CN109721738B - Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof - Google Patents

Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof Download PDF

Info

Publication number
CN109721738B
CN109721738B CN201811640303.4A CN201811640303A CN109721738B CN 109721738 B CN109721738 B CN 109721738B CN 201811640303 A CN201811640303 A CN 201811640303A CN 109721738 B CN109721738 B CN 109721738B
Authority
CN
China
Prior art keywords
formula
self
construction unit
temperature
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811640303.4A
Other languages
Chinese (zh)
Other versions
CN109721738A (en
Inventor
朱东雨
洪展鹏
袁丽军
陈欣杰
许舒芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN201811640303.4A priority Critical patent/CN109721738B/en
Publication of CN109721738A publication Critical patent/CN109721738A/en
Application granted granted Critical
Publication of CN109721738B publication Critical patent/CN109721738B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the technical field of supramolecular chemistry, and particularly relates to a supramolecular material, a self-healing temperature-sensitive hydrogel and a preparation method thereof. The invention comprises a first building unit, a second building unit and a third building unit, wherein the first building unit, the second building unit and the third building unit are self-assembled and connected to form a supramolecular material based on adamantane-cyclodextrin host-object. The invention also provides a hydrogel, which comprises the following steps: mixing the first building unit, the second building unit and the third building unit with water, dissolving and mixing adamantane-cyclodextrin host-object of the first building unit, the second building unit and the third building unit at 4-20 ℃ for self-assembly, and heating to 35-50 ℃ to form hydrogel. The hydrogel provided by the invention overcomes the technical defects that the existing hydrogel is disordered and uncontrollable in structure and needs manual bonding for macroscopic large crack self-repair.

Description

Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof
Technical Field
The invention belongs to the technical field of supramolecular chemistry, and particularly relates to a supramolecular material, a self-healing temperature-sensitive hydrogel and a preparation method thereof.
Background
Self-healing is the most fundamental property of living organisms, such as the ability to self-heal after skin and bone injuries. The hydrogel is soft and elastic, has high water content, and has the characteristics that the hydrogel is similar to a biological tissue structure, so that the hydrogel material can realize the self-repairing function similar to organisms through reasonable design. The hydrogel with the self-healing function can automatically repair regional damage of materials caused by extreme external conditions (such as large deformation or external force damage) and enable the damaged gel to recover the shape and the function of the gel, so that the service life and the use stability of the gel material are prolonged, the economic benefit is optimized, and the intellectualization, the high efficiency and the environmental friendliness of soft materials are realized. In the world, intelligent self-repairing materials are a new emerging comprehensive science. At present, hydrogel with self-repairing function as a novel intelligent soft material has become one of the research hotspots in the field of new materials.
The supermolecule hydrogel based on host-guest self-assembly is an important self-repairing material. The team of the teaching of Harada of osaka university, japan, designed two vinyl monomers that self-assemble in advance by the subject-guest self-assembly of β -cyclodextrin (β -CD) and adamantane (Ad), and then obtained a self-repairing hydrogel by radical polymerization, which was bonded immediately after cut sections of the hydrogel were fitted to each other (Kakuta t., Takashima y., nakata ham., Otsubo m., Yamaguchi h., Harada a., adv.mater.2013,25(20): 2849-.
However, for the self-repairing hydrogel prepared by the prior art, the preparation method is uncontrollable, and the structure of the gel network is not regular enough, flexible and adjustable. In addition, for the reported self-repairing hydrogel, only after the cut sections are manually attached together, self-repairing can be observed under certain conditions, namely, the self-repairing can be realized only when tiny cracks are generated inside the material and the polymer molecular chain segments can be contacted with each other in the process of free diffusion movement. When two sides of the section of the self-repairing material are not contacted with each other due to a large crack, the two ends of the section are often required to be manually attached together, otherwise, self-repairing cannot be completed.
Disclosure of Invention
In view of the above, the invention aims to disclose a hydrogel which has a regular and adjustable structure, is temperature sensitive, and can realize macroscopic large crack self-repair without manual bonding.
The invention provides a supramolecular material which comprises a first construction unit, a second construction unit and a third construction unit;
wherein the first building unit has a structure of formula:
Figure GDA0002904891880000021
wherein R is1Is selected from
Figure GDA0002904891880000022
One or two of them;
the second construction unit has a structure of formula two:
Figure GDA0002904891880000023
wherein R is2Is selected from
Figure GDA0002904891880000024
One or two of, L is
Figure GDA0002904891880000025
The third construction unit comprises a formula three structure or/and a formula four structure:
Figure GDA0002904891880000031
wherein X is selected from Br or N3；R3Is selected from
Figure GDA0002904891880000032
Figure GDA0002904891880000033
Wherein X is selected from Br or N3；R3Is selected from
Figure GDA0002904891880000034
The first building unit, the second building unit and the third building unit are connected to form a supramolecular material based on self-assembly of an adamantane-cyclodextrin host-object.
The first, second, and fourth structures may form a supramolecular material based on the self-assembly of the adamantane-cyclodextrin host-guest, or the first, second, third, and fourth structures may form a supramolecular material based on the self-assembly of the adamantane-cyclodextrin host-guest.
More preferably, in formula III, X is Br or N3；R3Is composed of
Figure GDA0002904891880000035
Most preferably, in formula three, X is Br; r3Is composed of
Figure GDA0002904891880000041
More preferably, in formula IV, X is Br or N3；R3Is composed of
Figure GDA0002904891880000042
Most preferably, in formula IV, X is Br; r3Is composed of
Figure GDA0002904891880000043
Preferably, in the formulae III and IV, the
Figure GDA0002904891880000044
Contains alpha-cyclodextrin, beta-cyclodextrin group or gamma-cyclodextrin group.
More preferably, in the formulae three and four, the
Figure GDA0002904891880000045
Contains beta-cyclodextrin groups.
Preferably, in the formula I, y is an integer of 50-100; in the formula II, z is an integer of 50-100; in the formula III and the formula IV, m is an integer of 50-100; and n is an integer of 0.5-10.
Preferably, the preparation method of the formula one is as follows: carrying out click reaction on the formula five and the formula six, or carrying out click reaction on the formula five and the formula seven to prepare the formula I, wherein the specific structures of the formula five, the formula six and the formula seven are as follows:
Figure GDA0002904891880000051
Figure GDA0002904891880000052
the preparation method of the formula II comprises the following steps: carrying out click reaction on the formula eight and the formula six, or carrying out click reaction on the formula eight and the formula seven to prepare a formula two, wherein the specific structures of the formula eight, the formula six and the formula seven are as follows:
Figure GDA0002904891880000053
wherein L is
Figure GDA0002904891880000054
Figure GDA0002904891880000061
Specifically, the preparation method of the formula I takes dipentaerythritol as a raw material, and the preparation route is as follows:
Figure GDA0002904891880000062
specifically, the preparation method of the formula I comprises the following steps: the method comprises the steps of preparing a dipentaerythritol hexabromoATRP initiator by esterification of dipentaerythritol and 2-bromoisobutyryl bromide, and carrying out ATRP polymerization on the dipentaerythritol hexabromoATRP initiator and N-isopropylacrylamide (NIPAM) to obtain a six-arm star-shaped temperature-sensitive polymer with bromine at the tail end. Then substituting bromine at the tail end of the six-arm star-shaped temperature-sensitive polymer into azide (-N)3) After this, formula five is obtained. Finally, carrying out click reaction on the compound with the formula five and the compound with the formula six to obtain the compound with the formula one, wherein R1Is composed of
Figure GDA0002904891880000063
Carrying out click reaction on the compound of the formula V and the compound of the formula VII to obtain the compound of the formula I, wherein R1Is composed of
Figure GDA0002904891880000071
The method comprises the following steps of designing and synthesizing polymers with various topological structures and functions by using ATRP and click chemistry technologies, synthesizing a six-functional-group ATRP initiator by using dipentaerythritol as a raw material, preparing a linear temperature-sensitive polymer by using ATRP reaction, and preparing a first formula with temperature-sensitive characteristics, wherein the first formula contains cyclodextrin residues or adamantane residues at the tail end by using click chemistry reaction and connecting an alkynylated cyclodextrin group or adamantane group to the tail end of a temperature-sensitive polymer chain after azidation.
Specifically, the preparation method of the formula II takes pentaerythritol or 1,3,5, 7-tetrahydroxy adamantane as a raw material, wherein the formula II, R2Is selected from
Figure GDA0002904891880000072
One or two of, L is
Figure GDA0002904891880000073
The reaction scheme of (a) is as follows:
Figure GDA0002904891880000074
wherein, the formula two (L is
Figure GDA0002904891880000075
) The specific method using pentaerythritol as the starting material comprises the following steps: pentaerythritol and 2-bromine-isobutyryl bromide are subjected to esterification reaction to prepare pentaerythritol-based tetrabromo ATRP initiator, ATRP polymerization is carried out on the pentaerythritol-based tetrabromo ATRP initiator and N-isopropyl acrylamide (NIPAM) to prepare four-arm star-shaped thermo-sensitive polymer with bromine at the tail end, and then bromine at the tail end of the four-arm star-shaped thermo-sensitive polymer with bromine at the tail end is substituted by azide (-N)3) Then, the formula eight (L is
Figure GDA0002904891880000081
) Click reaction is carried out on the formula eight and the formula six (or the formula eight and the formula seven) to obtain the formula two (L is
Figure GDA0002904891880000082
) Wherein the click reaction is represented by the general formula eight (L is
Figure GDA0002904891880000083
): formula six (or formula seven): ligand PMDETA: the catalyst cuprous bromide is prepared from (1), (4-6), (4-8): (4-8), passing through a neutral alumina column, dialyzing, precipitating the obtained product in glacial ethyl ether, filtering and drying to obtain the compound II (L is
Figure GDA0002904891880000084
) Wherein, if the formula six is added in the click reaction, R of the formula two2Is a cyclodextrin-containing residue, L is
Figure GDA0002904891880000085
If formula seven is added to the click reaction, R of formula two2Is a adamantane-containing residue, L is
Figure GDA0002904891880000086
Formula II(L is
Figure GDA0002904891880000087
) The specific method taking 1,3,5, 7-tetrahydroxy adamantane as a starting material comprises the following steps: preparing adamantyl tetrabromo ATRP initiator from 1,3,5, 7-tetrahydroxy adamantane and 2-bromo-isobutyryl bromide through esterification reaction, performing ATRP polymerization on the adamantyl tetrabromo ATRP initiator and N-isopropyl acrylamide (NIPAM) to prepare four-arm star-shaped temperature-sensitive polymer with bromine at the tail end, and substituting bromine at the tail end of the four-arm star-shaped temperature-sensitive polymer with bromine at the tail end with azide (-N)3) Then, the formula eight (L is
Figure GDA0002904891880000088
) Formula eight (L is
Figure GDA0002904891880000089
) Click reaction with the formula six (or the formula eight and the formula seven) to obtain the formula two (L is
Figure GDA00029048918800000810
) Wherein the click reaction is represented by the general formula eight (L is
Figure GDA00029048918800000811
): formula six (or formula seven): ligand PMDETA: the catalyst cuprous bromide is prepared from (1), (4-6), (4-8): (4-8), passing through a neutral alumina column, dialyzing, precipitating the obtained product in glacial ethyl ether, filtering and drying to obtain the compound II (L is
Figure GDA00029048918800000812
) Wherein, if the formula six is added in the click reaction, R of the formula two2Is a cyclodextrin-containing residue, L is
Figure GDA00029048918800000813
If a compound of formula VII is added, then R of formula VII2Containing a residue of adamantane, L is
Figure GDA0002904891880000091
The second formula is to design and synthesize polymers with various topological structures and functions by using ATRP and click chemistry technology, synthesize a four-functional-group ATRP initiator by using pentaerythritol or 1,3,5, 7-tetrahydroxy adamantane as a raw material, prepare a linear temperature-sensitive polymer by using ATRP reaction, and prepare the second formula with the temperature-sensitive characteristic of which the tail end contains cyclodextrin or adamantane by using click chemistry reaction to connect an alkynylated cyclodextrin group or adamantane group to the tail end of a temperature-sensitive polymer chain after azidation.
It should be noted that click chemistry is a new method for rapidly synthesizing a large number of compounds, mainly through small unit splicing, and a carbon-heteroatom bond (C-X-C) synthesis based combinatorial chemical reaction, the formula II of the invention is mainly through a copper (I) catalyzed azide-alkyne cycloaddition (CuAAC) reaction, the end of the four-arm polymer is subjected to azide to generate a four-arm polymer with an azide group at the end, and the formula II is prepared through a click chemical reaction of alkyne with low molecular weight on the basis of the four-arm polymer with the azide group at the end.
Specifically, the preparation method of the formula VI comprises the following steps:
dissolving beta-cyclodextrin and p-toluenesulfonylimidazole in an aqueous solution for reaction for a period of time, adding a sodium hydroxide solution for continuous reaction, dropwise adding an acid solution after the reaction is finished, adjusting the pH value to be neutral, cooling for crystallization, and reacting the crystallized solid product with propargylamine to obtain the formula VI.
Specifically, the preparation method of the formula VI comprises the following steps: after p-toluenesulfonylimidazole and beta-cyclodextrin are fully and uniformly mixed in water, adding a sodium hydroxide solution, continuing to react, filtering to remove insoluble substances after the reaction is finished, adding hydrochloric acid to adjust the pH value to be neutral, cooling and crystallizing the neutral product for 8-16h, filtering, washing the crude product with deionized water, and washing the crude product with acetone; heating and recrystallizing twice by using deionized water, and drying in vacuum to obtain a white solid (marked as OTs-CD); and reacting the OTs-CD with propargylamine under the protection of inert gas and keeping out of the sun to obtain a crude product of a formula VI. The preparation process of the formula six is as follows:
Figure GDA0002904891880000092
wherein, the crude product of the formula VI can be diluted by a mixed solution of methanol and water, precipitated in acetone, repeated for many times, and filtered to obtain the product, and the yield of the formula VI is 95%.
Wherein, the preparation method of the formula VI can obtain the yield of the formula VI of 42-60%.
In the preparation method of the formula VI, by mass, 1 part of p-toluenesulfonylimidazole, 2-4 parts of beta cyclodextrin, 5-6 parts of sodium hydroxide solution (the mass fraction of the sodium hydroxide solution is 20%), 1 part of hydrochloric acid with the concentration of 1-3mol/L, OTs-CD and 2-3 parts of propargylamine are adopted.
Wherein, the p-toluenesulfonylimidazole, the beta-cyclodextrin and the water are mixed, and the reaction time is 4 to 6 hours; adding sodium hydroxide solution, and mixing for 25-35 min; then cooling and crystallizing at the cooling temperature of 4 ℃; the vacuum drying time after crystallization is 48 hours; the inert gas is nitrogen; the OTs-CD and propargylamine are reacted at 50 ℃ in a dark place for 72-96 h.
Specifically, the preparation method of the formula VII is as follows:
adding adamantanecarboxylic acid into Dichloromethane (DCM), diluting oxalyl chloride with dichloromethane under an ice bath condition, and adding a mixed solution of adamantanecarboxylic acid and dichloromethane for reaction; and (4) spinning out the solvent and the redundant oxalyl chloride to obtain a light yellow solid 1-adamantane formyl chloride. Mixing triethylamine, 1-adamantane formyl chloride, anhydrous ether and propargyl alcohol for reaction, filtering to remove insoluble substances after the reaction is finished, and sequentially using hydrochloric acid solution and NaHCO3Washing with deionized water for three times, drying with anhydrous magnesium sulfate, filtering to remove magnesium sulfate, rotary evaporating, and passing through neutral alumina column to obtain formula VII which is colorless viscous liquid. The preparation process of the formula seven comprises the following chemical reaction formula:
Figure GDA0002904891880000101
wherein, in orderIn the preparation method of the formula VII, in terms of molar parts, 1 molar part of adamantanecarboxylic acid, 1 to 1.5 molar parts of oxalyl chloride, 1 molar part of 1-adamantanecarbonyl chloride, 1.2 molar parts of triethylamine, 1.2 molar parts of propargyl alcohol, 10 mass percent of hydrochloric acid solution and NaHCO3Is 5 percent.
Wherein, oxalyl chloride diluted by dichloromethane is added into a mixed solution of adamantane formic acid and dichloromethane through a constant pressure dropping funnel.
Wherein the reaction time of oxalyl chloride and adamantane carboxylic acid is 12-16 h.
Wherein triethylamine, 1-adamantane formyl chloride and anhydrous ether are added into a reaction bottle, propargyl alcohol is dissolved in the anhydrous ether and then added into the reaction bottle through a constant pressure dropping funnel, and the reaction is continued for 24 to 48 hours after the dropwise addition is finished.
Wherein the drying time of the anhydrous magnesium sulfate is 6-12 h.
Preferably, the preparation method of the formula III is as follows: the compound is obtained by reacting a formula nine, a formula ten and a formula eleven, wherein X of the formula III is Br, R3Is composed of
Figure GDA0002904891880000111
The specific structures of the formula nine, the formula ten and the formula eleven are as follows:
Figure GDA0002904891880000112
preferably, the preparation method of the formula IV is as follows: the compound is obtained by reacting nine, ten and twelve formulas, wherein X of the fourth formula is Br, R3Is composed of
Figure GDA0002904891880000113
The specific structures of the nine formula, the ten formula and the twelve formula are as follows:
Figure GDA0002904891880000114
preferably, the preparation method of the formula III is as follows: obtained by reacting nine, thirteen and eleven, wherein X of the third formula is Br, R3Is composed of
Figure GDA0002904891880000115
Wherein the specific structures of formula nine, formula thirteen and formula eleven are as follows:
Figure GDA0002904891880000121
preferably, the preparation method of the formula IV is as follows: obtained by reacting nine, thirteen and twelve formulas, wherein X of the fourth formula is Br, R3Is composed of
Figure GDA0002904891880000122
Wherein the specific structures of the formula nine, the formula thirteen and the formula twelve are as follows:
Figure GDA0002904891880000123
the first, second, third and fourth formulas are obtained by Atom Transfer Radical Polymerization (ATRP), and the compound having a low valence transition metal halide is used as a catalyst, the alkyl halogenated hydrocarbon (R-X) is used as an initiator, and the electron-bonding compound is used as a ligand. The polymerization reaction condition is simple and mild, and the molecular weight distribution of the obtained polymer is narrow.
The preparation method of the compound represented by the formula thirteen is as follows: the mono-6-ethylenediamine-cyclodextrin reacts with acryloyl chloride to obtain the product.
The invention also provides self-healing temperature-sensitive hydrogel, and the preparation method comprises the following steps:
the first construction unit, the second construction unit, the third construction unit and water are mixed, self-assembly is carried out by dissolving and mixing the adamantane-cyclodextrin host object of the first construction unit, the second construction unit and the third construction unit at 4-20 ℃, and self-healing temperature-sensitive hydrogel is formed by reheating to 35-50 ℃, wherein the first construction unit has a first structure, the second construction unit has a second structure, and the third construction unit comprises a third structure or/and a fourth structure.
The self-healing temperature-sensitive hydrogel is formed by self-assembly connection of the formula I, the formula II and the formula III and water based on the adamantane-cyclodextrin host and object, or formed by self-assembly connection of the formula I, the formula II and the formula IV and water based on the adamantane-cyclodextrin host and object, or formed by self-assembly connection of the formula I, the formula II, the formula III and the formula IV and water based on the adamantane-cyclodextrin host and object. The self-healing temperature-sensitive hydrogel is formed by self-assembling the first, second and third building units in an aqueous solution by utilizing the self-assembly function of the host and the object, tests and observations show that the self-healing temperature-sensitive hydrogel has temperature sensitivity and self-repairing performance, and the large crack self-repairing without manual bonding can be realized by exerting the synergistic function of the temperature sensitivity and the self-repairing.
The preparation method of the self-healing temperature-sensitive hydrogel comprises the following steps: dissolving the first construction unit, the second construction unit and the third construction unit in water under a low-temperature condition, standing for several hours, and then forming self-healing temperature-sensitive hydrogel under the promotion of slight heating; can also be prepared by the following steps: and dissolving the first construction unit, the second construction unit and the third construction unit in tetrahydrofuran, and dialyzing in water to obtain the self-healing temperature-sensitive hydrogel.
Preferably, the volume phase transition temperature of the self-healing temperature-sensitive hydrogel is 20-35 ℃.
Preferably, the ratio of the sum of the moles of the first and second formulae to the moles of the third building unit is 1: (0.4-6).
Preferably, the mixed mass concentration of the first, second and third building units in the aqueous solution is 5 to 25 wt%.
The invention creatively takes the formula I and the formula II as a cross-linking agent, and the polymer (the formula III or/and the formula IV) with the side chain containing the adamantane or/and the cyclodextrin group forms the self-healing temperature-sensitive hydrogel in a host-guest self-assembly mode. Therefore, the self-healing temperature-sensitive hydrogel forms a gel network through supermolecule physical cross-linking of the first construction unit, the second construction unit and the third construction unit based on self-assembly of the adamantane-cyclodextrin host-object, and the gel network is uniformly distributed with the physical cross-linking points based on self-assembly of the adamantane and the cyclodextrin host-object, so that the self-healing temperature-sensitive hydrogel can be firstly broken when damaged by external force and can be reassembled when two ends of the section are in contact with each other, and the self-healing temperature-sensitive hydrogel has an excellent self-healing function. In addition, the self-healing temperature-sensitive hydrogel disclosed by the invention utilizes the temperature-sensitive characteristics of the first construction unit, the second construction unit and the second construction unit, can respond to the change of temperature to generate volume expansion or contraction, and can realize volume expansion of the self-healing temperature-sensitive hydrogel through wetting and temperature reduction after the self-healing temperature-sensitive hydrogel generates large cracks, so that the crack spacing is reduced, and therefore, the large crack spacing of the self-healing temperature-sensitive hydrogel disclosed by the invention can be remotely controlled through temperature, and the self-healing of macroscopic large cracks without manual bonding is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a representation spectrum of a six-arm star-shaped temperature-sensitive polymer with bromine at the end prepared in example 3 provided by the present invention;
FIG. 2 shows an IR spectrum (b) of formula VIII prepared in example 5, and a spectrum (R) of formula II prepared in example 3 according to the present invention1Is composed of
Figure GDA0002904891880000141
) (ii) an infrared spectrum (c);
FIG. 3 is a GPC chart (b) of formula eight prepared by example 5 provided by the present invention, and formula two (R) prepared by example 31Is composed of
Figure GDA0002904891880000142
) GPC diagram (c);
FIG. 4 is a physical diagram of a self-healing temperature-sensitive hydrogel according to example 7 provided by the present invention;
FIG. 5 is a two-dimensional nuclear magnetic spectrum of the self-healing temperature-sensitive hydrogel of example 7 provided by the present invention;
FIG. 6 is a pictorial view of comparative example 1 provided by the present invention;
FIG. 7 is a pictorial view of comparative example 2 provided by the present invention;
FIG. 8 is a volume phase transition temperature profile of the self-healing temperature-sensitive hydrogel of example 7 provided by the present invention;
fig. 9 is a self-healing process diagram of the self-healing temperature-sensitive hydrogel according to embodiment 7, where a is a physical diagram of the self-healing temperature-sensitive hydrogel at 40 ℃, B is a physical diagram of a cut crack of the self-healing temperature-sensitive hydrogel, C is a size diagram of the cut crack of the self-healing temperature-sensitive hydrogel, D is a physical diagram of water added after the self-healing temperature-sensitive hydrogel is cut, E is a physical diagram of the self-healing temperature-sensitive hydrogel after self-healing for 2.5 hours at 20 ℃, and F is a physical diagram of the self-healing temperature-sensitive hydrogel after self-healing.
Detailed Description
The invention provides a supramolecular material, self-healing temperature-sensitive hydrogel and a preparation method thereof, and the hydrogel provided by the invention solves the technical defects that the traditional hydrogel is disordered and unadjustable in structure and cannot automatically repair macroscopic large cracks.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The raw materials used in the following examples are all commercially available or self-made.
Example 1
The embodiment of the invention provides a preparation method of a compound shown in the formula six and a compound shown in the formula seven, which comprises the following specific steps:
the preparation method of the formula VI is as follows: p-toluenesulfonylimidazole (8.9g, 40mmol) and beta-cyclodextrin (. beta. -CD, 35g, 30.84mmol) were added to 250ml of distilled water and stirred to give a white suspension. After reacting for 4 hours under stirring at room temperature, adding 50ml of sodium hydroxide solution with the mass fraction of 20%, and continuing stirring for 30 minutes until the reaction solution turns from milky white to light yellow. Insoluble matter was removed by filtration, and the filtrate was transferred to a 500ml beaker, and 1.5mol/L hydrochloric acid was added to adjust the pH to neutrality. And (3) placing the beaker in a low-temperature environment at 4 ℃ for cooling and crystallizing for 12 hours. Filtering, washing with deionized water, and washing the crude product with acetone. Heating and recrystallizing twice by deionized water, and drying for 48h in vacuum to obtain white solid (marked as OTs-CD) 16.7g with the yield of 42%. Adding OTs-CD (10g, 7.7mmol) into anhydrous oxygen-free bottle with stirrer, adding 20ml propargylamine, stirring, vacuumizing, and charging N2Three times in N2And reacting for 96 hours at 50 ℃ in a dark place under protection. After the reaction is finished, diluting the product by using a mixed solution of methanol and water, adding a large amount of acetone for precipitation, repeating the step for multiple times, and filtering to obtain 9.5g of the formula VI, wherein the yield of the formula VI is 95%.
Formula seven is prepared as follows: adamantanecarboxylic acid (9g, 50mmol) and 4 drops of anhydrous DMF were charged to a 150ml flask containing 50ml anhydrous dichloromethane. Oxalyl chloride (6.338g, 50mmol) was diluted with 20ml of anhydrous dichloromethane under ice-bath conditions and added to the reaction flask via an isobaric dropping funnel. After the reaction was warmed to room temperature, the reaction was stirred for 12 hours. After the reaction is finished, the liquid and the redundant oxalyl chloride are spun out to obtain the light yellow solid 1-adamantane formyl chloride. Triethylamine (6.07g, 60mmol) and the resulting solid 1-adamantanecarbonyl chloride were dissolved in 100ml of anhydrous ether. Propargyl alcohol (3.3636g, 60mmol) was dissolved in 50ml of anhydrous ether and added to the reaction flask via a constant pressure dropping funnel, and the reaction was continued for 48h after the addition was completed. Reaction junctionAfter completion, insoluble matter was removed by filtration. Respectively using 10% hydrochloric acid solution and 5% NaHCO3Washed three times with deionized water, and then the organic phase was dried over anhydrous magnesium sulfate for 12 h. Filtering to remove magnesium sulfate, rotary evaporating, and passing through neutral alumina column to obtain formula VII as colorless viscous liquid.
Example 2
The characterization tests performed on the formulas six and seven of example 1 resulted in the following:
the formula is 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]+。
the formula is 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。
example 3
The embodiment of the invention provides a preparation method of a formula I, which comprises the following specific steps:
formula I (R)1Is composed of
Figure GDA0002904891880000161
) The preparation method comprises the following steps: firstly, preparing dipentaerythritol hexabromide ATRP initiator from dipentaerythritol and 2-bromine isobutyryl bromide through esterification reaction, and then, preparing the hexabromide initiator with the weight of 0.0667g and 0.058mmol), NIPAM (4g and 35mmol) and Me6TREN (0.080g,0.35mmol) and 10mL of solvent (V)DMF:VWater (W)80: 20) adding into anhydrous oxygen-free bottle to dissolve completely. Vacuum-filling with N2Three times in N2Adding CuBr (0.0504g,0.35mmol) under protection, vacuumizing and charging N2Three times. In N2Stirring the mixture for reaction for 2 hours under protection, and finishing the reactionThen 15ml of THF is added for dilution, the mixture is placed in the air for stirring for 2 hours, and cuprous bromide is removed through a silica gel column. Excess solvent was spun off and the product was precipitated into glacial ethyl ether and repeated 2-3 times to remove the unpolymerized monomers thoroughly. Drying the filtered product in a vacuum drying oven at 60 ℃ for 24h to obtain the six-arm star-shaped temperature-sensitive polymer with the tail end carrying bromine. Reacting the prepared six-arm star-shaped temperature-sensitive polymer with the bromine at the tail end with sodium azide at a molar ratio of 1:32 in DMF at 60 ℃ for 2 days. And adding the reacted solution into a dialysis bag for dialysis, changing deionized water every 4 hours, and dialyzing for 2 days. Adding the dialyzed product into the ethyl acetate for precipitation, filtering and drying in vacuum to obtain the formula V. Click reaction: and (4) mixing the formula: the formula is seven: PMDETA: the reaction was carried out at a molar ratio of 1:6.5:6.5:6.5 of CuBr. Adding the formula V, the formula VII and the PMDETA into an anhydrous oxygen-free bottle according to the proportion, vacuumizing and filling nitrogen for three times, adding CuBr under the protection of nitrogen, vacuumizing and filling nitrogen for three times. The reaction was carried out at 60 ℃ for 24 h. After the reaction is finished, THF is added for dilution, and the mixture is placed in the air for stirring for 2 hours. Passing through silica gel column to remove cuprous bromide. Removing excessive solvent by rotary evaporation, adding the crude product into dialysis bag, dialyzing for 2 days, and changing deionized water every 6 h. Then precipitating in ether, filtering, and vacuum drying to obtain the formula I, wherein R1Is composed of
Figure GDA0002904891880000162
Formula I (R)1Is composed of
Figure GDA0002904891880000163
) The preparation method comprises the following steps: firstly, preparing dipentaerythritol hexabromide ATRP initiator from dipentaerythritol and 2-bromine isobutyryl bromide through esterification, and reacting hexabromide initiator (0.0667g, 0.058mmol), NIPAM (4g,35mmol) and Me6TREN (0.080g,0.35mmol) and 10mL of solvent (V)DMF:VWater (W)80: 20) adding into anhydrous oxygen-free bottle to dissolve completely. Vacuum-filling with N2Three times in N2CuBr (0.0504g,0.35mmol) was added rapidly under protection and vacuum-charged with N2Three times. In N2The reaction is stirred for 2 hours under protection, 15ml of THF is added for dilution after the reaction is finished, and the mixture is placed in the airStirring for 2h, and passing through a silica gel column to remove cuprous bromide. The product was precipitated by adding to glacial ethyl ether and repeated 2-3 times to sufficiently remove unpolymerized monomers. Drying the filtered product in a vacuum drying oven at 60 ℃ for 24h to obtain the six-arm star-shaped temperature-sensitive polymer with the tail end carrying bromine. Reacting the prepared six-arm star-shaped temperature-sensitive polymer with the bromine at the tail end with sodium azide at a molar ratio of 1:32 in DMF at 60 ℃ for 2 days. The solution after the reaction was dialyzed for 2 days. Adding the dialyzed product into the ethyl acetate for precipitation, filtering and drying in vacuum to obtain the formula V. Click reaction: and (4) mixing the formula: the formula is six: PMDETA: the reaction was carried out at a molar ratio of 1:6.5:6.5:6.5 of CuBr. Adding the formula V, the formula VI and the PMDETA into an anhydrous oxygen-free bottle according to the proportion, vacuumizing and filling nitrogen for three times, adding CuBr under the protection of nitrogen, vacuumizing and filling nitrogen for three times. The reaction was carried out at 60 ℃ for 24 h. After the reaction is finished, THF is added for dilution, and the mixture is placed in the air for stirring for 2 hours. Passing through silica gel column to remove cuprous bromide. Removing excessive solvent by rotary evaporation, and dialyzing the crude product in dialysis bag for 2 days. Then precipitating in ether, filtering, and vacuum drying to obtain the formula I, wherein R1Is composed of
Figure GDA0002904891880000171
Example 4
The embodiment of the invention is a six-arm star-shaped temperature-sensitive polymer with bromine at the tail end and a formula I (R) prepared in the embodiment 31Is composed of
Figure GDA0002904891880000172
) And carrying out verification tests before and after the click reaction.
The characterization map of the six-arm temperature-sensitive polymer (hereinafter referred to as polymer) with bromine at the end is shown in fig. 1, and it can be known from fig. 1 that the position in the nuclear magnetic spectrum is not clear because the polymer has a large molecular weight and the proportion of a hydrogen and b hydrogen in the structural formula is small and is influenced by other hydrogen in the polymer. The c hydrogen and d hydrogen are influenced by the electron withdrawing effect of the ester carbonyl and amide carbonyl respectively, shift to a low field, and coincide at 2.1 ppm. The f hydrogen itself is located on the tertiary carbon and is affected by the attached amine group with a low field shift at 3.9 ppm. The e hydrogen in the polymer chain is at 1.5-1.6 ppm; the hydrogen at 1.0ppm is the hydrogen on the methyl group in the isopropyl group, i.e., g hydrogen. According to GPC analysis of the polymer, the molecular weight of the polymer is Mn 11235, Mw 13115, PDI 1.16<1.2, the molecular weight distribution is narrow, and the polymer meets the requirement of chain length, so that the six-arm star-shaped temperature-sensitive polymer with bromine at the tail end is successfully synthesized.
Example 5
The embodiment of the invention provides a preparation method of a formula II, which comprises the following specific steps:
formula II (L is
Figure GDA0002904891880000181
) The preparation route is as follows:
A. firstly preparing the formula VIII (L is
Figure GDA0002904891880000182
R2Is composed of
Figure GDA0002904891880000183
) The four-arm temperature-sensitive polymer containing azido at the end of the formula eight is prepared into R of the formula two and R of the formula two by click chemistry reaction of the formula eight and the formula seven (prepared in example 1)2Is composed of
Figure GDA0002904891880000184
Formula eight (L is
Figure GDA0002904891880000185
R2Is composed of
Figure GDA0002904891880000186
) The four-arm temperature-sensitive polymer containing azido at the end of the formula eight is prepared into R of the formula two and R of the formula two by click chemistry reaction of the formula eight and the formula six (prepared in example 1)2Is composed of
Figure GDA0002904891880000187
Wherein, the formula is eight (L is
Figure GDA0002904891880000188
) The specific method using pentaerythritol as the starting material comprises the following steps: pentaerythritol and 2-bromine isobutyryl bromide are subjected to esterification reaction to prepare pentaerythritol tetrabromo ATRP initiator, and then pentaerythritol tetrabromo ATRP initiator (0.129g, 0.175mmol), NIPAM (8g,70mmol) and Me are subjected to esterification reaction6TREN (0.161g,0.7mmol) and 20mL of solvent (V)DMF:VWater (W)80: 20) adding into anhydrous oxygen-free bottle, vacuumizing, and charging N2Three times. In N2CuBr (0.1g, 0.7mmol) was added rapidly with protection. Under stirring, vacuumizing and charging N2Three times. In N2The reaction is continued for 2h under protection, and after the reaction is finished, 20ml of tetrahydrofuran is added for dilution and is placed in the air for stirring for 2 h. The catalyst was removed by silica gel column. The crude product was added dropwise to ethyl acetate at an appropriate concentration to precipitate, and filtered to give a white solid. This step was repeated 2-3 times to remove unreacted N-isopropylacrylamide monomer, and then the product and sodium azide (NaN)3: polymer is more than or equal to 20) are mixed according to the molar ratio of 1:25 and reacted for 48 hours in DMF solvent at 60 ℃. Then adding the reaction solution into a 3500Da dialysis bag for dialysis for 3 days, adding the product into diethyl ether for precipitation, and filtering to obtain formula VIII (L is
Figure GDA0002904891880000191
). Formula eight (L is
Figure GDA0002904891880000192
) The specific method taking 1,3,5, 7-tetrahydroxy adamantane as a starting material comprises the following steps: preparing adamantyl tetrabromo ATRP initiator from 1,3,5, 7-tetrahydroxyadamantane and 2-bromoisobutyryl bromide through esterification reaction, and preparing adamantyl tetrabromo ATRP initiator (0.2544g, 0.35mmol), NIPAM (16g, 140mmol) and Me from the adamantyl tetrabromo ATRP initiator (0.2544g, 0.35mmol)6TREN (0.325g, 1.4mmol) and 40mL of solvent (V)DMF:VWater (W)80: 20) adding into anhydrous oxygen-free bottle, vacuumizing, and charging N2Three times. In N2CuBr (0.21g, 1.4mmol) was added rapidly with protection. Under stirring, vacuumizing and charging N2Three times. In N2The reaction is continued for 2h under protection, and after the reaction is finished, 20ml of tetrahydrofuran is added for dilution and is placed in the air for stirring for 2 h. The catalyst was removed by silica gel column.The crude product is dropped into the ethyl glacial ether with proper concentration for precipitation, and is filtered to obtain white solid, the step is repeated for 2-3 times to remove the unreacted N-isopropyl acrylamide monomer, and then the product and sodium azide are mixed according to the molar ratio of 1:25 and react for 48 hours at 60 ℃ in DMF solvent. Dialyzing the reaction solution for 3 days, adding the product into diethyl ether for precipitation, and filtering to obtain the compound shown in formula VIII (L is
Figure GDA0002904891880000193
)。
B. Formula II (L is
Figure GDA0002904891880000194
R2Is composed of
Figure GDA0002904891880000195
) The preparation method comprises the following steps: mixing the compound of formula VIII obtained in the step A (L is
Figure GDA0002904891880000196
) Adding formula VI, PMDETA and catalyst CuBr according to a molar ratio of 1:4.5:4.5:4.5, dissolving formula VIII in an anhydrous oxygen-free reaction bottle with 15ml of DMF, adding formula VI and PMDETA into an anhydrous oxygen-free bottle with 20ml of DMF, stirring, vacuumizing and filling N2Qi is thrice. In N2Under protection, quickly adding CuBr, stirring, vacuumizing, and filling N2Three times. In N2Under the protection, the reaction temperature is 65 ℃, and the reaction time is 24 hours. After the reaction was complete, 15ml of THF was added to dilute the solution and the solution was stirred under air for 2 h. Removing CuBr by silica gel column, removing excessive solvent by rotary evaporation, and dialyzing the crude product for 48 h. Precipitating the product in glacial ethyl ether, filtering and drying to obtain the compound II (L is
Figure GDA0002904891880000197
R2Is composed of
Figure GDA0002904891880000198
) R of which2Is a cyclodextrin residue of the formula II (L is
Figure GDA0002904891880000199
R2Is composed of
Figure GDA0002904891880000201
) Is prepared from a compound of formula (II) and a compound of formula (II)
Figure GDA0002904891880000202
R2Is composed of
Figure GDA0002904891880000203
) The preparation process is similar, except that the formula II (L is
Figure GDA0002904891880000204
R2Is composed of
Figure GDA0002904891880000205
) The formula six raw materials used in the preparation method are replaced by the formula seven for reaction.
FIG. 2 shows the formula II (R)1Is composed of
Figure GDA0002904891880000206
) Infrared spectrograms before and after the click reaction, wherein b in figure 2 is an infrared spectrogram of formula eight, and c in figure 2 is a infrared spectrogram of formula two (R)1Is composed of
Figure GDA0002904891880000207
) (ii) an infrared spectrum; FIG. 3 shows the formula II (R)1Is composed of
Figure GDA0002904891880000208
) GPC charts before and after click reaction, wherein b in FIG. 3 is a GPC chart of formula eight, and c in FIG. 3 is a GPC chart of formula two (R)1Is composed of
Figure GDA0002904891880000209
) GPC diagram of (a). As can be seen from FIGS. 2 and 3, the outer spectrum of formula VIII shows that formula VIII is 2116cm-1Has obvious characteristic peak of azido. After the click reaction, the formula two (R)1Is composed of
Figure GDA00029048918800002010
) The infrared spectrum of the sample is 2116cm-1The characteristic peak of azido group disappears, so the click chemistry reaction is successfully carried out. Further, as can be seen from a comparison of the GPC curves of FIG. 3, the formula two (R)1Is composed of
Figure GDA00029048918800002011
) Is significantly greater than formula five, indicating that a large molar mass of adamantane groups was successfully attached at the end of formula eight, and formula two (R)1Is composed of
Figure GDA0002904891880000211
) Other impurities do not exist in the compound, so that the compound of the formula II (R) is successfully synthesized1Is composed of
Figure GDA0002904891880000212
)。
Example 6
The embodiment of the invention provides a preparation method of a compound shown in the formula III, a compound shown in the formula IV and a compound shown in the formula thirteen, which comprises the following steps:
A. formula III (X is Br, R)3Is composed of
Figure GDA0002904891880000213
) The preparation method comprises the following steps: mixing formula nine (8g,70.1mmol), formula ten (0.433g,2.1mmol), formula eleven (0.1365g,0.7mmol), Me6TREN (0.1613g,0.7mmol) and 20mL of solvent (V)DMF:VWater (W)80: 20) adding into anhydrous oxygen-free bottle to dissolve completely. Vacuum-filling with N2Three times in N2CuBr (0.1018g, 0.7mmol) was added rapidly under protection, vacuum-charged with N2Three times. In N2The reaction is continued to be stirred for 2h under protection, 15ml of THF is added for dilution after the reaction is finished, the mixture is placed in the air for stirring for 2h, and cuprous bromide is removed through a silica gel column. Excess solvent was spun off, then precipitated by addition of glacial ethyl ether, and repeated 2-3 times to sufficiently remove unpolymerized monomers. Drying the filtered product in a vacuum drying oven at 60 ℃ for 24h to obtain the compound of the formula III, wherein X is Br and R3Is composed of
Figure GDA0002904891880000214
Chemical synthesis thereofThe route is as follows:
Figure GDA0002904891880000221
wherein, the formula III (X is Br, R)3Is composed of
Figure GDA0002904891880000222
) Is prepared from the compound of formula III (wherein X is Br, R)3Is composed of
Figure GDA0002904891880000223
) The preparation method of (a) is similar, except that formula ten is replaced by formula thirteen.
Formula III (X is Br) can also be subjected to azide treatment, and specifically, formula III (X is Br) and sodium azide are reacted in DMF at a molar ratio of 1:10 at 60 ℃ for 2 days. And adding the reacted solution into a dialysis bag for dialysis, changing deionized water every 4 hours, and dialyzing for 2 days. Adding the dialyzed product into glacial ethyl ether for precipitation, filtering, and drying in vacuum to obtain the compound III (X is N)3)。
B. Formula IV (X is Br, R)3Is composed of
Figure GDA0002904891880000224
) The preparation method comprises the following steps: mixing formula nine (8g,70.1mmol), formula ten (0.433g,2.1mmol), formula twelve (0.126g,0.35mmol), Me6TREN (0.1613g,0.7mmol) and 20mL of solvent (V)DMF:VWater (W)80: 20) adding into anhydrous oxygen-free bottle to dissolve completely. Vacuum-filling with N2Three times in N2CuBr (0.1018g, 0.7mmol) was added rapidly under protection, vacuum-charged with N2Three times. In N2The reaction is continued to be stirred for 2h under protection, 15ml of THF is added for dilution after the reaction is finished, the mixture is placed in the air for stirring for 2h, and cuprous bromide is removed through a silica gel column. Excess solvent was spun off, then precipitated by addition of glacial ethyl ether, and repeated 2-3 times to sufficiently remove unpolymerized monomers. Drying the filtered product in a vacuum drying oven at 60 ℃ for 24h to obtain the product of the formula IV (X is Br, R)3Is composed of
Figure GDA0002904891880000225
) The chemical synthesis route is as follows:
Figure GDA0002904891880000231
wherein, the formula IV (X is Br, R)3Is composed of
Figure GDA0002904891880000232
) Is prepared from the compound of formula (II) and (III)3Is composed of
Figure GDA0002904891880000233
) The preparation method of (a) is similar, except that formula ten is replaced by formula thirteen.
Formula IV (X is Br) can also be subjected to azide treatment, and specifically, formula IV (X is Br) and sodium azide are reacted in DMF at a molar ratio of 1:12 at 60 ℃ for 2 days. And adding the reacted solution into a dialysis bag for dialysis, changing deionized water every 4 hours, and dialyzing for 2 days. Adding the dialyzed product into glacial ethyl ether for precipitation, filtering, and drying in vacuum to obtain the product of formula IV (X is N)3)。
C. The preparation method of the thirteen formula is as follows: dissolving mono-6-ethylenediamine-beta-cyclodextrin (10g, 8.5mmol) in 20ml of anhydrous DMF, adding 6ml of anhydrous triethylamine, stirring uniformly, dropwise adding acryloyl chloride (6ml, 42.5mmol) into the solution of mono-6-ethylenediamine-beta-cyclodextrin at 0 ℃, and reacting at room temperature for 24h after dropwise adding. Precipitating in a large amount of anhydrous ethanol to obtain a crude product, dissolving the crude product with a small amount of distilled water, and precipitating in acetone for 2-3 times for purification.
Example 7
The embodiment provides a self-healing temperature-sensitive hydrogel, and the preparation method comprises the following steps: the above examples were prepared to give (R) of the formula1Is composed of
Figure GDA0002904891880000234
) A formula II (L is
Figure GDA0002904891880000235
R2Is composed of
Figure GDA0002904891880000236
) And the formula III (wherein X is Br, R)3Is composed of
Figure GDA0002904891880000241
) A15 wt% aqueous solution prepared according to a molar ratio of 1:3:1 is uniformly mixed at a low temperature (5 ℃) and stands for 1 day, then the temperature is raised to 37 ℃ to form the self-healing temperature-sensitive hydrogel, the self-healing temperature-sensitive hydrogel is stored at 25 ℃ and 35 ℃ respectively, a real object diagram is shown in FIG. 4, the left side of the diagram is a real object diagram of the self-healing temperature-sensitive hydrogel at 25 ℃, the right side of the diagram is a real object diagram of the self-healing temperature-sensitive hydrogel at 35 ℃, and as can be seen from the diagram, the self-healing temperature-sensitive hydrogel is successfully prepared in the embodiment 7, and the difference of appearance transparency at different temperatures shows that the self-healing temperature-sensitive hydrogel has.
Example 8
This example is a two-dimensional nuclear magnetic spectrum of the self-healing temperature-sensitive hydrogel tested in example 7, and as shown in fig. 5, the cyclodextrin has a hydrophobic structure inside and a hydrophilic structure outside, and the adamantane group is a benign lipid-soluble structure and has a good complexation constant with cyclodextrin. H inside cyclodextrin3And H5Coupling with hydrogen on the adamantane group contained inside the cyclodextrin readily occurs. H inside cyclodextrin3And H5Occurring between 3.6 and 4.0ppm and the hydrogen on the adamantane radical occurring between 1.5 and 2.2 ppm. The two-dimensional nuclear magnetic spectrum of figure 2 shows the point of adamantane coupling to the cyclodextrin, which demonstrates that the adamantane group has been inserted into the internal cavity of the cyclodextrin.
Comparative example 1
This comparative example provides a first comparative example prepared by the method of: the above examples were prepared to give (R) of the formula1Is composed of
Figure GDA0002904891880000242
) A formula II (L is
Figure GDA0002904891880000243
R2Is composed of
Figure GDA0002904891880000244
) And the formula III (wherein X is Br, R)3Is composed of
Figure GDA0002904891880000245
) According to the following steps: 3:1 was uniformly mixed under the same conditions as in example 7, and the actual diagram was as shown in FIG. 6, with 25 ℃ on the left side and 35 ℃ on the right side, and no gel was formed at both temperatures.
Comparative example 2
This comparative example provides a second comparative example prepared by the method of: the preparation of formula one (R) from example 3 to example 5 above1Is composed of
Figure GDA0002904891880000251
) A formula II (L is
Figure GDA0002904891880000252
R2Is composed of
Figure GDA0002904891880000253
) And the formula III (wherein X is Br, R)3Is composed of
Figure GDA0002904891880000254
) According to the following steps: 3:1 was uniformly mixed under the same conditions as in example 5, and the actual diagram is shown in FIG. 7, in which the left side of the diagram is 25 ℃ and the right side is 35 ℃, and no gel was formed at both temperatures.
Example 9
This example is to test the volume phase transition temperature of the self-healing temperature-sensitive hydrogel of example 7, and the steps are as follows: the self-healing temperature-sensitive hydrogel sample fully swollen in example 6 was subjected to DSC analysis, the temperature rise range was 5 to 45 ℃, and the sample was left at 5 ℃ for 10min, the temperature rise rate was 3 ℃/min, the nitrogen atmosphere was dried, and the peak of the measured DSC curve was the Volume Phase Transition Temperature (VPTT) corresponding to the self-healing temperature-sensitive hydrogel, as shown in fig. 8, the Volume Phase Transition Temperature (VPTT) of the self-healing temperature-sensitive hydrogel of example 7 was 32.3 ℃.
Example 10
In this embodiment, the self-repairing capability of the self-healing temperature-sensitive hydrogel of example 7 is tested, as shown in fig. 9, a to F of fig. 9 are processes of self-repairing after gel is cut at 40 ℃ to form large cracks, the hydrogel cuts the cracks at 40 ℃, water is added dropwise after cutting, and then the gel is recovered to an initial state after self-repairing for 2.5 hours at 20 ℃, so that the self-healing temperature-sensitive hydrogel prepared has a temperature-sensitive assisted macroscopic large crack self-repairing function.
Example 11
The embodiment provides a second self-healing temperature-sensitive hydrogel, and the preparation method comprises the following steps: the above examples were prepared to give (R) of the formula1Is composed of
Figure GDA0002904891880000255
) A formula II (L is
Figure GDA0002904891880000256
R2Is composed of
Figure GDA0002904891880000257
) And the formula III (wherein X is Br, R)3Is composed of
Figure GDA0002904891880000258
) The molar ratio of the raw materials is 1:3: 2 preparing 10 wt% aqueous solution, mixing uniformly at low temperature (5 ℃), standing for 1 day, taking out, and heating to 35 ℃ to form the self-healing temperature-sensitive hydrogel. The self-healing temperature-sensitive hydrogel has temperature sensitivity and a self-healing function, and can realize self-healing of macroscopic large cracks without manual bonding through remote control of temperature.
Example 12
The embodiment provides a third self-healing temperature-sensitive hydrogel, and the preparation method comprises the following steps: the above examples were prepared to give (R) of the formula1Is composed of
Figure GDA0002904891880000261
) A formula II (L is
Figure GDA0002904891880000262
R2Is composed of
Figure GDA0002904891880000263
) And the formula III (wherein X is Br, R)3Is composed of
Figure GDA0002904891880000264
) The molar ratio of the raw materials is 2: 4: 1, preparing a 15 wt% aqueous solution, uniformly mixing at a low temperature (4 ℃), standing for 1 day, and heating at 40 ℃ to form the self-healing temperature-sensitive hydrogel. The temperature sensitivity and the self-healing performance of the self-healing temperature-sensitive hydrogel of the present example were measured. Experiments show that the self-healing temperature-sensitive hydrogel has temperature sensitivity and a self-healing function, and can realize self-healing of macroscopic large cracks without manual bonding through remote control of temperature.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A supramolecular material is characterized by comprising a first construction unit, a second construction unit and a third construction unit;
wherein the first building unit has a structure of formula:
Figure FDA0002946986500000011
wherein R is1Is selected from
Figure FDA0002946986500000012
One or two of them;
the second construction unit has a structure of formula two:
Figure FDA0002946986500000013
wherein R is2Is selected from
Figure FDA0002946986500000014
Figure FDA0002946986500000021
One or two of, L is
Figure FDA0002946986500000022
The third construction unit comprises a formula three structure or/and a formula four structure:
Figure FDA0002946986500000023
wherein X is selected from Br or N3；R3Is selected from
Figure FDA0002946986500000024
Figure FDA0002946986500000025
Wherein X is selected from Br or N3；R3Is selected from
Figure FDA0002946986500000026
The first building unit, the second building unit and the third building unit are connected by self-assembly based on adamantane-cyclodextrin host-object to form a supramolecular material;
wherein y is an integer of 50 to 100; in the formula II, z is an integer of 50-100; in the formula III and the formula IV, m is an integer of 50-100; and n is an integer of 0.5-10.
2. The supramolecular material as claimed in claim 1, wherein in formulae three and four, the supramolecular material
Figure FDA0002946986500000031
Contains beta-cyclodextrin.
3. The supramolecular material as claimed in claim 1, wherein the first formula is prepared by the following steps: carrying out click reaction on the formula five and the formula six, or carrying out click reaction on the formula five and the formula seven to prepare the formula I, wherein the specific structures of the formula five, the formula six and the formula seven are as follows:
Figure FDA0002946986500000032
the preparation method of the formula II comprises the following steps: carrying out click reaction on the formula eight and the formula six, or carrying out click reaction on the formula eight and the formula seven to prepare a formula two, wherein the specific structures of the formula eight, the formula six and the formula seven are as follows:
Figure FDA0002946986500000041
wherein L is
Figure FDA0002946986500000042
Figure FDA0002946986500000043
4. The supramolecular material as claimed in claim 1, wherein said process for the preparation of formula iii is: the compound is obtained by reacting a formula nine, a formula ten and a formula eleven, wherein X of the formula III is Br, R3Is composed of
Figure FDA0002946986500000044
The specific structures of the formula nine, the formula ten and the formula eleven are as follows:
Figure FDA0002946986500000045
the preparation method of the formula IV comprises the following steps: the compound is obtained by reacting nine, ten and twelve formulas, wherein X of the fourth formula is Br, R3Is composed of
Figure FDA0002946986500000046
The specific structures of the nine formula, the ten formula and the twelve formula are as follows:
Figure FDA0002946986500000051
5. the supramolecular material as claimed in claim 1, wherein said process for the preparation of formula iii is: obtained by reacting nine, thirteen and eleven, wherein X of the third formula is Br, R3Is composed of
Figure FDA0002946986500000052
Wherein the specific structures of formula nine, formula thirteen and formula eleven are as follows:
Figure FDA0002946986500000053
the preparation method of the formula IV comprises the following steps: the compound is obtained by reacting nine, thirteen and twelve formulas, wherein X of the fourth formula is Br,
R3is composed of
Figure FDA0002946986500000054
Wherein the specific structures of the formula nine, the formula thirteen and the formula twelve are as follows:
Figure FDA0002946986500000055
6. the self-healing temperature-sensitive hydrogel is characterized in that the preparation method comprises the following steps:
mixing a first construction unit, a second construction unit, a third construction unit and water, self-assembling through dissolving and mixing adamantane-cyclodextrin host object of the first construction unit, the second construction unit and the third construction unit at 4-20 ℃, and then heating to 35-50 ℃ to form the self-healing temperature-sensitive hydrogel, wherein the first construction unit has a structure of formula one in claim 1, the second construction unit has a structure of formula two in claim 1, and the third construction unit comprises a structure of formula three in claim 1 or/and a structure of formula four in claim 1.
7. The self-healing temperature-sensitive hydrogel according to claim 6, wherein the volume phase transition temperature of the self-healing temperature-sensitive hydrogel is 20 to 35 ℃.
8. A self-healing temperature-sensitive hydrogel according to claim 6, wherein the ratio of the sum of the moles of the first formula and the second formula to the moles of the third building unit is 1: (0.4-6).
9. A self-healing temperature-sensitive hydrogel according to claim 6, wherein the mixed mass concentration of the first, second and third building units in aqueous solution is 5 to 25 wt%.
CN201811640303.4A 2018-12-29 2018-12-29 Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof Active CN109721738B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811640303.4A CN109721738B (en) 2018-12-29 2018-12-29 Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811640303.4A CN109721738B (en) 2018-12-29 2018-12-29 Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109721738A CN109721738A (en) 2019-05-07
CN109721738B true CN109721738B (en) 2021-04-16

Family

ID=66298357

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811640303.4A Active CN109721738B (en) 2018-12-29 2018-12-29 Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109721738B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103483590A (en) * 2013-09-12 2014-01-01 华南理工大学 Method for preparing bottle-brush type polymer through subject and object self-assembly
CN103524751A (en) * 2013-09-11 2014-01-22 江南大学 Preparation method of double-sensitivity cyclodextrin supermolecule aggregate
CN104262643A (en) * 2014-10-21 2015-01-07 南京慧联生物科技有限公司 Supramolecular hydrogel microsphere prepared by taking liquid drop as template and preparation method thereof
CN106366225A (en) * 2016-10-27 2017-02-01 广东工业大学 Six-arm thermosensitive polymer and preparation method thereof
EP3281960A1 (en) * 2015-04-10 2018-02-14 Osaka University Self-repairing material and manufacturing method therefor
EP3492576A1 (en) * 2016-07-28 2019-06-05 Osaka University Polymer gel for medium, medium, and method and kit for culturing cells

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10828399B2 (en) * 2015-03-27 2020-11-10 The Trustees Of The University Of Pennsylvania Three dimensional printing of supramolecular (hydro)gels

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103524751A (en) * 2013-09-11 2014-01-22 江南大学 Preparation method of double-sensitivity cyclodextrin supermolecule aggregate
CN103483590A (en) * 2013-09-12 2014-01-01 华南理工大学 Method for preparing bottle-brush type polymer through subject and object self-assembly
CN104262643A (en) * 2014-10-21 2015-01-07 南京慧联生物科技有限公司 Supramolecular hydrogel microsphere prepared by taking liquid drop as template and preparation method thereof
EP3281960A1 (en) * 2015-04-10 2018-02-14 Osaka University Self-repairing material and manufacturing method therefor
EP3492576A1 (en) * 2016-07-28 2019-06-05 Osaka University Polymer gel for medium, medium, and method and kit for culturing cells
CN106366225A (en) * 2016-10-27 2017-02-01 广东工业大学 Six-arm thermosensitive polymer and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Direct 3D Printing of Shear-Thinning Hydrogels into Self-Healing Hydrogels;Christopher B. Highley等;《Adv. Mater.》;20150715;第27卷;第5075-5079页 *
Novel construction of supramolecular hydrogels;zhu,dongyu等;《254th ACS National Meeting》;20170824;575 *
Preorganized Hydrogel: Self-Healing Properties of Supramolecular Hydrogels Formed by Polymerization of Host–Guest-Monomers that Contain Cyclodextrins and Hydrophobic Guest Groups;Takahiro Kakuta等;《Adv. Mater.》;20130219;第25卷;第2849-2853页 *
聚（Ｎ－异丙基丙烯酰胺）－环糊精星形聚合物的RAFT聚合合成与表征;吴东升等;《材料导报Ｂ：研究篇》;20120831;第26卷(第8期);第42-46页 *

Also Published As

Publication number Publication date
CN109721738A (en) 2019-05-07

Similar Documents

Publication Publication Date Title
CN109851694B (en) Supramolecular material and self-repairing hydrogel
TWI475051B (en) Organic polysiloxane
CN109851804B (en) Supermolecular material, large-crack self-repairing hydrogel and preparation method thereof
CN109721738B (en) Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof
CN112920447A (en) Preparation method of polymer membrane with micropores and capable of being hydrolyzed and crosslinked simultaneously
CN109438723B (en) Supramolecular material, temperature-sensitive hydrogel and preparation method thereof
CN109705371B (en) Supramolecular material, six-arm star-shaped cross-linked hydrogel and preparation method thereof
CN109705372B (en) Supramolecular material, hydrogel and preparation method thereof
CN109694479B (en) Supermolecular material and host-guest self-assembly hydrogel and preparation method thereof
EP2930190A1 (en) Method for preparing acetylated cellulose ethers having improved anti-fouling properties, and acetylated cellulose ethers prepared by same
JP5282200B2 (en) Transparent hydrogelator
JP5352810B2 (en) Asymmetric hydrogelator
CN110776426B (en) 2-perfluoro epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester and preparation method and application thereof
CN110330570B (en) Preparation method of 6-amino-6-deoxy cellulose
JP2008063360A (en) Polyphenylacetylenic polymer, method for producing the same and phenylacetylene derivative
CN115477743B (en) Polylactic acid containing disulfide bonds and preparation method and application thereof
JP4895683B2 (en) Vinyl ether derivative polymer and production method and use thereof
CN115894958B (en) Metal main chain polymer with precise length and synthesis method and application thereof
CN116063666B (en) Multifunctional polyester material and preparation method and application thereof
JP5008053B2 (en) Star polymer
CN113121729B (en) Preparation method of polyvinyl chloride modified by saccharic (aldehydic) acid, polyvinyl chloride and application
CN110590979B (en) Preparation method of PVB resin powder with high acetal rate
JP2717587B2 (en) Polycrotonic acid sec-butyl ester and method for producing the same
KR20160075234A (en) Method of preparing acetylated cellulose ether
CN116041693A (en) Carboxyl-containing polyaryletherketone resin, preparation method and application of polyaryletherketone with crosslinked network structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant