阅读说明：本技术 一种蓝红光双发射荧光聚合物和其荧光纤维及制法和应用 (A kind of double transmitting fluorescent polymers of indigo plant feux rouges and its fluorescent fiber and preparation method and application ) 是由 乔金樑 胡晨曦 张晓红 茹越 赖金梅 蔡传伦 戚桂村 高建明 李秉海 王湘 宋志 于 2018-05-24 设计创作，主要内容包括：本发明涉及蓝红光双发射荧光聚合物及制法和应用。所述荧光聚合物为将马来酸酐共聚物经过有机溶剂溶解后加入金属氢氧化物充分反应后得到。所述荧光聚合物的激发范围处于330～450nm时,发射范围处于400～520nm；当激发范围处于330～600nm时,发射范围处于575～785nm。其溶液的荧光激发范围处于330～450nm时,发射范围处于380～530nm；当激发范围处于360～600nm时,发射范围处于560～740nm。本发明的荧光聚合物可制备蓝红光双发射荧光纤维,荧光强度高,生产成本低、生产工艺简单成熟,容易实现工业生产,可应用于防伪、生物成像、转光膜、太阳能电池密封胶、荧光染料等领域中。(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.)

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.

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.