Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02421439 2003-03-06
I
Vinylamine compounds
The present invention relates to compounds, in particular copolymers, which
contain vinylamine building blocks. The present invention furthermore relates
to a
process for the preparation of such compounds of copolymers, their use as
assistants in mineral oils, mineral oil distillates, combustion fuels and
power fuels
and in other areas, and concentrates and combustion fuel and power fuel
compositions containing them.
Vinylamine polymers can be obtained only indirectly by polymer-analogous
reactions since the base monomer, vinylamine, cannot be isolated. Vinylamine
polymers are prepared, for example, by hydrolysis of poly-N-vinylamides, such
as
poly-N-vinylformamide or poly-N-vinylacetamide, poly-N-vinylimides, such as
poly-N-vinylsuccinimide or poly-N-vinylphthalimide and by Hoffmann
degradation of polyacrylamide under the action of basic hypochlorite. These
synthesis routes start from poorly obtainable or expensive monomers and
include
complicated reaction or working-up steps. They have been used to date only in
a
few special applications, for example flocculants and retention aids.
Mineral oil distillates, in particular middle distillates, such as gas oils,
diesel oils or
heating oils, which are obtained from mineral oils by distillation and the
further
processing stages of the refineries, have, depending on the origin of the
crude oil,
different contents of n-paraffins, which may crystallize on cooling. This
point is
referred to as the cloud point (CP). On further cooling, the lamellar paraffin
crystals form a sort of house-of cards structure, so that a middle distillate
(MD)
sets although the predominant part is still liquid. This point is referred to
as the
pour point. The flowability, in particular of power fuels, is considerably
impaired
by the precipitated paraffins in the temperature range between cloud point and
pour
point. The paraffins block filters and, in the case of power fuels, cause an
uneven
fuel supply to the engine or completely stop said supply. Similar problems
arise in
the case of heating oils.
~3
It is known that the crystal growth of the paraffins in middle distillates and
kerosene middle distillate mixtures can be modified by introducing suitable
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2
additives into the mineral oil distillate. Effective additives prevent
paraffins in
middle distillates from forming such structures resembling a house of cards
and the
middle distillates from becoming solid at temperatures only a few °C
below the
temperature at which the first crystals are precipitated. They thus act as
flow
improvers. The improvement of the flow properties of middle distillates is
frequently determined as a reduction of the cold filter plugging point (CFPP),
for
example according to DIN EN 116. On the other hand, these additives result in
the
formation of fine, well crystallized, separate paraffin crystals which do not
settle
out and which cannot pass through the filters, so that trouble-free fuel
transport is
ensured. Here, they act as wax-anti-settling additives (WASA).
Copolymers which are derived from ethylene and vinyl acetate have widely been
described as flow improvers for mineral oil middle distillates (cf. for
example
DE-A-196 24 861). The copolymers described furthermore contain (meth)acrylate
building blocks which are derived from amino alcohols which may be
alkoxylated.
EP-A-0 964 052 relates to the use of nitrogen-containing ethylene copolymers
for
the preparation of fuel oils having an improved lubricating effect. In
addition to
structural units which are derived from ethylene, the copolymers also contain
those
structural units which are derived from ethylenically unsaturated compounds
which
have at least one aromatically or aliphatically bonded nitrogen atom.
Alkylamino
(meth)acrylates, alkyl(meth)acrylamides, vinylamides, aminoalkyl vinyl ethers,
allylamines and heterocycles containing a vinyl group are mentioned as such
comonomers. In particular, terpolymers which are derived from ethylene, vinyl
acetate and 1-vinyl-2-pyrrolidone, N-vinyl-N-methylacetamide or
dimethylaminoethyl methacrylate are used.
The nitrogen-containing vinylic comonomers have in some cases a complicated
structure and as a rule cannot be prepared in a simple manner and from
economical
raw materials.
EP-A-0 405 270 relates to a process for improving the flowability of mineral
oils
and mineral oil distillates by adding a mixture of an ethylene/vinyl acetate
copolymer and an ethylene/vinyl acetate/N-vinyl-pyrrolidone terpolymer.
WO 96/18706 relates to combustion and power fuel compositions which have a
low sulfur content and whose flowability is increased by adding nitrogen-
containing compounds. In particular, amine salts or amides, which are obtained
by
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3
reacting hydrocarbon-substituted amines with alkanoic acids, are used.
It is an object of the present invention to provide a process for the
preparation of
compounds which contain structural elements derived from vinylamine, it being
intended that the amino group be capable of being introduced simply and
economically.
In addition, it is intended to provide copolymers which have a number of
advantageous properties as assistants in mineral oil, mineral oil distillates
and
combustion and power fuels.
We have found that this object is achieved, according to the invention, by a
process
for the preparation of a compound which contains one or more groups of the
formula (I)
-CH2-CH(NR' RZ)- (I)
where
Rl and RZ, independently of one another, are each hydrogen, C1_2o-alkyl, C6_ls
aryl, C~_2o-alkaryl, C~_2o-aralkyl or a polyamine radical,
by reductive amination of compounds which contain one or more groups of the
formula (II)
-CH2-CH(O-C(O)-R3)- (II)
where
R3 is hydrogen, C1_2o-alkYl, C6_1g-aryl, C~_2o-alkaryl or C7_2o-aralkyl,
with amines of the formula (III)
HNRI R2 (III)
and hydrogen.
It was found, according to the invention, that structural elements derived
from
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vinyl esters and present in chemical compounds, for example polymers, can be
converted into structures derived from vinylamine by reductive amination with
amines and hydrogen.
The compounds which contain the structures of the formula (I) or (II) may be
low
molecular weight, oligomeric or polymeric structures. They may accordingly
have
1, 2, 3, 4, 5, 6 or more of the structures of the formulae (I) and (II).
Preferably, the
compounds having the structures of the formula (I) have altogether 4 to
100,000,
particularly preferably 10 to 10,000, in particular 10 to 1000, carbon atoms
if they
are low molecular weight or oligomeric compounds.
Particularly preferably, the compounds are polymers which contain vinylamine
building blocks of the formula (I) in the main chain. The polymers contain 1
or 2,
3, 4, 5, 6 or more of the building blocks of the formula (I).
They may be completely composed of building blocks of the formula (I). In this
case, they are homopolymers. Frequently, they are copolymers which contain
unconverted structures of the formula (II) in addition to the structures of
the
formula (I). Moreover, further building blocks as described below may be
present.
Preferably, the compounds are polymers which contain one or more vinylamine
building blocks of the formula (I) in the main chain and are obtained by
reductive
amination of polymers which contain one or more vinyl ester building blocks of
the formula (II) in the main chain.
Particularly preferably, the polymers to be aminated are copolymers which
contain
CZ-C12-olefin building blocks and vinyl esters of C1_12-monocarboxylic acids
as
building blocks.
In particular, the copolymers to be aminated are ethylene/vinyl acetate
copolymers.
In the groups of the formula (I) and in the amines of the formula (III), Rl
and RZ,
independently of one another, are each preferably hydrogen or C1_i2-alkyl,
particularly preferably hydrogen or C1~-alkyl, in particular hydrogen.
Particularly
preferably, ammonia is used as a compound of the formula (III).
In the structures of the formula (II), R3 is preferably hydrogen or C1_12-
alkyl,
particularly preferably C1~-alkyl, in particular methyl. These are therefore
in
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particular vinyl acetate building blocks.
Particularly preferred compounds which contain the structures of the formula
(I) or
(II) are polymers having a number average molecular weight of from 100 to
10,000,000, particular preferably from 500 to 100,000.
The novel reductive amination can be carried out analogously to known
processes
for the reductive amination of, for example, aldehydes, ketones or esters and
alcohols. It is preferably carned out using suitable catalysts. Suitable
catalysts are
known and are described, for example, in the non-prior-published DE-A-199 10
960 with the earlier priority.
Catalysts customary for the reductive amination are, for example, those based
on
Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Al, Si, Ti, Zr, Nb, Mg, Zn or a combination
thereof.
Typical reaction conditions are temperatures of from 50 to 300°C and
pressures of
up to about 600 bar.
A preferred catalyst contains as catalytically active material, before the
reduction
with hydrogen,
from 20 to 85, preferably from 20 to 65, particularly preferably from 25 to
49.7,
by weight of oxygen-containing compounds of zirconium, calculated as Zr02,
from 1 to 30, preferably from 5 to 25, particularly preferably from 10 to 25,
% by
weight of oxygen-containing compounds of copper, calculated as CuO,
from 14 to 70, preferably from 29.7 to 70, particularly preferably from 40 to
60,
by weight of oxygen-containing compounds of nickel, calculated as NiO,
from 0 to S, preferably from 0.3 to 3.5, % by weight of oxygen-containing
compounds of molybdenum, calculated as Mo03, and
from 0 to 10, particularly preferably from 0 to 5, % by weight of oxygen-
containing compounds of aluminum, calculated as A1203,
the total amount of which is 100% by weight.
A particularly preferred catalyst is composed of 51 % by weight of NiO, 17% by
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weight of CuO, 30.5% by weight of Zr02 and 1.5% by weight of Mo03.
The catalyst is preferably composed only of catalytically active material and,
if
required, a molding assistant, such as graphite or stearic acid. The catalyst
may be
used in any suitable form, for example as pellets, beads, rings or extrudates.
The catalytically active material can, if required, furthermore contain one or
more
elements, or inorganic or organic compounds thereof, selected from groups IA
to
IVA and IB to VIIB and VIII of the Periodic Table of the Elements.
Catalysts which, after the final heat treatment and before the reduction with
hydrogen, contain less than 20, preferably less than 10, in particular less
than 5,
very particularly less than 1, % by weight of cobalt, calculated as CoO, are
particularly preferred. Very particularly preferably, the catalytically active
material
contains no catalytically active amounts of cobalt or compounds thereof.
The catalysts can be prepared by various processes, for example by peptization
of
pulverulent mixtures of the hydroxides, carbonates, oxides and/or other salts
of the
components with water and subsequent extrusion and heating of the material
thus
obtained. In general, however, known precipitation methods are used for
preparing
the catalysts. In said methods, the individual components can be precipitated
individually or together as a coprecipitate.
The precipitation products are dried in general at from 80 to 200°C,
preferably
from 100 to 150°C and then calcined at from 300 to 800°C,
preferably from 400 to
600°C, in particular from 450 to 500°C.
The amines of the formula (III) can be used in stoichiometric amounts, based
on
the ester groups to be reacted. Preferably, however, an excess of the amines
is
used, for example more than a 5 molar excess. In particular, ammonia is
generally
used in a 5- to 250-fold, preferably 10- to 100-fold, in particular 25- to 80-
fold,
molar excess.
The novel process can be carried out batchwise or continuously, the catalyst
preferably being arranged as a fixed bed in the reactor. The reaction can be
carried
out in the liquid phase or in the gas phase.
Usually, the reaction is effected at from 50 to 300°C, preferably from
80 to 250°C,
particularly preferably from 80 to 230°C, in particular from 100 to
220°C.
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In general, the reaction is carried out at from 1 to 400, preferably from 10
to 250,
in particular from 20 to 200, bar.
In the reaction, the hydrogen is generally introduced in an amount of from 5
to
400, preferably from 50 to 250,1(S.T.P.) per mol of ester component to be
reacted.
The reaction may be carried out without additional solvent. The reaction
involving
high molecular weight starting compounds or products which are highly viscous
or
which are solid at room temperature is advantageously effected in a solvent
which
is inert under reaction conditions, for example in tetrahydrofuran, dioxane, N-
methylpyrrolidone, mihagol, ethylene glycol dimethyl ether, cyclohexane or
hexane or generally aliphatic or aromatic solvents.
The present invention also relates to the copolymers prepared by the novel
process,
particularly preferably a copolymer containing copolymerized vinylamine
building
blocks of the formula (I)
-CH2-CH(NR1R2)- (I)
where
Rl and R2, independently of one another, are each hydrogen, C1_2o-alkyl, C6_ig
aryl, C~_2o-alkaryl, C~_2o-aralkyl or a polyamine radical,
and, if required, different, polymerized vinyl comonomer building blocks of
the
formula (IV)
-CHZCR4R5- (IV)
where
R4 is hydrogen or C1~,-alkyl,
R5 is R6 or
-O-C(O)-R6,
_O_R6~
-C(O)-R6,
-C(O)-O-R6,
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-CN,
-halogen,
-(O-CH2-CHR~)n O-R6, where R~ is hydrogen or C1_4-alkyl and n has a
mean value of 1 to 100,
-C(O)-NHR6,
where R6 is hydrogen, C~_ZO-alkyl, C6_1g-aryl, C~_ZO-
alkaryl, C~_2o-aralkyl, which may be unsubstituted or substituted by
-ORB,
-NRBR9,
where RB and R9, independently of one another, are each hydrogen or C1~-
alkyl.
Here, Rl and R2 have the preferred meanings stated above. In the structure -O-
C(O)-R6, R6 has the preferred meanings stated above for R3.
In the building blocks of the formula (IV), R4 is preferably hydrogen or
methyl, in
particular methyl. RS is preferably R6 or -O-C(O)-R6. If RS is R6, R6 is
preferably
hydrogen, C1_12-alkyl, phenyl or C~_lo-alkaryl, particularly preferably
hydrogen,
methyl, ethyl or phenyl.
In addition to the polymerized vinylamine building blocks of the formula (I),
the
copolymer particularly preferably contains building blocks of the formula
(IVa)
-CH2-CR4(-O-C(O)-R6)- (IVa)
and/or of the formula (IVb)
-CH2-CHRS- (IVb)
where RS is hydrogen, C1_ZO-alkyl or C6_18-aryl.
In particular, the copolymers have the building blocks of the formulae (I),
(IVa)
and (IVb).
Such copolymers may also contain up to 20% by weight, based on the total
CA 02421439 2003-03-06
9
copolymer, of further building blocks; particularly preferably, they are
composed
essentially or only of the building blocks of the formulae (I), (IVa) and
(IVb).
Particularly preferably, they are ethylene/vinyl acetate/vinylamine
terpolymers.
The copolymers or terpolymers preferably have a number average molecular
weight of from 100 to 10,000,000, particularly preferably from 500 to 100,000.
The novel copolymers can be prepared by any desired suitable process.
Particularly
preferably, the preparation of the copolymers is carried out by free radical
copolymerization of vinyl esters of the formula (V)
H2C=CH(O-C(O)-R3) (V)
where R3 is hydrogen, C1_2o-alkyl, C6_lg-aryl, C~_ZO-alkaryl or C~_2o-aralkyl,
if required different vinyl comonomers of the formula (VI)
H2C=CR4R5 (VI)
where R4 and RS have the stated meanings, and, if required, further vinylic
comonomers to give a copolymer and subsequent reductive amination by the above
process.
The ethylene/vinyl acetate copolymers axe prepared, for example, by free
radical
polymerization by the high-pressure mass polymerization method, alternatively
in
stirred autoclaves, tubular reactors or segmented tubular reactors. Such
processes
are described, for example, in DE-A-197 54 039, DE-A-197 19 689 and M.
Ratzsch, Erdol and Kohle-Erdgas-Petrochemie in combination with Brennstoff
Cheniie, 42(4) 1989.
The novel copolymers can be used in a large number of applications. The use as
assistants in mineral oils, mineral oil distillates and combustion and power
fuels, in
chromatography, as ion exchangers, in dispersions, as emulsifiers, in
papermaking
(Wochenbl. Papierfabr. (1999) 127, 511 to 518), in membranes, in adhesives
(WO 00/01783), in the production of cellulose fibers (WO 99/36604), in
printing
inks and papers for these (EP-A-0 878 323, EP-A-0 911 374, WO 98/42787, for
the coating of fibers (US 6,077,794), as fixing compositions (US 6,039,768),
as
mold release agents, for wastewater treatment (WO 96/38493), in detergent
compositions, in particular as dye transfer inhibitors (US 5,863,879), for
CA 02421439 2003-03-06
1~
decolorizing paper mill wastewaters (US 5,476,594), for modifying metal
surfaces
(US 5,494,535), in films (US 5,492,765), in coating compositions and in other
applications is preferred.
Examples of specific applications are as follows:
(1) The copolymers are suitable for optimizing the retention and drainage and
for fixing anionic substances in papermaking (retention aids, drainage aids,
flocculants and fixing compositions). In addition, the polymers improve the
dry and wet paper strength (cf. also Wochenbl. Papierfabr. (1999), 127(8),
511-518).
(2) The copolymers are suitable for colorizing wastewaters from papermaking
or for removing dye from said wastewaters (according to US 5,476,594).
(3) In completely or partly protonated form, the polymers are suitable as
water-
soluble or water-swellable, cationic polyelectrolytes for aqueous adhesive
dispersions for the production of multilayer paper or paper materials
(according to DE 198 29 757).
(4) The copolymers are suitable for modifying cleaned or chemically pretreated
metal surfaces, which are then suitable in particular for electrodip coating
(according to EP 0 672 467).
(5) The copolymers are suitable as dye transfer inhibitors for detergents
(according to DE 441 3 720).
(6) The copolymers are suitable as a starting substance for the preparation of
polymers containing carbamate units. These polymers are suitable as
retention aids, drainage aids and flocculants and as fixing compositions in
the production of paper, as protective colloids for the preparation of
aqueous alkyldiketene dispersions and as dispersants for the preparation of
aqueous filler suspensions (according to WO 98/35999).
(7) The copolymers are suitable for the treatment and preparation of viscose
products with cationic polymers (according to WO 99/36604).
(8) The copolymers are suitable as water-soluble amine-based polymer
CA 02421439 2003-03-06
11
components in multilayer membranes for separating acidic gases from
gaseous mixtures (according to DE 196 00 954).
(9) The copolymers are suitable for the preparation of aqueous and organic
dispersions, emulsions or solutions of amine-based polymers. The amine-
based polymers, dispersions, emulsions or solutions are particularly
suitable for coating and imparting water repellency to surfaces (finish
surfaces, packaging coating, building material impregnation, particle
boards, stone, metal, textiles, plastics, leather, wood, paper), for the
treatment of various materials (stone, metal, textiles, plastics, leather,
wood, paper), as process chemicals in the textile industry, as additives in
printing inks and finishes, and as mold release agents.
(10) The copolymers are suitable as effective corrosion inhibitors in
radiation
protection mixtures.
The copolymers are particularly preferably used as flow improvers, wax-anti-
settling-additives and lubricity additives, for reducing fretting, as
corrosion
inhibitors and/or as internal combustion engine intake system cleaners in
mineral
oils, mineral oil distillates and combustion and power fuels.
When used as flow improvers, the novel copolymers are preferably employed in
combustion and power fuel compositions, in particular in middle distillates,
such as
diesel fuels and light heating oils. They can be used together with further
conventional additives.
The novel copolymers can be incorporated into the mineral oils, mineral oil
distillates and combustion and power fuels, in particular into a middle
distillate,
directly but preferably as 20 to 70% strength by weight solutions. Preferably
used
solvents are hydrocarbon solvents. Suitable solvents are described, for
example, in
DE-A-196 24 861 and DE-A-43 41 528. The novel copolymers may be dissolved
in a large amount in a hydrocarbon solvent; preferably, the solutions contain
from
to 80, particularly preferably from 20 to 70, particularly from 40 to 60, % by
weight of one or more novel copolymers alone or together with other
assistants, for
example according to the abovementioned applications. The present invention
also
relates to such concentrates or mixtures.
The concentrates may be further used, for example, for the preparation of
CA 02421439 2003-03-06
12
combustion and power fuel compositions (cf. DE-A-196 24 861 ).
The present invention also relates to combustion and power fuel compositions
which contain from 5 to 5000, preferably from 10 to 500, ppm by weight, based
on
the total weight of the composition, of the copolymer, alone or together with
other
assistants.
The Examples which follow illustrate the invention.
Examples
Preparation of the amination catalyst:
An aqueous solution of nickel nitrate, cobalt nitrate and zirconium acetate,
which
contained 4.48% of NiO, 1.52% of Cu0 and 2.82% of ZrOz, was precipitated
simultaneously in a stirred vessel in a constant stream with a 20% strength
aqueous
sodium carbonate solution at 70°C so that the pH of 7.0, measured using
a glass
electrode, was maintained.
The suspension obtained was filtered and the filter cake was washed with
demineralized water until the electrical conductivity of the filtrate was
about
20 mS. 1.5% of Mo03 in the form of an aqueous solution of ammonium
heptamolybdate were then stirred in. The filter cake was then dried at
150°C in a
drying oven or in a spray dryer. 'The basic carbonate mixture obtained in this
manner was heated at 500°C over a period of 4 hours.
The catalyst thus obtained had the following composition:
51 % by weight of NiO, 17% by weight of CuO, 30.5% by weight of Zr02 and
1.5% by weight of Mo03. The catalyst powder was mixed with 3% by weight of
graphite and molded to give 6 x 3 mm pellets.
Preparation of an ethylene/vinyl acetate/vinylamine terpolymer:
First, an ethylene/vinyl acetate copolymer which was composed of 70.3% by
weight of ethylene and 29.7% by weight of vinyl acetate was prepared. The melt
viscosity at 120°C was 65 mm2/s. The preparation was carried out as
described in
DE-A-197 54 039.
CA 02421439 2003-03-06
13
75 g of this copolymer were mixed with 75 g of cyclohexane as a solvent, and
850
g of liquid ammonia were added in an autoclave. They were then heated at
200°C
for 16 hours at a hydrogen pressure of 200 bar in the presence of 50 g of the
catalyst described above. Thereafter, cooling was carried out, the pressure
was let
down and the autoclave content was removed. After the catalyst had been
filtered
off and the cyclohexane separated off, 80 g of a liquid, colorless product
were
obtained.
The content of ethylene, vinyl acetate and vinylamine was determined by NMR
spectroscopy. The terpolymer contained 75.6% by weight of ethylene, 14.7% by
weight of vinyl acetate and 9.7% by weight of vinylamine. The kinematic melt
viscosity, determined using a rotational viscometer at 120°C, was 70
mm2/s.
Test oils
The novel terpolymer described above was used as an additive in various test
oils.
The test oils had the following characteristic data.
Table l:
Test Test Test Test Test
oil oil oil oil oil
1 2 3 4 5
Initial boiling point173 182 168 195 178
[C]
5% [C] 206 223 186 222 194
10% [C] 219 236 192 233 200
50% [C] 285 287 233 275 243
95% [C] 369 354 353 343 343
Final boiling point 380 365 367 354 355
[C]
90% - 20% [C] 115 87 127 80 115
FPB-90% [C] 27 25 39 27 30
Cloud point [C] 2.8 2 -6.4 -8.9 -7.7
CFPP [C] 0 0 -9 -12 -9
Sulfur [ m 2000 1800 450 310 45
The novel terpolymers were introduced into the test oils, and the cold filter
plugging point (CFPP) was determined according to EN 116. In addition, the
cloud
point (CP) was determined according to ISO 3015. The CFPP is shown in Table 2
below.
CA,02421439 2003-03-06
14
Table 2
Test oil Dose/ m CFPP [C]
1 100 -7
2 250 -2
3 50 -11
3 125 -18
4 25 -15
Lubricating effect:
The lubricating effect of the ethylene/vinyl acetate/vinylamine terpolymer
(II)
described was determined in test oil 5 according to DIN ISO 121546-1 (HFRR
measurement). The results in Table 3 are specified as a wear scar diameter (WS
1.4). A lower wear scar indicates a good lubricating effect. A commercial
lubricity
additive Kerokorr~ LA 99 (K) was used in comparison with the novel
ethylene/vinyl acetate/vinylamine terpolymer (T).
Table 3
Additive Dose/ppm Wear scar diameter
/gym
No additive -- 590
T 50 483
T 75 304
K 50 516
K 75 421
K 100 333
Paraffin sedimentation:
The effect on the paraffin sedimentation (wax-anti-settling) in test oil 3 was
determined by an ARAL method (cf. Table 4). 500 ml of the diesel fuel were
stored at -13°C for 16 hours. The additives tested were the
ethylene/vinyl acetate
copolymer (C) described and the novel vinyl acetate/vinylamine terpolymer (T).
The quality of the effect on the paraffin sedimentation (wax-anti-settling) is
determined by visual assessment:
CA 02421439 2003-03-06
~ Case (A): the sample is uniformly turbid and the paraffins are completely
dispersed.
Case (B): the sample consists of two phases having different turbidities:
~ Case (C): the sample consists of two phase, the lower phase being turbid and
the upper phase being clear.
Substances which lead to the results of case (A) and case (B) in the test are
efficient wax-anti-settling additives. In addition, the cloud point (CP) and
the
CFPP are determined for the lower 20%. A positive effect on the low-
temperature
behavior of the test oil is present when the cloud point of the 20% lower
phase is
slightly (1 - 2°C) above the cloud point before the storage test at -
13°C.
Table 4
Test oil 3
without
additive
CP: -6.4C
CFPP: -9C Visual
assessment 20% lower phase
CFPP/C Lower hase U er CP/C CFPP/C
hase
60 ppm of additive-20 42% 58% -0.0 -17
(C)
paraffms clear
settled out hase
60 ppm of additive-27 28% 72% -5.3 -27
(C)
paraffms turbid
75 ppm of additive settled out due
(T) to
dispersed
araffins
Table 4 shows that the ethylene/vinyl acetate copolymer used for the
preparation of
the ethylene/vinyl acetate/vinylamine terpolymer has no effect on the paraffin
sedimentation. A positive effect on the paraffin sedimentation is achieved by
adding the ethylene/vinyl acetate/vinylamine terpolymer to the ethylene/vinyl
acetate copolymer.
