CN108277683A - A kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose - Google Patents

A kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose Download PDF

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Publication number
CN108277683A
CN108277683A CN201810063395.8A CN201810063395A CN108277683A CN 108277683 A CN108277683 A CN 108277683A CN 201810063395 A CN201810063395 A CN 201810063395A CN 108277683 A CN108277683 A CN 108277683A
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solution
quantum dot
cell cellulose
azelon
cdse quantum
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CN108277683B (en
Inventor
杨尊先
郭太良
张玉飞
黄建华
郑康
胡海龙
周雄图
陈耿旭
徐胜
王丽萍
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Fuzhou University
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Fuzhou University
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/10—Composite fibres
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F13/00—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/28—Organic non-cellulose fibres from natural polymers
    • D21H13/34—Protein fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a kind of preparation methods of the flexible fluorescent paper based on azelon or cell cellulose, carry out handling simple processing using silk and cell cellulose, form one-dimensional azelon or cell cellulose；It is then dispersed in CdSe quantum dot solution, CdSe quantum dot is made to be attached on one-dimensional azelon or cell cellulose；Then the quantum dot being supported on one-dimensional azelon or cell cellulose is coated with PVP materials again；The fluorescent paper of various fluorescence can be sent out by finally being prepared using techniques such as vacuum filtration, vacuum dryings.Fluorescent paper mechanical strength produced by the present invention is higher, flexible to fold etc. and have higher luminescent properties, has wider warning visual angle compared to traditional reflective class material, special dress ornament, instruction and warning domain variability can be applied to replace the paster material of reflective class.

Description

A kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose
Technical field
The invention belongs to photoelectric materials and devices field, and in particular to a kind of soft based on azelon or cell cellulose The preparation method of property fluorescent paper.
Background technology
Believe with the development of science and technology with social progress, the continuous promotion of the awareness of safety of people, equity instruction and warning The attention degree of breath is increasingly reinforced.However reflectorized material is occupied an leading position in present instruction and warning field, due to reflective material Expect that light reflection direction is single, thereby indicate that it is small with the visual angle of warning, cannot preferably it play the role of due.It is this in order to break Due to the limitation of the reflective mechanism of reflectorized material itself, we have to find alternative material again so that increase instruction Warning can be visual angle.Make the visual range for having the presence of light that can play very much big visual angle.We have found fluorescent material tools There is this excellent performance.Therefore main material of the fluorescent material as warning indication is used, and due in order to play Instruction warning performance is therefore high to luminous power stability requirement, we are fluorescent material using quantum dot, for the ease of using More convenient simply to use its field, fluorescent material is made fluorescent paper by we, and coats PVP in quantum dot surface.Due to This material is fluorescent paper form so not only convenient but also angle of visibility is big.Therefore in traffic police's dress ornament, traffic sign, dangerous police Show that board etc. is not only convenient but also has good performance boost.
Invention content
It is an object of the invention to the deficiencies for existing reflectorized material warning indication angle of visibility, specially invent a kind of fluorescence Material replace reflectorized material, a kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose is provided. The preparation method of the present invention combines the techniques such as hot injection method, vacuum filtration and vacuum drying, and preparation process is simple, invention material It is more excellent than original reflectorized material, reflectorized material will be substituted in instruction warning field.Since this material is fluorescent paper form So not only facilitate but also angle of visibility is big, thus on traffic police's dress ornament, traffic sign, dangerous warning sign etc. it is not only convenient but also There is good performance boost.
To achieve the above object, the present invention adopts the following technical scheme that realization
A kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose, specifically includes following steps：
Step S1：Azelon solution and cell cellulose solution are prepared, and it is pre-processed before obtaining silk respectively Drive the precursor solution of liquid solution and cell cellulose；
Step S2：CdSe quantum dot solution is prepared, using obtained CdSe quantum dot as luminescence generated by light center；
Step S3：CdSe quantum dot solution made from step S2 is distributed to the precursor solution for the silk that step S1 processing obtains Or in the precursor solution of cell cellulose, CdSe quantum dot-silk complex solution or CdSe quantum dot-cell fiber is made Plain complex solution；
Step S4：Use polyvinylpyrrolidone（PVP）The CdSe quantum dot that step S3 is obtained-silk complex solution or CdSe Quantum dot-cell cellulose complex solution is coated；
Step S5：By filtering, vacuum drying process prepares the flexible fluorescent paper based on azelon or cell cellulose.
Further, the tool of the precursor solution of silk and the precursor solution of cell cellulose is prepared in the step S1 Body method is respectively：
Protein solution is prepared by the standard procedure of mulberry cocoon, including separation, degumming, dissolving and dialysis, then uses high speed Centrifugal process collection is reconfigured as 10wt% solution and obtains the precursor solution of silk；
Cell cellulose solution preparation be by quickly aoxidizing, ultrasonication and with a kind of method to cellulose nano-fibrous It is detached；Briefly, with tetramethyl piperidine nitrogen oxides（TEMPO）The aaerosol solution of wood pulp is added into sodium bromide In, in the NaClO solution to said mixture being then added at room temperature；Then it uses 1M NaOH to adjust pH, is ultrasonically treated simultaneously Cooperation centrifugal process, which is cleaned, collects the precursor solution that the solution for being reconfigured as 10wt% obtains cell cellulose.
Preferably, the preparation temperature of the cell cellulose precursor solution is room temperature, precursor solution pH is 10；Ultrasound Processing time is 1-2h, and centrifugal treating number is 3-5 times, and each centrifugation time is 10-30min.
Further, the specific method of the step S2 preparations CdSe quantum dot solution is：By selenium powder（Se）It is just pungent with three Base phosphine (TOP）It is prepared into Se precursor solutions after being mixed at 40-100 DEG C；Cadmium oxide（CdO）, oleic acid and octadecylene（ODE） It is heated to 100-200 DEG C under inert gas shielding, keeps the temperature 10-30min；Then 250 DEG C -350 DEG C are warming up to, 1-10min is kept the temperature, Cd precursor solutions are made；Se precursor solutions are injected into Cd precursor solutions and produce mixed solution, control Se's and Cd Molar ratio is 1:4,1-10min is kept the temperature at 250 DEG C -350 DEG C, is taken out solution cleaning purification and is obtained CdSe quantum dot solution.
Further, the specific method of the step S3 is：CdSe quantum dot solution and silk（Or cell cellulose） Precursor solution mix according to a certain percentage, be ultrasonically treated a period of time after, heating certain temperature keep a period of time, make CdSe quantum dot solution is distributed to silk（Or cell cellulose）Precursor solution in, be made CdSe quantum dot-silk it is compound Liquid solution or CdSe quantum dot-cell cellulose complex solution.
Preferably, the preparation condition is：CdSe quantum dot solution and silk（Or cell cellulose）Precursor solution According to volume ratio 1:3~3:1 mixing after being ultrasonically treated 10-20min, is heated to 50 DEG C of -80 DEG C of holding 10-30min, makes CdSe amounts Son point solution is distributed to silk（Or cell cellulose）Precursor solution in, be made CdSe quantum dot-silk complex solution Or CdSe quantum dot-cell cellulose complex solution；Albumen has been loaded to by decentralized processing actually CdSe quantum dot Fluorescence composite material is formed on fiber or cell cellulose material.
Further, the specific method of the step S4 is：It weighs PVP and is dissolved in absolute ethyl alcohol, be put into water-bath and add Hot certain temperature stirs certain time, the CdSe quantum dot-silk complex solution or CdSe that isometric step S3 is obtained is added Quantum dot-cell cellulose complex solution, after a period of time, forming the silk or cell fibre of PVP cladding CdSe quantum dots The plain complex solution of dimension.
Preferably, the preparation condition is：PVP weighs 0.3-0.5g and is dissolved in 30ml absolute ethyl alcohols, heating temperature 60- 80 DEG C, stir 10-30min, the CdSe quantum dot that isometric mixing step S3 is obtained-silk complex solution or CdSe quantum Point-cell cellulose complex solution forms the silk or cell cellulose of PVP cladding CdSe quantum dots by 30-60min Complex solution.
Further, the specific method of the step S5 is：Using teflon membrane filter or AAO filter membranes, vacuum is taken out The silk or cell cellulose complex solution for filtering PVP cladding CdSe quantum dots, strip down compound glimmering after being then air-dried Photoprotein fiber or cell cellulose paper patch, and pasted using the further oven-dry paper of vacuum drying oven, the moisture in making paper paste steams completely Hair forms flexible fluorescent paper.
Preferably, it is 70-80 DEG C that paper temperature is shone in the preparation condition drying, teflon membrane filter or AAO filter holes Diameter is 0.1-0.5um.
Compared with existing reflectorized material, the present invention is handled first obtains the appearance liquid of azelon or cell cellulose, utilizes Hot injection method prepares quantum dot, and two kinds of solution of mixing make quantum dot is combined to form compound fluorescent material on material, so Quantum dot is coated with PVP materials again afterwards, helps to improve the stability of quantum dot in this way.Finally by suction filtration, vacuum Composite fluorescence azelon or cell cellulose paper patch are stripped down after drying preparation technology, and are further dried using vacuum drying oven Dry paper patch, the moisture evaporating completely in making paper paste form flexible fluorescent paper.The azelon or cell of this incorporating quantum point are fine Fluorescent paper is made in dimension element, and not only mechanical strength is higher, has higher luminescent properties but also has wider array of warning visual angle.Compared to Reflective paper material, fluorescent paper compared to traditional reflectorized material there is the visual angle of bigger can preferably play instruction or police in this It is shown as using.
Description of the drawings
Fig. 1 is silk and cell cellulose structural schematic diagram；
Fig. 2 is the one-dimensional carbon material structural schematic diagram for being attached with quantum dot；
Fig. 3 is the one-dimensional carbon material structural schematic diagram of PVP coated quantum dots；
Fig. 4 is the structural schematic diagram of the fluorescent paper prepared；
Label declaration：1- silks and cell cellulose material, 2- quantum dots, 3-PVP.
Specific implementation mode
The present invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment 1
（1）Protein solution is prepared by the standard procedure of mulberry cocoon, including separation, degumming, dissolving and dialysis；Then height is used Fast centrifugal process collection is reconfigured as 10wt% solution and obtains the precursor solution of silk；The preparation of cell cellulose solution：It weighs Tetramethyl piperidine nitrogen oxides TEMPO 0.016g and sodium bromide 0.1g are added into 100ml 1wt% wood pulps in suspension, so Afterwards, 10 mmol of NaClO solution at room temperature the every gram of cellulose addition 12% of NaClO solution is added in said mixture Stirring；PH value is adjusted to being maintained at 10 using 1 M NaOH；Sonication treatment time is 1h, and centrifugal treating number is 3 times to be 10min；Then it is reconfigured as 10wt% solution and obtains the precursor solution of cell cellulose；
（2）Weigh selenium（Se）Powder 8mg and measurement tri-n-octyl phosphine (TPO）3ml is prepared into Se presomas after being heated to 40 DEG C of mixing Solution；Weigh 51.2mg cadmium oxides（CdO）, measure 6.5ml oleic acid and 20ml octadecylenes（ODE）It is added in three-neck flask and leads to such as N2Gas shield under 100 DEG C of heat preservation 10min of heating, be then raised to 250 DEG C of holding 1min, Cd precursor solutions be made；By Se Precursor solution, which is injected into obtained Cd precursor solutions, produces mixed solution, keeps the temperature 1min, takes out solution cleaning purification and obtains CdSe quantum dot solution；
（3）Purifying the step of obtaining CdSe quantum dot solution is：Sample is rapidly injected in n-hexane using syringe and is realized quickly It is cooling, the fluorescence property of quantum dot can be improved in this way；The CdSe quantum dot prepared is dissolved in n-hexane, was added The methanol (volume is at least 3 times of n-hexane) of amount, after ultrasonic disperse, there is apparent lamination in solution；Upper layer is meltage The hexane solution of son point, lower layer is methanol；Centrifuge tube ultrasound 10min in ultrasonic machine；The band quantum dot solution on upper layer is carried It takes out, continuously adds excessive methanol, ultrasound, extraction so operate 5 times and match 20ml solution；
（4）CdSe quantum dot solution and silk（Or cell cellulose）Precursor solution according to volume ratio 1:3 mixing, ultrasound After handling 10min, 50 DEG C of holding 10min are heated to, CdSe quantum dot-silk complex solution is made or CdSe quantum dot-is thin Born of the same parents' cellulose complex solution；
（5）It weighs 0.3g PVP and is dissolved in 30ml absolute ethyl alcohols, be put into water-bath and heat 60 DEG C, stir 10min, it is isometric mixed Close step（4）Obtained CdSe quantum dot-silk complex solution or CdSe quantum dot-cell cellulose complex solution, warp 30min is crossed, the silk or cell cellulose complex solution of PVP cladding CdSe quantum dots are formed；
（6）The use of teflon membrane filter or AAO filter sizes it is 0.1 μm, vacuum filtration load has the protein fiber of quantum dot Dimension or cell cellulose presoma strip down composite fluorescence azelon or cell cellulose paper patch after being then air-dried, And pasted for 70 DEG C of further oven-dry papers using vacuum drying oven drying temperature, the moisture evaporating completely in making paper paste forms flexible fluorescence Paper.Fig. 4 is the structural schematic diagram of the fluorescent paper prepared.1 silk and cell cellulose material, 2 quantum dots, 3 PVP.
Embodiment 2
（1）Protein solution is prepared by the standard procedure of mulberry cocoon, including separation, degumming, dissolving and dialysis；Then height is used Fast centrifugal process collection is reconfigured as 10wt% solution and obtains the precursor solution of silk；The preparation of cell cellulose solution：It weighs Tetramethyl piperidine nitrogen oxides TEMPO 0.048g and sodium bromide 0.3g are added into 300ml 1wt% wood pulps in suspension；So Afterwards, 10 mmol of NaClO solution at room temperature the every gram of cellulose addition 12% of NaClO solution is added in said mixture Stirring；PH value is adjusted to being maintained at 10 using 1 M NaOH；Supersound process sonication treatment time is 1.5h, and centrifugal treating number is 4 times are 20min；Then it is newly configured to 10wt% solution and obtains the precursor solution of cell cellulose；
（2）Weigh selenium（Se）Powder 24mg and measurement tri-n-octyl phosphine (TPO）9ml is prepared into Se forerunner after being heated to 60 DEG C of mixing Liquid solution；Weigh 153.6mg cadmium oxides（CdO）, measure 19.5ml oleic acid and 60ml octadecylenes（ODE）It is added in three-neck flask Logical such as N2150 DEG C of heat preservation 20min of the lower heating of body protection, be then raised to 300 DEG C of holding 5min, Cd precursor solutions be made；It will Se precursor solutions are injected into, and are made in Cd precursor solutions and are produced mixed solution, and 5min is kept the temperature, and are taken out solution cleaning and are purified To CdSe quantum dot solution；
（3）The step of purification obtains CdSe quantum dot solution is that sample is rapidly injected in n-hexane using syringe and realizes fast quickly cooling But, the fluorescence property of quantum dot can be improved in this way；The quantum dot prepared is dissolved in n-hexane, excessive first is added Alcohol (volume is at least 3 times of n-hexane), after ultrasonic disperse, there is apparent lamination in solution；Upper layer is dissolving quantum dot Hexane solution, lower layer are methanol；Centrifuge tube ultrasound 10min in ultrasonic machine, the band quantum dot solution on upper layer is extracted, Excessive methanol is continuously added, ultrasound, extraction so operate 5 times and match 20ml solution；
（4）CdSe quantum dot solution and silk（Or cell cellulose）Precursor solution according to volume ratio 1:1 mixing, ultrasound After handling 15min, 60 DEG C of holding 20min are heated to, such quantum dot solution is just distributed to silk（Or cell cellulose）Solution In, CdSe quantum dot-silk complex solution or CdSe quantum dot-cell cellulose complex solution is made；
（5）It weighs 0.4g PVP and is dissolved in 30ml absolute ethyl alcohols, be put into water-bath and heat 70 DEG C, stir 20min, it is isometric mixed Close step（4）Obtained CdSe quantum dot-silk complex solution or CdSe quantum dot-cell cellulose complex solution, warp 40min is crossed, the silk or cell cellulose complex solution of PVP cladding CdSe quantum dots are formed；
（6）The use of teflon membrane filter or AAO filter sizes it is 0.2 μm, vacuum filtration load has the protein fiber of quantum dot Dimension or cell cellulose presoma strip down composite fluorescence azelon or cell cellulose paper patch after being then air-dried, And pasted for 75 DEG C of further oven-dry papers using vacuum drying oven drying temperature, the moisture evaporating completely in making paper paste forms flexible fluorescence Paper.Fig. 4 is the structural schematic diagram of the fluorescent paper prepared.1 silk and cell cellulose material, 2 quantum dots, 3 PVP.
Embodiment 3
（1）Protein solution is prepared by the standard procedure of mulberry cocoon, including separation, degumming, dissolving and dialysis；Then height is used Fast centrifugal process collection is reconfigured as 10wt% solution and obtains the precursor solution of silk；The preparation of cell cellulose solution：It weighs Tetramethyl piperidine nitrogen oxides TEMPO 0.08g and sodium bromide 0.5g are added into 500ml 1wt% wood pulps in suspension；So Afterwards, 10 mmol of NaClO solution at room temperature the every gram of cellulose addition 12% of NaClO solution is added in said mixture Stirring；PH value is adjusted to being maintained at 10 using 1 M NaOH；Sonication treatment time is 2h, and centrifugal treating number is 5 times to be 30min；Then it is reconfigured as 10wt% solution and obtains the precursor solution of cell cellulose；
（2）Weigh selenium（Se）Powder 40mg and measurement tri-n-octyl phosphine (TPO）15ml be heated to 100 DEG C mixing after be prepared into Se before Drive liquid solution；Weigh 256mg cadmium oxides（CdO）, measure 32.5ml oleic acid and 100ml octadecylenes（ODE）It is added to three-neck flask In lead to such as N2Gas shield under 200 DEG C of heat preservation 30min of heating, be then raised to 350 DEG C of holding 10min, it is molten that Cd presomas be made Liquid；Se precursor solutions are injected to be made in Cd precursor solutions and produce mixed solution, keep the temperature 10min, solution cleaning is taken out and carries It is pure to obtain CdSe quantum dot solution；
（3）The step of purification obtains CdSe quantum dot solution is that sample is rapidly injected in n-hexane using syringe and is realized quickly It is cooling, the fluorescence property of quantum dot can be improved in this way；The quantum dot prepared is dissolved in n-hexane, is added excessive Methanol (volume is at least 3 times of n-hexane), after ultrasonic disperse, there is apparent lamination in solution；Upper layer is dissolving quantum dot Hexane solution, lower layer is methanol；Centrifuge tube ultrasound 10min in ultrasonic machine；The band quantum dot solution on upper layer is extracted Come, continuously add excessive methanol, ultrasound, extraction so operate 5 times and match 20ml solution.
（4）CdSe quantum dot solution and silk（Or cell cellulose）Precursor solution according to volume ratio 3:1 mixing, 80 DEG C of holding 30min are heated to after being ultrasonically treated 20min, CdSe quantum dot-silk complex solution or CdSe quantum dot-is made Cell cellulose complex solution；
（5）It weighs 0.5g PVP and is dissolved in 30ml absolute ethyl alcohols, be put into water-bath and heat 80 DEG C, stir 30min, it is isometric mixed Close step（4）Obtained CdSe quantum dot-silk complex solution or CdSe quantum dot-cell cellulose complex solution, warp 1h is crossed, the silk or cell cellulose complex solution of PVP cladding CdSe quantum dots are formed；
（6）The use of teflon membrane filter or AAO filter sizes it is 0.5 μm, vacuum filtration load has the protein fiber of quantum dot Dimension or cell cellulose presoma strip down composite fluorescence azelon or cell cellulose paper patch after being then air-dried, And pasted for 80 DEG C of further oven-dry papers using vacuum drying oven drying temperature, the moisture evaporating completely in making paper paste forms flexible fluorescence Paper.Fig. 4 is the structural schematic diagram of the fluorescent paper prepared.1 silk and cell cellulose material, 2 quantum dots, 3 PVP.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification should all belong to the covering scope of the present invention.

Claims (8)

1. a kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose, it is characterised in that：The preparation Method includes the following steps：
Step S1：Azelon solution and cell cellulose solution are prepared, and it is pre-processed before obtaining silk respectively Drive the precursor solution of liquid solution and cell cellulose；
Step S2：CdSe quantum dot solution is prepared, using obtained CdSe quantum dot as luminescence generated by light center；
Step S3：CdSe quantum dot solution made from step S2 is distributed to the precursor solution for the silk that step S1 processing obtains Or in the precursor solution of cell cellulose, CdSe quantum dot-silk complex solution or CdSe quantum dot-cell fiber is made Plain complex solution；
Step S4：The CdSe quantum dot that step S3 is obtained with polyvinylpyrrolidone-silk complex solution or CdSe quantum Point-cell cellulose complex solution is coated；
Step S5：By filtering, vacuum drying process prepares the flexible fluorescent paper based on azelon or cell cellulose.
2. a kind of preparation method of flexible fluorescent paper based on azelon or cell cellulose according to claim 1, It is characterized in that：The specific method of the step S1 is：Azelon solution be prepared by the standard procedure of mulberry cocoon, including Then separation, degumming, dissolving and dialysis are reconfigured as 10wt% solution to get to before silk using supercentrifugal process collection Drive liquid solution；The preparation of cell cellulose solution is by being added to the outstanding of wood pulp with tetramethyl piperidine nitrogen oxides and sodium bromide It in floating solution, is then added in NaClO solution to said mixture at room temperature, 1M NaOH is then used to adjust pH, at ultrasound It manages and centrifugal process cleaning is coordinated to collect and be reconfigured as the solution of 10wt% to get to the precursor solution of cell cellulose.
3. a kind of preparation method of flexible fluorescent paper based on azelon or cell cellulose according to claim 2, It is characterized in that：The preparation temperature of the cell cellulose precursor solution is room temperature, and the pH of precursor solution is 10；It is described super The sonication time is 1-2h, and centrifugal treating number is 3-5 times, and each centrifugation time is 10-30min.
4. a kind of preparation method of flexible fluorescent paper based on azelon or cell cellulose according to claim 1, It is characterized in that：The specific method of the step S2 is：It is prepared into after selenium powder and tri-n-octyl phosphine are mixed at 40-100 DEG C Se precursor solutions；Cadmium oxide, oleic acid and octadecylene are heated to 100-200 DEG C under inert gas protection, keep the temperature 10-30min, Then 250 DEG C -350 DEG C are warming up to, 1-10min is kept the temperature, Cd precursor solutions are made；Se precursor solutions are injected into Cd forerunner In liquid solution, the molar ratio of control Se and Cd is 1:4,1-10min is kept the temperature at 250 DEG C -350 DEG C, takes out solution cleaning purification Obtain CdSe quantum dot solution.
5. a kind of preparation method of flexible fluorescent paper based on azelon or cell cellulose according to claim 1, It is characterized in that：The specific method of the step S3 is：The presoma of CdSe quantum dot solution and silk or cell cellulose Solution is according to volume ratio 1:3~3:1 mixing after being ultrasonically treated 10-20min, is heated to 50 DEG C of -80 DEG C of holding 10-30min, makes CdSe quantum dot solution is distributed in the precursor solution of silk or cell cellulose, and CdSe quantum dot-silk complex is made Solution or CdSe quantum dot-cell cellulose complex solution.
6. a kind of preparation method of flexible fluorescent paper based on azelon or cell cellulose according to claim 1, It is characterized in that：The specific method of the step S4 is：It weighs 0.3-0.5g polyvinylpyrrolidones and is dissolved in the anhydrous second of 30ml Alcohol is put into water-bath and heats 60-80 DEG C, stirs 10-30min, CdSe quantum dot-silkworm that isometric step S3 is obtained is added Silk complex solution or CdSe quantum dot-cell cellulose complex solution form polyvinylpyrrolidine after 30-60min Ketone coats the silk or cell cellulose complex solution of CdSe quantum dot.
7. a kind of preparation method of flexible fluorescent paper based on azelon or cell cellulose according to claim 1, It is characterized in that：The specific method of the step S5 is：Using teflon membrane filter or AAO filter membranes, step is filtered by vacuum The silk or cell cellulose complex solution of polyvinylpyrrolidone cladding CdSe quantum dot, are shelled after being then air-dried in S4 It is pasted from composite fluorescence azelon or the cell cellulose paper patch of getting off, and using the further oven-dry paper of vacuum drying oven, in so that paper is pasted Moisture evaporating completely form flexible fluorescent paper.
8. a kind of preparation method of flexible fluorescent paper based on azelon or cell cellulose according to claim 7, It is characterized in that：The step S5 is prepared in the technique of fluorescent paper, and teflon membrane filter or AAO filter sizes are 0.1- 0.5um, vacuum drying temperature are 70-80 DEG C.
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