CN110527018A - A kind of double transmitting fluorescent polymers of indigo plant feux rouges and its fluorescent fiber and preparation method and application - Google Patents
A kind of double transmitting fluorescent polymers of indigo plant feux rouges and its fluorescent fiber and preparation method and application Download PDFInfo
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- CN110527018A CN110527018A CN201810505618.1A CN201810505618A CN110527018A CN 110527018 A CN110527018 A CN 110527018A CN 201810505618 A CN201810505618 A CN 201810505618A CN 110527018 A CN110527018 A CN 110527018A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
Abstract
The present invention relates to the double transmitting fluorescent polymers of blue feux rouges and preparation method and applications.The fluorescent polymer is that copolymer-maleic anhydride is added after metal hydroxides sufficiently reacts after organic solvent dissolves to obtain.When the excites scope of the fluorescent polymer is in 330~450nm, transmitting range is in 400~520nm；When excites scope is in 330~600nm, transmitting range is in 575~785nm.When the fluorescence excites scope of its solution is in 330~450nm, transmitting range is in 380~530nm；When excites scope is in 360~600nm, transmitting range is in 560~740nm.Fluorescent polymer of the invention can prepare the double transmitting fluorescent fibers of blue feux rouges, fluorescence intensity is high, production cost is low, simple production process is mature, industrial production easy to accomplish, can be applied in the fields such as anti-fake, bio-imaging, conversion film, solar cell sealing glue, fluorescent dye.
Description
Technical field
The present invention relates to technical field of polymer materials, furtherly, be related to the double transmitting fluorescent polymer of blue feux rouges and
Preparation method and a series of applications.
Background technique
Fluorescence is a kind of luminescence generated by light phenomenon, when substance is by certain wavelength incident light (usually ultraviolet light or X-ray)
Irradiation wait, absorb luminous energy and enter excitation state, energy level transition occurs for internal electron, to issue the outgoing lower than incident laser energy
Light.Fluorescent material can substantially be divided into inorganic and organic fluorescence materials, and organic fluorescence materials are due to its special photophysical property
And solar battery, agricultural conversion film, bio-imaging, in terms of extensive use and receive significant attention.
Common organic fluorescence materials contain pi-conjugated phenyl ring or heterocycle as illuminophore, and this kind of material is often quenched with aggregation inducing
It goes out or aggregation-induced emission effect, and its complicated synthesis step, low water solubility and biocompatibility hinder theirs
Practical application.In addition, traditional organic fluorescence materials cause these materials to have often with the unsaturated conjugated structure such as phenyl ring
Certain potential bio-toxicity.Therefore, application of the solid state fluorescent material of novel environment friendly for extension organic fluorescence materials is developed
It has a very important significance.
In recent years, more and more organic fluorescence materials without containing Conventional luminescent group are reported by researcher, this kind of material
Material is usually non-conjugated polymeric object.The study found that a series of, with lone pair electrons, (such as nitrogen, oxygen, sulphur, phosphorus, unsaturated carbon carbon are double
Key, carbon-to-nitrogen double bon etc.) non-conjugated fluorescent polymer in the capable of emitting stronger fluorescence of state of aggregation, and by being crosslinked, carbonizing, contract
The methods of poly-, physics aggregation, can be such that the fluorescence intensity of these non-conjugated polymeric objects further increases, representative material has poly-
Acyl ammonia amine, polyvinyl alcohol, polyvinylpyrrolidone, copolymer-maleic anhydride etc..This kind of material, which has, prepares simple, strand
The advantages that flexible big, stable structure, good hydrophilic property, high biocompatibility.Researcher constantly explores this kind of non-conjugated glimmering
Application of the luminescent material in every field such as chemical sensitisation, bio-imaging, electroluminescent.
Patent 201711042409.X has invented a kind of non-conjugated fluorescent polymer of high intensity, but can only issue blue
Fluorescence；A kind of 201711034920.5 invention of patent feux rouges non-conjugated fluorescent polymer, but its fluorescence intensity is lower, and needs
Red-light-emitting polymer can be just transformed by being heat-treated, in this way since will increase cost and operating procedure；Patent
201711039918.7 inventions are a kind of can be with blue light, the compositions of the double transmittings of feux rouges, but needs to be heat-treated and feux rouges just can be obtained
Polymer, and double transmittings are generated by two kinds of materials, and not being able to achieve a kind of material has pair emitting performances.
Up to the present, compared with traditional conjugation fluorescent polymer, non-conjugated fluorescent polymer usually only emits blue light,
Only few polymer emission green light and feux rouges, the quantum yield of this kind of material is usually all very low, and has double transmittings
Non-conjugated fluorescent polymer has not been reported, thus develop have high fluorescent, transmitting feux rouges and it is double be launched in it is integrated novel
Non-conjugated fluorescent polymer and its production procedure will have market value of crucial importance and economic significance.
Summary of the invention
Bio-toxicity and industrial application difficulty and non-conjugated fluorescence for organic fluorescence reagent in the prior art is poly-
Close object be difficult to emit feux rouges, a kind of material cannot double transmitting fluorescence the problems such as, the present invention proposes a kind of there is high fluorescent, indigo plant
The novel non-conjugated fluorescent polymer and its preparation method and application of the double transmittings of feux rouges.High fluorescent proposed by the present invention, indigo plant
Feux rouges is double to emit novel non-conjugated fluorescent polymers, and the reagent price in raw material and technique is cheap, mature production technology, environment
Pollution is low.High fluorescent of the invention, the novel non-conjugated fluorescent polymer preparation methods of the double transmittings of blue feux rouges are simply easy
Row, application form multiplicity, easily progress industrialization promotion, thus there is boundless application prospect.
One of the object of the invention is to provide a kind of double transmitting fluorescent polymers of blue feux rouges.
The double transmitting fluorescent polymers of indigo plant feux rouges of the present invention, structure representation is as shown in logical formula (I):
Wherein, x, y and z are natural number, x >=1, y+z >=0.
Its fluorescent characteristics is that blue emission range is 400~520nm, and red emission range is 575~785nm.
Further,
The group R1、R2、R4、R5For the group containing at least one of following functional group: ketone group, ester group, amido, benzene
At least one of base, metal ion, preferably ketone group, unitary alkali metal ion, more preferable CH3COCH2C(CH3)2, CH3COC
(CH3)2CH2, CH3COCH2CH2, at least one of unitary alkali metal ion.The group R1、R2、R4、R5In it is identical and
It is not identical to be not particularly limited, it can be different from, can also be more than two identical or even all identical, but group R1、R2、
R4、R5In at least one be metal ion, preferably up to there are three being metal ion, i.e., preferably at least have one not for metal
Ion.
The group R3、R6At least one selected from following group: hydroxyl, alkyl, ester group, preferably hydroxyl, CH3COO-、
CH3CH2COO-、CH3CH2CH2At least one of COO-.
In the logical formula (I), at least one in preferably y and z is 0；More preferable y=z=0.
Fluorescent polymer of the present invention, it is characterized in that copolymer-maleic anhydride is added after organic solvent dissolves
Metal hydroxides obtains after sufficiently reacting.
The second object of the present invention is to providing the preparation method of the double transmitting fluorescent polymers of the blue feux rouges.
The preparation method of the double transmitting fluorescent polymers of indigo plant feux rouges of the present invention, it may include pass through copolymer-maleic anhydride
The dissolution of the first organic solvent is crossed, and metal hydroxides is added and sufficiently reacts；The first organic solvent and drying are removed later, or are added
Entering the second organic solvent makes the double transmitting fluorescent polymers of the blue feux rouges be precipitated out and dry.
Specifically it can comprise the following steps that
Step 1: taking copolymer-maleic anhydride, the first organic solvent is added and is sufficiently dissolved, maleic anhydride is obtained
The solution of object；Wherein, the weight ratio range of copolymer-maleic anhydride and organic solvent is (5~30): 100, preferably (10~
20):100；The production of modified product can be improved in the proportional region of the specific copolymer-maleic anhydride of this step and organic solvent
Amount, also saves the use of organic solvent, to reduce cost.
Step 2: metal hydroxides is taken to be added in the copolymer-maleic anhydride solution that step 1 obtains, give simultaneously
Stirring sufficiently obtains the solution of the double transmitting fluorescent polymers of blue feux rouges after reaction；The copolymer-maleic anhydride and gold
Belonging to hydroxide can be arbitrary proportion in principle；Preferably, the metal hydroxides and the copolymer-maleic anhydride
Weight ratio range is (5~20): 100, preferably (5~15): 100.In the ratio of metal hydroxides and copolymer-maleic anhydride
In example range, the synergistic effect being both able to achieve between copolymer-maleic anhydride, metal hydroxides and acetone, while saving raw material
Cost.
Step 3: it is red that the solution of the double transmitting fluorescent polymers of indigo plant feux rouges made from step 2 is dried to obtain the indigo plant
The solid of the double transmitting fluorescent polymers of light；
Or the second organic solvent, which is added, makes the blue feux rouges is double to emit fluorescent polymer Precipitations, is dried to obtain institute
State the solid of the double transmitting fluorescent polymers of blue feux rouges；The polarity of second organic solvent is less than the first organic solvent.
Further,
Copolymer-maleic anhydride described in step 1 can be selected from existing copolymer-maleic anhydride in the prior art, preferably select
Autohemagglutination maleic anhydride/vinyl ester copolymer.More preferable polymaleic anhydride-vinyl acetate co-polymer, it may include polymaleic anhydride-
Vinylacetate linear alternated copolymer, polymaleic anhydride-vinylacetate are crosslinked alternate copolymer.
In general, the copolymer-maleic anhydride can be linear structure, or cross-linked structure, for example pass through
In the cross-linked structure that crosslinking agent realization is wherein added.Existing method in the prior art can be used in the copolymer-maleic anhydride
Self-control.It is preferred that CN1618826A (Chinese patent ZL200310115329.4) and (the Chinese patent Shen CN101338007A can be passed through
It please 200810118553.1) the middle method preparation proposed.
Organic solvent described in step 1, which is selected from, can dissolve the organic solvent of copolymer-maleic anhydride i.e. in the prior art
Can, at least one of preferably following solvent: acetone, butanone, 2 pentanone, propione, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, two
Pyruvic alcohol, benzyl alcohol, Ethyl formate, ethyl acetate, ethylenediamine, triethylamine, tetrahydrofuran, dimethyl sulfoxide preferably are selected from following
At least one of solvent: acetone, butanone, diacetone alcohol, ethyl acetate, triethylamine；More preferably from at least one of following solvent:
Acetone, diacetone alcohol.Solvent using diacetone alcohol as copolymer-maleic anhydride can shorten the reaction time, improve product conversion
The fluorescent polymer luminous intensity of rate, preparation is higher.It is most preferably diacetone alcohol in organic solvent described in step 1.
Metal hydroxides described in step 2 is selected from at least one of preferred unitary alkali metal hydroxide, preferably is selected from hydrogen
At least one of lithia, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, hydroxide francium, more preferably from hydrogen-oxygen
Change at least one of lithium, sodium hydroxide, potassium hydroxide.
The metal hydroxide solids are added to the copolymer-maleic anhydride first of step 1 preparation by step 2
In organic solution, and stirred.In whipping process, open loop and gold occur for the maleic anhydride in the copolymer-maleic anhydride
Belong to hydroxide and acid-base neutralization reaction occurs, when organic solvent is that alcohols or organic solvent generate under metal hydroxide catalysis
When alcohol, with alcohol esterification can occur for the maleic anhydride in the copolymer-maleic anhydride；Meanwhile original and newly-generated secondary
Self assembly aggregation can occur during the reaction for fluorogen (such as C=O, C-O), pass through spatial conjugation between newly-generated group
Form chromophore；Part maleic acid anhydro ring in Polymer Formulation of the invention is reacted with highly basic, remaining Malaysia
Acid anhydrides generate volume it is bigger, with the group that can more become fluorogen, so just form with the double transmittings of blue feux rouges
Non-conjugated fluorophore aggregation body, and then finally obtain the double transmitting fluorescent polymers of the blue feux rouges with high fluorescent.It is resulting
The group R of fluorescent polymer1、R2、R4And R5Even have for maleic anhydride open loop and metal hydroxides, organic solvent molecule
The group that solvent is reacted again with metal hydroxides reaction product.
In this step, maleic anhydride open loop in the copolymer-maleic anhydride and react slower with alcohol, it is therefore desirable to one
The fixed reaction time reacts it sufficiently.Reaction time described in step 2 is preferably 0.5~48 hour, and more preferable 2~36 hours,
Most preferably 4~24 hours；It can stop stirring after the reaction time to be achieved.
Reaction temperature described in step 2 and reaction pressure are not particularly limited, and reaction temperature is preferably made in step 1
With between the fusing point and boiling point of organic solvent, more preferable room temperature, the preferred normal pressure of reaction pressure；Equipment used in reacting does not have yet
The existing equipment of solution reaction in current techniques can be used in especially limitation.
In the step of preparation method of the present invention three, when the first organic solvent has strong volatility, it can be used existing
Common evaporation method removes organic solvent in technology, for example utilizes low-temperature treatment, and temperature and time is not particularly limited, and leads to
It often handles 8~48 hours, while can also be stirred at 20~60 DEG C.
In the step of preparation method of the present invention three, when the first organic solvent boiling point is higher, it is organic that second can be added
Solvent is precipitated out the double transmitting fluorescent polymers of the blue feux rouges, and the second organic solvent of the addition is selected from pentane, stone
At least one of oily ether, hexane, octane, heptane, carbon tetrachloride, toluene, dimethylbenzene, chloroform, methylene chloride, ether；
Preferably at least one of hexane, carbon tetrachloride, dimethylbenzene.The selection of second organic solvent and the maleic anhydride of step 1 are total
The polarity of first organic solvent of polymers is related, and first of the second organic solvent polarity than step 1 of in general step 3 has
The polarity of solvent is small.The dosage of the second organic solvent of step 3 makes the double transmitting fluorescent polymers of the blue feux rouges completely heavy
It forms sediment and comes out；Preferably, the weight of the first organic solvent of the second organic solvent and the step 1 copolymer-maleic anhydride
It is (10~50): 100, preferably (20~50): 100 than range.In the proportional region of the second solvent of this step and the first solvent,
The fluorescent polymer in fluorescent polymer solution can be made to precipitate more thorough, to realize better effect.
The fluorescent characteristics of the double transmitting fluorescent polymers of blue feux rouges of the invention are as follows: blue feux rouges is double to emit the molten of fluorescent polymers
When the fluorescence excites scope of liquid is in 330~450nm, transmitting range is in 380~530nm；When excites scope be in 360~
When 600nm, transmitting range is in 560~740nm.The excites scope of the double transmitting fluorescent polymers of the blue feux rouges being dried to obtain is in
When 330~450nm, transmitting range is in 400~520nm (i.e. blue emission range)；When excites scope is in 330~600nm
When, transmitting range is in 575~785nm (i.e. red emission range).Also, the solution of the double transmitting fluorescent polymers of blue feux rouges and
Solid all has high fluorescent, that is, aggregation inducing quenching effect is not present, therefore have diversified application form.
The double transmitting fluorescent polymers of blue feux rouges of the invention in specific application, can be directly using step in preparation method
The double transmitting fluorescence polymerizations of blue feux rouges that step 3 obtains also can be used in the two obtained double transmitting fluorescent polymer solution of blue feux rouges
Object solid.
The third object of the present invention is to provide a kind of double transmitting fluorescent fibers of blue feux rouges.
The double transmitting fluorescent fibers of indigo plant feux rouges of the present invention include the above-described blue double transmitting fluorescence of feux rouges of the present invention
Polymer and fibre-forming polymer, wherein the weight ratio range of the double transmitting fluorescent polymers of the indigo plant feux rouges and fibre-forming polymer is (1
~20): 100, preferably (5~10): 100.
Fibre-forming polymer of the present invention is common fibre-forming polymer in the prior art, and preferably following polymer is at least
It is a kind of: polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polystyrene, polymethyl methacrylate,
Polyvinylpyrrolidone, polyacrylonitrile, polyimides, sodium alginate；At least one of more preferable following polymer: poly- third
Alkene, polyvinyl alcohol, polyvinylpyrrolidone, sodium alginate, at least one of most preferably following polymer: polyvinyl alcohol, sea
Mosanom.
The double transmitting fluorescent fibers of blue feux rouges of the invention issue blue light, green respectively under the irradiation of ultraviolet light, blue light and green light
Light and feux rouges.
The fourth object of the present invention is to provide the preparation method of the double transmitting fluorescent fibers of blue feux rouges.
The preparation method of the double transmitting fluorescent fibers of indigo plant feux rouges of the present invention, including will include the double transmittings of blue feux rouges
Fluorescent polymer is mixed the method for carrying out melt spinning by the amount with the component including fibre-forming polymer, also includes by the indigo plant
The double transmitting fluorescent polymers of feux rouges and fibre-forming polymer are dissolved separately in solvent and form solution, will include the blue double transmittings of feux rouges
Component including fluorescent polymer solution and fibre-forming polymer solution is mixed into spinning solution by the amount, and spinning solution is carried out solution
The method of spinning.
The indigo plant feux rouges pair emits the solid content of fluorescent polymers or the double transmitting fluorescent polymer solution of blue feux rouges and at fibre
The weight ratio range of polymer solids or fibre-forming polymer solution solid content is (1~20): 100, preferably (5~10): 100.
In the preparation method of the double transmitting fluorescent fibers of blue feux rouges of the invention, the preferred solution-polymerized SBR of the spinning process.
Solution spinning preferred for this invention is that existing solution spinning, process conditions are also existing in the prior art
Common condition in technology.Specifically, the blue double transmitting fluorescent polymer solids of feux rouges or the double transmitting fluorescence of blue feux rouges are gathered
Polymer solution obtains spinning solution after mixing with the component including fibre-forming polymer solution by the amount, and spinning solution is injected coagulating bath
In obtain gelatinous fibre, then the double transmitting fluorescent fibers of blue feux rouges can be obtained by gelatinous fibre is dry.
Wherein in the spinning solution, the solvent be water, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide,
At least one of acetone, chloroform, tetrahydrofuran, toluene, preferably water, dimethyl sulfoxide, dimethylformamide, acetone at least one
Kind；The concentration range of the fibre-forming polymer is 0.5~15wt%, preferably in 5~10wt%；The coagulating bath is existing skill
Common coagulating bath in art, preferably pure solvent coagulating bath, more preferable methanol.The spinning nozzle internal diameter of the solution-polymerized SBR syringe pump is
160~2000 μm, preferably 230~340 μm.The injection speed of the spinning solution injection coagulating bath is 0.01~1mL/min, excellent
It is selected as 0.1~0.5mL/min.
The fifth object of the present invention is to provide the double transmitting fluorescent polymers of the blue feux rouges or the double transmittings of blue feux rouges are glimmering
The application of fiber optics.The double transmitting fluorescent polymers of indigo plant feux rouges and the double transmitting fluorescent fibers of blue feux rouges of the present invention can be anti-
Puppet, bio-imaging, conversion film, solar cell sealing glue, can be widely applied in fluorescent dye field.
Present invention applicant has found under study for action, carries out simple modification for copolymer-maleic anhydride, can be obtained
Lead to the high fluorescent of formula (I), the fluorescent polymer of the double transmittings of blue feux rouges with structure of the invention.Main advantage of the invention
Are as follows:
1. the copolymer-maleic anhydride is the by-product of Industrial polyolefin synthesis, raw material is easy to get, industrial process stream
It is mature；
2. aromatic group and conjugation without containing genotoxic potentials such as benzene, naphthalene, pyrenes in the polymer of the general structure (I)
Group, biological safety are high；
3. the copolymer-maleic anhydride is simple and easy to do as the preparation process of such fluorescent reagent of raw material, production
At low cost, reagent involved in technique such as acetone, sodium hydroxide, potassium hydroxide etc. is cheap conventional reagent.
4. high fluorescent of the invention, the double transmitting fluorescent polymers of blue feux rouges, the blue double emitting performances of feux rouges are not by it
The restriction of liquid solubility and solid forms, thus the application with a variety of commercial forms；
5. application of the double transmitting fluorescent polymers of indigo plant feux rouges of the invention in terms of fluorescent fiber, simple with preparation method,
Emit three primary colors fluorescence, fluorescence intensity stretches the advantages that enhancing.
Detailed description of the invention
Fig. 1 is the three-dimensional fluorescence spectrogram of the double transmitting fluorescent polymer acetone solns of blue feux rouges prepared by embodiment 1；
Fig. 2 is the three-dimensional fluorescence spectrogram of the double transmitting fluorescent polymer solids of blue feux rouges prepared by embodiment 1；
Fig. 3 is the energy spectrum diagram of the double transmitting fluorescent polymers of blue feux rouges prepared by embodiment 1.When being wherein sample preparation at 2.2keV
The nanogold particle of surface spray.
Fig. 4 is the three-dimensional fluorescence spectrogram of the double transmitting fluorescent polymer solids of blue feux rouges prepared by embodiment 2；
Fig. 5 is the three-dimensional fluorescence spectrogram of the double transmitting fluorescent polymer solids of blue feux rouges prepared by embodiment 3；
Fig. 6 is the three-dimensional fluorescence spectrogram of the double transmitting fluorescent polymer solids of blue feux rouges prepared by embodiment 4；
Fig. 7 is the three-dimensional fluorescence spectrogram of the double transmitting fluorescent polymer solids of blue feux rouges prepared by embodiment 5；
Fig. 8 is the three-dimensional fluorescence spectrogram of the double transmitting fluorescent polymer solids of blue feux rouges prepared by embodiment 6；
Fig. 9 is the fluorescent microscopy images of the double transmitting fluorescent fibers of blue feux rouges prepared by embodiment 7.Wherein a-c is respectively
Blue, green, red is presented under ultraviolet light, blue and green light irradiation.
Figure 10 is the FTIR spectrum figure of the double transmitting fluorescent polymers of blue feux rouges of embodiment 1-6 preparation.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.But the present invention is not restricted by the embodiments.
Experimental data in embodiment is measured using following instrument and measuring method:
(1) fluorescence phenomenon is observed: embodiment and comparative example sample is placed in darkroom, observes fluorescence under ultraviolet light
Phenomenon, ultraviolet lamp power are 24W, and ultraviolet wavelength uses 365nm.
(2) fluorescence data and absolute quantum yield use the JY FL3 Fluorescence Spectrometer of Horiba company, Japan to sample
Product carry out analysis test, using 450W xenon source, 250~650nm of excitation wavelength range, and emission spectrum range is 300~
1000nm。
(3) fluorescent microscopy images are shot using the Olympus BX51 fluorescence microscope of Olympus Corp, ultraviolet
Optical source wavelength is 365nm, and blue light source wavelength is 420nm, and green-light source wavelength is 546nm.
(4) energy spectrum diagram of fluorescent polymer carries out analysis test acquirement by energy disperse spectroscopy.
Copolymer-maleic anhydride used in embodiment is prepared as follows, other raw materials are commercially available and obtain.
Maleic anhydride used in embodiment-vinylacetate linear alternated copolymer (MVL), with reference to patent
In CN1618826A prepared by embodiment 4, main preparation condition and parameter: reaction monomers maleic anhydride and vinylacetate
Molar ratio is 1:1, and medium is butyl acetate, and initiator is dibenzoyl peroxide, 80 DEG C of reaction 5h, and microsphere average grain diameter is
440nm。
Maleic anhydride used in embodiment-vinylacetate cross-linked copolymer (MVC), with reference to patent CN101338007A
Prepared by middle embodiment 1, essential condition and parameter: the molar ratio of reaction monomers maleic anhydride and vinylacetate is 1:1, is situated between
Matter is butyl acetate, and initiator is dibenzoyl peroxide, and crosslinking agent is dimethacrylate (EGDMA), 80
DEG C reaction 4h, microsphere average grain diameter 460nm.
The double transmitting fluorescent polymers of blue feux rouges
Embodiment 1
Polymaleic anhydride-vinylacetate the linear alternated copolymer (MVL) for weighing quality 10g is dissolved in the dipropyl of 100g
In keto-alcohol solution；The sodium hydroxide for weighing quality 1.5g is put into the diacetone alcohol solution of MVL；It is made after being stirred to react 12 hours
The standby diacetone alcohol solution for obtaining the double transmitting fluorescent polymers of blue feux rouges.This blue double transmitting fluorescent polymer solution of feux rouges is ultraviolet
Bright rose pink purple is shown under lamp, three-dimensional fluorescence spectra is as shown in Figure 1, when excites scope is in 330~450nm
When, transmitting range is in 380~530nm；When excites scope is in 360~600nm, transmitting range is in 560~740nm.It will
The dry indigo plant that high fluorescent can be obtained after the double transmitting fluorescent polymer mixed liquors of the indigo plant feux rouges are handled 24 hours at 40 DEG C
The double transmitting fluorescent polymers of feux rouges, show bright lightpink in the UV lamp, absolute quantum yield 9.52%, thirdly
It is as shown in Figure 2 to tie up fluorescence spectra.When excites scope is in 330~450nm, transmitting range is in 400~520nm；Excitation
When range is in 330~600nm, transmitting range is in 575~785nm.The Fourier of the double transmitting fluorescent polymers of the indigo plant feux rouges
Infrared spectrogram is as shown in the curve 1 of Figure 10, wherein 3500,2972,1735,1593,1375,1245,1028cm-1Respectively-
OH ,-CH, C=O, COO-Ion ,-CH3, C-O-C, C-O group characteristic peak.COO-Ion refers to raw material and alkali metal hydroxide
Object reaction generates the carboxylic acid sodium in carboxylate, such as the present embodiment: COO-Na+As long as occurring COO in infrared spectrum-'s
Characteristic peak just illustrates the presence for having metal ion.The energy spectrum diagram of the double transmitting fluorescent polymers of the indigo plant feux rouges is as shown in figure 3, sodium element
Presence also demonstrate and have sodium ion in reaction product.
Comparative example 1
Polymaleic anhydride-vinylacetate the linear alternated copolymer (MVL, with embodiment 1) for weighing quality 10g is dissolved in
In the diacetone alcohol solution of 100g, the solution obtained after being stirred to react 12 hours only shows that very faint blue is glimmering in the UV lamp
Light.The polymer solids that the diacetone alcohol solution of this polymer obtains after handling 24 hours at 40 DEG C are only shown in the UV lamp
Very faint blue-fluorescence.
Embodiment 2
Polymaleic anhydride-vinylacetate the linear alternated copolymer (MVL, with embodiment 1) for weighing quality 20g is dissolved in
In 100g diacetone alcohol solution；The lithium hydroxide for weighing quality 1g is put into the diacetone alcohol solution of MVL；It is small to be stirred to react 4
When after the diacetone alcohol solution of the double transmitting fluorescent polymers of blue feux rouges are prepared.This blue double transmitting fluorescent polymer solution of feux rouges
Show bright rose pink purple in the UV lamp, when excites scope is in 330~450nm, transmitting range be in 380~
530nm；When excites scope is in 360~600nm, transmitting range is in 560~740nm.The double transmitting fluorescence of the indigo plant feux rouges are gathered
The dry double transmitting fluorescent polymers of the blue feux rouges that high fluorescent can be obtained after object mixed liquor is handled 24 hours at 40 DEG C are closed,
Bright lightpink, absolute quantum yield 8.95%, three-dimensional fluorescence spectra such as Fig. 4 institute are shown in the UV lamp
Show, when excites scope is in 330~450nm, transmitting range is in 400~520nm；Excites scope is in 330~600nm
When, transmitting range is in 575~785nm.FTIR spectrum figure such as Figure 10's of the double transmitting fluorescent polymers of the indigo plant feux rouges
Shown in curve 2, wherein 3500,2972,1735,1593,1375,1245,1028cm-1Respectively-OH ,-CH, C=O, COO-From
Son ,-CH3, C-O-C, C-O group characteristic peak.
Embodiment 3
Polymaleic anhydride-vinylacetate the linear alternated copolymer (MVL, with embodiment 1) for weighing quality 15g is dissolved in
In 100g diacetone alcohol solution；The sodium hydroxide for weighing quality 1g is put into the diacetone alcohol solution of MVL；It is small to be stirred to react 12
When after the diacetone alcohol solution of the double transmitting fluorescent polymers of blue feux rouges are prepared.This blue double transmitting fluorescent polymer solution of feux rouges
Show bright rose pink purple in the UV lamp, when excites scope is in 330~450nm, transmitting range be in 380~
530nm；When excites scope is in 360~600nm, transmitting range is in 560~740nm.It is double that the indigo plant feux rouges is added in 20g hexane
The double transmitting fluorescent polymers of blue feux rouges of high fluorescent can be obtained in filtration drying after transmitting fluorescent polymer mixed liquor, in purple
Bright lightpink is shown under outer lamp, absolute quantum yield 9.04%, three-dimensional fluorescence spectra is as shown in figure 5, work as
When excites scope is in 330~450nm, transmitting range is in 400~520nm；When excites scope is in 330~600nm, transmitting
Range is in 575~785nm.3 institute of curve of FTIR spectrum figure such as Figure 10 of the double transmitting fluorescent polymers of the indigo plant feux rouges
Show, wherein 3500,2972,1735,1593,1375,1245,1028cm-1Respectively-OH ,-CH, C=O, COO-Ion ,-CH3、
The characteristic peak of C-O-C, C-O group.
Embodiment 4
Polymaleic anhydride-vinylacetate the linear alternated copolymer (MVL, with embodiment 1) for weighing quality 15g is dissolved in
In 100g acetone soln；The sodium hydroxide for weighing quality 1g is put into the acetone soln of MVL；It is prepared after being stirred to react 12 hours
Obtain the double transmitting fluorescent polymer solution of blue feux rouges.This blue double transmitting fluorescent polymer solution of feux rouges shows bright in the UV lamp
Bright rose pink purple, when excites scope is in 330~450nm, transmitting range is in 380~530nm；Excites scope is in
When 360~600nm, transmitting range is in 560~740nm.The double transmitting fluorescent polymers of the indigo plant feux rouges are added in 20g hexane to mix
The double transmitting fluorescent polymers of blue feux rouges of high fluorescent can be obtained in filtration drying after liquid, show in the UV lamp bright
Lightpink, absolute quantum yield 6.74%, three-dimensional fluorescence spectra as shown in fig. 6, when excites scope is in 330~
When 450nm, transmitting range is in 400~520nm；When excites scope is in 330~600nm, transmitting range be in 575~
785nm.The indigo plant feux rouges pair emits the FTIR spectrum figures of fluorescent polymers as shown in the curve 4 of Figure 10, wherein 3500,
2972、1735、1593、1375、1245、1028cm-1Respectively-OH ,-CH, C=O, COO-Ion ,-CH3, C-O-C, C-O base
The characteristic peak of group.In terms of the absolute quantum yield of product, double transmitting fluorescent polymers manufactured in the present embodiment are in the UV lamp
Fluorescence intensity is significantly lower than fluorescent polymer prepared by embodiment 3.
Embodiment 5
Polymaleic anhydride-vinylacetate the cross-linked copolymer (MVC, self-control) for weighing quality 15g is dissolved in 100g dipropyl
In keto-alcohol solution；The potassium hydroxide for weighing quality 1g is put into the diacetone alcohol solution of MVC；It is prepared after being stirred to react 12 hours
Obtain the diacetone alcohol solution of the double transmitting fluorescent polymers of blue feux rouges.This blue double transmitting fluorescent polymer solution of feux rouges is in ultraviolet lamp
Under show bright rose pink purple, when excites scope is in 330~450nm, transmitting range is in 380~530nm；Swash
When hair range is in 360~600nm, transmitting range is in 560~740nm.The double transmitting fluorescent polymers of the indigo plant feux rouges are mixed
Liquid dry double transmitting fluorescent polymers of the blue feux rouges that high fluorescent can be obtained after being handled 24 hours at 40 DEG C, in ultraviolet lamp
Under show bright lightpink, three-dimensional fluorescence spectra is sent out as shown in fig. 7, when excites scope be in 330~450nm
It penetrates range and is in 400~520nm；When excites scope is in 330~600nm, transmitting range is in 575~785nm.The indigo plant feux rouges
It is double transmitting fluorescent polymers FTIR spectrum figures as shown in the curve 5 of Figure 10, wherein 3500,2972,1735,1593,
1375、1245、1028cm-1Respectively-OH ,-CH, C=O, COO-Ion ,-CH3, C-O-C, C-O group characteristic peak.
Embodiment 6
Polymaleic anhydride-vinylacetate the cross-linked copolymer (MVC, self-control) for weighing quality 10g is dissolved in 100g butanone
In solution；The rubidium hydroxide for weighing quality 1g is put into the butanone solution of MVC；Lan Hong is prepared after being stirred to react 12 hours
The double transmitting fluorescent polymer solution of light.This blue double transmitting fluorescent polymer solution of feux rouges shows bright light powder in the UV lamp
Reddish violet, when excites scope is in 330~450nm, transmitting range is in 380~530nm；Excites scope be in 360~
When 600nm, transmitting range is in 560~740nm.The double transmitting fluorescent polymer mixed liquors of the indigo plant feux rouges are added in 10g dimethylbenzene
The double transmitting fluorescent polymers of blue feux rouges of high fluorescent can be obtained in filtration drying afterwards, show in the UV lamp bright shallow
Pink colour, absolute quantum yield 5.39%, three-dimensional fluorescence spectra as shown in figure 8, when excites scope is in 330~
When 450nm, transmitting range is in 400~520nm；When excites scope is in 330~600nm, transmitting range be in 575~
785nm.The indigo plant feux rouges pair emits the FTIR spectrum figures of fluorescent polymers as shown in the curve 6 of Figure 10, wherein 3500,
2972、1735、1593、1375、1245、1028cm-1Respectively-OH ,-CH, C=O, COO-Ion ,-CH3, C-O-C, C-O base
The characteristic peak of group.
The double transmitting fluorescent fibers of blue feux rouges
Embodiment 7
The dimethyl sulphoxide solution and polyethylene that the blue double transmitting fluorescent polymer solids of feux rouges described in embodiment 1 are prepared
Spinning solution, the blue double transmitting fluorescent polymers of feux rouges in spinning solution are obtained after the mixing of alcohol (1799, Aladdin) dimethyl sulphoxide solution
It is 5:100 with the ratio between the solid content of polyvinyl alcohol, the concentration of polyvinyl alcohol is 5wt%, and coagulating bath is pure methanol, controls syringe pump
Spinning nozzle internal diameter be 230 μm, injection speed 0.2mL/min, complete obtained gelatinous fibre is dry after spinning, obtain
Red is presented in fiber under natural light, the ultraviolet of fluorescence microscope, blue light and green light irradiation under respectively present blue, green and
Red fluorescence, fluorescent microscopy images are as shown in Figure 9.
Comparative example 2
With the dimethyl sulphoxide solution of polyvinyl alcohol (1799, Aladdin) as spinning solution, polyvinyl alcohol in spinning solution
Concentration is 5wt%, and coagulating bath is pure methanol, and the spinning nozzle internal diameter for controlling syringe pump is 230 μm, injection speed 0.2mL/min,
After completion spinning that obtained gelatinous fibre is dry, white, the nothing under fluorescence microscope is presented in obtained fiber under natural light
Fluorescence.
Embodiment 8
The dimethyl sulphoxide solution and polyethylene that the blue double transmitting fluorescent polymer solids of feux rouges as described in example 2 are prepared
Spinning solution, the blue double transmitting fluorescent polymers of feux rouges in spinning solution are obtained after the mixing of alcohol (1799, Aladdin) dimethyl sulphoxide solution
It is 10:100 with the ratio between the solid content of polyvinyl alcohol, the concentration of polyvinyl alcohol is 10wt%, and coagulating bath is pure methanol, control injection
The spinning nozzle internal diameter of pump is 300 μm, injection speed 0.1mL/min, after completion spinning that obtained gelatinous fibre is dry, is obtained
Fiber red is presented under natural light, the ultraviolet of fluorescence microscope, blue light and green light irradiation under respectively present blue, green
And red fluorescence, as shown in Figure 9.
Embodiment 9
The dimethyl sulphoxide solution and polyethylene that the blue double transmitting fluorescent polymer solids of feux rouges described in embodiment 3 are prepared
Spinning solution, the blue double transmitting fluorescent polymers of feux rouges in spinning solution are obtained after the mixing of alcohol (1799, Aladdin) dimethyl sulphoxide solution
It is 8:100 with the ratio between the solid content of polyvinyl alcohol, the concentration of polyvinyl alcohol is 8wt%, and coagulating bath is pure methanol, controls syringe pump
Spinning nozzle internal diameter be 340 μm, injection speed 0.5mL/min, complete obtained gelatinous fibre is dry after spinning, obtain
Red is presented in fiber under natural light, the ultraviolet of fluorescence microscope, blue light and green light irradiation under respectively present blue, green and
Red fluorescence.
Embodiment 10
The double transmitting fluorescent polymer solids of blue feux rouges as described in example 4 are prepared aqueous solution and polyvinyl alcohol (1799,
Aladdin) aqueous solution mixing after obtain spinning solution, the double transmitting fluorescent polymers of blue feux rouges and polyvinyl alcohol consolidates in spinning solution
The ratio between content is 15:100, and the concentration of polyvinyl alcohol is 5wt%, and coagulating bath is pure methanol, controls the spinning nozzle internal diameter of syringe pump
It is 230 μm, injection speed 0.2mL/min, after completion spinning that obtained gelatinous fibre is dry, obtained fiber is in natural light
Lower presentation is red, and blue, green and red fluorescence is presented respectively under the irradiation of the ultraviolet of fluorescence microscope, blue light and green light.
Embodiment 11
The dimethyl sulphoxide solution and polyethylene that the double transmitting fluorescent polymer solids of blue feux rouges described in embodiment 5 are prepared
Spinning solution, the blue double transmitting fluorescence polymerizations of feux rouges in spinning solution are obtained after the dimethyl sulphoxide solution mixing of alcohol (1799, Aladdin)
The ratio between solid content of object and polyvinyl alcohol is 10:100, and the concentration of polyvinyl alcohol is 10wt%, and coagulating bath is pure methanol, control note
The spinning nozzle internal diameter for penetrating pump is 340 μm, injection speed 0.2mL/min, after completion spinning that obtained gelatinous fibre is dry, is obtained
Red is presented in the fiber arrived under natural light, presents respectively under the irradiation of the ultraviolet of fluorescence microscope, blue light and green light blue, green
Color and red fluorescence.
Claims (19)
1. a kind of double transmitting fluorescent polymers of indigo plant feux rouges, for the polymer with following general formula (I):
Wherein, x, y and z are natural number, x >=1, y+z >=0；
The group R1、R2、R4、R5For the group containing at least one of following functional group: ketone group, ester group, amido, phenyl, gold
Belong to ion, preferably at least one of ketone group, unitary alkali metal ion, more preferable CH3COCH2C(CH3)2, CH3COC(CH3)2CH2, CH3COCH2CH2, at least one of unitary alkali metal ion；The group R1、R2、R4、R5In at least one be
Metal ion；
The group R3、R6At least one selected from following group: hydroxyl, alkyl, ester group, preferably hydroxyl, CH3COO-、
CH3CH2COO-、CH3CH2CH2At least one of COO-.
2. fluorescent polymer according to claim 1, it is characterised in that:
In the logical formula (I), the group R1、R2、R4、R5At least one is not metal ion.
3. fluorescent polymer according to claim 1, it is characterised in that:
In the logical formula (I), at least one in y and z is 0；It is preferred that y=z=0.
4. fluorescent polymer according to claim 1, it is characterised in that:
The blue emission range of the fluorescent polymer is 400~520nm, and red emission range is 575~785nm.
5. described in any item fluorescent polymers according to claim 1~4, it is characterized in that by copolymer-maleic anhydride by having
It is added after metal hydroxides sufficiently reacts and obtains after solvent dissolution.
6. the preparation method of described in any item blue double transmitting fluorescent polymers of feux rouges according to claim 1~5, feature exist
In the following steps are included:
Step 1: taking copolymer-maleic anhydride, the first organic solvent is added and is sufficiently dissolved, copolymer-maleic anhydride is obtained
Solution；Wherein, the weight ratio range of copolymer-maleic anhydride and organic solvent is (5~30): 100, preferably (10~20):
100；
Step 2: metal hydroxides is taken to be added in the copolymer-maleic anhydride solution that step 1 obtains, while being stirred,
The solution of the double transmitting fluorescent polymers of blue feux rouges is sufficiently obtained after reaction；The metal hydroxides and maleic anhydride are total
The weight ratio range of polymers is (5~20): 100, preferably (5~15): 100；
Step 3: it is double that the solution of the double transmitting fluorescent polymers of indigo plant feux rouges made from step 2 is dried to obtain the blue feux rouges
Emit the solid of fluorescent polymer；
Or the second organic solvent, which is added, makes the blue feux rouges is double to emit fluorescent polymer Precipitations, is dried to obtain the indigo plant
The solid of the double transmitting fluorescent polymers of feux rouges；The polarity of second organic solvent is less than the first organic solvent.
7. preparation method according to claim 6, it is characterised in that:
The copolymer-maleic anhydride of the step 1 is selected from polymaleic anhydride-vinyl ester copolymers, preferably polymaleic anhydride-acetic acid
Vinyl ester copolymers.
8. preparation method according to claim 6, it is characterised in that:
First organic solvent of the step 1 is selected from at least one of following solvent: acetone, butanone, 2 pentanone, propione, first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, diacetone alcohol, benzyl alcohol, Ethyl formate, ethyl acetate, ethylenediamine, triethylamine, tetrahydro furan
It mutters, dimethyl sulfoxide, preferably is selected from at least one of following solvent: acetone, butanone, diacetone alcohol, ethyl acetate, triethylamine；More
It preferably is selected from at least one of following solvent: acetone, diacetone alcohol.
9. preparation method according to claim 6, it is characterised in that:
The metal hydroxides of the step 2 be selected from unitary alkali metal hydroxide at least one, preferably be selected from lithium hydroxide,
At least one of sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, hydroxide francium, more preferable lithium hydroxide, hydrogen-oxygen
Change at least one of sodium, potassium hydroxide.
10. preparation method according to claim 6, it is characterised in that:
The reaction time of the step 2 is 0.5~48 hour, preferably 2~36 hours, more preferable 4~24 hours.
11. preparation method according to claim 6, it is characterised in that:
The second organic solvent that the step 3 is added is selected from at least one of following solvent: pentane, petroleum ether, hexane, octane,
Heptane, carbon tetrachloride, toluene, dimethylbenzene, chloroform, methylene chloride, ether.
12. preparation method according to claim 6, it is characterised in that:
The weight ratio range of second organic solvent and the first organic solvent is (10~50): 100, preferably (20~50):
100。
13. a kind of double transmitting fluorescent polymers of indigo plant feux rouges, it is characterised in that by the preparation method system of one of claim 6~12
.
14. a kind of double transmitting fluorescent fibers of indigo plant feux rouges, include blue feux rouges described in one of claim 1-5 or claim 13
Double transmitting fluorescent polymers and fibre-forming polymer, wherein the weight of the double transmitting fluorescent polymers and fibre-forming polymer of indigo plant feux rouges
Specific gravity range is (1~20): 100, preferably (5~10): 100.
15. fluorescent fiber according to claim 14, it is characterised in that:
The fibre-forming polymer be following polymer at least one: polyethylene, polypropylene, ethylene-vinyl acetate copolymer,
Polyvinyl alcohol, polystyrene, polymethyl methacrylate, polyvinylpyrrolidone, polyacrylonitrile, polyimides, alginic acid
Sodium, at least one of preferably following polymer: polypropylene, polyvinyl alcohol, polyvinylpyrrolidone, sodium alginate.
16. the preparation method of 4 or 15 fluorescent fibers according to claim 1, comprising the following steps:
It is melted being mixed including component of the blue double transmitting fluorescent polymers of feux rouges including fibre-forming polymer by the amount
Melting spinning can be obtained the double transmitting fluorescent fibers of blue feux rouges.
17. the preparation method of 4 or 15 fluorescent fibers according to claim 1, comprising the following steps:
The blue double transmitting fluorescent polymers of feux rouges are dissolved separately in solvent with fibre-forming polymer and form solution, will include described
Component including the double transmitting fluorescent polymer solution of blue feux rouges and fibre-forming polymer solution is mixed into spinning solution by the amount, will spin
Silk liquid, which carries out solution-polymerized SBR, can be obtained the double transmitting fluorescent fibers of blue feux rouges.
18. the preparation method of 7 fluorescent fibers according to claim 1, it is characterised in that:
The solvent is water, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide, acetone, chloroform, tetrahydrofuran, first
At least one of at least one of benzene, preferably water, dimethyl sulfoxide, dimethylformamide, acetone, it is poly- at fibre in the spinning solution
The concentration range for closing object is 0.5~15wt%, preferably 5~10wt%.
19. the double transmitting fluorescent polymers of blue feux rouges described in any one or claim 13 according to claim 1~5 or power
Benefit requires 14~15 described in any item blue feux rouges pair to emit fluorescent fibers in anti-fake, bio-imaging, conversion film, solar-electricity
Application in pond sealant, fluorescent dye field.
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