[go: up one dir, main page]

WO2010026668A1 - Matériau nanocomposite, méthode de production d'un matériau nanocomposite et matériau isolant - Google Patents

Matériau nanocomposite, méthode de production d'un matériau nanocomposite et matériau isolant Download PDF

Info

Publication number
WO2010026668A1
WO2010026668A1 PCT/JP2008/066475 JP2008066475W WO2010026668A1 WO 2010026668 A1 WO2010026668 A1 WO 2010026668A1 JP 2008066475 W JP2008066475 W JP 2008066475W WO 2010026668 A1 WO2010026668 A1 WO 2010026668A1
Authority
WO
WIPO (PCT)
Prior art keywords
zno
nanocomposite material
resin
situ
nanoparticles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2008/066475
Other languages
English (en)
Inventor
Arantazu Gonzalez-Campo
Milo Shaffer
Charlotte Williams
Norio Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial College of London
Toyota Motor Corp
Original Assignee
Imperial College of London
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial College of London, Toyota Motor Corp filed Critical Imperial College of London
Priority to PCT/JP2008/066475 priority Critical patent/WO2010026668A1/fr
Publication of WO2010026668A1 publication Critical patent/WO2010026668A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • NANOCOMPOSITE MATERIAL METHOD FOR PRODUCING NANOCOMPOSITE MATERIAL, AND INSULATING MATERIAL
  • the present invention relates to a nanocomposite material having excellent thermal conductivity, in which nano-sized zinc oxide is highly dispersed in a polymer material, a method for producing the nanocomposite material, and an insulating material comprising the nanocomposite material.
  • Nanocompo sites are of great interest, as a means of improving properties (such as stiffness, hardness, toughness, conductivity, and optical effects) of a range of polymers.
  • the classic problem is how to control and disperse the nanophase within the polymer matrix.
  • the use of pre-synthesised nanoparticles is common but typically associated with agglomeration, high viscosity, and limited loading fractions.
  • silica nanoparticles can be grown directly in the presence of an epoxy resin, thereby avoiding these problems.
  • the chemistry is rather specific and the particles are amorphous, leading only to spherical morphology.
  • the in situ approach is particularly suitable for integration with other fillers to create hierarchical structures, without sacrificing processability.
  • Thermosetting polymers and epoxies in particular are widely used as adhesives, surface coatings, encapsulating materials, composites, casting materials and electrical laminates. They exhibit excellent mechanical and electrical properties, low shrinkage, good adhesion to many metals and solvent and chemical resistance.
  • the resins retain active chemical functionalities during processing that enable subsequent cross-linking reactions to form highly crosslinked, three -dimensional networks. After this cure process, the epoxy resins are hard, non-melting and rigid materials. Even though such resins have very interesting properties, there is considerable scope to improve their properties and hence suitability for technological application. There is currently huge interest in the preparation of epoxy-based nanocompo sites incorporating inorganic nano-fillers to improve their properties.
  • a composite material is the result of the combination of two different components, an organic and inorganic phase.
  • an organic and inorganic phase When at least one of the components has a size of the order of nanometres a nanocomposite material is obtained.
  • the nanocomposites usually have improved the properties with respect to their respective conventional composites.
  • One important example of these organic-inorganic materials is polymer nanocomposites, which are the result of incorporation of inorganic nanofillers. They combine the advantages of the organic polymers (flexibility and good processability, amongst others) and inorganic materials (for example, high thermal stability, chemical resistance, and thermal conductivity).
  • the thermal conductivity of a filled resin system may increase by more than simply the increased loading fraction of filler on adding the in situ nanoparticles, as they may enhance the thermal transfer between the larger particles which usually limits performance.
  • the in situ method provides a method to assemble coatings on other particles within the resin.
  • carbon nanotubes can be dispersed in the resin system; when the in situ synthesis occurs, the nanotubes become coated in newly generated filler material providing a useful function, such as an electrically insulating barrier, or a phonon-coupling layer.
  • the current method employs alkyl and/or alkylzinc alkoxide zinc precursors to generate zinc oxide nanoparticles in a cross-linkable pre-polymer.
  • a wide range of possible groups may be used in the formula ZnR 2 or Zn(OR) 2 , or ZnR(OR') with the same or different R-groups.
  • a diamide zinc or alkylzinc alkoxide or alkyl zinc amide or alkyl zinc thiolate may be used.
  • the ideal R-groups offer high reactivity under mild conditions, but lie at the less reactive end of the alkyl zincs in order to offer ease of handling and reaction control.
  • ZnEt 2 is preferable to ZnMe 2 due to its slower rate of hydrolysis.
  • these self-reactive compounds do not intrinsically react with the functionalities in cross-linking resins, such as epoxy, allowing the preparation, in situ, of zinc oxide nanoparticles (examples 1, 2, 3).
  • cross-linking resins such as epoxy
  • crystalline nanoparticles can be obtained.
  • the result is a nanocomposite pre-polymer system containing well-dispersed, crystalline zinc oxide particles that retains the cross-linking performance of the original resin.
  • the resin system can be cured to create a hard nanocomposite resin with enhanced properties.
  • the choice of zinc ligand offers the opportunity to modify the interaction between particle and matrix, either through non-covalent effect or the use of deliberately bifunctional ligands that can bind covalently between the ZnO phase and the matrix.
  • the bifunctional molecule can be added to the resin (example 4) or to the ZnO precursor (example 5). Such a reaction will be reactive the resin in general, but will lead to a strong direct bond forming between the resin and the nanoparticle, in order to improve the eventual properties.
  • Suitable epoxy resins include both glycidyl and non-glycidyl systems (some examples given below).
  • the glycidyl epoxies are further classified as glycidyl-ether, glycidyl-ester and glycidyl-amine. They are prepared reacting epichlorohydrin with for example polyphenols, monoamines and diamines, amino phenols, heterocyclic imides and amides and aliphatic diols. Among all of them the diglycidyl ether of bisphenol A (DGEBA) has been widely used and it is a typical commercial epoxy resin.
  • the non-glycidyl epoxies are either aliphatic or cycloaliphatic epoxy resins.
  • Hardeners include, amines, polyamides, phenolic resins, anhydrides, isocyanates and polymercaptans.
  • polystyrenic resin polysterene
  • polycarbonate resin polyester resin
  • epoxidized phenolic resin phenylenevinylene resin
  • fluorene resin fluorenevinylene resin
  • phenylene resin thiophene resin
  • the approach provides a unique 'one pot' solution to the preparation of a nanocomposite, since each component can be added sequentially to a single vessel.
  • the fabrication of hierarchical composites is easily achieved using this 'one-pot' strategy. If a combination of micro & nano particles are required, the nanoparticles can be generated in situ as described above. The viscosity remains low, and hence additional micron fillers can be added subsequently by conventional means (or at an earlier stage of the process) (example 10). Alternatively, if an in situ coating is required, the particles to be coated are added in the resin before the nanoparticle precursor.
  • the particles to be coated must be prepared such that their surface is compatible with the nanoparticles to be deposited; for oxide coating, the surface should be as polar as possible for maximum uniformity (compare examples 7 & 8).
  • the in situ particle will then nucleate on or associate with the secondary particles as the reaction proceeds, generating a hierarchical structure (example 9).
  • Complex hierarchical structures can be synthesised in a single pot, by combining these strategies (example 11).
  • the oxide synthesis chemistry may also be applied to generate coatings on other nanoparticles, for example carbon nanotubes (examples 7 & 8), ex situ (not in solvent).
  • the aim of the invention is to find a synthetic route to a new type of hierarchical structure (shown schematically in Figure 1).
  • This structure combines a variety of new features, many of which are interesting and potentially useful in their own right.
  • the hierarchical structure represents a new development in composite technology, whereby many different length-scales are controlled simultaneously, using, in this case, a chemical strategy that allows the preparation of a complex structure in a single step.
  • the individual components of the structure are as follows: a) Conventional micron-scale ZnO was specified to provide a cheap and readily available increase in thermal conductivity. The loading fraction of ZnO can then be significantly increased by adding ZnO nanoparticles to the resin system.
  • the coupling agent between the oxide and the polymer has a rigid, potentially liquid crystallince (or mesogenic) character, as discussed further below.
  • Individual carbon nanotubes have exceptional properties, particularly strength, stiffness, and thermal conductivity. In fact, they have been shown to have (axially) the highest thermal conductivity of any material, higher even that of diamond. The highest measured thermal conductivity is 3300 W/m/K, although theoretical predictions are even higher. Carbon nanotubes can, of course, generate other benefits for the matrix, such as improved wear resistance, flame retardance, or strength. On the other hand, they usually produce electrical conductivity through efficient percolation phenomena. To avoid excessive conductivity, an insulating coating of ZnO was specified, using the same chemistry as the in situ nanoparticle synthesis.
  • the coating was also intended to provide a coupling layer between the nanotubes and the matrix. c) As yet, there have been relatively few attempts to improve thermal conductivity with nanotubes, and those reported have tended to be less successful than hoped. It seems clear that the high thermal resistance of the interface between the nanotubes and the matrix is a major problem. Most commonly, the loss of the advantage of the nanotubes is attributed to the high (measured) value of the interfacial resistance. In the current project the aim was to reduce this resistance by providing a graded interface between the nanotube and the resin that will couple the components together much more effectively (Figure 2). Thus the coating of ZnO was intended to provide a stiff, intermediate thermal conductivity layer to maximize phonon transfer between the phases. A similar argument applies to the use of a rigid linking agent to bind the ZnO surface to the resin matrix (both the coating on the nanotubes and the nanoparticles).
  • Thermosetting polymers and epoxies in particular, are widely used as adhesives, surface coatings, encapsulating materials, composites, casting materials and electrical laminates. They exhibit excellent mechanical and electrical properties, low shrinkage, good adhesion to many metals and solvent and chemical resistance.
  • the resins retain active chemical functionalities during processing that enable subsequent cross-linking reactions to form highly crosslinked, three-dimensional networks. After this cure process, the epoxy resins are hard, non-melting and rigid materials. Even though such resins have very interesting properties, there is considerable scope to improve their properties and hence suitability for technological application. There is currently huge interest in the preparation of epoxy-based nanocomposites incorporating inorganic nano-fillers to improve their properties.
  • the invention developed the use of in situ synthesis of ZnO to create both nanoparticles and the coating on the nanotubes (Figure 3).
  • the underlying chemistry relies on the hydrolysis of organozinc precursors in situ within the epoxy (or other) resin system.
  • the general reaction is:
  • the reaction may also use Zn(OR) 2 or ZnROR' precursors, although the higher reactivity of the ZnR 2 (alkyl zincs) is likely to be preferable.
  • Zn(OR) 2 or ZnROR' precursors although the higher reactivity of the ZnR 2 (alkyl zincs) is likely to be preferable.
  • the key is to choose reagents that are compatible with the resin system (traditional ZnO precursors such as zinc chloride and acetate are not suitable), that have high reactivity leading to reactions under mild conditions, and that produce volatile byproducts that are readily removed from the resin after the in situ hydrolysis.
  • the in situ preparation method provides advantages in terms of simplicity, good dispersion, and high loading fraction.
  • the in situ prepared zinc oxide can be combined with carbon nanotubes to produce a hierarchical, coated structure. It is hoped that the presence of zinc oxide at the surface of the nanotubes will electrically insulate the nanotubes from each other and aid thermal conductivity by improving the interface with the matrix.
  • the nanoscaled, in situ zinc oxide can also be combined with traditional micron scale zinc oxide, again to improve potentially thermal transport between the larger structures.
  • suitable ligand chemistry is critical to establish good ZnO nanoparticle size-control and dispersion in the matrix, as well as to covalently couple the zinc oxide to the matrix.
  • ZnO zinc oxide
  • ZnO is a semiconductor material with a wide-band gap of 3.37 eV at 300K and a large exciton binding energy (60 meV) at room temperature.
  • ZnO can be applied in a wide range of applications such as UV lasers, solar cells, high sensitivity chemical gas, DNA sequence sensors, volatile organic compound sensors, transparent conducting films and materials for electrodes among others.
  • ZnO nanoparticles have also been investigated in cosmetic and medical applications due to their ability to absorb ultraviolet light.
  • ZnO nanoparticles have been prepared using physical methods such as thermal vapor-phase oxidation, thermal vapour transport and condensation (TVTC), and chemical vapour deposition methods (CVD). With these physical methods, high temperature is used to obtain crystalline nanoparticles. The required high temperature is a disadvantage when in situ nanoparticle-polymer preparation is desirable, as it is incompatible with organic components. Chemical methods, such as precipitation, sol-gel, microemulsions and solvothermal /hydrothermal reactions have the advantage that the nanoparticles are prepared at lower temperatures. However, the necessity to dry the particles and the presence of ionic or byproduct species in the colloidal solutions are significant disadvantages.
  • ZnO particles are prepared from zinc salts by metathesis reactions with alkaline hydroxides, such as lithium hydroxide or sodium hydroxide, yielding
  • Organometallic precursors such as alkyl zincs and alkylzinc alkoxides
  • present several advantages including low temperature reaction, volatile by-products, faster synthesis, high reactivity, and avoidance of alkaline hydroxides; in addition, these precursors enable the preparation of ZnO by thermolysis as well as hydrolysis or oxidation.
  • Alkyl zinc compounds are most often used in the context of high temperature oxidations, or variants of CVD using vapourised precursors.
  • Alkylzinc alkoxide and di(alkoxide)zinc compounds have been prepared by reaction between Zn(C 2 Hs) 2 or Zn(CH 3 ) 2 and one or two equivalents of the corresponding alcohol, to produce compounds such as Zn[OC(CH 3 ) 3 ] 2 , CH 3 ZnO(CH 2 ) 2 OCH 3 , CH3ZnOtBu, CH 3 Zn0CH(CH 3 ) 2 , EtZnOiPr, EtZnOtBu, and others EtZnOR. These precursors have also been converted, ex situ, to zinc oxide using low temperature solvent methods, vapour methods (eg CVD), and thermolysis.
  • thermoplastic matrices specifically polymethyl methacrylate (PMMA) and poly(ethylene glycol) (PEG)
  • PMMA polymethyl methacrylate
  • PEG poly(ethylene glycol)
  • a type of in situ preparation of ZnO from ZnEt 2 in a thermoplastic copolymer of ethylene and vinyl acetate (EVA) has been described, but involves swelling of a non-reactive polymer film with excess solvent and is limited to thin films.
  • Hierarchical structures are not widely known, particularly not those generated by in situ reactions. [ Statement of how this invention is better than what was done previously]
  • This patent describes a new in situ approach to prepare metal oxide nanoparticle-polymeric composites by a sol-gel process using organometallic complexes as metal oxide precursors that are compatible with cross-linking resin (thermoset) systems.
  • the invention relates to a method for the preparation of nanocomposites using at least one organometallic zinc precursor and a thermosetting epoxy resin.
  • the method takes the advantages of in situ preparation methods, namely simplicity, good dispersion, and high loading fraction, and extends them into new materials systems. It uses oxide precursors that are intrinsically highly reactive with each other, but not with the resin matrix system, leading to the production of nanocomposite resin systems under mild conditions. These resin systems can be later crosslinked to yield nanocomposite polymer components.
  • Hierachical structures provide an addition means to improve the properties of fillel polymer systems, allowing increases in loading fraction and additional synergies between fillers at different length scales.
  • the one-pot preparation methodology provides a surprisingly simple, practical, and effective means to generating complex functional structures. The full potential of this approach remains to be explored but is very promising.
  • the method developed presents several advantages over the existing in situ SiO 2 -epoxy composites.
  • One important advantage is the crystallinity of the particles, obtained under mild conditions; the crystallinity provides for improved intrinsic properties and the possibility of controlling shape by producing facetted, and especially elongated, nanoparticles.
  • the new method can be carried out in absence of solvents, or with the addition of only small quantities. Such solvents can be expensive, difficult to fully remove, and their use has environmental implications.
  • the in situ preparation of ZnO in the current case, yields only volatile, harmless by-products, greatly simplifying purification and practical application. Thus, this method could be compatible with a wide range of polymers and functionalities.
  • Figure 1 illustrates a schematic diagram of the hierarchical target structure.
  • Figure 2 shows theoretical effects of thermal resistance at the interface on composite thermal conductivity. Marked region indicates current CNT interfaces.
  • Inset Schematic of a graded interface
  • Figure 3 illustrates a schematic diagram showing the difference between conventional ex situ and the new in situ synthesis of ZnO nanoparticles. Nucleation of ZnO on the surface of carbon nanotubes to create a hierarchical structure in situ is also shown.
  • Figure 4 shows an UV spectrum of ZnO-composite from ZnEt 2 .
  • Figure 5 show HTEM images of ZnO-epoxy composite from ZnEt 2 .
  • Figure 6A shows a TEM spectrum of ZnO-epoxy composite from ZnEt 2
  • Figure 6B shows an EDXS spectrum of ZnO-epoxy composite from ZnEt 2 .
  • Figure 7 show HTEM images of ZnO-epoxy composite from EtZnO-i-Pr.
  • Figure 8 shows an UV spectrum of ZnO-epoxy composite from EtZnO-i-Pr.
  • Figure 9 show an UV spectrum of ZnO-epoxy composite from ZnEt 2 and EtZnO-Ph-CH 2 CH 2 -NH 2 .
  • Figure 10 shows a TGA data for ZnO-epoxy composites with various nanoparticle loadings/
  • Figure HA show TEM photographs of example 7: a) before EtOH wash
  • Figure HB show TEM photographs of example 7: b) after EtOH wash.
  • Figure 12 show TEM photographs of example 8 before EtOH wash.
  • Figure 13 show TEM photographs of example 9.
  • Figure 14 show TEM images of ZnO nanoparticles prepared from ZnEt 2 .
  • Figure 15 shows an UV spectrum of ZnO prepared from ZnEt 2 .
  • TGMDA Tetraglycidyl methylen dianiline
  • HRTEM images display ZnO nanoparticles with size ⁇ 10 nm and an indication of lattice fringes (crystallinity) and the selected area electron diffraction pattern (SAED) confirms the crystallinity of the particles, Figure 5.
  • SAED selected area electron diffraction pattern
  • Products with 10wt%, 20wt%, 30wt%, and 40wt% ZnO loadings are prepared by increasing the relative proportion of ZnEt 2 and H2O at the appropriate stages.
  • the oxide content of these samples was confirmed by TGA ( Figure 10), although this characterisation technique provides only a lower bound for the particle content, due to the potential loss of nanoparticles during combustion.
  • the viscosity of the resin containing the nanoparticles was assessed before the addition of hardener, no significant increase in viscosity was measured up to 30wt% ZnO.
  • Base-washed MWCNT are known to have a lower concentration of surface oxides, and to be less polar, and were prepared as reported elsewhere (Verdejo et al, Chem Comm, 5, 513, 2007 DOI: 10.1039/b611930a). The procedure was the same as for example 11 using 22.74 g of base-washed MWCNT 0.12 wt% in acetone, 0.36 mL (0.36 mmol) of 1 M solution Of ZnEt 2 in hexane and 13.0 ⁇ L (0.72 mmol) Of H 2 O in 0.25 mL of acetone. The workup was the same as for 2 to give 3 as a black solid. Yield: 29.6 mg, 50.7 %. (TEM photographs, Figure 12 )
  • the loading of nano-ZnO, generated in situ by reaction of ZnEt2 was estimated to be about 5 wt%; the loading of micron-scale ZnO particles was 20 wt%.
  • Products with 10wt%, 20wt%, 30wt% nano-ZnO, with 20 wt% micro-ZnO, are prepared by increasing the relative proportion of ZnEt 2 and H 2 O at the appropriate stages [EXAMPLE 11 ;
  • nanocomposite material of the present invention nano-sized zinc oxide is highly dispersed in a polymer material.
  • such nanocomposite material can significantly exert its function related to thermal conductivity and the like.
  • the nanocomposite material of the present invention is most appropriate as a material having the high insulating properties and high thermal conductivity required in an HV motor and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un matériau nanocomposite où des nanoparticules d'oxyde de zinc sont dispersées dans un matériau de type polymère de réticulation. Le matériau nanocomposite selon la présente invention est produit par dispersion d'un précurseur organozinc dans une résine polymère thermodurcissable et soumission du précurseur organique à une décomposition thermique in situ, hydrolyse ou oxydation pour générer des nanoparticules d'oxyde de zinc de granulométrie moyenne inférieure ou égale à 10 nm. Le matériau nanocomposite selon la présente invention présente d'excellentes propriétés isolantes et une excellente conductivité thermique.
PCT/JP2008/066475 2008-09-05 2008-09-05 Matériau nanocomposite, méthode de production d'un matériau nanocomposite et matériau isolant Ceased WO2010026668A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2008/066475 WO2010026668A1 (fr) 2008-09-05 2008-09-05 Matériau nanocomposite, méthode de production d'un matériau nanocomposite et matériau isolant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2008/066475 WO2010026668A1 (fr) 2008-09-05 2008-09-05 Matériau nanocomposite, méthode de production d'un matériau nanocomposite et matériau isolant

Publications (1)

Publication Number Publication Date
WO2010026668A1 true WO2010026668A1 (fr) 2010-03-11

Family

ID=40566421

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/066475 Ceased WO2010026668A1 (fr) 2008-09-05 2008-09-05 Matériau nanocomposite, méthode de production d'un matériau nanocomposite et matériau isolant

Country Status (1)

Country Link
WO (1) WO2010026668A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013129584A (ja) * 2011-12-22 2013-07-04 Osaka Gas Co Ltd 亜鉛化合物被覆炭素材及びその製造方法、並びに該亜鉛化合物被覆炭素材を用いた複合材
CN105597822A (zh) * 2015-12-29 2016-05-25 华东师范大学 有机多级孔负载型催化剂及其合成方法和应用
US9943840B2 (en) 2012-05-04 2018-04-17 Imperial Innovations Limited Process for producing nanoparticles
CN106179505B (zh) * 2016-07-18 2018-08-24 华东师范大学 含膦微孔有机纳米管骨架负载钯催化剂及其合成和应用
JP2021155741A (ja) * 2016-05-16 2021-10-07 東ソー・ファインケム株式会社 酸化アルミニウム形成用組成物及びその製造方法並びに酸化亜鉛粒子又は酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジット及びその製造方法
CN115160366A (zh) * 2022-06-21 2022-10-11 三峡大学 一种双（3-缩水甘油醚）苯基磷氧化合物的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007005831A2 (fr) * 2005-07-01 2007-01-11 Texas A & M University System Nanocomposites polymeres d'oxyde de zinc et procedes de production de nanocomposites polymeres d'oxyde de zinc

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007005831A2 (fr) * 2005-07-01 2007-01-11 Texas A & M University System Nanocomposites polymeres d'oxyde de zinc et procedes de production de nanocomposites polymeres d'oxyde de zinc

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ABDULLAH M; WULED LENGGORO I; OKUYAMA K; SHI F G: "In situ synthesis of polymer nanocomposite electrolytes emitting a high luminescence with a tunable wavelength", JOURNAL OF PHYSICAL CHEMISTRY B, vol. 107, 2003, pages 1957 - 1961, XP002525729 *
LI Y Q ET AL: "Preparation and characterization of transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 47, no. 6, 8 March 2006 (2006-03-08), pages 2127 - 2132, XP025231530, ISSN: 0032-3861, [retrieved on 20060308] *
YANG Y; LI Y-Q; FU S-Y; XIAO H-M: "Transparent and light-emitting epoxy nanocomposites containing ZnO quantum dots as encapsulating materials for solid state lighting", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 112, 17 July 2008 (2008-07-17), pages 10553 - 10558, XP002525730 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013129584A (ja) * 2011-12-22 2013-07-04 Osaka Gas Co Ltd 亜鉛化合物被覆炭素材及びその製造方法、並びに該亜鉛化合物被覆炭素材を用いた複合材
US9943840B2 (en) 2012-05-04 2018-04-17 Imperial Innovations Limited Process for producing nanoparticles
CN105597822A (zh) * 2015-12-29 2016-05-25 华东师范大学 有机多级孔负载型催化剂及其合成方法和应用
JP2021155741A (ja) * 2016-05-16 2021-10-07 東ソー・ファインケム株式会社 酸化アルミニウム形成用組成物及びその製造方法並びに酸化亜鉛粒子又は酸化アルミニウム粒子を含有するポリオレフィン系ポリマーナノコンポジット及びその製造方法
JP7162402B2 (ja) 2016-05-16 2022-10-28 東ソー・ファインケム株式会社 ポリオレフィン系ポリマーナノコンポジットの製造方法
US11795277B2 (en) 2016-05-16 2023-10-24 Tosoh Finechem Corporation Polyolefin-based polymer nanocomposite containing zinc oxide particles and method of producing same
US11820871B2 (en) 2016-05-16 2023-11-21 Tosoh Finechem Corporation Aluminum oxide-forming composition and method for producing same
CN106179505B (zh) * 2016-07-18 2018-08-24 华东师范大学 含膦微孔有机纳米管骨架负载钯催化剂及其合成和应用
CN115160366A (zh) * 2022-06-21 2022-10-11 三峡大学 一种双（3-缩水甘油醚）苯基磷氧化合物的制备方法

Similar Documents

Publication Publication Date Title
Zheng et al. Surface modification of hexagonal boron nitride nanomaterials: a review
Zhou et al. Hierarchical polyphosphazene@ molybdenum disulfide hybrid structure for enhancing the flame retardancy and mechanical property of epoxy resins
US7589240B2 (en) Quantum dots tailored with electronically-active polymers
WO2010026668A1 (fr) Matériau nanocomposite, méthode de production d'un matériau nanocomposite et matériau isolant
TW201107241A (en) Copper zinc tin chalcogenide nanoparticles
CN103059343B (zh) 一种改性碳纳米管及其制备方法
Kumar et al. Study on epoxy resin-based thermal adhesive filled with hybrid expanded graphite and graphene nanoplatelet
JP2010007124A (ja) 銀含有粉体の製造方法、銀含有粉体及びその分散液
CN114555719A (zh) 复合颗粒和复合颗粒的制造方法
Salahuddin et al. High‐performance flexible epoxy/ZnO nanocomposites with enhanced mechanical and thermal properties
Tseng et al. Synthesis of 1D, 2D, and 3D ZnO Polycrystalline Nanostructures Using the Sol‐Gel Method
CN107090205A (zh) 一种静电辅助石墨烯插层包覆钛纳米聚合物的制备方法
Liu et al. A new inorganic–organic hybrid In 2 Se 3 (en) as hollow nanospheres: hydrothermal synthesis and near-infrared photoluminescence properties
Zhang et al. Nonfluoride-modified halloysite nanotube-based hybrid: potential for acquiring super-hydrophobicity and improving flame retardancy of epoxy resin
CN102875844B (zh) 一种改性碳纳米管及其制备方法
CN102432873A (zh) 一种无机/有机杂化物的合成及其对环氧树脂的改性
CN101428857A (zh) 一种钼酸锌纳米材料的诱导控制合成方法
Mallakpour et al. A facile route for the preparation of novel optically active poly (amide–imide)/functionalized zinc oxide nanocomposites containing pyromellitoyl-bis-l-phenylalanine moieties
JP2010150321A (ja) ポリシロキサン組成物及びその製造方法
US8716424B2 (en) Process for synthesizing organic/inorganic composite
TW202144544A (zh) 組成物及其製造方法
EP3967729A1 (fr) Catalyseur de durcissement latent et composition de résine en contenant
KR101617176B1 (ko) 유기-무기 나노 복합체 및 이의 제조방법
CN102154705B (zh) 一种锑化铟纳米晶体的制备方法
Du et al. Low‐cost water soluble silicon quantum dots and biocompatible fluorescent composite films

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08810527

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08810527

Country of ref document: EP

Kind code of ref document: A1