Method for producing a nanocomposite dispersion comprising composite particles of inorganic nanoparticles and organic polymers

Patent metadata

Field	Value
Publication number	US-9650536-B2
Application number	US-201314413166-A
Country	US
Kind code	B2
Filing date	May 15, 2013
Priority date	Jul 6, 2012
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

The present invention relates to a method for producing nanocomposite dispersions comprising composite particles of inorganic nanoparticles and organic polymers in a continuous phase, especially in a dispersion medium, as well as to the nanocomposite dispersions thus obtained and to the use thereof.

First claim

The invention claimed is:

1. A method for producing a nanocomposite dispersion comprising composite particles of inorganic nanoparticles and organic polymers in a dispersion medium as a continuous phase,
wherein the method comprises the following method steps:
(a) providing inorganic nanoparticles in the form of a dispersion comprising the inorganic nanoparticles;
(b) then, subjecting the dispersion comprising the inorganic nanoparticles resulting from step (a) to a surface modification, wherein the surface modification comprises an at least two-stage surface treatment comprising: (i) one stage where the inorganic nanoparticles are contacted with at least one dispersing agent and (ii) another stage where the inorganic particles are provided with functional groups on their surfaces via chemical reaction;
wherein the dispersing agent used is a polymeric dispersant and is based on a functionalized polymer having a number-average molecular weight of at least 500 g/mol, and wherein the surface treatment stage (i) is performed by adding the at least one dispersing agent to the dispersion of the inorganic nanoparticles, followed by homogenizing the resulting dispersion and contacting the inorganic nanoparticles with the at least one dispersing agent for a time sufficient to allow for an interaction between the surface of the inorganic nanoparticles and the dispersing agent, thus modifying the surface of the inorganic nanoparticles by the dispersing agent, wherein the surface treatment stage (i) is performed with introduction of energy input with an energy amount introduced, calculated as energy introduced per inorganic nanoparticles amount, between 5,000 to 500,000 kJ/kg, and wherein by the surface treatment stage (ii) the inorganic nanoparticles are provided with functional groups which are compatible with or reactive with the polymerizable monomers used in step (c);

(c) subsequently, combining the dispersion comprising the surface-modified inorganic nanoparticles, resulting from step (b) with at least one kind of polymerizable monomers, followed by a polymerization of the polymerizable monomers in the presence of the surface-modified inorganic nanoparticles, via emulsion polymerization, thus resulting in a nanocomposite dispersion comprising composite particles of inorganic nanoparticles and organic polymers in a continuous phase dispersion medium, wherein polymerization is performed by polymerizing the polymerizable monomers in the presence of the surface-modified inorganic nanoparticles and, optionally, in the presence of at least one polymerization initiator, wherein polymerization is performed as an at least two-stage polymerization process comprising a first stage producing a seed of composite particles of inorganic nanoparticles and organic polymers, followed by a second stage where polymerization is continued, finalized by a post polymerization step.

2. The method according to claim 1 ,
wherein the inorganic nanoparticles are formed of metal or semimetal oxides, metal or semimetal hydroxides, metal or semimetal oxide hydroxides, metal or semimetal oxyhydroxides, metal or semimetal carbides, metal or semimetal nitrides, metal or semimetal sulfides, metal or semimetal tellurides, metal or semimetal selenides, metal or semimetal halides, metal or semimetal carbonates, metal or semimetal phosphates, metal or semimetal sulfates, metal or semimetal silicates, metal or semimetal borates, metal or semimetal vanadates, metal or semimetal tungstates, metal or semimetal aluminates, apatites, zeolites, graphenes, carbon nanotubes and carbon blacks as well as combinations and mixtures of these compounds and mixed compounds and alloys of different metals and/or semimetals.

3. The method according to claim 1 ,
wherein the inorganic nanoparticles have particle sizes in the range from 0.1 to 2,000 nm; and
wherein the inorganic nanoparticles have a granular, spherical, elongated or plate-like shape.

4. The method according to claim 1 ,
wherein the dispersion comprising the inorganic nanoparticles in step (a) is provided by at least one of precipitation methods, mechanochemical processing methods, comminution methods, sol-gel methods, hydrothermal or solvothermal methods, physical vapor deposition methods, chemical vapor deposition methods, flame pyrolysis methods, decomposition methods and combustion synthesis.

5. The method according to claim 1 ,
wherein, in step (b), the surface treatment stage (i) comprising contacting the inorganic nanoparticles with at least one dispersing agent is performed by adding the at least one dispersing agent to the dispersion of the inorganic nanoparticles, followed by homogenizing the resulting dispersion and contacting the inorganic nanoparticles with the at least one dispersing agent for a time sufficient to allow for an interaction between the surface of the inorganic nanoparticles and the dispersing agent, thus modifying the surface of the inorganic nanoparticles by the dispersing agent.

6. The method according to claim 1 ,
wherein, in step (b), the dispersing agent used is a polymeric dispersant having a number-average molecular weight in the range from 500 to 10,000,000 g/mol; and
wherein, in step (b), the dispersing agent is used in amounts in the range from 5 to 500% by weight, based on the inorganic nanoparticles.

7. The method according to claim 1 ,
wherein, in step (b), the surface treatment stage (i) comprising contacting the inorganic nanoparticles with at least one dispersing agent is performed for a duration from 0.001 to 24 hours and in a temperature range from 0 to 150° C.

8. The method according to claim 1 ,
wherein, in step (b), by the surface treatment stage (ii) the inorganic nanoparticles are provided with functional groups which are compatible with or reactive with the polymerizable monomers used in step (c).

9. The method according to claim 1 ,
wherein, in step (b), by the surface treatment stage (ii) the inorganic nanoparticles are provided with functional groups selected from isocyanate groups, urethane groups, carbamate groups, epoxy groups, carboxylic acid groups, carboxylic acid anhydride groups, carboxylate groups, hydroxy groups, thiol groups, amine groups, organic groups comprising carbon-carbon double bonds, vinyl groups, ethylenically unsaturated groups, acrylate groups, methacrylate groups, alkyl groups, alkenyl groups, alkinyl groups, aryl groups, aralkyl groups, cycloalkyl groups, cycloalkylene groups, halogens, alkoxy groups, acyloxy groups and combinations thereof.

10. The method according to claim 1 ,
wherein, in step (b), the surface treatment stage (ii) comprising providing the inorganic nanoparticles with functional groups on their surfaces is performed by contacting or reacting the inorganic nanoparticles with at least one surface-modification agent comprising functional groups, wherein the surface-modification agent comprising functional groups is selected from organofunctional silanes comprising at least one functional group selected from isocyanate groups, urethane groups, carbamate groups, epoxy groups, carboxylic acid groups, carboxylic acid anhydride groups, carboxylate groups, hydroxy groups, thiol groups, amine groups, organic groups comprising carbon-carbon double bonds, vinyl groups, ethylenically unsaturated groups, acrylate groups, methacrylate groups, alkyl groups, alkenyl groups, alkinyl groups, aryl groups, aralkyl groups, cycloalkyl groups, cycloalkylene groups, halogens, alkoxy groups, acyloxy groups; carboxylic acids; carboxylic acid anhydrides; carboxylates; and combinations thereof.

11. The method according to claim 1 ,
wherein, in step (b), the surface treatment stage (ii) comprising providing the inorgan

Assignees

• Akzo Nobel Coatings Int Bv
• Byk Chemie Gmbh
• Energenics Europe Ltd
• Univ Pais Vasco
• Yki Ytkemiska Inst Ab
• Energenics Europe Ltd
• Univ Del Paris Vasco

Inventors

• Ronne Nils Erik
• Hormann Melanie
• Tecklenburg Janin
• Nagel Carsten
• Nolte Ulrich
• Berkei Michael
• Xu Yingqian
• Leiza Jose Ramon
• Reyes Yuri
• Paulis Maria
• Arrese Miren Aguirre
• Ahniyaz Anwar
• Fornara Andrea
• Hanitzsch Ninja

Classifications

• C08J3/092

  Hydrocarbons · CPC title

• C08J5/005

  Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• C09D133/06

  of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical · CPC title

• C08J3/11

  from solid polymers · CPC title