Organoborane-containing compositions, and methods of using same

• US 10,513,583 B2
• Filed: 03/20/2015
• Issued: 12/24/2019
• Est. Priority Date: 03/27/2014
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Clough, Robert S., Karp, Gregory P., Thompson, Zachary J., Joly, Guy D.
• Primary Examiner(s): Moore, Margaret G
• Application Number:
  US15/129,331
• Publication Number:
  US 20170174839A1
• Time in Patent Office: 1,740 Days
• CPC Class Codes: C08F 222/103 of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• CPC Class Codes: C08F 236/20 unconjugated
• CPC Class Codes: C08F 4/54 together with other compounds thereof
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: C08G 75/12 Polythioether-ethers C08G75/0245 takes precedence
• CPC Class Codes: C08G 77/08 characterised by the catalysts used
• CPC Class Codes: C08G 77/28 sulfur-containing groups
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C09J 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Abstract

A polymerizable composition that includes: an organoborane-base complex, wherein the base is a complexing agent selected from a compound having one or more amine groups, amidine groups, hydroxide groups, alkoxide groups, or combinations thereof; a decomplexing agent that liberates the organoborane from the organoborane-base complex; a polymerizable thiol-containing component that includes at least one polymerizable thiol-containing compound having a plurality of thiol groups in which the sulfur atom of the thiol group is covalently bonded to carbon; and a polymerizable ethylenically unsaturated component that includes at least one polymerizable ethylenically unsaturated compound having a plurality of ethylenically unsaturated groups; wherein the total amount of the thiol-containing and ethylenically unsaturated compounds total at least 50% by weight of all polymerizable material in the composition.

Claims

1. A polymerizable composition comprising:

an organoborane-base complex, wherein the base is a complexing agent selected from a compound having one or more amine groups, amidine groups, hydroxide groups, alkoxide groups, or a combination thereof, wherein the complexing agent is free of aziridines;

a decomplexing agent that liberates the organoborane from the organoborane-base complex, wherein the decomplexing agent comprises a 1,3-dicarbonyl compound;

a polymerizable thiol-containing component comprising at least one polymerizable thiol-containing compound having a plurality of thiol groups in which the sulfur atom of the thiol group is covalently bonded to carbon; and

a polymerizable ethylenically unsaturated component comprising at least one polymerizable ethylenically unsaturated compound having a plurality of ethylenically unsaturated groups;

wherein the total amount of the thiol-containing and ethylenically unsaturated compounds total at least 50% by weight of all polymerizable material in the composition.

2. The polymerizable composition of claim 1, wherein upon reaction a —

C—

S—

C—

C—

linkage is formed.

3. The polymerizable composition of claim 1, wherein the thiol-containing compound and the ethylenically unsaturated compound are separate and distinct compounds.

4. The polymerizable composition of claim 1, wherein the organoborane-base complex does not include a thiol group.

5. The polymerizable composition of claim 1, wherein the organoborane portion of the organoborane-base complex is of the formula B(R¹)(R²)(R³) wherein:

R¹ represents an alkyl group having from 1 to 10 carbon atoms; and

R² and R³ independently represent;

alkyl groups having 1 to 10 carbon atoms;

cycloalkyl groups having 3 to 10 carbon atoms;

aryl groups having 6 to 12 carbon atoms;

or

aryl groups substituted with alkyl groups having 1 to 10 carbon atoms or cycloalkyl groups having 3 to 10 carbon atoms;

provided that any two of R¹, R², and R³ groups may optionally be part of a ring.

6. The polymerizable composition of claim 1, wherein the base portion of the organoborane-base complex is an amine comprising at least one primary or secondary amine group.

7. The polymerizable composition of claim 1, wherein the polymerizable composition is a multi-part polymerizable composition.

8. The polymerizable composition of claim 1, wherein the multi-part polymerizable composition comprises:

a part A composition comprising the organoborane-base complex; and

a part B composition comprising the decomplexing agent;

wherein the thiol-containing compound is in part A, part B, or another part distinct from parts A and B; and

wherein the ethylenically unsaturated compound is in part A, part B, or another part distinct from parts A and B.

9. The polymerizable composition of claim 1, wherein the thiol-containing component comprises at least one polymerizable thiol-containing compound selected from those prepared from a ring-opening reaction of epoxides with H₂S, those prepared from the addition of H₂S across carbon-carbon double bonds, polysulfides, polydimethylsiloxanes in which some of the methyl groups have been replaced by mercaptoalkyl groups, and those prepared from the esterification of polyols with thiol-containing carboxylic acids or their derivatives.

10. The polymerizable composition of claim 1, wherein the ethylenically unsaturated compound is selected from polyfunctional vinyl ethers, vinyl silicones, vinyl aliphatics, (meth)acrylates, allyl ethers, allyl esters, and allyl amides.

11. The polymerizable composition of claim 1, wherein the amount of the thiol groups in the thiol-containing component and the amount of the ethylenically unsaturated groups in the ethylenically unsaturated component are in a molar ratio range of 0.25:

1.0 to 4.0;

1.0.

12. A polymerizable composition comprising:

a part A composition comprising an organoborane-base complex, wherein the base is a complexing agent selected from a compound having one or more amine groups, amidine groups, hydroxide groups, alkoxide groups, or a combination thereof, wherein the complexing agent is free of aziridines; and

a part B composition comprising a decomplexing agent that liberates the organoborane from the organoborane-base complex, wherein the decomplexing agent comprises a 1,3-dicarbonyl compound;

wherein the polymerizable composition further comprises;

a polymerizable thiol-containing component comprising at least one polymerizable thiol-containing compound having a plurality of thiol groups in which the sulfur atom of the thiol group is covalently bonded to carbon; and

a polymerizable ethylenically unsaturated component comprising at least one polymerizable ethylenically unsaturated compound having a plurality of ethylenically unsaturated groups;

wherein the total amount of the thiol-containing and ethylenically unsaturated compounds total at least 50% by weight of all polymerizable material in the composition.

13. The polymerizable composition of claim 12, wherein upon reaction a —

C—

S—

C—

C—

linkage is formed.

14. The polymerizable composition of claim 12, wherein the organoborane portion of the organoborane-base complex is of the formula B(R¹)(R²)(R³) wherein:

R¹ represents an alkyl group having from 1 to 10 carbon atoms; and

R² and R³ independently represent;

alkyl groups having 1 to 10 carbon atoms;

cycloalkyl groups having 3 to 10 carbon atoms;

aryl groups having 6 to 12 carbon atoms;

or

aryl groups substituted with alkyl groups having 1 to 10 carbon atoms or cycloalkyl groups having 3 to 10 carbon atoms;

provided that any two of R¹, R², and R³ groups may optionally be part of a ring.

15. The polymerizable composition of claim 12, wherein the base portion of the organoborane-base complex is an amine comprising at least one primary or secondary amine group.

16. A composition prepared by combining components comprising:

a part A composition comprising an organoborane-base complex, wherein the base is a complexing agent selected from a compound having one or more amine groups, one or more amidine groups, one or more hydroxide groups, one or more alkoxide groups, or a combination thereof, wherein the complexing agent is free of aziridines; and

a part B composition comprising a decomplexing agent that liberates the organoborane from the organoborane-base complex, wherein the decomplexing agent comprises a 1,3-dicarbonyl compound;

wherein the part A composition and/or the part B composition further comprises;

a polymerizable thiol-containing component comprising at least one polymerizable thiol-containing compound having a plurality of thiol groups in which the sulfur atom of the thiol group is covalently bonded to carbon; and

a polymerizable ethylenically unsaturated component comprising at least one polymerizable ethylenically unsaturated compound having a plurality of ethylenically unsaturated groups;

wherein the total amount of the thiol-containing and ethylenically unsaturated compounds total at least 50% by weight of all polymerizable material in the composition.

17. The composition of claim 16, wherein the organoborane portion of the organoborane-base complex is of the formula B(R¹)(R²)(R³) wherein:

R¹ represents an alkyl group having from 1 to 10 carbon atoms; and

R² and R³ independently represent;

alkyl groups having 1 to 10 carbon atoms;

cycloalkyl groups having 3 to 10 carbon atoms;

aryl groups having 6 to 12 carbon atoms;

or

aryl groups substituted with alkyl groups having 1 to 10 carbon atoms or cycloalkyl groups having 3 to 10 carbon atoms;

provided that any two of R¹, R², and R³ groups may optionally be part of a ring.

18. The composition of claim 16, wherein the base portion of the organoborane-base complex is an amine comprising at least one primary or secondary amine group.