MARSAN BENOIT (CA)
HAMMAMI AMER (CA)
MARSAN BENOIT (CA)
| WO2006063441A1 | 2006-06-22 | |||
| WO2000035995A1 | 2000-06-22 | |||
| WO2001063683A2 | 2001-08-30 |
| CA1051143A | 1979-03-20 | |||
| CA2158487A1 | 1996-03-16 | |||
| US20050069780A1 | 2005-03-31 | |||
| CA2151770A1 | 1995-12-18 | |||
| CA2156502A1 | 1994-11-24 | |||
| US5371160A | 1994-12-06 | |||
| US3947526A | 1976-03-30 | |||
| CA1295219C | 1992-02-04 | |||
| CA2324963A1 | 1999-10-28 | |||
| CA2259919A1 | 1997-11-13 | |||
| CA2353617A1 | 2002-01-24 | |||
| CA2353378A1 | 2002-01-24 | |||
| US6025457A | 2000-02-15 | |||
| CA2507438A1 | 2004-10-14 |
| WHAT IS CLAIMED IS:
1. A polymer obtained by reacting together reactants comprising a compound of formula (I) and a compound of formula (VII) or a compound of formula (II) and a compound of formula (VIII):
Ri R3 R 4 R 6
V © x θ V© x θ
R 2 H (I) R5 H (II)
R 1 R 3 R 4 R 6
\ / \ /
N P
/
R 2 (VII) R 5 (VIII)
wherein
R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C12 cycloalkyl, C1-C12 heterocyclyl, C2-C8 alkenyl, C 2 -Cs alkynyl, C 6 -Ci 2 aryl, C 6 -C 2O aralkyl, C 6 -C 20 alkylaryl, Ci-Ci 2 heteroaryl,
or
R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 3 is a polymerizable moiety;
R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, Ci-Ci 2 alkyl which is linear or branched, C3-C12 cycloalkyl, CrC 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 2 O alkylaryl, Ci-Ci 2 heteroaryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CN;
or
R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 6 is a polymerizable moiety; and
X " is (FSO 2 ) 2 N-, (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CH 3 COO-, (CN) 2 N " , CN " , NO 3 " , HSO 4 ' , H 2 PO 3 -, PO 4 3" , F " , Cl " , Br " , I " , PF 6 " , BF 4 " , CIO 4 ' , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N-, or C 3 H 3 N 2 " ;
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , PO 4 3" , C n F 2n+1 , CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), C 6 HsCpH 2P -, C p H 2p+ iC 6 H 4 — , C p H 2p+ i C 6 H 4 C n H 2n -, CH 2 =CHCpH 2P -, CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2 p+i— ,
CH 2 =CHCpH 2p C 6 H 4 -, and a polymerizable moiety.
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
2. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Ia) and a compound of formula (Vila): R 7 R7
(Ia) (Vila)
wherein R 7 is a polymerizable moiety and X is as previously defined.
3. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Ib) and a compound of formula (VIIb):
(Ib) (VIIb)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
4. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Ic) and a compound of formula (VIIc):
(Ic) (VIIc)
wherein R 7 is a polymerizable moiety and X ' is as previously defined.
5. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Id) and a compound of formula (VIId):
R 7
H
( Id ) (VIId) wherein R >7 : is a polymerizable moiety and X " is as previously defined.
6. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Na) and a compound of formula (Villa):
(Ha) (Villa)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
7. The polymer of claim 1 , wherein said compound of formula (II) is a compound of formula (III) and said compound of formula (VIII) is a compound of formula (IX):
(III) (IX)
wherein
R 8 , R 9 and R 10 are same or different and each represent a polymerizable moiety; and
X " is as previously defined.
8. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
9. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
10. The polymer of claim 8 or 9, wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
11. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C4-C20 alkylcyclopropenyl, a C4-C20 cyclopropenylalkyl, an epoxide, a C3-C20 alkyloxirane, a C3-C20 oxiranealkyl, C2-C20 alkenyl, and C2-C20 alkynyl.
12. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C 2 -C 20 alkenyl, and C2-C20 alkynyl.
13. The polymer of any one of claims 2 to 6, wherein R 7 is vinyl.
14. The polymer of claim 7, wherein Rs, R9 and R-m, are a vinyl.
15. The polymer of any one of claims 1 to 14, wherein said reactants comprise a polymerization initiator.
16. The polymer of any one of claims 1 to 14, wherein said reactants comprise at least one other monomer.
17. The polymer of any one of claims 1 to 14, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, vinyl fluoride, chloro ethylene, fluoro ethylene, isobutadiene, vinyl sulfonic acid or salts thereof and mixtures thereof.
18. The polymer of any one of claims 1 to 14, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene, said additive being unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF 3 , -C 2 F 5 , -CN, -NO 3 " , -CrC 8 alkyl, phenyl and -SO 3 H or salts thereof.
19. A polymer obtained by polymerizing a compound of formula (I) or (II):
Ri R 3 R 4 R 6
V © x θ )/ © x θ
R 2 H (I) R 5 H (U)
wherein
R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C1 2 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrCi 2 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 o aralkyl, C6-C 20 alkylaryl, Ci-Ci 2 heteroaryl,
or
R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 3 is a polymerizable moiety;
R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C1 2 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, Ci-Ci 2 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C6-C12 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, C1-C12 heteroaryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CN;
or
R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 6 is a polymerizable moiety;
X- is (FSO 2 ) 2 N-, (CF 3 SO 2 ) 2 N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 " , CF 3 COO-, AsF 6 " , CH 3 COO-, (CN) 2 N-, CN " , NO 3 " , HSO 4 " , H 2 PO 3 " , PO 4 3" , F " , Cl " , Br " , I " , PF 6 " , BF 4 " , CIO 4 " , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N-, or C 3 H 3 N 2 " ;
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , PO 4 3" , C n F 2n+1 , Ci-Ci 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CeHsCpH 2P -, C p H 2p +iC 6 H 4 — , CpH 2P+ iC 6 H 4 C n H 2n — , CH 2 =CHCpH 2 p— , CH 2 =CHCeHs-, CH 2 =CHCeH 4 CpH 2P+ - I -,
CH 2 =CHCpH 2P C 6 H 4 -, and a polymerizable moiety.
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
20. The polymer of claim 19, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
21. The polymer of claim 19, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
22. The polymer of claim 20 or 21 , wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
23. The polymer of claim 19, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C 4 -C 2 O alkylcyclopropenyl, a C 4 -C 2 O cyclopropenylalkyl, an epoxide, a C3-C 2 o alkyloxirane, a C3-C 2 o oxiranealkyl, C 2 -C 2O alkenyl, and C 2 -C 2O alkynyl.
24. The polymer of claim 19, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C 2 -C 2O alkenyl, and C 2 -C 2 O alkynyl.
25. The polymer of any one of claims 19 to 24, wherein said reactants comprise a polymerization initiator.
26. The polymer of any one of claims 19 to 24, wherein said reactants comprise at least one other monomer.
27. The polymer of any one of claims 19 to 24, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, vinyl fluoride, chloro ethylene, fluoro ethylene, isobutadiene, vinyl sulfonic acid or salts thereof and mixtures thereof.
28. The polymer of any one of claims 19 to 24, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene, said additive being unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF 3 , -C 2 F 5 , -CN, -NO 3 " , -CrC 8 alkyl, phenyl and -SO 3 H or salts thereof.
29. The polymer of any one of claims 1 to 28, wherein X " is (FSO 2 ) 2 N " , (CF 3 SO 2 )2N-, (C 2 F 5 Sθ2) 2 N-, or (CN) 2 N-.
30. The polymer of any one of claims 1 to 28, wherein X ' is (CF 3 SO2)2N\
31. The polymer of any one of claims 1 to 28, wherein X- is (FSO 2 ) 2 N\
32. A compound of formula (I) or (II):
R 1 R 3 R4 R6
V © X θ )/© χ θ
R 2 H (I) R 5 H (II)
wherein
R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, CrC- I2 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C1-C1 2 heterocyclyl, C2-C8 alkenyl, C 2 -Cg alkynyl, C6-C12 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, C1-C12 heteroaryl,
or
R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 3 is a polymerizable moiety;
R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C-12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, Cβ-Ci 2 aryl, C6-C 20 aralkyl, C 6 -C2 0 alkylaryl, Ci-Ci 2 heteroaryl, C n H 2n+1 , Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CN; or
R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 6 is a polymerizable moiety; and
X- is (FSO 2 J 2 N " , (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N-, or (CN) 2 N " ;
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a CrCβ alkoxy, a C-i-Cε hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 , PO 4 3 , C n F 2n+I , CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+I , Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CeHsCpH 2P -, C p H 2p +iC 6 H 4 — , CpH 2P+ ICeH 4 C n H 2n -, CH 2 = CHCpH 2 p— , CH 2 =CHCeHs-, CH 2 = CHCeH 4 CpH 2 p + i— ,
CH 2 =CHC p H 2 pC 6 H4-, and a polymerizable moiety.
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
33. The compound of claim 32, wherein said compound is of formula (Ia):
(Ia)
wherein R 7 is a polymerizable moiety and X is as previously defined.
34. The compound of claim 32, wherein said compound is of formula (Ib):
(Ib)
wherein R 7 is a polymerizable moiety and X ' is as previously defined.
35. The compound of claim 32, wherein said compound is of formula (Ic):
(Ic)
wherein R 7 is a polymerizable moiety and X ' is as previously defined.
36. The compound of claim 32, wherein said compound is of formula (Id):
(Id)
37. The compound of claim 32, wherein said compound is of formula (Na):
(Iia)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
38. The compound of any one of claims 32 to 37, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
39. The compound of any one of claims 32 to 37, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
40. The compound of claim 38 or 39, wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
41. The compound of any one of claims 32 to 37, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C4-C20 alkylcyclopropenyl, a C4-C20 cyclopropenylalkyl, an epoxide, a C3-C20 alkyloxirane, a C3-C20 oxiranealkyl, C2-C20 alkenyl, and C2-C20 alkynyl.
42. The compound of any one of claims 32 to 37, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C2- C 2 O alkenyl, and C 2 -C 2 O alkynyl.
43. The compound of any one of claims 33 to 37, wherein R 7 is vinyl.
44. The compound of claim 32, wherein said compound is of formula (MIb):
(IHb) X
wherein X " is as previously defined.
45. The compound of any one of claims 32 to 44, wherein X " is (CF 3 SO 2 ) 2 N " .
46. The compound of any one of claims 32 to 44, wherein X " is (FSO 2 ) 2 N " .
47. A compound of formula (IV) or (V) or any tautomers thereof:
wherein
R 11 and R 12 are same or different and are chosen from a hydrogen atom, C1-C20 alkyl which is linear or branched, a C 3 -Cs cycloalkyl, a C 6 -Ci 2 aryl, C1-C12 heteroaryl, and a polymerizable moiety; and
X " is (FSOa) 2 N " , (CF 3 SO 2 ) 2 N " , (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C " , CF 3 SO 3 " , CF 3 COO " , AsF 6 -, CH 3 COO-, (CN) 2 N " , CN ' , NO 3 " , HSO 4 " , H 2 PO 3 " , PO 4 3" , F " , Cl " , Br " , I " , PF 6 " , BF 4 " , CIO 4 " , saccharin (o-benzoic sulfimide), (C 8 Hi 6 SO 2 ) 2 N " , or C 3 H 3 N 2 " ;
said alkyl, cycloalkyl, aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a d-C 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+ I, C-ι-C-12 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, C 6 HsCpH 2P -, CpH 2p +iC 6 H 4 -, C p H 2p +i C 6 H 4 C n H 2n -, CH 2 =CHCpH 2 p— , CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2p+ i— ,
CH 2 =CHC p H 2p C 6 H 4 -, and a polymerizable moiety;
n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
48. A compound of formula (Vl) or any tautomers thereof:
(Vl)
wherein
R 11 and R 12 are same or different and are chosen from a hydrogen atom, d-C 2 o alkyl which is linear or branched, a C 3 -C 8 cycloalkyl, a C 6 -C 12 aryl, C 1 -C-1 2 heteroaryl, and a polymerizable moiety; and
X- is (FSOs) 2 N-, (CF 3 SO 2 ) 2 N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 )SC-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CH 3 COO " , (CN) 2 N " , CN " , NO 3 " , HSO 4 " , H 2 PO 3 " , PO 4 3" , F ' , Cl " , Br " , r, PF 6 " , BF 4 " , CIO 4 " , saccharin(o-benzoic sulfimide), (C 8 Hi 6 SO 2 ) 2 N-, or C 3 H 3 N 2 " ,
m having a value of 1 , 2, or 3; and
said aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a CrC 6 alkoxy, a Ci-C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+ I, C1-C 12 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, C 6 H 5 CpH 2p -, CpH 2P+ IC 6 H 4 -, CpH 2P+I C 6 H 4 C n H 2n -, CH 2 =CHCpH 2P -, CH 2 =CHC 6 Hs-,
CH 2 =CHC 6 H 4 CpH 2P+I -, CH 2 =CHCpH2pC 6 H 4 - and a polymerizable moiety,
n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
49. The compound of claim 47 or 48, wherein R 11 and R 12 both represent an unsubstituted phenyl.
50. The compound of claim 47 or 48, wherein at least one of R 11 and R 12 represent a polymerizable moiety.
51. The compound of claim 50, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
52. The compound of claim 50, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
53. The compound of claim 51 or 52, wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
54. The compound of claim 50, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C4-C20 alkylcyclopropenyl, a C 4 -C 2 O cyclopropenylalkyl, an epoxide, a C3-C20 alkyloxirane, a C3-C20 oxiranealkyl, C2-C20 alkenyl, and C2-C20 alkynyl.
55. The compound of claim 50, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C 2 -C 2 O alkenyl, and C 2 -C 20 alkynyl.
56. A polymer obtained by polymerizing a compound as defined in any one of claims 32 to 46 and 50 to 55.
57. A polymer obtained by polymerizing a compound as defined in any one of claims 32 to 46 and 50 to 55 together with at least one other monomer.
58. Use of a compound as defined in any one of claims 32 to 46 as an antistatic agent.
59. Use of a compound as defined in any of claims 32 to 46 in the manufacture of a proton conducting membrane.
60. A method of using a compound as defined in any one of claims 32 to 46 and 50 to 55, comprising polymerizing said compound so as to obtain a polymer.
61. A method of using a compound as defined in any one of claims 32 to 46 and 50 to 55, comprising reacting said compound together with at least one other monomer so as to obtain a copolymer.
62. Use of a polymer as defined in any of claims 1 to 31 in the manufacture of a proton conducting membrane. |
IONIC COMPOUNDS HAVING BR0NSTED ACIDITY AND
USES THEREOF
TECHNICAL FIELD
The present invention relates to improvements in the field of electrochemistry. In particular, this invention relates to compounds that can be used for various purposes such as preparation of various polymers, proton exchange membranes for fuel cells, anti-static agents, static charge dissipators, or reversible switchable redox systems.
BACKGROUND OF THE INVENTION
Several manufacturers have undertaken the development of proton membrane fuel cells to power electric vehicles. However, improved membrane materials have to be developed to obtain high performance fuel cells and to overcome the main weakness of the existing materials. Traditional proton-conducting membranes (such as Nafion ® ), suffer from the volatility of water over 100 0 C and need to be hydrated continuously to transport protons. Such membranes are also very costly. It would therefore be desirable to be provided with some alternatives.
SUMMARY OF THE INVENTION
According to one aspect of the invention, there are provided compounds of formulas (I) or (II):
R 1 R 3 R 4 R 6 y ° _.θ y® J3
R2 X H (I) R 5 H (H)
wherein
R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C- 12 alkyl which is linear or
branched, C 3 -Ci 2 cycloalkyl, C-1-C12 heterocyclyl, C 2 -Cs alkenyl, C 2 -C 8 alkynyl, C 6 -Ci2 aryl, C 6 -C 20 aralkyl, C 6 -C2 0 alkylaryl, CrCi 2 heteroaryl,
or
R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 3 is a polymerizable moiety;
R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C- 12 alkyl which is linear or branched, C 3 -C-| 2 cycloalkyl, C 1 -C 12 heterocyclyl, C2-C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 20 alkylaryl, C1-C12 heteroaryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S) 1 Me 2 P(S), CN;
or
R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 6 is a polymerizable moiety;
X " is (FSOz) 2 N-, (CF 3 SO 2 ) 2 N-, (C 2 F 5 SOz) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CH 3 COO-, (CN) 2 N " , NO 3 ' , CN " , HSO 4 " , H 2 PO 3 " ,
PO 4 3" , F ' , CI " , Br " , I " , PF 6 " , BF 4 " , CIO 4 " , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N " , or C 3 H 3 N 2 " .
The alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I 1 a Ci-C 6 alkoxy, a Ci-C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , PO 4 3" , C n F 2n+I , Ci-Ci 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+I , Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), C 6 H 5 CpH 2P -, C p H 2p+1 C 6 H 4 - C p H 2P+I C 6 H 4 C n H 2n -, CH 2 =CHCpH 2 p— , CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2P+I -, CH 2 =CHC p H 2p C 6 H 4 -, and a polymerizable moiety; and
n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
According to another aspect of the invention, there are provided compounds of formula (III):
wherein
R 8 , R 9 and R 10 are same or different and are chosen from H, F, Cl, Br, I, OH, a d-C 6 alkoxy, a Ci-C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , PO 4 3" , C n F 2n+I , CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+I , Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), C 6 H 5 C p H 2 p- C p H 2p+ iC 6 H 4 - C p H 2p+ iC 6 H 4 C n H 2n — , CH 2 =CHC p H 2 p— , CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2p+ i— , CH 2 =CHC p H 2 pC 6 H 4 -, and a polymerizable moiety; and
X " is (FSO 2 ) 2 N " , (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N " , (CF 3 SO 2 ) 3 C " , CF 3 SO 3 " , CF 3 COO " , AsF 6 " , CH 3 COO " , (CN) 2 N " , NO 3 " , CN " , HSO 4 " , H 2 PO 3 " ,
PO 4 3" , F " , Cl " , Br " , I " , PF 6 " , BF 4 " , CIO 4 " , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 )2N " , or C 3 H 3 N 2 " .
n is an integer having a value from 0 to 48 and p is an integer having a value from 0 to 48.
According to another aspect of the invention, there are provided compounds of formula (IV) or (V) or any tautomers thereof:
X X
("V) (V)
wherein
R 11 and R 12 are same or different and are chosen from a hydrogen atom, C 1 -C 20 alkyl which is linear or branched, a C 3 -Ce cycloalkyl, a C 6 -Ci2 aryl and C1-C12 heteroaryl; and
X " is (FSOZ) 2 N " , (CF 3 SOZ) 2 N " , (C 2 F 5 SOZ) 2 N " , (CF 3 SO 2 ) 3 C " , CF 3 SO 3 " , CF 3 COO " , AsF 6 " , CH 3 COO " , (CN) 2 N " , NO 3 " , CN " , HSO 4 ' , H 2 PO 3 " , PO 4 3" , F " , Cl " , Br " , I " , PF 6 " , BF 4 " , CIO 4 " , saccharin (o-benzoic sulfimide), (C 8 Hi 6 SOz) 2 N " , or C 3 H 3 N 2 " .
The alkyl, cycloalkyl, aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a Ci-C 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+ I, C1-C 12 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, C 6 H 5 CpH 2p -, C p H 2p+ iC 6 H 4 -, CpH 2P+ IC 6 H 4 C n H 2n -, CH 2 =CHCpH 2P -, CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2p+ i— , CH 2 =CHCpH 2p C 6 H 4 -, and a polymerizable moiety.
n is an integer having a value from 0 to 48 and p is an integer having a value from 0 to 48.
According to another aspect of the invention, there are provided compounds of formula (Vl) or any tautomers thereof:
(Vl)
wherein
R 11 and R 12 are same or different and are chosen from a hydrogen atom, C 1 -C 20 alkyl which is linear or branched, a C3-C8 cycloalkyl, a C6-C 12 aryl and C 1 -C- 12 heteroaryl; and
X- is (FSOz) 2 N-, (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 " , CH 3 COO " , (CN) 2 N ' , NO 3 " , CN " , HSO 4 " , H 2 PO 3 " , PO 4 3" , F " , CI " , Br " , I " , PF 6 " , BF 4 " , CIO 4 -, saccharin(o-benzoic sulfimide), (C 8 Hi 6 SO 2 ) 2 N-, or C 3 H 3 N 2 " ,
m having a value of 1 , 2, or 3;
The aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a Ci-C 6
alkoxy, a Ci-C 6
hydroxy alkyl, NO 2
, CN, CF 3
, SO 3 "
, C n
F 2n
+i, C1-C12 alkyl which is linear or branched, C 6
-Ci 2
aryl, C n
H 2n
+i, C 6
H5C p
H 2p
— , C p
H 2p
+iC 6
H 4
— , C p
H 2p
+iC 6
H4CnH 2n
— , CH 2 =
CHC p
H 2p
— , C
n is an integer having a value from 0 to 48 and p is an integer having a value from 0 to 48.
According to another aspect of the invention, there are provided polymers obtained by reacting together reactants comprising a compound of formula (I) and a compound of formula (VII) or a compound of formula (II) and a compound of formula (VIII):
Ri R 3 R 4 R 6
V © X θ V© χ θ
L \ / \
R 2 H (I) R5 H (II)
R 1 R 3 R 4 R 6
\ / \ /
N P
/ /
R 2 cvin R 5 (VIII)
wherein
R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C12 alkyl which is linear or branched, C 3 -C12 cycloalkyl, C1-C12 heterocyclyl, C2-C 8 alkenyl, C 2 -Ce alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 20 alkylaryl, Ci-d 2 heteroaryl,
or
R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 3 is a polymerizable moiety;
R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C-1-C 12 alkyl which is linear or branched, C3-C12 cycloalkyl, Ci-C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -Ci2 aryl, Ce-C 20 aralkyl, Ce-C 20 alkylaryl, Ci-Ci 2 heteroaryl, C n H 2n +-!, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CN;
or
R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 6 is a polymerizable moiety;
X- is (FSO 2 ) 2 N-, (CF 3 SO 2 )2N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CHsCOO " , (CN) 2 N " , CN " , NO 3 " , HSO 4 " , H 2 PO 3 " , PO 4 3" , F " , Cl " , Br " , I " , PF 6 " , BF 4 " , CIO 4 " , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N-, or C 3 H 3 N 2 -;
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a Ci-C 6 alkoxy, a Ci-C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , PO 4 3" , C n F 2n+ I, C1-C12 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), C 6 H 5 CpH 2p -, C p H 2p+1 C 6 H 4 - CpH 2P+ IC 6 H 4 C n H 2n -, CH 2 =CHCpH 2p — , CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2 p + i— , CH 2 =CHC p H 2p C 6 H 4 -, and a polymerizable moiety,
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
It was found that by reacting the compounds of formula (I) and (II) with their respective unprotonated forms (compounds of formulas (VII) and (VIII)), very interesting polymers have been obtained. In particular, these polymers have been found to be very effective for proton exchange. The proton exchange is quite efficient since it occurs mainly between an acid (compounds of formula (I) or (II)) and its conjugated base (or unprotonated form) (compounds of formula (VII) or (VIII)).
According to another aspect of the invention, there are provided polymers obtained by polymerizing a compound of formula (I) or (II):
Ri R 3 R 4 R 6
V © x θ )P(® χ θ
R 2 H (I) R 5 H (H)
wherein
R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C-1-C1 2 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C-12 heterocyclyl, C2-C8 alkenyl, C 2 -Ce alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 20 alkylaryl, C1-C-12 heteroaryl,
or
R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 3 is a polymerizable moiety;
R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C12 cycloalkyl, C1-C12 heterocyclyl, C 2 -Cs alkenyl, C 2 -Cs alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C1-C12 heteroaryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CN;
or
R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R 6 is a polymerizable moiety;
X- is (FSO 2 ) 2 N-, (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CH 3 COO-, (CN) 2 N " , CN ' , NO 3 " , HSO 4 ' , H 2 PO 3 " , PO 4 3" , F " , Cl " , Br " , I " , PF 6 " , BF 4 " , CIO 4 " , saccharin(o-benzoic sulfimide), (C 8 Hi 6 SO 2 ) 2 N-, or C 3 H 3 N 2 " ;
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a Ci-C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , PO 4 3" , C n F 2n+ I, CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), C 6 H 5 CpH 2p -, CpH 2p+ iC 6 H 4 -, CpH 2P+ ICeH 4 C n H 2n -, CH 2 =CHCpH 2 p— , CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2 p + i— , CH 2 =CHCpH 2p C 6 H 4 -, and a polymerizable moiety,
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
The term "aryl" as used herein refers to a cyclic or polycyclic aromatic ring. Preferably, the aryl group is phenyl or napthyl.
The term "heteroaryl" as used herein refers to an aromatic cyclic or fused polycyclic ring system having at least one heteroatom selected from the group consisting of N, O, and S. Preferred heteroaryl groups are furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, and so on.
The term "heterocyclyl" includes non-aromatic rings or ring systems that contain at least one ring having at least one hetero atom (such as nitrogen, oxygen or sulfur). Preferably, this term includes all of the fully saturated and partially unsaturated derivatives of the above mentioned heteroaryl groups. Examples of heterocyclic groups include pyrrolidinyl, tetrahydrofuranyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, thiazolidinyl, isothiazolidinyl, and imidazolidinyl.
For example, the compound of formula (I) can be a compound of formula (Ia):
θ
(Ia)
wherein R 7 is a polymerizable moiety and X is as previously defined.
For example, the compound of formula (I) can be a compound of formula (Ib):
(Ib)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
For example, the compound of formula (I) can be a compound of formula (Ic):
(Ic)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
For example, the compound of formula (I) can be a compound of formula (Id):
(Id)
For example, the compound of formula (II) can be a compound of formula (Ha):
(Ha)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
For example, the compound of formula (III) can be a compound of formula (Ilia):
θ
(Ilia) X
wherein X " is as previously defined.
For example, the compound of formula (III) can be a compound of formula (1Mb):
wherein X ' is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ia) and a compound of formula (Vila):
(Ia) (Vila)
wherein R 7 is a polymerizable moiety and X is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ib) and a compound of formula (VIIb):
θ
R 7 -N^NH X R 7 -N^N
(Ib) (VIIb)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ic) and a compound of formula (VIIc):
(Ic) (VIIc)
wherein R 7 is a polymerizable moiety and X ' is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Id) and a compound of formula (VIId):
(Id) (VIId)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ma) and a compound of formula (Villa):
(Ha) (Vina)
wherein R 7 is a polymerizable moiety and X " is as previously defined.
For example, when preparing a polymer, the compound of formula (II) can be a compound of formula (III) and the compound of formula (VIII) can be a compound of formula (IX):
wherein
R 8 , R 9 and R 10 are same or different and each represent a polymerizable moiety; and
X " is as previously defined.
In one embodiment, R 7 , in the compounds and polymers of the present invention can be a C 2 -C 8 alkenyl such as vinyl or allyl.
In another embodiment, Rs, R 9 and Ri 0 , in the compounds and polymers of the present invention can be a C 2 -C 8 alkenyl such as vinyl or allyl.
In the compounds and polymers of the present invention, the polymerizable moiety can comprise at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound. For example, the polymerizable cyclic compound can be an epoxide, an aziridine, a cyclopropene, or a thiophene. For example, the polymerizable moiety can be chosen from a cyclopropenyl, a C 4 -C 2O alkylcyclopropenyl, a C 4 -C 2 O cyclopropenylalkyl, an epoxide, a C 3 -C 20 alkyloxirane, a C3-C 2 o oxiranealkyl, C2-C20 alkenyl, and C 2 -C 2 O alkynyl.
When preparing the polymers of the present invention, the reactants can comprise a polymerization initiator. The reactants can also comprise at least
one additive. For example, the at least one additive can be chosen from cross-linking agents, surfactants, spacers, and monomers. The additive can be a monomer chosen from chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, vinyl fluoride, chloro ethylene, fluoro ethylene, isobutadiene, vinyl sulfonic acid or salts thereof and mixtures thereof. Alternatively, the reactants can comprise an additive (monomer) chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene, said additive being unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF 3 , -C2F 5 , -CN, -NO 3 ' , -Cr Cs alkyl, phenyl and -SO 3 H or salts thereof.
For example, in the polymers and compounds of the present invention X " can be (FSO 2 ) 2 N-, (CF 3 SO 2 )2N-, (C 2 F 5 SOa) 2 N " , or (CN) 2 N-. Alternatively, X " can be (FSO 2 ) 2 N " or (CF 3 SO 2 J 2 N-. X can also be BF 4 " or PF 6 -.
R 11 and R 12 can both represent an unsubstituted phenyl. Alternatively, R 11 and R 12 represent a polymerizable moiety.
According to another aspect of the present invention there is provided a polymer obtained by polymerizing a compound as defined in the present invention.
According to another aspect of the present invention there is provided a polymer obtained by polymerizing a compound as defined in the present invention together with at least one other monomer.
According to another aspect of the present invention there is provided the use of a compound of the present invention as an antistatic agent.
According to another aspect of the present invention there is provided the use of a compound of the present invention in the manufacture of a proton conducting membrane.
According to another aspect of the present invention there is provided the use of a compound of the present invention in the manufacture of a polymer or copolymer.
According to another aspect of the present invention there is provided a method of using a compound as defined in the present invention, comprising polymerizing the compound so as to obtain a polymer.
According to another aspect of the present invention there is provided a method of using a compound as defined in the present invention, comprising reacting the compound together with at least one other monomer so as to obtain a copolymer.
According to another aspect of the present invention there is provided a composite material comprising at least one polymer as defined in the present invention and at least one other polymer. For example, the other polymer can be chosen from PVDF, HDPE, polybutadiene, polyisoprene, polyethylene, polypropylene, polyethylene oxide, and polyurethane.
According to another aspect of the present invention there is provided a method of using a polymer as defined in the present invention. The method comprises mixing the polymer with at least one other polymer in order to prepare a composite material. The other polymer can be one as previously discussed.
The person skilled in the art will understand that the compounds of the present invention can be copolymerized with various types of monomers. Such monomers can be chosen according to the desired properties of the polymer to be prepared. Non-limiting examples of such monomers are ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene. These monomers can be unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF 3 , -C 2 F 5 , -CN, -NO 3 " , -CrCs alkyl, phenyl and -SO 3 H or salts thereof. The compounds of the present invention can also be added as comonomers with monomers used for
preparing polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyvinylpyridines, polyvinylimidazoles, polyethylenes, polypropylenes, or polyethylenetherephtalates, PVC, or polyethyleneoxide. The compounds of the present invention, when used as anti-static agent, can be comprised within a matrix. The matrix can be a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a solvent, a textile, clothes, an ink, a wax, a cleaning composition, a softening composition or agent, a petroleum-based composition, a composition comprising volatile or flammable ingredients, molded objects, shaped articles, articles comprising a polymer, electronic devices (such as a computer, TV, DVD, CD player, etc.), static charge dissipators, proton exchange membranes for fuel cells, etc. The polymers of the present invention can also be used for similar purposes.
BRIEF DESCRIPTION OF DRAWINGS
In the following drawings, which represent by way of example only, various embodiments of the invention :
Fig. 1 is a graph showing the results obtained from a Differential Thermal Analysis (DTA) of an example of a polymer according to an embodiment;
Fig. 2 is a graph showing the results obtained from a Thermal Gravimetric Analysis (TGA) of the polymer analyzed in Fig. 1 ;
Fig. 3 is a graph showing the results obtained from a Differential Thermal Analysis (DTA) of an example of a polymer according to another embodiment;
Fig. 4 is a graph showing the results obtained from a Thermal Gravimetric Analysis (TGA) of the polymer analyzed in Fig. 3;
Fig. 5 is a plot showing the through-plan conductivity of examples of composite materials according to various embodiments;
Fig. 6 is another plot showing the through-plan conductivity of other examples of composite materials according to various embodiments; and
Fig. 7 is a plot showing the in-plan conductivity of examples of composite materials according to various embodiments.
DETAILLED DESCRIPTION OF THE INVENTION
Further features and advantages of the invention will become more readily apparent from the following description of non-limiting examples.
EXAMPLE 1
9.41 g (0.1 mol) of the 1-vinylimidazole 99+% was dissolved in 10OmL of distilled water and charged into a two-neck flask with magnetic stirrer. Hydrochloric acid (0.1 N) was slowly added into the flask until (pH = 0). Then, 30 mL of a solution of one equivalent of potassium bis(trifluoromethane sulfonimide) KTFSI in distilled water was added to the reaction mixture. A white precipitate was appearing (1-vinylimidazolium trifluoromethane sulfonimide). The ionic liquid was isolated by filtration, dissolved in 50 mL dichloromethane and extracted with 50 mL of distilled water. The organic layer was separated and dried with anhydrous MgSO 4 , the solvent was removed under vacuum and the desired product was oven dried at 4O 0 C under vacuum.
The structure was confirmed using 13 C, 1 H and IR
EXAMPLE 2
10.5 g (0.1 mol) of 4-vinylpyridine was dissolved in 100 mL of distilled water and charged into a two-neck flask with magnetic stirrer. Hydrochloric acid (0.1 N) was slowly added into the flask until (pH = 0). Then, 30 mL of a solution of one equivalent of KTFSI The ionic liquid obtained was isolated by filtration, dissolved in 50 mL dichloromethane and extracted with 50 mL of distilled water. The organic layer was separated and dried with anhydrous MgSO 4 , the solvent was removed under vacuum and the desired product was oven dried at 40°C under vacuum.
The structure was confirmed using 13 C, 1 H and IR
EXAMPLE 3
2.11 g (0.01 mol) of 1 ,3-diphenylguanidine was dissolved in 100 ml_ of anhydrous THF and charged into a two-neck flask with magnetic stirrer under argon. A solution of 2.81 g (0.01 mol) trifluoromethanesulfonimide in 5OmL of anhydrous THF was slowly added into the flask under argon. After ten minutes of stirring at room temperature, the solvent was removed under vacuum and the crude product was dissolved in 50 mL of CH 2 CI 2 and extracted with 3 times with 50 mL of distilled water. The organic layer was dried with a small amount of anhydrous MgSO4 and filtered off. The solvent was removed and the desired product obtained was dried under vacuum.
The structure was confirmed using 13 C, 1 H and IR
EXAMPLE 4 (Polymer A)
9.41 g (0.1 mol) of 1-vinylimidazole and 0.1 g AIBN, as initiator, were dissolved in 200 mL of toluene and mixed with one equivalent of 1- vinylimidazolium trifluoromethane sulfonimide (as prepared in Example 1) and the mixture was polymerized at 65°C under argon for 72h. The ratio 1- vinylimidazole : 1-vinylimidazolium trifluoromethane sulfonimide was thus 1 : 1. Then, the polymer (PVIM (polyvinylimidazole)) was precipitated in acetone and filtered out and oven-dried at 45 0 C for 24h. Finally, the polymer was purified by dissolution in methanol and precipitation in acetone. This last step was repeated three times.
EXAMPLE 5 (Polymer B)
Another polymer was prepared by following the same general method as described in Example 4 but, with the exception that the ratio 1-vinylimidazole : 1-vinylimidazolium trifluoromethane sulfonimide was 1.5 : 1.
EXAMPLE 6
Some test have been carried on Polymers A & B. Table 1 resumes the properties of the obtained polymers.
Table 1. Properties of Polymers of Polymers A & B.
Other tests have been made on these polymers at it can be seen in Figs. 1 to 4 in order to determine the thermal properties of these polymers. In particular a Differential Thermal Analysis (DTA) (see Fig. 1) and a Thermal Gravimetric Analysis (TGA) (see Fig. 2) have been carried on Polymer A. Analogously, a Differential Thermal Analysis (DTA) (see Fig. 3) and a Thermal Gravimetric Analysis (TGA) (see Fig. 4) have been carried on Polymer B. As it can be seen from Figs. 1 to 4, Polymers A and B have similar degradation curves. There is an onset around 340 0 C and two main degradation peaks at 400 0 C and 440 0 C. It should be noted that these analyses (Figs. 1 to 4) have been carried out under an air atmosphere and at a rate of 10 0 C / minute.
EXAMPLE 7
Films have been made using Polymers A and B as previously described. In particular, films of composite materials have been made by preparing composite material by mixing Polymers A and B with other polymers such as poly(vinylidene fluoride) (PVDF) and high density polyethylene (HDPE). The Tables 2 to 5 list various composite materials that have been used for preparing the films. The films have been prepared by hot pressing powder mixtures described in Tables 2 to 5. The tests have showed that such mixtures can be hot pressed at a temperature of about 220 0 C.
Table 2. Composite materials comprising Polymer A and PVDF.
Table 3. Composite materials comprising Polymer A and HDPE.
Table 4. Composite materials comprising Polymer B and PVDF.
Table 5. Composite materials comprising Polymer B and HDPE.
It was observed that films made with HDPE generally have better mechanical properties than the films made with PVDF. Moreover, the films comprising HDPE showed a good flexibility.
EXAMPLE 8
Ionic conductivity of the films prepared from the composite materials 1 to 10 listed in Tables 2 to 5 has been measured in the plan of the film (in-plan measurement) and through the plan of the film (through-plan measurement). The through-plan measurements have been carried out in deionized water (Milli-Q™ : 18.2 Mω.cm) at a temperature of 23 0 C. Figs. 5 and 6 show the
through-plan conductivity values obtained for various films. Figs. 5 and 6 thus permit to compare the results obtained for the conductivity of various films made of composite materials 1 to 10 as compared to the conductivity of films made solely of Polymer A or Polymer B. Fig. 5 shows the results of composite materials 1, 2, 6 and 7 and Fig. 6 shows the results of composite materials 3, 4, 5, 8, 9, and 10. The through-plan conductivity of a film made of Polymer A was previously measured and was 1.8 x 10 "5 S/cm. The conductivity of a film made of Polymer B was previously measured and was 5.0 x 10 "5 S/cm. It can thus be seen that by mixing Polymers A or B with either PVDF or HDPE lowers the conductivity of one or two order of magnitude.
Some in-plan measurements have also been carried out on the films made with the composite materials 1 to 10 listed in Tables 2 to 5. The results are shown in Fig. 7 as well as in Table 6. In Fig. 7, the measurements have been carried out in deionized water (Milli-Q™ : 18.2 Mω.cm) at a temperature of 23 0 C. The dotted lines represent composite materials comprising HDPE and full lines represent composite material comprising PVDF.
Table 6. In-plan measurements of films made of various composite materials
In can thus be seen that all the in-plan conductivity values are in the order of magnitude of 1O -4 S/cm, which is quite encouraging for application in the field of membranes used in fuel cells. It can also be seen from Table 6 and Fig. 7 that conductivity increases with the concentration of Polymer A or B. It is easier to have a high content of Polymer A or B when using HDPE. Therefore, composite materials comprising HDPE have a higher conductivity. It was observed that varying the ratio 1-vinylimidazole : 1-vinylimidazolium trifluoromethane sulfonimide does not have a very important impact on the
results when using PVDF (see the difference between the results of composite materials comprising Polymer A and composite materials comprising Polymer B (composite materials 1 and 2 as compared to composite materials 6 and 7)). However, in the composite materials comprising HDPE, it seems that a higher ratio of 1-vinylimidazole (Polymer B) permits to obtain a significant increase of the conductivity (see results of composite materials 3, 4, and 5 as compared to composite materials 8, 9, and 10). The composite material 8 had an interesting conductivity of 5.3 x 10 "4 S/cm.
DTA, TGA, and conductivity measurements have been carried out at Industrial Materials Institute of the National Research Council of Canada at Boucherville, Quebec.
The person skilled in the art would clearly understand that the conductivity as well as the mechanical and physicochemical properties of the compounds and polymers previously mentioned can be modified or controlled by adding at least one additive. The at least one additive can be chosen from cross-linking agents, surfactants, spacers, and various other monomers. Various nanocomposite materials can also be prepared by mixing together the previously mentioned compounds and polymers with at least one other polymer.
While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims.