CN114437272A - Fluorescent polymer and preparation method and application thereof - Google Patents

Fluorescent polymer and preparation method and application thereof Download PDF

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CN114437272A
CN114437272A CN202011201469.3A CN202011201469A CN114437272A CN 114437272 A CN114437272 A CN 114437272A CN 202011201469 A CN202011201469 A CN 202011201469A CN 114437272 A CN114437272 A CN 114437272A
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toluene
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CN114437272B (en
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范国强
宋建会
郭照琰
茹越
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses a fluorescent polymer, which contains a structural unit shown in a formula (I), a structural unit shown in a formula (II) and an optional structural unit shown in a formula (III):

Description

Fluorescent polymer and preparation method and application thereof
Technical Field
The invention relates to a fluorescent material, in particular to a fluorescent polymer and a preparation method and application thereof.
Background
The polymer fluorescent material can be used in the fields of light conversion, anti-counterfeiting, ultraviolet absorption, tracing, fluorescence detection, biomedical analysis, imaging and the like. At present, the polyolefin fluorescent material is mainly prepared by methods such as blending, grafting and the like.
Chinese patent CN107384369A discloses a polyolefin/rare earth complex/carbonate composite fluorescent material, which is prepared by firstly preparing a rare earth complex/carbonate complex, then mixing and stirring the rare earth complex/carbonate complex with a polyolefin solution, and finally filtering and drying the mixture to obtain the composite fluorescent material.
Chinese patent CN104387534A uses beta rays to carry out irradiation treatment on polyethylene, and then N-allyl-4-methoxy-1, 8-naphthalimide functional monomer is grafted on the pretreated polyethylene to obtain fluorescent polyethylene resin which can be used for preparing light conversion films.
Chinese patent CN108395607A blends thermoplastic resins such as polyolefin and the like with maleic anhydride copolymer to prepare fluorescent resin, and obtains ultraviolet-to-blue light conversion resin which can be used for preparing light conversion agricultural films.
In the prior art, the preparation process of the polyolefin fluorescent material and the resin composition are complex, so the development and production process flow is simple, and the fluorescent olefin polymer with single composition has important practical value and economic significance.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a fluorescent polymer, and a preparation method and application thereof, wherein a tetraphenylvinyl side chain is introduced into the fluorescent polymer to endow the fluorescent polymer with fluorescent characteristics.
One of the objects of the present invention is to provide a fluorescent polymer comprising a structural unit represented by formula (I), a structural unit represented by formula (II), and optionally a structural unit represented by formula (III):
Figure BDA0002755278400000021
wherein, in the formula (I), R1Is H or CH3(ii) a In the formula (II), R2Is selected from alkylene; in the formula (III), R3Is C2～C10Alkyl or C6～C10Aryl is shown.
In a preferred embodiment, in formula (I), R1Is H or CH3(ii) a In the formula (II), R2Is selected from C2～C6Alkylene (e.g., ethylene, butylene, hexylene); in the formula (III), R3Is C2～C6An alkyl group is shown.
In a preferred embodiment, the fluorescent polymer contains 0.001 to 2 mol% of the structural unit represented by formula (II) and 0 to 4 mol% of the structural unit represented by formula (III) based on 100% of the total molar amount of the structural unit represented by formula (I), the structural unit represented by formula (II) and the structural unit represented by formula (III).
In a further preferred embodiment, the fluorescent polymer contains 0.01 to 1% by mole of the structural unit represented by the formula (II) and 0 to 3% by mole of the structural unit represented by the formula (III), based on 100% by mole of the total molar amount of the structural unit represented by the formula (I), the structural unit represented by the formula (II) and the structural unit represented by the formula (III).
The second object of the present invention is to provide a method for preparing the fluorescent polymer, which comprises the following steps: and (2) carrying out copolymerization on the monomer shown in the formula (I '), the monomer shown in the formula (II ') and the optional monomer shown in the formula (III ') to obtain the fluorescent polymer.
Figure BDA0002755278400000031
Wherein, in the formula (I'), R1Is H or CH3(ii) a In the formula (II'), R2Is selected from alkylene; in the formula (III'), R3Is C2～C10Alkyl or C6～C10Aryl is shown.
In a preferred embodiment, in formula (I'), R1Is H or CH3(ii) a In the formula (II'), R2Is selected from C2～C6An alkylene group of (a); in the formula (III'), R3Is C2～C6An alkyl group is shown.
In a further preferred embodiment, the monomer of formula (I') is ethylene; and/or, the monomer shown in the formula (II') is selected from at least one of [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene, [1- (4-hexenyloxyphenyl) -1,2, 2-triphenyl ] ethylene and [1- (4-octenyloxy phenyl) -1,2, 2-triphenyl ] ethylene; and/or the monomer shown in the formula (III') is selected from at least one of 1-butene, 1-hexene and 1-octene.
In a preferred embodiment, the monomer of formula (II') is present in the polymerization system at a concentration of 1X10-4～1x10-1The concentration of the monomer shown in the formula (III') in a polymerization system is 0-2 mol/L.
In a further preferred embodiment, the concentration of the monomer of the formula (II') in the polymerization system is 1X10-3～1x10-2mol/L, and the concentration of the monomer shown in the formula (III') in a polymerization system is 0-1 mol/L.
In a preferred embodiment, the copolymerization is carried out in the presence of at least one catalyst from the group of Ziegler-Natta catalysts, metallocene catalysts and other single-site catalysts.
In the present invention, the copolymerization may be carried out in a solution, bulk or slurry state.
In a further preferred embodiment, the copolymerization is carried out in the presence of a metallocene catalyst.
In a still further preferred embodiment, the copolymerization is carried out in the presence of a catalyst composition comprising a metallocene catalyst and an alkylalumoxane.
Wherein the metallocene catalyst contains a metal active center, such as Ti, Hf or Zr. The metallocene catalyst contains at least one of cyclopentadienyl and/or derivatives thereof, indenyl and/or derivatives thereof, and fluorenyl and/or derivatives thereof, and is connected with the metal active center.
The metallocene catalyst of the present invention is selected from any metallocene catalysts disclosed in the prior art. The metallocene catalysts can be purchased directly or prepared themselves using methods disclosed in the prior art.
In a preferred embodiment, the alkylaluminoxane has the structure according to formula (V) and/or formula (VI):
Figure BDA0002755278400000041
in formula (V) and formula (VI), R is selected from alkyl, preferably C1～C15More preferably C1～C5Alkyl groups of (a), such as methyl; n is any integer of 4 to 30, preferably any integer of 10 to 30.
In a preferred embodiment, the molar ratio of the metallocene catalyst to Al in the alkylaluminoxane is 1 (50-20000), preferably 1 (200-10000), more preferably 1 (200-3000).
In a preferred embodiment, the monomer of formula (I') has a pressure of 0.05 to 5MPa, preferably 0.1 to 3 MPa.
In a preferred embodiment, the polymerization is carried out in an organic solvent.
In a further preferred embodiment, the organic solvent is selected from at least one of toluene, xylene, n-hexane, cyclohexane, n-heptane, n-octane.
In a preferred embodiment, the concentration of metallocene catalyst in the metallocene catalyst composition in the polymerization system is 1x10-8Mol/l-1 x10-3Mol/l, preferably 1X10-7Mol/l-1 x10-4Mol/l.
The reason why the metallocene catalyst is used in the present invention to catalyze the coordination polymerization is that: the metallocene catalyst has better copolymerization performance, can utilize the comonomer to the maximum extent, and the comonomer in the obtained copolymer is distributed more uniformly, and the obtained copolymer is a linear polymer and has good mechanical property.
The third object of the present invention is to provide the use of the fluorescent polymer of the first object of the present invention or the fluorescent polymer obtained by the preparation method of the second object of the present invention in fluorescent materials.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects: the preparation process of the method is simpler, and the single fluorescent olefin polymer can be obtained through coordination polymerization.
Drawings
FIG. 1 shows a three-dimensional fluorescence spectrum of a fluorescent olefin polymer prepared in example 2 of the present invention.
In FIG. 1, the left coordinate of the spectrum is the wavelength of the excitation light, and the bottom coordinate is the wavelength of the emission light, and it can be seen from the spectrum that the olefin polymer mainly converts the ultraviolet light with the wavelength of 300-400nm into the visible light with the wavelength of 420-560nm, wherein the wavelength of the strongest emission spectrum is 480-500nm, which indicates that the prepared olefin polymer has the fluorescence effect.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
Metallocene catalyst: ethylene bridge bisindenyl zirconium dichloride, toluene solution, 2. mu. mol/mL.
Cocatalyst: methylaluminoxane solution in toluene, 1.4 mol/L.
Functional monomer: [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene, [1- (4-hexenyloxyphenyl) -1,2, 2-triphenyl ] ethylene, [1- (4-octenyloxyphenyl) -1,2, 2-triphenyl ] ethylene were prepared in 0.1mol/L toluene solution and used.
The fluorescence phenomenon of the polymer is observed by using an ultraviolet lamp, a polymer sample is placed under the ultraviolet light with the wavelength of 365nm for irradiation, and blue-green fluorescence is observed, which indicates that the polymer has light conversion performance.
The fluorescence spectrum data were measured by means of a Horiba JY FL3 type fluorescence spectrometer using a 450W xenon lamp light source, the excitation wavelength range was 250nm-650nm, and the emission spectrum wavelength range was 300nm-1000 nm.
[ example 1 ]
Purging a polymerization reactor with nitrogen, replacing the nitrogen with ethylene, keeping the temperature to 30 ℃, respectively adding 39.0mL of toluene, 5.0mL of methylaluminoxane toluene solution and 5.0mL of functional monomer [1- (4-hexenyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting the polymerization reaction for 10 minutes, keeping the ethylene pressure constant in the polymerization process, precipitating the reactant with excessive hydrochloric acid ethanol after the polymerization reaction is finished, filtering to obtain white solid powder, the resulting polymer was then added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene, to remove unreacted functional monomers, and finally, after washing sufficiently with ethanol and water, vacuum drying was carried out to obtain 0.42g of an ethylene copolymer. The prepared ethylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 2 ]
Purging a polymerization reactor with nitrogen, replacing the nitrogen with ethylene, keeping the temperature to 50 ℃, respectively adding 39.0mL of toluene, 5.0mL of methylaluminoxane toluene solution and 5.0mL of functional monomer [1- (4-hexenyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting the polymerization reaction for 10 minutes, keeping the ethylene pressure constant in the polymerization process, precipitating the reactant with excessive hydrochloric acid ethanol after the polymerization reaction is finished, filtering to obtain white solid powder, the resulting polymer was then added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene, to remove unreacted functional monomers, and finally, thoroughly washed with ethanol and water and vacuum-dried to obtain 0.72g of an ethylene copolymer. The prepared ethylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 3 ]
Purging a polymerization reactor with nitrogen, replacing the nitrogen with ethylene, keeping the temperature to 30 ℃, respectively adding 45.5mL of toluene, 2.5mL of methylaluminoxane toluene solution and 1mL of functional monomer [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting the polymerization reaction for 10 minutes, keeping the ethylene pressure constant in the polymerization process, precipitating the reactant with excessive hydrochloric acid ethanol after the polymerization reaction is finished, filtering to obtain white solid powder, the resulting polymer was then added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene, to remove unreacted functional monomers, and finally, after fully washing with ethanol and water, vacuum drying was carried out to obtain 0.50g of an ethylene copolymer. The prepared ethylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 4 ]
Purging a polymerization reactor with nitrogen, replacing the nitrogen with ethylene, keeping the temperature to 30 ℃, respectively adding 36.5mL of toluene, 2.5mL of methylaluminoxane toluene solution and 10mL of functional monomer [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting the polymerization reaction for 10 minutes, keeping the ethylene pressure constant in the polymerization process, precipitating the reactant with excessive hydrochloric acid ethanol after the polymerization reaction is finished, filtering to obtain white solid powder, the resulting polymer was then added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene, to remove unreacted functional monomers, and finally, after fully washing with ethanol and water, vacuum drying was carried out to obtain 0.72g of an ethylene copolymer. The prepared ethylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 5 ]
Purging a polymerization reactor by using nitrogen, replacing nitrogen by using ethylene, keeping the temperature to 30 ℃, respectively adding 42.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 2mL of functional monomer [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution and 1mL of comonomer 1-hexene, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting the polymerization reaction for 10 minutes, keeping the ethylene pressure constant in the polymerization process, precipitating reactants by using excessive hydrochloric acid ethanol after the polymerization reaction is finished, filtering to obtain white solid powder, then adding the obtained polymer into the toluene, stirring at room temperature, filtering, washing by using a large amount of toluene to remove unreacted functional monomers, fully washing by using ethanol and water, and drying in vacuum, 1.32g of an ethylene copolymer was obtained. The prepared ethylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 6 ]
Purging a polymerization reactor with nitrogen, replacing nitrogen with ethylene, keeping the temperature to 30 ℃, respectively adding 43.0mL of toluene, 2.5mL of methylaluminoxane toluene solution, 2mL of functional monomer [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution and 0.5mL of comonomer 1-octene, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting polymerization, keeping the ethylene pressure constant in the polymerization process, precipitating reactants with excessive hydrochloric acid ethanol after the polymerization reaction is finished, filtering to obtain white solid powder, adding the obtained polymer into toluene, stirring at room temperature, filtering, washing with a large amount of toluene to remove unreacted functional monomers, fully washing with ethanol and water, and then drying in vacuum, 1.29g of an ethylene copolymer was obtained. The prepared ethylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 7 ]
Purging a polymerization reactor with nitrogen, replacing nitrogen with ethylene, keeping the temperature to 30 ℃, respectively adding 40.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 2mL of functional monomer [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution and 4.0mL of comonomer 1-hexene, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting polymerization, keeping the ethylene pressure constant in the polymerization process, precipitating reactants with excessive hydrochloric acid ethanol after the polymerization reaction is finished, filtering to obtain white solid powder, adding the obtained polymer into toluene, stirring at room temperature, filtering, washing with a large amount of toluene to remove unreacted functional monomers, fully washing with ethanol and water, and then drying in vacuum, 0.93g of an ethylene copolymer was obtained. The prepared ethylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 8 ]
Purging a polymerization reactor with nitrogen, replacing nitrogen with propylene, keeping the temperature to 30 ℃, respectively adding 45.5mL of toluene, 2.5mL of methylaluminoxane toluene solution and 1.0mL of functional monomer [1- (4-octyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution, stirring for 10 minutes, keeping the propylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting the polymerization reaction for 10 minutes, keeping the propylene pressure constant in the polymerization process, precipitating reactants with excessive ethanol hydrochloride after the polymerization reaction is finished, filtering to obtain white solid powder, the resulting polymer was then added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene, to remove unreacted functional monomers, and finally, after washing sufficiently with ethanol and water, vacuum drying was carried out to obtain 0.33g of a propylene copolymer. The prepared propylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
[ example 9 ]
Purging a polymerization reactor with nitrogen, replacing nitrogen with propylene, keeping the temperature to 30 ℃, respectively adding 44.5mL of toluene, 2.5mL of methylaluminoxane toluene solution and 2.0mL of functional monomer [1- (4-octyloxyphenyl) -1,2, 2-triphenyl ] ethylene toluene solution, stirring for 10 minutes, keeping the propylene pressure at 0.1MPa, adding 1.0mL of metallocene catalyst solution, starting the polymerization reaction for 10 minutes, keeping the propylene pressure constant in the polymerization process, precipitating reactants with excessive ethanol hydrochloride after the polymerization reaction is finished, filtering to obtain white solid powder, the resulting polymer was then added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene, to remove unreacted functional monomers, and finally, after washing sufficiently with ethanol and water, vacuum drying was carried out to obtain 0.37g of a propylene copolymer. The prepared propylene copolymer is observed under ultraviolet rays with the wavelength of 365nm, and the copolymer emits obvious blue-green fluorescence.
Comparative example 1
Purging a polymerization reactor with nitrogen, replacing the nitrogen with ethylene, keeping the temperature constant at 30 ℃, adding 46.5mL of toluene and 2.5mL of methylaluminoxane toluene solution respectively, stirring for 10 minutes, keeping the ethylene pressure at 0.1MPa, adding 1mL of metallocene catalyst solution, stirring for 10 minutes at a set temperature, keeping the pressure of reaction gas constant in the polymerization process, stopping introducing the ethylene, finishing the polymerization reaction, introducing a small amount of air to inactivate the catalyst, adding 10mL of [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene functional monomer solution, continuously stirring for 10 minutes, precipitating reactants with excessive hydrochloric acid ethanol, filtering to obtain white solid powder, adding the obtained polymer into the toluene, stirring at room temperature, filtering, washing with a large amount of toluene to remove unreacted functional monomers, finally, fully washing the mixture by using ethanol and water, and drying the mixture in vacuum to obtain the ethylene polymer. When the ethylene copolymer thus prepared was observed under ultraviolet rays having a wavelength of 365nm, the copolymer was not fluorescent.
Figure BDA0002755278400000121
Oxyphenyl) -1,2, 2-triphenyl ] ethylene
In table 1:
functional monomer: a: [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene, B: [1- (4-hexenyloxyphenyl) -1,2, 2-triphenyl ] ethylene, C: [1- (4-octyloxyphenyl) -1,2, 2-triphenyl ] ethylene;
"concentration" refers to the initial concentration of comonomer or functional monomer in the polymerization system (toluene solution);
"content" refers to the molar content of comonomer or functional monomer in the resulting polymer chain.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A fluorescent polymer comprising a structural unit of formula (I), a structural unit of formula (II), and optionally a structural unit of formula (III):
Figure FDA0002755278390000011
wherein, in the formula (I), R1Is H or CH3(ii) a In the formula (II), R2Is selected from alkylene; in the formula (III), R3Is C2～C10Alkyl or C6～C10An aryl group is shown.
2. Fluorescent polymer according to claim 1, characterized in that in formula (I), R1Is H or CH3(ii) a In the formula (II), R2Is selected from C2～C6An alkylene group of (a); in the formula (III), R3Is C2～C6An alkyl group is shown.
3. The fluorescent polymer according to claim 1, wherein the molar content of the structural unit represented by formula (II) is 0.001-2% and the molar content of the structural unit represented by formula (III) is 0-4% based on 100% of the total molar amount of the structural unit represented by formula (I), the structural unit represented by formula (II) and the structural unit represented by formula (III).
4. A method for preparing the fluorescent polymer of any one of claims 1 to 3, comprising: copolymerizing a monomer shown in a formula (I '), a monomer shown in a formula (II ') and an optional monomer shown in a formula (III ') to obtain the fluorescent polymer;
Figure FDA0002755278390000021
wherein, in the formula (I'), R1Is H or CH3(ii) a In the formula (II'), R2Is selected from alkylene; in the formula (III'), R3Is C2～C10Alkyl or C6～C10Aryl is shown.
5. The process according to claim 4, wherein in formula (I'), R is1Is H or CH3(ii) a In thatIn the formula (II'), R2Is selected from C2～C6An alkylene group of (a); in the formula (III'), R3Is C2～C6An alkyl group is shown.
6. The process according to claim 5, wherein the monomer represented by the formula (I') is ethylene; and/or, the monomer shown in the formula (II') is selected from at least one of [1- (4-butenyloxyphenyl) -1,2, 2-triphenyl ] ethylene, [1- (4-hexenyloxyphenyl) -1,2, 2-triphenyl ] ethylene and [1- (4-octenyloxy phenyl) -1,2, 2-triphenyl ] ethylene; and/or the monomer shown in the formula (III') is selected from at least one of 1-butene, 1-hexene and 1-octene.
7. The method according to claim 4, wherein the copolymerization is carried out in the presence of at least one catalyst selected from the group consisting of a Ziegler-Natta catalyst, a metallocene catalyst and other single-site catalysts.
8. The preparation method according to any one of claims 4 to 7, wherein the copolymerization is carried out in the presence of a catalyst composition comprising a metallocene catalyst and alkylaluminoxane, wherein the molar ratio of the metallocene catalyst to Al in the alkylaluminoxane is 1 (50 to 20000).
9. The method of claim 8, wherein the concentration of the metallocene catalyst in the metallocene catalyst composition in the polymerization system is 1x10-8～1x10-3mol/L, preferably 1X10-7～1x10-4mol/L。
10. Use of the fluorescent polymer according to any one of claims 1 to 3 or the fluorescent polymer according to any one of claims 4 to 9 in a fluorescent material.
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