Polymers containing borane or carborane cage compounds and related applications
View Patent ↗Polymers comprising residues of borane and/or carborane cage compound monomers having at least one polyalkoxy silyl substituent. Such polymers can further comprise one or more reactive matrices and/or co-monomers covalently bound with the cage compound monomer residues. Methods of making and applications for using such polymers are also disclosed.
1. A polymer comprising:
a plurality of residues of a borane and/or carborane cage compound monomer,
wherein said cage compound monomer comprises at least one 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,
wherein said cage compound monomer comprises at least 7 cage atoms; and
a plurality of residues of a curing agent.
2. 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 10; 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 11; 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.
3. The polymer of claim 1 , wherein said cage compound monomer is selected from the group consisting of:
and mixtures of two or more thereof,
wherein R is hydrogen or any substituted or unsubstituted C 1 to C 20 alkyl or aryl group that optionally includes heteroatoms,
wherein each R 10 ° is independently any substituted or unsubstituted alkylene or arylene groups having a carbon number of from 1 to 20 that optionally include heteroatoms,
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.
4. The polymer of claim 1 , wherein said cage compound monomer is n-propyl-triethoxysilyl-o-carborane.
5. The polymer of claim 1 , further comprising a plurality of residues of a reactive matrix.
6. The polymer of claim 5 , wherein said reactive matrix comprises at least one type of functional group capable of forming a covalent bond with said silyl substituent.
7. The polymer of claim 6 , wherein said functional group is a hydroxyl.
8. The polymer of claim 5 , 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, poly(vinyl alcohol), a nylon, a novolac, and mixtures of two or more thereof.
9. The polymer of claim 5 , wherein said reactive matrix is selected from the group consisting of EVA-OH, silanol-terminated polydimethylsiloxane (“PDMS”), and mixtures thereof.
10. The polymer of claim 9 , wherein said co-monomer comprises at least one type of functional group capable of forming a covalent bond with said silyl substituent.
11. The polymer of claim 1 , further comprising a plurality of residues of a co-monomer.
12. The polymer of claim 11 , wherein said functional group is a hydroxyl.
13. The polymer of claim 1 , wherein said residues of said cage compound monomer constitute at least 1 weight percent of said polymer.
14. The polymer of claim 1 , wherein said curing agent comprises diphenol-4,4′-methylenebis(phenylcarbamate) (“DP-MDI”).
15. A method of making a polymer, said method comprising:
combining a borane and/or a carborane cage compound monomer with a curing agent and a reactive matrix and/or a co-monomer to thereby form a polymerization reaction medium; and
subjecting said polymerization reaction medium to reaction conditions sufficient to polymerize at least a portion of said cage compound monomer with at least a portion of said curing agent and said reactive matrix and/or said co-monomer,
wherein said cage compound monomer comprises at least one 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,
wherein said reactive matrix and said co-monomer each comprise at least one type of functional group capable of forming a covalent bond with said silyl substituent,
wherein said cage compound monomer comprises at least 7 cage atoms.
16. The method of claim 15 , 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 10; 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 11; 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 30 , K 30 , 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 30 , 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.
17. The method of claim 15 , wherein said cage compound monomer is selected from the group consisting of:
and mixtures of two or more thereof,
wherein R is hydrogen or any substituted or unsubstituted C 1 to C 20 alkyl or aryl group that optionally includes heteroatoms,
wherein each R 10 is independently any substituted or unsubstituted alkylene or arylene groups having a carbon number of from 1 to 20 that optionally include heteroatoms,
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 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.
18. The method of claim 15 , wherein said cage compound monomer is n-propyl-triethoxysilyl-o-carborane.
19. The method of claim 15 , wherein said reactive matrix and/or said co-monomer each comprise a hydroxyl functional group.
20. The method of claim 15 , wherein said polymerization reaction medium comprises said reactive matrix, wherein said reactive matrix is selected from the group consisting of poly(ethylene-co-vinyl acetate-co-vinyl alcohol) (“EVA-OH”), silanol-terminated polydimethylsiloxane (“PDMS”), and mixtures thereof.
21. The method of claim 15 , wherein said reaction conditions include heating said polymerization reaction medium at an elevated temperature of at least 50° C.
22. An article of manufacture comprising a polymer, said polymer comprising:
a plurality of residues of a curing agent; and
a plurality of residues of a borane and/or a carborane cage compound monomer, wherein said cage compound monomer is selected from the group consisting of:
and mixtures of two or more thereof,
wherein R is hydrogen or any substituted or unsubstituted C 1 to C 20 alkyl or aryl group that optionally includes heteroatoms,
wherein each R 10 is independently any substituted or unsubstituted alkylene or arylene groups having a carbon number of from 1 to 20 that optionally include heteroatoms,
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 30 , Na 30 , K + , Cs 30 ,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.
23. The article of claim 22 , wherein said cage compound monomer is n-propyl-tri ethoxysilyl-o-carborane.
24. The article of claim 22 , wherein said polymer further comprises a plurality of residues of a reactive matrix and/or a co-monomer.
25. The article of claim 24 , wherein said reactive matrix and/or said co-monomer each comprise at least one type of functional group capable of forming a covalent bond with said silyl substituent.
26. The article of claim 25 , wherein said functional group is a hydroxyl.
27. The article of claim 24 , wherein said polymer comprises residues of said reactive matrix, wherein said reactive matrix is selected from the group consisting of poly(ethylene-co-vinyl acetate-co-vinyl alcohol) (“EVA-OH”), silanol-terminated polydimethylsiloxane (“PDMS”), and mixtures thereof.
28. The article of claim 22 , wherein said residues of said cage compound monomer constitute at least 1 weight percent of said polymer.
29. The article of claim 22 , 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.
30. A polymer comprising:
a plurality of residues of a borane and/or carborane cage compound monomer,
wherein said cage compound monomer comprises at least one 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,
wherein said cage compound monomer comprises at least 7 cage atoms; and
a plurality of residues of a reactive matrix, wherein said reactive matrix is selected from the group consisting of polyethylene-co-vinyl acetate-co-vinyl alcohol) (“EVA-OH”), silanol-terminated polydimethylsiloxane (“PDMS”), and mixtures thereof.
31. An article of manufacture comprising a polymer according to claim 30 .
32. A method of making a polymer, said method comprising:
combining a borane and/or a carborane cage compound monomer with a reactive matrix to thereby form a polymerization reaction medium; and
subjecting said polymerization reaction medium to reaction conditions sufficient to polymerize at least a portion of said cage compound monomer with at least a portion of said reactive matrix,
wherein said cage compound monomer comprises at least one 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,
wherein said cage compound monomer comprises at least 7 cage atoms,
wherein said reactive matrix is selected from the group consisting of poly(ethylene-co-vinyl acetate-co-vinyl alcohol) (“EVA-OH”), silanol-terminated polydimethylsiloxane (“PDMS”), and mixtures thereof.