CN103865180B - A kind of luminescent composite and preparation method thereof - Google Patents
A kind of luminescent composite and preparation method thereof Download PDFInfo
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- CN103865180B CN103865180B CN201210537744.8A CN201210537744A CN103865180B CN 103865180 B CN103865180 B CN 103865180B CN 201210537744 A CN201210537744 A CN 201210537744A CN 103865180 B CN103865180 B CN 103865180B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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Abstract
The invention discloses a kind of luminescent composite, this luminescent composite contains synthetic rubber and has the material of fluorescent characteristic, it is characterized in that, described in there is fluorescent characteristic material be si-nanocrystals, and the weight ratio of described synthetic rubber and described si-nanocrystals is 10-200:1. The invention also discloses a kind of preparation method of luminescent composite. The luminescent composite that adopts the method to obtain can keep fluorescent stability, and is nontoxic luminescent composite.
Description
Technical field
The present invention relates to a kind of luminescent composite and preparation method thereof.
Background technology
Along with the development of material science, the application of current high molecular polymer constantly expandsGreatly. The demand of macromolecule polymer material that has property for some is also for example, in continuous increase,Luminous high polymer polymer. Luminous high polymer polymer in road markings, luminous paint, rubber industry allThere is potential using value. Conventionally fluorescence polymer polymer is all to contain having of π key conjugated structureThe little molecular fluorescence compound of machine is introduced polymer lateral chain, the end of the chain or is passed through the method for fluorescent functional monomer polymerizationRealize. But, the at present common little molecular fluorescence compound with fluorescent characteristic used, oftenToxicity is higher, and they easily cause damage and contaminated environment to human body in synthetic and use procedure at material.
In recent years, si-nanocrystals, with its extraordinary bio-compatibility, is described as by scientists " green "Nano material, meanwhile, because its unique optics and characteristic electron get more and more people's extensive concerning always.Si-nanocrystals at room temperature has very strong photoluminescence property, and compared with organic light emission group, silicon is receivedMeter Jing Ti has the non-toxic and better anti-light fadedness that causes, and in addition, si-nanocrystals can be by regulatingParticle size, emission wavelength and the intensity of change luminescence generated by light. But si-nanocrystals is for such as inorganicAlkaline matter or nitrogenous comparatively sensitivity of organic matter, these materials easily make si-nanocrystals generation fluorescence quenchGo out, therefore, limited si-nanocrystals and applied more widely.
As can be seen here, need to solve the affected problem of fluorescent stability of si-nanocrystals.
Summary of the invention
The object of the invention is to solve the affected problem of fluorescent stability of si-nanocrystals, provide a kind ofLuminescent composite.
The present inventor finds, by si-nanocrystals is distributed to synthetic rubber in certain proportionIn, not only can keep the fluorescigenic stability of si-nanocrystals, and can obtain luminous synthetic rubber.
To achieve these goals, the invention provides a kind of luminescent composite, this luminescent composite containsHave synthetic rubber and there is the material of fluorescent characteristic, it is characterized in that, described in there is the material of fluorescent characteristicFor si-nanocrystals, and the weight ratio of described synthetic rubber and described si-nanocrystals is 10-200:1.
The present invention also provides a kind of preparation method of luminescent composite, and the method comprises: (1) will be byThe dispersion liquid that si-nanocrystals and the first organic solvent form, with to be dissolved with elastomeric organic solution mixedClose and obtain mixture; (2) remove the first organic solvent in described mixture and dissolve elastomeric theTwo organic solvents; The weight ratio of described synthetic rubber and described si-nanocrystals is 10-200:1, describedOne organic solvent and described the second organic solvent are identical or different.
The present invention also provides a kind of preparation method of luminescent composite, and the method comprises the following steps:(1) by HSiCl3Hydrolysis, hydrolysising condition comprises HSiCl3With the volume ratio of water be 1:1-3, hydrolysisTemperature is-80-0 DEG C that the time of hydrolysis is 15-45min; (2) step (1) gained solid product is existedRoasting 1-10h at 1100-1400 DEG C; (3) by step (2) products therefrom and reactant liquor at 20-30 DEG CAfter contact 30-180min, contact with the first organic solvent, then extract and separate is removed water, obtains silicon and receivesThe dispersion liquid that meter Jing Ti and the first organic solvent form; The body of described the first organic solvent and described reactant liquorLong-pending than being 1:3-6; Described reactant liquor contains HF, water and ethanol, described HSiCl3With HF moleThan being 1:15-45, the water in reactant liquor: the volume ratio of ethanol is 1:1-4; (4) by described dispersion liquidBe dissolved with elastomeric organic solution and be mixed to get mixture; (5) remove in described mixtureOne organic solvent and elastomeric the second organic solvent of dissolving; Wherein, described HSiCl3With described syntheticThe weight ratio of rubber is 1:0.25-10, described the first organic solvent identical with described the second organic solvent orDifferent.
The luminous composite wood that the present invention also provides a kind of preparation method who is provided by the invention described above to obtainMaterial.
By technique scheme, si-nanocrystals is mixed with certain proportion with synthetic rubber, not only makeSi-nanocrystals is subject to elastomeric protection, unlikely running into such as inorganic base substance or nitrogenous organicWhen solvent, the fluorescence radiation performance of si-nanocrystals is damaged, as shown in test case 1-4, wherein by siliconThe luminescent composite of nanocrystal and synthetic rubber composition is in the time running into NaOH and itrogenous organic substance, glimmeringThe long-time existence of light does not disappear; But while only having si-nanocrystals in comparative example 1, in the time running into NaOH,Fluorescence can only continue approximately 1 minute. By contrast, the phosphor persistence of luminescent composite provided by the inventionTime has improved greatly, has solved the affected problem of fluorescent stability of si-nanocrystals. And silicon is receivedMeter Jing Ti and synthetic rubber have formed a kind of new luminescent composite, because si-nanocrystals has veryGood bio-compatibility, does not have harmfulness to human body and environment, therefore, and this luminescent composite differenceIn existing fluorescence synthetic rubber, it is the luminescent composite of a kind of " green friendly ".
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 is the infrared spectrogram (FTIR) of luminescent composite F-1;
Fig. 2 is the Raman spectrogram of luminescent composite F-1;
Fig. 3 be fluorescence ethylene-propylene copolymer under ultra violet lamp (left figure) and under natural daylight (the right sideFigure) photo.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The present inventor, in experimentation, finds si-nanocrystals to join height with certain proportionIn molecule synthesis rubber, can obtain luminescent composite, weaken such as inorganic base substance or nitrogenousThe impact of organic matter on si-nanocrystals optical property, makes it have better fluorescent stability; And shapeThe luminescent composite becoming is environmentally friendly, non-toxic, completes thus the present invention.
The invention provides a kind of luminescent composite, this luminescent composite comprises synthetic rubber and hasThe material of fluorescent characteristic, is characterized in that, described in there is fluorescent characteristic material be si-nanocrystals, andThe weight ratio of described synthetic rubber and described si-nanocrystals is 10-200:1.
According to the present invention, as long as contain above-mentioned a certain amount of fluorescent characteristic that has in described luminescent compositeSi-nanocrystals just can there is the performance of sending fluorescence, the content of described si-nanocrystals can be widerScope in adjust. In the time that the weight ratio of described synthetic rubber and described si-nanocrystals is less than 10, canCan too much affect due to silicon nanocrystal body burden the performance of synthetic rubber part in luminescent composite; WhenThe weight ratio of described synthetic rubber and described si-nanocrystals is greater than at 200 o'clock, may be due to si-nanocrystalsContent is very few and make luminescent composite can not show the characteristics of luminescence. In order to obtain fluorescence property and reservationThe overall balance of the performance of synthetic rubber own, the weight ratio of described synthetic rubber and described si-nanocrystals is10-200:1。
In the present invention, use the si-nanocrystals with photoluminescence property as the thing with fluorescent characteristicMatter, forms described luminescent composite with synthetic rubber, and described si-nanocrystals can have fluorescent characteristic,And the si-nanocrystals of varying particle size, there is emission wavelength and the intensity of different luminescence generated by lights. ExcellentUnder selection condition, the particle size of described si-nanocrystals is below 10 nanometers; Further preferred described siliconThe particle size of nanocrystal is 1-8 nanometer.
The described si-nanocrystals using in the present invention, for without other element doping, has monocrystal silicon structure spyThe silicon materials of the nano-scale of levying.
According to the present invention, to obtaining the mode of described si-nanocrystals, there is no particular limitation, preferable caseUnder, after described si-nanocrystals is thermal decomposition silicon rich oxide, obtain by the method for hydrofluoric acid (HF) corrosionThe si-nanocrystals obtaining. Concrete grammar will be described hereinafter.
According to the present invention, the synthetic rubber in described luminescent composite can be multiple known synthetic rubberGlue, under preferable case, described synthetic rubber be ethylene-propylene copolymer, BS,One or more in polybutadiene and polyisoprene. The elastomeric molecular weight using can beIn wide scope, adjust, under preferable case, described elastomeric number-average molecular weight is 5000-1000000.Further preferred described synthetic rubber is ethylene-propylene copolymer, BS and poly-One or more in butadiene, wherein in ethylene-propylene copolymer, the mass percent of optimal ethylene is30%-80%; In BS, preferably the mass percent of butadiene is 40%-80%.
The present invention also provides a kind of preparation method of luminescent composite, and the method comprises: (1) will be byThe dispersion liquid that si-nanocrystals and the first organic solvent form, with to be dissolved with elastomeric organic solution mixedClose and obtain mixture; (2) remove the first organic solvent in described mixture and dissolve elastomeric theTwo organic solvents; The weight ratio of described synthetic rubber and described si-nanocrystals is 10-200:1, described inThe first organic solvent and described the second organic solvent are identical or different.
According to said method of the present invention, not only can well described si-nanocrystals be distributed to syntheticIn rubber, and do not damage si-nanocrystals, also do not affect the original main performance of synthetic rubber simultaneously.Described mixing can be for example general being uniformly mixed, and realizes described si-nanocrystals at described synthetic rubberIn dispersed, under preferable case, the condition of described mixing comprises: the temperature of described mixing is0-100 DEG C; The time of described mixing is 10-300 minute.
According to the present invention, under preferable case, described dispersion liquid can be by the preparation side comprising the following stepsMethod makes (improves " HSiO1.5Sol-gel polymerization structure and composition to the size of si-nanocrystals and send outThe impact of light characteristic " (InfluenceofHSiO1.5Sol-GelPolymerStructureandCompositionontheSizeandLuminescentPropertiesofSiliconNanocrystals，Chem.Mater.2009,21,5426-5434) in the preparation method that provides):
(1) by HSiCl3Hydrolysis, the condition of described hydrolysis comprises HSiCl3With the volume ratio of water be 1:1-3, the temperature of described hydrolysis is-80 DEG C to 0 DEG C, the time of described hydrolysis is 15-45min; Then subtractPress separated product and be dried under vacuum, collecting solid product; Wherein HSiCl3Density be 1.37g/ml;
(2) solid product step (1) being obtained roasting 1-10h at 1100-1400 DEG C; Preferably existReducing atmosphere (5 volume %H2/ 95 volume %Ar) lower heat treatment, heating rate is 15-20 DEG C/min;Product of roasting is further ground and obtains tiny product powder;
(3) step (2) products therefrom is contacted to 30-180min with reactant liquor at 20-30 DEG C after withThe first organic solvent contact, then extract and separate is removed water;
The volume ratio of described the first organic solvent and described reactant liquor is 1:3-6; Described reactant liquor containsHF, water and ethanol, described HSiCl3With the mol ratio of HF be 1:15-45, the water in reactant liquor:The volume ratio of ethanol is 1:1-4.
In the present invention, step (3) obtains the dispersion liquid being formed by si-nanocrystals and the first organic solvent.
In the present invention, HF preferably uses with the form of its aqueous solution. When described HF is with its aqueous solutionWhen form is used, the amount of water wherein also counts in the above-mentioned water yield. Step (3) can be first by step(2) products therefrom and H2O and CH3CH2OH contact forms uniform dispersion, subsequently that hydrofluoric acid is moltenLiquid (concentration is 48-49 % by weight, and density is 1.26g/ml) slowly adds. Control hydrofluoric acid solutionConsumption, and control the time that step (2) products therefrom contacts with reactant liquor, the silicon nanocrystal obtainingThe particle size of body can be, below 10 nanometers, to be preferably 1-8 nanometer.
The particle size of described si-nanocrystals can be by the si-nanocrystals particle in described dispersion liquidSize Expressing. In the present invention, described particle size refers to the maximum between two differences on particleAir line distance, when described particle is while being spherical, particle size refers to the diameter of this particle.
According to the present invention, described the first organic solvent is hydrophobic organic solvent. Under preferable case, described inThe first organic solvent is one or more in n-hexane, cyclohexane and pentane.
According to the present invention, while preparing described luminescent composite, described synthetic rubber can be by being dissolved intoIn the second organic solvent, form and be dissolved with after elastomeric organic solution, then mix with described dispersion liquid.At described dispersion liquid be dissolved with in the mixture that elastomeric organic solvent mixes, can think that silicon receivesMeter Jing Ti is distributed between synthetic rubber strand. Under preferable case, described in be dissolved with elastomeric organicSolvent is one or more in cyclohexane, n-hexane and pentane.
In the present invention, obtain after described mixture, then remove first organic molten through follow-up removal stepAgent and the second organic solvent. After removing step, obtain described luminescent composite, this luminescent composite is notOnly still there is the original performance of synthetic rubber of composition composite, there is again fluorescence radiation performance simultaneously.Described removal step can be used the method for this area routine.
The present invention also provides a kind of preparation method of luminescent composite, and the method comprises the following steps: (1)By HSiCl3Hydrolysis, hydrolysising condition comprises HSiCl3With the volume ratio of water be 1:1-3, the temperature of hydrolysisFor-80 DEG C to 0 DEG C, the time of hydrolysis is 15-45min; (2) by step (1) products therefrom at 1100-1400Roasting 1-10h at DEG C; (3) step (2) products therefrom is contacted at 20-30 DEG C with reactant liquorAfter 30-180min, contact with the first organic solvent, then extract and separate is removed water, obtains silicon nanocrystalThe dispersion liquid that body and the first organic solvent form; The volume ratio of described the first organic solvent and described reactant liquorFor 1:3-6; Described reactant liquor contains HF, water and ethanol, described HSiCl3With the mol ratio of HF be1:15-45, the water in reactant liquor: the volume ratio of ethanol is 1:1-4; (4) by described dispersion liquid and dissolvingThere is elastomeric organic solution to be mixed to get mixture; (5) remove first organic in described mixtureSolvent and elastomeric the second organic solvent of dissolving; Wherein, described HSiCl3With described elastomericWeight ratio is 1:0.25-10, and described the first organic solvent and described the second organic solvent are identical or different.
Experiment showed, and control described HSiCl3With described elastomeric weight ratio be 1:0.25-10 modelEnclose interior and adopt said method, the described synthetic rubber in the described luminescent composite obtaining and described siliconThe weight ratio of nanocrystal is 10-200:1.
In step (1), by HSiCl3After hydrolysis, then decompression separation product dry under vacuum,Collect product, wherein HSiCl3Density be 1.37g/ml.
In step (2), preferred described roasting is at reducing atmosphere (5 volume %H2/ 95 volume %Ar)Lower heat treatment, heating rate is 15-20 DEG C/min; And further product of roasting grinding is obtained tinyProduct powder.
In the present invention, step (3) obtains the dispersion liquid being formed by si-nanocrystals and the first organic solvent.
In the present invention, HF preferably uses with the form of its aqueous solution. When described HF is with its aqueous solutionWhen form is used, the amount of water wherein also counts in the above-mentioned water yield. Step (3) can be first by step(2) products therefrom and H2O and CH3CH2OH contact forms uniform dispersion, subsequently that hydrofluoric acid is moltenLiquid (concentration is 48-49 % by weight, and density is 1.26g/ml) slowly adds. Control hydrofluoric acid solutionConsumption, and control the time that step (2) products therefrom contacts with reactant liquor, the silicon nanocrystal obtainingThe particle size of body can be, below 10 nanometers, to be preferably 1-8 nanometer. Described si-nanocrystalsParticle size is described above, does not repeat them here.
According to the present invention, under preferable case, the condition of described mixing comprises: the temperature of described mixing is0-100 DEG C; The time of described mixing is 10-300 minute.
According to the present invention, under preferable case, described the first organic solvent and described the second organic solvent are for justOne or more in hexane, cyclohexane and pentane.
The luminescent composite that the present invention also provides a kind of preparation method who is provided by the invention described above to obtain.
According to the present invention, in described dispersion liquid, the content of si-nanocrystals can be described above, at this no longerRepeat, and can further calculate thus described synthetic rubber in described luminescent composite with described inThe weight ratio of si-nanocrystals is 10-200:1.
Below will describe the present invention by embodiment.
In following examples, the particle size of si-nanocrystals is by FEITitan80-300 rectification type AsiaDust resolution ratio transmission electron microscope records under 300kV condition.
Preparation example
This preparation example is for illustrating the dispersion being formed by si-nanocrystals and the first organic solvent of the present inventionThe preparation method of liquid.
According to " HSiO1.5Size and the luminous spy of sol-gel polymerization structure and composition to si-nanocrystalsThe impact of property " (InfluenceofHSiO1.5Sol-GelPolymerStructureandCompositionontheSizeandLuminescentPropertiesofSiliconNanocrystals，Chem.Mater.2009,21,5426-5434) in prepare after the method improvement that provides.
(1) by the HSiCl of 1.42ml3(density is 1.37g/ml) adds round-bottomed flask, use acetone-Dry ice is cooling, magnetic agitation. Treat HSiCl3Temperature is reduced to 0 DEG C, adds wherein rapidly 4.2ml to goIonized water also stirs. Reaction 30min to be to ensure complete hydrolysis, then decompression separation product under vacuumDry, obtain white solid product;
(2) white solid product is placed in high-temperature tubular roaster, at reducing atmosphere (5% volumeH2/ 95 volume %Ar) lower heat treatment, heating rate is 18 DEG C/min, treatment temperature is 1200 DEG C, roasting4 hours burning time. Heat-treated products cool to room temperature is obtained to dark brown solid product, and further grindMill obtains tiny dark brown solid powder;
(3) will in dark brown solid powder, add 6mlH2O and 12mlCH3CH2OH, stirs and makes itDispersed, slowly add subsequently the HF solution 20ml of 49 quality %, and stir at normal temperatures 150Minute, then add 10ml n-hexane, extract and separate si-nanocrystals, obtain si-nanocrystals with justThe dispersion liquid Si-1 that hexane forms.
Si-1 is carried out to the particle size determination of si-nanocrystals, the particle size that records si-nanocrystals is8 nanometers.
According to the content in document (Chem.Mater.2006,18,6139-6146), according to pass belowBe the theoretical quality of calculating the Si obtaining of formula (1), and further calculating obtain si-nanocrystals in Si-1Content be 0.01g/ml.
Formula (1):
Embodiment 1
The present embodiment is for illustrating the preparation method of luminescent composite of the present invention.
(1) by 5g BS, (China Petrochemical Industry produces, and trade mark SSBRY031 counts allMolecular weight is 18.3 ten thousand, butadiene content 73 % by weight) be dissolved in 50ml cyclohexane, dissolvedThere is the cyclohexane of BS;
(2) 10mlSi-1 is joined to 10ml(1) obtain be dissolved with BSCyclohexane in mix, mixing temperature is 25 DEG C, mixing time is 60 minutes, obtains mixture M-1;
(3) M-1 is placed on to the n-hexane and the cyclohexane that in vent cabinet, ventilate in volatilization M-1, obtainsLuminescent composite F-1.
Calculate the weight of BS and si-nanocrystals in F-1 according to inventoryThan being 10:1.
F-1 is carried out to infrared spectrum analysis, and its FTIR spectrogram as shown in Figure 1. Can from Fig. 1Go out, luminescent composite F-1 is at 2918cm-1And 2843cm-1There is very strong absworption peak at place, and this is materialIn material, hydrocarbon stretching vibration causes, at 1440cm-1Also there is the curved of the hydrocarbon singly-bound on saturated hydrocarbonsBent vibration peak. In addition, at 990cm-1、966cm-1、910cm-1Place is the hydrocarbon vibration peak on alkene,Meanwhile, 1641cm-1Place is carbon-carbon double bond stretching vibration absorption, and 724cm-1Place is monosubstituted phenyl ringAbsworption peak. Illustrate that BS structure still keeps, the introducing of si-nanocrystals is not rightItself structure impacts. And can observe fluorescence under ultra violet lamp.
Test case 1
This test case is for illustrating the fluorescent stability of luminescent composite of the present invention.
0.1gF-1 prepared by embodiment 1 adds stirring in 5.0mlNaOH solution (pH=13),Under ultra violet lamp, observing 2 hours fluorescence does not disappear.
Test case 2
This test case is for illustrating the fluorescent stability of luminescent composite of the present invention.
After 0.1gF-1 prepared by embodiment 1 is dissolved in 2.0ml cyclohexane, then add 5.0mlNaOHSolution (pH=13) stirs, and observes 20 minutes fluorescence and do not disappear under ultra violet lamp.
Comparative example 1
According to the method in test case 2, different, get the dispersion liquid of 2.0mlSi-1 and cyclohexane,Wherein Si-1 and cyclohexane volume ratio are 1:1, and alternative 0.1gF-1 is dissolved in 2.0ml cyclohexane and stirs,Under ultra violet lamp, observing approximately 1 minute fluorescence disappears.
Embodiment 2
The present embodiment is for illustrating the preparation method of luminescent composite of the present invention.
(1) by 5g ethylene-propylene copolymer, (number-average molecular weight is 6.9 for PetroChina Company Limited.'s product, trade mark J0030Ten thousand, ethylene contents 46-50 % by weight) be dissolved in 50ml n-hexane, obtain being dissolved with ethylene-propylene altogetherThe n-hexane of polymers;
(2) 5.0mlSi-1 is joined to 100ml(1) obtain be dissolved with ethylene-propylene copolymerIn n-hexane, mix, mixing temperature is 50 DEG C, and mixing time is 120 minutes, obtains mixture M-2;
(3) M-2 is placed on to the n-hexane ventilating in volatilization M-2 in vent cabinet, obtains luminous compoundMaterial F-2.
Calculating the weight ratio of ethylene-propylene copolymer and si-nanocrystals in F-2 by inventory is200：1。
F-2 is carried out to Raman spectrum analysis, and the Raman spectrogram of F-2 as shown in Figure 2. Can from Fig. 2Find out, luminescent composite F-2 is at 500cm-1There is wider absworption peak at place, contrast document (J.Phys.Chem.C2007,111,6956-6961) in the Raman spectrum data of disclosed si-nanocrystals, this suctionReceiving peak is that in material, si-nanocrystals causes, illustrates that si-nanocrystals is present in F-2.
Can find out from Fig. 3 (left figure), fluorescence ethylene-propylene copolymer demonstrates significantly orange red glimmeringLight. Visible, luminescent composite according to the present invention has fluorescent characteristic.
Test case 3
0.1gF-2 prepared by embodiment 2 is dissolved in 2.0ml n-hexane, adds 0.05mlN, N-The dimethyl formamide aqueous solution (concentration is 20mol/L) stirs. Under ultra violet lamp, observe approximately 4 pointsClock fluorescence does not disappear.
Comparative example 2
According to the method in test case 3, different, get the dispersion liquid of 2.0mlSi-1 and n-hexane,Wherein Si-1 and n-hexane volume ratio are 1:2, and alternative 0.1gF-2 is dissolved in 2.0ml n-hexane, addsEnter 0.05mlN, the dinethylformamide aqueous solution (concentration is 20mol/L). Under ultra violet lamp, enterRow stirs, and observes phosphor persistence and disappears for approximately 30 seconds.
Embodiment 3
(1) by 5g dienite, (number-average molecular weight is 13.0 for Sinopec product, LCBR1403Ten thousand) be dissolved in 50ml n-hexane, obtain being dissolved with the n-hexane of dienite;
(2) 1.0mlSi-1 is joined to 10ml(1) obtain be dissolved with dienite just oneselfIn alkane, mix, mixing temperature is 80 DEG C, and mixing time is 30 minutes, obtains mixture M-3;
(3) M-3 is placed in vent cabinet to n-hexane in the volatilization M-3 that ventilates, obtains luminous composite woodMaterial F-3.
Calculating the weight ratio of dienite and si-nanocrystals in F-3 by inventory is 100:1.
Test case 4
0.1gF-3 prepared by embodiment 3 is dissolved in 2.0ml pentane, adds 0.05ml anilineThe aqueous solution (concentration is 20mol/L) stirs. Under ultra violet lamp, observing 20 minutes fluorescence does not disappear.
Comparative example 3
According to the method in test case 4, different, get the dispersion liquid of 2.0mlSi-1 and pentane,Wherein Si-1 and pentane volume ratio are 1:10, and alternative 0.1gF-3 is dissolved in 2.0ml pentane, addsEntering 0.05ml aniline-water solution (concentration is 20mol/L) stirs. Under ultra violet lamp, observe 2 minutesFluorescence disappears.
Synthetic rubber in embodiment 1-3 itself is without photoluminescent property, from the infrared spectrum of embodiment 1Analysis result can find out, adding of si-nanocrystals do not affect contain in luminescent composite syntheticThe structure of rubber components. In Raman spectrogram result, prove in luminescent composite provided by the inventionReally have si-nanocrystals, and make this luminescent composite there is fluorescent characteristic. Testing thisWhen luminescent composite F-1, the F-2 providing in bright and the fluorescent stability of F-3 (seeing test case 1-4),F-1, F-2 and F-3 can have the longer phosphor persistence time, and the synthetic rubber that contains provided by the invention is describedThe luminescent composite of glue and si-nanocrystals can solve the fluorescent stability problem of si-nanocrystals, noBe subject to the impact such as inorganic base and itrogenous organic substance.
In test case 2,3,4, F-1, F-2 and F-3 are dissolved in the second organic solvent, but stillThan the si-nanocrystals in comparative example 1-3 (si-nanocrystals directly contacts with inorganic base or itrogenous organic substance)There is the longer fluorescence radiation duration, the adding of visible synthetic rubber component reached stable silicon nanocrystallineThe effect of the fluorescent stability of body.
Luminescent composite provided by the invention can prevent the fluorescent quenching of si-nanocrystals well, carriesThe high fluorescent stability of si-nanocrystals.
Luminescent composite provided by the invention is mixed to form by si-nanocrystals and synthetic rubber, because ofBe nontoxic and bio-compatibility that had for having the si-nanocrystals of fluorescent characteristic, therefore this is luminous multipleCondensation material is the luminescent composite of a kind of " green friendly ".
Claims (7)
1. a preparation method for luminescent composite, the method comprises the following steps:
(1) by HSiCl3Hydrolysis, hydrolysising condition comprises HSiCl3With the volume ratio of water be 1:1-3, waterThe temperature of separating is-80 DEG C to 0 DEG C, and the time of hydrolysis is 15-45min;
(2) by step (1) gained solid product roasting 1-10h at 1100-1400 DEG C;
(3) step (2) products therefrom is contacted to 30-180min with reactant liquor at 20-30 DEG C after withThe first organic solvent contact, then extract and separate is removed water, obtains si-nanocrystals and first organic moltenThe dispersion liquid that agent forms;
The volume ratio of described the first organic solvent and described reactant liquor is 1:3-6; Described reactant liquor containsHF, water and ethanol, described HSiCl3With the mol ratio of HF be 1:15-45, the water in reactant liquor:The volume ratio of ethanol is 1:1-4;
(4) by described dispersion liquid be dissolved with elastomeric organic solution and be mixed to get mixture;
(5) remove the first organic solvent in described mixture and dissolve elastomeric second organic moltenAgent;
Wherein, described HSiCl3With described elastomeric weight ratio be 1:0.25-10, described first hasMachine solvent and described the second organic solvent are identical or different.
2. method according to claim 1, wherein, the condition of described mixing comprises: described mixedThe temperature of closing is 0-100 DEG C; The time of described mixing is 10-300 minute.
3. method according to claim 1 and 2, wherein, described the first organic solvent and described inRespectively do for oneself one or more in n-hexane, cyclohexane and pentane of the second organic solvent.
4. the luminous composite wood being obtained by the preparation method described in any one in claim 1-3Material, this luminescent composite contains synthetic rubber and has the material of fluorescent characteristic, it is characterized in that instituteStating the material with fluorescent characteristic is si-nanocrystals, and described synthetic rubber and described si-nanocrystalsWeight ratio is 10-200:1.
5. luminescent composite according to claim 4, wherein, described si-nanocrystalsParticle size is below 10 nanometers.
6. luminescent composite according to claim 5, wherein, described si-nanocrystalsParticle size is 1-8 nanometer.
7. according to the luminescent composite described in any one in claim 4-6, wherein, described in closeOne-tenth rubber is ethylene-propylene copolymer, BS, polybutadiene and polyisopreneIn one or more.
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