U.S. patent application number 12/363960 was filed with the patent office on 2010-02-04 for performance additives for improving the wetting properties of ionic liquids on solid surfaces.
Invention is credited to Bernd Gloeckler, Stefan Kempka, Peter Schwab, Matthias Seiler.
Application Number | 20100029519 12/363960 |
Document ID | / |
Family ID | 40380693 |
Filed Date | 2010-02-04 |
United States Patent
Application |
20100029519 |
Kind Code |
A1 |
Schwab; Peter ; et
al. |
February 4, 2010 |
PERFORMANCE ADDITIVES FOR IMPROVING THE WETTING PROPERTIES OF IONIC
LIQUIDS ON SOLID SURFACES
Abstract
Composition containing at least one ionic liquid and at least
one performance additive and if appropriate a solvent and/or of
further auxiliaries or additives and its use as wetting agent for
solid surfaces.
Inventors: |
Schwab; Peter; (Essen,
DE) ; Kempka; Stefan; (Essen, DE) ; Seiler;
Matthias; (Griesheim, DE) ; Gloeckler; Bernd;
(Rodenbach, DE) |
Correspondence
Address: |
FROMMER LAWRENCE & HAUG
745 FIFTH AVENUE- 10TH FL.
NEW YORK
NY
10151
US
|
Family ID: |
40380693 |
Appl. No.: |
12/363960 |
Filed: |
February 2, 2009 |
Current U.S.
Class: |
508/208 ;
508/110 |
Current CPC
Class: |
C11D 1/82 20130101; C10M
2215/042 20130101; C10M 2207/289 20130101; C11D 3/36 20130101; C10M
171/00 20130101; C10M 2209/104 20130101; C10N 2030/00 20130101;
C11D 3/30 20130101; C10M 2211/06 20130101; C10M 2215/206 20130101;
C10N 2020/077 20200501; H01G 9/2013 20130101; C10M 2209/108
20130101; C11D 1/62 20130101; C10M 2207/283 20130101; C10M 2219/044
20130101; C10M 169/04 20130101; C10M 2209/103 20130101; C11D 3/34
20130101; C10M 2223/06 20130101; C10M 2209/109 20130101; C11D 1/60
20130101; C10M 2215/221 20130101; C11D 11/0023 20130101; C11D 3/28
20130101; C23G 5/06 20130101; D21H 21/24 20130101; C10M 2223/047
20130101; C10M 2211/044 20130101; C10M 2215/08 20130101; C10M
2215/082 20130101; C10M 2207/021 20130101 |
Class at
Publication: |
508/208 ;
508/110 |
International
Class: |
C10M 139/04 20060101
C10M139/04; C10M 169/04 20060101 C10M169/04 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 5, 2008 |
DE |
102008007745.3 |
Claims
1. Composition for the lasting wetting of solid surfaces, which
comprises at least one ionic liquid and at least one performance
additive and, if appropriate, solvents and/or further auxiliaries
or additives.
2. Composition according to claim 1, characterized in that a
wetting agent or spreading agent is used as performance
additive.
3. Composition according to claim 2, characterized in that the
composition consists of a single phase.
4. Composition according to claim 3, characterized in that one or
more surfactants are used as performance additives.
5. Composition according to claim 4, characterized in that the
surfactant or surfactants is/are selected from the group consisting
of non-ionic surfactants, cationic surfactants, amphoteric
surfactants and perfluorinated surfactants, either alone or as
mixtures thereof.
6. Composition according to claim 5, characterized in that organic
solvents or water and/or mixtures thereof are used as solvents.
7. Composition according to claim 6, characterized in that the
solvent is an organic solvent.
8. Composition according to claim 5, characterized in that an
organomodified siloxane is used as non-ionic surfactant.
9. Composition according to claim 8, characterized in that the
organomodified siloxane is a polyether siloxane.
10. Composition according to claim 9, characterized in that
compounds of the general Formula (XVIII) ##STR00045## where the
radical R.sup.f can be the radical R.sup.1, where R.sup.1 is an
alkyl radical having from 1 to 16 carbon atoms or an aryl radical,
or R.sup.f is the radical R.sup.2 or R.sup.3, with the proviso that
at least one radical R.sup.f is the radical R.sup.2, where R.sup.2
and R.sup.3 are, independently of one another, polyether radicals
of the Formula (XIX)
(F).sub.q(O(C.sub.2H.sub.4-dR'.sub.dO).sub.m(C.sub.xH.sub.2xO).sub.rZ).su-
b.w (XIX) where d is from 1 to 3, m is >1, q is 0 or 1, x is
from 2 to 10, r is >1, w is from 1 to 4, F is a hydrocarbon
radical which may also be branched, R' is a hydrogen radical, a
monovalent hydrocarbon radical having from 1 to 18 carbon atoms, Z
is an H atom or a monovalent organic radical such as alkyl or alkyl
ester or aryl ester, and where, in Formula (XVIII) b is from 0 to
8, a is from 1 to 100 when b is from 6 to 8, a is from 1 to 200
when b is from 3 to 6, a is from 1 to 300 when b is from 0 to 3,
are used as polyether siloxane.
11. Composition according to claim 10, characterized in that the
composition consists of a single phase.
12. A method of wetting a solid surface by ionic liquids by
applying composition according to claim 11, characterized in that
the wetted area has a contact angle of at least 100 less than the
contact angle achieved by a composition without a performance
additive.
13. The method of claim 12, characterized in that the wetted area
is at least 30% greater than without additive.
14. The method of claim 13, characterized in that the surface is
composed of glass, of a metal or a metal alloy, of ceramic, of
paper, of semiconductors, of polymers, of stone or of leather.
Description
INCORPORATION BY REFERENCE
[0001] This application claims benefit under 35 U.S.C. 119(a) of
German patent application DE 102008007745.3, filed on 5 Feb.
2008.
[0002] Any foregoing applications, including German patent
application DE 102008007745.3, and all documents cited therein or
during their prosecution ("application cited documents") and all
documents cited or referenced in the application cited documents,
and all documents cited or referenced herein ("herein cited
documents"), and all documents cited or referenced in herein cited
documents, together with any manufacturer's instructions,
descriptions, product specifications, and product sheets for any
products mentioned herein or in any document incorporated by
reference herein, are hereby incorporated herein by reference, and
may be employed in the practice of the invention.
FIELD OF THE INVENTION
[0003] The invention relates to improving the wetting properties of
ionic liquids on solid surfaces.
BACKGROUND
[0004] Ionic liquids are used and have been proposed for numerous
applications in which the wetting of solid surfaces plays an
important role. Examples of such applications are use as lubricant
and in separation processes, in particular distillative separation
processes. Ionic liquids often have an unsatisfactory wetting and
spreading behavior and therefore prove to be unsuitable despite an
excellent property profile because of this deficiency.
[0005] It is therefore an object of the invention to control the
wetting and spreading behavior of ionic liquids effectively and
thus make them universally and lastingly useable for applications
in which solid surfaces have to be wetted. The correct wetting
properties of the liquids can substantially improve performance in
the application.
OBJECT OF THE INVENTION
[0006] It has now surprisingly been found that additives which have
formerly been employed exclusively in aqueous systems achieve the
object of controlling the wetting and spreading behavior of ionic
liquids.
[0007] One object of the invention is a composition which comprise
from 50 to 99.999% by weight, preferably from 80 to 99.999% by
weight, in particular at least 95% by weight and particularly
preferably from >98 to 99.999% by weight, of one or more ionic
liquids,
and from 0 to 20% by weight, preferably from 0 to 10% by weight and
particularly preferably from 0 to 5% by weight, of solvents, and
from 0 to 20% by weight, preferably from 0 to 10% by weight and
particularly preferably from 0 to 5% by weight, of auxiliaries and
additives, and from 0.001 to 10% by weight, preferably from 0.001
to 5% by weight and particularly preferably from 0.05 to 1% by
weight, of one or more performance additives according to the
invention, where the sum of all components of the composition is
100% by weight.
[0008] In another embodiment of the invention, the amount of
solvents, auxiliaries and/or additives is present in the
composition in an amount of at least 0.01% by weight.
[0009] However, in the case of the present invention, the ionic
liquid itself is present in a very high concentration and should be
optimized in terms of its performance in, for example, lubrication
by means of a performance additive.
[0010] In contrast to cleaners which surface-actively promote
wetting (temporary wetting prevailing during the cleaning process)
of a surface, spreading is not necessarily an advantage with regard
to cleaning.
[0011] In addition, only brief contact with the surface to be
cleaned occurs in cleaning applications, while in the case of the
applications according to the invention lasting or periodically
recurring, regular use on the surface occurs. For example, when
used in a gearbox, wetting with ionic liquids takes place for at
least 95% of the time for which the gearbox is used; conversely,
for example, periodic use is ensured when the heat-exchange surface
in a falling film distillation process is repeatedly wetted with a
thin layer of the ionic liquid, which leads to the spreading action
of the ionic liquid and thus contributes to the advantageous effect
according to the invention.
[0012] This clearly shows that a brief rinse-off application is not
relevant to the invention, but instead a very long-lasting leave-on
application is desired. Overall, the surface should always or at
least mostly be wetted and remain wetted by the ionic liquid and
the surface tension should not be reduced only briefly as in
cleaning applications.
[0013] In the cleaning applications which are not subject matter of
the invention, the water or solvent concentration is normally also
of importance in addition to the ionic liquid.
[0014] In the case of the performance additives of the invention,
it is advantageous if high spreading is associated with good
wetting. This may once again be emphasized in contrast to cleaners
which are not according to the invention and which require high
wetting but do not offer good spreading in addition. In the case of
pure ionic liquids which are to be used as lubricants, film
formation on the surface to be lubricated is of critical
importance. If spreading is also very high, wetting of the surface
occurs with formation of a very thin film. This can reduce the
concentration of the wetting and spreading agent which is needed
and can save costs. In the case of distillative separation
processes, too, wetting and spreading of the material being
distilled on the evaporator surface is of critical importance. If
wetting/spreading is improved, then the liquid film on the
evaporator surface becomes thinner and the throughput can be
increased.
[0015] Ionic liquids are in general salts which melt at low
temperatures (<100.degree. C.) and represent a new class of
liquids made up exclusively of ions. In contrast to classical salt
melts, which are high-melting, highly viscous and very corrosive
media, ionic liquids are liquid and have a relatively low viscosity
even at low temperatures (K. R. Seddon J. Chem. Technol.
Biotechnol. 1997, 68, 351-356).
[0016] It is noted that in this disclosure and particularly in the
claims and/or paragraphs, terms such as "comprises", "comprised",
"comprising" and the like can have the meaning attributed to it in
U.S. Patent law; e.g., they can mean "includes", "included",
"including", and the like; and that terms such as "consisting
essentially of" and "consists essentially of" have the meaning
ascribed to them in U.S. Patent law, e.g., they allow for elements
not explicitly recited, but exclude elements that are found in the
prior art or that affect a basic or novel characteristic of the
invention.
[0017] It is further noted that the invention does not intend to
encompass within the scope of the invention any previously
disclosed product, process of making the product or method of using
the product, which meets the written description and enablement
requirements of the USPTO (35 U.S.C. 112, first paragraph) or the
EPO (Article 83 of the EPC), such that applicant(s) reserve the
right and hereby disclose a disclaimer of any previously described
product, method of making the product or process of using the
product.
DETAILED DESCRIPTION OF THE INVENTION
[0018] For the purposes of the present invention, ionic liquids are
salts of the general Formulae I, II or III:
[A].sub.n.sup.+[Y].sup.- (I)
where n is 1, 2, 3 or 4, [A].sup.+ is a quaternary ammonium cation,
an oxonium cation, a sulphonium cation or a phosphonium cation and
[Y].sup.n- is a monovalent, divalent, trivalent or tetravalent
anion; or mixed salts of the general Formulae (II)
[A.sup.1].sup.+[A.sup.2].sup.+[Y].sup.2- (IIa);
[A.sup.1].sup.+[A.sup.2].sup.+[A.sup.3].sup.+[Y].sup.3- (IIb);
or
[A.sup.1].sup.+[A.sup.2].sup.+[A.sup.3].sup.+[A.sup.4].sup.+[Y].sup.4-
(IIc),
where [A.sup.1].sup.+, [A.sup.2].sup.+ [A.sup.3].sup.+ and
[A.sup.4].sup.+ are selected independently from among the groups
mentioned for [A].sup.+ and [Y].sup.n- is as defined for Formula
(I); or mixed salts of the general Formulae (III)
[A.sup.1].sup.+[A.sup.2].sup.+[A.sup.3].sup.+[M.sup.1].sup.+[Y].sup.4-
(IIIa);
[A.sup.1].sup.+[A.sup.2].sup.+[M.sup.1]+[M.sup.2]+[Y].sup.4-
(IIIb);
[A.sup.1].sup.+[M.sup.1].sup.+[M.sup.2].sup.+[M.sup.3].sup.+[Y].sup.4-
(IIIc);
[A.sup.1].sup.+[A.sup.2].sup.+[M.sup.1].sup.+[Y].sup.3- (IIId);
[A.sup.1].sup.+[M.sup.1].sup.+[M.sup.2].sup.+[Y].sup.3- (IIIe);
[A.sup.1].sup.+[M.sup.1].sup.+[Y].sup.2- (IIIf);
[A.sup.1].sup.+[A.sup.2].sup.+[M.sup.4].sup.2+[Y].sup.4-
(IIIg);
[A.sup.1].sup.+[M.sup.1].sup.+[M.sup.4].sup.2+[Y].sup.4-
(IIIh);
[A.sup.1].sup.+[M.sup.5].sup.3+[Y].sup.4- (IIIi); or
[A.sup.1].sup.+[M.sup.4].sup.2+[Y].sup.3- (IIIj)
where [A.sup.1].sup.+, [A.sup.2].sup.+ and [A.sup.3].sup.+ are
selected independently from among the groups mentioned for
[A].sup.+, [Y].sup.n- is as defined for Formula (I) and
[M.sup.1].sup.+, [M.sup.2].sup.+, [M.sup.3].sup.+ are monovalent
metal cations, [M.sup.4].sup.2+ is a divalent metal cation and
[M.sup.5].sup.3+ is a trivalent metal cation; or mixtures of all
Formulae (I) to (III).
[0019] Ionic liquids comprise, for example, anions such as halides,
carboxylates, phosphates, thiocyanates, isothiocyanates,
dicyanamides, sulphates, alkylsulphates, sulphonates,
alkylsulphonates, tetrafluoroborate, hexafluorophosphate or
bis(trifluoromethylsulphonyl)imide combined with, for example,
substituted ammonium, phosphonium, pyridinium or imidazolium
cations, with the abovementioned anions and cations representing a
small selection from the large number of possible anions and
cations and no claim to completeness therefore being made or any
restriction being imposed.
[0020] The ionic liquids used according to the invention are
preferably composed of at least one quaternary nitrogen and/or
phosphorus compound and/or sulphur compound and at least one anion
and their melting points are below about +250.degree. C.,
preferably below about +150.degree. C., in particular below about
+100.degree. C. The ionic liquids used according to the invention
or mixtures thereof are particularly preferably liquid at room
temperature.
[0021] The ionic liquids which are preferably used for the purposes
of the invention can, for example, be composed of at least one
cation of the general formulae:
R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+ (IV)
R.sup.1R.sup.2N.sup.+.dbd.CR.sup.3R.sup.4 (V)
R.sup.1R.sup.2R.sup.3R.sup.4P.sup.+ (VI)
R.sup.1R.sup.2P.sup.+.dbd.CR.sup.3R.sup.4 (VII)
R.sup.1R.sup.2R.sup.3S.sup.+ (VIII)
where [0022] R.sup.1, R.sup.2, R.sup.3, R.sup.4 are identical or
different and are each hydrogen, a linear or branched aliphatic
hydrocarbon radical which has from 1 to 30 carbon atoms and may
contain double bonds, a cycloaliphatic hydrocarbon radical which
has from 5 to 40 carbon atoms and may contain double bonds, an
aromatic hydrocarbon radical having from 6 to 40 carbon atoms, an
alkylaryl radical having from 7 to 40 carbon atoms, a linear or
branched aliphatic hydrocarbon radical which has from 2 to 30
carbon atoms and is interrupted by one or more heteroatoms (oxygen,
NH, NR' where R' is a C.sub.1-C.sub.30-alkyl radical which may
contain double bonds, in particular --CH.sub.3) and may contain
double bonds, a linear or branched aliphatic hydrocarbon radical
which has from 2 to 30 carbon atoms and is interrupted by one or
more functions selected from the group consisting of --O--C(O)--,
--(O)C--O--, --NH--C(O)--, --(O)C--NH, --(CH.sub.3)N--C(O)--,
--(O)C--N(CH.sub.3)--, --S(O.sub.2)--O--, --O--S(O.sub.2)--,
--S(O.sub.2)--NH--, --NH--S(O.sub.2)--,
--S(O.sub.2)--N(CH.sub.3)--, --N(CH.sub.3)--S(O.sub.2)-- and may
contain double bonds, a linear or branched aliphatic or
cycloaliphatic hydrocarbon radical which has from 1 to 30 carbon
atoms and is functionalized terminally by OH, OR', NH.sub.2,
N(H)R', N(R').sub.2, where R' is a C.sub.1-C.sub.30-alkyl radical
which may contain double bonds, and may contain double bonds or a
polyether having a block or random structure of the formula
--(R.sup.5--O).sub.n--R.sup.6, [0023] where [0024] R.sup.5 is a
linear or branched hydrocarbon radical having from 2 to 4 carbon
atoms, [0025] n is from 1 to 100, preferably from 2 to 60, and
[0026] R.sup.6 is hydrogen, a linear or branched aliphatic
hydrocarbon radical which has from 1 to 30 carbon atoms and may
contain double bonds, a cycloaliphatic hydrocarbon radical which
has from 5 to 40 carbon atoms and may contain double bonds, an
aromatic hydrocarbon radical having from 6 to 40 carbon atoms, an
alkylaryl radical having from 7 to 40 carbon atoms or a
--C(O)--R.sup.7 radical where [0027] R.sup.7 is a linear or
branched aliphatic hydrocarbon radical which has from 1 to 30
carbon atoms and may contain double bonds, a cycloaliphatic
hydrocarbon radical which has from 5 to 40 carbon atoms and may
contain double bonds, an aromatic hydrocarbon radical having from 6
to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon
atoms.
[0028] Preference is given to quaternary ammonium salts of
alkylated fatty acids, also referred to as alkanolamine ester
quats, characterized by the generic formula of the type
R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+A.sup.- (IV) where R.sup.1 is an
alkyl radical having from 1 to 20 carbon atoms, R.sup.2 is an alkyl
radical having from 1 to 4 carbon atoms, R.sup.3 is a
(CH.sub.2CHRO).sub.n--H radical where n is from 1 to 200 and R is H
or CH.sub.3, R.sup.4 is an alkyl radical having from 1 to 4 carbon
atoms or a (CH.sub.2CHRO).sub.n--H radical where n is from 1 to 200
and R is H or CH.sub.3 and A.sup.- is a monovalent anion.
[0029] Among these compounds, preference is given to substances of
the formula
R.sup.6.sub.4-mN.sup.+[((CH.sub.2).sub.n-Q-R.sup.7].sub.mX.sup.-
(IX)
where: each radical R.sup.6 is independently an alkyl group or
hydroxyalkyl group having from 1 to 6 carbon atoms, or a benzyl
group, preferably a methyl group; the radicals R.sup.7 are each,
independently of one another, hydrogen, a linear or branched alkyl
group having from 11 to 22 carbon atoms, a linear or branched
alkenyl group having from 11 to 22 carbon atoms, with the proviso
that at least one radical R.sup.7 is not hydrogen; Q is selected
independently from among the groups of the formulae --O--CO)--,
--C(O)O, --NR.sup.8--C(O)--, --C(O)--NR.sup.8--, --O--C(O)--O,
--CHR.sup.9--O--C(O)-- or --CH(OCOR.sup.7)--CH.sub.2--O--C(O)--,
where R.sup.8 is hydrogen, methyl, ethyl, propyl or butyl and
R.sup.9 is hydrogen or methyl, and Q is preferably --O--C(O)-- or
--NH--C(O)--; m is from 1 to 4 and preferably 2 or 3; n is from 1
to 4 and preferably 2; and X is a plasticizer-compatible anion,
e.g. chloride, bromide, methylsulphate, ethylsulphate, sulphate or
nitrate, preferably chloride or methylsulphate. The quaternary
ammonium compounds can contain mixtures of the compounds which have
different groups R.sup.7 which are not hydrogen whose value extends
from 1 to m. Such mixtures preferably have an average of from 1.2
to 2.5 groups R.sup.7 which are not hydrogen. The proportion of
nonhydrogen groups R.sup.7 is preferably from 1.4 to 2.0 and more
preferably from 1.6 to 1.9. Preferred quaternary ammonium compounds
are the compounds of the type:
R.sup.6N.sup.+[CH.sub.2CHR.sup.9OH--][CH.sub.2CHR.sup.9OC(O)R.sup.7].sub-
.2X.sup.- (X)
R.sup.6N.sup.+[CH.sub.2CHR.sup.9OC(O)R.sup.7].sub.2X.sup.- (XI)
R.sup.6N.sup.+[CH.sub.2CHR.sup.9OH--][CH.sub.2CH.sub.2NHC(O)R.sup.7].sub-
.2X.sup.-, (XII)
where R.sup.6, R.sup.7 and X are as defined above for Formula (I),
with the proviso that R.sup.7 is not hydrogen.
[0030] The moiety --C(O)R.sup.7 is preferably a fat-containing acyl
group. Fat-containing acyl groups which can be used are derived
from natural sources of triglycerides, preferably tallow, vegetable
oils, partially hydrogenated tallow and partially hydrogenated
vegetable oils. Sources of triglycerides which can be used are
soybean oil, tallow, partially hydrogenated tallow, palm oil, palm
kernels, rapeseeds, lard, coconut, rape, safflower oil, maize, rice
and tall oil and mixtures of these components.
[0031] A person skilled in the art will know that the compositions
of the fatty acid-containing compounds are subject to certain
natural fluctuations, depending on harvest to harvest or on the
many vegetable oil sources. The R.sup.7 groups are usually mixtures
of linear and branched carbon chains of the saturated and
unsaturated aliphatic fatty acids.
[0032] The proportion of unsaturated groups R.sup.7 in such
mixtures is preferably at least 10%, particularly preferably at
least 25% and very particularly preferably from 40 to 70%. The
proportion of multiply unsaturated groups R.sup.7 in such mixtures
is less than 10%, preferably less than 5% and particularly
preferably less than 3%. If necessary, partial hydrogenation can be
carried out in order to increase the saturated character and thus
improve the stability (e.g. odour, colour, etc.) of the end
product. The content of unsaturated material, expressed by the
iodine number, should be in the range from 5 to 150 and preferably
in the range from 5 to 50. The ratio of cis and trans isomers of
the double bonds in the unsaturated groups R.sup.7 is preferably
greater than 1:1 and particularly preferably in the range from 4:1
to 50:1.
[0033] Preferred examples of compounds of the Formula (IX) are:
[0034] N,N-di(tallowyloxyethyl)-N,N-dimethylammonium chloride;
[0035] N,N-di(canolyloxyethyl)-N,N-dimethylammonium chloride;
[0036] N,N-di(tallowyloxyethyl)-N-methyl,N-(2-hydroxyethyl)ammonium
methylsulphate; [0037]
N,N-di(canolyloxyethyl)-N-methyl,N-(2-hydroxyethyl) ammonium
methylsulphate; [0038]
N,N-di(tallowylamidoethyl)-N-methyl,N-(2-hydroxyethyl) ammonium
methylsulphate; [0039]
N,N-di(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride;
[0040] N,N-di(2-canolyloxy-2-oxoethyl)-N,N-dimethylammonium
chloride; [0041]
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium
chloride; [0042]
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium
chloride; [0043]
N(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammoni-
um chloride; [0044]
N(2-canolyloxy-2-ethyl)-N(2-canolyloxy-2-oxoethyl)-N,N-dimethylammonium
chloride; [0045] N,N,N-tri(tallowyloxyethyl)-N-methylammonium
chloride; [0046] N,N,N-tri(canolyloxyethyl)-N-methylammonium
chloride; [0047] 1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropyl
chloride; and [0048]
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropyl chloride.
[0049] Further preferred quaternary ammonium salts are
ditallowedimethylammonium chloride, ditallowedimethylammonium
methylsulphate, dimethylammonium chloride of di(hydrogenated
tallow) distearyldimethylammonium chloride and
dibehenyldimethylammonium chloride.
[0050] Further possible cations are ions derived from saturated or
unsaturated cyclic compounds or from aromatic compounds having in
each case a trivalent nitrogen atom in a 4- to 10-membered,
preferably 5- or 6-membered, heterocyclic ring which may be
substituted. Such cations can be described in simplified form (i.e.
without indication of the precise position and number of the double
bonds in the molecule) by the general Formulae (XIII), (XIV) and
(XV), where the heterocyclic rings may, if appropriate, also
contain a plurality of heteroatoms.
##STR00001##
[0051] Here, R.sup.1 and R.sup.2 are as defined above, [0052]
R.sup.1 is a hydrogen atom, a linear or branched aliphatic
hydrocarbon radical which has from 1 to 30 carbon atoms and may
contain double bonds, a cycloaliphatic hydrocarbon radical which
has from 5 to 40 carbon atoms and may contain double bonds, an
aromatic hydrocarbon radical having from 6 to 40 carbon atoms or an
alkylaryl radical having from 7 to 40 carbon atoms. [0053] X is an
oxygen atom, a sulphur atom or a substituted nitrogen atom
(X.dbd.O, S, NR.sup.1).
[0054] Examples of cyclic nitrogen compounds of the abovementioned
type are pyrrolidine, dihydropyrrole, pyrrole, imidazoline,
oxazoline, oxazole, thiazoline, thiazole, isoxazole, isothiazole,
indole, carbazole, piperidine, pyridine, the isomeric picolines and
lutidines, quinoline and isoquinoline. The cyclic nitrogen
compounds of the general Formulae (XIII), (XIV) and (XV) can be
unsubstituted (R=H) or monosubstituted or polysubstituted by the
radical R, where in the case of polysubstitution by R, the
individual radicals R can be different.
[0055] Further possible cations are ions derived from saturated
acyclic, saturated or unsaturated cyclic compounds or from aromatic
compounds having in each case more than one trivalent nitrogen atom
in a 4- to 10-membered, preferably 5- or 6-membered, heterocyclic
ring. These compounds can be substituted either on the carbon atoms
or on the nitrogen atoms. They can also be fused to substituted or
unsubstituted benzene rings and/or cyclohexane rings to form
polycyclic structures. Examples of such compounds are pyrazole,
3,5-dimethylpyrazole, imidazole, benzimidazole, N-methylimidazole,
dihydropyrazole, pyrazolidine, pyridazine, pyrimidine, pyrazine,
2,3-, 2,5- and 2,6-dimethylpyrazine, cinnoline, phthalazine,
quinazoline, phenazine and piperazine. Cations derived from
imidazole and its alkyl and phenyl derivatives have been found to
be particularly useful as constituents of ionic liquids.
[0056] Possible cations also include ions which contain two
nitrogen atoms and are represented by the general Formula (XVI)
##STR00002##
where [0057] R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12 are
identical or different and are each hydrogen, a linear or branched
aliphatic hydrocarbon radical which has from 1 to 30 carbon atoms
and may contain double bonds, a cycloaliphatic hydrocarbon radical
which has from 5 to 40 carbon atoms and may contain double bonds,
an aromatic hydrocarbon radical having from 6 to 40 carbon atoms,
an alkylaryl radical having from 7 to 40 carbon atoms, a linear or
branched aliphatic hydrocarbon radical which has from 1 to 30
carbon atoms and is interrupted by one or more heteroatoms (oxygen,
NH, NR' where R' is a C.sub.1-C.sub.30-alkyl radical which may
contain double bonds) and may contain double bonds, a linear or
branched aliphatic hydrocarbon radical which has from 1 to 30
carbon atoms and is interrupted by one or more functions selected
from the group consisting of --O--C(O)--, --(O)C--O--,
--NH--C(O)--, --(O)C--NH, --(CH.sub.3)N--C(O)--,
--(O)C--N(CH.sub.3)--, --S(O.sub.2)--O--, --O--S(O.sub.2)--,
--S(O.sub.2)--NH--, --NH--S(O.sub.2)--,
--S(O.sub.2)--N(CH.sub.3)--, --N(CH.sub.3)--S(O.sub.2)-- and may
contain double bonds, a linear or branched aliphatic or
cycloaliphatic hydrocarbon radical which has from 1 to 30 carbon
atoms and is terminally functionalized by OH, OR', NH.sub.2,
N(H)R', N(R').sub.2 where R' is a C.sub.1-C.sub.30-alkyl radical
which may contain double bonds and may contain double bonds or a
polyether having a block or random structure corresponding to the
formula --(R.sup.5--O).sub.n--R.sup.6, [0058] where [0059] R.sup.5
is a hydrocarbon radical containing from 2 to 4 carbon atoms,
[0060] n is from 1 to 100 and [0061] R.sup.6 is hydrogen, a linear
or branched aliphatic hydrocarbon radical which has from 1 to 30
carbon atoms and may contain double bonds, a cycloaliphatic
hydrocarbon radical which has from 5 to 40 carbon atoms and may
contain double bonds, an aromatic hydrocarbon radical having from 6
to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon
atoms or a --C(O)--R.sup.7 radical where [0062] R.sup.7 is a linear
or branched aliphatic hydrocarbon radical which has from 1 to 30
carbon atoms and may contain double bonds, a cycloaliphatic
hydrocarbon radical which has from 5 to 40 carbon atoms and may
contain double bonds, an aromatic hydrocarbon radical having from 6
to 40 carbon atoms, an alkylaryl radical having from 7 to 40 carbon
atoms.
[0063] As very particularly preferred imidazolium ions (XII),
mention may be made of 1-methylimidazolium, 1-ethylimidazolium,
1-(1-butyl)imidazolium, 1-(1-octyl)imidazolium,
1-(1-dodecyl)imidazolium, 1-(1-tetradecyl)imidazolium,
1-(1-hexadecyl)imidazolium, 1,3-dimethylimidazolium,
1-ethyl-3-methylimidazolium, 1-(1-butyl)-3-methylimidazolium,
1-(1-butyl)-3-ethylimidazolium, 1-(1-hexyl)-3-methylimidazolium,
1-(1-hexyl)-3-ethylimidazolium, 1-(1-hexyl)-3-butylimidazolium,
1-(1-octyl)-3-methylimidazolium, 1-(1-octyl)-3-ethylimidazolium,
1-(1-octyl)-3-butylimidazolium, 1-(1-dodecyl)-3-methylimidazolium,
1-(1-dodecyl)-3-ethylimidazolium, 1-(1-dodecyl)-3-butylimidazolium,
1-(1-dodecyl)-3-octylimidazolium,
1-(1-tetradecyl)-3-methylimidazolium,
1-(1-tetradecyl)-3-ethylimidazolium,
1-(1-tetradecyl)-3-butylimidazolium,
1-(1-tetradecyl)-3-octylimidazolium,
1-(1-hexadecyl)-3-methylimidazolium,
1-(1-hexadecyl)-3-ethylimidazolium,
1-(1-hexadecyl)-3-butylimidazolium,
1-(1-hexadecyl)-3-octylimidazolium, 1,2-dimethylimidazolium,
1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium,
1-(1-butyl)-2,3-dimethylimidazolium,
1-(1-hexyl)-2,3-dimethylimidazolium,
1-(1-octyl)-2,3-dimethylimidazolium, 1,4-dimethylimidazolium,
1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium,
3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium,
1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium,
1,4,5-trimethyl-3-ethylimidazolium,
1,4,5-trimethyl-3-butylimidazolium and
1,4,5-trimethyl-3-octylimidazolium.
[0064] Further possible cations are ions which are, in particular,
composed of the abovementioned cations in the form of dications,
trications or polycations formed by dimerization, trimerization or
polymerization. These also include dications, trications and
polycations which have a polymeric backbone, for example a backbone
based on siloxanes, polyethers, polyesters, polyamides or
polyacrylates, in particular branched and hyperbranched
polymers.
[0065] Further possible ionic liquids are those in which the cation
[A].sup.+ is a pyridinium ion (XVIIa),
##STR00003##
where [0066] one of the radicals R.sub.1 to R.sub.5 is methyl,
ethyl or chlorine and the remaining radicals R.sub.1 to R.sub.5 are
each hydrogen; [0067] R.sub.3 is dimethylamino and the remaining
radicals R.sub.1, R.sub.2, R.sub.4 and R.sub.5 are each hydrogen;
[0068] all radicals R.sub.1 to R.sub.5 are hydrogen; [0069] R.sub.2
is carboxy or carboxamide and the remaining radicals R.sub.1,
R.sub.2, R.sub.4 and R.sub.5 are each hydrogen; or [0070] R.sub.1
and R.sub.2 or R.sub.2 and R.sub.3 are 1,4-buta-1,3-dienylene and
the remaining radicals R.sub.1, R.sub.2, R.sub.4 and R.sub.5 are
each hydrogen; and in particular one in which [0071] R.sub.1 to
R.sub.5 are each hydrogen; or [0072] one of the radicals R.sub.1 to
R.sub.5 is methyl or ethyl and the remaining radicals R.sub.1 to
R.sub.5 are each hydrogen.
[0073] As very particularly preferred pyridinium ions (XVIIa),
mention may be made of 1-methylpyridinium, 1-ethylpyridinium,
1-(1-butyl)pyridinium, 1-(1-hexyl)pyridinium,
1-(1-octyl)pyridinium, 1-(1-hexyl)pyridinium,
1-(1-octyl)pyridinium, 1-(1-dodecyl)pyridinium,
1-(1-tetradecyl)pyridinium, 1-(1-hexadecyl)pyridinium,
1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium,
1-(1-butyl)-2-methylpyridinium, 1-(1-hexyl)-2-methylpyridinium,
1-(1-octyl)-2-methylpyridinium, 1-(1-dodecyl)-2-methylpyridinium,
1-(1-tetradecyl)-2-methylpyridinium,
1-(1-hexadecyl)-2-methylpyridinium, 1-methyl-2-ethylpyridinium,
1,2-diethylpyridinium, 1-(1-butyl)-2-ethylpyridinium,
1-(1-hexyl)-2-ethylpyridinium, 1-(1-octyl)-2-ethylpyridinium,
1-(1-dodecyl)-2-ethylpyridinium,
1-(1-tetradecyl)-2-ethylpyridinium,
1-(1-hexadecyl)-2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium,
1,5-diethyl-2-methylpyridinium,
1-(1-butyl)-2-methyl-3-ethylpyridinium,
1-(1-hexyl)-2-methyl-3-ethylpyridinium and
1-(1-octyl)-2-methyl-3-ethylpyridinium,
1-(1-dodecyl)-2-methyl-3-ethylpyridinium,
1-(1-tetradecyl)-2-methyl-3-ethylpyridinium and
1-(1-hexadecyl)-2-methyl-3-ethylpyridinium.
[0074] Additional possible ionic liquids are those in which the
cation [A].sup.+ is a pyridazinium ion (XVIIb),
##STR00004##
where [0075] R.sub.1 to R.sub.4 are each hydrogen; or [0076] one of
the radicals R.sub.1 to R.sub.4 is methyl or ethyl and the
remaining radicals R.sub.1 to R.sub.4 are each hydrogen.
[0077] In addition, very particular preference is given to ionic
liquids in which the cation [A].sup.+ is a pyrimidinium ion
(XVIIc),
##STR00005##
where [0078] R.sub.1 is hydrogen, methyl or ethyl and R.sub.2 to
R.sub.4 are each, independently of one another, hydrogen or methyl;
or [0079] R.sub.1 is hydrogen, methyl or ethyl, R.sub.2 and R.sub.4
are each methyl and R.sub.3 is hydrogen.
[0080] Further possible ionic liquids are those in which the cation
[A].sup.+ is a pyrazinium ion (XVIId),
##STR00006##
where [0081] R.sub.1 is hydrogen, methyl or ethyl and R.sub.2 to
R.sub.4 are each, independently of one another, hydrogen or methyl;
[0082] R.sub.1 is hydrogen, methyl or ethyl, R.sub.2 and R.sub.4
are methyl and R.sub.3 is hydrogen; [0083] R.sub.1 to R.sub.4 are
each methyl; or [0084] R.sub.1 to R.sub.4 are each methyl or
hydrogen.
[0085] Further possible ionic liquids are those in which the cation
[A].sup.+ is a pyrazolium ion (XVIIf), (XVIIg) or (XVIIg'),
##STR00007##
where [0086] R.sup.1 is hydrogen, methyl or ethyl and R.sup.2 to
R.sup.4 are each, independently of one another, hydrogen or
methyl.
[0087] Possible ionic liquids are additionally those in which the
cation [A].sup.+ is a pyrazolium ion (XVIIh),
##STR00008##
where [0088] R.sup.1 to R.sup.4 are each, independently of one
another, hydrogen or methyl.
[0089] Suitable ionic liquids also include those in which the
cation [A].sup.+ is a 1-pyrazolinium ion (XVIIi),
##STR00009##
where [0090] R.sub.1 to R.sub.6 are each, independently of one
another, hydrogen or methyl.
[0091] Further possible ionic liquids are those in which the cation
[A].sup.+ is a 2-pyrazolinium ion (XVIIj),
##STR00010##
where [0092] R.sub.1 is hydrogen, methyl, ethyl or phenyl and
R.sub.2 to R.sub.6 are each, independently of one another, hydrogen
or methyl.
[0093] It is also possible to use ionic liquids in which the cation
[A].sup.+ is a 3-pyrazolinium ion (XVIIk) or (XVIIk'),
##STR00011##
where [0094] R.sub.1 and R.sub.2 are each, independently of one
another, hydrogen, methyl, ethyl or phenyl and R.sub.3 to R.sub.6
are each, independently of one another, hydrogen or methyl.
[0095] Further possible ionic liquids are those in which the cation
[A].sup.+ is an imidazolinium ion (XVIIl),
##STR00012##
where [0096] R is H or methyl, R.sub.1 and R.sub.2 are each,
independently of one another, hydrogen, methyl or ethyl or a linear
saturated or unsaturated acyl radical having from 14 to 22,
preferably from 16 to 18, carbon atoms and R.sub.3 to R.sub.6 are
each, independently of one another, hydrogen, a linear saturated
alkyl radical which has 1-4 carbon atoms and may contain OH groups,
preferably methyl, or a fatty acid radical; very particular
preference is given to R.sub.1 and R.sub.2 being fatty acyl
radicals and R or R.sub.2 and R.sub.3 being fatty acyl radicals.
These substances corresponding to Formula (XVIIm) are of particular
importance. Erroneous formulae (analogous to Formula XVIIm' or
XVIIl) are sometimes also used for these in the literature.
[0097] Additional possible ionic liquids are those in which the
cation [A].sup.+ is an imidazolinium ion (XVIIm) or (XVIIm'),
##STR00013##
where [0098] R is H or methyl, R.sub.1 and R.sub.2 are each,
independently of one another, hydrogen, methyl or ethyl or a linear
saturated or unsaturated acyl radical having from 14 to 22,
preferably from 16 to 18, carbon atoms and R.sub.3 to R.sub.6 are
each, independently of one another, hydrogen, a linear saturated
alkyl radical which has 1-4 carbon atoms and may contain OH groups,
preferably methyl, or a fatty acid radical; very particular
preference is given to R.sub.1 and R.sub.2 being fatty acyl
radicals and R or R.sub.2 and R.sub.3 being fatty acyl radicals.
These substances corresponding to the Formula (XIIIm) are of
particular importance. Erroneous formulae (analogous to Formula
XIIIm' or XIIIl) are sometimes also used for these in the
literature.
[0099] Further possible ionic liquids are those in which the cation
[A].sup.+ is an imidazolinium ion (XVIIn) or (XVIIn'),
##STR00014##
where [0100] R.sub.1 to R.sub.3 are each, independently of one
another, hydrogen, methyl or ethyl and R.sub.4 to R.sub.6 are each,
independently of one another, hydrogen or methyl.
[0101] Additional possible ionic liquids are those in which the
cation [A].sup.+ is a thiazolium ion (XVIIo) or (XVIIo') or an
oxazolium ion (XVIIp),
##STR00015##
where [0102] R.sub.1 is hydrogen, methyl, ethyl or phenyl and
R.sub.2 and R.sub.3 are each, independently of one another,
hydrogen or methyl.
[0103] Possible ionic liquids also include those in which the
cation [A].sup.+ is a 1,2,4-triazolium ion (XVIIq), (XVIIq') or
(XVIIq''),
##STR00016##
where [0104] R.sub.1 and R.sub.2 are each, independently of one
another, hydrogen, methyl, ethyl or phenyl and R.sub.3 is hydrogen,
methyl or phenyl.
[0105] Further possible ionic liquids are those in which the cation
[A].sup.+ is a 1,2,3-triazolium ion (XVIIr), (XVIIr') or
(XVIIr''),
##STR00017##
where [0106] R.sub.1 is hydrogen, methyl or ethyl and R.sub.2 and
R.sub.3 are each, independently of one another, hydrogen or methyl
or R.sub.2 and R.sub.3 together are 1,4-buta-1-3-dienylene.
[0107] Additional possible ionic liquids are those in which the
cation [A].sup.+ is a pyrrolidinium ion (XVIIs),
##STR00018##
where [0108] R.sub.1 is hydrogen, methyl, ethyl or phenyl and
R.sub.2 to R.sub.9 are each, independently of one another, hydrogen
or methyl.
[0109] Further possible ionic liquids are those in which the cation
[A].sup.+ is an imidazolidinium ion (XVIIt),
##STR00019##
where [0110] R.sub.1 and R.sub.4 are each, independently of one
another, hydrogen, methyl, ethyl or phenyl and R.sub.2 and R.sub.3
and also R.sub.5 to R.sub.8 are each, independently of one another,
hydrogen or methyl.
[0111] Possible ionic liquids also include those in which the
cation [A].sup.+ is an ammonium ion (IV),
##STR00020##
where [0112] R.sub.1 to R.sub.3 are each, independently of one
another, C.sub.1-C.sub.18-alkyl; or [0113] R.sub.1 to R.sub.3 are
each, independently of one another, hydrogen or
C.sub.1-C.sub.18-alkyl and R.sub.4 is 2-hydroxyethyl; or [0114]
R.sub.1 and R.sub.2 together are 1,5-pentylene or
3-oxa-1,5-pentylene and R.sub.3 is C.sub.1-C.sub.18-alkyl,
2-hydroxyethyl or 2-cyanoethyl.
[0115] As particularly preferred ammonium ions (IV), mention may
also be made of methyltri(1-butyl)ammonium, 2-hydroxyethylammonium,
bis(2-hydroxyethyl)dimethylammonium, N,N-dimethylpiperidinium and
N,N-dimethylmorpholinium.
[0116] Additional possible ionic liquids are those in which the
cation [A].sup.+ is a guanidinium ion (IVv),
##STR00021##
where [0117] R.sub.1 to R.sub.5 are each methyl; [0118] R.sub.1 to
R.sub.5 are each, independently of one another,
C.sub.1-C.sub.18-alkyl; or [0119] R.sub.1 to R.sub.5 are each,
independently of one another, hydrogen or C.sub.1-C.sub.18-alkyl or
2-hydroxyethyl. As very particularly preferred guanidinium ion
(IVv), mention may be made of
N,N,N',N',N'',N''-hexamethylguanidinium.
[0120] Possible ionic liquids also include those in which the
cation [A].sup.+ is a derivative of ethanolamine, e.g. a cholinium
ion (XVIIw), or of a diethanolamine (XVIIw'), or of a
triethanolamine (XVIIw''),
##STR00022##
where [0121] R.sub.1 and R.sub.2 are each, independently of one
another, methyl, ethyl, 1-butyl or 1-octyl and R.sub.3 is hydrogen,
methyl, ethyl, acetyl, --SO.sub.2OH or --PO(OH).sub.2; [0122]
R.sub.1 is methyl, ethyl, 1-butyl or 1-octyl, R.sub.2 is a
--CH.sub.2--CH.sub.2--OR.sub.4 group and R.sub.3 and R.sub.4 are
each, independently of one another, hydrogen, methyl, ethyl,
acetyl, --SO.sub.2OH or --PO(OH).sub.2; or [0123] R.sub.1 is a
--CH.sub.2--CH.sub.2--OR.sub.4 group, R.sub.2 is a
--CH.sub.2--CH.sub.2--OR.sub.5 group and R.sub.3 to R.sub.5 are
each, independently of one another, hydrogen, methyl, ethyl,
acetyl, --SO.sub.2OH or --PO(OH).sub.2; [0124] R.sub.1 is methyl,
ethyl, 1-butyl, 1-octyl, acetyl, --SO.sub.2OH or --PO(OH).sub.2 and
R.sub.3 to R.sub.5 are each, independently of one another,
hydrogen, methyl, ethyl, acetyl, --SO.sub.2OH, --PO(OH).sub.2 or
--(C.sub.nH.sub.2nO).sub.mR.sub.1 where n=1 to 5 and m=1 to
100.
[0125] Preference is also given to compounds in which R, R.sub.1
and R.sub.2 are alkyl groups having from 1 to 4 carbon atoms,
particularly preferably a methyl group, and R.sub.3 and/or R.sub.4
are saturated or unsaturated fatty acid or acyl radicals having
from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms.
It is also possible for mixtures of the acyl or fatty acid radicals
(in particular, for example, in naturally occurring ratios) to be
present.
[0126] Very particular preference is given in the case of Formula
(XVIIw'') to R, R.sub.1, R.sub.2 each being an alkyl radical having
from 1 to 4 carbon atoms, in particular a methyl group, and R.sub.3
being a fatty acid radical and R.sub.4 and R.sub.5 each being a
fatty acid radical or hydrogen.
[0127] Possible ionic liquids include those in which the cation
[A].sup.+ is a phosphonium ion (VI), where [0128] R.sub.1 to
R.sub.3 are each, independently of one another,
C.sub.1-C.sub.18-alkyl, in particular butyl, isobutyl, 1-hexyl or
1-octyl.
[0129] Among the abovementioned cations, preference is given to the
pyridinium ions (XVIIa), imidazolium ions (XVI) and ammonium ions
(IV), in particular 1-methylpyridinium, 1-ethylpyridinium,
1-(1-butyl)pyridinium, 1-(1-hexyl)pyridinium,
1-(1-octyl)pyridinium, 1-(1-hexyl)pyridinium,
1-(1-octyl)pyridinium, 1-(1-dodecyl)pyridinium,
1-(1-tetradecyl)pyridinium, 1-(1-hexadecyl)pyridinium,
1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium,
1-(1-butyl)-2-methylpyridinium, 1-(1-hexyl)-2-methylpyridinium,
1-(1-octyl)-2-methylpyridinium, 1-(1-dodecyl)-2-methylpyridinium,
1-(1-tetradecyl)-2-methylpyridinium,
1-(1-hexadecyl)-2-methylpyridinium, 1-methyl-2-ethylpyridinium,
1,2-diethylpyridinium, 1-(1-butyl)-2-ethylpyridinium,
1-(1-hexyl)-2-ethylpyridinium, 1-(1-octyl)-2-ethylpyridinium,
1-(1-dodecyl)-2-ethylpyridinium,
1-(1-tetradecyl)-2-ethylpyridinium,
1-(1-hexadecyl)-2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium,
1,5-diethyl-2-methylpyridinium,
1-(1-butyl)-2-methyl-3-ethylpyridinium,
1-(1-hexyl)-2-methyl-3-ethylpyridinium,
1-(1-octyl)-2-methyl-3-ethylpyridinium,
1-(1-dodecyl)-2-methyl-3-ethylpyridinium,
1-(1-tetradecyl)-2-methyl-3-ethylpyridinium,
1-(1-hexadecyl)-2-methyl-3-ethylpyridinium, 1-methylimidazolium,
1-ethylimidazolium, 1-(1-butyl)imidazolium, 1-(1-octyl)imidazolium,
1-(1-dodecyl)imidazolium, 1-(1-tetradecyl)imidazolium,
1-(1-hexadecyl)imidazolium, 1,3-dimethylimidazolium,
1-ethyl-3-methylimidazolium, 1-(1-butyl)-3-methylimidazolium,
1-(1-hexyl)-3-methylimidazolium, 1-(1-octyl)-3-methylimidazolium,
1-(1-dodecyl)-3-methylimidazolium,
1-(1-tetradecyl)-3-methylimidazolium,
1-(1-hexadecyl)-3-methylimidazolium, 1,2-dimethylimidazolium,
1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium,
1-(1-butyl)-2,3-dimethylimidazolium,
1-(1-hexyl)-2,3-dimethylimidazolium and
1-(1-octyl)-2,3-dimethylimidazolium, 1,4-dimethylimidazolium,
1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium,
3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium,
1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium,
1,4,5-trimethyl-3-ethylimidazolium,
1,4,5-trimethyl-3-butylimidazolium,
1,4,5-trimethyl-3-octylimidazolium and 2-hydroxyethylammonium.
[0130] The metal cations [M.sup.1].sup.+, [M.sup.2].sup.+,
[M.sup.3].sup.+, [M.sup.4].sup.2+ and [M.sup.5].sup.3+ mentioned in
the Formulae (IIIa) to (IIIj) are generally metal cations of groups
1, 2, 6, 7, 8, 9, 10, 11, 12 and 13 of the Periodic Table. Suitable
metal cations are, for example, Li.sup.+, Na.sup.+, K.sup.+,
Cs.sup.+, Mg.sup.2+, Ca.sup.2+, Ba.sup.2+, Cr.sup.3+, Fe.sup.2+,
Fe.sup.3+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+, Ag.sup.+, Zn.sup.2+ and
Al.sup.3+.
[0131] The ionic liquids used according to the invention comprise
at least one of the abovementioned cations combined with at least
one anion. Possible anions are in principle all anions which in
combination with the cation lead to an ionic liquid.
[0132] The anion [Y].sup.n- of the ionic liquid is selected, for
example, from: [0133] the group of halides and halogen-containing
compounds of the formulae: F.sup.- Cl.sup.-, Br.sup.-, I.sup.-,
BF.sub.4.sup.-, PF.sub.6.sup.-, AlCl.sub.4.sup.-,
Al.sub.2Cl.sub.7.sup.-, Al.sub.3Cl.sub.10.sup.-, AlBr.sub.4.sup.-,
FeCI.sub.4.sup.-, BCl.sub.4.sup.- SbF.sub.6.sup.-, AsF.sub.6.sup.-,
ZnCl.sub.3.sup.-, SnCl.sub.3.sup.-, CuCl.sub.2.sup.-,
CF.sub.3SO.sub.3.sup.-, (CF.sub.3SO.sub.3).sub.2N.sup.-,
CF.sub.3CO.sub.2.sup.-, CCl.sub.3.sup.CO.sub.2.sup.-, CN.sup.-,
SCN.sup.-, OCN.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-, N(CN).sup.-;
[0134] the group of sulphates, sulphites and sulphonates of the
general formulae: SO.sub.4.sup.2-, HSO.sub.4.sup.-,
SO.sub.3.sup.2-, HSO.sub.3.sup.-, R.sup.aOSO.sub.3.sup.-,
R.sup.aSO.sub.3.sup.-; [0135] the group of phosphates of the
general formulae: PO.sub.4.sup.3-, HPO.sub.4.sup.2-,
H.sub.2PO.sub.4-, R.sup.aPO.sub.4.sup.2-, HR.sup.aPO.sub.4.sup.-,
R.sup.aR.sup.bPO.sub.4.sup.-; [0136] the group of phosphonates and
phosphinates of the general formulae: R.sup.aHPO.sub.3.sup.-,
R.sup.aR.sup.bPO.sub.2.sup.-, R.sup.aR.sup.bPO.sub.3.sup.-; [0137]
the group of phosphites of the general formulae: PO.sub.3.sup.3-,
HPO.sub.3.sup.2-, H.sub.2PO.sub.3.sup.-, R.sup.aPO.sub.3.sup.2-,
R.sup.aHPO.sub.3.sup.-, R.sup.aR.sup.bPO.sub.3.sup.-; [0138] the
group of phosphonites and phosphinites of the general formulae:
R.sup.aR.sup.bPO.sub.2.sup.-, R.sup.aHPO.sub.2.sup.-,
R.sup.aR.sup.bPO.sup.-, R.sup.aHPO.sup.-; [0139] the group of
carboxylates of the general formula: R.sup.aCOO.sup.-; [0140] the
group of borates of the general formulae: BO.sub.3.sup.3-,
HBO.sub.3.sup.2-, H.sub.2BO.sub.3.sup.-,
R.sup.aR.sup.bBO.sub.3.sup.-, R.sup.aHBO.sub.3.sup.-,
R.sup.aBO.sub.3.sup.2-,
B(OR.sup.a)(OR.sup.b)(OR.sup.c)(OR.sup.d).sup.-,
B(HSO.sub.4).sup.-, B(R.sup.aSO.sub.4).sup.-; [0141] the group of
boronates of the general formulae: R.sup.aBO.sub.2.sup.2-,
R.sup.aR.sup.bBO.sup.-; [0142] the group of carbonates and carbonic
esters of the general formulae: HCO.sub.3.sup.-, CO.sub.3.sup.2-,
R.sup.aCO.sub.3.sup.-; [0143] the group of silicates and silicic
esters of the general formulae: SiO.sub.4.sup.4-,
HSiO.sub.4.sup.3-, H.sub.2SiO.sub.4.sup.2-, H.sub.3SiO.sub.4.sup.-,
R.sup.aSiO.sub.4.sup.3-, R.sup.aR.sup.bSiO.sub.4.sup.2-,
R.sup.aR.sup.bR.sup.cSiO.sub.4.sup.-, HR.sup.aSiO.sub.4.sup.2-,
H.sub.2R.sup.aSiO.sub.4.sup.-, HR.sup.aR.sup.bSiO.sub.4.sup.-;
[0144] the group of alkylsilane and arylsilane salts of the general
formulae: R.sup.aSiO.sub.3.sup.3-, R.sup.aR.sup.bSiO.sub.2.sup.2-,
R.sup.aR.sup.bR.sup.cSiO.sup.-,
R.sup.aR.sup.bR.sup.cSiO.sub.3.sup.-,
R.sup.aR.sup.bR.sup.cSiO.sub.2.sup.-,
R.sup.aR.sup.bSiO.sub.3.sup.2-; [0145] the group of carboximides,
bis(sulphonyl)imides and sulphonylimides of the general
formulae:
[0145] ##STR00023## [0146] the group of methides of the general
formula:
[0146] ##STR00024## [0147] the group of alkoxides and aryloxides of
the general formula: R.sup.aO.sup.-; [0148] the group of
halometalates of the general formula [M.sub.rHal.sub.t].sup.s-,
where M is a metal and Hal is fluorine, chlorine, bromine or
iodine, r and t are positive integers and indicate the
stoichiometry of the complex and s is a positive integer and
indicates the charge on the complex; [0149] the group of sulphides,
hydrogensulphides, polysulphides, hydrogenpolysulphides and
thiolates of the general formulae: [0150] S.sup.2-, HS.sup.-,
[S.sub.v].sup.2-, [HS.sub.v].sup.-, [R.sup.aS].sup.-, where v is a
positive integer from 2 to 10; [0151] the group of complex metal
ions such as Fe(CN).sub.6.sup.3-, Fe(CN).sub.6.sup.4-,
MnO.sub.4.sup.-, Fe(CO).sub.4.sup.-.
[0152] In these formulae, R.sup.a, R.sup.b, R.sup.c and R.sup.d are
each, independently of one another, [0153] hydrogen; [0154]
C.sub.1-C.sub.30-alkyl and their aryl-, heteroaryl-, cycloalkyl,
halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--, --CO--,
--CO--O-- or --CO--N<substituted components, for example methyl,
ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl
(isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl,
3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl,
3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl,
2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl,
2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl,
2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl,
2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl,
2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl,
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl,
docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,
octacosyl, nonacosyl, triacontyl, phenylmethyl (benzyl),
diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl,
cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl,
cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, methoxy,
ethoxy, formyl, acetyl or C.sub.qF.sub.2(q-a)+(1-b)H.sub.2a+b where
q<30, 0.ltoreq.a.ltoreq.q and b=0 or 1 (for example CF.sub.3,
C.sub.2F.sub.5, CH.sub.2CH.sub.2--C.sub.(q-2)F.sub.2(q-2)+1,
C.sub.6F.sub.13, C.sub.8F.sub.17, C.sub.10F.sub.21,
C.sub.12F.sub.25); [0155] C.sub.3-C.sub.12-cycloalkyl and their
aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-,
carboxy-, formyl-, --O--, --CO-- or --CO--O-substituted components,
for example cyclopentyl, 2-methyl-1-cyclopentyl,
3-methyl-1-cyclopentyl, cyclohexyl, 2-methyl-1-cyclohexyl,
3-methyl-1-cyclohexyl, 4-methyl-1-cyclohexyl or
C.sub.qF.sub.2(q-a)-(1-b)H.sub.2a-b where q.ltoreq.30,
0.ltoreq.a.ltoreq.q and b=0 or 1; [0156] C.sub.2-C.sub.30-alkenyl
and their aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-,
amino-, carboxy-, formyl-, --O--, --CO-- or --CO--O-substituted
components, for example 2-propenyl, 3-butenyl, cis-2-butenyl,
trans-2-butenyl or C.sub.qF.sub.2(q-a)-(1-b)H.sub.2a-b where
q.ltoreq.30, 0.ltoreq.a.ltoreq.q and b=0 or 1; [0157]
C.sub.3-C.sub.12-cycloalkenyl and their aryl-, heteroaryl-,
cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--,
--CO-- or --CO--O-substituted components, for example
3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl,
2,5-cyclohexadienyl or C.sub.qF.sub.2(q-a)-3(1-b)H.sub.2a-3b where
q.ltoreq.30, 0.ltoreq.a.ltoreq.q and b=0 or 1; [0158] aryl or
heteroaryl having from 2 to 30 carbon atoms and their alkyl-,
aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-,
carboxy-, formyl-, --O--, --CO-- or --CO--O-substituted components,
for example phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl
(3-tolyl), 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl,
4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,
2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,
3,5-dimethylphenyl, 4-phenylphenyl, 1-naphthyl, 2-naphthyl,
1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl, 3-pyridinyl,
4-pyridinyl or C.sub.6F.sub.(5-a)H.sub.a where 0.ltoreq.a.ltoreq.5;
or [0159] two radicals form an unsaturated, saturated or aromatic
ring which may be substituted by functional groups, aryl, alkyl,
aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles and may
be interrupted by one or more oxygen and/or sulphur atoms and/or
one or more substituted or unsubstituted imino groups.
[0160] Possible anions are, for example, chloride; bromide; iodide;
thiocyanate; hexafluorophosphate; trifluoromethanesulphonate;
methanesulphonate; formate; acetate; glycolate; lactate; oxalate;
citrate; malate; maleate; tartrate; mandelate; nitrate; nitrite;
trifluoroacetate; sulphate; hydrogensulphate; methylsulphate;
ethylsulphate; 1-propylsulphate; 1-butylsulphate; 1-hexylsulphate;
1-octylsulphate; phosphate; dihydrogenphosphate; hydrogenphosphate;
C.sub.1-C.sub.4-dialkylphosphates; propionate;
tetrachloroaluminate; Al.sub.2Cl.sub.7.sup.-; chlorozincate;
chloroferrate; bis(trifluoromethylsulphonyl)imide;
bis(pentafluoroethylsulphonyl)imide; bis(methylsulphonyl)imide;
bis(p-tolylsulphonyl)imide; tris(trifluoromethylsulphonyl)methide;
bis(pentafluoroethylsulphonyl)methide; p-tolylsulphonate;
tetracarbonylcobaltate; dimethylene glycol monomethyl ether
sulphate; oleate; stearate; acrylate; methacrylate; maleate;
hydrogencitrate; vinylphosphonate;
bis(pentafluoroethyl)phosphinate; borates such as
bis[salicylato(2-)]borate, bis[oxalato(2-)]borate,
bis[1,2-benzenediolato(2-)-O,O']borate, tetracyanoborate,
tetrafluoroborate; dicyanamide;
tris(pentafluoroethyl)trifluorophosphate;
tris(heptafluoropropyl)trifluorophosphate, cyclic aryl phosphates
such as catecholphosphate (C.sub.6H.sub.4O.sub.2)P(O)O.sup.- and
chlorocobaltate.
[0161] Preferred anions are selected from the group comprising,
without making any claim as to completeness, the halides,
bis(perfluoroalkylsulphonyl)amides or -imides such as
bis(trifluoromethylylsulphonyl)imide, alkyltosylates and
aryltosylates, perfluoroalkyltosylates, nitrate, sulphate,
hydrogensulphate, alkylsulphates and arylsulphates, polyether
sulphates and sulphonates, perfluoroalkylsulphates, sulphonate,
alkylsulphonates and arylsulphonates, perfluorinated
alkylsulphonates and arylsulphonates, alkylcarboxylates, and
arylcarboxylates, perfluoroalkylcarboxylates, perchlorate,
tetrachloroaluminate, saccharinate. Further possibilities are
dicyanamide, thiocyanate, isothiocyanate, tetraphenylborate,
tetrakis(pentafluorophenyl)borate, tetrafluoroborate,
hexafluorophosphate, polyether phosphates and phosphate.
[0162] Very particularly preferred anions are:
chloride, bromide, hydrogensulphate, tetrachloroaluminate,
thiocyanate, methylsulphate, ethylsulphate, methanesulphonate,
formate, acetate, glycolate, lactate, dimethylphosphate,
diethylphosphate, p-tolylsulphonate, tetrafluoroborate and
hexafluorophosphate.
[0163] In a further preferred embodiment of the invention, use is
made of ionic liquids or mixtures thereof which contain a
combination of a 1,3-dialkylimidazolium, 1,2,3-trialkylimidazolium,
1,3-dialkylimidazolinium and 1,2,3-trialkylimidazolinium cation
with an anion selected from the group consisting of the halides,
bis(trifluoromethylylsulphonyl)imide, perfluoroalkyltosylates,
alkylsulphates and -sulphonates, perfluorinated alkylsulphonates
and alkylsulphates, perfluoroalkylcarboxylates, perchlorate,
dicyanamide, thiocyanate, isothiocyanate, tetraphenylborate,
tetrakis(pentafluorophenyl)borate, tetrafluoroborate,
hexafluorophosphate, acetate, glycolate, lactate.
[0164] In addition, it is also possible to use simple, commercially
available, acyclic quaternary ammonium salts such as TEGO.RTM. IL
T16ES, TEGO.RTM. IL K5MS, TEGO.RTM. IL DS or TEGO.RTM. IL 2MS
(products of Evonik Goldschmidt GmbH).
[0165] Particularly preferred ionic liquids for the purposes of the
present disclosure are:
1-butyl-3-methylimidazolium 2-(2-methoxyethoxy)ethylsulphate,
1-butyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium
acetate, tetrabutylammonium benzoate, trihexyltetradecylphosphonium
bis(2,4,4-trimethylpentyl)phosphinate, 1-ethyl-3-methylimidazolium
bis(pentafluoroethylsulphonyl)imide, 1-butyl-1-methylpyrrolidinium
bis(trifluoromethylsulphonyl)imide, 1-butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylpyridinium
bis(trifluoromethylsulphonyl)imide,
1,2-dimethyl-3-propylimidazolium
bis(trifluoromethylsulphonyl)imide, 1-ethyl-3-methylimidazolium
bis(trifluoromethylsulphonyl)imide, 3-methyl-1-propylpyridinium
bis(trifluoromethylsulphonyl)imide, methyltrioctylammonium
bis(trifluoromethylsulphonyl)imide, tetrabutylammonium
bis(trifluoromethylsulphonyl)imide, trihexyltetradecylphosphonium
bis(trifluoromethylsulphonyl)imide, 1-butyl-1-methylpyrrolidinium
bromide, 1-butylpyridinium bromide, 1-ethyl-3-methylimidazolium
bromide, 4-methyl-N-butylpyridinium bromide, tetrabutylammonium
bromide, tetrabutylphosphonium bromide, tetraheptylammonium
bromide, tetrahexylammonium bromide, tetraoctylammonium bromide,
tetraoctylphosphonium bromide, tetrapentylammonium bromide,
tributylhexadecylphosphonium bromide, 1-allyl-3-methylimidazolium
chloride, 1-benzyl-3-methylimidazolium chloride,
1-butyl-1-methylpyrrolidinium chloride,
1-butyl-2,3-dimethylimidazolium chloride,
1-butyl-3-methylimidazolium chloride, 1-butyl-4-methylpyridinium
chloride, 1-ethyl-2,3-dimethylimidazolium chloride,
1-ethyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium
chloride, 1-methyl-3-octylimidazolium chloride, methylimidazolium
chloride, tetrabutylammonium chloride, tetrabutylphosphonium
chloride, tetraheptylammonium chloride, tetraoctylammonium
chloride, trihexyltetradecylphosphonium chloride,
butylammonium-.alpha.-cyano-4-hydrocinnamate,
diethylammonium-.alpha.-cyano-4-hydrocinnamate,
trihexyltetradecylphosphonium decanoate,
1-butyl-1-methylpyrrolidinium dicyanamide,
1-butyl-3-methylimidazolium dicyanamide,
1-ethyl-3-methylimidazolium dicyanamide,
trihexyltetradecylphosphonium dicyanamide,
1-ethyl-2,3-dimethylimidazolium ethylsulphate,
1-ethyl-3-methylimidazolium ethylsulphate,
1-benzyl-3-methylimidazoliumhexafluorophosphate,
1-butyl-2,3-dimethylimidazoliumhexafluorophosphate, 1-butyl-3-(3,3,
. . . -tridecafluorooctyl)imidazolium hexafluorophosphate,
1-butyl-3-methylimidazolium hexafluorophosphate,
1-ethyl-3-methylimidazolium hexafluorophosphate,
1-hexyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-(3,3, .
. . -tridecafluorooctyl)imidazolium hexafluorophosphate,
1-butyl-4-methylpyridinium hexafluorophosphate,
1-methyl-3-octylimidazolium hexafluorophosphate,
trihexyltetradecylphosphonium hexafluorophosphate,
1-butyl-3-methylimidazolium hydrogensulphate,
1-ethyl-3-methylimidazolium hydrogensulphate, methylimidazolium
hydrogensulphate, 1-dodecyl-3-methylimidazolium hydrogensulphate,
1-dodecyl-3-methylimidazolium iodide, tetrahexylammonium iodide,
1-butyl-3-methylimidazolium methanesulphonate,
1-ethyl-3-methylimidazolium methanesulphonate, tetrabutylammonium
methanesulphonate, tetrabutylphosphonium methanesulphonate,
1-butyl-3-methylimidazolium methylsulphate, 1,3-dimethylimidazolium
methylsulphate, methyltributylammonium methylsulphate,
1-ethyl-3-methylimidazolium methylsulphate,
1,2,3-trimethylimidazolium methylsulphate,
1-butyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium
nitrate, tetrabutylammonium nonafluorobutanesulphonate,
tetrabutylammonium heptadecafluorooctanesulphonate,
1-butyl-3-methylimidazolium octylsulphate,
4-(3-butyl-1-imidazolio)butane-1-sulphonate,
3-(triphenylphosphonio)propane-1-sulphonate,
1-butyl-3-methylimidazolium tetrachloroaluminate,
1-ethyl-3-methylimidazolium tetrachloroaluminate,
1-benzyl-3-methylimidazolium tetrafluoroborate,
1-butyl-2,3-dimethylimidazolium tetrafluoroborate,
1-butyl-3-methylimidazolium tetrafluoroborate,
1-ethyl-3-methylimidazolium tetrafluoroborate,
1-hexyl-3-methylimidazolium tetrafluoroborate,
1-methyl-3-octylimidazolium tetrafluoroborate,
1-butyl-1-methylpyrrolidinium tetrafluoroborate,
1-butyl-4-methylpyridinium tetrafluoroborate, tetrabutylammonium
tetrafluoroborate, tetrahexylammonium tetrafluoroborate,
tetrabutylphosphonium tetrafluoroborate,
trihexyltetradecylphosphonium tetrafluoroborate,
1-butyl-3-methylimidazolium thiocyanate,
1-ethyl-3-methylimidazolium thiocyanate, tetrapentylammonium
thiocyanate, trioctylmethylammonium thiosalicylate,
1-butyl-3-methylimidazolium tosylate, 1-ethyl-3-methylimidazolium
tosylate, tetrabutylphosphonium tosylate,
triisobutylmethylphosphonium tosylate,
3-(triphenylphosphonio)propane-1-sulphonyl tosylate,
tetraethylammonium trifluoroacetate,
4-(3-butyl-1-imidazolio)butane-1-sulphonyl
trifluormethanesulphonate, 1-butyl-3-methylimidazolium
trifluoromethanesulphonate, 1-ethyl-2,3-dimethylimidazolium
trifluoromethanesulphonate, 1-ethyl-3-methylimidazolium
trifluoromethanesulphonate, 1-hexyl-3-methylimidazolium
trifluoromethanesulphonate, 1-methyl-3-octylimidazolium
trifluoromethanesulphonate, tetraethylammonium
trifluoromethanesulphonate, 1,2,3-trimethylimidazolium
trifluoromethanesulphonate,
1-hydroxyethyl-3-methylimidazolium-2-(2-methoxyethoxy)ethylsulphate,
1-hydroxyethyl-3-methylimidazolium acetate,
1-hydroxyethyl-3-methylimidazolium trifluoroacetate,
1-hydroxyethyl-3-methylimidazolium
bis(trifluoromethylsulphonyl)imide,
1-hydroxyethyl-3-methylimidazolium bromide,
1-hydroxyethyl-3-methylimidazolium chloride,
1-hydroxyethyl-3-methylimidazolium decanoate,
1-hydroxyethyl-3-methylimidazolium dicyanamide,
1-hydroxyethyl-3-methylimidazolium hexafluorophosphate,
1-hydroxyethyl-3-methylimidazolium hydrogensulphate,
1-hydroxyethyl-3-methylimidazolium iodide,
1-hydroxyethyl-3-methylimidazolium methanesulphonate,
1-hydroxyethyl-3-methylimidazolium methylsulphate,
1-hydroxyethyl-3-methylimidazolium ethylsulphate,
1-hydroxyethyl-3-methylimidazolium nitrate,
1-hydroxyethyl-3-methylimidazolium phosphate,
1-hydroxyethyl-3-methylimidazolium octylsulphate,
1-hydroxyethyl-3-methylimidazolium tetrachloroaluminate,
1-hydroxyethyl-3-methylimidazolium tetrafluoroborate,
1-hydroxyethyl-3-methylimidazolium thiocyanate,
1-hydroxyethyl-3-methylimidazolium salicylate,
1-hydroxyethyl-3-methylimidazolium thiosalicylate,
1-hydroxyethyl-3-methylimidazolium tosylate,
1-hydroxyethyl-3-methylimidazolium trifluoromethanesulphonate,
1-hydroxyethyl-3-methylimidazolium lactate,
1-hydroxyethyl-3-methylimidazolium glycolate,
1-hydroxyethyl-3-methylimidazolium citrate,
1-hydroxyethyl-3-methylimidazolium oxalate,
1-hydroxyethyl-3-methylimidazolium tartrate,
bis-(hydroxyethyl)dimethylammonium acetate,
bis-(hydroxyethyl)dimethylammonium trifluoroacetate,
bis-(hydroxyethyl)dimethylammonium
bis(trifluoromethylsulphonyl)imide,
bis-(hydroxyethyl)dimethylammonium bromide,
bis-(hydroxyethyl)dimethylammonium chloride,
bis(hydroxyethyl)dimethylammonium decanoate,
bis(hydroxyethyl)dimethylammonium dicyanamide,
bis(hydroxyethyl)dimethylammonium hexafluorophosphate,
bis(hydroxyethyl)dimethylammonium hydrogensulphate,
bis(hydroxyethyl)dimethylammonium iodide,
bis-(hydroxyethyl)dimethylammonium methanesulphonate,
bis-(hydroxyethyl)dimethylammonium methylsulphate,
bis-(hydroxyethyl)dimethylammonium ethylsulphate,
bis-(hydroxyethyl)dimethylammonium nitrate,
bis-(hydroxyethyl)dimethylammonium phosphate,
bis-(hydroxyethyl)dimethylammonium octylsulphate,
bis-(hydroxyethyl)dimethylammonium tetrachloroaluminate,
bis(hydroxyethyl)dimethylammonium tetrafluoroborate,
bis(hydroxyethyl)dimethylammonium thiocyanate,
bis(hydroxyethyl)dimethylammonium salicylate,
bis(hydroxyethyl)dimethylammonium thiosalicylate, bis(hydroxyethyl)
dimethylammonium tosylate, bis-(hydroxyethyl)dimethylammonium
trifluoromethanesulphonate, bis(hydroxyethyl)dimethylammonium
lactate, bis-(hydroxyethyl)dimethylammonium glycolate,
bis-(hydroxyethyl)dimethylammonium citrate,
bis-(hydroxyethyl)dimethylammonium oxalate,
bis-(hydroxyethyl)dimethylammonium tartrate.
[0166] Addition of the following performance additives improves the
wetting properties of preferably single-phase compositions
containing ionic liquids on solid surfaces. For the present
purposes, performance additives are substances which improve the
wetting properties and/or the spreading behavior of ionic liquids
on solid surfaces. Here, wetting refers to the covering of the
surface by the liquid. Improved wetting behavior can be recognized
by fewer unwetted places existing and wetting being uniform.
[0167] Spreading is, for the present purposes, the spontaneous
wetting of the solid surface. The liquid spreads spontaneously in
the form of a flat disc on the surface. In the ideal case, a
monomolecular film is formed and the contact angle is zero. A
lowering of the surface tension of the liquid is a necessary but
not sufficient condition for spreading.
[0168] The discovery of the mainly surface-active substances
described below as effective wetting and spreading agents when used
together with ionic liquids is all the more surprising because the
additives were exclusively developed for water and water based
formulations.
[0169] The compositions of the invention serve for the lasting
wetting of solid surfaces and contain at least one ionic liquid and
at least one performance additive and if appropriate solvents
and/or further auxiliaries or additives.
[0170] The compositions of the invention comprise from 50 to
99.999% by weight, preferably from 80 to 99.999% by weight, in
particular at least 95% by weight and particularly preferably from
>98 to 99.999% by weight, of one or more ionic liquids,
and from 0 to 20% by weight, preferably from 0 to 10% by weight and
particularly preferably from 0 to 5% by weight, of solvents, and
from 0 to 20% by weight, preferably from 0 to 10% by weight and
particularly preferably from 0 to 5% by weight, of auxiliaries and
additives, and from 0.001 to 10% by weight, preferably from 0.001
to 5% by weight and particularly preferably from 0.05 to 1% by
weight, of one or more performance additives according to the
invention, where the sum of all components of the composition is
100% by weight.
[0171] Preference is given to using a wetting agent or spreading
agent as performance additive in the compositions of the
invention.
[0172] Furthermore, the compositions of the invention preferably
consist of a single phase.
[0173] Preference is given to using one or more surfactants as
performance additive in the compositions of the invention.
[0174] The compositions of the invention can contain organic
solvents or water and/or mixtures thereof as solvents; preference
is given to no solvents or organic solvents being present.
[0175] Surfactants as such are used in aqueous systems or organic
systems which have non-ionic character.
[0176] Surprisingly and completely unexpectedly, the surfactants
mentioned can also positively influence the wetting properties and
the spreading behavior of ionic liquids.
[0177] When used together with ionic liquids, they therefore offer
the advantage of being able to influence the dispersion behavior
and adhesion behavior of compositions containing these components
in a desired way.
[0178] In the formulae which follow below, the radical P is:
--(CH.sub.2--).sub.g(OC.sub.2H.sub.4--).sub.h(OC.sub.3H.sub.6--).sub.i(O-
C.sub.4H.sub.8).sub.j(OCH.sub.2CH(C.sub.6H.sub.5)).sub.kOR.sup.20
where R.sup.20 is a hydrogen, alkyl or carboxyl radical. R.sup.20
is preferably a hydrogen or methyl radical or acetyl radical. The
index g is from 0 to 6, the index h is from 0 to 20, the index i is
from 0 to 50, where h+i.gtoreq.1, the index j is from 0 to 10 and
the index k is from 0 to 10.
[0179] Preference is given to the index g being from 0 to 3, the
index h being from 5 to 80 and the index i being from 0 to 30, with
the indices j and k preferably being <5, in particular 0.
[0180] In the formulae which follow below, the radical R.sup.21
is:
hydrogen or a linear or branched, saturated or unsaturated alkyl
radical having 1-25 carbon atoms, for example methyl, ethyl,
1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl),
2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl,
2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl,
3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl,
2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl,
2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl,
2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl,
2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl,
2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl,
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl,
docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,
octacosyl, nonacosyl, triacontyl, phenylmethyl (benzyl),
diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl,
cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl,
cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, allyl,
undecaenyl, dodecaenyl, octadecaenyl, eicosaenyl, docosaenyl,
tetracosaenyl, octadecadienyl, octadecatrienyl, eicosatetraenyl,
eicosapentaenyl, docosapentaenyl or docosahexaenyl.
1. Nonionic Organic Surfactants:
[0181] alkylamine alkoxylates, e.g. polyethylene glycol cocosamine
(commercialized under the name VARONIC K-202 or K-202 P or K-205)
or polyethylene glycol stearylamine (commercialized under the name
Varonic S), of the general formula
[0181] ##STR00025## [0182] amidoamines, e.g.
stearylamidopropyldimethylamine (commercialized available under the
name ADOGEN S-18 V), of the general formula
[0182] ##STR00026## [0183] alkanolamides, e.g. diethanolamides
(commercialized under the name REWOMID DC212S or REWOMID S280 or
VARAMID 70), of the general formula
[0183] ##STR00027## [0184] ethoxylated monoethanolamides
(commercialized under the name REWOCOROS AC 100 or VARAMIDE T-55)
of the general formula
[0184] ##STR00028## [0185] alkylphosphine oxides, e.g.
dimethyldecylphosphine oxides (commercialized under the name APO
10) [0186] alkyl-N-glucamides, e.g. octyl-N-glucamide
(commercialized under the name MEGA-10) [0187] alkyl glucosides,
e.g. n-nonyl-.beta.-D-glucopyranoside or
octyl-.beta.-D-thioglucopyranoside (commercialized under the
AGNIQUE PG series) [0188] bile acids, e.g. cholanic acid or cholic
acid [0189] alkyl alkoxylates, e.g. polyethylene glycol
p-1,1,3,3-tetramethylbutyl)phenyl ether (commercialized under the
name TRITON X-100) or polyethylene glycol isotridecyl ether
(commercialized under the name GENAPOL X-080 or TEGO Alkanol TD 6)
or polyethylene glycol stearyl ether (commercialized under the name
TEGO Alkanol S 2, S 10, S 20P) or polyethylene glycol oleyl ether
(commercialized under the name TEGO Alkanol O 20) or polypropylene
glycol myristyl ether (commercialized under the name VARONIC APM)
or polyethylene glycol nonylphenyl ether (commercialized under the
name REWOPAL HV 10) or polyethylene glycol-polypropylene glycol
copolymers (commercialized under the name PLURONIC, e.g. F68 or
F127), of the general formula
[0189] R.sub.21--P [0190] polyether polyols (commercialized, for
example, under the names TERGITOL L-62 E and L-62 and L-81) [0191]
sorbitan esters, e.g. sorbitan monolaurate (commercialized under
the name TEGO SML) or sorbitan trioleate (commercialized under the
name TEGO STO), of the general formula
[0191] ##STR00029## [0192] sorbitan ester ethoxylates, e.g.
polyoxyethylenesorbitan monolaurate (commercialized under the name
TEGO SML 20) or polyethylene glycol monooleate (commercialized
under the name TEGO SMO) or polyethylene glycol sorbitan
tristearate (commercialized under the name TEGO STS) [0193] fatty
alcohols, e.g. isostearyl alcohol (commercialized under the name
TEGO Alkanol 66) or oleyl alcohol (commercialized under the name
TEGO Alkanol 80, 85 and 90), of the general formula
[0193] R.sub.21--OH [0194] fatty acid ethoxylates, e.g.
polyethylene glycol stearate (commercialized under the name TEGO
Acid S) or polyethylene glycol oleate (commercialized under the
name AROSURF 8-190 or REWOPAL EO 70), of the general formula
[0194] ##STR00030## [0195] ester oils, e.g. isopropyl palmitate
(commercialized under the name TEGOSOFT P) or ethylhexyl palmitate
(TEGOSOFT OP), of the general formula
[0195] ##STR00031## [0196] ester ethoxylates, e.g. polyethylene
glycol glyceryl laurate (commercialized under the name TAGAT L2) or
polyethylene glycol glyceryl oleoricinolate (commercialized under
the name TAGAT V20) or polyethylene glycol glyceryl cocoate
(commercialized under the name Varonic LI) [0197] organomodified
siloxanes, for example: polyether siloxanes, e.g. commercialized
under the TEGOPREN series or the TEGO WET series.
[0198] Particularly suitable polyether siloxane derivatives are
those of the general formula (XVIII):
##STR00032## [0199] where the radical [0200] R.sup.f can be the
radical R.sup.1, where [0201] R.sup.1 is an alkyl radical having
from 1 to 4 carbon atoms or an aryl radical, [0202] or [0203]
R.sup.f is the radical R.sup.2 or R.sup.3, with the proviso that at
least one radical R.sup.f is the radical R.sup.2, where [0204]
R.sup.2 and R.sup.3 are, independently of one another, polyether
radicals of the Formula (XIX)
[0204]
(F).sub.q(O(C.sub.2H.sub.4-dR'.sub.dO).sub.m(C.sub.xH.sub.2xO).su-
b.rZ).sub.w (XIX) [0205] where [0206] d is from 1 to 3, [0207] m is
>1, [0208] q is 0 or 1, [0209] x is from 2 to 10, [0210] r is
>1, [0211] w is from 1 to 4, [0212] F is a hydrocarbon radical
which may also be branched, [0213] R' is a hydrogen radical, a
monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
[0214] Z is an H atom or a monovalent organic radical such as alkyl
or alkyl ester or aryl ester, [0215] and where, in Formula (XIII)
[0216] b is from 0 to 8, [0217] a is from 1 to 100 when b is from 6
to 8, [0218] a is from 1 to 200 when b is from 3 to 6, [0219] a is
from 1 to 300 when b is from 0 to 3
[0220] The values of a and b are average values since the silicone
polyether copolymers which are concomitantly used according to the
invention are present in the form of generally equilibrated
mixtures.
[0221] The radicals R1 are alkyl radicals having from 1 to 4 carbon
atoms, e.g. methyl, ethyl, propyl or butyl radicals, or aryl
radicals, with phenyl radicals being preferred. For reasons of
production and price, methyl radicals are preferred, so that at
least 80% of the radicals R1 are methyl radicals. Particular
preference is given to polysiloxanes in which all radicals R1 are
methyl radicals.
[0222] The siloxane mixture can be linear (b=0) or branched (b>0
to 8). The value of a can, on the basis of experience, be combined
only in the indicated way with values of b since otherwise the
increased viscosity makes handling impossible.
[0223] Particularly preferred silicone polyether copolymers are
those of the general formula (xx)
##STR00033##
where [0224] m=0 to 30, [0225] k=1 to 5, [0226] R.sup.1 is an allyl
alcohol or an alkyl-initiated polyether which has been reacted with
from 1 to 10 ethylene oxide molecules and from 1 to 25 propylene
oxide molecules, [0227] functionalized polyether siloxanes, e.g.
commercialized under the product name TEGOPREN 7100 [0228]
polyether siloxanes having a block structure.
[0229] Suitable polyether siloxanes are structures of the Formula
(XXI)
##STR00034##
where the radical [0230] A is a polyoxyalkylene block of the
average Formula (XXII),
[0230]
[(C.sub.2H.sub.4-dR'.sub.dO).sub.n(C.sub.xH.sub.2xO).sub.r(C.sub.-
2H.sub.4-dR''.sub.dO).sub.t] (XXII)
where [0231] d is from 1 to 3, [0232] n is .gtoreq.0, [0233] x is
from 2 to 10, [0234] r is .gtoreq.0, [0235] t is .gtoreq.0, [0236]
n+r+t.gtoreq.1, [0237] and [0238] R' is a monovalent aromatic,
substituted or unsubstituted hydrocarbon radical, [0239] R'' is a
hydrogen radical or a monovalent hydrocarbon radical having from 1
to 18 carbon atoms, [0240] R.sup.1 is an H atom, a monovalent
organic linear or branched alkyl radical having a chain length of
C.sub.1-C.sub.40 or a carboxyl radical of a branched or unbranched
alkyl ester or aryl ester, [0241] B is a polysiloxane block of the
average Formula (XXIII),
##STR00035##
[0241] where [0242] the radicals R.sup.2 are identical or different
and are each an alkyl radical having from 1 to 4 carbon atoms or a
phenyl radical and [0243] y is from 5 to 200, [0244] m is from 2 to
100, [0245] p is 0 or 1 and [0246] q is 0 or 1,
or of the Formula (XXVI)
##STR00036##
[0247] where the radicals [0248] R.sup.1, A, B and m, p and q are
as defined above and [0249] C is a linear or branched alkylene
radical having from 2 to 20 carbon atoms.
[0250] The compounds of the structures indicated are present as
statistical mixtures and the indices indicated therefore correspond
to the arithmetic means of the mixtures.
2. Cationic Surfactants:
[0251] tetraalkylammonium salts, e.g. cetyltrimethylammonium
bromide [0252] alkylpyridinium salts, e.g. cetylpyridinium chloride
[0253] ester quats, e.g. commercially available under the names
REWOQUAT WE 15, VARISOFT WE 16 or REWOQUAT WE 38 DPG, of the
general formula
[0253] ##STR00037## [0254] diamidoamine quats, e.g. commercially
available under the names VARISOFT 110-75
[N,N-bis(hydrotallowamidoethyl)-N-polyethoxy-N-methylammonium
methylsulphate], VARISOFT 222 LT-90
[N,N-bis(oleylamidoethyl)-N-polyethoxy-N-methylammonium
methylsulphate], or REWOQUAT WE 38 DPG or VARIQUAT 238-90
[N,N-bis(tallowamidoethyl)-Npolypropoxy-N-methylammonium
methylsulphate], of the general formula
[0254] ##STR00038## [0255] imidazolinium quats, e.g. commercially
available under the names REWOQUAT W 90, VARIQUAT 55 or REWOQUAT
W3690 [0256] alkoxyalkyl quats, e.g. commercially available under
the name VARIQUAT 638
[N-methyl-N,N-bis(2-hydroxyethyl)-N-cocoammonium chloride [0257]
benzyl quats, e.g. commercially available under the names VARIQUAT
80 MC [dimethylalkyl(C12-C16)benzylammonium chloride and VARIQUAT
SDAC [dimethylstearylbenzylammonium chloride], of the general
formula
[0257] ##STR00039## [0258] silicone quats, e.g. commercially
available under the names TEGOPREN 6921 [diquaternary
polydimethylsiloxane], TEGOPREN 6924 [diquaternary
polydimethylsiloxane] and TEGOPREN 7990 [diquaternary polyether
polydimethylsiloxane].
3. Amphoteric Surfactants:
[0258] [0259] betaines, e.g.
3-[N,N-dimethyl(3-myristoylaminopropyl)ammonio]propanesulphonate
(commercially available under the name amidosulphobetaine-14) or
1-(3-sulphopropyl)pyridinium betaine or
3-dodecyldimethylammoniopropane-1-sulphonate (commercially
available under the name ZWITTERGENT 3-12) or
3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulphonates
(commercialized under the name CHAPS) or lauryl betaine
(commercialized under the name REWOTERIC AM DML-35) or
cocamidopropyl betaine (commercialized under the name TEGO Betain F
50 or L 7), alkylglycines, e.g. n-dodecyl-N,N-dimethylglycine
(commercialized under the name EMPIGEN BB) or tallowglycine
(commercialized under the name Rewoteric AM TEG), of the general
formula
[0259] ##STR00040## [0260] sultaines, e.g.
cocamidopropylhydroxysultaine (commercialized under the name
REWOTERIC AM CAS), of the general formula
[0260] ##STR00041## [0261] amphopropionates, e.g.
cocoamphopropionate (commercialized under the name REWOTERIC AM KSF
40), of the general formula
[0261] ##STR00042## [0262] amphoacetates, e.g. sodium
cocoamphoacetate (commercialized under the name REWOTERIC AM C), of
the general formula
[0262] ##STR00043## [0263] amine oxides, e.g.
cocamidopropyldimethylamine oxide (commercialized under the name
VAROX 1770), of the general formula
[0263] ##STR00044## [0264] silicone betaines, e.g. commercialized
under the name TEGOPREN 6950.
4. Perfluorinated Surfactants:
[0264] [0265] perfluorinated alkylsulphonates, e.g.
perfluorooctanesulphonate (PFOS) [0266] perfluorinated carboxylic
acids, e.g. perfluorooctanoic acid (PFOA) [0267] fluorinated
telomere alcohols.
5. Gemini Surfactants:
[0267] [0268] acetylene diols, e.g. commercialized under the name
SURFYNOL 104 [0269] acetylene diol alkoxylates, e.g. commercialized
under the name SURFYNOL 400 or SURFYNOL 2502 [0270] acetylene
glycols, e.g. commercialized under the name DYNOL 604 [0271] alkane
diols, alkanedicarboxylic acids and esters thereof, e.g.
commercialized under the names ENVIROGEM AD01, ENVIRONGEM AE01,
ENVIRONGEM AE02 and ENVIRONGEM AE03 [0272] ENVIRONGEM 360 [0273]
bispyridinioalkanes, e.g. 1,4-bis(.alpha.-octylpyridinio)butane
dibromide or 1,4-bis(adodecylpyridinium)butane dichloride [0274]
siloxane-based Gemini surfactants as described in EP A1-1 382 632
(US 2004229964), e.g. commercialized under the name TEGO TWIN 4000.
The contents of EP-A1-1 382 632 are fully incorporated by reference
into the present disclosure.
[0275] The compositions of the invention preferably contain one or
more nonionic surfactants, particularly preferably one or more
organo-modified siloxanes, particularly preferably one or more
polyether siloxanes and especially polyether siloxanes of the
Formula (XVIII), as performance additive.
[0276] Registered trademarks are rendered in upper case
letters.
[0277] The trademark proprietors are:
TEGO TEGOSURF AROSURF REWOQUAT VARONIC ADOGEN REWOMID VARAMID
REWOCOROS REWOPAL are trademarks of Evonik Goldschmidt GmbH
SURFYNOL, DYNOL, ENVIROGEM are trademarks of Air Products, Inc.
AGNIQUE is a trademark of Cognis TRITON is a trademark of DOW
Chemical Company GENAPOL is a trademark of Clariant PLURONIC is a
trademark of BASF AG EMPIGEN is a trademark of Albright&Wilson
VAROX is a trademark of R.T. Vanderbilt ZWITTERGENT is a trademark
of Calbiochem-Novachem
[0278] The abovementioned performance additives can be used either
alone or in any mixtures with one another together with the ionic
liquids. Further customary solvents, auxiliaries and additives can
likewise have been or be mixed in.
[0279] Examples of solid surfaces are glass, metal, semiconductors,
polymers, ceramic, stone and leather and fabrics or membranes
comprising these materials.
[0280] Examples of metal surfaces are surfaces of aluminium,
chromium, nickel, magnesium, titanium, vanadium, iron, copper,
zinc, cobalt, gallium, germanium, zirconium, molybdenum, palladium,
silver, tin, tungsten, platinum, gold, lead and alloys thereof,
also with other elements such as carbon, in particular steel. An
example of a steel surface is a surface of S235JRG2 steel.
[0281] Examples of semiconductor surfaces are surfaces of silicon
and titanium dioxide.
[0282] Examples of polymer surfaces are surfaces of natural or
synthetic thermoplastics, thermosets and elastomers.
[0283] Examples of plastic surfaces are polyacrylates such as
polymethyl methacrylate, polyacrylonitrile, polyacrylic acid,
polyvinyl halides such as polyvinyl chloride, polyvinyl alcohol,
polyethylene, polypropylene, polybutadiene, polyacrylonitrile,
polyethers, polysulphides, polysulphones, polyether sulphone,
polyketones, polyesters, polycarbonates, polystyrene, formaldehyde
resins, epoxy resins, polyamides, polyureas, polyurethanes,
polyimides, polyphenols, polypyrroles, polyfuran, polythiophene,
polybenzimidazoles, polyamines, polyanhydrides,
polytetrafluoroethylene, polyvinylidene fluoride, polylactates,
polysiloxanes, polysilanes, copolymers and blends thereof and
mixtures or copolymers, oligomers and block (co)polymers thereof.
Natural polymers are rubber, lignin, polysaccharides,
polyhydroxybutyric acid and proteins.
[0284] Examples of ceramic surfaces are surfaces of clay, kaolin,
clay minerals, aluminium oxide, beryllium oxide, zirconium oxide,
silicon carbide, silicon nitride, aluminium nitride, boron nitride,
boron carbide.
[0285] Among the solid surfaces, membrane surfaces are particularly
preferred.
[0286] The invention likewise provides for the use of the
compositions comprising one or more ionic liquids and one or more
performance additives and also further additives and/or
auxiliaries, wherein the composition has a contact angle with the
treated surface which is at least 100 smaller, preferably 200
smaller, particularly preferably 300 smaller and very particularly
preferably 400 smaller, than that without the addition of the
performance additive.
[0287] The invention likewise provides for the use in a method of
wetting solid surfaces by ionic liquids, preferably optimized
wetting by addition of the performance additive, with particular
preference being given here to the wetted surface being at least
30% greater, preferably 50% greater, particularly preferably 80%
greater and very particularly preferably 100% greater, than without
addition of the performance additive. This is also associated with
an increase in the diameter of the wetted area, which is likewise
at least 50% greater than the diameter of the wetted surface
without addition of the performance additive.
[0288] The mixing ratios of ionic liquid and performance additive
are in the range from 100 000:1 to 1:10 000, preferably from 10
000:1 to 1:1, particularly preferably from 10 000:1 to 10:1, very
particularly preferably from 1000:1 to 100:1 (all ratios are ratios
of % by weight).
[0289] The mixtures can contain further solvents, in particular
organic solvents and/or water. Preferred organic solvents are
aliphatic, cycloaliphatic, aromatic, heterocyclic, heteroaromatic
substituted or unsubstituted alcohols, aldehydes, ketones,
carboxylic esters, carboxamides, carboxylic anhydrides, carbonates,
carbamates, nitrites, ethers, polyethers, alkanes, alkenes,
halogenated hydrocarbons, thiols, thioethers, thioesters, amino
acids, polyols, sulphones, sulphoxides, ureas and thioureas.
[0290] The proportion of the solvent in the total mixture is in the
range from 99.9% to 0.01%, preferably from 50% to 0.05%,
particularly preferably from 25% to 0.1% and very particularly
preferably from 10% to 0.5% (all percentages are % by weight).
[0291] The increase in wettable area for the compositions of the
invention relative to composition without at least one performance
additive is in a range selected from the group consisting of about
40% to about 1500% and about 50% to about 1200%.
[0292] The mixtures can also be used advantageously for many other
chemical-industrial processes, thus generally in the metal
processing industry, for example in cooling lubricants, hardening
oils, hydraulic fluid emulsions, polishing pastes, mould release
agents, drawing oils, pickling agents or metal cleaners.
[0293] Furthermore, the mixtures of the invention can be used in
the leather, paper, printing, electroplating and photographic
industries.
[0294] Furthermore, the mixtures can be used in water treatment,
for example in the treatment of wastewater.
[0295] Furthermore, the mixtures can be used in crop protection
formulations.
[0296] The surfactants can be used either alone or in mixtures with
one another and can contain further additives and auxiliaries which
can be specifically selected according to the application.
[0297] Further subjects of the invention are characterized by the
claims, with the disclosure content of the claims being fully
incorporated by reference into the disclosure of the
description.
[0298] The performance additives of the invention and their use are
illustrated by way of example below, without the invention being
restricted to these illustrative embodiments. When ranges, general
formulae or classes of compounds are indicated below, these
encompass not only the corresponding ranges or groups of compounds
which are explicitly mentioned but also all subranges and subgroups
of compounds which can be obtained by leaving out individual values
(ranges) or compounds.
EXAMPLES
[0299] The present invention is described by way of example in the
following examples, without implying a restriction of the
invention, whose scope is indicated by the total description and
the claims, to the embodiments mentioned in the examples.
Experimental Procedure:
[0300] 8 g of ionic liquid (IL) were placed in a vessel and 0.04 g
of the performance additive was weighed in. The sample was stirred
with a spatula until it was homogeneous and 50 .mu.l were
subsequently pipetted onto a PP film. The maximum spread after 5
minutes was determined. The diameter (D) of the resulting circle is
determined in mm. The higher the measured value, the greater the
spreading and wetting and thus the effect of the performance
additive according to the invention.
TABLE-US-00001 TABLE 1 Wetting behavior/spreading behavior of ionic
liquids (spreading measured after 5 minutes). The concentration is
given by the experimental procedure above. The measurements were
carried out at room temperature. EMIM EMIM EMIM ES Increase IL 1
Increase Ac Increase DCA Increase D in in area D in in area D in in
area D in in area SURFACTANT/IL mm in % mm in % mm in % mm in %
Blank (pure 6 4 7 6 IL) TEGO WET 14 440.0 5 56.0 12 190.0 10 180.0
KL 245 TEGO Wet 505 10 178.0 8 300.0 10 100.0 TEGO Twin 20 1011.0
11 650.0 22 890.0 18 800 4000 TEGOPREN 5878 8 300.0 9 66.0 8 79
TEGO STO 10 100.0 85 V EMIM = 1-Ethyl-3-methylimidazolium ES =
Ethylsulphate Ac = Acetate DCA = Dicyanamide IL1 =
Bis-(hydroxyethyl)dimethylammonium methane-sulphonate IL2 =
Ethyltributylphosphonium diethylphosphate TEGO Wet KL 245 =
Polyether-modified polysiloxane (CAS No. 134180-76-0) TEGO WET 505
= Alkyl alkoxylate (CAS No. 303152-49-0) TEGO Twin 4000 =
Polyether-modified polysiloxane (CAS No. 780769-22-4) TEGOPREN 5878
= Polyether-modified polysiloxane (CAS No. 27306-78-1) TEGO STO 85
V = Polyoxyethylene(20)sorbitan trioleate (CAS No. 9005-70-3)
[0301] It can clearly be seen that the addition of the performance
additive leads to a significant increase in the wetted surface
area. The diameter of the wetted area is, in each case demonstrated
by way of example, more than 50% greater than the diameter of the
wetted area without the performance additive. The wetted area
itself has increased to an even greater extent in relative
terms.
[0302] The contact angle to polypropylene film (PP film) of the
ionic liquids measured changes significantly after the addition of
the performance additives.
[0303] The contact angle is a measure of the spreading properties
of the performance additives. The spreading capability is greater
the lower the contact angle (higher range value in the following
table).
[0304] The formulations used were produced according to the
above-described experimental procedure and the contact angles were
measured by means of a Pendant prop Tensiometer OCA 35 from
Dataphysics.
TABLE-US-00002 TABLE 2 Spreading capability of ionic liquids with
addition of a performance additive. The concentrations can be
obtained from the experimental procedure. The measurement
temperature is room temperature. SURFACTANT/ EMIM EMIM EMIM 3 HC 14
P IL ES IL 1 AC DCA DCA IL 2 Blank 2 1 3 3 6 6 TEGO WET 505 6 4 6
TEGO TWIN 9 9 9 9 9 9 4000 TEGOPREN 6 6 5878 TEGO STO 85 V 6 6 TEGO
Wet KL 8 4 245
[0305] 3 HC 14 P DCA=Trihexyltetradecylphosphonium dicyanamide To
assess the contact angle, the following ranges were set down:
TABLE-US-00003 TABLE 3 Range values Contact angle in [.degree.]
Range >90 1 80-89 2 70-79 3 60-69 4 50-59 5 40-49 6 30-39 7
20-29 8 <20 9
[0306] This indicates that a contact angle difference of at least
20.degree. is obtained when there are at least three value ranges
between the range values indicated.
[0307] Furthermore, mixtures of an ionic liquid and the performance
additives according to the invention were applied by means of a
doctor blade to a glass plate and the wetting properties and the
film formation of the products was checked.
[0308] For this purpose, 8 g of the ionic liquid were placed in a
vessel and from 0.04 g to 0.08 g of the performance additive were
weighed in. The products were stirred by means of a spatula until
they gave a homogeneous mixture. The appearance of the mixtures is
assessed and indicated in the table.
[0309] A glass plate was prepared by precleaning it using water and
cleaners, subsequently rinsed under running water and degreased by
means of ethanol. This glass plate was placed on a horizontal
substrate and the box doctor blade was placed at one end of the
glass plate. Part of the liquid was introduced into the box which
was drawn in one stroke over the glass plate. The applied layer
should be no more than 50 .mu.m. The layer formed was assessed
immediately afterwards. Here, the number of craters was counted.
The results show that the number of craters was significantly
reduced by addition of the performance additive compared to the
blank. The addition of a performance additive thus improves the
wetting properties of the ionic liquids.
[0310] Having thus described in detail various embodiments of the
present invention, it is to be understood that the invention
defined by the above paragraphs is not to be limited to particular
details set forth in the above description as many apparent
variations thereof are possible without departing from the spirit
or scope of the present invention.
* * * * *