Note: Descriptions are shown in the official language in which they were submitted.
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Title: COMPOSITIONS COMPRISING A DISPERSANT AND AN
OVERBASED CARBOXYLATE OR SULFONATE FOR
RHEOLOGY CONTROL IN COATINGS & INKS
SUMMARY OF THE INVENTION
A mixture of a calcium overbased carboxylate or sulfonate and a dispersant
provides rheology control in various resin and pigment containing organic
media.
These compositions can influence the flow properties under high shear and/or
elevated temperatures than non-modified compositions.
BACKGROUND OF THE INVENTION
When applying coatings that contain a high amount of solids such as
industrial coatings, maintenance coatings or paints, there is a tendency for
the
coating to sag or run if the viscosity is not controlled. This tendency is
especially
prevalent when a workpiece, which is to accept the coating, is in a vertical
position.
Regarding workpieces that are vertically oriented, the coating may droop or
sag due
to gravity so that the final film thickness of the coating is uneven. Some
sagging
may occur by influence of gravity when the coating is applied. However, such
sagging is more particularly a problem when baking the ~ applied coating. An
approach to overcome the sag problem is to include a rheology control agent in
the
coating. Such rheology control agents basically cause the coating to be shear
thinning and to have high viscosity (decreased fluidity) at low shear while
providing
sufficiently low viscosity at high shear to permit flow and leveling on the
workpiece.
U.S. Patent No. 4,451,597 (Victorius, May 29, 1984) relates to coating
composition useful as the exterior finish on automobiles and trucks and
contains
about 25-50% by weight of a binder of film-forming constituents and 50-75% by
weight of a volatile organic solvent carrier and additionally contains 2-150%
by
weight, based on the weight of the binder, of pigment; the binder is about 20-
70% by
weight of an acrylic polymer containing reactive hydroxyl, carboxyl, amide
groups
or any mixture of such groups, about 0-40% by weight of a hydroxy-terminated
polyester urethane resin and about 25-40% by weight of an alkylated melamine
formaldehyde crosslinking resin; in addition the composition contains about 4-
20%
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by weight, based on the weight of the binder, of a rheology control agent of
an
alcohol soluble cellulose acetate butyrate having a butyl (sic) content of
about 40-
50% by weight, a hydroxyl content of about 4-5% by weight and a viscosity of
about
0.2-0.4 second.
U.S. Patent No. 5,034,444 (Yun et al., July 23, 1991) discloses a rheology
additive for non-aqueous coating compositions. The additive may be the
reaction
product of an alkoxylated aliphatic nitrogen-containing compound, an aliphatic
diamine or mixtures thereof, and an organic polycarboxylic anhydride or acid,
an
alkanediol polyepoxide ether, or mixtures thereof. The additive provides
excellent
anti-sag and storage stability properties, particularly for high solids
coating
compositions, without causing a significant increase in viscosity. Also
disclosed are
coating compositions containing the additive.
U.S. Patent No. 5,086,104 (Wada et al., February 4, 1992) discloses polyester
resin compositions which include a crystalline thermoplastic polyester resin
(such as
polybutylene terephthalate), a polyester elastomer (such as a copolymer
including
recurring hard and soft segments) and between 0.005 to 10 parts by weight,
based on
100 parts of the crystalline and elastomeric resins, of an amide compound
having the
formula
H
R C-N-X-Y
n
wherein R is an organic group such as an aromatic ring, X is an alkylene of CZ
to C,o
such as ethylene and propylene, Y is -COOH, -OH, -SH or -NHZ and n is 2 to 4,
inclusive.
U.S. Patent No. 4,321,098 (Lal, June 14, 1994) relates to a composition
mixture comprising (i) at least one ester-acid, ester-salt or mixtures thereof
and (ii)
at least one amidic-acid, amidic-salt or mixtures thereof and polymer fabrics
treated
with the same. The treated polymer fabrics have improved wicking-wetting
characteristics. The treated polymer fabrics maintain these characteristics
upon
repeated exposure to aqueous fluids.
U.S. Patent No. 5,369,184 (Burgoyne, Jr. et al., November 29, 1994) relates
to resins which comprise polymers which contain multiple acetal groups that
have
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been developed which are useful for crosslinking and adhesion promotion in
coating
and adhesive applications. The polymers which make up these resins are
prepared
by the addition of aminoacetals to polymers containing anhydride
functionality. The
polymers are modified by titration with ammonia or a primary or secondary
amine
which solubilizes the polymer in aqueous systems.
U.S. Patent No. 5,374,682 (Gouda et al., December 20, 1994) is directed to a
thermosetting coating composition that contains (a) an acrylic resin having
hydroxyl
groups and epoxy groups in a molecule thereof; (b) a resin prepared from a
monomer
having an unsaturated group and an acid anhydride group the acid anhydride
group
being half-esterified, half-thioesterified and/or half-amidized; (c) at least
one of
hydroxyl group-containing resin selected from the group consisting of an
acrylic
resin containing hydroxyl groups and carboxyl groups, a fluorine-containing
copolymer resin and a polyester resin; and (d) a melamine resin.
U.S. Patent No. 5,536,871 (Santhanam, July 16, 1996) is directed to a liquid,
pourable rheology additive especially useful for thickening liquid organic
compositions which comprises the reaction product of a defined polyalkoxylated
nitrogen-containing compound, polycarboxylic acid and a liquid diamine. The
additive, which exists in a pourable, pumpable form at up to a 100%
rheologically
active composition, exhibits excellent thickening efficiency for systems
including
inks, epoxies, polyesters, paints, greases and other systems, including ease
of
dispersibility, without adversely affecting gloss. The additive operates by
both an
associative and a reaction mechanism to provide rheology properties to such
systems, and is also similarly useful for aqueous systems.
Printing inks are a special class of coatings formulated to transfer and
reproduce an image from a printing surface (plate or cylinder) to a substrate
such as
paper or plastic, etc. These inks consist of various pigments or colorants in
a varnish
which is typically a film former consisting of various resins, solvents, and
other
additives, so that the resulting fluid will distribute and transfer on to the
printing
press. Lithographic and letterpress inks are higher viscosity formulations
often
referred to paste inks. Most modern litho ink presses run at speeds of 1500-
2000
feet per minute but are capable of running to up to 3000 feet per minute. As
one
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would expect the temperature of the ink increases as speed increases and this
affects
the operating window under which the press can perform satisfactorily.
Therefore,
inks must be formulated to run under wide variations of conditions, to
minimize the
change in viscosity as a function of temperature. The viscosity of a fluid is
generally
dependent upon temperature among other factors. As the temperature of the
fluid is
increased, the viscosity usually decreases, and as the temperature is reduced,
the
viscosity usually increases. One of the functions of a rheology control agent
for the
purpose of this invention is to reduce the extent of the decrease in viscosity
as the
temperature is raised or to reduce the extent of the increase in viscosity as
the
temperature is lowered. Such rheology control agents in motor oil applications
are
generally usually polymeric materials and are often referred to as Viscosity
Index
improvers. Thus, a viscosity improver ameliorates the change of viscosity of
system
containing it with changes in temperature. In inks it is highly desirable that
the
rheology control agents do not adversely affect the low/ ambient temperature
viscosity of, the formulations containing same. Frequently, the rheology
control
agents simply act as thickeners to enhance the high temperature properties.
Accordingly, it is desirable to provide compositions that reduce the extent of
loss of
viscosity at high temperatures while not adversely increasing the low
temperature
viscosity of inks.
U. S. patent 3,819,386 (Higgins, June 25, 1974) is directed to the usage of an
alkaline earth metal salt of a fatty acid and a dispersant to act as
thickeners and to
provide plastic flow to printing inks.
DETAILED DESCRIPTION OF THE INVENTION
Overbased additives have been known for a long time. They have been used
extensively as industrial lubricants in engines, gears and other industrial
applications. Specifically they have been used as detergents, extreme pressure
and
antiwear agents, anticorrosion and antirust additives, and as rheology control
agents
in coatings. They are metal salts of acidic organic compounds. Overbased
materials
are single phase, homogenous, and generally apparently Newtonian systems
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characterized by a metal content in excess of that which would be present
according
to the stoichiometry of the metal and the particular acidic organic compound
reacted
with the metal. Overbasing, also referred to as superbasing or hyperbasing, is
a
means for supplying a large quantity of basic material in a form which is
soluble or
dispersible in organic medium. Overbased products have been long used in
lubricant technology to provide detergent additives.
Overbased materials are generally prepared by reacting an acidic material,
normally an acidic gas such as SOZ or C02, and most commonly carbon dioxide,
with a mixture comprising an acidic organic compound, a reaction medium
normally
comprising an oleophilic medium, a stoichiometric excess of a metal base, and
preferably a promoter.
The amount of excess metal is commonly expressed in terms of metal ratio.
The terminology "metal ratio" is used in the prior art and herein to designate
the ratio
of the total chemical equivalents of the metal in the overbased materials
(e.g., a
metal sulfonate or carboxylate) to the chemical equivalents of the metal in
the
product which would be expected to result in the reaction between the organic
material to be overbased (e.g., sulfonic or carboxylic acid) and the metal-
containing
reactant (e.g., calcium hydroxide, calcium oxide, etc.) according to the known
chemical reactivity and stoichiometry of the two reactants. The actual
stoichiometric
excess of metal can vary considerably, for example, from about 0.1 equivalent
to
about 30 or more equivalents depending on the reactions, the process
conditions, and
the like. Obviously, if there is present in the material to be overbased more
than one
compound capable of reacting with the metal, the "metal ratio" of the product
will
depend upon whether the number of equivalents of metal in the overbased
product is
compared to the number of equivalents expected to be present for a given
single
component or a combination of all such components. The methods for preparing
the
overbased materials as well as an extremely diverse group of overbased
materials are
well known in the prior art and are disclosed for example in the following
U.S. Pat.
Nos.: 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925;
2,617,049;
2,695,910; 2,723,234; 2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209;
2,777,874; 2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951;
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2,883,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463; 3,001,981;
3,027,325; 3,070,581; 3,108,960; 3,147,232; 3,133,019; 3,146,201; 3,152,991;
3,155,616; 3,170,880; 3,170,881; 3,172,855; 3,194,823; 3,223,630; 3,232,883;
3,242,079; 3,242,080; 3,250,710; 3,256,186; 3,274,135; 3,492,231; and
4,230,586.
These patents disclose processes, materials which can be overbased, suitable
metal
bases, promoters, and acidic materials, as well as a variety of specific
overbased
products useful in producing the disperse systems of this invention and are,
accordingly, incorporated herein by reference.
Within this preferred group of overbased carboxylic and sulfonic acids, the
calcium overbased mono-, di-, and tri-alkylated benzene and naphthalene
(including
hydrogenated forms thereof), and higher fatty acids are especially preferred.
Illustrative of the synthetically produced alkylated benzene and naphthalene
sulfonic
acids are those containing alkyl substituents having from about 8 to about 30
carbon
atoms, preferably about 12 to about 30 carbon atoms, and advantageously about
24
carbon atoms. Such acids include di-isododecyl-benzene sulfonic acid, wax-
substituted phenol sulfonic acid, wax-substituted benzene sulfonic acids,
polybutene-substituted sulfonic acid, cetyl-chlorobenzene sulfonic acid, di-
cetylnaphthalene sulfonic acid, di-lauryldiphenylether sulfonic acid, di-
isononylbenzene sulfonic acid, di-isooctadecylbenzene sulfonic acid, stearyl
naphthalene sulfonic acid, and the like.
The carboxylic acid of the present invention can include both saturated and
unsaturated carboxylic acid of 8 to 30 carbon atoms or reactive equivalents of
said
carboxylic acids. The phrase "reactive equivalent" of a material means any
compound or chemical composition other than the material itself which reacts
or
behaves like the material itself under the reaction conditions. Thus reactive
equivalents of carboxylic acids will include acid-producing derivatives such
as
anhydrides, alkyl esters, triglycerides, acyl halides, lactones and mixtures
thereof
unless specifically stated otherwise. It is to be noted that a reactive
equivalent of a
carboxylic acid as aforementioned, such as a triglyceride may itself contain
carbon
atoms in excess of the preferred range of 8-30 in that the triglyceride has
three ester
functionalities formed by reacting three moles of a carboxylic acid with one
mole of
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glycerol. The range of carbon numbers given above therefore refers only to the
carboxylic acid, and not to the total carbon atoms of any reactive equivalent.
Examples of useful carboxylic acids include but are not limited to caprylic
acid, capric acid, lauric acid, myristic acid, myristoleic acid, decanoic
acid,
dodecanoic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric
acid,
stearic acid, 12-hydroxystearic acid, oleic acid, ricinoleic acid, linoleic
acid, linoleic
acid, arachidic acid, gadoleic acid, eicosadienoic acid, behenic acid, erucic
acid,
mixtures of any of these acids or their reactive equivalent.
The carboxylic acid or its reactive equivalent can also comprise at least one
natural oil comprising an animal oil or vegetable oil comprising a
triglyceride of the
formula
O
CH2-OCRI
O 2
CH-OCR
H2-OCR3
I I
O
wherein R', RZ and R3 are independently hydrocarbyl groups containing 7 to 29
carbon atoms. Examples of suitable vegetable oils include coconut oil, soybean
oil,
tall oil, tung oil, rapeseed oil, sunflower oil, including high oleic
sunflower oil,
lesquerella oil and castor oil.
The calcium base of the present invention is selected from the group
consisting of calcium oxide (Ca0) and calcium hydroxide (Ca(OH)2).
When the carboxylic acid present in the form of a reactive equivalent such as
a triglyceride is initially reacted together with the calcium base, hydrolysis
of the
triglyceride takes place to form a saponified intermediate.
O
CH~OH
CHZ-OCR (R 1 COO) ZCa + (R 2C00) zCa + (R 3C00) ZC
p 3 Ca(OH)2 +
2 CH-OCR2 + °r --~ 2 CHOH + (R1C00)Ca(R 2C00) + (R 1C00)Ca(R 3C00)
3 Ca0 + 3 H20 +
Hz-OCR3 ~ HzOH (R2C00)Ca(R 3C00)
I I
a mixture of calcium salts
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The equivalent ratio of the calcium base to the carboxylic acid is between 2:1
and 10:1; thus sufficient calcium base is present to effect saponification
quantitatively (i.e. 100%). When the saponified intermediate is obtained,
glycerol is
also formed. It is important to note that this system differs from the prior
art in that
no free glycerol is added at the beginning of the saponification reaction. The
glycerol formed, although not considered to be a "promoter" (a term discussed
below), can aid in the incorporation of the excess calcium in the overbasing
process.
It can act as both a diluent and contact agent and remains within the
composition.
The carbonation of the mixture of (I) takes place through the use of carbon
dioxide, an acidic gas. The amount of carbon dioxide which is used depends in
some respects upon the desired basicity of the product in question and also
upon the
amount of calcium base employed, which as discussed above will vary (in total
amount) from 2-10 equivalents per equivalent of carboxylic acid. The carbon
dioxide is generally blown below the surface of the reaction mixture of (I)
along
with additional (i.e., amounts in excess of what is required to convert the
carboxylic
acid quantitatively to the calcium carboxylate salt) calcium base after the
calcium
carboxylate intermediate is formed. The calcium carboxylate intermediate is
formed
either from direct reaction of the carboxylic acid with the calcium base or
through
saponification of a reactive equivalent of the carboxylic acid, such as a
triglyceride.
The process of carbonation which is a part of the process of overbasing is
well
known to those skilled in the art. The carbon dioxide employed during the
carbonation step is used to react with the excess calcium base which may be
already
be present or which can be added during the carbonation step. The mixtures of
products obtained after carbonation are referred to herein as overbased
materials of
this invention which include calcium carbonate formed from the reaction of
carbon
dioxide and calcium hydroxide.
The carbonation is carried out in the presence of a promoter. Promoters are
chemicals which can be employed in the overbasing process to facilitate the
incorporation of the large excess metal into the overbased compositions.
Typical
examples of promoters used in overbasing include water; phenolic materials
such as
phenol; alcohols of various kinds, such as methanol, 2-propanol, the butyl
alcohols,
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the amyl alcohols, as well as mixtures of alcohols; mono-glycerides; di-
glycerides;
and amines such as aniline and dodecyl amine. The promoter system used in the
present invention consists of a mixture of water and an alcohol of 1 to 8
carbon
atoms. The alcohol can preferably be selected from the group consisting of 2-
propanol (isopropyl alcohol), 1-butanol, and 2-methyl-1-propanol (isobutyl
alcohol).
In a more preferred embodiment, the alcohol is 2-methyl-1-propanol.
These ordinary overbased materials can be gelled, i.e. converted into a gel-
like or colloidal structure, by homogenizing a "conversion agent" with the
overbased
starting material. "Ungelled" overbased materials are normally Newtonian
materials
which are homogeneous on a macroscopic scale. Gelled overbased materials are
well known materials. They can be converted from their original Newtonian form
to
a gelled form by a variety of treatments. The details of the process are
described in
U.S. patents 3,492,231; 5,300,242 and 5,508,331.
The terminology "conversion agent" is intended to describe a class of very
diverse materials which possess the property of being able to convert the
Newtonian
homogeneous, single-phase, overbased materials into non-Newtonian colloidal
disperse systems. The mechanism by which conversion is accomplished is not
completely understood. However, with the exception of carbon dioxide, these
conversion agents generally possess active hydrogens. The conversion agents
generally include lower aliphatic carboxylic acids, water, aliphatic alcohols,
polyethoxylated materials such as polyglycols, cycloaliphatic alcohols,
arylaliphatic
alcohols, phenols, ketones, aldehydes, amines, boron acids, phosphorus acids,
sulfur
acids, and carbon dioxide (particularly in combination with water). Mixtures
of two
or more of these conversion agents are also useful. Particularly useful
conversion
agents are alcohols having less than twelve carbon atoms while the lower
alcohols,
i.e., alcohols having less than six carbon atoms, are preferred for reasons of
economy
and effectiveness in the process.
The use of a mixture of water and one or more of the alcohols is known to be
especially effective for converting the overbased materials to colloidal
disperse
systems and is used as the conversion agent in the instant invention. For the
present
invention, the preferred alcohols are selected from the group consisting of 2-
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propanol, 1-butanol, 2-methyl-1-propanol and mixtures thereof, with the most
preferred being 2-methyl-1-propanol (isobutanol). Thus the same alcohols used
during carbonation can also be used in the gelation step. In one embodiment, a
mixture of water and 2-methyl-1-propanol is used in the gelation step. The
details of
the process are described in U.S. patents 3,492,231; 5,300,242 and 5,508,331,
5,401424, and 5,919,741.
Removal of volatile materials need not be limited to removal of the
conversion agents, however. It is possible, for instance, to completely
isolate the
solid components of the gelled material as dry or nearly dry solids. (In this
context
the term "solid" or "solids" includes not only sensibly dry materials, but
also
materials with a high solids content which still contain a relatively small
amount of
residual liquid.) Isolation of solids can be effected by preparing the
composition in
an oleophilic medium which is a volatile organic compound. The term "volatile"
as
used in this context describes a material which can be removed by evaporation.
Xylenes, for example, would be considered volatile organic compounds. Heating
of
the gel to a suitable temperature and/or subjecting it to vacuum can lead to
removal
of the volatile oleophilic medium to the extent desired. Typical methods of
drying
include bulk drying, vacuum pan drying, spray drying, flash stripping, thin
film
drying, vacuum double drum drying, indirect heat rotary drying, and freeze
drying.
Other methods of isolation of the solids can also be employed, and some of
those
methods do not require that the oleophilic medium be a volatile material. Thus
in
addition to evaporation, such methods as dialysis, precipitation, extraction,
filtration,
and centrifugation can be employed to isolate the solid components of the gel.
The solid material thus isolated may be stored or transported in this form and
later recombined with an appropriate amount of an oleophilic medium. The
redispersion into oil can be accomplished more readily when the solid material
is not
dried to absolute dryness, i.e. when a small amount of solvent remains in the
composition. Alternatively an appropriate amount of an oil such as a mineral
oil, a
natural oil such as vegetable'oil, e.g., coconut oil or the like, or synthetic
oil, or a
surfactant, can be present in the nominally dry powder to aid in dispersion.
The
solid materials, when dispersed in an appropriate medium, can provide a gel, a
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coating composition, a grease, another lubricant, or any of the materials
which can
be prepared from the originally gelled material. The solid materials can also
be used
without redispersion for their intrinsic lubricating properties.
The oleophilic medium used for preparing and containing overbased
materials will normally be an inert solvent for the acidic organic material.
The
oleophilic medium can be an oil or an organic material which is readily
soluble or
miscible with oil. The organic material can include an organic solvent which
can
include both aliphatic and aromatic organic solvents and mixtures thereof.
In one embodiment, the organic solvent comprises such materials as mineral
spirits and Stoddard Solvent. Mineral Spirits is often referred to as Heavy
Naphtha.
It has high flash point and solvent power and is extensively used in coatings
industry. In another embodiment of the invention, the organic solvent is a
petroleum
middle distillate fraction such as those available from Magie Bros. Oil
Company
under the trade name Magie Sol, or from Exxon Chemical under the trade name
Exxprint, etc. Such distillates are extensively used in lithographic inks and
are
typically aliphatic hydrocarbons with limited aromatic character and vary in
boiling
range from 200 C- 350 C.
Suitable aromatic solvents include benzene, alkylbenzenes, high flash solvent
naphtha, and mixtures thereof. Alkylbenzene includes toluene, xylenes and
ethylbenzene as well as benzene rings having different alkyl groups attached
thereto,
such as methyl ethyl benzene, and mixtures thereof. In one embodiment, the
aromatic solvent is SC 100 solvent, which is made up almost entirely of
aromatics,
comprising mostly high boiling toluenes.
It is also possible to remove the water and alcohol present in the overbased
mixture and add a diluent (such as an oil, organic solvent, or vegetable oil)
which
may be the same or different from the diluent used during overbasing.
Definitions
As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is
used in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it refers to a group having a carbon atom directly attached to
the
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remainder of the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
(1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-,
aliphatic-, and
alicyclic-substituted aromatic substituents, as well as cyclic substituents
wherein the
ring is completed through another portion of the molecule (e.g., two
substituents
together form an alicyclic radical);
(2) substituted hydrocarbon substituents, that is, substituents containing
non-hydrocarbon groups which, in the context of this invention, do not alter
the
predominantly hydrocarbon substituent (e.g., halo (especially chloro and
fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
(3) hetero substituents, that is, substituents which, while having a
predominantly hydrocarbon character, in the context of this invention, contain
other
than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms
include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl,
furyl,
thienyl and imidazolyl. In general, no more than two, preferably no more than
one,
non-hydrocarbon substituent will be present for every ten carbon atoms in the
hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in
the
hydrocarbyl group.
The term "lower" when used in conjunction with terms such as alkyl,
alkenyl, alkoxy, and the like, is intended to describe such groups that
contain a total
of up to 7 carbon atoms.
The term "water-soluble" refers to materials that are soluble in water to the
extent of at least one gram per 100 milliliters of water at 25°C.
The term "oil soluble" refers to materials that are soluble in mineral oil to
the
extent of at least one gram per 100 milliliters of mineral oil at 25°C.
The term "total acid number" (TAN) refers to a measure of the amount of
potassium hydroxide (KOH) needed to neutralize all of the acidity of a product
or a
composition. The sample to be tested is dissolved in a toluene and tert-butyl
alcohol
solvent and titrated potentiometrically with a solution of tetra-n-
butylammonium
hydroxide. The toluene and tert-butyl alcohol solvent is prepared by diluting
100 ml
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of 25% methanolic tent-butyl alcohol and 200 ml of isopropyl alcohol to one
liter
total volume with toluene. The solution of tetra-n-butylammonium hydroxide is
a
25% by weight solution in methyl alcohol. A Metrohm Standard pH Combination
Glass Electrode EA 120 (3M aq. KCl), which is a combination glass-plus-
reference
electrode, is used. The end-points corresponding to the inflections are
obtained from
the titration curve and the acid numbers calculated.
The term "total base number" (TBN) refers to a measure of the amount of
acid (perchloric or hydorchloric) needed to neutralize the basicity of a
product or a
composition, expressed as KOH equivalents. It is measured using Test Method
ASTM D 2896.
The number of "equivalents" of a hydrocarbyl substituted succinic acid or
anhydride is dependent on the number of carboxylic functions (e.g., -C(=0)-)
present
in the acid or anhydride. Thus, the number of equivalents of acid or anhydride
will
vary with the number of succinic groups present therein. In determining the
number
of equivalents of acid or anhydride, those carboxylic functions which are not
capable
of reacting with the polyol, polyamine or hydroxyamine (B) are excluded. In
general, however, there are two equivalents of acid or anhydride for each
succinic
group in the acid or anhydride. Conventional techniques are readily available
for
determining the number of carboxylic functions (e.g., acid number,
saponification
number) and, thus, the number of equivalents of the acid or anhydride
available to
react with component (B).
An "equivalent" of a polyol is that amount of polyol corresponding to the
total weight of polyol divided by the total number of hydroxyl groups present.
Thus,
glycerol has an equivalent weight equal to one-third its molecular weight.
An "equivalent" of a polyamine is that amount of polyamine corresponding
to the total weight of the polyamine divided by the number of nitrogen atoms
present
which are capable of reacting with a hydrocarbyl substituted succinic acid or
anhydride. Thus, octylamine has an equivalent weight equal to its molecular
weight;
ethylene diamine has an equivalent weight equal to one-half of its molecular
weight.
The equivalent weight of a commercially available mixture of polyalkylene
polyamines can be determined by dividing the atomic weight of nitrogen (14) by
the
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% N contained in the polyamine; thus, a polyalkylene polyamine mixture having
a %
N of 34 would have an equivalent weight of 41.2.
An "equivalent" of a hydroxyamine is that amount of hydroxyamine
corresponding to the total weight of hydroxyamine divided by the number of
hydroxyl groups and nitrogen atoms present which are capable of reacting with
a
hydrocarbyl substituted succinic acid or anhydride. Thus, diethanolamine has
an
equivalent weight equal to one-third its molecular weight.
The processes and compositions of the present invention can be used to
prepare a variety of materials useful as additives for coating compositions,
as
stabilizing agents or additives for such compositions as polymeric
compositions or
for drilling muds or other down-hole oil field applications, as rheology
control
agents for water solutions, such as paints and invert emulsions, as lubricants
(including greases) for oil field, automotive, steel mill, mining, railroad,
and
environmentally friendly applications, as lubricants for food-grade
applications,
metalworking, and preservative oils, as lubricants for abrasives (grinding
aids), as a
component of synthetic based invert lubricants, and in thermal stabilizer
composi-
tions for polymers such as polyvinyl chloride resin.
In a preferred embodiment, the overbased material prepared by the process of
this invention can be used in a coating composition as a rheology control
agent.
Coating compositions include paints, certain inks, and various varnishes and
lacquers. They often contain pigments in a dispersing medium or vehicle, a
film-
forming resin, and other conventional additives known to those skilled in the
art. In
inks, for example, typical resin is selected from at least one member of the
group
consisting of metal resinate, phenolic modified rosin, phenolic resin,
hydrocarbon
resin, hydrocarbon modified rosins, an acrylic resin, a plyamide resin, a
malefic
modified rosin, a fumaric modified rosin, and a cellulosic resin. Conventional
coatings as well as high solid systems typically contain from 10 to about 50%
by
weight of non-volatile resins, such as those based on polyester-melamine,
polyester-
urea/formaldehyde, alkyd-urea/formaldehyde, acrylic-melamine, arylic-
urea/formaldehyde, epoxy resins, epoxy-ester-melamines, polyurethane resins,
acrylic resins, oleoresins, unsaturated polyesters, polyvinyl acetates,
polyvinyl
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chlorides, or vinyl acrylics. Various other additives include additives for
microbiological control (bactericides and fungicides), additives for fire
retardance,
additives that are inhibitors for rusting and corrosion, anti-gassing agents,
additives
for surface lubrication and mar and scuff resistance, anti-static agents,
deodorants,
defoamers, antioxidants, gloss enhancers such as waxes, an anti-settling
agent, and
tannin stain suppressants.
In order to illustrate the invention, the following data is provided. It is
understood, however, that the data is for illustrative purposes and are not
intended to
be limiting of the scope of the invention as set forth in the claims.
Table I
Effect of Dispersants on Stormer Viscosity and Say
Control in a White Paint Alkyd Formulation
%Rheology Control Agents Stormer ViscositySag Test
(D856) (D4400)
A 0.75% Overbased acid of Example 73 9
3A
B 0.75% Overbased acid of Example 75 10
3A
0.5% LZ 2174 (an alkyl aminoester
according
to this disclosure)
C 0.75% Overbased acid of Example 78 > 12
3A 0.5%
PIBSA (a polyisobutylene substituted
succinic
anhydride where the polyisobutylene
has an
Mn 2000)
D 0.75% Overbased acid of Example 80 12
3A
1.0% LZ 2174
E 0.75% Overbased acid of Example 81 > 12
3A 1.0%
PIBSA (Mn 2000)
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As discussed in the background section, it highly desirable that rheology
control agents in this coatings formulation increase Stormer viscosity and
sag. The
results in Table I clearly demonstrate that the overbased acid of Example 3A
in
combination with either LZ 2174 or PIBSA achieve this effectively.
Table II
Effect of the Overbased Acids and Dispersants in
Hydrocarbon Resin Ink Varnish
Resinall % distillates% Rheology Control Viscosity Viscosity
514 Agents Q 26C Q 60C
A 50.5 49.5 0 25.73 1.11
B 43 50.7 6.3% Example 13A 67.71 4.57
C 49.6 45.6 4.8% Ircosperse 39.75 1.66
2176 (an alkenyl
succinic anhydride
according to
this disclosure
D 43.2 46.9 6.2% Example 13A 44.19 16.4
3.7% Ircosperse
2174 (an alkyl
aminoester according
to this
disclosure
E 42.6 47.3 6.3% Example 13A 28.75 7.66
3.8% Ircos erse
2176
lU The varnishes above were formulated to keep the tack to about 9.6~0.4 @ 400
rpm
The results of example B in Table II indicate that the overbased acid of
Example 13A works well as rheology control agent but also increases the
viscosity at
lower temperatures. Examples D and E of Table II on the other hand, indicate
that
when the overbased acid is present along with either dispersant Ircosperse
2174 or
2176 the viscosity was greatly reduced at lower temperatures and increased at
higher
temperatures and clearly demonstrate the invention.
Table III
Effect of Overbased Acids and Dispersants in a Sheetfed Ink Varnish
~ % ~
SylvaprintSylvaprintdistillatesSylvarSylfat % Rheology ViscosityViscosity
4550 6348 Alk 9012 Control A Q 26C ~?60C
d ents
A 25.5 20.5 37 12 5 0 55.55 1.96
B 22.3 17.5 37.3 11.7 4.9 6.4% Exam 170.3 12.32
le 13A
C 25 20 33 12 5 5.0% Ircos 44.26 1.87
erse 2176
D 23 18 34.7 12 5 5.3% Example79.49 4.41
13A
2.0% LZ 2174
E 20.5 15.8 38.6 10.9 4.5 6.0% Example59.22 7.56
13A
3.7% Ircos
erse 2176
The varnishes above were formulated to keep the tack to about 12.7~0.6 @ 400
rpm
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Table IV
Effect of Overbased Acids and Dispersants in a Sheetfed Rubine Ink
Varnish % Rubine % Thermol Viscosity Viscosity
Flush 96 C C~ 26 C ~ 60 C
Wax
60% III-A 35% 5% 336.5 2.1
baseline
62% III-E 35% 3% 145.5 5.71
Modified
Example lA.
A reactor is charged with 1725 grams of mineral spirits. The reactor is heated
to
32.2°C (90°F), and then 1254 grams (5.75 equivalents) of coconut
oil is charged to
the reactor. The alcohol 2-methyl-1-propanol (isobutanol; 148 grams; 2 moles)
is
then charged, followed by water (24 grams; 1.33 moles). Lime (Ca(OH)2; 223
grams; 6.03 equivalents) is then added and the contents are begun to be
stirred. The
contents of the reactor are heated to 99° -110°C (210°-
230°F) with stirring and held
at that temperature until a base number (phenolphthalein) of 4.7-14.1 is
reached.
The product obtained is saponified coconut oil (calcium carboxylate of coconut
acid)
in mineral spirits.
Example 2A
To the mixture of Example lA is added 2104 grams of mineral spirits. This
cools the reaction mixture to 92°C (200°F). Then carbonation is
carned out in seven
increments. Each increment of carbonation includes 155 grams (4.19 equivalent)
of
lime and blowing of carbon dioxide into the reaction mixture. In each
increment, the
lime is initially allowed to mix thoroughly with the reaction mixture before
carbon
dioxide is bubbled into the mixture. Carbon dioxide is initially bubbled
slowly into
the reaction mixture and then the rate is increased. The approximate time for
carbonation per increment is 3 hours. About 30 grams of COZ is used per hour
during each increment. Starting in the second increment and continuing in
subsequent increments, 2-methyl-1-propanol (54 grams; 0.73 mole) is charged
(this
corresponds approximately to 0.35 mole of 2-methyl-1-propanol per mole of
water
generated in the increment), followed by 155 g of lime and bubbling of carbon
dioxide in the manner disclosed in preceding sentences. The carbonation step
is
repeated in each increment. The mixture is cooled as needed to keep the rate
of
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bubbling of COZ at a maximum while not allowing the overbased calcium
carboxylate to freeze. (At a temperature above 95°C, COZ simply blows
through the
reaction mixture and is not absorbed by the lime to produce calcium carbonate,
while at a temperature of about 50°C, the overbased calcium carboxylate
freezes; it
is therefore important to maintain the temperature at about 55-90°C, so
that carbon
dioxide can be blown at a rate sufficiently high that it can actually be
absorbed by
the lime while not allowing the overbased carboxylate to freeze). At the end
of the
seventh and final increment of carbonation, C02 is continued to be bubbled to
a base
number (phenolphthalein) of about 4-7. The temperature at the end of this
carbonation procedure is about 70°C. The mixture at this point is an
overbased (but
not gelled) calcium carboxylate in mineral spirits.
Example 3A
To the mixture of Example 2A is charged 506 grams of 2-methyl-1-propanol
and 189 grams of water. The mixture is heated to 82.2°C (180°F).
The process is
monitored by infrared spectroscopy by monitoring the shift of an absorbance
peak
from approximately 864 cm-' to 877 cm' indicative of change to crystalline
carbonate from amorphous carbonate (conversion from homogeneous overbased
carboxylate to overbased carboxylate gel). About 1416 grams of mineral spirits
are
added when about 80% of total carbonate is converted to the crystalline form
(as
determined by the IR peaks at 864 and 877 cm-'). Another 2192 grams of mineral
spirits are added when 90-100% of the carbonate is converted from the
amorphous to
the crystalline form. The reaction mixture at this point is a gelled overbased
calcium
carboxylate.
Example 4A
3185 parts of methanol, 28.25 parts of calcium chloride and 226.5 parts of
tap water are added to a glass-lined reactor equipped with a heating mantle,
thermocouple, metal stirrer, gas inlet tube and condenser. The mixture is
heated to
48 °C. with stirnng. 644.5 parts of Silo lime (94% calcium hydroxide)
are added to
the mixture to provide a slurry. The temperature of the mixture is reduced to
45 °C.
7075 parts of polypropylene (MW=337) substituted benzene sulfonic acid are
added
to the mixture over a period of one hour. The temperature of the mixture
exotherms
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to 46°C. The mixture is stirred for one-half hour. 6275 parts of SC
Solvent 100 (a
high-boiling alkylated aromatic solvent) are added to the mixture and the
mixture is
stirred for 15 minutes. Three increments of 1772.75 parts of Silo lime are
added to
the mixture. Carbon dioxide at a rate of five standard cubic feet per hour is
bubbled
through the mixture after each increment. Total blowing with carbon dioxide is
approximately 10.5 hours with the temperature of the mixture varying from
40°C to
50°C. The mixture is stripped with nitrogen blowing at a rate of two
standard cubic
feet per hour while heating to reflux over a nine-hour period, the temperature
increasing over said period from 47°C to 160°C. The mixture is
cooled to room
temperature. The mixture is filtered through a Gyro Tester clarifier. The
solids
content is adjusted to 70% solids with SC Solvent 100. The product is a
overbased
sulfonate in SC-100.
Example 5A
15,000 parts of the product of Example 4A are placed in a glass-lined reactor
equipped with a heating mantle, thermocouple, gas inlet tube, condenser and
metal
stirrer, and heated to 40°C with stirnng. Carbon dioxide is bubbled
through the
mixture at a rate of one cubic foot per hour for 3.75 hours, the temperaure of
the
mixture varying from 38°C to 46°C during the carbon dioxide
blowing. 847.8 parts
of isopropyl alcohol, 847.8 parts of methanol and 1304 parts of distilled
water are
added to the mixture over a five-minute period. The mixture exotherms to
45°C and
is then heated to 67°C. 2500 parts of SC Solvent 100 are added to the
mixture. The
mixture is heated to 78°C and maintained at said temperature for 0.5
hour. The
mixture is stripped by bubbling nitrogen at a rate of two standard cubic feet
per hour
through the mixture over a period of 5.5 hours, the temperature of the mixture
increasing from 77°C to 155°C during stripping. The mixture is
cooled with cooling
water, and 16,700 parts of a gelled product having a solids content of 62.5%
by
weight are obtained. The product is an overbased sulfonate gel in SC-100.
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Example 6A
1200 parts of the product of Example SA are placed in a resin reactor
equipped with a heating mantle, metal stirrer, teflon bearing, gas inlet tube,
thermocouple, trap and condenser. 225.5 parts of polypropylene (MW=337)
substituted benzene sulfonic acid are added to the mixture over a 10-minute
period,
and the mixture exotherms to 34°C. The temperature of the mixture is
maintained at
34°C for 20 minutes. Water is stripped from the mixture by bubbling
nitrogen at a
rate of two standard cubic feet per hour through the mixture. The trap is
filled with
SC Solvent 100 to prevent solvent loss. The temperature increases to
162°C over a
two-hour period during stripping. The temperature is then maintained at
162°C for
0.5 hour. 7.5 cubic centimeters of water are collected. The mixture is cooled
to room
temperature, and 1413 parts of a low oil overbased sulfonate gel with a zero
base
number are obtained.
Example 7A
Distilled tall oil fatty acid, 580 g, is placed in a reactor and combined with
1200 g Stoddard Solvent (a solvent similar to mineral spirits) and 89 g of
calcium
hydroxide. The mixture is heated with stirring to 95-100°C and held for
1 hour. The
mixture is cooled to and maintained at 50-55°C; 100 g of isopropanol
and 136 g of
calcium hydroxide are added. Carbon dioxide is bubbled into the mixture at the
rate
of 28 L (1.0 standard cubic feet) per hour for 1 to 1.5 hours until a base
number to
phenolphthalein of 0-10 is reached. To the mixture are added 100 g of
isopropanol
and 136 g of calcium hydroxide, and additional carbon dioxide is bubbled into
the
mixture at the same rate for 1 to 1.5 hours until a base number
(phenolphthalein) of
0-10 is reached. Additional 100 g isopropanol and 136 g of calcium hydroxide
is
added and the mixture similarly carbonated for 1 to 1.5 hours to a base number
of
0-10. The mixture is then heated to 160°C to remove the alcohols and
water of
reaction. The material is cooled to ambient temperature and centrifuged for 1
hour
at 1800 rpm to remove impurities. The product obtained is an overbased calcium
tallate in Stoddard Solvent.
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Example 8A
Four hundred forty-nine g of purified low erucic rapeseed oil is placed in a
reaction flask and combined with 692 g of 100 N paraffinic oil, 33 g of
glycerin, and
37 g. of calcium hydroxide. This mixture is heated with stirring to
140°C and held
at temperature for 4 hours. The material is cooled to SO-55°C; 173 g of
isopropanol
and 92 g of calcium hydroxide are added. Carbon dioxide is bubbled into the
mixture at the rate of 28 L (1.0 standard cubic feet) per hour until a base
number
(phenolphthalein) of 0-10 is reached. Calcium hydroxide, 92 g, is added and
similarly carbonated to a final base number of 0-10. The mixture is heated to
160°C
to remove isopropanol and water of reaction. The material is cooled to ambient
temperature and centrifuged for 1 hour at 1800 rpm to remove impurities. The
resulting product is an overbased calcium rapeseed acid in oil.
Example 9A
Example 8A is substantially repeated except that the 100 N paraffinic oil is
replaced by "SC-100", an aromatic solvent approximately equivalent to methyl
ethyl
benzene. In place of the final heating to 160°C, the mixture is heated
to 140°C to
remove the isopropanol and water of reaction. After centrifugation, 93 g of SC-
100
is added to adjust the material to 51% non-volatile materials. The product is
an
overbased calcium rapeseed acid in SC-100.
Example l0A
Four hundred thirty-six g of purified coconut oil is placed in a reaction
flask
and combined with 500 g SC-100, 43 g of glycerin, and 89.5 g calcium
hydroxide.
The mixture is heated with stirring to 140°C and held at temperature
for 4 hours.
The mixture is cooled to and maintained at 90°C, and 1000 g SC-100
and 100 g
isopropanol are added. The temperature is further reduced to 50-55°C.
Calcium
hydroxide, 132.8 g, is added and carbon dioxide is bubbled into the mixture at
the
rate of 28 L (1.0 standard cubic feet) per hour for 1-1.5 hours to a
phenolphthalein
base number of 0-10. Another charge of 132.8 g calcium hydroxide and 100 g
isopropanol is added and the mixture is carbonated at the same rate for 1-1.5
hours
to the same base number. Finally, another 132.8 g calcium hydroxide and 100 g
isopropanol are added and, because of high viscosity, 1000 g of SC-100 is
added.
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The mixture is carbonated at the same rate for 1-1.5 hours to the same base
number.
The mixture is heated to 157°C to remove the isopropanol and water of
reaction.
The material is cooled to 50°C, 1220 g of SC-100 is added and mixed in
for 0.5
hours, and the material is centrifuged for 1 hour at 1800 rpm. The decantate
is the
product, which is an overbased calcium coconut acid in SC-100.
Example 11A
A reactor is charged with 1063 grams of Exxprint 588D solvent, 763 grams
(3.5 equivalents) of coconut oil, 2-methyl-1-propanol (90.6 grams), followed
by
water (13.8 grams). Calcium hydroxide (142.5 grams; 3.85 equivalents) is then
added and the contents are begun to be stirred. The contents of the reactor
are
heated to about 100°C (212°F) with stirnng and held at that
temperature until a base
number (phenolphthalein) of about 13 is reached. The product at this stage is
saponified coconut oil in Exxprint 588D solvent.
Example 12A
To 592 g (1.1 equivalents) of the mixture from Example 11A are added 206 grams
of Exx-588D and 76 grams of 2-methyl-1-propanol. Heated the mixture to 80 C
and
begin adding calcium hydroxide (61.7 grams, 1.67 equivalents). Carbon dioxide
(37.4 grams, 1.7 equivalents) was slowly bubbled into the mixture at about
27.8
grams/hour rate over approx. 1.2 hours. This process of adding additional
calcium
hydroxide and blowing carbon dioxide was repeated two more times at same
increments as in Example 2A. The mixture at this point is an overbased calcium
coconut acid in Exxprint 588D solvent.
Example 13A
To the mixture from example 12A was charged with 113 g of Exxprint
588D, 110 g of isobutanol, 56 g of water and 2.5 g of calcium hydroxide. The
mixture was heated to reflux at about 90 C under a blanket of nitrogen for
about 195
minutes. The mixture was then heated to about 98°C to strip out
isobutanol and
water. 393 grams of additional Exxprint 588D was added and the contents were
heated to 158 C to remove any residual alcohols or water. The product is
overbased
and gelled coconut acid in Exxprint 588D.
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The Dispersant
The dispersant in this application is a material that is useful to disperse
pigments in an oleophiliic media. These tend to be low molecular weight
emulsifiers or the anhydride or diacid precursor to the emulsifier. A
preferred
dispersant is a hydrocarbyl substituted succinic acid, its anhydride, or the
reaction
product of either with an alcohol, an amine, an amino alcohol (hydroxy amine)
etc.
to make an emulsifier as explained later. The hydrocarbyl substituted succinic
acid
or anhydride may be represented by the formulae
R-CH-COOH
CH2 COOH
or
O
O
v
O
wherein in each of the above formulae, R is a hydrocarbyl group of about 8 to
about
300 carbon atoms and in one embodiment about 30 to about 200 carbon atoms, and
in one embodiment about 12 to about 30 carbon atoms. R can be an alkyl or an
alkenyl group. Some of these alkenyl succinic anhydrides are commercially
available from companies such as Lubrizol under the trade name Ircosperse~.
In one embodiment, a mixture of at least two hydrocarbyl substituted
succinic acids or anhydrides. The hydrocarbyl group R in the above formulae
may
be derived from an alpha-olefin or an alpha-olefin fraction. The alpha-olefins
include 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-
heptadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-triacontene, and the
like. The
alpha olefin fractions that are useful include C,5_~$ alpha-olefins, Clz_1~
alpha-olefins,
Cia-16 alpha-olefins, C14_,8 alpha-olefins, C~6_,8 alpha-olefins, C~g_24 alpha-
olefins,
C,$_3o alpha-olefins, and the like. Mixtures of two or more of any of the
foregoing
alpha-olefins or alpha-olefin fractions may be used.
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In one embodiment, R in the above formulae is a hydrocarbyl group derived
from an olefin oligomer or polymer. The olefin oligomer or polymer may be
derived
from an olefin monomer of 2 to about 10 carbon atoms, and in one embodiment
about 3 to about 6 carbon atoms, and in one embodiment about 4 carbon atoms.
Examples of the monomers include ethylene; propylene; butene-l; butene-2;
isobutene; pentene-1; heptene-1; octene-1; nonene-1; decene-1; pentene-2; or a
mixture of two of more thereof.
In a particularly advantageous embodiment of the invention, the olefin
polymers are poly(isobutene)s such as obtained by polymerization of a C4
refinery stream having a butene content of about 35 to about 75% by weight and
an
isobutene content of about 30 to about 60% by weight in the presence of a
Lewis
acid catalyst such as aluminum chloride or boron trifluoride. These
polyisobutenes
preferably contain predominantly (that is, greater than about 80% of the total
repeat
units) isobutene repeat units of the configuration.
The hydrocarbyl-substituted carboxylic acids, and anhydrides, and ester and
amide derivatives thereof, can be prepared by any of several known procedures
which are described in the following U.S., British and Canadian patents: U.S.
Pat.
Nos. 3,024,237; 3,087,936; 3,172,982; 3,215,707; 3,219,666; 3,231,587;
3,245,910;
3,254,025; 3,271,310; 3,272,743; 3,272,746; 3,278,550; 3,288,714; 3,307,928;
3,312,619; 3,341,542; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179;
3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330;
3,912,764; and 4,368,133. British Pat. Nos. 944,136; 1,085,903; 1,162,436; and
1,440,219. Canadian Pat. No. 956,397. These patents are incorporated herein by
reference.
One procedure for preparing the hydrocarbyl-substituted carboxylic acids and
anhydrides, and ester and amide derivatives is illustrated, in part, in U.S.
Pat. No.
3,219,666. This procedure is conveniently designated as the "two-step
procedure". It
involves first chlorinating an olefin polymer until there is an average of at
least about
one chloro group for each molecular weight of olefin polymer. (For purposes of
this
invention, the molecular weight of the olefin polymer is the weight
corresponding to
the Mn value.) Chlorination involves merely contacting the olefin polymer with
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chlorine gas until the desired amount of chlorine is incorporated into the
chlorinated
polyolefin. Chlorination is generally carried out at a temperature of about
7°C to
about 125 °C . If a diluent is used in the chlorination procedure, it
should be one
which is not itself readily subject to further chlorination. Poly- and
perchlorinated
and/or fluorinated alkanes and benzenes are examples of suitable diluents.
The second step in the two-step chlorination procedure is to react the
chlorinated polyolefin with the alpha-beta olefinically unsaturated carboxylic
acid
reagent at a temperature usually within the range of about 100 °C to
about 200 °C.
The mole ratio of chlorinated polyolefin to carboxylic acid reagent is usually
about
1:1. (For purposes of this invention, one mole of a chlorinated polyolefin has
the
molecular weight of a chlorinated polyolefin corresponding to the Mn value of
the
unchlorinated polyolefin.) However, a stoichiometric excess of carboxylic acid
reagent can be used, for example, a mole ratio of 1:2. If an average of more
than
about one chloro group per molecule of polyolefin is introduced during the
chlorination step, then more than one mole of carboxylic acid reagent can
react per
mole of chlorinated polyalkene. Because of such situations, it is better to
describe
the ratio of chlorinated polyolefin to carboxylic acid reagent in terms of
equivalents.
_(An equivalent weight of chlorinated polyolefin, for purposes of this
invention, is the
weight corresponding to the Mn value divided by the average number of chloro
groups per molecule of chlorinated polyolefin. An equivalent weight of a
carboxylic
acid reagent is its molecular weight.) Thus, the ratio of chlorinated
polyolefin to
carboxylic acid reagent will normally be such as to provide about one
equivalent of
carboxylic acid reagent for each mole of chlorinated polyolefin up to about
one
equivalent of carboxylic acid reagent for each equivalent of chlorinated
polyolefin
with the understanding that it is normally desirable to provide an excess of
carboxylic acid reagent; for example, an excess of about 5% to about 25% by
weight. Unreacted excess carboxylic acid reagent may be stripped from the
reaction
product, usually under vacuum, or reacted during a further stage of the
process as
explained below.
The resulting polyolefin-substituted carboxylic acid or anhydride, or ester or
amide derivative, is, optionally, again chlorinated if the desired number of
CA 02506631 2005-05-19
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carboxylic groups are not present in the product. If there is present, at the
time of this
subsequent chlorination, any excess carboxylic acid reagent from the second
step,
the excess will react as additional chlorine is introduced during the
subsequent
chlorination. Otherwise, additional carboxylic acid reagent is introduced
during
and/or subsequent to the additional chlorination step. This technique can be
repeated until the total number of carboxylic groups per equivalent weight of
substituent groups reaches the desired level.
Another procedure for preparing hydrocarbyl-substituted carboxylic acids
and derivatives of the invention utilizes a process described in U.S. Pat. No.
3,912,764 and U.K. Pat. No. 1,440,219. Both of these patents are incorporated
herein
by reference. According to this procedure, the polyolefin and the carboxylic
acid
reagent are first reacted by heating them together in a direct alkylation
procedure.
When the direct alkylation step is completed, chlorine is introduced into the
reaction
mixture to promote reaction of the remaining unreacted carboxylic acid
reagent.
According to these patents, 0.3 to 2 or more moles of carboxylic acid reagent
are
used in the reaction for each mole of olefin polymer. The direct alkylation
step is
conducted at temperatures of about 180°C to about 250°C. During
the chlorine-
introducing stage, a temperature of about 160°C to about 225°C
is employed.
A preferred process for preparing the hydrocarbyl-substituted carboxylic
acids and derivatives of this invention, is the so-called "one-step" process.
This
process is described in U.S. Pat. Nos. 3,215,707 and 3,231,587. Both of these
patents
are incorporated herein by reference. Basically, the one-step process involves
preparing a mixture of the polyolefin and the carboxylic acid reagent
containing the
necessary amounts of both to provide the desired hydrocarbyl-substituted
carboxylic
acids or derivatives of this invention. Chlorine is then introduced into the
mixture,
usually by passing chlorine gas through the mixture with agitation, while
maintaining the mixture at a temperature of at least about 140°C. A
variation on this
process involves adding additional carboxylic acid reagent during or
subsequent to
the chlorine introduction. Usually where the polyolefin is sufficiently fluid
at 140°C
and above, there is no need to utilize an additional substantially inert,
normally
liquid solventldiluent in the one-step process. However, as explained
hereinbefore,
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if a solvent/diluent is employed, it is preferably one that resists
chlorination. Again,
the poly- and perchlorinated and/or -fluorinated alkanes, cycloalkanes, and
benzenes
can be used for this purpose.
Chlorine may be introduced continuously or intermittently during the one-
s step process. The rate of introduction of the chlorine is not critical
although, for
maximum utilization of the chlorine, the rate should be about the same as the
rate of
consumption of chlorine in the course of the reaction. When the introduction
rate of
chlorine exceeds the rate of consumption, chlorine is evolved from the
reaction
mixture. It is often advantageous to use a closed system, including super
atmospheric
pressure, in order to prevent loss of chlorine so as to maximize chlorine
utilization.
The minimum temperature at which the process is normally carned out is in
the neighborhood of 140°C. A preferred temperature range is between
about 160 °C
and about 220°C. Higher temperatures such as 250°C or even
higher may be used
but usually with little advantage. In fact, temperatures in excess of
220°C are often
disadvantageous because they tend to "crack" the polyolefins (that is, reduce
their
molecular weight by thermal degradation) and/or decompose the carboxylic acid
reagent. For this reason, maximum temperatures of about 200 °C to about
210°C are
normally not exceeded. The upper limit of the useful temperature in the one-
step
process is determined primarily by the decomposition point of the components
in the
reaction mixture including the reactants and the desired products. The
decomposition point is that temperature at which there is sufficient
decomposition of
any reactant or product such as to interfere with the production of the
desired
products.
In the one-step process, the molar ratio of carboxylic acid reagent to
chlorine
is such that there is at least about one mole of chlorine for each mole of
carboxylic
acid reagent to be incorporated into the product. Moreover, for practical
reasons, a
slight excess, usually in the neighborhood of about 5% to about 30% by weight
of
chlorine, is utilized in order to offset any loss of chlorine from the
reaction mixture.
Larger amounts of excess chlorine may be used but do not appear to produce any
beneficial results.
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The dispersant can be the reaction product of the reaction between the
hydrocarbyl substituted succinic acid or its anhydride with an alcohol, an
amine, or
an amino alcohol. This product may be an ester or a partial ester when the
second
reactant is an alcohol. This product may be an amide, imide, salt, amide/salt,
partial
amide or mixture of two or more thereof when the second component is a
polyamine. This product may be an ester, partial ester, amide, partial amide,
amide/salt, imide, ester/salt, salt, or a mixture of two or more thereof when
component (B) is a hydroxyamine, a mixture of polyol and polyamine, a mixture
of
polyol and hydroxyamine, or a mixture of polyamine and hydroxyamine. The salt
may be an internal salt involving residues of a molecule of the acid or
anhydride and
the polyamine or hydroxyamine wherein one of the carboxyl groups becomes
sonically bound to a nitrogen atom within the same group; or it may be an
external
salt wherein the ionic salt group is formed with a nitrogen atom that is not
part of the
same molecule.
During the first reaction step, the first and second components are mixed
together and heated at an effective temperature to form the product or a first
intermediate. In one embodiment, the temperature is in the range of from about
30°C to about 120°C, and in one embodiment from about
50°C to about 90°C. The
reaction time is typically from about 1 to about 120 minutes, and in one
embodiment
about 1 to about 60 minutes. The components may be dispersed or dissolved in a
normally liquid, substantially inert organic liquid solvent/diluent during the
reaction.
In one embodiment, the components are reacted in amounts sufficient to provide
an
equivalent ratio of from about 3:1 to about 1:2. In one embodiment, this ratio
is
from about 1:1 to about 1:2, and in one embodiment about 1:1.4 to about 1:1.9.
During the second reaction step the first intermediate product from the first
reaction step is heated at a sufficient temperature to form a second
intermediate
product with water of reaction being formed. The temperature may be in the
range
of about 130°C to about 210°C, and in one embodiment about
135°C to about
150°C. The reaction time is typically from about 1 to about 10 hours,
and in one
embodiment about 1.5 to about 3 hours. When the second component includes a
polyol, the second intermediate product comprises one or more bisesters,
triesters or
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low order (about 2 to about 6, and in one embodiment about 2 to about 4)
oligomers
containing ester, or ester and acid functionality. When the second component
is a
polyamine, the second intermediate product comprises one or more bisamides,
bisimides, amide/imide, or low order (about 2 to about 6, and in one
embodiment
about 2 to about 4) oligomers containing amide, imide, amide/imide, acid
and/or salt
functionality. When the second component is a hydroxyamine, the second
intermediate product comprises one or more bisamides, bisesters, ester/amides
or
low order (about 2 to about 6, and in one embodiment about 2 to about 4)
oligomers
containing ester, amide, acid and/or salt functionality. When the second
component
is a mixture of a polyol, polyamine and/or hydroxyamine, the second
intermediate
product comprises one or more of the above-mentioned products depending upon
which polyol, polyamine and/or hydroxyamine is used. During second step a
portion
of the water of reaction is separated from the second intermediate product
using
known techniques (e.g., distillation, azeotropic removal of water, molecular
sieves,
etc.) to provide the desired partially dehydrated product. When first
component is a
succinic anhydride, the amount of water of reaction that is removed is
generally from
about 0.2 to about 0.9 moles of water per equivalent of succinic anhydride,
and in
one embodiment about 0.3 to about 0.8 moles of water per equivalent of
succinic
anhydride, and in one embodiment about 0.4 to about 0.6 moles of water per
equivalent of succinic anhydride. When the first component is a succinic acid,
the
amount of water of reaction that is removed is generally from about 1.2 to
about 1.9
moles of water per equivalent of succinic acid, and in one embodiment about
1.3 to
about 1.8 moles of water per equivalent of succinic acid, and in one
embodiment
about 1.4 to about 1.6 moles of water per equivalent of succinic acid.
The reaction product may be used directly. Alternatively, it may be diluted
with a normally liquid organic diluent such as mineral oil, naphtha, benzene,
or
toluene to form an additive concentrate. The normally liquid organic diluent
may be
one or more of the precursors or reactants used to make the inventive reaction
product, or one or more of the oils or fuels used to make the inventive
emulsions
described herein.
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In one embodiment, the alcohol (e.g. polyol) is a compound represented by
the formula
R-(OH)",
wherein in the foregoing formula, R is an organic group having a valency of m,
R is
joined to the OH groups through carbon-to-oxygen bonds, and m is an integer
from 1
to about 10, and in one embodiment 1 to about 3. The polyol may be a
monohydric
alcohol, glycol, a polyoxyalkylene glycol, a carbohydrate, or a partially
esterfied
polyhydric alcohol. Mixtures of two or more of the foregoing can be used.
The amine may be aliphatic, cycloaliphatic, heterocyclic or aromatic
10' compound. Examples include alkylene polyamines and heterocyclic
polyamines.
The alkylene polyamines may be represented by the formula
HN-(Alkylene-N)"R
R R
wherein n has an average value between 1 and about 10, and in one embodiment
about 1 to about 3, the "Alkylene" group has from 1 to about 10 carbon atoms,
and
in one embodiment about 2 to about 6 carbon atoms, and each R is independently
hydrogen or an aliphatic or hydroxy-substituted aliphatic group of up to about
30
carbon atoms. These alkylene polyamines include ethylene polyamines, butylene
polyamines, propylene polyamines, pentylene polyamines, etc.
The hydroxyamine may be a primary, secondary or tertiary amine. The terms
"hydroxyamine" and "aminoalcohol" describe the same class of compounds and,
therefore, can be used interchangeably. In one embodiment, the hydroxyamine is
(a)
an N-(hydroxyl-substituted hydrocarbyl) amine, (b) a hydroxyl-substituted
poly(hydrocarbyloxy) analog of (a), or a mixture of (a) and (b). The
hydroxyamine
may be alkanolamine containing from 1 to about 40 carbon atoms, and in one
embodiment 1 to about 20 carbon atoms, and in one embodiment 1 to about 10
carbon atoms.
The hydroxyamine may be a primary, secondary or tertiary alkanol amine, or
a mixture of two or more thereof. These hydroxyamines may be represented,
respectively, by the formulae:
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HZN-R'-OH
H\
N-R'-OH
R
and
R\
N-R'-OH
R
wherein each R is independently a hydrocarbyl group of one to about eight
carbon
atoms or hydroxyl-substituted hydrocarbyl group of two to about eight carbon
atoms
and R' is a divalent hydrocarbon group of about two to about 18 carbon atoms.
Typically each R is a lower alkyl group of up to seven carbon atoms. The group
-R'-OH in such formulae represents the hydroxyl-substituted hydrocarbyl group.
R'
can be an acyclic, alicyclic or aromatic group. Typically, R' is an acyclic
straight or
branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene,
1,2-octadecylene, etc. group.
When two R groups are present in the same molecule they can be joined by a
direct carbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen
or
sulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples of such
heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines,
-thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and the like.
The hydroxyamines may be ether N-(hydroxy-substituted
hydrocarbyl)amines. These may be hydroxyl-substituted poly(hydrocarbyloxy)
analogs of the above-described hydroxy amines (these analogs also include
hydroxyl-substituted oxyalkylene analogs). Such N-(hydroxyl-substituted
hydrocarbyl) amines may be conveniently prepared by reaction of epoxides with
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afore-described amines and may be represented by the formulae:
H2N-(R'O)X-H
H \
~ N-(R'O)X-H
R
R
N-(R'O)x-H
R
wherein x is a number from about 2 to about 15, and R and R' are as described
above.
Polyamine analogs of these hydroxy amines, particularly alkoxylated
alkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine) may be used. Such
polyamines can be made by reacting alkylene amines (e.g., ethylenediamine)
with
one or more alkylene oxides (e.g., ethylene oxide, octadecene oxide) of two to
about
carbons. Similar alkylene oxide-alkanol amine reaction products can also be
used
such as the products made by reacting the afore-described primary, secondary
or ter-
tiary alkanol amines with ethylene, propylene or higher epoxides in a 1:1 or
1:2
20 molar ratio. Reactant ratios and temperatures for carrying out such
reactions are
known to those skilled in the art.
Specific examples of alkoxylated alkylene polyamines include
N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl)-ethylene-diamine,
1-(2-hydroxyethyl) piperazine, mono(hydroxypropyl)-substituted diethylene
triamine, di(hydroxypropyl)-substituted tetraethylene pentamine, N-(3-hydroxy
butyl)-tetramethylene diamine, etc. Higher homologs obtained by condensation
of
the above-illustrated hydroxy alkylene polyamines through amino groups or
through
hydroxy groups are likewise useful. Condensation through amino groups results
in a
higher amine accompanied by removal of ammonia while condensation through the
hydroxy groups results in products containing ether linkages accompanied by
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removal of water. Mixtures of two or more of any of the aforesaid mono- or
polyamines are also useful.
Examples of the N-(hydroxyl-substituted hydrocarbyl) amines include mono-,
di-, and triethanolamine, dimethylethanolamine, diethylethanolamine,
di-(3-hydroxylpropyl) amine, N-(3-hydroxylbutyl) amine, N-(4-hydroxylbutyl)
amine, N,N-di-(2-hydroxylpropyl) amine, N-(2-hydroxylethyl) morpholine and its
thio analog, N-(2-hydroxylethyl) cyclohexylamine, N-3-hydroxyl cyclopentyl
amine,
o-, m- and p-aminophenol, N-(hydroxylethyl) piperazine, N,N'-di(hydroxyl
ethyl)
piperazine, and the like.
Further hydroxyamines are the hydroxy-substituted primary amines described
in U.S. Patent 3,576,743 by the general formula
Ra NHZ
wherein Ra is a monovalent organic group containing at least one alcoholic
hydroxy
group. The total number of carbon atoms in Ra preferably does not exceed about
20.
Hydroxy-substituted aliphatic primary amines containing a total of up to about
10
carbon atoms are useful. The polyhydroxy-substituted alkanol primary amines
wherein there is only one amino group present (i.e., a ppmary amino group)
having
one alkyl substituent containing up to about 10 carbon atoms and up to about 6
hydroxyl groups are useful. These alkanol primary amines correspond to Ra-NHZ
wherein Ra is a mono-O or polyhydroxy-substituted alkyl group. It is desirable
that
at least one of the hydroxyl groups be a primary alcoholic hydroxyl group.
Specific
examples of the hydroxy - substituted primary amines include 2-amino-1-
butanol,2-
amino-2-methyl-1-propanol,p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-
amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-
propanediol, N-(betahydroxypropyl)-N'-(beta-aminoethyl)-pi-perazine, tris-
(hydroxymethyl) aminomethane (also known as trismethylolaminomethane), 2-
amino-1-butanol, ethanolamine, beta-(beta-hydroxyethoxy)-ethylamine,
glucamine,
glusoamine, 4-amino-3-hydroxy-3-methyl-1-butene (which can be prepared
according to procedures known in the art by reacting isopreneoxide with
ammonia),
N-3(aminopropyl)-4-(2-hydroxyethyl)-piperadine,2-amino-6-methyl-6-heptanol,5-
amino-1-pentanol, N-(beta-hydroxyethyl)-1,3-diamino propane, 1,3-diamino-2-
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hydroxypropane, N-(beta-hydroxy ethoxyethyl)-ethylenediamine, trismethylol
aminomethane and the like.
Hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl
substituents on the nitrogen atoms, are also useful. Useful hydroxyalkyl-
substituted
alkylene polyamines include those in which the hydroxyalkyl group is a lower
hydroxyalkyl group, i.e., having less than eight carbon atoms. Examples of
such
hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl) ethylene
diamine,
N,N-bis(2-hydroxyethyl) ethylene diamine, 1-(2-hydroxyethyl)-piperazine,
monohydroxypropyl-substituted diethylene triamine, dihydroxypropyl-substituted
tetraethylene pentamine, N-(3-hydroxybutyl) tetramethylene diamine, etc.
Higher
homologs as are obtained by condensation of the above-illustrated hydroxy
alkylene
polyamines through amino groups or through hydroxy groups are likewise useful.
Condensation through amino groups results in a higher amine accompanied by
removal of ammonia and condensation through the hydroxy groups results in
products containing ether linkages accompanied by removal of water.
In the following examples as well as throughout the specification and in the
claims, unless otherwise indicated, all parts and percentages are by weight,
all
temperatures are in degrees Celsius (mC), and all pressures are at or near
atmospheric.
Example 1B
A five-liter, four-neck flask fitted with a thermocouple, an addition funnel
topped with a Nz inlet, a Dean-Stark trap topped with a water condenser, and
an
overhead stirrer is charged with C18_3o alkenyl succinic anhydride (1740.8 g,
3.71
mol). The contents of the flask are stirred and heated to 64°C.
Diethanolamine (590
g, 5.62 mol) is added via the addition funnel over 35 minutes. The mixture
undergoes an exotherm to 105°C. The mixture is heated to 140°C
over 20 minutes
and held at that temperature for 2 hours and 40 minutes. Water of reaction (24
g) is
removed. The product has a TAN of 53 mg of KOH/g and a TBN of 53.7 mg of
KOH/g.
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Example 2B
A five-liter, four-neck flask fitted with a thermocouple, an addition funnel
topped with a NZ inlet, a Dean-Stark trap topped with a water condenser, and
an
overhead stirrer is charged with C1g-3o alkenyl succinic anhydride (1715 g,
3.66 mol).
The contents of the flask are stirred and heated to 50°C.
Diethanolamine (653 g, 6.22
mol) is added via the addition funnel over 25 minutes (reaction undergoes an
exotherm to 120°C). The mixture is heated to 140°C and held at
that temperature
for 5 hours. Water of reaction (35 g) is removed. The product has a TAN of 37
mg
of KOH/g, and a TBN of 57 mg of KOH/g.
Example 3B
A five-liter, four-neck flask fitted with a thermocouple, an addition funnel
topped with a NZ inlet, a Dean-Stark trap topped with a water condenser, and
an
overhead stirrer is charged with Cig_3o alkenyl succinic anhydride (2133 g,
4.55
mol). The contents of the flask are stirred and heated to 64°C.
Glycerol (628 g,
6.83 mol) is added via the addition funnel over 20-25 minutes. The mixture is
heated to 150°C over 40 minutes. The temperature of the reaction
mixture is
increased from 150°C to 170°C over a period of 5 hours and
maintained at 170°C for
an additional hour. Water of reaction (45 g) is removed. The product has a TAN
of
38 mg of KOH/g.
Example 4B
A three-liter, four-neck flask fitted with an overhead stirrer, a
thermocouple,
an addition funnel topped with a N2 inlet, and a Dean-Stark trap topped with a
condenser is charged with C1g-3o alkenyl succinic anhydride (1360.6 g, 2.90
mol).
The contents of the flask are stirred and heated to 63°C.
Diethanolamine (406 g, 3.87
mol) is added via the addition funnel over 27 minutes. During the addition,
the
reaction mixture undergoes an exotherm to 114°C. The temperature is
increased to
140°C over 15 minutes by external heating, and maintained at that
temperature for
45 minutes. Water of reaction (18 g) is removed. The mixture is cooled to room
temperature. The TAN of the final product is 60.7 mg of KOH/g.
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Example SB
A two-liter, four-neck flask equipped with a stopcock drain, an overhead
stirrer, a thermocouple, an addition funnel topped with a N2 inlet, and a Dean-
Stark
trap topped with a water condenser, is charged with C,8_3o alkenyl succinic
anhydride
(1050.3 g, 2.24 mol). The contents of the flask are heated to 60°C.
Triethanolamine
(158.7 g, 1.06 mol) and glycerol (293.9 g, 3.19 mol) are added sequentially
over a
30-minute period. During the triethanolamine addition, the reaction mixture
undergoes an exotherm to 90°C. Upon completion of glycerol addition,
the reaction,
mixture is stirred and heated to 140°C, and maintained at that
temperature for 5
hours to provide the final product which is in the form is a viscous brown
liquid.
Water of reaction (25 g) is removed. The product has a TAN of 29.3 mg of
KOH/g,
a TBN of 39.8 mg of KOH/g, and a nitrogen content of 0.98% by weight.
Example 6
A one-liter, four-neck flask fitted with a thermocouple, an addition funnel
topped with a NZ inlet, a Dean-Stark trap topped with a water condenser, and
an
overhead stirrer is charged with C1$_3o alkenyl succinic anhydride (251.4 g,
0.57 mol)
and a mixture of C,~ - C,8 alpha olefins (140.3 g). The contents of the flask
are
stirred and heated to 90°C. A polyamine bottoms product corresponding
predominately to tetraethylene pentamine (29.6 g, 0.71 mol), is added dropwise
via
the addition funnel. The mixture undergoes an exotherm to 110"'C. The mixture
is
maintained at 100~C for 3.5 hours. Water of reaction (3.15 g) is removed. The
product has a TAN of 49.7 mg of KOH/g.
Example 7B
A one-liter, four-neck flask fitted with a thermocouple, an addition funnel
topped with a N2 inlet, a Dean-Stark trap topped with a water condenser, and
an
overhead stirrer is charged with C1$_3o alkenyl succinic anhydride (315.6 g,
0.72 mol)
and a mixture of C16 - C~$ alpha olefins (167.0 g). The contents of the flask
are
stirred and heated to 90°C. A polyamine bottoms product corresponding
predominately to tetraethylene pentamine (30 g, 0.72 mol) is added via the
addition
funnel over 10 minutes. The mixture undergoes an exotherm to 120°C. The
mixture
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is maintained at100°C with stirnng for 3.5 hours. Water of reaction
(4.0 g) is
removed. The product has a TAN of 55.4 mg of KOH/g.
Example 8B
A one-pint jar is charged with propylene tetramer substituted succinic
anhydride (267 g) and diethanol amine (63 g) and heated to 160°C with
stirnng over
a period of 30 minutes. A nitrogen sparge at a rate of 5 standard cubic feet
per hour
is used during the heating period. Water of reaction is removed. The color of
the
liquid mixture changes from lemon-yellow to orange-amber.
Example 9B
A one-liter, five-neck flask is charged with propylene tetramer substituted
succinic anhydride (296 g), glycerine (96 g) and triethanol amine (176 g). The
mixture is heated to 110~C with stirnng and a nitrogen purge. The temperature
is
maintained at 110°C for 1 hour, then heated to 230°C over a
period of 3 hours.
Water (23 g) is removed. The mixture is cooled to 100°C and
filtered.
Example lOB
A two-liter, three-neck flask is charged with propylene tetramer substituted
succinic anhydride (592 g), glycerine (384 g), toluene (300 ml) and p-
CH3C~H4SO3'H2O (10 g). The mixture is heated to reflux with stirnng and a
nitrogen purge (0.05 standard cubic feet per hour) and held at reflux for 3
hours.
The temperature increases from 120°C to 135°C during this
period. Water (40 g)
and toluene (150 ml) are removed. The temperature is cooled to 90°C and
a 50%
aqueous solution of NaOH (4.3 g) is added dropwise with stirring. The mixture
is
stirred for 15 minutes. Toluene is stripped from the mixture at 110"'C and 15
mmHg. The mixture is filtered.
Each of the documents referred to above is incorporated herein by reference.
Except in the Examples, or where otherwise explicitly indicated, all numerical
quantities in this description specifying amounts of materials, reaction
conditions,
molecular weights, number of carbon atoms, and the like, are to be understood
as
modified by the word "about." Unless otherwise indicated, each chemical or
composition referred to herein should be interpreted as being a commercial
grade
material which may contain the isomers, by-products, derivatives, and other
such
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materials which are normally understood to be present in the commercial grade.
However, the amount of each chemical component is presented exclusive of any
solvent or diluent oil which may be customarily present in the commercial
material,
unless otherwise indicated. It is to be understood that the amount, range, and
ratio
limits set forth herein may be combined. As used herein, the expression
"consisting
essentially of" permits the inclusion of substances which do not materially
affect the
basic and novel characteristics of the composition under consideration. For
the
purposes of this application "consisting essentially of will exclude the use
of water
in oil emulsions and oil in water emulsions in the rheology additive, varnish
or
lacquer, and ink formulation as that would materially affect the rheology of
the
compositions. It is noted that U.S. 6,172,122 discloses emulsions of gelled
overbased substrates with surfactants and aqueous liquids.
38
