CN101321816A - Transparent polymer nanocomposites containing nanoparticles and method of making same - Google Patents

Abstract

The present invention relates to transparent nanocomposites comprising of metal oxide nanoparticles dispersed in polymer matrix. The nanoparticles have capping agents attached onto the nanoparticle surfaces and a precursor solution of capped nanoparticles and polymer is prepared and dried to obtain the nanocomposites. The nanocomposites exhibit UV absorption, low haze, and improved thermal stability. The present invention also relates to the methods associated with the preparation of capped nanoparticles, precursor solution and nanocomposites.

Description

Contain transparent polymer nanocomposites of nano particle and preparation method thereof

Related application

It is the U.S. Provisional Application sequence number 60/723 of the submission in 3 days October in 2005 of " containing transparent polymer nanocomposites of nano particle and preparation method thereof " that the application requires title, the U.S. Provisional Application sequence number 60/830 that on July 13rd, 344 and 2006 submitted to, 433 interests, and integrally introduce these applications for reference.

Invention field

The present invention relates to polymer nanocomposites.More particularly, the present invention relates to have the transparent polymer nanocomposites that contains finely divided nano crystal particles of numerous characteristics at optics and thermophysics aspect of performance.

Background of invention

Zinc oxide (ZnO) is the white crystals semiconductor material that obtains using in many and various application.It is used to the sun-screening agent of improving looks, varistor, the white pigment in plastics and the printing ink at present.It just is being considered to the potential material of photodiode, piezoelectric transducer, transparent electronics, transparent conductive oxide (TCO) film and gas sensor.Referring to people's such as Pearton " Recent progress inprocessing and properties of ZnO ", Prog.Mater.Sci., Vol.50, pp 293-340 (2005).The unique combination of the performance of ZnO (be that it is that transparent, UV absorbs, luminous, piezoelectricity, nontoxic and material cheaply) makes that it is technical important.

ZnO is particularly useful when combining with polymkeric substance when using.It is used for improving the UV stability of polymkeric substance.Organic UV absorption agent for example benzotriazole may ooze out in the length of life of polymeric articles.Ooze out surface smoothness and UV stability are reduced.Yet inorganic UV absorption agent such as ZnO do not ooze out.This makes that they are especially desirable in polymeric articles.

Be nano particle (granularity is less than 100nm) form, known ZnO improves polyacrylic ester and poly thermostability.Referring to people's such as Liufu " Thermal analysis and degradation mechanism ofpolyacrylate/ZnO nanocomposites ", Polym.Degrad.Stab., Vol 87, pp 103-110 (2005); People's such as Cho " Effects of ZnO Nano Particles on Thermal Stabilization ofPolymers ", Polym.Eng.Sci., Vol 44, pp 1702-1706 (2004).The ZnO nano particle also improves the wear resistance of polymkeric substance.Referring to people's such as Li " The friction andwear characteristics ofnanometer ZnO filled polytetrafluoroethylene ", Wear, Vol.249, pp 877-882 (2002).Large volume ZnO has about 2.0 refractive index and because reduce the visible light scattering during less than 20nm significantly when granularity, so the ZnO nano particle can be used to increase transparent polymer for example poly-(methyl methacrylate) (PMMA), the refractive index that waits of polystyrene (PSt), polyvinyl chloride (PVC), polyvinyl butyral acetal (PVB), keep transparent simultaneously.Yet, can bring the interests maximization of polymkeric substance in order to make ZnO, must reach fully decentralized polymer nanocomposites.

Used various types of Nanoparticulate fillers to prepare nano composite material.People's such as Border United States Patent (USP) discloses the nano composite material optical goods that use magnesium oxide and aluminium oxide nano filler for 6,586, No. 096.Yet these fillers do not show that the UV of ZnO absorbs and characteristic of semiconductor.People's such as Arney United States Patent (USP) has been described the nano level titanium oxide of high dispersing in polymeric matrix for 6,432, No. 526.This nano composite material shows and the similar UV absorption of ZnO nano composite material, refractive index and characteristic of semiconductor, yet the TiOx nano particle is not provided at the protection in the UVA bands of a spectrum, in addition, does not discuss the thermostability of this nano composite material.

Ultraviolet (UV) light is divided into three bands of a spectrum usually: UVC 200-290nm, UVB 290-315nm and UVA 315-400nm.UVA and UVB are the main types of the UV light that exists in the daylight.When being exposed to the easily degraded and of UVB polymkeric substance of following time and organic materials when human skin is exposed to UVA skin of following time tanning, painted and cancer may take place.Though titanium oxide and ZnO are used as the UV screener usually, TiO2 is presented at the cumulative absorption in the UVA zone, reaches peak absorption at about 330-350nm." Synthesis and characterization ofsurface-modified rutile nanoparticles and transparent polymer compositesthereof " referring to people such as Nussbaumer, J.Nanoparticle Res., Vol.4, pp 319-323 (2002).Because ZnO sharp-pointed absorption curve and it is being better than TiO2 aspect UV shielding in UVA.Large volume or micron order ZnO absorb the UV light less than 380nm, and when particle size reduction arrived less than 10nm, UV absorbed and is displaced to more short wavelength.Therefore, for the protection to UVA and UVB is provided, the ZnO particulate method that adds about 10nm is desirable.

In order in polymkeric substance, to disperse the ZnO nano particle, many trials have been made.A method that obtains the ZnO polymer nanocomposites is by form the ZnO nano particle on the spot in polymeric matrix.Normally, at first the precursor of zinc oxide is sneaked in the polymers soln, make then in many ways, comprise that hydrolysis by alkali or water and the oxidation by oxygen plasma impel Zinc oxide nanoparticle to form." Generating Blue and Red Luminescence from ZnO/Poly (ethylene glycol) Nanocomposite Prepared Using an In-Situ Method " referring to people such as Abdullah, AdV.Func.Mater, Vol 13, pp 800-804 (2003); People's such as Jeon " Synthesis of ZnO nanoparticlesembedded in a polymeric matrix; Effect of curing temperature ", Materials ScienceForum.Vol.449-452, Part 2, pp.1145-1148 (2004); People's such as Mulligan " Synthesisand Characterization of ZnO Nanostructures Templated Using DiblockCopolymers ", J.Appl.Polym.Sci., Vol.89, pp 1058-1061 (2003); People's such as Yoo " Self-assembled arrays of zinc oxide nanoparticles from monolayer films ofdiblock copolymer micelles ", Chem.Commun., Iss.24, pp 2850-2851 (2004).Though can obtain the ZnO polymer nanocomposites by good distribution, synthetic method needs complicated and many step and operable polymer type possible restricted usually.

Another method is by with ZnO nano particle and polymeric matrix simple blend.Referring to people's such as Xiong " Preparation and Characterization of Poly (styrene butylacrylate) Latex/Nano-ZnO Nanocomposites ", J.Appl.Polym.Sci., Vol.90, pp 1923-1931 (2003).Obtain the ZnO content of 9wt%.Yet nano composite material shows that under TEM agglomeration and light transmission are of poor quality.

Be prepared as follows transparent and high-content ZnO/PMMA matrix material: ZnO nano particle and PMMA are mixed in toluene solution, be spun on the base material then.Referring to people's such as Chen " ZnO/PMMA Thin Film nanocomposites for Optical Coatings ", Proc.SPIE, Vol5222, pp 158-162 (2003).So the transparent film that forms can have the nearly ZnO of 20wt%, but film thickness is limited in less than 300nm.

Can improve the quality of nano composite material by the surface modification of ZnO nano particle.Molecule attached can be improved the solvability of this oxide nano particles in polymeric matrix on the ZnO surface, thereby guarantee homodisperse.People such as Zhou have used a kind of simple method, and he uses industrial dispersion agent and ZnO nano particle and by ball milling and the blend of water soluble acrylic acid latex, the gained nano composite material does not reach the enough homogeneity and the transparency shown in the UV-Vis transmitted spectrum.Referring to people's such as Zhou " Dispersion and UV-VIS Properties of Nanoparticles in Coatings ", J.Dispersion Sci.Tech., Vol.25, pp.417-433,2004.Used other forms of this design, synthetic ZnO in the presence of polymeric surfactant wherein, then purifying and with PMMA blend and spin coating to form Clear coating.Referring to people's such as Khrenov " Surface Functionalized ZnOParticles Designed for the Use in Transparent Nanocomposites ", Macromol.Chem.Phys., Vol 206, pp 95-101 (2005).Yet formed nano particle shows that wide size-grade distribution and irregular shape and film maximum ga(u)ge only are 2.5 μ m.In addition, for this reason must special synthetic polymer tensio-active agent, therefore increase the complexity of this method.

By with methacrylic acid 3-(trimethoxysilyl) propyl diester with the surface of ZnO at first modification prepared (PHEMA) nanocomposite films of high-quality ZnO/ poly-(hydroxyethyl methylacrylate).ZnO nano particle with this modification mixes also polymerization to form transparent film with the HEMA monomer then.In this method, the original particle size of ZnO nano particle distributes and shape is maintained.Yet when identical method was applied to PMMA, the film quality that is obtained was more unsatisfactory." Effect of surface stabilization of nanoparticles on luminescentcharacteristics in ZnO poly (hydroxyethyl methacrylate) nanohybrid films " referring to people such as Hung, J.Mater.Chem., Vol.15, pp 267-274 (2005).Generally speaking, compare with hydrophobic polymer, easier of in the ZnO nano particle adding hydrophilic polymer.People such as Guo (Synthesis andCharacterization of Poly (vinylpyrrolidone)-Modified Zinc Oxide Nanoparticles, Chem.Mater Vol.12, pp 2268-2274 (2005)) illustrates, poly-(vinyl pyrrolidone) (PVP) fully applies in the article of ZnO nano particle with the people such as Hung that form shell and mentioning before this around them, and ZnO is well dispersed among the PHEMA to obtain the transparent nano matrix material.These examples show that all ZnO has the affinity good with hydrophilic polymer, think that a large amount of OH group on the ZnO surface greatly increases the affinity with hydrophilic polymer, yet this also causes and the hydrophobic polymer affinity of the difference of PMMA for example.

Still do not have to overcome relate to above restricted polymer materials.The ZnO nano particle is included in will give favourable performance in the polymeric matrix for example wear resistance, UV will stop, optical transparence, refractive index adjustment, thermostability, and without any with the relevant defective of organic additive that is commonly used to obtain identical performance.Yet the homodisperse of the nano-scale particle of ZnO is needed for showing advantageous property, and this type of nano composite material still can not on demand quality and quantity obtain.Therefore, still need be at transparent polymer, particularly produce finely divided ZnO nano particle in the hydrophobic polymer, this is simple and be applicable to polymeric matrix widely.

Summary of the invention

An object of the present invention is to provide nano composite material with High-quality transparent and high nano-particle content.

Another purpose provides polymer nanocomposites, the nano composite material of hydrophobic polymer especially, NO and excellent physicals before it shows.

Another purpose provides metal oxide or semi-conductor or metal nanoparticle is dispersed in the polymeric matrix to obtain the method for nano composite material.

Above-mentioned and other purpose realizes that according to the preparation method of nano composite material of the present invention and nano composite material goods described nano composite material comprises and do not show the remarkable metal oxide particle that weakens the transparency.Described nano composite material shows excellent optical property, comprises that UV absorbs and the improvement of thermostability.

Metal oxide particle is Zinc oxide particles preferably.Metal oxide particle has preferred granularity or particle diameter less than 20nm.When measuring under the thickness at least 100 microns, nano composite material shows the level of haze less than 5%.The present invention considers to use the mixture of metal oxide particle or metal oxide, semi-conductor or metallic particles and the combination of polymeric matrix.Insulating covering agent is attached on the particle surface and helps the dispersion of this particle in solvent or polymeric matrix.

The present invention also comprises the coated products with base material, and this base material has the Clear coating of the surface attachment of one deck and this base material at least.Described base material, its coating or both can comprise nano composite material, and this nano composite material comprises the inorganic nanoparticles that is dispersed in the polymeric matrix.

The present invention also comprises is dispersed in the polymeric matrix to obtain the method for nano composite material metal oxide, semi-conductor or metal nanoparticle.This method comprises the method for nanoparticulate dispersed in organic medium, comprises with mercaptan compound or the silane compound step (a) with this modified by nano particles.This mercaptan compound comprises thiol group and aromatic ring at least.This silane compound comprises hydrolyzable silylation and aromatic ring at least.Use the modification of these compounds to make this nanoparticulate dispersed in nitrogen-containing solvent, described nitrogen-containing solvent comprises solvent for example pyridine, the N that contains amine or acid amides, dinethylformamide etc.This method also is included in nitrogen-containing solvent, for example pyridine, N, in the dinethylformamide by the step (b) of the covering preparation of nanoparticles solution of step (a) and in the solvent that is fit to the step (c) of the solution of preparation polymkeric substance.Subsequently, carry out mix (b) and (c) in the middle method of nano particle and polymeric blends for preparing of step (e) of dry this solution of step (d) neutralization of prepared solution with the formation nano composite material.

When this uses, for the present invention, should use following term:

" covering (capping) " is meant the ionic linkage or the covalent linkage of the surface atom that forms organic molecule and nano particle, and this organic molecule is called insulating covering agent (capping agent).

" insulating covering agent " is meant the organic molecule with functional group, and this functional group can be by the surface atom keyed jointing of ionic linkage or covalent linkage and nano particle.

" colloid " or " colloidal solution " is meant the stabilising dispersions of nano particle in liquor.

" mist degree " is meant the scattering effect of light in transparent or semitransparent material.

" nano composite material " is meant polymkeric substance and particulate matrix material, wherein this particle have various forms and shape and at least one dimension less than 100 nanometers.

" nano particle " be meant various forms and shape and at least one dimension less than the particle of 100 nanometers.

" silane compound " is commonly referred to silane coupling agent, contains hydrolyzable silane base-Si-Hy, and wherein Hy is for example acyloxy, alkoxyl group, a chlorine etc. of hydrolyzable part.Described hydrolysable group can with inorganic atoms for example zinc and titanium and increase and organic medium for example the organo-functional group of the affinity of solvent and polymkeric substance form stable key.Described organo-functional group can also contain reactive part, thereby allows and the organic reaction medium keyed jointing.

The accompanying drawing summary

Fig. 1 is dispersed in the electron photomicrograph of the nano composite material that the ZnO nano particle that is coated with mercaptan compound in poly-(methyl methacrylate) forms by 4wt%.This electron photomicrograph is taken with 400,000 times magnification.

Fig. 2 is dispersed in the electron photomicrograph of the nano composite material that the ZnO nano particle that is coated with silane compound in poly-(methyl methacrylate) forms by 1.35wt%.This electron photomicrograph is taken with 400,000 times magnification.

Fig. 3 describes the figure of the ZnO of phenyltrimethoxysila,e covering with respect to the weight loss of temperature.Find that remaining solid is 82.7% of an original weight.

Fig. 4 is the optical transmittance of nano composite material in the visible region and the figure of the absorptivity in the ultraviolet region that describes the ZnO of pure poly-(methyl methacrylate) and mercaptan covering.

Fig. 5 is the optical transmittance of nano composite material in the visible region and the figure of the absorptivity in the ultraviolet region that describes the ZnO of pure polystyrene and mercaptan covering.

Fig. 6 is the optical transmittance of nano composite material in the visible region and the figure of the absorptivity in the ultraviolet region that describes the ZnO of pure poly-(methyl methacrylate) and silane covering.

Fig. 7 describes the weight loss of nano composite material of ZnO of pure poly-(methyl methacrylate) and mercaptan covering with respect to the figure of temperature.

Fig. 8 describes the weight loss of nano composite material of the ZnO that pure polystyrene and mercaptan covers with respect to the figure of temperature.

Fig. 9 describes the weight loss of nano composite material of ZnO of pure poly-(methyl methacrylate) and silane covering with respect to the figure of temperature.

Figure 10 is the synoptic diagram that has by the exemplary nano composite product of the coating of forming according to the nano composite material of one embodiment of the invention.

Detailed description of preferred embodiments

Referring now to accompanying drawing, especially with reference to Fig. 1, it is an electron photomicrograph, illustrates to comprise the transparent nano matrix material 10 that 4wt% is dispersed in the inorganic nanoparticles 12 in the polymeric matrix 14.This polymeric matrix 14 is selected from the polymkeric substance group that is made of transparent polymer, this transparent polymer is selected from thermoplastics, the vinyl polymer or the multipolymer that comprise polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers, described vinyl monomer are selected from (methyl) acrylate, aromatic ethylene (aromatic vinyl), vinyl cyanide, halogen ethene and vinylidene halide; It is preferably selected from the polycarbonate of polyalkylene terephthalates, bisphenol cpd, the vinyl polymer or the multipolymer of vinyl-containing monomers, and described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide; More preferably this transparent material should be selected from poly-(methyl) acrylate, polystyrene and their combination.This nano particle 12 comprises zinc oxide, or the mixture of the inorganic nanoparticles of metal oxide, semi-conductor or metal and zinc oxide.The surface of nano particle is covered by the mercaptan insulating covering agent.Nano particle has preferred 1-20nm maximum, and more preferably 1-10nm most preferably hangs down the median size to 1-8nm.Mean particle size can be obtained by transmission electron microscope photo as shown in Figure 1.Measure the diameter of the individual particle in this Photomicrograph and obtain mean value, this value is considered to mean particle size.

Fig. 2 is that expression comprises the electron photomicrograph that 1.35wt% is dispersed in the transparent nano matrix material 20 of the inorganic nanoparticles 22 in the polymeric matrix 24.This polymeric matrix 24 is selected from the polymkeric substance group that is made of transparent polymer, this transparent polymer is selected from thermoplastics, the vinyl polymer or the multipolymer that comprise polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers, described vinyl monomer are selected from (methyl) acrylate, aromatic ethylene, vinyl cyanide, halogen ethene and vinylidene halide; It is preferably selected from the polycarbonate of polyalkylene terephthalates, bisphenol cpd, the vinyl polymer or the multipolymer of vinyl-containing monomers, and described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide; More preferably this transparent material should be selected from poly-(methyl) acrylate, polystyrene and their combination.This nano particle 22 comprises zinc oxide, or the mixture of the inorganic nanoparticles of metal oxide, semi-conductor or metal and zinc oxide.The surface of nano particle is covered by the silane insulating covering agent.This insulating covering agent is made of silane compound, and this silane compound has and the hydrolyzable functional group of zinc oxide surface keyed jointing and improve organic aromatic functional group of affinity between polymkeric substance and nano particle.Nano particle has preferred 1-20nm maximum, and more preferably 1-10nm most preferably hangs down the median size to 1-8nm.

The transparency that key feature is a nano composite material of the present invention.The transparency can characterize by the haze value of nano composite material.Haze value is defined as when passing sample because direct scattering and the percentage of the transmitted light that departs from incident beam, and the total amount of the light that departs from this incident beam is called fills the air transmission.The low more expression transparency of haze value is high more.Following providing on the mathematics:

T=% transmissivity wherein

For many practical applications, haze value is desirable less than 5%, and preferred haze value should be less than 4%, and more preferably haze value should also be more preferably less than 2% less than 3%, most preferably less than 1%.This value may be subjected to the inherent transparency and the object surfaces quality influence of material simultaneously.In order to realize the transparency of this level, must satisfy some conditions.1) nano particle of Jia Ruing preferably diameter less than 20nm so that scattering of light minimizes, more preferably they should be less than 10nm, most preferably they should be less than 8nm.2) the transparent base material should be selected from thermoplastics, the vinyl polymer or the multipolymer that comprise polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers, described vinyl monomer are selected from (methyl) acrylate, aromatic ethylene, vinyl cyanide, halogen ethene and vinylidene halide; It is preferably selected from the polycarbonate of polyalkylene terephthalates, bisphenol cpd, the vinyl polymer or the multipolymer of vinyl-containing monomers, and described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide; More preferably this transparent material should be selected from poly-(methyl) acrylate, polystyrene and their combination.3) nano particle of Jia Ruing must fully disperse, and does not almost have agglomeration.4) nano composite material object surfaces condition should be preferably smooth enough to reduce scattering of light and to guarantee maximum optical transmittance.

The transparent base material is hydrophobic polymer or the multipolymer be made up of hydrophobic monomer and hydrophilic monomer preferably, and wherein this hydrophilic monomer preferably accounts for the 40wt% at the most of total polymer.In addition, the amount of hydrophilic monomer is more preferably the 30wt% at the most of total polymer, more preferably 20wt% at the most also, most preferably 10wt% at the most.Hydrophilic monomer can comprise functional group for example amide group, amino, carboxyl, hydroxyl, pyrrolidone and the ethylene glycol that hydrophilic nmature is provided.

Satisfy above-mentioned condition and show under the measuring condition of 100 micron thickness that the nano composite material of 5% level of haze is thought at the most and belong to a part of the present invention.In addition, haze value can be at the most 4%, preferably less than 3%, is more preferably less than 2%, most preferably is lower than 1%.

Providing ultraviolet screener to keep the high transparency simultaneously is distinguishing feature of the present invention.ZnO easily absorbs the UV-light that comprises the energy higher than its band-gap energy.Large volume ZnO absorbing wavelength is less than the light of 380nm.Yet the ZnO nano particle begins absorb light under the wavelength less than 380nm, and this widens owing to the band-gap energy that diminishes along with granularity, and this phenomenon is owing to the quantum size effect of knowing.Polymer samples can characterize by the UV visible spectrometry, can obtain transmittance spectrum by this.Cutoff wavelength can be defined as the wavelength that absorbs fully of observing light.Yet the sample that absorbs fully for light does not wherein take place can be defined as effective cut-off wavelength.Can followingly find effective cut-off wavelength: in the slope that at first begins aspect the intensity in transmission to descend location, the linear portion from this slope of this transmission curve prolongs straight line then, reads this cutoff wavelength at the point that this straight line and X-coordinate intersect with curve.In fact, effective cut-off wavelength can be as the wavelength that UV absorbs takes place.

Fig. 3 explanation ZnO that phenyltrimethoxysila,e (PTMS) covers when temperature is increased to 800 ℃ shows weight loss.This weight loss is owing to the solvent that absorbs and the organic constituent of silane compound.Can measure metal oxide content according to test method 2, in this case, weight loss is 17.3%, and metal oxide content is 76.4%.

Fig. 4 illustrates the short UV-light of ZnO/PMMA (nano composite material BM01) specific absorption 355nm that mercaptan covers, and this 380nm with large volume ZnO compares to blue shift.BM01 comprises the ZnO nano particle of the about 5nm of 4wt% mean particle size, and this mean particle size is similar to the nano particle 12 in the nano composite material 10 shown in Figure 1.Fig. 4 has shown that also straight polymer BM00 begins to absorb UV-light at 270nm.The adding of ZnO improves the ultraviolet screener of straight polymer significantly and the UV absorption is expanded in the UVA bands of a spectrum.Yet it is inadequate ZnO being added polymeric matrix simply.Fig. 5 explanation is compared with the straight polymer TM00 of the UV-light of specific absorption 270nm weak point, and the ZnO/PSt nano composite material TM01 that mercaptan covers is the short UV-light of specific absorption 325nm partly.In this case, TM01 also comprises the ZnO nano particle of the about 5nm of 4wt% mean particle size.The UV shielding of TM01 is compared very different with BM01, this is owing to the thickness of film, and that TM01 is 0.020mm, and that BM01 is 0.110mm.Thin polymeric film is not because the in shortage of ZnO nano particle may absorb all UV-light.Therefore, in order to improve the UV shielding, must increase film thickness or ZnO amount.In practice, will be preferred according to a kind of in these two kinds of methods of physical constraints.

Fig. 6 illustrates ZnO/PMMA (nano composite material PTMS01 and PTMS02) difference specific absorption 340nm and the short UV-light of 350nm that silane covers, and this 380nm with large volume ZnO compares to blue shift.The zinc oxide content of PTMS01 and PTMS02 is respectively 1.35wt% and 6.31wt%, and wherein ZnO nano particle mean particle size is approximately 5nm, and this mean particle size is similar to the nano particle 22 in the nano composite material 20 shown in Figure 2.Fig. 6 illustrates that also straight polymer PTMS00 begins to absorb UV-light at 280nm.The adding of ZnO improves the ultraviolet screener of straight polymer significantly and the UV absorption is expanded in the UVA bands of a spectrum.

The present invention does not absorb horizontal applying condition to UV to the add-on of ZnO yet, thereby the present invention is contained and is comprised the ZnO particulate and show less than 380nm, preferably less than 370nm, be more preferably less than 360nm, still be more preferably less than 355nm, most preferably absorb, under the thickness of 0.100mm, keep any polymer nanocomposites that level of haze is lower than 5% the transparency simultaneously less than the UV of 350nm.Nano composite material of the present invention is presented at the thermostability aspect and compares tangible improvement with straight polymer.Fig. 7 illustrates that the weight loss of the ZnO nano composite material that mercaptan covers is with variation of temperature.The ZnO/PMMA nano composite material BM01 that mercaptan covers compares the thermostability that shows 78 ℃ and improves with straight polymer BM00.Equally, Fig. 8 illustrates that the ZnO/PSt nano composite material TM01 that mercaptan covers compares the thermostability improvement that shows 14 ℃ with pure PSt polymkeric substance TM00.

Fig. 9 illustrates that the weight loss of the ZnO nano composite material that silane covers is with variation of temperature.The ZnO/PMMA nano composite material PTMS01 that silane covers and PTMS02 compare the thermostability improvement that shows 17 ℃ and 27 ℃ respectively with straight polymer PTMS00.If compare with the identical straight polymer that does not comprise the ZnO nano particle, nano composite material is reduced to 10 ℃ of 50% temperature increases of 25 ℃ of its original weights of measuring down at least, think that then nano composite material belongs to a part of the present invention.Nano composite material of the present invention can form the goods with different shapes and form.Nano composite material of the present invention can also be the coated products form, and wherein top coat or film are made up of described nano composite material and basic base material can be formed by maybe can't help described nano composite material.

Figure 10 explanation comprises the coated products 40 of base material 44, and this base material 44 has the Clear coating 50 of the surface attachment of one deck and this base material at least.Described base material 44, coating 50 or both comprise nano composite material, and this nano composite material comprises the inorganic nanoparticles that is dispersed in the polymeric matrix.This nano composite material comprises the nano particle of zinc oxide, and this nano particle is capped agent and covers.The transparent polymer body material is selected from thermoplastics, the vinyl polymer or the multipolymer that comprise polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers, described vinyl monomer are selected from (methyl) acrylate, aromatic ethylene, vinyl cyanide, halogen ethene and vinylidene halide; It is preferably selected from the polycarbonate of polyalkylene terephthalates, bisphenol cpd, the vinyl polymer or the multipolymer of vinyl-containing monomers, and described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide; More preferably this transparent material should be selected from poly-(methyl) acrylate, polystyrene and their combination.Coated products of the present invention can be Any shape or form.

Equally, the level of haze of this nano composite material is at most 5%.The UV of this nano composite material is absorbed under 380nm or the shorter wavelength and begins.Realized thermostability, wherein increased at least 10 ℃ than the temperature that is reduced to 50wt% with the polymer phase that does not have described nano particle.

The preparation method of nano composite material is also contained in the present invention, and this nano composite material comprises the inorganic nanoparticles that is dispersed in the organic medium, and wherein this organic medium is made up of organic solvent, monomer and polymkeric substance.Nano particle of the present invention can be a metal, semi-conductor or metallic oxide type, they are selected from: aluminium, cadmium, cerium, chromium, cobalt, copper, gallium, germanium, gold, indium, iron, iridium, plumbous, mercury, nickel, platinum, palladium, silicon, silver, tin, zinc, zirconium, aluminium arsenide, aluminium nitride, aluminium phosphide, cadmium selenide, Cadmium Sulfide, cadmium telluride, gallium arsenide, gan, gallium phosphide, gallium selenide, the sulfuration gallium, indium arsenide, indium phosphide, indium nitride, indium selenide, indium sulfide, the tellurium indium, lead selenide, lead sulfide, lead telluride, mercury selenide, zunsober, tellurium mercury, zinc selenide, zinc sulphide, zinc telluridse, aluminum oxide, Cadmium oxide, cerium oxide, chromic oxide, cobalt oxide, Indium sesquioxide, tin indium oxide, ferric oxide, plumbous oxide, nickel oxide, silicon-dioxide, stannic oxide, titanium oxide, zinc oxide and zirconium white.The present invention to metal oxide nanoparticles particularly Zinc oxide nanoparticle be especially effective.

Metal oxide nanoparticles can be synthetic by the forced hydrolysis of metal-salt in alcoholic solution.Many papers can obtain in the document of describing these class methods, some examples can find in following paper: people's such as Koch (Chem.Phys.Lett., 122 (5), pp 507-510 (1985)), people's such as Bahnemann (J.Phys.Chem., 91, pp 3789-3798, and people's such as Spanhel (J.Am.Chem.Soc. (1987)), 113, pp 2826-2833, (1991)).In the present invention, people's such as Bahnemann (J.Phys.Chem., 91, pp 3789-3798, (1987)) method and people's such as Li disclosed method in U.S. Patent Publication No. US20050260122 will be used for the Zinc oxide nanoparticle of synthetic granularity with improving one's methods less than 10nm.People such as Bahnemann improve one's methods, zinc acetate dihydrate is dissolved in the alcoholic solvent, after this, the alcoholic solution of sodium hydroxide is added in this acetic acid zinc solution.Mixture is put into the water-bath that is heated to 60 ℃ in advance to be kept 2 hours.Obtain 0.04MZnO colloidal solution by the rotary evaporation concentrated reaction solution then.People such as Li improve one's methods, zinc acetate dihydrate is dissolved in alcoholic solvent.The alcoholic solution that also prepares potassium hydroxide.Promptly zinc acetate dihydrate solution is poured in the alcoholic solution of potassium hydroxide and stirred simultaneously.Reaction was continued 2 hours, after this solution is cooled to 0～5 ℃ to stop further nanocrystal growth.So the solution of preparation is 1L 0.04M ZnO colloidal solution.Though provided the example of ZnO nanoparticulate dispersed in alcoholic solution, should be appreciated that the present invention also comprises the ZnO nano particle that is dispersed in the Non-alchoholic solvents.

At organic medium particularly in the polymkeric substance, some surface modifications need for the nano particle good distribution.The example that can serve as the surface-modifying agent of good insulating covering agent is to have the mercaptan of aromatic functional group and the silane with aromatic functional group and hydrolyzable functional group.Good material standed for is a benzyl sulfhydrate, and it is made of thiol functionalities and aromatic functional group.Benzyl sulfhydrate serves as insulating covering agent, and to the surface coverage of nano particle or adhere to, and this aromatic functional group increases the affinity between solvent and the nano particle to this insulating covering agent via thiol functionalities.Another kind of good material standed for is a phenyltrimethoxysila,e, and it is made of hydrolyzable alkoxysilane-functional group and aromatic functional group.Phenyltrimethoxysila,e is served as insulating covering agent, and to the surface coverage of nano particle or adhere to, similarly, this aromatic functional group increases the affinity between solvent and the nano particle to this insulating covering agent via-Si-O-metallic bond.Second effect of aromatic functional group is the affinity of improving between polymkeric substance and the nano particle.Deliquescent two kinds of possible methods are to guarantee that the hydrogen bonding ability is similar with solubility parameter between improvement inorganic particle and the organic substance.Zinc oxide nanoparticle originally is the height polar owing to there being the OH base on the surface, will make solubility parameter more approach organic solvent with this surface of lower polar molecule attached and shield simultaneously-OH group and the solvent phase mutual effect with lower hydrogen bond binding ability.In the present invention, the use of benzyl sulfhydrate, phenyltrimethoxysila,e and other associated molecule makes ZnO be dissolved in nitrogen-containing solvent, comprises the solvent that contains amine or acid amides and specifically, N, dinethylformamide and pyridine.The insulating covering agent that can use one or more types in combination with realize the required solvability in solvent and with the consistency of polymeric matrix.

Benzyl sulfhydrate directly adds this solution to then in the ZnO/2-propyl alcohol colloidal solution and stirs simultaneously to contain the formulations prepared from solutions of 2-propyl alcohol.The amount of the benzyl sulfhydrate that is added is as calculated in the 0.5-1.5 molar equivalent scope with respect to the zinc oxide in solution.The amount of zinc oxide is by supposing 100% from the zinc acetate estimation that is converted.Precipitation produces and allows this solution sedimentation immediately.Go out precipitation and in methyl alcohol, become suspension and this suspension centrifugation is come by methanol wash twice with collecting precipitation at least by centrifugation, then at room temperature dry this moist precipitate at least 2 hours in vacuum drying oven by redispersion.This dried powder that is formed by the ZnO that is covered by benzyl sulfhydrate can be dispersed in nitrogen-containing solvent and (comprise the solvent that contains amine or acid amides and specifically, N, dinethylformamide and pyridine) in, sometimes heating and gentle agitation may be needed and insoluble part may be observed, in this case, should be by filtering or centrifugal this insoluble part of from this solution, removing.

Selected mercaptan insulating covering agent is not limited to benzyl sulfhydrate and can be selected from has the following mercaptan compound that contains aryl structure (aromatic group of the struction), HS-R ₁-AR-R ₂Or HS-AR-R ₂, R wherein ₁Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain, the C of preferred side chain or straight chain _1-4Alkylidene group; And R ₂Be selected from the assorted alkynyl of assorted thiazolinyl, side chain or straight chain of assorted alkyl, side chain or straight chain of alkynyl, side chain or straight chain of thiazolinyl, side chain or straight chain of alkyl, side chain or the straight chain of sulfonic group, phosphonate group, halogen, hydrogen, epoxy group(ing), allyl group, amine, acid amides, aryl, heteroaryl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl ester, side chain or straight chain, the C of preferred side chain or straight chain _1-4Alkyl; Be by arylidene (preferred phenylene), encircle the aryl that arylidene, heteroarylidene or heterocycle arylidene constitute with AR.R ₁And R ₂Selection depend on polymeric matrix, for example, can introduce long alkyl chain or huge side group with the hydrophobicity of this polymeric matrix coupling.Can also introduce reactive functional groups, vinyl for example, described reactive functional groups can with unsaturated link(age) and the thiol group reaction in the polymkeric substance.Can select other functional group for example amine and epoxy base class to allow the resin reaction with ring-containing oxide functional group.

Can carry out surface treatment to nano particle with the silane compound of one or more types, described silane compound has structure, X _nY _(3-n)Si-(CH ₂) _m-R, wherein X is hydrolyzable functional group, comprises acryloxy, acyloxy, alkoxyl group, alkoxyl group alkoxyl group, amine, alkene oxygen base (enoxy), halogen, methacryloxy, oxime or phenoxy group, preferred C _1-4Alkoxyl group, Y be any non-hydrolysable functional group for example-CH ₃-H or-OSi; numerical value n can be 1; 2 or 3; with m be the integer of 0-18; R is the organic group with functionality, and it is selected from cycloalkyl; cycloalkenyl group; the alkyl of side chain or straight chain; the thiazolinyl of side chain or straight chain; the alkynyl of side chain or straight chain; the assorted alkyl of side chain or straight chain; the assorted thiazolinyl of side chain or straight chain; the assorted alkynyl of side chain or straight chain; acid anhydrides; acyloxy; alkoxyl group; allyl group; amino; amide group; the carboxylamine base; cyano group; epoxy group(ing); the epoxy group(ing) cycloalkyl; ester; glycidoxy (glycidoxy); halogen; halogenated alkyl; hydrogen; hydroxyl; sulfydryl; methacryloyl; phenyl; phosphonate group; sulfonic group; alkylsulfonyl; urea groups; vinyl and their combination.

The silane compound of having found to contain aromatic ring is compatible especially with polystyrene with for example poly-(methyl) methyl acrylate of vinyl polymer, and this type of examples for compounds is a phenyltrimethoxysila,e.The preferred type of insulating covering agent can be selected from has the following silane compound that contains the aryl structure, X ' _nY ' _(3-n)Si-R ₃-AR '-R ₄Or X ' _nY ' _(3-n)Si-AR '-R ₄, wherein X ' is hydrolyzable functional group, comprises acryloxy, acyloxy, alkoxyl group, alkoxyl group alkoxyl group, amine, alkene oxygen base, halogen, methacryloxy, oxime or phenoxy group, preferred C _1-4Alkoxyl group, Y ' be any non-hydrolysable functional group for example-CH ₃,-H or-OSi, numerical value n can be 1,2 or 3.R ₃Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain, the C of preferred side chain or straight chain _1-4Alkylidene group.R ₄Be the organic group with functionality, it is selected from the assorted alkynyl of assorted thiazolinyl, side chain or straight chain of assorted alkyl, side chain or straight chain of alkynyl, side chain or straight chain of thiazolinyl, side chain or straight chain of alkyl, side chain or the straight chain of cycloalkyl, cycloalkenyl group, side chain or straight chain.R ₃And R ₄All can also be selected from acid anhydrides, acyloxy, alkoxyl group, allyl group, amino, amide group, carboxylamine base, cyano group, epoxy group(ing), epoxy group(ing) cycloalkyl, ester, glycidoxy, halogen, halogenated alkyl, hydrogen, hydroxyl, sulfydryl, phosphonate group, sulfonic group, alkylsulfonyl, urea groups and their combination; And AR ' is the aryl that is made of arylidene (preferred phenylene), ring arylidene, heteroarylidene or heterocycle arylidene, comprises pyridine, pyrroles, thiophene etc.

If a plurality of functional groups among X, Y, X ' or the Y ' are present among the same molecule, then they can have identical or different structure, for example when having two parts of X, X can partly be made of two methoxyl groups parts or a methoxyl group part and an oxyethyl group.

The R of functional group, R ₃And R ₄Selection depend on the polymeric matrix kind, for example, can introduce long alkyl chain or huge side group with the hydrophobicity of this polymeric matrix coupling.Can also introduce reactive functional groups, vinyl for example, described reactive functional groups can with unsaturated link(age) and the sulfydryl reaction in the polymkeric substance.Can select other functional group for example amine and epoxy group(ing) to allow the resin reaction with ring-containing oxide functional group.Above-mentioned silane compound can be used in combination with the silane of other type or non-silane insulating covering agent to be implemented in required solvability in the solvent and the consistency in polymeric matrix.

Phenyltrimethoxysila,e is directly added this solution to then in the ZnO/ methyl alcohol colloidal solution and is stirred simultaneously to contain the formulations prepared from solutions of methyl alcohol.The amount of the phenyltrimethoxysila,e of being added is as calculated in the 0.01-1.5 molar equivalent scope with respect to the zinc oxide in solution.The amount of zinc oxide is by supposing 100% from the zinc acetate estimation that is converted.After concentrating, may take place because the precipitation that the flocculation of nano particle causes, and by further causing flocculation in the mixture of pouring 2-propyl alcohol and hexane into, at this moment, produce immediately to precipitate and also allow this solution sedimentation by solvent evaporation.Go out precipitation and in methyl alcohol, become suspension and this suspension centrifugation is come by methanol wash twice with collecting precipitation at least by centrifugation, then at room temperature dry this moist precipitate at least 2 hours in vacuum drying oven by redispersion.This can be dispersed in nitrogen-containing solvent by the dried powder that the ZnO that is covered by phenyltrimethoxysila,e forms, comprise amine or acid amides, and specifically, N is in dinethylformamide and the pyridine.Sometimes heating and gentle agitation may be needed and insoluble part may be observed, in this case, should be by filtering or centrifugal this insoluble part of from this solution, removing.

The solution of nano particle is added in the solution of polymkeric substance and mix to obtain homogeneous dispersion.On the other hand, this polymkeric substance directly can be added in this nanoparticles solution.This polymkeric substance is selected from the vinyl polymer of polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, derivatived cellulose, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers or the transparent polymer of multipolymer, and described vinyl monomer is selected from (methyl) acrylate, aromatic ethylene, vinyl cyanide, halogen ethene, vinylidene halide, vinyl alcohol and derivative, vinyl pyrrolidone and their combination.Pour the mixture of this nano particle and polymers soln into mould and dry and obtain clarification and transparent polymer nanocomposites under vacuum.

Embodiment 1

The preparation of ZnO/PMMA nano composite material

The particulate preparation

Solvent that uses in this embodiment and subsequent embodiment and reagent are reagent grades and use under situation about not being further purified.ZnO nano particle alcoholic solution by many method preparations that can obtain in the literature can be used for the preparation of diameter less than the nano particle of 10nm.In this embodiment, the method (J.Phys.Chem., 91:3789, (1987)) that has been used as people such as improved Bahnemann will be made.In brief, under agitation under 50 ℃, 0.439g (2mmol) zinc acetate dihydrate (98%) is dissolved in 160mL 2-propyl alcohol, after this this solution further is diluted to 1840mL.Under 50 ℃, 0.16g (4mmol) sodium hydroxide pellets (99.99%) is dissolved in 160mL 2-propyl alcohol, is stirring and under 0 ℃, this solution is being added in the described acetic acid zinc solution.Mixture is put into the water-bath that is heated to 60 ℃ in advance to be kept 2 hours.Concentrate this reaction soln by rotatory evaporator down at 30～35 ℃ then and obtain 0.04M ZnO colloidal solution to 50ml.

Cover the preparation of the ZnO of solution and covering

0.248g (2mmol) benzyl sulfhydrate (BM) (99%) is added in the 10ml Virahol.Under agitation promptly this BM solution is added in the reaction soln.This ZnO nanocrystal is covered by BM and the flocculation of nanocrystal causes the formation of little yellow or white precipitate.This precipitation sedimentation is made it and liquid phase separation by centrifugal then.With the precipitation redispersion collected in methyl alcohol to form muddy suspension and centrifugation.Repeat this purge process once.The precipitation 2 hours of dry purifying and obtain little yellow fine powder at room temperature in vacuum drying oven.Analyze the percentage of the ZnO that this powder exists with calculating by TGA.Usually, can the acquisition scope be the ZnO of 45-65wt%.This numerical value obtains according to test method 1.

The preparation of ZnO/PMMA nano composite material

In order to prepare the 4wt%ZnO nano composite material, suppose that the ZnO that 50wt% benzyl sulfhydrate (BM) covers is ZnO, the ZnO powder (0.08g) that BM is covered is dissolved in the 10ml pyridine.Heat the solution that this nanoparticles solution obtained optically clear in 30 minutes down at 60 ℃.PMMA (0.92g) is dissolved in the 30ml chloroform to form clarification, transparent solution.Described nanoparticles solution is mixed the solution of keeping optically clear simultaneously tempestuously with this PMMA solution, and the concentration of this solution contains ZnO and the PMMA that 1g covers in 40ml solution.At room temperature use rotatory evaporator with the volume of this solution concentration then to 10ml.This concentrated solution is poured on the glass mold to form film.Then this mould is put into vacuum drying oven with at room temperature dry 2 hours.Clarification, the transparent film of easy and this mold separation have been obtained.Thermogravimetric analysis (TGA) according to test method 1 confirms that the remaining weight of nano composite material is 4%.

Embodiment 2

The preparation of ZnO/PSt nano composite material

The particulate preparation

According to embodiment 1 in the same procedure described.

Cover the preparation of the ZnO of solution and covering

According to embodiment 1 in the same procedure described, only be to use right-(trimethyl silyl) phenyl thiomethyl alcohol (TMSPMT) that derives from Wako Chemicals to replace BM.

The solution of preparation 0.393g (2mmol) TMSPMT in methyl alcohol (10ml).Under agitation promptly this TMSPMT solution is added in the reaction soln.This ZnO nanocrystal is covered by TMSPMT and the flocculation of nanocrystal causes the formation of little yellow or white precipitate.This precipitation sedimentation is made it and liquid phase separation by centrifugal then.With the precipitation redispersion collected in methyl alcohol to form muddy suspension and centrifugation.Repeat this purge process once.The precipitation 2 hours of dry purifying and obtain little yellow fine powder at room temperature in vacuum drying oven.Analyze the percentage of the ZnO that this powder exists with calculating by TGA.Usually, can the acquisition scope be the ZnO of 50-70wt%.This value obtains according to test method 1.

The preparation of ZnO/PSt nano composite material

In order to prepare the 4wt%ZnO nano composite material, suppose that the ZnO that 50wt%TMSPMT covers is ZnO, the ZnO powder (0.08g) that TMSPMT is covered is dissolved in the 10ml pyridine.Heat this nanoparticles solution down at 60 ℃ and will obtain optically transparent solution in 30 minutes.PSt (0.92g) is dissolved in the 30ml chloroform to form clarification, transparent solution.This nanoparticles solution is mixed the solution of keeping optically clear simultaneously tempestuously with this PSt solution, and the concentration of this solution contains ZnO and the PSt that 1g covers in 40ml solution.At room temperature use rotatory evaporator with the volume of this solution concentration then to 10ml.This concentrated solution is poured on the open mold to form film.Then this mould is put into vacuum drying oven with at room temperature dry 2 hours.Clarification, the transparent film of easy and this mold separation have been obtained.Thermogravimetric analysis according to test method 1 confirms that the remaining weight of this nano composite material is 4%.

Embodiment 3

The preparation of ZnO/PMMA nano composite material

The particulate preparation

In this embodiment, will make disclosed method in U.S. Patent Publication No. US20050260122 such as the people that has been used as improved Li.In brief, stirring and under 60 ℃, 8.78g (0.04 mole) zinc acetate dihydrate (98%) being dissolved in 200mL methyl alcohol, after this this solution is cooled to 25 ℃.Use 4.489g (0.08 mole) potassium hydroxide pellet (85%) preparation alkaline solution, under agitation be dissolved in this potassium hydroxide pellet in the 800mL methyl alcohol and holding temperature under 60 ℃.Promptly zinc acetate dihydrate solution is poured in this alkaline solution and stirred simultaneously.Can observe the solution muddiness, this solution was finally clarified and the acquisition clear solution in one hour.Reaction was continued 2 hours, after this solution is cooled off 0～5 ℃ to stop further nanocrystal growth.So the solution of preparation obtains 1L 0.04M ZnO colloidal solution.

Cover the preparation of the ZnO of solution and covering

7.932g (0.04 mole) phenyltrimethoxysila,e (PTMS) (94%) is added in the 20ml methyl alcohol.Promptly this PTMS solution is added in the reaction soln and stir simultaneously.This ZnO nanocrystal is covered by PTMS and some flocculations of nanocrystal can cause the formation of white precipitate.By this solution concentration being arrived 500mL 40 ℃ of following evaporations.After concentrating, can observe some precipitation.The uniform mixture of preparation 500mL2-propyl alcohol and 2.5L hexane.Promptly spissated ZnO colloid is poured in this 2-propyl alcohol and the hexanes mixtures and stirred simultaneously.The flocculation of nanocrystal takes place and make this mixture sedimentation 1-3 hour.Be separated by will be white in color in the 20 minutes flocculation nanocrystal and the solution of precipitation forms of centrifugation under 6000rpm.The precipitation of collecting is added in the methyl alcohol to form muddy suspension and centrifugation.Repeat this purge process once.The precipitation 2 hours of dry purifying and obtain white powder at room temperature in vacuum drying oven.Analyze the percentage of the ZnO that this powder exists with calculating by TGA.Usually, can the acquisition scope be the solid residue of 60-85wt%.Then this numerical value is changed into the ZnO weight percent that obtains according to test method 2.The TGA graphic representation of exemplary formulations that derives from nano particle is shown in Figure 3.This weight loss is owing to the solvent that absorbs and the organic constituent of silane compound.Can calculate metal oxide content according to test method 2, in this case, weight loss is 17.3%, and metal oxide content is 76.4%.

The preparation of ZnO/PMMA nano composite material

In order to prepare the 1.35wt%ZnO nano composite material, wherein the ZnO of 76.4wt% phenyltrimethoxysila,e (PTMS) covering is ZnO, and the ZnO powder (0.0176g) that PTMS is covered is dissolved in 0.3344gDMF to prepare 5% solution.This nanoparticles solution of supersound process 30 minutes obtains the solution of optically clear.PMMA (0.9824g) is dissolved in 8.842g DMF to prepare 10% solution.This polymers soln is heated to 80 ℃ also stirs at least 1 hour to guarantee uniform mixing.This nanoparticles solution is mixed the solution of keeping optically clear simultaneously tempestuously with this PMMA solution.This nano particle/polymers soln is poured on the glass mold to form film.Then this mould is put into vacuum drying oven with at room temperature dry 5 hours.Clarification, the transparent film of easy and this mold separation have been obtained.Thermogravimetric analysis according to test method 2 confirms that the remaining weight of nano composite material is 1.45%, and this can be converted into and obtain 1.35% ZnO weight.This sample is appointed as PTMS01.In order to prepare the another kind of sample of 6.31wt%ZnO nano composite material, according to similar program before, wherein the ZnO powder (0.0822g) that PTMS is covered is dissolved in 1.5618g DMF to prepare 5% solution.PMMA (0.9178g) is dissolved in 8.260g DMF to prepare 10% solution.Thermogravimetric analysis according to test method 2 confirms that the remaining weight of nano composite material is 6.83%, and this can be converted into and obtain 6.31% ZnO weight.This sample is appointed as PTMS02.

Test method 1: the mensuration of the weight percent of the particulate metal oxide content that mercaptan covers and the thermostability of nano composite material

Use Shimadzu TGA-50 thermogravimetric analysis device to measure the metal oxide content of particle and nano composite material.For the particle according to embodiment 1 and 2 preparations, the speed with 20 ℃/minute in the airflow of 50 cc/min is heated to 800 ℃ with sample, and isothermal kept 10 minutes.The weight percent of remaining solid ascribes the metal oxide of having removed all volatile organic constituents to.For nano composite material, in baking oven, sample is heated to 120 ℃ and keeps 2 hours to drive away residual solvent according to embodiment 1 and 2 preparations.With thermogravimetric analysis device speed with 20 ℃/minute in the airflow of 50 cc/min this sample is heated to 800 ℃ then, and isothermal kept 10 minutes.In order to measure thermostability, record t ₅₀, be taken at 25 ℃ of weight of measuring down as benchmark, this t ₅₀Corresponding temperature when being defined as with sample residue 50wt%.The weight percent of remaining solid ascribes the metal oxide of having removed all polymkeric substance and volatile organic constituents to.

Test method 2: the mensuration of the weight percent of the particulate metal oxide content that silane covers and the thermostability of nano composite material

Use Shimadzu TGA-50 thermogravimetric analysis device to measure the metal oxide content of particle and nano composite material.For the particle according to embodiment 3 preparations, the speed with 20 ℃/minute in the airflow of 50 cc/min is heated to 800 ℃ with sample, and isothermal kept 10 minutes.The weight percent of remaining solid ascribes metal oxide and the silicon resistates of having removed all volatile organic constituents to.For nano composite material, in baking oven, sample is heated to 120 ℃ and keeps 2 hours to drive away residual solvent according to embodiment 3 preparations.With thermogravimetric analysis device speed with 20 ℃/minute in the airflow of 50 cc/min this sample is heated to 800 ℃ then, and isothermal kept 10 minutes.In order to measure thermostability, record t ₅₀, be taken at 25 ℃ of weight of measuring down as benchmark, this t ₅₀Corresponding temperature when being defined as with sample residue 50wt%.The weight percent of remaining solid ascribes metal oxide and the silicon resistates of having removed all polymkeric substance and volatile organic constituents to.

For the calculated value of the metal oxide content that obtains to cover ZnO powder, suppose that this resistates only contains metal oxide and from the Siliciumatom of initial silicon hydride compounds.The mark that is included in the metal oxide in this powder can obtain by following formula;

F wherein _MOThe weight fraction of=metal oxide, f _OrganicThe weight loss that the weight fraction of=organic constituent and equaling is measured by TGA, m _SiThe relative molecular weight of=Siliciumatom, and m _OrganicThe relative molecular weight of=the organic moiety that connected by the Si-C key, it is by C ₆H ₅Under the situation of the phenyltrimethoxysila,e that constitutes is 77.1.Under the situation of 50wt%ZnO, f _MO=0.5 and be 36.7% or f by the weight loss that TGA measures _Organic=0.367.

In order to obtain the calculated value of metal oxide content in the polymer nanocomposites, according to similar inference before.Yet polymkeric substance in the silane compound and organic moiety all constitute weight loss.Therefore, change this formula and suppose following form;

Wherein

The weight fraction of the remaining solids content that w=is measured by TGA, $A=\frac{1-f_{\mathrm{MO}}}{f_{\mathrm{MO}}}$ With

F wherein _MO, m _SiAnd m _OrganicHave and identical before meaning.Obtain under the situation of 4wt%ZnO in nano composite material f at the ZnO that uses the 50wt% phenyltrimethoxysila,e to cover _MO=0.5,

And the weight of the remaining solid content of being measured by TGA is 5% or w=0.05.

Test method 3: the mensuration of the level of haze of nano composite material

Mist degree is when passing sample because forward scattering and the percentage of the transmitted light that departs from incident beam, and the total amount of the light that departs from this incident beam is called fills the air transmission.The low more expression transparency of haze value is big more.It is defined as

Wherein T=% transmission

Mist degree can be caused by the undesirable appearance of the particle in the polymeric matrix or hole or polymkeric substance.It is the index of effectively measuring and can be used as nanoparticulate dispersed degree in the polymkeric substance of the optical property of nano composite material.The dispersion of the low more expression nano particle of mist degree is good more.Use Nippon DenshokuHazemeter NDH 2000, use standard C IE D65 light source (Colorometry, the third edition, Publication CIE 15:2004) to measure level of haze.The use of standard light source obtains more near observed haze measurements on the human eye vision.Standard light source D65 is contained the spectrum that approaches natural light.This is more accurate than measure transmittance under certain wavelength, because the small agglomeration of nano particle may display light scattering hardly under longer wavelength, thereby produce the haze value lower than expection, and wide spectrum will all show scattering effect to short and long wavelength.According to one of method among embodiment preparation nanocomposite films.It is 4 centimetres disc-shape that this nanocomposite films is diameter; Perhaps cut a film of 3 centimetres of 3 cm x, measure thickness by micrometer then from big film.Must careful operation not damaged by scratch or crackle with the surface of guaranteeing film, they may increase level of haze.Be arranged on the sample holder film sample and analysis, overturn then this film and analysis once more.The mean value of two readings is got the final level of haze of making film.

Test method 4: the mensuration of the UV-visible light transmittance rate of nano composite material

The UV specific absorption is measured by the UV-visible spectrophotometer.Film protection base material is not subjected to the ability of UV light not only to depend on wavelength region but also depends on the amount of the UV light that is absorbed.The amount of the UV light that is absorbed is measured by the amount and the film thickness of UV absorption agent.Wavelength region is by the particle size measurement of ZnO nano particle, and granularity is big more, and absorption region is wide more.Effectively the UV cutoff wavelength can be as follows by UV visible absorption curve determination: prolong straight line from the linear gradient of this curve; Read this cutoff wavelength at the point that this straight line and X-coordinate intersect.Nanocomposite films can absorb the UV beyond this effective cut-off wavelength fully, even if increase its thickness, its display part absorbs.According to one of method among embodiment preparation nanocomposite films.Cut the nanocomposite films of 3 centimetres of 3 cm x and measure thickness from big film by micrometer.Must careful operation not damaged by scratch or crackle with the surface of guaranteeing film, scratch or crackle may increase scattering of light and influence the transmittance reading.Use Hitachi spectrophotometer U-3310 to measure the ultraviolet ray-visible light transmittance rate of this film.Write down this UV-visible spectrum by % transmittance (%T).

The performance of nano composite material and feature

Be determined at the thermostability of the nano composite material of preparation in embodiment 1 and 2.Obtained the TGA curve described in the Figure 4 and 5 and in the result who reads from this curve shown in the table 1.Table 1 explanation t ₅₀Increasing in the presence of the ZnO and in PMMA and PSt, observing at least 14 ℃ thermostability and improve.

Table 1

Sample	Polymkeric substance	Insulating covering agent	Temperature, t 50When 50% weight loss (℃)	Remaining % weight under 700 ℃
					BM00 BM01 TM00 TM01	PMMA PMMA PSt PSt	-benzyl sulfhydrate-right-(trimethyl silyl) phenyl thiomethyl alcohol	310 388 390 404	0.37 4.48 0.80 4.11

Mensuration is according to the thermostability of the nano composite material of embodiment 3 preparations.Obtained the TGA curve described among Fig. 6 and in the result who reads from this curve shown in the table 1.Table 2 explanation t ₅₀In the presence of ZnO, increase and in PMMA, observe at least 17 ℃ thermostability and improve.

Table 2

Sample	Polymkeric substance	Insulating covering agent	Temperature, t 50When 50% weight loss (℃)	Remaining wt% under 700 ℃	ZnO% weight
						PTMS00 PTMS01 PTMS02	PMMA PMMA PMMA	-phenyltrimethoxysila,e phenyltrimethoxysila,e	365 382 392	0.44 1.45 6.83	0 1.35 6.31

Be determined at the level of haze and the UV absorptive character of the nano composite material of preparation in embodiment 1 and 2.Obtained the UV absorption spectrum described in Fig. 7 and 8 and in the result who reads from spectrum shown in the table 3.Table 3 explanation level of haze can be kept less than 3% UV and be absorbed in ZnO and be extended down to 355nm under existing.It should be noted that the level of haze of straight polymer because the surface quality of sample can ratio nano matrix material height.

Table 3

Be determined at the level of haze and the UV absorptive character of the nano composite material of preparation among the embodiment 3.Obtained the UV absorption spectrum described among Fig. 9 and in the result who reads from this spectrum shown in the table 4.Table 4 explanation level of haze can be kept less than 3% UV and be absorbed in ZnO and be extended down to 350nm under existing.

Table 4

Claims (32)

1. nano composite material comprises:

Be capped the nano particle and the polymkeric substance of the zinc oxide of agent covering;

Wherein this nano composite material shows following feature:

A) under the measuring condition of 100 micron thickness, level of haze at the most 5%,

B) ultraviolet radiation absorption beyond effective UV cutoff wavelength and

C) be reduced to the temperature of the original weights of under 25 ℃, measuring 50% than at least 10 ℃ of the polymerization object heights that does not have described nano particle.

2. the nano composite material of claim 1, wherein said nano particle is to use the mercaptan compound surface-treated, this mercaptan compound has following aryl structure, the HS-R of containing as insulating covering agent ₁-AR-R ₂Or HS-AR-R ₂, R wherein ₁Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain; Be selected from the assorted alkynyl of assorted thiazolinyl, side chain or straight chain of assorted alkyl, side chain or straight chain of alkynyl, side chain or straight chain of thiazolinyl, side chain or straight chain of alkyl, side chain or the straight chain of sulfonic group, phosphonate group, halogen, hydrogen, epoxy group(ing), allyl group, amine, acid amides, aryl, heteroaryl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl ester, side chain or straight chain with R2; Be by arylidene, encircle the aryl that arylidene, heteroarylidene or heterocycle arylidene constitute with AR; Above-mentioned mercaptan compound can be used in combination with the mercaptan compound or the non-mercaptan insulating covering agent of other type.

3. according to the nano composite material of claim 1, wherein said nano particle is the silane compound surface-treated with one or more types, and this silane compound has following structure, X as insulating covering agent _nY _(3-n)Si-(CH ₂) _m-R, wherein X is hydrolyzable functional group, comprise acryloxy, acyloxy, alkoxyl group, the alkoxyl group alkoxyl group, amine, alkene oxygen base, halogen, methacryloxy, oxime or phenoxy group, Y is the functional group of any non-hydrolysable, numerical value n can be 1,2 or 3, with numerical value m be the integer of 0-18, R is the organic group with functionality, and it is selected from: cycloalkyl, cycloalkenyl group, the alkyl of side chain or straight chain, the thiazolinyl of side chain or straight chain, the alkynyl of side chain or straight chain, the assorted alkyl of side chain or straight chain, the assorted thiazolinyl of side chain or straight chain, the assorted alkynyl of side chain or straight chain, acid anhydrides, acyloxy, alkoxyl group, allyl group, amino, amide group, the carboxylamine base, cyano group, epoxy group(ing), the epoxy group(ing) cycloalkyl, ester, glycidoxy, halogen, halogenated alkyl, hydrogen, hydroxyl, sulfydryl, methacryloyl, phenyl, phosphonate group, sulfonic group, alkylsulfonyl, urea groups, vinyl and their combination; Above-mentioned silane compound can be used in combination with the silane compound or the non-silane insulating covering agent of other type.

4. according to the nano composite material of claim 1, wherein said nano particle is the silane compound surface-treated with one or more types, and this silane compound has following aryl structure, the X ' of containing as insulating covering agent _nY ' _(3-n)Si-R ₃-AR-R ₄Or X ' _nY ' _(3-n)Si-AR '-R ₄Wherein X ' is hydrolyzable functional group, comprise acryloxy, acyloxy, alkoxyl group, alkoxyl group alkoxyl group, amine, alkene oxygen base, halogen, methacryloxy, oxime or phenoxy group, Y ' is the functional group of any non-hydrolysable, and numerical value n can be 1,2 or 3; R ₃Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain; R ₄Be the organic group with functionality, it is selected from: the assorted alkynyl of assorted thiazolinyl, side chain or the straight chain of assorted alkyl, side chain or the straight chain of the alkynyl of the thiazolinyl of the alkyl of cycloalkyl, cycloalkenyl group, side chain or straight chain, side chain or straight chain, side chain or straight chain, side chain or straight chain; R ₃And R ₄All can also be selected from acid anhydrides, acyloxy, alkoxyl group, allyl group, amino, amide group, carboxylamine base, cyano group, epoxy group(ing), epoxy group(ing) cycloalkyl, ester, glycidoxy, halogen, halogenated alkyl, hydrogen, hydroxyl, sulfydryl, phosphonate group, sulfonic group, alkylsulfonyl, urea groups and their combination; And AR ' is the aryl that is made of arylidene, ring arylidene, heteroarylidene or heterocycle arylidene, comprises pyridine, pyrroles, thiophene etc.; Above-mentioned silane compound can be used in combination with the silane compound or the non-silane insulating covering agent of other type.

5. according to the nano composite material of claim 1, wherein said polymeric matrix is hydrophobic polymer or the multipolymer that is made of hydrophobic monomer and hydrophilic monomer, and wherein this hydrophilic monomer accounts for the 40wt% at the most of total polymer; Wherein this hydrophilic monomer comprises the functional group that hydrophilic nmature is provided.

6. according to the nano composite material of claim 1, wherein this polymeric matrix is selected from following thermoplastics: the vinyl polymer or the multipolymer of polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers, described vinyl monomer are selected from (methyl) acrylate, aromatic ethylene, vinyl cyanide, halogen ethene, vinylidene halide and their combination.

7. according to the nano composite material of claim 1, wherein this polymeric matrix is selected from following thermoplastics: the polycarbonate of polyalkylene terephthalates, bisphenol cpd, the vinyl polymer of vinyl-containing monomers or multipolymer, described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide.

8. according to the nano composite material of claim 1, wherein this polymeric matrix is selected from following thermoplastics: poly-(methyl) acrylate and polystyrene, or the vinyl-containing monomers multipolymer, described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide.

9. according to the nano composite material of claim 1, wherein this nano particle comprises zinc oxide, or comprises the inorganic nanoparticles of metal oxide, semi-conductor or metal and the mixture of zinc oxide.

10. according to the nano composite material of claim 1, wherein said nano particle has the median size of 1-20 nanometer.

11. according to the nano composite material of claim 1, wherein said nano composite material has 380nm or shorter effective UV cutoff wavelength.

12. comprise coated products according to the nano composite material of claim 1.

13. the coated products of claim 12, wherein said nano particle are to use the mercaptan compound surface-treated, this mercaptan compound has following aryl structure, the HS-R of containing as insulating covering agent ₁-AR-R ₂Or HS-AR-R ₂, R wherein ₁Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain; And R ₂Be selected from the assorted alkynyl of assorted thiazolinyl, side chain or straight chain of assorted alkyl, side chain or straight chain of alkynyl, side chain or straight chain of thiazolinyl, side chain or straight chain of alkyl, side chain or the straight chain of sulfonic group, phosphonate group, halogen, hydrogen, epoxy group(ing), allyl group, amine, acid amides, aryl, heteroaryl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl ester, side chain or straight chain; Be by arylidene, encircle the aryl that arylidene, heteroarylidene or heterocycle arylidene constitute with AR; Above-mentioned mercaptan compound can be used in combination with the mercaptan compound or the non-mercaptan insulating covering agent of other type.

14. according to the coated products of claim 12, wherein said nano particle is the silane compound surface-treated with one or more types, this silane compound has following structure, X as insulating covering agent _nY _(3-n)Si-(CH ₂) _m-R, wherein X is hydrolyzable functional group, comprise acryloxy, acyloxy, alkoxyl group, the alkoxyl group alkoxyl group, amine, alkene oxygen base, halogen, methacryloxy, oxime or phenoxy group, Y is the functional group of any non-hydrolysable, numerical value n can be 1,2 or 3, with numerical value m be the integer of 0-18, R is the organic group with functionality, and it is selected from: cycloalkyl, cycloalkenyl group, the alkyl of side chain or straight chain, the thiazolinyl of side chain or straight chain, the alkynyl of side chain or straight chain, the assorted alkyl of side chain or straight chain, the assorted thiazolinyl of side chain or straight chain, the assorted alkynyl of side chain or straight chain, acid anhydrides, acyloxy, alkoxyl group, allyl group, amino, amide group, the carboxylamine base, cyano group, epoxy group(ing), the epoxy group(ing) cycloalkyl, ester, glycidoxy, halogen, halogenated alkyl, hydrogen, hydroxyl, sulfydryl, methacryloyl, phenyl, phosphonate group, sulfonic group, alkylsulfonyl, urea groups, vinyl and their combination; Above-mentioned silane compound can be used in combination with the silane compound or the non-silane insulating covering agent of other type.

15. according to the coated products of claim 12, wherein said nano particle is the silane compound surface-treated with one or more types, silane compound has following aryl structure, the X ' of containing as insulating covering agent _nY ' _(3-n)Si-R ₃-AR '-R ₄Or X ' _nY ' _(3-n)Si-AR '-R ₄Wherein X ' is hydrolyzable functional group, comprise acryloxy, acyloxy, alkoxyl group, alkoxyl group alkoxyl group, amine, alkene oxygen base, halogen, methacryloxy, oxime or phenoxy group, Y ' is the functional group of any non-hydrolysable, and numerical value n can be 1,2 or 3; R ₃Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain; R ₄Be the organic group with functionality, it is selected from: the assorted alkynyl of assorted thiazolinyl, side chain or the straight chain of assorted alkyl, side chain or the straight chain of the alkynyl of the thiazolinyl of the alkyl of cycloalkyl, cycloalkenyl group, side chain or straight chain, side chain or straight chain, side chain or straight chain, side chain or straight chain; R ₃And R ₄All can also be selected from acid anhydrides, acyloxy, alkoxyl group, allyl group, amino, amide group, carboxylamine base, cyano group, epoxy group(ing), epoxy group(ing) cycloalkyl, ester, glycidoxy, halogen, halogenated alkyl, hydrogen, hydroxyl, sulfydryl, phosphonate group, sulfonic group, alkylsulfonyl, urea groups and their combination; And AR ' is the aryl that is made of arylidene, ring arylidene, heteroarylidene or heterocycle arylidene, comprises pyridine, pyrroles, thiophene etc.; Above-mentioned silane compound can be used in combination with the silane compound or the non-silane insulating covering agent of other type.

16. according to the coated products of claim 12, the polymeric matrix of one deck at least of its floating coat is hydrophobic polymer or the multipolymer be made up of hydrophobic monomer and hydrophilic monomer, wherein this hydrophilic monomer accounts for the 40wt% at the most of total polymer; Wherein this hydrophilic monomer comprises the functional group that hydrophilic nmature is provided.

17. coated products according to claim 12, the polymeric matrix of one deck at least of its floating coat is selected from following thermoplastics: the vinyl polymer or the multipolymer of polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers, described vinyl monomer are selected from (methyl) acrylate, aromatic ethylene, vinyl cyanide, halogen ethene, vinylidene halide and their combination.

18. coated products according to claim 12, the polymeric matrix of one deck at least of its floating coat is selected from following thermoplastics: the polycarbonate of polyalkylene terephthalates, bisphenol cpd, the vinyl polymer of vinyl-containing monomers or multipolymer, described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide.

19. coated products according to claim 12, wherein this polymeric matrix is selected from following thermoplastics: poly-(methyl) acrylate and polystyrene, or the multipolymer of vinyl-containing monomers, described vinyl monomer is selected from methyl methacrylate, vinylbenzene and vinyl cyanide.

20. according to the coated products of claim 12, wherein base material comprises described nano composite material.

21. according to the coated products of claim 12, wherein this nano particle comprises zinc oxide, or comprises the inorganic nanoparticles of metal oxide, semi-conductor or metal and the mixture of zinc oxide.

22. according to the coated products of claim 12, wherein said nano particle has the median size of 1-20nm.

23. according to the coated products of claim 12, wherein one deck at least of this coating has 380nm or shorter effective UV cutoff wavelength.

24. the preparation method of nano composite material may further comprise the steps:

1) handle nano particle with insulating covering agent,

2) use nitrogen-containing solvent to prepare the solution of this nano particle, described nitrogen-containing solvent comprises amine, acid amides or their combination;

3) with the solution of this nano particle and mixed with polymers and

4) dry this mixture.

25. the method for claim 24, wherein said nano particle mercaptan compound treat surface, this mercaptan compound has following aryl structure, the HS-R of containing as insulating covering agent ₁-AR-R ₂Or HS-AR-R ₂, R wherein ₁Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain; And R ₂Be selected from the assorted alkynyl of assorted thiazolinyl, side chain or straight chain of assorted alkyl, side chain or straight chain of alkynyl, side chain or straight chain of thiazolinyl, side chain or straight chain of alkyl, side chain or the straight chain of sulfonic group, phosphonate group, halogen, hydrogen, epoxy group(ing), allyl group, amine, acid amides, aryl, heteroaryl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl ester, side chain or straight chain; Be by arylidene, encircle the aryl that arylidene, heteroarylidene or heterocycle arylidene constitute with AR; Above-mentioned mercaptan compound can be used in combination with the mercaptan compound or the non-mercaptan insulating covering agent of other type.

26. the method for claim 24, wherein said nano particle are the silane compound surface-treateds with one or more types, silane compound has following structure, X as insulating covering agent _nY _(3-n)Si-(CH ₂) _m-R, wherein X is hydrolyzable functional group, comprise acryloxy, acyloxy, alkoxyl group, the alkoxyl group alkoxyl group, amine, alkene oxygen base, halogen, methacryloxy, oxime or phenoxy group, Y is the functional group of any non-hydrolysable, numerical value n can be 1,2 or 3, with numerical value m be the integer of 0-18, R is the organic group with functionality, and it is selected from: cycloalkyl, cycloalkenyl group, the alkyl of side chain or straight chain, the thiazolinyl of side chain or straight chain, the alkynyl of side chain or straight chain, the assorted alkyl of side chain or straight chain, the assorted thiazolinyl of side chain or straight chain, the assorted alkynyl of side chain or straight chain, acid anhydrides, acyloxy, alkoxyl group, allyl group, amino, amide group, the carboxylamine base, cyano group, epoxy group(ing), the epoxy group(ing) cycloalkyl, ester, glycidoxy, halogen, halogenated alkyl, hydrogen, hydroxyl, sulfydryl, methacryloyl, phenyl, phosphonate group, sulfonic group, alkylsulfonyl, urea groups, vinyl and their combination; Above-mentioned silane compound can be used in combination with the silane compound or the non-silane insulating covering agent of other type.

27. the method for claim 24, wherein said nano particle are the silane compound surface-treateds with one or more types, this silane compound has following aryl structure, the X ' of containing as insulating covering agent _nY ' _(3-n)Si-R ₃-AR '-R ₄Or X ' _nY ' _(3-n)Si-AR '-R ₄Wherein X ' is hydrolyzable functional group, comprise acryloxy, acyloxy, alkoxyl group, alkoxyl group alkoxyl group, amine, alkene oxygen base, halogen, methacryloxy, oxime or phenoxy group, Y ' is the functional group of any non-hydrolysable, and numerical value n can be 1,2 or 3; R ₃Be selected from the assorted alkynylene of assorted alkenylene, side chain or straight chain of assorted alkylidene group, side chain or straight chain of alkynylene, side chain or straight chain of alkenylene, side chain or straight chain of alkylidene group, side chain or the straight chain of cycloalkylidene, inferior cycloalkenyl group, side chain or straight chain; R ₄Be the organic group with functionality, it is selected from: the assorted alkynyl of assorted thiazolinyl, side chain or the straight chain of assorted alkyl, side chain or the straight chain of the alkynyl of the thiazolinyl of the alkyl of cycloalkyl, cycloalkenyl group, side chain or straight chain, side chain or straight chain, side chain or straight chain, side chain or straight chain; R ₁And R ₂All can also be selected from acid anhydrides, acyloxy, alkoxyl group, allyl group, amino, amide group, carboxylamine base, cyano group, epoxy group(ing), epoxy group(ing) cycloalkyl, ester, glycidoxy, halogen, halogenated alkyl, hydrogen, hydroxyl, sulfydryl, phosphonate group, sulfonic group, alkylsulfonyl, urea groups and their combination; And AR ' is the aryl that is made of arylidene, ring arylidene, heteroarylidene or heterocycle arylidene, comprises pyridine, pyrroles, thiophene etc.; Above-mentioned silane compound can be used in combination with the silane compound or the non-silane insulating covering agent of other type.

28. the method for claim 24, wherein said metal, semi-conductor or metal oxide nanoparticles are selected from following material: aluminium, cadmium, cerium, chromium, cobalt, copper, gallium, germanium, gold, indium, iron, iridium, plumbous, mercury, nickel, platinum, palladium, silicon, silver, tin, zinc, zirconium, aluminium arsenide, aluminium nitride, aluminium phosphide, cadmium selenide, Cadmium Sulfide, cadmium telluride, gallium arsenide, gan, gallium phosphide, gallium selenide, the sulfuration gallium, indium arsenide, indium phosphide, indium nitride, indium selenide, indium sulfide, the tellurium indium, lead selenide, lead sulfide, lead telluride, mercury selenide, zunsober, tellurium mercury, zinc selenide, zinc sulphide, zinc telluridse, aluminum oxide, Cadmium oxide, cerium oxide, chromic oxide, cobalt oxide, Indium sesquioxide, tin indium oxide, ferric oxide, plumbous oxide, nickel oxide, silicon-dioxide, stannic oxide, titanium oxide, zinc oxide and zirconium white.

29. the method for claim 24, wherein said nano particle is a zinc oxide.

30. the method for claim 24, wherein said solvent is selected from N, dinethylformamide or pyridine and their combination.

31. the method for claim 24, wherein said polymkeric substance or multipolymer are selected from the vinyl polymer or the multipolymer of polyester, polycarbonate, polyolefine, polymeric amide, urethane, polyacetal, polyvinyl acetal, polyvinyl alcohol ketal, vinyl-containing monomers, and described vinyl monomer is selected from (methyl) acrylate, aromatic ethylene, vinyl cyanide, halogen ethene, vinylidene halide, vinyl alcohol and derivative, vinyl pyrrolidone and their combination.

32. the method for claim 24, wherein said polymkeric substance are selected from poly-(methyl) acrylate, polystyrene or contain the multipolymer of the vinyl monomer that is selected from methyl methacrylate, vinylbenzene and vinyl cyanide.

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