Polymerizable compositions made with polymerization initiator systems based on organoborane amine complexes

• US 5,539,070 A
• Filed: 02/22/1995
• Issued: 07/23/1996
• Est. Priority Date: 02/22/1994
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Zharov, Jury V., Krasnov, deceased, Jury N.
• Primary Examiner(s): Nagumo, Mark
• Application Number:
  US08/391,642
• Time in Patent Office: 517 Days
• Field of Search: 526/198
• US Class Current: 526/198
• CPC Class Codes: C08F 20/12 of monohydric alcohols or phenols
• CPC Class Codes: C08F 220/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
• 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
• CPC Class Codes: C09J 4/00 Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Abstract

A polymerizable acrylic composition comprises:

(a) at least one acrylic monomer;

(b) an effective amount of an organoborane amine complex having the structure: ##STR1## wherein: R¹ is an alkyl group having 1 to 10 carbon atoms;

R² and R³ are independently selected from phenyl-containing groups and alkyl groups having 1 to 10 carbon atoms;

R⁴ is selected from the group consisting of CH₂ CH₂ OH and (CH₂)_x NH₂ wherein x is an integer greater than 2;

R⁵ is hydrogen or an alkyl group having 1 to 10 carbon atoms; and

the nitrogen atom to boron atom ratio is about 1:1 to 1.5:1; and

(c) an effective amount of an acid for initiating polymerization of the acrylic monomer.

The polymerizable acrylic compositions are especially useful for bonding low surface energy substrates.

Claims

1. A polymerizable acrylic composition comprising:

(a) at least one acrylic monomer;

(b) an effective amount of an organoborane amine complex having the structure;

##STR15## wherein;

R¹ is an alkyl group having 1 to 10 carbon atoms;

R² and R³ are independently selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and phenyl-containing groups;

R⁴ is selected from the group consisting of CH₂ CH₂ OH and (CH₂)_x NH₂ wherein x is an integer greater than 2;

R⁵ is hydrogen or an alkyl group having 1 to 10 carbon atoms; and

the nitrogen atom to boron atom ratio is about 1;

1 to 1.5;

1; and

(c) an effective amount of an acid for initiating polymerization of the acrylic monomer.

2. A polymerizable acrylic composition according to claim 1 wherein R¹, R² and R³ are each independently selected from the group consisting of alkyl groups having 2 to 5 carbon atoms.

3. A polymerizable acrylic composition according to claim 2 wherein R⁴ is selected from the group consisting of CH₂ CH₂ OH and (CH₂)_x NH₂ wherein x is an integer from 2 to 6 and further wherein R⁵ is hydrogen.

4. A polymerizable acrylic composition according to claim 3 wherein R⁴ is selected from the group consisting of CH₂ CH₂ OH and (CH₂)₆ NH₂.

5. A polymerizable acrylic composition according to claim 1 wherein the nitrogen atom to boron atom ratio is about 1:

1.

6. A polymerizable acrylic composition according to claim 1 wherein the at least one acrylic monomer is a blend of an alkyl acrylate monomer and an alkyl methacrylate monomer.

7. A polymerizable acrylic composition according to claim 6 wherein the alkyl acrylate monomer is a butyl acrylate and the alkyl methacrylate monomer is methyl methacrylate.

8. A polymerizable acrylic composition according to claim 1 wherein the organoborane amine complex comprises about 0.15 to 5 mole %, based on the number of moles of acrylic functionality.

9. A polymerizable acrylic composition according to claim 1 further comprising a thickening agent for increasing the viscosity of the composition.

10. A polymerizable acrylic composition according to claim 1 wherein R⁴ is CH₂ CH₂ OH, the acrylic composition further comprising about 0.1to 7 mole %, based on the number of moles of acrylic functionality, of a substantially uncomplexed trialkylborane.

11. A polymerizable acrylic composition according to claim 1 comprising:

(a) about 0.5 to 7 wt. % of the organoborane complex, wherein R¹, R² and R³ are independently selected from the group consisting of alkyl groups having 2 to 5 carbon atoms and further wherein R⁴ is (CH₂)₆ NH₂ ;

(b) about 0.5 to 7 wt. % of the acid, wherein the acid is either acrylic acid or methacrylic acid;

(c) a blend of (i) a butyl acrylate that provides about 10 to 55 wt. % and (ii) methyl methacrylate that provides about 10 to 50 wt. %; and

(d) about 25 to 40 wt. % of a thickening agent;

wherein the sum of a+b+c+d equals 100 wt. %.

12. A polymerizable acrylic composition according to claim 1 comprising:

(a) about 0.5 to 5 wt. % of the organoborane amine complex, wherein R¹, R² and R³ are independently selected from the group consisting of alkyl groups having 2 to 5 carbon atoms and further wherein R⁴ is CH₂ CH₂ OH;

(b) about 0.5 to 5 wt. % of the acid;

(c) a blend of (i) an alkyl acrylate that provides about 5 to 65 wt. % and (ii) about 10 to 65 wt. % of an alkyl methacrylate;

(d) about 0.1 to 5 wt. % of a substantially uncomplexed trialkylborane, the alkyl groups of which may be the same or different, each having 1 to 10 carbon atoms; and

(e) about 20 to 40 wt. % of a thickening agent;

wherein the sum of a+b+c+d+e equals 100 wt. %.