U.S. patent number RE40,758 [Application Number 10/938,495] was granted by the patent office on 2009-06-23 for fuel oils having improved lubricity comprising mixtures of fatty acids with paraffin dispersants, and a lubrication-improving additive.
This patent grant is currently assigned to Clariant Produkte (Deutschland) GmbH. Invention is credited to Matthias Krull, Werner Reimann.
United States Patent |
RE40,758 |
Krull , et al. |
June 23, 2009 |
Fuel oils having improved lubricity comprising mixtures of fatty
acids with paraffin dispersants, and a lubrication-improving
additive
Abstract
The invention relates to low-temperature-stabilized additives
for fuel oils having a sulfur content of up 0.05% by weight,
comprising fatty acid mixtures of A1) from 1 to 99% by weight of at
least one saturated mono- or dicarboxylic acid having from 6 to 50
carbon atoms, A2) from 1 to 99% by weight of at least one
unsaturated mono- or dicarboxylic acid having from 6 to 50 carbon
atoms, and B) at least one polar nitrogen-containing compound which
is effective as paraffin dispersant in middle distillates, in an
amount of from 0.01 to 90% by weight, based on the total weight of
A1), A2) and B); and to the use of said mixtures for improving the
lubrication properties of low-sulfur middle distillates.
Inventors: |
Krull; Matthias (Oberhausen,
DE), Reimann; Werner (Frankfurt am Main,
DE) |
Assignee: |
Clariant Produkte (Deutschland)
GmbH (Frankfurt, DE)
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Family
ID: |
7664508 |
Appl.
No.: |
10/938,495 |
Filed: |
September 10, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
09993590 |
Nov 16, 2001 |
06610111 |
Aug 26, 2003 |
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Foreign Application Priority Data
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Nov 24, 2000 [DE] |
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100 58 359 |
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Current U.S.
Class: |
44/385; 44/403;
44/404; 44/412 |
Current CPC
Class: |
C10L
1/14 (20130101); C10L 1/143 (20130101); C10L
10/04 (20130101); C10L 10/08 (20130101); C10L
10/14 (20130101); C10L 1/1616 (20130101); C10L
1/1824 (20130101); C10L 1/1852 (20130101); C10L
1/1855 (20130101); C10L 1/1881 (20130101); C10L
1/1883 (20130101); C10L 1/1885 (20130101); C10L
1/1888 (20130101); C10L 1/19 (20130101); C10L
1/191 (20130101); C10L 1/1966 (20130101); C10L
1/1981 (20130101); C10L 1/221 (20130101); C10L
1/2222 (20130101); C10L 1/2225 (20130101); C10L
1/224 (20130101); C10L 1/2364 (20130101); C10L
1/238 (20130101); C10L 1/2383 (20130101); C10L
1/2387 (20130101) |
Current International
Class: |
C10L
1/18 (20060101); C10L 1/22 (20060101) |
Field of
Search: |
;44/385,403,404,412 |
References Cited
[Referenced By]
U.S. Patent Documents
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Smith et al. |
4985048 |
January 1991 |
Wirtz et al. |
5186720 |
February 1993 |
Feustel et al. |
5376155 |
December 1994 |
Dralle-Voss et al. |
5391632 |
February 1995 |
Krull et al. |
5789510 |
August 1998 |
Krull et al. |
5833722 |
November 1998 |
Davies et al. |
6010545 |
January 2000 |
Davies et al. |
6071993 |
June 2000 |
Wenderoth et al. |
6086645 |
July 2000 |
Quigley et al. |
6129772 |
October 2000 |
Weers et al. |
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Foreign Patent Documents
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0153176 |
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EP |
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0 155 171 |
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EP |
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0272889 |
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EP |
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0320766 |
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EP |
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0413279 |
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0597278 |
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EP |
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0597278 |
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EP |
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0606055 |
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EP |
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0829527 |
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EP |
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0780460 |
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Dec 1996 |
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EP |
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0 798 364 |
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Oct 1997 |
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EP |
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0 829 527 |
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Mar 1998 |
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EP |
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0909307 |
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Apr 1999 |
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EP |
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0138461 |
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May 2001 |
|
EP |
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WO9533805 |
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Dec 1995 |
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WO |
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WO9618706 |
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Jun 1996 |
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WO |
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WO9623855 |
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Aug 1996 |
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WO |
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00/15739 |
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Mar 2000 |
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WO |
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WO0138461 |
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May 2001 |
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WO |
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Other References
EPO Office Action and Search Report for Corresponding Appl. No.
07005871.4, dated Aug. 30, 2007. cited by other .
EPO Office Action and Search Report for Corresponding Appl. No.
07005870.6, dated Aug. 30, 2007. cited by other .
U.S. Appl. No. 09/993,847, filed Nov. 16, 2001. cited by examiner
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German office action for application 10058359, Jan. 11, 2001. cited
by examiner .
English abstract for JP 11-001692, Jan. 6, 1999. cited by examiner
.
J. March, Advanced Organic Chemistry, 2, Auflage, S. 347-360
(1977). cited by examiner .
N.A. Plate, et al., "Comb-Like Polymers--Structure and Properties",
J. Polymer Science: Macromolecular Reviews, vol. 8, 117-253 (1974).
cited by examiner .
H.A. Spikes; "The Lubricity of Diesel Fuels", Wear, 111 (1986) p.
217-235. cited by examiner.
|
Primary Examiner: Toomer; Cephia D.
Attorney, Agent or Firm: Silverman; Richard P.
Claims
What is claimed is:
1. A low-temperature-stabilized additive for fuel oils having a
sulfur content of up to 0.05 weight percent, comprising fatty acid
mixtures comprising A1) from 1 to 99 weight percent of at least one
saturated mono- or dicarboxylic acid having from 6 to 50 carbon
atoms, A2) from 1 to 99 weight percent of at least one unsaturated
mono- or dicarboxylic acid having from 6 to 50 carbon atoms, and
.Iadd.B) .Iaddend.at least one polar nitrogen-containing
compound.Iadd., being a product of a secondary fatty amine having
from 8 to 36 carbon atoms, .Iaddend.which is effective as paraffin
dispersant in middle distillates, in an amount of from 0.01 to 90
weight percent, based on the total weight of A1), A2), and
B.Iadd.).Iaddend., wherein a mixture of A1) and A2) has an iodine
number of at least 40 g of 1/100 g.Iadd., and said at least one
polar nitrogen-containing compound B) is a terpolymer comprising:
I)20-80 mol % of a divalent structural unit of formula 12 and a
divalent structural unit selected from the group consisting of
formula 14, 13, and mixtures thereof, ##STR00019## where R.sup.22
and R.sup.23, independently of one another, are hydrogen or methyl,
a and b are zero or one and a+b is one, R.sup.24 and R.sup.25 are
identical or different and are --NHR.sup.6, N(R.sup.6).sub.2 or
--OR.sup.27 or a combination thereof, and R.sup.27 is a cation of
the formula H.sub.2N(R.sup.6).sub.2 or H.sub.3NR.sup.6, and R.sup.6
is selected from the group consisting of C.sub.8-C.sub.36-alkyl,
C.sub.6-C.sub.36-cycloalkyl, and C.sub.8-C.sub.36-alkenyl, II)
19-80 mol % of a divalent structural unit of formula 15
##STR00020## in which R.sup.28 is hydrogen or
C.sub.1-C.sub.4-alkyl, and R.sup.29 is C.sub.6-C.sub.60-alkyl or
C.sub.6-C.sub.18-aryl, and III) 1-30 mol % of a divalent structural
unit of formula 16 ##STR00021## in which R.sup.30 is hydrogen or
methyl, R.sup.31 is hydrogen or C.sub.1-C.sub.4-alkyl, R.sup.33 is
C.sub.1-C.sub.4-alkylene, m is a number from 1 to 100, R.sup.32 is
C.sub.1-C.sub.24-alkyl, C.sub.5-C.sub.20-cycloalkyl,
C.sub.8-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.Iaddend..
.Iadd.2. The low-temperature-stabilized additive of claim 1 wherein
the secondary amine is selected from the group consisting of
dicoconut fatty amine, ditallow fatty amine, distearyl fatty amine
and mixtures thereof..Iaddend.
.Iadd.3. The low-temperature-stabilized additive of claim 1,
wherein component B comprises oil-soluble polar amine salts or
amides..Iaddend.
.Iadd.4. The low-temperature-stabilized additive of claim 1,
wherein component A) comprises from 1 to 40% by weight of resin
acids.Iaddend.
.Iadd.5. The low-temperature-stabilized additive of claim 1,
wherein A1) and A2) are each a mono-or dicarboxylic acid having
from 12 to 22 carbon atoms..Iaddend.
Description
BACKGROUND OF THE INVENTION
The present invention relates to mixtures of fatty acids and
paraffin dispersants of improved low-temperature stability, and to
their use for improving the lubricity of middle-distillate fuel
oils.
FIELD OF THE INVENTION
Mineral oils and mineral-oil distillates which are used as fuel
oils generally comprise 0.5% by weight or more of sulfur, which
causes the formation of sulfur dioxide on combustion. In order to
reduce the resultant environmental pollution, the sulfur content of
fuel oils is constantly being reduced further. The EN 590 standard,
which relates to diesel fuels, currently prescribes a maximum
sulfur content of 350 ppm in Germany. In Scandinavia, fuel oils
containing less than 50 ppm and in exceptional cases less than 10
ppm of sulfur are already in use. These fuel oils are generally
produced by subjecting the fractions obtained from crude oil by
distillation to reductive refining. During desulfurization,
however, other substances are also removed which give the fuel oils
a natural lubricity. These substances include, inter alia,
polyaromatic and polar compounds.
However, it has now been found that the friction- and wear-reducing
properties of fuel oils become worse with increasing degree of
desulfurization. These properties are frequently so unsatisfactory
that corrosion phenomena must be expected after only a short time
on the materials lubricated by the fuel, such as, for example,
distributor injection pumps of diesel engines. The maximum value
for a 95% distillation point of a maximum of 360.degree. C. which
has been prescribed in EN 590 since the year 2000 and the further
reduction in the 95% distillation point to below 360.degree. C. and
in some cases below 330.degree. C. which has in the meantime been
effected in Scandinavia intensify these problems further.
DESCRIPTION OF THE RELATED ART
The prior art has therefore described approaches which are intended
to represent a solution to this problem (so-called lubricity
additives).
EP-A-0 798 364 discloses salts and amines of mono- to
tetracarboxylic acids having from 2 to 50 carbon atoms and
aliphatic mono/polyamines having from 2 to 50 carbon atoms and from
1 to 10 nitrogen atoms as lubricity additives for low-sulfur diesel
fuel. Preferred amines have 8-20 carbon atoms, such as, for
example, coconut fatty amine, tallow fatty amine and
oleylamine.
WO-A-95/33805 discloses the use of cold-flow improvers for
improving the lubricity of low-sulfur middle distillates. The
suitable substances mentioned include polar nitrogen-containing
compounds which contain an NR.sup.13 group, where R.sup.13 is a
hydrocarbon radical having from 8 to 40 carbon atoms, and may be in
the form of a cation.
WO-A-96/18706 discloses, analogously to WO-A-95/33805, the use of
the nitrogen-containing compounds mentioned therein in combination
with lubricity additives.
WO-A-96123855 discloses, analogously to WO-A-95/33805, the use of
the nitrogen-containing compounds mentioned therein in combination
with detergent additives.
The fatty acids used in accordance with the prior art have the
disadvantage that they solidify on storage at low temperatures,
i.e. often at room temperature, usually at temperatures of from
0.degree. C. to at the latest -5.degree. C., or deposit crystalline
fractions and cause problems in handling. This problem can only be
partially solved even by dilution with organic solvents, since
fractions also crystallize from these solutions or the solution
gels and solidifies. For use as lubricity additives, they therefore
have to be diluted to a great extent or stored in heated storage
containers and dispensed via heated lines.
The effectiveness of cold-flow improvers as lubricity additives is
alone not sufficient, which means that either very high dispensing
rates or synergists have to be employed.
SUMMARY OF THE INVENTION
The object on which the present invention is based was to find
lubricity additives which improve the lubricity of middle
distillates at reduced dispensing rates, but remain homogeneous,
clear and in particular flowable even at low temperatures.
It has been found that mixtures of fatty acids with polar
nitrogen-containing compounds which are effective as paraffin
dispersants in middle distillates remain flowable and clear for an
extended time even at significantly reduced temperatures, in some
cases down to below -20.degree. C., in particular cases down to
below -30.degree. C. and in special cases down to below -40.degree.
C., and in addition improve the lubricity of middle distillates
more efficiently than pure fatty acids of the prior art.
The invention thus relates to low-temperature-stabilized additives
for fuel oils having a sulfur content of up to 0.05% by weight,
comprising fatty acid mixtures of A1) from 1 to 99% by weight of at
least one saturated mono- or dicarboxylic acid having from 6 to 50
carbon atoms, A2) from 1 to 99% by weight of at least one
unsaturated mono- or dicarboxylic acid having from 6 to 50 carbon
atoms, and at least one polar nitrogen-containing compound which is
effective as paraffin dispersant in middle distillates in an amount
of from 0.01 to 90% by weight, based on the total weight of A1),
A2) and B).
DETAILED DESCRIPTION OF THE INVENTION
The invention furthermore relates to low-temperature-stabilized
solutions of the additives according to the invention in organic
solvents, where the solutions comprise from 1 to 90% by weight of
solvent. Suitable solvents are aliphatic and/or aromatic
hydrocarbons or hydrocarbon mixtures. The additives according to
the invention preferably comprise 1-80%, especially 10-70%, in
particular 25-60%, of solvent. The low-temperature-stabilized
solutions according to the invention have a pour point of below
-40.degree. C., preferably -45.degree. C., in particular
-50.degree. C.
The invention furthermore relates to low-temperature-stabilized
fatty acid mixtures of A1) from 1 to 99% by weight of at least one
saturated mono- or dicarboxylic acid having from 6 to 50 carbon
atoms, A2) from 1 to 99% by weight of at least one unsaturated
mono- or dicarboxylic acid having from 6 to 50 carbon atoms, and at
least one polar nitrogen-containing compound which is effective as
paraffin dispersant in middle distillates, in an amount of from
0.01 to 90% by weight, based on the total weight of A1), A2) and
B).
The invention furthermore relates to fuel oils comprising, besides
a middle distillate having a sulfur content of up to 0.05% by
weight, fatty acid mixtures of A1) from 1 to 99% by weight of at
least one saturated mono- or dicarboxylic acid having from 6 to 50
carbon atoms, A2) from 1 to 99% by weight of at least one
unsaturated mono- or dicarboxylic acid having from 6 to 50 carbon
atoms, and at least one polar nitrogen-containing compound which is
effective as paraffin dispersant in middle distillates, in an
amount of from 0.01 to 90% by weight, based on the total weight of
A1), A2) and B).
The invention furthermore relates to the use of said mixtures
comprising constituents A and B for improving he lubrication
properties of low-sulfur middle distillates having a sulfur content
of up to 0.05% by weight.
Preferred fatty acids (constituent A) are those having 8-40 carbon
atoms, in particular 12-22 carbon atoms. The alkyl radicals in the
fatty acids essentially consist of carbon and hydrogen. However,
they may carry further substituents, such as, for example,
hydroxyl, hydrogen, amino or nitro groups, so long as these do not
impair the predominant hydrocarbon character.
Constituent A2) may contain one or more double bonds and be of
natural or synthetic origin. In the case of polyunsaturated
carboxylic acids, their double bonds may be isolated or conjugated.
The proportion of saturated fatty acids A1) in the mixture of A1)
and A2) is preferably less than 20% by weight, in particular less
than 10% by weight, especially less than 5% by weight. In preferred
fatty acid mixtures, which is taken to mean the combination of A1)
and A2) here, at least 50% by weight, in particular at least 75% by
weight, especially at least 90% by weight, of the constituents
contain one or more double bonds. These preferred fatty acid
(mixtures) have iodine numbers of at least 40 g of 1/100 g,
preferably at least 80 g of 1/100 g, in particular at least 125 g
of 1/100 g.
Examples of suitable fatty acids are lauric, tridecanoic, myristic,
pentadecanoic, palmitic, margaric, stearic, isostearic, arachic
arid behenic acid, oleic and erucic acid, palmitoleic, myristoleic,
linoleic, linolenic, elaeosteric and arachidonic acid, ricinoleic
acid and fatty acid mixtures obtained from natural fats and oils,
such as, for example, coconut oil, groundnut oil, fish, linseed
oil, palm oil, rape oil, ricinene oil, castor oil, colza oil,
soybean oil, sunflower oil and tall oil fatty acid.
Likewise suitable are dicarboxylic acids, such as dimeric fatty
acids and alkyl- and alkenylsuccinic acids containing
C.sub.8-C.sub.30-alk(en)yl radicals, preferably containing
C.sub.8-C.sub.40-, in particular containing C.sub.12-C.sub.22-alkyl
radicals. The alkyl radicals may be linear or branched
(oligomerized alkene, PIB).
The fatty acids may furthermore comprise 1-40% by weight,
especially 1-25% by weight, of resin acids, based on the weight of
A1) and A2) together.
The additives according to the invention comprise, as constituent
B, at least one polar nitrogen-containing compound which is
effective as paraffin dispersant in middle distillates. Paraffin
dispersants reduce the size of the paraffin crystals which
precipitate out at low temperatures and have the effect that the
paraffin particles do not settle out, but instead remain dispersed
in colloidal form with significantly reduced sedimentation
volition. Paraffin dispersants which have proven successful are oil
soluble polar compounds containing ionic or polar groups, for
example amine salts and/or amides, which are obtained by reaction
of aliphatic or aromatic amines, preferably long-chain aliphatic
amines, with aliphatic or aromatic mono-, di-, tri- or
tetracarboxylic acids or anhydrides thereof. Particularly preferred
paraffin dispersants comprise products of the reaction of secondary
fatty amines having from 8 to 36 carbon atoms, in particular
dicoconut fatty amine, ditallow fatty amine and distearyl fatty
amine. Other paraffin dispersants are copolymers of maleic
anhydride and .alpha.,.beta.-unsaturated compounds, which can, if
desired, be reacted with primary monoalkylamines and/or aliphatic
alcohols, the products of the reaction of alkenylspirobislactones
with amines, and products of the reaction of terpolymers based on
.alpha.,.beta.-unsaturated dicarboxylic anhydrides,
.alpha.,.beta.-unsaturated compounds and polyoxyalkylene ethers of
lower unsaturated alcohols. Alkylphenol-formaldehyde resins are
also suitable as paraffin dispersants. Some suitable paraffin
dispersants are listed below.
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 formula --(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.dbd.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,
independently of one another, are 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
Products of the reaction of alkenylspirobislactones of the formula
4 ##STR00001## 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 (4) with the
amines gives amides or amide ammonium salts.
Amides or ammonium salts of aminoalkylenepolycarboxylic acids with
secondary amines of the formulae 5 and 6 ##STR00002## in which
R.sup.10 is a straight-chain or branched alkylene radical having
from 2 to 6 carbons or the radical of the formula 7 ##STR00003## 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, where all or
some of the amide structures may also be in the form of the
ammonium salt structure of the formula 8 ##STR00004##
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., with continuous removal of the
water of reaction formed in order to prepare the amides. However,
the reaction does not have to be continued completely to the amide,
but instead from 0 to 100 mol % of the amine formed may be in the
form of the ammonium salt. Under analogous conditions, the
compounds mentioned under B1) can also be prepared.
Suitable amines of the formula 9 ##STR00005## 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.
Quaternary ammonium salts of the formula 10
.sup.+NR.sup.6R.sup.7R.sup.8R.sup.11 X.sup.- (10) 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, 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.
Examples which may be mentioned of quaternary ammonium salts of
this type are the following: dihexadecyldimethylammonium chloride,
distearyldimethylammonium 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-methyltriethanol-ammonium trilauryl estermethosulfate,
N-methyltriethanolammonium tristearyl ester methosulfate and
mixtures thereof.
Compounds of the formula 11 ##STR00006## 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 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.
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 formula (II) 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.
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).
Also suitable are polymers containing at least one amide or
ammonium group bonded directly to the polymer skeleton, where the
amide or ammonium group carries 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.
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).
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,
copolymers containing unsaturated carboxylic anhydrides give half
amide and half amine salts on reaction with a secondary amine owing
to the reaction with the anhydride group. Water can be eliminated
by heating with formation of the diamide.
Particularly suitable examples of amide group-containing polymers
for use in accordance with the invention are the following:
Copolymers (a) of a dialkyl fumarate, maleate, citraconate or
itaconate with maleic anhydride, or (b) of vinyl esters, for
example vinyl acetate or vinyl stearate, with maleic anhydride, or
(c) of a dialkyl fumarate, maleate, citraconate or itaconate with
maleic anhydride and vinyl acetate.
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.
In the above-mentioned examples of suitable polymers, the desired
amide is obtained by reaction of the polymer containing anhydride
groups with a secondary amine of the formula HNR.sup.6R.sup.7 (if
desired in addition 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.
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.
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 of the two or both radicals
R.sup.6 and R.sup.7 preferably contains at least 10 carbon atoms,
for example from 10 to 20 carbon atoms, for example dodecyl,
tetradecyl, hexadecyl or octadecyl.
Examples of suitable secondary amines are dioctylamine and those
which contain alkyl groups having a 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).
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-alkylpropylene-diamine),
N-(tallow)propylenediamine
(C.sub.12/C.sub.18-alkylpropylenediamine).
The amide-containing polymers usually have a mean molecular weight
(number average) of from 1000 to 500,000, for example from 10,000
to 100,000.
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.
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 with one another. Examples
which may be mentioned are the following: styrene,
.alpha.-methyl-styrene, dimethylstyrene, .alpha.-ethylstyrene,
diethylstyrene, i-propylstyrene, 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.
Examples of polymers which may be mentioned individually are the
following: polymaleic acid, a molar 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 i-butene. The molecular weights of the polymers
are generally from 500 g/mol to 20,000 g/mol, preferably from 700
to 2000 g/mol.
The reaction of the polymers or copolymers with the amines is
carried out at temperatures of from 50 to 200.degree. C. over the
course of from 0.3 o 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.
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 of advantage 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.
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, where the
copolymers have substantially been reacted with one or more primary
or secondary amines to give the monoamides or amide/ammonium salts
of the dicarboxylic acids.
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.
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.
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.
Suitable amines are compounds of the formula HNR.sup.6R.sup.7.
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
copolymerize better with the (meth)acrylates. The anhydride groups
of the copolymers can then be reacted directly with the amines. The
reaction of the polymers with the amines is carried out 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.
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 ammonium salt of the
dicarboxylic acid.
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
acids, and copolymerization is then no longer possible.
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 12 and/or 14, and, if desired, 13,
where the structural units 13 originate from unreacted anhydride
radicals, ##STR00007## where R.sup.22 and R.sup.23, independently
of one another, are hydrogen or methyl, a and b are zero or one and
a+b is one, R.sup.24 and R.sup.25 are identical or different and
are --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 15 ##STR00008## in which R.sup.28
is hydrogen or C.sub.1-C.sub.4-alkyl, and R.sup.29 is
C.sub.6-C.sub.60-alkyl or C.sub.6-C.sub.18-aryl, and 1-30 mol %,
preferably 1-20 mol %, of divalent structural units of the formula
16 ##STR00009## in which R.sup.30 is hydrogen or methyl, R.sup.31
is hydrogen or C.sub.1-C.sub.4-alkyl, R.sup.33 is
C.sub.1-C.sub.4-alkylene, m is a number from 1 to 100, 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.
The above-mentioned 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,
halogen, such as fluorine, chloride, bromine and iodine, preferably
chloride, and (C.sub.1-C.sub.6)-alkoxy.
Alkyl here is a straight-chain or branched hydrocarbon radical.
Specific mention may be made of the following: 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.
Cycloalkyl here is a cyclic aliphatic radical having 5-20 carbon
atoms. Preferred cycloalkyl radicals are cyclopentyl and
cyclohexyl.
Aryl here is a substituted or unsubstituted aromatic ring system
having from 6 to 18 carbon atoms.
The terpolymers consist of the divalent structural units of the
formulae 12 and 14, and 15 and 16, and, if desired, 13. They
additionally only contain, in a manner known per se, the end groups
formed in the polymerization by initiation, inhibition and chain
termination.
In detail, structural units of the formulae 12 to 14 are derived
from .alpha.,.beta.-unsaturated dicarboxylic anhydrides of the
formulae 17 and 18 ##STR00010## such as maleic anhydride, itaconic
anhydride, citraconic anhydride, preferably maleic anhydride. The
structural units of the formulae 15 are derived from
.alpha.-.beta.-unsaturated compounds of the formula 19.
##STR00011##
The following .alpha.,.beta.-unsaturated olefins may be mentioned
by way of example: 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 preferably
.alpha.-olefins having from 12 to 20 carbon atoms.
The structural units of the formula 16 are derived from
polyoxyalkylene ethers of lower, unsaturated alcohols of the
formula 20 ##STR00012##
The monomers of the formula 20 are products of the etherification
(R.sup.32+--C(O)R.sup.34) or esterification (R.sup.32+--C
(O)R.sup.34) of polyoxyalkylene ethers (R.sup.32.dbd.H).
The polyoxyalkylene ethers (R.sup.32.dbd.H) can be prepared by
processes known per se 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 21
##STR00013##
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. Subsequent etherification of these polyoxyalkylene ethers
to give compounds of the formula 20 in which
R.sup.32+C.sub.1-C.sub.24-alkyl, cycloalkyl or aryl is carried out
by processes known per se. Suitable processes are disclosed, for
example, in J. March, Advanced Organic Chemistry, 2nd Edition, pp.
357f (1977). These products of the etherification of
polyoxyalkylene ethers can also be prepared by adding
.alpha.-olefin oxides, preferably ethylene oxide, propylene oxide
and/or butylene oxide, onto alcohols of the formula 22.
In the monomers of the formula 20, the index m indicates the degree
of alkoxylation, i.e. the number of moles of .alpha.-olefin which
are adducted per mole of the formula 20 or 21.
Examples which may be mentioned of suitable primary amines for the
preparation of the terpolymers are the following: n-hexylamine,
n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine
or also N,N-dimethylaminopropylene-diamine, cyclohexyl-amine,
dehydroabietylamine and mixtures thereof.
Examples which may be mentioned of secondary amines which are
suitable for the preparation of the terpolymers are the following:
didecylamine, ditetradecylamine, distearylamine, dicoconut fatty
amine, ditallow fatty amine and mixtures thereof.
The terpolymers have K values (measured by the Ubbelohde method in
5% strength by weight solution in toluene at 25.degree. C.) of from
8 to 100, preferably from 8 to 50, corresponding to mean molecular
weights (M.sub.w) of from about 500 to 100,000. Suitable examples
are listed in EP 606 055.
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 25 and 27 and, if desired, 26.
##STR00014## where R.sup.22 and R.sup.23, independently of one
another, are hydrogen or methyl, a and b are zero or 1, and a+b is
1, R.sup.37=--OH, --O--[C.sub.1-C.sub.30-alkyl], --NR.sup.6R.sup.7,
--O'N'R.sup.6R.sup.7H.sub.2 R.sup.38=R.sup.37 or NR.sup.6R.sup.39
R.sup.39=--(A--O).sub.x--E where A=an ethylene or propylene group,
x=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 80-20 mol
%, preferably 60-40 mol %, of divalent structural units of the
formula 15.
In detail, the structural units of the formulae 25, 26 and 27 are
derived from .alpha.,.beta.-unsaturated dicarboxylic anhydrides of
the formulae 17 and/or 18.
The structural units of the formula 15 are derived from the
.alpha.,.beta.-unsaturated olefins of the formula 19. The
above-mentioned alkyl, cycloalkyl and aryl radicals have the same
meanings as under 8.
The radicals R.sup.37 and R.sup.38 in the formula 25 and R.sup.39
in the formula 27 are derived from polyether-amines or
alkanolamines of the formulae 28 a) and b), amines of the formula
NR.sup.6R.sup.7R.sup.8 and, where appropriate, alcohols having from
1 to 30 carbon atoms. ##STR00015## In these formulae, R.sup.53 is
hydrogen, C.sub.6-C.sub.40-alkyl or ##STR00016## R.sup.54 is
hydrogen or C.sub.1-C.sub.4-alkyl, 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.30-aryl R.sup.56 and R.sup.57, independently of one another,
are hydrogen, C.sub.1- to C.sub.22-alkyl, C2- to C.sub.22-alkenyl
or Z--OH, Z is C.sub.2- to C.sub.4-alkylene, and n is a number from
1 to 1000.
The structural units of the formulae 17 and 18 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 28 a) and b).
The polyether-amines employed can be prepared, for example, by
reductive amination of polyglycols. Polyether-amines containing a
primary amino group are furthermore prepared by addition of
polyglycols onto acrylonitrile followed by catalytic hydrogenation.
In addition, polyether-amines can be obtained by reaction of
polyethers with phosgene or thionyl chloride followed by amination
to give the polyether-amine. The polyether-amines employed in
accordance with the invention are commercially available (for
example) under the name .RTM.Jeffamine (Texaco). Their molecular
weight is up to 2000 g/mol, and the ethylene oxide/propylene oxide
ratio is from 1:10 to 6:1. Another possibility for the
derivatization of the structural units of the formulae 17 and 18
comprises employing an alkanolamine of the formula instead of the
polyether-amines and subsequently subjecting the product to
oxyalkylation.
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 as temperatures above
100.degree. C. (imide formation).
The oxyalkylation is usually 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.
Examples of suitable alkanolamines which may be mentioned are the
following: monoethanolamine, diethanolamine, N-methylethanolamine,
3-amino-propanol, isopropanol, diglycolamine,
2-amine-2-methylpropanol and mixtures thereof.
Examples of primary amines which may be mentioned are the
following: n-hexylamine, n-octylamine, n-tetradecylamine,
n-hexadecylamine, n-stearylamine or also
N,N-dimethylaminopropylenediamine, cyclohexylamine,
dehydroabietylamine and mixtures thereof.
Examples of secondary amines which may be mentioned are the
following: didecylamine, ditetradecylamine, distearylamine,
dicoconut fatty amine, ditallow fatty amine and mixtures
thereof.
Examples of alcohols which may be mentioned are the following:
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.
Copolymers and terpolymers of N-C.sub.6-C.sub.24-alkylmaleimide
with C.sub.1-C.sub.30-vinyl esters, vinyl ethers and/or olefins
having from 1 to 30 carbon atoms, such as, for example, styrene or
.alpha.-olefins. These can be obtained firstly 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.
The mixing ratio between A and B can vary within broad limits.
Thus, even small amounts of B of from 100 ppm to 50,000 ppm,
preferably from 1000 ppm to 10,000 ppm, in fatty acid solutions act
as low-temperature additive for A. They are capable of suppressing
the inherent crystallization of the fatty acid, which results in a
reduction in the cloud point, and prevent the sedimentation of
crystals formed and thus facilitate easy handling at reduced
temperatures. For specific problem solutions, however, from 5% to
50%, in particular cases up to 90%, of constituent B, based on the
amount of constituent A, may also be present. In particular, the
inherent pour point of the additive is lowered and the lubricity of
the additive-containing oil is improved. Accordingly, the preferred
mixing ratio of A:B is from 1:10 to 1:0.0001, in particular from
1:4 to 1:0.0005, especially from 1:1 to 1:0.001.
The additives according to the invention are added to oils in
amounts of from 0.001 to 0.5% by weight, preferably from 0.001 to
0.1% by weight. They can be employed as such or also dissolved in
solvents, such as, for example, aliphatic and/or aromatic
hydrocarbons or hydrocarbon mixtures, such as, for example,
toluene, xylene, ethylbenzene, decane, pentadecane, gasoline
fractions, kerosine or commercial solvent mixtures, such as solvent
naphtha, .RTM.Shellsol AB, .RTM.Solvesso 150, .RTM.Solvesso 200,
.RTM.Exxsol, .RTM.Isopar and .RTM.Shellsol D grades. The additives
according to the invention preferably comprise 1-80%, especially
10-70%, in particular 25-60%, of solvent. The additives, which can
also be employed without problems at low temperatures of, for
example, -40.degree. C. or lower, improve the lubricity of the
additive-containing oils and their low-temperature and
corrosion-protection properties.
For the preparation of additive packages for special problem
solutions, the additives according to the invention may also be
employed together with one or more oil-soluble co-additives which,
even on their own, improve the low-temperature flow properties
and/or lubricity of crude oils, lubricating oils or fuel oils.
Examples of co-additives of this type are vinyl acetate-containing
copolymers or terpolymers of ethylene, comb polymers,
alkylphenol-aldehyde resins and oil-soluble amphiphiles.
Thus, mixtures of the additives according to the invention with
copolymers which comprise from 10 to 40% by weight of vinyl acetate
and from 60 to 90% by weight of ethylene have proven highly
successful. According to a further embodiment of the invention, the
additives according to the invention are employed as a mixture with
ethylene-vinyl acetate-vinyl neononanoate terpolymers or
ethylene-vinyl acetate-vinyl neodecanoate terpolymers for improving
the flow properties of mineral oils or mineral oil distillates.
Besides ethylene, the terpolymers of vinyl neononanoate or of vinyl
neodecanoate comprise from 10 to 35% by weight of vinyl acetate and
from 1 to 25% by weight of the respective neo compound. Besides
ethylene and from 10 to 35% by weight of vinyl esters, further
preferred copolymers also comprise from 0.5 to 20% by weight of
olefin, such as diisobutylene, 4-methylpentene or norbornene. The
mixing ratio of the additives according to the invention with the
ethylene-vinyl acetate copolymers described above or the
terpolymers of ethylene, vinyl acetate and the vinyl esters of
neononanoic or of neodecanoic acid is (in parts by weight) from
20:1 to 1:20, preferably from 10:1 to 1:10.
The additives according to the invention can thus be employed
together with alkylphenol formaldehyde resins. In a preferred
embodiment of the invention, these alkylphenol-formaldehyde resins
are those of the formula ##STR00017## in which R.sup.50 is
C.sub.4-C.sub.50-alkyl or -alkenyl, R.sup.51 is ethoxy and/or
propoxy, n is a number from 5 to 100, and p is a number from 0 to
50.
Finally, in a further embodiment of the invention, the additives
according to the invention are used together with comb polymers.
These are taken to mean polymers in which hydrocarbons 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 contain at least 8 and in particular at
least 10 carbon atoms. In the case of copolymers, at least 20%,
preferably at least 30%, of the monomers have side chains (cf.
Comb-like Polymers-Structure and Properties; N.A. Plate 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 (of. EP 0 153 176 A1), copolymers of a
C.sub.6-C.sub.24-.alpha.-olefin and and and
N--C.sub.8-C.sub.22-alkylmaleimide (cf. EP 0 320 766), furthermore
esterified olefin/maleic anhydride copolymers, polymers and
copolymers of .alpha.-olefins and esterified copolymers of styrene
and maleic anhydride.
Comb polymers can be described, for example, by the formula
##STR00018## in which A is R', COOR', OCOR', R''--COOR' or OR'; D
is H, CH.sub.3, A or R; E is H or A; G is H, R'', R''--COOR', an
aryl radical or a heterocyclic radical; M is H, COOR'', OCOR'',
OR'' or COOH; N is H, R'', COOR'', OCOR, COOH or an aryl radical;
R' is a hydrocarbon chain having 8-150 carbon atoms; R'' is a
hydrocarbon chain having from 1 to 10 carbon atoms; m is a number
from 0.4 to 1.0; and n is a number from 0 to 0.6.
The mixing ratio (in parts by weight) of the additives according to
the invention with resins or comb polymers is in each case from
1:10 to 20:1, preferably from 1:1 to 10:1.
The additives according to the invention are suitable for improving
the lubrication properties of animal, vegetable, mineral or
synthetic fuel oils in only small added amounts. Their improved
low-temperature properties make warming and/or dilution during
storage and use unnecessary. In addition, they simultaneously
improve the low-temperature and corrosion-protection properties of
the additive-containing oils. At the same time, the emulsification
properties of the additive-containing oils are impaired less than
is the case with the lubrication additives from the prior art. The
additives according to the invention are particularly suitable for
use in middle distillates. The term middle distillates is taken to
mean, in particular, mineral oils which are obtained by
distillation of crude oil and boil in the range from 120 to
450.degree. C., for example kerosine, jet fuel, diesel and heating
oil. The oils may also comprise or consist of alcohols, such as
methanol and/or ethanol. The additives according to the invention
are preferably used in middle distillates which contain 0.05% by
weight or less of sulfur, particularly preferably less than 350 ppm
of sulfur, in particular less than 200 ppm of sulfur and in special
cases less than 50 ppm of sulfur. In general, these are middle
distillates which have been subjected to reductive refining and
which therefore only contain small proportions of polyaromatic and
polar compounds which give them a natural lubricity. The additives
according to the invention are furthermore preferably used in
middle distillates which have 95% distillation points below
370.degree. C., in particular 350.degree. C. and in special cases
below 330.degree. C. They can also be employed as components in
lubricating oils.
The mixtures can be used alone or also together with other
additives, for example with other pour point depressants or
dewaxing auxiliaries, with corrosion inhibitors, antioxidants,
sludge inhibitors, dehazers, conductivity improvers, lubricity
additives and additives for lowering the cloud point. They are
furthermore successfully employed together with additive packages
which comprise, inter alia, known ash-free dispersion additives,
detergents, antifoams and corrosion inhibitors.
The improved low-temperature stability and the effectiveness of the
additives according to the invention as lubricity additives is
explained in greater detail by the following examples.
EXAMPLES
The following substances were employed: A1) Tall oil fatty acid
comprising, as principal constituents, 30% of oleic acid, 60% of
linoleic acid and other polyunsaturated fatty acids and 4% of
saturated fatty acids. Iodine number 155 g of 1/100 g A2) Oleic
acid (technical-grade) comprising, as principal constituents, 69%
of oleic acid, 12% of linoleic acid, 5% of hexadecenoic acid and
10% of saturated fatty acids. Iodine number 90 g of 1/100 g. B1)
Product of the reaction of a terpolymer of
C.sub.14/.sub.16-.alpha.-olefin, maleic anhydride and
allylpolyglycol with 2 equivalents of ditallow fatty amine, 50% in
solvent naphtha B2) Product of the reaction of a
dodecenylspirobislactone with a mixture of primary and secondary
tallow fatty amine, 60% in solvent naphtha B3)
Nonylphenol-formaldehyde resin, 50% in solvent naphtha B4) Mixture
of 2 parts of B1 and 1 part of B2 B5) Amide/ammonium salt based on
ethylenediaminetetraacetic acid with 3 equivalents of ditallow
fatty amine in accordance with EP 0597278. B6) Mixture of
amide/ammonium salt based on ethylenediaminetetraacetic acid with 4
equivalents of ditallow fatty amine and copolymer comprising equal
parts of maleic anhydride and C.sub.20/.sub.24-olefin, imidated
with N-tallow fatty propylenediamine in accordance with EP-0 909
307 B7) Amide/ammonium salt made from 1 mol of phthalic anhydride
and 2 mol of a mixture of equal parts of ditallow and dicoconut
fatty amine B8) Mixture of equal parts of amide/ammonium salt made
from 1 mol of phthalic anhydride and 2 mol of ditallow fatty amine
and copolymer of di(tetradecyl) fumarate, 50% in solvent
naphtha.
In order to assess the low-temperature properties, the pour point
of the mixtures according to the invention was measured in
accordance with ISO 3016 (Table 1) .[.and the cloud point was
measured in accordance with ISO 3015 (Table 2).]. . The additive
mixtures according to the invention were then stored for a number
of days at various temperatures and subsequently assessed visually
(Tables 3 to 5). C denotes comparative examples.
TABLE-US-00001 TABLE 1 Pour point of the additives according to the
invention Composition (parts by weight) Pour Example A1 A2 B1 B2 B3
B4 point 1 80 20 -9 2 50 50 -24 3 20 80 0 4 80 20 -9 5 50 50 -24 6
20 80 -6 7 80 20 0 8 50 50 -15 9 20 80 -48 10 80 20 -9 11 50 50 -18
12 20 80 -15 13 80 20 -27 14 50 50 -27 15 20 80 -6 16 80 20 -27 17
50 50 -54 18 20 80 -45 19 80 20 -21 20 50 50 -30 21 20 80 -21 22 80
20 -21 23 50 50 -21 24 20 80 -9 25* 99.95 0.05 -36 26* 99.95 0.05
-36 27 99.95 0.05 -15 C1 100 -9 C2 100 6 C3 100 9 C4 100 -12 C5 100
0 C6 100 -6 C7* 100 -36 *These examples are obtained with a 50% by
weight formulation of the fatty acid in solvent naphtha.
TABLE-US-00002 .[.TABLE 2 Cloud points of the additives according
to the invention Composition (parts by weight) Example A1 A2 B1 B2
B3 B4 Cloud point C8* 100 -27.0 28* 99.9995 0.0005 -33.0 29*
99.9995 0.0005 -30.5 30* 99.998 0.002 -33.5 31* 99.998 0.002 -33.5
32* 99.995 0.005 -31.0 33* 99.995 0.005 -32.2 34** (B5) 99.998
0.002 -29.0 35** (B6) 99.998 0.002 -31.0 36** (B7) 99.998 0.002
-35.5 37** (B8) 99.998 0.002 -37.0 *These examples were obtained
with a 50% by weight formulation of the fatty acid in solvent
naphtha. **These examples relate to mixtures of A1 with in each
case 2000 ppm of B5 to B8 and are obtained with a 50% by weight
formulation of the fatty acid in solvent naphtha..].
TABLE-US-00003 TABLE 3 Storage stability of the additives (storage
for 3 days at -20.degree. C.) Composition (parts by weight) Example
A2 B1 B2 B3 Assessment 38 50 50 viscous 39 80 20 liquid 40 20 80
liquid 41 50 50 liquid 42 20 80 liquid C9 100 solid, waxy C10 100
solid C11 100 solid C12 100 viscous
TABLE-US-00004 TABLE 4 Storage stability of the additives according
to the invention dissolved in solvents at -20.degree. C., unless
stated otherwise Constituent Constituent Amount Then 1 day Example
A B ppm After 1 day After 3 days After 5 days After 7 days at
-28.degree. C. C13 A1 No additive clear, sediment clear, sediment
clear, sediment clear, sediment clear, sediment (50% in S.N.)
(crystalline) (crystalline) (crystalline) (crystalline) (-
crystalline) 43 A1 B1 100 clear, few crystals clear, few crystals
clear, few crystals clear, few crystals clear, sediment (50% in
S.N.) on the base on the base on the base on the base (crystalline)
44 A1 '' 500 clear, no sediment clear, few crystals clear, few
crystals clear, few crystals clear, sediment (50% in S.N.) on the
base on the base on the base (crystalline) 45 A1 '' 1000 clear, no
sediment clear, no sediment clear, no sediment clear, no sediment
cloudy, no (50% in S.N.) sediment 46 A1 '' 5000 clear, no sediment
clear, no sediment clear, no sediment clear, no sediment clear, no
sediment (50% in S.N.) 47 A1 '' 10,000 clear, no sediment clear, no
sediment clear, no sediment clear, no sediment clear, no sediment
(50% in S.N.) 48 A1 '' 50,000 cloudy, no cloudy, no cloudy, no
cloudy, no cloudy, no (50% in S.N.) sediment sediment sediment
sediment sediment 49 A1 B4 100 clear, few crystals clear, few
crystals clear, few crystals clear, few crystals clear, sediment
(50% in S.N.) on the base on the base on the base on the base
(crystalline) 50 A1 '' 500 clear, no sediment clear, no sediment
clear, few crystals clear, few crystals clear, sediment (50% in
S.N.) on the base on the base (crystalline) 51 A1 '' 1000 clear, no
sediment clear, no sediment clear, no sediment clear, no sediment
clear, no sediment (50% in S.N.) 52 A1 '' 5000 clear, no sediment
clear, no sediment clear, no sediment clear, no sediment clear, no
sediment (50% in S.N.) 53 A1 '' 10,000 clear, no sediment clear, no
sediment clear, no sediment clear, no sediment clear, no sediment
(50% in S.N.) 54 A1 '' 50,000 clear, no sediment clear, no sediment
clear, no sediment clear, no sediment slightly cloudy, (50% in
S.N.) no sediment 55 A1 B3 5000 clear, crystalline clear,
crystalline clear, crystalline clear, crystalline cloudy, (50% in
S.N.) suspended suspended suspended suspended crystalline
crystalline crystalline crystalline crystalline suspended
precipitations precipitations precipitations precipitations
crystallin- e precipitations S.N. = solvent naphtha
TABLE-US-00005 TABLE 5 Storage stability of the additives according
to the invention dissolved in solvents at -20.degree. C., unless
stated otherwise Amount Then 1 day Example Constituent A
Constituent B ppm After 3 days After 7 days at -28.degree. C. C14
A1 (50% in MS) no additive clear, sediment (crystalline) clear,
sediment (crystalline) clear, sediment (crystalline), solid 56 ''
B1 1000 clear, no sediment clear, no sediment cloudy, sediment 57
'' '' 5000 cloudy, no sediment cloudy, no sediment cloudy, no
sediment 58 '' '' 10,000 cloudy, no sediment cloudy, no sediment
cloudy, no sediment 59 '' B4 1000 clear, no sediment clear, little
sediment slightly cloudy, sediment 60 '' '' 5000 clear, no sediment
clear, no sediment cloudy, no sediment 61 '' '' 10,000 clear,
slight cloudiness on cloudy, no sediment cloudy, no sediment the
base, no sediment 62 '' '' 50,000 cloudy, no sediment cloudy, no
sediment cloudy, no sediment
MS is a mixture of series of aliphatic and cyclic, non-aromatic
hydrocarbons. The principal constituents of MS are shown in the
following table:
TABLE-US-00006 TABLE 6 Constituents of MS Concentration range
Constituent (% by weight) Di-2-ethylhexylether 10-25 2-Ethylhexyl
2-ethylhexanoate 10-25 C.sub.16-Lactones 4-20 2-Ethylhexyl butyrate
3-10 2-Ethyl-1,3-hexanediol mono-n-butyrate 5-15 2-Ethylhexanol
4-10 C.sub.4- to C.sub.8-acetates 2-10 2-Ethyl-1,3-hexanediol 2-5
Ethers and esters .gtoreq. C.sub.20 0-20
Lubricity in Middle Distillates
The lubricity of the additives was measured on additive-containing
oils at 60.degree. C. by means of an HFRR instrument from PCS
Instruments. The high frequency reciprocating rig (HFRR) test is
described in D. Wei, H. Spikes, Wear, Vol. 111, No.2, p.217, 1986.
The results are given as the friction coefficient and wear scar (WS
1.4). A low friction coefficient and a low wear scar indicate good
lubricity.
TABLE-US-00007 TABLE 7 Characterization of the test oils: In order
to test the lubricity, test oils having the following
characteristics were employed: Test Oil 1 Test Oil 2 Boiling range
170-344.degree. C. 182-304.degree. C. Density 0.830 g/cm.sup.3
0.821 g/cm.sup.3 Cloud point -9.degree. C. -33.degree. C. Sulfur
content 45 ppm 6 ppm
The boiling characteristics are determined in accordance with ASTM
D-86 and the cloud point is determined in accordance with ISO
3015.
TABLE-US-00008 TABLE 8 Wear scar in Test Oil 1 Example Additive
Wear scar Friction C15 none 555 .mu.m 0.33 63 100 ppm acc. to Ex.
37 385 .mu.m 0.18 64 100 ppm A1 + 150 ppm B4 381 .mu.m 0.18 C16 100
ppm A1 421 .mu.m 0.18 C17 150 ppm B4 549 .mu.m 0.34
TABLE-US-00009 TABLE 9 Wear scar in Test Oil 2 Example Additive
Wear scar Friction C18 none 637 .mu.m 0.30 65 200 ppm acc. to Ex.
42 386 0.18 66 200 ppm acc. to Ex. 48 395 0.18 C19 200 ppm acc. to
Ex. C13 405 0.19
* * * * *