Hybrid organic-inorganic nano-particles
View Patent ↗The invention relates to a method of making hybrid organic-inorganic core-shell nano-particles, comprising the steps of a) providing colloidal organic particles comprising a synthetic polyampholyte as a template; b) adding at least one inorganic oxide precursor; and c) forming a shell layer from the precursor on the template to result in core-shell nano-particles. With this method it is possible to make colloidal organic template particles having an average particle size in the range of 10 to 300 nm; which size can be controlled by the comonomer composition of the polyampholyte, and/or by selecting dispersion conditions. The invention also relates to organic-inorganic or hollow-inorganic core-shell nano-particles obtained with this method, to compositions comprising such nano-particles, to different uses of said nano-particles and compositions, and to products comprising or made from said nano-particles and compositions, including anti-reflective coatings and composite materials.
1. A method of making hybrid organic-inorganic core-shell nano-particles, comprising the steps of:
a) providing colloidal organic particles as a template;
b) adding at least one inorganic oxide precursor; and
c) forming an inorganic shell layer from the precursor on the template to result in core-shell nano-particles; wherein
the colloidal particles are comprised of an organic synthetic polyampholyte having an average particle size of 5-500 nm as measured by Dynamic Light Scattering (DLS), and wherein
the organic synthetic polyampholyte is a copolymer of at least one comonomer having a positively charged group and at least one comonomer having a negatively charged group such that the copolymer has opposite charges on different pending groups.
2. The method according to claim 1 , wherein the method further comprises the step of forming the polyampholyte from vinyl monomers by addition copolymerization.
3. The method according to claim 1 , wherein the polyampholyte is a copolymerization reaction product of monomers comprising:
(i) at least one cationic or basic monomer (M1) selected from the group consisting of compounds with a pending group that can combine with a proton;
(ii) at least one anionic or acidic monomer (M2) selected from the group consisting of compounds with a pending group that can yield a proton;
(iii) at least one neutral or non-ionic monomer (M3); and
(iv) optionally at least one cross-linking monomer (M4).
4. The method according to claim 3 , wherein the polyampholyte is a copolymerization reaction product of monomers comprising:
(i) 5-40 mole % of at least one monomer M1;
(ii) 0.5-20 mole % of at least one monomer M2;
(iii) 38-94.5 mole % of at least one monomer M3; and
(iv) 0-2 mole % of at least one monomer M4.
5. The method according to claim 3 , wherein the polyampholyte is a copolymerization reaction product of monomers comprising:
(i) 8-20 mole % of at least one monomer M1 selected from the group consisting of amino-functional (meth)acrylates and (meth)acrylamides;
(ii) 1-4 mole % of at least one monomer M2 selected from the group of (meth)acrylic monomers with a carboxylic acid group; and
(iii) 76-91 mole % of at least one monomer M3 selected from the group of C1-C18 alkyl (meth)acrylates.
6. The method according to claim 3 , wherein the at least one cationic or basic monomer (M1) comprises a compound having pending tertiary amine group that can combine with a proton.
7. The method according to claim 1 , wherein the colloidal organic particles are provided by dispersing the synthetic polyampholyte in an aqueous medium, and by adjusting particle size by changing both pH and temperature.
8. The method according to claim 1 , wherein the colloidal organic particles have average particle size of 20-200 nm as measured by DLS.
9. The method according to claim 1 , wherein the colloidal organic particles consist of synthetic polyampholyte, water, and organic solvent.
10. The method according to claim 1 , wherein the inorganic oxide precursor is at least one compound selected from the group consisting of metal salts, metal chelates and organo-metallic compounds of Si, Al, Ti, and Zr.
11. The method according to claim 10 , wherein the inorganic oxide precursor comprises an alkoxy silane.
12. The method according to claim 1 , wherein the polyampholyte is a copolymerization reaction product of monomers comprising:
(a) at least one cationic or basic monomer (M1) comprising a tertiary amine group;
(b) at least one anionic or acidic monomer (M2) comprising a carboxylic acid group;
(c) at least one neutral or non-ionic monomer (M3); and
(d) optionally at least one cross-linking monomer (M4).