Triorganoborane-amino functionalized nanoparticles, compositions, and methods

• US 9,908,904 B2
• Filed: 12/11/2013
• Issued: 03/06/2018
• Est. Priority Date: 12/20/2012
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Garbe, James E., Baran, Jr., Jimmie R.
• Primary Examiner(s): Le, Hoa T
• Application Number:
  US14/652,462
• Publication Number:
  US 20150353587A1
• Time in Patent Office: 1,546 Days
• Field of Search: 428403, 428407
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 35/146 Compounds containing boron and nitrogen, e.g. borazoles ammonium tetrafluoborates C01B35/063; ammonium borates C01B35/12
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C07F 7/1804 Compounds having Si-O-C linkages Si-O-acyl linkages C07F7/1896
• CPC Class Codes: C08F 120/12 of monohydric alcohols or phenols
• CPC Class Codes: C08F 120/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 120/68 Esters
• CPC Class Codes: C09C 1/3081 Treatment with organo-silicon compounds
• CPC Class Codes: C09C 1/3684 Treatment with organo-silicon compounds
• CPC Class Codes: C09C 3/08 Treatment with low-molecular-weight non-polymer organic compounds C09C3/006, C09C3/048 take precedence
• CPC Class Codes: C09C 3/12 Treatment with organosilicon compounds C09C3/006 takes precedence
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

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—NHR¹—B(R²)₃ wherein: Z is a divalent organic group; R¹ is H or an organic group; and each R² 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.

Claims

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—

NHR¹—

B(R²)₃ wherein;

Z is a divalent organic group;

R¹ is H or an organic group; and

each R² 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;

R¹ is H, an alkyl group, or a cycloalkyl group; and

each R² 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;

R¹ is H or a (C1-C6)alkyl group or a (C4-C8)cycloalkyl group; and

each R² 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;

R¹ is H; and

each R² is independently a (C1-C6)alkyl group.

6. The nanoparticle of claim 1 wherein each R² is the same in the structure —

Z—

NHR¹—

B(R²)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(R²)₃ wherein each R² 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—

NHR¹—

B(R²)₃ wherein;

Z is a divalent organic group;

R¹ is H or an organic group; and

each R² 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—

NHR¹—

B(R²)₃ wherein;

Z is a divalent organic group;

R¹ is H or an organic group; and

each R² 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.