CN110003427A - A kind of light stimulus responsive gel material, its preparation and application - Google Patents
A kind of light stimulus responsive gel material, its preparation and application Download PDFInfo
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- CN110003427A CN110003427A CN201910247062.5A CN201910247062A CN110003427A CN 110003427 A CN110003427 A CN 110003427A CN 201910247062 A CN201910247062 A CN 201910247062A CN 110003427 A CN110003427 A CN 110003427A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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Abstract
The invention belongs to mechanochemistry conductive material technical fields, more particularly, to a kind of light stimulus responsive gel material, its preparation and application.Under dark conditions and inert gas shielding, organic solution, poly-dihydric alcohol and the small molecule polyol of six aryl bisglyoxaline class molecules of polyhydroxy modification are mixed, mixed solution is obtained；Diisocyanate is mixed with the mixed solution, crosslinks reaction under the action of catalyst, the light stimulus responsive gel material comprising organic solvent is obtained after curing molding；The gel rubber material is placed in solvent that photic stimuli response is sensitive, and deformation degree can be regulated and controled by light application time, and irradiation time is longer, and deformation is more obvious.Intelligent gel rubber material prepared by the present invention is double cross-linked network structures, contains six aryl bisglyoxalines on main chain, can take into account the deformability and mechanical property of gel.The gel reaction process for the optical drive that the present invention prepares is simple, low in cost, applied widely.
Description
Technical field
The invention belongs to mechanochemistry conductive material technical fields, more particularly, to a kind of light stimulus responsive gel
Material, its preparation and application.
Background technique
Intelligent gel is one kind of gel.Traditional hydrogel has a good water imbibition, water-retaining property and degradable excellent
Point.Intelligent aqueous gel also has good slow release, biocompatibility and external environment responsiveness, thus pesticide, agricultural,
The fields such as industry and food have a wide range of applications, and are the high molecular materials of a kind of great exploitation potential.Intelligent aqueous gel and people
Body blood has good biocompatibility, is easy to be degraded when body fluid and tissue liquid contacts.Therefore it is widely used in biological doctor
Medicine, the aspect of human tissue engineering are used as pharmaceutical carrier, sustained release agent and medical adhesives.
By reasonably designing, Photosensitive Polymer Hydrogel can produce photo-deformable or have shape memory function, complete
At the movement for some complexity such as stretch, be bent, creep, rotate, and a variety of flexible intelligent actuators can be fabricated to,
The fields such as artificial-muscle, artificial skin, microrobot, Micropump, micro-valve have a wide range of applications.
However, existing literature report is mostly thermal response-type deformation gel, ratio is required to the external environment of material
It is harsher.Although the prior art reports some light responsive hydrogels, but its principle is that oxidation stone is added in material system
Black alkene, graphene oxide can convert illumination to heat, substantially this photoresponse or thermal response gel-type material.It is this in material
Material system internal physical adulterates some other functional materials, will affect the mechanical and physical performance of material.And it is light-operated achievable remote
Journey accurately contactless control, explaining clearly from this layer of meaning, it is significant to send out Photosensitive hydrogel pure.
Emphasis of the invention is exactly discovery and develops the hydrogel with photoresponse, and existing technology and is found to have
The material of this function is rarely reported or preparation process is complicated or cost of material is higher.This material has preparation process letter
Single, low in raw material price has the advantages such as the potentiality of large-scale production.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of light stimulus responsive gel materials
Material, its preparation and application, its object is to the organic solutions for the six aryl bisglyoxaline class molecules for modifying polyhydroxy, poly-dihydric alcohol
And small molecule polyol is mixed with diisocyanate, crosslinks reaction, finally together with organic solvent curing molding, is obtained
The material arrived is gel structure, which is carried out light stimulus, it is found that it, with light stimulus responsiveness deformation and reversible, is thus solved
Certainly the prior art lacks the technical issues of light stimulus responsive intelligent gel rubber material.
To achieve the above object, according to one aspect of the present invention, a kind of light stimulus responsive gel material is provided
Preparation method includes the following steps:
(1) under dark conditions and inert gas shielding, by having for six aryl bisglyoxaline class molecules of polyhydroxy modification
Machine solution, poly-dihydric alcohol and small molecule polyol are mixed, and obtain mixed solution；
(2) diisocyanate is mixed with step (1) described mixed solution, crosslinks reaction under the action of catalyst,
The light stimulus responsive gel material comprising organic solvent is obtained after curing molding；
Wherein, six aryl bisglyoxaline class molecules of the polyhydroxy modification are as the dynamic crosslinking point in the gel rubber material；
The small molecule polyol is as the fixation crosslinking points in the gel rubber material；The Long carbon chain that the poly-dihydric alcohol contains be used for so that
The gel rubber material being prepared has flexibility；The six aryl bisglyoxaline classes point that the diisocyanate is used to modify with polyhydroxy
Organic solution, poly-dihydric alcohol and the small molecule polyol of son crosslink reaction.
Preferably, the preparation method, further comprises the steps of:
(3) the light stimulus responsive gel material by described containing organic solvent is vacuumizing, is removing it under heating condition
In organic solvent, obtain the light stimulus responsive gel material.
Preferably, organic solution, the small molecule of six aryl bisglyoxaline class molecules of step (1) the polyhydroxy modification are polynary
The molar ratio of alcohol, poly-dihydric alcohol and diisocyanate is 6:1:(25~30): (45~60).
Preferably, step (1) poly-dihydric alcohol is oligomer dihydric alcohol, and the oligomer dihydric alcohol molecular weight is not more than
10000g/mol。
Preferably, the molecular weight of the oligomer dihydric alcohol is 400-8000g/mol.
Preferably, six aryl bisglyoxaline class molecules of the polyhydroxy modification are to repair by molecular bulk of 2-Cl-HABI
The molecule that decorations design obtains, the 2-Cl-HABI have the structure as shown in formula (one):
Preferably, the organic solvent in step (1) described organic solution is that boiling point is organic higher than 100 DEG C or more of higher boiling
Solvent is used to dissolve six aryl bisglyoxaline molecules of institute's hydroxyl modified.
Preferably, step (2) curing molding is to carry out in insulating box, and temperature range is 30-60 DEG C.
Preferably, step (2) diisocyanate is aliphatic diisocyanate or aromatic diisocyanate；It is described
The mole of diisocyanate is 7~10 times of the mole of six aryl bisglyoxaline class molecules of the polyhydroxy functionalization.
Other side according to the invention provides a kind of light stimulus responsive gel material, according to the preparation
Method is prepared.
Other side according to the invention provides the application of light stimulus responsive gel material described in one kind, uses
Make light stimulus responsiveness deformation intellectual material.
Preferably, when concrete application, the gel rubber material is placed in solvent, with the side of the ultraviolet light material,
The material is to the curving of backlight, and the material can change colour；As light application time increases, the bending deformation degree is bigger；Stop
The only illumination of the material side, then another survey illumination to material, deformation are gradually recovered；If continuous light, which be will continue to
To the curving of backlight.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) preparation method of a kind of light stimulus responsive gel material provided by the invention, by the six of polyhydroxy modification
Organic solution, poly-dihydric alcohol and the small molecule polyol of aryl bisglyoxaline class molecule are mixed with diisocyanate, are crosslinked
Reaction, finally together with organic solvent curing molding, for organic solvent dispersion in the polymer, obtained material is gel knot
Structure.
(2) gel rubber material obtained comprising organic solvent is further carried out removing solvent processing by the present invention, obtains one
Kind light stimulus responsiveness xerogel.
(3) a kind of light stimulus responsive gel material proposed by the present invention, for double cross-linked structures, tetrahydroxy function
The six aryl bisglyoxaline class molecular switches and small molecule polyol changed are crosslinking agent, and six aryl bisglyoxalines in network structure serve as
Dynamic crosslinking point, small molecule polyol are fixed crosslinking points.Material can constant rule under ultraviolet lighting for the gel rubber material
Movement, and this process is reversible.It is primarily due to, the material includes in material two sides with dual network structure in dicyandiamide solution
Solvent molecule is in dynamic balance state.Network structure can deformation occurs after the illumination of side, leads to two sides solvent molecule
Quantity is different, causes material two sides stress different, obvious deformation occurs.
(4) in solvent such as water intelligent response deformation can occur for gel rubber material proposed by the present invention under illumination condition, make
For a kind of intelligent gel rubber material, there is the mechanical and physical performances such as good toughness, ductility and fatigue resistance, can be used as
Intellectual material, driver, soft robot, bioartificial organs, sensor, manufacturing industry, health care, wearable device and
Medical instrument etc. has potential application market.
(5) it is proposed by the present invention can light-operated hydrogel material preparation method it is extremely simple to the pre-processing of raw material, instead
It answers one step of process to complete, is easy to industrial scale production.
(6) intelligent gel rubber material prepared by the present invention is double cross-linked network structures, contains six aryl bisglyoxalines on main chain, can be with
Take into account the deformability and mechanical property of gel.The gel reaction process for the optical drive that the present invention prepares is simple, low in cost,
It is applied widely.
Detailed description of the invention
Fig. 1 is the swelling test chart that optical Response gel rubber material prepared by the present invention is placed in water under non-illuminated conditions；
Fig. 2 be light stimulus responsive gel material made from the embodiment of the present invention 1 in water (be put into pure water vertically, on
End is fixed), response deformation photo record figure occurs under illumination condition.
Fig. 3 is that (level is put into pure water light stimulus responsive gel material made from the embodiment of the present invention 1, no in water
It is fixed), the response deformation photo record figure that occurs under illumination condition.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of preparation methods of light stimulus responsive gel material, include the following steps:
(1) under dark conditions and inert gas shielding, by having for six aryl bisglyoxaline class molecules of polyhydroxy modification
Machine solution, poly-dihydric alcohol and small molecule polyol are mixed, and obtain mixed solution；
(2) diisocyanate is mixed with step (1) described mixed solution, crosslinks reaction under the action of catalyst,
The light stimulus responsive gel material comprising organic solvent is obtained after curing molding；
Wherein: six aryl bisglyoxaline class molecules of the polyhydroxy modification are as the dynamic crosslinking point in the gel rubber material；
The small molecule polyol is as the fixation crosslinking points in the gel rubber material；The Long carbon chain that the poly-dihydric alcohol contains be used for so that
The gel rubber material being prepared has flexible and toughness；The diisocyanate is used for the six aryl bisglyoxalines modified with polyhydroxy
Organic solution, poly-dihydric alcohol and the small molecule polyol of class molecule crosslink reaction.
In some embodiments, six aryl bisglyoxaline class molecules of the polyhydroxy modification are as the dynamic in the gel rubber material
Crosslinking points, for six aryl bisglyoxaline class molecules of trihydroxy modification or six aryl bisglyoxaline class molecules of tetrahydroxy modification；Institute
Small molecule polyol is stated as the fixation crosslinking points in the gel rubber material, is small molecule trihydroxylic alcohol or small molecule tetrahydroxylic alcohol.
Small molecule polyol of the present invention refers to for polymer, for there is no the polyalcohols of polymerization
Molecule, and molecular weight is not more than 500.
Lead to above-mentioned preparation method, organic solvent has obtained wherein being dispersed with organic molten together with each raw material curing molding
The elastomeric gel material of agent medium, in order to avoid wherein organic solvent bring toxic side effect during subsequent applications, one
In a little embodiments, further comprise the steps of:
(3) the light stimulus responsive gel material by described containing organic solvent is vacuumizing, is removing it under heating condition
In organic solvent, obtain the light stimulus responsive gel material.
Six aryl bisglyoxaline class molecules of step (1) the polyhydroxy modification is organic molten in some embodiments of the invention
Liquid, small molecule polyol, poly-dihydric alcohol and diisocyanate molar ratio be 6:1:(25~30): (45~60).
Poly-dihydric alcohol of the present invention mainly to provide certain flexibility for gel rubber material obtained, is contained using its own
Long carbon chain so that the material being prepared be elastomeric material.Simultaneously in order to ensure cross-linking process has enough polymerizations
Unit, in some embodiments, step (1) poly-dihydric alcohol is oligomer dihydric alcohol, and the oligomer dihydric alcohol molecular weight is little
In 10000g/mol, preferably 400-8000.Meanwhile it being rung for the ease of its subsequent light stimulus in water or other polar solvents
It answers, for the oligomer dihydric alcohol as the main component in gel rubber material, hydrophilic and hydrophobic directly affects the parent of gel rubber material product
Therefore hydrophobicity selects preferable (contact angle the is not more than 90 °) oligomer polyol of hydrophily, such as polyethylene glycol.
Six aryl bisglyoxaline class molecules of polyhydroxy modification of the present invention are handed over as the dynamic in gel rubber material obtained
Join point, to modify the molecule that design obtains by molecular bulk of HABI, the HABI has the structure as shown in formula (one):
In some embodiments, six aryl bisglyoxaline class molecules of the polyhydroxy modification are the six aryl connection of tetrahydroxy modification
Imidazole derivative, with the structure as shown in formula (two) to any one of formula (six) and the isomer structure that does not include and
The structure of any modification group modification:
Wherein, R of the formula (two) into formula (six) is the alkyl chain containing 2 hydroxyls.For example, R can be-CH2CHOHCH2OH。
In some embodiments, the organic solvent in step (1) described organic solution is high boiling organic solvent, is used for molten
Six aryl bisglyoxaline molecules of the polyhydroxy modification are solved, preferably boiling point is higher than 100 DEG C or more of organic solvent, further excellent
It is selected as anhydrous dimethyl formamide (DMF).The present invention is prepared especially by organic solvent together with reactant curing molding
It is dispersed with the gel rubber material of organic solvent, organic solvent is further removed and obtains xerogel material.In order to ensure solidifying after crosslinking
In the process, organic solvent can be saved and is dispersed in the dual network cross-linked structure to be formed to form gel rubber material, solidification process
Middle temperature should not be too high, and on the other hand, organic solvent is preferably selected high boiling solvent.
In order to avoid organic solvent volatilizees during curing molding, lead to cannot to be formed gel rubber material, in some embodiments,
Step (2) curing molding is to carry out in insulating box, and 30-60 DEG C of temperature range is advisable.
The cyanic acid ester bond of diisocyanate of the present invention be used for modify with polyhydroxy six aryl bisglyoxaline class molecules, gather
The hydroxyl of dihydric alcohol and polyalcohol crosslinks reaction, is also used as chain extender, so that forming the gel of double cross-linked network structures
Material is possibly realized.In some embodiments, step (2) diisocyanate is that aliphatic diisocyanate or aromatic series two are different
Cyanate；Preferred diisocyanate is two isocyanide of hexamethylene diisocyanate, toluene di-isocyanate(TDI) or diphenyl methane
Acid esters.The mole of the diisocyanate is the 7 of the mole of six aryl bisglyoxaline class molecules of the polyhydroxy functionalization
~10 times.
Since the organic solvent that uses of the present invention is high boiling solvent, in order to remove having in gel rubber material after curing molding
Solvent, in some embodiments, step (3) the heating condition temperature is not less than 50 DEG C.
The common catalyst of the prior art can be selected for being catalyzed above-mentioned cross-linking reaction in catalyst of the invention.Some realities
It applies in example, the catalyst is dibutyl tin dilaurate.
The small molecule polyol that the present invention uses does not change under illumination condition as fixed crosslinking points, is three
First alcohol or tetrahydroxylic alcohol are glycerol trihydroxylic alcohol or pentaerythrite in some embodiments.
Above-mentioned preparation method is substantially whole all to be carried out in shading, inert atmosphere such as nitrogen or ar gas environment, mainly
Six aryl bisglyoxaline class molecules are allowed for the sensibility of light and oxygen, main purpose is to prevent it rotten.
The present invention also provides a kind of light stimulus responsive gel materials, are prepared according to above-mentioned preparation method.It should
Gel rubber material has double cross-linked network structures, wherein the six aryl bisglyoxalines modified comprising dynamic crosslinking point trihydroxy or tetrahydroxy
Class molecule, fixed crosslinking points small molecule trihydroxylic alcohol or small molecule tetrahydroxylic alcohol, the poly-dihydric alcohol to provide elastomer structure and
Chain extender diisocyanate.
The present invention also provides a kind of applications of light stimulus responsive gel material, are used as the deformation of light stimulus responsiveness
Intellectual material.
When concrete application, the gel rubber material is placed in solvent, with the side of the ultraviolet light material, the material to
The curving of backlight, and the material can change colour；As light application time increases, the bending deformation degree is bigger；Stop material one
The illumination of side, then another survey illumination to material, deformation are gradually recovered；If continuous light, which be will continue to backlight
Curving.Possible mechanism is: side of the gel rubber material with dual network cross-linked structure by ultraviolet lighting, as dynamic
The C-N key of six aryl bisglyoxaline class molecules of state crosslinking points is broken, and solvent molecule runs through key breaking part into the material, and
So that the material is swollen in the side by illumination, the side for being not affected by the backlight of illumination is not swollen, material two sides
Solvent molecule quantity is different, so that material two sides stress is variant, so that deformation occurs.
Above-mentioned mechanism is confirmed substantially during the experiment, is placed in solvent, such as water when by gel rubber material obtained
Certain time, gel rubber material water suction are swollen, and test its swellbility；Then the gel rubber material is equally placed in water identical
Time, unlike, be subject to ultraviolet lighting, test its degree of swelling, test results are shown in figure 1.As seen from the figure, the material
It is swollen in water phase, degree of swelling is increasing as time increases, can tend to balance later.Illustrate the material in water
Swelling occurs and has a threshold value (maximum value).After with ultraviolet light, it can be found that degree of swelling is continued growing and is reached
One higher threshold value.Illustrate the material after ultraviolet light, water absorbing capacity enhancing.
Due to response thinner thickness of the gel rubber material under ultraviolet lighting, be typically only several millimeters, for example, 4 millimeters with
It is interior, therefore, the curing molding of the material is generally carried out in a mold, laminar gel rubber material is obtained, in order to further answer
With.
Gel rubber material produced by the present invention, which can be not only placed in water, carries out the intelligent DEFORMATION RESPONSE of light stimulation initiation, but also
It can also be placed in other polar solvents, can be applied in different environment according to actual needs.
Raw material used in the embodiment of the present invention removes six aryl bisglyoxaline class molecules of the tetrahydroxy functionalization voluntarily synthesized
Switch is outer, other raw materials can market buy, or can be obtained by the method for maturation known in the art.The six of polyhydroxy functionalization
Aryl bisglyoxaline class molecule 2-Cl-4-diol-HABI can be prepared using the preparation method of the prior art.
The following are embodiments:
Embodiment 1
A kind of light stimulus responsive gel material, is prepared as follows to obtain:
(1) PEG is weighed1000(1.1g, 1.072mol) is put into a neck round bottom flask, is vacuumized and is dried at 70 DEG C
One hour, after be cooled to room temperature.
(2) in nitrogen atmosphere, four hydroxyls being dissolved in anhydrous dimethyl formamide (DMF) (1.5mL) are injected with syringe
The six aryl bisglyoxalines (2-Cl-4-diol-HABI) (192mg, 0.228mmol) and processed season penta is pre-dried that base is modified
Tetrol (5.2mg, 0.038mmol), stirring.
(3) hexamethylene diisocyanate (HDI) (0.33g, 0.32mL) is injected in above-mentioned mixed solution, catalyst two
Dibutyl tin laurate 8mg, is again stirring for 30min.
(4) the above-mentioned mixed solution stirred evenly is taken, is injected in preprepared mold, and the constant temperature for being put into 40 DEG C is dry
In dry case, taking out molding gel thicknesses after reaction 12h is about 2-4 millimeters, then which is put into 80 DEG C of freeze-day with constant temperature
The organic solvent that the dry removal of case contains.It is used to test after placing 12h at room temperature.
The soak is done into illumination test in water, material vertical is put into pure water, upper end is fixed, and makes material natural
It is sagging.As shown in Fig. 2, working as the right from figure uses the 30 second time of ultraviolet light, it can be observed that the material is bent about toward the left side
60 degree.
The soak is done into illumination test in water, material horizontal is placed in pure water, both ends are all not fixed.Such as Fig. 3
It is shown, when with ultraviolet light material middle section 30 seconds, it can be observed that the material is domed to bent intermediate.
Six aryl bisglyoxaline (2-Cl-4-diol-HABI) preparation methods of the tetrahydroxy modification wherein used are as follows:
At (1) 80 DEG C under nitrogen atmosphere, chloro- 4 hydroxy benzaldehyde of 2- and 3- chlorine-1,2-propylene glycol are added to hydroxide
React 12h in the aqueous solution of sodium, after be cooled to room temperature, be added a certain amount of concentrated hydrochloric acid and liquid separation chromatography, the chloro- 4- of 2- is prepared
(bis- propoxyl of 2,3-) benzaldehyde；
The product of the first step, benzil are added in a certain amount of acetic acid solution with ammonium acetate at (2) 90 DEG C and reacted
12h, rear to separate, crystallization and purification obtains 2- chlorine tetrahydroxy triphenylimidazolyl；
(3) at room temperature, the product of second step, potassium ferricyanide solid and potassium hydroxide are added to the organic solution of methylene chloride
Molecule shown in formula (two) structure can be obtained in middle reaction 8h, separating-purifying, and wherein R is-CH2CHOHCH2OH。
Embodiment 2
A kind of light stimulus responsive gel material, is prepared as follows to obtain:
(1) PEG is weighed1000(1.169g, 1.140mol) is put into a neck round bottom flask, is vacuumized and is done at 70 DEG C
Dry one hour, after be cooled to room temperature.
(2) in nitrogen atmosphere, four hydroxyls being dissolved in anhydrous dimethyl formamide (DMF) (1.5mL) are injected with syringe
The six aryl bisglyoxalines (2-Cl-4-diol-HABI) (192mg, 0.228mmol) and processed season penta is pre-dried that base is modified
Tetrol (5.2mg, 0.038mmol), stirring.
(3) '-diphenylmethane diisocyanate (MDI) (0.49g, 0.32mL) is injected in above-mentioned mixed solution, catalyst two
Dibutyl tin laurate 10mg, is again stirring for 30min.
(4) the above-mentioned mixed solution stirred evenly is taken, is injected in preprepared mold, and the constant temperature for being put into 40 DEG C is dry
In dry case, molding hydrogel is taken out after reacting 12h, then contains the dry removal of thermostatic drying chamber that the gel is put into 80 DEG C
Organic solvent.It is used to test after placing 12h at room temperature.
Illumination test is carried out by using method same as Example 1, it can be observed that identical light stimulus responds shape
Become.
Embodiment 3
A kind of light stimulus responsive gel material, is prepared as follows to obtain
(1) PEG is weighed1000(0.981g, 0.957mol) is put into a neck round bottom flask, is vacuumized and is done at 70 DEG C
Dry one hour, after be cooled to room temperature.
(2) in nitrogen atmosphere, four hydroxyls being dissolved in anhydrous dimethyl formamide (DMF) (1.5mL) are injected with syringe
The six aryl bisglyoxalines (2-Cl-4-diol-HABI) (192mg, 0.228mmol) and processed season penta is pre-dried that base is modified
Tetrol (5.2mg, 0.038mmol), stirring.
(3) toluene di-isocyanate(TDI) (TDI) (0.341g) is injected in above-mentioned mixed solution, two fourth of catalyst dibutyltin cinnamic acid
Base tin 9mg, is again stirring for 30min.
(4) the above-mentioned mixed solution stirred evenly is taken, is injected in preprepared mold, and the constant temperature for being put into 40 DEG C is dry
In dry case, molding hydrogel is taken out after reacting 12h, is used to test after placing 12h at room temperature.
Illumination test is carried out by using method same as Example 1, it can be observed that identical light stimulus responds shape
Become.
The optical Response deformation hydrogel of preferred embodiment of the present invention preparation is dual network structure, is mainly modified by tetrahydroxy
The double-layer network structure that six aryl bisglyoxalines and diisocyanate are formed.In dicyandiamide solution, which is placed on wherein, two sides
The network structure solvent molecule that includes be in dynamic balance state.After side is in illumination, six aryl bisglyoxalines two are caused
The fracture of C-N key between a imidazole ring.Cause the network structure of shadow surface different with non-shadow surface network structure, to make two sides
Solvent molecule quantity it is different more, then can deformation occurs.After light no longer irradiates, six imidazole rings of aryl bisglyoxaline two are multiple
It is former.So the process can restore.The optical Response deformation hydrogel of the method preparation has excellent mechanical strength and height multiple
Originality.
The present invention passes through using six aryl bisglyoxaline (HABI) class photochromic molecules and polyalcohol as elastomeric material
Crosslinking agent constructs out the intelligent aqueous gel material of double cross-linked network structures, and correspondingly obtaining a kind of pair of ultraviolet light has quickly
The intelligent aqueous gel material of response.Intelligent aqueous gel material prepared by the present invention believes the light of ultraviolet-visible region range
Number, there is apparent stimuli responsive.The intelligent aqueous gel material can observe apparent deformation in aqueous systems, for item
Part requires simply, have very wide application prospect.Intelligent aqueous gel material prepared by the present invention is translucent flexible material, tool
There are good toughness and ductility.The optical Response deformation hydrogel material photic stimuli synthesized according to the method described above is sensitive,
Deformation degree and light application time are directly proportional, and light application time is longer, and deformation is more obvious.By carrying out different journeys to six aryl bisglyoxalines
The MOLECULE DESIGN and modification of degree, the optical Response deformation gel designed based on it can show different deformation under light illumination.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of light stimulus responsive gel material, which comprises the steps of:
(1) under dark conditions and inert gas shielding, by the organic molten of six aryl bisglyoxaline class molecules of polyhydroxy modification
Liquid, poly-dihydric alcohol and small molecule polyol are mixed, and obtain mixed solution；
(2) diisocyanate is mixed with step (1) described mixed solution, crosslinks reaction under the action of catalyst, solidified
The light stimulus responsive gel material comprising organic solvent is obtained after molding；
Wherein, six aryl bisglyoxaline class molecules of the polyhydroxy modification are as the dynamic crosslinking point in the gel rubber material；It is described
Small molecule polyol is as the fixation crosslinking points in the gel rubber material；The Long carbon chain that the poly-dihydric alcohol contains is used for so that preparation
Obtained gel rubber material has flexibility；The six aryl bisglyoxaline class molecules that the diisocyanate is used to modify with polyhydroxy
Organic solution, poly-dihydric alcohol and small molecule polyol crosslink reaction.
2. preparation method as described in claim 1, which is characterized in that further comprise the steps of:
(3) the light stimulus responsive gel material by described containing organic solvent vacuumize, removed under heating condition it is therein
Organic solvent obtains the light stimulus responsive gel material.
3. preparation method as described in claim 1, which is characterized in that six aryl of step (1) the polyhydroxy modification join miaow
The organic solution of azole molecule, small molecule polyol, poly-dihydric alcohol and diisocyanate molar ratio be 6:1:(25~30):
(45~60).
4. preparation method as described in claim 1, which is characterized in that step (1) poly-dihydric alcohol is oligomer dihydric alcohol,
The oligomer dihydric alcohol molecular weight is not more than 10000g/mol.
5. preparation method as described in claim 1, which is characterized in that six aryl bisglyoxaline class molecules of the polyhydroxy modification
To modify the molecule that design obtains by molecular bulk of 2-Cl-HABI, the 2-Cl-HABI has to be tied as shown in formula (one)
Structure:
6. preparation method as described in claim 1, which is characterized in that the organic solvent in step (1) described organic solution is
Boiling point is higher than 100 DEG C or more of high boiling organic solvent, is used to dissolve six aryl bisglyoxaline molecules of institute's hydroxyl modified.
7. preparation method as described in claim 1, which is characterized in that step (2) curing molding be in insulating box into
Row, temperature range are 30-60 DEG C.
8. preparation method as described in claim 1, which is characterized in that step (2) diisocyanate is that aliphatic two is different
Cyanate or aromatic diisocyanate；The mole of the diisocyanate is that six aryl of the polyhydroxy functionalization join miaow
7~10 times of the mole of azole molecule.
9. a kind of light stimulus responsive gel material, which is characterized in that according to preparation as claimed in any one of claims 1 to 8
Method is prepared.
10. the application of light stimulus responsive gel material as claimed in claim 9, which is characterized in that be used as light stimulus and respond
Property deformation intellectual material.
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| CN107602816A (en) * | 2017-09-22 | 2018-01-19 | 华中科技大学 | One kind stretching color-changing polyurethane elastomeric material and preparation method thereof |
| US20190064548A1 (en) * | 2017-08-22 | 2019-02-28 | Hon Hai Precision Industry Co., Ltd. | Photochromic composition, photochromic ophthalmic lens, and method for making photochromic ophthalmic lens |
| CN109456461A (en) * | 2018-09-12 | 2019-03-12 | 华中科技大学 | A kind of phototropism shape memory polymer material, preparation method and application |
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| US20190064548A1 (en) * | 2017-08-22 | 2019-02-28 | Hon Hai Precision Industry Co., Ltd. | Photochromic composition, photochromic ophthalmic lens, and method for making photochromic ophthalmic lens |
| CN107602816A (en) * | 2017-09-22 | 2018-01-19 | 华中科技大学 | One kind stretching color-changing polyurethane elastomeric material and preparation method thereof |
| CN109456461A (en) * | 2018-09-12 | 2019-03-12 | 华中科技大学 | A kind of phototropism shape memory polymer material, preparation method and application |
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