U.S. patent number 3,621,004 [Application Number 04/870,777] was granted by the patent office on 1971-11-16 for copolymer of an alkene, an alkyl ester of an unsaturated carboxylic acid and a hydroxyalkyl ester of an unsaturated carboxylic acid.
This patent grant is currently assigned to Shell Oil Company, New York, NY. Invention is credited to Rudolf J. A. Eckert.
United States Patent |
3,621,004 |
|
November 16, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
COPOLYMER OF AN ALKENE, AN ALKYL ESTER OF AN UNSATURATED CARBOXYLIC
ACID AND A HYDROXYALKYL ESTER OF AN UNSATURATED CARBOXYLIC ACID
Abstract
Lubricating oil compositions containing a copolymer of (1)
ethylene, (2) an alkyl ester of an unsaturated monocarboxylic acid
and (3) a hydroxyalkyl ester of an unsaturated carboxylic acid
exhibit excellent properties relative to thermal stability,
viscosity index improvement and dispersant activity. 4 Claims, No
Drawings
Inventors: |
Rudolf J. A. Eckert (Amsterdam,
NL) |
Assignee: |
Shell Oil Company, New York, NY
(N/A)
|
Family
ID: |
26252536 |
Appl.
No.: |
04/870,777 |
Filed: |
September 15, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Apr 14, 1967 [GB3] |
|
|
17,198/67 |
|
Current U.S.
Class: |
526/320;
526/318.44; 526/318.45; 508/472; 526/933 |
Current CPC
Class: |
C08F
210/00 (20130101); C08F 4/28 (20130101); C08F
10/00 (20130101); C08L 33/06 (20130101); C10M
145/14 (20130101); C08F 10/00 (20130101); C08F
8/14 (20130101); C08F 8/14 (20130101); C10M
2209/086 (20130101); C10N 2020/01 (20200501); C10M
2209/084 (20130101); C10M 2207/40 (20130101); C10N
2050/10 (20130101); C10M 2207/404 (20130101); C10N
2070/02 (20200501); C10M 2209/109 (20130101); C10N
2050/02 (20130101); Y10S 526/933 (20130101) |
Current International
Class: |
C10M
145/00 (20060101); C10M 145/14 (20060101); C08F
10/00 (20060101); C08F 8/14 (20060101); C08F
8/00 (20060101); C08L 33/00 (20060101); C08L
33/06 (20060101); C08f 015/40 () |
Field of
Search: |
;260/80.75,80.8,78.5HC |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Joseph L. Schofer
Assistant Examiner: Stanford M. Levin
Attorney, Agent or Firm: Marion W. Western Harold L.
Denkler
Parent Case Text
This is a divisional application of Ser. No 721,092, filed Apr. 12,
1968, and now Pat. No. 3,518,197.
Claims
1. An oil-soluble copolymer of ethylene with one or more
C.sub.8.sub.-20 alkyl methacrylates and .beta.-hydroxyethyl
methacrylate, said copolymer having an average molecular weight
between 5,000 and 150,000 and in which the molecular ratios of
monomers in the copolymer are 11- 300 moles ethylene to 10 moles
C.sub.8.sub.-20 alkyl methacrylates to 1- 15 moles
2. The copolymer of claim 1 in which the copolymer is a copolymer
of ethylene, a member selected from the group consisting of lauryl
methacrylate and stearyl methacrylate and mixtures thereof, and
3. The copolymer of claim 1 in which the copolymer is a copolymer
of
4. The copolymer of claim 1 in which the copolymer is a copolymer
of ethylene, lauryl methacrylate, stearyl methacrylate and
.beta.-hydroxyethyl methacrylate.
Description
This invention relates to novel lubricant compositions containing
polymeric compounds which have dispersant properties and
viscosity-improving characteristics. This invention further relates
to novel polymeric compounds which are suitable for use as
lubricant additives.
In the past a number of polymeric compounds have been proposed
which proved capable of imparting dispersant properties to a
lubricating oil in addition to improving the viscosity of the
lubricating oil. A drawback of most of these compounds is that they
possess a low thermal stability. If the lubricant in which they
have been incorporated is exposed to high temperature, they are
decomposed, whereby their favorable reaction is greatly reduced or
disappears entirely. In those cases where the lubricants are
exposed to high temperature, for example as lubricating oils in
combustion engines, it is desirable that the additives incorporated
in the lubricants possess a sufficiently high thermal stability, so
that their favorable action is retained at high temperature.
A class of polymeric compounds has now been found which impart
dispersant properties to a lubricating oil, improve the viscosity
characteristics of the lubricating oil and in addition possess a
very high thermal stability. These novel polymeric compounds are
those which have been obtained by copolymerization of one or more
olefins containing from two to six carbon atoms per molecule with
one or more alkyl esters of unsaturated carboxylic acids and one or
more esters of unsaturated carboxylic acids containing at least one
free hydroxyl group located in the part of the molecule derived
from the alcohol.
The invention therefore relates to novel lubricant compositions
containing one or more lubricants and polymeric compounds which
have been obtained by copolymerization of one or more olefins
containing two carbon atoms per molecule with one or more alkyl
esters of unsaturated carboxylic acids and with one or more esters
of unsaturated carboxylic acids containing at least one free
hydroxyl group located in the part of the molecule derived from the
alcohol.
By an appropriate choice of the molar ratio of the olefins to the
esters of the unsaturated carboxylic acids in the mixture to be
polymerized and by the use of alkyl esters with a suitable
alkyl-chain length one may obtain thermally stable copolymers which
are not only active as dispersants and VI improvers and/or
thickeners but are also capable of depressing the pour point of the
lubricating oils into which they have been incorporated.
The preparation of the present polymers may be accomplished in two
manners. The polymers may be prepared directly by copolymerization
of a monomer mixture consisting of one or more olefins with two to
six carbon atoms per molecule, one or more alkyl esters of
unsaturated carboxylic acids and one or more esters of unsaturated
carboxylic acids which contain at least one free hydroxyl group
located in the part of the molecule derived from the alcohol.
However, the polymers are preferably prepared by an indirect route
comprising copolymerization of a monomer mixture consisting of one
or more olefins having two to six carbon atoms per molecule, one or
more unsaturated carboxylic acids and one or more alkyl esters of
unsaturated carboxylic acids, followed by after-treatment of the
acid copolymers so obtained in which the carboxyl groups are
converted into --COOR groups, in which R represents a monovalent
alkyl radical containing at least one free hydroxyl group.
The olefins suitable for use as monomers in the preparation of the
present copolymers may be either monoolefins or diolefins. Mixtures
of olefins may also be used. Examples of suitable monoolefins are
ethylene, propylene, butene and pentene. Examples of suitable
diolefins are, among others, butadiene, isoprene and
dimethylbutadiene. Copolymers prepared with the aid of ethylene are
preferred. Copolymers which have been prepared by copolymerization
with diolefins may be used for the preparation of lubricant
compositions as such or may be hydrogenated, thereby saturating at
least part of the olefinically unsaturated bonds with hydrogen.
The alkyl esters of unsaturated carboxylic acids suitable for use
as monomers in the preparation of the present copolymers may be
either alkyl esters of unsaturated monobasic carboxylic acids of
alkyl esters of unsaturated polybasic carboxylic acids. Mixtures of
esters of unsaturated carboxylic acids can be used as well.
Examples of suitable alkyl esters of unsaturated monobasic
carboxylic acids which may be mentioned are methyl methacrylate,
isobutyl acrylate, lauryl methacrylate and stearyl methacrylate.
Some examples of suitable alkyl esters of unsaturated polybasic
carboxylic acids are diethyl maleate, dioctyl fumarate and
di(2-ethylhexyl)itaconate. Preference is given to polymers prepared
with the aid of alkyl esters of monobasic carboxylic acids wherein
the alkyl group contains eight or more carbon atoms, in particular
lauryl methacrylate or a mixture of lauryl and stearyl
methacrylate.
The esters of unsaturated carboxylic acids, wherein the part of the
molecule derived from the alcohol contains at least one free
hydroxyl group may be esters of both monobasic carboxylic acids and
polybasic carboxylic acids. Mixtures of these esters are useful
also. Examples of such esters are partial esters of polyvalent
alcohols, such as glycol, glycerol, trimethylolpropane,
pentaerythritol and p-dimethylolbenzene, with monobasic carboxylic
acids, such as acrylic acid and methacrylic acid, or with polybasic
carboxylic acids, such as maleic acid, fumaric acid and itaconic
acid, in which partial esters part of the hydroxyl groups
originally present in the polyvalent alcohols remains as such.
Other examples of such esters are products of the reaction of
cyclic ethers wherein the ring contains an oxygen atom and two or
three carbon atoms, such as ethylene oxide and trimethylene oxide,
with unsaturated monobasic carboxylic acids, such as acrylic acid
and methacrylic acid, or with unsaturated polybasic carboxylic
acids, such as maleic acid, fumaric acid and itaconic acid, in
which reaction products the part of the molecule derived from the
cyclic ether contains a free hydroxyl group. Preference is given to
copolymers which have been derived from one or more hydroxyalkyl
esters of unsaturated monocarboxylic acids, in particular from
.beta.-hydroxyethyl methacrylate.
If the preparation of the present copolymers takes place along the
indirect route by copolymerization of a monomer mixture consisting
of one or more olefins having two to six carbon atoms per molecule,
one or more unsaturated carboxylic acids and one or more alkyl
esters of unsaturated carboxylic acids followed by aftertreatment
of the copolymers so obtained, the unsaturated carboxylic acids may
be either monobasic or polybasic carboxylic acids. Mixtures of
unsaturated carboxylic acids may also be used. Examples of suitable
unsaturated monobasic carboxylic acids are acrylic acid and
methacrylic acid. Examples of appropriate unsaturated polybasic
carboxylic acids are fumaric acid, maleic acid and itaconic acid.
Preferred copolymers are those prepared by the indirect route using
one or more unsaturated monocarboxylic acids. Particularly
preferred are copolymers prepared using methacrylic acid.
The aftertreatment of the copolymers containing free carboxyl
groups may be carried out in different ways. What is important is
that the carboxyl groups are converted into --COOR groups, in which
R represents a monovalent alkyl radical containing at least one
free hydroxyl group. For example, the copolymers containing free
carboxyl groups may be caused to react with polyvalent alcohols
such as glycol, glycerol, trimethylolpropane, pentaerythritol or
p-dimethylolbenzene. The aftertreatment is preferably carried out
by reacting the copolymers containing free carboxyl groups with
cyclic ethers wherein the ring contains an oxygen atom and two or
three carbon atoms, i.e., ethylene oxide and trimethylene oxide.
Ethylene oxide is especially preferred.
The copolymerization of olefins with unsaturated carboxylic acids
and alkyl esters of unsaturated carboxylic acids is preferably
carried out in solution in the presence of a free radical
initiator, such as an azo compound or a peroxide.
The ratio in which the monomers are incorporated into a growing
copolymer molecule depends on the reactivity of the monomers
involved. If there are differences in reactivity, the molar ratio
of the monomers in the mixture to be polymerized will be subject to
considerable changes as the copolymerization proceeds, since the
more reactive monomer is incorporated more rapidly. As a result,
the composition of the copolymer also changes continually. As a
general rule it may be said that, if in the polymerization of
monomers which differ strongly in reactivity no special measures
are taken, the products obtained are of an extremely heterogeneous
composition. Such a case arises in the copolymerization of olefins,
unsaturated carboxylic acids and alkyl esters of unsaturated
carboxylic acids, since three types of monomers are involved which
differ in reactivity. In the copolymerization of unsaturated
carboxylic acids with alkyl esters of unsaturated carboxylic acids
it has been found that the rates of incorporation or reaction of
these monomers can be equalized by conducting the copolymerizations
in the presence of a substance which associates with the
unsaturated carboxylic acid. Since the rates of the incorporated
monomers becomes equal to that of the monomers in the starting
mixture. Associating substances which may be used are aliphatic
compounds containing an oxygen atom attached to carbon, such as
alcohols, ethers, ketones and carboxylic acids. Preference is given
to lower aliphatic alcohols, such am methanol, ethanol, isopropanol
and, in particular, to tert-butanol. The solvent in which the
copolymerizations are carried out may be an aromatic solvent such
as benzene, toluene or xylene, with benzene being preferred. In the
preparation of copolymers of olefins, unsaturated carboxylic acids
and alkyl esters thereof in the presence of the aforementioned
associating substances the number of monomers with different
reactivity is in principle reduced by one, since the unsaturated
carboxylic acids and the alkyl esters thereof behave as monomers
with the same reactivity.
In the copolymerization of olefins with unsaturated carboxylic
acids and alkyl esters thereof it has been found that, despite the
very different reactivity of these monomers, it is nevertheless
possible to prepare copolymers of uniform composition. To
accomplish this care must be taken that the ratio between the
concentrations of the monomers in the mixture to be polymerized
remain constant during the copolymerization. For example, the more
reactive monomer or a mixture of monomers rich in the more reactive
monomer may be added gradually to the mixture to be polymerized.
This method is known as programmed copolymerization. It is also
possible to stop the polymerization at a time when the
concentrations of the monomers in the mixture to be polymerized
remain substantially unchanged. This is called copolymerization to
low conversion. The polymerizations may be conducted both batchwise
and continuously. Continuous polymerization may take place in a
tubular reactor or by continuously adding all reaction components
in the ratio in which they are consumed in the process to a
reaction mixture whose composition is kept homogenous, for example
by intensive stirring, while simultaneously discharging part of the
reaction mixture.
The aftertreatment of the copolymers containing free carboxyl
groups, in which the carboxyl groups are converted into --COOR
groups in which R represents a monovalent alkyl radical containing
at least one free hydroxyl group, is preferably carried out with
the aid of a cyclic ether, and in particular, ethylene oxide. This
conversion may take place under the influence of a substance giving
an alkaline reaction as a catalyst. Suitable substances giving an
alkaline reaction are alkali metals, alkali metal oxides, alkali
metal hydroxides, alkaline earth metals, alkaline earth metal
oxides, alkaline earth metal hydroxides and organic compounds, such
as trimethylamine, N-methylmorpholine, pyridine, quinoline and
.beta.-picoline. By preference a lithium compound is employed as a
catalyst. Examples of suitable lithium compounds are lithium
hydroxide, lithium hydride, lithium alkoxides, lithium carbonate
and lithium acetate. Very favorable results may be obtained by
using lithium hydroxide as a catalyst.
In an alternative aftertreatment process the reaction of the acid
polymer with the cyclic ether is not conducted in the presence of a
substance giving an alkaline reaction as a catalyst. Rather this
catalyst is incorporated in the acid polymer beforehand.
Incorporation of the catalyst in the acid polymer may take place by
first combining one or more salts of substances giving an alkaline
reaction with unsaturated carboxylic acids in the monomer mixture
from which the acid polymer is prepared. The acid copolymer
obtained by polymerization of this monomer mixture may then be
reacted with a cyclic ether without using an additional catalyst.
In this process, too, lithium salts are preferred.
The reaction of the acid copolymer with the cyclic ether may take
place at room temperature, but is preferably conducted at elevated
temperatures between about 95.degree. and 130.degree. C. If the
final product is liquid, the reaction may proceed without a
solvent. The solvent, if employed, may be either polar or nonpolar.
The polymer containing free carboxyl groups tends to form
intramolecular hydrogen bridges, especially in a nonpolar solvent,
as a result of which the viscosity greatly increases. The reaction
with the cyclic ether is therefore preferably carried out in the
presence of a polar substance which prevents the formation of
intramolecular hydrogen bridges. For this purpose a low-boiling
aliphatic alcohol is preferred. A very suitable medium for the
reaction to be carried out is a mixture of a low-boiling aliphatic
alcohol and an aromatic hydrocarbon such as benzene or toluene.
In the preparation of the present polymeric compounds by
copolymerization to acid polymers followed by after treatment with
a cyclic ether it is not necessary that the acid copolymers be
isolated before they are caused to react with the cyclic ether. The
cyclic ether may be added directly to the reaction mixture obtained
in the copolymerization. If, in the preparation of the acid
copolymer, an alcohol was used as an associating substance, this
one-step procedure offers the additional advantage that the alcohol
present in the reaction mixture prevents the formation of
intramolecular hydrogen bridges in the acid copolymer.
The molecular weight of the copolymers according to the invention
may vary between wide limits. The invention relates in particular
to lubricant compositions containing copolymers with a molecular
weight (M.sub.n) between 5,000 and 150,000 and in particular to
lubricant compositions containing copolymers with a molecular
weight between 15,000 and 100,000. The ratio of monomers in the
copolymer may also vary between wide limits. In general copolymers
having a molecular ratio of 11 to 300 moles of olefin, 10 moles of
an alkyl ester of unsaturated carboxylic acids and 1 to 15 moles of
a hydroxyalkyl ester of unsaturated carboxylic acids may be
used.
The invention relates in general to lubricant compositions
containing polymeric compounds which have been obtained by
copolymerization of one or more olefins containing from two to six
carbon atoms per molecule with one or more alkyl esters of
unsaturated carboxylic acids and with one or more esters of
unsaturated carboxylic acids in which the part of the molecule
derived from the alcohol contains at least one free hydroxyl
group.
The invention relates in particular to lubricant compositions
containing polymeric compounds which have been obtained by
copolymerization of ethylene with one or more alkyl esters of
C.sub.3 --C.sub.4 unsaturated monocarboxylic acids, in which the
alkyl group contains eight to 20 carbon atoms, and with one or more
hydroxyalkyl esters of C.sub.3 --C.sub.4 unsaturated monocarboxylic
acids in which the hydroxyalkyl group contains two to three carbon
atoms. Favorable results were obtained by application of the
following copolymers of this type in a mineral lubricating oil: 1.
ethylene/lauryl methacrylate/.beta.-hydroxyethylmethacrylate
copolymers; 2. ethylene/lauryl methacrylate/stearyl
methacrylate/.beta.-hydroxyethyl methacrylate copolymers. These
copolymers were prepared by ethoxylating ethylene/lauryl
methacrylate/methacrylic acid copolymers and ethylene/lauryl
methacrylate/stearyl methacrylate/methacrylic acid copolymers,
respectively, with ethylene oxide. The ethylene/lauryl
methacrylate/methacrylic acid copolymers and the ethylene/lauryl
methacrylate/stearyl methacrylate/methacrylic acid copolymers as
well as the ethylene/lauryl methacrylate/.beta. -hydroxyethyl
methacrylate copolymers and the ethylene/lauryl
methacrylate/stearyl methacrylate/.beta.-hydroxyethyl methacrylate
copolymers, respectively, obtained therefrom by ethoxylation are
novel substances.
The base oils suitable for the preparation of the lubricant
compositions according to the invention may be mineral lubricating
oils of varying viscosity, and also synthetic lubricating oils or
lubricating oils containing fatty oils. The present lubricant
additives may also be incorporated into lubricating greases. The
invention is of particular importance in improving the quality of
mineral lubricating oils or mixtures thereof. The polymeric
compounds may be added to the lubricant as such or in the form of a
concentrate obtained, by mixing the polymeric compounds with a
small quantity of oil. The concentration of the present polymers in
the lubricants may vary between wide limits. In general, the
desired dispersant action and improvement of the viscometric
properties is obtained when the quantity added is from 0.1 to 10
percent by weight and, in particular, when this quantity is from
0.5 to 5 percent by weight of the lubricating oil composition.
In addition to the present polymers, the lubricant compositions
according to the invention may also contain other additives, such
as antioxidants, anticorrosive agents, antifoaming agents, agents
to improve the lubricating action and other substances which are
usually added to lubricants.
The invention will now be further described with the aid of the
following examples which are considered to be illustrative
only.
EXAMPLE I
Five copolymers of ethylene, methacrylic acid stearyl methacrylate
and lauryl methacrylate and four copolymers of ethylene,
methacrylic acid and lauryl methacrylate (designated as polymers
1-9 were prepared as follows: A specific mixture of methacrylic
esters, methacrylic acid, azodiisobutyronitrile, 300 g. of
tert-butanol and 100 g. of benzene was passed into a 2-liter
autoclave. After the air had been expelled from the autoclave with
the aid of pure nitrogen, ethylene was introduced into the
autoclave at room temperature under a pressure of up to 170 to 200
atm. The mixture was heated for a specified period, during which
the pressure increased to 380- 480 atm. After the pressure had been
released, the mixture was discharged and concentrated by partial
evaporation of the solvent. The polymer was purified by
precipitating three times in methanol. Finally the polymer was
dissolved in benzene, the solution filtered and the polymer
separated by freeze-drying.
Further details on the copolymerizations described above and the
resulting acid polymers are tabulated in tables I and
II.-----------------------------------------------------------------------
----TABLE II Molar Ratio of the Monomers in the Acid Copolymer
Lauryl Stearyl Methacrylic Polymer Methacrylate Methacrylate Acid
Ethylene
_________________________________________________________________________
_ 1 5 5 3.1 22 2 5 5 2.8 20 3 5 5 3.0 21 4 5 5 3.7 19 5 5 5 3.9 12
6 10 2.6 30 7 10 3.7 19 8 10 2.9 27 9 10 2.7 44
_________________________________________________________________________
_
EXAMPLE II
The acid copolymers (1 to 9) from example I were converted into
polymers I- IX according to the invention as follows:
To a solution composed of 20 g. of the acid copolymer and 48 mg. of
lithium hydroxide in a solvent mixture comprising 9 g. of toluene
and 71 g. of methanol, ethylene oxide was added at room
temperature. The solution was kept at 95.degree. for 24 hours and
subsequently cooled down to room temperature. The ethoxylated
polymer was purified by precipitating two times in methanol.
Further details on the ethyoxylation described above are collected
in table III. ##SPC1##
EXAMPLE III
In order to assess the viscometric behavior of the polymers I- IX
according to the invention they were dissolved in a concentration
of 1.5 percent weight in a paraffinic base oil. The results of the
viscometric determinations are listed in table IV. ##SPC2##
the above results definitely show the advantages of the polymers of
the present invention with regards to improvement in viscosity
index (VI) of a lubricating oil composition.
EXAMPLE IV
The thermal stabilities of the polymers according to the invention
are recorded in table V. They were determined in vacuum at a rate
of heating of 3.degree. C./min. The values T.sub.10, t.sub.20 and
T.sub.50 represent the temperatures at which 10, 20 and 50 percent
weight loss, respectively, of the polymer was attained. To test the
present polymers as dispersants they were subjected to a
peptization test. In this test the lowest concentration of additive
is determined that is capable of keeping 0.015 percent weight of
carbon in mineral oil in suspension for 15 minutes at 250.degree.
C. Concentrations below 0.008 are considered favorable. The results
of these peptization tests are also listed in table
V.------------------------------------------------------------------
---------TABLE V Polymer T.sub.10 T.sub.20 T.sub.50 Peptization
Test, %w
_________________________________________________________________________
_ I 330 355 390 0.001- 0.003 II 325 350 380 0.001- 0.003 III 350
375 405 0.004 IV 345 360 390 0.001- 0.003 V 335 360 390 0.003 VI
360 385 420 0.001- 0.003 VII 340 365 395 0.001- 0.003 VIII 340 365
395 0.005 IX 340 365 395 0.005
_________________________________________________________________________
_
the results of the peptization tests (in all cases <0.005
percent weight) may be considered very favorable.
From the above it is evident that the polymers of the present
invention impart excellent dispersancy and viscosity index
characteristics to lubricating oil as well as possessing excellent
thermal stability.
* * * * *