CN107056974A - A kind of preparation method of nanocrystal/polymer solid solution - Google Patents
A kind of preparation method of nanocrystal/polymer solid solution Download PDFInfo
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- CN107056974A CN107056974A CN201610136707.4A CN201610136707A CN107056974A CN 107056974 A CN107056974 A CN 107056974A CN 201610136707 A CN201610136707 A CN 201610136707A CN 107056974 A CN107056974 A CN 107056974A
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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Abstract
The present invention relates to a kind of new nanocrystal/polymer solid-solution material preparation method.Wherein nanocrystal can be noble metal nanocrystalline (Au, Ag etc.), the nanocrystal of semiconductor nano (such as II VI races semiconductor nano) and metal/semiconductor heterostructure, solid-solution material is made by the nanocrystalline home position polymerization reaction between polymer monomer (such as MMA, DMS etc.) in the present invention.In the nanocrystal/polymer solid-solution material, the oleic oil amine key of polymer monomer and quantum dot surface is utilized to carry out ion-exchange reactions, it is to avoid nanocrystalline reunion in the polymer, and then realize preparation of the inorganic nano-crystal in polymer solid solution.Preparation process is carried out at room temperature in atmosphere, cost is low, harsh environment condition is not needed, process green, environmental protection, and the preparation from Centimeter Level to meter level material can be realized, the practical application of nanocrystalline material is realized, finished product can be widely applied to many fields such as solar energy capture, building, luminescent device.
Description
Technical field
Inorganic nanocrystal/organic polymer composite material field is prepared the invention belongs to chemical method, and in particular to nanometer
Crystal, such as noble metal nanocrystalline (Au, Ag etc.), semiconductor nano (such as II-VI group semiconductor nano) and metal/semiconductor are led
The nanocrystal of bulk heterojunction structure, is uniformly compounded to form block or film-form solid solution in polymer (such as PDMS, PMMA)
Method.Characterized in that, nanocrystal surface utilizes polymer precursor such as first class methyl acrylate (MMA), dimethyl silica
Alkane (DMS) ion exchange, makes nanocrystal surface stable by polymer precursor.Sent out by polymer precursor in nanocrystal surface
Raw home position polymerization reaction, realizes the synthesis of nanocrystal/polymer solid solution.Preparation can in atmosphere at room temperature, and cost is low, no
Need harsh environment condition, process green, environmental protection.The polymer solid solution size of preparation can reach macro-size, such as from
Centimetre arrive meter level, shape can arbitrarily regulate and control, and avoid the reunion of nanocrystal, both maintained nanocrystal physics, change
Property is learned, the destruction that the addition of nano material is caused to polymer architecture is turn avoid.
Technical background
Currently, nano crystal material, such as noble metal nanocrystalline, semiconductor nano material, because its abundant optics, electricity
Learn property, such as surface plasma body resonant vibration (SPR) effect, fluorescence property and the efficient light of metal/semiconductor hetero-nanocrystals
Raw electrons separation effect, makes it be captured in solar energy, photocatalysis, luminescent device, photoelectric device, the application side such as laser
Face has good application.How nanocrystalline skin effect is fully being kept, size also can the nanometer such as effect and quantum effect
Effect, is that the nanocrystalline materials such as metal, semiconductor are able in photoelectricity while being assembled into macroscopical, controllable size by nanocrystalline
The required premise of application in terms of device, photovoltaic glass.In recent years, it is prepared as the above-mentioned photoelectric device that can be used
A kind of critically important approach is exactly will be dispersed in high molecular polymer, and it is a kind of effectively method to form solid solution,
And the flexibility of polymeric material can be made full use of, do flexible device.But be due to nanocrystalline material itself have compared with
Strong surface-active and interfacial effect, it is difficult to dispersed and easily reunited in the polymer, causes it to lose
Excellent light, the electrical properties having originally are removed, the addition of nanocrystal in addition also results in polymeric material self performance
Decline, it is difficult to realize good utilization.
In view of drawbacks described above, the invention provides a kind of method for preparing inorganic nanocrystal/polymer solid solution, wherein
Inorganic nanocrystal can be noble metal nanocrystalline (Au), metal-doped semiconductor nano (CdS of the doping such as Ag, Cu, Co,
CdSe is nanocrystalline), heterojunction structure metal-semiconductor nanocrystalline (Au/CdS nano-crystal with core-shell structure, Au/ZnS nuclear shell structure nanos
Crystalline substance etc.), polymeric matrix can be PMMA or PDMS etc..The innovative point of the present invention is to utilize ion-exchange reactions, passed through
Polymer precursor occurs home position polymerization reaction in nanocrystal surface and prepares solid solution, makes nanocrystalline not reunite.Compound
Solid solution bulk can form centimetre macro-size for arriving meter level, and preparation process is carried out at room temperature in atmosphere, and cost is low, is not required to
Want harsh environment condition, process green, environmental protection can be widely applied to solar energy capture, photovoltaic glass, building, flexible light
Many fields such as device.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of new nanocrystal/polymer solid solution, to solve
Certainly above-mentioned technological deficiency.
To achieve the above object, the technical solution adopted by the present invention is, by inorganic nanocrystal in first class acrylic acid first
Disperse and in-situ polymerization in ester (MMA) or dimethyl siloxane (DMS).Realize that nanocrystalline wherein dispersed is made.
It is described nanocrystalline including simple metal is nanocrystalline, semiconductor nano, core shell structure metal/semiconductor hetero-nanocrystals, it is prepared
Block solid solution there is good translucency, the photoelectric properties that inorganic nano-crystal itself can be kept excellent.
Secondly there is provided a kind of manufacture method for preparing above-mentioned new nanocrystal/polymer solid solution, including following step
Suddenly：
Step 1：The toluene colloidal sol of the inorganic nano-crystal of a certain amount of oleic acid/oleyl amine surface modification is taken, 60 DEG C are placed on very
Dry 1-2h is vacuumized in empty baking oven, it is stand-by；
Step 2：Methyl methacrylate (MMA) monomer is purified, the 0.1mol/L NaOH aqueous solution is prepared, by matter
Amount compares 1：1 mixes a certain amount of MMA monomers with the above-mentioned aqueous solution, is placed in separatory funnel, shakes repeatedly, then outwells lower floor
Liquid, adds with taking the deionized water of the quality such as MMA monomers to repeat concussion washing 2-3 times, then takes out supernatant liquid
Addition anhydrous calcium chloride powder in beaker is placed in, 0.5h, filtering, the MMA monomers purified, in the MMA monomers of purifying is stood
Middle dissolving mass fraction obtains MMA/PMMA mixed solutions for 10% PMMA.
Step 3：By in the nanocrystalline MMA/PMMA mixed solutions being distributed to described in step 2 described in step 1, ultrasonic 1h is extremely
It is uniformly dispersed, is subsequently added the initiator that mass fraction is 800ppm and shakes uniform, be placed in 85 DEG C of oil bath pan and carry out pre-polymerization
Change, intermittently shaken during reaction, the control in reaction time is：The viscosity for carrying out reactant with reaction will gradually increase, to one
Implode will be occurred by determining degree, shown as reactant vigorous reaction and started bubble occur, be now immediately placed in reactant cold
Reaction is quenched in water, the thick liquid that pre- dimerization is completed is obtained, curing degree now is about 20-30%；
Step 4：Performed polymer is poured into mould and good seal, in the baking oven for being placed in 50 DEG C, solidifies 32h, sample is substantially solid
Change and complete, curing degree now is about 80-90%, then sample is placed in 120 DEG C of baking ovens solidifies 2h, complete last solidification,
Now curing degree reaches more than 90%.
Nanocrystal/PDMS solid solution preparation steps：
Step 1：The toluene colloidal sol of the inorganic nano-crystal of a certain amount of oleic acid/oleyl amine surface modification is taken, 60 DEG C are placed on very
Dry 1-2h is vacuumized in empty baking oven, it is stand-by；
Step 2：Nanocrystalline by above-mentioned drying is distributed in PDMS curing agent, and ultrasonic 1h is subsequently added to being uniformly dispersed
It is 1 with curing agent mass ratio：10 polymer monomer, stirs at room temperature, then ultrasound 0.5h again；
Step 3：Above-mentioned reactant is placed in room temperature in vacuum drying oven and vacuumizes about 10min, the bubble in reactant is removed,
Reactant is then poured into mould, is placed in 120 DEG C of baking ovens and solidifies 1h, obtain finished product.
Wherein described polymer precursor is methyl methacrylate (MMA) or dimethyl siloxane (DMS).
It is wherein described it is nanocrystalline be Au nanocrystalline；Ag doping CdS or CdSe is nanocrystalline；Cu doping CdS is nanocrystalline；Cu mixes
The metal-doped CdS of the miscellaneous nanocrystalline Ag＆Mx of CdS (Mx=Mn, Co, Ni, Fe) is nanocrystalline；Au/CdS or Au/ZnS core shell structures
It is nanocrystalline；Its preparation method is preferably, but not limited to, following method：
Au nanometers of crystal preparation methods：
0.1mmol HAuCl4·4H22min, Zhi Houxun is stirred at room temperature in O, 0.5ml oleyl amine (Yi Nuokai), 5ml toluene
Speed is transferred in oil bath, leads to nitrogen protection, using condensation reflux unit, is cooled to room temperature after stirring 5h in 95 DEG C, is obtained dark red
Color gel.Be diluted to after 15ml, in 2000r/10min remove precipitate, remaining supernatant to add 3ml ethanol every time,
4000r/10min carries out substep centrifugation, can be precipitated completely for 5 times when adding 3ml ethanol *, and the precipitation after centrifugation is disperseed again every time
Into 20ml toluene.
The brilliant synthesis of Au/CdS, Au/ZnS core-shell nano
Step 1：Take above-mentioned Au 2.5ml to be diluted to after 16ml, be transferred to after adding 1ml oleyl amines (Yi Nuokai) ultrasound 10min
In 20ml screw sockets bottle, the AgNO that 2ml now matches somebody with somebody is added3- absolute methanol solution (the two ratio is 0.1g/10ml, ultrasonic 30min) is vertical
After sealing, it is placed in baking oven, 24h is reacted in 70 DEG C.Reaction taken out after terminating it is cold go, colloidal sol is in orange red in bottle.It is every afterwards
Secondary addition 5ml absolute ethyl alcohols 4500r/10min carries out substep centrifugation, every batch of precipitate size difference, it should use in batches.
Step 2：10ml oleic acid, 5ml oleyl amines are sequentially added to stir at room temperature in 50ml round-bottomed flask, adds
64mg S powder, is stirred after 2min at room temperature, and 40min is stirred in 100 DEG C of oil baths, then adds 15ml toluene thereto, and stirring is equal
Even, it is stand-by that temperature is down to room temperature.
Step 3：Certain a batch of Au Ag precipitation of substep centrifugation gained is taken, is dispersed in 16ml toluene, is stirred at room temperature down and adds
Enter colloidal sol after 2ml S presomas, stirring 30min and become blackish green or green black colour, the ethanol for adding equivalent is complete in 5000r/10min
Centrifugation, is precipitated stand-by.
Step 4：By Au@Ag2S precipitations are scattered in 20ml toluene, are stirred at room temperature down, add 200ul oleic acid, 100ul
Cd (NO3) 2- methanol solutions or Zn (NO that 4ml now matches somebody with somebody are added after oleyl amine, stirring 5min3)2(ratio is 0.2g/ to-methanol solution
10ml, ultrasonic dissolution) continue to stir after 10min, 120ul TBP are added, continue to be transferred in oil bath after stirring 2min, in 80 DEG C
Stir 2h.After reaction terminating, be centrifuged off prior to 5000r/10min after precipitation, supernatant to add 5ml absolute ethyl alcohols every time,
Substep centrifugation is carried out under 5000r/10min.It can precipitate completely for substantially 5ml*3 times.Precipitation is dispersed in 5ml toluene again.
Au/CdS is in turquoise in green, Au/ZnS after scattered.
Ag CdS or CdSe nanometers of crystal preparation method of doping：
Step 1：N is first passed through into three-necked flask2, and 20ml oleic acid 20ml oleyl amines are rapidly joined, it is stirred at room temperature, weighs one
Quantitative silver nitrate powder is added in above-mentioned mixed solution, after appropriate stirring, weighs the appropriate nitric hydrate iron of catalysts four brilliant
Body is added thereto, and is warming up to 120React 1h；Ethanol purification is centrifuged, and gained sediment is distributed in 14ml toluene, obtained
To the toluene colloidal sol of 5nm silver.
Step 2：Added into round-bottomed flask and sequentially add 10ml oleyl amines, 20ml oleic acid, 128mg sulphur powders, in 100Oil
Stirring reaction 40min in bath, is cooled to room temperature, and the presoma that addition q. s. toluene solution obtains sulphur into above-mentioned mixed solution is molten
Liquid；
16ml octadecylenes are taken in three-necked flask, 158mg selenium powders is weighed and adds in three-necked flask, heated in heating mantle,
Temperature is set as 280Until selenium powder all dissolves, the solution of yellow clarification is obtained.And add thereto appropriate toluene,
Oleic acid, oleyl amine, magnetic agitation are uniform, obtain the precursor solution of selenium
Step 3：The monodispersed 5nm Ag of 350 μ L (10nm Ag) toluene colloidal sol is taken in 25ml round-bottomed flask, Xiang Qi
Middle addition 6ml toluene and 3ml sulphur or selenium precursor solution, in 50Stirred in water bath reaction 1h, ethanol centrifuge washing,
Obtain monodispersed Ag2S nano particles, are distributed in 6~10ml toluene, obtain Ag2The toluene colloidal sol of X nano particle.
Cu CdS or CdSe nanometers of crystal preparation method of doping：
Step 1：5mmol (1.5323g) odium stearate is weighed in 250ml round-bottomed flasks, 70ml n-hexanes, stirring is added
3min, then adds 40ml methanol.Take 2.5mmol (426.2mg) Hydrated copper chloride to be dissolved in 10ml methanol, instill above-mentioned mixing
In solution, 10ml pure water is eventually adding, 52 DEG C of stirred in water bath react 4h, take out lower floor blueness Cu (St) in flask2, ethanol
Centrifuge washing twice, is placed in 60 DEG C of baking ovens and dried.
Step 2：0.25mmol (157.7mg) Cu (St) 2 powder is weighed in 10ml reactors, 5ml oil is added thereto
Acid, 3ml oleyl amines stir 5min, take 0.25ml n- dodecyl mereaptans to add in above-mentioned mixed liquor, stir, and seal, are placed in 200
2.5h in DEG C baking oven, takes out the Cu2S solution of brown, the purifying of ethanol centrifuge washing, and gained precipitation is distributed in 8ml toluene.
Step 3：The methanol of toluene colloidal sol nanocrystalline above-mentioned Cu2S and 1ml Cd (NO3) 2.4H2O (0.1g/ml) is molten
Liquid is mixed in 25ml round-bottomed flask, is stirred, and adds 0.1ml TBP, and 56 DEG C of stirred in water bath react 2h, ethanol
Centrifuge washing is purified, and gained precipitation is distributed in 1ml toluene, obtains finished product.
CdS nanometer crystal preparation methods ion co-doped Ag＆Mx (Mx=Mn, Co, Ni, Fe)：
Step 1：Single dispersing Ag2S is prepared, CdS nanometers of crystal preparation methods of above-mentioned Ag doping are referred to.
Step 2：By Ag2S nano particle colloidal sols, under magnetic stirring, add 0.2ml oleic acid, 0.1ml oleyl amines and appropriate
Cd2+ ion alcoholic solutions, stir 5min, then add into above-mentioned mixed solution the corresponding salting liquids of appropriate Mx, magnetic agitation
2min, adds 0.1ml TBP, in 60In water-bath, stirring reaction 2h, ethanol centrifugal purification.
Compared with prior art, beneficial effects of the present invention are：
1. inorganic nanocrystal prepared by the present invention/polymer solid solution, by the nanocrystalline with polymerizeing of surface modification
Home position polymerization reaction is carried out between thing monomer, nanocrystalline in the polymer dispersed is realized, had both maintained nanocrystalline script
The photoelectric property being had, turn avoid destruction of the nanocrystalline addition to polymeric material structure.
What 2. the present invention was used nanocrystalline can involve noble metal nanocrystalline, semiconductor nano, heterojunction structure metal/semiconductor
Conductor is nanocrystalline etc. nanocrystalline, and the solid solution of preparation remains nanocrystalline light, the electrical property of itself, and application field is enriched, such as too
Sun can capture field-solar energy fluorescence collector, building field --- energy-saving glass, luminescent device --- nano laser etc.
Many fields.
3. the invention provides the preparation method of nanocrystal/polymer solid solution, manufacturing condition is gentle, and device is simple,
Green easy, cost is low, can large area, macro-size (from centimetre to meter level) manufacture, have broad application prospects.
4. the invention provides the preparation method of nanocrystal/PMMA solid solution, pre- dimerization temperature is 85 DEG C, can be direct
Carried out in oil bath pan, the initiator used is oil-soluble azo initiator azodiisobutyronitrile, and it is used as initiator for reaction
It is stable, it is first order reaction, without side reaction, relatively good control.
Brief description of the drawings
Fig. 1 is that in-situ polymerization prepares nanocrystal/polymer solid solution schematic diagram
Fig. 2 be the doping such as different shape Ag, Cu, Co CdS prepared by embodiment 1 it is nanocrystalline/outside drawing of PMMA solid solution
And the luminous picture under 365nm ultraviolet lights；
Fig. 3 is that the doping such as Ag, Cu, Co prepared by embodiment 1 CdS is nanocrystalline forms solid solution in toluene matrix and with PMMA
UV spectrograms contrast afterwards；
Fig. 4 is that the doping such as Ag, Cu, Co prepared by embodiment 1 CdS is nanocrystalline forms solid solution in toluene matrix and with PMMA
PL spectrograms contrast afterwards；
Au/CdS core-shell nanos crystalline substance/PMMA, Au/ZnS nucleocapsid that Fig. 5 is embodiment 2, prepared by embodiment 3, embodiment 4 is received
Meter Jing/PMMA, Au/PMMA, mixed nano-crystal/PMMA solid solution outside drawings；
Au/CdS core-shell nanos crystalline substance/PMMA, Au/ZnS core-shell nano prepared by Fig. 6 embodiments 2, embodiment 3, embodiment 4
Crystalline substance/PMMA, Au/PMMA, mixed nano-crystal/PMMA solid solution UV spectrograms contrast；
Fig. 7 is Ag doping CdS/PDMS solid solses made from embodiment 5 and Cu doping CdS/PDMS outside drawing.
Embodiment
In order to absolutely prove the characteristic of the present invention and implement the mode of the present invention, embodiment is given below.
Embodiment 1
(1) 1mLAg, Cu, Co, Ni, Mn doping nanocrystalline toluene colloidal sols of CdS are taken, are placed in vacuum drying chamber, 60 DEG C of vacuum
1h is dried, Ag, Cu, Co, Ni, Mn doping CdS semiconductor nano particles are obtained stand-by；
(2) 0.1mol/L NaOH aqueous solution 10g are prepared, are placed in after being mixed with 10gMMA monomers in separatory funnel, repeatedly
Concussion for several times, then outwells lower floor's liquid, adds 10g deionized waters, repeats concussion washing 2-3 times, until the lower floor poured out
Untill liquid shows neutral；Then supernatant liquid is taken out to be placed in beaker and add a certain amount of anhydrous calcium chloride powder, stood
0.5h, filtering, the MMA monomers purified add the PMMA that mass fraction is 10%, 60 degrees Celsius in purifying MMA monomers
Stirring in water bath dissolves, and obtains MMA/PMMA mixed solutions；
(3) by it is above-mentioned it is nanocrystalline be distributed in MMA/PMMA mixed solutions, ultrasonic 1h is subsequently added quality to being uniformly dispersed
Fraction is uniform for 800ppm initiator azodiisobutyronitrile concussion, is placed in 85 DEG C of oil bath pan and carries out pre- dimerization, reacts the phase
Between intermittently shake, the time of reaction controlling is：The viscosity for carrying out reactant with reaction will gradually increase, to a certain degree will
Generation implode, shows as reactant vigorous reaction and starts bubble occur, and now reactant is placed in cold water immediately and is quenched instead
Should, the thick liquid that pre- dimerization is completed is obtained, curing degree now is about 20-30%；
(4) above-mentioned mucus is poured into mould and good seal, in the baking oven for being placed in 50 DEG C, solidifies 32h, sample solidifies substantially
Complete, curing degree now is about 80-90%, then sample is placed in 120 DEG C of baking ovens solidifies 2h, complete last solidification, this
When curing degree reach more than 90%；Metal-doped semiconductor nano/PMMA solid solution prepared by the present invention, preparation method letter
Single, nanocrystalline to be uniformly dispersed in PMMA, finished product light transmittance is good, and fluorescence intensity is higher.This method is in the low temperature less than 80 DEG C
Lower to realize, synthesis condition is gentle, and device is simple, and green is easy, and reduces cost.
Embodiment 2
(1) the brilliant toluene colloidal sol of 1mLAu/CdS core-shell nanos crystalline substance, Au/ZnS core-shell nanos is taken, is placed in vacuum drying chamber, 60
DEG C vacuum drying 1h, it is stand-by.
(2) 0.1mol/L NaOH aqueous solution 10g are prepared, are placed in after being mixed with 10gMMA monomers in separatory funnel, repeatedly
Concussion for several times, then outwells lower floor's liquid, adds 10g deionized waters, repeats concussion washing 2-3 times, until the lower floor poured out
Untill liquid shows neutral；Then supernatant liquid is taken out to be placed in beaker and add a certain amount of anhydrous calcium chloride powder, stood
0.5h, filtering, the MMA monomers purified add the PMMA that mass fraction is 10%, 60 degrees Celsius in purifying MMA monomers
Stirring in water bath dissolves, and obtains MMA/PMMA mixed solutions；
(3) by it is above-mentioned it is nanocrystalline be distributed in MMA/PMMA mixed solutions, ultrasonic 1h is subsequently added quality to being uniformly dispersed
Fraction is uniform for 800ppm initiator azodiisobutyronitrile concussion, is placed in 85 DEG C of oil bath pan and carries out pre- dimerization, reacts the phase
Between intermittently shake, the time of reaction controlling is：The viscosity for carrying out reactant with reaction will gradually increase, to a certain degree will
Generation implode, shows as reactant vigorous reaction and starts bubble occur, and now reactant is placed in cold water immediately and is quenched instead
Should, the thick liquid that pre- dimerization is completed is obtained, curing degree now is about 20-30%；
(4) above-mentioned mucus is poured into mould and good seal, in the baking oven for being placed in 50 DEG C, solidifies 32h, sample solidifies substantially
Complete, curing degree now is about 80-90%, then sample is placed in 120 DEG C of baking ovens solidifies 2h, complete last solidification, this
When curing degree reach more than 90%.
Au/CdS core-shell nanos crystalline substance/PMMA solid solses prepared by the present invention, Au/ZnS core-shell nanos crystalline substance/PMMA solid solses,
Preparation method is simple, nanocrystalline to be uniformly dispersed in PMMA, and finished product light transmittance is good, spectral investigation its remain the optics of script
Property.
Embodiment 3
(1) the nanocrystalline toluene colloidal sols of 10mLAg doping CdS, Au/CdS core-shell nanos crystalline substance, the brilliant first of Au/ZnS core-shell nanos are taken
Benzosol, is placed in vacuum drying chamber after mixing respectively, and 60 DEG C are dried in vacuo 1h, stand-by.
(2) 0.1mol/L NaOH aqueous solution 10g are prepared, are placed in after being mixed with 10gMMA monomers in separatory funnel, repeatedly
Concussion for several times, then outwells lower floor's liquid, adds 10g deionized waters, repeats concussion washing 2-3 times, until the lower floor poured out
Untill liquid shows neutral；Then supernatant liquid is taken out to be placed in beaker and add a certain amount of anhydrous calcium chloride powder, stood
0.5h, filtering, the MMA monomers purified add the PMMA that mass fraction is 10%, 60 degrees Celsius in purifying MMA monomers
Stirring in water bath dissolves, and obtains MMA/PMMA mixed solutions；
(3) by it is above-mentioned it is nanocrystalline be distributed to respectively in MMA/PMMA mixed solutions, ultrasonic 1h is subsequently added to being uniformly dispersed
Mass fraction is uniform for 800ppm initiator azodiisobutyronitrile concussion, is placed in 85 DEG C of oil bath pan and carries out pre- dimerization, instead
Should during interval shake, the time of reaction controlling is：The viscosity for carrying out reactant with reaction will gradually increase, to a certain degree
Will occur implode, show as reactant vigorous reaction and start bubble occur, now reactant is placed in cold water immediately and quenched
Go out reaction, obtain the thick liquid that pre- dimerization is completed, curing degree now is about 20-30%；
(4) above-mentioned mucus is poured into mould and good seal, in the baking oven for being placed in 50 DEG C, solidifies 32h, sample solidifies substantially
Complete, curing degree now is about 80-90%, then sample is placed in 120 DEG C of baking ovens solidifies 2h, complete last solidification, this
When curing degree reach more than 90%.
Au prepared by the present invention is nanocrystalline/and PMMA solid solses preparation method is simple, nanocrystalline to be uniformly dispersed in PMMA, into
Product light transmittance is good, spectral investigation its remain the optical property of script.
Embodiment 4
(1) the nanocrystalline toluene colloidal sols of 10mLAu are taken, are placed in vacuum drying chamber, 60 DEG C are dried in vacuo 1h, stand-by.
(2) 0.1mol/L NaOH aqueous solution 10g are prepared, are placed in after being mixed with 10gMMA monomers in separatory funnel, repeatedly
Concussion for several times, then outwells lower floor's liquid, adds 10g deionized waters, repeats concussion washing 2-3 times, until the lower floor poured out
Untill liquid shows neutral；Then supernatant liquid is taken out to be placed in beaker and add a certain amount of anhydrous calcium chloride powder, stood
0.5h, filtering, the MMA monomers purified add the PMMA that mass fraction is 10%, 60 degrees Celsius in purifying MMA monomers
Stirring in water bath dissolves, and obtains MMA/PMMA mixed solutions；
(3) by it is above-mentioned it is nanocrystalline be distributed in MMA/PMMA mixed solutions, ultrasonic 1h is subsequently added quality to being uniformly dispersed
Fraction is uniform for 800ppm initiator azodiisobutyronitrile concussion, is placed in 85 DEG C of oil bath pan and carries out pre- dimerization, reacts the phase
Between intermittently shake, the time of reaction controlling is：The viscosity for carrying out reactant with reaction will gradually increase, to a certain degree will
Generation implode, shows as reactant vigorous reaction and starts bubble occur, and now reactant is placed in cold water immediately and is quenched instead
Should, the thick liquid that pre- dimerization is completed is obtained, curing degree now is about 20-30%；
(4) above-mentioned mucus is poured into mould and good seal, in the baking oven for being placed in 50 DEG C, solidifies 32h, sample solidifies substantially
Complete, curing degree now is about 80-90%, then sample is placed in 120 DEG C of baking ovens solidifies 2h, complete last solidification, this
When curing degree reach more than 90%.
Embodiment 5
Step 1：The toluene for taking the Ag doping CdS for oleic acid/oleyl amine surface modification that the organic phase reactions of 10ml obtain nanocrystalline
Colloidal sol, is placed in 60 DEG C of vacuum drying ovens and vacuumizes dry 1-2h, stand-by.
Step 2：Nanocrystalline by above-mentioned drying is distributed in PDMS curing agent, and ultrasonic 1h is subsequently added to being uniformly dispersed
It is 1 with curing agent mass ratio：10 polymer monomer, stirs at room temperature, then ultrasound 0.5h again；
Step 3：Above-mentioned reactant is placed in room temperature in vacuum drying oven and vacuumizes about 10min, the bubble in reactant is removed,
Reactant is then poured into mould, is placed in 120 DEG C of baking ovens and solidifies 1h, obtain finished product.
Ag doping CdS/PDMS solid solses preparation methods prepared by the present invention are simple, nanocrystalline to be uniformly dispersed in PDMS,
Finished product light transmittance is good, spectral investigation its remain the optical property of script.
Claims (6)
1. the preparation method of a kind of nanocrystal/polymer solid solution, specifically by inorganic metal nanocrystal, metal-doped half
The nanocrystal of conductor nanocrystal and metal/semiconductor heterostructure, is uniformly combined in polymer (such as PDMS, PMMA)
Form block or film-form solid solution；Characterized in that, nanocrystal surface carries out ion exchange with polymer precursor, make to receive
The brilliant surface of rice is stable by polymer precursor, and occurs home position polymerization reaction in nanocrystal surface by polymer precursor, real
The synthesis of existing dispersed nanocrystal/polymer solid solution；The polymer solid solution size of preparation to meter level from centimetre reaching
To macro-size, shape can arbitrarily regulate and control, and avoid the reunion of nanocrystal, can keep the nano effect of nanocrystal.
2. according to the method described in claim 1, it is described it is nanocrystalline be Au nanocrystalline；Ag doping CdS or CdSe is nanocrystalline；Cu
The CdS that adulterates is nanocrystalline；Cu doping CdS nanocrystalline Ag＆Mx (Mx=Mn, Co, Ni, Fe) metal-doped CdS is nanocrystalline；Au/CdS or
Person's Au/ZnS nano-crystal with core-shell structure.
3. according to the method described in claim 1, polymer precursor is methyl methacrylate (MMA) or dimethyl silica
Alkane (DMS).
4. the method according to one of claim 1-3, it is characterised in that comprise the following steps：
Nanocrystal/PMMA solid solution preparation steps：
Step 1：The toluene colloidal sol of the inorganic nano-crystal of a certain amount of oleic acid/oleyl amine surface modification is taken, 60 DEG C of vacuum bakings are placed on
Dry 1-2h is vacuumized in case, it is stand-by；
Step 2：Methyl methacrylate (MMA) monomer is purified, the 0.1mol/L NaOH aqueous solution is prepared, in mass ratio
1：1 mixes a certain amount of MMA monomers with the above-mentioned aqueous solution, is placed in separatory funnel, shakes repeatedly, then outwells lower floor's liquid,
Add with taking the deionized water of the quality such as MMA monomers to repeat concussion washing 2-3 times, then supernatant liquid is taken out and is placed in burning
Anhydrous calcium chloride powder is added in cup, 0.5h is stood, filtering, the MMA monomers purified dissolve in the MMA monomers of purifying
Mass fraction obtains MMA/PMMA mixed solutions for 10% PMMA；
Step 3：By in the nanocrystalline MMA/PMMA mixed solutions being distributed to described in step 2 described in step 1, ultrasonic 1h extremely divides
Dissipate uniform, be subsequently added the initiator that mass fraction is 800ppm and shake uniform, be placed in 85 DEG C of oil bath pan and carry out pre- dimerization,
Intermittently shaken during reaction, the control in reaction time is：The viscosity for carrying out reactant with reaction will gradually increase, to certain journey
Implode will occur for degree, show as reactant vigorous reaction and start bubble occur, now reactant is placed in cold water immediately
Reaction is quenched, the thick liquid that pre- dimerization is completed is obtained, curing degree now is about 20-30%；
Step 4：Performed polymer is poured into mould and good seal, in the baking oven for being placed in 50 DEG C, solidifies 32h, sample has solidified substantially
Into curing degree now is about 80-90%, then sample is placed in 120 DEG C of baking ovens solidifies 2h, completes last solidification, now
Curing degree reaches more than 90%；
Nanocrystal/PDMS solid solution preparation steps：
Step 1：The toluene colloidal sol of the inorganic nano-crystal of a certain amount of oleic acid/oleyl amine surface modification is taken, 60 DEG C of vacuum bakings are placed on
Dry 1-2h is vacuumized in case, it is stand-by；
Step 2：Nanocrystalline by above-mentioned drying is distributed in PDMS curing agent, and ultrasonic 1h is subsequently added and solid to being uniformly dispersed
Agent mass ratio is 1：10 polymer monomer, stirs at room temperature, then ultrasound 0.5h again；
Step 3：Above-mentioned reactant is placed in room temperature in vacuum drying oven and vacuumizes about 10min, the bubble in reactant is removed, then
Reactant is poured into mould, is placed in 120 DEG C of baking ovens and solidifies 1h, obtain finished product.
5. nanocrystal according to claim 3/PMMA solid solution preparations, it is characterised in that pre- dimerization reaction is adopted
Initiator is azodiisobutyronitrile.
6. nanocrystal according to claim 3/PMMA solid solution preparations, it is characterised in that the temperature of pre- dimerization
For 85 DEG C, pre- dimerization reaction deadline is that untill performed polymer has just started bubble occur, performed polymer immediately is placed in into cold water
In be quenched.
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| CN106883332A (en) * | 2017-02-15 | 2017-06-23 | 厦门市京骏科技有限公司 | A kind of quantum dot-doped PMMA bulk techniques, light guide plate technique processed and light guide plate |
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| CN109277563A (en) * | 2018-09-17 | 2019-01-29 | 东莞理工学院 | A method of preparing water phase Au@CdS nano core-shell material |
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| CN101343536A (en) * | 2008-07-16 | 2009-01-14 | 东北师范大学 | Surface functionalized nano-particle and method for preparing its polymer nanometre composite material |
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| CN106883332B (en) * | 2017-02-15 | 2018-06-19 | 厦门市京骏科技有限公司 | A kind of quantum dot-doped PMMA bulk techniques, light guide plate technique processed and light guide plate |
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| CN114013028A (en) * | 2021-11-03 | 2022-02-08 | 北京理工大学 | Method for constructing semiconductor nanocrystalline device microstructure with highlight overflow effect |
| CN117106131A (en) * | 2023-08-28 | 2023-11-24 | 恒光新材料(江苏)股份有限公司 | Explosion polymerization method for preventing N-phenylmaleimide copolymerization system |
| CN117106131B (en) * | 2023-08-28 | 2024-04-12 | 恒光新材料(江苏)股份有限公司 | Explosion polymerization method for preventing N-phenylmaleimide copolymerization system |
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