Note: Descriptions are shown in the official language in which they were submitted.
~ BASF Aktiengesellschaft 950193 O.Z. 0050/45722
Copolymers of unsaturated dicarboxylic acids or anhydrides
thereof and vinyl-terminated oligoolefins and reaction products
thereof with nucleophilic agents
The present invention relates to novel copolymers which carry
functional groups and are obtained from unsaturated dicarboxylic
acids or anhydrides thereof and vinyl-terminated oligoolefins, a
process for the preparation of these copolymers and reaction
10 products thereof with nucleophilic agents. The present invention
furthermore relates to various uses of such reaction products.
The published German Patent Application P 43 30 971.2 (1)
discloses terpolymers which contain functional groups and are
15 obtained from
- 20-60 mol% of monoethylenically unsaturated C4-C6-dicarboxylic
acids or anhydrides thereof,
20 - 10-70 mol% of oligomers of propene or of branched l-olefins
of 4 to 10 carbon atoms having an average molecular weight of
from 300 to 5000 and
- 1-50 mol% of copolymerizable monoethylenically unsaturated
compounds.
oil-soluble reaction products of these terpolymers with amines
are suitable as fuel additives and lubricant additives.
30 W0-A 90/03359 (2) describes polymers which can be used as
additives in lubricating oils and in some cases have dispersant
properties for sludge and solid particles contained therein. Some
of these polymers are also viscosity index improvers, ie. they
ensure that, when the temperature increases, the viscosity of
35 lubricating oil decreases to a substantially lesser extent than
in a lubricating oil without such an additive.
The polymers disclosed in (2) are composed of maleic acid or
fumaric acid or derivatives thereof and an olefin whose molecular
40 weight is sufficiently high for the polymer prepared from these
monomers to be oil-soluble, and are reacted with amines. This
olefin must carry at least 20% of alkylvinylidene groups.
The polymers disclosed in publication (2) do not have
45 satisfactory properties for all applications, in particular the
viscosity/temperature behavior of lubricating oils which contain
these polymers as additives is still unsatisfactory in many
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cases. Furthermore, the dispersant action of these compounds in
industrial use is not satisfactory in all cases.
It is an object of the present invention to provide lubricating
5 oil additives which no longer have the disadvantages of the prior
art.
We have found that this object is achieved by copolymers I which
carry functional groups and consist of:
(a) from 30 to 70 mol% of at least one monoethylenically
unsaturated C4-Cl2-dicarboxylic acid or the anhydride thereof
and
15 (b) from 30 to 70 mol% of at least one oligomer of a 1-olefin of
3 to 14 carbon atoms, at least 85% of which is present as an
isomer having a terminal vinyl group of the formula -CH=CH2
and which has an average molecular weight of from 300 to
10, 000.
The novel copolymers I contain no further comonomers apart from
(a) and (b).
The novel copolymers I are used as intermediates for the
25 preparation of a very wide range of industrial compositions
having in some cases outstanding performance characteristics, as
described below.
Preferred monomers (a) are monoethylenically unsaturated
30 C4-C6-dicarboxylic acids or anhydrides thereof, eg. maleic acid,
fumaric acid, itaconic acid, mesaconic acid, methylenemalonic
acid, citraconic acid, maleic anhydride, itaconic anhydride,
citraconic anhydride and methylenemalonic anhydride and mixtures
thereof with one another. Maleic anhydride is preferred.
Suitable monomers (b) are oligomers of propene or of a linear
1-olefin of 4 to 14 carbon atoms. These oligomers are as a rule
composed of at least 3 olefin molecules. They contain at least
85%, in particular at least 90%, of vinyl-terminated isomer.
40 Vinyl-terminated oligoolefins are more reactive than the
corresponding vinylidene-terminated macromers. In the free
radical copolymerization, it is therefore possible to achieve
higher degrees of polymerization and consequently higher
molecular weights, which has an advantageous effect on the
45 performance characteristics of the end products. Their average
molecular weight is from 300 to 10,000, in particular from 500 to
5000. Examples are oligomers of propene, of n-butene, of
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n-pentene, of n-hexene and of n-decene, at least 85% of the
copolymerizable terminal groups of the oligomer being present in
the form of a vinyl group. Oligopropenes and oligopropene
mixtures of 9 to 400, in particular of 12 to 300, carbon atoms
5 are preferred. Such vinyl-terminated oligoolefins are obtainable,
for example, according to EP-A 268 214 (Example 2), by means of a
metallocene catalyst of the bis-pentamethylcyclopentadienyl-
zirconium dichloride type.
10 The copolymers I contain the monomers (a) in amounts of from 30
to 70, preferably from 40 to 60, mol% and the monomers (b) in
amounts of from 30 to 70, preferably from 40 to 60, mol%.
Copolymers I which carry functional groups and in which the
15 component (a) is maleic anhydride and the component (b) is an
oligopropene or an oligopropene mixture, each of 9 to 400 carbon
atoms, are particularly preferred.
The present invention also relates to a process for the
20 preparation of copolymers I which carry functional groups, which
comprises subjecting
(a) from 30 to 70 mol% of at least one monoethylenically
unsaturated C4-C12-dicarboxylic acid or the anhydride thereof
to free radical polymerization with
(b) from 30 to 70 mol% of at least one oligomer of a 1-olefin of
3 to 14 carbon atoms, at least 85% of which is present as an
isomer having a terminal vinyl group of the formula -CH=CH2
and which has an average molecular weight of from 300 to
10, 000.
The copolymers I can be prepared by all known conventional
polymerization methods, for example by mass, emulsion,
35 suspension, precipitation and solution polymerization. All stated
polymerization processes are usually carried out in the absence
of oxygen, preferably in a nitrogen stream.
The conventional apparatuses, for example autoclaves and kettles,
40 are used for all polymerization methods. The mass polymerization
of the monomers (a) and (b) is particularly preferred. It can be
carried out at from 60 to 300 C, preferably from 80 to 200 C, the
lowest polymerization temperature to be chosen preferably being
about 20 C above the glass transition temperature of the polymer
45 formed. The polymerization conditions are chosen according to the
desired molecular weight of the copolymers. Polymerizations at
high temperatures usually give copolymers having low molecular
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weights, whereas polymers having higher molecular weights are
usually formed at lower polymerization temperatures.
The copolymerization is preferably carried out in the presence of
5 compounds which form free radicals. Up to 10, preferably 0.2 to
5, % by weight, based on the monomers used in the
copolymerization, of these compounds are required. Examples of
suitable polymerization initiators are peroxide compounds, such
as tert-butyl perpivalate, tert-butyl perneodecanoate, tert-butyl
10 perethylhexanoate, tert-butyl perisobutyrate, di-tert-butyl
peroxide, di-tert-amyl peroxide, diacetyl peroxodicarbonate and
dicyclohexyl peroxodicarbonate, and azo compounds, eg.
2,2'-azobisisobutyronitrile. These initiators may be used alone
or as a mixture with one another. In the mass polymerization,
15 they are preferably introduced separately or in the form of a
solution into the polymerization reactor. The monomers (a) and
(b) can be copolymerized at above 200 C also in the absence of
polymerization initiators.
20 In order to prepare low molecular weight polymers, it is often
advantageous to carry out the copolymerization in the presence of
regulators. Conventional regulators, such as C1-C4-aldehydes,
formic acid or organic SH-containing compounds, such as
2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid,
25 tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan or
tert-dodecyl mercaptan, may be used for this purpose. The
polymerization regulators are generally used in amounts of from
0.1 to 10% by weight, based on the monomers.
30 In order to prepare higher molecular weight copolymers, it is
often advantageous to carry out the polymerization in the
presence of chain extenders. Such chain extenders are compounds
having diethylenically or polyethylenically unsaturated groups,
such as divinylbenzene, pentaerythrityl triallyl ether or esters
35 of glycols, such as glycol diacrylate, glyceryl triacrylate or
polyethylene glycol diacrylates. They may be added in the
polymerization in amounts of up to 5% by weight.
The copolymerization can be carried out continuously or
40 batchwise. The molecular weight of the copolymers I are as a rule
from 1000 to 100,000, in particular from 5000 to 50,000.
The copolymers I can be reacted with nucleophilic agents, ie.
with compounds cont~in;ng NH, OH or SH functional groups, and can
45 thus be derivatized for various fields of use. Accordingly, the
present invention also relates to such reaction products II.
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Thus, the reaction of the copolymers I with an aqueous alkali
metal or alkaline earth metal hydroxide, for example with aqueous
potassium or sodium hydroxide solution, gives stable aqueous
dispersions (reaction products IIa) which are suitable as
5 dispersants for detergent and cleaning agent formulations and as
water repellents for leather and skin. The present invention also
relates to aqueous detergent and cleaning agent formulations
which contain the reaction products IIa as dispersants in
conventional amounts.
The reaction of the copolymers I with saturated or unsaturated
aliphatic alcohols of 8 to 30, in particular 10 to 22, carbon
atoms, ie. fatty alcohols, such as stearyl alcohol or behenyl
alcohol, gives oil-soluble reaction products IIb, which are
15 suitable as flow improvers and paraffin dispersants for crude
oils and refined mineral oil fractions. The present invention
also relates to crude oils and refined mineral oil fractions
which contain the oil-soluble reaction products IIb as flow
improvers and paraffin dispersants in conventional amounts.
The reaction of the copolymers I with primary, secondary or
tertiary mono- or polyamines or mixtures thereof which carry at
least one C6-C30-alkyl, in particular C8-C22-alkyl, or alkenyl
radical, ie. fatty amines, such as tridecylamine, gives reaction
25 products IIc which are suitable as corrosion inhibitors for metal
substrates.
The reaction of the copolymers I with amines of the formula
NHR1R2, where R1 and R2 may be identical or different and may each
30 be hydrogen, an aliphatic or aromatic hydrocarbon radical, a
primary or secondary, aromatic or aliphatic aminoalkylene
radical, a polyaminoalkylene radical, hydroxyalkylene radical or
a polyoxyalkylene radical, which may carry terminal amino groups,
or may each be a hetaryl or heterocyclyl radical which may carry
35 terminal amino groups, or, together with the nitrogen atom to
which they are bonded, form a ring in which further heteroatoms
may also be present, gives reaction products IId which are
suitable as additives for lubricants and fuels.
40 Examples of suitable amine components HNRlR2 are:
- ammonia;
- aliphatic and aromatic, primary and secondary amines of 1 to
50 carbon atoms, such as methylamine, ethylamine,
propylamine, di-n-butylamine or cyclohexylamine;
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- amines in which Rl and R2, together with the nitrogen atom to
which they are bonded, form a common ring which may also
contain further heteroatoms, such as morpholine, pyridine,
piperidine, pyrrole, pyrimidine, pyrroline, pyrrolidine,
S pyrazine or pyridazine;
- amines which carry hydroxyalkylene and polyoxyalkylene
radicals and in which Rl and/or R2 are a radical
--E R3 O ~ H III
where R3 is a C2-C10-alkylene and m is an integer from 1 to
30, such as ethanolamine, 2-aminopropan-1-ol or
neopentanolamine;
- polyoxyalkyleneamines which carry terminal amino groups and
in which Rl and/or R2 are a radical
- R4 o ~ R3 - ~ 3 R5 NR6R7 IV
m
where R3~ R4 and R5 are each C2-C10-alkylene, m has the
abovementioned meanings and R6 and R7 are each hydrogen,
unsubstituted or hydroxyl- or amino-substituted C1-C10-alkyl
or C6-C10-aryl, such as polyoxypropylenediamines or
bis(3-aminopropyl)tetrahydrofurans.
However, preferred amine components are polyamines in which
and/or R2 are a radical of the formula V
R3 - N 3 R7 V
~ n
R6
40 where R3, R6 and R7 have the abovementioned meanings and n is an
integer from 1 to 6. Particularly suitable polyamines are
ethylenediamine, propylenediamine, dimethylaminopropylamine,
diethylenetriamine, dipropylenetriamine, triethylenetetramine,
tripropylenetetramine, tetraethylenepentamine,
45 ethylaminoethylamine, dimethylaminoethylamine, isopropylamino-
propylamine, ethylenedipropylenetetramine,
2-diisopropylaminoethylamine, aminoethylethanolamine,
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ethylenepropylenetriamine,
N,N,N',N'-tetra(3-aminopropyl)ethylenediamine,
2-(3-aminopropyl)cyclohexylamine, 2,5-dimethylhexane-2,5-diamine
and N,N,N',N'',N''-penta-(3-aminopropyl)dipropylenetriamine.
5 Other preferred polyamines are those which contain a heterocyclic
structure as a structural component, eg. aminoethylpiperazine.
Mixtures of different amines may also be used as the amine
component.
The novel reaction products IId are obtained in a manner known
per se, by reacting copolymers I with the stated amines. The
molar ratio of the components depends on the number of acid or
anhydride groups in the copolymer I. This can be determined in a
15 known manner, for example by titration with a strong base. In
general, from 0.1 to 3 equivalents of acid or anhydride groups in
the polymer are used per mol of amine. As a rule, the starting
materials are mixed for the reaction and are heated to 30-200 C.
The reaction is preferably carried out under an inert gas
20 atmosphere. The reaction can be effected in the presence or
absence of solvents. Examples of inert solvents are aliphatic and
aromatic hydrocarbons, such as toluene and xylene, as well as
mineral oils. The progress of the reaction can be monitored by IR
spectroscopy.
The present application also relates to lubricants and fuels
which contain the oil-soluble reaction products IId in the
amounts stated below.
30 The lubricants are additive-containing synthetic, semisynthetic
and mineral oils, preferably those which are used as engine oils.
The synthetic oils comprise synthetic esters and polymers of
~-olefins. The reaction products IId are added to the lubricants
in general as a concentrate in an inert solvent, such as a
35 mineral oil. These concentrates may contain further conventional
additives, such as corrosion inhibitors, antiabrasion agents,
detergents, antioxidants and pour point improvers.
The reaction products IId are added to the lubricants in amounts
40 of from 1 to 15, preferably from 0.5 to 10, % by weight.
In fuels, such as gasoline or diesel fuel, the reaction products
IId are used as detergents for keeping the intake system clean.
Owing to their dispersant properties, they also have an
45 advantageous effect on engine lubricants, which they may enter
during operation of the engine. From 20 to 5000 ppm, preferably
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from 50 to 1000 ppm, based on the fuel, are added for this
purpose.
The novel oil-soluble reaction products IId generally have
5 excellent viscosity/temperature behavior in virtually all
lubricants. They also exhibit an excellent dispersant effect in
virtually all cases. The superior performance characteristics of
the reaction products IId are illustrated in the Examples below.
lO Example
1. Preparation of the vinyl-terminated oligopropenes (b)
General preparation method:
30 ml of a 1.5 molar solution of methylalumoxane in toluene were
initially taken in a stirred 2 l autoclave, and 900 ml (13.3 mol)
of a liquid propene were condensed and heated to the temperature
stated in Table 1. The resulting pressure was 20 bar. Thereafter,
20 64.3 mg (0.17 mmol) of bis-pentamethylcyclopentadienylzirconium
dichloride, dissolved in 7 ml of a 1.5 molar solution of
methylalumoxane in toluene, were added and oligomerization was
carried out for the time stated in Table 1. The aluminum/
zirconium atomic ratio was 250:1. A yield of 590 ml of oligomer
25 mixture was obtained. The average molecular weights were
determined by means of gel permeation chromatography and using
polystyrene standards having a narrow molecular weight
distribution.
30 Table 1: Data for the oligopropenes (b) used
Oligo- Oligomerization Oligomerization Average Vinyl
propene temperature [~C] time [min] molecular content
weight [%]
bl 50 60 750 92
b2 35 120 900 93
b3 20 180 1400 93
2. Preparation of the copolymers I
Example 2.1
45 200 g of the oligomer bl were heated to 100 C in a gentle stream
of nitrogen in a reactor, and 32.7 g of maleic anhydride (in
liquid form as a melt at about 75 C) were metered in over 4 hours.
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At the same time, a solution of 3.5 g of tert-butyl peroctoate,
dissolved in 10 g of toluene, was metered in over 4 hours.
Thereafter, the mixture was heated to 150 C and a solution of
2.3 g of di-tert-butyl peroxide in 10 g of toluene was metered in
5 over 1 hour and, after the end of the reaction, polymerization
was continued for a further 0.5 hour at this temperature. The
copolymer thus obtained had a molecular weight of 12,000.
Example 2.2
95 g of the oligomer b2 were heated to 150 C in a gentle stream of
nitrogen in a reactor, and 10.3 g of maleic anhydride (in liquid
form as a melt at about 75 C) were metered in over 4 hours. At the
same time, a solution of 2.1 g of di-tert-butyl peroxide,
15 dissolved in 5 g of toluene, was metered in over 4.5 hours.
Polymerization was then continued for a further hour at this
temperature. The copolymer thus obtained had a molecular weight
of 48,000.
20 Example 2.3
201.5 g of the oligomer b3 were heated to 150 C in a gentle stream
of nitrogen in a reactor, and 7.3 g of maleic anhydride tin
liquid form as a melt at about 75 C) were metered in over 4 hours.
25 At the same time, a solution of 3.1 g of di-tert-butyl peroxide,
dissolved in 10 g of toluene, was metered in over 4.5 hours.
Polymerization was then continued for a further hour at this
temperature. The copolymer thus obtained had a molecular weight
of 15,600.
The molecular weights of the copolymers from Examples 2.1, 2.2
and 2.3 were determined with the aid of high pressure gel
permeation chromatography. The eluent used was tetrahydrofuran.
Calibration was effected with polystyrene fractions having a
35 narrow molecular weight distribution.
3. Preparation of the oil-soluble reaction products IId
General preparation method:
A copolymer according to Examples 2.1 to 2.3 in xylene was
initially taken at 70 C, an amine or polyamine was added and
refluxing was carried out until the expected amount of water of
reaction had separated off. After removal of the solvent, the
45 product was obtained in the form of a pale yellow to amber,
viscous residue. The IR absorption bands of the products were at
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about 1770 and about 1700 cm-l. The reactions carried out are
shown in Table 2 below:
Table 2
Example Polymer Amine component Molar ratio
according to anhydride/amine
example
lO 3.1 2.1 Triethylenetetramine 1:1
3.2 2.1 Triethylenetetramine 1.85:1 -
3.3 2.1 N-Aminoethylpiperazine 1.5:1
3.4 2.1 N-Aminoethylpiperazine 2:1
3.5 2.2 Triethylenetetramine 1:1
3.6 2.2 N-Aminoethylpiperazine 1.5:1
3.7 2.2 Polyoxypropylenediamine 2:1
(molecular weight about
400)
3.8 2.3 Triethylenetetramine 1:1
3.9 2.3 Triethylenetetramine 2:1
25 4. Preparation of the comparative products
Comparative additive Vl
Reaction product of the copolymer according to Example 6 of
30 WO-A-90/03359 (2) and triethylenetetramine
The stated starting materials were reacted similarly to the above
Examples 3, in a molar ratio of 1:1.
Comparative additive V2
Reaction product of the copolymer according to Example 6 of (2)
and triethylenetetramine
40 The stated starting materials were reacted similarly to the above
Examples 3, in a molar ratio of 2:1.
5. Testing of the viscosity/temperature behavior
45 The additives were tested in a concentration of 6% by weight in a
5W-30 engine oil. The results are listed in Table 3.
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Table 3
Additive Viscosity at Viscosity at -25 C Solubility
according to 100 C [mm2s~l] [mPas] CCS
Exampleaccording to
Ubbelohde
no additive 7.55 1900
3.1 10.89 2950 clear
solution
3.2 10.23 3100 clear
solution
3.5 13.33 3200 slightly
cloudy
solution
3.8 12.42 3300 clear
solution
3.9 14.40 3400 clear
solution
Vl 9.00 3100 cloudy
solution
V2 9.19 3200 cloudy
solution
25 The novel additives ~3.1, 3.2, 3.5, 3.8 and 3.9) are clearly
superior to those of the prior art (Vl and V2) owing to their
greater viscosity-enhancing effect at high t~mrerature. The
low-temperature viscosity of the oils to which additives had been
added according to the invention is in the range of the prior
30 art.
6. Testing of the dispersant effect
The dispersant effect was tested by means of a ~pot test as
35 described in Les Huiles pour Moteurs et la Graissage des Moteurs,
A.Schilling, Vol. 1, page 89 et seq., 1962. For this purpose, 3%
strength by weight mixtures of the additives in a diesel oil were
prepared. The dispersions thus obtained were developed on a
filter paper in the same way as a chromatogram. The evaluation
40 scale extended from 0 to 1000: the higher the value obtained, the
better the dispersant effect of the additive. The results are
listed in Table 4.
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Table 4
Additive 10 min at 10 min at RT 10 min at 10 min at
according to RT without 1% of water 250 C 250 C with
5 Example water without water
water
3.2 651 624 658 638
3.5 671 670 652 676
10 3.8 659 675 688 671
3.9 679 694 706 718
V1 583 593 511 603
15 V2 S70 686 605 558
RT= room temperature
The novel additives (3.2, 3.5, 3.8 and 3.9) have a significantly
better dispersant effect than the prior art additives (V1 and V2)
20 in virtually all cases.
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