded manually.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the phenogram of six arm star temperature sensing polymers of the end with bromine prepared by embodiment 5 provided by the invention
Spectrum；
Fig. 2 is the infrared spectrum (b) of formula ten prepared by embodiment 5 provided by the invention and formula three prepared by embodiment 5
Infrared spectrum (c)；
Fig. 3 is the GPC curve graph (b) of formula ten prepared by embodiment 5 provided by the invention and formula three prepared by embodiment 5
GPC curve graph (c)；
Fig. 4 is the pictorial diagram of the hydrogel of embodiment 8 provided by the invention；
Fig. 5 is the two-dimentional nuclear magnetic spectrum of the hydrogel of embodiment 8 provided by the invention；
Fig. 6 is the pictorial diagram of comparative example 1 provided by the invention；
Fig. 7 is the pictorial diagram of comparative example 2 provided by the invention；
Fig. 8 is the pictorial diagram of comparative example 3 provided by the invention；
Fig. 9 is the Volume-phase transition temperature map of the hydrogel of embodiment 8 provided by the invention；
Figure 10 is the procedure chart of the selfreparing of the hydrogel of embodiment 8 provided by the invention, wherein A is hydrogel 40
DEG C pictorial diagram, B be hydrogel cutting pictorial diagram, C be to hydrogel cut crack size pictorial diagram, D be hydrogel it is normal
The pictorial diagram of water is added dropwise after temperature cutting, E is pictorial diagram of the hydrogel after 20 DEG C of selfreparing 2h, and F is that hydrogel is heated to 40 DEG C
Pictorial diagram.
Specific embodiment
The present invention provides a kind of supramolecular materials and hydrogel and preparation method thereof, hydrogel of the invention solves biography
Structure existing for hydrogel of uniting is mixed and disorderly, non-adjustable, cannot be automatically repaired the technological deficiency of macroscopical big crackle.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to what the present invention protected
Range.
Wherein, it is commercially available or self-control that following embodiment is raw materials used.
Embodiment 1
The embodiment of the invention provides the preparation methods of formula seven and formula eight, the specific steps are as follows:
Formula seven the preparation method is as follows: by tolysulfonyl imidazoles (8.9g, 40mmol), beta cyclodextrin (β-CD, 35g,
It 30.84mmol) is added in the distilled water of 250ml and stirs white suspension.After lower reaction being stirred at room temperature 4 hours, 50ml is added
The sodium hydroxide solution that mass fraction is 20% continues to stir 30min, and reaction solution becomes faint yellow from milky.It is filtered to remove
Filtrate is transferred in 500ml beaker by insoluble matter, and the hydrochloric acid that 1.5mol/L is added adjusts PH to neutrality.Place the beaker 4 DEG C it is low
Crystallisation by cooling 12h under warm environment.Acetone washing crude product is used in filtering after being washed with deionized water.It is tied again with deionized water heating again
It is brilliant to be dried in vacuo 48h twice, white solid (being denoted as OTs-CD) finally is obtained, OTs-CD 16.7g, yield 42%.Again by OTs-
CD (10g, 7.7mmol) addition has in the anhydrous and oxygen-free bottle of stirrer, addition 20ml propargylamine, under stirring condition, vacuumizes-fills
N2Three times, in N2Under protection, 50 DEG C are protected from light 96h.After reaction, it is diluted, is added a large amount of with the mixed liquor of first alcohol and water
It is precipitated in acetone, this step of repetition is multiple, filters to obtain seven 9.5g of formula, and the purity of formula seven is 95%.
Preparing for formula eight is as follows: adamantanecarboxylic acid (9g, 50mmol) and 4 drop anhydrous DMFs are added and the anhydrous dichloro of 50ml are housed
In the 150ml flask of methane.It is under condition of ice bath, the oxalyl chloride of (6.338g, 50mmol) is dilute through 20ml anhydrous methylene chloride
It is added in reaction flask after releasing by constant pressure funnel.After reaction is warmed to room temperature, continue to be stirred to react 12h.After reaction,
Liquid and extra oxalyl chloride are screwed out, faint yellow solid 1- adamantane formyl chloride is obtained.By triethylamine (6.07g, 60mmol) and
Obtained solid 1- adamantane formyl chloride is dissolved in 100ml anhydrous ether.By propargyl alcohol (3.3636g, 60mmol) be dissolved in 50ml without
Water ether is added in reaction flask by constant pressure funnel, the reaction was continued 48h after being added dropwise.After reaction, it is filtered to remove
Insoluble matter.Respectively with 10% hydrochloric acid solution, 5% NaHCO3, deionized water is washed three times, then dry with anhydrous magnesium sulfate
Organic phase 12h.It is filtered to remove magnesium sulfate, is rotated, neutral alumina column is crossed, obtains formula eight, formula eight is colorless viscous shape liquid.
Embodiment 2
The characterization detection that formula seven and formula eight to embodiment 1 carry out, as a result as follows:
Formula seven:
1HNMR(400MHz,DMSO-d6): 5.60~5.89 (m, 14H), 4.75~4.81 (m, 7H), 4.15~4.62 (m,
6H), 3.45~3.72 (m, 28H), 3.15~3.47 (m, 14H), 2.41 (s, 3H), 2.90-3.04 (m, 2H), 2.69-2.79
(m,1H).FT-IR(KBr,cm-1):3354,2929,2131,1705,1638,1414,1366,1233,1156,1028,946,
859,756,706,580.ESI-MS(m/z):calc ulated,1171.4for C45H73O34N,found 1172.5for[M+
H]+。
Formula eight:
1HNMR(400MHz,CDCl3-d):4.64(2H),2.4(1H),2.0(3H),1.9(6H),1.7(6H).FT-IR
(KBr,cm-1):3308,2907,2853,2129,1731,1453,1365,1345,1323,1269,1225,1183,1157,
1103,1073,997。
Embodiment 3
The embodiment of the invention provides the preparation methods of formula one, the specific steps are as follows:
(L1 is formula oneR1For) the preparation method is as follows: anti-by ethylene glycol and 2- bromine isobutyl acylbromide
The two-way ATRP initiator of the dihydroxy adamantine base that should be prepared, by the two-way ATRP initiator of dihydroxy adamantine base (0.127g,
0.35mmol), n-isopropyl acrylamide (8g, 70mmol), Me6TREN (0.161g, 0.70mmol) and 20mL solvent (VDMF:
VWater=80:20) it is added in anhydrous and oxygen-free bottle.Under stirring, vacuumize-inflated with nitrogen three times, under nitrogen protection, rapidly join
CuBr (0.1g, 0.70mmol), then vacuumize-inflated with nitrogen three times, under nitrogen protection, react at room temperature 2h.After reaction, add
Enter the dilution of 15ml tetrahydrofuran, and is exposed in air to terminate reaction.Silicagel column is crossed, cuprous bromide is removed.Revolving, will slightly produce
Product are added in a large amount of ice ether and precipitate, and the solid was filtered.Dissolution-precipitating-filtering 2-3 times is repeated to remove unreacted monomer, is obtained
To 60 DEG C of solid at be dried in vacuo 12h, obtain both arms Thermo-sensitive linear polymer.Azido reaction: the both arms temperature that will be obtained
Quick property linear polymer is dissolved in the DMF of 15ml, and the Sodium azide of 17 times of molar equivalents is added, is stirred to react for 24 hours at 60 DEG C.
After reaction, product being added in the bag filter of 3500Da and is dialysed 2 days, solvent is removed in rotation, and product is added in ether and is precipitated,
Solid is collected, 40 DEG C of dryings for 24 hours, obtain formula six.Click-reaction: by formula six: formula eight: ligand PMDETA: catalyst CuBr presses 1:
The molar ratio of 2.7:2:2 is reacted.Anhydrous and oxygen-free bottle is added in the DMF of formula six, formula eight, PMDETA and 20ml in the above ratio
In, vacuumize-inflated with nitrogen three times, under nitrogen protection be added CuBr after vacuumize-inflated with nitrogen three times, 60 DEG C under nitrogen protection
React 48h.After reaction, the dilution of 15ml tetrahydrofuran is added, and is exposed in air and stirs 1h to terminate reaction, crosses silica gel
Column removes cuprous bromide, and extra solvent is removed in rotation, and crude product is added in 3500Da bag filter and is dialysed 2 days, and solvent is removed in rotation, then
It precipitates, filters in ether, vacuum drying obtains formula one, and (L1 isR1For)。
(L1 is formula oneR1For) the preparation method is as follows: being reacted by ethylene glycol with 2- bromine isobutyl acylbromide
The two-way ATRP initiator of the dihydroxy adamantine base prepared, by the two-way ATRP initiator of dihydroxy adamantine base (0.127g,
0.35mmol), n-isopropyl acrylamide (8g, 70mmol), Me6TREN (0.161g, 0.70mmol) and 20mL solvent (VDMF:
VWater=80:20) it is added in anhydrous and oxygen-free bottle.Under stirring, vacuumize-inflated with nitrogen three times, under nitrogen protection, rapidly join
CuBr (0.1g, 0.70mmol), then vacuumize-inflated with nitrogen three times, under nitrogen protection, react at room temperature 2h.After reaction, add
Enter the dilution of 15ml tetrahydrofuran, and is exposed in air to terminate reaction.Silicagel column is crossed, cuprous bromide is removed.Revolving, will slightly produce
Product are added in a large amount of ice ether and precipitate, and the solid was filtered.Dissolution-precipitating-filtering 2-3 times is repeated to remove unreacted monomer, is obtained
To 60 DEG C of solid at be dried in vacuo 12h, obtain both arms Thermo-sensitive linear polymer.Azido reaction: the both arms temperature that will be obtained
Quick property linear polymer is dissolved in the DMF of 15ml, and the Sodium azide of 17 times of molar equivalents is added, is stirred to react for 24 hours at 60 DEG C.
After reaction, product being added in the bag filter of 3500Da and is dialysed 2 days, solvent is removed in rotation, and product is added in ether and is precipitated,
Solid is collected, 40 DEG C of dryings for 24 hours, obtain formula six.Click-reaction: with formula six: formula seven: ligand PMDETA: catalyst CuBr presses 1:
The molar ratio of 2.7:2:2 is reacted.Anhydrous and oxygen-free bottle is added in the DMF of formula six, formula seven, PMDETA and 20ml in the above ratio
In, vacuumize-inflated with nitrogen three times, under nitrogen protection be added CuBr after vacuumize-inflated with nitrogen three times, 60 DEG C under nitrogen protection
React 48h.After reaction, the dilution of 15ml tetrahydrofuran is added, and is exposed in air and stirs 1h to terminate reaction, crosses silica gel
Column removes cuprous bromide, and extra solvent is removed in rotation, and crude product is added in 3500Da bag filter and is dialysed 2 days, and solvent is removed in rotation, then
It precipitates, filters in ether, vacuum drying obtains formula one, and (L1 isR1For)。
(L1 is formula oneR1For) (L1 is He ShiyiR1For)
(L1 is for preparation method and formula oneR1For) (L1 is He ShiyiR1For) preparation side
Method is similar, and difference is that (L1 is by formula oneR1For) (L1 is He ShiyiR1For)
Ethylene glycol raw material used is substituted for 1,3- adamantane glycol.
Embodiment 4
The embodiment of the invention provides the preparation methods of formula two, the specific steps are as follows:
(its L2 is formula two) preparation route:
1, (its L2 is first preparation formula nineR2For), the four arm Thermo-sensitives that azido is contained in the end of formula nine are poly-
Close object；2, formula nine, which is reacted with formula eight (embodiment 1 is prepared) by click chemistry, is made formula two, the R of formula two2ForOr
Person, formula nine, which is reacted with formula seven (embodiment 1 is prepared) by click chemistry, is made formula two, the R of formula two2For
Wherein, (its L2 is for A, formula nine), using pentaerythrite as starting material method particularly includes: will be by Ji Wusi
Pure and mild 2- bromine isobutyl acylbromide prepares pentaerythrite base tetrabromo ATRP initiator, then pentaerythrite base tetrabromo ATRP by esterification
Initiator (0.129g, 0.175mmol), NIPAM (8g, 70mmol), Me6TREN (0.161g, 0.7mmol) and 20mL solvent
(VDMF:VWater=80:20) it is added separately in anhydrous and oxygen-free bottle, vacuumize-fill N2Three times.In N2CuBr is rapidly added under protection
(0.1g, 0.7mmol).Under stiring, vacuumize-fill N2Three times.In N2The reaction was continued under protection, and 2h adds 20ml after reaction
Tetrahydrofuran dilution, which is placed in air, stirs 2h.Copper ion is removed by silicagel column, revolving removes extra solvent.It will slightly produce
Product are instilled in ice ether with suitable concentration and are precipitated, and are filtered, are obtained white solid.It is unreacted to repeat the 2-3 removing of this step
N-isopropyl acrylamide monomer, then by product and sodium azide (NaN3: polymer >=20) it is mixed in molar ratio for 1:25,
48h is reacted at 60 DEG C in DMF solvent.Then will reaction solution be added 3500Da bag filter in dialyse 3 days, after product is added
It precipitates, filters in ether, obtaining formula nine, (L2 is).(its L2 is formula nine), with 1,3,5,7- tetrahydroxy adamantane
For starting material method particularly includes: prepare gold by esterification by 1,3,5,7- tetrahydroxy adamantane and 2- bromine isobutyl acylbromide
Rigid alkyl tetrabromo ATRP initiator, then by adamantyl tetrabromo ATRP initiator (0.2544g, 0.35mmol), NIPAM (16g,
140mmol), Me6TREN (0.325g, 1.4mmol) and 40mL solvent (VDMF:VWater=80:20) it is added separately to anhydrous and oxygen-free bottle
In, vacuumize-fill N2Three times.In N2CuBr (0.21g, 1.4mmol) is rapidly added under protection.Under stiring, vacuumize-fill N2
Three times.In N2The reaction was continued under protection, and 2h adds the dilution of 20ml tetrahydrofuran to be placed in air and stirs 2h after reaction.It is logical
It crosses silicagel column and removes copper ion, revolving removes extra solvent.Crude product is instilled in ice ether with suitable concentration and is precipitated, mistake
Filter, obtains white solid, repeats this step 2-3 time and removes unreacted n-isopropyl acrylamide monomer, then by product with
Sodium azide is 1:25 mixing in molar ratio, reacts 48h at 60 DEG C in DMF solvent.Then reaction solution is added 3500Da's
Dialyse 3 days in bag filter, after product is added in ether precipitate, filter, obtaining formula nine, (L2 is)。
B, (its L2 is formula twoR2For) preparation method: the formula nine that the above step A is obtained
(L2 is), formula seven, PMDETA and catalyst CuBr feed by the molar ratio of 1:4.5:4.5:4.5, by formula
Nine are dissolved in the anhydrous and oxygen-free reaction flask for having 15ml DMF, and formula seven and PMDETA are added in the anhydrous and oxygen-free bottle for having 20mlDMF,
Stirring, vacuumize-fill N2Gas is three times.In N2Under protection, CuBr is rapidly joined, is stirred, vacuumize-fill N2Three times.In N2Protection
Under, 65 DEG C of reaction temperature, reaction is for 24 hours.The THF dilution of 15ml is added after reaction, is placed in air and stirs 2h.Cross silica gel
Column removes CuBr, and revolving removes extra solvent, crude product is fitted into 3500Da bag filter the 48h that dialyses, every 6h changes a water.
Product is precipitated in ice ether, after filtration drying formula two (L2 isR2For), formula two
(L2 isR2For) preparation method and formula two (its L2 isR2For
) preparation method it is similar, difference is that (its L2 is by formula twoR2For) preparation method used in formula
Seven raw materials change formula eight into and are reacted.
Embodiment 5
The embodiment of the invention provides the preparation methods of formula three, the specific steps are as follows:
Three (R of formula4For) the preparation method is as follows: being passed through first by dipentaerythritol and 2- bromine isobutyl acylbromide
Esterification prepares dipentaerythritol base hexabromo ATRP initiator, by the hexabromo initiator (0.0667g, 0.058mmol),
NIPAM (4g, 35mmol), Me6TREN (0.080g, 0.35mmol) and 10mL solvent (VDMF:V water=80:20) are added to nothing
It is sufficiently dissolved in water anaerobic bottle.It vacuumizes-fills N2 three times, rapidly join CuBr (0.0504g, 0.35mmol) under N2 protection,
Vacuumize-fill N2Three times.In N2Continue to be stirred to react 2h under protection, the THF dilution of 15ml is added after reaction, is placed in sky
2h is stirred in gas, is crossed silicagel column and is removed cuprous bromide.Extra solvent is removed in rotation, and product is added in ice ether and is precipitated, and repeats 2-3
It is secondary sufficiently to remove unconverted monomer.60 DEG C of dryings for 24 hours, obtain six of end with bromine to filtered product in a vacuum drying oven
Arm star temperature sensing polymer.Six arm star temperature sensing polymers and sodium azide by prepared end with bromine are by 1:32's
Molar ratio is reacted 2 days at 60 DEG C in DMF.Solution after reaction, which is added in bag filter, dialyses, and every 4h changes a deionized water,
Dialysis 2 days.Product after dialysis, which is added in ice ether, to be precipitated, and is filtered, vacuum drying obtains formula ten.Click-reaction: by formula ten: formula
Eight: PMDETA:CuBr=1:6.5:6.5:6.5 molar ratio is reacted.Formula ten, formula eight, PMDETA are added in the above ratio
Enter in anhydrous and oxygen-free bottle, vacuumize-inflated with nitrogen three times, under nitrogen protection be added CuBr after, vacuumize-inflated with nitrogen three times.Instead
It should be reacted for 24 hours at 60 DEG C.After reaction plus THF dilutes, and is placed in air and stirs 2h.It crosses silicagel column and removes protobromide
Copper.Revolving removes excess of solvent, and crude product is added in bag filter and is dialysed 2 days, every 6h changes a deionized water.Then in ether
Middle precipitating, filtering, vacuum drying obtain formula three, wherein R4For
Three (R of formula4For) the preparation method is as follows: passing through ester by dipentaerythritol and 2- bromine isobutyl acylbromide first
Change reaction preparation dipentaerythritol base hexabromo ATRP initiator, by the hexabromo initiator (0.0667g, 0.058mmol), NIPAM
(4g, 35mmol), Me6TREN (0.080g, 0.35mmol) and 10mL solvent (VDMF:V water=80:20) are added to anhydrous and oxygen-free
It is sufficiently dissolved in bottle.It vacuumizes-fills N2 three times, rapidly join CuBr (0.0504g, 0.35mmol) under N2 protection, vacuumize-
Fill N2Three times.In N2Continue to be stirred to react 2h under protection, the THF dilution of 15ml is added after reaction, is placed in air and stirs
2h crosses silicagel column and removes cuprous bromide.Extra solvent is removed in rotation, and product is added in ice ether and is precipitated, and repeats 2-3 times with abundant
Remove unconverted monomer.60 DEG C of dryings for 24 hours, obtain six arm star temperature of the end with bromine to filtered product in a vacuum drying oven
Sensitive polymer.Six arm star temperature sensing polymers and sodium azide by prepared end with bromine exist by the molar ratio of 1:32
It is reacted 2 days at 60 DEG C in DMF.Solution after reaction, which is added in bag filter, dialyses, and every 4h changes a deionized water, dialyses 2 days.
Product after dialysis, which is added in ice ether, to be precipitated, and is filtered, vacuum drying obtains formula ten.Click-reaction: by formula ten: formula seven:
The molar ratio of PMDETA:CuBr=1:6.5:6.5:6.5 is reacted.Nothing is added in the above ratio in formula ten, formula seven, PMDETA
In water anaerobic bottle, vacuumize-inflated with nitrogen three times, under nitrogen protection be added CuBr after, vacuumize-inflated with nitrogen three times.Reaction exists
It is reacted for 24 hours at 60 DEG C.After reaction plus THF dilutes, and is placed in air and stirs 2h.It crosses silicagel column and removes cuprous bromide.Rotation
Excess of solvent is evaporated off, crude product is added in bag filter and is dialysed 2 days, every 6h changes a deionized water.Then it sinks in ether
It forms sediment, filtering, vacuum drying obtains formula three, wherein R4For
Embodiment 6
The embodiment of the present invention is six arm star temperature sensing polymers and formula three (R of the end with bromine prepared by embodiment 54For) verification test.
The characterization map of six arm star temperature sensing polymers (call polymer) of the end with bromine prepared by embodiment 5 is as schemed
Shown in 1, since the polymer molecular weight is larger, a hydrogen and b hydrogen proportion in structural formula are smaller, by hydrogen other in polymer
It influences, the position in nuclear magnetic spectrogram is very unintelligible.The electrophilic of c hydrogen and d hydrogen respectively by ester carbonyl group and amidocarbonylation is imitated
It should influence, to low field displacement, be overlapped at 2.1ppm.F hydrogen itself is located on tertiary carbon, and is influenced hair by connected amido
Raw low field displacement, is located at 3.9ppm.E hydrogen in polymer chain is located at 1.5-1.6ppm；Hydrogen at 1.0ppm is isopropyl
Hydrogen on middle methyl, i.e. g hydrogen.And according to the gpc analysis of polymer, polymer molecular weight Mn=11235, Mw=13115,
PDI=1.16 < 1.2, molecular weight distribution is relatively narrow, meets chain length requirement, therefore it is temperature sensitive to successfully synthesize six arm stars of the end with bromine
Property polymer.
Fig. 2 is three (R of formula4For) infrared spectrum before and after click-reaction, wherein the b of Fig. 2 is the infrared of formula ten
Spectrogram, the c of Fig. 2 are three (R of formula4For) infrared spectrum；Fig. 3 is three (R of formula4For) before click-reaction
GPC curve graph afterwards, wherein the b of Fig. 3 is the GPC curve graph of formula ten, and the c of Fig. 3 is three (R of formula4For) GPC it is bent
Line chart.From Fig. 2 and Fig. 3 it is found that the outer spectrogram of formula ten shows that formula ten is in 2116cm-1There is apparent azido characteristic peak at place.It clicks
After reaction, three (R of formula4For) infrared spectrum in 2116cm-1Azido characteristic peak disappears, therefore click chemistry reacts
Success carries out.In addition, can be seen that three (R of formula by the comparison of the GPC curve of Fig. 34For) molecular weight it is obvious
It is bigger than formula ten, illustrate that the adamantane group of big molal weight is successfully connected in the end of formula ten, and three (R of formula4For
) in other impurity are not present, therefore successfully synthesize three (R of formula4For)。
Embodiment 7
The embodiment of the invention provides formulas four, the preparation method of formula five and formula 15, the specific steps are as follows:
A, (its X is Br, R to formula four3For) the preparation method comprises the following steps: by formula 11 (8g, 70.1mmol), formula 12
(0.433g, 2.1mmol), formula 13 (0.1365g, 0.7mmol) Me6TREN (0.1613g, 0.7mmol) and 20mL solvent
(VDMF:VWater=80:20) it is added separately to sufficiently dissolve in anhydrous and oxygen-free bottle.Vacuumize-fill N2Three times, in N2Protection is lower quickly to be added
Enter CuBr (0.1018g, 0.7mmol), vacuumize-fill N2Three times.In N2Continue to be stirred to react 2h under protection, after reaction plus
The THF dilution for entering 15ml, is placed in air and stirs 2h, crosses silicagel column and removes cuprous bromide.Rotation remove extra solvent, then plus
Enter and precipitated in ice ether, repeats 2-3 times sufficiently to remove unconverted monomer.60 DEG C in a vacuum drying oven of filtered product
Drying for 24 hours, obtains formula four, X Br, R3ForIts chemical synthesis route is as follows:
Wherein, (its X is Br, R to formula four3For) preparation method and above-mentioned formula four (its X is Br, R3For)
Preparation method it is similar, difference is, formula 12 is replaced with formula 15.
(its X is Br, R to formula four3For) nitrine processing, specially formula four (X Br) and Azide can also be carried out
Sodium is reacted 2 days at 60 DEG C in DMF by the molar ratio of 1:10.Solution after reaction, which is added in bag filter, dialyses, and every 4h changes one
Secondary deionized water is dialysed 2 days.Product after dialysis, which is added in ice ether, to be precipitated, and is filtered, vacuum drying obtains (the X N of formula four3, R3
For)。
B, (its X is Br, R to formula five3For) the preparation method comprises the following steps: by formula 11 (8g, 70.1mmol), formula 12
(0.433g, 2.1mmol), formula 14 (0.126g, 0.35mmol), Me6TREN (0.1613g, 0.7mmol) and 20mL solvent
(VDMF:VWater=80:20) it is added separately to sufficiently dissolve in anhydrous and oxygen-free bottle.Vacuumize-fill N2Three times, in N2Protection is lower quickly to be added
Enter CuBr (0.1018g, 0.7mmol), vacuumize-fill N2Three times.In N2Continue to be stirred to react 2h under protection, after reaction plus
The THF dilution for entering 15ml, is placed in air and stirs 2h, crosses silicagel column and removes cuprous bromide.Rotation remove extra solvent, then plus
Enter and precipitated in ice ether, repeats 2-3 times sufficiently to remove unconverted monomer.60 DEG C in a vacuum drying oven of filtered product
Drying for 24 hours, obtains formula five (X Br, R3For), chemical synthesis route is as follows:
Wherein, (its X is Br, R to formula five3For) preparation method and above-mentioned formula five (its X is Br, R3For) preparation method it is similar, difference is, formula 12 is replaced with formula 15.
(its X is Br, R to formula five3For) nitrine processing, specially formula five (X Br) and Azide can also be carried out
Sodium is reacted 2 days at 60 DEG C in DMF by the molar ratio of 1:12.Solution after reaction, which is added in bag filter, dialyses, and every 4h changes one
Secondary deionized water is dialysed 2 days.Product after dialysis, which is added in ice ether, to be precipitated, and is filtered, vacuum drying obtains (the X N of formula five3, R3
For)。
C, formula 15 the preparation method comprises the following steps: mono- 6- ethylenediamine-beta-cyclodextrin (10g, 8.5mmol) is dissolved in 20ml's
In anhydrous DMF, 6ml anhydrous triethylamine is added and stirs, at 0 DEG C dropwise by acryloyl chloride (6ml, 42.5mmol)
It is added in mono- 6- ethylenediamine-beta-cyclodextrin solution, is reacted at room temperature for 24 hours after dripping.Precipitating obtains thick in a large amount of dehydrated alcohols
Product dissolves crude product and precipitating 2-3 times in acetone with a small amount of distilled water and is purified.
Embodiment 8
A kind of hydrogel is present embodiments provided, (L1 is the preparation method comprises the following steps: formula one is prepared in above embodimentsR1For), (L2 is formula twoR2For), three (R of formula4For) (its X is He Shisi
Br, R3For) be uniformly mixed and stand for (5 DEG C) at low temperature for the 2:2:1:1 aqueous solution for being made into 5wt% in molar ratio
Be warming up to 37 DEG C of formation gels after 1 day again, pictorial diagram of the gained hydrogel at 25 DEG C and 35 DEG C as shown in figure 4, Fig. 4 left side
Right side for material object of the gel at 35 DEG C, figure is pictorial diagram of the gel at 25 DEG C, and as seen from the figure, the present embodiment 8 is successfully made
The difference of standby hydrogel and its appearance transparence at different temperatures shows it with temperature sensitivity.
Embodiment 9
The present embodiment is the two-dimentional nuclear magnetic spectrum of the hydrogel of testing example 8, as shown in figure 5, cyclodextrin inner is thin
Water-bound, outside are hydrophilic-structure, and adamantane group has good complexing normal as a kind of benign fat-soluble structure, with cyclodextrin
Number.The H of cyclodextrin inner3And H5Be easy with include cyclodextrin inner fat-soluble group on hydrogen couple.In cyclodextrin
The H in portion3And H5It appears between 3.6-4.0ppm, the hydrogen on adamantane group appears between 1.5-2.2ppm.The two dimension of Fig. 5
Occurs the Coupling point of adamantane and cyclodextrin in nuclear magnetic spectrogram, this proves that adamantane group has been embedded in the interior of cyclodextrin
Chamber.
Comparative example 1
This comparative example provides the first comparative example, the preparation method comprises the following steps: formula one is prepared in above embodiments, (L1 isR1For) and after water mixed under conditions of same embodiment 8, pictorial diagram as shown in fig. 6, figure left side
For 25 DEG C of material object, the right side of figure is 35 DEG C of material object, at two temperatures not formed gel.
Comparative example 2
This comparative example provides second of comparative example, the preparation method comprises the following steps: formula two is prepared in above embodiments, (L1 isR2For) and after water mixed under conditions of same embodiment 8, pictorial diagram as shown in fig. 7, figure left side
For 25 DEG C of material object, the right side of figure is 35 DEG C of material object, at two temperatures not formed gel.
Comparative example 3
This comparative example provides the third comparative example, the preparation method comprises the following steps: three (R of formula is prepared in above embodiments4For) and after water mixed under conditions of same embodiment 8, pictorial diagram is as shown in figure 8, the left side of figure is 25 DEG C
Material object, the material object that the right side of figure is 35 DEG C, not formed gel at two temperatures.
Embodiment 10
The present embodiment is the Volume-phase transition temperature of the hydrogel of testing example 8, and steps are as follows: will fill in embodiment 8
The hydrogel sample of swelling is divided to carry out dsc analysis, temperature elevating range is 5-45 DEG C, and in 5 DEG C of stop 10min, heating rate 3
DEG C/min, dry nitrogen atmosphere, the peak value for the DSC curve surveyed be corresponding hydrogel Volume-phase transition temperature (VPTT,
Volume phase transition temperature), as shown in figure 9, the Volume-phase transition temperature of the hydrogel of embodiment 8
Spending (VPTT) is 31.95 DEG C.
Embodiment 11
The present embodiment is the self-reparing capability of the hydrogel of testing example 8, and as shown in Figure 10, the A-F of Figure 10 is in 3 water
Gel self-repair procedure, A are pictorial diagram of the hydrogel at 40 DEG C, and B is the pictorial diagram of hydrogel cutting, and C is to cut to hydrogel
The pictorial diagram of crack size, D are the pictorial diagram of dropwise addition water after the cutting of hydrogel room temperature, and E is hydrogel after 20 DEG C of selfreparing 2h
Pictorial diagram, F is that hydrogel is heated to 40 DEG C of pictorial diagram.It can be seen that hydrogel has self-reparing capability at normal temperature, it is real
The hydrogel for applying the preparation of example 6 has the function of the big Crack Self of the macroscopic view of Thermo-sensitive auxiliary.
Embodiment 12
Second of hydrogel is present embodiments provided, (L1 is the preparation method comprises the following steps: formula one is prepared in above embodimentsR1For), (L2 is formula twoR2For), three (R of formula4For) (its X is He Shisi
Br, R3For) being made into the aqueous solution of 10wt% in molar ratio for 3:3:1:2, (5 DEG C) after mixing simultaneously at low temperature
It is further taken out after standing 1 day and is heated to form hydrogel at 35 DEG C.The hydrogel of the present embodiment has Thermo-sensitive and self-repair function,
And the selfreparing of the big crackle of the macroscopic view for not having to be bonded manually may be implemented by the remote control of temperature.
Embodiment 13
The third hydrogel is present embodiments provided, (L1 is the preparation method comprises the following steps: formula one is prepared in above embodimentsR1For), (L2 is formula twoR2For), three (R of formula4For) He Shisi (its
X is Br, R3For) being made into the aqueous solution of 15wt% in molar ratio for 4:2:1:2, (4 DEG C) after mixing simultaneously at low temperature
It is further taken out after standing 1 day and is thermally formed hydrogel in 40 DEG C.Measure the Thermo-sensitive and self-healing properties of the present embodiment hydrogel.It is real
It tests and shows that the hydrogel of the present embodiment has Thermo-sensitive and self-repair function, and can be realized and not had to by the remote control of temperature
The selfreparing of the big crackle of the macroscopic view being bonded manually.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of supramolecular materials, which is characterized in that including the first construction unit, secondary building units, third construction unit and
4th construction unit；
Wherein, first construction unit has one structure of formula:
Wherein, R1It is selected from One or both of, L1 is
The secondary building units have two structure of formula:
Wherein, R2It is selected from One or both of, L2 is
The third construction unit has three structure of formula:
Wherein, R4It is selected fromOne or both of；
4th construction unit includes polymer shown in polymer shown in formula four or/and formula five:
Wherein, X is selected from Br or N3；R3It is selected from
First construction unit, secondary building units, third construction unit and the 4th construction unit are based on adamantane-cyclodextrin
Subjective and Objective self assembly connects to form supramolecular materials.
2. supramolecular materials according to claim 1, which is characterized in that in formula one, the y is the integer of 50-100；Formula two
In, the z is the integer of 50-100；In formula three, the w is the integer of 50-100；Shown in polymer shown in formula four and formula five
Polymer in, the m be 50-100 integer；The n is the integer of 0.5-10.
3. supramolecular materials according to claim 1, which is characterized in that described in formula oneContain beta-cyclodextrin.
4. supramolecular materials according to claim 1, which is characterized in that the formula one the preparation method comprises the following steps: by formula six and formula
Seven carry out click-reactions, or formula six and formula eight are carried out click-reaction, and formula one is made, wherein formula six, formula seven and formula eight it is specific
Structure is as follows:
Wherein, L1 is
The formula two the preparation method comprises the following steps: formula nine and formula seven are carried out click-reaction, or formula nine and formula eight or eight click anti-
It answers, formula two is made, wherein the specific structure of formula nine, formula seven and formula eight is as follows:
Wherein, L2 is
The formula three the preparation method comprises the following steps: formula ten and formula six are carried out click-reaction, or formula five and formula seven are subjected to click-reaction,
Formula three is made, wherein the specific structure of formula five, formula six and formula seven is as follows:
5. supramolecular materials according to claim 1, which is characterized in that the formula four the preparation method comprises the following steps: by formula 11, formula
12 and formula 13 reacted to obtain, the X of the formula four is Br, R3ForWherein, the formula 11, the formula 12
It is as follows with the specific structure of the formula 13:
The formula five the preparation method comprises the following steps: formula 11, formula 12 and formula 14 are reacted to obtain, the X of the formula five is Br,
R3ForWherein, the specific structure of the formula 11, the formula 12 and the formula 14 is as follows:
6. supramolecular materials according to claim 1, which is characterized in that the formula four the preparation method comprises the following steps: by formula 11, formula
15 and formula 13 reacted to obtain, the X of the formula four is Br, R3ForWherein, the formula 11, the formula ten
Five and the formula 13 specific structure it is as follows:
The formula five the preparation method comprises the following steps: formula 11, formula 15 and formula 14 are reacted to obtain, the X of the formula five is Br,
R3For
Wherein, the specific structure of the formula 11, the formula 15 and the formula 14 is as follows:
7. a kind of hydrogel, which is characterized in that preparation method the following steps are included:
By first construction unit, the secondary building units, the third construction unit and the 4th construction unit and
Water mixing, constructs list by first construction unit, the secondary building units, the third construction unit and the described 4th
Adamantane-cyclodextrin Subjective and Objective of member dissolves mixing under the conditions of 4-20 DEG C and carries out self assembly, is heated at 35-50 DEG C and is formed
Hydrogel, wherein first construction unit has one structure of formula, and the secondary building units have two structure of formula, and described the
Three construction units have three structure of formula, and the 4th construction unit includes gathering shown in polymer shown in formula four or/and formula five
Close object.
8. hydrogel according to claim 7, which is characterized in that the Volume-phase transition temperature of the hydrogel is 20-35
℃。
9. hydrogel according to claim 7, which is characterized in that mole of the formula one, the formula two and the formula three
The sum of, the molar ratio with the 4th construction unit is 1:(0.1-10).
10. the preparation method of hydrogel according to claim 7, which is characterized in that the formula one, the formula two, described
The mass concentration that formula three and the 4th construction unit mix in aqueous solution is 5-25wt%.
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