Note: Descriptions are shown in the official language in which they were submitted.
CA 02542812 2006-04-18
1
Additive mixture as component of mineral oil compositions
DESCRIPTION
This invention relates to an additive mixture as
component of compositions with mineral oil as the main
component and trace portions of an additive mixture as
well as a method for producing mineral oil compositions
that contain the additive mixture.
Compositions of mineral oil as the main component and
trace portions of additive mixtures of ethylene-vinylace-
tate copolymers, hydrocarbon polymers, esterified malefic
anhydride-olefin copolymers, polar nitrogen compounds
such as amine salts of multivalent carboxylic acids and
esterified polyoxyalkylenes are known (WO 94/10 267 A1,
WO 95/33 012 A1, EP 0 921 183 A1, WO 93/14 178 A1, EP 0
889 323 A1).
Disadvantages include insufficient flow properties and
stability in storage of these compositions at low tempe-
ratures as well as limited lubricating ability of these
formulations when the mineral oil component has a sulfur
content below 0.005 mass o.
?5
It is the object of this invention to provide an additive
mixture as component for compositions of mineral oil as
their main component and trace portions of an additive
mixture that have improved flow properties and improved
stability in storage at low temperatures and improved
lubricity. The improved flow behavior is to result in
energy savings at the pump sets through which these
formulations are transported. These additive mixtures are
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CA 02542812 2006-04-18
2
to be developed taking into account that mineral oils
with a very low sulfur content are to be used to make
fuels with improved environmental compatibility as
regards pollutant emissions.
The object of the invention was achieved by an additive
mixture as component of compositions of mineral oil as
main component and trace portions of an additive mixture
comprising the following additive components according to
the invention:
a) ethylene-vinylester copolymers with molecular mass
weight averages from 3000 to 50000 and an ethylene
portion of 50 to 90 mass o, and
b) mixed esters of glycerine, in which 50 to 80 mol o
of the hydroxy groups are esterified with
unsaturated C1z-C4o monocarboxylic acids and 20 to 50
mol % of the hydroxy groups are esterified with
partially imidated and/or partially esterified
malefic anhydride copolymers, and/or
c) partially andlor completely imidated copolymers of
malefic anhydride and a-methylstyrene with molecular
mass weight averages from 1500 to 15000 and at least
one terminal group based on dimeric a-methylstyrene,
and/ or
d) wax compositions based on natural starting materials
of type
d1) wax-like oligomeric esters based on glyceryl
monostearate and dimeric acid in which the
conversion product corresponds to the
I:eu-21515_engl H~ith amenc~nents.doc
CA 02542812 2006-04-18
3
CH2 - O - CO - (CHZ)Z - CH3
s I
Y O-CH
I
CH2 - O - CO - (CHZ)a - CH - (CH2)b - CH3
I
CH3 - (CH2)~ CH - (CH2)d-- CO OX
n structure by
at least 90 mass o,
where n = 1 to 20, the total of a+b+c+d = 30, z = 12
IS to 20
Y = H or - CO - (CH2)d- CH - (CH2)b - CH3
I
H3C - (CH2)~ - CH - (CH2)a - CO - OH
X = H or -CHZ-CH ( OH ) -CHz-O-CO- ( CH2 ) Z-CH3 , and / or
d2) wax esters with the vaseline-like consistency based
on at least two different straight-chain and/or
branched C14-C36-alcohols and dimeric acids in which
the conversion product corresponds to the
H3C - (CH2); - O - CO - (CH2)k - CH - CH - (CHZ)m - CH3
I I
HsC - (CH2)n (CHz)P - CO - O - (CH2)S - CH3
structure by at least 80 mass o,
where i = 13 to 35; s= 13 to 35,
the total of k + m + n + p is 30 to 34, and
(CH2)i or (CH2)S are straight-chain or straight-chain
and branched,
whereby the content of the additive mixture in the
mineral oil is 0.005 to 1 mass o and the mass
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CA 02542812 2006-04-18
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proportion of the additive components a/b or a/c or
a/d is in the range from 10 . 90 to 90 . 10,
respectively.
Examples of vinyl ester components that may be contained
as additive component a) in the ethylene-vinylester
copolymers are vinyl acetate, vinyl propionate, 2-
ethylhexyl vinylester, vinyl laurate, 2-hydroxyethyl
vinylester, and 4-hydroxybutyl vinylester.
The ethylene-vinylester copolymers may contain 1 to 30
mass %, in relation to the vinyl ester, of other
unsaturated ester components~such as (meth)acrylic esters
like methyl methacrylate, acrylic methyl ester,
methacrylic ethyl ester, butyl acrylate, 2-ethylhexyl
acrylate, dodecyl acrylate, ethyleneglycol dimethacrylate
or hydroxyethyl methacrylate and/or vinyl ethers such as
octylvinyl ether or hexanediol monovinyl ether.
Such ethylene-vinylester copolymers are preferred as
additive component a) in the ethylene-vinylacetate
copolymer additive mixture that has a vinyl acetate
content of 12 to 50 mass %.
Another preferred variant of the ethylene-vinylester
copolymers contained as additive component a) in the
additive mixture is that the ethylene-vinylester copoly-
mers are mixtures of 10 to 90 mass o of unmodified ethyl-
ene-vinylester copolymers and 90 to 10 mass o of
ethylene-vinylester copolymers modified with polar
groups.
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CA 02542812 2006-04-18
The ethylene-vinylester copolymers are modified by polar
groups in that specific terminal groups such as aldehyde
terminal groups, preferably terminal groups from
acetaldehyde, propionaldehyde, butyraldehyde, or
5 isobutyraldehyde, carboxyalkylmercapto terminal groups,
preferably terminal groups from mercaptoacetic acid or
mercaptopropionic acid, or alkoxy terminal groups are
incorporated into the copolymer, in that hydroxy and/or
carboxy groups are incorporated into the copolymer by
partial oxidation, saponification, or acetalation as well
as by grafting polar, ethylenically unsaturated monomers
onto the copolymer.
Preferred are the modified ethylene-vinylester copolymers
oxidized ethylene-vinylester copolymers, partially sapo-
nified ethylene-vinylester copolymers, hemiacetals of
partially saponified ethylene-vinylester copolymers
and/or ethylene-vinylester copolymers grafted with polar
unsaturated monomers of the vinyl ester, (meth)acryl
ester, and/or vinyl ether type.
The oxidized ethylene-vinylester copolymers preferably
are oxidized ethylene-vinylacetate copolymers with
molecular mass number averages from 800 to 5000, acid
numbers from 2 to 40 mg KOH/g and OH numbers from 20 to
150 mg KOH/g.
The partially saponified ethylene-vinylester copolymers
preferably are ethylene-vinylacetate copolymers with
molecular mass number averages from 800 to 5000, 5 to 30
mass o of whose vinyl acetate units are saponified.
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In another preferred variant, the modified ethylene-
vinylester copolymers are hemiacetals of ethylene-
vinylester-vinylalcohol copolymers with butyraldehyde.
Examples of hemiacetals of ethylene-vinylester-
vinylalcohol copolymers with butyraldehyde are hemia-
cetals of ethylene-vinylacetate-vinylalcohol copolymers
that were reacted in heterogenic phase with butyraldehyde
as described in DD 295 507 A7.
Grafted ethylene-vinylester copolymers can be produced by
reacting the unsaturated monomers in an extruder (DD 282
462 B5) or stirred tank reactor (DD 293 125 B5) in the
presence of thermally decomposing radical formers. It is
also possible to perform the modification during the
production of the copolymer according to the high-
pressure process by adding the monomer dose to the
polymer melt in a low-pressure separator or in a
discharging extruder.
In particular, the grafted ethylene-vinylester copolymers
as additive component a) are ethylene-vinylacetate
copolymers grafted with vinylacetate and having molecular
mass number averages from 800 to 5000 and a total
vinylacetate content of 20 to 60 mass o, the vinylacetate
content of the copolymer backbone chain being from 10 to
40 mass o, and the portion of the grafted vinylacetate
branches making up 10 to 20 mass %.
The ethylene-vinylester copolymers in the additive
compositions may contain up to 35 mass o of poly-C6-C36
alkyl (meth)acrylate.
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Examples of malefic anhydride copolymers that may be
present partially imidated or partially esterified as
acid component in the mixed esters of glycerine as
additive component b) the additive mixture are copolymers
of malefic anhydride and the comonomer components C2-C2o-
olefins, Ca-C2o-vinyl aromatics, C4-C21-acrylic esters, C5-
C22-methacrylic esters, CS-C14-vinylsilane, C6-C15 acrylate
silanes, acrylic acid, methacrylic acid, acrylnitrile,
vinyl pyridine, vinyl oxazoline, isopropenyl oxazoline,
vinyl pyrrolidone, amino-C1-C8-alkyl-(meth)acrylate, C3-
C2o-vinylester, C3-C2o-vinylether and/or hydroxy-Cl-C8-
alkyl-(meth)acrylate. Particularly preferred comonomer
components are isobutylene,-diisobutylene, vinylacetate,
styrene and a-methylstyrene.
The malefic anhydride copolymers preferably have a molar
ratio of malefic anhydride to comonomer from 1 . 1 to 1 .
9 and molecular mass weight averages from 5000 to 500000.
Partial imidation can be performed using ammonia, C1-C24-
monoalkyl amines, C6-C18-aromatic mono amines, C2-C1$-mono-
aminoalcohols, monoaminated poly(Cz-C4-alkylene) oxides
with a molar weight of 400 to 3000 and/or monoetherified
poly(C2-C4-alkylene) oxides with a molar weight of 100 to
10000, the molar ratio of anhydride groups copolymer /
ammonia, C1-C24-monoalkylamine, C6-C1$-aromatic monoamines,
C2-Cla-monoaminoalcohols or monoaminated poly- (Cz-C4-alky-
lene) oxide, respectively, being in the range from 1 . 1
to 20 . 1.
Examples of suitable amines with which malefic anhydride
copolymers are partially imidated are C12-Cz4-monoalkyl
amines such as oleylamine, dodecylamine, hexadecylamine,
octadecylamine, or eicosylamine, monosubstituted diamines
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CA 02542812 2006-04-18
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such as N-dodecyl-1,3-diaminopropane, N-octadecyl-1,3-
diaminopropane, or N-octadecyl propylene triamine, or
aminoalcohols such as aminodecane-10-of or aminohexade-
cane-16-ol.
Examples of suitable alcohols with which the malefic
anhydride copolymers are partially esterified as acid
components in the mixed esters of glycerine as additive
component b) of the additive mixture are Cl-Cla-alcohols
such as methanol, ethanol, ethyl hexanol, or stearyl
alcohol.
Examples of the unsaturated C12-C4o-monocarboxylic acids
contained as esterifying component in the mixed esters of
glycerine of the additive mixture are oleic acid,
elaidinic acid, ricinoleic acid, eleostearic acid,
linolic acid, linolenic acid, and erucaic acid, or
dimeric acids based on oleic acid or linolenic acid.
Examples of suitable methods for producing the mixed
esters of glycerine in which 50 to 80 mol o of the
hydroxy groups are esterified with unsaturated C12-Cao-
monocarboxylic acids and 20 to 50 mol o of the hydroxy
groups are esterified with partially imidated and/or
partially esterifed malefic anhydride copolymers are
partial reaction of glycerine with unsaturated C12-C4o-
monocarboxylic acids and subsequently with partially
imidated and/or partially esterified malefic anhydride
copolymers or partial reaction of glycerine with
partially imidated and/or partially esterified malefic
anhydride copolymers and subsequently with unsaturated
C1z-Coo-monocarboxylic acids . The reaction can be
performed in the melt, preferably in continuous kneaders
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at temperatures from 50 to 135°C under vacuum degassing
or as a solvent process preferably in aromatic solvents
at 85 to 140°C.
In the mixed esters of glycerine of the additive mixture,
the C12-C4o-monocarboxylic acids contained as esterifying
component preferably consist of 45 to 52 mass o Czz-
monocarboxylic acids in relation to the overall weight of
the C12-C4o-monocarboxylic acids .
The partially imidated malefic anhydride copolymers
contained as esterifying components in the mixed esters
of glycerine as additive component b) of the additive
mixture preferably are malefic anhydride-a-methylstyrene
copolymers partially imidated with C6-C24-monoalkylamines
in which the mole ratio of anhydride groups in the
copolymer / bound C6-C24-monoalkylamine in the copolymer
is in the range from 8 . 1 to 2 . 1.
Examples of partially imidated copolymers of malefic
anhydride and a-methylstyrene as additive component c)
are copolymers with an approximately equimolar ratio of
both monomers in which the partial and/or complete
imidation was performed with ammonia, C1-Cz4-
monoalkylamines, C6-C18-aromatic monoamines, C2-C18-
monoaminoalcohols, monoaminated poly-(Cz-C4-alkylene)
oxides, and/or monoetherified poly(Cz-C4-alkylene) oxides
whereas the mole ratio of anhydride groups copolymer /
ammonia, amino group C1-Cz4 monoalkylamines, C6-C1g-
aromatic monoamines, Cz-C18 monoaminoalcohols and
monoaminated poly(Cz-CQ-alkylene) oxide, respectively is
1 . 1 to 20 . 1.
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CA 02542812 2006-04-18
The partially imidated copolymers consisting of malefic
anhydride and a-methylstyrene as additive component c)
preferably are malefic anhydride-a-methylstyrene
copolymers partially imidated with C6-C24-monoalkylamines
5 in which the mole ratio of anhydride groups in the
colpolymer to bound C6-C24-monoalkylamine in the copolymer
is 8 . 1 to 1.3 . 1.
Examples of C12-Ca4-monoalkylamines with which the par-
10 dally imidated malefic anhydride-a-methylstyrene copoly-
mers contained in the additive mixture can be imidated
are dodecylamine, tetradecylamine, hexadecylamine, octa-
decylamine, oleylamine, or eicosylamine.
The wax-like oligomeric esters on the basis of glyceryl
monostearate and dimeric acid as additive component d1)
are the oligomeric esters described in EP 0 934 921 A1.
The glyceryl monostearate component can be produced by
enzymatically cleaving rape-seed oil, isolating the
glycerine monooleate that forms, and subsequent hydra-
tion. A suitable method for producing the dimeric acid
component is the splitting of vegetable oils and subse-
quent dimerization of the unsaturated fatty acids that
form. The oligomeric esters are produced by solvent-free
oligocondensation with acid catalysis.
Preferred as additive components d1) are wax-like oligo-
meric esters that have a degree of oligomerization from 2
to 8.
The wax esters with the vaseline-like consistency d2) are
the wax esters described in EP 0 970 998 Al.
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Preferred as wax esters with the vaseline-like con-
sistency d2) contained in the additive mixture are wax
esters based on Guerbet alcohols of the 2-hexyldecane-1-
ol, 2-octyldecane-1-of or 2-octyldecane-1-of type and
dimeric acids obtained by splitting vegetable oils with a
high oleic acid content and subsequent catalytic dimeri-
zation. The wax esters can be produced from the Guerbet
alcohols and the dimeric acid by catalytic esterification
in the presence of acidic catalysts at temperatures from
100 to 160°C in stirred tank reactors by applying a
vacuum of - 0.5 to -1.5 bar.
Examples of mineral oils that form the main component in
the mineral oil compositions are crude oils and petroleum
distillates with a distillation range from 100 to 500°C
such as lubricating oils, kerosine, diesel oil, heating
oil, heavy fuel oils, petroleum, tractor fuel, and
cracked gasoline. The mineral oils may also contain up to
30 mass % of synthesized hydrocarbons from the Fischer-
Tropsch process, up to 20 mass o of modified vegetable
oils based on sunflower oil, soybean oil, rape-seed oil,
or animal oils, biodiesel and/or up to 10 mass o of
alcohols such as methanol or ethanol.
?5 Preferred are mineral oils crude oils, or fuel oils from
a middle distillate with a sulfur content of under 0.05
mass o, particularly fuel oils, gas oils, or diesel oils.
The compositions of mineral oil may contain a total of up
to 200 mass % in relation to the additive components a+b,
a+c, a+d, a+b+c, a+b+c+d, or a+c+d, other additive
components of the type of fatty acid mixtures, polar
nitrogen compounds, preferably polyamines, etheramines,
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aminoalcohols, amine salts, amides or imides of
multivalent carboxylic acids; modified copolymers of
ethylenically unsaturated C4-C2o-dicarboxylic anhydrides,
non-modified ethylene-vinylester copolymers, C~-C3o-
alcohols, polyalkylene glycols, esters or ethers of
polyoxyalkylene compounds, CZ-C6-oxyalkyl-bridged C12-C9o-
monocarboxylic acids, preferably C3-C4-oxyalkyl-bridged
unsaturated C16-Caa monocarboxylic acids with a content of
C22-monocarboxylic acids in relation to the overall
weight of the C16-C24 monocarboxylic acids of 45 to 52
mass o, hydrocarbon polymers, alkylphenol-aldehyde copo-
lymers, aromatic compounds with C$-Cloo-alkyl substi-
tuents, carboxylated polyamines, detergents, corrosion
inhibitors, demulsifiers, metal deactivators, cetane num-
ber improvers, defoaming agents and/or cosolvents.
Examples of the fatty acid mixtures contained as other
additive components in the mineral oil compositions are
mixtures of saturated and/or unsaturated C6-C4o-carboxylic
acids such as lauric acid, palmitic acid, oleic acid,
linolenic acid, dimeric fatty acids, and alkenyl succinic
acids.
Examples of the polar nitrogen compounds of the polyamine
type contained as other additive components in the
mineral oil compositions are N-hexadecyl-1,3-
diaminopropane, N-octadecyl dipropylenetriamine, N-
dodecyl-1,3-diaminopropane, N,N'-didodecyl-1,3-diamino-
propane, and N,N'-dioctadecyl-dipropylenetriamine.
Examples of the polar nitrogen compounds of the ether-
amine type contained as other additive components in the
mineral oil compositions are 3-methoxypropylamine, 3-N-
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CA 02542812 2006-04-18
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octyloxypropyl-1,3-diaminopropane, and 3-N-(2,4,6-trime-
thyldecyloxypropyl)-1,3-diaminopropane.
Examples of the polar nitrogen compounds of the amino-
alcohol type contained as other additive components in
the mineral oil compositions are aminopentane-5-ol,
aminoundecane-11-ol, and 2-amino-2-methylpropanol.
Examples of the amines on which polar nitrogen compounds
of the amine salt, amide, or imide type of multivalent
carboxylic acids are based are C8-C4o-amines such as
hydrated tallamine, tetradecylamine, eicosylamine, di
octadecylamine, methyl behenylamine, N-oleyl-1,3-diamino
propane, N-stearyl-1-methyl-1,3-diaminopropane or N
oleyldipropylenetriamine.
Examples of the multivalent carboxylic acids on which
polar nitrogen compounds of the amine salt or amide of
multivalent carboxylic acids types are based are phthalic
acid, isophthalic acid, terephthalic acid, naphthalene
dicarboxylic acid, ethylene diamine tetraacetic acid, and
cyclohexane dicarboxylic acid.
Special examples of the polar nitrogen compounds of the
amine salt type contained as other additive components in
the mineral oil compositions are N-methyl triethanol
ammonium distearyl ester chloride and N-methyl triethanol
ammonium distearyl ester methosulfate.
Examples of ethylenically unsaturated C4-Czo-dicarboxylic
anhydrides that may be contained as the monomeric
component in the modified copolymers of ethylenically
unsaturated C4-C~>~-dicarboxylic anhydrides as another
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additive component are allylsuccinic anhydride, bicycle-
heptene dicarboxylic anhydride, bicyclooctene dicarboxy-
lic anhydride, carbomethoxymaleic anhydride, citraconic
anhydride, cyclohexene dicarboxylic anhydride, dodecencyl
succinic anhydride, glutaconic anhydride, itaconic
anhydride, malefic anhydride, mesaconic anhydride, methyl
bicycloheptene dicarboxylic anhydride and/or methyl
cyclohexene dicarboxylic anhydride, of which malefic
anhydride and/or itaconic anhydride are preferred.
Examples of suitable comonomers for ethylenically
unsaturated C4-Czo-dicarboxylic anhydrides that may be
contained as the monomeriC' component in the modified
copolymers of ethylenically unsaturated C4-Czo-dicarboxy-
L5 lic anhydrides as another additive component are ethyl-
eneically unsaturated monomers such as Cz-Czo-olefins, C8-
Czo-vinyl aromatics, C4-Czl-acrylic esters, CS-Czz-
methacrylic esters, CS-C14-vinylsi lanes, C6-C15-acrylate
silanes, acrylic acid, methacrylic acid, acrylnitrile,
vinyl pyridine, vinyl oxazoline, isopropenyl oxazoline,
vinyl pyrrolidone, amino-C1-Ca-alkyl-(meth)acrylate, C3-
Czo-vinyl ester, C3-Czo-vinylether and/or hydroxy-C1-Ca-
alkyl-(meth)acrylate. Particularly preferred ethyl-
enically unsaturated monomers are isobutylene, diisobuty-
lene, vinylacetate, styrene and a-methylstyrene.
Particularly preferred as modified copolymers are copo-
lymers of C4-Czo-ethylenically unsaturated acid anhydrides
and ethylenically unsaturated monomers with a mole ratio
from 1 . 1 to 1 . 9 and molecular mass weight averages
from 5000 to 500000 that were reacted with ammonia, C1-
Cz4-monoalkyl amines, C6-C1a-aromatic mono amines, Cz-Cla-
monoaminoalcohols, monoaminated poly(Cz-C4-alkylene) oxi-
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CA 02542812 2006-04-18
des with a molar weight of 400 to 3000 and/or mono-
etherified poly(Cz-C4-alkylene) oxides with a molar
weight of 100 to 10000, the molar ratio of anhydride
groups copolymer / ammonia, C1-Cz4-monoalkylamine, C6-C1a-
5 aromatic monoamines, Cz-C1$-monoaminoalcohols or mono-
aminated poly-(CZ-C4-alkylene) oxide amino groups, re-
spectively, being in the range from 1 . 1 to 20 . 1.
Particularly suited as partially or completely imidated
10 copolymers from ethylenically unsaturated C4-Czo-dicar-
boxylic anhydrides are malefic anhydride copolymers imida-
ted with Clz-Cz4-monoalkyl amines such as oleylamine, do-
decylamine, hexadecylamine,'octadecylamine, or eicosyl-
amine, monosubstituted diamines such as N-dodecyl-1,3-
15 diaminopropane, N-octadecyl-1,3-diaminopropane, or N-
octadecyl propylene triamine, or aminoalcohols such as
aminodecane-10-of or aminohexadecane-16-ol.
Examples of C~-C3o-alcohols that can be contained as other
additive components in the mineral oil compositions are
dodecanol, stearyl alcohol, and ceryl alcohol.
Examples of polyalkylene glycols that can be contained as
other additive components in the mineral oil compositions
2~ are polyethylene glycols, polypropylene glycols, and
ethylene oxide-propylene oxide copolymers with molar
weights from 500 to 5000.
Examples of esters of polyoxyalkylene compounds that can
be contained as other additive components in the mineral
oil compositions are Clo-Cz4-monoalkyl esters or dialkyl
esters of polyalkylene glycols such as polyethylene
glycol monostearyl ester or polypropylene glycol dio-
leate.
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Examples of ethers of polyoxyalkylene compounds that can
be contained as other additive components in the mineral
oil compositions are C1-CQ-monoalkyl ethers or dialkyl
ethers of polyalkylene glycols such as polyethylene gly-
col monomethyl ether or polypropylene glycol dibutyl
ether.
The CZ-C6-oxyalkyl-bridged C12-CQO-monocarboxylic acids
that can be contained as other additive components in the
mineral oil compositions consist of a C2-C6-polyalcohol
component and a Clz-C4o-monocarboxylic acid component.
Examples of polyalcohols that can be contained as alcohol
component in the Cz-C6-oxyalkyl-bridged C12-C4o-monocar-
boxylic acids that may form another additive component
are ethylene glycol, polyalkylene glycols, glycerine,
1,1,1-tris-(hydroxymethyl) propane, pentaerythrite, and
sorbite.
Examples of C12-CQO-monocarboxylic acids that may be
contained as carboxylic acid component in the Cz-C6-
oxyalkyl-bridged Clz-C4o-monocarboxylic acid that may form
another additive component are laurinic acid, palmitic
acid, stearic acid, oleic acid, elaidic acid, ricinoleic
acid, eleostearic acid, linolic acid, linolenic acid, and
erucic acid or dimeric acids based on oleic acid or
linolenic acid.
Also preferred as Cz-C6-oxyalkyl-bridged C12-C4o-
monocarboxylic acids are mixed esters of polyalcohols in
which the polyalcohols are esterified by mixtures of C1z-
C9o-monocarboxylic acids . Special examples of Cz-C6-
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17
oxyalkyl-bridged Clz-C4o-monocarboxylic acids are the
monoester of ethylene glycol with dilinolenic acid, a
C36-dimeric acid, the diester of propylene glycol with
oleic acid, and the triester of pentaerythrite with
stearic acid.
Particularly preferred as Cz-C6-oxyalkyl-bridged Clz-C9o-
monocarboxylic acids are esters of unsaturated C16-Czn-
monocarboxylic acids with C3-C4-polyalcohols, the Czz-
monocarboxylic acid content in relation to the overall
weight of the C16-C24-monocarboxylic acids being 45 to 52
mass o .
Examples of unsaturated C16-Cz4-monocarboxylic acids that
may be contained in the preferred esters of unsaturated
C16-Cz4-monocarboxylic acids with C3-C4-polyalcohols are
oleic acid, linolic acid, linolenic acid, and erucic
acid.
Examples of hydrocarbon polymers that may be contained as
other additive components in the mineral oil compositions
are copolymers of ethylene and C3-Czo-a-olefins such as
ethylene-propylene copolymers or ethylene-dodecene
copolymers or hydrated polymers of multiply unsaturated
monomers of the hydrated dime copolymer type such as
hydrated polybutadiene or hydrated polyisoprene with
molecular mass number averages up to 30000.
Examples of alkyl phenol-aldehyde copolymers that may be
contained as other additive components in the mineral oil
compositions are copolymers that can be produced by
reacting alkylated phenols such as phenol-propylene
oligomer adducts with paraformaldehyde.
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18
Examples of aromatic compounds with C8-Cloo-alkyl
substituents that may be contained as other additive
components in the mineral oil compositions are compounds
that can be produced by means of Friedel-Krafts
condensation of halogenated hydrocarbons such as
halogenated polyethylene wax with aromatic hydrocarbons
like benzene or naphthalene.
Examples of detergents that may be contained as other
additive components in the mineral oil compositions are
aliphatic sulfonic acids such as Ca-C3o-alkane sulfonates
or aromatic-aliphatic alkane sulfonates, especially
nonylbenzene sulfonic acid, dodecylbenzene sulfonic acid,
didodecylbenzene sulfonic acid, and nonylnaphthaline
sulfonic acid.
Examples of demulsifiers that may be contained as other
additive components in the mineral oil compositions are
oxalkylated phenol-formaldehyde condensates, polyalkylene
glycol-modified diglycid ethers, polyesteramines or
alkoxylated fatty acids.
Examples of cetane number improvers that may be contained
as other additive components in the mineral oil
compositions are organic nitric esters such as ethylhexyl
nitrate, cyclohexyl nitrate, or ethoxyethyl nitrate, or
soluble organic peroxides, hydroperoxides, or peresters.
Preferred defoaming agents that may be contained as other
additive components in the mineral oil compositions are
polyalkylene oxide-siloxane block copolymers and
carboxylated polyamines.
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Examples of polyalkylene oxide-siloxane block copolymers
are block copolymers that contain a combination of
trifunctional siloxane blocks such as monomethyl siloxane
groups, difunctional siloxane groups such as dimethyl
siloxane groups, and monofunctional siloxane groups such
as trimethyl siloxane groups; a preferred length of the
siloxane blocks is from 5 to 20 monomeric units. The
preferred block length for the polyalkylene oxide blocks
is 2 to 40 monomeric units, preferred are polyoxyalkylene
blocks consisting of ethylene oxide and/or propylene
oxide units.
Examples of carboxylated polyamines as defoaming agents
are reaction products of C8-C24-fatty acids and amines
such as ethylene diamine, butylene diamine, diethylene
triamine, and pentaethylene hexamine-1,2-diaminobutanol.
Examples of cosolvents that may be contained as other
additive components in the mineral oil compositions are
gasoline fractions, toluene, xylene, ethyl benzene,
isononanol, ethyl hexanol, dodecyl phenol, epoxidized
rape-seed oil, and epoxidized soybean oil.
The compositions of mineral oil as the main component and
trace portions of an additive mixture are produced using
a method in which, according to the invention, mineral
oil compositions that comprise the additive components
a) ethylene-vinylester copolymers with molar mass
averages from 3000 to 50000 and an ethylene portion
of 50 to 90 mass o, and
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b) mixed esters of glycerine wherein 50 to 80 mol o of
the hydroxy groups are esterified with unsaturated
Ciz-C4o monocarboxylic acids and 20 to 50 mol o of
the hydroxy groups are esterified with partially
5 imidated and/or partially esterified malefic
anhydride copolymers, and/or
c) partially and/or completely imidated copolymers of
malefic anhydride and a-methylstyrene with molecular
mass weight averages from 1500 to 15000 and at least
10 one terminal group based on dimeric a-methylstyrene,
and/or
d) wax compositions based on natural starting materials
of type '
d1) wax-like oligomeric esters based on glyceryl
15 monostearate and dimeric acid in which the
conversion product corresponds to the
CH2 - O - CO - (CHZ)Z - CH3
20 I
Y-O-CH
I
CH2 - O - CO - (CH2)a - CH - (CH2)b - CH3
I
CH3 - (CH2)~ CH - (CH2)d- CO OX
structure by at least 90 mass o,
n
where n = 1 to 20, the total of a+b+c+d = 30, z = 12
to 20
Y = H or - CO - (CH2)d- CH - (CH2)b - CH3
I
H3C - (CH2)~ - CH - (CH2)a - CO - OH
X = H or -CH2-CH ( OH ) -CHz-O-CO- ( CHz ) Z-CH3 ,
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CA 02542812 2006-04-18
21
and/or
d2) wax esters with vaseline-like consistency based on
at least two different straight-chain and/or
branched C14-C36 alcohols and dimeric acids in which
the conversion product corresponds to the
HsC - (CH2)~ - O - CO - (CH2)k - CH - CH - (CH2)m - CH3
I I
H3C - (CH2)~ (CHz)a - CO - O - (CH2)S - CH3
structure by at least 80 mass o,
where i = 13 to 35; s= 13 to 35,
the total of k + m + n + p is 30 to 34, and
(CH2)i or (CHZ)S are straight-chain or straight-chain
and branched,
whereby the content of the additive mixture in the
mineral oil is 0.005 to 1 mass o and the mass
proportion of the additive components a/b or a/c or
a/d is in the range from 10 . 90 to 90 . 10,
respectively,
are produced in a prehomogenization process in which
- solutions containing 1 to 60 mass o of additive
components in mineral oil middle distillates are
produced at 20 to 90°C in a first process step, and
- the solutions containing the additive components are
homogenized with the mineral oil as the main
component in a second process step,
while other additive components of a total of 0 to 200
mass o in relation to the additive components a+b, a+c,
a+d, a+b+c, a+b+c+d, or a+c+d are added to the mineral
oil in the first and/or second process step.
The compositions of mineral oil as the main component and
trace portions of an additive mixture are especially
suitable as flowable media to be transported at low
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22
temperatures and as mineral oil with high lubricity and
flowability.
Examples of the flowable media to be transported at low
temperatures are the transport of crude oil formulations
from the extraction site of the crude oil through
pipelines to loading and storage and the transport of
diesel or heating oil formulations in pipelines.
The invention is explained in greater detail by the
examples below.
EXAMPLES
The characteristic numbers were determined in accordance
with the following test methods:
Cloud point (CP): DIN EN 23 015
Cold filter plugging point (CFPP): EN 116
Distillation analysis: EN ISO 3405, ASTM D 86
Acid number: DIN 53402
Saponification number: DIN 53401
Kinematic viscosity: DIN 51562
Solidification point: DIN ISO 2207
Penetration: DIN 51580
Vinyl acetate content: modified method according to ISO
8995, DIN 16778 Part 2
2 g of sample are weighed in with 0.001 g precision and
dissolved in a 300 ml Erlenmeyer flask with 70 ml
distilled xylene and 2 boiling beads under refluxing for
ca. 15 minutes. Then ca. 30 ml of ethanol are slowly
added via the reflux cooler, the Erlenmeyer flask is
taken off the heating plate, 30 ml of ethanol, 0.5 n KOH
from the burette and 2 boiling beads are added, and the
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23
sample is refluxed for 1 hour. The sample is taken off
the reflux again, mixed with 30 ml of methanolic-aqueous
0.5 n HCl and 2 boiling beads, and refluxed for another
15 minutes. After adding 2 to 3 drops of phenolphthaleine
solution (1 mass ~ in ethanol), the sample is titrated
drop by drop under shaking with ethanolic 0.5 n KOH until
its color changes to red. A blank value has to be
determined at the same time.
( V - BV ) x F x 43
Vinyl acetate content in mass % - ----------------------
10 x E
E = original sample weight in g
F = factor of the ethanolic 17.5 n KOH
V = consumption in ml of 0.5 n ethanolic KOH for the
sample
B - consumption in ml of 0.5 n ethanolic KOH for the
blank value
Lubricating ability: Lubricity test (adjusted "wear scar
diameter" at 60°C)
according to ISO 12156-1
Short-time sedimentation test:
To test the sedimentation tendency of recrystallized
paraffins in mineral oil, a 500 ml sample is stored in a
graduated cylinder for 16 hours, then the top 80 volume
percent of the sample are drawn off and discarded. The
remaining 20 volo of the sample (100 ml) are homogenized
at 40°C, then the cloud point (CP) is determined
according to DIN EN 23 015.
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SEDAB filtration test:
A 500 ml mineral oil sample is shaken vertically 20
times, kept at 10°C for 16 hours, shaken vertically 10
times, and the entire sample is filtered all at once
through a filter of cellulose nitrate (50 mm in diameter,
0.8 um pore size) that sits on a suction cap with a
vacuum of approx. 200 hPa. The time in which the sample
runs through the filter is measured. The SEDAB filtration
test is deemed passed if the sample passes through the
filter in a period < 120 s.
Example 1
1.1 Parent products
1.1.1 Diesel without additives
Batch: 16080601 test DF 1
Characterization:
Cloud point (CP): +6°C;
?0 Cold filter plugging point (CFPP): +2°C
Lubricity test: 563 um
Distillation analysis:
Distilled quantity (vol.o) / temperature (°C)
IBP 10 20 30 40 50 60 70 80 90 FBP
189 243 259 271 281 292 303 317 334 357 385
1.1.2 Additive component a)
Ethylene-vinylacetate copolymer wax (manufactured by
LEUNA Polymer GmbH, vinyl acetate content 28.3 mass o,
molecular mass weight average 3150 g/mol).
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1.1.3 Additive component b)
The mixed ester of glycerine was produced in a melt
5 esterification process.
A malefic anhydride-octadecene copolymer partially esteri-
fied with dodecyl alcohol (mole ratio 1 . 2.2, acid
number 40, molecular mass number average 2400) is dosed
10 at 3.8 kg/h into the feed screw of a Werner&Pfleiderer
ZSK 30 twin-screw extruder, L/D ratio 48, with a side
stream dosing unit for liquid media and two vacuum
degassing zones and a belt ~weigher continuous scale for
dosing and melted at 90°C. Glycerine dierucic ester from
15 a storage tank heated to 90°C is added to the melt via
the side stream dosing unit at 2.0 kg/h, reacted in the
first reaction zone (dwell time 4.5 min) at 110°C,
degassed, reacted in the second reaction zone at 130°C
(dwell time 3.5 min), degassed, delivered at 85°C into a
20 self-cleaning melt filter using a melt gear pump (extrex
SP, Maag pump systems) and molded into pastilles in a
briqueting press with cooling conveyor.
The resulting mixed ester of glycerine has an acid number
25 of 8.5 and a melting range from 52 to 59°C.
1.2 Production of solutions containing the additive
components in mineral oil middle distillates
20 kg of the additive component b) are mixed in a stirred
tank reactor with 60 kg of a 50o solution of additive
component a) in an aromatic hydrocarbon mixture
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26
(Solvesso) at 65°C for 120 minutes and the mixture is
transferred into a storage tank.
1.3 Production and testing of the mineral oil
compositions
The additive solution according to 1.2 is injected at
0.48 kg/min into a product stream of diesel without
additives, batch 16080601, flowing at 800 kg/min and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -10°C. The lubricity
test shows a "wear scar diameter" of 405 um.
The CP value of the short-time sedimentation test is
+7°C. The SEDAB filtration test is deemed passed (500 ml
in 84 s).
If a mineral oil formulation that only contains the
copolymer wax as an additive is produced under the same
conditions, the CFPP value is -3°C and the "wear scar
diameter" is 520 um. The CP value of the short-time
sedimentation test is +10°C. The SEDAB filtration test
is deemed failed (468 ml in >120 s).
Example 2
2.1 Parent products
2.1.1 Diesel without additives
Batch: 030210 test DF 2
Characterization:
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27
Cloud point (CP): +7°C ;
Cold filter plugging point (CFPP): +2°C
Lubricity test: 556 um
Distillation analysis:
Distilled quantity (vol.o) / temperature (°C)
IBP 10 20 30 40 50 60 70 80 90 FBP
235 266 279 291 301 310 320 337 342 357 374
2.1.2 Additive component a)
mass o of a partially saponified ethylene-vinylacetate
10 copolymer wax (molecular mass weight average 1850 g/mol,
vinyl acetate content of the unsaponified ethylene-
vinylacetate copolymer wax 32.5 mass o, degree of
saponification 15 moleo) and 90 mass o of an unsaponified
ethylene-vinylacetate copolymer wax (manufactured by
LEUNA Polymer GmbH, vinylacetate content 31 mass o,
molecular mass weight average 2800 g/mole) are
intermixed.
2.1.3 Additive component b)
The mixed ester of glycerine was produced in a melt
esterification process.
An a-methylstyrene malefic anhydride-octadecene copolymer
?5 partially imidated with C16-C1$-fatty amine (mole ratic
1.3 . 1.0, acid number 42, melting point 70°C) is dosed
at 3.6 kg/h via a belt weigher continuous scale into the
feed screw of a Werner&Pfleiderer ZSK 30 twin-screw
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28
extruder, L/D ratio 48, with side stream dosing unit for
liquid media and two vacuum degassing zones and dissolved
by heat at 110°C. Glycerine dioleyl ester is added to the
melt from a storage tank heated to 90°C via the side
stream dosing unit at 1.14 kg/h, the melt is reacted in
the first reaction zone (dwell time 4.5 min) at 115°C,
degassed, reacted in the second reaction zone at 130°C
(dwell time 3 .5 min) , degassed, delivered at 85°C into a
self-cleaning melt filter using a melt gear pump (extrex
SP, Maag pump systems) and molded into pastilles in a
briqueting press with cooling conveyor.
The resulting mixed ester of glycerine has an acid number
of 4.5 and a melting range from 55 to 66°C.
2.1.4 Other additive components
Dodecylacrylate-ethylacrylate copolymer (mole ratio 2
1, molecular mass number average 13500)
2.2 Production of solutions containing the additive
components in mineral oil middle distillates
20 kg of additive component b), 40 kg of a 60o solution
of additive component a) in C8-C9-diesel aromatic
fraction, and 20 kg of a 10% solution of the other
additive component, dodecylacrylate-ethylacrylate
copolymer in toluene are stirred for 120 minutes in a
stirred tank reactor at 65°C and the mixture is
transferred into a storage tank.
2.3 Production and testing of the mineral oil
compositions
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29
The additive solution according to 2.2 is injected at
0.12 kg/min into a product stream of diesel without
additives, batch 030210 DGO, flowing at 800 kg/min and
the mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -11°C. The lubricity
test shows a "wear scar diameter" of 402 um.
The CP value of the short-time sedimentation test is
+9°C. The SEDAB filtration test is deemed passed (500 ml
in 96 s) .
If a mineral oil formulation that only contains the
unsaponified copolymer wax as an additive is produced
under the same conditions, the CFPP value is -5°C and the
"wear scar diameter" is 528 um. The CP value of the
short-time sedimentation test is +12°C. The SEDAB
filtration test is deemed failed (468 ml in >120 s).
Example 3
3.1 Starting materials
3.1.1 Heating oil without additives
Batch: 030225 test HEL type 1
Characterization:
Cloud point (CP): +1°C ;
Cold filter plugging point (CFPP): -1°C
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Distillation analysis:
Distilled quantity (vol.o) / temperature (°C)
IBP 10 20 30 40 50 60 70 80 90 FBP
165 196 213 230 249 269 290 310 327 344 363
3.1.2 Additive component a)
5 15 mass % of an oxidized ethylene-vinylacetate copolymer
wax (molecular mass weight average 950 g/mol, acid number
18 mg KOH/g, OH number 70 mg KOH/g) and 85 mass o of an
unoxidized ethylene-vinylacetate copolymer wax
(manufactured by LEUNA Polymer GmbH, vinyl acetate
10 content 32 mass %, molecular mass weight average
2300 g/mol) are intermixed.
3.1.3 Additive component b)
1~ The mixed ester of glycerine was produced in a melt
esterification process.
An octadecene malefic anhydride-octadecene copolymer
partially imidated with C16-Clg-fatty amine (mole ratio
20 1.4 . 1.0, acid number 57, melting point 55°C) is dosed
at 4.2 kg/h via a belt weigher continuous scale into the
feed screw of a Werner&Pfleiderer ZSK 30 twin-screw
extruder, L/D ratio 48, with a side stream dosing unit
for liquid media and two vacuum degassing zones, and
27 dissolved by heat at 115°C. Glycerine and an acid mixture
of erucic acid and oleic acid are added to the melt from
a storage tank heated to 90°C via the side stream dosing
unit at 2.72 kg/h, the melt is reacted in the first
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31
reaction zone (dwell time 4.5 min) at 120°C, degassed,
reacted in the second reaction zone at 130°C (dwell time
3.5 min), degassed, delivered at 95°C into a self-
cleaning melt filter using a melt gear pump (extrex SP,
Maag pump systems) and molded into pastilles in a
briqueting press with cooling conveyor.
The resulting mixed ester of glycerine has an acid number
of 3.5 and a melting range from 55 to 64°C.
3.2 Production of solutions containing the additive
components in mineral oil middle distillates
25 kg of the additive componente b) are mixed with 50 kg
of a 60 o solution of additive component a) in a Cg-C9-
diesel aromatic fraction at 65°C in a stirred tank
reactor for 120 minutes and the mixture is transferred
into a storage tank.
3.3 Production and testing of the mineral oil
compositions
The additive solution according to 3.2 is injected at
0.24 kg/min into a product stream of heating oil without
2S additives, batch 030225, flowing at 800 kg/min, and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation 'for low-temperature
resistance revealed a CFPP value of -15°C.
If a mineral oil formulation containing only the
copolymer wax as an additive is produced under the same
conditions, the CFPP value is -12°C.
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32
Example 4
4.1 Starting materials
4.1.1 Heating oil without additives
Batch: 030218 test HEL 2
Characterization:
Cloud point (CP): +2°C ;
Cold filter plugging point (CFPP): -1°C
Distillation analysis:
Distilled quantity (vol.%) / temperature (°C)
IBP 10 20 30 40 50 60 70 80 90 FBP
173 194 207 225 247 273 299 320 337 355 379
l~
4.1.2 Additive component a)
10 mass o of an ethylene-vinylacetate copolymer wax
grafted with vinyl acetate (produced according to
DD 293 125 A5, total vinyl acetate content 38 mass o,
molecular mass weight average 3400 g/mol, vinyl acetate
content of the ungrafted ethylene-vinylacetate copolymer
wax 32.5 mass o, degree of saponification 32 moleo) and
90 mass % of an ungrafted ethylene-vinylacetate copolymer
2J wax (manufactured by LEUNA Polymer GmbH, vinylacetate
content 32.5 mass %, molecular mass weight average
2400 g/mol) are intermixed.
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4.1.3 Additive component b)
The mixed ester of glycerine was produced in a melt
esterification process.
An a-methylstyrene malefic anhydride copolymer partially
esterified with octadecyl alcohol (mole ratio 1.1 . 1.0,
acid number 55, melting point 64°C) is dosed at 4.0 kg/h
via a belt weigher continuous scale into the feed screw
of a Werner&Pfleiderer zSK 30 twin-screw extruder, L/D
ratio 48, with a side stream dosing unit for liquid media
and two vacuum degassing zor~es, and dissolved by heat at
90°C. An ester of glycerine and an acid mixture of erucic
acid/oleic acid/linolenic acid (mole ratio 6:1:1:1) are
added to the melt from a storage tank heated to 110°C via
the side stream dosing unit at 2.4 kg/h, the melt is
reacted in the first reaction zone (dwell time 4.5 min)
at 125°C, degassed, reacted in the second reaction zone
at 135°C (dwell time 3.5 min), degassed, delivered at
95°C into a self-cleaning melt filter using a melt gear
pump (extrex SP, Maag pump systems) and molded into
pastilles in a briqueting press with cooling conveyor.
The resulting mixed ester of glycerine has an acid number
of 5.5 and a melting range from 53 to 63°C.
4.1.4 Other additive components
Polyethylene glycol monomethyl ether, molecular mass
number average 1500
2-ethylhexylacrylate-ethylacrylate copolymer (mole ratio
2 . 1)
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4.2 Production of solutions containing the additive
components in mineral oil middle distillates
20 kg of additive component b), 20 kg of a 60o solution
of additive component a) in C8-C9-diesel aromatic
fraction, and 1 kg of the other additive component,
polyethylene glycol monomethyl ether, molecular mass
number average 1500, and 8 kg of a 10o solution of the
other additive component, ethylhexylacrylate-
ethylacrylate copolymer (mole ratio 2 . 1) in toluene are
introduced into a stirred tank reactor, stirred for 120
minutes at 65°C, and the mixture is transferred into a
storage tank.
4.3 Production and testing of the mineral oil
compositions
Additive solution according to 4.2 is injected at
0.28 kg/min into a product stream of heating oil without
additives, batch 030225, flowing at 800 kg/min, and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -14°C.
If a mineral oil formulation containing only the
copolymer wax as an additive is produced under the same
conditions, the CFPP value is -1°C.
Example 5
5.1 Starting materials
5.1.1 Diesel without additives
Leu-21515-engl with arr~endments.doc
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Batch: 16080601 test DF 1
Characterization:
Cloud point (CP): +6°C;
Cold filter plugging point (CFPP): +2°C
5
Distillation analysis:
Distilled quantity (vol.%) / temperature (°C)
IBP 10% 20% 30% 40% 50% 60% 70% 80% 90% FBP
189 243 259 271 281 292 303 317 334 357 385
5.1.2 Additive component a)
10 Ethylene-vinylacetate copolymer wax. (manufactured by
LEUNA Polymer GmbH, vinyl acetate content 32 mass %,
molecular mass weight average 2300 g/mol).
5.1.3 Additive component c)
a-Methylstyrene-malefic anhydride copolymer, partially
imidated with C16-C1$-fatty amine, molecular mass number
average 12800 g/mol, acid number 35
Production of additive component c)
81 1 of a-methylstyrene, 7 1 of a-methylstyrene-dimer,
and 20 liters of acetone are placed in a 500 1 stirred
tank reactor, and the stirred tank reactor is heated to
?5 59°C. A solution of 52 kg malefic anhydride and 2.4 kg of
azoisobutyric acid dinitrile in 150 1 of acetone is
evenly dosed into a stirred tank reactor over 6 hours and
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36
the reaction mixture is stirred for 6 more hours at 70 to
73°C.
An analysis sample of the copolymer (MCPS) has an acid
S number of 445 mg KOH per gram of copolymer. NMR
examinations result in 1.3 a-methylstyrene-dimer terminal
groups per mole.
The polymer solution that is still at 54 to 56°C is now
continuously fed into a twin-drum vacuum drier and split
into a powdered copolymer with a residual content of 1.1
mass o of volatile ingredients and acetone.
382 kg of a C8-C9-diesel aromatic fraction boiling above
17 160°C and 122 kg of C16-C18-fatty amine are placed in a
500 1 stirred tank reactor and heated to 130°C for
partial imidation of the copolymer. 135.5 kg of the
copolymer are continuously added to this solution over 4
hours. This raises the temperature inside the stirred
tank reactor to 180 to 185°C, and water is formed that is
distilled off azeotropically with an approximately equal
quantity of C8-C9-diesel aromatic fraction. After a total
reaction time of 6 hours at 160 to 190°C, 8.5 kg of water
and 10.2 kg of solvent are distilled off. A 40o solution
of the partially imidated copolymer with an acid number
of 35 and a molecular mass number average of 12800 g/mole
is obtained.
5.1.4 Other additive components
Mixture of C3-oxyalkyl-bridged unsaturated C18-Cz4-
carboxylic acids, degree of esterification 92 mol o,
content of C18-unsaturated fatty acids 32 mass o, content
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37
of C22-unsaturated fatty acids 48 mass o, iodine number
96
Ethylacrylate-ethylhexylacrylate copolymer (mole ratio 3
. 2, molecular mass number average 13500)
5.2 Production of solutions containing the additive
components in mineral oil middle distillates
25 kg of a 40 o solution of additive component c) in CS-
Cg-diesel aromatic fraction, 50 kg of a 50o solution of
additive component a) in an aromatic hydrocarbon mixture
(Solvesso), 20 kg of a mixture of C3-oxyalkyl-bridged
unsaturated C18-C29-carboxylic acids as other additive
component and 19 kg of a 20o solution of another additive
component, ethylacrylate-ethylhexylacrylate copolymer in
toluene are intermixed in a stirred tank reactor for 90
minutes at 65°C, and the mixture is transferred into a
storage tank.
5.3 Production and testing of the mineral oil
formulation
Additive solution according to 5.2 is injected at
0.48 kg/min into a product stream of diesel without
additives, batch 16080601, flowing at 800 kg/min and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -16°C. The CP value
of the short-time sedimentation test is +5°C. The SEDAB
filtration test is deemed passed (500 ml in 76 s).
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38
If a mineral oil formulation containing only the
copolymer wax as an additive is produced under the same
conditions, the CFPP value is -3°C. The CP value of the
short-time sedimentation test is +10°C. The SEDAB
filtration test is deemed failed (468 ml in >120 s).
Example 6
6.1 Starting materials
6.1.1 Diesel without additives
Batch: 030210 test DF 2
Characterization:
Cloud point (CP): +7°C ;
Cold filter plugging point (CFPP): +2°C
Distillation analysis:
Distilled quantity (vol.%) / temperature (°C)
IBP 10% 200 30% 400 50a 600 700 800 90o FBP
235 374
266 279 291 3.01 310 320 337 342 357
6.1.2 Additive component a)
10 mass o of a partially saponified ethylene-vinylacetate
?~ copolymer wax (molecular mass weight average 1600 g/mol,
vinyl acetate content of the unsaponified ethylene-
vTinylacetate copolymer wax 32 mass o, degree of
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saponification 15 moleo) and 90 mass o of an ethylene-
vinylacetate copolymer wax (manufactured by LEUNA Polymer
GmbH, vinylacetate content 32 mass %, molecular mass
weight average 2300 g/mol) are intermixed.
6.1.3 Additive component c)
a-Methylstyrene-malefic anhydride copolymer, partially
imidated with dodecylamine, molecular mass number average
14200 g/mol, acid number 56
Production of additive component c)
83 1 of a-methylstyrene, 5.1 of a-methylstyrene-dimer,
and 62 kg of malefic anhydride, and 110 1 of 2-butanone
1S are placed in a 500 1 stirred tank reactor, and the
stirred tank reactor is heated to 70°C. A solution of
1.9 kg of dibenzoyl peroxide and 52 1 of 2-butanone is
evenly dosed into a stirred tank reactor over 2 hours and
the reaction mixture is stirred for 10 more hours at 72
to 73°C.
An analysis sample of the copolymer has an acid number of
452 mg KOH per gram of copolymer. NMR examinations result
in 1.1 a-methylstyrene-dimer terminal groups per mole.
The polymer solution that is still at a temperature of
70°C is now continuously dosed into a 500 1 stirred tank
reactor containing 280 1 of 2-ethyl hexanol and heated to
150°C while 2-butanone-2 is removed by distillation.
104 kg od a C16-C18-fatty amine are added over 4 hours
while the temperature is raised to 165 to 185°C to remove
the water together with a small quantity of 2-ethyl
hexanol by distillation.
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A 40o solution of the partially imidated copolymer c)
with an acid number of 56 and a molecular mass number
average of 14200 g/mole is obtained.
5 6.1.4 Other additive components
Triesters of pentaerythrite with oleic acid
Diethylene glycol monolauroyl ester
10 6.2 Production of solutions containing the additive
components in mineral oil middle distillates
25 kg of a 40% solution of'additive component c) in 2-
ethyl hexanol, 50 kg of a 60o solution of additive
15 component a) in Ca-C9-diesel aromatic fraction, 20 kg of
triester of pentaerythrite with oleic acid as other
additive component, and 1 kg of another additive
component, diethylene glycol monolaurol ester are
introduced into a stirred tank reactor, stirred for 90
20 minutes at 65°C, and the mixture is transferred into a
storage tank.
6.3 Production and testing of the mineral oil
formulation
The additive solution according to 6.2 is injected at
0.24 kg/min into a product stream of diesel without
additives, batch 030210, flowing at 800 kg/min and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -7°C. The CP value of
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the short-time sedimentation test is +7°C. The SEDAB
filtration test is deemed passed (500 ml in 82 s).
If a mineral oil formulation containing only the
copolymer wax as an additive is produced under the same
conditions, the CFPP value is -5°C. The CP value of the
short-time sedimentation test is +12°C. The SEDAB
filtration test is deemed failed (468 ml in >120 s).
Example 7
7.1 Starting materials
7.1.1 Heating oil without additives
Batch: 030225 test HEL 1
Characterization:
Cloud point (CP) : +1°C ;
Cold filter plugging point (CFPP): -1°C
Distillation analysis:
Distilled quantity (vol.o) / temperature (°C)
IBP 10% 20% 300 400 500 600 70% 800 90o FBP
165 196 213 230 249 269 290 310 327 344 363
7.1.2 Additive component a)
15 mass o of an oxidized ethylene-vinylacetate copolymer
wax (molecular mass weight average 950 g/mol, acid number
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18 mg KOH/g, OH number 70 mg KOH/g) and 85 mass o of an
unoxidized ethylene-vinylacetate copolymer wax
(manufactured by LEUNA Polymer GmbH, vinyl acetate
content 32 mass o, molecular mass weight average
2300 g/mol) are intermixed.
7.1.3 Additive component c)
a-Methylstyrene-malefic anhydride copolymer, partially
imidated with C12-Ci4-fatty amine, molecular mass number
average 7000 g/mol, acid number 25
Production of additive component c)
83 1 of a-methylstyrene, 12 1 of a-methylstyrene-dimer,
and 62 kg of malefic anhydride, and 140 1 of 1,2-
dichloroethane are placed in a 500 1 stirred autoclave,
and the stirred autoclave is heated to 90°C . A solution
of 2.5 kg of tert.-butylperoxy-2-ethyl hexanoate and 55 1
of 1,2-dichloroethane is evenly dosed into a stirred
autoclave over 2 hours and the reaction mixture is
stirred for 10 more hours at 90 to 93°C.
An analysis sample of the copolymer has an acid number of
?5 430 mg KOH per gram of copolymer. NMR examinations result
in 1,4 a-methylstyrene-dimer terminal groups per mole.
The polymer solution that is still at ca. 90°C is now
continuously fed into a 500 1 stirred tank reactor
containing 280 1 of a Cg-C9-diesel aromatic fraction and
122 kg of a C12-C1Q-fatty amine mixture and was heated up
to 160°C while 1,2-dichloroethane and the reaction water
from the imidation were removed by distillation.
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A 40o solution of the partially imidated copolymer c) in
a C8-C~-diesel aromatic fraction with an acid number of
25 and a molecular mass number average of 7000 g/mol is
obtained.
7.1.4 Other additive components
Diesters of ethylene glycol with erucic acid
N-(2-hydroxyethyl)oleylamine
7.2 Production of solutions containing the additive
components in mineral oil middle distillates
50 kg of a 60 o solution of additive component a) in Ca-
1~ C9-diesel aromatic fraction, 20 kg of diester of ethylene
glycol with erucic acid as other additive component, and
3 kg of another additive component, N-(2-hydroxyethyl)
oleylamine, are added to a stirred tank reactor
containing 25 kg of a 40% solution of additive component
c) in C8-C9-diesel aromatic fraction at 65°C, stirred for
90 minutes at 65°C, and the mixture is transferred into a
storage tank.
7.3 Production and testing of the mineral oil
formulation
Additive solution according to 7.2 is injected at
0.24 kg/min into a product stream of heating oil without
additives, batch 030225, flowing at 800 kg/min, and the
mix is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -15°C.
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If a mineral oil formulation containing only the
copolymer wax as an additive is produced under the same
conditions, the CFPP value is -13°C.
Example 8
8.1 Starting materials
8.1.1 Diesel without additives
Batch: 16080601 test DF 1
Characterization:
Cloud point (CP): +6°C;
Cold filter plugging point (CFPP): +2°C
Distillation analysis:
Distilled quantity (vol.%) / temperature (°C)
IBP 100 200 30% 400 500 600 700 800 90o FBP
189 243 259 271 281 292 303 317 334 357 385
8.1.2 Additive component a)
Ethylene-vinylacetate copolymer wax (manufactured by
LEUNA Polymer GmbH, vinyl acetate content 32 mass o,
molecular mass weight average 2300 g/mol).
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8.1.3 Additive component c)
a-Methylstyrene-malefic anhydride copolymer, partially
imidated with stearyl amine, molecular mass weight
5 average 13750 g/mol, acid number 51
Production of additive component c)
81 1 of a-methylstyrene, 7 1 of a-methylstyrene-dimer,
10 and 20 liters of acetone are placed in a 500 1 stirred
tank reactor, and the stirred tank reactor is heated to
59°C. A solution of 52 kg malefic anhydride and 2.4 kg of
azoisobutyric acid dinitrile in 150 1 of acetone is
evenly dosed into a stirred tank reactor over 6 hours and
IS the reaction mixture is stirred for 6 more hours at 70 to
73°C.
An analysis sample of the copolymer has an acid number of
445 mg KOH per gram of copolymer. NMR examinations result
20 in 1.3 a-methylstyrene-dimer terminal groups per mole.
The polymer solution that is still at 54 to 56°C is now
continuously fed into a twin-drum vacuum drier and split
into a powdered copolymer with a residual content of 1.10
25 of volatile ingredients and acetone.
382 kg of a Ca-C~-diesel aromatic fraction boiling above
160°C and 135 kg of stearyl amine are placed in a 500 1
stirred tank reactor and heated to 130°C for partial
30 imidation of the copolymer. 135.5 kg of the copolymer are
continuously added to this solution over 4 hours. This
raises the temperature inside the stirred tank reactor to
180 to 185°C, and water is formed that is distilled off
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azeotropically with an approximately equal quantity of
Cg-C9-diesel aromatic fraction. After a total reaction
time of 6 hours at 160 to 190°C, 8.5 kg of water and
10.2 kg of solvent are distilled off.
A 40% solution of the copolymer partially imidated with
stearyl amine with an acid number of 51 and an molecular
mass weight average of 13750 g/mole is obtained.
8.1.4 Other additive components
Mixture of C3-oxyalkyl-bridged unsaturated C18-Cz4
carboxylic acids, degree of esterification 92 mol %,
content of C18-unsaturated fatty acids 32 mass o, content
of C22-unsaturated fatty acids 48 mass o, iodine number
96
Ethylacrylate-octadecylacrylate copolymer (mole ratio 4
1, molecular mass number average 8400)
8.2 Production of solutions containing the additive
?0 components in mineral oil middle distillates
kg of a 40 o solution of additive . component c) in C8-
C9-diesel aromatic fraction, 50 kg of a 50o solution of
additive component a) in an aromatic hydrocarbon mixture
25 (Solvesso), 20 kg of a mixture of C3-oxyalkyl-bridged
unsaturated C18-C24-carboxylic acids as other additive
component and 19 kg of a 20o solution of another additive
component, ethylacrylate-octadecylacrylate copolymer in
toluene are intermixed in a stirred tank reactor for 90
minutes at 65°C, and the mixture is transferred into a
storage tank.
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8.3 Production and testing of the mineral oil
formulation
The additive solution according to 8.2 is injected at
0.48 kg/min into a product stream of diesel without
additives, batch 16080601, flowing at 800 kg/min and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -17°C.
If a mineral oil formulation containing only the
copolymer wax as an additive is produced under the same
conditions, the CFPP value is -3°C.
Example 9
9.1 Starting materials
9.1.1 Diesel without additives
Batch: 16080601 test DF 1
Characterization:
Cloud point (CP): +6°C;
Cold filter plugging point (CFPP): +2°C
Lubricity test: 563 um
Distillation analysis:
Distilled quantity (vol.%) / temperature (°C)
IBP l00 20% 300 400 50% 60% 70% 800 90o FBP
189 243 259 271 281 292 303 317 334 357 385
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9.1.2 Additive component a)
Ethylene-vinylacetate copolymer wax (manufactured by
LEUNA Polymer GmbH, vinyl acetate content 32 mass %,
molecular mass weight average 2300 g/mol).
9.1.3 Additive component d2)
Wax ester with vaseline-like consistency, acid number
7.9 mg KOH/g, saponification number 113 mg KOH/g,
kinematic viscosity 20.6 mm2/s, solidification point
34.5°C.
Production of additive component d2)
A mixture of 25 kg dimeric acid (dimerization product
from unsaturated Cl8-fatty acids, mean carbon number 36),
5 kg of stearyl alcohol, and 7 kg of cetyl alcohol are
dissolved by heat in a 70 1 stirred tank reactor at 120°C
with inert gas introduction and reacted while adding 50 g
H2S04 and removing the reaction water until an acid
number of 7.9 mg KOH/g is reached. After allowing the
melt to cool down, the catalyst is neutralized with 0.5 1
of 10o NaHC03, the aqueous phase is separated, and the
wax ester drawn off.
9.1.4 Other additive components
Ethylacrylate-ethylhexylacrylate copolymer (mole ratio
3 . 2, molecular mass number average 13500)
9.2 Production of solutions containing the additive
components in mineral oil middle distillates
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25 kg of a 40% solution of additive component d2 ) in C8-
C9-diesel aromatic fraction, 50 kg of a 50o solution of
additive component a) in an aromatic hydrocarbon mixture
(Solvesso), and 15 kg of a 20o solution of another
additive component, ethylacrylate-ethylhexylacrylate
copolymer in toluene are intermixed in a stirred tank
reactor for 90 minutes at 65°C, and the mixture is
transferred into a storage tank.
9.3 Production of the mineral oil composition
The additive solution according to 9.2 is injected at
0.48 kg/min into a product stream of diesel without
additives, batch 16080601, flowing at 800 kg/min and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -14°C. The lubricity
test shows a "wear scar diameter" of 412 um.
If a mineral oil composition containing only the
unmodified copolymer wax a) as an additive is produced
under the same conditions, the CFPP value is -3°C.
Example 10
10.1 Starting materials
10.1.1 Diesel without additives
Batch: 030210 test DF 2
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Characterization:
Cloud point (CP): +7°C;
Cold filter plugging point (CFPP): +2°C
Lubricity test: 556 um
Distillation analysis:
Distilled quantity (vol.o) / temperature (°C)
IBP 100 20% 300 400 500 600 700 800 90o FBP
235 374
266 279 291 301 310 320 337 342 357
10.1.2 Additive component a)
20 mass % of a partially saponified ethylene-vinylacetate
copolymer wax (molecular mass weight average 1600 g/mol,
vinyl acetate content of the unsaponified ethylene-
vinylacetate copolymer wax 32 mass o, degree of
saponification 15 moleo) and 80 mass % of an ethylene-
vinylacetate copolymer wax (manufactured by LEUNA Polymer
GmbH, vinylacetate content 32 mass o, molecular mass
weight average 2300 g/mol) are intermixed.
10.1.3 Additive component d2)
Wax ester with vaseline-like consistency, acid number
8.6 mg KOH/g, saponification number 118 mg KOH/g,
kinematic viscosity 23.1 mm2/s, solidification point
2J 35.2°C.
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Production of additive component d2)
A mixture of 25 kg dimeric acid (dimerization product
from unsaturated C18-fatty acids, mean carbon number 36),
5 kg of stearyl alcohol, and 8 kg of eicosane alcohol are
dissolved by heat in a 70 1 stirred tank reactor at 120°C
with inert gas introduction and reacted while adding 50 g
H2S04 and removing the reaction water until an acid
number of 8.6 mg KOH/g is reached. After allowing the
melt to cool down, the catalyst is neutralized with 1.0 1
of 10% NaHC03, the aqueous phase is separated, and the
wax ester drawn off.
10.1.4 Other additive components
Triesters of pentaerythrite with oleic acid
10.2 Production of solutions containing the additive
components in mineral oil middle distillates
22 kg of a 50o solution of additive component d2) in 2-
ethyl hexanol, 50 kg of a 60% solution of additive
component a) in C8-C9-diesel aromatic fraction, and 20 kg
of a triester of pentaerythrite with oleic acid as other
additive component are introduced into a stirred tank
reactor, stirred for 90 minutes at 65°C, and the mixture
is transferred into a storage tank.
10.3 Production of the mineral oil composition
Additive solution according to 10.2 is injected at 0,30
kg/min into a product stream of diesel without additives,
batch 030210, flowing at 800 kg/min and the mixture is
transferred into a storage tank.
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Testing the mineral oil composition for low-temperature
resistance revealed a CFPP value of -8°C. The lubricity
test shows a "wear scar diameter" of 425 um.
If a mineral oil composition that only contains the
unmodified copolymer wax a) as an additive is produced
under the same conditions, the CFPP value is -5°C and the
"wear scar diameter" is 528 um.
Example 11
11.1 Starting materials
11.1.1 Heating oil without additives
Batch: 030225 test HEL 1
Characterization:
Cloud point (CP): +1°C;
Cold filter plugging point (CFPP): -1°C
Distillation analysis:
Distilled quantity (vol.o) / temperature (°C)
IBP 100 20a 300 400 500 60~ 700 800 90o FBP
165 196 213 230 249 269 290 310 327 344 363
11.1.2 Additive component a)
mass % of an oxidized ethylene-vinylacetate copolymer
25 wax (molecular mass weight average 950 g/mol, acid number
18 mg KOH/g, OH number 70 mg KOH/g) and 75 mass o of an
unoxidized ethylene-vinylacetate copolymer wax (manufac
tured by LEUNA Polymer GmbH, vinyl acetate content
32 mass o, molecular mass weight average 2300 glmol) are
intermixed.
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11.1.3 Additive component d1)
Oligomeric ester, acid number 12 mg KOH/g, saponification
number 175 mg KOH/g, kinematic viscosity (100°C)
65 mm2/s, solidification point 42°C, produced in
accordance with EP 0 934 921 A1 from glyceryl
monostearate and dimeric acid (dimerization product from
unsaturated C18-fatty acids, mean carbon number 36) by
solvent-free oligocondensation with acid catalysis.
11.1.4 Other additive components
N-(2-hydroxyethyl)oleylamine
11.2 Production of solutions containing the additive
components in mineral oil middle distillates
50 kg of a 60o solution of additive component a) in C8-
C9-diesel aromatic fraction, and 3 kg of another additive
component, N-(2-hydroxyethyl oleylamine, are added to a
stirred tank reactor containing 23 kg of a 40% solution
of additive component d1) in C8-C9-diesel aromatic
fraction at 65°C, stirred for 90 minutes at 65°C, and the
mixture is transferred into a storage tank.
11.3 Production of the mineral oil composition
The additive solution according to 11.2 is injected at
0.28 kg/min into a product stream of heating oil without
additives, batch 030225, flowing at 800 kg/min, and the
mixture is transferred into a storage tank.
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Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -16°C.
If a mineral oil composition containing only the
unmodified copolymer wax a) as an additive is produced
under the same conditions, the CFPP value is -13°C.
Example 12
12.1 Starting materials
12.1.1 Diesel without additives
Batch: 16080601 test DF 1
17 Characterization:
Cloud point (CP): +6°C;
Cold filter plugging point (CFPP): +2°C
Distillation analysis:
Distilled quantity (vol.o) / temperature (°C)
IBP 10% 200 300 40% 50% 60~ 700 800 90% FBP
189 243 259 271 281 292 303 317 334 357 385
12.1.2 Additive component a)
Ethylene-vinylacetate copolymer wax (manufactured by
LEUNA Polymer GmbH, vinyl acetate content 32 mass o,
2> molecular mass weight average 2300 g/mol).
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12.1.3 Additive component d1)
Oligomeric ester, acid number 14 mg KOH/g, saponification
number 185 mg KOH/g, kinematic viscosity (100°C)
5 76 mm2/s, solidification point 42°C, produced in
accordance with EP 0 934 921 A1 from glyceryl
monostearate and dimeric acid (dimerization product from
unsaturated C18-fatty acids, mean carbon number 36) by
solvent-free oligocondensation with acid catalysis.
12.1.4 Other additive components
Mixture of C3-oxyalkyl-bridged unsaturated C18-C24-
carboxylic acids, degree of esterification 92 mol %,
content of C18-unsaturated fatty acids 32 mass o , content
of C22-unsaturated fatty acids 48 mass o, iodine number
96
Ethylacrylate-octadecylacrylate copolymer (mole ratio 4
1, molecular mass number average 8400)
12.2 Production of solutions containing the additive
components in mineral oil middle distillates
kg of a 50% solution of additive component d1) in C8-
25 C9-diesel aromatic fraction, 50 kg of a 50% solution of
additive component a) in an aromatic hydrocarbon mixture
(Solvesso), 12 kg of a mixture of C3-oxyalkyl-bridged
unsaturated C18-Cz4-carboxylic acids as other additive
component and 15 kg of a 20% solution of another additive
component, ethylacrylate-octadecylacrylate copolymer in
toluene are intermixed in a stirred tank reactor for 90
minutes at 65°C, and the mixture is transferred into a
storage tank.
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12.3 Production and testing of the mineral oil
composition
The additive solution according to 12.2 is injected at
0,52 kglmin into a product stream. of diesel without
additives, batch 16080601, flowing at 800 kg/min and the
mixture is transferred into a storage tank.
Testing the mineral oil formulation for low-temperature
resistance revealed a CFPP value of -18°C.
If a mineral oil composition containing only the
unmodified copolymer wax a) as an additive is produced
under the same conditions, the CFPP value is -3°C.
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