WO2011069771A1 - Microcapsules thermo-expansibles contenant des particules magnétiques à base d'oxyde métallique - Google Patents

Microcapsules thermo-expansibles contenant des particules magnétiques à base d'oxyde métallique Download PDF

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Publication number
WO2011069771A1
WO2011069771A1 PCT/EP2010/067286 EP2010067286W WO2011069771A1 WO 2011069771 A1 WO2011069771 A1 WO 2011069771A1 EP 2010067286 W EP2010067286 W EP 2010067286W WO 2011069771 A1 WO2011069771 A1 WO 2011069771A1
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WO
WIPO (PCT)
Prior art keywords
metal oxide
oxide particles
microcapsule
shell
coated metal
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/EP2010/067286
Other languages
English (en)
Inventor
Harald Herzog
Stipan Katusic
Uwe Paulmann
Friedel Schultheis
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of WO2011069771A1 publication Critical patent/WO2011069771A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking

Definitions

  • Heat-expandable microcapsules comprising magnetic metal oxide particles
  • the invention relates to heat-expandable microcapsules which comprise magnetic metal oxide particles enclosed by a shell, their production and use.
  • US 6106946 discloses heat-expandable microcapsules which comprise magnetic particles having an average particle diameter of from 5 to 200 nm.
  • the microcapsules are a constituent of sound-absorbing and insulating materials, as are used in electrical devices, vehicles or building materials .
  • EP-A-1185594 discloses heat-expandable microcapsules which expand as a result of the introduction of heat and thereby weaken the cohesion of adhesives and the interfacial bonds.
  • a disadvantage of this process is considered to be that the entire object warms up as a result of introducing the heat and not just the area where the bonds are to be broken.
  • such a process can only be used to a limited extent.
  • it is not very energy-efficient to heat large parts when it is only necessary to heat small areas in a targeted manner .
  • WO 2006/042782 discloses a process for recycling
  • the adhesive mass here can comprise ferromagnetic, ferrimagnetic or superparamagnetic particles which permit inductive heating of the adhesive mass.
  • the adhesive mass can comprise heat-expandable microcapsules which are
  • magnetic particles and the microcapsules are spatially separate from one another, meaning that the advantages of inductive heating are only partly translated. Furthermore, the application of the magnetic particles involves
  • the invention provides a microcapsule consisting of a capsule shell made of a thermoplastic resin and a
  • the capsule shell which comprises magnetic particles and one or more hydrocarbons with a boiling point of -15°C to 220°C, or consists thereof, where the magnetic particles are magnetic metal oxide particles with a shell comprising silicon dioxide,
  • the coated metal oxide particles have an average primary particle diameter of from 2 to 100 nm, preferably 10 to 80 nm and particularly preferably 20 to 70 nm, and where the average diameter of the microcapsules is 5 to 50 ym, preferably 10 to 30 ym.
  • magnetic metal oxide particles are to be understood as meaning those which have ferromagnetic, ferrimagnetic and/or superparamagnetic properties. In the presence of electrical, magnetic or electromagnetic alternating fields, these particles lead to a heating of the dispersion located in the microcapsule and thus to an expansion of the microcapsule.
  • coated metal oxide particles may be isolated
  • aggregated particles may be present here in a form in which metal oxide particles have become intergrown and the shell surrounds the intergrown metal oxide particles.
  • the microcapsule according to the invention can comprise, essentially or exclusively, such coated metal oxide particles, in which the metal oxide particles have become intergrown and the shell surrounds the intergrown metal oxide particles.
  • the average diameter of the microcapsules according to the invention can increase upon heating to 80 to 220°C by a hundred times, preferably by 40 to 80 times, the original average diameter without leading to destruction of the microcapsule .
  • invention is preferably 1 to 10 mm, particularly
  • the fraction of the coated metal oxide particles is 0.001 to 5% by weight, based on the microcapsule.
  • a fraction of from 0.01 to 1% by weight is adequate for an expansion of the microcapsule by a factor of 40 to 80 in the presence of electromagnetic alternating fields.
  • the fraction of the coated metal oxide particles, based on the dispersion can be 0.1 to 10% by weight, preferably 0.5 to 5.
  • the metal oxide particles present in the microcapsule according to the invention are preferably selected from the group consisting of the oxides of cobalt, chromium, dysprosium, iron, erbium, gadolinium, holmium, nickel and terbium.
  • the metal oxides are iron oxides, such as haematite, magnetite and
  • maghemite may be present individually or in the form of a mixture.
  • the coated metal oxide particles have a) a BET surface area of from 10 to 80 m 2 /g, b) a thickness of the shell of from 2 to 30 nm and c) a content of iron oxide of from 60 to 90% by weight and of silicon dioxide of from 10 to 40% by weight, in each case based on the coated metal oxide particles.
  • metal oxide particles may also be present, the shell of which has been surface-modified. These can be obtained by treating the coated metal oxide particles with a surface-modifying agent, in particular one with which a hydrophobicization of the surface results. By virtue of this measure, the stability of the dispersion in the inside of the microcapsule can be improved.
  • Preferred surface-modifying agents may be in particular the following silanes:
  • R alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl
  • R' alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl
  • R' cycloalkyl
  • n 1-20
  • y l, 2.
  • R ' ' ' ' ' H, alkyl .
  • cyclic polysiloxanes D3, D4, D5 and also polysiloxanes and silicone oils can also be used.
  • D3, D4 and D5 are to be understood as meaning cyclic polysiloxanes having 3, 4 or 5 units of the type
  • dimethylpolysiloxanes can be used particularly
  • the dispersion in the inside of the microcapsule also comprises one or more hydrocarbons having a boiling point of from -15°C to 220°C.
  • hydrocarbon is also intended to include a halogenated hydrocarbon.
  • the capsule shell of the microcapsule according to the invention is a thermoplastic resin. It can be obtained from one or more polymerizable monomers, the monomers being selected from the group consisting of acrylamide, acrylonitrile, acrylic acid, benzyl methacrylate,
  • N, -dimethylacrylamide, N, -dimethylmethacrylamide, tert- butyl methacrylate and N-vinylpyrrolidone N, -dimethylacrylamide, N, -dimethylmethacrylamide, tert- butyl methacrylate and N-vinylpyrrolidone .
  • one or more polymerizable crosslinking monomers having two or more polymerizable double bonds may be present. Examples thereof are ethylene glycol
  • the invention further provides a process for producing the microcapsule according to the invention, in which a) an organic dispersion which comprises coated metal
  • oxide particles having an average primary particle diameter of from 2 to 100 nm, the shell of which comprises amorphous silicon dioxide, b) an aqueous solution or water c) and one or more monomers, if appropriate in the
  • polymerization catalyst in both variants are, for example, peroxides, such as benzoyl peroxide, tert-butyl perbenzoate, cumyl hydroperoxides, tert-butyl peracetate, lauryl peroxide and diisopropyl
  • peroxides such as benzoyl peroxide, tert-butyl perbenzoate, cumyl hydroperoxides, tert-butyl peracetate, lauryl peroxide and diisopropyl
  • azobisdimethylvaleronitrile and azobisisobutyronitrile and also azo compounds such as azoamide compounds and alkylazo compounds.
  • the dispersion polymerization preferably takes place at temperatures of from 40 to 80°C. Preference is likewise given to an embodiment in which the dispersion polymerization is carried out under shearing conditions at an energy density of at least 1000 KJ/m 3 .
  • the invention further provides the use of the
  • thermoplasts as a constituent of thermosets, as a constituent of paper products and in technical textile fabrics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

L'invention concerne une microcapsule constituée d'une coque de capsule en résine thermoplastique contenant une dispersion composée de particules magnétiques et d'un ou de plusieurs hydrocarbures dont le ou les points d'ébullition sont compris entre -15 °C et 220 °C. Les particules magnétiques sont des particules magnétiques à base d'oxyde métallique dotées d'une coque en dioxyde de silicium. Les particules d'oxyde métallique enrobées présentent un diamètre moyen de particule primaire allant de 2 nm à 100 nm et le diamètre moyen de la microcapsule est compris entre 5 µm et 50 µm. La microcapsule peut être obtenue en soumettant a) une dispersion organique contenant des particules d'oxyde métallique enrobées ayant un diamètre moyen de particule primaire allant de 2 nm à 100 nm, leur coque contenant du dioxyde de silicium amorphe, b) une solution aqueuse ou de l'eau et c) un ou plusieurs monomères, le cas échéant en présence d'un ou de plusieurs catalyseurs de polymérisation, à une polymérisation en dispersion.
PCT/EP2010/067286 2009-12-09 2010-11-11 Microcapsules thermo-expansibles contenant des particules magnétiques à base d'oxyde métallique Ceased WO2011069771A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009047718.7 2009-12-09
DE102009047718 2009-12-09

Publications (1)

Publication Number Publication Date
WO2011069771A1 true WO2011069771A1 (fr) 2011-06-16

Family

ID=43385628

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/067286 Ceased WO2011069771A1 (fr) 2009-12-09 2010-11-11 Microcapsules thermo-expansibles contenant des particules magnétiques à base d'oxyde métallique

Country Status (1)

Country Link
WO (1) WO2011069771A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446965A (zh) * 2013-09-09 2013-12-18 青岛科技大学 一种镍掺杂α-Fe2O3多级结构刺状微球的制备方法
CN115368695A (zh) * 2022-08-08 2022-11-22 贵州师范大学 一种功能化热膨胀型发泡微胶囊及其制备方法和应用
DE102024205627A1 (de) 2024-06-18 2025-12-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Additiv und Verfahren zu dessen Herstellung sowie das Additiv umfassende Klebstoffzusammensetzung und Verfahren zu deren Herstellung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6106946A (en) 1996-03-15 2000-08-22 Matsumoto Yushi-Seiyaku Co., Ltd. Microcapsule containing magnetic fluid, manufacturing method, and use thereof
EP1185594A1 (fr) 1999-06-02 2002-03-13 Peter Stewart Bain Composition adhesive comprenant des microcapsules thermoextensibles
US20040249037A1 (en) * 2001-11-13 2004-12-09 Jana Kolbe Curable bonded assemblies capable of being dissociated
WO2006042782A1 (fr) 2004-10-18 2006-04-27 Tesa Ag Procede pour recycler des composants electroniques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6106946A (en) 1996-03-15 2000-08-22 Matsumoto Yushi-Seiyaku Co., Ltd. Microcapsule containing magnetic fluid, manufacturing method, and use thereof
EP1185594A1 (fr) 1999-06-02 2002-03-13 Peter Stewart Bain Composition adhesive comprenant des microcapsules thermoextensibles
US20040249037A1 (en) * 2001-11-13 2004-12-09 Jana Kolbe Curable bonded assemblies capable of being dissociated
WO2006042782A1 (fr) 2004-10-18 2006-04-27 Tesa Ag Procede pour recycler des composants electroniques

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446965A (zh) * 2013-09-09 2013-12-18 青岛科技大学 一种镍掺杂α-Fe2O3多级结构刺状微球的制备方法
CN115368695A (zh) * 2022-08-08 2022-11-22 贵州师范大学 一种功能化热膨胀型发泡微胶囊及其制备方法和应用
CN115368695B (zh) * 2022-08-08 2023-09-19 贵州师范大学 一种功能化热膨胀型发泡微胶囊的应用方法
DE102024205627A1 (de) 2024-06-18 2025-12-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Additiv und Verfahren zu dessen Herstellung sowie das Additiv umfassende Klebstoffzusammensetzung und Verfahren zu deren Herstellung

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