Method of forming a non-random copolymer
View Patent ↗A non-random copolymer is formed, and its structure controlled, using a method including the step of combining a mixture of a first radical polymerizable compound and an organoborane initiator, a second radical polymerizable compound, and an organoborane decomplexing agent, at a rate sufficient to form the non-random copolymer. The non-random copolymer may be a silicon gradient polymer. To form the silicon gradient copolymer, the first and second radical polymerizable compounds are polymerized in the presence of the organoborane initiator and the organoborane decomplexing agent. The silicon gradient copolymer has a polymer backbone consisting of organic moieties and has at least one silicon containing pendent group.
1. A silicon gradient copolymer comprising a polymerization product of:
i. a first radical polymerizable compound comprising at least one silicon atom; and
ii. a second radical polymerizable compound,
wherein said first radical polymerizable compound and said second radical polymerizable compound are polymerized in the presence of an organoborane-organonitrogen complex and an organoborane decomplexing agent, and
wherein said gradient polymer has a polymer backbone consisting of organic moieties and has at least one silicon-containing group pending from said polymer backbone, and
comprising 10 to 10,000 parts by weight of boron per one million parts by weight of said first and second radical polymerizable compounds.
2. A gradient copolymer as set forth in claim 1 having at least one glass transition temperature that has a breadth of at least 25° C.
3. A gradient copolymer as set forth in claim 1 wherein said first and second radical polymerizable compounds are different from each other and each is independently selected from the group of an organosilane, an organopolysiloxane, and combinations thereof.
4. A gradient copolymer as set forth in claim 1 wherein said first radical polymerizable compound is selected from the group of an organosilane, an organopolysiloxane, and combinations thereof and said second radical polymerizable compound is organic and free of silicon atoms.
5. A gradient copolymer as set forth in claim 4 wherein said first radical polymerizable compound is further defined as a polyorganosiloxane having the average unit formula:
(R′ 3 SiO 1/2 ) x (R′ 2 SiO 2/2 ) y (R′SiO 3/2 ) z
wherein x and y are positive numbers, z is greater than or equal to zero, and at least one R′ is a free radical polymerizable group, and said second radical polymerizable compound is selected from the group of acrylates, alkenoates, carbonates, phthalates, acetates, itaconates, and combinations thereof.
6. A gradient copolymer as set forth in claim 5 wherein said polyorganosiloxane is further defined as an acrylate- or methacrylate-functional polyorganosiloxane.
7. A gradient copolymer as set forth in claim 6 wherein said polyorganosiloxane is further defined as monomethacryloxypropyl terminated polydimethylsiloxane.
8. A gradient copolymer as set forth in claim 4 wherein said second radical polymerizable compound is further defined as an acrylate.
9. A gradient copolymer as set forth in claim 1 wherein one of said first and second radical polymerizable compounds is further defined as an organosilane having the general structure:
R n Si(OR′) 4-n
wherein n is an integer of less than or equal to 4; and
wherein at least one of R and R′ independently comprises a free radical polymerizable group, and the other is selected from the group of acrylates, alkenoates, carbonates, phthalates, acetates, itaconates, and combinations thereof.
10. A gradient copolymer as set forth in claim 1 wherein said first and second radical polymerizable compounds are different from each other and said second radical polymerizable compound is organic and free of silicon atoms.
11. A gradient copolymer as set forth in claim 1 wherein said first radical polymerizable compound is selected from the group of an organosilane, an organopolysiloxane, and combinations thereof and said second radical polymerizable compounds is further defined as an organic macromonomer that is free of silicon atoms.
12. A gradient copolymer as set forth in claim 1 wherein said organoborane-organonitrogen complex is further defined as an organoborane-amine complex.
13. A method of forming a silicon gradient copolymer comprising a polymerization product of a first radical polymerizable compound comprising at least one silicon atom and a second radical polymerizable compound and also comprising 10 to 10,000 parts by weight of boron per one million parts by weight of the first and second radical polymerizable compounds, said method comprising the step of combining (1) a mixture of the first radical polymerizable compound and an organoborane-organonitrogen complex comprising a concentration of boron, (2) the second radical polymerizable compound, and (3) an organoborane decomplexing agent, at a rate sufficient to form the silicon gradient copolymer.
14. A method as set forth in claim 13 wherein one of the first and second radical polymerizable compounds is selected from the group of an organosilane, an organopolysiloxane, and combinations thereof, and the other of the first and second radical polymerizable compounds is organic and free of silicon atoms.
15. A method as set forth in claim 14 wherein one of the first and second radical polymerizable compounds is further defined as a polyorganosiloxane having the average unit formula:
(R′ 3 SiO 1/2 ) x (R′ 2 SiO 2/2 ) y (R′SiO 3/2 ) z
wherein x and y are positive numbers, z is greater than or equal to zero, and at least one R′ is a free radical polymerizable group, and the other of the first and second radical polymerizable compounds is selected from the group of acrylates, alkenoates, carbonates, phthalates, acetates, itaconates, and combinations thereof.
16. A method as set forth in claim 15 wherein the polyorganosiloxane is further defined as monomethacryloxypropyl terminated polydimethylsiloxane.
17. A method as set forth in claim 13 wherein the second radical polymerizable compound and the organoborane decomplexing agent are combined before combination with the mixture of the first radical polymerizable compound and the organoborane-organonitrogen complex.
18. A method as set forth in any claim 13 wherein the step of combining is further defined as adding the mixture of the first radical curable compound and the organoborane-organonitrogen complex to a mixture of the second radical polymerizable compound and the organoborane decomplexing agent.
19. A method as set forth in claim 13 wherein the silicon gradient copolymer has at least one glass transition temperature that has a breadth of at least 25° C. and the step of combining is further defined as adding the mixture of the first radical polymerizable compound and the organoborane-organonitrogen complex to a mixture of the second radical polymerizable compound and the organoborane decomplexing agent at a rate of from greater than 0.0043 to 0.015 moles of the first radical polymerizable compound per minute per mole of the second radical polymerizable compound.
20. A method as set forth in claim 13 wherein the step of combining is further defined as adding droplets of the mixture to the second radical polymerizable compound.
21. A method as set forth in claim 20 wherein the step of adding droplets is further defined as spraying the mixture.
22. A method as set forth in claim 13 wherein the first and second radical polymerizable compounds are polymerized at a temperature of from 15° C. to 35° C.
23. A method as set forth in claim 1 wherein the silicon gradient copolymer has at least one glass transition temperature having a breadth of at least 25° C.