Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICANT SPRAY POLYMERS
Field of Invention
[0001] This invention relates to a copolymer, its synthesis and methods
of
using it.
Technical Background
[0002] The primary function of lubricants is to decrease friction.
Frequently,
however, lubricating oils need additional properties to be used effectively.
For
example, lubricants used in the crankcases of large diesel engines, such as,
for
example, marine diesel engines, are often subjected to operating conditions
requiring special considerations.
[0003] Marine diesel engines may generally be classified as slow-speed,
medium-speed, or high-speed engines, with the slow-speed variety being used
for the largest, deep shaft marine vessels and certain other industrial
applications. Slow-speed diesel engines are unique in size and method of
operation. The larger units may approach 200 tons in weight and be upward of
10 feet wide and 45 feet high. The output of these engines can be as high as
100,000 horsepower with engine revolutions of 60 to about 200 revolutions per
minute. They are typically of crosshead design and operate on a two-stroke
cycle.
[0004] In large diesel engines of the crosshead type used in marine and
heavy stationary applications, the piston cylinders are lubricated separately
from the other engine components. The cylinders are lubricated on a total loss
basis with the cylinder oil being injected separately into each cylinder by
means
of lubricators positioned around the cylinder liner. Oil is distributed to the
lubricators by means of pumps, which are, in modern engine designs, actuated
to apply the oil directly onto the rings to reduce oil wastage.
[0005] The unique design of these engines creates the need for
lubricants
with enhanced rheology properties. Because slow-speed engines run at a lower
temperature than mid- or fast-speed engines, they are more prone to corrosion.
Accordingly, lubricants used in a marine engine must protect the engine parts
from corrosion, especially rust. Rust is produced when ferrous metal engine
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components come in contact with water, which is typically produced by the
internal combustion process or from external sources. Regardless of the
source,
rust and corrosion reduce engine efficiency and lifetime.
[0006] Also, the fuels commonly used in these diesel engines typically
contain significant quantities of sulfur. During the combustion process, the
sulfur
can combine with water to form sulfuric acid, the presence of which leads to
corrosive wear. In particular, in two-stroke engines for ships, areas around
the
cylinder liners and piston rings can be corroded and worn by the acid.
Therefore,
it is important for diesel engine to resist such corrosion and wear by being
properly lubricated.
[0007] To prevent corrosion, the lubricant must be applied to the
cylinder
wall, typically by a pulse lubricating system or by spraying the lubricant
onto the
cylinder wall through an injector. In marine engines the lubricant is injected
or
sprayed on the cylinder liner and spread horizontally by the sprayer or
injector
and vertically by the piston rings when the piston is in its upward motion.
The
lubricant is not used in a circulating system; when the excess lubricant comes
to
the bottom of cylinder it is discarded. Typically fresh lubricant is injected
every
four to eight strokes depending on the engine speed.
[0008] Thus, there is a need for a lubricant additive that will provide
effective
oxidation and corrosion resistance without posing the environmental hazards
and cost of other oxidation and corrosion inhibitors. Additionally, because
the
lubricating oil is not circulated in marine engines, any rheology improvements
that enhance lubricating efficacy or reduce the amount of oil used could
significantly increase engine life and decrease costs.
SUMMARY
[0009] We have found new copolymers that can modify the rheology of a
marine lubricant to provide enhanced lubrication properties. In particular,
marine
engine lubricating oils comprising the copolymers of the disclosure as an
additive surprisingly cover marine engine piston cylinder walls more
completely
than prior art oils (with or without additional additives), thereby leading to
better
lubrication and less engine cylinder wear and corrosion.
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[0 0 1 0] We
have also recognized that the method in which the copolymer is
made can control the properties of the copolymer.
[0011] In
a first aspect, the present disclosure provides a copolymer of alkyl
methacrylate monomers wherein said alkyl methacrylate monomers comprise at
least:
a. Monomers (A) selected from 06-010 alkyl methacrylate monomers, and
b. Monomers (B) selected from 010-018 alkyl methacrylate monomers. The
ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is
about 99:1 to about 10:90 by weight. In an embodiment, A is selected from 06-
09 alkyl methacrylate monomers. In another embodiment, B is selected from
011-018 alkyl methacrylate monomers. In another embodiment, the ratio of
Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1
to about 60:40 by weight.
[0012] In
a second aspect, the present disclosure provides a copolymer
obtained by combining at least Monomers (A) and Monomers (B) in a mixture
and co-polymerizing the monomers, wherein the monomers are present in a
mass ratio of about 99:1 to about 10:90, preferably about 99:1 to about 60:40,
Monomers (B) to Monomers (A), and wherein Monomers (A) and Monomers (B)
are distinct from one another.
[0013] In a third aspect, the present disclosure provides a method of
making
a copolymer as described above.
[0014] All
publications referenced herein are incorporated by reference in
their entirety to the extent they are not inconsistent with the teachings
presented
herein.
DETAILED DESCRIPTION
[0015] In
the first aspect, the present disclosure provides a copolymer of
alkyl methacrylate monomers wherein said alkyl methacrylate monomers
comprise at least:
[0016] a. Monomers (A) selected from 06-010 alkyl methacrylate
monomers, and
b. Monomers (B) selected from 010-018 alkyl methacrylate monomers, wherein
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the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the
copolymer is about 99:1 to about 10:90, preferably 99:1 to 60:40, by weight.
[0017] The
ratio of monomers in all aspects of the disclosure can be
adjusted to manipulate the characteristics of the copolymer as desired. For
example, the monomers can be present in ratios of Monomers (B) to Monomers
(A) of 10:90, 15;85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45,
60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 99:1. In one
embodiment, the monomers are present in ratios of Monomers (B) to Monomers
(A) of 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 99:1.
[0018] In some embodiments of all aspects of the disclosure, the Monomers
(A) are linear or branched C8alkyl. In some embodiments, Monomers (A) are 2-
ethylhexyl methacrylate.
[0019] In
some embodiments of all aspects of the disclosure, the copolymer
used in the lubricant composition according to the invention is prepared from
a
mixture of monomers that comprises at least two monomers: one monomer (A)
and one monomer (B), distinct from one another. The monomers are preferably
chosen from monomers which, when polymerized, form a copolymer that is
soluble in liquid, preferably in oil, more preferably in marine diesel engine
oil
lubricants.
[0020] In another embodiment of all aspects of the disclosure, the
copolymer
is a copolymer of a mixture of monomers comprising at least: a 08 alkyl
methacrylate, a 012 alkyl methacrylate, a 014 alkyl methacrylate, and a 016
alkyl methacrylate, and they are present in the mixture in weight ratio of:
- from 5 to 30 (:)/0 08 alkyl methacrylate,
- from 40 to 70 (:)/0 012 alkyl methacrylate,
- from 12 to 35 (:)/0 014 alkyl methacrylate,
- from 1 to 12 (:)/0 016 alkyl methacrylate,
-
from 0.1 to 15 %, preferably from 0.5 to 10 %, more preferably from 1 to
5 (:)/0 other methacrylates, by weight with regard to the total weight of the
mixture.
[0021] In
another embodiment of all aspects of the disclosure, the copolymer
is substantially free of monomers other than monomer (A) and monomer (B),
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particularly free of methacrylates having a 01-05 alkyl group, including, for
example, methyl methacrylate. Monomers such as methyl methacrylate
decrease the solubility of the resulting copolymer in oil, and the presence of
such monomers are limited or omitted in some embodiments.
[0022] In another embodiment of all aspects of the disclosure, the
copolymer
is free of methacrylates other than monomer (A) and monomer (B), particularly
methacrylates having a C1-05 alkyl group, including, for example, methyl
methacrylate.
[0023] Typically, copolymers according to the disclosure have an average
Root Mean Square Radius of Gyration (Rg) as measured by Hydrodynamic
Column Chromotography-Multi Angle Light Scattering (HCC-MALS) from about
100 to about 200 (nm) Rg, from about 120 to about 190 (nm), from about 130
to 180, or from about 140 to about 170 (nm) Rg.
[0024] In the second aspect, the copolymer is obtained by combining at
least
Monomers (B) and Monomers (A) in a mixture and co-polymerizing the
monomers, wherein the monomers are present in a mass ratio of about 99:1 to
about 10:90 Monomers (B) to Monomers (A).
[0025] The copolymer may be synthesized by conventional methods for
vinyl
addition polymerization known to those skilled in the art, such as, but not
limited
to, solution polymerization, precipitation polymerization, and dispersion
polymerizations, including suspension polymerization and emulsion
polymerization.
[0026] In some embodiments, the polymer is formed by suspension
polymerization, wherein monomers that are insoluble in water or poorly soluble
in water are suspended as droplets in water. The monomer droplet suspension
is maintained by mechanical agitation and the addition of stabilizers. Surface
active polymers such as cellulose ethers, poly(vinyl alcohol-co-vinyl
acetate),
poly(vinyl pyrrolidone) and alkali metal salts of (meth)acrylic acid
containing
polymers and colloidal (water insoluble) inorganic powders such as tricalcium
phosphate, hydroxyapatite, barium sulfate, kaolin, and magnesium silicates can
be used as stabilizers. In addition, small amounts of surfactants such as
sodium
dodecylbenzene sulfonate can be used together with the stabilizer(s).
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Polymerization is initiated using an oil soluble initiator. Suitable
initiators include
peroxides such as benzoyl peroxide, peroxy esters such as tert-butylperoxy-2-
ethylhexanoate, and azo compounds such as 2,2'-azobis(2-methylbutyronitrile).
At the completion of the polymerization, solid polymer product can be
separated
.. from the reaction medium by filtration and washed with water, acid, base,
or
solvent to remove unreacted monomer or free stabilizer.
[0027] In other embodiments the polymer is formed by emulsion
polymerization, one or more monomers are dispersed in an aqueous phase and
polymerization is initiated using a water soluble initiator. The monomers are
io .. typically water insoluble or very poorly soluble in water, and a
surfactant or soap
is used to stabilize the monomer droplets in the aqueous phase. Polymerization
occurs in the swollen micelles and latex particles. Other ingredients that
might
be present in an emulsion polymerization include chain transfer agents such as
mercaptans (e.g. dodecyl mercaptan) to control molecular weight, electrolytes
to control pH, and small amounts of organic solvent, preferably water soluble
organic solvents, including but not limited to acetone, b-butanone, methanol,
ethanol, and isopropanol, to adjust the polarity of the aqueous phase.
Suitable
initiators include alkali metal or ammonium salts of persulfate such as
ammonium persulfate, water-soluble azo compounds such as 2,2'-azobis(2-
aminopropane)dihydrochloride, and redox systems such as Fe(II) and cumene
hydroperoxide, and tert-butyl hydroperoxide-Fe(II)-sodium ascorbate. Suitable
surfactants include anionic surfactants such as fatty acid soaps (e.g. sodium
or
potassium stearate), sulfates and sulfonates (e.g. sodium dodecyl 20 benzene
sulfonate), sulfosuccinates (e.g. dioctyl sodium sulfosuccinate); non-ionic
surfactants such as octylphenol ethoxylates and linear and branched alcohol
ethoxylates; cationic surfactants such as cetyl trimethyl ammonium chloride;
and amphoteric surfactants. Anionic surfactants and combinations of anionic
surfactants and non-ionic surfactants are most commonly used. Polymeric
stabilizers such as poly(vinyl alcohol-co-vinyl acetate) can also be used as
surfactants. The solid polymer product free of the aqueous medium can be
obtained by a number of processes including destabilization/coagulation of the
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final emulsion followed by filtration, solvent precipitation of the polymer
from
latex, or spray drying of the latex.
[0028] The polymer can be isolated by conventional methods known to
those
skilled in the art, such as, but not limited to, solvent exchange, evaporation
of
solvent, spray drying and freeze-drying.
[0029] The characteristics of the copolymer obtained by combining at
least
Monomers (A) and Monomers (B) in a mixture and co-polymerizing can be
manipulated by controlling the additional reagents added to the polymerization
mixture. These reagents include, but are not limited to, initiator systems and
surfactants.
[0030] The type and amount initiator system used in the polymerization
mixture can influence the properties of the resulting copolymer. An initiator
system can be a single initiator compound (e.g., a persulfate salt) or a
mixture
of two or more components (e.g., hydrogen peroxide and sodium ascorbate). In
some examples, the initiator system can include an oxidant, reductant, and
optionally a metal salt. The oxidant can be a persulfate, such as, for
example,
ammonium persulfate, or a peroxide, such as, for example, hydrogen peroxide
(H202) or tert-butyl hydroperoxide (TBHP). A desirable copolymer may be
obtained, for example, when the polymerization mixture includes tert-butyl
hydroperoxide in about 0.01 to about 0.06 mass percent of all monomers in the
mixture. In other examples, the mixture may include tert-butyl hydroperoxide
in
about 0.01 to about 0.03 mass percent of the monomers in the mixture. In some
examples, the mixture further comprises tert-butyl hydroperoxide in about
0.013
mass percent of the monomers in the mixture. Useful initiators for the
copolymers of the present disclosure include any conventional initiator,
including any conventional redox initiator.
[0031] In some embodiments the reductant of the redox initiator system
can
be ascorbic acid or a salt thereof. For example, the polymerization mixture
can
include sodium ascorbate in about 0.04 to about 0.1 mass percent of the
monomers in the mixture. In other examples, the sodium ascorbate may be
present in about 0.08 to about 0.1 mass percent of the monomers in the
mixture.
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In some embodiments, the polymerization mixture includes sodium ascorbate in
about 0.098 mass percent of the monomers in the mixture.
[0032] The initiator system may also include a metal salt. The metal may
be
any suitable transition metal, such as, for example, iron. In some
embodiments,
the metal salt of the initiator system can be ferrous sulfate (FeSO4). In some
embodiments, the metal salt is present in the polymerization mixture in about
0.0005 to about 0.1 mass percent of the monomers in the mixture. In some
examples, the metal salt is added to the polymerization mixture as a solution.
[0033] The copolymer may also be obtained for a polymerization mixture
further including a surfactant. In some embodiments, the surfactant may
contain
a sulfonate group. For example, the surfactant may include a dialkyl
sulfosuccinate, such as, for example, dioctyl sulfosuccinate sodium salt. In
some examples, the surfactant may be Aerosol OT.
[0034] The copolymer can be a random copolymer, block copolymer, or
mixture thereof. In some embodiments, the copolymer is a substantially random
copolymer (e.g., greater than 90, 95, 98, or 99 mass percent). In other
examples, the copolymer is a partially a random copolymer and partially a
block
copolymer. In these examples the weight percent ratio of random copolymer to
block copolymer is generally 90:10, 80:20, 70: 30, 60:40, 50:50, 40:60, 30:70;
20:80 or 10:90. The copolymer may also be a substantially block copolymer
(e.g., greater than 90, 95, 98, or 99 weight percent). In other examples, the
copolymer can contain additional monomers in addition to Monomers (A) and
Monomers (B) discussed. These additional monomers can be present in an
amount less than 10 weight percent. In some embodiments, the additional
monomers are present in an amount from about 0.5 to 10 weight percent, or
about 1 to 10 weight percent or about 1 to 5 weight percent or about 5 to 10
weight percent. In other embodiments, the additional monomers are present in
an amount less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or about 0.5 weight
percent. The additional monomers can include, for example, cross-linking
monomers, acrylate, styrene, C1-C3alkyl methacrylate and other similar
monomers.
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[0035] The copolymer may also be crosslinked. That is, the copolymer can
contain monomeric units that connect one or more of the backbone chains of
the polymer. In some examples, the copolymer contains crosslinked monomeric
units present in up to about 5% by weight of the copolymer. In other
.. embodiments, the copolymer is not crosslinked, or uncrosslinked, and is
substantially free of monomers that function as a crosslinking agent. In other
embodiments, the monomer mixture to make the copolymer is substantially free
of crosslinking agents.
[0036] The crosslinked copolymer may be obtained when the polymerization
mixture includes a crosslinking agent. In some embodiments, the crosslinking
agent is a diacrylate or dimethacrylate crosslinking agent, such as, for
example,
1,6-hexanediol dimethacrylate. In some examples, the mixture includes a
crosslinking agent in up to about 0.005 mass percent of the monomers in the
mixture.
[0037] Example copolymers are shown in Tables 1 and 2. For each example,
Table 1 shows the ratio of Monomers (B) to Monomers (A) (e.g., 2-ethylhexyl
methacrylate), and the amount of acetone, the components of the redox
initiator
system and surfactant used. Table 2 shows the molecular weight, Rg and
viscosity of each example copolymer.
[0038] In a third aspect, a method of making a copolymer as described
above is disclosed. The method includes the polymerization of Monomers (A)
and a Monomers (B), wherein the mass ratio of Monomers (B) in the copolymer
to Monomers (A) in the copolymer is about 99:1 to about 10:90 by weight (e.g.,
10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40,
65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, 99:1).
[0039] In some embodiments, the method includes: combining Monomers
(B) and Monomers (A) in a ratio of about 10:90, 15:85, 20:80, 25:75, 30:70,
35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15,
90:10, 95:5, 99:1 and initiating the polymerization of the monomers to provide
a
copolymer.
[0040] In some embodiments, the ratio of monomers and the initiator, or
initiator system, can be selected as described above. The method may include
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further components to provide a copolymer with desirable properties. For
example, the method may include a surfactant, such as, for example, Aerosol
OT, or a crosslinker, such as, for example, 1,6-hexanediol dimethacrylate.
[0041] Polymerization can occur in an aqueous mixture or a mixture that
comprises both aqueous and organic solvents. For example, the polymerization
mixture can include a mixture of water and acetone. In some embodiments the
polymerization mixture may require an organic solvent. Often it will be
desirable
to include an organic solvent when lauryl methacrylate is in the
polymerization
mixture. Organic solvents for use in such polymerization reactions are known
io and routinely selectable by those of ordinary skill in the field of
polymer
synthesis. Suitable organic solvents include, for example and without
limitation,
acetone, 2-butanone, methanol, ethanol, and isopropanol.
[0042] The copolymer of the first or second aspect can be present in the
oil
in an amount from about 0.5% to about 25% by weight. Depending on the oil
used the, the copolymer may be present in the oil in an amount from about
1`)/0
to about 25.
[0043] The oil may be selected from those known in the art, and may be a
mineral oil, i.e., those obtained from the processing of crude oil, or a
synthetic
oil, i.e., an artificially made oil typically containing polyglycols or
esters, or a
semi-synthetic oil, i.e., a blend of mineral and synthetic oils. In some
embodiments, the oil is a mineral base oil, i.e., a complex mixture of
paraffins,
naphthenes, and aromatics. In some examples, the oil may be a paraffinic base
oil, such as 150 Neutral Solvent, 600 Solvent Neutral or a bright stock. The
oil
composition may include further components, particularly those used in marine
diesel engine oil lubricants.
[0044] A test measuring the enhanced lubrication properties and
usability of
oil containing a copolymer of the first or second aspect was undertaken under
the following conditions. The oil/polymer compositions were examined for
performance/suitability as a lubricant by a finger pull test, which is
performed by
pipetting a droplet of sample fluid (about 65p1) onto the thumb of a gloved
hand.
The thumb and forefinger are gently squeezed together to ensure contact of the
droplet with both fingers, and then the fingers are pulled apart vertically
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about 1 second over a distance of about 7.5 cm., while observing the amount of
time the composition provides a fluid connection between the thumb and
forefinger once the fingers are moved apart. All finger pull tests were
performed
at ambient temperature, about 21 C. The performance of the sample was
characterized as "very short," "short," "medium," "long," or "very long"
depending
upon the duration that the sample provided a fluid connection between thumb
and forefinger remain . Compositions with "very short" performance in the
finger
pull test being less than 1 second, "short" ranging from 1-4 seconds, "medium"
ranging from 4-7 seconds, "long" ranging from 7-60 seconds, and "very long"
describing the situation where the composition remains connected to both
fingers indefinitely . Compositions with "very short" and "very long" textures
do
not exhibit enhanced suitability or performance as a lubricant. Compositions
with "short," "medium," or "long" textures exhibit improved suitability as a
lubricant to varying degrees because, for example, their ability to
effectively
.. spread on the cylinder wall of the engine being lubricated is enhanced.
Compositions with "long" texture have particularly good suitability as a
lubricant.
The results of the finger pull test are shown in Table 2.
[0045] One advantage of the copolymers disclosed herein is that they can
be
used to enhance the performance of an oil as a lubricant, while at the same
.. time maintaining the ability to handle the oil in a manner necessary for
use in
the field. For example, many lubricants are pumped via a fluid pump, and
therefore the lubricant should have an appropriate viscosity to allow it to be
pumped without creating mechanical complications or damage to the pumping
equipment. A lubricant with improper viscosity (particularly a viscosity that
is
.. too high) can prevent the lubricant from being pumped properly, or
otherwise
require the exertion of much higher power to pump the lubricant. The polymers
disclosed herein maintain the balance between enhancing lubricant oil
performance while at the same time maintaining the viscosity at a sufficient
level to allow for efficient handling in the field. It has been unexpectedly
discovered that the combination of Monomer B homopolymer with oil also
provides enhanced lubricant performance at a viscosity that allows for
efficient
handling. The combination of oil with a copolymer having a 5:95 Monomer B to
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Monomer A ratio results in a substance having a viscosity and other physical
handling properties that prevent this composition from being efficiently
handled
in the field.
[0046] In an embodiment the polymers have a molecular weight >20000 D.
[0047] In an embodiment the polymers have a bimodal molecular weight
distribution.
[0048] Copolymers having a molecular weight (Mw), average root mean
square radius of gyration (Rg) and viscosity correlation in a certain range
are
particularly suitable as an oil additive to enhance the performance of oil as
a
lo lubricant while maintaining the ability to handle and pump the oil. A
preferred
correlation of a bimodal Mw, Rg and viscosity values for one embodiment of the
copolymers disclosed herein is represented by the following formula:
Performance X = 1139.69418+(2.54756* Peak 1 Mw)-(0.91396* Peak 1 Rg)-
(66.18535* Peak 2 Mw)-(0.23020* Viscosity+1.18947E-003* Peak 1 Rg)
*(Viscosity),
where the units for Mw is 106 g/mol, Rg is nm, and Viscosity is mPa.s, as set
forth in Table 2. A performance X value between 500 and 900, more preferably
between 550 and 800, and most preferably between 600 and 750 is indicative
of a copolymer having properties that are particularly suitable to enhance the
performance of oil as a lubricant.
Definitions
[0049] As used herein, lauryl methacrylate is dodecyl methacrylate (012;
CAS 142-90-5) or a mixture of 014-16alkyl methacrylates including dodecyl
methacrylate. That is, lauryl methacrylate may include a mixture of which
dodecyl methacrylate is a component, but which also includes one or more
other C14_16alkyl methacrylates such as tetradecyl methacrylate (014; CAS 2549-
53-3) and hexdecyl methacrylate (016; CAS 2495-27-4). For example, the lauryl
methacrylate could be a mixture of about 40-70 weight percent dodecyl
methacrylate, 15-40 weight percent tetradecyl methacrylate, and 4-10 weight
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percent hexdecyl methacrylate, such as commercially available methacrylic
ester 13.0 (Evonik trade name: VISIOMERO Terra 013,0-MA).
[0050] As used herein, the term "about" refers to the given value 10
(:)/0 of
the value.
[0051] As used herein, the term "08a1ky1" refers to a group comprised of
eight saturated carbon atoms connected in a linear or branched configuration.
Examples of linear 08a1ky1 groups include n-octyl. Examples of branched
08a1ky1 groups include, but are not limited, to 2-ethylhexyl.
[0052] As used herein, the term "alkyl methacrylate" refers to compounds
io wherein a methacrylol radical is bonded to a linear or branched,
saturated or
unsaturated alkyl group.
[0053] As used herein, the term "substantially free of monomers" means
that
there is no more than 3.0 (:)/0 by weight of the copolymer, preferably no more
than 1.0% by weight, and more preferably no more than 0.5% by weight of the
monomer present in the copolymer.
[0054] As used herein, the term "substantially free of crosslinking
agents"
means that there is no more than 1.0 (:)/0 by weight of the copolymer,
preferably
no more than 0.5% by weight, of monomeric units that connect two or more of
the backbone chains of the polymer.
[0055] It is noted that any embodiment disclosed herein can be combined
with any other embodiment with the result being subject matter in accordance
with the invention.
[0056] It is noted that, unless use differently, " /0" means percent by
weight.
Examples
[0057] Lauryl methacrylate as used in Examples 1-8 was provided as
methacrylic ester 13.0, which is commercially available as VISIOMER Terra
013,0-MA from Evonik Industries.
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Example 1
[0058] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
the subsurface nitrogen purge was started. To the reaction was then added
container 270.0 g of lauryl methacrylate, 30.0 g of 2-ethylhexyl methacrylate
and 129.9 g of acetone. The reaction was heated up to 43 C by using a
temperature controlled water batch set at 45 C. Once the reaction reached
io 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5
minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of
a
0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was
then changed to a nitrogen blanket. The reaction was held an additional 5
hours,
cooled to room temperature and isolated.
Example 2
[0059] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
the subsurface nitrogen purge was started. To the reaction was then added
container 240.0 g of lauryl methacrylate, 60.0 g of 2-ethylhexyl methacrylate
and 129.9 g of acetone. The reaction was heated up to 43 C by using a
temperature controlled water batch set at 45 C. Once the reaction reached
43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5
minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of
a
0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was
then changed to a nitrogen blanket. The reaction was held an additional 5
hours,
cooled to room temperature and isolated.
Example 3
[0060] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
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the subsurface nitrogen purge was started. To the reaction was then added
container 210.0 g of lauryl methacrylate, 90.0 g of 2-ethylhexyl methacrylate
and 129.9 g of acetone. The reaction was heated up to 43 C by using a
temperature controlled water batch set at 45 C. Once the reaction reached
43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5
minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of
a
0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was
then changed to a nitrogen blanket. The reaction was held an additional 5
hours,
cooled to room temperature and isolated.
Example 4
[0061] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
the subsurface nitrogen purge was started. To the reaction was then added
container 180.0 g of lauryl methacrylate, 120.0 g of 2-Ethylhexyl Methacrylate
and 129.9 g of acetone. The reaction was heated up to 43 C by using a
temperature controlled water batch set at 45 C. Once the reaction reached
43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5
minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of
a
0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was
then changed to a nitrogen blanket. The reaction was held an additional 5
hours,
cooled to room temperature and isolated.
Example 5
[0062] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
the subsurface nitrogen purge was started. To the reaction was then added
container 120.0 g of lauryl methacrylate, 180.0 g of 2-Ethylhexyl Methacrylate
and 129.9 g of acetone. The reaction was heated up to 43 C by using a
temperature controlled water batch set at 45 C. Once the reaction reached
43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5
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minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of
a
0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was
then changed to a nitrogen blanket. The reaction was held an additional 5
hours,
cooled to room temperature and isolated.
Example 6
[0063] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
io the subsurface nitrogen purge was started. To the reaction was then added
container 60.0 g of lauryl methacrylate, 240.0 g of 2-Ethylhexyl Methacrylate
and 129.9 g of acetone. The reaction was heated up to 43 C by using a
temperature controlled water batch set at 45 C. Once the reaction reached
43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5
minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of
a
0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was
then changed to a nitrogen blanket. The reaction was held an additional 5
hours,
cooled to room temperature and isolated.
Example 7
[0064] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
the subsurface nitrogen purge was started. To the reaction was then added
30.0 g of lauryl methacrylate, 270.0 g of 2-Ethylhexyl Methacrylate and 129.9
g
of acetone. The reaction was heated up to 43 C by using a temperature
controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g
of
t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of
sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of
iron sulfate hexahydrate was added. The nitrogen purge was then changed to a
nitrogen blanket. The reaction was held an additional 5 hours, cooled to room
temperature and isolated.
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Example 8
[0065] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a
condenser, a thermocouple and a subsurface nitrogen purge was added 645.5
g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
the subsurface nitrogen purge was started. To the reaction was then added
15.0 g of lauryl methacrylate, 285.0 g of 2-Ethylhexyl Methacrylate and 129.9
g
of acetone. The reaction was heated up to 43 C by using a temperature
controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g
of
t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of
sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of
iron sulfate hexahydrate was added. The nitrogen purge was then changed to a
nitrogen blanket. The reaction was held an additional 5 hours, cooled to room
temperature and isolated.
Preparation of 5% Solids Solution of Copolymer in Oil
[0066] To a 4-neck 1000mL flask equipped with an overhead stirrer, a
Barrett distillation trap with a condenser and a thermocouple was added an
amount of the emulsion of any of Examples 1-8 to give 20.0 g of polymer.
Neutral Solvent 600 was then added to bring the total up to 400.0 g, followed
by
150.0 g of toluene. The stirring was turned up to 200 rpm and the mixture was
brought up to reflux. As water condensed in the Barrett trap it was drained
off.
Once the water stopped overflowing, the contents of the reactor were brought
up to 130 C to distill of a majority of the toluene. The remaining material
was
transferred to a 1000mL single neck round bottom and concentrated at vacuum
with a bath at 60 C until the material reached a constant weight.
Method for Determining Molecular Weight and Radius of Gyration
[0067] The Molecular Weight and Radius of Gyration of the polymer
samples,
supplied at 5% solids in base oil, was determined by the procedure outlined
below:
[0068] Eluant: HPLC Grade Tetrahydrofuran stabilized with 0.01`)/0
Butylated
Hydroxytoluene
[0069] Column: Phenogel Column 100A 10um 300mm x 7.8mm.
17
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[0070] Flow Rate: 0.50 ml/min.
[0071] Detectors: Wyatt Dawn Heleos-II MultiAngle Light Scattering
(MALS)
at 663nm and room temperature and Wyatt Optilab T-rEX Refractive Index
Detector at 658nm and 40 C
[0072] Pump/Autosampler: Agilent 1100 Isocratic HPLC Pump and
Autosampler
[0073] Column Compartment: 40 C.
[0074] Standards: There were no standards directly correlated with the
analysis, but the Heleos-II MALS calibration constant was established with
lo Toluene and the Optilab T-rEX calibration constant was established with
NaCI
in water. The 17 angles on the Heleos-II were normalized with a narrow range
polystyrene standard at 28,500 Molecular Weight and the detector delay volume
was adjusted with the same standard.
[0075] Sample Preparation: The samples were prepared by gravimetrically
diluting about 8.0 mg of sample with about 5.0 g of tetrahyrofuran. The actual
concentration of polymer in mg/ml was calculated based on the density of
tetrahydrofuran (0.889 g/m1) and the percentage solids in the sample solutions
(5.0 A) by weight).
[0076] Injection: 50 pl.
[0077] Run time: 20 minutes.
[0078] Software: Wyatt Astra Version 6.1.4.25.
[0079] Calculations: The Astra software provides several choices of
formalisms and exponent order to fit the data. All samples were fit with a 2nd
order Berry. The angles used were adjusted to give the best fit, using a
minimum of 13 angles and up to the maximum of 17. The dn/dc was calculated
from the refractive index data assuming 100% recovery. The software reported
the average Molecular Weight as Mw and the average Root Mean Square
Radius of Gyration as Rg. The results are shown in Table 2.
Method for Determining Viscosity
The shear viscosity of the polymer samples, supplied at 5% solids in base oil,
was determined by stress-controlled rheometer MCR 302, manufactured by
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Anton Paar GmbH, located at Anton Paar Strasse 20, 8054, Graz, Austria. The
Double Gap System of Measurement was used for good accuracy (Instruction
Manual, MCR Series, Modular Compact Rheometer MCR 52/102/302/502,
page 50, Anton Parr, Graz, Austria, 2011). The temperature was set at 22 C
with the accuracy of 0.1 C. The shear rate was gradually increased from 1/sec
to 100/sec with 10 points of viscosity reading per decade. At each of these
points, 10 second equilibrium time was given before the reading, which lasted
3
seconds. The viscosity at 10/sec shear rate is shown in Table 2. Software for
instrument control and data acquisition is RheoCompassTM, version 1.13.445.
io Table 1
FeSO4
2
Exampl LMA 2- Acetone TBHP Ascorbate
Aeroso
e 1 EHMA1 2 2 2
(0.25% I 0T2
)
1 90 10 43.3 0.013 0.098 0.20 2.90
2 80 20 43.3 0.013 0.098 0.20 2.90
3 70 30 43.3 0.013 0.098 0.20 2.90
4 60 40 43.3 0.013 0.098 0.20 2.90
5 40 60 43.3 0.013 0.098 0.20 2.90
6 20 80 43.3 0.013 0.098 0.20 2.90
7 10 90 43.3 0.013 0.098 0.20 2.90
8 5 95 43.3 0.013 0.098 0.20 2.90
NS600
Base Oil
1 Percentage of monomer as a mass percent of the total amount of monomer
2 Weight percent based on the total amount of monomer
LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate.
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Table 2, Hydrodynamic Chromatography/MALS
Mw Rg
Mw Peak 5%S
Peak Rg Peak 2
1 NS600 Finger
Example LMA1 2- 1 2 Peak 1
EHMA' (106 (nm) viscosityPull
Test
(106 (nm)
g/mol) [mPa=s]
g/mol)
1 90 10 133 6.4 140 108 3610 I
I
2 80 20 133 7.0 104 135 2152
3 70 30 146 7.0 132 106 2572 m
4 60 40 169 9.7 135 119 2294 m
40 60 129 8.1 133 111 4865 I
6 20 80 132/131 8.1/7.6 152/152 122/1204089 I
7A3 10 90 92 5.3 166 101 8213 I
7B 10 90 136/149 6.4/7.2 176/176 112/11810600 I
8 5 95 36 5.4 192 112 41083 vi
NS600 -- vs
--- --- --- --- 300
Base Oil -
1 Percentage of monomer as a mass percent of the total amount of
monomer
LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate;
2
5 VS = very short, s = short, m = medium, I = long, vi = very long
3 Two duplicate samples for Example 7 were created using the Example 7
preparation method described
lo
