CN114437272B - Fluorescent polymer and preparation method and application thereof - Google Patents
Fluorescent polymer and preparation method and application thereof Download PDFInfo
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- CN114437272B CN114437272B CN202011201469.3A CN202011201469A CN114437272B CN 114437272 B CN114437272 B CN 114437272B CN 202011201469 A CN202011201469 A CN 202011201469A CN 114437272 B CN114437272 B CN 114437272B
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Abstract
The invention discloses a fluorescent polymer which comprises 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
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. The polyolefin fluorescent material is mainly prepared by blending, grafting and other methods at present.
Chinese patent CN107384369a discloses a polyolefin/rare earth complex/carbonate composite fluorescent material, which is prepared by first preparing rare earth complex/carbonate complex, then mixing with polyolefin solution, stirring, finally filtering, and drying.
Chinese patent CN104387534A irradiates polyethylene with beta rays, then grafts N-allyl-4-methoxy-1, 8-naphthalimide functional monomer onto the pretreated polyethylene to obtain fluorescent polyethylene resin, which can be used for preparing light conversion films.
The Chinese patent CN108395607A prepares fluorescent resin by blending thermoplastic resin such as polyolefin and maleic anhydride copolymer, and the obtained ultraviolet light-to-blue light resin can be used for preparing light-to-agricultural film.
In the prior art, the preparation process and the resin composition of the polyolefin fluorescent material are complex, so that 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, a preparation method and application thereof, wherein a tetraphenyl vinyl side chain is introduced into the fluorescent polymer, and the fluorescent polymer is endowed with fluorescent characteristics.
It is an object of the present invention 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):
wherein in formula (I), R 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II), R 2 Selected from alkylene groups; in formula (III), R 3 Is C 2 ～C 10 Alkyl or C as shown 6 ～C 10 Aryl is shown.
In a preferred embodiment, in formula (I), R 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II), R 2 Selected from C 2 ～C 6 Alkylene (e.g., ethylene, butylene, hexylene); in formula (III), R 3 Is C 2 ～C 6 Alkyl groups are shown.
In a preferred embodiment, in the fluorescent polymer, the molar content of the structural unit represented by formula (II) is 0.001 to 2% and the molar content of the structural unit represented by formula (III) is 0 to 4% based on 100% of the total molar amounts 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, in the fluorescent polymer, the molar content of the structural unit represented by formula (II) is 0.01 to 1% and the molar content of the structural unit represented by formula (III) is 0 to 3% based on 100% of the total molar amounts of the structural unit represented by formula (I), the structural unit represented by formula (II) and the structural unit represented by formula (III).
The second object of the present invention is to provide a method for preparing the fluorescent polymer according to one of the objects of the present invention, comprising: the fluorescent polymer is obtained by copolymerizing a monomer shown in a formula (I '), a monomer shown in a formula (II ') and optionally a monomer shown in a formula (III ').
Wherein in formula (I'), R 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II'), R 2 Selected from alkylene groups; in formula (III'), R 3 Is C 2 ～C 10 Alkyl or C as shown 6 ～C 10 Aryl is shown.
In a preferred embodiment, in formula (I'), R 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II'), R 2 Selected from C 2 ～C 6 An alkylene group of (a); in formula (III'), R 3 Is C 2 ～C 6 Alkyl groups are shown.
In a further preferred embodiment, the monomer of formula (I') is ethylene; and/or the monomer shown in the formula (II') is at least one of [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] ethylene, [1- (4-hexenyloxyphenyl) -1, 2-triphenyl ] ethylene and [1- (4-octenyloxyphenyl) -1, 2-triphenyl ] ethylene; and/or the monomer shown in the formula (III') is at least one selected from 1-butene, 1-hexene and 1-octene.
In a preferred embodiment, the concentration of the monomer of formula (II') in the polymerization system is 1X10 -4 ～1x10 -1 The concentration of the monomer represented by the formula (III') in the polymerization system is 0 to 2mol/L.
In a further preferred embodiment, the concentration of the monomer of formula (II') in the polymerization system is 1X10 -3 ～1x10 -2 The concentration of the monomer represented by the formula (III') in the polymerization system is 0 to 1mol/L.
In a preferred embodiment, the copolymerization is carried out in the presence of at least one catalyst selected from the group consisting of Ziegler-Natta catalysts, metallocene catalysts, and other single-site catalysts.
In the present invention, the copolymerization may be performed 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 alkylaluminoxane.
Wherein a metal active center, such as Ti, hf or Zr, is contained in the metallocene catalyst. The metallocene catalyst contains at least one of cyclopentadienyl and/or derivatives thereof, indenyl and/or derivatives thereof, 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 catalyst disclosed in the prior art. The metallocene catalyst can be purchased directly or prepared by itself using methods disclosed in the prior art.
In a preferred embodiment, the alkylaluminoxane has a structure according to formula (V) and/or formula (VI):
in the formula (V) and the formula (VI), R is selected from alkanesRadicals, preferably C 1 ～C 15 More preferably C 1 ～C 5 Alkyl groups of (2), such as methyl; n is an integer of 4 to 30, preferably 10 to 30.
In a preferred embodiment, the molar ratio of the metallocene catalyst to Al in the alkylaluminoxane is 1 (50 to 20000), preferably 1 (200 to 10000), more preferably 1 (200 to 3000).
In a preferred embodiment, the pressure of the monomer of formula (I') is from 0.05 to 5MPa, preferably from 0.1 to 3MPa.
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 metallocene catalyst composition has a concentration of the metallocene catalyst in the polymerization system of 1x10 -8 Molar/liter-1 x10 -3 Moles/liter, preferably 1X10 -7 Molar/liter-1 x10 -4 Moles/liter.
The reason for using the metallocene catalyst to catalyze coordination polymerization in the present invention is that: the metallocene catalyst has better copolymerization performance, can utilize comonomer to the greatest extent, and the obtained copolymer has more uniform comonomer distribution, and the obtained copolymer is a linear polymer and has good mechanical properties.
The third object of the present invention is to provide the use of the fluorescent polymer according to one of the objects of the present invention or the fluorescent polymer obtained by the two preparation methods according to the second object of the present invention in a fluorescent material.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give 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 excitation light wavelength, and the bottom coordinate is the emission light wavelength, and it can be seen from the spectrum that the olefin polymer mainly converts ultraviolet light with the wavelength of 300-400nm into 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 a fluorescent effect.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are 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, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly 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.
And (3) a cocatalyst: methyl aluminoxane toluene solution, 1.4mol/L.
Functional monomer: [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] ethylene, [1- (4-hexenoyloxy phenyl) -1, 2-triphenyl ] ethylene, [1- (4-octenoyloxy phenyl) -1, 2-triphenyl ] ethylene was prepared into toluene solutions of 0.1mol/L, respectively.
The fluorescence phenomenon of the polymer is observed by using an ultraviolet lamp, and a polymer sample is irradiated under ultraviolet light with the wavelength of 365nm, so that blue-green fluorescence is observed, and the polymer has light conversion performance.
The fluorescence spectrum data were measured using a JY FL3 fluorescence spectrometer from Horiba company, using a 450W xenon lamp light source, excitation wavelength range of 250nm-650nm, and emission spectrum wavelength range of 300nm-1000nm.
[ example 1 ]
The polymerization reactor was purged with nitrogen, then replaced with ethylene, thermostated to 30 ℃, 39.0mL of toluene, 5.0mL of methylaluminoxane toluene solution, 5.0mL of functional monomer [1- (4-hexenyloxyphenyl) -1, 2-triphenyl ] vinyltoluene solution were respectively added, stirred for 10 minutes, the ethylene pressure was maintained at 0.1MPa, 1.0mL of metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the ethylene pressure was maintained constant during the polymerization, after completion of the polymerization, the reactant was precipitated with an excessive amount of hydrochloric acid ethanol, filtered to obtain a white solid powder, then the obtained polymer was added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene to remove unreacted functional monomer, and finally, after washing with ethanol and water sufficiently, vacuum-dried, 0.42g of 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 2 ]
The polymerization reactor was purged with nitrogen, then replaced with ethylene, thermostated to 50 ℃, 39.0mL of toluene, 5.0mL of methylaluminoxane toluene solution, 5.0mL of functional monomer [1- (4-hexenyloxyphenyl) -1, 2-triphenyl ] vinyltoluene solution were respectively added, stirred for 10 minutes, the ethylene pressure was maintained at 0.1MPa, 1.0mL of metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the ethylene pressure was maintained constant during the polymerization, after completion of the polymerization, the reactant was precipitated with an excessive amount of hydrochloric acid ethanol, filtered to obtain a white solid powder, then the obtained polymer was added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene to remove unreacted functional monomer, and finally, after washing with ethanol and water sufficiently, vacuum-dried, 0.72g of 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 3 ]
The polymerization reactor was purged with nitrogen, then replaced with ethylene, thermostated to 30 ℃, 45.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 1mL of functional monomer [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] vinyltoluene solution were respectively added, stirred for 10 minutes, the ethylene pressure was maintained at 0.1MPa, 1.0mL of metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the ethylene pressure was maintained constant during the polymerization, after completion of the polymerization, the reactant was precipitated with an excessive amount of ethanol hydrochloride, filtered to obtain a white solid powder, then the obtained polymer was added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene to remove unreacted functional monomer, and finally sufficiently washed with ethanol and water, and then vacuum-dried to obtain 0.50g of 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 ]
The polymerization reactor was purged with nitrogen, then replaced with ethylene, thermostated to 30 ℃, 36.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 10mL of functional monomer [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] vinyltoluene solution were respectively added, stirred for 10 minutes, the ethylene pressure was maintained at 0.1MPa, 1.0mL of metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the ethylene pressure was maintained constant during the polymerization, after completion of the polymerization, the reactant was precipitated with an excessive amount of ethanol hydrochloride, filtered to obtain a white solid powder, then the obtained polymer was added to toluene, stirred at room temperature, then filtered and washed with a large amount of toluene to remove unreacted functional monomer, and finally sufficiently washed with ethanol and water, and then vacuum-dried to obtain 0.72g of 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 ]
The polymerization reactor was purged with nitrogen, then replaced with ethylene, thermostated to 30 ℃, 42.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 2mL of functional monomer [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] vinyltoluene solution, 1mL of comonomer 1-hexene were respectively added, stirred for 10 minutes, the ethylene pressure was kept at 0.1MPa, 1.0mL of metallocene catalyst solution was added, polymerization was started, the ethylene pressure was kept constant during the polymerization for 10 minutes, after the completion of the polymerization, the reactant was precipitated with an excessive amount of ethanol hydrochloride, filtered to obtain a white solid powder, then the obtained polymer was added to toluene, stirred at room temperature, filtered and washed with a large amount of toluene to remove unreacted functional monomer, and finally sufficiently washed with ethanol and water, and then vacuum-dried to obtain 1.32g of 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 6 ]
The polymerization reactor was purged with nitrogen, then replaced with ethylene, thermostated to 30 ℃, 43.0mL of toluene, 2.5mL of methylaluminoxane toluene solution, 2mL of functional monomer [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] vinyltoluene solution, 0.5mL of comonomer 1-octene were respectively added, stirred for 10 minutes, the ethylene pressure was maintained at 0.1MPa, 1.0mL of metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the ethylene pressure was maintained constant during the polymerization, after the completion of the polymerization, the reactant was precipitated with an excessive amount of ethanol hydrochloride, filtered to obtain a white solid powder, then the obtained polymer was added to toluene, stirred at room temperature, filtered and washed with a large amount of toluene to remove unreacted functional monomer, finally washed with ethanol and water, and then dried in vacuo to obtain 1.29g of 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 7 ]
The polymerization reactor was purged with nitrogen, then replaced with ethylene, thermostated to 30 ℃, 40.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 2mL of functional monomer [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] vinyltoluene solution, 4.0mL of comonomer 1-hexene were respectively added, stirred for 10 minutes, the ethylene pressure was kept at 0.1MPa, 1.0mL of metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the ethylene pressure was kept constant during polymerization, after the completion of polymerization, the reactant was precipitated with an excessive amount of ethanol hydrochloride, filtered to obtain a white solid powder, then the obtained polymer was added to toluene, stirred at room temperature, filtered and washed with a large amount of toluene to remove unreacted functional monomer, finally washed with ethanol and water, and then dried in vacuo to obtain 0.93g of 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 8 ]
The polymerization reactor was purged with nitrogen, then replaced with propylene, thermostated to 30 ℃, 45.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 1.0mL of a functional monomer [1- (4-octenoxyphenyl) -1, 2-triphenyl ] ethylene toluene solution were respectively added, stirred for 10 minutes, the propylene pressure was kept at 0.1MPa, 1.0mL of a metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the propylene pressure was kept constant during polymerization, after completion of the polymerization, the reactant was precipitated with an excessive amount of hydrochloric acid ethanol, filtered to obtain a white solid powder, then the obtained polymer was 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 with ethanol and water sufficiently, vacuum drying was carried out to obtain 0.33g of a propylene copolymer. The prepared propylene copolymer was observed under ultraviolet rays with a wavelength of 365nm, and the copolymer emitted significant blue-green fluorescence.
[ example 9 ]
The polymerization reactor was purged with nitrogen, then replaced with propylene, thermostated to 30 ℃, 44.5mL of toluene, 2.5mL of methylaluminoxane toluene solution, 2.0mL of a functional monomer [1- (4-octenoxyphenyl) -1, 2-triphenyl ] ethylene toluene solution were respectively added, stirred for 10 minutes, the propylene pressure was kept at 0.1MPa, 1.0mL of a metallocene catalyst solution was added, polymerization was started, polymerization was carried out for 10 minutes, the propylene pressure was kept constant during polymerization, after completion of the polymerization, the reactant was precipitated with an excessive amount of ethanol hydrochloride, filtered to obtain a white solid powder, then the obtained polymer was 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 with ethanol and water sufficiently, vacuum drying was carried out to obtain 0.37g of a propylene copolymer. The prepared propylene copolymer was observed under ultraviolet rays with a wavelength of 365nm, and the copolymer emitted significant blue-green fluorescence.
Comparative example 1
The method comprises the steps of purging a polymerization reactor with nitrogen, replacing nitrogen with ethylene, keeping the temperature to 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 reaction gas pressure constant in the polymerization process, stopping introducing ethylene, ending the polymerization reaction, introducing a small amount of air to deactivate the catalyst, adding 10mL of [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] ethylene functional monomer solution, continuously stirring for 10 minutes, precipitating the reactant with excessive ethanol hydrochloride, 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, washing with ethanol and water fully, and then drying in vacuum to obtain the ethylene polymer. The ethylene copolymer prepared was observed under ultraviolet rays having a wavelength of 365nm, and the copolymer was not fluorescent.
Oxyphenyl) -1, 2-triphenylethylene
In table 1:
functional monomer: a: [1- (4-butenoxyphenyl) -1, 2-triphenyl ] ethylene, B: [1- (4-hexenoxyphenyl) -1, 2-triphenyl ] ethylene, C: [1- (4-octenoxyphenyl) -1, 2-triphenyl ] ethylene;
"concentration" refers to the initial concentration of comonomer or functional monomer in the polymerization reaction 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 in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art 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, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (11)
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):
wherein in formula (I), R 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II), R 2 Selected from alkylene groups; in formula (III), R 3 Is C 2 ～C 10 Alkyl or C as shown 6 ～C 10 Aryl is shown.
2. The fluorescent polymer according to claim 1, whereinIn the formula (I), R is 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II), R 2 Selected from C 2 ～C 6 An alkylene group of (a); in formula (III), R 3 Is C 2 ～C 6 Alkyl groups are shown.
3. The fluorescent polymer according to claim 1, wherein the molar content of the structural unit represented by the formula (II) is 0.001 to 2% and the molar content of the structural unit represented by the formula (III) is 0 to 4% based on 100% of the total molar amounts 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).
4. A method of 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;
wherein in formula (I'), R 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II'), R 2 Selected from alkylene groups; in formula (III'), R 3 Is C 2 ～C 10 Alkyl or C as shown 6 ～C 10 Aryl is shown.
5. The process according to claim 4, wherein R in the formula (I') 1 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the In formula (II'), R 2 Selected from C 2 ～C 6 An alkylene group of (a); in formula (III'), R 3 Is C 2 ～C 6 Alkyl groups are shown.
6. The process according to claim 5, wherein the monomer of formula (I') is ethylene; and/or the monomer shown in the formula (II') is at least one of [1- (4-butenyloxy phenyl) -1, 2-triphenyl ] ethylene, [1- (4-hexenyloxyphenyl) -1, 2-triphenyl ] ethylene and [1- (4-octenyloxyphenyl) -1, 2-triphenyl ] ethylene; and/or the monomer shown in the formula (III') is at least one selected from 1-butene, 1-hexene and 1-octene.
7. The process of claim 4 wherein the copolymerization is carried out in the presence of at least one of Ziegler-Natta, metallocene and other single-site catalysts.
8. The process 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 an alkylaluminoxane, wherein the molar ratio of the metallocene catalyst to Al in the alkylaluminoxane is 1 (50 to 20000).
9. The process of claim 8, wherein the metallocene catalyst composition has a concentration of 1x10 in the polymerization system -8 ～1x10 -3 mol/L。
10. The process according to claim 9, wherein the metallocene catalyst composition has a concentration of 1x10 in the polymerization system -7 ～1x10 -4 mol/L。
11. Use of a fluorescent polymer according to any one of claims 1 to 3 or obtained by a method according to any one of claims 4 to 10 in a fluorescent material.
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|---|---|---|---|---|
| CN105777981A (en) * | 2016-03-15 | 2016-07-20 | 常州大学 | Preparation method of pH response fluorescent polymer |
| CN108517023A (en) * | 2017-12-19 | 2018-09-11 | 湖南科技大学 | It is a kind of can the hypochlorous polymer nano-particle of ratio fluoroscopic examination preparation and application |
| WO2020196695A1 (en) * | 2019-03-26 | 2020-10-01 | 積水化学工業株式会社 | Shrinking fluorescent gel, analyte concentration measurement method, testing kit, and testing device |
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2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777981A (en) * | 2016-03-15 | 2016-07-20 | 常州大学 | Preparation method of pH response fluorescent polymer |
| CN108517023A (en) * | 2017-12-19 | 2018-09-11 | 湖南科技大学 | It is a kind of can the hypochlorous polymer nano-particle of ratio fluoroscopic examination preparation and application |
| WO2020196695A1 (en) * | 2019-03-26 | 2020-10-01 | 積水化学工業株式会社 | Shrinking fluorescent gel, analyte concentration measurement method, testing kit, and testing device |
Non-Patent Citations (1)
| Title |
|---|
| Xuejing Liu,等.Facile construction of a hyperbranched poly(acrylamide) bearing tetraphenylethene units: a novel fluorescence probe with a highly selective and sensitive response to Zn2+.《Royal society of chemistry》.2018,(第第8期期),第5776–5783页. * |
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