WO2013004659A1 - Procédé de modification de solides particulaires par photopolymérisation - Google Patents

Procédé de modification de solides particulaires par photopolymérisation Download PDF

Info

Publication number
WO2013004659A1
WO2013004659A1 PCT/EP2012/062830 EP2012062830W WO2013004659A1 WO 2013004659 A1 WO2013004659 A1 WO 2013004659A1 EP 2012062830 W EP2012062830 W EP 2012062830W WO 2013004659 A1 WO2013004659 A1 WO 2013004659A1
Authority
WO
WIPO (PCT)
Prior art keywords
radical
hydrocarbon radical
particulate
finely divided
bonded
Prior art date
Application number
PCT/EP2012/062830
Other languages
German (de)
English (en)
Inventor
Rainer Jordan
Timo KORFMANN
Original Assignee
Wacker Chemie Ag
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 Wacker Chemie Ag filed Critical Wacker Chemie Ag
Publication of WO2013004659A1 publication Critical patent/WO2013004659A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/14—Organic medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Definitions

  • the invention relates to a process for the modification of particulate solids by photopolymerization, the modified particulate solids thus obtained and their use.
  • the surface modification can be carried out ex-situ, ie before mixing in of the particles, or in-situ, ie the polymer modifier is added to the corresponding modifier and the unmodified particles are subsequently mixed in, so that the particles are surface-modified during the mixing and compounding process ,
  • the fillers are preferably chemically irreversibly modified. That the modifier is chemically attached to the particle surface.
  • Typical modifiers that chemically react with the particle surface are organosilanes. These form stable filler-silicon-oxygen bonds with the filler surface.
  • R is the same or different and is hydrogen, or optionally substituted with -CN, -NCO, -NR 2 2 , -GOOH, -COOR 2 , -halogen, -acrylic, -epoxy, -SH, -OH or -CONR 2 2 substituted C-linked Ci-C2o ⁇ K ° hlenwasserstoff est, preferably a C ⁇ -CQ-
  • Hydrocarbon radical particularly preferably a C -C3-
  • organosiloxanes are preferably liquid at the temperature of use.
  • organosiloxanes are linear or cyclic dialkylsiloxanes having an average number of dialkylsiloxy units of greater than 2, preferably greater than 5.
  • the end groups can be the same or different.
  • the silane of the general formula II is preferably used as liquid added added and in particular the powdered metal oxide.
  • a gas-supported fluidization can be carried out by all inert gases that do not react with the silane of the general formula II, the solid, and the silylated solid, so do not lead to side reactions, degradation reactions, oxidation processes and flame and explosion phenomena, as preferential N2, Ar, other noble gases, CO2, etc.
  • the supply of the gases for fluidization is preferably in the range of Leerrohrgas- speeds of 0.05 to 5 cm / s, more preferably from 0.5 to 2.5 cm / s.
  • This recycling is preferably carried out in non-condensed phase, ie as gas or as vapor.
  • This recycling can be carried out as mass transfer along a pressure equalization or as controlled material transport with the technically usual systems of gas transport, such as fans, pumps, compressed air membrane pumps. Since the return of the non-condensed phase is preferred, the heating of the returning lines is recommended if appropriate.
  • the reaction time is 5 minutes to 48 hours, preferably 10 minutes to 5 hours.
  • protic solvents may be added, such as liquid or volatilizable alcohols or water; typical alcohols are iso-propanol, ethanol and methanol. It is also possible to add mixtures of the abovementioned protic solvents. Preferably, 1 to 50% by weight of protic solvent, based on the solid, are added, in particular preferably 5 to 25%. Particularly preferred is water.
  • acidic catalysts of acidic character in the sense of a Lewis acid or a Brönsted acid such as hydrogen chloride or basic catalysts, of a basic character, in the sense of a Lewis base or a Brönsted base, such as ammonia, may be added.
  • these are added in traces, i.e. less than 1000 ppm. Most preferably, no catalysts are added.
  • % By weight, preferably less than 18% by weight and more preferably less than 15% by weight.
  • Extractable components in this context are preferably to be understood as meaning components which are separated by means of organic solvents, such as e.g. Extract the THF or toluene extractively from the particle surface and remove it by analytical methods, e.g. Quantify elemental analysis or other methods.
  • the proportion of particulate solid which has been dispersed in the vinylic monomer of the general formula (I) is preferably from 0.1 to 50% by weight, preferably from 0.1 to 25% by weight and more preferably from 0.5 to 15% by weight.
  • the dispersion can be done e.g. by stirring by means of preferably fast-running stirrers such as dissolvers, rotor-stator systems, or by treatment with ultrasound such as ultrasonic baths or sonotrodes.
  • the dispersion is preferably carried out over a period of 10 seconds to 2 hours.
  • the inert solvents are preferably used in proportions of 70% to 99% based on the particulate solid.
  • a photosensitizer-free reaction mixture is preferably used, ie the reaction mixture contains no photosensitizer such as benzophenone.
  • radiation is preferably electromagnetic radiation, preferably electromagnetic radiation in a wavelength range of 1 nm to 10,000 nm, such as light radiation in the visible range of about 400 nm - 800 nm, or UV radiation having a wavelength range of 1 nm to 400 nm, preferably 100 nm to 400 nm and particularly preferably 180 - 380 nm used.
  • the radiation source (s) may be introduced into the reaction mixture in the form of a submersion source or externally, i. act on the mixture above the mixture or through the wall of the reaction vessel. Preference is given to an external effect.
  • the excess monomer is removed. This can be done by condensation in vacuo or filtration. Preference is given to condensing off in vacuo.

Abstract

L'invention concerne un procédé de préparation de solides finement dispersés particulaires ayant une surface modifiée, caractérisé en ce qu'il consiste à disperser un monomère vinylique de formule générale (I): (R1 aR1 bC=CR1 cR1 d) avec un solide finement dispersé particulaire ayant une grande surface, pour former un mélange, le solide finement dispersé particulaire ayant une grande surface étant silylé par traitement avec des silanes de formule générale (II): X1+x'-SiR4 2-x'-(CH2)v-Y, seul ou dans des mélanges quelconques, et ce mélange étant mis en réaction à l'aide d'un rayonnement par polymérisation radicalaire.
PCT/EP2012/062830 2011-07-04 2012-07-02 Procédé de modification de solides particulaires par photopolymérisation WO2013004659A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011078613.9 2011-07-04
DE201110078613 DE102011078613A1 (de) 2011-07-04 2011-07-04 Verfahren zur Modifikation von partikulären Feststoffen durch Photopolymerisation

Publications (1)

Publication Number Publication Date
WO2013004659A1 true WO2013004659A1 (fr) 2013-01-10

Family

ID=46466504

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/062830 WO2013004659A1 (fr) 2011-07-04 2012-07-02 Procédé de modification de solides particulaires par photopolymérisation

Country Status (2)

Country Link
DE (1) DE102011078613A1 (fr)
WO (1) WO2013004659A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112689612A (zh) * 2018-08-27 2021-04-20 株式会社大阪钛技术 SiO粉末的制造方法及球形颗粒状SiO粉末

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5426136A (en) * 1993-03-24 1995-06-20 Ppg Industries, Inc. Particulate amorphous silica associated with thin polymeric film
EP0703192A1 (fr) * 1994-04-11 1996-03-27 Ube-Nitto Kasei Co. Ltd. Particules fines de silices a enrobage de resine reticule et leur procede de production
EP1479734A1 (fr) * 2003-05-20 2004-11-24 DSM IP Assets B.V. Procede de preparation d'un revetement de surface nanostructure, revetements nanostructures et articles contenant le revetement
US20060160916A1 (en) 2004-08-13 2006-07-20 Dyer Daniel J Process for modifying substrates with grafted polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5426136A (en) * 1993-03-24 1995-06-20 Ppg Industries, Inc. Particulate amorphous silica associated with thin polymeric film
EP0703192A1 (fr) * 1994-04-11 1996-03-27 Ube-Nitto Kasei Co. Ltd. Particules fines de silices a enrobage de resine reticule et leur procede de production
EP1479734A1 (fr) * 2003-05-20 2004-11-24 DSM IP Assets B.V. Procede de preparation d'un revetement de surface nanostructure, revetements nanostructures et articles contenant le revetement
US20060160916A1 (en) 2004-08-13 2006-07-20 Dyer Daniel J Process for modifying substrates with grafted polymers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112689612A (zh) * 2018-08-27 2021-04-20 株式会社大阪钛技术 SiO粉末的制造方法及球形颗粒状SiO粉末
CN112689612B (zh) * 2018-08-27 2024-04-19 株式会社大阪钛技术 SiO粉末的制造方法及球形颗粒状SiO粉末

Also Published As

Publication number Publication date
DE102011078613A1 (de) 2013-01-10

Similar Documents

Publication Publication Date Title
EP2279226B1 (fr) Particules de dioxyde de silicium modifiées en surface
DE60008677T2 (de) Schuppenartige Siliciumdioxidteilchen und diese enthaltende härtbare Zusammensetzung
EP1963437B1 (fr) Particules d'agglomerat, procede de production de nanocomposites et leur utilisation
EP1357156B1 (fr) Charge de type oxyd ou silicate modifiée au silane, procédé de sa fabrication et son utilisation
EP2054150B1 (fr) Tamis moléculaire à revêtement hydrophobe
EP1954631A1 (fr) Nanoparticules d'oxyde de zinc
WO2010066640A1 (fr) Nanoparticules d'oxydes métalliques modifiées par des silanes
EP1711538B1 (fr) Composition durcissable contenant des particules modifiees en surface
DE10241510A1 (de) Nanokomposite, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2008077814A2 (fr) Couches de résine silicone organofonctionnelles sur des oxydes métalliques
US20100092761A1 (en) Nanoparticles
EP1926685A1 (fr) Procede pour realiser un corindon nanometrique a surface modifiee par des silanes
EP1680462B1 (fr) Procede de fabrication d'un corps moule a revetement antistatique
EP1609516A1 (fr) Procédé et dispositif pour extraire des substances des charges modifiées aux silanes
EP1711537A1 (fr) Composition durcissable contenant des particules modifiees en surface
EP2145928B1 (fr) Dispersion de particules de dioxyde de silicium hydrophobes et granulé ainsi obtenu
WO2013004659A1 (fr) Procédé de modification de solides particulaires par photopolymérisation
EP1694780A2 (fr) Fonctionnalisation de la surface de particules oxydiques, particules a surface ainsi fonctionnalisee et leur utilisation
EP1526115A1 (fr) Particule de silice greffée
DE102006053156A1 (de) Zusammensetzungen enthaltend Phosphonat-funktionelle Partikel
DE102006058202A1 (de) Verfahren zur Herstellung von Dispersionen
EP3663365A1 (fr) Dispersion et préparation pour laque aqueuse contenant du dioxyde de silicium hydrophile et du silanol
EP2825600B1 (fr) Procédé de modification de la surface de solides particulaires
WO2008000674A2 (fr) Oligomère à fonction alcoxysilyle et particules à surface ainsi modifiée
WO2008055817A2 (fr) Nanoparticules dispersibles

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: 12733080

Country of ref document: EP

Kind code of ref document: A1

DPE2 Request for preliminary examination filed before 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: 12733080

Country of ref document: EP

Kind code of ref document: A1