CN116622068A - Preparation and application of fluorescent polymer and high-elasticity flexible fluorescent composite fiber - Google Patents
Preparation and application of fluorescent polymer and high-elasticity flexible fluorescent composite fiber Download PDFInfo
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- CN116622068A CN116622068A CN202310567375.5A CN202310567375A CN116622068A CN 116622068 A CN116622068 A CN 116622068A CN 202310567375 A CN202310567375 A CN 202310567375A CN 116622068 A CN116622068 A CN 116622068A
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- fiber
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- electrostatic spinning
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- composite fiber
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- 239000000835 fiber Substances 0.000 title claims abstract description 76
- 229920001109 fluorescent polymer Polymers 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 15
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 10
- -1 ketone anhydride Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-methyl-PhOH Natural products CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 238000005253 cladding Methods 0.000 claims 2
- 210000004177 elastic tissue Anatomy 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 125000003717 m-cresyl group Chemical group [H]C1=C([H])C(O*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 229920002725 thermoplastic elastomer Polymers 0.000 claims 1
- 229920002397 thermoplastic olefin Polymers 0.000 claims 1
- 239000004416 thermosoftening plastic Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 13
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
- D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
- D02G3/328—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic containing elastane
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/12—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
- D10B2321/121—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain polystyrene
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
Abstract
The invention belongs to the technical field of fluorescent polymer materials, and particularly relates to a preparation method and application of a fluorescent polymer and high-elasticity flexible fluorescent composite fiber. The method takes two diamine monomers and a dianhydride monomer as raw materials, and synthesizes a fluorescent polymer through a one-step polycondensation method. The fluorescent polymer is prepared into an electrostatic spinning film by an electrostatic spinning method, then the electrostatic spinning film is coated on the surface of the thermoplastic polymer fiber by taking the thermoplastic polymer fiber as an inner core through a spray-compression rolling coating mode, and the flexible fluorescent composite fiber with high elasticity is prepared.
Description
Technical Field
The invention belongs to the technical field of fluorescent polymer materials, and particularly relates to a preparation method and application of a fluorescent polymer and high-elasticity flexible fluorescent composite fiber.
Background
The organic fluorescent material has good solution processability and relatively low cost, and has uniform chromophore distribution, stable content and good luminous performance, however, most traditional organic fluorophores can cause fluorescence quenching when aggregated, and are not beneficial to processing into solid-state devices. There is therefore a need for a method that avoids quenching of fluorescence of fluorescent materials due to molecular aggregation as much as possible.
Among fluorescent materials, fluorescent polymers have the advantages of light weight, high stretchability, good biocompatibility and the like, and have great potential in future applications. Therefore, enhancing the tensile properties of the flexible fluorescent fibers is an important aspect of further enhancing the properties of the luminescent fibers and thereby expanding the application area.
Disclosure of Invention
The invention aims at overcoming the defects, and provides a fluorescent polymer, a flexible fluorescent fiber, a preparation method and application thereof, wherein the fluorescent polymer has good solubility and emits orange light under ultraviolet light. The fluorescent fiber prepared from the fluorescent polymer also has good luminous performance.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a fluorescent polymer having a weight average molecular weight of 10.5 to 13.6 tens of thousands (the polymer having a molecular weight which is advantageous for the subsequent processing of the fiber), the fluorescent polymer having a structural formula:
the synthetic route of the fluorescent polymer is as follows:
further, the preparation method of the fluorescent polymer comprises the following steps:
under the protection of nitrogen, mixing two diamine monomers and a ketone anhydride monomer into an organic solvent, and stirring for 0.5-1 h at room temperature, so that the monomers are fully dissolved, and the reaction is ensured to be fully contacted;
adding a catalyst, raising the temperature to 195 ℃, and continuously reacting for 6-10 hours;
after the reaction is finished, pouring the reaction solution into 300-500 mL of absolute ethyl alcohol, filtering after sedimentation is finished, and washing with deionized water to obtain a target polymer; the resulting polymer was dried in vacuo at 100-150 ℃ for 10-15 h to ensure complete drying of the sample.
Preferably, the tetramethyldiamine monomer: 2, 6-dimethylaniline: the molar ratio of the ketone anhydride monomers is 2:8:10.
In order to obtain the high molecular polymer with the target molecular weight and meet the requirements of fiber preparation and spinnability, preferably, the dosage of the organic solvent is 4-10 times of the total mass of diamine monomer and ketone anhydride monomer, and the dosage of the catalyst is 1-4% of the mass of the organic solvent.
Preferably, the organic solvent is m-cresol; the catalyst is isoquinoline.
The fluorescent composite fiber comprises thermoplastic polymer fibers and an electrostatic spinning fiber film wrapped on the surfaces of the thermoplastic polymer fibers, and the preparation of the electrostatic spinning fiber film comprises the following steps: and dissolving the fluorescent polymer in an organic solvent to prepare an electrostatic spinning solution, and obtaining the electrostatic spinning fiber membrane through an electrostatic spinning method.
Preferably, the organic solvent is a mixture of two organic solvents, wherein one solvent is N, N-dimethyl
One of the formamide, the N, N-dimethylacetamide and the tetrahydrofuran, and the other solvent is one of ethanol, acetone, methylene dichloride and chloroform, wherein the volume ratio of one solvent to the other solvent is 9:1-7:3;
and/or the concentration of the electrostatic spinning solution is 15-25 wt%; and/or, the electrostatic spinning process parameters are as follows: the spinning voltage is 12-15 kV, the receiving distance is 15-25 cm, the spinning solution is 1-5 mL, the nozzle aperture is 0.5-1 mm, the advancing speed of the spinning solution is 1-5 mL/h, the room temperature and the relative humidity are 25-50%.
More preferably, the organic solvent is a mixed solvent of N, N-dimethylacetamide and ethanol, and the volume ratio is 9:1;
and/or the concentration of the electrostatic spinning solution is 18wt%.
And/or, the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, the receiving distance is 20cm, the spinning solution is 2mL, the nozzle aperture is 0.5mm, the advancing speed of the spinning solution is 1.5mL/h, and the room temperature and the relative humidity are 35%.
The preparation method of the flexible fluorescent composite fiber comprises the following steps:
cutting the electrostatic spinning fiber membrane into uniform size, taking the thermoplastic polymer fiber as an inner core, spraying a layer of adhesive on the surface of the thermoplastic polymer fiber in a spray-pressing mode, and then winding the cut electrostatic spinning fiber on the surface of the thermoplastic polymer fiber to prepare the fluorescent composite fiber. The invention adopts a spray-press winding mode to prepare the composite fiber, and solves the technical problem that the electrostatic spinning fiber yarn is too thin and has the phenomenon of falling off and floating yarn.
Preferably, the electrospun fibrous membrane is cut to a size of 20X 2cm.
Preferably, the adhesive is one of water-based polyacrylate, polyvinyl alcohol and organic silica gel adhesive; the viscosity of the adhesive is between 300 and 10000cps, more preferably the adhesive is polyvinyl alcohol.
Preferably, the spray-pressing method adopts a nozzle with the inner diameter of 0.4mm, the spray-pressing distance of 10cm, the spray-pressing speed of 5ml/min and the spray-pressing time of 1min.
Preferably, the diameter of the thermoplastic polyurethane fiber is one of 0.4-1 mm, the diameter of the fiber in the electrospun fiber membrane is 0.5-2 μm, and the thickness of the coating layer is 100-120 μm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a brand-new fluorescent polymer and a preparation method thereof, which adopt two diamine monomers and a ketone anhydride monomer for copolymerization, thereby improving the molecular weight of the polymer, promoting the spinnability of the polymer when preparing fibers, and expanding the application range of the polymer in processing solid devices. The introduced tetramethyldiamine monomer can increase the steric hindrance of the polymer structure and avoid fluorescence quenching caused by pyrene aggregation of the fluorescent polymer in a solid state.
(2) The preparation method of the flexible fluorescent composite fiber is simple to operate, and the thickness of the composite fiber coating layer can be effectively controlled by adjusting the size of the electrospun fiber membrane.
(3) The flexible fluorescent composite fiber has good stretchability and bending resistance, and has bright orange-yellow fluorescence under ultraviolet irradiation.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the fluorescent polymer prepared in example 1;
FIG. 2 is an SEM image of the composite fiber prepared in example 2;
FIG. 3 is a stress-strain diagram of the fluorescent composite fiber prepared in example 3;
FIG. 4 is a graph showing the comparison of daily light irradiation and ultraviolet light irradiation of fluorescent composite fibers under the complex weaving process described in FIG. 4.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings and specific examples.
The tetramethyldiamine monomers used in the examples below were prepared by reference to patent 202011492069.2.
2, 6-dimethylaniline and the ketone anhydride monomer are commercially available from TCI company.
Example 1
The present embodiment provides a fluorescent polymer having the following structural formula:
the synthetic route is as follows:
the preparation method comprises the following steps:
(1) Under the protection of nitrogen, adding 2mmol of tetramethyl diamine monomer, 8mmol of 2, 6-diaminotoluene and 10mmol of ketone anhydride monomer into m-cresol, and stirring for 0.5h at room temperature;
(2) Isoquinoline is added as a catalyst, the temperature is raised to 195 ℃ and the reaction is continued for 8 hours;
(3) After the reaction is finished, pouring the reaction solution into 400mL of absolute ethyl alcohol, filtering after sedimentation is finished, and washing with deionized water to obtain a target polymer; the resulting polymer was dried in vacuo at 120 ℃ for 12h to ensure complete drying of the sample.
FIG. 1 is a nuclear magnetic resonance spectrum of a prepared fluorescent polymer, and it can be observed that the integral value of each absorption peak of the synthesized polymer completely accords with the proton number in the designed structural formula, which indicates that the target polymer is successfully synthesized, and the fluorescence quantum yield reaches 24%.
Example 2
The embodiment provides a preparation method of an electrospun fiber membrane, which comprises the following steps:
1.0284g of the fluorescent polymer described in example 1 was weighed, mixed with 5mL of N, N-dimethylacetamide, and shaken until the polymer was sufficiently dissolved to prepare an 18wt% fluorescent polymer solution. And setting electrostatic spinning voltage at 12kV under the condition of room temperature and relative humidity of 25%, receiving the spinning solution at a distance of 20cm, sucking 2mL of the spinning solution, adjusting the nozzle aperture to 0.5mm, and receiving the spinning solution with aluminum foil paper at a spinning solution advancing speed of 1.5mL/h to obtain the electrostatic spinning fiber membrane.
Example 3
The embodiment provides a preparation method of a flexible fluorescent composite fiber, which comprises the following steps:
cutting the fiber membrane prepared in the example 2 into uniform size of 20 multiplied by 2cm, taking thermoplastic polyurethane fiber as an inner core, coating a layer of polyvinyl alcohol as an adhesive on the surface, and then winding the cut electrostatic spinning fiber on the surface of the thermoplastic polyurethane fiber to prepare the pyrene-containing polyimide/thermoplastic polyurethane composite fiber.
As shown in FIG. 2, the prepared composite fiber is uniformly coated, the average diameter of the electrospun fiber of the surface layer is about 500nm, the thickness is uniform, and beads hardly exist. As can be seen from FIG. 3, the prepared flexible fluorescent composite fiber has an elongation at break of 150.83% and a stress at break of 25.51MPa, and has very good tensile properties.
Example 4
This example provides the use of the flexible fluorescent composite fiber of example 3.
As shown in fig. 4, which is a comparative graph of the crimped state of the flexible fluorescent fiber and the fluorescent braided rope under the daily light irradiation and the ultraviolet light irradiation, it can be observed that the crimped fluorescent composite fiber and the fluorescent braided rope still have orange-yellow fluorescence under the ultraviolet light irradiation. The embodiment weaves the flexible fluorescent composite fiber and is applied to fabric anti-counterfeiting.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described, and these modifications and variations should also be considered as being within the scope of the invention.
Claims (10)
1. A fluorescent polymer characterized in that: the weight average molecular weight is 10.5-13.6 ten thousand, and the structural formula of the fluorescent polymer is as follows:
2. the method for preparing a fluorescent polymer according to claim 1, wherein: the synthetic route is as follows:
3. the method for producing a fluorescent polymer according to claim 2, wherein: the method comprises the following steps: under the protection of nitrogen, mixing tetramethyl diamine monomer, 2, 6-dimethyl aniline and ketone anhydride monomer into an organic solvent, and carrying out catalytic stirring reaction for 0.5-1 h at room temperature, wherein the catalyst is isoquinoline, the dosage of the organic solvent is 4-10 times of the total mass of the diamine monomer and the ketone anhydride monomer, and the dosage of the catalyst is 1-4% of the mass of the organic solvent.
4. A method of preparing a fluorescent polymer according to claim 3, wherein: the organic solvent is m-cresol.
5. A high-elasticity flexible fluorescent composite fiber is characterized in that: comprises thermoplastic polymer fibers and an electrostatic spinning fiber membrane wrapped on the surfaces of the thermoplastic polymer fibers; the preparation of the electrospun fiber membrane comprises the following steps: dissolving the fluorescent polymer of claim 1 in an organic solvent to prepare an electrostatic spinning solution, and obtaining an electrostatic spinning fiber membrane by an electrostatic spinning method; the thermoplastic polymer fiber is any one of styrene thermoplastic elastomer fiber, thermoplastic polyurethane fiber, thermoplastic polyolefin elastic fiber and thermoplastic polyester elastic fiber.
6. The high elasticity flexible fluorescent composite fiber according to claim 5, wherein: the organic solvent is a mixture of two organic solvents, wherein one solvent is one of N, N-dimethylformamide, N, N-dimethylacetamide and tetrahydrofuran, the other solvent is one of ethanol, acetone, dichloromethane and chloroform, and the volume ratio of one solvent to the other solvent is 9:1-7:3;
and/or the concentration of the electrostatic spinning solution is 15-25 wt%; and/or, the electrostatic spinning process parameters are as follows: the spinning voltage is 12-15 kV, the receiving distance is 15-25 cm, the spinning solution is 1-5 mL, the nozzle aperture is 0.5-1 mm, the advancing speed of the spinning solution is 1-5 mL/h, the room temperature and the relative humidity are 25-50%.
7. The high elasticity flexible fluorescent composite fiber according to claim 5, wherein: the organic solvent is a mixed solvent of N, N-dimethylacetamide and ethanol, and the volume ratio is 9:1;
and/or the concentration of the electrostatic spinning solution is 18wt%;
and/or, the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, the receiving distance is 20cm, the spinning solution is 2mL, the nozzle aperture is 0.5mm, the advancing speed of the spinning solution is 1.5mL/h, and the room temperature and the relative humidity are 35%.
8. The method for producing a highly elastic flexible fluorescent composite fiber according to any one of claims 5 to 7, comprising the steps of: cutting the electrostatic spinning fiber membrane into uniform size, taking the thermoplastic polymer fiber as an inner core, spraying a layer of adhesive on the surface of the thermoplastic polymer fiber in a spray-pressing mode, and then winding the cut electrostatic spinning fiber on the surface of the thermoplastic polymer fiber to prepare the high-elasticity flexible fluorescent composite fiber.
9. The method for preparing the high-elasticity flexible fluorescent composite fiber as claimed in claim 7, wherein,
the adhesive is any one of water-based polyacrylate, polyvinyl alcohol and organic silica gel adhesive; the viscosity of the adhesive is 300-10000 cps;
and/or the spray pressure method adopts a nozzle with the inner diameter of 0.4-1 mm, the spray pressure distance of 5-20 cm, the spray pressure speed of 5-10 ml/min and the spray pressure time of 0.5-1.5 min;
and/or the diameter of the thermoplastic polymer fiber of the inner core is 0.4-1 mm, the diameter of the cladding fiber is 0.5-2 mu m, and the thickness of the cladding layer is 50-120 mu m.
10. The method for preparing the high-elasticity flexible fluorescent composite fiber according to claim 7, wherein the spray-pressing method adopts a nozzle with an inner diameter of 0.4mm, a spray-pressing distance of 10cm, a spray-pressing speed of 5ml/min and a spray-pressing time of 1min, and the adhesive is polyvinyl alcohol.
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