WO2011013637A1 - Particules nanocristallines de zircone modifiées en surface et leur procédé de fabrication, et matériau composite de silicone et son procédé de fabrication - Google Patents

Particules nanocristallines de zircone modifiées en surface et leur procédé de fabrication, et matériau composite de silicone et son procédé de fabrication Download PDF

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WO2011013637A1
WO2011013637A1 PCT/JP2010/062566 JP2010062566W WO2011013637A1 WO 2011013637 A1 WO2011013637 A1 WO 2011013637A1 JP 2010062566 W JP2010062566 W JP 2010062566W WO 2011013637 A1 WO2011013637 A1 WO 2011013637A1
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modified
zirconia
nanocrystal particles
zirconia nanocrystal
modified zirconia
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PCT/JP2010/062566
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Japanese (ja)
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秀造 徳光
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Hoya株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black

Definitions

  • the present invention relates to surface-modified zirconia nanocrystal particles and a method for producing the same, and a silicone-based composite material obtained using the surface-modified zirconia nanocrystal particles and a method for producing the same. More particularly, the present invention relates to surface-modified zirconia nanocrystal particles stably dispersible in a thermosetting silicone resin matrix, an effective method for producing the same, and the surface-modified zirconia nano particles in the thermosetting silicone resin matrix.
  • the present invention relates to a silicone-based composite material useful as an LED (light emitting diode) sealing material or the like, which contains crystal particles with high dispersibility, and an effective manufacturing method thereof.
  • thermosetting silicone resin used as an LED sealing material is excellent in heat resistance and weather resistance, but has a problem that the refractive index is low and the light extraction efficiency from the LED is low.
  • Properties necessary for nanocrystalline particles for producing a composite with silicone resin include crystallinity of nanocrystalline particles themselves for securing refractive index, high dispersibility in silicone resin matrix, and dispersion in silicone resin matrix Stability etc. are mentioned.
  • the nanoparticles described in the patent document 1 have an integrated structure because the coating portion for coating the surface of the nanoparticles and the surface modifier for solvent dispersibility are derived from the same raw material. There is. Therefore, when it is intended to apply to various purposes, there is a problem that the range of selection of surface modifiers on the surface of titania nanocrystalline particles is narrow. In addition, when changing the surface modifier, it is necessary to review the synthesis method each time.
  • Patent Document 1 forms a bond by a crosslinking reaction due to condensation between the silicone resin and the surface modifier of the surface of the nanocrystal particle
  • the method of Patent Document 1 is tried in practice.
  • the dispersion stability of the nanocrystal particles is low, the dispersion in the silicone resin matrix is low, and furthermore, the stability of the physical properties of the product is low, and the method of Patent Document 1 has many problems. It has been found.
  • titania nanocrystalline particles exhibit photochromism that is colored in blue upon irradiation with ultraviolet light, the visible light transmittance is significantly changed. Therefore, it was found that a composite using titania nanocrystalline particles is unsuitable as an LED encapsulant.
  • zirconia nanocrystalline particles can be substituted for titania nanocrystalline particles as high refractive index, high strength materials.
  • Non-Patent Document 1 describes a method of producing solvent-dispersible zirconia nanocrystal particles by synthesizing surface-non-dispersible zirconia nanocrystal particles and then modifying the surface of the nanocrystal particle. .
  • Non-Patent Document 1 describes that solvent dispersible zirconia nanocrystal particles were obtained by optimizing the concentration.
  • this non-patent document 1 is characterized by the benzyl alcohol decomposition method which is an anhydrous system, and the surface of the produced zirconia nanocrystal particles is characterized by being covered with molecules derived from benzyl alcohol (generally The sol-gel method is covered with hydroxyl groups, which allows modification by surface modifiers.
  • Non-Patent Document 1 the benzyl alcohol decomposition method of Non-Patent Document 1 is problematic in that it uses a large amount of benzyl alcohol having a boiling point close to 200 ° C. and that the zirconium alkoxide as a raw material is expensive, and is not suitable for mass production. .
  • Non-Patent Document 1 reports that the concentration of zirconia nanocrystal particles in THF solvent is very low, about 1 mass%, and that the solvent dispersibility is obtained, it was intended for mixing into a silicone resin matrix.
  • the nanocrystal particles can not be said to have sufficient functions.
  • an oxygen-containing organic solvent is used as a reaction medium for the reaction in which the metal oxide precursor is converted to metal oxide nanocrystals, and as a solvent for supplying oxygen to the metal oxide precursor. I use it. Furthermore, modifying the obtained metal oxide nanocrystal with carboxylic acids is also described by adding carboxylic acids as an additive different from the oxygen-containing organic solvent.
  • Patent Document 2 metal oxide nanocrystals are modified with an organic component to improve the dispersibility of metal oxide nanocrystals in an organic compound.
  • Patent Document 1 since only the surface modifier is added as an additive, even if only nanocrystal particles are isolated from the dispersion by centrifugation etc. The possibility of remaining on the surface of nanocrystalline particles is low.
  • a first object of the present invention is to provide surface-modified zirconia nanocrystal particles that can be stably dispersed in a thermosetting silicone resin matrix and a method for producing the same. is there.
  • a second object of the present invention is to provide a silicone-based composite material including the surface-modified zirconia nanocrystal particles well dispersed in a thermosetting silicone resin matrix, and a method for producing the same.
  • the present inventor has found that, in one molecule, a dispersive contribution to a dispersion medium such as organosiloxane or a modification such as carboxylic acid carboxyl group. Besides, it has been found that stable solvent dispersibility can be imparted by modifying the surface of the zirconia nanocrystal with a compound having a predetermined carbon skeleton and provided with a portion capable of imparting stability to dispersibility.
  • the polyorganosiloxane chain of a specific length which contributes mainly to the improvement of the dispersibility in the thermosetting silicone resin matrix, and furthermore, a coordinator for the specific length of this polyorganosiloxane chain (ie, As a role of stabilizing the improved dispersibility, it was conceived to surface-modify zirconia nanocrystal particles with a compound having an aliphatic carboxylic acid residue of a specific carbon number. And it discovered that the above-mentioned purpose could be achieved by this surface modification zirconia nanocrystal particle.
  • the above-mentioned object can be achieved by subjecting zirconia nanocrystal particles, which are surface-modified with an arylsulfonic acid residue, to substitution with the above-mentioned aliphatic carboxylic acid residue in an organic solvent. I found out.
  • the present invention has been completed based on such findings.
  • the present invention (1) a modification for surface modification of zirconia nanoparticles; A stability contribution consisting of a carbon skeleton bound to said modification; A dispersive contribution to a dispersion medium consisting of a polymer chain coupled to the stability contributing part; A surface-modified zirconia nanocrystal particle, wherein the zirconia nanoparticle is modified by a compound provided in one molecule, (2)
  • the dispersion contributing portion is a polyorganosiloxane chain having 4 to 100 organosiloxane units,
  • a combination of the stability contributing portion and the modifying portion is a group derived from an aliphatic carboxylic acid, and is an aliphatic carboxylic acid residue having 2 to 18 carbon atoms in the aliphatic group,
  • the surface-modified zirconia nanocrystal particle according to (1) which is obtained by surface-modifying a zirconia nanoparticle with the aliphatic carboxylic acid residue.
  • thermosetting silicone resin the silicone resin before crosslinking and curing
  • silicone resin after crosslinking and curing is referred to as "thermosetting silicone resin”.
  • a group derived from an aliphatic carboxylic acid and chemically bonded to the surface of the zirconia nanocrystal eg, “a carboxyl group in an aliphatic carboxylic acid”, “aliphatic carboxy group”, etc.
  • aliphatic carboxylic acid residue a group derived from an aliphatic carboxylic acid and chemically bonded to the surface of the zirconia nanocrystal
  • aryl sulfonic acid residue includes those having a substituent on the aromatic ring and those having no substituent on the aromatic ring.
  • thermosetting silicone resin matrix stably dispersible in a thermosetting silicone resin matrix
  • a method for producing the same and the surface-modified zirconia nanocrystal particles in the thermosetting silicone resin matrix with good dispersibility It is possible to provide a silicone based composite material containing the same and a method for producing the same.
  • Embodiment 1 First, in the present embodiment, the surface modified zirconia nanocrystal particles manufactured by this method will be described while describing the manufacturing method.
  • a zirconia precursor is reacted with an organic sulfonic acid, preferably an arylsulfonic acid such as benzenesulfonic acid or p-toluenesulfonic acid, particularly preferably p-toluenesulfonic acid,
  • an organic sulfonic acid preferably an arylsulfonic acid such as benzenesulfonic acid or p-toluenesulfonic acid, particularly preferably p-toluenesulfonic acid
  • Aryl sulfonic acid residue modified zirconia nanocrystal particles particularly preferably p-toluene sulfonic acid residue (sometimes abbreviated as PTSH) modified zirconia nanocrystal particles are formed.
  • PTSH p-toluene sulfonic acid residue
  • zirconia precursor used at this time zirconyl chloride, tetraalkoxyzirconium and the like can be used, but zirconyl chloride is preferable from the viewpoint of reactivity, and zirconyl chloride octahydrate (ZrOCl 2 ⁇ 8H 2 O) is particularly preferable. It is suitable.
  • the molar ratio of Zr to p-toluenesulfonic acid in the zirconia precursor is preferably 8: 1 to 1: 2. If the proportion of p-toluenesulfonic acid is less than the above range, the dispersibility of the PTSH modified zirconia nanocrystal particles may be reduced. A more preferable molar ratio of Zr to p-toluenesulfonic acid is in the range of 4: 1 to 1: 1.
  • the organic solvent A is not particularly limited as long as it can effectively form PTSH modified zirconia nanocrystal particles, and for example, a mixed solvent of ethanol and triethyl orthoformate can be preferably used.
  • the reaction is carried out in a pressure vessel, preferably at a temperature of 100 to 240 ° C., more preferably 120 to 200 ° C.
  • the reaction time depends on the reaction temperature, the amount of p-toluenesulfonic acid, and the like, and can not be generally determined, but is usually about 8 to 120 hours, preferably 12 to 60 hours.
  • the crystal structure of zirconia nanocrystals can be selected depending on the reaction time. That is, although the optimum reaction time changes depending on the raw material concentration, the molar ratio of the zirconia precursor and the sulfonic acid, and the reaction temperature, shortening the reaction temperature produces tetragonal zirconia nanocrystals, and lengthening the monoclinic zirconia nanocrystals It tends to generate. Tetragonal zirconia nanocrystals have a higher refractive index than monoclinic zirconia nanocrystals, and monoclinic zirconia nanocrystals appear to be more chemically stable than tetragonal zirconia nanocrystals. It is possible to make each separately according to a use application.
  • the solvent in the reaction solution is preferably distilled off under reduced pressure to obtain PTSH-modified zirconia nanocrystal particles having a structure represented by the following formula (1).
  • the PTSH modified zirconia nanocrystal particles are obtained as a white powder, can be redispersed in an organic solvent such as methanol or methylene chloride, and a colorless and transparent zirconia nanocrystal particle dispersion can be obtained.
  • the dispersion contributing portion is a polyorganosiloxane chain having 4 to 100 organosiloxane units
  • the combination of the stability contributing portion and the modifying portion is an aliphatic carboxylic acid.
  • the polyorganosiloxane chain preferably has 4 to 100 organosiloxane units.
  • the organosiloxane unit of the polyorganosiloxane chain is smaller than 4, the dispersibility of the zirconia nanocrystal particles in the silicone resin matrix is reduced.
  • the organosiloxane chain unit is more than 100, the formation of the zirconia nanocrystal particles modified with the aliphatic carboxylic acid residue is significantly delayed. The reason is speculated to be due to steric hindrance of the polyorganosiloxane chain.
  • a polydimethylsiloxane (hereinafter sometimes abbreviated as PDMS) chain is preferable.
  • the carbon number of the aliphatic group is preferably 2 to 18, and a linear saturated monocarboxylic acid is preferable.
  • the carbon number of the aliphatic group is less than 2, the aliphatic carboxylic acid becomes unstable and is decomposed during the reaction. If the carbon number of the aliphatic group is more than 18, the volume occupied by the aliphatic group becomes extremely large, and the meaning of the improvement of the refractive index is lost.
  • the methylene chain has a small contribution to the dispersibility in silicone, it is better to be as short as possible.
  • the COOH group in the aliphatic carboxylic acid having a polyorganosiloxane chain may be present at the end of the polyorganosiloxane chain or may be present in the side chain, but it is required to be present at the end preferable.
  • an aliphatic carboxylic acid having a polyorganosiloxane chain as a surface modification may be abbreviated as POS-COOH
  • an aliphatic carboxylic acid having a polydimethylsiloxane chain may be abbreviated as PDMS-COOH.
  • the surface modifier may be abbreviated as a residue of an aliphatic carboxylic acid (PDMS-COOH) having a polydimethylsiloxane chain (hereinafter, referred to as “PDMS-COOH residue”. Is preferred.
  • the PTSH modified zirconia nanocrystal particles obtained as described above are re-dispersed in a suitable organic solvent B, The above PDMS-COOH is added to this, sodium carbonate is further added, and it is possible to stir at room temperature overnight.
  • the organic solvent B is not particularly limited, but, for example, a mixed solvent of methanol and methylene chloride is preferably used. After completion of the reaction, for example, the following operation is performed.
  • n represents the number of dimethylsiloxane units
  • m represents the number of carbon atoms of the aliphatic group in the aliphatic carboxylic acid residue
  • the silicone-based composite material of the present embodiment is a dispersion medium, which is crosslinked and cured in the thermosetting silicone resin matrix, and the zirconia nano-porous material is surface-modified with the above-mentioned POS-COOH residue, preferably PDMS-COOH residue. It is characterized in that crystal particles are dispersed.
  • the zirconia nanocrystal particles surface-modified with the above POS-COOH residue, preferably PDMS-COOH residue, have a siloxane unit in the modifier, so they are crosslinked and cured in a thermosetting silicone resin (ie, dispersed) Very well and in a stable manner).
  • the content of the surface-modified zirconia nanocrystal particles is preferably 5 to 80% by mass, and preferably 10 to 50% by mass as ZrO 2 from the viewpoint of improvement of the refractive index and dispersibility. More preferable.
  • the content of nanocrystalline particles is less than 5% by mass, the improvement of the refractive index has little meaning.
  • the content of the nanocrystal particles exceeds 80%, the possibility of devitrification due to the aggregation of the particles increases, and even if it is transparent, it is extremely fragile, and the properties of the resin are impaired.
  • the content of the surface-modified zirconia nanocrystal particles is more preferably 10 to 50% by mass as ZrO 2 .
  • the said silicone type composite material can be efficiently manufactured according to the method of this embodiment shown below.
  • the method for producing the silicone-based composite material of the present invention is (A) Preparation of mixed solution containing thermosetting silicone resin, organic solvent dispersion of zirconia nanocrystal particles surface-modified with the above POS-COOH residue, preferably PDMS-COOH residue, and curing catalyst The process to (B) distilling off the solvent in the liquid mixture; (C) heat treating the mixture after evaporation of the solvent to crosslink and cure the thermosetting silicone resin.
  • thermosetting silicone resin used at the said (a) process the mixture of an addition reaction type silicone resin and a silicone type crosslinking agent can be used.
  • this addition reaction type silicone resin for example, at least one selected from polyorganosiloxanes having an alkenyl group as a functional group in the molecule can be mentioned.
  • Preferred examples of the polyorganosiloxane having an alkenyl group as a functional group in the molecule include polydimethylsiloxane having a vinyl group as a functional group, polydimethylsiloxane having a hexenyl group as a functional group, and a mixture thereof. .
  • silicone type crosslinking agent for example, a polyorganosiloxane having at least two silicon-bonded hydrogen atoms in one molecule, specifically, a dimethylhydrogensiloxy end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, Examples thereof include trimethylsiloxy end-capped dimethylsiloxane-methyl hydrogen siloxane copolymer, trimethylsiloxane end-capped poly (methyl hydrogen siloxane), poly (hydrogensilsesquioxane) and the like.
  • a platinum compound is usually used as a curing catalyst.
  • the platinum-based compound include particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium catalyst and the like. .
  • the highly colorless and transparent zirconia nanocrystal particle-containing silicone resin dispersion can be obtained by the steps (a) and (b).
  • step (c) the thermosetting resin is crosslinked and cured by heating the silicone resin dispersion, for example, at a temperature of 100 to 200 ° C. for about 1 to 12 hours.
  • a base composite material is obtained.
  • the silicone-based composite material thus obtained is transparent, and the refractive index is usually about 1.4 to 1.6, though it depends on the content of the zirconia nanocrystal particles.
  • the surface-modified zirconia nanocrystal particles capable of stably maintaining good dispersibility in the dispersion medium can be contained in the thermosetting silicone resin matrix with high dispersibility.
  • Embodiment 3 The technical scope of the present invention is not limited to the above-described embodiments, and includes various modifications and improvements as long as specific effects obtained by the constituent elements of the invention and the combination thereof can be derived. Therefore, in the present embodiment, various modifications in the first embodiment will be described. The points not particularly mentioned are the same as in the first embodiment.
  • the compound having the modifying portion, the stability contributing portion and the dispersibility contributing portion in one structural formula is mentioned, and as a specific example thereof, a fat having both the modifying portion and the stability contributing portion Are listed for the group carboxylic acid residue.
  • a fat having both the modifying portion and the stability contributing portion Are listed for the group carboxylic acid residue.
  • the zirconia nanoparticles it may be considered that they may not be aliphatic carboxylic acid residues.
  • ketone groups or aldehyde groups may be applicable.
  • a predetermined number of carbon chains may be bonded to these modified portions.
  • the dispersibility contributing portion other than the polyorganosiloxane chain may be used as long as the surface modified zirconia nanoparticles can be well dispersed.
  • the adjustment for stabilizing the dispersibility may be performed by changing the number of carbon atoms in the stability contributing portion, providing a substituent in the carbon skeleton, or the like.
  • a modification part a stability contribution part, and a dispersibility contribution part, if another functional group, a carbon chain, etc. are combined to the functional group in each part, if each function can be exhibited, here Those containing other functional groups and carbon chains mentioned in the above are referred to as a modified portion, a stability contributing portion and a dispersive contributing portion.
  • the zirconia nanoparticles modified by aliphatic carboxylic acid residues but also the steps before this modification is performed, that is, the steps modified by aryl sulfonic acid residues are also described.
  • the arylsulfonic acid residue is described, but what can be used for the pretreatment is not limited to the arylsulfonic acid residue, as long as it can be substituted by the above-mentioned compound later.
  • organic sulfonic acids other than aryl sulfonic acids may be used, and those having a ketone group or an aldehyde group may be applicable.
  • Example 1 [1. Preparation of PTSH modified zirconia nanocrystal particles] Oxide chloride, zirconium octahydrate (ZrOCl 2 ⁇ 8H 2 O, manufactured by Kanto Kagaku) 1.29 g and (4 mmol) p-toluenesulfonic acid monohydrate (manufactured by Kanto Chemical) 190 mg (1 mmol), ethanol (Wako Pure It was made to melt
  • the solution was filled in a pressure vessel (stainless steel with a 50 ml Teflon (registered trademark) inner cylinder), heated in an oven at 170 ° C. for 40 hours, allowed to cool to room temperature, and then released. At this time, the reaction solution was clear and colorless, and no precipitation was observed.
  • a pressure vessel stainless steel with a 50 ml Teflon (registered trademark) inner cylinder
  • reaction solution was subjected to an evaporator, and then methanol was added in excess, and centrifugation was performed to collect a precipitate. It was confirmed that the precipitate was well dispersed in toluene. The same methanol wash was repeated several times.
  • the obtained toluene dispersion is filtered to remove sodium carbonate, p-toluenesulfonic acid is substituted, and a dispersion of zirconia nanocrystals surface-modified with PDMS-COOH residues (ie PDMS-COO group) is obtained. It was done.
  • the surface modifier of the surface of the zirconia nanocrystal particle was substituted from a PTSH to a PDMS-COOH residue because the sulfur almost disappeared.
  • the portion of the zirconia nanocrystal did not change from the nanocrystal obtained in Example 1. That is, it was confirmed that the crystal form was a tetragonal zirconium oxide crystal as it was, and it was a microcrystalline with a diameter of 2 to 3 nm.
  • Example 2 The surface-modified zirconia nanocrystals obtained in the above (1) were added to 2 g of “SS-6001” (thermosetting silicone resin) A and B mixed in equal amounts by Saint-Yurek Co., Ltd. 1 g of a toluene dispersion of particles was added as ZrO 2 and mixed well to prepare a mixture.
  • SS-6001 thermosetting silicone resin
  • this silicone resin dispersion was heated and cured in an oven at 160 ° C. for 12 hours to obtain a transparent ZrO 2 -silicone composite material.
  • the ZrO 2 content in this composite material was 50% by mass, and the refractive index of the composite material was 1.51.
  • the refractive index of the silicone resin prepared without adding the zirconia nanocrystals was 1.41, and it was shown that mixing with the zirconia nanocrystals is effective for improving the resin refractive index.
  • the surface-modified zirconia nanocrystal particles of the present invention can be stably dispersed in a thermosetting silicone resin matrix, and can provide a silicone-based composite material useful as an LED sealing material or the like.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur des particules nanocristallines de zircone modifiées en surface qui sont obtenues par modification en surface de particules de zircone par un composé qui comprend, dans chaque molécule, une fraction de modification pour la modification de surface d'une nanoparticule de zircone, une fraction fournissant une stabilité qui est composée d'un squelette de carbone lié à la fraction de modification, et une fraction fournissant la dispersibilité qui est composée d'une chaîne polymère liée à la fraction fournissant la stabilité et dote le milieu de dispersion de la dispersibilité. L'invention porte également sur un matériau composite de silicone qui est obtenu par dispersion des particules nanocristallines de zircone modifiées en surface dans une matrice de résine de silicone thermodurcie qui est durcie par réticulation.
PCT/JP2010/062566 2009-07-28 2010-07-27 Particules nanocristallines de zircone modifiées en surface et leur procédé de fabrication, et matériau composite de silicone et son procédé de fabrication WO2011013637A1 (fr)

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CN103922397A (zh) * 2013-01-15 2014-07-16 日挥触媒化成株式会社 改性氧化锆微粒粉末、改性氧化锆微粒分散溶胶及其制造方法
JP2017115111A (ja) * 2015-12-21 2017-06-29 住友大阪セメント株式会社 表面修飾無機粒子含有分散液、シリコーン樹脂組成物、硬化体、光学部材、発光装置、表示装置及び表面修飾無機粒子
EP3134462A4 (fr) * 2014-04-24 2017-12-13 Rensselaer Polytechnic Institute Nanocomposites polymères sans matrice et produits et procédés associés
JP2018009099A (ja) * 2016-07-14 2018-01-18 信越化学工業株式会社 硬化性シリコーン樹脂組成物及び硬化性シリコーン樹脂組成物の調製方法
CN114634737A (zh) * 2022-05-23 2022-06-17 潍坊工程职业学院 一种高氯化聚乙烯涂料及其制备方法

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Publication number Priority date Publication date Assignee Title
CN103922397A (zh) * 2013-01-15 2014-07-16 日挥触媒化成株式会社 改性氧化锆微粒粉末、改性氧化锆微粒分散溶胶及其制造方法
EP3134462A4 (fr) * 2014-04-24 2017-12-13 Rensselaer Polytechnic Institute Nanocomposites polymères sans matrice et produits et procédés associés
US10138331B2 (en) 2014-04-24 2018-11-27 Rensselaer Polytechnic Institute Matrix-free polymer nanocomposites and related products and methods thereof
JP2017115111A (ja) * 2015-12-21 2017-06-29 住友大阪セメント株式会社 表面修飾無機粒子含有分散液、シリコーン樹脂組成物、硬化体、光学部材、発光装置、表示装置及び表面修飾無機粒子
JP2018009099A (ja) * 2016-07-14 2018-01-18 信越化学工業株式会社 硬化性シリコーン樹脂組成物及び硬化性シリコーン樹脂組成物の調製方法
CN114634737A (zh) * 2022-05-23 2022-06-17 潍坊工程职业学院 一种高氯化聚乙烯涂料及其制备方法

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