U.S. patent application number 12/176573 was filed with the patent office on 2009-01-29 for use of ionic liquids for the noncutting forming of metallic workpieces.
Invention is credited to Brigitte Finger, Rene Hansel, Peter Schwab, Bernd Weyershausen.
Application Number | 20090029887 12/176573 |
Document ID | / |
Family ID | 40010864 |
Filed Date | 2009-01-29 |
United States Patent
Application |
20090029887 |
Kind Code |
A1 |
Schwab; Peter ; et
al. |
January 29, 2009 |
USE OF IONIC LIQUIDS FOR THE NONCUTTING FORMING OF METALLIC
WORKPIECES
Abstract
The invention relates to the use of at least one ionic liquid or
a mixture of ionic liquids for noncutting forming processes for
metallic workpieces.
Inventors: |
Schwab; Peter; (Essen,
DE) ; Weyershausen; Bernd; (Essen, DE) ;
Hansel; Rene; (Dorsten, DE) ; Finger; Brigitte;
(Essen, DE) |
Correspondence
Address: |
FROMMER LAWRENCE & HAUG
745 FIFTH AVENUE- 10TH FL.
NEW YORK
NY
10151
US
|
Family ID: |
40010864 |
Appl. No.: |
12/176573 |
Filed: |
July 21, 2008 |
Current U.S.
Class: |
508/283 |
Current CPC
Class: |
C10M 2207/122 20130101;
C10M 2215/04 20130101; C10N 2030/08 20130101; C10M 2219/042
20130101; C10N 2020/077 20200501; B21D 22/201 20130101; C10M
2219/044 20130101; B21D 37/18 20130101; C10N 2040/24 20130101; C10M
2215/222 20130101; C10M 105/00 20130101; C10M 2215/226 20130101;
B21D 26/02 20130101 |
Class at
Publication: |
508/283 |
International
Class: |
C10M 133/46 20060101
C10M133/46 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 24, 2007 |
DE |
102007034353.3 |
Claims
1. An ionic liquid which comprises of an ionic salt of the general
formulae I, II or III: [A]n.sup.+ [Y].sup.n- (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) [A1].sup.+ [A2].sup.+ [Y].sup.2-
(IIa) [A1].sup.+ [A2].sup.+ [A3].sup.+ [Y].sup.3- (IIb) or
[A1].sup.+ [A2].sup.+ [A3].sup.+ [A4].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 the groups
mentioned for [A].sup.+ and [Y].sup.n- is as defined for formula I;
or mixed salts of the general formulae (III) [A1].sup.+ [A2].sup.+
[A3].sup.+ [M1].sup.+ [Y].sup.4- (IIIa); [A1].sup.+ [A2].sup.+
[M1].sup.+ [M2].sup.+ [Y].sup.4- (IIIb); [A1].sup.+ [M1].sup.+
[M2].sup.+ [M3].sup.+ [Y].sup.4- (IIIc); [A1].sup.+ [A2].sup.+
[M1].sup.+ [Y].sup.3- (IIId); [A1].sup.+ [M1].sup.+ [M2].sup.+
[Y].sup.3- (IIIe); [A1].sup.+ [M1].sup.+ [Y].sup.2- (IIIf);
[A1].sup.+ [A2].sup.+ [M4].sup.2+ [Y].sup.4- (IIIg); [A1].sup.+
[M1].sup.+ [M4].sup.2+ [Y].sup.4- (IIIh); [A1].sup.+ [M5].sup.3+
[Y].sup.4- (IIIi); or [A1].sup.+ [M4].sup.2+ [Y].sup.3- (IIIj)
where [A.sup.1].sup.+, [A.sup.2].sup.+ and [A.sup.3].sup.+ are
selected independently from 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 the formulae
(I)-(III).
2. The ionic liquid of claim 1, wherein the ionic salt comprises of
at least one anion selected from the group consisting of halides,
carboxylates, phosphates, thiocyanates, isothiocyanates,
dicyanamides, sulphates, alkylsulphates, sulphonates,
alkylsulphonates, tetrafluoroborate, hexafluorophosphate and
bis(trifluoromethylsulphonyl)imide combined with, substituted
ammonium, phosphonium, pyridinium or imidazolium cations,
3. The ionic liquid of claim 1 wherein the ionic salt comprises 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+ (VIII) where 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 hydro-carbon radical which has from 1 to 30
carbon atoms and may contain a double bond, a cycloaliphatic
hydrocarbon radical which has from 5 to 40 carbon atoms and may
contain a double bond, 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 hetero-atoms (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 which may have a block or random structure and has the
formula --(R.sup.5--O).sub.n--R.sup.6, where R.sup.5 is a linear or
branched hydrocarbon radical containing from 2 to 4 carbon atoms, n
is from 1 to 100, preferably from 2 to 60, and R.sup.6 is hydrogen,
a linear or branched aliphatic hydrocarbon radical which has from 1
to 30 carbon atoms that 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 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 cyclo-aliphatic
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.
4. A method of noncutting forming of metallic workpieces which
comprises applying at least one ionic liquid or a mixture of ionic
liquids as defined in claim 1 to a precursor metallic object.
5. The method of claim 4, wherein the noncutting forming is
internal high-pressure forming.
6. The method of claim 5, wherein the ionic liquid or the mixture
of ionic liquids is used as external lubrication and/or as pressure
medium and/or as heat transfer fluid.
7. The method of claim 6, wherein the ionic liquid or the mixture
or ionic liquids has a melting point below 100.degree. C.
8. The method of claim 7, wherein the ionic liquid or the mixture
or ionic liquids has a melting point below 50.degree. C.
9. The method of claim 6, wherein the ionic liquid used as external
lubrication in a noncutting forming process or the mixture of ionic
liquids has a melting point above room temperature.
10. The method of claim 6, wherein the ionic liquid or the mixture
of ionic liquids has a liquid range from -50.degree. C. to
400.degree. C.
11. The method of claim 6, wherein the ionic liquid or the mixture
of ionic liquids has a liquid range from -40.degree. C. to
380.degree. C.
12. The method of claim 6, wherein the ionic liquid or the mixture
of ionic liquids has a liquid range from -30.degree. C. to
350.degree. C.
13. The method of claim 6, wherein the ionic liquid or the mixture
of ionic liquids has a decomposition temperature above 300.degree.
C.
Description
[0001] This application claims benefit under 35 U.S.C. 119(a) of
German patent application DE 10 2007 034 353.3, filed on 24 Jul.
2007.
[0002] Any foregoing applications, including German patent
application DE 10 2007 034 353.3, 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.
[0003] The invention relates to the use of ionic liquids for the
noncutting forming of metallic workpieces according the description
herein for purposes such as internal high-pressure forming.
BACKGROUND
[0004] In the noncutting forming of workpieces made of metal, a
force is exerted on the workpiece and leads to forming of the metal
by flow processes. Examples are forming by pressing, cold flow
pressing, drawing, deep drawing and internal high-pressure forming,
which is often also referred to as "hydroforming". In these forming
processes, friction occurs between the surfaces of the workpiece
and the tool used, which can, for example, be a die, punch, draw
mould, draw ring or hollow mould. The friction has to be reduced by
the use of suitable lubricants since otherwise damage to the tool
and/or workpiece can occur, for example as a result of cold
welding. In addition, the lubricant can help reduce the force to be
applied for forming and also the energy requirement associated
therewith.
[0005] Internal high-pressure forming is a specific forming process
in which hollow sheet metal parts or sheet metal strips are brought
to the desired shape by means of a liquid medium ("pressure
medium") in a moulding tool (F. Klocke, W. Konig,
"Fertigungsverfahren 4. Umformtechnik: Umformen", Springer Verlag
Berlin, 5th edition, August 2006). Here, the workpiece is widened
by means of the internal pressure and at the same time compressed
axially. Before widening, the workpiece is introduced into a closed
tool and as a result of the internal pressure acquires the shape of
the hollow space of the tool. In this process, material can
continually be supplied via one end of the tube in order to achieve
a desired thickness of the material. The internal pressure of from
200 bar to 3000 bar is transmitted, for example, by a water-oil
emulsion, usually at room temperature. The axial force for
controlling the thickness of the material of the forming product
can be applied via two liquid-tight rams at the ends of the tube.
The oil in the forming medium serves to provide lubrication in the
process, in particular of valves, and can be provided with biocidal
properties.
[0006] The process of internal high-pressure forming is at present
preferably employed in areas which require a high degree of
forming, in particular in the case of hollow parts. Examples are
A-columns, rear axles, catalysts and exhaust pipes in the
automobile industry or fittings and water faucets in the bathroom
sector.
[0007] A further variant of internal high-pressure forming
comprises heating processes which operate in a lower pressure range
at elevated temperatures up to about 300.degree. C. This enables,
for example, high-grade materials such as aluminium alloys or
magnesium alloys to be processed. A heat transfer fluid is used for
heating.
[0008] During forming, there is always relative motion between tool
and workpiece and thus friction between the surfaces. It is
therefore necessary to apply a lubricant between workpiece and
tool. In the case of internal high-pressure forming, this is also
referred to as external lubrication, while lubrication by means of
the pressure medium can also be referred to as internal
lubrication. Lubricants known for external lubrication are drawing
oils and drawing greases and also soaps on conversion layers such
as phosphating layers or Eloxal layers, lubricant surface coatings
containing graphite, molybdenum sulphide or Teflon, waxes and
drawing films. DE 101 15 696 A1 additionally discloses specific
low-water mixtures of oils and waxes with addition of lubricating
additives as external lubrication.
[0009] Hydraulic oils are used as pressure media or internal
lubrication because of their compressibility up to pressures of
about 1500 bar. Alternatives are aqueous media based on
water-miscible lubricants containing mineral oil or synthetic
lubricants. The lubricant additives added to aqueous pressure media
are also referred to as cooling lubricants. Water-oil emulsions are
usually employed.
[0010] These previously known lubricants, especially those for
external lubrication, each have different disadvantages. Drawing
greases and drawing films and likewise lubricant surface coatings
can only be applied manually and are therefore unsuitable for mass
production. Soap-covered conversion layers are complicated to
produce and can, especially in the case of entrainment of the soaps
in the pressure medium, lead to undesirable foaming. Lubricant
surface coatings can be removed from the finished workpiece only
with great difficulty, usually only by means of a grinding process,
and remain in pieces either on the tool or on the workpiece. Waxes
can get into the pressure medium and, as particles, block the very
fine filters of the pressure transducers.
[0011] In general, when choosing the external lubrication and the
internal lubrication it has to be ensured that, firstly, the
external lubricant can easily be removed from the finished
workpiece. Secondly, introduction of external lubrication into the
pressure medium can occur at any time during practical use. For
this reason, either good separability of the two media is desirable
to avoid impairment of the lubricating action and make it possible
for the individual media to be reused or, as an alternative, it
would be desirable to match the two media to one another so that
good compatibility is ensured and only a single homogeneous
lubricant system has to be used.
OBJECT OF THE INVENTION
[0012] It is therefore an object of the invention to provide a
lubricant for noncutting forming processes which makes a simple
handling and an improved property profile possible, ideally with
the same lubricant being able to be used as external lubrication,
as pressure medium and also as heat transfer fluid.
[0013] This is achieved according to the invention by use of at
least one ionic liquid or a mixture of ionic liquids according to
Claim 1.
[0014] The use according to the invention of at least one ionic
liquid provides a novel lubricant for noncutting forming processes
which can be used as external lubrication, as pressure medium
and/or as heat transfer fluid.
[0015] 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.
[0016] 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.
[0017] This makes it possible for the first time to use a lubricant
which can easily be removed from the finished workpiece and
displays a property profile which can be adjusted over a wide range
in respect of viscosity, density, thermal stability and
anticorrosion properties. On this basis, it is possible to produce
a tailored lubricant for each forming process, which fully meets
requirements in respect of the abovementioned properties.
[0018] In addition, use of ionic liquid or a mixture of ionic
liquids as lubricant in noncutting forming processes enables
simplified handling to be achieved by application of the lubricant
being able to be effected in liquid form by means of, for example,
spraying or in solid form by means of dipping into a lubricant bath
which has been liquefied by heating and subsequent cooling.
[0019] Particularly in the case of use according to the invention
of an ionic liquid or a mixture of ionic liquids as external
lubrication in internal high-pressure forming using a water-oil
emulsion as pressure medium, preference is given to selecting ionic
liquids which are not miscible with the water-oil emulsion and can
therefore easily be separated off from the pressure medium. In this
way, reuse of the pressure medium can be ensured.
[0020] Ionic liquids are in general terms salts which melt at low
temperatures (<100.degree. C.) and represent a novel class of
liquids which are made up exclusively of ions. In contrast to the
classical salt melts, which are high-melting, highly viscous and
very corrosive media, ionic liquids are liquid even at low
temperatures and have a relatively low viscosity (K. R. Seddon J.
Chem. Technol. Biotechnol. 1997, 68, 351-356).
[0021] For the purposes of the present invention, ionic liquids are
preferably salts of the general formulae I, II or III:
[A].sup.n+ [Y].sup.n- (I)
[0022] 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
[0023] mixed salts of the general formulae (II)
[A1].sup.+ [A2].sup.+ [Y].sup.2- (IIa)
[A1].sup.+ [A2].sup.+ [A3].sup.+ [Y].sup.3- (IIb) or
[A1].sup.+ [A2].sup.+ [A3].sup.+ [A4].sup.+ [Y].sup.4- (IIc)
[0024] where [A.sup.1].sup.+, [A.sup.2].sup.+, [A.sup.3].sup.+ and
[A.sup.4].sup.+ are selected independently from the groups
mentioned for [A].sup.+ and [Y].sup.n- is as defined for formula I;
or
[0025] mixed salts of the general formulae (III)
[A1].sup.+ [A2].sup.+ [A3].sup.+ [M1].sup.+ [Y].sup.4- (IIIa);
[A1].sup.+ [A2].sup.+ [M1].sup.+ [M2].sup.+ [Y].sup.4- (IIIb);
[A1].sup.+ [M1].sup.+ [M2].sup.+ [M3].sup.+ [Y].sup.4- (IIIc);
[A1].sup.+ [A2].sup.+ [M1].sup.+ [Y].sup.3- (IIId);
[A1].sup.+ [M1].sup.+ [M2].sup.+ [Y].sup.3- (IIIe);
[A1].sup.+ [M1].sup.+ [Y].sup.2- (IIIf);
[A1].sup.+ [A2].sup.+ [M4].sup.2+ [Y].sup.4- (IIIg);
[A1].sup.+ [M1].sup.+ [M4].sup.2+ [Y].sup.4- (IIIh);
[A1].sup.+ [M5].sup.3+ [Y].sup.4- (IIIi); or
[A1].sup.+ [M4].sup.2+ [Y].sup.3- (IIIj)
[0026] where [A.sup.1].sup.+, [A.sup.2].sup.+ and [A.sup.3].sup.+
are selected independently from 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;
[0027] or mixtures of all the formulae (I)-(III).
[0028] Ionic liquids preferably comprise anions such as halides,
carboxylates, phosphates, thiocyanates, iso-thiocyanates,
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 therefore making no claim to completeness or implying
any restrictions.
[0029] 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 point is 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 their
mixtures are particularly preferably liquid at room
temperature.
[0030] The ionic liquids which are preferably used according to the
invention in the noncutting forming process can, for example,
comprise 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+ (VIII)
[0031] where [0032] 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 hydro-carbon radical which has from 1 to 30 carbon atoms
and may contain a double bond, a cycloaliphatic hydrocarbon radical
which has from 5 to 40 carbon atoms and may contain a double bond,
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 hetero-atoms
(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 which may have a block or random structure and has the
formula --(R.sup.5--O).sub.n--R.sup.6, [0033] where [0034] R.sup.5
is a linear or branched hydrocarbon radical containing from 2 to 4
carbon atoms, [0035] n is from 1 to 100, preferably from 2 to 60,
and [0036] R.sup.6 is hydrogen, a linear or branched aliphatic
hydrocarbon radical which has from 1 to 30 carbon atoms that 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 [0037] 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 cyclo-aliphatic
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.
[0038] Further possible cations are cations derived from saturated
or unsaturated cyclic compounds or aromatic compounds having in
each case at least one 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 precise position and number of the
double bonds in the molecule) by the general formulae (IX), (X) and
(XI) below, where the heterocyclic rings may also contain a
plurality of heteroatoms.
##STR00001##
[0039] Here, R.sup.1 and R.sup.2 are as defined above, [0040] R 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
cyclo-aliphatic 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, [0041] X is an oxygen atom, a sulphur
atom or a substituted nitrogen atom (X.dbd.O, S, NR.sup.1).
[0042] Examples of cyclic nitrogen compounds of the above-mentioned
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 (IX), (X) and (XI) can be
unsubstituted (R.dbd.H) or mono-substituted or polysubstituted by
the radical R, and in the case of multiple substitution by R, the
individual radicals R can be different.
[0043] 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 both on the carbon atoms
and on the nitrogen atoms. They can also be fused with
unsubstituted or substituted 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.
[0044] Preference is given to quaternary ammonium salts of
alkoxylated fatty acids, also referred to as alkanolamine ester
quats, having the generic formula of the type
R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+ A.sup.- (IV) in which 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.
[0045] 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.m X.sup.-
(XII)
[0046] where
[0047] 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, [0048] 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, [0049] the
radicals Q are selected independently from among the groups of the
formulae --O--C(O)--, --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)--; [0050] m is from 1
to 4, preferably 2 or 3; [0051] n is from 1 to 4, preferably 2; and
[0052] X is a use-compatible anion, e.g. methylsulphate,
ethylsulphate, methylsulphonate, butylsulphate, octylsulphate,
phosphinate or 2-(2-methoxyethoxy)-ethylsulphate, preferably
methylsulphate, 2-(2-methoxyethoxy)ethylsulphate, octylsulphate or
phosphinate. [0053] The quaternary ammonium compound can contain
mixtures of compounds having different groups R.sup.7 which are not
hydrogen and whose number extends from 1 up to m. Such mixtures
preferably comprise an average of from 1.2 to 2.5 groups R.sup.7
which are not hydrogen. The proportion of groups R.sup.7 which are
different from hydrogen is preferably from 1.4 to 2.0, more
preferably from 1.6 to 1.9.
[0054] The preferred quaternary ammonium compounds are compounds of
the type:
R.sup.6N.sup.+[CH.sub.2CHR.sup.9OH--][CH.sub.2CHR.sup.9OC(O)R.sup.7].sub-
.2 X.sup.- (XIII)
R.sup.6N.sup.+[CH.sub.2CHR.sup.9OC(O)R.sup.7].sub.2 X.sup.-
(XIV)
R.sup.6N.sup.+[CH.sub.2CHR.sup.9OH--][CH.sub.2CH.sub.2NHC(O)R.sup.7].sub-
.2 X.sup.-, (XV)
[0055] where R.sup.6, R.sup.7 and X have the same meanings as
defined above for formula (XII).
[0056] The fragment --C(O)R.sup.7 is preferably a fat-containing
acyl group. Fat-containing acyl groups which can be used are
derived from the natural sources of triglycerides, preferably
tallow, vegetable oils, partially hydrogenated tallow and partially
hydrogenated vegetable oils. Usable sources of triglycerides are,
for example, soybean oil, tallow, partially hydrogenated tallow,
palm oil, palm kernels, rapeseed, lard, coconut, rapeseed oil,
safflower oil, maize, rice and tall oil and mixtures of these
components.
[0057] A person skilled in the art will know that the composition
of the compounds containing fatty acids is subject to certain
natural fluctuations, depending on the particular harvest or on the
large number of vegetable oil sources. The R.sup.7 groups are
normal mixtures of linear and branched carbon chains of saturated
and unsaturated aliphatic fatty acids.
[0058] 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, a partial hydrogenation can
be carried out to increase the saturated character and thus improve
the stability (e.g. odour, colour, etc) of the end product. The
content of unsaturated components, 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 to 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.
[0059] Preferred examples of compounds of the formula (XII)
are:
[0060] N,N-di(tallowyloxyethyl)-N,N-dimethylammonium chloride;
[0061] N,N-di(canolyloxyethyl)-N,N-dimethylammonium chloride;
[0062]
N,N-di(tallowyloxyethyl)-N-methyl-N-(2-hydroxyethyl)-ammonium
methylsulphate;
[0063] N,N-di(canolyloxyethyl)-N-methyl-N-(2-hydroxyethyl)-ammonium
methylsulphate;
[0064]
N,N-di(tallowylamidoethyl)-N-methyl-N-(2-hydroxyethyl)-ammonium
methylsulphate;
[0065] N,N-di(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium
chloride;
[0066] N,N-di(2-canolyloxy-2-oxoethyl)-N,N-dimethylammonium
chloride;
[0067]
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium
chloride;
[0068]
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium
chloride;
[0069]
N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxoethyl)-N,N-dimethyl-
ammonium chloride;
[0070]
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxoethyl)-N,N-dimethylam-
monium chloride;
[0071] N,N,N-tri(tallowyloxyethyl)-N-methylammonium chloride;
[0072] N,N,N-tri(canolyloxyethyl)-N-methylammonium chloride;
[0073] 1,2-ditallowyloxy-3-N,N,N-trimethylammoniumpropyl chloride;
and
[0074] 1,2-dicanolyloxy-3-N,N,N-trimethylammoniumpropyl
chloride.
[0075] Further preferred quaternary ammonium salts are
ditallowdimethylammonium chloride, ditallowdimethyl-ammonium
methylsulphate, dimethylammonium chloride, di(hydrogenated
tallow)distearyldimethylammonium chloride and
dibehenyldimethylammonium chloride.
[0076] Further possible cations are ions which contain two nitrogen
atoms and have the general formula (XII)
##STR00002##
[0077] where [0078] 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 cyclo-aliphatic
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 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 which may have a block or random structure and is made up
of --(R.sup.5--O).sub.n--R.sup.6, [0079] where [0080] R.sup.5 is a
hydrocarbon radical containing from 2 to 4 carbon atoms, [0081] n
is from 1 to 100 and [0082] 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 [0083] 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 cyclo-aliphatic
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.
[0084] As very particularly preferred imidazolinium ions (XVI),
mention may be made of 1-methylimidazolium, 1-ethyl-imidazolium,
1-(1-butyl)imidazolium, 1-(1-octyl)-imidazolium,
1-(1-dodecyl)imidazolium, 1-(1-tetradecyl)-imidazolium,
1-(1-hexadecyl)imidazolium, 1,3-dimethyl-imidazolium,
1-ethyl-3-methylimidazolium, 1-(1-butyl)-3-methylimidazolium,
1-(1-butyl)-3-ethylimidazolium, 1-(1-hexyl)-3-methylimidazolium,
1-(1-hexyl)-3-ethyl-imidazolium, 1-(1-hexyl)-3-butylimidazolium,
1-(1-octyl)-3-methylimidazolium, 1-(1-octyl)-3-ethyl-imidazolium,
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-di-methylimidazolium,
1-(1-hexyl)-2,3-dimethylimidazolium,
1-(1-octyl)-2,3-dimethylimidazolium, 1,4-dimethyl-imidazolium,
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.
[0085] Further possible cations are ions which, in particular, are
made up of the abovementioned cations as a result of dimerization,
trimerization or polymerization to form dications, trications or
polycations. These include dications, trications and polycations
which have a polymeric backbone, for example one based on
siloxanes, polyethers, polyesters, polyamides or polyacrylates, in
particular branched and hyperbranched polymers.
[0086] In a preferred embodiment of the present invention, use is
made of ionic liquids in which the cation [A].sup.+ is a pyridinium
ion (XVIIa),
##STR00003##
[0087] where [0088] 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 hydrogen; [0089] R.sub.3 is dimethylamino and the
remaining radicals R.sub.1, R.sub.2, R.sub.4 and R.sub.5 are
hydrogen; [0090] all radicals R.sub.1 to R.sub.5 are hydrogen;
[0091] 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 hydrogen; or [0092]
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 hydrogen;
[0093] in particular one in which [0094] R.sub.1 to R.sub.5 are
each hydrogen; or [0095] 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
hydrogen. 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-di-methylpyridinium, 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-methyl-pyridinium, 1-methyl-2-ethylpyridinium,
1,2-di-ethylpyridinium, 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.
[0096] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a pyridazinium ion (XVIIb),
##STR00004##
[0097] where [0098] R.sub.1 to R.sub.4 are each hydrogen; or [0099]
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 hydrogen.
[0100] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a pyrimidinium ion (XVIIc),
##STR00005##
[0101] where [0102] 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 [0103] R.sub.1 is hydrogen, methyl or ethyl, R.sub.2
and R.sub.4 are each methyl and R.sub.3 is hydrogen.
[0104] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a pyrazinium ion (XVIId),
##STR00006##
[0105] where [0106] 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; [0107] R.sub.1 is hydrogen, methyl or ethyl, R.sub.2 and
R.sub.4 are each methyl and R.sub.3 is hydrogen; [0108] R.sub.1 to
R.sub.4 are each methyl; or [0109] R.sub.1 to R.sub.4 are each
methyl or hydrogen.
[0110] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a pyrazolium ion (XVIIf), (XVIIg) or
(XVIIg'),
##STR00007##
[0111] where [0112] 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.
[0113] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a pyrazolium ion (XVIIh),
##STR00008##
[0114] where [0115] R.sub.1 to R.sub.4 are each, independently of
one another, hydrogen or methyl.
[0116] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a 1-pyrazolinium ion (XVIIi),
##STR00009##
[0117] where [0118] R.sub.1 to R.sub.6 are each, independently of
one another, hydrogen or methyl.
[0119] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a 2-pyrazolinium ion (XVIIj),
##STR00010##
[0120] where [0121] 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.
[0122] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a 3-pyrazolinium ion (XVIIk) or
(XVIIk'),
##STR00011##
[0123] where [0124] 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.
[0125] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is an imidazolinium ion (XVIIl),
##STR00012##
[0126] where [0127] R.sub.1 and R.sub.2 are each, independently of
one another, hydrogen, methyl, ethyl, 1-butyl or phenyl, R.sub.3
and R.sub.4 are each, independently of one another, hydrogen,
methyl or ethyl and R.sub.5 and R.sub.6 are each, independently of
one another, hydrogen or methyl.
[0128] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is an imidazolinium ion (XVIIm) or
(XVIIm'),
##STR00013##
[0129] where [0130] R.sub.1 and R.sub.2 are each, independently of
one another, hydrogen, methyl or ethyl and R.sub.3 to R.sub.6 are
each, independently of each other hydrogen or methyl.
[0131] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is an imidazolinium ion (XVIIn) or
(XVIIn'),
##STR00014##
[0132] where [0133] 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.
[0134] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a thiazolium ion (XVIIo) or (XVIIo')
or an oxazolium ion (XVIIp),
##STR00015##
[0135] where [0136] 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.
[0137] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a 1,2,4-triazolium ion (XVIIq),
(XVIIq') or (XVIIq''),
##STR00016##
[0138] where [0139] 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.
[0140] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a 1,2,3-triazolium ion (XVIIr),
(XVIIr') or (VIIr''),
##STR00017##
[0141] where [0142] 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.
[0143] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a pyrrolidinium ion (XVIIs),
##STR00018##
[0144] where [0145] 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.
[0146] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is an imidazolidinium ion (XVIIt),
##STR00019##
[0147] where [0148] 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.
[0149] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is an ammonium ion (XVIII),
##STR00020##
[0150] where [0151] R.sub.1 to R.sub.3 are each, independently of
one another, C.sub.1-C.sub.18-alkyl; or [0152] 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 [0153]
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.
[0154] As particularly preferred ammonium ions (XVIII), mention may
also be made of methyltri(1-butyl)ammonium, 2-hydroxyethylammonium,
bis(2-hydroxyethyl)dimethyl-ammonium, N,N-dimethylpiperidinium and
N,N-dimethyl-morpholinium.
[0155] Particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a guanidinium ion (XVIIIv),
##STR00021##
[0156] where [0157] R.sub.1 to R.sub.5 are each methyl; [0158]
R.sub.1 to R.sub.5 are each, independently of one another,
C.sub.1-C.sub.18-alkyl; or [0159] 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.
[0160] As very particularly preferred guanidinium ion (XVIIIv),
mention may be made of N,N,N',N',N'',N''-hexamethylguanidinium.
[0161] Very particular preference is also given to ionic liquids in
which the cation [A].sup.+ is a derivative of an ethanolamine, e.g.
a cholinium ion (XIXw), or of a diethanolamine (XIXw') or of a
triethanolamine (XIXw''),
##STR00022##
[0162] where [0163] 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;
[0164] 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 [0165] 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, [0166] 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, 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.
[0167] Very particular preference is given to ionic liquids in
which the cation [A].sup.+ is a phosphonium ion (VI) in which
R.sub.1 to R.sub.4 are each, independently of one another,
C.sub.1-C.sub.18-alkyl, in particular butyl, isobutyl, 1-hexyl or
1-octyl.
[0168] Among the abovementioned cations, preference is given to the
pyridinium ions (XVIIa), imidazolium ions (XVI) and ammonium ions
(XVIII), 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-dimethyl-pyridinium, 1-ethyl-2-methylpyridinium,
1-(1-butyl)-2-methylpyridinium, 1-(1-hexyl)-2-methylpyridinium,
1-(1-octyl)-2-methylpyridinium, 1-(1-dodecyl)-2-methyl-pyridinium,
1-(1-tetradecyl)-2-methylpyridinium,
1-(1-hexadecyl)-2-methylpyridinium, 1-methyl-2-ethyl-pyridinium,
1,2-diethylpyridinium, 1-(1-butyl)-2-ethyl-pyridinium,
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-ethyl-pyridinium,
1-(1-octyl)-2-methyl-3-ethylpyridinium,
1-(1-dodecyl)-2-methyl-3-ethylpyridinium,
1-(1-tetra-dedyl)-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-methyl-imidazolium, 1-(1-octyl)-3-methylimidazolium,
1-(1-do-decyl)-3-methylimidazolium,
1-(1-tetradecyl)-3-methyl-imidazolium,
1-(1-hexadecyl)-3-methylimidazolium, 1,2-dimethylimidazolium,
1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium,
1-(1-butyl)-2,3-di-methylimidazolium,
1-(1-hexyl)-2,3-dimethylimidazolium, and
1-(1-octyl)-2,3-dimethylimidazolium, 1,4-dimethyl-imidazolium,
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-ethyl-imidazolium,
1,4,5-trimethyl-3-butylimidazolium,
1,4,5-trimethyl-3-octylimidazolium and 2-hydroxyethyl-ammonium.
[0169] 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+.
[0170] The ionic liquids which are preferably used according to the
invention comprise at least one of the abovementioned cations in
combination with at least one anion in each case. As anions, it is
in principle possible to use all anions which in combination with
the cation lead to an ionic liquid.
[0171] The anion [Y].sup.n- of the ionic liquid is, for example,
selected from: [0172] 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.-,
FeCl.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.3CO.sub.2.sup.-, CN.sup.-, SCN.sup.-, OCN.sup.-,
NO.sub.2.sup.-, NO.sub.3.sup.-, N(CN).sup.-; [0173] 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.-; [0174] the group of
phosphates of the general formulae: PO.sub.4.sup.3-,
HPO.sub.4.sup.2-, H.sub.2PO.sup.4-, R.sup.aPO.sub.4.sup.2-,
HR.sup.aPO.sub.4.sup.-, R.sup.aR.sup.bPO.sub.4.sup.-; [0175] the
group of the 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.-; [0176] 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-; [0177] 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.-; [0178] the group of
carboxylates of the general formula: R.sup.aCOO.sup.-; [0179] 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.-; [0180] the group of
boronates of the general formulae R.sup.aBO.sub.2.sup.2-,
R.sup.aR.sup.bBO.sup.-; [0181] 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.-; [0182] 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.-;
[0183] the group of alkylsilane or 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.cRSiO.sub.3.sup.-,
R.sup.aR.sup.bR.sup.cSiO.sub.2.sup.-,
R.sup.aR.sup.bSiO.sub.3.sup.2-; [0184] the group of carboximides,
bis(sulphonyl)imides and sulphonylimides of the general
formulae:
[0184] ##STR00023## [0185] the group of methides of the general
formula:
[0185] ##STR00024## [0186] the group of alkoxides and aryloxides of
the general formula: R.sup.aO.sup.-; [0187] the group of the
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; [0188] the group of sulphides,
hydrogensulphides, polysulphides, hydrogenpolysulphides and
thiolates of the general formulae: 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; [0189] 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.-.
[0190] In these formulae, R.sup.a, R.sup.b, R.sup.c and R.sup.d are
each, independently of one another [0191] hydrogen; [0192]
C.sub.1-C.sub.30-alkyl or an aryl-, heteroaryl-, cycloalkyl-,
halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--, --CO--,
--CO--O-- or --CO--N-substituted derivative thereof, 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,-di-methyl-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, cyclo-hexylmethyl,
2-cyclohexylethyl, 3-cyclohexyl-propyl, 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); C.sub.3-C.sub.12-cycloalkyl or an aryl-,
heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxyl-,
formyl-, --O--, --CO-- or --CO--O-substituted derivative thereof,
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; [0193] C.sub.2-C.sub.30-alkenyl
or an aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-,
carboxy-, formyl-, --O--, --CO-- or --CO--O-substituted derivative
thereof, 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; [0194]
C.sub.3-C.sub.12-cycloalkenyl or an aryl-, heteroaryl-,
cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--,
--CO-- or --CO--O-substituted derivative thereof, for example
3-cyclopentenyl, 3-cyclo-hexenyl, 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; [0195] aryl or
heteroaryl having from 2 to 30 carbon atoms or an alkyl-, aryl-,
heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-,
formyl-, --O--, --CO-- or --CO--O-substituted derivative thereof,
for example phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl
(3-tolyl), 4-methyl-phenyl, 2-ethylphenyl, 3-ethylphenyl,
4-ethyl-phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,
2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,
3,5-dimethylphenyl, 4-phenyl-phenyl, 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 [0196] 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.
[0197] Very particularly preferred anions are, for example,
chloride; bromide; iodide; thiocyanate; hexafluoro-phosphate;
trifluoromethanesulphonate; methane-sulphonate; formate; acetate;
glycolate; lactate; mandelate; nitrate; nitrite; trifluoroacetate;
sulphate; hydrogensulphate; methyl sulphate; ethyl sulphate;
1-propyl sulphate; 1-butyl sulphate; 1-hexyl sulphate; 1-octyl
sulphate; phosphate; dihydrogen-phosphate; hydrogenphosphate;
C.sub.1-C.sub.4-dialkylphosphates; propionate;
tetrachloroaluminate; Al.sub.2Cl.sub.7.sup.-; chlorozincate;
chloroferrate; bis(trifluoromethyl-sulphonyl)imide;
bis(pentafluoroethylsulphonyl)imide; bis(methylsulphonyl)imide;
bis(p-toluenesulphonyl)-imide;
tris(trifluoromethylsulphonyl)methide;
bis(pentafluoroethylsulphonyl)methide; p-toluene-sulphonate;
tetracarbonylcobaltate; dimethylene glycol monomethyl ether
sulphate; oleate; stearate; acrylate; methacrylate; maleate,
hydrogencitrate; vinyl-phosphonate;
bis(pentafluoroethyl)phosphinate; borates such as
bis[salicylato(2-)borate; bis[oxalato(2-)]-borate,
bis[1,2-benzoldiolato(2-)-O,O']borate, tetra-cyanoborate,
tetrafluoroborate; dicyanamide;
tris(pentafluoroethyl)trifluorophosphate;
tris(hepta-fluoropropyl)trifluorophosphate, cyclic arylphosphates
such as catecholphosphate (C.sub.6H.sub.4O.sub.2)P(O)O.sup.- and
chlorocobaltate.
[0198] Preferred anions are selected from the group consisting of,
without making any claim as to completeness, halides
bis(perfluoroalkylsulphonyl)amides and
bis(perfluoroalkylsulphonyl)imides such as
bis(tri-fluoromethylylsulphonyl)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
aryl-carboxylates, perfluoroalkylcarboxylates, perchlorate,
tetrachloroaluminate, saccharinate. Further preferred anions are
dicyanamide, thiocyanate, isothiocyanate, tetraphenylborate,
tetrakis(pentafluorophenyl)borate, tetrafluoroborate,
hexafluorophosphate, polyether phosphates and phosphate.
[0199] Very particularly preferred anions are chloride, bromide,
hydrogensulphate, tetrachloroaluminate, thiocyanate,
methylsulphate, ethylsulphate, methanesulphonate, formate, acetate,
glycolate, lactate, dimethylphosphate, diethylphosphate,
p-toluenesulphonate, tetrafluoroborate and
hexafluoro-phosphate.
[0200] In a further particularly preferred embodiment of the
invention, use is made of ionic liquids or mixtures thereof which
contain a combination of a 1,3-dialkyl-imidazolium,
1,2,3-trialkylimidazolium, 1,3-dialkyl-imidazolinium or
1,2,3-trialkylimidazolinium cation with an anion selected from the
group consisting of halides, bis(trifluoromethylylsulphonyl)imide,
per-fluoroalkyltosylates, alkylsulphates and alkyl-sulphonates,
perfluorinated alkylsulphonates and alkylsulphates,
perfluoroalkylcarboxylates, perchlorate, dicyanamide, thiocyanate,
isothiocyanate, tetraphenylborate,
tetrakis(pentafluorophenyl)borate, tetrafluoroborate,
hexafluorophosphate.
[0201] Furthermore, 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).
[0202] Owing to the fact that some ionic liquids can be selected so
as to have a property profile so that they are stable at high
temperatures, noncombustible, corrosion-inhibiting and easy to wash
from the finished workpiece, these ionic liquids can be used
advantageously as external lubrication, as pressure medium and as
heat transfer fluid, in particular in internal high-pressure
forming. In addition, ionic liquids do not display any vapour
pressure below their decomposition temperature.
[0203] Furthermore, particular preference is given to selecting
ionic liquids which are biodegradable and at the same time
nontoxic. Apart from the abovementioned advantages, these two
additional properties are important criteria in the choice of
lubricants for mass production in an industrial environment.
[0204] Compared to the previous systems for internal high-pressure
forming using a lubricant coating, for example graphite, and
aqueous pressure media as water-oil emulsions, the finished
workpiece and also the workpiece surface can be cleaned more easily
of the external lubrication when ionic liquids are used as external
lubricant, which is of particular importance for mass production.
In addition, the ionic liquid used as external lubrication can be
chosen so that it is not miscible with the emulsion pressure
medium. In this case, the pressure medium in the form of the
water-oil emulsion can advantageously be reused. In addition, the
viscosity of the ionic liquid can be matched to the requirement
profile. Firstly, it is desirable for the external lubrication not
to run off, but on the other hand the lubricant must not be so
viscous that it is difficult to remove.
[0205] In an advantageous embodiment of the invention, the ionic
liquid used as external lubrication in a noncutting forming process
or the mixture of ionic liquids can have a melting point above room
temperature. In this case, the workpiece can, for example, be
dipped into a bath of the external lubrication which has been
liquefied by heating in order to be provided on the outside with
the lubrication before forming. When the workpiece cools, the
external lubrication solidifies and the workpiece can be inserted
into the tool without further contamination. After forming, the
external lubrication can either be liquefied by heating and thus
removed or it can be washed off the workpiece by means of an
aqueous washing solution.
[0206] The choice of the ionic liquid or the mixture of ionic
liquids is made according to the requirement profile for the
forming process selected.
[0207] Overviews of ionic liquids, their preparation and their
properties may be found, for example, in "Ionic Liquids in
Synthesis", P. Wasserscheid, T. Welton (eds.), Wiley, in "Green
Industrial Applications of Ionic Liquids", NATO Science Series, Li.
Mathematics, Physics and Chemistry, 92, or in "Ionic Liquids:
Industrial Applications for Green Chemistry", Robin D. Rogers
(ed.), Acs. Symposium Series, 818.
[0208] In a preferred embodiment of the invention, the noncutting
forming process is internal high-pressure forming. In this process
in particular, the ionic liquid or the mixture of ionic liquids
with their above-described property profile can achieve great
simplification.
[0209] The ionic liquid or the mixture of ionic liquids can
preferably be used as external lubrication and/or as pressure
medium and/or as heat transfer fluid. In particular, the
simultaneous use as external lubrication and as pressure medium is
accompanied by further synergies since incompatibility of the two
media is ruled out here and only a single environmentally friendly
lubricant is used. In addition, the high pressure and temperature
stability of the ionic liquid combined with the ease with which it
can be washed off the finished workpiece make excellent results and
improved mass production possible.
[0210] In a further embodiment of the present invention, the ionic
liquid or the mixture of ionic liquids has a melting point below
100.degree. C. and preferably below 50.degree. C.
[0211] The ionic liquid or the mixture of ionic liquids can
particularly preferably have a liquid range from -50.degree. C. to
400.degree. C., preferably from -40.degree. C. to 380.degree. C.
and particularly preferably from -30.degree. C. to 350.degree.
C.
[0212] A further preferred embodiment of the invention provides for
the use of an ionic liquid or a mixture of ionic liquids having a
decomposition temperature above 300.degree. C.
[0213] This ensures that the ionic liquid used as external
lubrication, as pressure medium and/or as heat transfer fluid has a
sufficient thermal stability for repeated use in mass production to
be possible.
[0214] In summary, use of at least one ionic liquid or of mixtures
of ionic liquids for noncutting forming, by means of which
considerable simplification of manufacturing processes can be
achieved, is proposed. Owing to the fact that the ionic liquid has
a property profile which can be tailored so that the liquid is
stable at high temperatures, noncombustible, corrosion-inhibiting
and can easily be washed off the finished workpiece, it can
advantageously be used as external lubrication, as pressure medium
and as heat transfer fluid, especially in internal high-pressure
forming. In addition, ionic liquids do not display any vapour
pressure below the decomposition temperature, are biodegradable and
are nontoxic.
EXAMPLES
[0215] In the examples presented below, the present invention is
described by way of example without the invention, whose scope is
determined by the total description and the claims, being
restricted to the embodiments mentioned in the examples.
Experimental Procedure
[0216] Forming experiments using identical steel tubes (same
material (St 52 name according to German industrial norn DIN
17100), same wall thickness (3 mm), same length (280 mm) and
diameter (50 mm)) were carried out in a hydraulic three-column
press (Dunkes Maschinenbau HS 3 1500) at a pressing force of 15000
kN. The steel tubes were painted uniformly with the lubricant and
then placed in the press. A simple T-piece was used as tool.
[0217] In the first series of experiments, the spacing of the
vertical column was kept constant (spacing Z5) and the area formed
in the forming process at the top of the resulting T-piece by
direct contact with the piston of the vertical column was measured.
This area is greater the better the lubrication and is thus a
measure of the quality of the lubricant.
TABLE-US-00001 TABLE 1 Max. pressure Spacing Z5 Area Lubricant
[bar] [mm] [mm.sup.2] Tego IL IM55 1000 65 573 Tego IL T16ES 1000
65 475 IL 3 1000 65 409 Hydrodraw 768 1000 65 355 Hydrodraw 768 is
a high-performance lubricant for hydroforming which is based on
mineral oil and is marketed by the DA Stuart Company. Tego IL IM55
=
1-ethyl-4,5-dihydro-3-(2-hydroxyethyl)-2-(8-heptadecenyl)-1H-imidazolium
ethylsulphate CAS No. 68039-12-3 Tego IL T16ES = tetraalkylammonium
sulphate, CAS No. 68071-95-4 IL 3 = dimethylditallowammonium
acetate
[0218] Hydrodraw 768 is a high-performance lubricant for
hydroforming which is based on mineral oil and is marketed by the
DA Stuart Company.
[0219] Tego IL
IM55=1-ethyl-4,5-dihydro-3-(2-hydroxyethyl)-2-(8-heptadecenyl)-1H-imidazo-
lium ethylsulphate CAS No. 68039-12-3
[0220] Tego IL T16ES=tetraalkylammonium sulphate, CAS No.
68071-95-4
[0221] IL 3=dimethylditallowammonium acetate
[0222] In the second series of experiments, the spacing of the
vertical column was increased in steps of 0.5 mm until the tube
ruptured during the forming process. A greater maximum height of
the formed T-piece (greater .DELTA. spacing Z5) means better
lubrication during the forming process and thus corresponds to a
higher lubricant quality.
TABLE-US-00002 TABLE 2 Max. pressure .DELTA. spacing Z5 Lubricant
[bar] [mm] Tego IL IM55 990 2 Tego IL T16ES 990 2 IL 3 990 3 Il 4
990 4 4:1 mixture of 990 4 IL 4 and Tego IL IM55 Hydrodraw 768 990
1.5 Hydrodraw 768 is a high-performance lubricant for hydroforming
which is marketed by the DA Stuart Company. Tego IL IM55 =
1-ethyl-4,5-dihydro-3-(2-hydroxyethyl)-2-(8-heptadecenyl)-1H-imidazolium
ethylsulphate CAS No. 68039-12-3 Tego IL T16ES = tetraalkylammonium
sulphate, 68071-95-4 IL 3 = dimethylditallowammonium acetate IL 4 =
hydroxyethylmethylmorpholinium methylsulphonate
[0223] Hydrodraw 768 is a high-performance lubricant for
hydroforming which is marketed by the DA Stuart Company.
[0224] Tego IL
IM55=1-ethyl-4,5-dihydro-3-(2-hydroxyethyl)-2-(8-heptadecenyl)-1H-imidazo-
lium ethylsulphate CAS No. 68039-12-3
[0225] Tego IL T16ES=tetraalkylammonium sulphate, 68071-95-4
[0226] IL 3=dimethylditallowammonium acetate
[0227] IL 4=hydroxyethylmethylmorpholinium methylsulphonate
[0228] The results clearly show that the ionic liquids according to
the invention are significantly better lubricants in hydroforming
processes than the industrial solutions used hitherto. The
experiments also show that mixing of various ionic liquids makes it
possible to produce lubricants having adjustable viscosity values
(Tego IL IM55 and IL4 give a lubricant whose viscosity is between
the low viscosity of Tego IL IM55 and the high viscosity of IL4)
which can advantageously be used in the hydroforming process.
[0229] Having thus described in detail various embodiments of the
present invention, it is to be understood that many apparent
variations thereof are possible without departing from the spirit
or scope of the present invention.
* * * * *