US 20040097755A1

( 12) Patent Application Publication ( 10) Pub. N o. : US 2004/ 0097755 A1

( 19) United States
Abbott et al. ( 43 ) Pub. D ate: May 20, 2004
( 54) ION IC LIQUID S AN D THEIR USE AS
SOLVEN TS
( 76 ) Inv entor s : Andr ew P. Abbott, Leices ter ( G B ) ;
D av id L. D av ies , Leices ter ( G B ) ; G len
Capper , Ex m outh ( G B ) ; Raym ond K .
Ras h eed, B r am pton ( G B ) ; Vas uk i
Tam byr aj ah , D eh iW ala ( G B )
Cor r es pondence Addr es s :
J ones Tullar & Copper
Eads Station
PO B ox 226 6
Ar ling ton, VA 22202 ( US)
( 21) Appl. N o. : 10/ 3 8 1, 06 0
( 22) PCT F iled: Sep. 26 , 2001
( 8 6 ) PCT N o. : PCT/ G B 01/ 043 00
( 3 0) F or eig n Application Pr ior ity D ata
Sep. 27, 2000 ( G B ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0023 706 5
Publication Clas s i? cation
1 m . . . . . . . . . . . . . . . . . . . . . . . 7 55 ; c07c 229/ 06 ; 5 I c17 c0 c 2 / 24
c07c 211/ 6 3
( 52) US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 2/ 553 ; 56 2/ 6 05; 56 4/ 28 1
( 57) AB STRACT
Ionic com pounds W ith a f r eez ing point of up to 100 C. ar e
f or m ed by th e r eaction of an one am ine s alt of f or m ula ( I)
R1R2R3 R4N +X_, s uch as ch oline ch lor ide W ith an or g anic
com pound ( II) capable of f or m ing a h ydr og en bond W ith X;
s uch as ur ea, W h er ein th e m olar r ation of I to II is f r om 111. 5
to 1: 25. R1, R2, R3 and R4 m ay be H, optionally s ubs tituted
C1 to C5 alk yl, optionally s ubs tituted C6 to C10 cycloalk yl,
optionally s ubs tituted C6 to C12 ar yl, optionally s ubs tituted
C7 to C12 alk ar yl, or R1 and R2 tak en tog eth er m ay r epr es ent
a C4 to C10 optionally s ubs tituted alk ylene g r oup, th er eby
f or m ing W ith th e N atom of f or m ula I a 5 to ll-m em ber ed
h eter ocyclic r ing and all of R1, R2, R3 and R4 ar e not
identical, X m ay be N 03 , F , Cl, B r ' , I, B 13 4, C104,
CN , 503 C13 3 , or COOCF J . Th e ionic com pounds ar e
us ef ul as s olv ents , and electr olytes f or ex am ple in electr o
plating , electr oW inning , and electr opolis h ing , and as cata
lys ts .
US 2004/ 0097755 A1
ION IC LIQUID S AN D THEIR USE AS SOLVEN TS
[ 0001] Th is inv ention r elates to ionic com pounds and
m eth ods f or th eir pr epar ation. In par ticular th e inv ention
r elates to ionic com pounds W h ich ar e liq uid at r elativ ely loW
tem per atur es , i. e. g ener ally beloW about 100 C. , and pr ef
er ably beloW about 6 0 C. and m or e pr ef er ably W h ich ar e
liq uid at or near to am bient tem per atur e.
[ 0002] Th er e is m uch cur r ent inter es t in th e ? eld of ionic
liq uids . Such s ys tem s , W h ich ar e ex am ples of m olten s alts ,
h av e a num ber of inter es ting and us ef ul ch em ical pr oper ties ,
and h av e utility, f or ex am ple, as h ig h ly polar s olv ents f or us e
in pr epar ativ e ch em is tr y, and as catalys ts . Th ey als o h av e
par ticular application in electr och em is tr y, f or ex am ple in
batter ies , f uel cells , ph otov oltaic dev ices and electr odepo
s ition pr oces s es , f or ex am ple in bath s f or th e electr oplating
of m etals .
[ 0003 ] G ener ally s peak ing , ionic liq uids h av e v er y loW
v apour pr es s ur e and th us , in contr as t to m any conv entional
s olv ents , ar e v er y adv antag eous in th at th ey pr oduce v ir tu
ally no h aZ ar dous v apour s . Th ey ar e th er ef or e adv antag eous
f r om a h ealth , s af ety and env ir onm ental point of v ieW .
[ 0004] One s uch s ys tem W h ich h as been k noW n f or m any
year s is th at f or m ed f r om 1-eth yl-3 -m eth ylim idaZ olium
ch lor ide-alum inium ch lor ide ( EMIC-AlCl3 ) . Th is s ys tem is
a th er m ally s table liq uid betW een 100 C. to ca. 200 C. ,
dependent on th e m olar r atio of EMIC to AICl3 utilis ed.
[ 0005] Such EMIC-AlCl3 s ys tem s h av e been us ed ex ten
s iv ely as s olv ents f or v ar ious ionic r eactions and as electr o
lytes , as des cr ibed, f or ex am ple in US. Pat. N o. 5, 525, 56 7,
F R-A-26 11700, F R-A-26 26 572, W O95/ 218 72, and EP-A
8 3 8 447. Th er e ar e a num ber of dif f iculties in utilis ing s uch
com pounds . Th es e ar is e pr incipally f r om th eir cos t, and
f r om th eir W ater s ens itiv ity.
[ 0006 ] In r ecent year s , oth er ionic com pounds h av e been
m ade W h ich ar e liq uid at r elativ ely loW tem per atur es . F or
ex am ple, US. Pat. N o. 4, 76 4, 440 dis clos es loW tem per atur e
m olten com pos itions , f or m ed by r eacting , f or ex am ple,
tr im eth ylph enylam m onium ch lor ide W ith alum inium
tr ich lor ide. Th e r es ulting ionic com pound h as a loW f r eeZ ing
point ( ar ound 75 C. ) , but s uf f er s f r om th e s am e W ater
s ens itiv ity as EMIC-AlCl3 , becaus e of th e pr es ence of
alum inium tr ich lor ide.
[ 0007] Pr opos als h av e been m ade to utilis e oth er m etal
h alides , in place of alum inium tr ich lor ide. F or ex am ple, US.
Pat. N o. 5, 73 1, 101 dis clos es th e us e of ir on and Z inc h alides
as th e anion por tion of an ionic liq uid com pos ition. Th e
cation por tion is f or m ed by an am ine h ydr oh alide s alt, of th e
f or m ula R3 N . HX ( X= h alide) . Th is r ef er ence indicates h oW
ev er th at th e alum inium com pounds ar e pr ef er r ed.
[ 0008 ] PCT/ G B 00/ 01090 dis clos es ionic liq uids , f or m ed
by th e r eaction of q uater nar y am m onium com pounds s uch as
ch oline ch lor ide W ith h alides of Z inc, tin, or ir on.
[ 0009] SAITO, SHUJ I ET AL: Com plex es of ur ea and
s ym m etr ical tetr aalk ylam m onium h alides J . AM. CHEM.
SOC. ( 196 6 ) , 8 8 ( 22) , 5107-12 dis clos es com plex es of ur ea
and s ym m etr ical Tetr aalk ylam m onium h alides . Th e com
plex es ar e cr ys talline, and th er e is no dis clos ur e of th e us e
of as ym m etr ical am m onium com pounds , nor of th e us e of
liq uids f or m ed f r om s uch com plex es as s olv ents .
May 20, 2004
[ 0010] K OICHI TAN AK A ET AL: Molecular ag g r eg a
tion of alk yltr im eth ylam m onium br om ide and alcoh ol in th e
s olid s tate MOL. CRYST. LIQ. CRYST. , Vol. 277, 1996 ,
pag es 13 9-143 is concer ned W ith th e s epar ation of pr im ar y
alcoh ols f r om m ix tur es of pr im ar y and s econdar y alcoh ols ,
by com plex ation W ith q uater nar y am m onium br om ides W ith
an alk yl ch ain leng th of at leas t 10.
[ 0011] O. K RISTIAN SSON ET AL: Inter action betW een
m eth anol and Cl, B r , I, N 03 , C104-, SO3 CF 3 and
PF 6 Anions s tudied by F TIR s pectr os copy ACTA
CHEMICA SCAN D IN AVICA, v ol. 51, 1997, pag es 270
273 dis clos es com pounds f or m ed betW een q uater nar y
am m onium cations and m eth anol
[ 0012] K EIJ U SAW AD A ET AL: X-Ray analys es of
com plex es f or m ed betW een s ur f actants and ar om atic com
pounds . I. A com m on s tr uctur al patter n of com plex es
B ULLETIN OF THE CHEMICAL SOClETY OF J APAN . ,
Vol. 71, 1998 , pag es 2109-2118 dis clos es th e pr oduction of
v ar ious s olid m ater ials f r om q uater nar y am ines and a v ar iety
of ar om atic com pounds
[ 0013 ] N EG ITA ET AL: 14N N uclear q uadr opole r es o
nance of th e m olecular com plex es of ur ea B ULLETIN OF
THE CHEMICAL SOClETY OF J APAN . , Vol. 54, 198 1,
pag es 3 91-3 93 dis clos es s olid com plex es of ur ea W ith q ua
ter nar y am ines .
[ 0014] MASOOD A. K AHN : Hydr og en bonding and
cr ys tal pack ing tr ends in tetr aalk ylam m onium h alide-cat
ech ol com plex es : Synth es is , s pectr os copic and cr ys tal s tr uc
tur e s tudies of Me4N Cl-catech ol, Et4N C1-catech ol,
Et4N B r -catech h ol and Pr 4N B r -catech ol com plex es .
[ 0015] J OURN AL OF MOLECULAR STRUCTURE,
Vol. 145, 198 6 , pag es 203 -218 dis clos es cr ys talline com
pounds pr epar ed f r om s ym m etr ical am ines and catech ol
[ 0016 ] US. Pat. N o. 5, 73 1, 101 A ( LACROIX CHRIS
TIN E P M ET AL) 24 Mar . 1998 ( 1998 -03 -04) and
MASOOD A. K AHN ET AL: nov el h ydr og en bonding in
cr ys talline tetr a-n-butylam m onium s alts of catech ol h alides
CAN AD IAN J OURN AL OF CHEMISTRY, Vol. 6 3 , 198 5,
pag es 2119-2122 dis clos e loW tem per atur e ionic liq uid com
pos itions pr epar ed f r om alum inium tr ich lor ide and tr ieth y
lam ine
[ 0017] Q. LI; T. C. W . MAK : N ov el inclus ion com pounds
cons olidated by h os t-h os t and by h os t-g ues t h ydr og en bond
ing : com plex es of th iour ea W ith ( 2-h ydr ox yeth yl) tr im eth y
lam m onium car bonate and ox alate dis clos es s olid inclus ion
com pounds pr epar ed f r om th iour ea and q uater nar y am m o
nium com pounds .
[ 0018 ] W e h av e noW f ound th at it is pos s ible to f or m
com pounds W h ich ar e liq uid at tem per atur es of 100 C. or
beloW by r eacting an am ine s alt, pr ef er ably a q uater nar y
am ine s alt, W ith an or g anic m ater ial, pr ef er ably one W h ich is
a s olid at 20 C. , and W h ich is capable of f or m ing a h ydr og en
bond W ith th e anion of th e am ine s alt. Com pounds s uitable
f or f or m ing s uch h ydr og en bonds include am ides , s uch as
ur ea, th iour ea, and acetam ide, car box ylic acids s uch as
ox alic acid, benZ oic acid and citr ic acid, alcoh ols , ph enol,
and s ubs tituted ph enols , as W ell as s ug ar s s uch as f r uctos e.
Alth oug h it is not intended to be bound by any par ticular
th eor y of oper ation, it is believ ed th at h ydr og en bonding of
th e or g anic com pound W ith th e anion of th e am m onium
US 2004/ 0097755 A1
com pound allows ch ar g e delocalis ation, W h ich s tabilis es th e
liq uid f or m of th e com pound.
[ 0019] Accor ding to th e inv ention, th er e is pr ov ided an
ionic com pound, h av ing a f r eez ing point of up to 100 C.
pr ef er ably up to 6 0 C. , f or m ed by th e r eaction of at leas t
one am ine s alt of th e f or m ula
R1R2R3 R4 N *X ( I)
[ 0020] W ith at leas t one or g anic com pound ( II) W h ich is
pr ef er ably a s olid at 20 C. , and W h ich is capable of f or m ing
a h ydr og en bond W ith X,
[ 0021] W h er ein R1R2R3 and R4 ar e each independently:
[ 0022] H,
[ 0023 ] optionally s ubs tituted C1 to C5 alk yl,
[ 0024] optionally s ubs tituted C6 to C10 cycloalk yl,
[ 0025] optionally s ubs tituted C6 to C12 ar yl
[ 0026 ] optionally s ubs tituted C7 to C12 alk ar yl, or
W h er ein
[ 0027] R1 and R2 tak en tog eth er r epr es ent a C4 to
C10 optionally s ubs tituted alk ylene g r oup, th er eby
f or m ing W ith th e N atom of f or m ula I a 5 to
11-m em ber ed h eter ocyclic r ing , X is N 03 , F ,
Cl, B r , I, B F 4_, C104, CN , SO3 CF 3 _, or
COOCF 3 _, and W h er ein th e ter m optionally s ub
s tituted m eans th at th e g r oup in q ues tion m ay or
m ay not be s ubs tituted W ith at one or m or e g r oups
( pr ef er ably f r om 0 to 6 g r oups ) s elected f r om OH,
SH, SR5, Cl, B r , F , I, N H2, CN , N O2, COORS,
CHO, coR5 and CR5, W h er ein R5 is a c1 to C10
alk yl or cycloalk yl g r oup, and W h er ein th e m olar
r atio of I to II is f r om 111. 5 to 112. 5.
[ 0028 ] Com pound II is pr ef er ably a com pound of th e
f or m ula R COOH, R7R8 N H, RQCZ N HZ , or R1 OH,
W h er ein:
[ 0029] R6 , R7, R8 , R10 ar e each H, a Cl-C8 alk yl
g r oup, an ar yl g r oup, or a C7-C12 alk ar yl g r oup
optionally s ubs tituted W ith f r om 0 to 6 g r oups
s elected f r om OH, SR5, Cl, B r , F , I, N H2, CN , N O2,
COORS, coR5 and CR5, W h er ein R5 is H, a c1 to
C alk yl or cycloalk yl g r oup
10
003 0 R9 is a r ou as de? ned f or R , or N HRll, g p
W h er ein R11 is H or a Cl-C6 alk yl g r oup, and Z is O
or S.
[ 003 1] Pr ef er ably, Com pound II is ur ea, aniline, or a
s ubs tituted aniline, a Cl-C6 aliph atic acid, a Cl-C6 aliph atic
am ine, a Cl-C6 h ydr ox y aliph atic acid, or a dicar box ylic acid
of th e f or m ula HOOC( CH2) nCOOH, W h er ein n is 0 or 1
acetam ide, a ph enol or a s ubs tituted ph enol, an alk ylene
g lycol, or citr ic acid. Mos t pr ef er ably, com pound II is ur ea,
acetam ide, ox alic acid dih ydr ate, ph enol, eth ylene g lycol, or
citr ic acid.
[ 003 2] Th e Com pounds I and II ar e m ix ed in a m olar r atio
of f r om 1: 1. 5 to 112. 5, pr ef er ably about 1: 2. In g ener al, th e
am ine s alts ( I) us ed in th e pr epar ation of th e ionic com
pounds accor ding to th e inv ention ar e pr ef er ably as ym m et
r ic, i. e. , th e s ubs tituent g r oups ( R1, R2, R3 and R4) ar e
pr ef er ably not all identical.
May 20, 2004
[ 003 3 ] Th e pr ef er r ed am ine s alts of F or m ula I ar e th e s am e
as th os e W h ich ar e pr ef er r ed in PCT/ G B 00/ 01090, nam ely
ones W h er e R4 is a C1 to C10 alk yl or a cycloalk yl g r oup,
s ubs tituted W ith at leas t one g r oup s elected f r om OH, Cl, B r ,
F , I, N H3 , CN , N 02, 0R5, COORS, CH0, and CORS. It is
par ticular ly pr ef er r ed th at R4 is an eth yl g r oup, s ubs tituted
W ith one or m or e of h ydr ox yl, ch lor ine, or an es ter ( i. e. th at
th e s ubs tituent R4 is der iv ed f r om ch oline, ch lor och oline, or
a ch lor och oline es ter ) . Speci? c ex am ples of R4 g r oups
W h ich h av e been f ound to be s uitable ar e 2-h ydr ox yeth yl,
2-br om oeth yl, 2-ch lor oeth yl, 2-acetoeth yl, N -decyl, cyclo
h ex yl, 2-h ydr ox y 3 -ch lor opr opyl, and 3 -br om opr opyl. In a
f ur th er pr ef er r ed em bodim ent, th e am ine cation is ch ir al.
[ 003 4] Th e counter -ion X of com pound ( I) is pr ef er ably
h alide, f or ex am ple br om ide or ch lor ide.
[ 003 5] Th e ionic com pounds accor ding to th e inv ention
m ay be pr epar ed s im ply by m ix ing th e am ine s alt ( I) , W ith
th e h ydr og en bond donor ( II) . Th e r eaction is g ener ally
endoth er m ic, and is us ually car r ied out by h eating , f or
ex am ple to a tem per atur e of 100 C. or m or e.
[ 003 6 ] Th e ionic com pounds accor ding to th e inv ention
m ay be utilis ed f or a W ide r ang e of pur pos es , f or ex am ple as
electr olytes in electr och em ical dev ices s uch as batter ies or
f uel cells , in ph otov oltaic or electr och r om ic dev ices , and in
electr och em ical depos ition electr opolis h ing , or electr o-r e
? ning . Th e com pounds ? nd par ticular application f or car
r ying out applications W h er e a polar but non-aq ueous s ol
v ent is r eq uir ed. Th ey m ay als o be em ployed as iner t m edia,
f or dis s olv ing ionic s pecies s uch as tr ans ition m etal com
plex es , and, eith er alone, or af ter com plex ing W ith oth er
m etal ions , as catalys ts , or as ch em ical r eag ents . Th ey m ay
als o be us ed f or ex tr acting a s olute f r om an im m is cible
s olv ent.
[ 003 7] Th e ionic com pounds accor ding to th e inv ention
als o m ay be us ed as an alter nativ e to th e tr aditional m ix tur es
of s tr ong acids as s olv ents f or th e electr opolis h ing of m etals ,
f or ex am ple s tainles s s teel and alum inium . At leas t th e
pr ef er r ed com pounds accor ding to th e inv ention ar e m or e
env ir onm entally f r iendly th an th e tr aditional acid m ix tur es
us ed f or electr opolis h ing s tainles s s teel, as W ell as being
ch eap and r eus able. In addition th ey can r es ult in loW er
poW er cons um ption and r educed local env ir onm ental h aZ
ar ds in th e W or k place, f or ex am ple th os e caus ed by g as
ev olution s uch as m is ting of conv entional acid m ix tur es .
[ 003 8 ] A num ber of pr ef er r ed em bodim ents of th e inv en
tion ar e illus tr ated in th e f olloW ing ex am ples . Th e com po
s ition of all of th e pr oducts W as ch ar acter is ed us ing 1H N MR
s pectr os copy, and th eir ionic ch ar acter W as ch ar acter is ed by
conductiv ity m eas ur em ents , us ing a J enW ay 4071 conduc
tiv ity m eter and tem per atur e pr obe. All of th e com pounds
h ad an electr ical conductiv ity of at leas t 10 #5 cm ' 1 at 10
C. abov e th eir f r eeZ ing point. Th e s tar ting m ater ials us ed in
th e Ex am ples W er e all anh ydr ous m ater ials , and W er e dr ied
under v acuum f or 2 h our s pr ior to us e.
EXAMPLE 1
[ 003 9] Ch oline ch lor ide ( a q uater nar y am m onium com
pound of th e g ener al f or m ula I abov e, in W h ich R1, R2, and
R3 ar e m eth yl, R4 is C2H4OH, and X is Cl' ) 1. 40 g ( 0. 01
m ol) W as added to 1. 2 g of ur ea ( 0. 02 m ol) in a labor ator y
tes t tube. Th e m ix tur e W as h eated to a tem per atur e of 70 C.
US 2004/ 0097755 A1
f or a per iod of 20 m in, to pr oduce a clear colour les s liq uid.
Th e m elt W as allowed to cool at a r ate of appr ox im ately 1
C. per m inute, and th e tem per atur e r ecor ded at W h ich initial
cr ys tal f or m ation W as obs er v ed and r ecor ded as th e f r eez ing
point. ( F or all eutectic m ix tur es , com plete f r eez ing of th e
com pos ition tak es place at a tem per atur e m uch loW er th an
th at of initial cr ys tal f or m ation, but th e s olidi? cation is s loW ,
and in s om e cas es th e m ater ials can r em ain as g els f or
s ev er al days bef or e s olidi? cation) . Th e conductiv ity of th e
2: 1 Ur ea/ ch oline ch lor ide ionic liq uid at 19 C. W as 3 3 8 MS
cm _1. Th e f r eeZ ing point of th e m ix tur e W as 12 C.
EXAMPLES 2 TO 15
[ 0040] Th e pr ocedur e of Ex am ple 1 W as r epeated, us ing
0. 02 m ols of th e com pounds II identi? ed in Table 1, in
place of ur ea. Th e r es ults ar e s h oW n in Table 1. In each cas e,
th e h eating W as car r ied out until a clear m elt W as f or m ed,
and th e f r eeZ ing point W as th en deter m ined by th e ? r s t
appear ance of cr ys tal f or m ation, at a cooling r ate of 1 C. per
m inute.
TAB LE 1
Ex am ple N o Com pound II F r Pt. of Melt ( C. )
Am ides
1 Ur ea, N HZ CON H2 12
2 Acetam ide, CH3 CON H2 51
3 Th iour ea, N HZ CSN H2 6 9
4 Salicylam ide, oHOC6 H4CON H2 91
5 B enz am ide, CSHSCON H2 92
Car box ylic acids
6 G lyox ylic acid below 0
7 Malonic acid, HOOCCHZ COOH below 0
8 Ox alic acid, HOOCCOOH 48
9 B enz oic acid, C6 H5COOH 95
Alcoh ols
1O B enz yl alcoh ol, C6 H5CH2OH 6 1
11 Ph enol C6 H5OH 3 0
12 p Meth yl ph enol 10
13 o Meth yl ph enol 8
14 m Meth yl ph enol B eloW 3 5
15 p Ch lor o ph enol B eloW 3 5
16 D -F r uctos e 5
17 Vanilin p-HO r n OCH3 C6 H3 CHO 42
18 p Am ino ph enol 93
Am ines
19 Aniline 44
2O Hydr ox ylam ine h ydr och lor ide 8 1
[ 0041] In or der to dem ons tr ate th at th e f or m ation of th e
liq uid ionic com pound is th e r es ult of h ydr og en bonding
betW een Com pound II and th e ch lor ide anion, attem pts W er e
m ade to pr epar e s im ilar m ater ials us ing v ar ious oth er s tar t
ing m ater ials , us ing th e s am e pr ocedur e as Ex am ple 1. Th e
r es ults ar e s h oW n in Table 2, as Com par ativ e Ex am ples 1 to
8 .
[ 0042] In th e s am e m anner as des cr ibed in Ex am ple 1,
com pounds W er e pr epar ed f r om ch oline ch lor ide ( 0. 01
m oles ) and each of th e com pounds s h oW n in Table 1A ( 0. 02
m oles ) . Th e f r eeZ ing point of th e r es ulting com pound is
s h oW n in Table 1A
[ 0043 ] B y contr as t, th e s ubs tances indicated in Table 2A,
W h en s ubs tituted in th e s am e m olar q uantity f or th e ur ea of
May 20, 2004
Ex am ple 1 did not g iv e an ionic liq uid W ith a f r eeZ ing point
of 100 C. or les s .
TAB LE 2
Com p Ex . N o Com pound II F r Pt. of Melt ( C. )
Am ides
1 D im eth ylur ea, N HCH3 CON HCH3 149
Es ter s and Eth er s
2 Anis ole C6 H5OCH3 no m elt f or m ed.
3 4-Iodoanis ole no m elt f or m ed.
4 D ieth ylox alate ( CZ HSOOC) 2 no m elt f or m ed.
5 D ieth ylm alonate no m elt f or m ed.
Aldeh ydes and K etones
6 B enz yl m eth yl k etone no m elt f or m ed
Oth er
7 Hex ach lor oeth ane no m elt f or m ed.
8 Cycloh ex ane no m elt f or m ed
[ 0044]
TAB LE 1A
Com pound II F r Pt. of Melt ( C. )
Am ides
Allyl ur ea 9
Ur ea/ H2O2 com plex 19
Car box ylic acids
Tr i? uor oacetic acid B eloW 40
Tr ich lor oacetic acid 24
Citr ic acid 26
Mandelic acid 3 3
Valer ic acid 22
Tar tar ic acid 74
Ph enyl acetic acid 5
m -nitr obenz oic acid 8 5
p-h ydr ox ybenz oic acid 97
G lutam ic acid 13
m -am inobenz oic acid 3 9
Alcoh ols
Eth anediol 20
Tr ieth anolam ine 24
2-ch lor oeth anol 6
Vanillin 17
p-h ydr ox ybenz aldeh yde 29
Sug ar s
D ( ) F r uctos e 5
D -g lucos e 14
Am ines
D iam inoeth ane 29
1, 2-diam inopr opane 6 3
Mis c.
W ater 11
p-toluenes ulph onic acid m onoh ydr ate 27
D ibenz enes ulf onam ide 3 9
US 2004/ 0097755 A1
[ 0045]
TAB LE 2A
Com pound II F r Pt. of Melt ( C. )
Car box ylic acids
s alicylic acid 103
tr ans -cinnam ic acid 101
3 , 5-dinitr obenz oic acid 104
nicotinic acid 126
s tear ic acid no m elt f or m ed
h ippur ic acid no m elt f or m ed
oleic acid no m elt f or m ed
ter eph th alic acid no m elt f or m ed
Alcoh ols
9-Anth r acenem eth anol no m elt f or m ed.
Eth anol no m elt f or m ed.
Pr opan-2-ol no m elt f or m ed.
Mannitol 108
8 -h ydr ox yq uinoline no m elt f or m ed
2-m eth yl s alicylate no m elt f or m ed
2-ph enyl s alicylate no m elt f or m ed
Sug ar s
Lactos e no m elt f or m ed
Sacch ar in no m elt f or m ed
Am ines
Pyr idine no m elt f or m ed.
B enz yl am ine no m elt f or m ed.
tr ieth ylam ine no m elt f or m ed
Es ter s and eth er s
Eth yl cinnam ate no m elt f or m ed
Aldeh ydes and k etones
B enz aldeh yde no m elt f or m ed.
Am ino acids
G lycine no m elt f or m ed.
Alanine no m elt f or m ed.
Lys ine no m elt f or m ed
Ph enylalanine no m elt f or m ed
Mis c.
F er r ocene no m elt f or m ed.
Sar cos ine N o m elt f or m ed.
Tetr abutylam m onium h ydr og en s ulph ate 159
1, 2-dich lor oeth ane N o m elt f or m ed.
Ur ic acid N o m elt f or m ed
N itr oeth ane N o m elt f or m ed.
G lycer ol tr iacetate N o m elt f or m ed
[ 0046 ] Th e r es ults in Tables 1, 2, 1A and 2A dem ons tr ate
th at m any but not all com pounds wh ich ar e in pr inciple
capable of donating a h ydr og en atom to a h ydr og en bond ar e
capable of f or m ing ionic liq uids with ch oline ch lor ide, by
th e m eth od of Ex am ple 1. In g ener al, th e com pounds wh ich
ar e f or m th e m os t us ef ul ionic com pounds ( i. e. , th os e with
th e lowes t f r eez ing points ) ar e ones in wh ich th e Com
pound II em ployed h as a r elativ ely low f r eez ing point, f or
ex am ple, les s th an 150 C. , pr ef er ably les s th an 100 C. ,
m or e pr ef er ably les s th an 50 C. , and yet m or e wh ich h av e
a f r eez ing point of 20 C. , or les s ( i. e. , wh ich ar e s olid at
am bient tem per atur e) .
[ 0047] An additional f actor wh ich h as an im por tant bear
ing upon wh eth er a par ticular h ydr og en bond donor com
pound ( II) is capable of f or m ing an ionic liq uid h av ing a
f r eez ing point of 100 C. or les s is th e dif f er ence between th e
deg r ee of s tr uctur e of th e com pound in th e s olid and liq uid
s tates . Com pounds capable in pr inciple of f or m ing a h ydr o
May 20, 2004
g en bond, but in wh ich dif f er ence between th e deg r ee of
s tr uctur e in th e s olid and liq uid s tates is low ar e g ener ally
not pr ef er r ed. F or ex am ple long ch ain aliph atic acids wh ich
h av e a low f r eez ing point but a low deg r ee of s tr uctur e in th e
s olid s tate ar e g ener ally uns atis f actor y. Lik ewis e, com
pounds wh ich ar e h ig h ly or der ed in th e liq uid s tate ( s uch as
tr i? uor oaceticacid) ar e g ener ally f av our ed.
[ 0048 ] Yet a f ur th er f actor with im por tant bear ing upon
wh eth er a par ticular h ydr og en bond donor com pound ( II) is
capable of f or m ing an ionic liq uid h av ing a f r eez ing point of
100 C. or les s is th e pr es ence of dif f er ent types of f unctional
g r oups capable of acting as h ydr og en bond donor s . It is
s tr ong ly pr ef er r ed th at only one type of f unctional g r oup
capable of acting as h ydr og en bond donor is pr es ent in th e
com pounds II. F or Ex am ple, alth oug h two car box ylic acid
g r oups m ay be pr es ent, com pounds containing both a
COOH g r oup and an N H2 g r oup, ( am ino acids ) ar e g ener ally
not pr ef er r ed.
[ 0049] One of s k ill in th e ar t will g ener ally be capable of
s electing a s uitable h ydr og en bond donor f or th e pur pos es of
th e inv ention, bas ed on th e f or eg oing cr iter ia, and th e
s peci? c Ex am ples h er ein.
EXAMPLE 16
[ 0050] Th e ef f ect of ch ang ing th e natur e of th e anion X
was inv es tig ated, by r epeating th e pr ocedur e of Ex am ple 1,
us ing ch oline nitr ate, and ch oline tetr a? uor obor ate ( 0. 01
m ol) ins tead of ch oline ch lor ide, in th e pr ocedur e of
Ex am ple 1. Th e f r eez ing points of th e r es ulting com pounds
ar e s h own in Table 3 .
TAB LE 3
Ex am ple N o X' F r Pt. / C.
21 B R, 6 7
22 N 03 4
EXAMPLES 23 TO 41
[ 0051] Th e ef f ect was inv es tig ated of s ubs tituting v ar ious
oth er am ine s alts of F or m ula I, f or th e ch oline ch lor ide of
Ex am ple 1. In each cas e, 0. 01 m ol of th e am ine s alt, as
s h own in Table 4, was h eated with 0. 02 m ol of ur ea, until a
clear m elt was f or m ed. F r eez ing points wer e m eas ur ed by
cooling , as bef or e. Th e f r eez ing points ar e s h own in Table 4.
TAB LE 4
F r .
Ex . R1 R2 R3 R4 X Pt. / C.
1 Me Me Me C2H4OH Cl 12
23 Me Me B enz yl C2H4OH Cl 3 3
24 Me Me Et C2H4OH Cl 3 8
25 Me Me Me B enz yl Cl 26
26 Me Me Me C2H4OCOMe Cl 14
27 Me Me Me C2H4Cl Cl 15
28 Me Me Me ClCH2CHOHCH2 ( R) Cl 6 5
29 Me Me Me ClCH2CHOHCH2 ( S) Cl 8 3
3 0 Me H H H Cl 3 3
3 1 Me Me H H Cl 29
3 2 Et Et Et H Cl 95
3 3 Et Et Et B enz yl Cl 3 6
3 4 Me B enz yl C2H4OH C2H4OH Cl 6
3 5 Me H H CH2COOH Cl 3
US 2004/ 0097755 A1
TAB LE 4-continued
F r .
Ex . R1 R2 R3 R4 X Pt. / C.
3 6 Me Me Me B r C2H4 B r 8 4
3 7 Me Me Me C2H4F B r 55
3 8 Me Me Me Me( CH2) 11 B r 92
3 9 Et Et Et Me B r 9
4O Et Et Et B enz yl B F 4 59
41 Me Me C2H4OH C2H4OH I 46
COMPARATIVE EXAMPLES 9 TO 15
[ 0052] In th e s am e W ay, s alts of a s ym m etr ical am ine, as
W ell as oth er am ines of r elativ ely h ig h m olecular W eig h t
W er e inv es tig ated, th e r es ults ar e s h oW n in Table 5, as
com par ativ e ex am ples 9 to 12. Th es e r es ults dem ons tr ate
th at uns ym m etr ical am ine s alts ( R1R2R3 R4 ar e not all iden
tical) of r elativ ely loW m olecular W eig h t, ar e pr ef er r ed.
TAB LE 5
Com p R1 R2 R3 R4 x - c.
9 B u4N B u B u B u B u Cl 112
10 Me( CH2) 13 ( Me) 3 N Me Me Me Me( CH2) 13 B r no m elt
f or m ed
11 Me( CH2) 17( Me) 3 N Me Me Me Me( CH2) 17 B r no m elt
f or m ed
12 Hex ( Et) 3 N Et Et Et n-h ex yl B r 108
EXAMPLES 42 TO 44
[ 0053 ] Th e ef f ect of v ar ying th e anion X- W as inv es ti
g ated, us ing tetr aeth ylam m onium s alts of v ar ious anions , in
com bination W ith ur ea, in th e m eth od of Ex am ple 1. Th e
r es ults ar e s h oW n in Table 6 .
TAB LE 6
Ex am ple Com pound I cation X' F Pt. / C.
42 ( Et) 4N C104 99
43 ( Et) 4N O3 SCF 3 59
44 ( Et) 4N CN 72
Com p. 25 ( Et) 4N B R, 13 0
Com p 26 ( Et) 4N MeC6 H4SO3 107
Com p 27 ( Et) 4N B r 113
[ 0054] Com par is on of Ex am ple 21 W ith Com par ativ e
Ex am ple 25 illus tr ates br oadly th at as ym m etr ical am ines ar e
pr ef er r ed.
[ 0055] Mis cibility Tes ts
[ 0056 ] Th e m is cibility of th e m ater ial pr epar ed in
Ex am ple 1 W ith a num ber of com m on s olv ents W as inv es
tig ated. It W as f ound to be m is cible W ith m eth anol, D MSO,
and W ater , and to f or m tW o layer s W ith acetone, acetonitr ile,
acetoph enone, br om obenZ ene, dich lor oeth ane, dieth yleth er ,
eth ylacetate, h ex ane, pr opylene car bonate, and toluene.
W ith THE, a W h ite pr ecipitate W as f or m ed.
EXAMPLE 45
[ 0057] Us e of Ionic Liq uids as B atter y Electr olytes
[ 0058 ] LoW f r eez ing point ionic liq uids pr epar ed f r om
com pound II and am ine s alts can be us ed as electr olytes in
May 20, 2004
batter ies . TW o s uch ex am ples ar e des cr ibed beloW . In th e
? r s t, 7 m l of th e m ater ial of Ex am ple 1 ( 2: 1 ur ea-ch oline
ch lor ide) W as pr epar ed and pour ed into s epar ated com par t
m ents of a s m all g las s cell. Th e com par tm ents W er e s epa
r ated by g las s f r it and each contained 3 . 5 m l of ionic liq uid.
Th e cell W as s us pended in an oil bath s o th at th e liq uid
tem per atur e W as m aintained at 45 C. In one com par tm ent
0. 06 g of F eCl3 W as dis s olv ed and a car bon electr ode
ins er ted. A Z inc electr ode W as im m er s ed in th e liq uid con
tained in th e oth er com par tm ent. An Ecoch em ie PG s tat 10
potentios tat W as us ed to m eas ur e th e potential dif f er ence
betW een th e electr odes th e m ax im um r ecor ded v alue W as
1. 45V. Th e h alf cell r eactions f or th is batter y ar e;
Z n> Z n2*+2e ( neg ativ e electr ode)
[ 0059] In th e s econd ex am ple 7 m l of 2: 1 ur ea-ch oline
ch lor ide W as pr epar ed and div ided betW een th e tW o com
par tm ents of a g las s cell as bef or e. To one com par tm ent 0. 05
m l of B r 2 W as added and a car bon electr ode W as ins er ted. A
Z inc electr ode W as im m er s ed in th e liq uid contained in th e
oth er com par tm ent. Th e m ax im um v alue W as 2. 14V at 22
C. Th e h alf r eactions f or th is batter y ar e;
( pos itiv e electr ode)
Z n> Z n2++2e ( neg ativ e electr ode)
and,
1/ 2B r 2+e> B r ( pos itiv e electr ode)
EXAMPLE 46
D is s olution of Metal Ox ides
[ 006 0] An ionic liq uid W as pr epar ed by h eating tW o m olar
eq uiv alents of ur ea W ith one m olar eq uiv alent of ch oline
ch lor ide in a s uitable r eaction v es s el at appr ox im ately 70 C.
Ruth enium ox ide, copper ( II) ox ide, ch r om ium ( VI) ox ide,
v anadium pentox ide, lead ( IV) ox ide, m ang anes e ( IV) ox ide
and Z inc ox ide W er e all f ound to be s oluble in th e ionic
liq uid, in th e tem per atur e r ang e 6 0 C. to 120 C. N one of
th e ox ides of ir on or alum inium h av e s h oW n s ig ni? cant
s olubility in th e ionic liq uids and h ence th es e ionic liq uids
can be us ed to pr ef er entially ex tr act m etal ox ides f r om th eir
or es . Th e m etals can be ex tr acted f r om th e ionic liq uids
us ing electr oW inning .
[ 006 1] Th e 2: 1 ur ea-ch oline ch lor ide ionic liq uid can als o
be us ed to pr oces s com plex m ix tur es of m etal ox ides and
alloW electr oW inning to be us ed to r ecov er th e m etals . Th is
pr oper ty of th e ionic liq uid and its r elativ ely loW bulk cos t
g iv es it th e potential to be us ed to tr eat ar c f ur nace dus t on
an indus tr ial s cale. Electr ic ar c f ur nace dus t containing ir on
( III) ox ide ( > 3 0% ) , Z inc ox ide ( > 3 0% ) , alum inium ox ide
( ~ 10% ) , s ilica ( ~ 5% ) , calcium ox ide ( ~ 5% ) and lead com
pounds ( ~ 5% ) W as us ed in th is ex per im ent. N or m ally it is
tr eated as a W as te pr oduct and bur ied in land ? ll s ites .
HoW ev er th is is an ex pens iv e pr oces s and th e lead content
caus es com plications due to its h ig h tox icity.
[ 006 2] Z inc ox ide and lead com pounds can be dis s olv ed in
2: 1 ur ea-ch oline ch lor ide and th e r es pectiv e m etals s ubs e
q uently electr odepos ited onto a s uitable cath ode. Ox ides of
F e, Al, Si and Ca W er e f ound to be alm os t totally ins oluble
in th e abov e ionic liq uid. Ur ea-ch oline ch lor ide ionic liq uid
W as pr epar ed by com bining ur ea ( 0. 02 m oles ) W ith ch oline
ch lor ide ( 0. 01 m oles ) in a beak er and h eating at 8 0 C. Ar c
f ur nace dus t ( 0. 5 g ) W as added to th e r es ulting clear colour
les s liq uid and th e m ix tur e W as h eated at 8 0 C. f or 1 h our .
Af ter 1 h our a br oW n s us pens ion W as obtained W h ich W as
tr ans f er r ed to an electr och em ical cell. Metal electr odepos i
tion W as ach iev ed us ing a nick el cath ode and a titanium
US 2004/ 0097755 A1
anode ( both electr odes W er e 50 m m by 10 m m and 1 m m
th ick ) and applying a potential dif f er ence of 3 . 5 V f or 1 h our .
Pr ior to electr odepos ition th e electr odes W er e g ently abr aded
W ith g las s paper and cleaned W ith acetone. Af ter 1 h our of
electr odepos ition th e nick el cath ode W as r em ov ed f r om th e
br oW n s us pens ion, W as h ed W ith acetone and dr ied. A th ick
ch ar coal colour ed depos it W as obtained. Th e electr odepos
ited m ater ial W as analys ed us ing Ener g y D is per s iv e Analys is
by X-r ays . Th e r es ults of th e analys is r ev ealed th e pr es ence
of lead ( 77% ) , Z inc ( 16 % ) and copper ( 7% ) . Th er e W as no
tr ace of ir on in th e depos it th us s h oW ing th at Z inc ox ide and
ir on ( III) ox ide can be s epar ated and h ar m f ul lead com
pounds r em ov ed f r om ar c f ur nace dus t.
[ 006 3 ] D is s olution of Pr ecious Metal Ox ides
[ 006 4] Oth er com m er cially im por tant ox ides f or r epr o
ces s ing include pr oces s es f or th e r ecov er y of pr ecious
m etals , in par ticular platinum and palladium , f r om m ater ials
in W h ich th ey ar e pr es ent as ox ides . Such m ix tur es occur , f or
ex am ple, in s pent catalys t r ecov er ed f r om autom obile cata
lytic conv er ter s . It W ould be h ig h ly des ir able to be able to
r ecov er s uch m ater ials in a pr oces s W h ich is econom ically
v iable. G ener ally th e r ecov er y of s uch m etals f r om ox ide
m ix tur es inv olv es dis s olution of th e ox ide in s tr ong acids ,
s uch as aq ua r eg ia.
[ 006 5] W e h av e dis cov er ed th at th e ionic liq uids accor ding
to th e inv ention, and in par ticular th os e W h er e com pound II
is a car box ylic acid ( pr ef er ably ox alic acid) ar e ef f ectiv e
s olv ents f or th e dis s olution of platinum and palladium
ox ides . Th e dis s olv ed m etals m ay be r ecov er ed f r om s uch
s olutions by electr oW inning . F or ex am ple, palladium ox ide
( in th e f or m of s pent catalys t s uppor ted on v ar ious s ub
s tr ates ) can be dis s olv ed in th e 2: 1 ox alic acid-ch oline
ch lor ide ionic liq uid. In or der to ef f ect th e dis s olution, th e
tem per atur e is pr ef er ably m aintained beloW 6 0 C. Palla
dium m etal can s ubs eq uently be r ecov er ed by depos ition
onto a v ar iety of s ubs tr ates .
EXAMPLE 47
[ 006 6 ] An ionic liq uid W as f or m ed by m ix ing ox alic acid
( 17. 7 g ) and ch oline ch lor ide ( 9. 8 g ) at 6 0 C. To th is a
s am ple of autom obile catalys t W as added ( 3 . 16 g ) W h ich W as
pr incipally PdO on an alum ina s uppor t. A g r ey s us pens ion
W as initially f or m ed W h ich tur ned into a g r een s olution W h en
th e Pd dis s olv ed and th e s olid pr ecipitated to th e bas e of th e
cell. Th e s olution W as electr olys ed us ing a N i cath ode and a
titanium anode and an applied v oltag e of 5V f or 3 0 m in W ith
an appr ox im ate cur r ent dens ity of 1 m A cm _2. At th e end of
th is tim e a black depos it W as obtained on th e cath ode. Th is
W as analys ed us ing ener g y dis per s iv e analys is by x -r ays and
f ound to be pr im ar ily Pd m etal.
EXAMPLE 48
Metal Electr odepos ition
[ 006 7] Th e ionic liq uids als o ? nd application in m etal
electr odepos ition. Us ing , f or ex am ple a 2: 1 ur ea-ch oline
ch lor ide m ix tur e copper , nick el, lead and Z inc can be elec
tr odepos ited f r om th eir ch lor ide s alts and th is ? nds appli
cation in r epr oces s ing th e s aid m etals f r om indus tr ial W as te
pr oducts .
[ 006 8 ] F our por tions of 2: 1 ur ea-ch oline ch lor ide m ix tur e
( 0. 2 m ol ur ea and 0. 1 m ol ch oline ch lor ide) W er e pr epar ed
and h eated at 8 0 C. Th e pr epar ations W er e per f or m ed in
s am ple tubes . A s m all q uantity ( 0. 001 m ol) of a m etal
containing com pound ( eith er CuSO4. 5H2O, N iSO4. 6 H2O,
PbCl2 and Z nO) W as added to one s am ple of ionic liq uid and
May 20, 2004
lef t to dis s olv e. Electr odepos ition W as th en per f or m ed in
each ionic liq uid in tur n us ing Pt electr odes 3 m m in
diam eter polis h ed W ith 1 pm A1203 pas te. In each ex per i
m ent a potential dif f er ence of 3 V W as applied f or 10 m in and
th e tem per atur e W as m aintained at 8 0 C. F or each of th e
m etals , ch ar acter is tic depos its W er e obtained on th e neg ativ e
Pt electr ode.
[ 006 9] 2: 1 ur ea-ch oline ch lor ide ionic liq uid ( 16 m l) W as
pr epar ed by com bining th e r eactants in a beak er and h eating
at 8 0 C. Cobalt ( II) ch lor ide h ex ah ydr ate ( 1. 5% W t) W as
added to th e clear colour les s ionic liq uid and dis s olv ed to
g iv e a blue liq uid. Th e blue liq uid W as th en pour ed into a
PTF E electr och em ical cell of inter nal dim ens ions 41 m m
long , 16 m m W ide and 3 2 m m deep. A m ild s teel plate and
a s tainles s s teel plate, both 55 m m by 40 m m and 1 m m
th ick , W er e g ently abr aded W ith g las s paper , cleaned W ith
acetone and ? am e annealed. Th e s teel plates W er e th en
placed par allel to each oth er along th e inner leng th s of th e
PTF E electr och em ical cell. Cobalt depos ition W as ach iev ed
by connecting th e m ild s teel and s tainles s s teel plates to th e
neg ativ e and pos itiv e ter m inals r es pectiv ely of a Th ur lby
Th ander poW er pack . A potential W as applied and adj us ted
s o as to m aintain a cur r ent dens ity of 2 m Acm ' 2 f or 3 0
m inutes . An ISO-TECH ID M 6 6 D ig ital Voltm eter con
nected in s er ies W as us ed to m onitor th e cur r ent. Th e
ex per im ent W as car r ied out at 6 0 C. Af ter 3 0 m inutes th e
m ild s teel plate W as r em ov ed f r om th e cell, r ins ed W ith
acetone and dr ied. W ith a cur r ent dens ity of 2 m Acm ' 2 a
s em i-br ig h t pale g r ey/ br oW n h om og enous depos it W as
obtained.
[ 0070] A s epar ate por tion of 2: 1 ur ea-ch oline ch lor ide
ionic liq uid ( ~ 5 m l) containing cobalt ( II) ch lor ide h ex ah y
dr ate ( 1. 5% W t) W as pr epar ed and pour ed into an electr o
ch em ical cell at 6 0 C. Voltam m etr y W as per f or m ed us ing a
platinum m icr oelectr ode ( 10 pm diam eter ) , a platinum
counter electr ode and a cobalt r ef er ence electr ode. An Auto
lab PG STAT12 Potentios tat contr olled by G PES s of tW ar e
W as us ed to car r y out th e cyclic v oltam m etr y.
[ 0071] Reactions in Ionic Liq uids
[ 0072] Heck Reaction
1. 4 eq
X 5 m ol % Pd( OAc) 2,
1. 1 eq N aOAc
Ur ea: Ch oline
M6 0 ch lor 1de( 2: 1)
1 eq
OMe
x = 1, B r , c1
[ 0073 ] Th e r eaction betW een s tyr ene and 4-iodoanis ole in
th e pr es ence of Pd( OAc) 2 and N aOAc at 13 0 C. f or 2 days
US 2004/ 0097755 A1
g av e 4-Iodoanis ole W ith a 6 0% conv er s ion to th e pr oduct.
Us ing 4-B r om oanis ole g av e 50% conv er s ion to th e pr oduct
af ter 2 days under th e s am e r eaction conditions . 4-Ch lor o
anis ole did not r eact W ith s tyr ene under s im ilar conditions .
[ 0074] Us ing PdCl2 as th e catalys t th e r eaction is f as ter
g iv ing a 90% yield of th e s am e pr oduct in 1. 5 days .
[ 0075] W h en N aZ CO3 is us ed as th e bas e ins tead of
N aOAc W ith PdCl2 as th e catalys t, th e r eaction tim e
decr eas ed and yield im pr ov ed W ith 4-iodoanis ole g iv ing
pr oduct W ith 96 % yield in 16 h . Af ter r em ov al of th e pr oduct
by dis tillation, th e s am e m elt and PdCl2 catalys t ( W ith th e
addition of m or e N a2CO3 ) W as r eus ed f or th e s am e r eaction,
g iv ing pr oduct in 90% yield.
[ 0076 ] Polym er is ation Reactions in Ionic Liq uids
Ur ea: Ch oline ch lor ide( 2: 1)

110 c. , 16 h
( AIB N )
1 r nol %
polym er
[ 0077] Th is r eaction yielded a polym er W ith a num ber
av er ag e m olecular W eig h t of 12, 000 W ith a polydis per s ity
indeX of 3 . 2
AIB N Ur ea: Ch oline ch lor ide( 2: 1)
>
1m 01% 110 c. , 16 h
COOMe
polym er
[ 0078 ] Th is r eaction yielded a polym er W ith a num ber
av er ag e m olecular W eig h t of 12, 8 00 W ith a polydis per s ity
indeX of 3 . 2
[ 0079] Stainles s Steel Electr opolis h ing Us ing 2: 1 Ur ea
Ch oline Ch lor ide Ionic Liq uid
[ 008 0] Ur ea and ch oline ch lor ide in a m olar r atio of 2: 1
( 16 0 m l in total) W er e com bined in a beak er and h eated at
8 0 C. until a clear colour les s liq uid W as obtained. Th e ionic
liq uid W as th en pour ed into a cylindr ical electr och em ical
cell ( inter nal diam eter of 8 0 m m ) s us pended in an oil bath
at 6 0 C. A Z inc s h eet W as g ently abr aded us ing g las s paper ,
deg r eas ed W ith acetone, s h aped into a cylinder W ith a
diam eter of about 78 m m and s lid into th e electr och em ical
cell. Th e Z inc electr ode W as th en connected to th e neg ativ e
ter m inal of a Th ur lby Th ander poW er pack . A s tainles s s teel
collar , appr ox im ately 40 m m in diam eter , W as s us pended in
th e centr e of th e 2: 1 ur ea-ch oline ch lor ide ionic liq uid W ith
th e aid of a lead connected to th e pos itiv e ter m inal of th e
Th ur lby Th ander poW er pack . Apotential dif f er ence of 12 V
W as applied f or 6 m inutes af ter W h ich tim e th e s tainles s s teel
collar W as r em ov ed f r om th e ionic liq uid, r ins ed W ith
acetone and dr ied. Th e s tainles s s teel collar W as f ound to be
May 20, 2004
br ig h t and r e? ectiv e all ov er its s ur f ace. Th e pr ocedur e W as
r epeated us ing oth er s tainles s s teel collar s and s tainles s s teel
f as tener s of s im ilar dim ens ion and each tim e br ig h t r e? ec
tiv e ? nis h es W er e obtained.
[ 008 1] Stainles s Steel Electr opolis h ing Us ing 2: 1
Eth anediol-Ch oline Ch lor ide
[ 008 2] Eth anediol and ch oline ch lor ide in a m olar r atio of
2: 1 ( 20 m l) W er e com bined in a beak er and h eated at 8 0 C.
until a clear colour les s liq uid W as obtained. Th e ionic liq uid
W as th en pour ed into an alum inium electr och em ical cell
( inter nal leng th of 6 0 m m , inter nal W idth of 10 m m and
inter nal depth of 40 m m ) s us pended in an oil bath at 25 C.
Th e outer W all of th e alum inium cell W as connected to th e
neg ativ e ter m inal of a Th ur lby Th ander poW er pack . A
s tainles s s teel plate, 50 m m by 10 m m and 1 m m th ick , W as
deg r eas ed and s us pended in th e centr e of th e alum inium cell
W ith th e aid of a lead connected to th e pos itiv e ter m inal of
th e Th ur lby Th ander poW er pack . Apotential dif f er ence W as
applied and adj us ted s o as to m aintain a cur r ent dens ity
betW een 6 0 and 70 m Acm ' 2 at th e s tainles s s teel plate f or 6
m inutes . Af ter 6 m inutes th e s tainles s s teel plate W as
r em ov ed f r om th e 2: 1 eth anediol-ch oline ch lor ide ionic
liq uid, r ins ed W ith acetone and dr ied. Th e s tainles s s teel
plate W as f ound to be br ig h t and r e? ectiv e all ov er its
s ur f ace. Th e 2: 1 eth anediol-ch oline ch lor ide ionic liq uid can
be m odi? ed by th e addition of lith ium ch lor ide ( 5% W t) . Th e
incr eas ed ch lor ide content of th e ionic liq uid incr eas es th e
conductiv ity and th us loW er s th e poW er cons um ption dur ing
electr opolis h ing . Stainles s s teel polis h ed in 2: 1 eth anediol
ch oline ch lor ide containing lith ium ch lor ide is als o v er y
br ig h t and r e? ectiv e.
1. An ionic com pound, h av ing a f r eeZ ing point of up to
100 C. f or m ed by th e r eaction of at leas t one am ine s alt of
th e f or m ula
R1R2R3 R4 N *X ( I)
W ith at leas t one or g anic com pound ( II) W h ich is capable
of f or m ing a h ydr og en bond W ith X, W h er ein R1, R2,
R3 and R4 ar e each independently:
H,
optionally s ubs tituted C1 to C5 alk yl,
optionally s ubs tituted C6 to C10 cycloalk yl,
optionally s ubs tituted C6 to C12 ar yl
optionally s ubs tituted C7 to C12 alk ar yl, or W h er ein
R1 and R2 tak en tog eth er r epr es ent a C4 to C10 option
ally s ubs tituted alk ylene g r oup, th er eby f or m ing W ith
th e N atom of f or m ula I a 5 to 11-m em ber ed h et
er ocyclic r ing , X is N 03 , F , Cl, B r , I, B 13 4,
C104, CN , SO3 CF 3 _, or COOCF J , and W h er ein
th e ter m optionally s ubs tituted m eans th at th e
g r oup in q ues tion m ay or m ay not be s ubs tituted W ith
at one or m or e g r oups s elected f r om OH, SH, SR5,
Cl, B r , F , I, N H2, CN , N 02, COORS, CHO, coR5
and ORS, W h er ein R5 is a C1 to C10 alk yl or
cycloalk yl g r oup,
W h er ein th e m olar r atio of I to II is f r om 1: 1. 5 to 1: 2. 5.
2. An ionic com pound as claim ed in claim 1, W h er ein all
of R1, R2, R3 and R4 ar e not identical.
US 2004/ 0097755 A1
3 . An ionic com pound as claim ed in claim 1 or claim 2,
wh er ein com pound II is an or g anic com pound W h ich is s olid
at 20 C.
4. An ionic com pound as claim ed in any one of th e
pr eceding claim s , W h er ein com pound II is a com pound of
th e f or m ula R COOH, R7R8 N H, RQCZ N HZ , or R1 OH,
W h er ein:
R , R7, R8 , R10 ar e each H, a Cl-C8 alk yl g r oup, an ar yl
g r oup, or a C7-C12 alk ar yl g r oup optionally s ubs tituted
W ith f r om 0 to 6 g r oups s elected f r om OH, SR5, Cl, B r ,
F , I, N H2, CN , N 02, COORS, coR5 and CR5, W h er ein
R5 is H, a C1 to C10 alk yl or cycloalk yl g r oup
R9 is a Cl-C8 alk yl g r oup, Cl-C12 an ar yl g r oup, or a
C7-C12 alk ar yl g r oup optionally s ubs tituted W ith f r om 0
to 6 g r oups s elected f r om OH, SR5, Cl, B r , F , I, N H2,
CN , N 02, COORS, coR5 and CR5, W h er ein R5 is H, a
C1 to C10 alk yl or cycloalk yl g r oup, or N HRll, W h er ein
R11 is H or a Cl-C6 alk yl g r oup, and Z is O or S.
5. An ionic com pound as claim ed in claim 4, W h er ein
com pound II is ur ea, acetam ide, th iour ea, g lyoXylic acid,
m alonic acid, ox alic acid dih ydr ate, tr i? uor oacetic acid,
benz oic acid, benz yl alcoh ol, ph enol p-m eth yl ph enol, o-m e
th yl ph enol, m -m eth yl ph enol, p-ch lor o ph enol, D -f r uctos e,
or v anillin.
6 . An ionic com pound as claim ed in claim 4, W h er ein
com pound II is ur ea, aniline or a s ubs tituted aniline, a Cl-C6
aliph atic acid, a Cl-C6 h ydr oXyaliph atic acid or a dicar boXy
lic acid of th e f or m ula HOOC( CH2) nCOOH, W h er ein n is 0
or 1, acetam ide, a ph enol or a s ubs tituted ph enol, an alk ylene
g lycol, or citr ic acid.
7. An ionic com pound as claim ed in claim 4, W h er ein
com pound II is ur ea, acetam ide, oXalic acid dih ydr ate,
ph enol, eth ylene g lycol, or citr ic acid.
8 . An ionic com pound as claim ed in claim 1, W h er ein
Com pound II h as f r eez ing point of les s th an 16 0 C.
9. An ionic com pound as claim ed in claim 7, W h er ein
Com pound II h as a f r eez ing point of 20 C. or les s .
10. An ionic com pound as claim ed in claim 1, W h er ein
Com pound II contains only one type of f unctional g r oup
capable of acting as h ydr og en bond donor .
11. An ionic com pound as claim ed in claim 1, W h er ein th e
m olar r atio of I to II is about 1: 2.
12. An ionic com pound as claim ed in any one of th e
pr eceding claim s , W h er ein R4 is a C1 to C10 alk yl or a
cycloalk yl g r oup, s ubs tituted W ith at leas t one g r oup
s elected f r om OH, Cl, B r , F , I, N H2, CN , N O2, COORS,
CORS, CH0 and ORS, W h er ein R5 is as de? ned in claim 1.
13 . An ionic com pound as claim ed in any one of th e
pr eceding claim s , W h er ein each of R1, R2, R3 , independently
is a C1 to C5 alk yl or a cycloalk yl g r oup, and R4 is h ydr oXy
alk yl.
14. An ionic com pound as claim ed in claim 9, W h er ein
each of R1, R2, R3 , is m eth yl, and R4 is h ydr oXyeth yl.
15. An ionic com pound as claim ed in any one of th e
pr eceding claim s , W h er ein X is ch lor ide.
16 . An ionic com pound as claim ed in any one of th e
pr eceding claim s , W h er ein R1, R2, R3 , and R4 h av e th e
f olloW ing m eaning
May 20, 2004
Me Me Me C2H4OH
Me Me B enz C2H4OH
Me Me Et C2H4OH
Me Me Me B enz
Me Me Me C2H4OCOMe
Me Me Me C2H4Cl
Me Me Me CICHZ CHOHCH2 ( R)
Me Me Me CICHZ CHOHCH2 ( S)
Me H H H
Me Me H H
Et Et Et H
Et Et Et B enz
Me H H CH2COOH
Me Me Me Et
Me Me Me C2H4F
Me Me Me Me( CH2) 11
Et Et Et Me
Et Et Et B enz
17. An ionic com pound accor ding to any one of th e
pr ev ious claim s in W h ich th e am ine cation is ch ir al.
18 . A m eth od of pr epar ing an ionic com pound, h av ing a
f r eez ing point of up to 100 C. , W h ich m eth od com pr is es
r eacting at leas t one am ine s alt of th e f or m ula
R1R2R3 R4N *X ( I)
W ith at leas t one or g anic com pound ( II) W h ich is capable
of f or m ing a h ydr og en bond W ith X, W h er ein R1, R2,
R3 and R4 ar e each independently:
H,
optionally s ubs tituted C1 to C5 alk yl,
optionally s ubs tituted C6 to C10 cycloalk yl,
optionally s ubs tituted C6 to C12 ar yl
optionally s ubs tituted C7 to C12 alk ar yl, or W h er ein
R1 and R2 tak en tog eth er r epr es ent a C4 to C10 option
ally s ubs tituted alk ylene g r oup, th er eby f or m ing W ith
th e N atom of f or m ula I a 5 to 11-m em ber ed h et
er ocyclic r ing ,
X- is N 03 , F , Cl, B r , I, B F 4_, C104, CN ,
SO3 CF 3 _, or COOCF 3 _, and W h er ein th e ter m
optionally s ubs tituted m eans th at th e g r oup in
q ues tion m ay or m ay not be s ubs tituted W ith at one
or m or e g r oups s elected f r om OH, SH, SR5, Cl, B r ,
F , I, N H2, CN , N O2, COORS, CHO, COR5 and ORS,
W h er ein R5 is a C1 to C10 alk yl or cycloalk yl g r oup,
W h er ein th e m olar r atio of I to II is f r om 111. 5 to
112. 5 .
19. A m eth od as claim ed in claim 18 , W h er ein th e r eaction
is car r ied out by h eating th e com pound of f or m ula I W ith th e
com pound of f or m ula II
20. Th e us e of an ionic com pound accor ding to any of
claim s 1 to 17 as a s olv ent, as an electr olyte or as a catalys t.
21. A m eth od of r ecov er ing a m etal f r om a m etal oXide,
W h ich m eth od com pr is es f or m ing a s olution of th e m etal
oXide in an ionic liq uid as claim ed in any one of claim s 1 to
17, and electr olys ing th e s olution to r ecov er th e m etal.
22. A m eth od as claim ed in claim 17, W h er ein th e m etal
is platinum or palladium .
US 2004/ 0097755 A1 May 20, 2004
23 . A m eth od of electr opolis h ing a m etal ar ticle, W h ich optionally s ubs tituted C6 to C12 ar yl
m eth od com pr is es im m er s ing th e m etal ar ticle in an ionic
liq uid as claim ed in any one of claim s 1 to 17, and applying opnonany Subs m uted C7 to C12 alk ar yl or W h er em
a v oltag e to th e ar ticle to electr opolis h th e m etal. R1 and R2 tak en t0g eth er r epr es ent a C4 to C10 Option
24. A m eth od of f or m ing a s olution of a s olute, W h ich ally Subs tituted alk ylene g r oup, th er eby f or m ing W ith
m eth od com pr is es dis s olv ing th e s olute in an ionic com - th e N atOIIl 0f f Or IIlllla I a 5 t0 ll-m em ber ed h et
pound, h av ing a f r eeZ ing point of up to 100 C. f or m ed by er ocyclic r ing , X_ iS N 03 1 F , Cl_, B F , I_, B F 4T,
th e r eaction of at leas t one am ine s alt of th e f or m ula C1O4_, CN _, SO3 CF 3 _, 0r COOCF J , and W h ef eln
1 2 3 4 i th e ter m optionally s ubs tituted m eans th at th e
R R R R N *X ( I) . . . .
g r oup in q ues tion m ay or m ay not be s ubs tituted W ith
W ith at leas t one or g anic com pound ( II) W h ich is capable at one or m or e g r oups Selected f r om OH, SH, SR5,
of f or m ing a h ydr og en bond W ith X, W h er ein R1, R2, Cl, B r , 1: , I, N HZ , CN , N 02, COORS, CH0, COR5
R3 and R4 ar e each independent1y3 and 0R5, W h er ein R5 is a C1 to C10 alk yl or
H, cycloalk yl g r oup,
Optionally Subs tituted C1 to C5 alk yl, W h er ein th e m olar r atio of I to II is f r om 1: 15 to 112. 5 .
optionally s ubs tituted C6 to C10 cycloalk yl, * * * * *