CN111675788B - 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 PDF

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CN111675788B
CN111675788B CN202010091341.XA CN202010091341A CN111675788B CN 111675788 B CN111675788 B CN 111675788B CN 202010091341 A CN202010091341 A CN 202010091341A CN 111675788 B CN111675788 B CN 111675788B
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cyclohexadiene
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CN111675788A (en
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韩丙勇
尹晴
鲁建民
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Beijing University of Chemical Technology
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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.
Figure DDA0002383823750000011

Description

Conjugated polymer containing tetraphenylethylene structure and preparation method and application thereof
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, followed by purification of the monomer by a complicated purification operation, and finally, a coupling reaction is carried out under the catalytic action of a transition metal, followed by removal of the transition metal catalyst by a series of purification operations to obtain the target conjugated polymer. Therefore, the synthesis and purification processes of the methods are complicated, and the transition metal catalyst is inevitably left in the polymerization product, which causes the waste of the transition metal and has the problems of high cost, low efficiency and the like.
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 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):
Figure GDA0003072075440000021
in the present invention, the alternating copolymer has a number average molecular weight of 1X 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):
Figure GDA0003072075440000031
the number average molecular weight of the conjugated polymer is 1.2X 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 further comprises 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 selected from toluene, 1, 2-dichlorobenzene, 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 concentration of the conjugated polymer in a mixed solution of 10% tetrahydrofuran/90% water is 10-5～3.5×10-5g/ml。
As an embodiment, the application of the conjugated polymer in explosive detection comprises the following steps:
forming a certain amount of conjugated polymer into an aggregation state in a mixed solution of 10% tetrahydrofuran and 90% water, wherein 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. Exciting at an excitation wavelength of 388nm, 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 detected with that of the original conjugated polymer solution to obtain the detection effect of the conjugated polymer on explosives.
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 mixed solution of 10% tetrahydrofuran/90% water according to an embodiment of the present invention; is example 2-1#Aggregate fluorescence spectrum of the sample.
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
All vessels and reactors must be evacuated and protected with nitrogen. Adding 1.54g of trans-1, 2-diphenylethylene and 20ml of tetrahydrofuran into a 100ml reaction bottle in sequence to fully dissolve the trans-1, 2-diphenylethylene, adding 0.46g of 1, 3-cyclohexadiene, stirring uniformly, adding 1mmol of n-butyllithium, reacting for 5.5h at 25 ℃, stopping the reaction with anhydrous methanol, washing the polymer with a large amount of anhydrous methanol, precipitating, and drying in a vacuum oven at 50 ℃ to obtain the 1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer. The obtained polymer had a number average molecular weight of 2X 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 are substantially the same except that: the mass of the 1, 3-cyclohexadiene was 0.55g, the mass of the trans-1, 2-diphenylethylene was 1.45g, and 0.04mmol of n-butyllithium was added to initiate polymerization for 18 hours. The obtained polymer had a number average molecular weight of 5X 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 are substantially the same except that: the mass of the 1, 3-cyclohexadiene was 0.62g, the mass of the trans-1, 2-diphenylethylene was 1.38g, and 0.04mmol of n-butyllithium was added to initiate polymerization for 17 hours. The obtained polymer had a number average molecular weight of 4.6X 104The molecular weight distribution was 1.04.
#Preparation of 1-41, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-1#The 1, 3-cyclohexadiene-trans 1, 2-diphenylethylene alternating copolymers are substantially the same except that: 0.24mmol of n-butyllithium was added to initiate the polymerization. The reaction system is an argon system, the polymerization temperature is 50 ℃, and the reaction time is 7 hours. The obtained polymer had a number average molecular weight of 8.2X 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 copolymers are substantially the same except that: the reaction system was an argon system, the initiator was replaced with sec-butyllithium and 0.17mmol sec-butyllithium was added to initiate the polymerization. The reaction solvent is benzene, the polymerization temperature is 50 ℃, and the reaction time is 8 h. The obtained polymer had a number average molecular weight of 1.2X 104The molecular weight distribution was 1.07.
#1-61, 3-cyclohexadiene-trans-1, 2-diphenylPreparation of ethylene alternating copolymer
Preparation process and 1-1#The 1, 3-cyclohexadiene-trans 1, 2-diphenylethylene alternating copolymers are substantially the same except that: the reaction system was an argon system, the initiator was replaced with sec-butyllithium and 2mmol sec-butyllithium was added to initiate the polymerization. The reaction solvent is toluene, the polymerization temperature is 40 ℃, and the reaction time is 5 h. The obtained polymer had a number average molecular weight of 1X 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 are substantially 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 ℃ and the solvent was toluene. The initiator was replaced by sec-butyllithium and 0.13mmol sec-butyllithium was added to initiate the polymerization over a reaction time of 11 h. The obtained polymer had a number average molecular weight of 2.3X 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 are substantially 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 ℃ and the solvent was benzene. The initiator was replaced by sec-butyllithium and 0.10mmol sec-butyllithium was added to initiate the polymerization for 12 h. The obtained polymer had a number average molecular weight of 2.9X 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 copolymers are substantially the same except that: the polymerization temperature was 50 ℃ and the solvent was toluene. Replacement of initiator by secondaryButyl lithium, and 0.04mmol sec-butyl lithium was added to initiate the polymerization for 18 h. The obtained polymer had a number average molecular weight of 4.8X 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 copolymers are substantially the same except that: the reaction system is an argon system, the polymerization temperature is 50 ℃, the mass of the 1, 3-cyclohexadiene is 0.92g, the mass of the trans-1, 2-diphenylethylene is 2.08g, 0.09mmol of n-butyllithium is added to initiate the polymerization reaction, and the reaction time is 13 h. The obtained polymer had a number average molecular weight of 3.4X 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 copolymers are substantially the same except that: the reaction system is an argon system, the polymerization temperature is 40 ℃, the initiator is replaced by sec-butyl lithium, and 0.05mmol of sec-butyl lithium is added to initiate the polymerization reaction. The reaction time was 14 h. The obtained polymer had a number average molecular weight of 3.7X 104The molecular weight distribution was 1.70.
#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 are substantially the same except that: 0.05mmol of n-butyllithium was added to initiate the polymerization. The polymerization temperature is 30 ℃ and the reaction time is 15 h. The obtained polymer had a number average molecular weight of 4.1X 104The molecular weight distribution was 1.79.
#Preparation of 1-131, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer
Preparation process and 1-3#1, 3-cyclohexadiene-trans-1, 2-diphenylethylene alternating copolymer approximate phaseThe difference is that: the reaction system was an argon system, the initiator was replaced with sec-butyllithium and 0.39mmol sec-butyllithium was added to initiate the polymerization. The reaction solvent is benzene, the polymerization temperature is 50 ℃, and the reaction time is 6 h. The obtained polymer had a number average molecular weight of 5.1X 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 copolymers are substantially the same except that: the reaction system was an argon system, the initiator was replaced with sec-butyllithium and 0.06mmol sec-butyllithium was added to initiate the polymerization. The reaction solvent is toluene, the polymerization temperature is 40 ℃, and the reaction time is 13 h. The obtained polymer had a number average molecular weight of 3.2X 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 fully dissolved in 6ml of toluene, reacted at 100 ℃ for 24 hours, and then the polymer was washed with a large amount of anhydrous methanol and 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 1.1X 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 the mass of 2, 3-dichloro-5, 6-dicyan p-benzoquinone was found to be 0.62 g. The number average molecular weight of the obtained conjugated polymer was 4.7X 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 2, 3-dichloro-5, 6-dicyan-p-benzoquinone was found to have a mass of 0.47 g. The number average molecular weight of the obtained conjugated polymer was 4.2X 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 dehydrogenation agent of the alternating copolymer obtained in the step (1) is replaced by tetrachloro-p-benzoquinone, and the organic solvent is 1,2, 4-trichlorobenzene. The number average molecular weight of the obtained conjugated polymer was 8X 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 dehydrogenation agent of the alternating copolymer obtained in the step (1) is replaced by 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, and the organic solvent is 1, 2-dichlorobenzene. The number average molecular weight of the obtained conjugated polymer was 9.9X 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#The dehydrogenation agent of the alternating copolymer obtained in the step (1) is replaced by 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, and the organic solvent is 1, 2-dichlorobenzene. Dehydrogenation of hydrogenThe temperature is 90 ℃, and the dehydrogenation time is 30 h. The number average molecular weight of the obtained conjugated polymer was 1X 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#The dehydrogenation agent of the alternating copolymer obtained in the step (1) is replaced by tetrachloro-p-benzoquinone, and the organic solvent is 1,2, 4-trichlorobenzene. The dehydrogenation temperature is 90 ℃, and the dehydrogenation time is 30 h. The number average molecular weight of the obtained conjugated polymer was 2X 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 (1), 2, 4-trichlorobenzene. The dehydrogenation temperature is 90 ℃, and the dehydrogenation time is 32 h. The number average molecular weight of the obtained conjugated polymer was 2.6X 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#The organic solvent of the alternating copolymer obtained in (1, 2-dichlorobenzene). The dehydrogenation temperature is 90 ℃, and the dehydrogenation time is 36 h. The number average molecular weight of the obtained conjugated polymer was 4.2X 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 argonGas system, selected from examples 1-10#The organic solvent of the alternating copolymer obtained in (1, 2-dichlorobenzene). The dehydrogenation temperature is 90 ℃, and the dehydrogenation time is 36 h. The number average molecular weight of the obtained conjugated polymer was 3.2X 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 dehydrogenation agent of the alternating copolymer obtained in the step (1) is replaced by tetrachloro-p-benzoquinone, and the organic solvent is 1,2, 4-trichlorobenzene. The number average molecular weight of the obtained conjugated polymer was 3.5X 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 dehydrogenation agent of the alternating copolymer obtained in the step (1) is replaced by 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, and the organic solvent is 1, 2-dichlorobenzene. The number average molecular weight of the obtained conjugated polymer was 4X 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 examples 1 to 13#The dehydrogenation agent of the alternating copolymer obtained in the step (1) is replaced by 3,4,5, 6-tetrachloro-1, 2- (ortho-) -benzoquinone, and the organic solvent is 1, 2-dichlorobenzene. The dehydrogenation temperature is 90 ℃, and the dehydrogenation time is 36 h. The number average molecular weight of the obtained conjugated polymer was 5X 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, and the organic solvent is 1, 2-dichlorobenzene. The dehydrogenation temperature is 90 ℃, and the dehydrogenation time is 30 h. The number average molecular weight of the obtained conjugated polymer was 3.1X 104The molecular weight distribution was 2.05 and the conversion was 100%.
Experimental example 3 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) Delta (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 FIG. 2, 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 to 5.80ppm 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 to 3.5ppm 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 4 fluorescent detection application of conjugated Polymer
The conjugated polymer prepared in example 2 was prepared as an aggregated solution of 10% tetrahydrofuran/90% water, 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 results of the previous measurement shown in FIG. 5, andcompared with the solution added with 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.
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. 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.
2-6 to the sample#The conjugated polymer aggregation solution is added with the concentrations of 10 MuM, 20 MuM, 30 MuM, 40 MuM and 50 MuM respectively70. mu.M, 0.1mM, 0.3mM, 0.5mM, 0.7mM, 1mM, 1.2mM, 1.4mM, 1.6mM, 1.8mM, 2.0mM of 2,4, 6-trinitrotoluene, 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. Their fluorescence intensity was dependent on 2,4, 6-trinitrotoluene, compared with the solution without 2,4, 6-trinitrotolueneThe concentration of the 6-trinitrotoluene gradually decreases, which shows that 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. 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 2-13 of the sample#The conjugated polymer aggregation solution is added with the concentrations of 4 MuM, 6 MuM, 8 MuM, 10 MuM, 20 MuM, 30 MuM and 40 MuMM, 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 of 2,4, 6-trinitrotoluene, 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. An alternating copolymer of 1, 3-cyclohexadiene and trans-1, 2-diphenylethylene characterized by: the structural formula is shown as the formula (I):
    Figure FDA0003122121700000011
    the number average molecular weight of the alternating copolymer is 1 x 103Da～5×104Da; the molecular weight distribution of the alternating copolymer is 1.04-2.50.
  2. 2. A process for preparing the alternating copolymer of 1, 3-cyclohexadiene and trans-1, 2-diphenylethylene 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. 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. 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. 5. The method of claim 2, further comprising the steps of precipitating, washing and drying after the polymerization is completed.
  6. 6. A conjugated polymer, characterized in that, as shown in formula (II), the conjugated polymer comprises a tetraphenylethylene unit in the chain:
    Figure FDA0003122121700000021
    the number average molecular weight of the conjugated polymer is 1.2X 103Da～4.7×104Da, the molecular weight distribution is 1.34-3.08.
  7. 7. A process for preparing the conjugated polymer of claim 6, comprising the steps of:
    dehydrogenating the copolymer 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. 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-benzoquinone;
    the organic solvent is at least one selected from toluene, 1, 2-dichlorobenzene and 1,2, 4-trichlorobenzene;
    the concentration of the copolymer is 1.0 wt.% to 2.5 wt.%; the mole ratio of the dehydrogenation agent to the copolymer 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. 9. Use of the conjugated polymer of claim 6 in a fluorescent sensor material;
    the conjugated polymer is used for detecting nitroaromatic explosives.
  10. 10. Use according to claim 9, characterized in that it comprises the following steps:
    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) exciting at an excitation wavelength of 388nm, measuring the fluorescence intensity of the sample at an emission wavelength of 400 nm-600 nm, and comparing the fluorescence intensity of the solution to be measured with that 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～3.5×10-5
    g/mL; the nitroaromatic explosive is 2,4, 6-trinitrotoluene.
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