CN1204170C - Preparation method of nano particles with high refractive index and polymer nano composite film material - Google Patents
Preparation method of nano particles with high refractive index and polymer nano composite film material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 19
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
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Abstract
The present invention relates to a method for preparing a nano composite film material by compounding nano particles with a high refractive index with polymer. The method comprises the following steps: preparing ZnS nano particles for surface modification, preparing an organic polymer monomer and polymer with high refractive index, and preparing a nano composite film. An organic small molecule surface modifier which can have a functional group is added in an organic solvent of a zinc metal salt, and hydrogen sulfide gas is introduced to make ZnS nano colloidal particles synthesized; a polymer base material for compounding the ZnS nano particles can be polymethyl methacrylate, polybutyl methacrylate, polystyrene, polyurethane, epoxy resin or a polymer macromer, preferably a polyurethane oligomer and an urethane acrylate macromer with high refractive index and better effect; finally, the ZnS nano particles and the polymer base material are prepared into the nano composite film by a transfer and dispersion polymerization method. The compounded film material can be used for constructing surface antireflection coatings of optical devices, display devices and solar cells.
Description
Technical field:
The present invention relates to a kind of preparation method of high refractive index, thin film materials, relate to a kind of nanoparticle of high refractive index and the method that the compound back of polymkeric substance prepares nano composite film specifically.The synthetic thin-film material can be used to construct the surperficial antireflection coatings of optics, display device and solar cell in this way.
Technical background:
Current, the high refractive index optical coating mainly is divided into two big classes: polymkeric substance optical coating and inorganic optical coating.The polymkeric substance optical coating has advantages such as light weight, shock resistance, easy machine-shaping, however low, the poor heat resistance of polymer surfaces hardness, the narrower (n of change of refractive scope
dBetween 1.35～1.7).Although some specific polymers has higher specific refractory power (n=2.12) as poly-thiophene phenol, it has the coupling of intensive optical absorption at visible region, and this has just limited it at high refractive index (n
d＞1.7) application on the optical component.Inorganic materials generally has higher specific refractory power (n
d=2.0～5.0), bigger Abbe number, but its density is big, material is more crisp.When particularly using as antireflection coatings, the value of its specific refractory power can not be adjustable continuously, and having relatively high expectations to complete processing.
Traditional optical material comprises inorganic materials and organic materials two big classes.An inorganic organic hybrid material then can have the advantage of above two kinds of materials concurrently, and therefore people begin inorganic nano-particle is incorporated into the nano composite material for preparing high refractive index in the polymkeric substance in recent years.This material is having broad application prospects aspect the antireflective coating of solar cell, material of infrared window and optical component.
At present aspect an inorganic organic hybrid high refractive index polymer optical material research more be PbS, Si nanoparticle simply to be entrained in the water miscible polymkeric substance (as polyoxyethylene, polyvinyl alcohol) improve specific refractory power.Yet owing to be water-soluble polymers, so the water tolerance of final matrix material is relatively poor, and physical strength is relatively poor.In addition, inorganic nano-particle is to be present in the polymkeric substance with simple adulterated form, does not have chemical bond between particulate and the polymer molecule, so nanoparticle assembles in polymeric substrate easily, and the less stable of material.Though TiO
2/ polymer hybrid material can overcome above shortcoming, but this class material shrinking percentage in solidification process is bigger, and film-forming properties is bad, influences the optics and the mechanical property of material the most at last.
Summary of the invention:
The present invention is by being incorporated into the ZnS nanoparticle in the oil-soluble polymers, thereby provides a kind of technology simply to prepare the novel method of high refractive index nano composite film material.The ZnS of body phase is as a kind of high refractive index (n
620nm=2.36) inorganic semiconductor material, because it has low-down uptake factor in the wider wavelength region of 400～14000nm, so it has many different application at optical field.This class high refractive index nano composite film material good film-forming property, the optical property homogeneous, the form with covalent linkage between nanoparticle and the polymkeric substance exists, and material has stability preferably, therefore has actual application value more aspect antireflection film layer.
The preparation method of nano particles with high refractive index and polymer nano composite film material of the present invention comprises following three steps:
1, synthetic surface modified ZnS Nano sol;
2, synthetic high refractive index organic polymer monomer and polymkeric substance;
3, the nanometer film layer material of the compound preparation high refractive index by Nano sol and polymeric substrate;
At last the nano composite material performance is tested.
One, the ZnS Nano sol of finishing is synthetic:
In the organic solvent of zinc metal-salt, add the organic molecule coating materials, and feed hydrogen sulfide, the ZnS Nano sol of preparation finishing.Described Nano sol can synthesize in second cyanogen, methyl alcohol, dimethyl formamide organic solvent, with synthetic effect the best in the dimethyl formamide organic solvent, and through the modification of organic molecule coating materials, coating materials is the modifier that has functional group; The molar ratio of the coating materials of nanoparticle and metal-salt (as acetate, perchlorate or vitriol) is 0.2: 1～1.0: 1, and the feeding amount of hydrogen sulfide is normal 6～10 times an of metal-salt; Feed speed-controllable built in 0.1 milliliter～5 ml/min.The coating materials of ZnS particulate can be thiophenol, to the methylbenzene thiophenol, to ethyl thiophenol, to the methylol thiophenol, to hydroxyethylbenzene thiophenol, thiopurine methyltransferase vinylbenzene, mercaptoethanol, mercaprol, thioglycerol etc., can mix with one or both of above compound and modify the ZnS nanoparticle, total coating materials and metal-salt equivalence ratio are 0.2: 1～1.0: 1.
Certainly above method is not limited only to the synthetic of ZnS Nano sol, is suitable for synthesizing of other semiconductor nano colloidal sol such as CdS too, and these Nano sols all can be compound in the following polymkeric substance.
Two, high refractive index organic polymer monomer and polymkeric substance is synthetic:
Top synthetic ZnS Nano sol is mixed with polymkeric substance or the big monomer of polymkeric substance.Employed polymkeric substance can be polymethylmethacrylate (PMMA), poly-n-butyl methacrylate, polystyrene (PS), urethane and Resins, epoxy etc.; The big monomer of polymkeric substance can be the big monomer of acrylate, polyurethane oligomer etc.These polymkeric substance can be synthetic from the corresponding polymer monomer, for preparation high refractive index nano matrix material, the polymer-based carbon bottom material of high refractive index is even more ideal, and the polymkeric substance or the big monomer of polymkeric substance that therefore design the synthesizing new high refractive index are very important.
Provide the preparation embodiment of several high refractive index polymer monomers and polymkeric substance below, wherein big monomeric urethane segment of urethane acrylate and polyurethane oligomer can be prepared through polyaddition by dibasic alcohol or binary mercaptan and vulcabond.Here, dibasic alcohol or binary mercaptan can be ethylene glycol, propylene glycol, dihydroxyethylsulfide, mercaptoethanol, 2,2 '-dimercapto ethyl-sulfide, dithioglycol etc.; Vulcabond can be 2,4 '-tolylene diisocyanate, isophorone diisocyanate, '-diphenylmethane diisocyanate etc.The equivalence ratio of dibasic alcohol or binary mercaptan and vulcabond is 1: 1.1～1: 2, and reaction solvent can be benzene, toluene, tetrahydrofuran (THF), dimethyl formamide etc., and temperature of reaction can be controlled at 45～85 ℃, and the reaction times can be at 2～10 hours.The big monomer of urethane acrylate can be obtained with the hydroxyethyl methylacrylate end-blocking by polyurethane oligomer, and it can pass through uv-light polymerization, also available initiator thermopolymerization.
Three, the preparation of ZnS nanoparticle/polymer nano composite film material:
Prepare ZnS nanoparticle/polymer nano composite film by shifting diffuse-aggregate method, wherein polymer materials can be a polymeric linear polymer in advance, as polymethylmethacrylate (PMMA), polystyrene (PS), urethane etc. mix the direct dried coating film in back with it and can obtain composite material film with nanoparticle colloidal sol; Also can be that polymerization on the throne forms, film earlier with after nanoparticle colloidal sol mixes that repolymerization forms polymkeric substance-nanoparticle composite film material as polymer monomer.Nanoparticle is to be present in the polymkeric substance with simple adulterated form in preceding a kind of method; Then a kind of method then has certain advantage, because the ZnS microparticle surfaces has functional group's (two keys, hydroxyl), can react with the acrylate or the polyurethane oligomer of polyfunctionality, nanoparticle is fixed in the polymer network by covalent linkage, formed polymkeric substance is a cross-linked form, and therefore the composite film material that finally obtains has mechanical property and thermal stability preferably.
The performance test of nano compound film: the specific refractory power of measuring 632.8nm place film with ellipsometer; Measure the thermal characteristics and the content of actual ZnS in film of film with thermogravimetric analyzer; With the transmitance of uv-vis spectra MEASUREMENTS OF THIN at the 550nm place.
Before the film forming, the composition in the film liquid includes two kinds of situations: contain ZnS Nano sol and polyurethane oligomer, then direct spin-coating film; It is monomeric greatly to contain ZnS Nano sol and urethane acrylate, repolymerization after the film forming; The doping of ZnS Nano sol is 0～97wt% in the film liquid, and its lower limit content is not 0.For coating process, spin speed can be regulated between 500～4000 rev/mins according to the viscosity of coating liquid and the thickness of final coating; For curing process, can adopt uv-light polymerization, AIBN or BPO etc. to cause radical polymerization and thermopolymerization.Certainly also can adopt first uv photopolymerization, the method that initiation radical polymerization such as back AIBN or BPO and thermopolymerization combine.The time of uv photopolymerization was generally 20 seconds～5 minutes, and generally between 60～180 ℃, the time was generally 3～10 hours the temperature of thermal-initiated polymerizations such as AIBN.
Below in conjunction with embodiment the present invention is further set forth.
Embodiment:
Embodiment 1: synthetic (1) of the ZnS colloidal nanoparticles of finishing
On ice bath, under the vigorous stirring, in 100ml contains the solution of Glacial acetic acid zinc/dimethyl formamide (DMF) of 0.2M thiophenol and the cinnamic 0.5M of 0.1M thiopurine methyltransferase, feed excessive 6 times to the normal dry hydrogen sulfide of zinc acetate, control feeding speed is 0.5 ml/min, remove excessive hydrogen sulfide with nitrogen at last, obtain water white ZnS Nano sol.
Utilize transmission electron microscope (TEM) that surperficial modified ZnS nanoparticle is observed and show that the particle diameter of particulate is in 2～5 nanometers, electron diffraction and X-ray diffraction show that the ZnS particle is a cubic structure.With the ZnS Nano sol vacuum-drying that obtains above, the ZnS nanoparticle powder that obtains finishing is through Infrared Characterization result following (KBr): v (cm
-1): 3404,2920,2855,1647,1629,1603,1577,1508,1406～1477cm
-1, 690～990. characterize by ultimate analysis and plasma body linking atom emmission spectrum and to find: C, 30.5; H, 2.66; S, 25.30; Zn, 42.90. according to the chemical constitution that feed ratio calculates the ZnS nanoparticle that can release finishing is: Zn
2+: S
2-: RS
-=1: 0.6: 0.6, show that most coating materials all is coated on the surface of ZnS particulate.
Embodiment 2: synthetic (2) of the ZnS colloidal nanoparticles of finishing
Except replacing the thiopurine methyltransferase vinylbenzene with mercaptoethanol, other condition is with embodiment 1.
The particle diameter of analysis revealed ZnS particulate is also in 2～5 nanometers, and crystal formation is a cubic structure.The chemical constitution of the ZnS nanoparticle of finishing is Zn
2+: S
2-: RS
-=1: 0.78: 0.6.
Equally, among the top embodiment, coating materials can be simple thiophenol, thiopurine methyltransferase vinylbenzene or mercaptoethanol etc., and their concentration separately can change between 0.1～0.5M.
Preparing the nanometer ZnS colloid with the coating materials of other kind can be with method same as described above.
Embodiment 3: the big monomeric synthetic and polymerization of urethane acrylate
2,4 of 2,2 of 15.4g '-dimercapto ethyl-sulfide (MES) and 26.1g '-tolylene diisocyanate (TDI) is dissolved in 100ml anhydrous dimethyl formamide (DMF) solution, adds a spot of dibutyl tin laurate and make catalyzer.This reaction mixture 55 ℃ of reactions 4 hours, drips the 6.5g hydroxyethyl methylacrylate then under nitrogen protection, continue reaction 2 hours, obtains the big monomeric DMF solution of urethane acrylate of 23wt% at last.IR spectrum (KBr): v (cm
-1) 3292,3047,2930,2924,2857,1726,1654,1639,1618,1602,1540,1454,1448,1418,1300,1215,1194,1031,878,815,768.IR spectroscopic analysis result shows 1639cm
-1The place is the characteristic peak of the two keys of methacrylic ester, 1654,3239 cm
-1Be the eigen vibration peak of urethane bonds, and the characteristic peak of sulfydryl and isocyanic ester disappears, so the gained compound is the big monomer of urethane acrylate.
The big monomer of top synthetic urethane acrylate can pass through uv-light polymerization, also available initiator thermopolymerization.As through 2,2-dimethyl-2-hydroxy acetophenone (1173) light initiation polymerization and azo-bis-isobutyl cyanide (AIBN) thermal-initiated polymerization, the polymeric film that obtains has higher specific refractory power, and specific refractory power is 1.64.
Embodiment 4: polyurethane oligomer synthetic
The isophorone diisocyanate (IPDI) of 2,2 of 15.4g '-dimercapto ethyl-sulfide (MES) and 33.4g is dissolved in about 100ml exsiccant toluene, adds a spot of dibutyl tin laurate again and make catalyzer.This reaction mixture reacted 9 hours at 75～80 ℃ under nitrogen protection.A part of toluene is removed in decompression at last, obtains the toluene solution of the polyurethane oligomer of the water white 61wt% of containing.IR spectrum (KBr): v (cm
-1) 3290 (N-H), 2268 (N=C=O), 1667 (COS-), 1254,1530 (N-H).From the visible institute of ir data synthetic is polyurethane oligomer.The specific refractory power of the pure polyurethane oligomer film of gained is 1.57.
Embodiment 5:
Prepare nano compound film with thiophenol (PhSH)/big monomer of thiopurine methyltransferase vinylbenzene (TMSt) modified ZnS nanoparticle (1) composite polyurethane acrylate.
By desired doping ZnS colloidal nanoparticles, the big monomer of urethane acrylate and initiator (comprise 1173 and AIBN) are mixed in DMF, the big monomeric ratio of ZnS colloidal particle and urethane acrylate is pressed table 1 and is calculated, TCZnS in the table 1
aRepresent the percentage composition of thiophenol (PhSH)/thiopurine methyltransferase vinylbenzene (TMSt) modified ZnS nanoparticle, and the big monomeric consumption of urethane acrylate is 100%-TCZnS%, the consumption of initiator is 3/1000ths of a big monomer weight, and the vacuum concentration mixing solutions is to certain viscosity under 40 ℃ of conditions.The gained mixed solution is spin-coated on (as silicon chip, sheet glass or plastics sheet) on the surface-treated substrate, spin speed can be regulated (promptly between 500～4000 rev/mins according to the viscosity of coating liquid and the thickness of final coating, the less solution of viscosity will obtain thicker coating and need adopt the low speed spin coating, and the coating that the bigger solution of viscosity will obtain approaching need adopt the high speed spin coating).The coating that spin coating is good 40 ℃ of dryings 20 minutes under vacuum, ultraviolet light polymerization 3 minutes under the medium pressure mercury lamp of 1KW then solidified 4 hours at 70 ℃ then, and 100 ℃ solidified 2 hours, 160 ℃ of thermal treatment 0.5 hour.Obtain the optical coating of water white homogeneous at last.Show the actual content of ZnS particulate in the film and Theoretical Calculation amount (seeing Table 1) in full accord through thermogravimetric analysis (TGA).The specific refractory power of the pure urethane acrylic acid ester polymer of doped ZnS is not 1.645, and the specific refractory power of the laminated film of doping 57wt%ZnS is near 1.8.Table 1 has been listed the performance of PhSH/TMSt modified ZnS-urethane acrylate polymer nano composite film.
The performance of table 1.PhSH/TMSt modified ZnS-urethane acrylate polymer nano composite film
| TCZnS a | ZnS b | h() c | n(632.8nm) d | T d(℃) e | 750℃ residue f | T％ g |
| 0 | 0 | 1795 | 1.645 | 200 | 0 | 96 |
| 16 | 11 | 1463 | 1.672 | 201 | 12 | 96 |
| 32 | 21 | 1386 | 1.706 | 205 | 22 | 95 |
| 48 | 31 | 1508 | 1.728 | 204 | 32 | 95 |
| 63 | 46 | 1614 | 1.749 | 202 | 44 | 95 |
| 79 | 52 | 1370 | 1.766 | 206 | 53 | 95 |
| 86 | 57 | 1162 | 1.796 | 203 | 57 | 95 |
aThe theoretical weight mark of the ZnS particulate that mercaptan coats in the film;
bThe theoretical weight mark of pure ZnS particulate in the film;
cThe thickness of nano compound film;
dNano compound film is in the specific refractory power at 632.8nm place;
eThe initial decomposition temperature of nano compound film;
fInorganics is at 750 ℃ residual rate (thermogravimetic analysis (TGA) result) in the film;
gThe thick nano compound film of about 1 μ m is in the transmitance at 550nm place.
Embodiment 6:
Prepare nano compound film with thiophenol (PhSH)/mercaptoethanol (ME) modified ZnS nanoparticle (2) composite polyurethane oligopolymer.
In desired doping ZnS colloidal nanoparticles, polyurethane oligomer are mixed back (the big monomeric ratio of ZnS colloidal particle and urethane acrylate is pressed table 2 and calculated) in dry DMF, the vacuum concentration mixing solutions is to certain viscosity (can regulate according to film-forming properties and thicknesses of layers) under 40 ℃ of conditions.The gained mixed solution is spin-coated on surface-treated substrate (on silicon chip, sheet glass or plastics sheet), and spin speed can be regulated between 500～4000 rev/mins according to the viscosity of coating liquid and the thickness of final coating.The coating that spin coating is good was solidified 4 hours at 70 ℃, and 100 ℃ solidified 2 hours, and 120 ℃ solidified 1 hour, 160 ℃ of thermal treatment 0.5 hour.Obtain water white optical coating at last.Show also basically identical (seeing Table 2) of the actual content of ZnS particulate in the film and Theoretical Calculation amount through thermogravimetric analysis (TGA).The specific refractory power of the pure polyether polyols with reduced unsaturation of doped ZnS is not 1.574, and the specific refractory power of the laminated film of doping 63wt%ZnS is near 1.85.Table 2 has been listed the performance of PhSH/ME modified ZnS-polyether polyols with reduced unsaturation nano compound film.
The performance of table 2.PhSH/ME modified ZnS-polyurethane nano laminated film.
| TCZnS a | ZnS b | h() c | n(632.8nm) d | T d(℃) e | 750℃reisdue f |
| 0 | 0 | 1760 | 1.574 | 202 | 0 |
| 16 | 10 | 1282 | 1.592 | 207 | 11 |
| 32 | 20 | 1551 | 1.635 | 209 | 21 |
| 47 | 31 | 1311 | 1.70 | 204 | 30 |
| 63 | 41 | 1586 | 1.754 | 203 | 43 |
| 80 | 52 | 1542 | 1.789 | 198 | 52 |
| 88 | 58 | 1601 | 1.821 | 206 | 57 |
| 97 | 63 | 1477 | 1.848 | 208 | 61 |
*The meaning of footmark is with table 1.
Claims (6)
1, a kind of preparation method of nano particles with high refractive index and polymer nano composite film material, comprise ZnS Nano sol, the preparation big monomer of high refractive index organic polymer or polymkeric substance, three steps of preparation nano compound film of preparing finishing, it is characterized in that:
(1) in the organic solvent of zinc metal-salt, add thiophenol, thiopurine methyltransferase vinylbenzene or mercaptoethanol organic molecule coating materials, and feeding hydrogen sulfide, the molar ratio of coating materials and metal-salt is 0.2: 1～1.0: 1, the feeding amount of hydrogen sulfide is normal 6～10 times an of metal-salt, feeding speed 0.1 milliliter～5 ml/min, thus prepare the ZnS Nano sol of finishing;
(2) with polyurethane oligomer or the compound ZnS Nano sol of the big monomer of urethane acrylate, polyurethane oligomer is prepared through polyaddition by dibasic alcohol or binary mercaptan and vulcabond, the equivalence ratio of dibasic alcohol or binary mercaptan and vulcabond is 1: 1.1～1: 2, temperature of reaction is 45～85 ℃ in the solvent, reaction times is 2～10 hours, the big monomer of urethane acrylate is obtained with the hydroxyethyl methylacrylate end-blocking by polyurethane oligomer, by uv-light polymerization or by the initiator thermopolymerization, obtain big monomer of high refractive index organic polymer or polymkeric substance;
(3) nano compound film is by shifting the preparation of diffuse-aggregate method, contains ZnS Nano sol and polyurethane oligomer in the film liquid, then direct spin-coating film; It is monomeric greatly to contain ZnS Nano sol and urethane acrylate, repolymerization after the film forming; The doping of ZnS Nano sol is 16～97wt% in the film liquid, is 500～4000 rev/mins in on-chip spin speed, gets nano composite film.
2, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1 is characterized in that: the zinc metal-salt is a kind of in zinc acetate, zinc perchlorate or the zinc sulfate.
3, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1 is characterized in that: organic solvent is a kind of in second cyanogen, methyl alcohol or the dimethyl formamide.
4, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 3 is characterized in that: organic solvent is a dimethyl formamide.
5, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1, it is characterized in that: the dibasic alcohol or the binary mercaptan of preparation big monomer of urethane acrylate or polyurethane oligomer are ethylene glycol, propylene glycol, dihydroxyethylsulfide, mercaptoethanol, 2,2 '-dimercapto ethyl-sulfide or dithioglycol; Vulcabond is 2,4 '-tolylene diisocyanate, isophorone diisocyanate or '-diphenylmethane diisocyanate, reaction solvent is benzene, toluene, tetrahydrofuran (THF) or dimethyl formamide.
6, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1, it is characterized in that: polymerization adopts uv-light polymerization, AIBN or BPO to cause radical polymerization and thermopolymerization, or adopt first uv photopolymerization, the method that back AIBN or BPO initiation radical polymerization and thermopolymerization combine, the time of uv photopolymerization is 20 seconds～5 minutes, AIBN or BPO cause the temperature of radical polymerization and thermopolymerization between 60～180 ℃, and the time is 3～10 hours.
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