CN1320051C - Method for preparing transparent optical material of polymer in high nano phase - Google Patents
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- CN1320051C CN1320051C CNB2005100166578A CN200510016657A CN1320051C CN 1320051 C CN1320051 C CN 1320051C CN B2005100166578 A CNB2005100166578 A CN B2005100166578A CN 200510016657 A CN200510016657 A CN 200510016657A CN 1320051 C CN1320051 C CN 1320051C
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Abstract
The present invention relates to a method for preparing a nanometer composite material by compounding nanometer sulfur semiconductor particles and a polymer, which comprises three steps: the synthesis of nanometer semiconductor particles with surface modification, the dispersion of the nanometer particles in polymerizing monomers, and body polymerization. A metal salt reacts with sulphur sources, such as thiourea, thioacetamide, sodium sulfide or hydrogen sulphide, etc. in a polar organic solvent under the existence of mercaptoethanol, mercaptopropyl alcohol and thioglycerol as surface modifiers and the mixture of the surface modifiers and benzenethiol, mercapto-methylbenzenethiol, etc. to synthesize nanometer particles with surface modification; then, the nanometer particles are dispersed in the polymerizing monomers in an ultrasonic mode, and the polymer monomers are dimethylacrylamide and diethyl acrylamide or mixed monomers of the dimethylacrylamide, the diethyl acrylamide, styrene, vinyl acetate, etc.; finally, the transparent optical material of a high nanometer phase polymer is prepared by a method of thermal polymerization, ultraviolet light solidification or radiation polymerization. The optical composite material of a high nanometer phase polymer prepared in the present invention can be used for manufacturing optical devices, display devices and resin lens.
Description
Technical field
The present invention relates to a kind of preparation method of transparent optical material of polymer in high nano phase, relate to the method that the compound back of a kind of chalcogen semiconductor nanoparticle and polymkeric substance prepares the nano complex material specifically.The synthetic optical material can be applied to aspects such as optics, display device and resin lens material in this way.
Technical background
Along with science and technology development and progress, traditional single composition material can not satisfy the more and more higher requirement that performance proposed of people to material.Entered since 20th century, along with the development of nanoscale science and technology, nano composite material becomes one of new vegetative point of current matrix material.Therefore, the nano composite material with functions such as special light, electricity, magnetic is showing tempting application prospect as aspects such as photoelectricity information material, absorbing material, magneticsubstance and catalytic material uses.Be committed to application such as functional performances such as nonlinear optics, high refractive index, fluorescence with material forms with what inorganic nano-particle had, and must realize that it was with the compound of certain form and body phase material and assembling.And polymkeric substance is as the body material of a kind of optical clear, working properties excellence, for the application of inorganic nano-particle optical function provides an important carrier.But, inorganic nano-particle size less (being generally less than 100nm), surface effects is big, assembles (when particularly content is higher) easily, therefore is difficult to homodisperse in polymeric matrix, influences the transparency and the optics homogeneity of material the most at last.At present, aspect the preparation of nanoparticle/polymer composites, people mainly concentrate on the film material.Yet preparation nanoparticle/polymer body phase material is more important than the preparation film material to a certain extent, this is because all need polymer nanocomposites to exist with the form of blocks phase material in many field of optical applications, particularly also require the transparency of matrix material to get well for the body phase material with high refractive index, luminosity, this also just controls for nano-particles size and the even nothing gathering in body gathering compound disperses to have higher requirement.In addition, a kind of functional nano particle to be compound to the function (as high refractive index, high rigidity etc.) that obtains in the polymkeric substance in a certain respect, the content of nanoparticle in polymkeric substance must reach certain amount, and therefore preparing polymer in high nano phase body material is one of difficult point of current nanometer composite technology Gonna breakthrough.
Summary of the invention
The invention provides the novel method of the simple preparation of a kind of technology high nanophase dispersive chalcogen semiconductor nanoparticle/polymkeric substance transparent optical body material, promptly surface coated semi-conductor nano particles is distributed to earlier in the polymerization single polymerization monomer, prepares the transparent polymer optical material of high nanoparticle content again through situ aggregation method by shifting diffuse-aggregate method.The optical property homogeneous of this class optical material of polymer in high nano phase, form that can covalent linkage between nanoparticle and the polymkeric substance exists, and material has stability preferably, can be used for constructing optics, display device and as optical resin material.
The present invention includes following steps: 1. the chalcogen semiconductor nanoparticle modified of synthetic surface; 2. the dispersion of nanoparticle in polymerization single polymerization monomer; 3. the mass polymerization of nanoparticle in monomer.
The present invention realizes by following experimental program: the present invention adopts wet chemical synthetic chalcogen semiconductor nanoparticle in organic solvent, in the presence of the organic molecule modifier, react at a certain temperature in metal-salt presoma and sulphur source, can prepare the nanoparticle of different size size and dispersity by the ratio in control modifier and metal-salt and sulphur source.Semi-conductor nano particles can be precipitated out from reaction system by poor solvent, and can obtain pressed powder through centrifugation.Nanoparticle can directly be distributed in the polymer monomer, can obtain the optical material of appearance transparent more at last through mass polymerization.
1. the chalcogen semiconductor nanoparticle modified of synthetic surface:
Adopt once to feed intake, at N
2Under the gas shiled sulphur source, zinc salt or cadmium salt, organic molecule coating materials are joined in the polar organic solvent, the concentration of zinc salt or cadmium salt is controlled at 3.0 * 10
-2M is between the 0.5M, the molar ratio in organic molecule coating materials, zinc salt or cadmium salt, sulphur source is 1.0～2.0: 1: 0.5～0.9, reaction mixture was 80～180 ℃ of reactions 6～12 hours, be precipitated out with poor solvent such as hexane, hexanaphthene or methyl alcohol, ethanol, acetone etc. again, centrifugation, wash, obtain the chalcogen semiconductor nanoparticle of solid finishing after the drying.
Chalcogen semiconductor nanoparticle synthesis phase is raw materials used to be zinc salt or cadmium salt, sulphur source, organic molecule coating materials.Zinc salt can be zinc acetate, ZnCl
2, Zn (ClO
4)
2, ZnSO
4Deng, cadmium salt can be cadmium acetate, CdCl
2, Cd (ClO
4)
2Deng; The sulphur source can be thiocarbamide, thioacetamide, sodium sulphite or hydrogen sulfide etc.; The organic molecule coating materials can be mercaptoethanol, mercaprol, thioglycerol etc. or they with thiophenol, to the methylbenzene thiophenol, to ethyl thiophenol, to the methylol thiophenol, hydroxyethylbenzene thiophenol, thiopurine methyltransferase vinylbenzene etc. are mixed modifier (when mercaptan and thiophenol mixture during as modifier, the molar ratio of the two is 1.0～2.0: 1, except that thiopurine methyltransferase vinylbenzene synthesized in this patent, other all can directly buy).The organic medium that synthesizing nano-particle is used is polar organic solvent such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) etc., wherein with dimethyl formamide organic solvent best results.
The nanoparticle and the polymerization single polymerization monomer that adopt the surface directly to have two keys carry out bulk copolymerization, and the optical material of polymer that obtains has the crosslinking structure of height, and its optical property is transparent and thermal characteristics is more excellent.Therefore, can further the chalcogen semiconductor nanoparticle be carried out the two keyed jointing branch modifications in surface.Chalcogen semiconductor nanoparticle by finishing and methacrylic chloride react in organic solvent and carry out grafting.The chalcogen semiconductor nanoparticle that mercaptoethanol is modified and the weight ratio of methacrylic chloride in 2～8 hours reaction times, are added drop-wise to reaction solution in a large amount of ethanol centrifugation, and vacuum-drying collection pressed powder at last generally 1: 1～10.
Above method is not only applicable to the synthetic of ZnS nanoparticle, is suitable for the synthetic of CdS and CdS/ZnS and CdTe (Se)/other nucleocapsid structure semi-conductor nano particles such as ZnS too, and these nanoparticles all can be compound in the polymkeric substance.
2. the dispersion of nanoparticle in polymerization single polymerization monomer of step 1 preparation: the dispersion of nanoparticle in polymerization single polymerization monomer can be adopted the method for ultra-sonic dispersion, and the weight fraction of nanoparticle in monomer generally is controlled at 5～80wt%.
The bulk polymerization stage used monomer of nanoparticle in polymerization system can be DMAA, the diethyl acrylamide, can also be DMAA or diethyl acrylamide and methyl methacrylate, vinylbenzene, Vinylstyrene, vinyl acetate, the diallyl diglycol carbonates, hydroxyethyl methylacrylate, 1 kind or 2 kinds of monomeric mix monomers in several monomers such as triethylene glycol diacrylate, DMAA or diethyl acrylamide and other monomeric weight ratio are 0.5～10: 1.0 in the mix monomer, wherein with DMAA and vinylbenzene, the mix monomer effect of Vinylstyrene is best.
3. the monomer mass polymerization that is dispersed with nanoparticle that step 2 is prepared: monomer adopts radical polymerization fashionable, use BPO, AIBN or other oil-soluble initiator, the consumption of initiator is 0.1～0.3% of a reaction monomers gross weight, 45～55 ℃ of following polymerizations 12～36 hours, then at 60～70 ℃, 80～90 ℃, the difference polymerization is 1～3 hour under 100～110 ℃, 150～160 ℃ of thermal treatments 1～5 hour, the demoulding obtained transparent chalcogen semiconductor nanoparticle/polymer composite body phase material at last;
When monomer adopted the gamma-radiation radio polymerization, the polymerization system that directly will not add initiator was exposed to 60Co source (7 * 10
4Curie), irradiation dose is 75～200KGy/hr, and irradiation time is 3～20 hours, and irradiation temperature is 35～40 ℃, last matrix material was 150～160 ℃ of following thermal treatments 1～5 hour, and the demoulding obtains transparent chalcogen semiconductor nanoparticle/polymer composite body phase material;
Polymerization system also can adopt ultraviolet light polymerization, light trigger can be selected benzoin ether, 2 for use, 2-diethoxy methyl phenyl ketone, α, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone (1173) etc., consumption generally accounts for 0.5～2% of reaction monomers gross weight, ultraviolet source can adopt 1～4KW high voltage mercury lamp, and the solidified time was generally 20 seconds～10 minutes; Last matrix material was 150～160 ℃ of following thermal treatments 1～5 hour, and the demoulding obtains transparent chalcogen semiconductor nanoparticle/polymer composite body phase material.
Below in conjunction with embodiment the present invention is further elaborated, rather than will limits the invention with this.
Embodiment
Embodiment one
1. with zinc acetate, thiocarbamide, mercaptoethanol are raw material synthetic ZnS nanoparticle in dimethyl formamide
In the 1000ml reaction flask, add 0.95g (0.0125mol) thiocarbamide; 3.22g (0.015mol) zinc acetate adds 400ml dimethyl formamide (DMF) again, after waiting to dissolve; stir adding 1.70g (0.022mol) mercaptoethanol under nitrogen protection, mixture refluxed 10 hours down at 160 ℃.Reaction solution is added drop-wise in a large amount of ethanol nanoparticle is precipitated out, centrifugation, then dry under vacuum with the acetone time back of giving a baby a bath on the third day after its birth, obtain the white ZnS nanoparticle that the 0.9g mercaptoethanol is modified.Utilize transmission electron microscope (TEM) that surperficial modified ZnS nanoparticle is observed and show that the particle diameter of particle is in 2～5 nanometers, electron diffraction and X-ray diffraction show that the ZnS particle is a cubic structure.
2.ZnS dispersion and the body radio polymerization of nanoparticle in polymerization single polymerization monomer
10g mercaptoethanol modified ZnS nanoparticle is distributed in the 10g DMAA (corresponding weight fraction is 50%) under action of ultrasonic waves, then liquid is poured in the glass mold (15 * 10 * 4mm), in cobalt source (7 * 10
4Curie) radiation polymerization under, irradiation dose is 100KGy/hr, and irradiation temperature is 35-40 ℃, and irradiation time is 16 hours, and last matrix material was 150 ℃ of following thermal treatments 2 hours, and the demoulding obtains transparent ZnS nanoparticle/polydimethylacrylamiin complex body phase material.Because DMAA has stronger wetting ability, so the water tolerance of the ZnS/ DMAA matrix material that obtains here is relatively poor.
Embodiment two
1. the method for synthetic mercaptoethanol modified ZnS nanoparticle is as described in the embodiment one;
2.ZnS dispersion and the ultraviolet light polymerization of nanoparticle in polymerization single polymerization monomer
5g mercaptoethanol modified ZnS nanoparticle is distributed under action of ultrasonic waves (corresponding weight fraction is 20%) in the mix monomer of 15g DMAA and 5g triethylene glycol diacrylate, 1173 light triggers that add 1% monomer weight, then liquid is poured in the glass mold, under the medium pressure mercury lamp of 2KW, shine 5min, last matrix material was 150 ℃ of following thermal treatments 2 hours, and the demoulding obtains transparent ZnS nanoparticle/polymer composite body phase material.The gained matrix material has higher degree of crosslinking, and water-intake rate is compared obvious reduction with the material among the embodiment one, and other performance variation is little.
Embodiment three
1. the method for synthetic mercaptoethanol modified ZnS nanoparticle is as described in the embodiment one.
2. with the monomer among DMAA and cinnamic mix monomer (weight ratio is 1: 1) the replacement embodiment one, other condition is with embodiment one.By cinnamic introducing, further improved the water tolerance of matrix material, and other better performances.
Embodiment four
1. the method for synthetic mercaptoethanol modified ZnS nanoparticle is as described in the embodiment one.
2. respectively the mercaptoethanol modified ZnS nanoparticle of 5～60% weight fractions is mixed with DMAA, vinylbenzene and divinyl benzene monomer (weight ratio of polymerization single polymerization monomer is 12: 5: 1), other condition is with embodiment one.Table 1 has been listed the performance of mercaptoethanol modified ZnS nanoparticle/poly-(DMAA-vinylbenzene-Vinylstyrene) optical material of polymer.
The performance of table 1.ZnS nanoparticle/poly-(DMAA-vinylbenzene-Vinylstyrene) optical material
| TCZnS a | ZnS b | nd c | vd d | Td(℃) e | 750 ℃ of residual rates f | T％ g |
| 5 | 3 | 1.553 | - | |||
| 10 | 6 | 1.560 | 301 | 5.8 | 83 | |
| 15 | 9 | 1.567 | - | |||
| 20 | 12 | 1.572 | 37.5 | - | - | 80 |
| 25 | 15 | 1.578 | - | |||
| 30 | 18 | 1.593 | 36 | 281 | 15.9 | 71 |
| 40 | 24 | 1.602 | - | - | - | |
| 50 | 30 | 1.635 | 272 | 31.5 | - | |
| 60 | 36 | - | - | - | - |
aThe theoretical weight mark of mercaptoethanol modified ZnS nanoparticle in the nano complex material;
bThe theoretical weight mark of pure ZnS nanoparticle in the nano complex material;
cThe specific refractory power of nano complex material;
dThe Abbe number of nano complex material;
eThe decomposition temperature of body material when 5% weightlessness;
fThe residual rate of body material inorganics in the time of 750 ℃;
gThe thick body material of about 4mm is at the transmittance at 600nm place.
Embodiment five
1. the method for synthetic mercaptoethanol modified ZnS nanoparticle is as described in the embodiment one.
2.ZnS dispersion and the initiator of nanoparticle in polymerization single polymerization monomer causes thermopolymerization
Mercaptoethanol modified ZnS nanoparticle with 5～60% weight fractions is distributed to DMAA under action of ultrasonic waves respectively, in the mix monomer of vinylbenzene and Vinylstyrene (weight ratio is 12: 5: 1), the initiator A IBN that adds mix monomer gross weight 0.3%, after the degassing liquid is poured in the glass mold, 50 ℃ of polymerizations are 24 hours in baking oven, then at 60 ℃, 80 ℃, the difference polymerization is 2 hours under 100 ℃, at last 150 ℃ of thermal treatments 1 hour, the demoulding promptly gets transparent ZnS nanoparticle/polymer body phase material, and the performance of the optical material of polymer that employing thermopolymerization method obtains is identical with embodiment's four.
Embodiment six
1.4-thiopurine methyltransferase is cinnamic synthetic
With 15.3g benzyl chloride vinylbenzene, 9.12g thiocarbamide and 200ml ethanol join in the 500ml four-hole bottle.This reaction mixture is under nitrogen protection, and back flow reaction 4h is cooled to 30 ℃ then; Add the NaOH solution of 75ml 20%, and be warming up to 80 ℃ of reaction 0.5h rapidly.At last, with the reaction solution cool to room temperature and use 100mlCHCl
3Extraction is washed till neutrality, anhydrous Na with the organic phase separation and with distilled water
2SO
4Dry.Decompression is removed organic solvent and is obtained 4-thiopurine methyltransferase vinylbenzene.
2. with the mercaptoethanol among the mixing modifier replacement embodiment one of thiopurine methyltransferase vinylbenzene/mercaptoethanol (mol ratio is 1: 1), other condition is with embodiment one.
3.ZnS dispersion and the body radio polymerization of nanoparticle in polymerization single polymerization monomer
Thiopurine methyltransferase vinylbenzene/mercaptoethanol modified ZnS the nanoparticle of 20% weight is distributed in the DMAA under action of ultrasonic waves, then liquid is poured in the glass mold, radiation polymerization under the cobalt source, irradiation dose is 82KGy/hr, irradiation time is 16 hours, irradiation temperature is 35 ℃, and last matrix material can be 150 ℃ of following thermal treatments 2 hours, and the demoulding obtains transparent ZnS nanoparticle/polymer composite body phase material.The ZnS nanoparticle is fixed in the polymer network by covalent linkage in the matrix material that this method obtains, and performance is more stable, and the thermotolerance of matrix material improves.
Embodiment seven
1.ZnS the two keyed jointing branch modifications in the surface of nanoparticle
The synthetic method of mercaptoethanol modified ZnS nanoparticle powder is as described in the embodiment one.The two keyed jointing branch method of modifying in the surface of ZnS nanoparticle are as follows: 10g mercaptoethanol modified ZnS nanoparticle is distributed among the 200ml exsiccant DMF, drips the 10g methacrylic chloride, added in 1 hour, reacted at last 3 hours again.Reaction solution is added drop-wise in a large amount of ethanol centrifugal collection pressed powder and vacuum-drying.
2.ZnS dispersion and the initiator of nanoparticle in polymerization single polymerization monomer causes thermopolymerization
The ZnS nanoparticle of the two keys of the surface grafting that 20% weight is obtained above is distributed under action of ultrasonic waves in the mix monomer (weight ratio is 3: 1) of DMAA and methyl methacrylate, the initiator A IBN that adds mix monomer gross weight 0.3%, after the degassing liquid is poured in the glass mold, 50 ℃ of polymerizations are 24 hours in baking oven, then respectively at 60 ℃, 80 ℃, 100 ℃ of each polymerizations 2 hours, handled 2 hours at 150 ℃ at last, the demoulding promptly gets ZnS nanoparticle/optical material of polymer.This method is owing to adopted surperficial nanoparticle and the polymerization single polymerization monomer that directly has two keys to carry out bulk copolymerization, so the optical material of polymer that obtains has the crosslinking structure of height, its optical property is transparent and thermal characteristics is more excellent.
Claims (4)
1, the preparation method of transparent optical material of polymer in high nano phase may further comprise the steps: 1. the chalcogen semiconductor nanoparticle modified of synthetic surface; 2. the dispersion of nanoparticle in polymerization single polymerization monomer; 3. the mass polymerization of nanoparticle in monomer; It is characterized in that:
(1) the chalcogen semiconductor nanoparticle of synthetic surface modification: adopt once to feed intake, at N
2Under the gas shiled sulphur source, zinc salt or cadmium salt, organic molecule coating materials are joined in the polar organic solvent, the concentration of zinc salt or cadmium salt is controlled at 3.0 * 10
-2M is between the 0.5M, the molar ratio in organic molecule coating materials, zinc salt or cadmium salt, sulphur source is 1.0～2.0: 1: 0.5～0.9, reaction mixture was 80～180 ℃ of reactions 6～12 hours, precipitate, separate, obtain the chalcogen semiconductor nanoparticle of solid finishing after washing, the drying; Zinc salt is zinc acetate, ZnCl
2, Zn (ClO
4)
2Or ZnSO
4, cadmium salt is cadmium acetate, CdCl
2Or Cd (ClO
4)
2, the sulphur source is thiocarbamide, thioacetamide, sodium sulphite or hydrogen sulfide; The organic molecule coating materials is mercaptoethanol, mercaprol or thioglycerol, or mercaptoethanol, mercaprol or thioglycerol be with thiophenol, to the methylbenzene thiophenol, to ethyl thiophenol, to the methylol thiophenol, to hydroxyethylbenzene thiophenol or cinnamic mercaptan of thiopurine methyltransferase and thiophenol mixing modifier, and the molar ratio of mercaptan and thiophenol is 1.0～2.0: 1; Polar organic solvent is dimethyl formamide, N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO);
(2) dispersion of nanoparticle in polymerization single polymerization monomer of step (1) preparation: the method for ultra-sonic dispersion is adopted in the dispersion of nanoparticle in polymerization single polymerization monomer, the weight fraction of nanoparticle in monomer is 5～80%, used monomer is DMAA or diethyl acrylamide, or DMAA or diethyl acrylamide and methyl methacrylate, vinylbenzene, Vinylstyrene, vinyl acetate, hydroxyethyl methylacrylate, 1 kind or 2 kinds of monomeric mix monomers in the triethylene glycol diacrylate monomer, in the mix monomer DMAA or diethyl acrylamide and other monomer and mass ratio be 0.5～10: 1.0;
(3) the monomer mass polymerization that is dispersed with nanoparticle that step (2) is prepared:
Adopt radical polymerization, use BPO, AIBN or other oil-soluble initiators, the consumption of initiator is 0.1～0.3% of a reaction monomers gross weight, 45～55 ℃ of following polymerizations 12～36 hours, at 60～70 ℃, 80～90 ℃, 100～110 ℃ are descended polymerization respectively 1～3 hour then, 150～160 ℃ of thermal treatments 1～5 hour, the demoulding obtained transparent chalcogen semiconductor nanoparticle/polymer composite body phase material at last;
Or when adopting the gamma-radiation radio polymerization, the polymerization system that directly will not add initiator is exposed to 7 * 10
4Curie
60The Co source, irradiation dose is 75～200KGy/hr, and irradiation time is 3～20 hours, and irradiation temperature is 35～40 ℃, last matrix material was 150～160 ℃ of following thermal treatments 1～5 hour, and the demoulding obtains transparent chalcogen semiconductor nanoparticle/polymer composite body phase material;
Or, adopt ultraviolet light polymerization, benzoin ether, 2,2-diethoxy methyl phenyl ketone or α, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone light trigger consumption is 0.5～2% of a reaction monomers gross weight, adopts 1～4KW high voltage mercury lamp as ultraviolet source, and the solidified time was generally 20 seconds～10 minutes; Last matrix material was 150～160 ℃ of following thermal treatments 1～5 hour, and the demoulding obtains transparent chalcogen semiconductor nanoparticle/polymer composite body phase material.
2, the preparation method of transparent optical material of polymer in high nano phase as claimed in claim 1 is characterized in that:
Polar organic solvent is a dimethyl formamide.
3, the preparation method of transparent optical material of polymer in high nano phase as claimed in claim 1 is characterized in that:
The chalcogen semiconductor nanoparticle of the finishing that step (1) is obtained and methacrylic chloride react in organic solvent and carry out grafting, the weight ratio of chalcogen semiconductor nanoparticle and methacrylic chloride is 1: 1～10,2～8 hours reaction times, reaction solution is added drop-wise in a large amount of ethanol at last, centrifugation, and vacuum-drying collection pressed powder, again pressed powder is carried out the described dispersion in polymerization single polymerization monomer of step (2) afterwards.
4, the preparation method of transparent optical material of polymer in high nano phase as claimed in claim 1 is characterized in that:
The bulk polymerization stage used monomer of nanoparticle in polymerization system is the mix monomer of DMAA and vinylbenzene, Vinylstyrene.
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| GB0916700D0 (en) | 2009-09-23 | 2009-11-04 | Nanoco Technologies Ltd | Semiconductor nanoparticle-based materials |
| CN101840743B (en) * | 2010-05-06 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Method for preparing transparent conductive oxide nano powder slurry |
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