CN107540855A - A kind of intelligent gel of light regulation and control sol-gel transformation and its application - Google Patents
A kind of intelligent gel of light regulation and control sol-gel transformation and its application Download PDFInfo
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- CN107540855A CN107540855A CN201710766235.5A CN201710766235A CN107540855A CN 107540855 A CN107540855 A CN 107540855A CN 201710766235 A CN201710766235 A CN 201710766235A CN 107540855 A CN107540855 A CN 107540855A
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Abstract
The invention discloses a kind of intelligent gel of light regulation and control sol-gel transformation and its application, the crosslinking points of the intelligent gel are six aryl bisglyoxalines, click chemistry occurs under cuprous bromide catalytic action by alkynyl and nitrine to react to form cross-linked network polymer, six aryl bisglyoxalines are introduced polymer gel by success, and maintain the excellent switch performance of small molecule.The intelligent gel can be changed into flowable " liquid " colloidal sol under visible light stimulation from solid gel, and the gel is had no progeny with self-reparing capability in xerogel state incision.Intelligent gel prepared by the present invention is due to the dynamic crosslinking point of the light regulation and control with uniqueness, it can be used as light valve of drug release carrier, self-repair material, sensor etc., have potential application in fields such as biochemical chemistry, medicine, chemical machinery, artificial intelligence.
Description
Technical field
The invention belongs to organogel to synthesize field, and the intelligence of Gel-sol transition is regulated and controled more particularly, to a kind of light
Gel and its application, the gel have unique light-operated rheological property and self-healing properties.
Background technology
Compared to conventional gel, intelligent hydrogels can perceive extraneous small stimulation, as pH, temperature, light, electric field, magnetic field,
Pressure etc. simultaneously makes certain response, is a kind of functional high molecule material with broader applications prospect.Under the stimulation of light,
Chemical bond rupture, and the molecule that chemical bond and can is returned under original state in the presence of another light beam or heat is referred to as photic
Photochromic molecule.At present, this kind of photochromic molecules are widely used in building intellectual material, are moved in light control materials, light-operated power
Etc. field all has potential application.
Early in nineteen sixty, six aryl bisglyoxalines are found and reported by Japanese researcher Hayashi and Maede.With
This quasi-molecule is also gradually available for the initiator and photo development of light initiation polymerization thing afterwards, but researchers are mainly made
Studied for a kind of photochromic material.In recent years, researchers are mainly by the modification to molecular structure or again
Design, has synthesized that a series of fade rates are fast, the good molecule of fatigue resistance.In addition, our seminars are successful as one kind
Molecular switch, it is connected with fluorogen in the form of covalent bond, has synthesized a series of role in fluorescent molecule switch of excellent performances, and successfully
Which part role in fluorescent molecule switch is applied to the super-resolution imaging of organic material.
Six aryl bisglyoxaline class materials are as a nova in photochromic material, with continuous research in recent years,
The synthesis of small molecule is more perfect with optimizing.But if polymeric system can be introduced into, prepared material is set to keep
The photochromic properties of six aryl bisglyoxaline small molecules, while have the premium properties of polymer concurrently, this will cause its functionalization more
Add conveniently, expand its application.In the last few years, researchers were attempted to introduce this micromolecular in the form of covalent bond
In polymer architecture, but due to the particularity of self structure, it is difficult to which the radical polymerization by routine is introduced directly into, cause correlation
Progress is slow.It has been reported that incorporation way have two classes, the first kind：The presoma triarylimidazoles list of six aryl bisglyoxalines
It is first to be copolymerized with other functional monomers, aoxidized again after forming polymer.This method synthesis is simple, has universality, but
The problem of oxidation efficiency is low, and the material property of synthesis is poor be present.Second class：Using the method for non-free radical polymerization by six aryl
Bisglyoxaline unit introduces polymeric system.The material property of this method synthesis is preferable, but finds suitable polymerization means to pass
Important, that has such as reported has six aryl bisglyoxaline units with hydroxy functionalized, is then drawn by being copolymerized with isocyanate units
Enter polymeric system.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of light to regulate and control Gel-sol transition
Intelligent gel and its application.The intelligent gel is urged using six aryl bisglyoxalines as crosslinking points, by alkynyl with nitrine in catalyst
The lower generation click chemistry of change effect is reacted to form cross-linked network polymer, and six aryl bisglyoxalines successfully are introduced into polymer gel,
And the intelligent gel has unique light-operated rheological property；Meanwhile based on the dynamic thermal balance of six aryl bisglyoxaline chemical bonds
Matter, and self-healing properties can be realized under without any stimulation, thus solve prior art and be difficult to six aryl bisglyoxaline units
Polymeric system is introduced, so that prepared material can keep the photochromic properties of six aryl bisglyoxaline small molecules, simultaneously
Have the technical problem of the premium properties of polymer concurrently.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of crosslinking agent, a kind of crosslinking agent, it is special
Sign is, six aryl bisglyoxaline construction units is contained in the crosslinking agent, also containing alkynyl or azido；The crosslinking agent has
General structure as shown in formula (one)：
Formula (one)
Wherein, R is (CH2)nCCH、(CH2CH2O)nCCH、(CH2)nN3Or (CH2CH2O)nN3, n is 1~20 integer.
Preferably, the crosslinking agent is 2- bromo- 4, the aryl bisglyoxaline of 4 '-diine propoxyl group six.
Preferably, the crosslinking agent is 2- bromo- 4, the aryl bisglyoxaline of 4 '-two nitrine alkoxy six.
According to another aspect of the present invention, there is provided a kind of preparation method of crosslinking agent, comprise the following steps：
(1) by 4,4 '-dihydroxy benzil, 3- propargyl bromides and acid binding agent according to mol ratio 1：2.5~5：2.5~5 mixing
And N is scattered in, in N '-dimethyl formamide, react 1~3 day at 20~30 DEG C, collected organic layer and pass through after the completion of reaction
Column chromatography purifies to obtain product 4,4 '-dipropargyl benzil；
(2) the 4,4 '-dipropargyl benzil and 2- bromobenzaldehydes and ammonium acetate obtained step (1) is according to mol ratio 1：
1.2~2：5 are mixed and dispersed in acetic acid, stirring reaction 1~3 day under the conditions of 80~100 DEG C；After reaction terminates, collection has
Machine phase, is spin-dried for Rotary Evaporators, and dried residue is further purified with column chromatography, finally gives glassy state product 2-
Bromo- 4,4 '-diine propoxyl group triphenylimidazolyl；
(3) 2- bromo- 4 for obtaining step (2), 4 '-diine propoxyl group triphenylimidazolyl are scattered in toluene solvant, are stirred
Under the conditions of the mixed aqueous solution of potassium ferricyanide and potassium hydroxide is added dropwise thereto, react at room temperature 2~24 hours, react under dark conditions
After end, collect organic phase and be spin-dried for, and end-product 2- bromo- 4,4 '-diine propoxyl group six are obtained with unmodified packed column chromatogram purification
Aryl bisglyoxaline.
Preferably, step (1) described acid binding agent be potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide in one kind or
It is a variety of.
Preferably, step (3) described potassium ferricyanide is K3Fe(CN)6, the 2- bromo- 4,4 '-diine propoxyl group triphenyl miaow
Azoles, K3Fe(CN)6Mol ratio with potassium hydroxide is 1：5~8:10~16.
Preferably, step (3) described solvent is toluene or dichloromethane.
According to another aspect of the present invention, there is provided a kind of intelligent gel of light regulation and control Gel-sol transition, it is served as reasons
The first gel monomers containing alkynyl, the second gel monomers containing azido and catalysis of the described crosslinking agent in catalyst are made
The cross-linked network polymer to be formed is reacted with lower generation click chemistry, the cross-linked network polymer is using six aryl bisglyoxalines as crosslinking
Point.
Preferably, the alkynyl sum contained in the crosslinking agent, first gel monomers and second gel monomers
Amount is equal with azido total quantity.
Preferably, first gel monomers are the polyglycol ether chain with alkynyl, and second gel monomers are 1,6-
Two nitrine hexanes, the crosslinking agent are 2- bromo- 4, the aryl bisglyoxaline of 4 '-diine propoxyl group six.
Preferably, the catalyst is the catalyst containing copper ion or cuprous ion.
Preferably, the catalyst is cuprous bromide.
Preferably, the repeat unit as shown in formula (two) is included in the intelligent gel structural formula：
Formula (two)
Preferably, from Solid State Transformation it is flowable colloidal sol after the intelligent gel lyosoption under visible ray illumination
State；Illumination is withdrawn from, it can revert to solid gel.
Preferably, by the intelligent gel cut off after, two sections of acquisition are fit together, the section part due to
The dynamic chemical key matter of crosslinking points, realize that selfreparing reconnects described two sections.
According to another aspect of the present invention, there is provided a kind of application of described intelligent gel, applied to insoluble drug release
The light valve of carrier, self-repair material or sensor.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect.
(1) the invention provides a kind of crosslinking agent, contain six aryl bisglyoxaline construction units in the crosslinking agent, also contain alkynes
Base or azido, the crosslinking agent can be used for intelligent gel of the synthesis using six aryl bisglyoxalines as crosslinking points；
(2) synthetic method of crosslinking agent provided by the invention is simply controllable, and product purity is high；
(3) the invention provides a kind of new strategy that six aryl bisglyoxalines are introduced to polymeric system, selection to contain alkynyl
Gel monomers, the gel monomers containing azido, contain six aryl bisglyoxaline construction units and azido or alkynes above-mentioned
Under the crosslinking agent existence condition of base, click chemistry is occurred under cuprous bromide catalytic action by alkynyl and nitrine and reacts to form friendship
Join network polymer, intelligent gel as of the present invention, six aryl bisglyoxalines are successfully introduced into polymer gel；Maintain
The excellent switch performance of small molecule；Intelligent gel of the present invention is polymerize using the reaction of classical click chemistry, and gel is at room temperature
A few minutes (in 5 minutes) reaction is complete, can efficiently be prepared very much；
(4) intelligent gel that synthesizes of the present invention has good mechanical performance and Swelling Capacity, with the increase of the degree of cross linking,
The Swelling Capacity enhancing of the gel, when the 2- bromo- 4 as crosslinking agent, the equivalent that feeds intake of the aryl bisglyoxaline of 4 '-diine propoxyl group six
For 1,6- dibromo nitrine hexanes 1.25% when, expansion factor Q reaches 18.3；And with the raising of the degree of cross linking, although swelling energy
Power weakens, but the mechanical strength of gel is higher；
(5) intelligent gel provided by the invention has light-operated rheological characteristic, can regulate and control to realize turning for gel-sol by light
Becoming, the gel is using six aryl bisglyoxalines as crosslinking points, after lyosoption, polymer network spread apart, in the work of illumination
Under, six aryl bisglyoxalines are because photochromic reactions form two molecule triphenylimidazolyl free radicals, while macroscopic view can be observed
By solid state change it is flowable " liquid sol " to gel, i.e., the gel shows the solid-state of the light regulation and control of uniqueness and liquid turns
Change；
(6) after intelligent gel cut-out provided by the invention, section is sticked together, section is due to the dynamic chemical of crosslinking points
Key matter, can at room temperature, without realizing selfreparing in the presence of any stimulation；
(7) intelligent gel prepared by the present invention can be used as medicine and release due to the dynamic crosslinking point of the light regulation and control with uniqueness
Carrier, self-repair material, light valve of sensor etc. are put, in fields such as biochemical chemistry, medicine, chemical machinery, artificial intelligence
There is potential application.
Brief description of the drawings
Fig. 1 is the synthetic route chart of the bromo- aryl bisglyoxalines of 4,4 '-diine propoxyl group six of crosslinking agent 2-；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the bromo- aryl bisglyoxalines of 4,4 '-dipropargyl oxygen six of crosslinking agent 2-；
Fig. 3 is the mass spectrogram of the bromo- aryl bisglyoxalines of 4,4 '-dipropargyl oxygen six of crosslinking agent 2-；
Fig. 4 is the synthetic route that intelligent gel is synthesized using the bromo- aryl bisglyoxalines of 4,4 '-diine propoxyl group six of 2- as crosslinking agent
Figure；
Fig. 5 is UV absorption figure before and after the gel illumination that the embodiment of the present invention 2 is prepared；
Fig. 6 is the Q values of swelling equilibrium of the gel in DMF under the different degrees of cross linking that the present invention is prepared；
Fig. 7 is the metamorphosis of the Pentagram shape gel of the invention being prepared under light illumination；
Fig. 8 is the gel light regulation and control fusing schematic diagram that the present invention is prepared；
Fig. 9 is the xerogel self-repair procedure displaying figure that the present invention is prepared.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
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 each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
The invention discloses a kind of intelligent gel and preparation method thereof, intelligent gel pattern meeting under visible light stimulation
Change and the gel is had no progeny with selfreparing behavior in xerogel state incision.The crosslinking points of the gel are that six aryl join miaow
Azoles, click chemistry is occurred under cuprous bromide catalytic action by alkynyl and nitrine and reacts to form cross-linked network polymer.
Therefore, the present invention has synthesized a kind of crosslinking agent first, six aryl bisglyoxaline construction units are contained in the crosslinking agent, also
Containing alkynyl or azido, there is the general structure as shown in formula (one)：
Formula (one)
Wherein, R is (CH2)nCCH、(CH2CH2O)nCCH、(CH2)nN3Or (CH2CH2O)nN3, n is 1~20 integer；R is excellent
Elect R=(CH as2)nCCH (n=1).The bromo- aryl of 4,4 '-diine propoxyl group six of crosslinking agent with above general structure such as 2-
Bromo- aryl bisglyoxaline of 4,4 '-two nitrine alkoxy six of bisglyoxaline, 2- etc..
One of which crosslinking agent with constituted above formula, 2- bromo- 4, the aryl bisglyoxaline of 4 '-diine propoxyl group six, its
Synthetic method comprises the following steps：
(1) by 4,4 '-dihydroxy benzil, 3- propargyl bromides and acid binding agent potassium carbonate according to mol ratio 1：2.5~5：2.5~
5 mix and are scattered in N, and in N '-dimethyl formamide, acid binding agent can be potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide
In one or more.(20~30 DEG C) are reacted 1~3 day at room temperature, and thin-layer chromatography tracking and monitoring is used in course of reaction, has been reacted
Cheng Houxian is filtered to remove unnecessary potassium carbonate, and remaining reaction solution chloroform is extracted and washed, and collected organic layer revolving instrument revolves
Final product 4,4 '-dipropargyl benzil is further purified to obtain by column chromatography in dry doubling；Acid binding agent can also be sodium carbonate, hydrogen
Potassium oxide or sodium hydroxide.
(2) the 4,4 '-dipropargyl benzil and 2- bromobenzaldehydes and ammonium acetate obtained step (1) is according to mol ratio 1：
1.2~1.5：5 are mixed and dispersed in acetic acid, stirring reaction 1~3 day under the conditions of 80~100 DEG C；After reaction terminates, reaction
Liquid is slowly instilled in the bittern of stirring and neutralized with ammoniacal liquor.The sticky grease dichloromethane of gained is extracted and washed three times,
Collect organic phase to be spin-dried for obtaining brown solid with Rotary Evaporators, dried residue is mobile phase with absolute dichloromethane
Column chromatography is further purified, and collects organic phase, is spin-dried for Rotary Evaporators, dried residue is further pure with column chromatography
Change, finally give glassy state product 2- bromo- 4,4 '-diine propoxyl group triphenylimidazolyl；
(3) 2- bromo- 4 for obtaining step (2), 4 '-diine propoxyl group triphenylimidazolyl are scattered in toluene solvant, are stirred
Under the conditions of potassium ferricyanide K is added dropwise thereto3Fe(CN)6With the mixed aqueous solution of potassium hydroxide, the 2- bromo- 4,4 '-diine propoxyl group
Triphenylimidazolyl, K3Fe(CN)6Mol ratio with potassium hydroxide is 1：5~8：10~16.2~24 are reacted at room temperature under dark conditions
Hour, course of reaction is monitored with thin-layer chromatography, after reaction terminates, collects organic phase and is spin-dried for, and with silicone filler column chromatography
(mobile phase：Dichloromethane：Ethyl acetate：N-hexane=3:3：7) it is further purified to obtain the bromo- 4,4 '-diines of final product 2-
The aryl bisglyoxaline of propoxyl group six.
Present invention also offers a kind of intelligent gel, and it is to be joined with the aryl of functional unit six contained in above-mentioned crosslinking agent
Imidazoles is crosslinking points, under catalyst effect click chemistry occurs by alkynyl and nitrine and react the cross-linked network to be formed to gather
Compound.Catalyst is the catalyst containing copper ion or cuprous ion, preferably cuprous bromide.Specifically, by containing alkynyl
First gel monomers, the second gel monomers containing azido are clicked on above-mentioned crosslinking agent under cuprous bromide catalytic action
Chemically react the cross-linked network polymer formed, and the cross-linked network polymer is using six aryl bisglyoxalines as crosslinking points；As preferred
Scheme, the first cross-linking monomer is the polyglycol ether chain with alkynyl, and second gel monomers are the nitrine hexanes of 1,6- bis-, hand over
Connection agent is the bromo- aryl bisglyoxalines of 4,4 '-diine propoxyl group six of 2-.
In order that the gel that synthesis obtains is more stable, contain in above-mentioned crosslinking agent, the first gel monomers and the second gel monomers
Some alkynyl total quantitys are equal with azido total quantity.Above-mentioned crosslinking agent crosslinks instead with monomer under catalyst existence condition
Intelligent gel should be synthesized.Wherein, when the group R in crosslinking agent is azido, the quantity and monomer of azido group in crosslinking agent
The quantity summation of middle azido group is equal to the quantity of alkynyl in another monomer.Conversely, when the functional group substituted in crosslinking agent is alkynes
During base, the alkynyl quantity sum in the alkynyl and monomer in crosslinking agent is equal to the quantity of azido in another monomer.Therefore, no matter
The crosslinking agent used is containing azido group either alkynyl, as long as azido group is equal with alkynyl quantity in control reaction raw materials, i.e.,
Adjust crosslinking agent, the different proportion of two kinds of monomers, you can a series of intelligent gels with different structure of synthesis.
Such as with the polyglycol ether chain with alkynyl and the nitrine hexane of 1,6- bis- for gel monomers, with the 2- of above-mentioned synthesis
Bromo- 4, the aryl bisglyoxaline of 4 '-diine propoxyl group six is crosslinking agent, and of the present invention one is obtained using click chemistry reaction synthesis
Intelligent gel is planted, the repeat unit as shown in formula (two) is included in its structure：
Formula (two)
Specifically, the preparation method of the intelligent gel is：By dipropargyl polyglycol ether, bromo- 4,4 '-two propinyls of 2-
The adjacent aryl bisglyoxaline of bromine six, the nitrine hexanes of 1,6- bis- and N, N, N', N, ' N "-five methyl diethylentriamine mixing, add simultaneously
Solvent DMF is completely dissolved reaction raw materials, wherein propargyl polyglycol ether, 2- bromo- 4,4 '-diine third
The mol ratio of the aryl bisglyoxaline of base neighbour bromine six and the nitrine hexanes of 1,6- bis- is 0.5~0.95:0.025~0.25:1, and N, N, N',
N, ' the mol ratio of N "-five methyl diethylentriamine and the nitrine hexanes of 1,6- bis- is 0.1~1:1；N, N, N', N, ' the first of N "-five
Base diethylenetriamines can promote the dissolving of catalyst.Followed by oil pump and high pure nitrogen by above-mentioned reaction solution Frozen-thawed cycled
2~5 times, remove oxygen therein.Now, quickly catalyst cuprous bromide is added thereto and pipe vacuumizes again, denitrogen gas.
Catalyst is sufficiently mixed with reaction solution under nitrogen atmosphere, along with heat release, 5 minutes inner gels of reaction solution.To ensure that this is poly-
The abundant completion of reaction is closed, continues heating one hour under the conditions of 40 DEG C.React gained gel after terminating EDTA-2Na's
3 days are dialysed in the aqueous solution to remove Cu2+.The color that dialysis terminates rear gel is also become in order to light yellow by blue-green.Finally, will be solidifying
Glue removes water drying, standby.
The gel that the degree of cross linking is 5%~50% can be made in the method, i.e., wherein the aryl of two propinyl neighbour bromine six joins miaow
0.025~0.25 of the molar content of azoles equivalent to 1,6- dibromo-hexanes.Within this range, prepared gel cross-linkage degree is got over
Low, light regulation and control Gel-sol transition is quicker, and the degree of cross linking is higher, and the self-reparing capability that gel is showed is stronger.
The gel is by the use of six aryl bisglyoxalines as crosslinking points, and gel is after lyosoption, polymer network spread apart,
In the presence of illumination, six aryl bisglyoxalines are while grand because photochromic reactions form two molecule triphenylimidazolyl free radicals
See it is observed that gel by solid state change be flowable " liquid sol ", i.e., what the gel showed that unique light regulates and controls consolidates
State and liquid conversion.Under visible ray such as 405nm light actions, six aryl bisglyoxalines in the gel quickly can dissociate to be formed
Two triphenylimidazolyl free radicals, realize crosslinking points solution crosslinking, while have effigurate gel switch to it is flowable molten
Glue.When withdrawing light source, two molecule triphenylimidazolyl free radicals are mutually collided in conjunction with six aryl bisglyoxalines of formation so that linear
Polymer chain is crosslinked again, and " liquid sol " spontaneously will switch to form solid gel again.
For the xerogel alreadyed switch off, in the presence of no any solvent, two sections are sticked together, two
Section, can at room temperature, without realizing selfreparing in the presence of any stimulation due to the dynamic chemical key matter of crosslinking points.This is solidifying
The basic mechanism of the reparation behavior of glue is that triphenylimidazolyl free radical is bound to each other to form six aryl bisglyoxalines, this process sheet
Body is thermodynamic process, it is not necessary to by means of extra condition.One clotting glue inherently has part six after the cut, in interface
Aryl bisglyoxaline is destroyed, and after splicing again, can be formed chemical bond by directly contacting and is realized selfreparing.
The gel can be used as drug release carrier due to the dynamic crosslinking point of the light regulation and control with uniqueness, self-repair material,
Light valve of sensor etc., there is potential application in fields such as biochemical chemistry, medicine, chemical machinery, artificial intelligence.And should
Gel employs classical click chemistry reaction and polymerize, and a few minutes (in 5 minutes) reaction is complete at room temperature for gel, can be with non-
It is often efficient to prepare.
It is embodiment below：
Embodiment 1
2- bromo- 4 is present embodiments provided, a kind of synthetic method of the aryl bisglyoxaline of 4 '-diine propoxyl group six, it synthesizes road
Line is as shown in figure 1, comprise the following steps：
The synthesis of (1) 4,4 '-dipropargyl benzil
In a 100ml bottle with two necks, 4,4 '-dihydroxy benzil (2.42g, 10mmol), 3- propargyl bromides (3ml,
40mmol) and potassium carbonate (5.52g, 40mmol) is scattered in 50ml N, in N '-dimethyl formamide.The reaction mixture is in room
Stirred 2 days under the conditions of temperature.Thin-layer chromatography tracking and monitoring is used in course of reaction, unnecessary carbonic acid is first filtered to remove after the completion of reaction
Potassium, remaining reaction solution chloroform are extracted and washed, and collected organic layer is spin-dried for revolving instrument and by column chromatography (mobile phase：First
From ethyl acetate：Petroleum ether=1:4, polarity is slowly increased to 1:1, to last with pure ethyl acetate) be further purified.Finally
Product is 2.6g, yield 82%.
(2) synthesis of the bromo- 4,4 '-dipropargyl oxygen triphenylimidazolyls of 2-
In 25ml bottle with two necks, 4,4 '-two propinyl benzils (0.34g, 1.1mmol), 2- bromobenzaldehydes
(0.3g, 1.7mmol) and ammonium acetate (0.42g, 5.5mmol), is scattered in 5ml acetic acid, the mixed liquor stirs under the conditions of 90 DEG C
Mix 1 day.After reaction terminates, reaction solution is slowly instilled in the bittern of stirring and neutralized with ammoniacal liquor.The sticky grease of gained is with two
Chloromethanes is extracted and washed three times, is collected organic phase and is spin-dried for obtaining brown solid, dried residue with Rotary Evaporators
It is further purified with the column chromatography that absolute dichloromethane is mobile phase, finally gives 0.46g glassy solids, yield 87%.
(3) synthesis of the bromo- aryl bisglyoxalines of 4,4 '-diine propoxyl group six of 2-
In 100ml flask, 4, the bromo- triphenylimidazolyls of 4 '-dipropargyl oxygen -2- (0.2g, 0.41mmol) point
Dissipate in 12ml toluene, at the same time, by K3Fe(CN)6(0.69g, 2.1mmol) and potassium hydroxide (0.29g, 5.1mmol) are molten
Solution is transferred in 25ml constant pressure funnels, the reaction solution in flask is acutely stirring in 11ml deionized waters after dissolving completely
Slowly the aqueous solution in dropping funel is put under conditions of mixing.Reaction room temperature vigorous stirring overnight under dark conditions, reaction
Process is monitored with thin-layer chromatography, after reaction terminates, is collected organic phase and is spin-dried for and uses column chromatography (mobile phase：Dichloromethane：Second
Acetoacetic ester：N-hexane=3:3:7) it is further purified, yield 70%.
The nucleus magnetic hydrogen spectrum and liquid chromatography mass spectrometric for the product being prepared referring to Fig. 2 and Fig. 3, figure it is seen that δ 6.3~
24 hydrogen are shared at 7.86, are respectively from six phenyl ring, 8 hydrogen that δ 4.7~4.92 is integrated correspond to the alkyl in propynyloxy base
Hydrogen, and the peak of Terminal Acetylenes hydrogen is then at δ 3.51~3.66.Accurate point of the bromo- aryl bisglyoxalines of 4,4 '-diine propoxyl group six of 2-
Son amount【M】For 962.11, and as can be seen from Figure 3【M+H+】For 963.4, understand that synthesized product confirms with reference to Fig. 2 and Fig. 3
For the bromo- aryl bisglyoxaline molecules of 4,4 '-diine propoxyl group six of 2-.
Embodiment 2
Present embodiments provide it is a kind of using embodiment 1 prepare the bromo- aryl bisglyoxalines of 4,4 '-diine propoxyl group six of 2- as
The method that crosslinking agent synthesizes intelligent gel, its synthetic route are as shown in Figure 4.
A 10ml sample cell is chosen, by two propinyl polyglycol ethers (208mg, 0.2mmol), two propinyl neighbour bromines six
Aryl bisglyoxaline (24.1mg, 0.025mmol), the nitrine hexanes (43mg, 0.25mmol) of 1,6- bis- and N, N, N', N, ' the first of N "-five
Base diethylenetriamines (52ul, 0.25mmol) is added thereto, while adding 500ul DMFs makes reaction former
Material is completely dissolved.Followed by oil pump and high pure nitrogen by above-mentioned reaction solution Frozen-thawed cycled three times, remove sample cell in oxygen.
Now, sample cell is quickly opened, catalyst cuprous bromide (28mg, 0.2mmol) is added thereto and sample cell taken out very again
Sky, denitrogen gas.Catalyst is sufficiently mixed with reaction solution under nitrogen atmosphere, along with heat release, 5 minutes inner gels of reaction solution,
To ensure the abundant completion of the polymerisation, sample cell is continued to heating one hour under the conditions of 40 DEG C.React institute after terminating
Gel dialyses 3 days to remove Cu in the EDTA-2Na aqueous solution2+.The color that dialysis terminates rear gel is also changed into from blue-green
It is light yellow.Finally, gel is removed water into drying, it is standby.
Embodiment 3
Molar ratio is the synthesis of the intelligent gel of 2.5% crosslinking agent：
A 10ml sample cell is chosen, by two propinyl polyglycol ether 297mg, the aryl bisglyoxaline of two propinyl neighbour bromine six
7.23mg, the nitrine hexane 50.5mg of 1,6- bis- and N, N, N', N, ' N "-five methyl diethylentriamine 35ul is added thereto, simultaneously
Adding 300ul N,N-dimethylformamides is completely dissolved reaction raw materials.Followed by oil pump and high pure nitrogen by above-mentioned reaction
Liquid Frozen-thawed cycled three times, removes the oxygen in sample cell.Now, sample cell is quickly opened, by catalyst cuprous bromide 21.5mg
It is added thereto and sample cell is vacuumized again, denitrogen gas.Catalyst is sufficiently mixed with reaction solution under nitrogen atmosphere, along with
Heat release, 5 minutes inner gels of reaction solution, reaction gained gel is dialysed in the EDTA-2Na aqueous solution after terminating 3 days with except
Remove Cu2+.The color that dialysis terminates rear gel is also become in order to light yellow by blue-green.Finally, gel is removed water into drying, it is standby.
Embodiment 4
Molar ratio is the synthesis of the intelligent gel of 20% crosslinking agent：
A 10ml sample cell is chosen, two propinyl polyglycol ether 62.5mg, the aryl of two propinyl neighbour bromine six are joined into miaow
Azoles 19.3mg, the nitrine hexane 16.8mg of 1,6- bis- and N, N, N', N, ' N "-five methyl diethylentriamine 17ul is added thereto, together
When add 400ul N,N-dimethylformamides be completely dissolved reaction raw materials.Will be above-mentioned anti-followed by oil pump and high pure nitrogen
Answer liquid Frozen-thawed cycled three times, remove the oxygen in sample cell.Now, sample cell is quickly opened, by catalyst cuprous bromide
21.5mg is added thereto and sample cell is vacuumized again, denitrogen gas.Catalyst is sufficiently mixed with reaction solution under nitrogen atmosphere,
Pension gelation is reacted after several minutes, is become after gained gel permeation in order to light yellow.Finally, gel is removed water into drying, it is standby.
Embodiment 4
Crosslinking agent molar ratio is the synthesis of the intelligent gel of 20% crosslinking agent：
A 10ml sample cell is chosen, two propinyl polyglycol ether 62.5mg, the aryl of two propinyl neighbour bromine six are joined into miaow
Azoles 19.3mg, the nitrine hexane 16.8mg of 1,6- bis- and N, N, N', N, ' N "-five methyl diethylentriamine 17ul is added thereto, together
When add 400ul N,N-dimethylformamides be completely dissolved reaction raw materials.Will be above-mentioned anti-followed by oil pump and high pure nitrogen
Answer liquid Frozen-thawed cycled three times, remove the oxygen in sample cell.Now, sample cell is quickly opened, by catalyst cuprous bromide
21.5mg is added thereto and sample cell is vacuumized again, denitrogen gas.Catalyst is sufficiently mixed with reaction solution under nitrogen atmosphere,
Pension gelation is reacted after several minutes, is become after gained gel permeation in order to light yellow.Finally, gel is removed water into drying, it is standby.
Embodiment 5
The gel that the degree of cross linking that embodiment 2 is prepared is 10% is swelled in N, N '-dimethyl formamide, is then cut
One small pieces gel does UV absorption test, in wavelength is that gel has no obvious absorption, but illumination at 600nm before illumination such as accompanying drawing 5
Afterwards, detect occur obvious absworption peak at 600nm.Meanwhile we also observe that obvious light occurs in gel in experiment
Metachromatism is caused, illustrates that the gel of the invention synthesized still saves the excellent switch performance of six aryl bisglyoxaline small molecules.
Gel is the high molecular polymer with cross-linked structure, in various solvents immersion can not dissolve but can be molten
Swollen, swelling of this patent to the gel of the different degrees of cross linking of synthesis is studied, and detailed results, can by result referring to accompanying drawing 6
Know, the degree of cross linking is smaller, and gel swelling ability is stronger.When the bromo- aryl of the 4,4 '-diine propoxyl group six connection miaows of 2- as class crosslinking agent
Azoles feed intake equivalent be 1,6- dibromo nitrine hexanes 1.25% when, expansion factor Q reaches 18.3.And carrying with the degree of cross linking
Height, although Swelling Capacity weakens, the mechanical strength of gel is higher.
The crosslinking points of the gel are the six aryl bisglyoxalines of four polytriazoles of band.Under 405nm light actions, six in gel
Aryl bisglyoxaline dissociates to form two triphenylimidazolyl free radicals, realizes the solution crosslinking of crosslinking points, has effigurate gel
Switch to liquid.When withdrawing light source, arbitrary two triphenylimidazolyl free radicals are mutually collided in conjunction with formation four polytriazoles of band
Six aryl bisglyoxalines, spontaneous switch to solid-state by liquid again.As shown in Figure 7, one piece is chosen in N, N '-dimethyl formyl
The gel of saturation is swelled in amine solvent, a five-pointed star is cut into, in 405nm laser (100mw/cm3) under the conditions of Continuous irradiation,
We can see that gel gradually becomes green, when irradiating 2 minutes, five acute angles of star obvious rust.
Xerogel prepared in case study on implementation 2 is soaked in N, in N '-dimethyl formamide solvent, treats that gel swelling is satisfied
With it is rear, the slitting type of gel is hung on 1ml syringe needles, as shown in Figure 8, Fig. 8 the present invention is prepared
Gel light regulation and control fusing schematic diagram, now, opens 405nm (100mw/cm3) laser, by light cover in the solidifying of suspension
The center of glue, strip gel turns into two sections by light " shearing " after 12s.
Under the conditions of no any extra outside stimulus, the xerogel prepared by the present invention reviews one's lessons by oneself reactivation with good
Power.As shown in Figure 9：At ambient temperature, the xerogel that embodiment 2 is prepared is completely cut through such as Fig. 9 with scalpel
In a figures, then the gel of fracture is close together again, wrapped up with masking foil, is kept in dark place one day at ambient temperature, so
Sample is taken out into the b in Fig. 9 such as afterwards to scheme, it is found that gel place of incision achieves good selfreparing effect.The reparation of the gel
The basic mechanism of behavior is that triphenylimidazolyl free radical is bound to each other to form six aryl bisglyoxalines, and this process is heating power in itself
Process, it is not necessary to by means of extra condition.One clotting glue after the cut, inherently there is the aryl connection miaow of part six in interface
Azoles is destroyed, and after splicing again, can be formed chemical bond by directly contacting and is realized selfreparing.
1~8 in accompanying drawing 9 is the picture of the gradual drawing process of gel after repairing, and the stretching of the gel after repairing 1 day should
Become more than 240%.
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, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (10)
- A kind of 1. crosslinking agent, it is characterised in that contain six aryl bisglyoxaline construction units in the crosslinking agent, also containing alkynyl or Azido；The crosslinking agent has the general structure as shown in formula (one)：Wherein, R is (CH2)nCCH、(CH2CH2O)nCCH、(CH2)nN3Or (CH2CH2O)nN3, n is 1~20 integer.
- 2. crosslinking agent as claimed in claim 1, it is characterised in that the crosslinking agent is 2- bromo- 4, and 4 '-diine propoxyl group six is fragrant Base bisglyoxaline.
- 3. crosslinking agent as claimed in claim 1, it is characterised in that the crosslinking agent is the nitrine alkoxies six of 2- bromo- 4,4 '-two Aryl bisglyoxaline.
- 4. the preparation method of crosslinking agent as claimed in claim 2, it is characterised in that comprise the following steps：(1) by 4,4 '-dihydroxy benzil, 3- propargyl bromides and acid binding agent according to mol ratio 1:2.5~5:2.5~5 mix and divide Dissipate in N, N '-dimethyl formamide, reacted 1~3 day at 20~30 DEG C, collected organic layer and pass through post color after the completion of reaction Spectrum purifying obtains product 4,4 '-dipropargyl benzil；(2) the 4,4 '-dipropargyl benzil and 2- bromobenzaldehydes and ammonium acetate obtained step (1) is according to mol ratio 1:1.2 ~2:5 are mixed and dispersed in acetic acid, stirring reaction 1~3 day under the conditions of 80~100 DEG C；After reaction terminates, collect organic Phase, it is spin-dried for Rotary Evaporators, dried residue is further purified with column chromatography, and it is bromo- to finally give glassy state product 2- 4,4 '-diine propoxyl group triphenylimidazolyl；(3) 2- bromo- 4 for obtaining step (2), 4 '-diine propoxyl group triphenylimidazolyl are scattered in toluene solvant, stirring condition Under the mixed aqueous solution of potassium ferricyanide and potassium hydroxide is added dropwise thereto, react 2~24 hours under dark conditions at 20~30 DEG C, instead After should terminating, collect organic phase and be spin-dried for, and end-product 2- bromo- 4,4 '-diine propoxyl group are obtained with unmodified packed column chromatogram purification Six aryl bisglyoxalines.
- 5. preparation method as claimed in claim 4, it is characterised in that step (3) described potassium ferricyanide is K3Fe(CN)6, the 2- Bromo- 4,4 '-diine propoxyl group triphenylimidazolyl, K3Fe(CN)6Mol ratio with potassium hydroxide is 1:5~8:10~16.
- 6. a kind of intelligent gel of light regulation and control Gel-sol transition, it is characterised in that it is by the first gel list containing alkynyl Body, the second gel monomers containing azido and catalysis of the crosslinking agent as described in any one of claims 1 to 3 in catalyst are made The cross-linked network polymer to be formed is reacted with lower generation click chemistry, the cross-linked network polymer is using six aryl bisglyoxalines as crosslinking Point；Preferably, the alkynyl total quantity contained in the crosslinking agent, first gel monomers and second gel monomers is with folding Nitrogen base total quantity is equal.
- 7. intelligent gel as claimed in claim 6, it is characterised in that first gel monomers are the polyethylene glycol with alkynyl Ether chain, second gel monomers are the nitrine hexanes of 1,6- bis-, and the crosslinking agent is 2- bromo- 4, the aryl of 4 '-diine propoxyl group six Bisglyoxaline；The catalyst is the catalyst containing copper ion or cuprous ion, preferably cuprous bromide.
- 8. intelligent gel as claimed in claim 7, it is characterised in that the repetition list as shown in formula (two) is included in its structural formula Member：。
- 9. intelligent gel as claimed in claim 6, it is characterised in that under visible ray illumination, the intelligent gel absorbs molten From Solid State Transformation it is flowable dissolved colloidal state after agent；Illumination is withdrawn from, it can revert to solid gel.
- 10. the application of a kind of intelligent gel as described in any one of claim 6~9, it is characterised in that applied to insoluble drug release The light valve of carrier, self-repair material or sensor.
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