Triorganoborane-amino functionalized nanoparticles, compositions, and methods

Patent metadata

Field	Value
Publication number	US-9908904-B2
Application number	US-201314652462-A
Country	US
Kind code	B2
Filing date	Dec 11, 2013
Priority date	Dec 20, 2012
Publication date	Mar 6, 2018
Grant date	Mar 6, 2018

Abstract

Surface-modified nanoparticles wherein each nanoparticle includes an inorganic core and surface modifying groups, wherein the surface modifying groups include at least one triorganoborane-amine complex having the structure —Z—NHR 1 —B(R 2 ) 3 wherein: Z is a divalent organic group; R 1 is H or an organic group; and each R 2 is independently an organic group bound to the boron atom through a carbon atom. The inorganic core is typically an inorganic oxide core, e.g., silica, zirconia, or alumina.

First claim

What is claimed is:

1. A surface-modified nanoparticle comprising an inorganic core and surface modifying groups, wherein the surface modifying groups comprise at least one triorganoborane-amine complex having the structure —Z—NHR 1 —B(R 2 ) 3 wherein:
Z is a divalent organic group;
R 1 is H or an organic group; and
each R 2 is independently an organic group bound to the boron atom through a carbon atom; and
wherein the surface modifying groups further comprise non-amine functional stabilizing organic groups bound to the nanoparticles.

2. The nanoparticle of claim 1 wherein the inorganic core comprises an inorganic oxide core.

3. The nanoparticle of claim 1 wherein:
Z is a divalent organic group having 1 to 30 carbon atoms;
R 1 is H, an alkyl group, or a cycloalkyl group; and
each R 2 is independently an alkyl group, a cycloalkyl group, an aralkyl group, or an alkaryl group.

4. The nanoparticle of claim 3 wherein:
Z is a divalent organic group having 1 to 20 carbon atoms;
R 1 is H or a (C1-C6)alkyl group or a (C4-C8)cycloalkyl group; and
each R 2 is independently a (C1-C20)alkyl group, a (C4-C8)cycloalkyl group, a (C6-C14)ar(C1-C10)alkyl group, or a (C1-C10)alk(C6-C14)aryl group.

5. The nanoparticle of claim 4 wherein:
Z is a divalent organic group having 1 to 3 carbon atoms;
R 1 is H; and
each R 2 is independently a (C1-C6)alkyl group.

6. The nanoparticle of claim 1 wherein each R 2 is the same in the structure —Z—NHR 1 —B(R 2 ) 3 .

7. The nanoparticle of claim 1 wherein the surface modifying groups further comprise amine-functional organic groups not complexed with a triorganoborane.

8. The nanoparticle of claim 1 wherein the stabilizing organic group comprises a (C3-C16)alkyl group, a (C6-C14)aryl group, or combinations thereof.

9. A dispersion of a plurality of surface-modified nanoparticles of claim 1 in a liquid.

10. The nanoparticle of claim 1 wherein the inorganic core comprises a particle size of at least 5 nanometers.

11. The nanoparticle of claim 1 wherein the inorganic core comprises a particle size of at least 1 nanometer and no greater than 100 nanometers.

12. The nanoparticle of claim 1 wherein the nanoparticle is provided in a dispersion of a plurality of surface-modified nanoparticles in a liquid.

13. A method of making surface-modified nanoparticles, the method comprising:
providing amine-functional inorganic nanoparticles comprising bound stabilizing organic groups selected to stabilize a plurality of the amine-functional inorganic nanoparticles when dispersed in a liquid; wherein providing amine-functional inorganic nanoparticles comprising bound stabilizing organic groups, comprises:
providing inorganic nanoparticles comprising bound stabilizing organic groups selected to stabilize a plurality of the nanoparticles when dispersed in a liquid;
providing an amine-functional compound; and
combining the amine-functional compound and inorganic nanoparticles comprising bound stabilizing organic groups under conditions effective to form amine-functional inorganic nanoparticles comprising bound stabilizing organic groups;

providing a triorganoborane compound of the formula B(R 2 ) 3 wherein each R 2 is an organic group bound to the boron atom through a carbon atom; and
combining the amine-functional inorganic nanoparticles and the triorganoborane compound under conditions effective to form surface-modified nanoparticles, wherein each surface-modified nanoparticle comprises an inorganic core and surface modifying groups, wherein the surface modifying groups comprise at least one triorganoborane-amine complex having the structure —Z—NHR 1 —B(R 2 ) 3 wherein:
Z is a divalent organic group;
R 1 is H or an organic group; and
each R 2 is independently an organic group bound to the boron atom through a carbon atom, and
wherein the surface modifying groups further comprise non-amine functional stabilizing organic groups bound to the nanoparticles.

14. The method of claim 13 wherein combining the amine-functional compound and inorganic nanoparticles occurs in a solvent selected from water, an alcohol, or a combination thereof.

15. The method of claim 13 wherein combining the amine-functional inorganic nanoparticles and the triorganoborane compound occurs by mixing them in a solvent, which is subsequently removed from the resultant surface-modified nanoparticles that include an inorganic core and the surface modifying groups.

16. A polymerizable composition comprising a polymerizable component and surface-modified nanoparticles, wherein each surface-modified nanoparticle comprises an inorganic core and surface modifying groups, wherein the surface modifying groups comprise at least one triorganoborane-amine complex having the structure —Z—NHR 1 —B(R 2 ) 3 wherein:
Z is a divalent organic group;
R 1 is H or an organic group; and
each R 2 is independently an organic group bound to the boron atom through a carbon atom.

17. The polymerizable composition of claim 16 which is part of a dual-cure system.

Assignees

• 3M Innovative Properties Co

Inventors

• Garbe James E
• Baran Jr Jimmie R

Classifications

• Y10T428/2982

  Particulate matter [e.g., sphere, flake, etc.] · CPC title

• C09C3/08

  Treatment with low-molecular-weight {non-polymer} organic compounds {(C09C3/006, C09C3/048 take precedence)} · CPC title

• C08F120/12

  of monohydric alcohols or phenols · CPC title

• C07F7/1804 Primary

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title