Organoborane polyamine complexes and adhesive composition made therewith

• US 5,616,796 A
• Filed: 04/14/1995
• Issued: 04/01/1997
• Est. Priority Date: 04/14/1995
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Pocius, Alphonsus V., Nigatu, Tadesse G.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Cheng, Wu C.
• Application Number:
  US08/422,443
• Time in Patent Office: 718 Days
• Field of Search: 526/198, 564/9
• US Class Current: 564/9
• CPC Class Codes: B32B 27/30 comprising vinyl (co)polymers; comprising acrylic (co)polymers
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C07F 5/00 Compounds containing elements of Groups 3 or 13 of the Periodic Table
• CPC Class Codes: C07F 5/027 Organoboranes and organoborohydrides
• 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: C08F 4/52 selected from boron, aluminium, gallium, indium, thallium or rare earths C08F4/14 takes precedence
• 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
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer

Abstract

A complex comprises organoborane and polyamine. The polyamine is the reaction product of a diprimary amine-terminated material and a material having at least two groups reactive with primary amine. The complexes are useful in systems for initiating the polymerization of acrylic monomer, which systems further include a material reactive with amine. Polymerizable acrylic monomer compositions useful as adhesives can be prepared.

Claims

1. A complex comprising organoborane and polyamine, wherein the polyamine comprises the reaction product of a diprimary amine-terminated material and a material having at least two groups reactive with primary amine, wherein a majority of the terminal groups in the polyamine are primary amine.

2. A complex according to claim 1 wherein the organoborane has structure ##STR23## wherein:

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

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

3. A complex according to claim 1 wherein the diprimary amine-terminated material is selected from the group consisting of polyoxyalkylenediamine, alkyl diamine, aryl diamine, alkaryl diamine, and blends thereof.

4. A complex according to claim 1 wherein the material having at least two groups reactive with primary amine has the structure Y--R--Z, wherein Y and Z are moieties reactive with primary amine and are independently selected from the group consisting of carboxylic acid, carboxylic acid halide, ester, aldehyde, epoxide, amino alcohol, and acrylic, and R is a divalent organic radical.

5. A complex according to claim 1 that is not pyrophoric under ambient conditions.

6. An organoborane polyamine complex having the structure ##STR24## wherein:

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

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

Am is a polyamine that comprises the reaction product of a diprimary amine-terminated material and a material having at least two groups reactive with primary amine, wherein a majority of the terminal groups in the polyamine are primary amine; and

the value of v is selected so as to provide an effective ratio of primary amine nitrogen atoms to boron atoms in the complex.

7. An organoborane polyamine complex according to claim 6 wherein R¹, R² and R³ are independently selected from alkyl groups having 1 to 5 carbon atoms.

8. An organoborane polyamine complex according to claim 7 wherein R¹, R² and R³ are the same.

9. An organoborane polyamine complex according to claim 6 wherein the diprimary amine-terminated material is polyoxyalkylenediamine.

10. An organoborane polyamine complex according to claim 9 wherein the polyoxyalkylenediamine has the structure H₂ NR⁴ O--(R⁵ O)_w --(R⁶ O)_x --(R⁵ O)_y --R⁴ NH₂ wherein

R⁴, R⁵, and R⁶ are alkylene groups having 1 to 10 carbon atoms and which may be the same or which may be different;

w is ≧

1;

x is ≧

0; and

y is ≧

0.

11. An organoborane polyamine complex according to claim 10 wherein R⁴ is an alkyl group having 2 to 4 carbon atoms, R⁵ is an alkyl group having 2 or 3 carbon atoms, and R⁶ is an alkyl group having 2 or 3 carbon atoms.

12. An organoborane polyamine complex according to claim 6 wherein the diprimary amine-terminated material is a linear alkyldiamine in which the alkyl group has from 1 to 12 carbon atoms.

13. An organoborane polyamine complex according to claim 6 wherein the material having at least two groups reactive with primary amine has the structure Y--R--Z wherein Y and Z are moieties independently selected from the group consisting of carboxylic acid, carboxylic acid halide, ester, aldehyde, epoxide, amino alcohol, and acrylic, and R is a divalent organic radical.

14. An organoborane polyamine complex according to claim 13 wherein Y and Z are the same and the polyamine is substantially linear.

15. An organoborane polyamine complex according to claim 6 wherein the ratio of primary amine nitrogen atoms to boron atoms in the complex is about 0.5:

1 to 4.1.

16. An organoborane polyamine complex according to claim 15 wherein the ratio of primary amine nitrogen atoms to boron atoms in the complex is about 1:

1.

18. A system according to claim 16 wherein the complex has the structure ##STR25## wherein:

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

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

E--(L--E)_z --L--E is a polyamine wherein;

each E is the residue of a material that is selected from the group consisting of;

(a) polyoxyalkylenediamine having the structure H₂ NR⁴ O--(R⁵ O)_w --(R⁶ O)_x --(R⁵ O)_y --R⁴ NH₂ wherein

R⁴, and R⁶, and R⁶ are alkylene groups having 1 to 10 carbon atoms and which may be the same or which may be different;

w is ≧

1;

x is ≧

0;

y is ≧

0; and

(b) linear alkyldiamine in which the alkyl group has from 1 to 12 carbon atoms; and

each L is a linking group that is the residue of a material having the structure Y--R⁷ --X, wherein Y and X are independently selected from the group consisting of carboxylic acid, carboxylic acid halide, ester, aldehyde, epoxide, amino alcohol, and acrylic and R⁷ is a divalent organic radical

z≧

0; and

the value of v is selected so as to provide an effective ratio of primary amine nitrogen atoms to boron atoms in the complex.

19. A system according to claim 18 wherein:

R¹, R² and R³ are alkyl groups having 1 to 5 carbon atoms and are the same;

R⁴ is an alkyl group having 2 to 4 carbon atoms;

R⁵ is an alkyl group having 2 or 3 carbon atoms;

R⁶ is an alkyl group having 2 or 3 carbon atoms;

Y and X are the same and are selected from the group consisting of epoxide, acrylic and carboxylic acid;

the value of v is selected such that the ratio of to primary amine nitrogen atoms to boron atoms in the complex is about 1;

1 to 2;

1; and

the complex is a liquid at room temperature and is substantially linear.

20. A system according to claim 18 wherein the compound that is reactive with amine for liberating organoborane is selected from the group consisting of isocyanate, acid, acid chloride, sulfonyl chloride, and aldehyde.

21. A system according to claim 20 wherein the compound that is reactive with amine for liberating organoborane is acrylic acid or methacrylic acid.

17. A system capable of initiating the polymerization of an acrylic monomer, the system comprising:

a) a complex comprising organoborane and polyamine, the polyamine comprising the reaction product of a diprimary amine-terminated material and a material having at least two groups reactive with primary amine, wherein a majority of the terminal groups in the polyamine are primary amine; and

b) an effective amount of a compound that is reactive with amine for liberating the organoborane.