CN109721738A - Supramolecular materials, self-healing temperature-sensitive hydrogel and preparation method thereof - Google Patents
Supramolecular materials, self-healing temperature-sensitive hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical fields of supramolecular chemistry more particularly to supramolecular materials, self-healing temperature-sensitive hydrogel and preparation method thereof.The present invention includes the first construction unit, secondary building units and third construction unit, and the first construction unit, secondary building units and third construction unit are based on adamantane-cyclodextrin Subjective and Objective self assembly and connect to form supramolecular materials.The present invention also provides a kind of hydrogels, the following steps are included: the first construction unit, secondary building units, third construction unit and water are mixed, mixing is dissolved under the conditions of 4-20 DEG C by adamantane-cyclodextrin Subjective and Objective of the first construction unit, secondary building units and third construction unit and carries out self assembly, is heated at 35-50 DEG C and is formed hydrogel.Hydrogel of the invention 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 supramolecular materials, self-healing temperature-sensitive hydrogel
And preparation method thereof.
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.,HaradaA.,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 and third to construct list
Member；
Wherein, first construction unit has one structure of formula:
Formula one, wherein R1It is selected from
WithOne or both of；
The secondary building units have two structure of formula:
Formula two, wherein R2It is selected fromWith
One or both of, L isOr
The third construction unit includes four structure of three structure of formula or/and formula:
Formula three, wherein X is selected from Br or N3；R3Choosing
FromOr
Formula four, wherein X is selected from Br or N3；R3It is selected fromOr
First construction unit, the secondary building units and the third construction unit are based on adamantane-cyclodextrin
Subjective and Objective self assembly connects to form supramolecular materials.
It is connect it should be noted that formula one, formula two are based on adamantane-cyclodextrin Subjective and Objective self assembly with three structure three of formula
Supramolecular materials are formed, is also possible to formula one, formula two and four structure three of formula and is based on adamantane-cyclodextrin Subjective and Objective self assembly
Connection forms supramolecular materials, is also possible to formula one, formula two, formula three and four structure of formula 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 three3；R3For
Most preferably, in formula three, X Br；R3For
It is furthermore preferred that X is Br or N in formula four3；R3For
Most preferably, in formula four, X Br；R3For
Preferably, in formula three and formula four, it is describedContain alpha-cyclodextrin, beta-cyclodextrin group or γ-ring paste
Smart group.
It is furthermore preferred that in formula three and formula four, 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；Three He of formula
In formula four, the m is the integer of 50-100；The n is the integer of 0.5-10.
Preferably, the formula one the preparation method comprises the following steps: formula five and formula six are carried out click-reaction, or by formula five and formula seven
Click-reaction is carried out, formula one is made, wherein the specific structure of formula five, formula six and formula seven is as follows:
Formula five,Formula six；Formula seven；
The formula two the preparation method comprises the following steps: formula eight and formula six are carried out click-reaction, or formula eight and formula seven are clicked
Formula two is made, wherein the specific structure of formula eight, formula six and formula seven is as follows in reaction:
Formula eight, wherein L isOr Formula six；Formula seven.
Specifically, the preparation method of formula one, using dipentaerythritol as raw material, preparation route is as follows:
Wherein, specifically, formula one the preparation method is as follows: passing through esterification by dipentaerythritol and 2- bromine isobutyl acylbromide
Dipentaerythritol base hexabromo ATRP initiator is prepared, 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 polymerize
The bromine of object end is substituted by nitrine (- N3) after, obtain formula five.Finally, formula five and six compound of formula, which are carried out click-reaction, obtains formula
One, wherein R1ForFormula five and seven compound of formula are subjected to click-reaction and obtain formula one, wherein R1For
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 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 one of property.
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 fromWithOne or both of, L isOrReaction route such as
Under:
Wherein, (L 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, obtaining formula eight, (L is), formula eight and formula six (or formula eight and formula seven) carry out click-reaction, and obtaining formula two, (L is), wherein point
Reaction is hit as (L is by formula eight): formula six (or formula seven): ligand PMDETA: catalyst cuprous bromide presses 1:(4~6):
(4~8): the molar ratio of (4~8) is reacted, rear to cross neutral alumina column, then is dialysed, and obtained product is sunk in ice ether
It forms sediment dry after filtering, obtaining formula two, (L is), wherein if adding type six in click-reaction, the R of formula two2For containing cyclodextrin
Residue, L isIf adding type seven in click-reaction, the R of formula two2For the residue containing adamantane, L is
(L is formula two), with 1,3,5,7- tetrahydroxy adamantane for starting material method particularly includes: will be by
1,3,5,7- tetrahydroxy adamantane and the bromo- isobutyl acylbromide of 2- prepare adamantyl tetrabromo ATRP initiator by esterification, then
Adamantyl tetrabromo ATRP initiator and n-isopropyl acrylamide (NIPAM) are subjected to ATRP polymerization, four of end with bromine are made
Arm star temperature sensing polymer, then the bromine of the end of the four arm star temperature sensing polymers by end with bromine be substituted by nitrine (-
N3) after, obtaining formula eight, (L is), (L is formula eight) clicked with formula six (or formula eight and formula seven)
Reaction obtains formula two, and (L is), wherein click-reaction is that (L is by formula eight): formula six (or formula
Seven): ligand PMDETA: catalyst cuprous bromide is by 1:(4~6): (4~8): the molar ratio of (4~8) is reacted, after excessively in
Property alumina column, then dialyse, obtained product precipitated in ice ether dry after filtering, obtaining formula two, (L is),
Wherein, if adding type six, the R of formula two in click-reaction2For the residue containing cyclodextrin, L isIf adding type seven
Compound, the then R of formula two2Containing the residue for adamantane, L is
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.
Specifically, the formula six 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 six.
Specifically, the formula six 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 six.For example following chemical equations of the preparation process of formula six:
Wherein, the crude product of formula six 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, six yield of formula is 95%.
Wherein, it is 42-60% that the preparation method of formula six, which obtains the yield of formula six,.
Wherein, in the preparation method of above formula six, 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.
Specifically, the formula seven 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 seven, seven property of formula is colorless viscous shape liquid.Formula
For example following chemical equations of seven preparation process:
Wherein, in the preparation method of above formula seven, 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.
Preferably, the formula three the preparation method comprises the following steps: formula nine, formula ten and formula 11 are reacted to obtain, the formula
Three X is Br, R3For
Wherein, the specific structure of the formula nine, the formula ten and the formula 11 is as follows:
Formula nine；Formula ten；Formula 11.
Preferably, the formula four the preparation method comprises the following steps: formula nine, formula ten and formula 12 are reacted to obtain, the formula
Four X is Br, R3For
Wherein, the specific structure of the formula nine, the formula ten and the formula 12 is as follows:
Formula nine；Formula ten；Formula 12.
Preferably, the formula three the preparation method comprises the following steps: formula nine, formula 13 and formula 11 are reacted to obtain, it is described
The X of formula three is Br, R3For
Wherein, the specific structure of the formula nine, the formula 13 and the formula 11 is as follows:
Formula nine；Formula 13；Formula 11.
Preferably, the formula four the preparation method comprises the following steps: formula nine, formula 13 and formula 12 are reacted to obtain, it is described
The X of formula four is Br, R3For
Wherein, the specific structure of the formula nine, the formula 13 and the formula 12 is as follows:
Formula nine；Formula 13；Formula 12.
It should be noted that the formula one, described two, the formula three and the formula are fourth is that poly- by atom transferred free radical
It closes ATRP to react to obtain, using low-valent transition metals halide as catalyst, with halogenated alkyl hydrocarbon (R-X) for initiator, electronics is given
Body 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 13 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 self-healing temperature-sensitive hydrogel, preparation method the following steps are included:
First construction unit, the secondary building units, the third construction unit and water are mixed, by described
The adamantane of first construction unit, the secondary building units and the third construction unit-cyclodextrin Subjective and Objective is at 4-20 DEG C
Under the conditions of dissolution mixing carry out self assembly, be heated at 35-50 DEG C formation self-healing temperature-sensitive hydrogel, wherein described the
One construction unit has one structure of formula, and the secondary building units have two structure of formula, and the third construction unit includes formula three
Four structure of structure or/and formula.
It connect and to be formed it should be noted that formula one, formula two are based on adamantane-cyclodextrin Subjective and Objective self assembly with formula three and water
Self-healing temperature-sensitive hydrogel, is also possible to formula one, formula two and formula four and water is based on adamantane-cyclodextrin Subjective and Objective self assembly
Connection forms self-healing temperature-sensitive hydrogel, is also possible to formula one, formula two, formula three and formula four and water is based on adamantane-cyclodextrin
Subjective and Objective self assembly connects to form self-healing temperature-sensitive hydrogel.The present invention is acted on using Subjective and Objective self assembly, by formula one, formula two
It carries out Subjective and Objective in aqueous solution with third construction unit and is self-assembly of self-healing temperature-sensitive hydrogel, by testing and observing
Show that self-healing temperature-sensitive hydrogel of the invention has Thermo-sensitive and self-healing properties, and by playing Thermo-sensitive and reviewing one's lessons by oneself
The big Crack Self for not having to be bonded manually may be implemented in multiple synergistic function.
Wherein, the preparation method of the self-healing temperature-sensitive hydrogel, comprising the following steps: under cryogenic, by
One construction unit, secondary building units and third construction unit dissolve in water, in the promotion of mild heat after static a few hours
Lower formation self-healing temperature-sensitive hydrogel；Can also be prepared by following steps: by the first construction unit, secondary building units and
Third construction unit dissolves in tetrahydrofuran, then obtains self-healing temperature-sensitive hydrogel after dialysing in water.
Preferably, the Volume-phase transition temperature of the self-healing temperature-sensitive hydrogel is 20-35 DEG C.
Preferably, the sum of mole of the formula one and formula two, with the third construction unit mole ratio be 1:
(0.4-6)。
Preferably, the formula one, the mixing quality concentration of the formula two and the third construction unit in aqueous solution
For 5-25wt%.
The invention regard formula one and formula two as " crosslinking agent ", and side chain is contained adamantane or/and Beta-cyclodextrin-based
The polymer (formula three or/and formula four) of group forms self-healing temperature-sensitive hydrogel by way of Subjective and Objective self assembly, due to formula
Containing containing there are six the end of cyclodextrin or/and adamantane group, formula two, there are four cyclodextrin or/and adamantyls for one end
Group, easily on the side chain of formula three or/and formula four adamantane or Cyclodextrin groups carry out Subjective and Objective assembling.Therefore, of the invention
It is super based on adamantane-cyclodextrin Subjective and Objective self assembly by the first construction unit, secondary building units and third construction unit
Molecular physics are crosslinked and form gel network, due to being uniformly distributed the Subjective and Objective based on adamantane and cyclodextrin in gel network
The physical crosslinking point of self assembly, can first disconnect when being destroyed by external force, and can weigh when section both ends contact with each other
It is newly assembled together, to assign self-healing temperature-sensitive hydrogel of the invention excellent self-repair function.In addition, the present invention utilizes
Formula one, formula two and secondary building units have temperature sensitive characteristic, and the expansion or receipts of volume occur for the variation that can respond temperature
Self-healing Thermo-sensitive water may be implemented by wet and reduction temperature after self-healing temperature-sensitive hydrogel generates big crackle in contracting
The volume expansion of gel is to reduce crack spacing, therefore, self-healing temperature-sensitive hydrogel that can be of the invention by temperature remote control
Big crack spacing, to realize the selfreparing for the big crackle of 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 3 provided by the invention
Spectrum；
Fig. 2 is the infrared spectrum (b) of formula eight prepared by embodiment 5 provided by the invention and formula two prepared by embodiment 3
(R1For) infrared spectrum (c)；
Fig. 3 is prepared by the GPC curve graph (b) of the formula eight of preparation prepared by embodiment 5 provided by the invention and embodiment 3
Two (R of formula1For) GPC curve graph (c)；
Fig. 4 is the pictorial diagram of the self-healing temperature-sensitive hydrogel of embodiment 7 provided by the invention；
Fig. 5 is the two-dimentional nuclear magnetic spectrum of the self-healing temperature-sensitive hydrogel of embodiment 7 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 Volume-phase transition temperature map of the self-healing temperature-sensitive hydrogel of embodiment 7 provided by the invention；
Fig. 9 is the procedure chart of the selfreparing of the self-healing temperature-sensitive hydrogel of embodiment 7 provided by the invention, wherein A is
Pictorial diagram of the self-healing temperature-sensitive hydrogel at 40 DEG C, B are the pictorial diagram that crackle is cut to self-healing temperature-sensitive hydrogel, and C is
Self-healing temperature-sensitive hydrogel cuts flaw size figure, and D is the pictorial diagram of dropwise addition water after the cutting of self-healing temperature-sensitive hydrogel,
E is pictorial diagram of the self-healing temperature-sensitive hydrogel after 20 DEG C of selfreparing 2.5h, and F is after the selfreparing of self-healing temperature-sensitive hydrogel
Pictorial diagram.
Specific embodiment
The present invention provides supramolecular materials, self-healing temperature-sensitive hydrogel and preparation method thereof, hydrogels of the invention
It solves that structure existing for conventional hydrogels is mixed and disorderly, non-adjustable, the technological deficiency of macroscopical big crackle cannot be automatically repaired.
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 six and formula seven, the specific steps are as follows:
Formula six 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 six 9.5g of formula, and the yield of formula six is 95%.
Preparing for formula seven 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 seven, formula seven is colorless viscous shape liquid.
Embodiment 2
The characterization detection that formula six and formula seven to embodiment 1 carry out, as a result as follows:
Formula six:
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 seven:
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:
One (R of formula1For) 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:VWater=80:20) it is added to anhydrous and oxygen-free bottle
In sufficiently dissolve.Vacuumize-fill N2Three times, in N2CuBr (0.0504g, 0.35mmol) is rapidly joined under protection, is vacuumized-is filled
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 five.Click-reaction: by formula five: 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 five, 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 one, wherein R1For
One (R of formula1For) 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:VWater=80:20) it is added to anhydrous and oxygen-free bottle
In sufficiently dissolve.Vacuumize-fill N2Three times, in N2Rapidly joined under protection CuBr (0.0504g, 0.35mmol) vacuumize-fill N2
Three times.In N2Continue to be stirred to react 2h under protection, the THF dilution of 15ml be added after reaction, is placed in air and stirs 2h,
It crosses silicagel column and removes cuprous bromide.Product is added in ice ether and is precipitated, repeats 2-3 times sufficiently to remove unconverted monomer.
60 DEG C of dryings for 24 hours, obtain six arm star temperature sensing polymers of the end with bromine to filtered product in a vacuum drying oven.It will be made
Six arm star temperature sensing polymers of the standby end with bromine and sodium azide are reacted at 60 DEG C in DMF by the molar ratio of 1:32
2 days.Solution after reaction is dialysed 2 days.Product after dialysis, which is added in ice ether, to be precipitated, and is filtered, vacuum drying obtains formula five.Point
It hits reaction: formula five: the molar ratio of formula six: PMDETA:CuBr=1:6.5:6.5:6.5 is reacted.By formula five, formula six,
PMDETA in the above ratio be added anhydrous and oxygen-free bottle in, vacuumize-inflated with nitrogen three times, under nitrogen protection be added CuBr after, take out
Vacuum-inflated with nitrogen is three times.Reaction 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 removes cuprous bromide.Revolving removes excess of solvent, and crude product is added in bag filter and is dialysed 2 days.Then in ether
Precipitating, filtering, vacuum drying obtain formula one, wherein R1For
Embodiment 4
The embodiment of the present invention is six arm star temperature sensing polymers and formula one (R of the end with bromine prepared by embodiment 31For) carry out click-reaction before and after verification test.
The characterization maps of six arm temperature sensing polymers (call polymer) of the end with bromine as shown in Figure 1, from fig. 1, it can be seen that
Since the polymer molecular weight is larger, a hydrogen and b hydrogen proportion in structural formula are smaller, are influenced by hydrogen other in polymer,
Position in nuclear magnetic spectrogram is very unintelligible.The sucting electronic effect of c hydrogen and d hydrogen respectively by ester carbonyl group and amidocarbonylation is influenced,
To low field displacement, it is overlapped at 2.1ppm.F hydrogen itself is located on tertiary carbon, and is influenced that low field occurs by connected amido
Displacement is located at 3.9ppm.E hydrogen in polymer chain is located at 1.5-1.6ppm；Hydrogen at 1.0ppm is methyl in isopropyl
On hydrogen, 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 successfully synthesizes six arm star Thermo-sensitives polymerization of the end with bromine
Object.
Embodiment 5
The embodiment of the invention provides the preparation methods of formula two, the specific steps are as follows:
(its L is formula twoOr) preparation route:
A, (its L is first preparation formula eightR2For), four arm temperature of azido are contained in the end of formula eight
Sensitive polymer is reacted by click chemistry with formula seven (embodiment 1 is prepared) by formula eight and formula two, the R of formula two is made2For(its L is formula eightR2For), the four arm Thermo-sensitives that azido is contained in the end of formula eight are poly-
Object is closed, is reacted with formula six (embodiment 1 is prepared) by click chemistry by formula eight and formula two, the R of formula two is made2For
Wherein, (its L is formula eight), using pentaerythrite as starting material method particularly includes: will be by pentaerythrite
Pentaerythrite base tetrabromo ATRP initiator is prepared by esterification with 2- bromine isobutyl acylbromide, then by pentaerythrite base tetrabromo ATRP
Initiator (0.129g, 0.175mmol), NIPAM (8g, 70mmol), Me6TREN (0.161g, 0.7mmol) and 20mL solvent
(VDMF:VWater=80:20) it is added in anhydrous and oxygen-free bottle, vacuumize-fill N2Three times.In N2Be rapidly added under protection CuBr (0.1g,
0.7mmol).Under stiring, vacuumize-fill N2Three times.In N2The reaction was continued under protection, and 2h adds 20ml tetrahydro furan after reaction
Dilution of muttering, which is placed in air, stirs 2h.Catalyst is removed by silicagel column.Crude product is instilled into ice ether with suitable concentration
Middle precipitating, filtering, obtains white solid.It repeats this step 2-3 times and removes unreacted 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 will product be added ether in precipitate, filtering, obtain formula eight
(L is).(its L is formula eight), it take 1,3,5,7- tetrahydroxy adamantane as the specific method of starting material
Are as follows: adamantyl tetrabromo ATRP is prepared by esterification by 1,3,5,7- tetrahydroxy adamantane and 2- bromine isobutyl acylbromide and is caused
Agent, 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 in anhydrous and oxygen-free bottle, vacuumize-fill N2Three times.
In N2CuBr (0.21g, 1.4mmol) is rapidly added under protection.Under stiring, vacuumize-fill N2Three times.In N2Protection is lower to be continued
2h is reacted, after reaction, adds the dilution of 20ml tetrahydrofuran to be placed in air and stirs 2h.Catalyst is removed by silicagel column.
Crude product is instilled in ice ether with suitable concentration and is precipitated, is filtered, white solid is obtained, this step 2-3 times is repeated and removes not
Then product and sodium azide are that 1:25 is mixed, in DMF solvent by the n-isopropyl acrylamide monomer of reaction in molar ratio
48h is reacted at 60 DEG C.Then reaction solution is dialysed 3 days, after product is added in ether precipitate, filter, obtaining formula eight, (L is)。
B, (its L is formula twoOrR2For) preparation method: the above step A is obtained
To formula eight (L isOr), formula six, PMDETA and catalyst CuBr press mole of 1:4.5:4.5:4.5
Than feeding, formula eight is dissolved in the anhydrous and oxygen-free reaction flask for having 15ml DMF, formula six and PMDETA addition are had into 20mlDMF
Anhydrous and oxygen-free bottle in, stirring vacuumizes-fill N2Gas is three times.In N2Under protection, CuBr is rapidly joined, is stirred, vacuumize-fill N2
Three times.In N2Under protection, 65 DEG C of reaction temperature, reaction is for 24 hours.The THF dilution of 15ml is added after reaction, is placed in air
Stir 2h.It crosses silicagel column and removes CuBr, revolving removes extra solvent, and crude product is dialysed 48h.Product is sunk in ice ether
Form sediment, after filtration drying formula two (L isOrR2For), R2For cyclodextrin residue, formula two
(L isOrR2For) preparation method and formula two (its L isOr
R2For) preparation method it is similar, difference is that (its L is formula twoOrR2For)
Preparation method used in six raw material of formula change formula seven into and reacted.
Fig. 2 is two (R of formula1For) infrared spectrum before and after click-reaction, wherein the b of Fig. 2 is the infrared of formula eight
Spectrogram, the c of Fig. 2 are two (R of formula1For) infrared spectrum；Fig. 3 is two (R of formula1For) before click-reaction
GPC curve graph afterwards, wherein the b of Fig. 3 is the GPC curve graph of formula eight, and the c of Fig. 3 is two (R of formula1For) GPC it is bent
Line chart.From Fig. 2 and Fig. 3 it is found that the outer spectrogram of formula eight shows that formula eight is in 2116cm-1There is apparent azido characteristic peak at place.It clicks
After reaction, two (R of formula1For) infrared spectrum in 2116cm-1Azido characteristic peak disappears, therefore click chemistry reacts
Success carries out.In addition, can be seen that two (R of formula by the comparison of the GPC curve of Fig. 31For) molecular weight obviously compare
Formula five is big, illustrates that the adamantane group of big molal weight is successfully connected in the end of formula eight, and two (R of formula1For)
In other impurity are not present, therefore successfully synthesize two (R of formula1For)。
Embodiment 6
The embodiment of the invention provides formulas three, the preparation method of formula four and formula 13, the specific steps are as follows:
A, (its X is Br, R to formula three3For) the preparation method comprises the following steps: by formula nine (8g, 70.1mmol), formula ten
(0.433g, 2.1mmol), formula 11 (0.1365g, 0.7mmol), Me6TREN (0.1613g, 0.7mmol) and 20mL solvent
(VDMF:VWater=80:20) it is added in anhydrous and oxygen-free bottle and sufficiently dissolves.Vacuumize-fill N2Three times, in N2It is rapidly joined under protection
CuBr (0.1018g, 0.7mmol), vacuumize-fill N2Three times.In N2Continue to be stirred to react 2h under protection, be added after reaction
The THF of 15ml dilutes, and is placed in air and stirs 2h, crosses silicagel column and removes cuprous bromide.Extra solvent is removed in rotation, is then added
It is precipitated in ice ether, repeats 2-3 times sufficiently to remove unconverted monomer.Filtered product is done for 60 DEG C in a vacuum drying oven
It is dry for 24 hours, obtain formula three, X Br, R3ForIts chemical synthesis route is as follows:
Wherein, (its X is Br, R to formula three3For) preparation method and formula three (its X be Br, R3For) preparation
Method is similar, and difference is, formula ten is replaced with formula 13.
Formula three (its X is Br) can also carry out nitrine processing, specially formula three (X Br) and sodium azide rubbing by 1:10
You react 2 days at 60 DEG C at ratio in DMF.Solution after reaction, which is added in bag filter, dialyses, and every 4h changes a deionized water, thoroughly
Analysis 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 three3)。
B, (its X is Br, R to formula four3For) the preparation method comprises the following steps: by formula nine (8g, 70.1mmol), formula ten (0.433g,
2.1mmol), formula 12 (0.126g, 0.35mmol), Me6TREN (0.1613g, 0.7mmol) and 20mL solvent (VDMF:VWater=
It 80:20) is added in anhydrous and oxygen-free bottle and sufficiently dissolves.Vacuumize-fill N2Three times, in N2CuBr is rapidly joined under protection
(0.1018g, 0.7mmol), vacuumize-fill N2Three times.In N2Continue to be stirred to react 2h under protection, 15ml is added after reaction
THF dilution, be placed in air and stir 2h, cross silicagel column remove cuprous bromide.Extra solvent is removed in rotation, and ice second is then added
It is precipitated in ether, repeats 2-3 times sufficiently to remove unconverted monomer.The 60 DEG C of dryings in a vacuum drying oven of filtered product
For 24 hours, formula four (X Br, R are obtained3For), chemical synthesis route is as follows:
Wherein, (its X is Br, R to formula four3For) preparation method and formula four (its X be Br, R3For)
Preparation method is similar, and difference is, formula ten is replaced with formula 13.
Formula four (its X is Br) can also carry out nitrine processing, specially formula four (X Br) and sodium azide rubbing by 1:12
You react 2 days at 60 DEG C at ratio in DMF.Solution after reaction, which is added in bag filter, dialyses, and every 4h changes a deionized water, thoroughly
Analysis 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)。
C, formula 13 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 7
A kind of self-healing temperature-sensitive hydrogel is present embodiments provided, the preparation method comprises the following steps: above embodiments are prepared
One (R of formula1For), (L is formula twoR2For) (its X is Br, R to He Shisan3For)
The aqueous solution of 15wt% is made into molar ratio for 1:3:1 to be uniformly mixed at low temperature and be warming up to 37 DEG C again after standing 1 day for (5 DEG C)
Self-healing temperature-sensitive hydrogel is formed, gained self-healing temperature-sensitive hydrogel is separately stored in the pictorial diagram at 25 DEG C and 35 DEG C such as
Shown in Fig. 4, the left side of Fig. 4 is material object of the self-healing temperature-sensitive hydrogel at 25 DEG C, and the right side of figure is self-healing Thermo-sensitive water
Pictorial diagram of the gel at 35 DEG C, as seen from the figure, the present embodiment 7 be successfully prepared self-healing temperature-sensitive hydrogel and its not
The difference of synthermal lower appearance transparence shows it with temperature sensitivity.
Embodiment 8
The present embodiment is the two-dimentional nuclear magnetic spectrum of the self-healing temperature-sensitive hydrogel of testing example 7, as shown in figure 5, ring
It is hydrophobic structure inside dextrin, outside is hydrophilic-structure, and adamantane group has as a kind of benign fat-soluble structure with cyclodextrin
Good complexation constant.The H of cyclodextrin inner3And H5Hydrogen on adamantane group that is easy and including cyclodextrin inner occurs
Coupling.The H of cyclodextrin inner3And H5Appear between 3.6-4.0ppm, the hydrogen on adamantane group appear in 1.5-2.2ppm it
Between.Occurs the Coupling point of adamantane and cyclodextrin in the two-dimentional nuclear magnetic spectrogram of Fig. 2, this proves that adamantane group has been embedded in
The inner cavity of cyclodextrin.
Comparative example 1
This comparative example provides the first comparative example, the preparation method comprises the following steps: one (R of formula is prepared in above embodiments1For), (L is formula twoR2For) (its X is Br, R to He Shisan3For) by 1:3:1's
Molar ratio carries out after evenly mixing under conditions of same embodiment 7, and pictorial diagram is as shown in fig. 6, the reality that the left side of figure is 25 DEG C
Object, the right side of figure are 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: above embodiments 3 to embodiment 5 are prepared
One (R of formula1For), (L is formula twoR2For) (its X is Br, R to He Shisan3For) press
The molar ratio of 1:3:1 carries out after evenly mixing under conditions of same embodiment 5, and pictorial diagram is as shown in fig. 7, 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 9
The present embodiment is the Volume-phase transition temperature of the self-healing temperature-sensitive hydrogel of testing example 7, and steps are as follows: will
The self-healing temperature-sensitive hydrogel sample being sufficiently swollen in embodiment 6 carries out dsc analysis, and temperature elevating range is 5-45 DEG C, and at 5 DEG C
10min is stopped, heating rate is 3 DEG C/min, and dry nitrogen atmosphere, the peak value for the DSC curve surveyed is that corresponding self-healing is temperature sensitive
The Volume-phase transition temperature (VPTT, volume phase transition temperature) of property hydrogel, as shown in figure 8,
The Volume-phase transition temperature (VPTT) of the self-healing temperature-sensitive hydrogel of embodiment 7 is 32.3 DEG C.
Embodiment 10
The present embodiment is the self-reparing capability of the self-healing temperature-sensitive hydrogel of testing example 7, as shown in figure 9, Fig. 9
A-F is the process of selfreparing after cutting gel-forming big crackle under the conditions of 40 DEG C, and hydrogel is in 40 DEG C of cutting crackles, after cutting
Water is added dropwise, then after 20 DEG C of selfreparing 2.5h, gel is returned to original state, it can be seen that, prepared self-healing is temperature sensitive
Property hydrogel have the function of the big Crack Self of macroscopic view of Thermo-sensitive auxiliary.
Embodiment 11
Second of self-healing temperature-sensitive hydrogel is present embodiments provided, the preparation method comprises the following steps: above embodiments are prepared
One (R of formula1For), (L is formula twoR2For) (its X is Br, R to He Shisan3For)
Heating is further taken out after mixing and after standing 1 day at low temperature (5 DEG C) in molar ratio for the 1:3:2 aqueous solution for being made into 10wt%
Self-healing temperature-sensitive hydrogel is formed to 35 DEG C.The self-healing temperature-sensitive hydrogel of the present embodiment has Thermo-sensitive and selfreparing
Function, and the selfreparing for the macroscopical big crackle that may be implemented not having to be bonded manually by the remote control of temperature.
Embodiment 12
The third self-healing temperature-sensitive hydrogel is present embodiments provided, the preparation method comprises the following steps: above embodiments are prepared
One (R of formula1For), (L is formula twoR2For) (its X is Br, R to He Shisan3For)
It is further taken out after mixing and after standing 1 day in 40 at low temperature (4 DEG C) for the 2:4:1 aqueous solution for being made into 15wt% in molar ratio
DEG C it is thermally formed self-healing temperature-sensitive hydrogel.Measure the Thermo-sensitive and self-repairability of the present embodiment self-healing temperature-sensitive hydrogel
Energy.Experiment shows that the self-healing temperature-sensitive hydrogel of the present embodiment has Thermo-sensitive and self-repair function, and can pass through temperature
The selfreparing of the big crackle of the macroscopic view for not having to be bonded manually is realized in the remote control of degree.
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 and third construction unit；
Wherein, first construction unit has one structure of formula:
Wherein,
R1It is selected fromOne or both of；
The secondary building units have two structure of formula:
Wherein, R2It is selected from
One or both of, L is
The third construction unit includes four structure of three structure of formula or/and formula:
Wherein, X is selected from Br or N3；R3It is selected from
Wherein, X is selected from Br or N3；R3It is selected from
First construction unit, the secondary building units and the third construction unit are based on adamantane-cyclodextrin host and guest
Body 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 and formula four, the m is the integer of 50-100；The n is the integer of 0.5-10.
3. supramolecular materials according to claim 1, which is characterized in that described in formula three and formula fourContain β-ring
Dextrin.
4. supramolecular materials according to claim 1, which is characterized in that the formula one the preparation method comprises the following steps: by formula five and formula
Six carry out click-reactions, or formula five and formula seven are carried out click-reaction, and formula one is made, wherein formula five, formula six and formula seven it is specific
Structure is as follows:
The formula two the preparation method comprises the following steps: formula eight and formula six are carried out click-reaction, or formula eight and formula seven are subjected to click-reaction,
Formula two is made, wherein the specific structure of formula eight, formula six and formula seven is as follows:
Wherein, L is
5. supramolecular materials according to claim 1, which is characterized in that the formula three the preparation method comprises the following steps: by formula nine, formula ten
It is reacted to obtain with formula 11, the X of the formula three is Br, R3For
Wherein, the specific structure of the formula nine, the formula ten and the formula 11 is as follows:
The formula four the preparation method comprises the following steps: formula nine, formula ten and formula 12 are reacted to obtain, the X of the formula four is Br, R3For
Wherein, the specific structure of the formula nine, the formula ten and the formula 12 is as follows:
6. supramolecular materials according to claim 1, which is characterized in that the formula three the preparation method comprises the following steps: by formula nine, formula ten
Three and formula Ⅸ reacted to obtain, the X of the formula three is Br, R3For
Wherein, the specific structure of the formula nine, the formula 13 and the formula 11 is as follows:
The formula four the preparation method comprises the following steps: formula nine, formula 13 and formula 12 are reacted to obtain, the X of the formula four is Br, R3
For
Wherein, the specific structure of the formula nine, the formula 13 and the formula 12 is as follows:
7. a kind of self-healing temperature-sensitive hydrogel, which is characterized in that preparation method the following steps are included:
First construction unit, the secondary building units, the third construction unit and water are mixed, pass through described first
The adamantane of construction unit, the secondary building units and the third construction unit-cyclodextrin Subjective and Objective is in 4-20 DEG C of condition
Lower dissolution mixing carries out self assembly, is heated to formation self-healing temperature-sensitive hydrogel at 35-50 DEG C, wherein first structure
Unit is built with one structure of formula, the secondary building units have two structure of formula, and the third construction unit includes three structure of formula
Or/and four structure of formula.
8. self-healing temperature-sensitive hydrogel according to claim 7, which is characterized in that the self-healing temperature-sensitive hydrogel
Volume-phase transition temperature be 20-35 DEG C.
9. self-healing temperature-sensitive hydrogel according to claim 7, which is characterized in that the formula one and formula two mole it
With, with the third construction unit mole ratio be 1:(0.4-6).
10. self-healing temperature-sensitive hydrogel according to claim 7, which is characterized in that the formula one, the formula two and institute
Stating the mixing quality concentration of third construction unit in aqueous solution is 5-25wt%.
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