CN106928447B - A kind of monodispersity ring-type azobenzene-tetraethylene glycol copolymer - Google Patents
A kind of monodispersity ring-type azobenzene-tetraethylene glycol copolymer Download PDFInfo
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Abstract
The invention discloses a kind of monodispersity ring-type azobenzene-tetraethylene glycol copolymers.Monodispersity ring-type azobenzene-tetraethylene glycol copolymer preparation method of the invention includes preparing chain extender, preparing brominated intermediate of each generation, prepare linear copolymer intermediate and prepare cyclocopolymer.Compared to the polydispersion polymer obtained using conventional method, monodispersity cyclocopolymer of the invention has the optical characteristics and processing performance surmounted.In addition, polymer of the invention has amphipathic, optical Response nano material can get for biological detection and drug controlled release field by polymer self assembles, have extensively and important potential using value.
Description
The application is that application No. is the divisional application of 201510771906.8 Chinese invention patent application, the Shens of original application
It please day are as follows: on November 10th, 2015, application No. is: 201510771906.8, a kind of denomination of invention are as follows: monodispersity ring-type azo
Benzene-tetraethylene glycol copolymer and its preparation method and application.
Technical field
The invention belongs to polymeric material fields, and in particular to one kind has photo absorption property and amphiphilic monodispersity
Cyclic annular azobenzene-tetraethylene glycol copolymer, preparation method, and its preparing the purposes in optical material and biomaterial.
Background technique
Precision synthesis, which has, determines that the monodisperse polymer of chain length and chemical structure not only can accurately learn molecular structure
With the relationship between its performance, and the performance of material can be predicted and optimized.Currently, the method master of synthesis monodisperse polymer
It to include two kinds: gradually growth method and exponential increase method.Gradually growth method is used primarily for synthesis polypeptide, is used subsequently to synthesis chain length
And the oligomer that structure is precisely controlled；And exponential increase method refers to that the chain length of polymer exponentially increases in its synthesis process
Long relationship (the n times side that the length of chain is 2), to obtain long-chain monodisperse polymer.The growth of chain length is being studied for single point
When dissipating the influence of the performance of polymer, gradually growth method would indicate that significant advantage.
Cyclic polymer not only reduces intermolecular mutual winding due to not having end group, and there are the restraining force of ring,
Therefore cyclic polymer shows the physicochemical property different from having the linear polymer of identical molecular weight.Percec et al. is utilized
The mode gradually increased has synthesized a series of backbone cyclic liquid crystal oligomers.The study found that the clearing point of the cyclic oligomer with
It is in odd even relationship between its degree of polymerization, is different from its linear oligomer precursor (referring to V. Percec, M. Kawasumi, P.
L. Rinaldi, et. al., Macromolecules1992,25, pp3851-3861) it can be seen that synthetic molecules
The determining cyclic polymer of amount provides new platform for the relationship more accurately probed between structure and its property, thus has
Important theory and application study meaning.However, due to accurate synthetic molecular weight determine cyclic polymer so far still have compared with
Big difficulty, therefore relevant report is still less.
Under the irradiation of ultraviolet light and visible light, reversible cis-trans isomerization can occur for azobenzene compound, thus
The fields such as optical material, drug release, grating, optical information storage, liquid crystal material have a wide range of applications, and report in succession so far
The a variety of topological structure polymer containing azobenzene group in road (mainly include that block copolymer, dendritic, star are poly-
Close object and cyclic polymer etc.).For azobenzene molecule, photoisomerization and thermal isomerization performance are by its molecule
Structure is affected, especially when the volume of its ortho-substituent is larger or azobenzene group is in cyclic structure, institute
It is impacted it is particularly evident (referring to R. Siewertsen, H. Neumann, B. Buchheim-Stehn,et. al., J. Am. Chem. Soc.,2009,131, pp15594-15595 and N. J. Bunce, G. Ferguson, C. L.
Forber, et. al., J. Org. Chem.,1987,52, pp394-398).Therefore, synthesis of cyclic azobenzene molecule is simultaneously
The special performance for studying its photoisomerization has important scientific research and economic value.
Currently, most of is containing there are three below azo-benzene units in the reported cyclic structure containing azobenzene
Small molecule compound.In addition to this, the molecular weight of some cyclic annular azobenzene polymers is polydispersity.Therefore, synthesis point
The monodispersity ring-type azobenzene polymer that son amount is controllable, structure sequence precision controls, and provide a kind of efficient, modular
Preparation method is particularly important.
Summary of the invention
For above situation, present invention firstly provides a kind of monodispersity ring-type azobenzene-tetraethylene glycol copolymers.This is total
In polymers totally six generation, all have exact molecular weight.Since the copolymer has the alternating structure of azobenzene and tetraethylene glycol, tool
There is optical Response and amphipathic, and above-mentioned performance can show certain variation with the increase of strand repetitive unit
Rule.
Specifically, monodispersity ring-type azobenzene-tetraethylene glycol copolymer of the invention (c-Azon+1-TEGn, wherein Azo
Indicate azobenzene segment, TEG represents tetraethylene glycol segment) there is general structure as follows:
Wherein: n=1,2,3,4,5 or 6.
Above-mentioned monodispersity ring-type azobenzene-tetraethylene glycol copolymer from single aggressiveness (c-Azo2-TEG1) to six aggressiveness (c-
Azo7-TEG6) molecular weight ranges be 830 ~ 4085 g/mol.Pass through infrared spectroscopy, nuclear magnetic spectrum, macromolecular mass spectrum and gel
The methods of chromatography, the cyclic annular azobenzene-tetraethylene glycol copolymer determined to above-mentioned molecular weight characterize, it was demonstrated that successfully obtain expection
Copolymer.
Secondly, the present invention provides a kind of by way of gradually chain growth to prepare above-mentioned monodispersity ring-type azo
Benzene-tetraethylene glycol copolymer method.The preparation method synthesizes the four sweet containing an azobenzene segment and one of TMS protection first
The chain extender (TMS- alkynyl-Azo-TEG- nitrine) of alcohol segment, passes through chain extender and the brominated intermediate of 1st generation (alpha-acetylenes base-
(Azo-TEG)1- ω-bromine) between CuAAC reaction, be stepped up in structure the number of (Azo-TEG) unit, obtain a series of
Brominated intermediate (alpha-acetylenes base-(Azo-TEG) containing different number of (Azo-TEG) unitn- ω-bromine), then contain these
Bromine intermediate carries out etherification reaction with 3- alkynyl -4 '-hydroxyazobenzene (HAAzo) respectively, converts alkynyl for terminal bromine atoms,
Increase an azo-benzene units simultaneously, obtains a series of linear α, the bis- alkynyl copolymer intermediates of ω-(l-(Azon+1-TEGn)),
Finally under the catalysis of cuprous salt, these linear copolymer intermediates is made to carry out the head and the tail Glaser coupling reaction of intramolecular,
Can be obtained corresponding cyclic annular azobenzene-tetraethylene glycol copolymer (c-(Azon+1-TEGn)).
Specifically, the preparation method of above-mentioned monodispersity ring-type azobenzene-tetraethylene glycol copolymer the following steps are included:
(1) preparation of tetraethylene glycol intermediate (Br-TEG-OH):
Under agitation, according to tetraethylene glycol: acid binding agent=1:1 ~ 2, preferably tetraethylene glycol: acid binding agent=1:1 molar ratio, to
Tetraethylene glycol is added in solvent dissolved with acid binding agent, and control system temperature is 0 ~ 5 DEG C, then according to tetraethylene glycol: 6- bromine hexanoyl
Chlorine=1:1 ~ 2, preferably tetraethylene glycol: 6- bromine caproyl chloride=1:1 molar ratio is added dropwise into above-mentioned system dissolved with 6- bromine caproyl chloride
Solvent, and controlling reaction temperature is 0 ~ 5 DEG C, reacts at room temperature 2 ~ 4 hours after being added dropwise, obtains tetraethylene glycol intermediate；
；
(2) preparation of 3- alkynyl -4 '-hydroxyazobenzene (HAAzo):
Under agitation, according to 3-aminophenylacetylene: sodium nitrite=1:1 ~ 1.5, preferably 3-aminophenylacetylene: nitrous
Sodium nitrite in aqueous solution is added dropwise into the 3-aminophenylacetylene acidic aqueous solution of pH=1 ~ 2 in the molar ratio of sour sodium=1:1.2, control
Reaction temperature is 0 ~ 5 DEG C, and the reaction was continued 0.5 ~ 1 hour after being added dropwise, and obtains the diazonium salt solution of 3-aminophenylacetylene；It is stirring
Under the conditions of mixing, according to diazonium salt: phenol=1:1 ~ 2, preferably diazonium salt: phenol=1:1.5 molar ratio, to the phenol of pH=9 ~ 10
The diazonium salt solution of 3-aminophenylacetylene is added dropwise in alkaline aqueous solution, control reaction temperature is 0 ~ 5 DEG C, and it is anti-that rear room temperature is added dropwise
It answers 2 ~ 4 hours, obtains 3- alkynyl -4 '-hydroxyazobenzene；
；
(3) preparation of azobenzene-tetraethylene glycol intermediate (alkynyl-Azo-TEG-OH):
Under agitation, according to tetraethylene glycol intermediate: potassium carbonate=1:1 ~ 2, preferably tetraethylene glycol intermediate: potassium carbonate=1:
2 molar ratio tetraethylene glycol intermediate is added into the solvent dissolved with potassium carbonate and catalytic amount potassium iodide, then according to tetraethylene glycol
Intermediate: 3- alkynyl -4 '-hydroxyazobenzene=1:1 ~ 3, preferably tetraethylene glycol intermediate: 3- alkynyl -4 '-hydroxyazobenzene=1:3
Molar ratio is added dropwise into above-mentioned system and is dissolved with 3- alkynyl -4 '-hydroxyazobenzene solvent, is heated to reflux 2 ~ 3 hours, obtains
Azobenzene-tetraethylene glycol intermediate；
；
(4) the brominated intermediate of 1st generation (alpha-acetylenes base-(Azo-TEG)1- ω-bromine) preparation:
Under agitation, according to azobenzene-tetraethylene glycol intermediate: acid binding agent=1:1 ~ 3, preferably in azobenzene-tetraethylene glycol
Mesosome: azobenzene-tetraethylene glycol intermediate is added into the solvent dissolved with acid binding agent, and controls for acid binding agent=1:2 molar ratio
System temperature is 0 ~ 5 DEG C, and then according to azobenzene-tetraethylene glycol intermediate: 6- bromine caproyl chloride=1:1 ~ 3, preferably azobenzene-four are sweet
Alcohol intermediate: the solvent for being dissolved with 6- bromine caproyl chloride is added dropwise into above-mentioned system, and controls for 6- bromine caproyl chloride=1:2 molar ratio
Reaction temperature is 0 ~ 5 DEG C, reacts at room temperature 2 ~ 3 hours after being added dropwise, obtains the brominated intermediate of 1st generation；
；
(5) preparation of alkynyl-Azo-TEG- nitrine:
Under agitation, according to the brominated intermediate of 1st generation: the brominated intermediate of sodium azide=1:2 ~ 4, preferably 1st generation:
The brominated intermediate of 1st generation is added into the solvent dissolved with sodium azide for sodium azide=1:3 molar ratio, and in 50 ~ 60 DEG C
Reaction 12 ~ 24 hours, obtains alkynyl-Azo-TEG- nitrine；
；
(6) preparation of chain extender (TMS- alkynyl-Azo-TEG- nitrine):
Under agitation, according to alkynyl-Azo-TEG- nitrine: acid binding agent=1:1 ~ 2, preferably alkynyl-Azo-TEG- are folded
Nitrogen: alkynyl-Azo- is added into the solvent dissolved with acid binding agent and catalytic amount trifluoromethanesulfonic acid zinc for acid binding agent=1:2 molar ratio
TEG- nitrine, then according to alkynyl-Azo-TEG- nitrine: Trimethylsilyl trifluoromethanesulfonate=1:2 ~ 2.5, preferably alkynyl-Azo-
TEG- nitrine: trifluoromethanesulfonic acid trimethyl silicane is added into above-mentioned system for Trimethylsilyl trifluoromethanesulfonate=1:2 molar ratio
Ester reacts at room temperature 8 ~ 12 hours after sealing, obtains chain extender；
；
(7) the 2nd ~ 6 generation brominated intermediate (alpha-acetylenes bases-(Azo-TEG)2- ω-bromine ~ alpha-acetylenes base-(Azo-TEG)6- ω-bromine)
Preparation:
Under inert gas protection, according to the brominated intermediate of 1st generation: the brominated centre of chain extender=1:1 ~ 2, preferably 1st generation
Body: chain extender=1:1.2 molar ratio carries out the CuAAC reaction of the brominated intermediate of 1st generation and chain extender in a solvent,
In using cuprous salt as catalyst, using polyamine compounds as ligand, the two dosage is catalytic amount and equimolar, room temperature reaction 1 ~ 2
Hour, obtain the brominated intermediate of 2nd generation (α-TMS- alkynyl-(Azo-TEG) of TMS protection2- ω-bromine)；Then in stirring condition
Under, according to the brominated intermediate of 2nd generation of TMS protection: the brominated centre of 2nd generation of tetrabutyl ammonium fluoride=1:3 ~ 6, preferably TMS protection
Body: tetrabutyl ammonium fluoride=1:5 molar ratio carries out the elimination reaction of TMS protecting group, reacts at room temperature 1 ~ 2 hour, obtains 2nd generation
Brominated intermediate；CuAAC by constantly repeating brominated intermediate and chain extender reacts and the removing of TMS protecting group is anti-
It answers, the 3rd ~ 6 generation brominated intermediate can be obtained；
；
(8) linear copolymer intermediate (l-(Azon+1-TEGn) preparation:
Under agitation, according to brominated intermediate: potassium carbonate=1:1 ~ 3, preferably brominated intermediate: potassium carbonate=1:1
Brominated intermediate is added into the solvent dissolved with potassium carbonate and catalytic amount potassium iodide in molar ratio, then according to brominated intermediate:
3- alkynyl -4 '-hydroxyazobenzene=1:1 ~ 10, preferably brominated intermediate: 3- alkynyl -4 '-hydroxyazobenzene=1:2 molar ratio,
It is added dropwise into above-mentioned system and is dissolved with 3- alkynyl -4 '-hydroxyazobenzene solvent, be heated to reflux 4 ~ 8 hours, be linearly copolymerized
Object intermediate；
；
(9) cyclocopolymer (c-(Azon+1-TEGn) preparation:
Under agitation, according to cuprous salt: polyamine compounds: triethylamine=1:2 ~ 4:1 ~ 3, preferably cuprous salt: polyaminated
Object: triethylamine=1:4:2 molar ratio is closed, cuprous salt, polyamine compounds and triethylamine are added into solvent, then according to linear
Copolymer intermediate: cuprous iodide=1:50 ~ 500, preferably linear copolymer intermediate: cuprous iodide=1:500 molar ratio, to
Injection is dissolved with the solvent of linear copolymer intermediate in above-mentioned system, and injection speed is 0.4 mL/h, room temperature after the completion of injection
Reaction 24 ~ 48 hours, finally obtains monodispersity ring-type azobenzene-tetraethylene glycol copolymer；
。
Preferably, in the above preparation method, acid binding agent described in step (1) is in diethylamine, triethylamine, pyridine
Any one, preferred triethylamine.
Preferably, in the above preparation method, solvent described in step (1) is in methylene chloride, chloroform, carbon tetrachloride
Any one, preferred methylene chloride.
Preferably, in the above preparation method, 3-aminophenylacetylene acidic aqueous solution described in preparation steps (2) is used
Any one in concentrated hydrochloric acid, sulfuric acid, nitric acid of acid, preferred concentrated hydrochloric acid.
Preferably, in the above preparation method, alkali used in phenol alkaline aqueous solution described in preparation steps (2) is selected from
Sodium hydroxide, potassium hydroxide, sodium carbonate, any one in sodium bicarbonate, preferably sodium hydroxide.
Preferably, in the above preparation method, solvent described in step (3) is selected from dimethylformamide, dimethyl sulfoxide, four
Any one in hydrogen furans, preferably dimethylformamide.
Preferably, in the above preparation method, acid binding agent described in step (4) is in diethylamine, triethylamine, pyridine
Any one, preferred triethylamine.
Preferably, in the above preparation method, solvent described in step (4) is in methylene chloride, chloroform, carbon tetrachloride
Any one, preferred methylene chloride.
Preferably, in the above preparation method, solvent described in step (5) is selected from dimethylformamide, dimethyl sulfoxide, four
Any one in hydrogen furans, preferably dimethylformamide.
Preferably, in the above preparation method, acid binding agent described in step (6) is in diethylamine, triethylamine, pyridine
Any one, preferred triethylamine.
Preferably, in the above preparation method, solvent described in step (6) is in methylene chloride, chloroform, carbon tetrachloride
Any one, preferred methylene chloride.
Preferably, in the above preparation method, the appointing in nitrogen, helium, argon gas of inert gas described in step (7)
It anticipates one kind, preferably argon gas.
Preferably, in the above preparation method, solvent described in step (7) is in methylene chloride, chloroform, carbon tetrachloride
Any one, preferred methylene chloride.
Preferably, in the above preparation method, cuprous salt described in step (7) is selected from stannous chloride, cuprous bromide, iodate
Any one in cuprous, preferably cuprous bromide.
Preferably, in the above preparation method, polyamine compounds described in step (7) are selected from tetramethylethylenediamine, five first
Any one in base diethylenetriamine, hexamethyl triethylene tetramine, preferably pentamethyl-diethylenetriamine.
Preferably, in the above preparation method, solvent described in step (8) is selected from dimethylformamide, dimethyl sulfoxide, four
Any one in hydrogen furans, preferably dimethylformamide.
Preferably, in the above preparation method, solvent described in step (9) is in acetone, methylene chloride, tetrahydrofuran
Any one, preferred acetone.
Preferably, in the above preparation method, cuprous salt described in step (9) is selected from stannous chloride, cuprous bromide, iodate
Any one in cuprous, preferably cuprous iodide.
Preferably, in the above preparation method, polyamine compounds described in step (9) are selected from tetramethylethylenediamine, five first
Any one in base diethylenetriamine, hexamethyl triethylene tetramine, preferably tetramethylethylenediamine.
Finally, due to which monodispersity ring-type azobenzene-tetraethylene glycol copolymer structure of the invention and chain length obtain accurately
Control, therefore compared to the polydispersion polymer obtained using conventional method, polymer of the invention has the optics surmounted special
Property and processing performance, there is potential application in the fields such as liquid crystal material and light shutter device.In addition, polymer of the invention has
Have amphipathic, can get optical Response nano material for biological detection and drug controlled release field by polymer self assembles
(such as preparing biological detection material and drug controlled release carrier material).More importantly using preparation side of the invention
Method need to only adjust the structure of monomer, can prepare the functional polymer that various structures accurately control.Therefore, the present invention has
Extensive and important potential using value.
Due to the implementation of above-mentioned technical proposal, compared with prior art, the present invention having the advantage that
(1) click-reaction (CuAAC) and alkynyl-alkynyl Glaser between the alkynyl and azido that copper is catalyzed by the present invention
Coupling reaction combines, and passes through the method for gradually chain growth and controls reaction time and reactant ratio, is successfully prepared for the first time
It is that a series of molecular weight determine, there is various sizes of cyclic annular azobenzene-tetraethylene glycol copolymer, preparation method of the invention is not only
Reaction condition is mild, high-efficient, and have diversity, can be used for preparing it is various with various sizes of, more blocks, point
The functional copolymer of son amount and structure determination；
(2) copolymer prepared by the method for the present invention has azobenzene and tetraethylene glycol (Azo-TEG) repetitive unit knot
Structure, thus there is optical Response and amphipathic, and the performance of copolymer shows one with being stepped up for repetitive unit
Fixed gradation law facilitates the variation relation further accurately probed between copolymer structure and its performance；
(3) azobenzene polymer in existing report is mostly polydispersity, and performance study more or less has essence
The not high problem of exactness, and a series of linear and cyclic annular azobenzene-tetraethylene glycol copolymer that the present invention synthesizes all has monodisperse
Property, molecular weight and structure determination, therefore the present invention can accurately probe into cyclic annular and linear polymer performance and its difference with
And with the increased gradation law of molecular weight.
Detailed description of the invention
Fig. 1 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) GPC elution curve figure.
Fig. 2 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) GPC molecular weight and theoretical molecular weight it is increased with algebra
Alternation figure.
Fig. 3 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) macromolecular mass spectrogram.
Fig. 4 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) nucleus magnetic hydrogen spectrum figure.
Fig. 5 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) infrared spectrogram.
Fig. 6 isl-(Azon+1-TEGn) (being expressed as 1-L) andc-(Azon+1-TEGn) (being expressed as 1-C) molten in methylene chloride
Ultraviolet/visible absorption spectra figure in liquid.
Fig. 7 isl-(Azon+1-TEGn) (being expressed as 1-L) andc-(Azon+1-TEGn) (being expressed as 1-C) molten in methylene chloride
First order kinetics curve in liquid.
Fig. 8 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) photoisomerization rate constant (k H) increase with algebra
Alternation figure.
Fig. 9 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) in it is cis- (trans) and trans- (cis) azobenzene structure
Maximum absorption wavelength (the λ of corresponding n- π * and π-π * characteristic peakmax) with the increased alternation figure of algebra.
Figure 10 isl-(Azon+1-TEGn) andc-(Azon+1-TEGn) fluorescence pattern before and after ultraviolet lighting.
Figure 11 isl-(Azon+1-TEGn) (being expressed as n-L) andc-(Azon+1-TEGn) (being expressed as n-C) before ultraviolet lighting
Fluorescence intensity afterwards compares figure.
Specific embodiment
Further description is made to the present invention below in conjunction with attached drawing and specific embodiment.
Embodiment one: the preparation of 1st generation brominated intermediate and chain extender.
1, the preparation of tetraethylene glycol intermediate (Br-TEG-OH).
Take 3.88 g(20 mmol) tetraethylene glycol, 1.4 mL(20 mmol) triethylamine and 10 mL dry methylene chlorides, it is placed in
In the 50 mL three-neck flasks equipped with agitating device, ice salt bath is cooling and controlled at 0 ~ 5 DEG C.By 3 mL(20 mmol) 6- bromine
Caproyl chloride is dissolved in 5 mL dry methylene chlorides, is added dropwise in three-neck flask with constant pressure funnel, and solution is controlled
Temperature is 0 ~ 5 DEG C.2.5 h are reacted at room temperature after being added dropwise to complete.Filter after reaction, filtrate successively use dilute hydrochloric acid, 1M NaOH and
Saturation NaCl aqueous solution is washed to pH=7.Gained organic phase is dried overnight through anhydrous magnesium sulfate, filters, rotating, column chromatographic purifying,
Obtain tetraethylene glycol intermediate (3.15 g of yield, yield 50%).
2, the preparation of 3- alkynyl -4 '-hydroxyazobenzene (HAAzo).
Weighing 5.85 g(50 mmol) 3-aminophenylacetylene is placed in 250 mL beakers, 30.0 are added under agitation
ML deionized water and 15.0 mL concentrated hydrochloric acids, ice salt bath are cooling and controlled at -5 ~ 0 DEG C.It is added in another beaker
4.14 g(60 mmol) NaNO2, with 5.0 mL deionized water dissolvings, it is slowly dropped in above-mentioned 3-aminophenylacetylene solution, controls
Reaction temperature processed is 0 ~ 5 DEG C, the reaction was continued 1 h after being added dropwise to complete, and reaction solution is in golden yellow (diazonium salt solution).Period weighs
7.05 g(75 mmol) phenol, 4.0 g(100 mmol) NaOH and 4.2 g(50 mmol) NaHCO3, it is placed in 1000 mL burning
In cup and 500 mL water are added, ice-water bath is cooling and control system temperature is -5 ~ 0 DEG C.With vigorous stirring, by the diazonium of synthesis
Salting liquid is added dropwise in above-mentioned phenol solution, and control reaction temperature is 0 ~ 5 DEG C, continues to stir at room temperature after being added dropwise to complete
Overnight.It filters after reaction, dry, column chromatographic purifying, obtains 3- alkynyl -4 '-hydroxyazobenzene (7.2 g of yield, yield
65%).
3, the preparation of azobenzene-tetraethylene glycol intermediate (alkynyl-Azo-TEG-OH).
Take 3.70 g(10 mmol) tetraethylene glycol intermediate (Br-TEG-OH), 2.76 g(20 mmol) K2CO3, 0.17 g(1
Mmol) KI and 50 mL DMF is placed in the 100 mL round-bottomed flasks equipped with agitating device.By 6.66 g(30 mmol) 3- alkynes
Base -4 '-hydroxyazobenzene (HAAzo) is dissolved in 15 mL DMF, is slowly dropped in reaction system, and 2 h are reacted at 80 DEG C.
Reaction solution cooled to room temperature, is subsequently poured into ethyl acetate, then three times with deionized water extraction, by the anhydrous sulphur of organic layer
Sour magnesium is dried overnight, filters, rotating, column chromatographic purifying, obtains azobenzene-tetraethylene glycol intermediate (4.61 g of yield, yield
95%).
4, the brominated intermediate of 1st generation (alpha-acetylenes base-(Azo-TEG)1- ω-bromine) preparation.
Take 2.98 g(5.6 mmol) azobenzene-tetraethylene glycol intermediate (alkynyl-Azo-TEG-OH), 1.13 g(11.2
Mmol) triethylamine and 10 mL dry methylene chlorides are placed in the 50 mL three-neck flasks equipped with agitating device, and ice salt bath is cooling simultaneously
Controlled at 0 ~ 5 DEG C.2.39 g(11.2 mmol) 6- bromine caproyl chloride is dissolved in 5 mL dry methylene chlorides, constant pressure is used
Dropping funel is added dropwise in three-neck flask, and control solution temperature is 0 ~ 5 DEG C.2.5 h are reacted at room temperature after being added dropwise to complete.Reaction knot
Revolving, column Chromatographic purification, obtain the brominated intermediate of 1st generation (3.1 g of yield, yield 97%) after beam.
5, the preparation of alkynyl-Azo-TEG- nitrine.
Take 4.65 g(6 mmol) alpha-acetylenes base-(Azo-TEG)1- ω-bromine, 1.2 g(18 mmol) NaN3With 25 mL DMF,
It is placed in the 50 mL round-bottomed flasks equipped with agitating device, and reacts 12 h in 60 DEG C of oil bath pans.After reaction, reaction solution
Cooled to room temperature is subsequently poured into ethyl acetate, then three times with deionized water extraction, and organic layer is dry with anhydrous magnesium sulfate
Overnight, it filters, revolving, obtains alkynyl-Azo-TEG- nitrine (4.29 g of yield, yield 99%).
6, the preparation of chain extender (TMS- alkynyl-Azo-TEG- nitrine).
Take 0.3265 g(0.5 mmol) alkynyl-Azo-TEG- nitrine, 0.018 g(0.05 mmol) trifluoromethanesulfonic acid zinc
With 2 mL dry methylene chlorides, it is placed in the 5 mL ampoule bottles equipped with agitating device, 0.155 is added thereto with micro syringe
ML(1 mmol) triethylamine and 0.184 mL(1 mmol) Trimethylsilyl trifluoromethanesulfonate, it is reacted at room temperature overnight after sealing.Instead
After answering, with deionized water extraction three times, organic layer is dried overnight with anhydrous magnesium sulfate, filters, rotate, column chromatography it is pure
Change, obtains chain extender (0.31 g of yield, yield 97%).
The preparation of embodiment two: the 2 ~ 6 generation brominated intermediate.
1, the brominated intermediate of 2nd generation (alpha-acetylenes base-(Azo-TEG)2- ω-bromine) preparation.
1.82 g(2.5 mmol are added into 50mL three-necked bottle) the brominated intermediate of 1st generation (alpha-acetylenes base-(Azo-TEG)1-
ω-bromine) and 20 mL dry methylene chlorides, after leading to 30 min of argon gas, 35.8 mg(0.25 mmol are added) CuBr and 0.06 mL
(0.25 mmol) PMDETA, is slowly added dropwise 1.82 g(3 mmol under protection of argon gas) chain extender (TMS- alkynyl-Azo-
TEG- nitrine), 1 h is reacted at room temperature after completion of dropwise addition, obtains the brominated intermediate of 2nd generation of TMS protection；It states in system then up
0.4 mL(0.8 mmol is added) TBAF, 1 h is stirred at room temperature, is subsequently poured into ethyl acetate, then three times with deionized water extraction,
Organic layer is dried overnight with anhydrous magnesium sulfate, filters, rotate, column chromatographic purifying, obtains 2nd generation brominated intermediate (yield 3.1
G, yield 95%).
2, the 3rd generation brominated intermediate (alpha-acetylenes base-(Azo-TEG)3- ω-bromine) preparation.
Referring to the method in project 1, according to alpha-acetylenes base-(Azo-TEG)2- ω-bromine: chain extender=1:1.2 molar ratio
CuAAC reaction is carried out, and according to TMS- alpha-acetylenes base-(Azo-TEG)3- ω-bromine: the molar ratio of TBAF=1:5 carries out TMS protecting group
Elimination reaction, obtain the 3rd generation brominated intermediate (4.77 g of yield, yield 94%).
3, the 4th generation brominated intermediate (alpha-acetylenes base-(Azo-TEG)4- ω-bromine) preparation.
Referring to the method in project 1, according to alpha-acetylenes base-(Azo-TEG)3- ω-bromine: chain extender=1:1.2 molar ratio
CuAAC reaction is carried out, and according to TMS- alpha-acetylenes base-(Azo-TEG)4- ω-bromine: the molar ratio of TBAF=1:5 carries out TMS protecting group
Elimination reaction, obtain the 4th generation brominated intermediate (2.93 g of yield, yield 90%).
4, the 5th generation brominated intermediate (alpha-acetylenes base-(Azo-TEG)5- ω-bromine) preparation.
Referring to the method in project 1, according to alpha-acetylenes base-(Azo-TEG)4- ω-bromine: chain extender=1:1.2 molar ratio
CuAAC reaction is carried out, and according to TMS- alpha-acetylenes base-(Azo-TEG)5- ω-bromine: the molar ratio of TBAF=1:5 carries out TMS protecting group
Elimination reaction, obtain the 5th generation brominated intermediate (2.23 g of yield, yield 90%).
5, the 6th generation brominated intermediate (alpha-acetylenes base-(Azo-TEG)6- ω-bromine) preparation.
Referring to the method in project 1, according to alpha-acetylenes base-(Azo-TEG)5- ω-bromine: chain extender=1:1.2 molar ratio
CuAAC reaction is carried out, and according to TMS- alpha-acetylenes base-(Azo-TEG)6- ω-bromine: the molar ratio of TBAF=1:5 carries out TMS protecting group
Elimination reaction, obtain the 6th generation brominated intermediate (2.51 g of yield, 85 % of yield).
Embodiment three: the preparation of linear copolymer intermediate and cyclocopolymer.
1,1st generation linear copolymer intermediate (l-(Azo2-TEG1)) and cyclocopolymer (c-(Azo2-TEG1)) system
It is standby.
(a)l-(Azo2-TEG1) preparation: take 0.548 g(1 mmol) alpha-acetylenes base-(Azo-TEG)1- ω-bromine, 0.552
G(1 mmol) K2CO3, 0.017 g(0.1 mmol) KI and 40 mL DMF, be placed in the 100 mL round bottoms equipped with agitating device and burn
In bottle.0.444 g(2 mmol) 3- alkynyl -4 '-hydroxyazobenzene (HAAzo) is dissolved in 15 mL DMF, is slowly dropped to
In reaction system, 4 h are reacted at 80 DEG C.Reaction solution cooled to room temperature, is subsequently poured into ethyl acetate, then uses deionized water
Extraction three times, organic layer is dried overnight with anhydrous magnesium sulfate, filters, rotate, column chromatographic purifying, is obtainedl-(Azo2-TEG1)
(yield 0.824g, yield 90%).
(b)c-(Azo2-TEG1) preparation: take 0.955 g(50 mmol) CuI, 30 mL(200 mmol) TMEDA, 14
ML(100 mL) triethylamine and 200 mL acetone, it is placed in the 500 mL three-neck flasks equipped with agitating device.By 0.083 g(0.1
Mmol)l-(Azo2-TEG1) with 20.0 mL acetone solutions, it is slowly added in system by micro syringe, flow velocity is 0.4 mL/
h.24 h are reacted at room temperature after the completion of injection, column chromatographic purifying obtainsc-(Azo2-TEG1) (0.082 g of yield, yield 95%).
2,2nd generation linear copolymer intermediate (l-(Azo3-TEG2)) and cyclocopolymer (c-(Azo3-TEG2)) system
It is standby.
Referring to the method in project 1(a), according to HAAzo: alpha-acetylenes base-(Azo-TEG)2- ω-bromine=3:1 molar ratio, obtains
It arrivesl-(Azo3-TEG2) (1.33 g of yield, yield 90%).
Referring to project 1(b) in method, according tol-(Azo3-TEG2): the molar ratio of CuI=1:100 obtainsc-(Azo3-
TEG2) (0.082 g of yield, yield 70%).
3, the 3rd generation linear copolymer intermediate (l-(Azo4-TEG3)) and cyclocopolymer (c-(Azo4-TEG3)) system
It is standby.
Referring to the method in project 1(a), according to HAAzo: alpha-acetylenes base-(Azo-TEG)3- ω-bromine=3:1 molar ratio, obtains
It arrivesl-(Azo4-TEG3) (2.06 g of yield, yield 97%).
Referring to project 1(b) in method, according tol-(Azo4-TEG3): the molar ratio of CuI=1:150 obtainsc-(Azo4-
TEG3) (0.137 g of yield, yield 92%).
4, the 4th generation linear copolymer intermediate (l-(Azo5-TEG4)) and cyclocopolymer (c-(Azo5-TEG4)) system
It is standby.
Referring to the method in project 1(a), according to HAAzo: alpha-acetylenes base-(Azo-TEG)4- ω-bromine=5:1 molar ratio, obtains
It arrivesl-(Azo5-TEG4) (1.28 g of yield, yield 92%).
Referring to project 1(b) in method, according tol-(Azo5-TEG4): the molar ratio of CuI=1:300 obtainsc-(Azo5-
TEG4) (0.121 g of yield, yield 87%).
5, the 5th generation linear copolymer intermediate (l-(Azo6-TEG5)) and cyclocopolymer (c-(Azo6-TEG5)) system
It is standby.
Referring to the method in project 1(a), according to HAAzo: alpha-acetylenes base-(Azo-TEG)5- ω-bromine=8:1 molar ratio, obtains
It arrivesl-(Azo6-TEG5) (0.465 g of yield, yield 86%).
Referring to project 1(b) in method, according tol-(Azo6-TEG5): the molar ratio of CuI=1:400 obtainsc-(Azo6-
TEG5) (0.06 g of yield, yield 90%).
6, the 6th generation linear copolymer intermediate (l-(Azo7-TEG6)) and cyclocopolymer (c-(Azo7-TEG6)) system
It is standby.
Referring to the method in project 1(a), according to HAAzo: alpha-acetylenes base-(Azo-TEG)6- ω-bromine=10:1 molar ratio,
It obtainsl-(Azo7-TEG6) (0.35 g of yield, yield 86%).
Referring to project 1(b) in method, according tol-(Azo7-TEG6): the molar ratio of CuI=1:500 obtainsc-(Azo7-
TEG6) (0.073 g of yield, yield 90%).
Gained compound is characterized via GPC, macromolecular mass spectrum, infared spectrum and nuclear magnetic spectrum, as a result as described below:
Fig. 1 is linear and cyclocopolymer molecule GPC elution curve figure, and Fig. 2 is linear and cyclocopolymer molecule
GPC molecular weight and theoretical molecular weight are with the increased alternation figure of algebra.As seen from Figure 1, every generation is linear and ring molecule is equal
With relatively narrow single distribution GPC elution curve, and every generation ring molecule is shown than it with longer for linear precursor
Elution time, because the more compact ring molecule of structure has hydrodynamic volume more smaller than its linear precursor.It can by Fig. 2
To find out, every generation that GPC is measured is linearly and the molecular weight of cyclocopolymer meets level-one linear power with the growth of algebra
It learns and is incremented by relationship.In addition, the linear difference between the GPC molecular weight of ring molecule also increases with the growth of algebra, this is said
The bright growth with chain, ring molecule has smaller hydrodynamic volume than its linear precursor, thus shows more to extend
GPC elution time.The molecular weight that linear polymer GPC is measured is all larger than its true molecular amount, and with the increasing of molecular weight
Add, difference between the two is also increase accordingly.Since GPC is tested using polystyrene as standard specimen, and contain rigidity in polymer chain
Azobenzene, diacetylene and triazole group, these rigid radicals will lead to polymer hydrodynamic volume be greater than flexibility
Polystyrene, thus the molecular weight that GPC is measured is bigger than normal relative to polystyrene standards, and as molecular weight increases, just
Property group also accordingly increases, thus difference is gradually increased.Cyclic polymer is less than due to compact-sized by 1st generation gpc measurement value
True value is greater than true value to the 6th generation gpc measurement value, also shows the trend being gradually increased with molecular weight increase.
Fig. 3 is linear and cyclocopolymer molecule macromolecular mass spectrogram, whereinl-(Azo2-TEG1) it is labeled as 1-L,c-
(Azo2-TEG1) it is labeled as 1-C, remaining and so on.Each of figure quasi-molecular ions can find very identical with theoretical value
Ownership, the corresponding linear and theoretical molecular weight of ring molecule and the molecular weight of macromolecular mass spectrometric measurement are as shown in table 1.In addition,
When carrying out macromolecular mass spectrometric measurement, one group of ion that 23 Da are differed with theoretical molecular weight can be generated under the conditions of laser ionization
Peak this is because loop wire polymer has taken a sodium ion (22.99) with this condition, thus causes quasi-molecular ions than corresponding
Big 23 Da of loop wire polymer.
Fig. 4 is linear and cyclocopolymer molecule nucleus magnetic hydrogen spectrum figure, whereinl-(Azo2-TEG1) it is labeled as 1-L,c-
(Azo2-TEG1) it is labeled as 1-C, remaining and so on.There it can be seen that cyclic polymer exists compared to linear polymer
Alkynyl hydrogen absorption peak (label is in figure) at 3.14 ppm disappears, and the chemical shift of other absorption peaks does not change, shows
Linear polymer completes intramolecular Glaser coupling reaction, successfully obtains cyclic polymer.
Fig. 5 is linear and cyclocopolymer molecule infrared spectrogram, whereinl-(Azo2-TEG1) it is labeled as 1-L,c-
(Azo2-TEG1) it is labeled as 1-C, remaining and so on.Therefrom it can clearly be seen that linear structure is in 3300cm-1There are alkynyls at place
Absorption of vibrations band, and cyclic structure is in 3300cm-1Place does not observe alkynyl absorption of vibrations band, shows that Glaser intramolecular cyclization is anti-
The complete progress answered.
These results suggest that the linear and cyclocopolymer that molecular weight determines has successfully been obtained in the present invention.
Example IV: linear and cyclocopolymer optical performance test.
Linear and cyclocopolymer molecule containing azobenzene group can occur " cis- under Uv and visible light irradiation
Instead " and " trans- suitable " photoisomerization.Fig. 6 is that ultraviolet/visible absorption spectra figure of the 1-L and 1-C in dichloromethane solution is (dense
Degree is 3.6 × 10-8Mol/mL).Before illumination, 1-L and 1-C major part azobenzene exists with anti-configuration, with 365 nm
Ultraviolet light (0.5 mW/cm2) irradiation, the π-π * transition characteristics peak of the trans-azobenzene near 351 nm weakens quickly, and
The weaker n- π * transition characteristics peak of cis-azobenzene near 450 nm shows slow enhancing trend, irradiates through 180s
Afterwards, reach trans- suitable isomerization equilibrium state (PSSUV).The PSSuv solution of 1-L and 1-C is receiving 435 nm visible lights (0.53
mW/cm2) irradiation after, the absorption peak at 351nm slowly rises, and after 340s irradiates, reaches cis-trans isomerization equilibrium state
(PSSvis), and absorption peak strength also reaches the original state before illumination.Other several generations are linear and cyclocopolymer has and 1-
Similar ultraviolet/visible absorption spectra the figure of L and 1-C.
By uv-visible absorption spectra corresponding to the linear and photoisomerization of cyclocopolymer at 350 nm
The absorbance value of trans-azobenzene brings following formula into respectively, calculates linear and cyclocopolymerk eWithk H。
Wherein:k eFor trans- suitable isomerization rate constant,k HFor cis-trans isomerization recovery rate constant, A0For in corresponding light
According to absorbance value of (t=0) trans-azobenzene near 350 nm before, AtFor idol trans- after corresponding light application time (t)
Absorbance value of the pyridine near 350 nm, A∞For under PSSuv or PSSvis state trans-azobenzene near 350 nm
Absorbance value.For example, as shown in fig. 7, the photoisomerization rate of 1-L and 1-C follows level-one linear dynamics relationship.
The dichloromethane solution of the linear and cyclocopolymer obtained by formula 1 and formula 2 is irradiated in Uv and visible light
Under " trans- suitable " and " cis- anti-" photoisomerization rate constant it is as shown in table 2.There it can be seen that all ring molecules is photic
Trans- genial cis-trans isomerization rate constant is all bigger than corresponding linear molecule, illustrate the photoisomerization speed of ring molecule compared with
Its linear precursor is fast, this is because ring molecule dereliction chain end group is waved and the rigidity of cyclic structure makes the curling of its strand
Degree is lower than linear precursor, therefore its azobenzene group isomerization relatively easily carries out.
Note: ke and k ' e is respectively that cyclic annular and linear molecule trans- frontlighting causes isomerization rate constant, and kH and k ' H are respectively
Cyclic annular and linear molecule cis-trans isomerization recovery rate constant；Wherein: ke tests the Mean Speed taken by five times, exists
± 15% deviation, kH test the Mean Speed taken by five times, there is ± 10% deviation.
Fig. 8 is linear and cyclocopolymer photoisomerization rate constant with the increased alternation figure of algebra.It therefrom can be with
Find out, in 365 nm ultraviolet lighting after, cyclic annular 1-C'sk eValue is more much bigger than linear 1-L, illustrates the trans- suitable isomerization speed of 1-C
Much faster, this may be thus to lead to the azo in main chain since small ring structures have certain rigidity and tension to rate ratio 1-L
The photoisomerization of benzene from transconfiguration to the curved cis-structure of plane is relatively easy.And when 435 nm visible lights shine
Afterwards, with the growth of algebra, the cis-trans isomerization recovery rate of the 6th generation molecule is varied less.
Fig. 9 is n- π * and π-π * transition characteristics corresponding to cis and trans azobenzene in linear and cyclocopolymer molecule
The increased alternation figure of maximum absorption wave personal attendant's algebra at peak.There it can be seen that all six generations are linear and ring molecule in it is cis-
The maximum absorption wavelength of azobenzene is in 439 nm, and as the increase of algebra remains unchanged.The difference is that institute is linear
The maximum absorption wavelength of trans-azobenzene is near 351 ~ 352nm in molecule, and varies less.However, in algebra n < 5
In the case of, in other three generations's ring molecules in addition to 1st generation the maximum absorption wavelength of trans-azobenzene be kept at 341 ~
Near 343nm, 10 nm of blue shift or so about than linear structure；But when n reaches 5, the maximum absorption wave long hair of trans-azobenzene
Raw red shift, and substantially reach unanimity with linear precursor.The blue shift of the maximum absorption wavelength of trans-azobenzene in ring molecule
It may be mainly due to the rigidity of the diacetylene structure being connected in cyclic structure with azobenzene and ring itself.
Typically, azobenzene compound does not have fluorescence or only has faint fluorescence, but certain conditions may
The fluorescence enhancement for making azobenzene compound, as aggregation inducing and light induced fluorescence enhancing and ring topologies increase fluorescence
By force.Figure 10 is linear and cyclocopolymer molecule fluorescence pattern, and Figure 11 is linear and cyclocopolymer molecule fluorescence intensity
Compare figure.Therefrom it can be found thatl-(Azon+1-TEGn) andc-(Azon+1-TEGn) (n≤5) have at 400 ~ 500nm it is weaker
Fluorescence emission peak.In general, relative to linear molecule, the fluorescence intensity of ring molecule has different degrees of raising, especially
It is that the raising of 1st generation ring molecule (1-C) fluorescence intensity is the most obvious, this may be since its cyclic structure more or less has
There are some rigidity, the opposite amount of crimp of strand is less than corresponding linear molecule, thus in cyclic structure between chromophore
It is spaced relatively large, reduces its fluorescent quenching effect.Whenl-(Azon+1-TEGn) andc-(Azon+1-TEGn) in n value difference
When increasing to 5 and 6, all basic unstressed configuration, this may be the strand since the rigidity of growth and ring with strand disappears
Opposite amount of crimp increase, force chromophore close to each other, lead to fluorescent quenching.
Monodisperse azobenzene copolymer prepared by the present invention, since structure and chain length accurately control, compared to use
The polydispersion polymer that conventional method obtains, this polymer have the optical characteristics and processing performance that surmount, in liquid crystal material and
The fields such as light shutter device have potential application.This polymer have it is amphipathic, by polymer self assembles can get light ring
Answering property nano material is used for biological detection and drug controlled release.More importantly only being needed using preparation method of the invention
The structure for adjusting monomer can prepare various structures and functional polymer that molecular weight accurately controls.Therefore, the present invention has
Extensive and important potential using value.
Claims (8)
1. a kind of monodispersity ring-type azobenzene-tetraethylene glycol copolymer, with general structure as follows:
Wherein: n=1,2,3,4,5 or 6.
2. monodispersity ring-type azobenzene-tetraethylene glycol copolymer according to claim 1, it is characterised in that: described single point
The preparation method for dissipating property ring-type azobenzene-tetraethylene glycol copolymer includes the following steps:
1) preparation of tetraethylene glycol intermediate:
Under agitation, according to tetraethylene glycol: it is sweet that four are added into the solvent dissolved with acid binding agent for acid binding agent=1:1 ~ 2 molar ratios
Alcohol, and control system temperature is 0 ~ 5 DEG C, then according to tetraethylene glycol: 6- bromine caproyl chloride=1:1 ~ 2 molar ratio, into above-mentioned system
The solvent for being dissolved with 6- bromine caproyl chloride is added dropwise, and controlling reaction temperature is 0 ~ 5 DEG C, reacts at room temperature 2 ~ 4 hours, obtains after being added dropwise
To tetraethylene glycol intermediate；
；
2) 3- alkynyl -4 '-hydroxyazobenzene preparation:
Under agitation, according to 3-aminophenylacetylene: sodium nitrite=1:1 ~ 1.5 molar ratio, to the m-aminophenyl of pH=1 ~ 2
It is added dropwise sodium nitrite in aqueous solution in acetylene acidic aqueous solution, control reaction temperature is 0 ~ 5 DEG C, the reaction was continued after being added dropwise 0.5 ~
1 hour, obtain the diazonium salt solution of 3-aminophenylacetylene；Under agitation, according to diazonium salt: phenol=1:1 ~ 2 mole
Than the diazonium salt solution of above-mentioned 3-aminophenylacetylene being added dropwise into the phenol alkaline aqueous solution of pH=9 ~ 10, control reaction temperature is
It 0 ~ 5 DEG C, is reacted at room temperature 2 ~ 4 hours after being added dropwise, obtains 3- alkynyl -4 '-hydroxyazobenzene；
；
3) azobenzene-tetraethylene glycol intermediate preparation:
Under agitation, according to tetraethylene glycol intermediate: potassium carbonate=1:1 ~ 2 molar ratio, to dissolved with potassium carbonate and catalytic amount
Tetraethylene glycol intermediate is added in the solvent of potassium iodide, then according to tetraethylene glycol intermediate: 3- alkynyl -4 '-hydroxyazobenzene=1:1 ~
3 molar ratio is added dropwise into above-mentioned system and is dissolved with 3- alkynyl -4 '-hydroxyazobenzene solvent, is heated to reflux 2 ~ 3 hours, obtains
To azobenzene-tetraethylene glycol intermediate；
；
4) preparation of the brominated intermediate of 1st generation:
Under agitation, according to azobenzene-tetraethylene glycol intermediate: acid binding agent=1:1 ~ 3 molar ratio, to dissolved with acid binding agent
Solvent in be added azobenzene-tetraethylene glycol intermediate, and control system temperature be 0 ~ 5 DEG C, then according in azobenzene-tetraethylene glycol
Mesosome: the solvent for being dissolved with 6- bromine caproyl chloride is added dropwise into above-mentioned system for 6- bromine caproyl chloride=1:1 ~ 3 molar ratio, and controls anti-
Answering temperature is 0 ~ 5 DEG C, reacts at room temperature 2 ~ 3 hours after being added dropwise, obtains the brominated intermediate of 1st generation；
；
5) preparation of alkynyl-Azo-TEG- nitrine:
Under agitation, according to the brominated intermediate of 1st generation: sodium azide=1:2 ~ 4 molar ratio, to dissolved with sodium azide
Solvent in be added the brominated intermediate of 1st generation, and in 50 ~ 60 DEG C react 12 ~ 24 hours, obtain alkynyl-Azo-TEG- nitrine；
；
6) preparation of chain extender:
Under agitation, according to alkynyl-Azo-TEG- nitrine: acid binding agent=1:1 ~ 2 molar ratio, to dissolved with acid binding agent and
Alkynyl-Azo-TEG- nitrine is added in the solvent of catalytic amount trifluoromethanesulfonic acid zinc, then according to alkynyl-Azo-TEG- nitrine: three
Fluorine methanesulfonic acid trimethylsilyl group=1:2 ~ 2.5 molar ratio, Trimethylsilyl trifluoromethanesulfonate is added into above-mentioned system, sealing
It reacts at room temperature 8 ~ 12 hours afterwards, obtains chain extender；
；
7) preparation of the 2nd ~ 6 generation brominated intermediate:
Under nitrogen or inert gas shielding, according to the brominated intermediate of 1st generation: chain extender=1:1 ~ 2 molar ratio, molten
The CuAAC reaction that the brominated intermediate of 1st generation and chain extender are carried out in agent, wherein using cuprous salt as catalyst, with polyamines chemical combination
Object is ligand, and the two dosage is catalytic amount and equimolar, is reacted at room temperature 1 ~ 2 hour, obtain TMS protection 2nd generation it is brominated in
Mesosome；Then under agitation, the brominated intermediate of 2nd generation protected according to TMS: tetrabutyl ammonium fluoride=1:3 ~ 6 mole
Than carrying out the elimination reaction of TMS protecting group, reacting at room temperature 1 ~ 2 hour, obtain the brominated intermediate of 2nd generation；By constantly repeating to contain
The CuAAC of bromine intermediate and chain extender reaction and the elimination reaction of TMS protecting group, can be obtained the 3rd ~ 6 generation brominated centre
Body；
；
8) preparation of linear copolymer intermediate:
Under agitation, according to brominated intermediate: potassium carbonate=1:1 ~ 3 molar ratio, to dissolved with potassium carbonate and catalytic amount iodine
Change in the solvent of potassium and brominated intermediate is added, then according to brominated intermediate: rubbing 3- alkynyl -4 '-hydroxyazobenzene=1:1 ~ 10
That ratio, is added dropwise into above-mentioned system and is dissolved with 3- alkynyl -4 '-hydroxyazobenzene solvent, be heated to reflux 4 ~ 8 hours, obtain line
Property copolymer intermediate；
；
9) preparation of cyclocopolymer:
Under agitation, according to cuprous iodide: polyamine compounds: triethylamine=1:2 ~ 4:1 ~ 3 molar ratios is added into solvent
Cuprous iodide, polyamine compounds and triethylamine, then according to linear copolymer intermediate: cuprous iodide=1:50 ~ 500 mole
Than into above-mentioned system, injection is dissolved with the solvent of linear copolymer intermediate, and injection speed is 0.4 mL/h, after the completion of injection
Room temperature reaction 24 ~ 48 hours, finally obtains monodispersity ring-type azobenzene-tetraethylene glycol copolymer；
。
3. monodispersity ring-type azobenzene-tetraethylene glycol copolymer according to claim 2, it is characterised in that:
Acid binding agent described in step 1) and step 4) is independently selected from any one in diethylamine, triethylamine, pyridine；
Solvent described in step 1) and step 4) is independently selected from any one in methylene chloride, chloroform, carbon tetrachloride.
4. monodispersity ring-type azobenzene-tetraethylene glycol copolymer according to claim 3, it is characterised in that: step 1) and
Solvent described in step 4) is methylene chloride.
5. monodispersity ring-type azobenzene-tetraethylene glycol copolymer according to claim 2, it is characterised in that:
Preparation steps 2) described in acid used in 3-aminophenylacetylene acidic aqueous solution in concentrated hydrochloric acid, sulfuric acid, nitric acid
Any one；
Preparation steps 2) described in alkali used in phenol alkaline aqueous solution be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid
Any one in hydrogen sodium.
6. monodispersity ring-type azobenzene-tetraethylene glycol copolymer according to claim 2, it is characterised in that:
Solvent described in step 3), step 5) and step 8) is independently selected from dimethylformamide, dimethyl sulfoxide, tetrahydrofuran
Any one.
7. monodispersity ring-type azobenzene-tetraethylene glycol copolymer according to claim 2, it is characterised in that:
Any one of inert gas described in step 7) in helium, argon gas；
Any one of solvent described in step 7) in methylene chloride, chloroform, carbon tetrachloride；
Any one of cuprous salt described in step 7) in stannous chloride, cuprous bromide, cuprous iodide；
Polyamine compounds described in step 7) are selected from tetramethylethylenediamine, pentamethyl-diethylenetriamine, hexamethyl triethylene tetramine
In any one.
8. monodispersity ring-type azobenzene-tetraethylene glycol copolymer according to claim 2, it is characterised in that:
Any one of solvent described in step 9) in acetone, methylene chloride, tetrahydrofuran；
Polyamine compounds described in step 9) are selected from tetramethylethylenediamine, pentamethyl-diethylenetriamine, hexamethyl triethylene tetramine
In any one.
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| CN105254880A (en) | 2016-01-20 |
| CN105254880B (en) | 2017-07-07 |
| CN106928447A (en) | 2017-07-07 |
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