Polymers containing borane or carborane cage compounds and related applications
View Patent ↗Polymers comprising residues of cage compound monomers having at least one polyalkoxy silyl substituent are provided. The cage compound monomers are selected from borane cage compound monomers comprising at least 7 cage atoms and/or carborane cage compound monomers comprising 7 to 11 cage compound monomers. Such polymers can further comprise one or more reactive matrices and/or co-monomers covalently bound with the cage compound monomer residues. Articles of manufacture comprising such polymers are also disclosed.
1. A polymer comprising:
a polymer backbone;
a plurality of residues of a borane and/or carborane cage compound monomer, said residues being in said polymer backbone and/or pendant to said polymer backbone, wherein said borane cage compound monomer comprises at least 7 cage atoms, and wherein said carborane cage compound monomer comprises from 7 to 11 cage atoms,
wherein said cage compound monomer comprises at least one polyalkoxy silyl substituent.
2. The polymer of claim 1 , said polyalkoxy silyl substituent having the formula
—R 6 Si(OR 7 ) n R 8 3−n
wherein R 6 is a C 0 to C 20 alkylene or arylene group, oxygen, or —OR 9 —, wherein R 9 is a C 1 to C 20 alkylene or arylene group; wherein each R 7 is independently any alkyl group; wherein n is at least 2; and wherein R 8 is hydrogen, an alkyl group, an aryl group, an alkaryl group, or an aralkyl group.
3. The polymer of claim 1 , wherein said cage compound monomer is a borane cage compound monomer comprising at least 7 cage atoms.
4. The polymer of claim 1 , wherein said cage compound monomer is selected from the group consisting of:
(a) a closo-carborane having the general formula R x [C 2 B n H n+2−x ], wherein n is in the range of from 5 to 9; x is in the range of from 1 to 2; and each R is independently selected from the group consisting of said silyl substituent, a C 1 to C 20 n-alkyl, a hydroxyl, a carboxyl, an epoxy, and an isocyanate, with the proviso that at least one R group is said silyl substituent;
(b) a closo-carborane salt having the general formula R[CB n H n ]X, wherein n is in the range of from 6 to 10; X is selected from the group consisting of Li + , Na + , K + , Cs + , and a quaternary ammonium; and R is said silyl substituent;
(c) a nido-carborane salt having the general formula R x [C 2 B n H n+2−x ]X 2 , wherein x is in the range of from 1 to 2; n is in the range of from 5 to 9; X is selected from the group consisting of Li + , Na + , K + , Cs + , and a quaternary ammonium; and each R is independently selected from the group consisting of said silyl substituent, a C 1 to C 20 n-alkyl, a hydroxyl, a carboxyl, an epoxy, and an isocyanate, with the proviso that at least one R group is said silyl substituent;
(d) a nido-carborane salt having the general formula R[CB n H n ]X 3 , wherein n is in the range of from 6 to 10; X is selected from the group consisting of Li + , Na + , K + , Cs + , and a quaternary ammonium; and R is said silyl substituent; and
(e) a closo-borane salt having the general formula [B n H m (OR) p ]X 2 , wherein n is in the range of from 7 to 12; m+p=n, with p being in the range of from 1 to 12; X is selected from the group consisting of Li + , Na + , K + , Cs + , and a quaternary ammonium; and each R is independently selected from the group consisting of a hydrogen atom and said silyl substituent, with the proviso that at least one R group is said silyl substituent and R 6 is a C 0 to C 20 alkylene or arylene group.
5. The polymer of claim 1 , wherein said cage compound monomer is:
wherein each R 14 is independently oxygen or —OR 9 —, wherein R 9 is a C 1 to C 20 alkylene or arylene group,
wherein R 11 , R 12 , and R 13 are independently any substituted or unsubstituted C 1 to C 20 alkyl groups that optionally include heteroatoms,
wherein each R 15 is independently hydrogen or any substituted or unsubstituted C 1 to C 20 alkyl group that optionally includes heteroatoms,
wherein X is selected from the group consisting of Li + , Na + , K + , Cs + , and quaternary ammonium cations,
wherein y is in the range of from 0 to 11,
wherein z is in the range of from 0 to 11−y.
6. The polymer of claim 1 , further comprising a plurality of residues of a reactive matrix.
7. The polymer of claim 6 , wherein said reactive matrix comprises at least one type of functional group capable of forming a covalent bond with said silyl substituent.
8. The polymer of claim 7 , wherein said functional group is a hydroxyl.
9. The polymer of claim 6 , wherein said reactive matrix is selected from the group consisting of poly(ethylene-co-vinyl acetate-co-vinyl alcohol) (“EVA-OH”), an epoxy polymer, a polyurethane, a silicone, a polyalkylene glycol, polytetramethylene ether, a polyester, a polyether, a cellulose polymer, a cellulose ester, polyvinyl alcohol), a nylon, a novolac, and mixtures of two or more thereof.
10. The polymer of claim 6 , wherein said reactive matrix is selected from the group consisting of EVA-OH, silanol-terminated polydimethylsiloxane (“PDMS”), and mixtures thereof.
11. The polymer of claim 1 , further comprising a plurality of residues of a co-monomer.
12. The polymer of claim 11 , wherein said co-monomer comprises at least one type of functional group capable of forming a covalent bond with said silyl substituent.
13. The polymer of claim 12 , wherein said functional group is a hydroxyl.
14. The polymer of claim 1 , further comprising a plurality of residues of a curing agent.
15. The polymer of claim 14 , wherein said curing agent comprises diphenol-4,4′-methylenebis(phenylcarbamate) (“DP-MDI”).
16. An article of manufacture comprising a polymer according to claim 1 .
17. The article of claim 16 , wherein said article is selected from the group consisting of tires, o-rings, gaskets, cable sheathing and/or insulation, foams, cushions, footwear soles, pads, floatation devices, waterproofing sheets, flooring, cables, membranes, potting materials, adhesives, glues, paints, coatings, fibers, fabric coatings, hoses, encapsulation materials for an electronic or photovoltaic device, separators in HEPA filters, sensor components, neutron shielding materials, nanotubes, and drug delivery systems.
18. A polymer comprising a plurality of residues of a carborane cage compound monomer, said cage compound monomer comprising at least one polyalkoxy silyl substituent, wherein said cage compound monomer is selected from the group consisting of:
a closo-carborane salt having the general formula R[CB n H n ]X, wherein n is in the range of from 6 to 11; X is a cationic species; and R is said polyalkoxy silyl substituent; and
a nido-carborane salt having the general formula R[CB n H n ]X 3 , wherein n is in the range of from 6 to 10; X is a cationic species; and R is said polyalkoxy silyl substituent.
19. The polymer of claim 18 , said polyalkoxy silyl substituent having the formula
—R 6 Si(OR 7 ) n R 8 3−n
wherein R 6 is a C 0 to C 20 alkylene or arylene group, oxygen, or —OR 9 , wherein R 9 is a C 1 to C 20 alkylene or arylene group; wherein each R 7 is independently any alkyl group; wherein n is at least 2; and wherein R 8 is hydrogen, an alkyl group, an aryl group, an alkaryl group, or an aralkyl group.
20. The polymer of claim 18 , wherein X is a cationic species selected from the group consisting of Li + , Na + , K + , Cs + , and a quaternary ammonium.