CN109438700A - A kind of poly- methyl-triazole formic acid esters and the preparation method and application thereof - Google Patents
A kind of poly- methyl-triazole formic acid esters and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of poly- methyl-triazole formic acid esters and the preparation method and application thereof to obtain poly- methyl-triazole formic acid esters by solution or bulk polymerization using binary butine acid ester monomer and binary organic nitrine monomer as raw material.Reaction raw materials disclosed by the invention are easy to get, and can be synthesized by simple organic reaction；No coupling product generates in polymerization process, meets Atom economy；Using green solvent or without using solvent in polymerization process, non-environmental-pollution meets Green Chemistry feature；Polymerization process does not use metallic catalyst, can eliminate influence of the catalyst residual to polymer material biology and photoelectric properties；The polymerization reaction has extensive substrate applicability and good functional group compatibility, can easily introduce several functions group.Therefore the polymerization reaction has important scientific meaning and application value in terms of Polymer Synthesizing and Functionally structure preparation.
Description
Technical field
The invention belongs to polymer chemistry and materials science field, and in particular to a kind of poly- methyl-triazole formic acid esters and its system
Preparation Method and application.
Background technique
The research hotspot that functional polymer is polymer chemistry and Material Field is prepared based on novel polymeric reaction.
Known most polymerization reaction is developed by small organic molecule reaction.Organic nitrine and acetylene compound generate
1, the 3- Dipolar Cycloaddition of 1,2,3- ring triazole, in early days due to reaction speed is slow and regioselectivity difference etc. without
It receives extensive attention.Monovalence copper catalysis organic nitrine is reported from the prior art to react with end alkyne compound and only generate 1,
Since 4- bis- replaces 1,2,3-triazoles compound, the reaction with raw material due to being easy to get, reaction condition is mild, regiospecificity and
The features such as yield is high and be referred to as " click-reaction ", have evolved into a kind of novel polymerization reaction and be widely used in polymerizeing
The synthesis of object and Post functionalization modification etc..
But utilize and contain ring triazole structure in the polymer of polymerization reaction preparation, with the copper ion meeting in catalyst
Coordination, which occurs, often will affect the dissolubility of the polymer.In addition, the residual of copper catalyst will affect the biology of polymer
And luminescent properties, limit application of the polymerization reaction in bio-medical and opto-electrical polymers field of material preparation.In addition,
Active alkynes monomer used in the click polymerization reaction of existing no metal catalytic is only limitted to end alkyne compound, and polymerize anti-
Answer that the degree of regioregularity of prepared polymer is poor, reaction condition is harsher.
Most organic and polymer luminescent material often shines strongly in the solution, and issues in solid-state or state of aggregation
Light, which weakens, not to shine even, and Fluorescence quenching effect caused by this aggregation limits the use scope of luminescent material.In recent years, one
Class aggregation-induced emission (AIE), instant liquid does not shine and state of aggregation shines strong material, due to its special luminescent behavior
And be widely used in the fields such as electroluminescent, chemical detection and bio-sensing (Chem. Rev.2015,115,11718).With
Organic small molecule material is compared, and polymer material usually has preferable processing performance, for example can pass through the side of simple spin coating
Method prepares large area film.Therefore, new structural AIE living polymer is prepared with important using novel polymerization reaction
Application value.
Summary of the invention
The present invention provides a kind of poly- methyl-triazole formic acid esters, and provide the preparation method and application of the quasi polymer,
Such as the application in the detection of nitro-aromatic substance, luminous pattern preparation, cell imaging.
To achieve the above object, the technical solution used in the present invention is:
A kind of poly- methyl-triazole formic acid esters has chemical structure shown in formula I:
Formula I
Wherein, n is 2~200；Any one group of R in 1~20, any one base of R ' in 1~9,19~28
Group: described 1~28 unit structure formula is as follows:
Wherein, the integer that m is 1~18；* the position of substitution is indicated.
The invention also discloses the preparation methods of above-mentioned poly- methyl-triazole formic acid esters, include the following steps, with binary butine
Acid ester monomer and binary organic nitrine monomer are raw material, and polymerization obtains poly- methyl-triazole formic acid esters.
The invention discloses a kind of detection methods of nitro-aromatic compound in system to be detected, comprising the following steps:
(1) using binary butine acid ester monomer and binary organic nitrine monomer as raw material, polymerization obtains poly- methyl-triazole formic acid esters；Match
The solution of the poly- methyl-triazole formic acid esters is made, the fluorescence spectrum of the solution of the poly- methyl-triazole formic acid esters is tested, is obtained just
Beginning fluorescence intensity；
(2) system to be detected is mixed with the poly- methyl-triazole formic acid ester solution, obtains mixed liquor, tests the fluorescence of mixed liquor
Spectrum obtains fluorescence intensity；
(3) compare initial fluorescent intensity and fluorescence intensity, complete the detection of nitro-aromatic compound in system to be detected.
Preferably, nitro-aromatic compound is picric acid.
Preferably, in the solution of poly- methyl-triazole formic acid esters, solvent is the mixed liquor of tetrahydrofuran, water, the preferably body of water
Product percentage is 90%.
When comparing initial fluorescent intensity and fluorescence intensity, if initial fluorescent intensity is consistent with fluorescence intensity,
Nitro-aromatic compound is then free of in system to be detected, it is to be detected if initial fluorescent intensity is higher than fluorescence intensity
Contain nitro-aromatic compound in system.
The invention discloses a kind of preparation methods of luminous pattern, comprising the following steps: with binary butine acid ester monomer with
Binary organic nitrine monomer is raw material, and polymerization obtains poly- methyl-triazole formic acid esters；By the solution of the poly- methyl-triazole formic acid esters
Thin polymer film is formed on silicon wafer by the method for spin coating, then will be carved figuratum copper mast and is covered in thin polymer film table
Then face is irradiated under ultraviolet lamp, is finally dried in vacuo, obtains luminous pattern.
It preferably, is 1,2- dichloroethanes by solvent in the solution of poly- methyl-triazole formic acid esters；Poly- methyl-triazole formic acid esters
Solution concentration be 5 mg/mL；Polymer is formed through being dried in vacuo on silicon wafer after spin coating；The wavelength of ultraviolet lamp is 365
nm。
A kind of preparation method of ionomeric polymer, comprising the following steps: organic with binary butine acid ester monomer and binary
Nitrine monomer is raw material, and polymerization obtains poly- methyl-triazole formic acid esters；The poly- methyl-triazole formic acid esters is dissolved in DMSO, is added
Alkyl halide after being stirred to react, is cooled to room temperature, is then filtered, washed, dry to constant weight, obtains ionomeric polymer, is soluble in
Water can be used for biological field.
Preferably, it is stirred to react and is stirred to react 24 hours for 60 DEG C.
The preparation method of above-mentioned poly- methyl-triazole formic acid esters is specially by binary butine acid ester monomer and binary organic nitrine
Monomer dissolves in a solvent, and heating polymerization obtains poly- methyl-triazole formic acid esters；Or it is binary butine acid ester monomer and binary is organic
The mixing of nitrine monomer, is added without solvent, and heating polymerization obtains poly- methyl-triazole formic acid esters.
In the present invention, the molar ratio of binary butine acid ester monomer and binary organic nitrine monomer is 1:1；When solvent is organic
When solvent, binary butine acid ester monomer and binary organic nitrine monomer are dissolved in a solvent, it is dense to be configured to butine acid ester monomer
Degree is the mixed liquor of 0.2~0.8 mol/L, obtains poly- methyl-triazole formic acid esters within polymerization reaction 2~36 hours in 80~180 DEG C；
When solvent is water, it is configured to the mixed liquor that butine acid ester monomer concentration is 0.2~0.8 mol/L, is polymerize in 80~120 DEG C
Reaction obtains poly- methyl-triazole formic acid esters in 2~36 hours；It is when being added without solvent, binary butine acid ester monomer and binary is organic
The mixing of nitrine monomer, obtains poly- methyl-triazole formic acid esters in polymerization reaction 2~36 hours in 80~180 DEG C.
In the present invention, using 2- tetrolic acid and dihydric phenol or dihydric alcohol as raw material, reaction preparation binary butine acid ester monomer；
Preferably, in the presence of an additive, reaction preparation binary butine acid ester monomer, the additive are in a solventN,N- two rings
One or more of hexyl carbodiimide (DCC), 4-dimethylaminopyridine (DMAP), p-methyl benzenesulfonic acid (TsOH), it is described molten
Agent is one or more of methylene chloride, tetrahydrofuran, toluene；Preferably, the temperature of reaction is 0 DEG C~room temperature, time 8
~24 hours.
In the present invention, the chemical structural formula of binary butine acid ester monomer is as follows:
Wherein R is any one group in above-mentioned 1~20；
The chemical structural formula of the binary nitrine monomer is as follows:
Wherein R is any one group in above-mentioned 1~9,19~28.
The preparation method of poly- methyl-triazole formic acid esters disclosed by the invention can be such that
(1) binary butine acid ester monomer is prepared
It is molten in the mixing of methylene chloride or methylene chloride and tetrahydrofuran using 2- tetrolic acid and dihydric phenol or dihydric alcohol as raw material
In agent, it is addedN,NDicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP) and p-methyl benzenesulfonic acid (TsOH), 0
DEG C~room temperature, it reacts 8~24 hours, prepares binary butine acid ester monomer；Or it is with 2- tetrolic acid and dihydric phenol or dihydric alcohol
Raw material, in toluene, 12~36 hours preparation binary butine acid ester monomers of back flow reaction under the catalysis of TsOH.
(2) poly- methyl-triazole formic acid esters is prepared
It is anti-by solution polymerization or bulk polymerization using the binary butine acid ester monomer and binary organic nitrine monomer of preparation
It should obtain.
In the present invention, solution polymerization are as follows: add binary butine acid ester monomer and binary nitrine monomer with molar ratio 1:1
Enter into polymerization pipe, be added solvent, at 80~180 DEG C preferably 100~150 DEG C, heating reaction 2~36 hours preferably 8~
24 hours, end of reaction was post-treated to obtain the poly- methyl-triazole formic acid esters.The solvent can be selectedN,NDimethyl
Formamide (DMF),N,NDimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO),NIn methyl pyrrolidone (NMP), water
It is one or more of.
In the present invention, bulk polymerization are as follows: add binary butine acid ester monomer and binary nitrine monomer with molar ratio 1:1
Enter into polymerization pipe, not solubilizer, at 80~180 DEG C preferably 100~150 DEG C, heating reaction 2~36 hours preferably 8~
24 hours, end of reaction was post-treated to obtain the poly- methyl-triazole formic acid esters.In the present invention, poly- methyl-triazole first is prepared
When acid esters, after the completion of polymerization reaction, reaction solution instills in petroleum ether after chloroform dilutes, is settled out polymer poly methyl-triazole
Formic acid esters.
Above-mentioned reaction formula are as follows:
The poly- methyl-triazole formic acid esters containing AIE unit is prepared in the present invention, can be used as fluorescent optical sensor for detecting nitro
Arene compounds, it is with important application prospects in terms of explosive and environment measuring, it may be additionally used for preparing luminous pattern；
Prepared polymer, which contains ester group, to degrade under alkaline condition, have potential application in bio-medical field；It is prepared
The triazole ring structure that contains of polymer pass through the polymer material further protonated have in biology and antibiosis it is potential
Application.The present invention further discloses above-mentioned poly- methyl-triazole formic acid esters to prepare luminous pattern material, nitro-aromatic class
Close the application in terms of the detection of object, biotechnology.
The poly- methyl-triazole formic acid esters for containing AIE unit is prepared as fluorescent optical sensor for detecting nitro in the present invention
The specific steps of arene compounds are as follows:
(1) above-mentioned poly- methyl-triazole formic acid ester solution is prepared, the fluorescence spectrum of the poly- methyl-triazole formic acid ester solution is tested, obtains
To initial fluorescent intensity；
(2) system to be detected is mixed with the poly- methyl-triazole formic acid ester solution, obtains mixed liquor, tests the fluorescence of mixed liquor
Spectrum obtains fluorescence intensity；
(3) compare initial fluorescent intensity and fluorescence intensity, complete the detection of nitro-aromatic compound.
The specific steps that the poly- methyl-triazole formic acid esters containing AIE unit is used to prepare luminous pattern are prepared in the present invention
Are as follows: the solution of above-mentioned poly- methyl-triazole formic acid esters is formed into thin polymer film by the method for spin coating on silicon wafer, then will be carved
Figuratum copper mast is covered in polymeric film surface, then irradiates under ultraviolet lamp, is finally dried in vacuo, obtains illuminated diagram
Case.
It preferably, is 1,2- dichloroethanes by solvent in the solution of poly- methyl-triazole formic acid esters；Poly- methyl-triazole formic acid esters
Solution concentration be 5 mg/mL；Polymer is formed through being dried in vacuo on silicon wafer after spin coating；The wavelength of ultraviolet lamp is 365
nm。
Poly- methyl-triazole formic acid esters prepared by the present invention has preferable dissolubility, and it is molten to dissolve in the machine of common are at room temperature
Agent, such as methylene chloride, chloroform, tetrahydrofuran, n,N-Dimethylformamide and dimethyl sulfoxide, higher thermal stability can drop
Xie Xing.
In the method for preparing poly- methyl-triazole formic acid esters in the present invention, reaction raw materials are easy to get, and directly can buy or pass through
Simple reaction synthesis；No coupling product generates in polymerization process, meets Atom economy；It can not used in polymerization process
Solvent, non-environmental-pollution meet Green Chemistry feature；Polymerization process does not use metallic catalyst, can eliminate catalyst residual
Influence to polymer material biology and photoelectric properties；The polymerization reaction has extensive substrate applicability and good function
Group's compatibility, can easily introduce several functions group.Therefore the polymerization reaction is in polymer synthetic chemistry field and polymerization
Object functional material preparation aspect has important scientific meaning and application value.
Detailed description of the invention
Fig. 1 is poly- methyl-triazole formic acid esters prepared by embodiment one and its corresponding monomer in CDCl3In hydrogen nuclear magnetic resonance
Spectrogram (# represents solvent peak)；
Fig. 2 is the thermogravimetric curve of poly- methyl-triazole formic acid esters prepared by embodiment one；
Fig. 3 is the AIE curve of poly- methyl-triazole formic acid esters prepared by embodiment one；
Fig. 4 is to detect picric fluorescence spectra under poly- methyl-triazole formic acid esters state of aggregation prepared by embodiment one；
Fig. 5 is fluorescent weakening degree during poly- methyl-triazole formic acid esters prepared by embodiment one detects picric acid under state of aggregation
With the relation curve of bitter taste acid concentration；
Fig. 6 is that poly- methyl-triazole formic acid esters prepared by embodiment one is used to prepare luminous pattern；
Fig. 7 is the water-soluble implementations (22 mg/mL) of poly- methyl-triazole formic acid esters prepared by embodiment one.
Specific embodiment
The present invention is specifically described below in conjunction with embodiment, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment one
1.04g (10 mmol) neopentyl glycol, 6.20 g (30 mmol) DCC, 0.488 are added in 250 mL twoport flasks
It is molten that the stirring of 100 mL methylene chloride is added in g (4 mmol) DMAP, 0.76 g (4 mmol) TsOH, vacuum nitrogen gas
Solution, then under ice water bath environment, 1.85 g (22 mmol) 2- tetrolic acid is dissolved in 20 mL methylene chloride, and is led to
It crosses constant pressure funnel and is added dropwise to reaction system dropwise, be stirred to react at room temperature overnight, filtering is washed with methylene chloride
It washs, filtrate is spin-dried for obtain crude product, through column chromatographic isolation and purification, be dried under vacuum to constant weight, obtain 1.25 g of white solid
(yield 53%) is the first monomer binary butine acid ester monomer.1H NMR (400 MHz, CDCl3), δ (TMS, ppm):
3.98 (s 4H), 1.99 (s, 6H), 0.97 (d, 6H).Second comonomer binary organic nitrine monomer is existing product.
70.8 mg of the first monomer (0.3 mmol) and 184.3 mg of second comonomer is added in the polymerization pipe of 10 mL
(0.3mmol), to system vacuum nitrogen gas, 100 DEG C are reacted 12 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains the poly- methyl-triazole formic acid esters of subject polymer, is characterized as below.
Characterize data: light yellow solid, yield 89.6%.Gel permeation chromatography (GPC) is as the result is shown: weight average molecular weight
(M w) it is 16700, molecular weight distribution (PDI) is 1.77.1H NMR (400 MHz, CDCl3) , δ (TMS, ppm):
7.04–6.59,4.67, 4.24, 2.56, 1.90–1.08.The hydrogen nuclear magnetic resonance spectrogram of its corresponding monomer of the polymer
See attached drawing 1, can determine that the polymer is poly- methyl-triazole formic acid esters from figure, wherein binary organic nitrine monomer existsδ 3.28
There is resonance absorbing peak at place, and the peak disappears in the polymer, and two new peaks occursδ4.24 (a), 4.67 (b), it proves
The polymerization reaction has occurred, and there are two kinds of isomers A and B in polymer.According to the integral face of a and b in polymer spectrogram
It is respectively 85.6% and 14.4% that the content of isomers A and B in polymer, which is calculated, in product, shows polymer area with higher
Domain regularity efficiently solves the defect of existing triazole urethane polymers degree of regioregularity difference.
Prepared poly- methyl-triazole formic acid esters is soluble in methylene chloride, 1,2- dichloroethanes, chloroform, tetrahydro at room temperature
Furans,N,NThe common organic solvents such as dimethylformamide and dimethyl sulfoxide have good machinability and film forming.It should
The thermal weight loss temperature of polymer 5% is 377 DEG C (see attached drawing 2), shows its thermal stability with higher.It is molten in tetrahydrofuran
It shines in liquid extremely faint, fluorescence significantly increases after poor solvent is added, and shows that it, with aggregation-induced emission performance, sees attached drawing
3。
Application of the poly- methyl-triazole formic acid esters in nitro-aromatic compound detection:
Nitro-aromatic compound is widely used in the production of the products such as explosive, pesticide, dyestuff, medicine, plastics, coating.In recent years,
Being continuously increased for nitro-aromatic organic emission amount and become environmental risk.Detection nitro-aromatic compound can be applied to explode
Object and environment measuring.With trinitrophenol (picric acid, picric acid, PA) for model compound, the process of PA is detected: first
First prepare 10-5The aqueous tetrahydrofuran solution (volume content of water is 90%) of the above-mentioned poly- methyl-triazole formic acid esters of mol/L is as inspection
Object is surveyed, different amounts of detected material PA is sequentially added, tests fluorescence spectrum.As a result, it has been found that: before PA is added, the fluorescence of detectable substance is non-
Chang Qiang；When PA is added, fluorescent weakening, and being sequentially increased of PA content, fluorescence successively weakens with being added, detection limit is down to 1 μ
G/mL (attached drawing 4).The additional amount of fluorescent weakening multiple and PA to detectable substance makees graph discovery, when detected material PA content is lower
When, which is straight line；When PA content is higher, which deviates straight line and is bent upwards, i.e. the fluorescent weakening degree of detectable substance
Significantly become larger (attached drawing 5), calculates resulting quenching constant and is up to 55000 M-1, sudden higher than polyphenylene triazole formic acid esters detection PA
Go out constant (up to 48800 M-1), show that poly- methyl-triazole formic acid esters of the invention can detect nitro-aromatic in high sensitivity
Class compound is expected to be applied to explosive and environment measuring.The preparation of luminous pattern: above-mentioned poly- methyl-triazole formic acid esters is dissolved in
1,2- dichloroethanes is made into the solution of 5mg/mL, and film is formed on silicon wafer by the method for spin coating.The film of preparation is through vacuum
It is dried overnight.Figuratum copper mast will be carved and be covered in polymeric film surface, film is then placed in ultraviolet lamp, and (wavelength is
365 nm) under irradiate, after illumination, pattern is obtained after vacuum drying, and (attached drawing 6) is taken pictures under fluorescence microscope.
The ionization of polymer: weighing poly- 42.5 mg of methyl-triazole formic acid esters, be dissolved in 0.75 mL DMSO, is added
0.125 mL iodomethane, 60 DEG C are stirred to react 24 hours, after being cooled to room temperature, and are filtered, washed, dry to constant weight, obtain ion
The product of change, quality 81.5mg, yield 96%.The polymer of prepared ionization is soluble easily in water, 1 mL water soluble depolymerization
Object amount is closed up to 22 mg(attached drawings 7), it can be used for biotechnology, and existing polyphenyl triazole formic acid esters can not be obtained with iodomethane reaction
To water soluble ion fluidized polymer, it is not used to biological field.
Embodiment two
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment one.It is single that first is added in the polymerization pipe of 10 mL
47.2 mg of body (0.2 mmol) and 122.9 mg of second comonomer (0.2 mmol), to system vacuum nitrogen gas, 120 DEG C anti-
It answers 12 hours, is diluted after being cooled to room temperature with the chloroform of 5 mL, and solution is added drop-wise to 200 by being plugged with the dropper of cotton
It in the petroleum ether that mL is vigorously stirred, stands, filtering, it is dry to constant weight, obtain subject polymer, yield 80%.GPC result is aobvious
Show:M w = 35300, PDI = 1.84.Discovery polymer regio-regular with higher is characterized by nuclear magnetic resonance spectroscopy
Degree, the content of isomers A and B are respectively 84.8% and 15.2%.The polymer also has preferable dissolubility and thermal stability,
With aggregation-induced emission performance, it can be used for the detection of nitro-aromatic compound and the preparation of luminous pattern, it in addition can also be with
Further ionization prepares water-soluble polymer, with embodiment one；The present invention utilizes bulk polymerization to prepare triazole formic acid esters for the first time
Polymer overcomes the prior art and thinks that this quasi polymer requires the prejudice of solvent polymeric.
Embodiment three
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment one.It is single that first is added in the polymerization pipe of 10 mL
23.6 mg of body (0.1 mmol) and 61.4 mg of second comonomer (0.1 mmol), to system vacuum nitrogen gas, is then added
0.2 mL dry DMF dissolution, 150 DEG C are reacted 4 hours, with the chloroform dilution of 5 mL after being cooled to room temperature, and by solution
Dropper by being plugged with cotton is added drop-wise in the petroleum ether that 200 mL are vigorously stirred, and is stood, filtering, dry to constant weight, is gathered
Close object, yield 87%.GPC is as the result is shown:M w = 22200, PDI = 1.97.It is made by nuclear magnetic resonance spectroscopy characterization discovery
The content of two kinds of isomers A and B are respectively 86.7% and 13.3% in standby polymer, show polymer region with higher
Regularity.The polymer also has preferable dissolubility and thermal stability, it may have aggregation-induced emission performance can be used for nitro
In addition the detection of arene compounds and the preparation of luminous pattern further ionization can also prepare water-soluble polymer, together
Embodiment one.
Example IV
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment one.It is single that first is added in the polymerization pipe of 10 mL
23.6 mg of body (0.1 mmol) and 61.4 mg of second comonomer (0.1 mmol), to system vacuum nitrogen gas, is then added
0.2 mL dry DMF dissolution, 150 DEG C are reacted 12 hours, are diluted after being cooled to room temperature with the chloroform of 5 mL, and will be molten
Liquid is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, is stood, filtering, dry to constant weight, is obtained
Polymer, yield 83.5%.GPC is as the result is shown:M w = 33200, PDI = 1.85.It is characterized and is found by nuclear magnetic resonance spectroscopy
The content of two kinds of isomers A and B are respectively 87.5% and 12.5% in prepared polymer, show that the polymer is with higher
Degree of regioregularity.The polymer also has preferable dissolubility and thermal stability, it may have aggregation-induced emission performance can be used for
In addition the detection of nitro-aromatic compound and the preparation of luminous pattern can also further ionize preparation water-soluble polymeric
Object, with embodiment one.
Embodiment five
Binary butine acid ester monomer is as in the first embodiment, binary organic nitrine monomer is existing.
70.8 mg of the first monomer (0.3 mmol) and 167.5 mg of second comonomer is added in the polymerization pipe of 10 mL
(0.3 mmol), to system vacuum nitrogen gas, 100 DEG C are reacted 12 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains polymer, yield 85.4%.GPC is as the result is shown: Mw=10500, PDI=1.72.The polymer also has
There are preferable dissolubility and thermal stability, it may have aggregation-induced emission performance can be used for the detection of nitro-aromatic compound
And the preparation of luminous pattern, in addition further ionization water-soluble polymer can also be prepared, with embodiment one.
Embodiment six
Binary butine acid ester monomer is as in the first embodiment, binary organic nitrine monomer is existing.
54 mg (0.15 of 35.4 mg of the first monomer (0.15 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 100 DEG C are stirred to react 12 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains polymer, yield 74.2%.GPC is as the result is shown:M w= 11900, PDI = 1.69.The polymer have compared with
High degree of regioregularity, it may have preferable dissolubility and thermal stability, and can further ionize preparation water-soluble polymeric
Object, with embodiment one.
Embodiment seven
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment six.
54 mg (0.15 of 35.4 mg of the first monomer (0.15 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 120 DEG C are stirred to react 12 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains polymer, yield 93.9%.GPC is as the result is shown:M w= 25000, PDI = 1.72.The polymer have compared with
High degree of regioregularity, it may have preferable dissolubility and thermal stability, and can further ionize preparation water-soluble polymeric
Object, with embodiment one.
Embodiment eight
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment six.
54 mg (0.15 of 35.4 mg of the first monomer (0.15 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 120 DEG C are stirred to react 2 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains polymer, yield 66.0%.GPC is as the result is shown:M w= 7600, PDI = 1.66.The polymer have compared with
High degree of regioregularity, it may have preferable dissolubility and thermal stability, and can further ionize preparation water-soluble polymeric
Object, with embodiment one.
Embodiment nine
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment six.
54 mg (0.15 of 35.4 mg of the first monomer (0.15 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 120 DEG C are reacted 4 hours, are diluted after being cooled to room temperature with the chloroform of 5 mL, and
Solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, is stood, filtering, drying to constant weight,
Obtain polymer, yield 88.9%.GPC is as the result is shown:M w= 17100, PDI = 1.50.The polymer is with higher
Degree of regioregularity, it may have preferable dissolubility and thermal stability, and further ionization water-soluble polymer can be prepared, together
Embodiment one.
Embodiment ten
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment six.
54 mg (0.15 of 35.4 mg of the first monomer (0.15 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 120 DEG C are stirred to react 8 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains polymer, yield 83.8%.GPC is as the result is shown:M w= 19700, PDI = 2.27.The polymer have compared with
High degree of regioregularity, it may have preferable dissolubility and thermal stability, and can further ionize preparation water-soluble polymeric
Object, with embodiment one.
Embodiment 11
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment six.
54 mg (0.15 of 35.4 mg of the first monomer (0.15 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 120 DEG C are stirred to react 24 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains polymer, yield 89.4%.GPC is as the result is shown:M w= 16300, PDI = 2.14.The polymer have compared with
High degree of regioregularity, it may have preferable dissolubility and thermal stability, and can further ionize preparation water-soluble polymeric
Object, with embodiment one.
Embodiment 12
0.9 g of 1,4- butanediol (10 mmol), right is added in the 250 mL twoport flasks equipped with water segregator, spherical condensation tube
0.19 g of toluenesulfonic acid (1 mmol), 2.1 g of 2- tetrolic acid (25 mmol) and 80 mL of toluene, after being heated to reflux 24 hours,
Reaction solution is concentrated and is diluted with methylene chloride, and after sodium bicarbonate solution and salt washing, dry organic phase is spin-dried for, with chromatography
Column separating purification, vacuum drying, obtains 1.64 g of white solid (yield 74%), is the first monomer binary butine acid ester monomer.1H NMR (400 MHz, CDCl3), δ (TMS, ppm): 4.19 (s, 4H), 2.00 (s, 6H), 1.80 (d,
4H)。
Binary organic nitrine monomer is the same as embodiment six.
54 mg (0.15 of 33.3 mg of the first monomer (0.15 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 100 DEG C are stirred to react 12 hours, and the chloroform after being cooled to room temperature with 5 mL is dilute
It releases, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand, filtering, drying is extremely
Constant weight obtains polymer, yield 68.7%.GPC is as the result is shown:M w= 10000, PDI = 1.64.The polymer have compared with
High degree of regioregularity, it may have preferable dissolubility and thermal stability, and can further ionize preparation water-soluble polymeric
Object, with embodiment one.
Embodiment 13
Equipped with water segregator, spherical condensation tube 250 mL twoport flasks in be added 1.38 g of terephthalyl alcohol (10 mmol),
0.19 g of p-methyl benzenesulfonic acid (1 mmol), 2.1 g of 2- tetrolic acid (25 mmol) and 80 mL of toluene, are heated to reflux 24 hours
Afterwards, reaction solution is concentrated and is diluted with methylene chloride, and after sodium bicarbonate solution and salt washing, dry organic phase is spin-dried for, with layer
Column separating purification is analysed, vacuum drying obtains 1.07 g of white solid (yield 39.6%), is the first monomer binary butine acid esters list
Body.1H NMR (400 MHz, CDCl3), δ (TMS, ppm): 7.37 (s, 4H), 5.17 (s, 4H), 1.98 (s,
6H)。
Second comonomer binary organic nitrine monomer is the same as embodiment six.
36 mg (0.1 of 27 mg of the first monomer (0.1 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 0.2 mL distilled water is then added, 100 DEG C are reacted 12 hours, are used after being cooled to room temperature
The chloroform of 5 mL dilutes, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton,
It stands, filtering, it is dry to constant weight, obtain polymer, yield 76.3%.GPC is as the result is shown:M w = 12000, PDI =
2.01.Polymer degree of regioregularity with higher, it may have preferable dissolubility and thermal stability, and can further from
Sub-ization prepares water-soluble polymer, with embodiment one.
Embodiment 14
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment 13.
36 mg (0.1 of 27 mg of the first monomer (0.1 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 100 DEG C are reacted 12 hours, are diluted after being cooled to room temperature with the chloroform of 5 mL, and
Solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, is stood, filtering, drying to constant weight,
Obtain polymer, yield 84.4%.GPC is as the result is shown:M w= 16100, PDI = 1.94.The polymer is with higher
Degree of regioregularity, it may have preferable dissolubility and thermal stability, and further ionization water-soluble polymer can be prepared, together
Embodiment one.
Embodiment 15
2.28 g (10 mmol) bisphenol-A, 6.20 g (30 mmol) DCC, 0.488 g are added in 250 mL twoport flasks
(4 mmol) DMAP, 0.76 g (4 mmol) TsOH, vacuum nitrogen gas is three times.It is molten that the stirring of 100 mL methylene chloride is added
Solution, then under ice water bath environment, 1.85 g (22 mmol) 2- tetrolic acid is dissolved in 20 mL methylene chloride, and is passed through
Dropping funel is added dropwise to reaction system dropwise, is stirred to react at room temperature overnight, and filtering is washed with methylene chloride, will be filtered
Liquid is spin-dried for, and obtains crude product, is used column chromatography purifying, is dried under vacuum to constant weight, is obtained 2.62 g(yield of white solid and is
It 72.8%), is the first monomer binary butine acid ester monomer.1H NMR (400 MHz, DMSO-d 6), δ (TMS, ppm):
7.27 (d, 4H), 7.1 (t, 4H), 2.11 (s,6H), 1.65 (s, 6H)。
Second comonomer binary organic nitrine monomer is the same as embodiment six.
It is single that the first monomer binary butine acid ester monomer 36mg (0.1 mmol) and second is added into the polymerization pipe of 10 mL
Then 0.2 mL is added by side arm to system vacuum nitrogen gas in 36 mg (0.1 mmol) of body binary organic nitrine monomer
Dry DMF, after monomer is completely dissolved, 150 DEG C are reacted 12 hours, are diluted after being cooled to room temperature with the chloroform of 5 mL,
And be added drop-wise to solution in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, it stands, filtering, it is dry to perseverance
Weight, obtains subject polymer, light yellow solid, yield 92.7%.GPC is as the result is shown:M w = 17500, PDI = 1.91。
Polymer degree of regioregularity with higher, it may have preferable dissolubility and thermal stability, and can further ionize
Water-soluble polymer is prepared, with embodiment one.
Embodiment 16
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment 15.
36 mg (0.1 of 36 mg of the first monomer (0.1 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, the dry DMF of 0.2 mL is then added, after monomer is completely dissolved, 150 DEG C of reactions 2
Hour, it is diluted after being cooled to room temperature with the chloroform of 5 mL, and solution is added drop-wise to 200 mL by being plugged with the dropper of cotton
It in the petroleum ether being vigorously stirred, stands, filtering, it is dry to constant weight, obtain polymer, yield 53%.GPC is as the result is shown:M w =
9400, PDI = 1.37.Polymer degree of regioregularity with higher, it may have preferable dissolubility and thermal stability, and
Further ionization water-soluble polymer can be prepared, with embodiment one.
Embodiment 17
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment 15.
36 mg (0.1 of 36 mg of the first monomer (0.1 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, in triplicate, the DMF and 0.2 mL water of 0.2 mL is then added, it is completely molten to monomer
Xie Hou, 100 DEG C are reacted 12 hours, are diluted after being cooled to room temperature with the chloroform of 5 mL, and by solution by being plugged with cotton
Dropper is added drop-wise in the petroleum ether that 200 mL are vigorously stirred, and is stood, filtering, dry to constant weight, obtains polymer, yield 45%.
GPC is as the result is shown:M w= 4900, PDI = 1.49.Polymer degree of regioregularity with higher, it may have preferable molten
Solution property and thermal stability, and further ionization water-soluble polymer can be prepared, with embodiment one.
Embodiment 18
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment 15.
36 mg (0.1 of 36 mg of the first monomer (0.1 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 0.2 mL water is then added, 100 DEG C are reacted 12 hours, with 5 mL after being cooled to room temperature
Chloroform dilution, and solution is added drop-wise in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, stand,
Filtering, it is dry to constant weight, obtain polymer, yield 72.8%.GPC is as the result is shown:M w= 15600, PDI = 1.75.It should
Polymer degree of regioregularity with higher, it may have preferable dissolubility and thermal stability, and can further ionize system
Standby water-soluble polymer, with embodiment one.
Embodiment 19
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment 15.
36 mg (0.1 of 36 mg of the first monomer (0.1 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, in triplicate, 0.2 mL water is then added, 80 DEG C are reacted 12 hours, are cooled to room temperature
It is diluted afterwards with the chloroform of 5 mL, and solution is added drop-wise to the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton
In, it stands, filtering, it is dry to constant weight, obtain polymer, yield 53%.GPC is as the result is shown:M w = 4200, PDI =
1.45.Polymer degree of regioregularity with higher, it may have preferable dissolubility and thermal stability, and can further from
Sub-ization prepares water-soluble polymer, with embodiment one.
Embodiment 20
Binary butine acid ester monomer and binary organic nitrine monomer are the same as embodiment 15.
36 mg (0.1 of 36 mg of the first monomer (0.1 mmol) and second comonomer is added in the polymerization pipe of 10 mL
Mmol), to system vacuum nitrogen gas, 100 DEG C are stirred 12 hours, are diluted after being cooled to room temperature with the chloroform of 5 mL,
And be added drop-wise to solution in the petroleum ether that 200 mL are vigorously stirred by being plugged with the dropper of cotton, it stands, filtering, it is dry to perseverance
Weight, obtains polymer, yield 85%.GPC is as the result is shown:M w= 24600, PDI = 1.91.The polymer is with higher
Degree of regioregularity, it may have preferable dissolubility and thermal stability, and further ionization water-soluble polymer can be prepared, together
Embodiment one.
Claims (10)
1. a kind of poly- methyl-triazole formic acid esters has chemical structural formula shown in formula I:
Formula I
Wherein, n is 2~200；Any one group of R in 1~20, any one base of R ' in 1~9,19~28
Group；The chemical structural formula of described 1~28 group is as follows:
Wherein, m is 1~18.
2. the preparation method of poly- methyl-triazole formic acid esters described in claim 1, which is characterized in that include the following steps, with binary
Butine acid ester monomer and binary organic nitrine monomer are raw material, and polymerization reaction obtains poly- methyl-triazole formic acid esters.
3. the preparation method of poly- methyl-triazole formic acid esters according to claim 2, it is characterised in that: the polymerization reaction is in nitrogen
It is carried out in gas atmosphere；Binary butine acid ester monomer and binary organic nitrine monomer are dissolved in a solvent, polymerization reaction is gathered
Methyl-triazole formic acid esters；Or mix binary butine acid ester monomer with binary organic nitrine monomer, it is added without solvent, polymerization reaction
Obtain poly- methyl-triazole formic acid esters；The solvent includes organic solvent or water；The organic solvent includesN,NDimethyl formyl
Amine,N,NDimethyl acetamide, dimethyl sulfoxide orNMethyl pyrrolidone.
4. the preparation method of poly- methyl-triazole formic acid esters according to claim 3, it is characterised in that: binary butine acid ester monomer
Molar ratio with binary organic nitrine monomer is 1:1；When solvent is organic solvent, binary butine acid ester monomer is had with binary
Machine nitrine monomer dissolves the mixed liquor for being configured to that monomer concentration is 0.2~0.8 mol/L in a solvent, poly- in 80~180 DEG C
It closes reaction and obtains poly- methyl-triazole formic acid esters in 2~36 hours；It is when solvent is water, binary butine acid ester monomer and binary is organic
Nitrine monomer dissolves the mixed liquor for being configured to that monomer concentration is 0.2~0.8 mol/L in a solvent, polymerize in 80~120 DEG C
Reaction obtains poly- methyl-triazole formic acid esters in 2~36 hours；It is when being added without solvent, binary butine acid ester monomer and binary is organic
The mixing of nitrine monomer, obtains poly- methyl-triazole formic acid esters in polymerization reaction 2~36 hours in 80~180 DEG C.
5. the preparation method of poly- methyl-triazole formic acid esters according to claim 2, it is characterised in that: with 2- tetrolic acid and binary
Phenol or dihydric alcohol are raw material, and esterification prepares tetrolic acid binary ester type compound.
6. the preparation method of poly- methyl-triazole formic acid esters according to claim 5, it is characterised in that: in the presence of an additive,
In a solvent, using 2- tetrolic acid and dihydric phenol or dihydric alcohol as raw material, esterification prepares tetrolic acid binary ester type compound；
The additive isN,NOne or more of dicyclohexylcarbodiimide, 4-dimethylaminopyridine, p-methyl benzenesulfonic acid, institute
Stating solvent is one or more of methylene chloride, tetrahydrofuran, toluene；The temperature of the esterification is 0 DEG C~room temperature, when
Between be 12~36 hours.
7. the preparation method of poly- methyl-triazole formic acid esters according to claim 2, which is characterized in that the binary butine acid esters
The chemical structural formula of monomer is as follows:
Wherein R is any one group in above-mentioned 1~20；
The chemical structural formula of the binary nitrine monomer is as follows:
Wherein R is any one group in above-mentioned 1~9,19~28.
8. poly- methyl-triazole formic acid esters described in claim 1 is preparing the application in luminous pattern；Or gather described in claim 1
Application of the methyl-triazole formic acid esters in nitro-aromatic compound detection；Or poly- methyl-triazole formic acid described in claim 1
Ester is preparing the application in ionomeric polymer.
9. application according to claim 8, it is characterised in that:
Prepare the specific steps of luminous pattern are as follows: by the solution of the poly- methyl-triazole formic acid esters by the method for spin coating in silicon wafer
Then upper formation thin polymer film will carve figuratum copper mast and be covered in polymeric film surface, then shines under ultraviolet lamp
It penetrates, is finally dried in vacuo, obtain luminous pattern；
The specific steps of nitro-aromatic compound detection are as follows:
(1) the poly- methyl-triazole formic acid ester solution is prepared, the fluorescence spectrum of the poly- methyl-triazole formic acid ester solution is tested, obtains
To initial fluorescent intensity；
(2) system to be detected is mixed with the poly- methyl-triazole formic acid ester solution, obtains mixed liquor, tests the fluorescence of mixed liquor
Spectrum obtains fluorescence intensity；
(3) compare initial fluorescent intensity and fluorescence intensity, complete the detection of nitro-aromatic compound；
The method for preparing ionomeric polymer, comprising the following steps: with binary butine acid ester monomer and binary organic nitrine monomer
For raw material, polymerization obtains poly- methyl-triazole formic acid esters；The poly- methyl-triazole formic acid esters is dissolved in DMSO, iodomethane is added,
It after being stirred to react, is cooled to room temperature, is then filtered, washed, it is dry to constant weight, obtain ionomeric polymer.
10. application according to claim 9, which is characterized in that when preparing luminous pattern, by poly- methyl-triazole formic acid esters
Solvent is 1,2- dichloroethanes in solution, and the concentration of the solution of poly- methyl-triazole formic acid esters is 5mg/mL, dry through vacuum after spin coating
Dry that polymer is formed on silicon wafer, the wavelength of ultraviolet lamp is 365 nm；When nitro-aromatic compound detects, nitro-aromatic class
Conjunction object is picric acid, and in the solution of poly- methyl-triazole formic acid esters, solvent is the mixed liquor of tetrahydrofuran, water；Preparation ionization is poly-
When closing object, it is stirred to react and is stirred to react 24 hours for 60 DEG C.
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