U.S. patent application number 10/459180 was filed with the patent office on 2004-01-22 for oxidation-stabilized lubricant additives for highly desulfurized fuel oils.
This patent application is currently assigned to Clariant GmbH. Invention is credited to Krull, Matthias.
Application Number | 20040010965 10/459180 |
Document ID | / |
Family ID | 29737617 |
Filed Date | 2004-01-22 |
United States Patent
Application |
20040010965 |
Kind Code |
A1 |
Krull, Matthias |
January 22, 2004 |
Oxidation-stabilized lubricant additives for highly desulfurized
fuel oils
Abstract
An additive for improving the lubricity of fuel oils having a
maximum sulfur content of 0.035% by weight, comprising A) at least
one partial ester composed of a di- or polyhydric alcohol and
unsaturated and optionally also saturated fatty acids whose carbon
chain lengths are between 8 and 30 carbon atoms, at least 60% of
the fatty acid radicals containing at least one double bond, and B)
at least one alkylphenol-aldehyde resin, obtainable by the
condensation of (i) at least one alkylphenol having at least one
C.sub.6-C.sub.24-alkyl or C.sub.6-C.sub.24-alkenyl radical and (ii)
at least one aldehyde or ketone, to a degree of condensation of
between 2 and 50 alkylphenol units.
Inventors: |
Krull, Matthias; (Harxheim,
DE) |
Correspondence
Address: |
Clariant Corporation
Industrial Property Department
4000 Monroe Road
Charlotte
NC
28205
US
|
Assignee: |
Clariant GmbH
|
Family ID: |
29737617 |
Appl. No.: |
10/459180 |
Filed: |
June 11, 2003 |
Current U.S.
Class: |
44/385 |
Current CPC
Class: |
C10L 1/191 20130101;
C10L 1/224 20130101; C10N 2030/43 20200501; C10L 1/221 20130101;
C10L 1/1981 20130101; C10M 169/044 20130101; C10N 2030/10 20130101;
C10L 1/143 20130101; C10L 10/08 20130101; C10N 2020/013 20200501;
C10L 1/1835 20130101; C10L 1/2364 20130101; C10L 1/19 20130101;
C10L 1/1905 20130101; C10N 2030/06 20130101; C10M 169/04 20130101;
C10M 2207/282 20130101; C10N 2020/067 20200501; C10L 1/1973
20130101; C10M 2209/101 20130101; C10M 2205/022 20130101; C10L
1/1966 20130101 |
Class at
Publication: |
44/385 |
International
Class: |
C10L 001/18 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 9, 2002 |
DE |
10230771.7 |
Nov 14, 2002 |
DE |
10252973.6 |
Claims
What is claimed is:
1. An additive for improving the lubricity of fuel oils having a
maximum sulfur content of 0.035% by weight, comprising A) at least
one partial ester composed of a di- or polyhydric alcohol and
unsaturated and optionally also saturated fatty acids whose carbon
chain lengths are between 8 and 30 carbon atoms, at least 60% of
the fatty acid radicals containing at least one double bond, and B)
at least one alkylphenol-aldehyde resin, obtainable by the
condensation of (i) at least one alkylphenol having at least one
C.sub.6-C.sub.24-alkyl or C.sub.6-C.sub.24-alkenyl radical and (ii)
at least one aldehyde or ketone, to a degree of condensation of
between 2 and 50 alkylphenol units.
2. An additive as claimed in claim 1, wherein the iodine number of
constituent A) is more than 50 g of I/100 g of ester.
3. An additive as claimed in claim 1 and/or 2, wherein the OH
number of constituent A) is between 10 and 200 mg of KOH/g of
ester.
4. An additive as claimed in one or more of claims 1 to 3, wherein
the fatty acids which are a constituent of the fatty acid mixture
contain from 10 to 26 carbon atoms.
5. An additive as claimed in one or more of claims 1 to 4, wherein
the fatty acid mixtures comprise up to 20% by weight of saturated
fatty acids.
6. An additive as claimed in one or more of claims 1 to 5, wherein
the fatty acid mixtures comprise one or more dicarboxylic
acids.
7. An additive as claimed in one or more of claims 1 to 6, wherein
the alcohols contain from 2 to 6 carbon atoms.
8. An additive as claimed in one or more of claims 1 to 7, wherein
the alcohols contain from 2 to 5 hydroxyl groups, but a maximum of
one hydroxyl group per carbon atom.
9. An additive as claimed in one or more of claims 1 to 8, which
also comprises at least one nitrogen-containing paraffin
dispersant.
10. An additive as claimed in one or more of claims 1 to 9, which
also comprises at least one ethylene copolymer.
11. An additive as claimed in one or more of claims 1 to 10, which
also comprises at least one comb polymer.
12. A fuel oil having a maximum sulfur content of 0.035% by weight,
comprising an additive as claimed in one or more of claims 1 to 11
in amounts of from 0.001 to 0.5% by weight, based on the fuel
oil.
13. The use of an additive as claimed in one or more of claims 1 to
11 in amounts of from 0.001 to 0.5% by weight, based on the fuel
oil, for improving the lubricity of fuel oils having a maximum
sulfur content of 0.035% by weight.
Description
[0001] The present invention relates to additives which are
composed of esters between polyols and fatty acid mixtures and
alkylphenol resins having improved oxidation stability, and also to
their use for improving the lubricity of highly desulfurized fuel
oils.
[0002] Mineral oils and mineral oil distillates which are used as
fuel oils generally contain 0.5% by weight or more of sulfur which
causes the formation of sulfur dioxide on combustion. In order to
reduce the resulting environmental pollution, the sulfur content of
fuel oils is being ever further reduced. The standard EN 590
relating to diesel fuels has prescribed a maximum sulfur content of
350 ppm in Europe since November 1999. Further reductions of the
sulfur content are in the pipeline. In Scandinavia, fuel oils
having fewer than 50 ppm, and in exceptional cases having fewer
than 10 ppm, of sulfur are already being used. These fuel oils are
generally produced by refining, under hydrogenating conditions, the
fractions obtained from crude oil by distillation. However, the
desulfurization also removes other substances which confer a
natural lubricity on the fuel oils. Among others, these substances
include polyaromatic and polar compounds.
[0003] However, it has now been found that the wear- and
attrition-reducing properties of fuel oils deteriorate with an
increasing degree of desulfurization. These properties are often so
inadequate that instances of corrosion are to be expected even
after a short time on the materials lubricated by the fuel, for
example the distributor injection pumps of diesel engines. The
maximum value for the 95% distillation point of 360.degree. C. laid
down by EN 590 since the year 2000 and the further reduction of the
95% distillation point to below 350.degree. C. and sometimes below
330.degree. C. which has been undertaken in the meantime in
Scandinavia aggravates these problems further.
[0004] The prior art therefore describes attempts which are
intended to provide a solution to this problem (lubricity
additives).
[0005] EP-A-0 680 506 discloses that esters of fatty acids confer
improved lubricity to highly desulfurized fuel oils. Particular
mention is made of glycerol monooleate and diisodecyl adipate.
[0006] EP-A-0 739 970 discloses the suitability of glycerol ester
mixtures for improving the lubricity of low-sulfur fuel oils.
Compositions having different degrees of esterification of the
polyol and different degrees of saturation of the fatty acids are
disclosed.
[0007] EP-A-0 839 174 discloses fuel oils with improved lubricity
which are low in sulfur and comprise a mixture of polyolesters with
unsaturated fatty acids.
[0008] DE 19614722 discloses mixtures of partial esters of highly
unsaturated fatty acids with different polyols which have improved
cold stability. Among other uses, these may be added to low-sulfur
diesel oils as lubricant additives.
[0009] EP 0743972 discloses fuel oils having improved lubricity
which comprise a lubricity improver and a nitrogen compound.
[0010] EP 0935645 discloses the use of C.sub.1-C.sub.30-alkylphenol
resins as lubricity additives for low-sulfur diesel. The examples
relate to C.sub.18-- and C.sub.2-4-alkylphenol resins.
[0011] WO-99/61562 discloses mixtures of alkylphenol resins,
nitrogen compounds and ethylene copolymers as cold and lubricity
additives for low-sulfur diesel.
[0012] WO 01/19941 discloses partial esters of polyhydric alcohols
with unsaturated fatty acids (pentaerythritol esterified with tall
oil fatty acid) as lubricity additives having improved cold
stability.
[0013] The lubricity additives based on unsaturated fatty acids and
their derivatives can resinify on prolonged storage of the
additive, and of the additized oils, in particular at elevated
temperature, to give products which only have limited oil
solubility. This can lead to the formation of separate viscous
layers and deposits in the storage container of the additive, in
the fuel oil and also in the engine. The combustion and
condensation products of glycerol, for example, are suspected of
being responsible for coke residues and deposits on the injection
nozzles of highly supercharged diesel engines.
[0014] The effectiveness of the lubricity additives currently used
is often unsatisfactory, so that either very high dosages or
synergists have to be used.
[0015] The fatty acid esters based on commercial fatty acid
mixtures of the prior art additionally show a marked tendency to
emulsify in the fuel oils additized by them. This means that
emulsification of the water in the fuel oil takes place on contact
of such a fuel oil with water. These emulsions to be found in
particular on the oil/water phase boundary can only be removed with
great difficulty, if at all. Since these emulsions as such cannot
be used directly as fuel oils, they reduce the value of the
products. This problem occurs to a particularly high degree when
esters based on natural fatty acid mixtures are used.
[0016] It is an object of the present invention to find
lubricity-improving additives for desulfurized fuel oils which have
an improved oxidation stability and, at the same time, an improved
effectiveness as lubricity additive compared to the prior art.
[0017] It has been found that, surprisingly, combinations of
partial esters of unsaturated fatty acids and polyols with
alkylphenol-aldehyde resins have a distinctly improved oxidation
stability and, in the case of selected combinations of hydroxyl
number and iodine number, have a particularly low emulsifiability.
In addition, they display a lubricity superior to the individual
constituents in low-sulfur fuel oils.
[0018] The invention therefore provides an additive for improving
the lubricity of fuel oils having a maximum sulfur content of
0.035% by weight, comprising
[0019] A) at least one partial ester composed of a di- or
polyhydric alcohol and unsaturated and optionally also saturated
fatty acids whose carbon chain lengths are between 8 and 30 carbon
atoms, at least 60% of the fatty acid radicals containing at least
one double bond, and
[0020] B) at least one alkylphenol-aldehyde resin, obtainable by
the condensation of
[0021] (i) at least one alkylphenol having at least one
C.sub.6-C.sub.24-alkyl or C.sub.6-C.sub.24-alkenyl radical and
[0022] (ii) at least one aldehyde or ketone,
[0023] to a degree of condensation of between 2 and 50 alkylphenol
units.
[0024] The invention further provides fuel oils having a maximum
sulfur content of 0.035% by weight which comprise the additives
according to the invention.
[0025] The invention further provides the use of the additives
according to the invention for improving the lubricity of fuel oils
having a maximum sulfur content of 0.035% by weight.
[0026] The invention further provides a process for improving the
lubricity of fuel oils having a maximum sulfur content of 0.035% by
weight by adding the additive according to the invention to the
fuel oils.
[0027] Preferred fatty acids which are a constituent of the esters
A) are those having from 10 to 26 carbon atoms, in particular from
12 to 22 carbon atoms. The alkyl radicals or alkenyl radicals of
the fatty acids consist substantially of carbon and hydrogen.
However, they can also bear further substituents, for example
hydroxyl, halogen, amino or nitro groups, as long as these do not
impair the predominant hydrocarbon character. The fatty acids
preferably contain at least one double bond. They can contain a
plurality of double bonds, for example 2 or 3 double bonds, and be
of natural or synthetic origin. In the case of polyunsaturated
carboxylic acids, their double bonds can be isolated or else
conjugated. Preference is given to mixtures of two or more
unsaturated fatty acids having from 10 to 26 carbon atoms. In
particularly preferred fatty acid mixtures, at least 50% by weight,
in particular at least 75% by weight, especially at least 90% by
weight, of the fatty acids contain one or more double bonds. The
iodine numbers of the parent fatty acids or fatty acid mixtures of
the esters according to the invention are preferably above 100 g of
I/100 g, more preferably between 105 and 190 g of I/100 g, in
particular between 110 and 180 g of I/100 g and especially between
120 and 180 g of I/100 g, of fatty acid or fatty acid mixture.
[0028] Examples of suitable unsaturated fatty acids include oleic
acid, erucic acid, palmitoleic acid, myristoleic acid, linoleic
acid, linolenic acid, elaeosteric acid, arachidonic acid and/or
ricinoleic acid. According to the invention, preference is given to
using fatty acid mixtures and fractions obtained from natural fats
and oils, for example peanut oil fatty acid, fish oil fatty acid,
linseed oil fatty acid, palm oil fatty acid, rapeseed oil fatty
acid, ricinoleic oil fatty acid, castor oil fatty acid, colza oil
fatty acid, soya oil fatty acid, sunflower oil fatty acid,
safflower oil fatty acid and tall oil fatty acid, which have
appropriate iodine numbers.
[0029] Likewise suitable as fatty acids are dicarboxylic acids such
as dimerized fatty acids and alkyl- and also alkenylsuccinic acids
having C.sub.8-C.sub.50-alk(en)yl radicals, preferably having
C.sub.8-C.sub.40-, in particular having C.sub.12-C.sub.22-alkyl
radicals. The alkyl radicals can be linear or branched
(oligomerized alkenes, polyisobutylene) and saturated or
unsaturated. The dicarboxylic acids can be used as such or in
mixtures with monocarboxylic acids, and preference is given to
proportions of the dicarboxylic acids in mixtures of up to 10% by
weight, in particular less than 5% by weight.
[0030] In addition, the fatty acid mixtures can contain minor
amounts, i.e. up to 20% by weight, preferably less than 10% by
weight, in particular less than 5% by weight and especially less
than 2% by weight, of saturated fatty acids, for example lauric
acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic
acid, margaric acid, stearic acid, isostearic acid, arachidic acid
and behenic acid.
[0031] The fatty acids can also contain 1-40% by weight, especially
1-25% by weight, in particular 1-5% by weight, of resin acids.
[0032] Suitable alcohols contain preferably from 2 to 6, in
particular from 3 to 4, carbon atoms, and from 2 to 5, in
particular from 3 to 4, hydroxyl groups, but a maximum of one
hydroxyl group per carbon atom. Particularly suitable alcohols are
ethylene glycol, diethylene glycol, propylene glycol, glycerol,
trimethylolpropane, neopentyl glycol and pentaerythritol, and also
the oligomers obtainable therefrom by condensation and having from
2 to 10 monomer units, for example polyglycerol.
[0033] The partial esters can be prepared from alcohols and fatty
acids by esterification in a known manner. As an alternative, it is
also possible to partially hydrolyze naturally occurring fats and
oils. Esters according to the invention are those which can be
prepared from a di- or polyhydric alcohol and a fatty acid or a
mixture of fatty acids. These include mixtures, for example, of
mono-, di- and/or triesters, or optionally higher esters, of an
alcohol with different fatty acids, of mono-, di- and/or triesters,
or optionally higher esters, different alcohols with different
fatty acids, or else mixtures of mono-, di- and/or triesters, or
optionally higher esters, of one or more alcohols with different
fatty acids. Preference is given to those esters which can be
prepared from a fatty acid mixture.
[0034] The esters according to the invention preferably have iodine
numbers of more than 50 g of I/100 g of ester, more preferably
between 90 and 200 g of I/100 g of ester, in particular between 100
and 180 g of I/100 g of ester and especially between 110 and 150 g
of I/100 g of ester. The iodine numbers correspond to the iodine
number of the parent fatty acid mixture and the alcohol used for
esterification in a stoichiometric manner.
[0035] Preference is likewise given to partial esters whose OH
numbers are between 10 and 200 mg of KOH/g of ester, more
preferably between 100 and 200 mg of KOH/g of ester, in particular
between 110 and 195 mg of KOH/g of ester, especially between 130
and 190 mg of KOH/g of ester. In general, these are mixtures of
different esters, for example mixtures of mono-, di- and
triglycerides, and mixtures as result from the esterification of
polyols.
[0036] The partial esters having OH numbers of between 110 and 200
mg of KOH/g of ester are notable for a very low tendency to
emulsify, in particular in combination with the alkylphenol resins
B). The HLB range of the additives which is limited by the OH
number presumably effects a reduced affinity of the amphiphilic
active ingredients for water; at the same time, the formation of
surface-active and micellar structures is disrupted by the number
of double bonds in the alkyl radicals characterized by means of the
iodine number.
[0037] The alkylphenol-aldehyde resins (B) present in the additive
according to the invention are known in principle and described,
for example, in Rompp Chemie Lexikon, 9th edition, Thieme Verlag
1988-92, Volume 4, p. 3351ff. The alkyl or alkenyl radicals of the
alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon
atoms. They may be linear or branched, and the branch may contain
secondary and also tertiary structures. They are preferably n- and
isohexyl, n- and isooctyl, n- and isononyl, n- and isodecyl, n- and
isododecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and also
tripropenyl, tetrapropenyl, pentapropenyl and polyisobutenyl up to
C.sub.24. In this context, the prefix iso means that the alkyl
chain has one or more secondary branches.
[0038] The alkylphenol-aldehyde resin may also contain up to 20 mol
% of phenol units and/or alkylphenols having short alkyl chains,
for example butylphenol. For the alkylphenol-aldehyde resin, the
same or different alkylphenols may be used.
[0039] The aldehyde in the alkylphenol-aldehyde resin has from 1 to
10, preferably from 1 to 4, carbon atoms, and may bear further
functional groups. It is preferably an aliphatic aldehyde, more
preferably formaldehyde.
[0040] The molecular weight of the alkylphenol-aldehyde resins is
preferably 350-10,000, in particular 400-5000 g/mol. This
preferably corresponds to a degree of condensation n of from 3 to
40, in particular from 4 to 20. A prerequisite is that the resins
are oil-soluble.
[0041] In a preferred embodiment of the invention, these
alkylphenol-formaldehyde resins are those which are oligomers or
polymers having a repeating structural unit of the formula 1
[0042] where R.sup.A is C.sub.6-C.sub.24-alkyl or -alkenyl and n is
a number from 2 to 50.
[0043] The alkylphenol-aldehyde resins are prepared in a known
manner by basic catalysis to give condensation products of the
resol type, or by acidic catalysis to give condensation products of
the novolak type.
[0044] The condensates obtained in both ways are suitable for the
compositions according to the invention. Preference is given to the
condensation in the presence of acidic catalysts.
[0045] To prepare the alkylphenol-aldehyde resins, an alkylphenol
having 6-24, preferably 8-22, in particular 9-18, carbon atoms per
alkyl group, or mixtures thereof, are reacted with at least one
aldehyde, using about 0.5-2 mol, preferably 0.7-1.3 mol and in
particular equimolar amounts of aldehyde, per mole of alkylphenol
compound.
[0046] Suitable alkylphenols are in particular n- and
isohexylphenol, n- and isooctylphenol, n- and isononylphenol, n-
and isodecylphenol, n- and isododecylphenol, tetradecylphenol,
hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol,
tetrapropenylphenol and poly(isobutenyl)phenol up to C.sub.24.
[0047] The alkylphenols are preferably para-substituted. The
alkylphenols may bear one or more alkyl radicals. The proportion
substituted by more than one alkyl group is preferably at most 5
mol %, in particular at most 20 mol % and especially at most 40 mol
%. At most 40 mol %, in particular at most 20 mol %, of the
alkylphenols used preferably bear an alkyl radical in the
ortho-position. Especially, the alkylphenols are unsubstituted by
tertiary alkyl groups in the ortho-position to the hydroxyl
group.
[0048] The aldehyde may be a mono- or dialdehyde and bear further
functional groups such as --COOH. Particularly suitable aldehydes
are formaldehyde, acetaldehyde, butyraldehyde, glutardialdehyde and
glyoxalic acid, preferably formaldehyde. The formaldehyde may be
used in the form of paraformaldehyde or in the form of a preferably
20-40% by weight aqueous formalin solution. It is also possible to
use corresponding amounts of trioxane.
[0049] Alkylphenol is customarily reacted with aldehyde in the
presence of alkaline catalysts, for example alkali metal hydroxides
or alkylamines, or of acidic catalysts, for example inorganic or
organic acids, such as hydrochloric acid, sulfuric acid, phosphoric
acid, sulfonic acid, sulfamido acids or haloacetic acids. The
condensation is preferably carried out without solvent at from 90
to 200.degree. C., preferably at from 100 to 160.degree. C. In a
further preferred embodiment, the reaction is effected in the
presence of an organic solvent which forms an azeotrope with water,
for example toluene, xylene, higher aromatics or mixtures thereof.
The reaction mixture is heated to a temperature of from 90 to
200.degree. C., preferably 100-160.degree. C., and the water of
reaction formed is removed during the reaction by azeotropic
distillation. Solvents which release no protons under the
conditions of the condensation can remain in the products after the
condensation reaction. The resins may be used directly or after
neutralization of the catalyst, optionally after further dilution
of the solution with aliphatic and/or aromatic hydrocarbons or
hydrocarbon mixtures, for example petroleum fractions, kerosene,
decane, pentadecane, toluene, xylene, ethylbenzene or solvents such
as .RTM.Solvent Naphtha, .RTM.Shellsol AB, .RTM.Solvesso 150,
.RTM.Solvesso 200, .RTM.Exxsol, .RTM.ISOPAR and .RTM.Shellsol D
types.
[0050] The proportions by weight of the constituents A) and B) in
the additives according to the invention may vary within wide
limits depending on the application. They are preferably between 10
and 99.999% by weight of A) to from 90 to 0.001% by weight of B),
in particular between 20 and 99.995% by weight of A) to from 80 to
0.005% by weight of B). To stabilize the fatty acids, preference is
given to using smaller proportions of component B of from 0.001 to
10% by weight, preferably from 0.005 to 5% by weight, of B), but in
contrast, to optimize the lubricity, larger proportions of B of,
for example, from 5 to 90% by weight, preferably from 10 to 80% by
weight and in particular from 25 to 75% by weight, are used.
[0051] It has likewise been found that, surprisingly, a further
increase in effectiveness as a lubricity additive is achieved when
the mixtures according to the invention are used together with
nitrogen-containing paraffin dispersants. Paraffin dispersants are
additives which reduce the size of the precipitating paraffin
crystals on cooling of the oil and in addition prevent the paraffin
particles from depositing, but instead keep them dispersed
colloidally with distinctly reduced tendency to sediment.
[0052] The nitrogen-containing paraffin dispersants are preferably
low molecular weight or polymeric, oil-soluble nitrogen compounds,
for example amine salts, imides and/or amides which are obtained by
reacting aliphatic or aromatic amines, preferably long-chain
aliphatic amines, with aliphatic or aromatic mono-, di-, tri-,
tetra- and/or polycarboxylic acids or their anhydrides.
Particularly preferred paraffin dispersants contain reaction
products of secondary fatty amines having from 8 to 36 carbon
atoms, in particular dicoconut fatty amine, ditallow fatty amine
and distearylamine. Other paraffin dispersants are copolymers of
maleic anhydride and .alpha.,.beta.-unsaturated compounds which can
optionally be reacted with primary monoalkylamines and/or aliphatic
alcohols, the reaction products of alkenyl-spiro-bislactones with
amines and the reaction products of terpolymers based on
.alpha.,.beta.-unsaturated dicarboxylic anhydrides,
.alpha.,.beta.-unsaturated compounds and polyoxyalkyl ethers of
lower unsaturated alcohols with amines and/or alcohols. Some
suitable paraffin dispersants are listed hereinbelow.
[0053] Some of the paraffin dispersants mentioned below are
prepared by reaction of compounds containing an acyl group with an
amine. This amine is a compound of the formula
NR.sup.6R.sup.7R.sup.8, in which R.sup.6, R.sup.7 and R.sup.8 may
be identical or different, and at least one of these groups is
C.sub.8-C.sub.36-alkyl, C.sub.6-C.sub.36-cycloalkyl,
C.sub.8-C.sub.36-alkenyl, in particular C.sub.12-C.sub.24-alkyl,
C.sub.12-C.sub.24-alkenyl or cyclohexyl, and the other groups are
either hydrogen, C.sub.1-C.sub.36-alkyl, C.sub.2-C.sub.36-alkenyl,
cyclohexyl, or a group of the formulae -(A-O).sub.x-E or
--(CH.sub.2).sub.n--NYZ, in which A is an ethylene or propylene
group, x is a number from 1 to 50, E=H, C.sub.1-C.sub.30-alkyl,
C.sub.5-C.sub.12-cycloalkyl or C.sub.6-C.sub.30-aryl, and n is 2, 3
or 4, and Y and Z are each; independently H, C.sub.1-C.sub.30-alkyl
or -(A-O).sub.x. The term acyl group here is taken to mean a
functional group of the following formula:
>C.dbd.O
[0054] 1. Products of the reaction of alkenyl-spiro-bislactones of
the formula 2
[0055] in which each R is C.sub.8-C.sub.200-alkenyl, with amines of
the formula NR.sup.6R.sup.7R.sup.8. Suitable reaction products are
mentioned in EP-A-0 413 279. Depending on the reaction conditions,
the reaction of compounds of the formula with the amines gives
amides or amide ammonium salts.
[0056] 2. Amides or ammonium salts of aminoalkylenepolycarboxylic
acids with secondary amines of the formulae 3
[0057] in which
[0058] R.sup.10 is a straight-chain or branched alkylene radical
having from 2 to 6 carbon atoms or the radical of the formula 4
[0059] in which R.sup.6 and R.sup.7 are, in particular, alkyl
radicals having from 10 to 30, preferably from 14 to 24, carbon
atoms, and all or some of the amide structures may also be in the
form of the ammonium salt structure of the formula 5
[0060] The amides or amide ammonium salts or ammonium salts, for
example of nitrilotriacetic acid, of ethylenediaminetetraacetic
acid or of propylene-1,2-diaminetetraacetic acid, are obtained by
reaction of the acids with from 0.5 to 1.5 mol of amine, preferably
from 0.8 to 1.2 mol of amine, per carboxyl group. The reaction
temperatures are from about 80 to 200.degree. C., and continuous
removal of the water of reaction formed is required to prepare the
amides. However, the conversion to the amide does not have to be
completed, but instead from 0 to 100 mol % of the amine used may be
in the form of the ammonium salt. Under analogous conditions, the
compounds mentioned under B1) can also be prepared.
[0061] Suitable amines of the formula 6
[0062] are, in particular, dialkylamines in which R.sup.6 and
R.sup.7 are a straight-chain alkyl radical having from 10 to 30
carbon atoms, preferably from 14 to 24 carbon atoms. Specific
mention may be made of dioleylamine, dipalmitylamine, dicoconut
fatty amine and dibehenylamine and preferably ditallow fatty
amine.
[0063] 3. Quaternary ammonium salts of the formula
.sup.+NR.sup.6R.sup.7R.sup.8R.sup.11 X.sup.-
[0064] in which R.sup.6, R.sup.7 and R.sup.8 are as defined above,
and R.sup.11 is C.sub.1-C.sub.30-alkyl, preferably
C.sub.1-C.sub.22-alkyl, C.sub.1-C.sub.30-alkenyl, preferably
C.sub.1-C.sub.22-alkenyl, benzyl or a radical of the formula
--(CH.sub.2--CH.sub.2--O).sub.n--R.sup.12 where R.sup.12 is
hydrogen or a fatty acid radical of the formula C(O)--R.sup.13
where R.sup.13=C.sub.6-C.sub.40-alkenyl, n is a number from 1 to
30, and X is halogen, preferably chlorine, or a methosulfate.
[0065] Examples of quaternary ammonium salts of this type include
the following: dihexadecyldimethylammonium chloride,
distearyldimethylammoniu- m chloride, products of the
quaternization of esters of di- and triethanolamine with long-chain
fatty acids (lauric acid, myristic acid, palmitic acid, stearic
acid, behenic acid, oleic acid and fatty acid mixtures, such as
coconut fatty acid, tallow fatty acid, hydrogenated tallow fatty
acid and tall oil fatty acid), such as N-methyltriethanolammonium
distearyl ester chloride, N-methyltriethanolammonium distearyl
ester methosulfate, N,N-dimethyldiethanolammonium distearyl ester
chloride, N-methyltriethanolammonium dioleyl ester chloride,
N-methyltriethanolammonium trilauryl ester methosulfate,
N-methyltriethanolammonium tristearyl ester methosulfate and
mixtures thereof.
[0066] 4. Compounds of the formula 7
[0067] in which R.sup.14 is CONR.sup.6R.sup.7 or CO.sub.2.sup.-
+H.sub.2NR.sup.6R.sup.7, R.sup.15 and R.sup.16 are each H,
CONR.sup.17.sub.2, CO.sub.2R.sup.17 or OCOR.sup.17, --OR.sup.17,
--R.sup.17 or --NCOR.sup.17, and R.sup.17 is alkyl, alkoxyalkyl or
polyalkoxyalkyl and has at least 10 carbon atoms.
[0068] Preferred carboxylic acids or acid derivatives are phthalic
acid (anhydride), trimellitic and pyromellitic acid (dianhydride),
isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid
(anhydride), maleic acid (anhydride) and alkenylsuccinic acid
(anhydride). The formulation (anhydride) means that the anhydrides
of said acids are also preferred acid derivatives. If the compounds
of the above formula are amides or amine salts, they are preferably
obtained from a secondary amine which contains a hydrogen- and
carbon-containing group having at least 10 carbon atoms.
[0069] R.sup.17 preferably contains from 10 to 30, in particular
from 10 to 22, for example from 14 to 20, carbon atoms, and is
preferably straight-chain or branched in the 1- or 2-position. The
other hydrogen- and carbon-containing groups may be shorter, for
example contain fewer than 6 carbon atoms, or may, if desired, have
at least 10 carbon atoms. Suitable alkyl groups include methyl,
ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and
docosyl (behenyl).
[0070] Also suitable are polymers containing at least one amide or
ammonium group bonded directly to the polymer skeleton, the amide
or ammonium group bearing at least one alkyl group having at least
8 carbon atoms on the nitrogen atom. Polymers of this type can be
prepared in various ways. One method is to use a polymer which
contains a plurality of carboxyl or carboxylic anhydride groups and
to react this polymer with an amine of the formula NHR.sup.6R.sup.7
in order to obtain the desired polymer.
[0071] Suitable polymers for this purpose are generally copolymers
of unsaturated esters, such as C.sub.1-C.sub.40-alkyl
(meth)acrylates, di(C.sub.1-C.sub.40-alkyl) fumarates,
C.sub.1-C.sub.40-alkyl vinyl ethers, C.sub.1-C.sub.40-alkyl vinyl
esters or C.sub.2-C.sub.40-olefins (linear, branched or aromatic)
with unsaturated carboxylic acids or reactive derivatives thereof,
such as, for example, carboxylic anhydrides (acrylic acid,
methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic
acid, citraconic acid, preferably maleic anhydride).
[0072] Carboxylic acids are preferably reacted with from 0.1 to 1.5
mol, in particular from 0.5 to 1.2 mol, of amine per acid group,
while carboxylic anhydrides are preferably reacted with from 0.1 to
2.5 mol, in particular from 0.5 to 2.2 mol, of amine per acid
anhydride group, with amides, ammonium salts, amide ammonium salts
or imides being formed, depending on the reaction conditions. Thus,
when copolymers containing unsaturated carboxylic anhydrides are
reacted with a secondary amine, half of them give amide and half of
them give amine salts owing to the reaction with the anhydride
group. Water can be eliminated by heating to form the diamide.
[0073] Particularly suitable examples of amide group-containing
polymers for use in accordance with the invention are the
following:
[0074] 5. Copolymers (a) of a dialkyl fumarate, maleate,
citraconate or itaconate with maleic anhydride, or (b) of vinyl
esters, for example vinyl acetate, vinyl propionate, vinyl
2-ethylhexanoate or vinyl stearate, with maleic anhydride, or (c)
of a dialkyl fumarate, maleate, citraconate or itaconate with
maleic anhydride and vinyl acetate.
[0075] Particularly suitable examples of these polymers are
copolymers of didodecyl fumarate, vinyl acetate and maleic
anhydride; ditetradecyl fumarate, vinyl acetate and maleic
anhydride; dihexadecyl fumarate, vinyl acetate and maleic
anhydride; or the corresponding copolymers in which the itaconate
is used instead of the fumarate.
[0076] In the abovementioned examples of suitable polymers, the
desired amide is obtained by reaction of the polymer containing
anhydride groups with a secondary amine of the formula HNR1R.sup.7
(optionally also with an alcohol if an ester amide is formed). If
polymers containing an anhydride group are reacted, the resultant
amino groups will be ammonium salts and amides. Polymers of this
type can be used with the proviso that they contain at least two
amide groups.
[0077] It is essential that the polymer containing at least two
amide groups contains at least one alkyl group having at least 10
carbon atoms. This long-chain group, which may be a straight-chain
or branched alkyl group, may be bonded via the nitrogen atom of the
amide group.
[0078] The amines which are suitable for this purpose may be
represented by the formula R.sup.6R.sup.7NH and the polyamines by
R.sup.6NH[R.sup.19NH].sub.xR.sup.7 where R.sup.19 is a divalent
hydrocarbon group, preferably an alkylene- or
hydrocarbon-substituted alkylene group, and x is an integer,
preferably between 1 and 30. One or both radicals R.sup.6 and
R.sup.7 preferably contain at least 10 carbon atoms, for example
from 10 to 20 carbon atoms, for example dodecyl, tetradecyl,
hexadecyl or octadecyl.
[0079] Examples of suitable secondary amines are dioctylamine and
those which contain alkyl groups having at least 10 carbon atoms,
for example didecylamine, didodecylamine, dicoconut amine (i.e.
mixed C.sub.12-C.sub.14-amines), dioctadecylamine,
hexadecyloctadecylamine, di(hydrogenated tallow) amine
(approximately 4% by weight of n-C.sub.14-alkyl, 30% by weight of
n-C.sub.10-alkyl, 60% by weight of n-C.sub.18-alkyl, the remainder
is unsaturated).
[0080] Examples of suitable polyamines are
N-octadecylpropanediamine, N,N'-dioctadecylpropanediamine,
N-tetradecylbutanediamine and N,N'-dihexadecylhexanediamine,
N-(coconut)propylenediamine
(C.sub.12/C.sub.14-alkylpropylenediamine),
N-(tallow)propylenediamine
(C.sub.16/C.sub.18-alkylpropylenediamine). The amide-containing
polymers typically have a number average molecular weight of from
1000 to 500,000, for example from 10,000 to 100,000.
[0081] 6. Copolymers of styrene, derivatives thereof or aliphatic
olefins having from 2 to 40 carbon atoms, preferably having from 6
to 20 carbon atoms, and olefinically unsaturated carboxylic acids
or carboxylic anhydrides which have been reacted with amines of the
formula HNR.sup.6R.sup.7. The reaction can be carried out before or
after the polymerization.
[0082] In detail, the structural units of the copolymers are
derived from, for example, maleic acid, fumaric acid,
tetrahydrophthalic acid, citraconic acid, preferably maleic
anhydride. They can be employed either in the form of their
homopolymers or in the form of the copolymers. Suitable comonomers
are the following: styrene and alkylstyrenes, straight-chain and
branched olefins having from 2 to 40 carbon atoms, and mixtures
thereof. Examples include the following: styrene,
.alpha.-methylstyrene, dimethylstyrene, .alpha.-ethylstyrene,
diethylstyrene, isopropylstyrene, tert-butylstyrene, ethylene,
propylene, n-butylene, diisobutylene, decene, dodecene,
tetradecene, hexadecene and octadecene. Preference is given to
styrene and isobutene, particular preference is given to
styrene.
[0083] Examples of specific polymers include the following:
polymaleic acid, an equimolar styrene-maleic acid copolymer with an
alternating structure, styrene-maleic acid copolymers with a random
structure in the ratio 10:90 and an alternating copolymer of maleic
acid and isobutene. The molecular weights of the polymers are
generally from 500 g/mol to 20,000 g/mol, preferably from 700 to
2000 g/mol.
[0084] The polymers or copolymers are reacted with the amines at
temperatures of from 50 to 200.degree. C. over the course of from
0.3 to 30 hours. The amine here is used in amounts of approximately
one mole per mole of copolymerized dicarboxylic anhydride, i.e.
from about 0.9 to 1.1 mol/mol. The use of larger or smaller amounts
is possible, but does not bring any advantage. If larger amounts
than one mole are used, ammonium salts are partly obtained, since
the formation of a second amide group requires higher temperatures,
longer residence times and separation of water. If smaller amounts
than one mole are used, complete conversion to the monoamide does
not take place, and a correspondingly reduced action is
obtained.
[0085] Instead of the subsequent reaction of the carboxyl groups in
the form of the dicarboxylic anhydride with amines to give the
corresponding amides, it is sometimes advantageous to prepare the
monoamides of the monomers and then to copolymerize them directly
in the polymerization. Usually, however, this is much more
technically complex, since the amines are able to add onto the
double bond of the monomeric mono- and dicarboxylic acid, and
copolymerization is then no longer possible.
[0086] 7. Copolymers consisting of from 10 to 95 mol % of one or
more alkyl acrylates or alkyl methacrylates having
C.sub.1-C.sub.26-alkyl chains and from 5 to 90 mol % of one or more
ethylenically unsaturated dicarboxylic acids or anhydrides thereof,
the copolymers having been substantially reacted with one or more
primary or secondary amines to give the monoamide or amide/ammonium
salt of the dicarboxylic acid.
[0087] The copolymers consist of from 10 to 95 mol %, preferably
from 40 to 95 mol % and particularly preferably from 60 to 90 mol
%, of alkyl (meth)acrylates and from 5 to 90 mol %, preferably from
5 to 60 mol % and particularly preferably from 10 to 40 mol %, of
the olefinically unsaturated dicarboxylic acid derivatives. The
alkyl groups of the alkyl (meth)acrylates contain from 1 to 26,
preferably from 4 to 22 and particularly preferably from 8 to 18,
carbon atoms. They are preferably straight-chain and unbranched.
However, it is also possible for up to 20% by weight of cyclic
and/or branched components to be present.
[0088] Examples of particularly preferred alkyl (meth)acrylates are
n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl
(meth)acrylate, n-tetradecyl (meth)acrylate, n-hexadecyl
(meth)acrylate and n-octadecyl (meth)acrylate, and mixtures
thereof.
[0089] Examples of ethylenically unsaturated dicarboxylic acids are
maleic acid, tetrahydrophthalic acid, citraconic acid and itaconic
acid, and anhydrides thereof, and fumaric acid. Preference is given
to maleic anhydride.
[0090] Suitable amines are compounds of the formula
HNR.sup.6R.sup.7.
[0091] In general, it is advantageous to employ the dicarboxylic
acids in the form of the anhydrides, if available, in the
copolymerization, for example maleic anhydride, itaconic anhydride,
citraconic anhydride and tetrahydrophthalic anhydride, since the
anhydrides generally copolymerize better with the (meth)acrylates.
The anhydride groups of the copolymers can then be reacted directly
with the amines.
[0092] The polymers are reacted with the amines at temperatures of
from 50 to 200.degree. C. over the course of from 0.3 to 30 hours.
The amine here is used in amounts of from approximately one to two
moles per mole of copolymerized dicarboxylic anhydride, i.e. from
about 0.9 to 2.1 mol/mol. The use of larger or smaller amounts is
possible, but does not bring any advantage. If larger amounts than
2 mol are used, free amine is present. If smaller amounts than one
mole are used, complete conversion to the monoamide does not take
place, and a correspondingly reduced action is obtained.
[0093] In some cases, it may be advantageous for the amide/ammonium
salt structure to be built up from two different amines. Thus, for
example, a copolymer of lauryl acrylate and maleic anhydride can
firstly be reacted with a secondary amine, such as hydrogenated
ditallow fatty amine, to give the amide, after which the free
carboxyl group originating from the anhydride is neutralized using
another amine, for example 2-ethylhexylamine, to give the ammonium
salt. The reverse procedure is equally conceivable: reaction is
firstly carried out with ethylhexylamine to give the monoamide,
then with ditallow fatty amine to give the ammonium salt.
Preferably at least one amine is used here which has at least one
straight-chain, unbranched alkyl group having more than 16 carbon
atoms. It is not important here whether this amine is present in
the build-up of the amide structure or as the ammonium salt of the
dicarboxylic acid.
[0094] Instead of the subsequent reaction of the carboxyl groups or
of the dicarboxylic anhydride with amines to give the corresponding
amides or amide/ammonium salts, it may sometimes be advantageous to
prepare the monoamides or amide/ammonium salts of the monomers and
then to copolymerize these directly in the polymerization. Usually,
however, this is much more technically complex, since the amines
are able to add onto the double bond of the monomeric dicarboxylic
acid, and copolymerization is then no longer possible.
[0095] 8. Terpolymers based on .alpha.,.beta.-unsaturated
dicarboxylic anhydrides, .alpha.,.beta.-unsaturated compounds and
polyoxyalkylene ethers of lower, unsaturated alcohols which
comprise 20-80 mol %, preferably 40-60 mol %, of divalent
structural units of the formulae 1 and/or 3, and optionally 2, the
structural units 2 originating from unreacted anhydride radicals,
8
[0096] where
[0097] R.sup.22 and R.sup.23 are each independently hydrogen or
methyl, a and b are zero or one and a+b is one,
[0098] R.sup.24 and R.sup.25 are identical or different and are
each --NHR.sup.6, N(R.sup.6).sub.2 and/or --OR.sup.27 groups, and
R.sup.27 is a cation of the formula H.sub.2N(R.sup.6).sub.2 or
H.sub.3NR.sup.6, 19-80 mol %, preferably 39-60 mol %, of divalent
structural units of the formula 4 9
[0099] in which
[0100] R.sup.28 is hydrogen or C.sub.1-C.sub.4-alkyl, and
[0101] R.sup.29 is C.sub.6-C.sub.60-alkyl or C.sub.6-C.sub.18-aryl,
and
[0102] 1-30 mol %, preferably 1-20 mol %, of divalent structural
units of the formula 5 10
[0103] in which
[0104] R.sup.30 is hydrogen or methyl,
[0105] R.sup.31 is hydrogen or C.sub.1-C.sub.4-alkyl,
[0106] R.sup.33 is C.sub.1-C.sub.4-alkylene,
[0107] m is a number from 1 to 100,
[0108] R.sup.32 is C.sub.1-C.sub.24-alkyl,
C.sub.5-C.sub.20-cycloalkyl, C.sub.6-C.sub.18-aryl or
--C(O)--R.sup.34 where R.sup.34 is C.sub.1-C.sub.40-alkyl,
C.sub.5-C.sub.10-cycloalkyl or C.sub.6-C.sub.18-aryl.
[0109] The abovementioned alkyl, cycloalkyl and aryl radicals may
be substituted or unsubstituted. Suitable substituents of the alkyl
and aryl radicals are, for example, (C.sub.1-C.sub.6)-alkyl,
halogens, such as fluorine, chlorine, bromine and iodine,
preferably chlorine, and (C.sub.1-C.sub.6)-alkoxy.
[0110] Alkyl here is a straight-chain or branched hydrocarbon
radical. Specific examples include: n-butyl, tert-butyl, n-hexyl,
n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl,
dodecenyl, tetrapropenyl, tetradecenyl, pentapropenyl, hexadecenyl,
octadecenyl and eicosanyl, or mixtures, such as coconut alkyl,
tallow fatty alkyl and behenyl.
[0111] Cycloalkyl here is a cyclic aliphatic radical having 5-20
carbon atoms. Preferred cycloalkyl radicals are cyclopentyl and
cyclohexyl.
[0112] Aryl here is a substituted or unsubstituted aromatic ring
system having from 6 to 18 carbon atoms.
[0113] The terpolymers consist of the divalent structural units of
the formulae 1 and 3, and 4 and 5, and optionally 2. They
additionally only contain, as known per se, the end groups formed
in the polymerization by initiation, inhibition and chain
termination.
[0114] In detail, structural units of the formulae 1 to 3 are
derived from .alpha.,.beta.-unsaturated dicarboxylic anhydrides of
the formulae 6 and 7 11
[0115] such as maleic anhydride, itaconic anhydride, citraconic
anhydride, preferably maleic anhydride.
[0116] The structural units of the formula 4 are derived from the
.alpha.-.beta.-unsaturated compounds of the formula 8. 12
[0117] Examples include the following .alpha.,.beta.-unsaturated
olefins: styrene, .alpha.-methylstyrene, dimethylstyrene,
.alpha.-ethylstyrene, diethylstyrene, i-propylstyrene,
tert-butylstyrene, diisobutylene and .alpha.-olefins, such as
decene, dodecene, tetradecene, pentadecene, hexadecene, octadecene,
C.sub.20-.alpha.-olefin, C.sub.24-.alpha.-olefin,
C.sub.30-.alpha.-olefin, tripropenyl, tetrapropenyl, pentapropenyl
and mixtures thereof. Preference is given to .alpha.-olefins having
from 10 to 24 carbon atoms and styrene, particularly preference to
.alpha.-olefins having from 12 to 20 carbon atoms.
[0118] The structural units of the formula 5 are derived from
polyoxyalkylene ethers of lower, unsaturated alcohols of the
formula 9. 13
[0119] The monomers of the formula 9 are products of the
etherification (R.sup.32.dbd.--C(O)R.sup.34) or esterification
(R.sup.32.dbd.--C(O)R.sup- .34) of polyoxyalkylene ethers
(R.sup.32.dbd.H).
[0120] The polyoxyalkylene ethers (R.sup.32.dbd.H) can be prepared
by processes known per se, for example by the addition of
.alpha.-olefin oxides, such as ethylene oxide, propylene oxide
and/or butylene oxide, onto polymerizable, lower, unsaturated
alcohols of the formula 10 14
[0121] and subsequent esterification or etherification.
Polymerizable, lower, unsaturated alcohols of this type are, for
example, allyl alcohol, methallyl alcohol, butenols, such as
3-buten-1-ol and 1-buten-3-ol, or methylbutenols, such as
2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol and
3-methyl-3-buten-1-ol. Preference is given to the products of the
addition of ethylene oxide and/or propylene oxide onto allyl
alcohol.
[0122] Examples of primary amines suitable for the preparation of
the terpolymers include the following:
[0123] n-hexylamine, n-octylamine, n-tetradecylamine,
n-hexadecylamine,
[0124] n-stearylamine or also N,N-dimethylaminopropylenediamine,
cyclohexylamine, dehydroabietylamine and mixtures thereof.
[0125] Examples of secondary amines which are suitable for the
preparation of the terpolymers include the following: didecylamine,
ditetradecylamine, distearylamine, dicoconut fafty amine, ditallow
fatty amine and mixtures thereof.
[0126] The terpolymers have K values (measured by the Ubbelohde
method in 5% by weight solution in toluene at 25.degree. C.) of
from 8 to 100, preferably from 8 to 50, corresponding to average
molecular weights (M.sub.w) of from about 500 to 100,000. Suitable
examples are listed in EP 606 055.
[0127] 9. Products of the reaction of alkanolamines and/or
polyether-amines with polymers containing dicarboxylic anhydride
groups, which comprise 20-80 mol %, preferably 40-60 mol %, of
divalent structural units of the formulae 13 and 15 and optionally
14 15
[0128] where
[0129] R.sup.22 and R.sup.23 are each independently hydrogen or
methyl,
[0130] a and b are zero or 1, and a +b is 1,
[0131] R.sup.37.dbd.--OH, --O--[C.sub.1-C.sub.30-alkyl],
--NR.sup.6R.sup.7, --O.sup.5N.sup.rR.sup.6R.sup.7H.sub.2
[0132] R.sup.38.dbd.R.sup.37 or NR.sup.6R.sup.39
[0133] R.sup.39=-(A-O).sub.x-E
[0134] where
[0135] A=an ethylene or propylene group,
[0136] x=from 1 to 50,
[0137] E=H, C.sub.1-C.sub.30-alkyl, C.sub.5-C.sub.12-cycloalkyl or
C.sub.6-C.sub.30-aryl,
[0138] and 80-20 mol %, preferably 60-40 mol %, of divalent
structural units of the formula 4.
[0139] In detail, the structural units of the formulae 13, 14 and
15 are derived from .alpha.,.beta.-unsaturated dicarboxylic
anhydrides of the formulae 6 and/or 7.
[0140] The structural units of the formula 4 are derived from the
.alpha.,.beta.-unsaturated olefins of the formula 8. The
abovementioned alkyl, cycloalkyl and aryl radicals have the same
meanings as under 8.
[0141] The radicals R.sup.37 and R.sup.38 in formula 13 and
R.sup.39 in formula 15 are derived from polyether-amines or
alkanolamines of the formulae 16 a) and b), amines of the formula
NR.sup.6R.sup.7R.sup.8 and optionally alcohols having from 1 to 30
carbon atoms. 16
[0142] R.sup.54 is hydrogen or C.sub.1-C.sub.4-alkyl
[0143] R.sup.55 is hydrogen, C.sub.1- to C.sub.4-alkyl, C.sub.5- to
C.sub.12-cycloalkyl or C.sub.6-- to C.sub.3-0-aryl
[0144] R.sup.56 and R.sup.57 are each independently hydrogen,
C.sub.1- to C.sub.22-alkyl, C.sub.2- to C.sub.22-alkenyl or
Z-OH
[0145] Z is C.sub.2- to C.sub.4-alkylene
[0146] n is a number from 1 to 1000.
[0147] The structural units of the formulae 6 and 7 have preferably
been derivatized using mixtures of at least 50% by weight of
alkylamines of the formula HNR.sup.6R.sup.7R.sup.8 and at most 50%
by weight of polyether-amines or alkanolamines of the formulae 16
a) and b).
[0148] Another possibility for the derivatization of the structural
units of the formulae 6 and 7 comprises employing an alkanolamine
of the formulae 16a) or 16b) instead of the polyether-amines and
subsequently subjecting the product to oxyalkylation.
[0149] From 0.01 to 2 mol, preferably from 0.01 to 1 mol, of
alkanolamine are employed per mole of anhydride. The reaction
temperature is from 50 to 100.degree. C. (amide formation). In the
case of primary amines, the reaction is carried out at temperatures
above 100.degree. C. (imide formation).
[0150] The oxyalkylation is typically carried out at temperatures
of from 70 to 170.degree. C. with catalysis by bases, such as NaOH
or NaOCH.sub.3, by introducing gaseous alkylene oxides, such as
ethylene oxide (EO) and/or propylene oxide (PO). From 1 to 500 mol,
preferably from 1 to 100 mol, of alkylene oxide are usually added
per mole of hydroxyl groups.
[0151] Examples of suitable alkanolamines include the following:
monoethanolamine, diethanolamine, N-methylethanolamine,
3-aminopropanol, isopropanol, diglycol amine,
2-amino-2-methylpropanol and mixtures thereof.
[0152] Examples of primary amines include the following:
n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine,
n-stearylamine or else N,N-dimethylaminopropylenediamine,
cyclohexylamine, dehydroabietylamine and mixtures thereof.
[0153] Examples of secondary amines include the following:
didecylamine, ditetradecylamine, distearylamine, dicoconut fatty
amine, ditallow fatty amine and mixtures thereof.
[0154] Examples of alcohols include the following:
[0155] methanol, ethanol, propanol, isopropanol, n-, sec-, and
tert-butanol, octanol, tetradecanol, hexadecanol, octadecanol,
tallow fatty alcohol, behenyl alcohol and mixtures thereof.
Suitable examples are listed in EP-A-688 796.
[0156] 10. Copolymers and terpolymers of
N--C.sub.6-C.sub.24-alkylmaleimid- e with C.sub.1-C.sub.30-vinyl
esters, vinyl ethers and/or olefins having from 1 to 30 carbon
atoms, for example styrene or .alpha.-olefins. These can be
obtained either by reaction of a polymer containing anhydride
groups with amines of the formula H.sub.2NR.sup.6 or by imidation
of the dicarboxylic acid followed by copolymerization. The
preferred dicarboxylic acid here is maleic acid or maleic
anhydride. Preference is given here to copolymers comprising from
10 to 90% by weight of C.sub.6-C.sub.24-.alpha.-olefins and from 90
to 10% by weight of N--C.sub.6-C.sub.22-alkylmaleimide.
[0157] The polar nitrogen-containing paraffin dispersants may be
added to the additives according to the invention or added
separately to the additized middle distillate. The ratio between
paraffin dispersants and the additives according to the invention
is between 5:1 and 1:5 and preferably between 3:1 and 1:3.
[0158] To prepare additive packages for specific solutions to
problems, the additives according to the invention may also be used
together with one or more oil-soluble coadditives which in
themselves improve the lubricity and/or cold-flow properties of
crude oils, lubricant oils or fuel oils. Examples of such
coadditives are vinyl acetate-containing copolymers or terpolymers
of ethylene, comb polymers and also oil-soluble amphiphiles.
[0159] For instance, mixtures of the additives according to the
invention with copolymers which contain from 10 to 40% by weight of
vinyl acetate and from 60 to 90% by weight of ethylene have proven
outstandingly suitable. In a further embodiment of the invention,
the additives according to the invention are used in a mixture with
ethylene/vinyl acetate/vinyl 2-ethylhexanoate terpolymers,
ethylene/vinyl acetate/vinyl neononanoate terpolymers and/or
ethylene/vinyl acetate/vinyl neodecanoate terpolymers to
simultaneously improve the flowability and lubricity of mineral
oils or mineral oil distillates. Apart from ethylene, the
terpolymers of vinyl 2-ethylhexanoates, vinyl neononanoates or
vinyl neodecanoates contain from 10 to 35% by weight of vinyl
acetate and from 1 to 25% by weight of the particular long-chain
vinyl ester. In addition to ethylene and from 10 to 35% by weight
of vinyl esters, further preferred copolymers also contain from 0.5
to 20% by weight of olefin having from 3 to 10 carbon atoms, for
example isobutylene, diisobutylene, 4-methylpentene or
norbornene.
[0160] Finally, in a further embodiment of the invention, the
additives according to the invention are used together with comb
polymers. This refers to polymers in which hydrocarbon radicals
having at least 8, in particular at least 10, carbon atoms are
bonded to a polymer backbone. These are preferably homopolymers
whose alkyl side chains have at least 8 and in particular at least
10 carbon atoms. In copolymers, at least 20%, preferably at least
30%, of the monomers have side chains (cf. Comb-like
Polymers-Structure and Properties; N. A. Plat and V. P. Shibaev, J.
Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of
suitable comb polymers are, for example, fumarate/vinyl acetate
copolymers (cf. EP 0 153 76 A1), copolymers of a
C.sub.6-C.sub.24-.alpha.-olefin and an
N--C.sub.6-C.sub.22-alkylmaleimide (cf. EP 0 320 766), and also
esterified olefin/maleic anhydride copolymers, polymers and
copolymers of a-olefins and esterified copolymers of styrene and
maleic anhydride.
[0161] Comb polymers can be described, for example, by the formula
17
[0162] In this formula:
[0163] A is R', COOR', OCOR', R"-COOR' or OR';
[0164] D is H, CH.sub.3, A or R;
[0165] E is H or A;
[0166] G is H, R", R"--COOR', an aryl radical or a heterocyclic
radical;
[0167] M is H, COOR", OCOR", OR" or COOH;
[0168] N is H, R", COOR", OCOR, COOH or an aryl radical;
[0169] R' is a hydrocarbon chain having 8-150 carbon atoms;
[0170] R" is a hydrocarbon chain having from 1 to 10 carbon
atoms;
[0171] m is a number between 0.4 and 1,0; and
[0172] n is a number between 0 and 0.6.
[0173] The mixing ratio (in parts by weight) of the additives
according to the invention with ethylene copolymers or comb
polymers is in each case from 1:10 to 20:1, preferably from 1:1 to
10:1.
[0174] The additives according to the invention are added to oils
in amounts of from 0.0001 to 1% by weight, preferably from 0.001 to
0.1% by weight and especially from 0.002 to 0.05% by weight. They
may be used as such or else dissolved in solvents, for example
aliphatic and/or aromatic hydrocarbons or hydrocarbon mixtures, for
example toluene, xylene, ethylbenzene, decane, pentadecane,
petroleum fractions, diesel, kerosene or commercial solvent
mixtures such as Solvent Naphtha, .RTM.Shellsol AB, .RTM.Solvesso
150, .RTM.Solvesso 200 and .RTM.Exxsol, .RTM.Isopar and
.RTM.Shellsol D types, and also polar solvents such as alcohols,
glycols and esters, for example fatty acid alkyl esters and in
particular rapeseed oil methyl ester (RME). The additives according
to the invention preferably contain up to 70%, especially 5-60%, in
particular 10-40% by weight of solvent.
[0175] The additives according to the invention can be stored
without aging effects at elevated temperature over a long period,
without any symptoms of aging occurring, such as resinification and
the formation of insoluble structures or deposits in storage
containers and/or engine parts. In addition, they improve the
oxidation stability of the additized oils with simultaneous reduced
tendency to emulsify. This is advantageous in particular in oils
which contain relatively large fractions of oils from cracking
processes.
[0176] In addition, they exhibit an improvement in lubricity of
middle distillates superior to the individual components. This
allows the dosage required for the setting of the specification to
be reduced.
[0177] A further advantage of the additives according to the
invention is their reduced crystallization temperature compared to
the fatty acid esters used as lubricity additives in the prior art.
For instance, they can also be used at low temperatures of, for
example, from 0.degree. C. to -20.degree. C. and sometimes even
lower without any problem.
[0178] The additives according to the invention are particularly
well suited to use in middle distillates. Middle distillates refer
in particular to those mineral oils which are obtained by
distillation of crude oil and boil in the range from 120 to
450.degree. C., for example kerosene, jet fuel, diesel and heating
oil. The oils can also contain alcohols such as methanol and/or
ethanol or consist of these. The additives according to the
invention are preferably used in those middle distillates which
contain fewer than 350 ppm of sulfur, in particular fewer than 200
ppm of sulfur and in special cases fewer than 50 ppm or fewer than
10 ppm, of sulfur. These are generally those middle distillates
which have been subjected to refining under hydrogenating
conditions, and therefore only contain small fractions of
polyaromatic and polar compounds which confer a natural lubricity
on them. The additives according to the invention are also
preferably used in those middle distillates which have 95%
distillation points below 370.degree. C., in particular 350.degree.
C. and in special cases below 330.degree. C. The additives
according to the invention are equally suitable for use in
synthetic fuels likewise having low lubricity, for example as
produced in the Fischer-Tropsch process. The oils having improved
lubricity have a Wear Scar Diameter measured in the HFRR test of
preferably less than 460 .mu.m, especially less than 450 .mu.m. The
additives according to the invention can also be used as components
in lubricant oils.
[0179] The mixtures can be used alone or else together with other
additives, for example with pour point depressants, corrosion
inhibitors, antioxidants, sludge inhibitors, dehazers, conductivity
improvers, lubricity additives, and additives for reducing the
cloud point. They are also used successfully together with additive
packages which contain, inter alia, known ashless dispersing
additives, detergents, antifoams, antioxidants, dehazers,
demulsifiers and corrosion inhibitors.
[0180] The advantages of the additives according to the invention
are illustrated in detail by the examples which follow.
EXAMPLES
[0181]
1TABLE 1 Characterization of the test oils used Test oil 1 Test oil
2 Test oil 3 Distillation IBP [.degree. C.] 202 182 164 20%
[.degree. C.] 237 221 214 90% [.degree. C.] 321 280 342 FBP
[.degree. C.] 348 304 367 Cloud Point [.degree. C.] -5.9 -29.7 -7.7
CFPP [.degree. C.] -8 -33 -13 Density at 15.degree. C. [g/cm.sup.3]
0.8348 0.8210 0.8293 Sulfur [ppm] 32 6 195
[0182] The additives used are characterized hereinbelow. The OH
numbers were determined to DIN 53240 by reacting with a defined
amount of excess acetic anhydride and subsequently titrating the
acetic acid formed.
[0183] Iodine numbers are determined according to Kaufmann. In this
method, the sample is admixed with a defined amount of a methanolic
bromine solution, which results in an amount of bromine equivalent
to the content of double bonds adding onto them. The excess of
bromine is back-titrated using sodium thiosulfate.
2TABLE 2 Characterization of the lubricity additives used OH number
[mg Iodine number Example Chemical description KOH/g] [gl/100 g] A1
Partial ester of glycerol and soya oil fatty 158 103 acid A2
Partial ester of glycerol and tall oil fatty acid 88 116 A3 Partial
ester of glycerol and tall oil fatty acid 193 122 A4 Partial ester
of glycerol and tallow fatty acid 181 52 A5 Partial ester of
glycerol and olein 278 77 A6 Partial ester of glycerol and olein
153 76 A7 Glycerol monooleate, technical grade 197 83 A8 Glycerol
dioleate 68 86 A9 Pentaerythritol monooleate 111 85
[0184]
3TABLE 3 Characterization of the alkylphenol resins used B1
Nonylphenol-formaldehyde resin, prepared by condensing a mixture of
nonylphenol having 0.5 mol% of dinonylphenol with formaldehyde, Mw
2000 g/mol; 50% in Solvent Naphtha B2 Dodecylphenol-formaldehyde
resin, prepared by condensing a mixture of dodecylphenol having 1.3
mol % of didodecylphenol with formaldehyde, Mw 2200 g/mol: 50% in
Solvent Naphtha B3 C.sub.20-C.sub.24-Alkylphenol-formaldehyde
resin, prepared by condensing a mixture of C.sub.20-C.sub.24-
alkylphenol having 35 mol % of di-(C.sub.20-C.sub.24-alkyl)phenol
with formaldehyde, Mw 2500 g/mol; 50% in Solvent Naphtha
[0185]
4TABLE 4 Characterization of the polar nitrogen-containing
compounds used C1 Reaction product of a dodecenyl-spiro-bislactone
with a mixture of primary and secondary tallow fatty amine, 60% in
Solvent Naphtha (prepared according to EP 0413279) C2 Reaction
product of a terpolymer of a C14/16-.alpha.-olefin, maleic
anhydride and allyl polyglycol with 2 equivalents of ditallow fatty
amine, 50% in Solvent Naphtha (prepared according to EP 0606055) C3
Reaction product of phthalic anhydride and 2 equivalents of
di(hydrogenated tallow fatty) amine, 50% in Solvent Naphtha
(prepared according to EP 0061894) C4 Reaction product of
ethylenediaminetetraacetic acid with 4 equivalents of ditallow
fatty amine to give the amide-ammonium salt (prepared according to
EP 0398101)
[0186] Oxidation Stability of the Additives
[0187] 10 g of the additive (mixture) to be tested are weighed into
a 500 ml Erlenmeyer flask. The flask is stored in a drying cabinet
at a temperature of 90.degree. C. for three days, and the
atmosphere above the additive is changed daily by passing over an
air stream.
[0188] After the conditioning, the mixture is allowed to cool to
room temperature for one hour. Subsequently, the mixture is admixed
with 500 ml of diesel fuel (test oil 3) and mixed thoroughly. After
standing for a period of two hours, the mixture is visually
examined for any deposits, cloudiness, insoluble fractions, etc.,
which give indications of oxidative changes (visual examination).
The mixture is then filtered through a 0.8 .mu.m filter at a
pressure differential of 800 mbar. The entire amount has to be
filterable within 2 minutes, otherwise the volume which has been
filtered after 2 minutes is noted.
5TABLE 5 Oxidation stability Example A B Visual examination
Filtration 1 (comp.) -- -- clear 34 s 2 10 g A1 -- cloudy;insoluble
n.a. fractions 3 (comp.) 9.9 g A1 0.1 g B1 clear 62 s 4 9.9 g A1
0.1 g B2 clear 57 s 5 (comp.) 10 g A2 -- cloudy;insoluble n.a.
fractions 6 9.9 g A2 0.1 g B1 clear 53 s 7 (comp.) 10 g A4 --
cloudy 120 s/260 ml 8 9.9 g A4 0.1 g B1 clear 49 s 9 9 g A4 1 g B2
clear 52 s 10 (comp.) 10 g A5 -- cloudy;insoluble n.a. fractions 11
9.9 g A5 0.1 g B1 clear 57 s 12 (comp.) 10 g A3 -- cloudy;insoluble
n.a. fractions 13 5 g A3 5 g B1 clear 68 s 14 9.9 g A3 0.1 g B2
clear 63 s 15 9.99 g A3 0.01 g B3 clear 76 s 16 (comp.) 10 g A8 --
cloudy;insoluble na. fractions 17 5 g A8 5 g B1 clear 84 s 18 9.9 g
A8 0.1 g B1 clear 60 s 19 9.99 g A8 0.01 g B1 clear 72 s 20 9.9 g
A8 0.1 g B3 clear 62 s
[0189] n.a.=not applicable, since not completely soluble
Example 21
[0190] A mixture of 9 g of A 7, 1 g of B1 and 2 g of C2, after
storage at 90.degree. C. for three days and subsequent dilution
with 500 ml of test oil 3, gave a clear solution and a filtration
time of 65 s.
[0191] Cold Stability of the Additives
[0192] Various esters were stored at 15.degree. C., +5.degree. C.
and -5.degree. C., each for 5 days, and examined visually after 3
or 5 days for flowability and any deposits or cloudiness. The
assessments have the following meanings:
[0193] + flowable and clear
[0194] .smallcircle. flowable but cloudy or with deposits
[0195] - solid
6TABLE 6 Cold stability of the additives Additive 15.degree. C.
+5.degree. C. -5.degree. C. Example Fraction A Fraction B 3 days 5
days 3 days 5 days 3 days 5 days 22 A5 -- .smallcircle. -- --
(comp.) 23 2 parts of A5 1 part of B1 + .smallcircle. .smallcircle.
-- -- 24 1 part of A5 1 part of B1 + + + .smallcircle. -- 25 1 part
of A5 2 parts of B1 + + + + -- 26 A6 -- + + .smallcircle. --
(comp.) 27 2 parts of A6 1 part of B2 + + + + .smallcircle.
.smallcircle. 28 1 part of A6 1 part of B2 + + + + + + 29 1 part of
A6 2 parts of B2 + + + + + + 30 A7 -- .smallcircle. -- -- (comp.)
31 2 parts of A7 1 part of B1 + + + + -- 32 1 part of A7 1 part of
B1 + + + + -- 33 1 part of A7 2 parts of B1 + + + + + + 34 A3 -- +
+ + + .smallcircle. -- (comp.) 35 2 parts of A3 1 part of B1 + + +
+ + + 36 1 part of A3 1 part of B1 + + + + + + 37 1 part of A3 2
parts of B1 + + + + + + 38 A8 -- + + + .smallcircle. -- (comp.) 39
2 parts of A8 1 part of B1 + + + + .smallcircle. .smallcircle. 40 1
part of A8 1 part of B1 + + + + + + 41 1 part of A8 2 parts of B1 +
+ + + + + 42 A9 -- + + + .smallcircle. .smallcircle. -- (comp.) 43
2 parts of A9 1 part of B1 + + + + + + 44 1 part of A9 1 part of B1
+ + + + + + 45 1 part of A9 2 parts of B1 + + + + + +
[0196] Lubricity in Middle Distillates
[0197] The lubricity of the additives was tested on additized oils
at 60.degree. C. by means of an HFRR instrument from PCS
Instruments. The high frequency reciprocating rig test (HFRR) is
described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217,
1986. The results are quoted as friction coefficient and wear scar
(WS 1.4). A low wear scar and a low coefficient of friction
indicate good lubricity. Wear scar values of less than 460 .mu.m
are regarded as an indication of sufficient lubricity, although
values of less than 400 .mu.m are sought in practice. The dosages
in Table 6 relate to the amount of added active ingredient.
7TABLE 7 Wear scar in test oil 1 Wear Example Dosage of A Dosage of
B Dosage of C Scar Friction 46 (comp.) -- -- -- 575 0.38 47 (comp.)
80 ppm A1 -- -- 536 0.32 48 (comp.) 100 ppm A1 -- -- 427 0.22 49 80
ppm A1 20 ppm B2 -- 380 0.21 50 70 ppm A1 20 ppm B2 10 ppm 364 0.18
51 (comp.) 50 ppm A3 -- -- 566 0.37 52 (comp.) 75 ppm A3 -- -- 523
0.25 53 (comp.) 100 ppm A3 -- -- 395 0.23 54 (comp.) -- 50 ppm B1
-- 570 0.38 55 (comp.) -- -- 40 ppm C2 566 0.34 56 (comp.) 75 ppm
A3 -- 40 ppm C2 412 0.23 57 (comp.) -- 20 ppm B1 40 ppm C2 550 0.34
58 75 ppm A3 20 ppm B1 -- 366 0.20 59 75 ppm A3 20 ppm B1 40 ppm C2
276 0.18 60 50 ppm A3 50 ppm B1 -- 425 0.22 61 50 ppm A3 20 ppm B1
-- 458 0.24 62 50 ppm A3 20 ppm B1 30 ppm C2 378 0.20
[0198]
8TABLE 8 Wear scar in test oil 2 Wear Example Dosage of A Dosage of
B Dosage of C Scar Friction 63 (comp.) -- -- -- 611 0.41 64 (comp.)
100 ppm A2 -- -- 551 0.25 65 (comp.) 120 ppm A2 -- -- 352 0.19 66
(comp.) -- 10 ppm B1 -- 613 0.41 67 (comp.) -- -- 10 ppm C1 603
0.41 68 90 ppm A2 10 ppm B1 -- 457 0.23 69 100 ppm A2 10 ppm B2 --
322 0.17 70 80 ppm A2 10 ppm B1 10 ppm C1 384 0.20 71 70 ppm A2 10
ppm B2 10 ppm C1 436 0.22 72 80 ppm A2 10 ppm B1 10 ppm C3 413 0.21
73 80 ppm A2 10 ppm B1 10 ppm C4 407 0.21
* * * * *