CN113791060B - Cyanostyrene derivative, preparation method and application thereof, polymer detection probe and fluorescence detection method - Google Patents

Cyanostyrene derivative, preparation method and application thereof, polymer detection probe and fluorescence detection method Download PDF

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CN113791060B
CN113791060B CN202111098243.XA CN202111098243A CN113791060B CN 113791060 B CN113791060 B CN 113791060B CN 202111098243 A CN202111098243 A CN 202111098243A CN 113791060 B CN113791060 B CN 113791060B
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徐斌
武志远
田文晶
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Abstract

The invention provides a cyanostyrene derivative, a preparation method and application thereof, a polymer detection probe and a fluorescence detection method, and belongs to the technical field of polymer detection. The cyano styrene derivative is a typical D-Pi-A structure, and when strong electron donors such as methoxyl or triphenylamine and the like are introduced into one side or two sides of dicyano styrene through double bond connection, the length of a conjugated chain is increased, so that the cyano styrene derivative is beneficial to obtaining a high-quality two-photon imaging probe with a large two-photon absorption sectional area. The cyanostyrene derivatives provided by the invention have different dispersivity in different polymer phases, so that fluorescent molecules doped in different polymers have different fluorescence intensities, and a fluorescence method can be used for high-contrast imaging and directly distinguishing phase separation forms in a polymer blend.

Description

Cyanostyrene derivative, preparation method and application thereof, polymer detection probe and fluorescence detection method
Technical Field
The invention relates to the technical field of polymer detection, in particular to a cyanostyrene derivative, a preparation method and application thereof, a polymer detection probe and a fluorescence detection method.
Background
The polymer blending method has the characteristics of simplicity and good repeatability, and is an important means for modifying the polymer. For blending, the properties of the material are affected not only by the chemical composition and structure of the various polymers, but also by the microscopic phase separation obtained during the forming process. In order to study the relationship between the microphase separation morphology and the macroscopic mechanical properties of the polymer blends, Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) are widely used. Images obtained by these techniques provide information about two-dimensional hybrid morphologies, but the lack of three-dimensional information may lead to misinterpretation of the true morphology.
The imaging technology based on the confocal fluorescence microscope has the advantages of high sensitivity, high contrast, visible detection, high response speed and the like. Although fluorescence microscopy has found widespread use in biosensing and imaging in life sciences, research on polymers has been less explored, mainly because most commercial polymers do not have or have very weak fluorescence themselves, and therefore require additional fluorescent probes to label the polymer for observation under a fluorescence microscope. However, there is currently a lack of efficient fluorescent probes to distinguish between different polymer materials in a blended polymer.
Disclosure of Invention
The invention aims to provide a cyanostyrene derivative, a preparation method and application thereof, a polymer detection probe and a fluorescence detection method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a cyanostyrene derivative which has a structure shown in a formula I:
Figure BDA0003269792510000011
in the formula I, X is
Figure BDA0003269792510000021
Y is Br, or Y ═ X.
The invention provides a preparation method of the cyanostyrene derivative in the technical scheme, which comprises the following steps:
mixing p-bromophenylacetonitrile, iodine, a sodium methoxide solution and a first solvent, and performing bimolecular oxidative coupling reaction to obtain a bisbromine intermediate product;
the double bromine intermediate product, a compound containing an electron-donating group, Pd (OAc) 2 、Ag 2 CO 3 And mixing with a second solvent, and carrying out Heck reaction to obtain the cyano-styrene derivative.
The compound containing the single-atom group has a structure shown in a formula II:
Figure BDA0003269792510000022
formula II; in the formula II, X is
Figure BDA0003269792510000023
Figure BDA0003269792510000024
Preferably, when Y is Br, the double bromine intermediate, the compound containing electron donating group, Pd (OAc) 2 And Ag 2 CO 3 In a molar ratio of 1:1:0.05: 0.6.
Preferably, when Y ═ X, the bisbromo intermediate, the compound containing an electron donating group, pd (oac) 2 And Ag 2 CO 3 In a molar ratio of 1:2:0.1: 1.2.
Preferably, the temperature of the bimolecular oxidative coupling reaction is 0 ℃ and the time is 4 hours.
Preferably, the molar ratio of the p-bromophenylacetonitrile to the iodine to the sodium methoxide in the sodium methoxide solution is 1:1: 0.2.
Preferably, the temperature of the Heck reaction is 110 ℃ and the time is 18 h.
The invention provides application of the cyanostyrene derivative in the technical scheme or the cyanostyrene derivative prepared by the preparation method in the technical scheme in fluorescence detection of the polymer blend.
The invention provides a polymer detection probe based on a cyanostyrene derivative, which comprises the cyanostyrene derivative in the technical scheme or the cyanostyrene derivative prepared by the preparation method in the technical scheme.
The invention provides a fluorescence detection method of a blended polymer, which comprises the following steps:
mixing a cyanostyrene derivative, a polymer blend and a good solvent, coating the obtained mixed solution on a substrate, carrying out fluorescence test on the obtained film, and distinguishing different polymer materials in the polymer blend according to the fluorescence intensity of the obtained fluorescence emission curve; the cyanostyrene derivative is the cyanostyrene derivative in the technical scheme or the cyanostyrene derivative prepared by the preparation method in the technical scheme.
The invention provides a cyanostyrene derivative which is of a typical D-pi-A structure, wherein strong electron donors such as methoxyl or triphenylamine and the like are introduced into one side or two sides of dicyanostyrene through double bond connection, and meanwhile, the length of a conjugated chain is increased, so that a large two-photon absorption cross-sectional area is obtained, the fluorescence imaging depth is further improved, and the cyanostyrene derivative can be used as a high-quality two-photon imaging probe.
The cyanostyrene derivatives provided by the invention have different dispersivity in different polymer phases, so that the stacking modes of the cyanostyrene derivatives in different polymers are different, fluorescent molecules doped in different polymers have different fluorescence intensities, and a fluorescence method can be used for high-contrast imaging and directly distinguishing phase separation forms in a polymer blend.
The cyanostyrene derivative provided by the invention has better dispersibility in a polymer containing benzene rings, so that the vibrational motion of molecules is limited, non-radiative transition is limited, the molecules are accumulated in a structural form favorable for fluorescence generation, fluorescence emission is favorable, strong fluorescence is obtained in the polymer doped with the benzene rings, almost no fluorescence is obtained in the polymer doped with the benzene rings, the contrast is high, the result is visual and accurate, and the microscopic phase separation of various incompatible polymer blends can be easily observed. Moreover, the doping amount of the cyanostyrene derivative is 1 wt%, so that the change of the fluorescence intensity can be displayed, and the performance of the polymer can not be influenced.
Drawings
FIG. 1 is a nuclear magnetic spectrum of TB prepared in example 1;
FIG. 2 is a nuclear magnetic spectrum of DOB prepared in example 1;
FIG. 3 is a nuclear magnetic spectrum of DPB prepared in example 1;
FIG. 4 is a nuclear magnetic spectrum of DTB prepared in example 1;
FIG. 5 is a nuclear magnetic spectrum of DTTB prepared in example 1;
FIG. 6 is a nuclear magnetic spectrum of OB prepared in example 1;
FIG. 7 is a nuclear magnetic spectrum of PB prepared in example 1;
FIG. 8 is a nuclear magnetic spectrum of TTB prepared in example 1;
FIG. 9 shows the absorption (a) and emission (b) spectra of TB prepared in example 1 doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 10 shows an emission spectrum (a), fluorescence lifetime (b) and fluorescence photograph (c) of TB prepared in example 1 after being doped with different polymers (PP, PMPO, PVP, PCL, PES, PAMS, SBS and PS), respectively;
FIG. 11 is a DSC (a and b) and free energy characterization (c) plots of a physical mixture of TB doped with different volume fractions of PP and PS, respectively;
FIG. 12 is a graph of the theoretical simulated dispersion of TB molecules in PS and PP;
FIG. 13 is a two-photon three-dimensional imaging graph of a PS/PP film with TB used as a two-photon fluorescence probe;
FIG. 14 is a graph of emission spectra of DOB doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 15 is a graph of the emission spectra of DPB doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 16 is a graph showing emission spectra of DTB doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 17 is a graph showing emission spectra of DTTB doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 18 is a graph showing emission spectra of OB doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 19 is a graph showing the emission spectra of PB doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 20 is a graph showing the emission spectra of TTB doped with PS (polystyrene) and PP (polypropylene), respectively;
FIG. 21 is a graph of the transient absorption spectra of TB doped with PS (polystyrene) and PP (polypropylene), respectively.
Detailed Description
The invention provides a cyanostyrene derivative which has a structure shown in a formula I:
Figure BDA0003269792510000041
in the formula I, X is
Figure BDA0003269792510000051
Y is Br, or Y ═ X.
In the present invention, when X is
Figure BDA0003269792510000052
And when Y ═ Br, the resulting cyanostyrene derivative is denoted PB;
when X is
Figure BDA0003269792510000053
And when Y ═ Br, the resulting cyanostyrene derivative is denoted OB;
when X is
Figure BDA0003269792510000054
And when Y ═ Br, the resulting cyanostyrene derivative is denoted TB;
when X is
Figure BDA0003269792510000055
And when Y ═ Br, the resulting cyanostyrene derivative is denoted as TTB;
when X is
Figure BDA0003269792510000056
And when Y ═ X, the resulting cyanostyrene derivative is designated DPB;
when X is
Figure BDA0003269792510000057
And when Y ═ X, the resulting cyanostyrene derivative is noted as DOB;
when X is
Figure BDA0003269792510000058
And when Y ═ X, the resulting cyanostyrene derivative is designated DTB;
when X is
Figure BDA0003269792510000061
And Y ═ X, the resulting cyanostyrene derivative was designated DTTB.
The invention provides a preparation method of the cyanostyrene derivative in the technical scheme, which comprises the following steps:
mixing p-bromophenylacetonitrile, iodine, a sodium methoxide solution and a first solvent, and performing bimolecular oxidative coupling reaction to obtain a bisbromine intermediate product;
the double bromine intermediate product, a compound containing an electron-donating group, Pd (OAc) 2 、Ag 2 CO 3 And mixing with a second solvent, and carrying out Heck reaction to obtain the cyano-styrene derivative.
The compound containing the single atom group has a structure shown in a formula II:
Figure BDA0003269792510000062
formula II; in the formula II, X is
Figure BDA0003269792510000063
Figure BDA0003269792510000064
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The method comprises the steps of mixing p-bromophenylacetonitrile, iodine, sodium methoxide solution and a first solvent, and carrying out bimolecular oxidative coupling reaction to obtain a bisbromine intermediate product. In the present invention, the molar ratio of the p-bromophenylacetonitrile to iodine to sodium methoxide in the sodium methoxide solution is preferably 1:1: 0.2.
In the present invention, the solvent used for the sodium methoxide solution is preferably methanol; the amount ratio of sodium methoxide to methanol in the sodium methoxide solution is preferably 5.3mmol:14.61 mL.
In the present invention, the first solvent is preferably diethyl ether, and the diethyl ether is preferably dried before use, and the drying process is not particularly limited in the present invention and may be performed according to a process well known in the art. The amount of the first solvent is not particularly limited, and the smooth reaction can be ensured.
In the present invention, the p-bromophenylacetonitrile, iodine, and the sodium methoxide solution are preferably mixed with the first solvent by dissolving the p-bromophenylacetonitrile and iodine in the first solvent, adding the sodium methoxide solution, and stirring in a dry ice bath for 0.5 h. The stirring process is not particularly limited in the present invention, and may be carried out according to a process known in the art.
After the mixing is finished, the invention preferably heats the obtained mixed material to 0 ℃, and replaces the dry ice bath with ice water to carry out bimolecular oxidative coupling reaction.
In the invention, the temperature of the bimolecular oxidative coupling reaction is preferably 0 ℃, and the time is preferably 4 hours; the bimolecular oxidative coupling reaction is preferably carried out under stirring, and the stirring process is not particularly limited in the present invention and may be carried out according to a process known in the art. During the bimolecular oxidative coupling reaction, the secondary carbon atoms adjacent to the acetonitrile of the two p-bromophenylacetonitrile molecules form double bonds.
After the bimolecular oxidative coupling reaction is completed, the obtained product is preferably quenched by hydrochloric acid with the mass concentration of 5%, then stirred for 12 hours, the obtained solution is filtered, the separated solid is washed by cold methanol at 0 ℃ and then by water, and the obtained washed material is dried to obtain the bisbromine intermediate product. The process of stirring, filtering, washing and drying is not particularly limited in the present invention and may be performed according to a process well known in the art.
In the present invention, the bis-bromo intermediate has the structure shown in formula III:
Figure BDA0003269792510000071
after obtaining the double-bromine intermediate product, the invention uses the double-bromine intermediate product, a compound containing electron-donating group, Pd (OAc) 2 、Ag 2 CO 3 Mixing with a second solvent, and carrying out Heck reaction to obtain the cyanostyrene derivative。
In the invention, the compound containing the electron-donating group has a structure shown in a formula II:
Figure BDA0003269792510000072
formula II; in the formula II, X is
Figure BDA0003269792510000073
Figure BDA0003269792510000074
In the present invention, the electron-donating group-containing compound is preferably styrene (corresponding to PB, DPB), 4-methoxystyrene (corresponding to OB, DOB), 4-diphenylaminostyrene (corresponding to TB, DTB) or phenyl- (4-tristyryl-phenyl) - (4-vinyl-phenyl) -amine (corresponding to TTB, DTTB).
In the present invention, when Y is Br, the double bromine intermediate, the compound containing an electron donating group, Pd (OAc) 2 And Ag 2 CO 3 Is preferably 1:1:0.05: 0.6; when Y is X, the double bromine intermediate, compound containing electron donating group, Pd (OAc) 2 And Ag 2 CO 3 Is preferably 1:2:0.1: 1.2.
In the invention, the second solvent is preferably toluene, and the amount of the second solvent is not particularly limited, so that smooth reaction of materials can be ensured.
The invention is to the double bromine intermediate product, the compound containing electron donating group, Pd (OAc) 2 、Ag 2 CO 3 The process of mixing with the second solvent is not particularly limited, and the materials can be uniformly mixed according to a process well known in the art.
In the present invention, the Heck reaction is preferably carried out at a temperature of 110 ℃ for a time of 18 hours. In the Heck reaction process, halogen atom bromine and activated unsaturated hydrocarbon (compound containing a donor monomer group) generate a cyanostyrene derivative under the catalysis of palladium.
After the Heck reaction is finished, the obtained material is preferably subjected to silica gel column purification to obtain a cyanostyrene derivative; the reagent used for purifying the silica gel column is preferably a mixture of dichloromethane and petroleum ether; the volume ratio of the dichloromethane to the petroleum ether is preferably 1:1.
The invention provides application of the cyanostyrene derivative in the technical scheme or the cyanostyrene derivative prepared by the preparation method in the technical scheme in fluorescence detection of the polymer blend.
The invention provides a polymer detection probe based on a cyanostyrene derivative, which comprises the cyanostyrene derivative in the technical scheme or the cyanostyrene derivative prepared by the preparation method in the technical scheme.
The invention provides a fluorescence detection method of a blended polymer, which comprises the following steps:
mixing a cyanostyrene derivative, a polymer blend and a good solvent, coating the obtained mixed solution on a substrate, carrying out fluorescence test on the obtained film, and distinguishing different polymer materials in the polymer blend according to the fluorescence intensity of the obtained fluorescence emission curve; the cyanostyrene derivative is the cyanostyrene derivative in the technical scheme or the cyanostyrene derivative prepared by the preparation method in the technical scheme.
In the invention, the dosage ratio of the cyanostyrene derivative, the polymer blend and the good solvent is preferably 1mg:100mg:1mL, and the good solvent is preferably selected according to the polymer blend to be tested and can dissolve different polymers in the polymer blend. .
In the present invention, the mixing of the cyanostyrene derivative, the polymer blend and the good solvent is preferably performed under stirring conditions, and the stirring time is preferably 1 h; the stirring rate is not particularly limited in the present invention, and the stirring may be performed at a rate well known in the art.
In the invention, the coating mode is preferably spin coating, the substrate is preferably a quartz plate, and the speed of the spin coating is preferably 300 r/s.
After the coating is completed, the present invention preferably dries the resulting film, preferably in an oven at 100 ℃.
The invention has no special limit on the fluorescence test and the process of obtaining the fluorescence emission curve, and the fluorescence emission curve can be obtained by adopting a fluorescence spectrometer according to the well-known process in the field; according to the invention, different polymer materials in the polymer blend are distinguished according to the fluorescence intensity of a fluorescence emission curve, the polymer with strong fluorescence is a polymer containing benzene rings, and the polymer without benzene rings is weak in fluorescence.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention.
Example 1
Dissolving p-bromophenylacetonitrile (5.00g,25.5mmol) and iodine (6.57g,25.5mmol) in dry diethyl ether (100mL), dissolving sodium methoxide (2.89g,5.3mmol) in methanol solution (8.68g,14.61mL), mixing the obtained diethyl ether mixture with the sodium methoxide solution, stirring in a dry ice bath for 0.5h, heating to 0 ℃, replacing the dry ice bath with ice water, stirring for reaction for 4h, and after the reaction is finished, quenching the obtained materials by hydrochloric acid with the mass concentration of 5%; stirring the obtained mixed material for 12 hours, filtering the obtained material, washing the obtained separated solid with methanol at 0 ℃, washing with water, and drying the obtained mixture to obtain a bisbromine intermediate product;
adding an electron-donating group compound 4-diphenylaminostyrene (0.52nmol), the double bromine intermediate product (0.52mmol), Pd (OAc) 2 (0.026mmol) and Ag 2 CO 3 (0.31mmol) is placed in a 50mL Schlenk test tube, added with 15mL toluene, stirred and reacted for 18h at 110 ℃, and the product system is subjected to silica gel column purification by using dichloromethane and petroleum ether (volume ratio is 1:1) as reagents to obtain the cyanostyrene derivative with the structural formula as follows:
Figure BDA0003269792510000101
denoted as TB.
Example 2
The preparation of the dibromine intermediate according to the method of example 1;
4-methoxy styrene (1.04nmol) containing electron-donating group compound, the double-bromine intermediate product (0.52mmol), Pd (OAc) 2 (0.052mmol) and Ag 2 CO 3 (0.62mmol) is placed in a 50mL Schlenk tube, added with 15mL toluene, stirred and reacted for 18h at 110 ℃, and the obtained product system is subjected to silica gel column purification by using dichloromethane and petroleum ether (volume ratio is 1:1) as reagents to obtain the cyanostyrene derivative with the structural formula as follows:
Figure BDA0003269792510000102
is recorded as DOB.
Example 3
The preparation of the dibromine intermediate according to the method of example 1;
styrene (1.04nmol) containing electron-donating group compound, the double bromine intermediate product (0.52mmol), Pd (OAc) 2 (0.052mmol) and Ag 2 CO 3 (0.62mmol) is placed in a 50mL Schlenk tube, added with 15mL toluene, stirred and reacted for 18h at 110 ℃, and the obtained product system is purified by a silica gel column by using dichloromethane and petroleum ether (volume ratio is 1:1) as reagents to obtain the cyanostyrene derivative with the structural formula as follows:
Figure BDA0003269792510000103
denoted as DPB.
Example 4
The preparation of the dibromine intermediate according to the method of example 1;
adding an electron-donating group compound 4-diphenylaminostyrene (1.04nmol), the double bromine intermediate product (0.52mmol), Pd (OAc) 2 (0.052mmol) and Ag 2 CO 3 (0.62mmol) was placed in a 50mL Schlenk tube and 15mL toluene was addedStirring and reacting at 110 ℃ for 18h, and purifying the product system by a silica gel column by using dichloromethane and petroleum ether (the volume ratio is 1:1) as reagents to obtain the cyanostyrene derivative, wherein the structural formula is as follows:
Figure BDA0003269792510000111
and is noted as DTB.
Example 5
The preparation of the dibromine intermediate according to the method of example 1;
the compound phenyl- (4-tristyryl-phenyl) - (4-vinyl-phenyl) -amine (1.04nmol) containing electron donating group, the bis-bromo intermediate (0.52mmol), Pd (OAc) 2 (0.052mmol) and Ag 2 CO 3 (0.62mmol) is placed in a 50mL Schlenk tube, added with 15mL toluene, stirred and reacted for 18h at 110 ℃, and the obtained product system is subjected to silica gel column purification by using dichloromethane and petroleum ether (volume ratio is 1:1) as reagents to obtain the cyanostyrene derivative with the structural formula as follows:
Figure BDA0003269792510000112
is recorded as DTTB.
Example 6
The only difference from example 1 is: the compound containing electron-donating groups is 4-methoxy styrene, and the structural formula of the obtained cyano styrene derivative is as follows:
Figure BDA0003269792510000113
and noted OB.
Example 7
The only difference from example 1 is: the compound containing the electron-donating group is styrene, and the structural formula of the obtained cyano-styrene derivative is as follows:
Figure BDA0003269792510000121
denoted as PB.
Example 8
The only difference from example 1 is: the compound containing the electron-donating group is phenyl- (4-triphenylethylene-phenyl) - (4-vinyl-phenyl) -amine, and the structural formula of the obtained cyano styrene derivative is as follows:
Figure BDA0003269792510000122
denoted as TTB.
Characterization and Performance testing
1) Performing nuclear magnetic characterization on the cyanostyrene derivatives prepared in examples 1 to 8, and obtaining results shown in figures 1 to 8 respectively; as can be seen from FIGS. 1 to 8, the present invention successfully synthesized the cyanostyrene derivatives having the corresponding structures prepared in examples 1 to 8.
2) After the TB prepared in example 1 was doped with PS (polystyrene) and PP (polypropylene) respectively in an amount of 1% by mass, the resulting mixture was subjected to absorption spectrum and emission spectrum tests, and the results are shown in fig. 9; FIG. 9 shows the absorption spectrum (a) and emission spectrum (b) of TB prepared in example 1 doped with PS (polystyrene) and PP (polypropylene), respectively; as can be seen from a in fig. 9, TB molecules have two main absorption peaks in the two polymers, which are located around 370nm and 480nm, respectively, and mainly result from the intermolecular pi-pi transition. As can be seen from b in fig. 9, the fluorescence intensity of TB molecules doped in PS is significantly higher than that doped in PP.
3) FIG. 10 shows an emission spectrum (a), a fluorescence lifetime (b), and a fluorescence photograph (c) of TB prepared in example 1 doped with various polymers (PP, PMPO, PVP, PCL, PES, PAMS, SBS, and PS) at 1% by mass, respectively. As can be seen from a and c in FIG. 10, TB-doped polymer has strong fluorescence intensity in various polymers (PES, PAMS, SBS and PS) containing benzene rings, and hardly fluoresces in several polymers (PP, PMPO, PVP and PCL) without benzene rings, which proves that the molecules have universality in polymer resolution. As can be seen from b in FIG. 10, when TB is doped in a polymer containing a benzene ring, the fluorescence lifetime is longer because the vibrational transport of the molecule is restricted and the nonradiative transition is restricted.
4) When the heating rate is 20 ℃/min, respectively doping 50-100% of TB in the PP-PS physical mixture with different volume fractions (in the figure, 50-100% represents the mass percentage of the TB in the PP-PS physical mixture) to perform DSC test, and obtaining results shown in figure 11, wherein a is the DSC test in which the TB is respectively doped in the PS with different volume fractions, and b is the DSC test in which the TB is respectively doped in the PP with different volume fractions; the free energies of the two doped polymers were calculated from a and b and the results are shown in c of FIG. 11. As can be seen from c in FIG. 11, the free energy of PS/TB is smaller, indicating that TB is more dispersible in PS and more miscible with polymers containing benzene rings.
5) The dispersion of TB molecules in PS and PP is theoretically simulated by molecular dynamics simulation (MD simulation), and the obtained result is shown in FIG. 12, wherein the left graph is the distribution of TB in PS, and the right graph is the dispersion of TB in PP; as can be seen from FIG. 12, TB was more dispersed in PS, whereas TB molecules were stacked in PP.
6) Two-photon three-dimensional imaging of PS/PP films was performed using TB prepared in example 1 as a two-photon fluorescence probe: dissolving 0.8g of PP and 0.2g of PS in 100mL of toluene solvent, adding 0.01g of TB fluorescent probe prepared in the embodiment 3 under the stirring condition, dripping a film on a polarizer after complete dissolution, keeping the temperature of a hot table at 180 ℃ for 10min, volatilizing the toluene solvent, and then cooling to room temperature at the speed of 1 ℃/min, 10 ℃/min and 50 ℃/min respectively; modulating the laser wavelength of the multi-photon laser confocal microscope to 800nm, scanning the Z axis, scanning once every 5 microns during imaging, receiving a fluorescence signal by using a red channel until no fluorescence signal exists at the scanning depth, and obtaining a result shown in figure 13; wherein a is the microcosmic phase separation theoretical appearance of the polymer blend when the speed of 50 ℃/min is reduced to the room temperature, b is the microcosmic phase separation theoretical appearance of the polymer blend when the speed of 10 ℃/min is reduced to the room temperature, c is the microcosmic phase separation theoretical appearance of the polymer blend when the speed of 1 ℃/min is reduced to the room temperature, d is the bright field photograph of the polymer film under a two-photon microscope when the speed of 50 ℃/min is reduced to the room temperature, e is the bright field photograph of the polymer film under the two-photon microscope when the speed of 10 ℃/min is reduced to the room temperature, f is the bright field photograph of the polymer film under the two-photon microscope when the speed of 1 ℃/min is reduced to the room temperature, g is the two-photon fluorescence imaging of the polymer film under the two-photon microscope when the speed of 50 ℃/min is reduced to the room temperature, and h is the two-photon fluorescence imaging of the polymer film under the two-photon microscope when the speed of 10 ℃/min is reduced to the room temperature, i is two-photon fluorescence imaging of the polymer film under a two-photon microscope when the temperature of the polymer film is reduced to room temperature at the speed of 1 ℃/min; as can be seen from a in FIG. 13, when the rate of 50 ℃/min is decreased to room temperature, the polymer blend micro-phase separation theoretically should be such that PS and PP interpenetrate each other and present a bicontinuous phase; from c in FIG. 13, it can be seen that when the rate of 1 ℃/min is decreased to room temperature, the polymer blend micro-phase separation theoretically should be such that PS is dispersed in PP like islands in the sea, and takes on an island structure; as can be seen from b in FIG. 13, when the micro-phase separation of the polymer blend is reduced to room temperature at a rate of 10 ℃/min, the micro-phase separation should theoretically be an intermediate state of the morphology when the micro-phase separation of the polymer blend is reduced to room temperature at a rate of 50 ℃/min and 1 ℃/min, and the PS part presents a sea-island structure and the part presents a bicontinuous structure; as can be seen from d-f in fig. 13, different annealing rates have significant influence on the phase separation morphology of the polymer blend; as can be seen from the microscopic bright field photograph in fig. 13, when the speed of 50 ℃/min is reduced to room temperature, the microscopic phase separation of the polymer blend is actually the interpenetration of PS and PP, and a bicontinuous phase is presented; from the bright field photograph of the microscope in fig. 13, it can be seen that the micro-phase separation of the polymer blend when the speed of 1 ℃/min is reduced to room temperature is actually that the PS is dispersed in the PP like islands in the sea, and the islands-in-the-sea structure is present; as can be seen from the bright field photograph of the microscope in FIG. 13, the micro-phase separation of the polymer blend when the temperature of the polymer blend is decreased to room temperature at a rate of 10 ℃/min is actually an intermediate state of the morphology when the temperature of the polymer blend is decreased to room temperature at a rate of 50 ℃/min and 1 ℃/min, and the PS part presents a sea-island structure and a bicontinuous structure, which is consistent with the theoretical results. As can be seen from g in FIG. 13, when the temperature of the blended polymer is decreased to room temperature at a rate of 50 ℃/min, the micro-phase separation of the blended polymer is that the PS and the PP are mutually penetrated in the film, and a bicontinuous phase is presented; as can be seen from h in FIG. 13, when the rate of 10 ℃/min is decreased to room temperature, the micro-phase separation of the polymer blend is that PS is mostly dispersed in PP in a sea-island structure inside the film; from i in FIG. 13, it can be seen that when the rate of 1 ℃/min is reduced to room temperature, the micro-phase separation of the polymer blend is carried out, and PS is dispersed in PP in a sea-island structure in the film; therefore, the method can complete the in-situ three-dimensional visualization of the blend polymer film micro-phase separation without damaging the sample, and display the internal structure of the two-dimensional image which cannot be displayed.
7) The cyanostyrene derivatives prepared in the embodiments 2 to 8 are doped in PS (polystyrene) and PP (polypropylene) respectively, and the specific method is as follows: dissolving 100mg of PS and PP in 1mL of decahydronaphthalene respectively, adding 1mg of the cyanostyrene derivative prepared in the embodiment 2-8 respectively, and fully stirring for 1 h; spin-coating 100 microliters of the obtained mixed solution on a quartz plate at a speed of 300r/s, drying in a 100 ℃ oven, placing the obtained film in a fluorescence spectrometer, and carrying out emission spectrum test by using 365nm laser as an excitation light source, wherein the obtained results are respectively shown in FIGS. 14-20; as can be seen from fig. 14 to 20, the cyanostyrene derivatives prepared in examples 2 to 8 have an obvious fluorescent signal after being doped in PS, and basically no fluorescent signal is generated after being doped in PP, which indicates that the cyanostyrene derivatives provided by the present invention have consistent selectivity to polymers.
8) Respectively doping TB into a PS toluene solution and a PP toluene solution according to the mass ratio of 1:100 of the TB to the polymer (the concentrations of the PS toluene solution and the PP toluene solution are both 1g/100mL), respectively coating the obtained mixed solution on a substrate, respectively placing the obtained polymer film into a transient absorption spectrum tester for transient absorption test, wherein the laser wavelength of the tester is 405nm during the test, and the obtained result is shown in a graph 21, wherein a is a transient absorption spectrum graph of the TB-doped PP polymer film; b is a transient absorption spectrum chart of the TB doped PS polymer film; as can be seen in fig. 21, the presence of excited radiation in PS with TB doping, while none in PP, indicates that TB is stacked in PS in a configuration more favorable for fluorescent emission.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The application of the cyanostyrene derivative in fluorescence detection of the polymer blend is characterized in that the cyanostyrene derivative, the polymer blend and a good solvent are mixed, the obtained mixed solution is coated on a substrate, a fluorescence test is carried out on the obtained film, the in-situ three-dimensional visualization of the microscopic phase separation of the polymer blend film is completed, the polymer with strong fluorescence is a polymer containing benzene rings, and the polymer without benzene rings is weak in fluorescence;
wherein the cyanostyrene derivative is selected from compounds represented by the following structural formula:
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、
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、
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、
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、
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、
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、
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、
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。
2. use according to claim 1, characterized in that: the preparation method of the cyanostyrene derivative comprises the following steps:
mixing p-bromophenylacetonitrile, iodine, a sodium methoxide solution and a first solvent, and performing bimolecular oxidative coupling reaction to obtain a bisbromine intermediate product;
the double bromine intermediate product, a compound containing an electron-donating group, Pd (OAc) 2 、Ag 2 CO 3 Mixing with a second solvent, and carrying out Heck reaction to obtain a cyanostyrene derivative;
the compound containing an electron-donating group is selected from: 4-dianilinostyrene, 4-methoxystyrene, styrene, phenyl- (4-tristyryl-phenyl) - (4-vinyl-phenyl) -amine.
3. The use according to claim 2, wherein the bimolecular oxidative coupling reaction is carried out at a temperature of 0 ℃ for a period of 4 hours.
4. The use according to claim 2, wherein the molar ratio of p-bromobenzonitrile, iodine and sodium methoxide in sodium methoxide solution is 1:1: 0.2.
5. The use according to claim 2, wherein the Heck reaction is carried out at a temperature of 110 ℃ for a period of 18 hours.
6. A fluorescence detection method for blended polymers is characterized by comprising the following steps:
mixing a cyanostyrene derivative, a polymer blend and a good solvent, coating the obtained mixed solution on a substrate, and carrying out fluorescence test on the obtained film to complete in-situ three-dimensional visualization of the microscopic phase separation of the polymer blend film, wherein the polymer with strong fluorescence is a polymer containing benzene rings, and the polymer with weak fluorescence is a polymer without benzene rings;
wherein the cyanostyrene derivative is selected from compounds represented by the following structural formula:
Figure 294709DEST_PATH_IMAGE001
、
Figure 426613DEST_PATH_IMAGE002
、
Figure 421114DEST_PATH_IMAGE003
、
Figure 31087DEST_PATH_IMAGE004
、
Figure 545376DEST_PATH_IMAGE005
、
Figure 848182DEST_PATH_IMAGE006
、
Figure 329979DEST_PATH_IMAGE007
、
Figure 25533DEST_PATH_IMAGE008
。
7. the fluorescence detection method according to claim 6, characterized in that: the preparation method of the cyanostyrene derivative comprises the following steps:
mixing p-bromophenylacetonitrile, iodine, a sodium methoxide solution and a first solvent, and performing bimolecular oxidative coupling reaction to obtain a bisbromine intermediate product;
the double bromine intermediate product, a compound containing an electron-donating group, Pd (OAc) 2 、Ag 2 CO 3 Mixing with a second solvent, and carrying out Heck reaction to obtain a cyanostyrene derivative;
the compound containing an electron-donating group is selected from: 4-dianilinostyrene, 4-methoxystyrene, styrene, phenyl- (4-tristyryl-phenyl) - (4-vinyl-phenyl) -amine.
8. The fluorescence detection method of claim 7, wherein the bimolecular oxidative coupling reaction is carried out at a temperature of 0 ℃ for 4 hours.
9. The fluorescence detection method according to claim 7, wherein the molar ratio of p-bromobenzonitrile, iodine and sodium methoxide in a sodium methoxide solution is 1:1: 0.2.
10. The fluorescence detection method according to claim 7, wherein the Heck reaction is performed at a temperature of 110 ℃ for 18 hours.
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