Method of dissociating an organoborane-amine complex

• US 8,647,716 B2
• Filed: 06/24/2010
• Issued: 02/11/2014
• Est. Priority Date: 06/26/2009
• Status: Active Grant

• Current Assignee: BASF Coatings GmbH (BASF SE)
• Original Assignee: BASF SE
• Inventors: Gutowski, Keith E., Cranfill, David
• Primary Examiner(s): Cameron, Erma
• Application Number:
  US13/379,377
• Publication Number:
  US 20120100293A1
• Time in Patent Office: 1,328 Days
• Field of Search: None
• US Class Current: 427/341
• CPC Class Codes: B05D 3/107 Post-treatment of applied coatings
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Abstract

A method of dissociating an organoborane-amine complex in a coating composition is provided. The method includes the step of introducing the organoborane-amine complex, the radical polymerizable compound, and optionally an amine, onto a substrate to form the coating composition. The method also includes the step of introducing carbon dioxide into the coating composition in a molar ratio of at least 1:1 of the carbon dioxide to free amine groups present in the coating composition. More specifically, a carbamic zwitterion is formed in-situ from reaction of the carbon dioxide and the free amine groups. The formation of the carbamic zwitterion leads to dissociation of the organoborane-amine complex and formation of a radical. The radical is then used to polymerize the radical polymerizable compound.

Claims

1. A method of forming a coating composition, said method comprising the steps of:

A. introducing an organoborane-amine complex, a radical polymerizable compound, and optionally an amine onto a substrate to form a coating composition;

B. introducing carbon dioxide into the coating composition in a molar ratio of at least 1;

1 of the carbon dioxide to free amine groups present in the coating composition;

C. reacting the carbon dioxide and the free amine groups to form a carbamic zwitterion in-situ and to dissociate the organoborane-amine complex thereby forming a radical; and

D. polymerizing the radical polymerizable compound using the radical.

2. The method as set forth in claim 1, wherein the substrate is an automobile component and the step of polymerizing is further defined as polymerizing to cure the coating composition on the automobile component, and optionally wherein the method further comprises the step of electrocoating the automobile component with a first composition wherein the coating composition is applied to the first composition on the automobile component.

3. The method as set forth in claim 1, wherein a molar ratio of the free amine groups to the amine of the organoborane-amine complex is about 1:

1.

4. The method as set forth in claim 1, wherein the step of reacting is reacting the carbamic zwitterion with a bound amine of the organoborane-amine complex thereby dissociating the organoborane-amine complex into an organoborane initiator and the reaction product of the amine and the carbamic zwitterion.

5. The method as set forth in claim 1, wherein the coating composition further comprises water and the step of reacting is transferring a proton from the carbamic zwitterion to the water to form an acidic species which protonates the bound amine of the organoborane-amine complex causing dissociation of the organoborane-amine complex.

6. The method as set forth in claim 1, wherein the step of reacting is transferring a proton from a nitrogen atom of the carbamic zwitterion to an oxygen atom of the carbamic zwitterion thereby forming an unstable carbamic acid compound which protonates the bound amine of the organoborane-amine complex causing dissociation of the organoborane-amine complex.

7. The method as set forth in claim 1, further comprising the step of limiting an amount of oxygen introduced into the coating composition, in a molar ratio of from 1:

1 to 5;

1 with the organoborane of the organoborane-amine complex.

8. The method as set forth in claim 1, wherein the step of introducing the organoborane-amine complex, the radical polymerizable, and optionally the amine, is further defined as spraying the organoborane-amine complex, the radical polymerizable compound, and optionally the amine onto the substrate.

9. The method as set forth in claim 1, wherein the step of introducing the carbon dioxide is as spraying the carbon dioxide from a nozzle of a spray gun, and optionally wherein the step of spraying the carbon dioxide is combining the organoborane-amine complex, the radical polymerizable compound, and optionally the amine with the carbon dioxide as the organoborane-amine complex, the radical polymerizable compound, and optionally the amine are being sprayed.

10. The A method as set forth in claim 1, further comprising the step of introducing a second gas to the coating composition wherein the second gas is sulfur dioxide.

11. The method as set forth in claim 1, wherein the organoborane-amine complex has the following formula:

12. The method as set forth in claim 1, wherein the radical polymerizable compound is selected from the group consisting of a) unsaturated acrylic and methacrylic ester, resin, b) functional acrylic and methacrylic ester monomer and combinations thereof.

13. The method as set forth in claim 1 wherein the radical polymerizable compound is present in an amount of from 50 to 80 parts by weight per 100 parts by weight of the coating composition and the organoborane-amine complex is present in an amount of from 2 to 5 parts by weight per 100 parts by weight of the coating composition.

14. The method as set forth in claim 1, wherein the step of introducing the organoborane-amine complex, the radical polymerizable compound, and optionally the amine occurs before the step of introducing the carbon dioxide.

15. The method as set forth in claim 1, wherein the step of introducing the carbon dioxide is exposing the coating composition to an atmosphere of carbon dioxide in a gas sink.

16. The method as set forth in claim 1, wherein in step D is carried out in the absence of external heating.

17. The method as set forth in claim 1, wherein in step D is carried out at a temperature of from 20°

C. to 30°

C.

18. The method as set forth in claim 1, wherein a molar ratio of the free amine groups to the amine of the organoborane-amine complex is from about 0.5:

1 to 1;

1.

19. The method as set forth in claim 1, wherein a molar ratio of the free amine groups to the amine of the organoborane-amine complex is less than about 1:

1.

20. The method as set forth in claim 1, further comprising the step of limiting an amount of oxygen introduced into the coating composition, in an amount of 0.5 to 5 parts by weight of the oxygen per 100 parts by weight of the carbon dioxide present in the coating composition.

21. A method of forming a coating composition, said method comprising the steps of:

A. introducing an organoborane-amine complex, a radical polymerizable compound, carbon dioxide and optionally an amine onto a substrate to form a coating composition and wherein a molar ratio of at least 1;

1 of the carbon dioxide to free amine groups present in the coating composition;

B. reacting the carbon dioxide and the free amine groups to form a carbamic zwitterion in-situ and to dissociate the organoborane-amine complex thereby forming a radical; and

C. polymerizing the radical polymerizable compound using the radical.