CN110527062A - Coloud coding supramolecular hydrogel and preparation method thereof - Google Patents
Coloud coding supramolecular hydrogel and preparation method thereof Download PDFInfo
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- CN110527062A CN110527062A CN201910860039.3A CN201910860039A CN110527062A CN 110527062 A CN110527062 A CN 110527062A CN 201910860039 A CN201910860039 A CN 201910860039A CN 110527062 A CN110527062 A CN 110527062A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/329—Hydroxyamines containing aromatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
The present invention relates to a kind of coloud coding supramolecular hydrogels and preparation method thereof, the present invention is colored chain extender using red, yellow, blue (blueness) three primary colors (pigment three primary colors) small molecule dihydric alcohol, is prepared for three primary colors colour polyurethane urea macromolecular gelator.And then high intensity (fracture strength about 8MPa, elongation at break are up to 750%-1200%) supramolecular hydrogel of full-color system's coloud coding is constructed by adjusting the ratio of three primary colors colour macromolecular gelator according to trichromatic mixing color theory.For the first time with color come the performances such as intuitive label, physical property, chemical constituent, mechanics and the purposes of the high-intensitive supramolecular hydrogel of identification gained.
Description
Technical field
The present invention relates to colored hydrogels more particularly to a kind of coloud coding supramolecular hydrogel and preparation method thereof.
Background technique
Hydrogel is to pass through the three-dimensional network being physically or chemically cross-linked to form by hydrophily/amphipathic small molecules or polymer
Large quantity of moisture swelling can be absorbed but not soluble in water in soft substance.Due to its high-moisture characteristic and biocompatibility, hydrogel
It is with a wide range of applications.Application No. is the Chinese patents of 201310518085.8,201410046298.X to individually disclose
High-strength polyurethane urea supramolecular hydrogel, but hydrogel reported at present is mostly colorless and transparent or light, and face
Color is single.But the hydrogel of different chemical constituents, physical property, purposes is different, suitable for different application places.Its is similar
Appearance, single color can bring certain puzzlement to the identification of hydrogel and use for non-gel professional.
If a series of hydrogel of different colours can be prepared, hydrogel is encoded using color, so that it may intuitive to pass
It passs, identify the information such as the corresponding physics of hydrogel, chemistry, convenient for the intuitive discrimination and use of material, device.
And prepared in the method for colored hydrogel at present, simple physical is adsorbed, there are colors for the colored hydrogel of embedding pigment
The problems such as spending loosely (small molecule pigment is easy to migrate)；Schemochrome hydrogel has that preparation process is cumbersome, color is single, stability again
The disadvantage of difference.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of coloud coding supramolecular hydrogel and its preparations
Method, the present invention is based on three primary colors mixing principles to obtain panchromatic system's colour supramolecular hydrogel, is carried out using color to hydrogel
Coding, the intuitive coding of the performances such as Lai Shixian physical property, chemical constituent, mechanics and purposes, the hydrogel preparation method is simple,
It will be keyed in polymer molecular structure with coloured group with chemistry, coloration is stronger.
On the one hand, the present invention provides a kind of colored supramolecular hydrogels comprising one or more of following general formula
Polymer:
Wherein, A1For the aliphatic chain containing 4-10 carbon atom；A2For aobvious red, yellow or blue group, R ' be containing
Aliphatic chain, alcyl or the aromatic radical of 4-18 carbon atom, any integer in m=4-450, any natural number in a=1-100, b
Any natural number in=0-100, any natural number in c=1-100, any natural number in d=1-100 are any in n=1-100
Integer.
The compound of above-mentioned general formula, when the group wherein comprising aobvious red, yellow or blue (three primary colors), colored oversubscription
The color of sub- hydrogel is red, yellow or blue；According to trichromatic mixing color theory, three primary colors colour supermolecule is utilized
At least two of polymer are mixed by different proportion, and other colors can be obtained, such as green, cyan, orange or purple color
Hydrogel.Since the mechanical strength and water absorption rate of the supramolecular hydrogel of different colours are also different, different colours can be used
Hydrogel is encoded, these hydrogels with different coding have different water absorption rate and mechanical property.
Further, the color of colored supramolecular hydrogel is red, yellow, blue, green, cyan, orange or purple.
Further, green, cyan, orange or purple supramolecular hydrogel by trichromatic supramolecular hydrogel extremely
Few two kinds mixed according to different proportion after obtain, three's mass ratio is x:y:z, and x, y, z is the natural number within 10.
Further, the tension fracture elongation rate of colored supramolecular hydrogel is 750%-1200%, tensile break stress
For 7-9MPa.
Preferably, it shows in the group of red and contains anthraquinonyl, contain azobenzene in the group of displaing yellow, show the base of blue
Contain anthraquinonyl in group.
Further, showing red group is
The group of displaing yellow is
Show blue group beOn the other hand, the present invention also provides a kind of above-mentioned colours
The preparation method of supramolecular hydrogel, comprising the following steps:
(1) a parts of polyethylene glycol are dissolved in organic solution A, the first chain extender of b part and c parts is then added thereto
Second chain extender；D parts of diisocyanate are added thereto again, are carried out under conditions of 30~90 DEG C under the effect of the catalyst pre-
Poly- reaction, reaction time are 1~6 hour；
Wherein, in molar ratio, a:(b+c)=0.1-10:1, b:c=0-100:1, d:a=0.1-20:1；
First chain extender is the aliphatic dihydroxy alcohol containing 4-10 carbon atom, and the second chain extender is to show red binary
One or more of alcohol, the dihydric alcohol of displaing yellow and the dihydric alcohol for showing blue；
Diisocyanate is the aliphatic diisocyanate containing 4-18 carbon atom, alicyclic diisocyanate or fragrance
(cyclo) aliphatic diisocyanates；
(2) water is added in the product obtained to step (1) as indirect chain extender, the reaction was continued at 20~80 DEG C 12~
72 hours, in molar ratio, the amount that water is added was 2 (d-a-b-c) parts；
(3) one or more of products that step (2) obtains are precipitated in organic solvent B, after drying precipitate
It is swollen in distilled water, obtains colored supramolecular hydrogel.
Further, in step (1), the molecular weight of polyethylene glycol (PEG) is 200~20000g/mol.It can change
The molecular weight of polyethylene glycol can prepare the hydrogel with different water absorption rates and different mechanical strengths.
Further, in step (1), the first chain extender includes the compound of one or more of following structural formulas:
(dimethylolpropionic acid, DMBA), HO- (CH2)4-OH、HO-(CH2)2-OH、
Further, in step (1), the dihydric alcohol for showing red is the compound of one or more of following structural formulas:
Further, in step (1), the dihydric alcohol of displaing yellow is the compound of one or more of following structural formulas:
Further, in step (1), the dihydric alcohol for showing blue is
Further, in step (1), aliphatic diisocyanate isONC-
(CH2)4-NCO、ONC-(CH2)6-NCO、ONC-(CH2)8-NCO、ONC-(CH2)12- NCO or 1,5- diisocyanate -2- methylpent
Alkane；
Alicyclic diisocyanate is
Aromatic diisocyanate is
Further, in step (1), catalyst is stannous octoate, dibutyl tin dilaurate, N-ethylmorpholine, N-
Methyl morpholine, pyridine or N, N '-lutidines.
Further, in step (1), organic solvent A DMAC, DMF, acetone, chloroform, methylene chloride, dichloroethanes
One of.
Further, in step (3), organic solvent B is n-hexane, normal heptane, isohexane, isoheptane, hexamethylene, second
One of ether.
Further, in step (3), after dry, further comprising the steps of before swelling: dried object being dissolved in organic molten
In agent C, then volatile organic solvent C and form in a mold.Organic solvent C is methanol, ethyl alcohol, chloroform, acetone or dichloromethane
One of alkane.
In the present invention, all there is oneself using three primary colors small molecule chain extender (aobvious red, yellow or blue dihydric alcohol)
Characteristic absorption wavelength, bonding enter polyurethane-urea long-chain in post-consumer polymer also all have respective characteristic absorption wavelength, pass through
Three primary colors polymer compound and obtain the polymer of other colors.By adjusting the ratio of three primary colors polymer, to realize
The preparation of panchromatic system's colour supramolecular hydrogel.
According to the above aspect of the present invention, the present invention has at least the following advantages:
The present invention provides a series of colored supramolecular hydrogels, user can be super come intuitive label, identification according to color
The performances such as physical property, chemical constituent, mechanics and the purposes of molecule hydrogel.
Using the method gradually polymerizeing in the present invention, three primary colors small molecule chain extender is introduced into polyurethane-urea macromolecular
In main chain, coloured supermolecule polymer is prepared, and be further formed hydrogel.By three primary colors polyurethaneurea polymer by difference
Ratio mixing can prepare panchromatic system's coloured polymer hydrogel, and the hydrogel of these different colours has different performances, because
This can use color and encodes to hydrogel, realize the physics of color intuitive label, the high-intensitive supramolecular hydrogel of identification gained
The performances such as performance, chemical constituent, mechanics and purposes.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after cooperating drawings in detail to illustrate such as.
Detailed description of the invention
Fig. 1 is the synthetic route schematic diagram of polyurethaneurea polymer of the present invention；
Fig. 2 is the difference of the infrared spectrum of red polyurethane-urea film and colourless polyurethane-urea film in the embodiment of the present invention 1
Spectrum；
Fig. 3 is the difference of the infrared spectrum of yellow urethane urea film and colourless polyurethane-urea film in the embodiment of the present invention 2
Spectrum；
Fig. 4 is the difference of the infrared spectrum of blue polyurethane urea film and colourless polyurethane-urea film in the embodiment of the present invention 3
Spectrum；
Fig. 5 is the UV absorption normalization spectrogram of three primary colors colour supramolecular hydrogel in 1-3 of the embodiment of the present invention；
Fig. 6 is the digital photograph of full-color system's colour hydrogel prepared in the present invention；
Fig. 7 is the stress-strain diagram of the tension test of full-color system's colour supramolecular hydrogel prepared in the present invention.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Embodiment 1
A kind of preparation method of red supramolecular hydrogel (RPUU hydrogel) is present embodiments provided, specific steps are such as
Under:
(1) 4.00g (2mmol) PEG (Mn=2000g/mol) is weighed in 100mL three-necked flask, is placed on 80 DEG C
It is drying over night in vacuum drying oven, while a small amount of phosphorus pentoxide is placed in vacuum drying oven to eliminate moisture.After drying,
Three-necked flask is taken out, places it in the oil bath pan of room temperature, 10mL is added into three-necked flask with graduated cylinder and uses anhydrous sulphur in advance
Magneton stirring is added in the dried DMAC of sour sodium.0.1450g (0.98mmol) dimethylolpropionic acid (DMBA) is added,
0.02mmol red small molecule chain extender, the isophorone diisocyanate (IPDI) of 2.67g (12mmol) and the February of 20 μ L
Two fourth tin (catalyst) of cinnamic acid.Wherein, the structural formula of red small molecule chain extender is as follows:
(2) heating stirring reacts 4h after the above mixture being warming up to 70 DEG C, and reaction system is then cooled to 50 DEG C, is added
Enter the H of 18mmol2O continues to be stirred to react.After water is added, with the progress of reaction, solution viscosity constantly increases, in reaction process
DMAC (about 30-35mL) constantly is added to control the concentration of solution, prevents system gelation, after reaction for 24 hours, stops reaction simultaneously
Cooling.
(3) after reaction solution is cooled to room temperature, reaction solution is poured slowly into the ether of 10 times of volumes of reaction dissolvent and is sunk
It forms sediment, obtains blocks of solid, then shredded, change ether ultrasound 45min (in order to sufficiently cement out high boiling DMAC).Again
Solid is placed on in 60 DEG C of vacuum drying oven dry 12h, RPUU polymer is obtained, takes on a red color.
(4) it takes the RPUU polymer of 1.0g in 10mL vial, 4g methanol is added, 50 DEG C of heating is molten on blender
Solution is poured into 5cm × 5cm × 1cm Teflon mould after sample dissolution, filter paper is put on mold by solution, is prevented
Only methanol volatilization is too fast will appear bubble.Naturally dry 1-2 days at room temperature are subsequently placed in 40 DEG C of vacuum oven further
Drying obtains RPUU polymer dry film until constant weight.The RPUU polymer dry film prepared is fully immersed in excessive distillation
It is swollen in water, it is primary to change water at regular intervals, and RPUU hydrogel is obtained after swelling equilibrium.
In order to prepare colourless hydrogel according to step (1)-(4) as control, difference is, will be in step (1)
The DMBA of 0.98mmol replaces with the DMBA of 1.00mmol, and without using red small molecule chain extender.
Referring to attached drawing 2, it is the colourless polyurethane that RPUU polymer dry film provided in this embodiment and use DMBA are obtained
The difference spectrum of the infrared spectrum of urea dry film；In figure as it can be seen that due to only having micro red chain extender to be linked into polyurethaneurea polymer
In long-chain, so being barely perceivable the characteristic absorption peak of red chain extender in the infrared spectroscopy of polyurethane-urea film, therefore
The difference spectrum of RPUU polymer dry film and colourless polyurethane-urea dry film is studied.1596cm-1, 1492cm-1It is the C=C of phenyl ring
Stretching vibration characteristic peak, 792cm-1It is the out-of-plane bending vibration characteristic peak of the C-H of phenyl ring, these are all the features of red chain extender
Absorption peak, it can be seen that red small molecule chain extender, which is successfully bonded, to be entered in polyurethaneurea polymer.
Embodiment 2
A kind of preparation method of yellow supramolecular hydrogel (YPUU hydrogel) is present embodiments provided, specific steps are such as
Under:
(1) 4.00g (2mmol) PEG (Mn=2000g/mol) is weighed in 100mL three-necked flask, is placed on 80 DEG C
It is drying over night in vacuum drying oven, while a small amount of phosphorus pentoxide is placed in vacuum drying oven to eliminate moisture.After drying,
Three-necked flask is taken out, places it in the oil bath pan of room temperature, 10mL is added into three-necked flask with graduated cylinder and uses anhydrous sulphur in advance
Magneton stirring is added in the dried DMAC of sour sodium.Add 0.1450g (0.98mmol) DMBA, 0.02mmol yellow small molecule
The dibutyl tin dilaurate (catalyst) of chain extender, the IPDI of 2.67g (12mmol) and 20 μ L.Wherein, yellow small molecule chain extension
The structural formula of agent is as follows:
(2) heating stirring reacts 4h after the above mixture being warming up to 70 DEG C, and reaction system is then cooled to 50 DEG C, is added
Enter the H of 18mmol2O continues to be stirred to react.After water is added, with the progress of reaction, solution viscosity constantly increases, in reaction process
DMAC (about 30-35mL) constantly is added to control the concentration of solution, prevents system gelation, and reaction for 24 hours, stops reacting and dropping
Temperature.
(3) after reaction solution is cooled to room temperature, reaction solution is poured slowly into the ether of 10 times of volumes of reaction dissolvent and is sunk
It forms sediment, obtains blocks of solid, then shredded, change ether ultrasound 45min (in order to sufficiently cement out high boiling DMAC).Again
Solid is placed on in 60 DEG C of vacuum drying oven dry 12h, obtains YPUU polymer after dry, is in yellow.
(4) YPUU hydrogel is prepared according to step (4) method in embodiment 1, difference is to replace in RPUU polymer
It is changed to the YPUU polymer of the present embodiment.
Referring to attached drawing 3, it is the INFRARED SPECTRUM of YPUU polymer dry film provided in this embodiment Yu colourless polyurethane-urea dry film
The difference spectrum of figure；Wherein, 1650cm-1It is the C=C stretching vibration characteristic peak of phenyl ring, 1591cm-1It is the stretching vibration feature of N=N
C=C stretching vibration characteristic peak, 771cm in peak and phenyl ring-1、711cm-1It is the out-of-plane bending vibration characteristic peak of the C-H of phenyl ring,
These are all the characteristic absorption peaks of yellow chain extender, it can be seen that yellow small molecule chain extender is successfully bonded poly- into polyurethane-urea
It closes in object.
Embodiment 3
A kind of preparation method of blue supramolecular hydrogel (BPUU hydrogel) is present embodiments provided, specific steps are such as
Under:
(1) 4.00g (2mmol) PEG (Mn=2000g/mol) is weighed in 100mL three-necked flask, is placed on 80 DEG C
It is drying over night in vacuum drying oven, while a small amount of phosphorus pentoxide is placed in vacuum drying oven to eliminate moisture.After drying,
Three-necked flask is taken out, places it in 70 DEG C of oil bath pan, 10mL is added into three-necked flask with graduated cylinder and uses anhydrous sulphur in advance
Magneton stirring is added in the dried DMAC of sour sodium.Add 0.1450g (0.98mmol) DMBA, 0.02mmol blue small molecule
The dibutyl tin dilaurate (catalyst) of chain extender, the IPDI of 12mmol and 20 μ L.Wherein, the structure of blue small molecule chain extender
Formula is as follows:
(2) heating stirring reacts 4h after the above mixture being warming up to 70 DEG C, and reaction system is then cooled to 50 DEG C, is added
Enter the H of 18mmol2O continues to be stirred to react.After water is added, with the progress of reaction, solution viscosity constantly increases, in reaction process
DMAC (about 30-35mL) constantly is added to control the concentration of solution, prevents system gelation, for 24 hours, stopping reaction is simultaneously cold for reaction
But.
(3) after reaction solution is cooled to room temperature, reaction solution is poured slowly into the ether of 10 times of volumes of solvent and is precipitated, obtained
It to blocks of solid, then is shredded, changes ether ultrasound 45min (in order to sufficiently cement out high boiling DMAC).It will consolidate again
Body is placed in 60 DEG C of vacuum drying oven dry 12h, obtains BPUU polymer after dry, blue.
(4) BPUU hydrogel is prepared according to step (4) method in embodiment 1, difference is to replace in RPUU polymer
It is changed to the BPUU polymer of the present embodiment.
Referring to attached drawing 4, it is the INFRARED SPECTRUM of BPUU polymer dry film provided in this embodiment Yu colourless polyurethane-urea dry film
The difference spectrum of figure；Wherein, 1631cm-1、1492cm-1It is that C=C stretching vibration absorbs in phenyl ring, 1562cm-1It is then the breathing of phenyl ring
Vibration, while 1097cm-1It is that C-O stretching vibration absorbs, 1245cm-1It is then the telescope features peak of fragrant C-N, these are all yellow
The characteristic absorption peak of color chain extender, it can be seen that blue small molecule chain extender, which is successfully bonded, to be entered in polyurethaneurea polymer.
Referring to attached drawing 5, it is the normalization spectrum of the UV absorption of the three primary colors supramolecular hydrogel prepared in embodiment 1-3
Figure.Three primary colors chain extender absorption peak after accessing polyurethaneurea polymer is consistent with monomer, so color is also consistent.
Embodiment 5
The present embodiment provides the methods for obtaining panchromatic system's supramolecular hydrogel by three primary colors hydrogel, and steps are as follows:
The polymer of different colours obtained in Example 1-3 step (3) is mixed, and specifically gathers 0.5gRPUU
Close object and 0.5gYPUU polymer, 0.66gYPUU polymer and 0.34gBPUU polymer, 0.34gYPUU polymer and
0.66gBPUU polymer, 0.5gRPUU polymer and 0.5gBPUU polymer are separately added into 10mL vial, and 4g first is added
Alcohol heats 50 DEG C of dissolutions on blender, and after sample dissolution, solution is poured into 5cm × 5cm × 1cm polytetrafluoroethylene (PTFE) mould
In tool, filter paper is put on mold, prevents methanol volatilization is too fast from will appear bubble.Naturally dry 1-2 days at room temperature are subsequently placed in
It is further dried in 40 DEG C of vacuum oven until constant weight, the polymer for respectively obtaining orange, green, cyan and purple are dry
Film.
The polymer dry film of the different colours prepared is fully immersed in excessive distilled water and is swollen, when one section
Between change that water is primary, the hydrogel of corresponding color is obtained after swelling equilibrium, to obtain panchromatic system's colour hydrogel.
Referring to attached drawing 6, it is panchromatic system's supramolecular hydrogel as obtained from three primary colors mixed with polymers in the present embodiment
The digital photograph figure of glue, Fig. 6 a-g are followed successively by red, yellow, blue, green, cyan, orange and purple hydrogel, and Fig. 6 h is to make
For the colourless hydrogel of control.
Referring to attached drawing 7, it is the stretching survey of the polyurethane-urea hydrogel of the different colours of above embodiments preparation of the present invention
Curve graph is tried, the hydrogel of synthesis is strong physical crosslinking point with the nanometer microcell that the short chain aggregation of hydrophobicity strong hydrogen bonding polyureas is formed,
Swelling equilibrium state, which can be formed, still has the physical crosslinking supramolecular hydrogel of superhigh intensity.Stretch test result shows red water
The break-draw strain of gel is about 1100%, and fracture strength is about 9MPa；The break-draw strain of yellow hydrogel glue is about
1000%, fracture strength is about 9MPa；The break-draw strain of blue hydrogel glue is about 920%, and fracture strength is about 8MPa；
The break-draw strain of green hydrogel glue is about 1200%, and fracture strength is about 9MPa；The break-draw of cyan hydrogel glue
Strain about 800%, fracture strength is about 8MPa；The break-draw strain of orange-coloured hydrogel glue is about 900%, and fracture strength is about
For 8MPa；The break-draw strain of purple hydrogel is about 900%, and fracture strength is about 7.8MPa.To sum up, present invention gained is molten
Swollen equilibrium state coloud coding supramolecular hydrogel fracture strength is in 8.0MPa or so, and elongation at break is up to 750%-
1200%.It can be seen that three primary colors small molecule chain extender does not have too big influence, panchromatic system's colour supramolecular hydrogel of synthesis
There is preferable intensity.
The above is only the preferred embodiment of the present invention, are not intended to restrict the invention, it is noted that this technology is led
For the those of ordinary skill in domain, without departing from the technical principles of the invention, several improvements and modifications can also be made,
These improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of colour supramolecular hydrogel, which is characterized in that it includes the polymer of one or more of following general formula:
Wherein, A1For the aliphatic chain containing 4-10 carbon atom；A2For aobvious red, yellow or blue group, R ' is to contain 4-18
Aliphatic chain, alcyl or the aromatic radical of a carbon atom, any integer in m=4-450, any natural number in a=1-100, b=0-
Any natural number in 100, any natural number in c=1-100, any natural number in d=1-100, any integer in n=1-100.
2. it is according to claim 1 colour supramolecular hydrogel, which is characterized in that its color be red, yellow, blue,
Green, cyan, orange or purple.
3. colour supramolecular hydrogel according to claim 1, which is characterized in that its tension fracture elongation rate is 750%-
1200%, tensile break stress 7-9MPa.
4. colour supramolecular hydrogel according to claim 1, which is characterized in that the group for showing red is
The group of displaing yellow is
Show blue group be
5. a kind of preparation method of colored supramolecular hydrogel described in claim 1, which comprises the following steps:
(1) a parts of polyethylene glycol are dissolved in organic solution A, the first chain extender of b part and c part second is then added thereto
Chain extender；D parts of diisocyanate are added thereto again, it is anti-to carry out pre-polymerization under conditions of 30~90 DEG C under the effect of the catalyst
It answers, the reaction time is 1~6 hour；
Wherein, in molar ratio, a:(b+c)=0.1-10:1, b:c=0-100:1, d:a=0.1-20:1；
First chain extender is the aliphatic dihydroxy alcohol containing 4-10 carbon atom, and second chain extender is the two of aobvious red
One or more of first alcohol, the dihydric alcohol of displaing yellow and the dihydric alcohol for showing blue；
The diisocyanate is the aliphatic diisocyanate containing 4-18 carbon atom, alicyclic diisocyanate or fragrance
(cyclo) aliphatic diisocyanates；
(2) water is added in the product obtained to step (1) as indirect chain extender, it is 12~72 small that the reaction was continued at 20~80 DEG C
When, in molar ratio, the amount that water is added is 2 (d-a-b-c) parts；
(3) one or more of products that step (2) obtains are precipitated in organic solvent B, will be being steamed after drying precipitate
It is swollen in distilled water, obtains the colored supramolecular hydrogel.
6. preparation method according to claim 5, it is characterised in that: in step (1), first chain extender includes one
The compound of kind or several following structural formulas:
HO-(CH2)4OH、HO-(CH2)2-OH、
7. preparation method according to claim 5, it is characterised in that: in step (1), the dihydric alcohol of the aobvious red is
The compound of one or more of following structural formulas:
8. preparation method according to claim 5, it is characterised in that: in step (1), the dihydric alcohol of the displaing yellow is
The compound of one or more of following structural formulas:
9. preparation method according to claim 5, it is characterised in that: in step (1), the dihydric alcohol of the aobvious blue is
10. preparation method according to claim 5, it is characterised in that: in step (1), the aliphatic diisocyanate
Ester isONC-(CH2)4-NCO、ONC-(CH2)6-NCO、ONC-(CH2)8-NCO、ONC-
(CH2)12- NCO or 1,5- diisocyanate -2- methylpentane；
Alicyclic diisocyanate is
Aromatic diisocyanate is
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