CN109384869A - Fluorine-containing azobenzene amphiphilic polymer, visible light-responded polymer nanotube and preparation method thereof - Google Patents
Fluorine-containing azobenzene amphiphilic polymer, visible light-responded polymer nanotube and preparation method thereof Download PDFInfo
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Abstract
The invention discloses fluorine-containing azobenzene amphiphilic polymers, visible light-responded polymer nanotube and preparation method thereof.Specifically, firstly, polymer of the invention is prepared with structure shown in formula I, and by the inclusion of the method for the following steps: 1) synthesis of fluorine-containing azo benzene monomer；2) synthesis of large hydrophilic molecular initiator；3) synthesis of amphiphilic polymer.The present invention uses new method to obtain, and a series of molecular weight are controllable, and the specific amphipathic nature block polymer of hydrophobe block ratio simultaneously carries out solution self-assembling nanotubes.It is compared with the traditional method, the method is simple, and neatly design can prepare the nanotube of different-shape.The nanotube can occur reversible deformation, provide a kind of new approaches for the design and synthesis of light-operated polymer nanotube, have broad application prospects under blue green light irradiation；In addition, chemical reagent used in method of the invention is stable in the air, and it is easy to operate, it is high-efficient, it is convenient for industrialized production.
Description
Technical field
The invention belongs to the soft material spheres of stimuli responsive, are related to amphiphilic polymer, visible light-responded multiple pattern polymerization
The preparation of object nanotube and performance study.
Background technique
In the past twenty years, various nanostructures are constructed by solution self assembly, designing material from bottom to top
Property obtain expected performance, increasingly attract scientist interest.Amphiphilic polymer can be self-assembly of not
With the nanoparticle of pattern, spherical micelle, rod-shaped micelle, vesica, nanometer sheet etc. are generally included.The pattern of nanoparticle answers it
With there is important influence.Such as spherical micelle can be reduced oil paint friction (Tribol. Trans.2009, 53, 97−
107), in terms of biologic applications, rod-shaped micelle has longer circulation time in vivo, can change into cell approach (Nat. Nanotechnol.2007,2,249 255).Laminated structure be widely used in terms of nanolithographic (Adv. Mater.2009,
21,4,769 4792.), and vesica is widely used in drug and conveys, in protein transmitting and nano-reactor (Prog. Polym. Sci.2007,32,838 857,Macromolecules2010,43,1159 1168).Nano wire, nanometer
Band, the monodimension nanometer materials such as nanotube are transported in microphysics, manufacture separation, sensing, ion, tool in terms of the function elements such as catalysis
Have extensively potential application value (Adv. Mater.2003,15,353 389).However the type majority office of current nanotube
It is limited to inorganic nano-tube, biomolecule nanotube, metal organic frame, organic molecule nanotube etc..The report of polymer nanotube
Road is fewer, mainly prepares nanotube by template or by the method for solution self assembly.Template, complex procedures take off
Template is relatively difficult.And solution self assembly usually requires that polymeric amount, high hydrophobic block ratio, or requires assembly core
Inside can form orderly structure, such as crystallization or smectic.Which greatly limits the scopes of design of polymer nanotube.If can look for
To a kind of simple method of polymer architecture, by the MOLECULE DESIGN ability of broadening building polymer/nanometer pipe significantly.
Soft substance is widely used it in terms of intelligent response profile material the sensitivity of extraneous small effect.Environmental stimuli packet
Include light, electric field, magnetic field, temperature, PH, solvent, ionic strength, reductant-oxidant etc..Light has fast as a kind of clean energy resource
Not the advantages that speed, remote control do not change system chemical environment, and controllability is good.Star of the azobenzene as light responsive material field
Molecule is widely used in photoresponse gel, liquid crystal elastic body, membrane material, molecular recognition, the fields such as nanoparticle.Azobenzene is even
Pyridine group has special responsiveness to ultraviolet light and visible light, and reversible cis-trans isomerism can occur under light stimulus,
And along with the change in size between 9.0 (trans-) and 5.5 (cis-), the variation of dipole moment and changing for shape
Become.Since ultraviolet light will cause irreversible damage to material, at the same it is also poor to the penetrability of material, general azobenzene
Photo-isomerisable limits it in various applications to the dependence of ultraviolet light.Therefore developing visible light-responded material is to grind at present
The hot spot studied carefully.In such a way that the method for solution self assembly building photoresponse nanoparticle is a kind of has been widely adopted, but can
The building of light-exposed response nano pipe is currently without report.
Summary of the invention
For above situation, the purpose of the present invention is to provide two that a kind of side chain contains visible light-responded azobenzene group
Parent's property method for producing polymer and the new method and purposes that polymer nanotube is constructed by solution self assembly.The present invention by
Four ortho positions of azobenzene introduce the structure that fluorine atom changes azobenzene molecule, change the energy of molecular orbit, make azobenzene point
Son itself has stimulating responsive to visible light, prepares visible light-responded azobenzene.Solves the photo-isomerisable of existing azobenzene
To the Dependence Problem of ultraviolet light.
Specifically, the present invention is synthesized first with visible light-responded fluorine-containing azo benzene monomer and big point hydrophilic
Sub- initiator PEG5K- Br, using CuBr and PMDETA as catalyst system polymerize to obtain a series of hydrophilic sections fix, hydrophobic section not
The long Amphipathilic block polymer of medium well.The nanotube of different-shape is then obtained by the method for solution self assembly.It is formed
Nanotube has good responsiveness to blue green light.And reversible deformation can occur under the irradiation of different light.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of fluorine-containing azobenzene amphiphilic polymer, structure are shown in formula I:
Wherein n is 20~100, such as 20,35,51,78,100；M is 100~120.
Preferably, n 78,100, m 113.The excellent nanotube of structural behaviour can be formed.
It is used to prepare the fluorine-containing azo benzene monomer of fluorine-containing azobenzene amphiphilic polymer described in Formulas I, structure such as III institute of formula
Show:
Formula III
The invention discloses a kind of preparation methods of fluorine-containing azobenzene amphiphilic polymer, comprising the following steps:
(1) adjacent tetrafluoro azobenzene is reacted with the bromo- 1- hexanol of 6-, obtains fluorine-containing azobenzene alkyl chain；
(2) esterification occurs for fluorine-containing azobenzene alkyl chain and methacrylic chloride, obtains fluorine-containing azo benzene monomer；
(3) poly glycol monomethyl ether and alpha-brominated isobutyryl bromine reaction, obtain end group bromine polyethylene glycol；
(4) using end group bromine polyethylene glycol as initiator, in the presence of catalyst and ligand, fluorine-containing azo benzene monomer is gathered
It closes, obtains fluorine-containing azobenzene amphiphilic polymer.
The invention discloses a kind of preparation methods of visible light-responded polymer nanotube, comprising the following steps:
(1) adjacent tetrafluoro azobenzene is reacted with the bromo- 1- hexanol of 6-, obtains fluorine-containing azobenzene alkyl chain；
(2) esterification occurs for fluorine-containing azobenzene alkyl chain and methacrylic chloride, obtains fluorine-containing azo benzene monomer；
(3) poly glycol monomethyl ether and alpha-brominated isobutyryl bromine reaction, obtain end group bromine polyethylene glycol；
(4) using end group bromine polyethylene glycol as initiator, in the presence of catalyst and ligand, fluorine-containing azo benzene monomer is gathered
It closes, obtains fluorine-containing azobenzene amphiphilic polymer；
(5) at room temperature, by the dioxane solution filter membrane of fluorine-containing azobenzene amphiphilic polymer, filtrate is obtained；Then it stirs
Under, water is added into filtrate, continues to stir, obtains visible light-responded polymer nanotube.
In above-mentioned technical proposal, each substance chemical structural formula is as follows:
Adjacent tetrafluoro azobenzene VI:
VI
Fluorine-containing azobenzene alkyl chain V:
V
Fluorine-containing azo benzene monomer III:
III
End group bromine polyethylene glycol II:
II
In above-mentioned technical proposal, in step (1), reaction carries out in the presence of potassium carbonate, catalytic amount potassium iodide, adjacent tetrafluoro azo
The bromo- 1- hexanol of benzene, 6-, potassium carbonate molar ratio be 1:1~3:1~2, preferably 1:2.5:1.2, the temperature of reaction is 70~80
DEG C, the time is 3~4 hours.
In above-mentioned technical proposal, in step (2), esterification carries out in the presence of triethylamine, fluorine-containing azobenzene alkyl chain,
Methacrylic chloride, triethylamine molar ratio be 1:1~2:1~2, preferably 1:2:2, the temperature of esterification is 0 DEG C~room temperature.
In above-mentioned technical proposal, in step (3), reaction carries out in the presence of triethylamine, poly glycol monomethyl ether, alpha-brominated
Isobutyl acylbromide, triethylamine molar ratio be 1:5~10:1~2, preferably 1:5:2, the temperature of reaction is 0 DEG C~room temperature, and the time is
20~30 hours.
In above-mentioned technical proposal, in step (4), catalyst preferred cuprous bromide CuBr, the preferred PMDETA of ligand；Fluorine-containing idol
Pyridine monomer, end group bromine polyethylene glycol, catalyst, ligand molar ratio be 50~200:1:1~3:2~6, preferably 50~
200: 1: 3: 6；The temperature of polymerization is 70~90 DEG C, and the time is 10~14 hours.
In above-mentioned technical proposal, in step (5), the concentration of the dioxane solution of fluorine-containing azobenzene amphiphilic polymer is
1mg/mL；Filter membrane is oily phase 220nm filter membrane；The speed that water is added is 0.1mL/h；The speed of stirring is 300 revs/min；Continue
The time of stirring is 4 hours.Preferably, the amount that water is added is the dioxane solution of water and fluorine-containing azobenzene amphiphilic polymer
The 35%~60% of total volume, preferably 36%~40%, the available nanotube for having fine responsiveness to blue green light, and in difference
Light irradiation is lower can to occur reversible deformation.
The preparation method of above-mentioned fluorine-containing azobenzene amphiphilic polymer can carry out as follows:
A) in ice-water bath under stirring condition, with n2,6- difluoroanilines:nNitrous acid:nConcentrated hydrochloric acid=1:1 ~ 1.5:2 ~ 4, preferably n2,6- difluoroanilines:
nSodium nitrite:nConcentrated hydrochloric acidThe molar ratio of=1:1.125:2.5 adds sodium nitrite in aqueous solution into 2,6- difluoroaniline aqueous hydrochloric acid solution, protects
Holding reaction temperature is 0 ~ 5 DEG C, and the reaction was continued 20 ~ 30 minutes after being added dropwise, and obtains diazonium salt solution；
B) in ice-water bath under stirring condition, with nDiazonium salt:n 3,5- difluorophenol:nSodium hydroxide:nSodium bicarbonate=1:1.1 ~ 2:1 ~ 3:4 ~ 6, preferably
nDiazonium salt:n 3,5- difluorophenol:nSodium hydroxide:nSodium bicarbonateThe molar ratio of=1:1.25:1.5:6, to the hydrogen-oxygen of 3, the 5- difluorophenol of pH=9 ~ 10
Change diazonium salt solution obtained in a dropping step a) in sodium water solution, keeping reaction temperature is 0 ~ 5 DEG C, is continued after being added dropwise anti-
It answers 2 ~ 4 hours, obtains fluorine-containing azophenol VI；
C) under stirring condition, adjacent tetrafluoro is added into the acetone dissolved with potassium carbonate, the bromo- 1- hexanol of 6- and catalytic amount potassium iodide
Azobenzene, heating reflux reaction 3~4 hours at 70 ~ 80 DEG C obtain fluorine-containing azobenzene alkyl chain；
D) fluorine-containing azobenzene alkane is added dropwise into the anhydrous methylene chloride for dissolving methacrylic chloride, triethylamine under 0 DEG C of ice-water bath
Base chain is restored to room temperature after reacting half an hour, and TLC contact plate, which tracks to reaction, to be terminated, and fluorine-containing azo benzene monomer is obtained；
Under 0 DEG C of ice-water bath, to PEG5kMonomethyl ether, triethylamine methylene chloride in be added dropwise 2- bromine isobutyl acylbromide methylene chloride it is molten
Liquid is restored to room temperature after reacting half an hour, and normal-temperature reaction is overnight (about reacting 24 h), obtains end group bromine polyethylene glycol；
Using end group bromine polyethylene glycol as initiator, in the presence of catalyst and ligand, fluorine-containing azo benzene monomer is polymerize,
Fluorine-containing azobenzene amphiphilic polymer is obtained, wherein the preferred cuprous bromide CuBr of catalyst, the preferred PMDETA of ligand, solvent is benzene
Methyl ether, polymerizing condition are deoxygenation sealing, and polymerization system is reacted 10 ~ 14 hours in 70 ~ 90 DEG C.
The fluorine-containing azobenzene amphiphilic polymer dioxane that fluorine-containing azobenzene amphiphilic polymer is made into 1mg/mL is molten
Liquid stirs sufficiently dissolution in 24 hours, and excessively oily phase 220nm filter membrane is except large particles such as dusts, for use；Take 1mL is above-mentioned to prepare
Milli-Q water is added dropwise in 5mL vial in solution while stirring, is 0.1mL/h with micro-injection pump control plus water speed, adds
Water is setting value, and mixing speed is 300 revs/min, and temperature is 25 DEG C, continues to stir 4h after being added dropwise to get to relatively
Stable assembling liquid solution, to obtain visible light-responded polymer nanotube.
Fluorine-containing azobenzene amphiphilic polymer disclosed by the invention is self-assembly of photoresponse nanotube, in different environment
In have different patterns, while blue green light shine under conditions of, nanotube is able to achieve length, diameter, the change of film thickness.
The invention discloses above-mentioned fluorine-containing azobenzene amphiphilic polymers to prepare visible light-responded polymer nanotube
In application.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
1, the present invention obtains that a series of molecular weight are controllable, and it is total that hydrophobe block ratio explicitly has visible light-responded amphipathic block
Polymers.
2, by this amphipathic nature block polymer simply and flexibly design prepare different-shape have it is visible light-responded
Nanotube.
3, polymer nanotube stability is good, is conducive to storage.
4, the nanotube has visible light-responded property, can be realized length, diameter under blue green light irradiation, film thickness changes
Become.
5, this light-operated polymer nanotube has unique performance and wide application prospect.
Detailed description of the invention
Fig. 1 is PEG113-b-PFAZOnNuclear magnetic spectrogram (A) and SEC elution curve (B)；
Fig. 2 is PEG113-b-PFAZO78The differentiation TEM photo that multiple pattern nanotube changes with amount of water；
Fig. 3 is PEG113-b-PFAZO78In ultraviolet/visible absorption spectra figure of micellar aqueous solution, (a) green light, (b) blue light；
Fig. 4 transmission electron microscope picture (TEM): (A, a) nanotube original state, under the irradiation of (B, b) green light, polymer nanocomposite is tubular
Looks, under (C, c) blue light illumination, polymer nanotube pattern.
Specific embodiment
Further description is made to the present invention in the following with reference to the drawings and specific embodiments.
Chemical reagent:
2,6- difluoroanilines, Chinasun Specialty Products Co., Ltd
3,5- difluorophenols, AR Chinasun Specialty Products Co., Ltd
Concentrated hydrochloric acid, Jiangsu prosperity functionalized chemical Co., Ltd；
Sodium nitrite, Tianjin great Mao chemical reagent factory；
Sodium hydroxide, Jiangsu prosperity functionalized chemical Co., Ltd；
Sodium bicarbonate, Jiangsu prosperity functionalized chemical Co., Ltd；
Potassium carbonate, Jiangsu prosperity functionalized chemical Co., Ltd；
Potassium iodide, Jiangsu prosperity functionalized chemical Co., Ltd；
6- bromine hexanol, Chinasun Specialty Products Co., Ltd
Methacrylic chloride, Chinasun Specialty Products Co., Ltd
Triithylamine pacifies resistance to Jilin Chemical
α-bromine isobutyl acylbromide, Chinasun Specialty Products Co., Ltd
Cuprous bromide, Solution on Chemical Reagents in Shanghai；
Pentamethyl-diethylenetriamine (PMDETA), lark waffle；
PEG5k, Chinasun Specialty Products Co., Ltd
Sodium carbonate, Jiangsu prosperity functionalized chemical Co., Ltd；
Dimethylformamide, acetone, tetrahydrofuran, ethyl acetate, anhydrous ether, anhydrous sodium sulfate, anhydrous magnesium sulfate, just oneself
Alkane, methylene chloride, methyl phenyl ethers anisole are to analyze pure, Sinopharm Chemical Reagent Co., Ltd..
Deionized water, laboratory self-control.
Test equipment and condition:
Gel permeation chromatography (GPC) is tested on agilent company PL-50；
Nuclear magnetic resonance spectroscopy (1H-NMR) on BRUKER 300MHz nuclear magnetic resonance spectrometer, with CDCl3、DMSO-d 6For solvent, it is with TMS
Internal standard measures at room temperature；
Ultra-violet absorption spectrum (UV) measures on the UV-3150 ultraviolet-visible spectrometer of Japanese Shimadzu Corporation；
Transmission electron microscope (TEM) is obtained in HITACHIHT7700 instrument photographs, acceleration voltage 120KV.
Embodiment one: the synthesis of azo benzene monomer
1. the synthesis of fluorine-containing azobenzene (compound 3)
Diazo reaction is as follows: 2,6- difluoroaniline is added in 100 mL beakers, is added with stirring 1:1 hydrochloric acid (the dense salt of 4.95 mL
Sour+4.95 mL deionized waters) and deionized water (30 mL), it is sufficiently stirred at room temperature until 2,6- difluoroaniline dissolves.Then
It places the beaker and continues stirring cooling in ice-water bath.0-5 is down to temperatureoWhen C, NaNO is slowly added dropwise into system2Aqueous solution
(by 17.25 mmol NaNO2It is dissolved in 15 mL deionized waters), reaction temperature 0-5 is kept during being added dropwiseoC.It is added dropwise to complete
Afterwards in 0-5oContinue stirring 20 minutes under C, adds a small amount of sulfamic acid and destroy excessive sub- sodium, continue in 0-5oC stirring
20 minutes, obtain the diazonium salt solution of 2,6- difluoroaniline.
Coupling reaction is as follows: deionized water (150 mL), NaOH(15.0 mmol being added in 200 mL beakers) and 3,5-
NaHCO is added by amount under difluorophenol (15.00 mmol), stirring3(1.94 g) adjusts pH to 9 or so, places the beaker ice
Continue to stir in water-bath.0-5 is down to temperatureoWhen C, the above-mentioned diazonium salt solution prepared is slowly added drop-wise to reaction system
In, pH is remained during diazonium salt is added dropwise between 8~10 and temperature is in 0-5oC.After diazonium salt is added dropwise to complete,
Continue in 0-5oC is stirred one hour, then continues stirring 2-4 hours at room temperature.Reaction solution filtering, filter cake deionized water
Washing is three times.(phase can use 50 after washingoThe rinsing of C hot water), filtrate is extracted with ethyl acetate three times, merges organic phase, anhydrous
Magnesium sulfate is dry, filters, revolving, and column chromatography obtains red compound 3(1.90 g).
2. the synthesis of fluorine-containing azobenzene alkyl chain (compound 4)
Stirrer is separately added into 50 mL round-bottomed flasks, compound 3(10.0 mmol, 2.70 g), K2CO3(25.0
Mmol, 3.45 g), and (25.0 mmol, 4.53 g), catalytic amount potassium iodide (0.01g), 50 mL DMF for 6- bromine hexanol.By round bottom
Flask is placed on is transferred to 70 in advanceoThe oil bath pan of C reacts 3 h.It is extracted with appropriate ethyl acetate/deionized water (water is excessive), then
With saturated common salt water washing 2 times, organic phase is dry with anhydrous magnesium sulfate, filters, revolving, and column chromatography obtains orange red compound 4
(2.89 g, 78 % of yield).
3. fluorine-containing azo benzene monomer TF6MMA(compound 5) synthesis
Stirrer, compound 4(2.00 g, 5.4 mmol are added in 100 mL round-bottomed flasks), 40 mL THF, triethylamine
(1.5 mL, 10.8 mmol), stirring at normal temperature are cooled to 0 in ice-water bath to dissolvingoC .It is added in constant pressure funnel mixed
It closes solution (methacrylic chloride (0.52 mL, 10.8 mmol) is dissolved in 5 mL THF).It is slowly added dropwise under the conditions of ice-water bath mixed
Close liquid.After being added dropwise to complete, it is allowed the reaction was continued 0.5 h, normal-temperature reaction, TLC contact plate tracking, until raw material fully reacting.It will reaction
Complete reaction solution is spin-dried for, and adds water, three times with the extraction of appropriate ethyl acetate, merges organic phase, dry, is filtered, revolving, column chromatography,
Settled in cold n-hexane, obtain orange/yellow solid TFMMA(1.94 g, 82 % of yield), it is compound 5.
Embodiment two: the preparation and characterization of polymer
1. the synthesis of macromole evocating agent
Stirrer, PEG is added in 100 mL three-neck flasks5k(3.0 g, 0.6 mmol), 30 mL CH2Cl2, triethylamine
(0.17 mL, 1.2 mmol) lead to argon gas protection, and for stirring at normal temperature to dissolving, ice-water bath is cooled to 0oC.In constant pressure funnel
(2- bromine isobutyl acylbromide (372.0 μ L, 3.0 mmol) is dissolved in 20 mL CH to middle addition mixed solution2Cl2), and in ice-water bath condition
Under (about 1.5 h) is slowly added dropwise.After mixed liquor is added dropwise to complete, it is allowed the reaction was continued 0.5 h, normal-temperature reaction is overnight (about to react 24
H).30 mL deionized waters of reaction solution are extracted three times, by organic phase with anhydrous MgSO4It is dry, it filters, revolving to the left side 15 mL
The right side settles twice in anhydrous ether, and solid is dry to constant weight in vacuum drying oven in room temperature after suction filtration, obtains macromolecular initiation
Agent PEG5k-Br。
2. amphiphilic polymer PEG113-b-PFAZOnSynthesis and characterization
Polymerization system includes the side chain benzene monomer of azo containing tetrafluoro (TF6MMA), radical initiator (PEG5k- Br), cuprous salt
(CuBr), containing n-donor ligand (PMDETA) reagent, wherein with n (TF6MMA): n (PEG5k-Br) : n(CuBr) : n
(PMDETA)=50: 1: 3: 6 for:
With molar ratio above in 5 mL ampoule bottles, CuBr (5.0 mg, 0.033 mmol), PEG are sequentially added5k-Br
(55.0 mg, 0.011 mmol), and TF6MMA (250.0 mg, 0.55 mmol), PMDETA (15.0 μ L, 0.066
Mmol, 2 mL methyl phenyl ethers anisole solution lead to argon gas, and freezing pumping-defrosting inflation is repeated 3 times to remove the oxygen in pipe, next molten
Melt tube sealing, ampoule bottle is put into 70 mixed up in advanceoIt is heated in the oil bath pan of C.After reacting 12 h, ampoule bottle is taken out, at once
It is cooling to terminate reaction, a small amount of THF of solution is diluted, is added drop-wise in 150 mL anhydrous ethers and precipitates, is taken out after object sedimentation to be precipitated
Filter, obtains polymer.By its vacuum air drying to constant weight, weighing calculates conversion ratio, and tests it.
A series of ratio of adjusting monomer and initiator available different hydrophobic block length between 50:1 ~ 200:1
Amphiphilic polymer.Its nuclear-magnetism and GPC characterization such as Fig. 1.
Embodiment three: the preparation of different-shape amphiphilic polymer nanotube
1. amphiphilic polymer PEG113-b-PFAZOnSolution self assembly
By the PEG of different molecular weight113-b-PFAZOnIt is made into the dioxane solution of 1mg/mL, stirs sufficiently dissolution in 24 hours,
Cross oily phase 220nm filter membrane except large particles such as dusts, for use.
It takes the above-mentioned solution prepared of 1mL in 5mL vial, Milli-Q water is added dropwise while stirring.With micro-injection pump control
System plus water speed are 0.1mL/h, and amount of water is setting value, and mixing speed is 300 revs/min, and temperature is 25 DEG C.After being added dropwise
Continue to stir 4h to get metastable assembling liquid solution is arrived, to obtain nanotube.
PEG113-b-PFAZOnAs the increase of hydrophobic segment sequentially forms spherical micelle, vesica and nanotube.Wherein
PEG113-b-PFAZO78、PEG113-b-PFAZO100It is nanotube.
2. the regulation of multiple pattern nanotube
PEG113-b-PFAZO78It is assembled by above-mentioned assembling condition, it is available by controlling the amount of water of assembling process
The nanotube of different-shape.Amount of water is 16.6%(0.2 milliliters) when, primarily form the Giant Vesicles of diameter 1400nm, amount of water
When for 16.6%-34.4%, tadpole type vesica is primarily formed, with the increase of amount of water, the head of tadpole type vesica constantly becomes smaller,
Tail portion is constantly elongated.Amount of water primarily forms nanotube when being 37.5%.When amount of water is 60%, nanotube segment region is along straight
Diameter direction is recessed inwardly, and forms beading nanotube.As shown in Fig. 2, percentage indicates amount of water.
Example IV: nanotube visible light photoisomerization performance study
By PEG113-b-PFAZO78Amount of water be 37.5% when the nanotube that is formed, dialysis removes organic solvent, is made into
The nanotube aqueous solution of 0.04mg/mL, realizes photo-isomerisation process under the irradiation of 405 nano blue lights and 530 nanometers of green lights.
It can be found that absorption value when green light irradiates in 330nm wavelength constantly declines, illustrate the transition that π-π * has occurred, fluorine-containing azo
Benzene is converted from transconfiguration to cis-structure.Similarly, variation of the cis-isomer to transisomer occurs when blue light illumination.From
As can be seen that the cis-trans isomerization time is shorter on uv-spectrogram, nanoparticle can be realized quick sound under visible light illumination
It answers, such as Fig. 3, (a) green light, (b) blue light；The response time of beading nanotube lengthens.
Embodiment five: nanotube photo-deformable research
By PEG113-b-PFAZO78Amount of water be 37.5% when the nanotube that is formed be exposed to green light lower 5 minutes, sampling TEM is seen
Examine, then under blue light illumination after five minutes, the deformation for observing nanotube is can be found that: nanotube length shortens after green light irradiation, directly
Diameter becomes larger, and the wall thickness of nanotube becomes larger, and after blue light illumination, nanotube length is elongated, and diameter becomes smaller, and the wall thickness of nanotube becomes
It is small；Deformation process such as Fig. 4, (A, a) nanotube original state, under the irradiation of (B, b) green light, polymer nanotube pattern, (C,
C) under blue light illumination, polymer nanotube pattern.
The present invention is to the research of the photoresponse behavior of visible light-responded nanotube by the kind of abundant photoresponse nanoparticle
Class.The exploration of formation mechenism is facilitated accurately to control nanotube formation and pattern.While it by the optical Response of azobenzene and receiving
The unique performance advantage of mitron combines, and is expected to the nano material that exploitation has special performance.Fluorine-containing azobenzene is introduced two by the present invention
The side chain of the hydrophobic block of parent's property polymer assigns its bluish-green optical Response, while passing through limitation hydrophobic block length, temperature,
The formation of the conditions control nanotube such as solvent composition and pattern, in drug release, nano-reactor, nanotube template etc. has
Potential application.
Claims (10)
1. a kind of fluorine-containing azobenzene amphiphilic polymer, structure are shown in formula I:
Wherein n is 20~100；M is 100~120.
2. being used to prepare the fluorine-containing azo benzene monomer of fluorine-containing azobenzene amphiphilic polymer described in claim 1, structure such as formula
Shown in III:
Formula III.
3. the preparation method of fluorine-containing azobenzene amphiphilic polymer described in claim 1, comprising the following steps:
(1) adjacent tetrafluoro azobenzene is reacted with the bromo- 1- hexanol of 6-, obtains fluorine-containing azobenzene alkyl chain；
(2) esterification occurs for fluorine-containing azobenzene alkyl chain and methacrylic chloride, obtains fluorine-containing azo benzene monomer；
(3) poly glycol monomethyl ether and alpha-brominated isobutyryl bromine reaction, obtain end group bromine polyethylene glycol；
(4) using end group bromine polyethylene glycol as initiator, in the presence of catalyst and ligand, fluorine-containing azo benzene monomer is gathered
It closes, obtains fluorine-containing azobenzene amphiphilic polymer.
4. a kind of preparation method of visible light-responded polymer nanotube, comprising the following steps:
(1) adjacent tetrafluoro azobenzene is reacted with the bromo- 1- hexanol of 6-, obtains fluorine-containing azobenzene alkyl chain；
(2) esterification occurs for fluorine-containing azobenzene alkyl chain and methacrylic chloride, obtains fluorine-containing azo benzene monomer；
(3) poly glycol monomethyl ether and alpha-brominated isobutyryl bromine reaction, obtain end group bromine polyethylene glycol；
(4) using end group bromine polyethylene glycol as initiator, in the presence of catalyst and ligand, fluorine-containing azo benzene monomer is gathered
It closes, obtains fluorine-containing azobenzene amphiphilic polymer；
(5) at room temperature, by the dioxane solution filter membrane of fluorine-containing azobenzene amphiphilic polymer, filtrate is obtained；Then it stirs
Under, water is added into filtrate, continues to stir, obtains visible light-responded polymer nanotube.
5. according to method described in claim 3 or 4, which is characterized in that in step (1), react in potassium carbonate, catalytic amount iodine
Change potassium in the presence of carry out, the bromo- 1- hexanol of adjacent tetrafluoro azobenzene, 6-, potassium carbonate molar ratio be 1:1~3:1~2, the temperature of reaction
Degree is 70~80 DEG C, and the time is 3~4 hours；In step (2), esterification carries out in the presence of triethylamine, fluorine-containing azobenzene alkane
Base chain, methacrylic chloride, triethylamine molar ratio be 1:1~2:1~2, the temperature of esterification is 0 DEG C~room temperature.
6. according to method described in claim 3 or 4, which is characterized in that in step (3), reaction in the presence of triethylamine into
Row, poly glycol monomethyl ether, alpha-brominated isobutyl acylbromide, triethylamine molar ratio be 1:5~10:1~2, the temperature of reaction is 0 DEG C
~room temperature, time are 20~30 hours.
7. according to method described in claim 3 or 4, which is characterized in that in step (4), catalyst is cuprous bromide CuBr,
Ligand is PMDETA；Fluorine-containing azo benzene monomer, end group bromine polyethylene glycol, catalyst, ligand molar ratio be 50~200:1:1
~3:2~6；The temperature of polymerization is 70~90 DEG C, and the time is 10~14 hours.
8. the preparation method of visible light-responded polymer nanotube according to claim 4, which is characterized in that step (5)
In, the concentration of the dioxane solution of fluorine-containing azobenzene amphiphilic polymer is 1mg/mL；Filter membrane is oily phase 220nm filter membrane；Add
The speed for entering water is 0.1mL/h；The speed of stirring is 300 revs/min；The time for continuing stirring is 4 hours.
9. the visible light-responded of the preparation method preparation of visible light-responded polymer nanotube gathers according to claim 4
Close object nanotube.
10. fluorine-containing azobenzene amphiphilic polymer is in preparing visible light-responded polymer nanotube described in claim 1
Using.
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