CN101333297B - Organic/inorganic hybridization material and method for forming same - Google Patents
Organic/inorganic hybridization material and method for forming same Download PDFInfo
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Abstract
The invention provides an organic/inorganic hybrid material and the formation method. Firstly, polymerizing copolymer from multiple functional monomers; then, enabling the copolymer to have sol-gel reaction with metal alcoxyl oligomer so as to form organic/inorganic hybrid material. With high refractive index, low hydroscopic property, good light permeability and high glass transition temperature, the organic/inorganic hybrid material is suitable for high-absorption efficiency LED sealing material, light and thin myopia or hyperopia lenses, light optical lens for a projector, high-brightness LCD prism film, refracting photoelectric conversion lens for a solar battery as well as lens for a mobile phone with a camera, and a digital camera.
Description
Technical field
This bright organic/inorganic hybridization material (hybrid material) and forming method thereof that relates to, relate more specifically to the application of organic/inorganic hybridization material relevant with the metal oligomer and forming method thereof, Application Areas contains: height is got optical efficiency LED packaged material, slim lightweight myopia/hyperopic lens, light and handy projector optical camera lens (lens), high brightness LCD prism film, solar cell refraction opto-electronic conversion mirror or camera cell phone/digital camera eyeglass.
Background technology
Materials science roughly can be categorized as organic materials and inorganic materials two big classes.Organic polymer has preferable ductility, and also than easy-formation, and inorganic materials has preferable physical strength, chemical resistant properties and thermostability.In recent years, how with two kinds of material sortings and then make material have the advantage of organic, be the problem that those skilled in the art are concerned about always, below will introduce the exploitation present situation of optical grade organic/inorganic hybridization material respectively.
(1) exploitation of the optical grade polymethyl methacrylate of high glass-transition temperature (hereinafter to be referred as Tg) (Polymethyl Methacrylate is hereinafter to be referred as PMMA) material:
The exploitation that the high Tg/ that uses for high-performance, optical material hangs down moisture absorption PMMA copolymer material, its research method at first is that basic comonomer constituent and rerum natura thereof are assessed.Will from many have to improve product Tg and reduce hygroscopic numerous monomer filter out the optimum monomer, in every different assessment factor, main have three considerations.First: monomeric cost and the easness that obtains; Though many polymerization single polymerization monomers can increase substantially the thermal properties of product, but it costs an arm and a leg and does not have the merchandise resources of volume production, this will cause greatest uncertainty to the mass production of product, so when selecting the monomer of every use, will be with this as most important reference factor.But under special circumstances, for example some special inexpensive monomer but can increase substantially the character of product at quite low use addition (low cost) down, and this point is worth discussing very much, and is the main emphasis of this research.Second: monomer itself can not cause too big influence to the finished product rerum natura, should strict examine or check as factors such as transmittance, degree of birefringence, xanthochromia, shaping processability and blue light transmittances.The 3rd: monomer comprises the condition of reaction to the specific effect of reaction procedure and reaction design, and whether the erosion resistance of reacting phase corresponding equipment, operation ease and monomer itself have every factors such as toxicity, stench and inflammableness.
In the past in the research paper and patent at the Tg that improves PMMA, to import comparatively hard and to have the monomer and the MMA monomer copolymerization of sterically hindered side chain, improve its second-order transition temperature thus usually.The comonomer that for example improves the Tg of PMMA in the prior art has three ring decyl methacrylic acids (Tricyclodecyl methacrylic acid), three ring decyl vinylformic acid (Tricyclodecyl acrylicacid), cyclohexyl methyl vinylformic acid (Cyclohexyl methacrylic acid), Octadecane ylmethyl vinylformic acid (n-octadecyl methacrylic acid), or norcamphyl methacrylic acid (Norbornylmethacrylic acid) etc. has the acryl class monomer of space bit resistance type side group, itself and MMA are carried out copolymerization, but its shortcoming is that copolymerization composition addition is very high, needs at least the Tg of PMMA to be brought up to more than 120 ℃ more than the 70mol%.Because these monomeric prices with sterically hindered side group are not cheap, therefore do not meet very much economic benefit.In addition, because the characteristic group of PMMA itself is a carbonyl, has very strong dipole reactive force, according to discovering before this laboratory, if polymer has carbonyl, and another polymer monomers then will seriously reduce the second-order transition temperature of these copolymerized macromolecules if effective molecular force can't be provided.Therefore result of study in the past mostly can not effectively improve the second-order transition temperature of PMMA with lower-cost comonomer.Therefore this research will utilize this acceptor as hydrogen bond of PMMA from the Intermolecular Forces between polymer, import the copolymerized macromolecule of another hydrogen bond donor, and expectation can utilize hydrogen bond action power to increase substantially the second-order transition temperature of PMMA thus.Once mentioned in many documents in the past, and utilized hydrogen bond action power can effectively reduce high molecular free volume, and then increase high molecular second-order transition temperature.But because the introducing of hydrogen bond can increase substantially the water-intake rate of polymer base material, so this research will import the thinner of another hydrogen bond thus again, as inexpensive vinylbenzene, expect to reduce the high molecular water-intake rate of whole copolymerization, reduce cost simultaneously.
(2) organic/inorganic hybridization material technological development:
Making at present high-index material mainly imports in the polymer base material with physics blending (blending) or chemical sol-gel method (sol-gel) metal oxide with high refractive index.Often limit the content of inorganic powder in polymer base material by physics strength dispersive method, can't effectively improve the specific refractory power and the light transmission of material.
Another kind of sol-gel method is dissolved in acidic solution with metal alkoxide, nonmetal alkoxide or inorganic salt and organic polymer, forms the material of Sol-gel States behind this saline hydrolysis with organic polymer.
As disclosed in JP2002516249-W and two pieces of patents of JP2000344504-A, obtain the polymer of blending TiO2 in the sol-gel mode, be that the inorganic precursors monomer is dissolved in the solvent with organic monomer, surface-modifying agent, be hydrolyzed-form particulate after the condensation reaction, see through polyreaction again to obtain the product of specific refractory power＞1.5.
As disclosed in the U.S. Pat 6103854, people such as Arakawa are skeleton with the multipolymer of ester class and aromatics, and metal alkoxide (metal alkoxide) is a functional group, and the alkoxide oligomer of silicon is as organic/inorganic hybridization material.
Disclosed as U.S. Pat 6228796 B1 and US 6068690, Arakawa is still with the functional group of metal alkoxide as organic/inorganic hybridization material, with organic molecule as skeleton.Though in the 6th embodiment of US 6228796 B1, the oligomer that has used alkyl titanium oxide does not break away from the thinking of organic molecule as the material skeleton yet as photocatalysis layer.
The oligomer of metal alcoxyl class has been applied to field in many ways.For instance, in U.S. Pat 5429889, people such as Chiba have disclosed a kind of magnetic memory substance, can be applicable to audiotape or disc.This magnetic substance contains the oligomer of titanium alcoxyl class, comprises that multiple pattern is as follows:
The X of above-claimed cpd comprises multiple functional groups such as alcohol radical, ether, halogen.
But above-mentioned titanium alcoxyl class oligomer only mixes the back as the magnetic coating material with organic molecule, titanium molecule is not integrated in the macromolecular scaffold.
Disclosed in the application of another kind of metal species alkoxide such as the U.S. Pat 6068609, Aizawa mixes the solution of titanium alcoxyl class oligomer with zirconium alcoxyl class oligomer, further obtain Ti-O-Zr, then form Pb (Ti-O-Zr), with material as ferroelectric membranc with plumbane oxygen class oligomer.Though this patent is used multiple titanium alcoxyl class oligomer, does not disclose its application on organic/inorganic hybridization material.
Summary of the invention
The object of the present invention is to provide a kind of organic/inorganic hybridization material with high heat-resisting, low moisture absorption, high transparent, high refractive index and forming method thereof, this hybrid material is applied to height and gets optical efficiency LED packaged material, slim lightweight myopia/hyperopic lens, light and handy projector optical camera lens, high brightness LCD prism film, solar cell refraction opto-electronic conversion mirror or camera cell phone/digital camera eyeglass.
For reaching above-mentioned purpose, the present invention mainly uses inorganic forerunner's oligomer and reduces the required time of sol gel reaction, cooperate the covalent linkage acceptor to make inorganic oxide particle produce chemical bonded refractory with polymer base material, cooperate other functional monomer to carry out copolymerization together simultaneously and form organic/inorganic hybridization material, take into account dispersiveness and the content of inorganic powder simultaneously at polymer base material, the specific refractory power that reaches material improves, and keeps simultaneously or improves characteristics such as light transmission, thermostability, agent of low hygroscopicity.
The invention provides a kind of formation method of organic/inorganic hybridization material, comprise: carry out copolyreaction to form multipolymer with multiple functional monomer, and multipolymer and metal alcoxyl class oligomer carried out the gel-sol reaction, to obtain organic/inorganic hybridization material.
The present invention also provides a kind of organic/inorganic hybridization material, and wherein multipolymer and metal alcoxyl class oligomer form reticulated structure through gel-sol reaction, and has high refractive index, low water absorbable, good light transmittance and high glass-transition temperature.
Particularly, the invention provides following aspect:
1. the formation method of an organic/inorganic hybridization material comprises: carry out the gel-sol reaction with multipolymer and the metal alcoxyl class oligomer with functional functional group, obtain organic/inorganic hybridization material; Wherein this multipolymer with functional functional group is methyl methacrylate, Methacrylamide, and cinnamic multipolymer.
2. as the formation method of 1 a described organic/inorganic hybridization material, wherein this metal alcoxyl class oligomer comprises the oligomer of following metal: many metals alcoxyl class oligomer of Ti, Zn, Zr, Al or above-mentioned metal.
3. as the formation method of 1 a described organic/inorganic hybridization material, wherein this gel-sol required time of reaction is lower than 30 minutes.
4. as the formation method of 1 a described organic/inorganic hybridization material, wherein this has the multipolymer of functional functional group: the weight ratio of this metal alcoxyl class oligomer is 20: 80～80: 20.
5. an organic/inorganic hybridization material comprises: the multipolymer that is had functional functional group by (a); And (b) reticulated structure that becomes through the gel-sol reaction bonded of metal alcoxyl class oligomer; Wherein this multipolymer with functional functional group is methyl methacrylate, Methacrylamide, and cinnamic multipolymer.
6. as 5 a described organic/inorganic hybridization material, wherein this metal alcoxyl class oligomer comprises the oligomer of following metal: many metals alcoxyl class oligomer of Ti, Zn, Zr, Al or above-mentioned metal.
7. as 5 a described organic/inorganic hybridization material, wherein this has the multipolymer of functional functional group: the weight ratio of this metal alcoxyl class oligomer is 20: 80～80: 20.
8. as 5 a described organic/inorganic hybridization material, its second-order transition temperature is greater than 160 ℃.
9. as 5 a described organic/inorganic hybridization material, its specific refractory power is greater than 1.67.
10. as 5 a described organic/inorganic hybridization material, its transmittance is greater than 88%.
11. as 5 a described organic/inorganic hybridization material, its water-absorbent is less than 0.5%.
12., be to get optical efficiency LED packaged material, slim lightweight myopia/hyperopic lens, light and handy projector optical camera lens, high brightness LCD prism film, solar cell refraction opto-electronic conversion mirror or camera cell phone/digital camera eyeglass as height as 5 a described organic/inorganic hybridization material.
Description of drawings
Fig. 1 is the infrared spectrum of 60% multipolymer for PMMA content;
Fig. 2 is the infrared spectrum of 80% multipolymer for PMMA content;
Fig. 3 is the infrared spectrum of 85% multipolymer for PMMA content;
Fig. 4 is the infrared spectrum of 90% multipolymer for PMMA content;
Fig. 5 is the water-intake rate of the multipolymer of different PMMA content.
Embodiment
The present invention is in order to improve the ratio of metallic molecule in organic/inorganic hybridization material, improves in the prior art metal oxide (as TiO
2) directly to sneak into the time that organic polymer needs with sol-gel method long, and shortcoming such as skewness, especially with metal alcoxyl class oligomer as precursor (Mw=500-5000,20-80wt%), (Mw=3000-12000 80-20wt%) reacts to obtain the organic/inorganic hybridization material of high heat-resisting, low moisture absorption, high transparent, high refractive index with multipolymer.
The present invention system forms organic/inorganic hybridization material with sol-gel method, use the metal alkoxide monomer methods to need more than tens hours in the prior art, and reacted finished product is because of TiO
2Particle very easily produces agglomeration, causes product inhomogeneous, and then the multiple character of deterioration product.For improving this problem, spy of the present invention, can reduce in reaction times to one hour as precursor significantly with the metal alcoxyl class oligomer of hyperergy, and major part is about 30 minutes, and improves the uniformity coefficient of reaction and improve multiple character.Compare with the metal alkoxide oligomer, metal alkoxide need carry out two kinds of reactions simultaneously: form oligomer with other metal alkoxide monomer after the hydrolysis, and crosslinked with organic polymer.It is that skeleton, metal alkoxide are the hybrid material of functional group that above-mentioned reaction will produce polymer, and the polymerization degree between metal alkoxide is not sufficient to form another skeleton.Because the polymerization degree of metal alcoxyl class oligomer will be subjected to factor affecting such as metal alkoxide and polymer ratio, temperature, solvent species, therefore changing above-mentioned factor a little promptly may obtain complete organic/inorganic hybridization material of different nature, and this will cause many puzzlements in the improvement of material.Therefore the present invention with in advance the metal alcoxyl class (molecular weight is between 500-5000) of oligomerization as the precursor of organic/inorganic hybridization material, with the uppity problem of reaction of avoiding metal alcoxyl monomer to cause.The suitable metal of metal alcoxyl class oligomer of the present invention comprises Ti, Zr, Al, Zn, and its configuration comprises scalariform, trellis or chain, the oligomer as shown in US 5429889, and its reaction formula can be represented by following formula:
In the following formula, R is C
1-8Alkyl, P refer to multipolymer (copolymer).Can know that by following formula discovery organic/inorganic hybridization material of the present invention has two kinds of skeletons: the skeleton of multipolymer and metal alkoxide oligomer skeleton.Following formula is only illustrated not limit reticulated structure of the present invention a multipolymer and can only form covalent linkage with two metal alkoxide oligomers.More common situation is, a multipolymer and a plurality of metal alkoxide multipolymer form covalent linkage, and these metal alkoxide multipolymers form covalent linkage with other multipolymer, form cancellated hybrid material at last.
The monomer that forms multipolymer comprises following at least two kinds of monomers: binding property monomer (molar ratio is preferably between 30-70%), hydrogen bond donor (molar ratio is preferably between 20-50%), hydrophobic monomer (molar ratio is preferably between 5-10%), covalent linkage acceptor (molar ratio is preferably between 0.5-2%).Above-mentioned functional monomer can further comprise other functional monomer.The monomeric function series of binding property improves the sticking power between organic/inorganic hybridization material and base material, comprises the monomer of methacrylate based or epoxy group(ing), comprises methacrylic ester.The hydrogen bond donor improves the bond density of multipolymer, and improves the second-order transition temperature of hybrid material of the present invention.The hydrogen bond donor is the monomer with hydroxyl, carboxylic acid group, amido, amide group, comprises Methacrylamide.The function of hydrophobic monomer is to reduce the water absorbability of organic/inorganic hybridization material, and it is the monomer with aromatic nucleus, comprises vinylbenzene.The covalent linkage acceptor makes multipolymer and this metal alcoxyl class oligomer produce the covalency bond, improves the cohesive strength of organic/inorganic, in order to increase the dispersity of metal alcoxyl class oligomer between composite base material, improves the light transmission and the specific refractory power of matrix material.The covalent linkage acceptor is the terminal monomer of hydroxyl, carboxylic acid group or amido that is, can carry out condensation reaction with metal alcoxyl class oligomer and produce the covalency bond, the carbon-carbon double bond of itself then forms the skeleton of multipolymer, and both all can improve bond strength, comprises 2-hydroxyethyl methacrylic ester.These monomeric kinds, ratio or arrangement mode are from adjusting with those skilled in the art are required, it can be staggered (alternative) or block patterns such as (block), ratio also is not limited to 1: 1: 1: 1, and can comprise monomer with other functional functional group.
The method that forms above-mentioned multipolymer comprises that light-initiated method, thermal initiation method or microwave cause method.Light trigger is including but not limited to aromatic base ketone such as benzophenone (benzophenone), acrylate benzophenone (acrylated benzophenone), 2-ethyl-anthraquinone (2-ethylanthraquinone), phenyl anthraquinone (phenanthraquinone), 2-tertiary butyl anthraquinone (2-tert-butylanthraquinone), 1,2-benzo anthraquinone (1,2-benzanthraquinone), 2,3-benzo anthraquinone (2,3-benzanthraquinone), 2, the 3-dichlone (2,3-dichloronaphthoquinone), benzyl dimethyl ketal (benzyl dimethyl ketal); St-yrax class (benzoin) comprises following substances: benzoin ether (benzoin ethers) is as st-yrax ylmethyl ether (benzoin methyl ether), st-yrax benzyl ethyl ether (benzoin ethyl ether), the perfume base isobutyl ether of resting in peace (benzoin isobutyl ether) or the perfume base phenyl ether of resting in peace (benzoin phenyl ether), benzoin methyl (methyl benzoin), ethyl st-yrax (ethyl benzoin) or other st-yrax.Thermal initiator is including but not limited to saturated or undersaturated organo-peroxide (substituted orunsubstituted organic peroxides), azo compound (azo compounds), tetramethyl ethylene ketone (pinacols), thiuram (thiurams), or the mixture of above-mentioned substance.Superoxide comprises benzoyl peroxide base (benzoyl peroxide); chloro benzoyl peroxide base (p-chlorobenzoylperoxide); methyl ethyl ketone peroxide (methyl ethyl ketone peroxide); t-butylperoxyl benzoate (tert-butyl perbenzoate); Cumene Hydroperoxide 80 (cumene hydroperoxide); peroxidation two sec-butyls (di-sec-butyl peroxide); or 1; 1-two (tert-butyl peroxide)-3; 3; 5-trimethyl-cyclohexane (1; 1;-di (tert-butylperoxy)-3; 3,5-trimethylcyclohexane).Suitable azo compound comprises, Diisopropyl azodicarboxylate (2,2 '-azobisisobutyronitrile), (1-phenylethyl) azo ditan ((1-phenylethyl) azodiphenylmethane), two methyl-2, two (1-the cyclohexanenitrile) (dimethyl-2 of 2 '-azo, 2 '-azobis (1-cyclohexanecarbonitrile)) or 2,2 '-azo two (2-methylpropane) (2,2 '-azobis (2-methylpropane)).Microwave causes Guttae Phacosylini with 500 watts microwave heating 3-5 minute, or with 90 watts microwave heating 10-20 minute.
Organic/inorganic hybridization material of the present invention has character such as high glass-transition temperature, high refractive index, high transmission rate, low water absorbable, the second-order transition temperature of preferred embodiment is greater than 160 ℃, specific refractory power is greater than 1.67, and transmittance is greater than 88%, and water-absorbent is lower than 0.5%.Above-mentioned characteristic makes hybrid material of the present invention for example can be applicable to multiple industry: height is got optical efficiency LED packaged material, slim lightweight myopia/hyperopic lens, light and handy projector optical camera lens, high brightness LCD prism film, solar cell refraction opto-electronic conversion mirror or camera cell phone/digital camera eyeglass.
Preferred embodiment
Embodiment 1:
High-tg polymer is birdsed of the same feather flock together synthesizing of (methacrylic acid formic acid-be total to-Methacrylamide-be total to-vinylbenzene) Poly (methyl methacrylate-co-methacrylamide-co-styrene):
The solution copolymerization reaction of methyl methacrylate, Methacrylamide and styrene monomer is that these three kinds of monomers are dissolved in 1,4-diox (1,4-dioxane) and place in the round bottom two-neck bottle, logical nitrogen is removed the air in the reactive system, add AIBN after being preheated to 80 ℃, 24 hours reaction times.With Virahol the product precipitation is separated out, again product is dissolved in 1, the 4-diox, repeat this step several times, dried 12 hours poly-(methyl methacrylate-be total to-Methacrylamide-be total to-vinylbenzene) multipolymer (PMMA-co-PMAAM-co-PS multipolymer) that gets final product whitely again behind the filtration under diminished pressure down in 70 ℃.The formula table of this multipolymer poly-(methyl methacrylate-be total to-Methacrylamide-be total to-vinylbenzene) sees Table one:
Table one
The infrared spectrum of the polymkeric substance of different PMMA content is shown in Fig. 1-4 in the table one, and pure PMAAM has two kinds of crests, is respectively 1650 and 1600, separately corresponding to the flexural vibration of stretching vibration and the N-H of C=O in the amide group.Usually the absorption intensity of the flexural vibration of N-H be about C=O stretching vibration 1/2 to 1/3.And the carbonyl of pure PMMA is not fettered by hydrogen bond, appears at 1730cm
-1Can find out that the amido on this PMAAM-co-PMMA multipolymer absorbs meeting past high wave-number migration along with the adding of PMMA amount, and its intensity descends gradually.The carbonyl that PMMA has been described moves toward lower wave number along with the adding of PMAAM, shows the existence of hydrogen bond reactive force.In addition, the stretching vibration of the C=O of no hydrogen bond constraint moves toward high wave number, and the ratio regular meeting of stretching vibration of not having a C=O of hydrogen bond constraint reduces along with the adding of polystyrene.This presentation of results following phenomenon: carbonyl and the amido on the PMAAM on the PMMA have hydrogen bond action power, and PS has dilution segmental effect really for PMAAM.
It is because its carbonyl is easy and water generates hydrogen bond action power that pure PMMA has bigger water-intake rate, therefore imports hydrophobic group such as polystyrene in this copolymer system, and it has lower water-absorbent is to cause its hydrophobic property because of its nonpolar group.As Fig. 5 is pure PMMA homopolymer, and the water-absorbent rate analytical results of PMMA-co-PMAAM-co-PS multipolymer partly.Compare with pure PMMA homopolymer, PMAAM-co-PMMA has higher water-intake rate, and this is because PMAAM is easier and the water generates hydrogen bond, but along with the adding of PS can significantly reduce its water-intake rate.This has three of high Tg and agent of low hygroscopicity dual nature simultaneously forms copolymerization systems and can replace pure PMMA or PC, being applied to the field of high-performance optics subassembly product, and has advantage cheaply simultaneously.
Get 100g, the straight chain shape titanium alcoxyl oligomer of molecular weight about 2000 is dissolved in the THF of the 100mL of pH=1.After above-mentioned solution being added the multipolymer (MW=10000) of 80g embodiment 1, can obtain organic/inorganic hybridization material at room temperature 30 minutes, its synthesis mode and structure are as follows:
Metal alcoxyl class oligomer can effectively improve the second-order transition temperature and the specific refractory power of molecule under the situation that influences transmittance a little.
Table two
Though the present invention discloses as above with a plurality of preferred embodiments; right its is not in order to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; Ying Kezuo changes arbitrarily and retouches, so protection scope of the present invention should be as the criterion with the claims restricted portion.
Claims (10)
1. the formation method of an organic/inorganic hybridization material comprises:
Carry out the gel-sol reaction with multipolymer and metal alcoxyl class oligomer, obtain organic/inorganic hybridization material with functional functional group;
Wherein this multipolymer with functional functional group is methyl methacrylate, Methacrylamide, reaches cinnamic multipolymer, and this metal alcoxyl class oligomer comprises the oligomer of following metal: many metals alcoxyl class oligomer of Ti, Zn, Zr, Al or above-mentioned metal.
2. the formation method of organic/inorganic hybridization material as claimed in claim 1, wherein this gel-sol required time of reaction is lower than 30 minutes.
3. the formation method of organic/inorganic hybridization material as claimed in claim 1, wherein this has the multipolymer of functional functional group: the weight ratio of this metal alcoxyl class oligomer is 20: 80～80: 20.
4. organic/inorganic hybridization material comprises:
The multipolymer that has functional functional group by (a); And
(b) metal alcoxyl class oligomer
Reticulated structure through gel-sol reaction bonded one-tenth;
Wherein this multipolymer with functional functional group is methyl methacrylate, Methacrylamide, reaches cinnamic multipolymer, and this metal alcoxyl class oligomer comprises the oligomer of following metal: many metals alcoxyl class oligomer of Ti, Zn, Zr, Al or above-mentioned metal.
5. organic/inorganic hybridization material as claimed in claim 4, wherein this has the multipolymer of functional functional group: the weight ratio of this metal alcoxyl class oligomer is 20: 80～80: 20.
6. organic/inorganic hybridization material as claimed in claim 4, its second-order transition temperature is greater than 160 ℃.
7. organic/inorganic hybridization material as claimed in claim 4, its specific refractory power is greater than 1.67.
8. organic/inorganic hybridization material as claimed in claim 4, its transmittance is greater than 88%.
9. organic/inorganic hybridization material as claimed in claim 4, its water-absorbent is less than 0.5%.
10. organic/inorganic hybridization material as claimed in claim 4 is to get optical efficiency LED packaged material, slim lightweight myopia/hyperopic lens, light and handy projector optical camera lens, high brightness LCD prism film, solar cell refraction opto-electronic conversion mirror or camera cell phone/digital camera eyeglass as height.
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| US5859128A (en) * | 1997-10-30 | 1999-01-12 | E. I. Du Pont De Nemours And Company | Modified cationic starch composition for removing particles from aqueous dispersions |
| CN1263063A (en) * | 2000-02-18 | 2000-08-16 | 孙景宽 | Fly ash microconcrete brick and its preparation method |
| CN1263876A (en) * | 2000-02-18 | 2000-08-23 | 唐涛 | Additive of powdered coal ash product and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5859128A (en) * | 1997-10-30 | 1999-01-12 | E. I. Du Pont De Nemours And Company | Modified cationic starch composition for removing particles from aqueous dispersions |
| CN1263063A (en) * | 2000-02-18 | 2000-08-16 | 孙景宽 | Fly ash microconcrete brick and its preparation method |
| CN1263876A (en) * | 2000-02-18 | 2000-08-23 | 唐涛 | Additive of powdered coal ash product and its preparing process |
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