Azinium salts as splayant for layered materials
View Patent ↗The present invention relates to a splayant, that is, an intercalant/exfoliant, comprising an azinium compound capable of splaying a layered material.
1. A splayed material comprising a layered material splayed with an azinium compound capable of splaying a layered material and represented by the following formula I:
wherein A and B independently represent a carbon, C—R 5 , C—R 6 or nitrogen;
X is independently O, N, S, C═O, C═S, O—C═O or R 7 —C—R 8 ; R 1 is an alkyl or aryl group; each of R 2 , R 3 , R 4 , R 6 , R 5 , R 7 , and R 8 is independently hydrogen, alkyl or an aryl group; and Y is a charge balancing anion, wherein Y is part of said A, B, or R groups.
2. The splayed material of claim 1 wherein said layered material comprises a clay.
3. The splayed material of claim 2 wherein said clay comprises smectite clay.
4. The splayed material of claim 2 wherein said clay comprises layered double hydroxide clay.
5. The splayed material of claim 1 wherein said layered material comprises a nonclay.
6. The splayed material of claim 1 further comprising a matrix polymer.
7. The splayed material of claim 6 wherein said matrix polymer is water soluble.
8. The splayed material of claim 7 wherein said water soluble matrix polymer is at least one member selected from the group consisting of gelatin, poly(vinyl alcohol), poly(ethylene oxide), polyvinylpyrrolidone, poly(acrylic acid), poly(styrene sulfonic acid), poly(acrylamide), and quaternized polymer.
9. The splayed material of claim 6 wherein said matrix polymer comprises polyester.
10. The splayed material of claim 6 wherein said matrix polymer is an aqueous emulsion of addition-type homopolymer or copolymer prepared from ethylenically unsaturated monomers.
11. The splayed material of claim 6 wherein said matrix polymer is selected from the group consisting of polyester, polycarbonate, epoxy resin, cellulose nitrate, cellulose acetate, poly(vinyl acetate), polystyrene, polyolefin, polyamide, polyurethane, polyacrylonitrile, poly(methyl methacrylate), and interpolymers thereof.
12. The splayed material of claim 1 wherein said A, B and R groups are able to join to form a ring.
13. The splayed material of claim 1 wherein said azinium compound is represented by the following formulas III and IV:
wherein R 1 is an alkyl or an aryl group;
R 10 or R 9 are independently a hydrogen atom, alkyl, aryl, heterocyclic, carboxylic, carboxylate, carbonamido, sulfonamido, nitryl, groups, —CO—R 11 wherein R 11 is an alkyl group or aryl group, or —(CH═CH) m —R 12 group wherein R 12 is an aryl or heterocyclic group and m is 1 or 2;
G is an alkylene group;
X is independently O, N, S, C═O, C═S, O—C═O or R 7 —C—R 8 ; and
R 7 , and R 8 are independently hydrogen, alkyl or an aryl group.
14. The splayed material of claim 13 wherein G is —(CH 2 ) n — wherein n is from 1 to 12.
15. The splayed material of claim 13 wherein X is O.
16. The splayed material of claim 13 wherein R 9 , R 10 , R 1 and G are:
R 10 or R 9
R 1 or G
R 10 = 4-Ph
R 1 = Me
R 10 = 4-Ph
R 1 = (CH 2 ) 3 —Ph
R 10 = 4-Ph
R 1 = (CH 2 ) 3 —SO 3 -
R 10 = 4-Ph
R 10 = 4-Ph
R 10 = 4-CN
R 1 = Me
R 10 = 3-CO 2 Me
R 1 = Me
R 10 = 3-CO 2 —(CH 2 ) 2 —Ph
R 1 = Me
R 9 = 4-Ph
G = (CH 2 ) 3
R 9 = 4-Ph
G = (CH 2 ) 4
R 9 = 4-Ph
G = (CH 2 ) 5
R 10 = 3-Ph
R 1 = Me
R 10 = 3,4-benzo
R 1 = Me
R 9 = 3,4-benzo
G = (CH 2 ) 3
R 10 = H
R 1 = (CH 2 ) 3 —SO 3 -
R 10 = H
R 1 = 4-nitrophenyl
R 9 = H
G = (CH 2 ) 2
R 9 = H
G = (CH 2 ) 3
R 10 = 2-Me
R 1 = Me
R 10 = 2-Me
R 1 = (CH 2 ) 3 —SO 3 -
R 10 = 4-Me
R 1 = Me
R 9 = 4-Me
G = (CH 2 ) 4
R 10 = 4-CO 2 -
R 1 = Me
R 10 = 4-CON(CH 2 CH 2 OH) 2
R 1 = (CH 2 ) 3 —SO 3 - .
17. The splayed material of claim 13 wherein R 9 , R 10 , R 1 and G are:
R 9 = 3,4-benzo
G = (CH 2 ) 3
R 10 = H
R 1 = (CH 2 ) 3 -SO 3 − .
18. The splayed material of claim 1 wherein said azinium compound is represented by the following formulae
I-1
I-2
I-3
I-4
I-5
I-6
I-7
I-8
I-9
I-10
I-11
I-12
I-13
I-14
I-15
I-16
19. A splayant comprising an azinium compound capable of splaying a layered material and represented by the following formula II:
wherein A represents a carbon, C—R 5 , nitrogen, sulfur or oxygen atom with sufficient bonds and substituents to form a 5-membered heteroaromatic ring and each R independently represents a hydrogen or a substituent;
X is independently O, N, S, C═O, C═S, O—C═O or R 7 —C—R 8 ; R 1 is an alkyl or aryl group; each of R 2 , R 3 , R 4 , R 7 , and R 8 is independently hydrogen, alkyl or an aryl group; and Y is a charge balancing anion.
20. The splayant of claim 19 wherein said any two or more R substituents are able to form a ring.
21. The splayant of claim 19 wherein Y is a separate moiety or part of an R group.
22. A splayed material comprising a layered material splayed with an azinium compound capable of splaying a layered material.
23. The splayed material of claim 22 wherein said layered material comprises a clay.
24. The splayed material of claim 23 wherein said clay comprises smectite clay.
25. The splayed material of claim 23 wherein said clay comprises layered double hydroxide clay.
26. The splayed material of claim 22 wherein said layered material comprises a nonclay.
27. The splayed material of claim 22 further comprising a matrix polymer.
28. The splayed material of claim 27 wherein said matrix polymer is water soluble.
29. The splayed material of claim 28 wherein said water soluble matrix polymer is at least one member selected from the group consisting of gelatin, poly(vinyl alcohol), poly(ethylene oxide), polyvinylpyrrolidone, poly(acrylic acid), poly(styrene sulfonic acid), poly(acrylamide), and quaternized polymer.
30. The splayed material of claim 27 wherein said matrix polymer comprises polyester.
31. The splayed material of claim 27 wherein said matrix polymer is an aqueous emulsion of addition-type homopolymer or copolymer prepared from ethylenically unsaturated monomers.
32. The splayed material of claim 27 wherein said matrix polymer is selected from the group consisting of polyester, polycarbonate, epoxy resin, cellulose nitrate, cellulose acetate, poly(vinyl acetate), polystyrene, polyolefin, polyamide, polyurethane, polyacrylonitrile, poly(methyl methacrylate), and interpolymers thereof.
33. The splayed material of claim 5 wherein said azinium compound is represented by the following formula II:
wherein A represents a carbon, C—R 5 , nitrogen, sulfur or oxygen atom with sufficient bonds and substituents to form a heteroaromatic ring and each R independently represents a hydrogen or a substituent;
X is independently O, N, S, C═O, C═S, O—C═O or R 7 —C—R 8 ; R 1 is an alkyl or aryl group; each of R 2 , R 3 , R 4 , R 7 , and R 8 is independently hydrogen, alkyl or an aryl group; and Y is a charge balancing anion.
34. The splayed material of claim 33 wherein said any two or more R substituents are able to form a ring.
35. The splayed material of claim 33 wherein Y is a separate moiety or part of an R group.