CN111675788A - Conjugated polymer containing tetraphenylethylene structure and preparation method and application thereof - Google Patents
Conjugated polymer containing tetraphenylethylene structure and preparation method and application thereof Download PDFInfo
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Abstract
A conjugated polymer containing a tetraphenylethylene structure, a preparation method and application thereof relate to the field of synthesis of high molecular materials. The alternating copolymer of the 1, 3-cyclohexadiene and the trans-1, 2-diphenylethylene has a structure shown in a formula (I), and the conjugated polymer containing tetraphenylethylene units in the chain has a structure shown in a formula (II). The conjugated polymer is prepared by the steps of firstly carrying out anionic copolymerization on 1, 3-cyclohexadiene and trans-1, 2-diphenylethylene to obtain the alternating copolymer, and then further dehydrogenating the alternating copolymer. The method has the advantages of simple synthesis, high efficiency and low cost. The conjugated polymer can be used as a fluorescence sensor to be applied to detection of nitroarene explosives.
Description
Technical Field
The invention relates to the field of synthesis of high polymer materials, in particular to a conjugated polymer containing tetraphenylethylene units in a chain, and a preparation method and application thereof.
Background
The polymer material is an important organic photoelectric material, has a wide application range due to a unique molecular structure and good processability, and particularly, the conjugated polymer has a large conjugated structure, so that electrons or energy can rapidly migrate on the whole molecular chain, and rapid response can be carried out on a trace amount of quencher in the surrounding environment, thereby realizing rapid detection of a target substance. The conjugated polymer containing tetraphenylethylene units is the most important class of conjugated polymers because of excellent photoelectric properties. Among them, the conjugated polymers containing tetraphenylethylene units of linear structure are the simplest and the easiest to synthesize.
The connection mode of the tetraphenylethylene unit in the polymer is mainly divided into two modes, one mode is that the tetraphenylethylene unit is introduced into a conjugated main chain of the polymer [ Hanting, Jangjia, Linglong, Tang Benzhou. At present, the most common method for synthesizing conjugated polymers containing tetraphenylethylene units in the main chain is cross-coupling reaction of transition metals, including reactions of Suzuki, Sonogashira, Wittig, McMurry, Hay-Glaser, etc. [ Chentao. design, synthesis and property research of conjugated polymers containing tetraarylethylene. These reactions are the most commonly used reactions for the synthesis of compounds with unique optical properties and conjugated structures. However, these reactions usually involve a plurality of steps to obtain a monomer having a specific substituent, purifying the monomer by a complicated purification operation, finally performing a coupling reaction under the catalytic action of a transition metal catalyst, and removing the transition metal catalyst by a series of purification operations to obtain the target conjugated polymer. Therefore, the synthesis and purification processes of these methods are complicated, and the residual transition metal catalyst, especially the residual noble metal catalyst, in the polymerization product inevitably causes the waste of noble metal, so the method has many problems of high cost, low efficiency, etc.
Disclosure of Invention
The first object of the present invention is to provide two polymers of novel structure: alternating copolymers of 1, 3-cyclohexadiene and trans-1, 2-diphenylethylene, conjugated polymers containing tetraphenylethylene in the chain.
The second object of the present invention is to provide a process for the preparation of the above two polymers. The 1, 3-cyclohexadiene and the trans-1, 2-diphenylethylene can be polymerized by anion to obtain an alternating copolymer of the two. The alternating copolymer can be subjected to dehydrogenation to obtain a conjugated polymer containing tetraphenylethylene in the chain. Compared with the existing preparation method of the conjugated polymer containing tetraphenylethylene in the chain, the method has the advantages of few synthesis steps, high efficiency, low cost, no use of a transition metal catalyst in the polymerization process and the like.
The third object of the present invention is to provide the use of the above-mentioned conjugated polymer containing tetraphenylethylene in the chain. The conjugated polymer is used as a fluorescence sensor for detecting nitro-aromatic explosives.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
an alternating copolymer of 1, 3-cyclohexadiene and trans-1, 2-diphenylethylene having a structure represented by formula (I):
in the present invention, the alternating copolymer has a number average molecular weight of 1 × 103Da～5×104Da，
The molecular weight distribution of the alternating copolymer is 1.04-2.50.
A conjugated polymer containing tetraphenylethylene in the chain, having a structure represented by formula (ii):
the number average molecular weight of the conjugated polymer was 1.2 × 103Da～4.7×104Da, the molecular weight distribution is 1.34-3.08.
According to another object of the present invention, there is provided a method for preparing the above two polymers, comprising the steps of:
under the inert gas atmosphere, the reaction mixture containing the polymerization monomers is heated to the polymerization temperature, and an initiator is added to initiate the anionic polymerization of the reaction mixture, so that the alternating copolymer is obtained.
Optionally, the polymerized monomers include 40 mol% to 50 mol% of 1, 3-cyclohexadiene, and the balance of trans-1, 2-diphenylethylene.
Optionally, the total concentration of monomers in the reaction mixture is from 10 wt.% to 15 wt.%.
Optionally, the inert gas is selected from nitrogen, argon.
Alternatively, the initiator is selected from organolithium; the organic lithium is selected from at least one of n-butyl lithium and sec-butyl lithium.
Optionally, the molar ratio of the initiator to the monomer is 0.3-14: 100.
Optionally, the reaction mixture includes a polymerization monomer and an organic solvent, and the organic solvent is at least one selected from tetrahydrofuran and benzene.
Optionally, the polymerization temperature is 25-70 ℃, and the polymerization reaction time is 1-24 h.
Preferably, the polymerization temperature is 25-50 ℃, and the polymerization reaction time is 5-18 h.
Optionally, the method further comprises: and (3) terminating the reaction after the polymerization is finished, precipitating and drying to obtain the alternating copolymer.
As an embodiment, a method for preparing an alternating copolymer of 1, 3-cyclohexadiene and trans 1, 2-diphenylethylene, comprising the steps of:
under the protection of nitrogen or argon, dissolving trans-1, 2-diphenylethylene in an organic solvent, fully dissolving, adding 1, 3-cyclohexadiene, uniformly mixing, heating to a reaction temperature, adding an initiator to initiate polymerization, stopping the reaction after a period of reaction, and precipitating, washing and drying to obtain the alternating copolymer.
Subjecting the alternating copolymer to a dehydrogenation reaction to obtain a conjugated polymer containing tetraphenylethylene units in the chain, comprising the steps of:
under inert gas atmosphere, dissolving the alternating copolymer in an organic solvent, adding a toluene solution of a dehydrogenating agent, and heating to the dehydrogenation temperature to obtain the conjugated polymer containing the tetraphenylethylene unit in the chain.
Preferably, the alternating copolymer has a concentration of 1.0 wt.% to 2.5 wt.%.
Preferably, the mole content of the dehydrogenation agent is 6 to 7 times of that of the alternating copolymer.
Preferably, the inert gas is selected from nitrogen, argon.
Optionally, the dehydrogenation agent is at least one selected from 2, 3-dichloro-5, 6-dicyan p-benzoquinone, tetrachloro p-benzoquinone, and 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone.
Optionally, the organic solvent is at least one selected from toluene, 1, 2-dichlorobenzene and 1,2, 4-trichlorobenzene.
Optionally, the dehydrogenation temperature is 25-100 ℃, and the dehydrogenation reaction time is 6-50 h.
Preferably, the dehydrogenation temperature is 90-100 ℃, and the dehydrogenation reaction time is 24-36 h.
Optionally, the method further comprises: and precipitating, drying and washing after the dehydrogenation is finished to obtain the conjugated polymer containing the tetraphenylethylene unit in the chain.
As an embodiment, a method for preparing a conjugated polymer containing tetraphenylethylene units in the chain, comprising the steps of:
under the protection of nitrogen or argon, dissolving an alternating copolymer of 1, 3-cyclohexadiene and trans-1, 2-diphenylethylene in an organic solvent, fully dissolving, adding an organic solution of a dehydrogenating agent, uniformly mixing, heating to a reaction temperature, reacting for a period of time, and then precipitating, washing and drying to obtain a conjugated polymer containing tetraphenylethylene units in the chain.
According to another object of the present invention, there is provided the use of the above conjugated polymer in the detection of explosives.
Preferably, the nitroarene explosive is 2,4, 6-trinitrotoluene.
Preferably, the conjugated polymer has a water contentThe concentration of the 90% tetrahydrofuran/water mixed solution is 10-5～3.5×10-5g/ml。
As an embodiment, the application of the conjugated polymer in explosive detection comprises the following steps:
the quantitative conjugated polymer is made to form an aggregation state in a tetrahydrofuran/water mixed solution with the water content of 90 percent, and the concentration of the solution is 10-5g/ml. And adding a concentration gradient standard substance prepared from 2,4, 6-trinitrotoluene into the solution to prepare a solution to be detected. The fluorescence intensity of the conjugated polymer is measured at the position of the emission wavelength of 400 nm-600 nm by excitation with the excitation wavelength of 388nm, and the fluorescence quenching behavior of the 2,4, 6-trinitrotoluene on the conjugated polymer is obtained by comparing the fluorescence intensity of the solution to be measured and the original conjugated polymer solution.
Compared with the prior art, the invention has the beneficial effects that:
(1) the alternating copolymer of 1, 3-cyclohexadiene and trans-1, 2-diphenylethylene and the conjugated polymer containing tetraphenylethylene units in the chain have novel structures and originality.
(2) The invention provides a novel method for preparing a conjugated polymer containing a tetraphenylethylene unit in a chain, which is simple, convenient and feasible, has low cost, and overcomes the problems of complicated synthesis and purification steps, high cost, low efficiency and the like of the conventional method.
(3) The conjugated polymer containing the tetraphenyl ethylene unit in the chain can be used as a fluorescence sensor and applied to detection of nitroaromatic explosives.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scheme showing the synthesis of a conjugated polymer containing tetraphenylethylene units in the chain in one embodiment of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of an alternating copolymer (b) and a conjugated polymer (a) according to an embodiment of the present invention; wherein: (a) and (b) represent examples 2-1, respectively#、1-1#Spectra of the samples.
FIG. 3 is a GPC chart of an alternating copolymer (b) and a conjugated polymer (a) in the embodiment of the present invention; wherein: (a) and (b) represent examples 2-1, respectively#、1-1#GPC curve of the sample.
FIG. 4 is a graph showing a fluorescence spectrum of a conjugated polymer in an aggregate state in a tetrahydrofuran/water mixed solution having a water content of 90% in accordance with an embodiment of the present invention; is example 2-1#Aggregate state of the sample
Fluorescence spectrum.
FIG. 5 is a fluorescence quenching spectrum of 2,4, 6-trinitrotoluene on the conjugated polymer aggregation state solution in the embodiment of the present invention; is 2,4, 6-trinitrotoluene to example 2-1#Fluorescence quenching spectrum of sample aggregation state solution.
Detailed Description
Embodiments of the present invention will now be further described with reference to specific examples and the accompanying drawings, which are provided for illustration only and should not be construed as limiting the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the present invention, all chemicals were purchased from Beijing YinuoKai science and technology, Inc. Wherein, the 1, 3-cyclohexadiene needs to be refluxed in calcium hydride and distilled in dry nitrogen; recrystallizing trans-1, 2-stilbene with methanol for three times, and recrystallizing with n-hexane for two times; adding calcium hydride powder into tetrahydrofuran, soaking for 24h, transferring the soaked tetrahydrofuran into a distillation device, heating and refluxing for 1h, steaming into a second distillation device containing sodium naphthalene by a normal pressure distillation method, reacting for 48h, heating and refluxing for 1h, and steaming out for use by the normal pressure distillation method. Benzene and toluene are refluxed in calcium hydride and distilled under reduced pressure in dry nitrogen. The dehydrogenating agent was purchased and used directly.
EXAMPLE 1 preparation of alternating copolymer
#Preparation of 1-11, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Vacuum pumping and nitrogen protection are carried out on all containers and reactors, 1.54g of trans-1, 2-diphenylethylene and 20ml of tetrahydrofuran are sequentially added into a 100ml reaction bottle to be fully dissolved, then 0.46g of 1, 3-cyclohexadiene is added, 1mmol of n-butyllithium is added after uniform stirring, after reaction for 5.5h at 25 ℃, absolute methanol is used for stopping reaction, a large amount of absolute methanol is used for washing and precipitating the polymer, and the polymer is dried in a vacuum oven at 50 ℃ to obtain the 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer, wherein the number average molecular weight of the obtained polymer is 2 × 103The molecular weight distribution was 1.44.
#Preparation of 1-21, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-1#The 1, 3-cyclohexadiene-trans 1, 2-diphenylethylene alternating copolymers were approximately the same except that the mass of 1, 3-cyclohexadiene was 0.55g and the mass of trans 1, 2-diphenylethylene was 1.45g, 0.04mmol of n-butyllithium was added to initiate the polymerization for 18 hours, and the resulting polymer had a number average molecular weight of 5 × 104The molecular weight distribution was 1.10.
#Preparation of 1-31, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-1#The 1, 3-cyclohexadiene-trans 1, 2-diphenylethylene alternating copolymers were substantially the same except that the mass of 1, 3-cyclohexadiene was 0.62g and the mass of trans 1, 2-diphenylethylene was 1.38g, 0.04mmol of n-butyllithium was added to initiate the polymerization for 17 hours, and the resulting polymer had a number average molecular weight of 4.6 × 104The molecular weight distribution was 1.04.
#Preparation of 1-41, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-1#1, 3-cyclohexadiene-trans-1, 2-diphenylThe ethylene alternating copolymer was approximately the same except that 0.24mmol n-butyllithium was added to initiate the polymerization in an argon system at 50 ℃ for 7 hours to give a polymer having a number average molecular weight of 8.2 × 103The molecular weight distribution was 1.15.
#Preparation of 1-51, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-1#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer was substantially the same except that the reaction system was an argon system, the initiator was replaced with sec-butyl lithium, 0.17mmol of sec-butyl lithium was added to initiate polymerization in benzene as the reaction solvent, the polymerization temperature was 50 ℃ and the reaction time was 8 hours, and the number average molecular weight of the resulting polymer was 1.2 × 104The molecular weight distribution was 1.07.
#Preparation of 1-61, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-1#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer was substantially the same except that the reaction system was an argon system, the initiator was replaced with sec-butyl lithium, and 2mmol of sec-butyl lithium was added to initiate polymerization in toluene as the reaction solvent, at 40 ℃ for 5 hours, the resulting polymer had a number average molecular weight of 1 × 103The molecular weight distribution was 1.76.
#Preparation of 1-71, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-2#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymers were approximately the same except that the mass of 1, 3-cyclohexadiene was 0.68g, the mass of trans-1, 2-diphenylethylene was 2.32g, the polymerization temperature was 30 ℃, the solvent was toluene, the initiator was replaced with sec-butyllithium, 0.13mmol of sec-butyllithium was added to initiate the polymerization, the reaction time was 11h, the number average molecular weight of the resulting polymer was 2.3 × 104The molecular weight distribution was 2.04.
#Preparation of 1-81, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-2#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymers were approximately the same except that the mass of 1, 3-cyclohexadiene was 0.81g, the mass of trans-1, 2-diphenylethylene was 2.19g, the polymerization temperature was 40 ℃, the solvent was benzene, the initiator was replaced with sec-butyllithium, 0.10mmol of sec-butyllithium was added to initiate the polymerization, the reaction time was 12 hours, and the resulting polymer had a number average molecular weight of 2.9 × 104The molecular weight distribution was 2.50.
#Preparation of 1-91, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-2#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer was approximately the same except that the polymerization temperature was 50 deg.C, the solvent was toluene, the initiator was replaced with sec-butyl lithium, 0.04mmol of sec-butyl lithium was added to initiate the polymerization for 18h, and the resulting polymer had a number average molecular weight of 4.8 × 104The molecular weight distribution was 1.34.
#Preparation of 1-101, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-3#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer was substantially the same except that the reaction system was an argon system, the polymerization temperature was 50 ℃, the mass of 1, 3-cyclohexadiene was 0.92g, the mass of trans-1, 2-diphenylethylene was 2.08g, 0.09mmol of n-butyllithium was added to initiate the polymerization, the reaction time was 13 hours, and the number average molecular weight of the obtained polymer was 3.4 × 104The molecular weight distribution was 2.12.
#Preparation of 1-111, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-3#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer was substantially the same except that the reaction system was an argon system, the polymerization temperature was 40 ℃, the initiator was replaced with sec-butyl lithium, 0.05mmol of sec-butyl lithium was added to initiate the polymerization, the reaction time was 14h, and the number average molecular weight of the resulting polymer was 3.7 × 104Having a molecular weight distribution of1.70。
#Preparation of 1-121, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-3#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymers were approximately the same except that 0.05mmol of n-butyllithium was added to initiate the polymerization at 30 ℃ for 15 hours to give a polymer having a number average molecular weight of 4.1 × 104The molecular weight distribution was 1.79.
#Preparation of 1-131, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-3#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer was substantially the same except that the reaction system was an argon system, the initiator was replaced with sec-butyl lithium, 0.39mmol of sec-butyl lithium was added to initiate polymerization in benzene as the reaction solvent at 50 ℃ for 6 hours to give a polymer having a number average molecular weight of 5.1 × 103The molecular weight distribution was 1.34.
#Preparation of 1-141, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-3#The 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer was substantially the same except that the reaction system was an argon system, the initiator was replaced with sec-butyl lithium, 0.06mmol of sec-butyl lithium was added to initiate polymerization, the reaction solvent was toluene, the polymerization temperature was 40 ℃ and the reaction time was 13 hours, and the number average molecular weight of the resulting polymer was 3.2 × 104The molecular weight distribution was 1.77.
EXAMPLE 2 preparation of conjugated Polymer
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-1 chain
All vessels and reactors must be protected with nitrogen. EXAMPLES 1-1#0.15g of the 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer and 0.91g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone obtained in the above step were sufficiently dissolved in 6ml of toluene, reacted at 100 ℃ for 24 hours, and then the polymer was washed with a large amount of anhydrous methanolThen, the solution was precipitated and dried in a vacuum oven at 50 ℃ to obtain a conjugated polymer containing tetraphenylethylene units in the chain, the number average molecular weight of the obtained conjugated polymer was 1.1 × 103The molecular weight distribution was 3.08 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-2 chain
Preparation process and 2-1#Conjugated polymers containing tetraphenylethylene units in the chain are substantially the same, with the difference that: alternative examples 1 to 2#The alternating copolymer obtained in (1) was found to have a mass of 0.12g and a mass of 2, 3-dichloro-5, 6-dicyan p-benzoquinone of 0.62g, and the conjugated polymer obtained had a number average molecular weight of 4.7 × 104The molecular weight distribution was 1.34 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-3 chain
Preparation process and 2-1#Conjugated polymers containing tetraphenylethylene units in the chain are substantially the same, with the difference that: alternative examples 1 to 3#The alternating copolymer obtained in (1) was found to have a mass of 0.09g and a mass of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone of 0.47g, and the conjugated polymer obtained had a number average molecular weight of 4.2 × 104The molecular weight distribution was 1.56 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-4 chain
Preparation process and 2-1#Conjugated polymers containing tetraphenylethylene units in the chain are substantially the same, with the difference that: alternative examples 1 to 4#The dehydrogenating agent is replaced by tetrachloro-p-benzoquinone, the organic solvent is 1,2, 4-trichlorobenzene, and the number average molecular weight of the obtained conjugated polymer is 8 × 103The molecular weight distribution was 1.50 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-5 chain
The preparation process is the same as that of a 2-1# conjugated polymer containing tetraphenylethylene units in the chain, except that: alternative examples 1 to 5#The alternating copolymer obtained in (1) and the dehydrogenating agent are replaced by 3,4,5, 6-tetrachloro-1,2- (ortho-) -benzoquinone, organic solvent 1, 2-dichlorobenzene, the obtained conjugated polymer number average molecular weight 9.9 × 103The molecular weight distribution was 1.45 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-6 chain
The preparation process is the same as that of a 2-1# conjugated polymer containing tetraphenylethylene units in the chain, except that: alternative examples 1 to 6#Replacing the dehydrogenating agent with 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, using 1, 2-dichlorobenzene as organic solvent, at 90 deg.C and 30h, and obtaining conjugated polymer with number-average molecular weight of 1 × 103The molecular weight distribution was 1.85 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-7 chain
The preparation process is the same as that of a 2-1# conjugated polymer containing tetraphenylethylene units in the chain, except that: the reaction system is an argon system, and examples 1-7 are selected#Replacing the dehydrogenating agent with tetrachloro-p-benzoquinone to obtain the alternating copolymer, wherein the organic solvent is 1,2, 4-trichlorobenzene, the dehydrogenation temperature is 90 ℃, the dehydrogenation time is 30 hours, and the number average molecular weight of the obtained conjugated polymer is 2 × 104The molecular weight distribution was 2.26 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-8 chain
The preparation process is the same as that of a 2-2# conjugated polymer containing tetraphenylethylene units in the chain, except that: alternative examples 1 to 8#The organic solvent of the alternating copolymer obtained in the step (1), 2, 4-trichlorobenzene, the dehydrogenation temperature is 90 ℃, the dehydrogenation time is 32 hours, and the number average molecular weight of the obtained conjugated polymer is 2.6 × 104The molecular weight distribution was 2.72 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-9 chain
The preparation process is the same as that of a 2-2# conjugated polymer containing tetraphenylethylene units in the chain, except that: alternative examples 1 to 9#To obtainThe organic solvent is 1, 2-dichlorobenzene, the dehydrogenation temperature is 90 ℃, the dehydrogenation time is 36 hours, and the number average molecular weight of the obtained conjugated polymer is 4.2 × 104The molecular weight distribution was 1.47 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-10 chain
The preparation process is the same as that of a 2-2# conjugated polymer containing tetraphenylethylene units in the chain, except that: the reaction system is argon system, and examples 1-10 are selected#The organic solvent of the alternating copolymer obtained in the step (1), 2-dichlorobenzene is adopted as an organic solvent, the dehydrogenation temperature is 90 ℃, the dehydrogenation time is 36 hours, and the number average molecular weight of the obtained conjugated polymer is 3.2 × 104The molecular weight distribution was 2.29 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-11 chain
The preparation process is the same as that of the 2-3# conjugated polymer containing tetraphenylethylene units in the chain, except that: the reaction system is argon system, and examples 1-11 are selected#The dehydrogenating agent is replaced by tetrachloro-p-benzoquinone, the organic solvent is 1,2, 4-trichlorobenzene, and the number average molecular weight of the obtained conjugated polymer is 3.5 × 104The molecular weight distribution was 1.90 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-12 chain
The preparation process is the same as that of the 2-3# conjugated polymer containing tetraphenylethylene units in the chain, except that: the reaction system is argon system, and examples 1-12 are selected#The alternating copolymer obtained in the step (1) is prepared by replacing a dehydrogenating agent with 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, and an organic solvent is 1, 2-dichlorobenzene, wherein the number average molecular weight of the obtained conjugated polymer is 4 × 104The molecular weight distribution was 1.89 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-13 chain
The preparation process is the same as that of the 2-3# conjugated polymer containing tetraphenylethylene units in the chain, except that: alternative implementationExamples 1 to 13#Replacing the dehydrogenating agent with 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, using 1, 2-dichlorobenzene as organic solvent, at 90 deg.C and 36h, and obtaining conjugated polymer with number-average molecular weight of 5 × 103The molecular weight distribution was 1.69 and the conversion was 100%.
#Preparation of conjugated polymers containing tetraphenylethylene units in the 2-14 chain
The preparation process is the same as that of the 2-3# conjugated polymer containing tetraphenylethylene units in the chain, except that: alternative examples 1 to 14#The dehydrogenation agent of the alternating copolymer obtained in the step (1) is 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, the organic solvent is 1, 2-dichlorobenzene, the dehydrogenation temperature is 90 ℃, the dehydrogenation time is 30 hours, and the number average molecular weight of the obtained conjugated polymer is 3.1 × 104The molecular weight distribution was 2.05 and the conversion was 100%.
Experimental example 1 characterization of Polymer Structure and molecular weight
The structures of the alternating copolymer and the conjugated polymer were characterized and confirmed by means of an AV600(600MHz) nuclear magnetic resonance apparatus manufactured by Brookfield; the molecular weights and their distributions of the alternating copolymer and the conjugated polymer were characterized and confirmed by a differential gel permeation chromatograph model Waters-150C.
FIG. 2(a)1H NMR(600MHz,CDCl3) (ppm)7.53-6.34(m,10H),5.90-5.39(m,2H),3.75-2.59(m,2H),2.59-1.10(m,6H). The microstructure composition of the 1, 3-cyclohexadiene units in the polymer can be calculated from the integrated area of the allyl protons and the integrated area of the protons on the unsaturated carbon. From the second graph, it can be seen that the characteristic absorption peak of the proton on the unsaturated carbon of the 1, 3-cyclohexadiene unit at the chemical shift of 5.30-5.80ppm is substantially disappeared, and the characteristic absorption peak of the proton of the non-benzene ring in the trans 1, 2-diphenylethylene structural unit at the chemical shift of 2.2-3.5ppm is substantially disappeared after dehydrogenation, which proves that the alternating copolymer is almost 100% dehydrogenated.
In FIG. 3, conjugated polymer sample 2-1 is shown#And alternating copolymer samples 1-1#GPC spectrum of (1).
Experimental example 2 fluorescent detection application of conjugated Polymer
The conjugated polymer prepared in example 2 was prepared as a tetrahydrofuran/water mixed solution having a water content of 90%, and the respective solution concentrations were as listed in table 1. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Wherein, sample 2-1#The fluorescence spectrum of (A) is shown in FIG. 4.
TABLE 1 concentration of conjugated Polymer solution
| Sample (I) | Concentration of conjugated Polymer (g/mL) |
| 2-1# | 10-5 |
| 2-2# | 1.3×10-5 |
| 2-3# | 1.5×10-5 |
| 2-4# | 1.2×10-5 |
| 2-5# | 2.2×10-5 |
| 2-6# | 2.5×10-5 |
| 2-7# | 2.7×10-5 |
| 2-8# | 3×10-5 |
| 2-9# | 10-5 |
| 2-10# | 1.4×10-5 |
| 2-11# | 1.6×10-5 |
| 2-12# | 3×10-5 |
| 2-13# | 3.2×10-5 |
| 2-14# | 3.5×10-5 |
To 2-1 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.4mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, and 2.9mM, respectively, to obtain 11 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. The fluorescence quenching spectrogram is shown in fig. 5, and the fluorescence intensity of the solution measured before and after the addition of 2,4, 6-trinitrotoluene is compared, and the fluorescence intensity is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, which shows that the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-2 of the sample#15 groups of solutions to be detected were obtained by adding 2,4, 6-trinitrotoluene to the solution of the conjugated polymer in the state of aggregation at a concentration of 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, 2.6mM, 2.8mM, 2.9mM, respectively. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Similar to the measurement results shown in FIG. 5, the fluorescence intensity of the conjugated polymer gradually decreased with the increase of the concentration of 2,4, 6-trinitrotoluene, compared with the solution without 2,4, 6-trinitrotoluene, indicating that 2,4, 6-trinitrotoluene has good fluorescence quenching performance for the conjugated polymer.
2-3 to the sample#The conjugated polymer aggregation state solution was added with 2,4, 6-trinitrotoluene at concentrations of 0.1mM, 0.3mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, 2.6mM, and 2.9mM, respectively, to obtain 13 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-4 of the sample#The conjugated polymer aggregation state solution was added with 2,4, 6-trinitrotoluene at concentrations of 0.1mM, 0.3mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, 2.6mM, and 2.9mM, respectively, to obtain 12 sets of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-5 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, and 2.0mM, respectively, to obtain 16 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. And not adding 2And compared with the solution of the 4, 6-trinitrotoluene, the fluorescence intensity of the solution of the 4, 6-trinitrotoluene gradually decreases along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
2-6 to the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, and 2.0mM, respectively, to obtain 16 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-7 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, 2.6mM, 2.8mM, respectively, to obtain 20 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-8 of the sample#To the solution of the conjugated polymer in the aggregated state was added 2,4, 6-trinitrotoluene at concentrations of 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, respectively, to obtain 18 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-9 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, and 2.0mM, respectively, to obtain 12 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-10 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, respectively, to obtain 14 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-11 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM, 2.2mM, and 2.4mM, respectively, to obtain 16 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-12 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 4. mu.M, 6. mu.M, 8. mu.M, 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 1mM, 1.2mM, 1.4mM, 1.8mM, 2.0mM, 2.2mM, respectively, to obtain 18 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. With or without 2,4, 6-trinitroCompared with the solution of the toluene, the fluorescence intensity of the toluene gradually decreases along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-13 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 4. mu.M, 6. mu.M, 8. mu.M, 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, 2.6mM, 2.8mM, respectively, to obtain 22 groups of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
To 2-14 of the sample#The conjugated polymer aggregation solution was added with 2,4, 6-trinitrotoluene at concentrations of 1. mu.M, 2. mu.M, 4. mu.M, 6. mu.M, 8. mu.M, 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, 70. mu.M, 0.1mM, 0.3mM, 0.5mM, 1mM, 1.2mM, 1.4mM, 1.8mM, 2.0mM, 2.2mM, 2.4mM, 2.8mM, respectively, to obtain 22 sets of solutions to be detected. The fluorescence intensity of the fluorescent material is measured at 400 nm-600 nm after excitation at an excitation wavelength of 388 nm. Compared with the solution without the 2,4, 6-trinitrotoluene, the fluorescence intensity of the solution is gradually reduced along with the increase of the concentration of the 2,4, 6-trinitrotoluene, and the 2,4, 6-trinitrotoluene has good fluorescence quenching performance on the conjugated polymer.
The experimental results show that: the synthesized conjugated polymer has higher fluorescence intensity in an aggregation state, has higher response speed to 2,4, 6-trinitrotoluene, and can be used as a fluorescence sensor to be applied to the detection of nitroarene explosives.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer characterized by: the structural formula is shown as the formula (I):
the alternating copolymer has a number average molecular weight of 1 × 103Da～5×104Da; the molecular weight distribution of the alternating copolymer is 1.04-2.50.
2. A method of making the polymer of claim 1, comprising the steps of:
under the atmosphere of inert gas, heating a reaction mixture containing a polymerization monomer to a polymerization temperature, and adding an initiator to initiate polymerization; the reaction mixture comprises a polymerization monomer and an organic solvent; the polymerization temperature is 25-70 ℃, and the polymerization time is 1-24 h;
the polymerized monomer comprises 40mol percent to 50mol percent of 1, 3-cyclohexadiene and the balance of trans-1, 2-diphenylethylene;
the total monomer concentration in the reaction mixture is 10 wt.% to 15 wt.%;
the inert gas is selected from nitrogen and argon.
3. The method of claim 2, wherein the initiator is selected from the group consisting of organolithium;
the molar ratio of the initiator to the monomer is 0.3-14: 100;
the organic solvent comprises at least one of tetrahydrofuran, benzene and toluene.
4. The method according to claim 2, wherein the polymerization temperature is 25 ℃ to 50 ℃ and the polymerization time is 5 to 18 hours.
5. The method of claim 2, further comprising precipitating, washing, and drying after the polymerization is completed.
6. A conjugated polymer, characterized in that, as shown in formula (II), the conjugated polymer comprises a tetraphenylethylene unit in the chain:
the number average molecular weight of the conjugated polymer was 1.2 × 103Da～4.7×104Da, the molecular weight distribution is 1.34-3.08.
7. A method of preparing the conjugated polymer of claim 6, comprising:
dehydrogenating the polymer of claim 1 in the presence of an inert gas atmosphere, a dehydrogenating agent, and an organic solvent to obtain the conjugated polymer; the dehydrogenation temperature is 25-100 ℃, and the dehydrogenation time is 6-50 h; and precipitating, drying and washing after dehydrogenation.
8. The method of claim 7, wherein the dehydrogenation agent is at least one selected from the group consisting of 2, 3-dichloro-5, 6-dicyano-p-benzoquinone, tetrachloro-p-benzoquinone, 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone;
the organic solvent is at least one selected from toluene, 1, 2-dichlorobenzene and 1,2, 4-trichlorobenzene;
the concentration of the polymer is 1.0 wt.% to 2.5 wt.%; the mole ratio of the dehydrogenation agent to the polymer is 6-7: 1;
the inert gas is selected from nitrogen or argon;
the dehydrogenation temperature is 90-100 ℃, and the dehydrogenation reaction time is 24-36 h.
9. Use of the conjugated polymer of claim 6 in a fluorescent sensor material;
the conjugated polymer is used for detecting nitroaromatic explosives.
10. Use according to claim 9, characterized in that it comprises:
a) adding a concentration gradient standard substance of a nitroaromatic explosive into the conjugated polymer solution forming the aggregation state to obtain a solution to be detected;
b) measuring the fluorescence intensity of the conjugated polymer at the emission wavelength of 400 nm-600 nm, and comparing the fluorescence intensity of the solution to be measured with the fluorescence intensity of the original conjugated polymer solution to obtain the fluorescence quenching behavior of the 2,4, 6-trinitrotoluene on the conjugated polymer;
the solvent of the conjugated polymer solution is a tetrahydrofuran/water mixed solvent with water content accounting for 90% of the total volume;
the concentration of the conjugated polymer solution was 10-5g/mL～3.5×10-5g/mL；
The nitro aromatic explosive is 2,4, 6-trinitrotoluene;
the excitation wavelength was 388 nm.
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| CN106893080A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院化学研究所 | One class is based on conjugated polymer of benzo [5] helicene and its preparation method and application |
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| CN106397743A (en) * | 2016-09-05 | 2017-02-15 | 齐鲁工业大学 | Application of water-soluble fluorescent conjugated polymer to detection of nitroaromatic hydrocarbon |
| CN109294557A (en) * | 2018-10-12 | 2019-02-01 | 北京化工大学 | A kind of preparation method and application of the composite nano materials with aggregation-induced emission property and photothermal conversion property |
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