CATIONICALLY CURABLE BENZOXAZINE COMPOSITIONS
A curable composition is provided, which includes a benzoxazine component; and a cationic catalyst comprised of a lithium cation and an anion comprising a hexahalogenated Group 15 element.
1 . A curable composition comprising:
(a) a benzoxazine component; and
(b) a cationic catalyst comprised of a lithium cation and an anion comprising a hexahalogenated Group 15 element.
2 . The composition of claim 1 , wherein the hexahalogenated Group 15 element is selected from P, Sb or As.
3 . The composition of claim 1 , wherein the halogen of the hexahalogenated Group 15 element is selected from F, Cl, Br or I.
4 . The composition of claim 1 , wherein the composition demonstrates over 90 percent polymerization conversion.
5 . The composition of claim 1 , wherein the composition demonstrates over 93 percent polymerization conversion.
6 . The composition of claim 1 , wherein the composition demonstrates over 95 percent polymerization conversion.
7 . The composition of claim 1 , wherein the composition demonstrates over 98 percent polymerization conversion.
8 . The composition of claim 1 , wherein the benzoxazine component comprises one or more of
wherein o is 1-4, X is selected from the group consisting of a direct bond (when o is 2), alkyl (when o is 1), alkylene (when o is 2-4), carbonyl (when o is 2), thiol (when o is 1), thioether (when o is 2), sulfoxide (when o is 2), and sulfone (when o is 2), R 1 is selected from the group consisting of hydrogen, alkyl, and aryl, and R 4 is selected from hydrogen, halogen, alkyl, and alkenyl, or
wherein p is 1-4, Y is selected from the group consisting of biphenyl (when p is 2), diphenyl methane (when p is 2) and derivatives thereof, diphenyl isopropane (when p is 2), diphenyl sulfide (when p is 2), diphenyl sulfoxide (when p is 2), diphenyl sulfone (when p is 2), and diphenyl ketone (when p is 2), and R 4 is selected from the group consisting of hydrogen, halogen, alkyl and alkenyl.
9 . The composition of claim 1 , wherein the benzoxazine component comprises one or more of
wherein X is selected from the group consisting of a direct bond, CH 2 , C(CH 3 ) 2 , C═O, S, S═O and O═S═O, and R 1 , R 2 , R 3 and R 4 are the same or different and are selected from the group consisting of hydrogen, alkyl, alkenyl and aryl.
10 . The composition of claim 1 , wherein the benzoxazine component comprises one or more of
11 . The composition of claim 1 , further comprising a member selected from the group consisting of epoxy, episulfide, oxetane, acrylate, methacrylate, maleimide, and cyanate ester.
12 . The composition of claim 1 , further comprising a silica component.
13 . The composition of claim 12 , wherein the silica component is present in an amount between about 0.5 to about 80 percent by weight.
14 . The composition of claim 1 , further comprising a toughening agent.
15 . The composition of claim 14 , wherein the toughening agent is a core-shell rubber, a CTBN elastomer, or a block copolymer.
16 . The composition of claim 14 , wherein the toughening agent is present in an amount between about 2 to about 25 percent by weight.
17 . A catalyst composition comprising:
(a) a lithium salt, an anion of which has a conjugate acid with a pKa of less than 5; and
(b) a carboxylic acid, a sulfonic acid, or a combination thereof.
18 . The composition of claim 17 , wherein the acid in (b) has a pKa of 6 or less.
19 . The composition of claim 18 , wherein the anion in (a) is a hexahalogenated Group 15 element.
20 . The composition of claim 19 , wherein the hexahalogenated Group 15 element is selected from P, Sb or As.
21 . The composition of claim 19 , wherein the halogen of the hexahalogenated Group 15 element is selected from F, Cl, Br or I.
22 . The composition of claim 17 , wherein the lithium salt in (a) is lithium hexafluoroantimonate.
23 . The composition of claim 17 , wherein the acid in (b) is adipic acid.
24 . A catalyst composition comprising:
(a) a lithium salt, an anion of which has a conjugate acid with a pKa of less than 5; and
(b) a salt having as an anion a hexahalogenated Group 15 element.
25 . The composition of claim 24 , wherein the anion in (a) is a hexahalogenated Group 15 element.
26 . The composition of claim 24 , wherein the hexahalogenated Group 15 element is selected from P, Sb or As.
27 . The composition of claim 24 , wherein the halogen of the hexahalogenated Group 15 element is selected from F, Cl, Br or I.
28 . The composition of claim 24 , wherein the lithium salt in (a) is lithium hexafluoroantimonate.
29 . The composition of claim 24 , wherein the salt in (b) has as an anion hexafluorophosphate.
30 . The composition of claim 24 , wherein the salt in (b) has as a cation a tetraalkyl ammonium.
31 . A curable composition comprising:
(a) the catalyst composition of claim 17 ; and
(b) a benzoxazine component.
32 . The composition of claim 31 , further comprising a member selected from the group consisting of epoxy, episulfide, oxetane, acrylate, methacrylate, maleimide, and cyanate ester.
33 . The composition of claim 31 , wherein the composition demonstrates over 90 percent polymerization conversion.
34 . The composition of claim 31 , wherein the composition demonstrates over 93 percent polymerization conversion.
35 . The composition of claim 31 , wherein the composition demonstrates over 95 percent polymerization conversion.
36 . The composition of claim 31 , wherein the composition demonstrates over 98 percent polymerization conversion.
37 . A curable composition comprising:
(a) the catalyst composition of claim 24 ; and
(b) a benzoxazine component.
38 . The composition of claim 37 , further comprising a member selected from the group consisting of epoxy, episulfide, oxetane, acrylate, methacrylate, maleimide, and cyanate ester.
39 . The composition of claim 37 , wherein the composition demonstrates over 90 percent polymerization conversion.
40 . The composition of claim 37 , wherein the composition demonstrates over 93 percent polymerization conversion.
41 . The composition of claim 37 , wherein the composition demonstrates over 95 percent polymerization conversion.
42 . The composition of claim 37 , wherein the composition demonstrates over 98 percent polymerization conversion.
43 . The composition of claim 11 , wherein the epoxy is selected from the group consisting of glycidylated bisphenols (bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol E diglycidyl ether), glycidylated biphenyls, cycloaliphatic epoxy resins, glycidylated anilines and glycidylated hydroxyanilines.
44 . The composition of claim 32 , wherein the epoxy is selected from the group consisting of glycidylated bisphenols, glycidylated biphenyls, cycloaliphatic epoxy resins, glycidylated anilines and glycidylated hydroxyanilines.
45 . The composition of claim 38 , wherein the epoxy is selected from the group consisting of glycidylated bisphenols, glycidylated biphenyls, cycloaliphatic epoxy resins, glycidylated anilines and glycidylated hydroxyanilines.
46 . The catalyst of claim 17 , wherein the lithium salt is selected from lithium perchlorate, lithium tetrafluoroborate, lithium perchlorate, lithium carboxylates, lithium sulfonates, and combinations thereof.
47 . The catalyst of claim 46 , wherein the lithium salt is selected from lithium palmitate, lithium trifluoromethanesulfonate and combinations thereof.
48 . The catalyst of claim 24 , wherein the lithium salt is selected from lithium perchlorate, lithium tetrafluoroborate, lithium perchlorate, lithium carboxylates, lithium sulfonates, and combinations thereof.
49 . The catalyst of claim 48 , wherein the lithium salt is selected from lithium palmitate, lithium trifluoromethanesulfonate and combinations thereof.