Amine organoborane complex initiated polymerizable compositions containing siloxane polymerizable components

• US 20040242812A1
• Filed: 06/09/2004
• Published: 12/02/2004
• Est. Priority Date: 02/28/2003
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies, Inc. (Dow, Inc.)
• Inventors: Sonnenschein, Mark F., Webb, Steven P., Harrington, Daniel R., Wendt, Benjamin L.
• Granted Patent: US 7,157,399 B2
• Time in Patent Office: Days
• US Class Current: 526/124.6
• CPC Class Codes: C08G 77/00 Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08K 5/55 Boron-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• 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

In one embodiment the invention is a polymerizable composition comprising a) an organoborane amine complex; b) one or more of monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization by free radical polymerization; c) one or more compounds, oligomers or prepolymers having a siloxane backbone and reactive moieties capable of polymerization; and d) a catalyst for the polymerization of the one or more compounds, oligomers or prepolymers having a siloxane backbone and reactive moieties capable of polymerization. This composition may further comprise a compound which causes the organoborane amine complex to disassociate. In a preferred embodiment, the two part composition further comprises a compound which is reactive with both the b) one or more of monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization by free radical polymerization; and the c) one or more compounds, oligomers or prepolymers having a siloxane backbone and reactive moieties capable of polymerization. This composition can be polymerized by contacting the two parts of the composition. In another embodiment the invention is an organoborane amine complex comprising an alkyl borane having ligands which are alkyl, cycloalkyl or both and an amino siloxane.

Claims

1-7. -7. (cancelled).

8. A complex comprising a borane, having three ligands selected separately in each occurrence from alkyl and cycloalkyl, and an amino siloxane.

9. A complex according to claim 8 wherein the complex corresponds to one of the formulas

(R²)₃—

B←

NH₂(CH₂)_b—

(C(R¹²)₂)_a—

Si—

((R¹¹)_q(Q)_p)- or

wherein

B represents boron;

R² is separately in each occurrence C_1-10alkyl,

C_3-10cycloalkyl, or two or more of R² may combine to form a cycloaliphatic ring;

Q is a hydrolyzable moiety;

R¹¹ is independently in each occurrence hydrogen, alkyl, alkoxy, alkenyl, alkyl amino or corresponds to the formula ((CR¹⁴H)_rO)_n—

(NR⁴)—

(CH₂)_o—

NH₂ with the proviso that at least (R¹¹)′

is a primary amine leave this as is;

R¹² is independently in each occurrence hydrogen, alkyl, aryl, alkoxy, and may further contain one or more primary, secondary or tertiary amines;

R¹⁴ is separately in each occurrence hydrogen or alkyl;

R⁴ is hydrogen, C_1-10alkyl, C_6-10aryl or C_7-10alkaryl;

a is a number of form 1 to 10;

b is a number of from 0 to 1;

m is separately in each occurrence a whole number of 1 or greater;

p is separately in each occurrence a number of from 1 to 3;

q is separately in each occurrence an integer from 1 to 2 wherein the sum of p and q on each silicon atom is 3;

n is separately in each occurrence an integer of about 4 to about 400;

o is separately in each occurrence an integer of about 1 to about 9; and

r is separately in each occurrence an integer of 2 or 4.

21. Complexes according to claim 9

wherein

R² is separately in each occurrence C_1-4alkyl,

Q is a hydrogen atom, halogen atom, alkoxy group, acyloxy group, heteroaromatic group, amino group, amido group, amino-oxy group, mercapto group or alkenyloxy group;

R¹¹ is independently in each occurrence C_1-20alkyl, C_2-20vinyl terminated alkenyl or corresponds to the formula

((CR¹⁴H)_rO)_n—

(NR⁴)—

(CH₂)_o—

NH₂.

R¹² is independently in each occurrence hydrogen, C_1-20alkyl, C_6-20aryl, or C_1-20alkoxy;

R¹⁴ is separately in each occurrence hydrogen or C_1-20alkyl;

R⁴ is hydrogen or a C_1-10alkyl;

a is a number of from 2 to 6;

b is 1;

m is separately in each occurrence a whole number of 1 or greater;

p is separately in each occurrence a number of from 2 or 3;

q is separately in each occurrence an integer from 0 or 1;

n is separately in each occurrence an integer of about 10 to about 100;

22. Complexes according to claim 21 wherein

R² is C_2-4alkyl;

Q is independently in each occurrence an alkoxy group;

R¹¹ is independently in each occurrence C_1-4alkyl, C_2-8alkenyl, or corresponds to the formula

((CR¹⁴1H)_rO)_n—

(NR⁴)—

(CH₂)_o—

NH₂.

R¹² is independently in each occurrence C_1-4alkyl, C_6-12 or C_1-4alkoxy;

R¹⁴ is independently in each occurrence hydrogen, methyl or ethyl; and

m is selected such that the molecular weight of the amine compound is between about 250 and 100,000 daltons.

10-20. -20. (cancelled).

23. An amine organoborane complex corresponding to the formula

24. Complexes according to claim 23 wherein

R² is separately in each occurrence C_1-4alkyl;

R¹⁵ is separately in each occurrence hydrogen or amino alkyl;

R¹⁶ is separately in each occurrence hydrogen, alkyl, alkenyl acyl, alkaryl, aralkyl having up to 8 carbon atoms;

R¹⁷ is separately in each occurrence hydrogen, fluorine, C_1-8alkyl or C_1-8fluoroalkyl;

j is separately in each occurrence a number of 20 or greater; and

k is independently in each occurrence number of about 1 to about 8.