Note: Descriptions are shown in the official language in which they were submitted.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
1
TITLE: QUENCHING OIL COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to oil compositions that are useful as quenching oils
used in heat treating of metals, particularly ferrous metals such as steel.
BACKGROUND OF THE INVENTION
Desired hardness and strength properties of metals, particularly ferrous
metals and especially metal alloys such as carbon steel and alloy steel, are
secured
by heat treatment of the metal object. The properties usually depend upon
establishment of certain physical structures in the metal. The production of
the
desired physical structures is obtained by heating the metal to a temperature
where
the structure is present, then by arresting at the desired point the changes
in the
internal structure which take place during cooling of the metal from high
temperatures. Quick cooling by quenching the heated object in a quenching
medium
makes it possible to arrest the physical changes at the desired point during
cooling.
Quenching in the quenching medium is carried out in such a manner that the
physical changes in the metal are arrested at the desired point, usually at
the point at
which maximum hardness is obtained. Subsequently, the heat treated and
quenched
object may be subjected to treatment at lower temperature (annealing or
tempering)
to provide the desired degree of toughness and ductility.
For many years mineral oil based quenching fluids have been used.
Previously, aqueous quenching media were employed. The aqueous fluids provided
extremely rapid cooling setting up excessive amounts of internal stress in the
object.
Mineral oil based fluids avoided this difficulty, but often did not provide a
sufficiently high cooling rate to secure desirable properties in pieces formed
of
materials having high critical cooling rates to develop maximum strength and
hardness or to quench pieces of high mass to surface ratios to develop
hardness and
strength to maximum depth.
It is also desirable to provide quench oils that possess sufficient
durability,
cleanliness and consistency. Durability refers to additive lifetime after
being
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
2
exposed to thermal stressing while consistency relates to constant additive
performance over time. Cleanliness is measured using a coker test.
A detailed description of heat treating of steel appears at pages 961 et seq
of
the Metals Handbook, Desk Edition, Second Edition, J.R. Davis, Ed., ASM
International, Metals Park, OH, USA (1998). A discussion of quenching appears
at
pages 973-975 of that text.
U.S. Patent 2,340,724 relates to quenching oils comprising a light mineral
quenching oil and an oil-soluble, heat stable, high molecular weight iso-
olefin
polymerization product in a controlled amount adequate to produce a quenching
oil
composition having an initial S-second quenching speed of at least 22.0
percent
without substantially modifying the stress-reducing characteristics of the
oil.
Polymers of molecular weigh 1,000 to 10,000, and particularly, isobutylene
polymerization product, are said to be particularly advantageous.
U.S. Patent 3,489,619 relates to oil compositions described as having good
high temperature stability and useful as a heat transfer oil for the quenching
of
metals. The oil comprises a major proportion of a hydrocarbon lubricating oil
into
which has been dispersed a minor proportion of an alkali metal phosphate,
silicate or
borate with the aid of a minor proportion of a high molecular weight mono-
carboxylic acid, dicarboxylic acid or dicarboxylic acid anhydride.
U.S. Patent 3,567,640 describes a quenching oil composition comprised of a
major portion of a petroleiun oil having a viscosity within the range of about
40 to
about 300 SUS at 100°F and a flash point in excess of 250°F and
about 2% to about
15% by weight of a quench oil additive, which is an oil soluble petroleum
resin
produced from distillates of cracked petroleum stock having a melting point of
at
least 40°C and an aniline point value of less than 50°C.
U.S. Patent 3,855,014 describes an improved quenching oil composition
comprising a major amount of a quench oil of lubricating viscosity; a minor
amount
of at least one carbon-linked poly-phenate metal compound sufficient to
improve
the anti-staining properties of the composition and at least one naphthyl
amine
sufficient to improve the resistance to oxidation of the composition. The
composition may also include a minor amount of at least one of certain diamine
components said to provide further improved oxidation resistance.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
3
U.S. Patent 5,015,404 describes an oil composition containing 100 parts by
weight of a base oil selected from the group consisting of mineral base oil,
synthetic
base oil and mixtures thereof, and 0.1 to 20 parts by weight of a hydrogenated
oil
obtained by hydrogenating an oil selected from the group consisting of coal
type tar,
oil produced by fractionating coal type tar, a hydrocarbon obtained by
thermally
cracking petroleum and having a boiling point of not lower than 200°C,
a
hydrocarbon obtained by catalytically cracking petroleum and having a boiling
point
of not lower than 200°C, a hydrocarbon obtained by catalytically
reforming
petroleum and having a boiling point of not lower than 200°C, and
mixtures thereof,
whereby the hydrogenated oil has the hydrogen-donating properties of not lower
than three times the hydrogen-donating properties of the base oil at
temperatures of
not lower than 350°C.
U.S. Patent 5,250,122 discloses a heat treating oil composition which
comprises (A) at least one base oil selected from a mineral oil and a
synthetic oil
each having a sulfur content of not more than 300 ppm and (B) at least one
member
selected from alkaline earth metal salts of salicylic acid. There is also
disclosed a
heat treating oil composition which comprises (I) a base oil having a sulfur
content
of 3 to 1000 ppm consisting of said (A) component and (C) at lease one member
selected from a sulfur and a sulfur compound, along with (II) various
additives for
quenching. This heat treating oil composition is said to be suitable for
quenching
under the condition of a high oil temperature and capable of obtaining a
treated
metal excellent in brightness and having a minimized distortion.
U.S. Patent 5,376,186 describes a heat treating oil composition which
comprises a base oil adjusted to have a total sulfur content of 3 to 1000 ppm
comprising (A) at least one base oil selected from a mineral oil and a
synthetic oil
each having a sulfur content of not more than 300 ppm and (C) at least one
member
selected .from a sulfur and a sulfur compound, and (B) at least one additive
selected
from an alkaline earth metal salt of sulfonic acid, that of a phenol, alkenyl
succinic
acid derivatives, fatty acid or its derivatives and phenol-based and amine-
based
antioxidants. The above-mentioned heat treating oil composition is said to be
suitable for quenching under a condition of a high oil temperature to realize
a treated
metal product having a excellent brightness and little distortion.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
4
U.S. Patent 5,487,796 relates to a method of quenching metals, in particular
steel alloys includes treatment of the article being quenched in a boiling
aqueous
solution of sodium tetraborate, with gas being additionally introduced into
the
quench bath. The supply of gas enables a continuous operation in a wide range
of
application and avoids the use of conventional less environmentally friendly
quenching media (oils).
U.S. Patent 5,879,743 describes a wear-resistant hardfacing and a method
for applying such a hardfacing. A finely powdered, wear-resistant alloy and a
polyvinyl alcohol (PVA) solution slurry is coated onto the metal surface of a
tool,
implement, or similar item to be hardfaced. Alternatively, a binding coating
of PVA
solution may be applied to the metal surface followed by application of a
layer of a
powdered alloy. After the slurry or PVA binding coating has dried, leaving a
dry
coat of alloy in a PVA matrix, the metal surface is heated to the fusion
temperature
of the alloy in vacuum, in an inert gas atmosphere, or in hydrogen atmosphere.
The
metal item with the fused coating is heat treated to impart desired mechanical
properties to the part substrate material. The method of the present invention
gives a
smooth, dense coating of the wear-resistant hardfacing without nonmetallic
inclusions.
U.S. Patent 6,239,082 describes petroleum quench oils described as effective
for high speed cooling of heated metals and metal hardening. The petroleum
quench
oils contain natural or synthetic base oils having a minimum flash point of
about
120°C and a combination of poly(iso)alkylene and poly(iso)alkylene
succinic
anhydride or succinic acid. A method for cooling heated metal to harden it,
improve
the metallurgical consistency, improve machinability and reduce residue on
quenched metal parts is also disclosed comprising quenching the heated metal
part
in a quench oil containing natural or synthetic base oils having a minimum
flash
point of about 120°C and a combination of poly(iso)alkylene and
poly(iso)alkylene
succinic anhydride or succinic acid.
The quench oils of the instant invention afford durability, consistency and
suitable quenching characteristics. Suitable quenching characteristics include
a high
maximum cooling rate and a high maximum cooling rate temperature signifying
collapse of the vapor barrier between the workpiece and the quenching oil, and
a
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
lower cooling rate (6-8°C) after the workpiece has reached 300°C
to prevent thermal
distortionlcracking.
SUMMARY OF THE INVENTION
The instant invention is directed to a quenching oil composition comprising
5 (1) an oil having kinematic viscosity (ASTM Test Method D-445) at
40°C
ranging from about 4 to about 45 mmZSec ~ (about 40 to about 210 Saybolt
Universal Seconds (SUS)) and having a saturated content from about 80% to
about
100%;
(2) an aliphatic polyolefin having Mn ranging from about 300 to about
10,000; and
(3) at least one member selected from members of the groups consisting of
(a) a metal salt of hydrocarbyl substituted phenols, salicylic acids,
carboxylic acids, and sulfonic acids and alkaline earth metal salts of
hydrocarbyl
substituted saligenin derivatives; and optionally, at least one member
selected from
members of the groups consisting of
(b) hydrocarbyl substituted succinic esters, amides, ester-amides,
imides, amine salts, acid-esters, acid-amides ester-amine salts, amide-amine-
salts
and acid-amine salts.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As used herein, the terms "hydrocarbyl" or "hydrocarbon based" mean that
the group being described has predominantly hydrocarbon character within the
context of this invention. These include groups that are purely hydrocarbon in
nature, that is, they contain only carbon and hydrogen. They may also include
groups containing substituents or atoms which do not alter the predominantly
hydrocarbon character of the group. Such substituents may include halo-,
alkoxy-,
nitro-, hydroxyl, etc. These groups also may contain heteroatoms. Suitable
heteroatoms will be apparent to those skilled in the art and include, for
example,
sulfur, nitrogen and oxygen. Therefore, while remaining predominantly
hydrocarbon in character within the context of this invention, these groups
may
contain atoms other than carbon present in a chain or ring otherwise composed
of
carbon atoms.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
6
In general, no more than about three non-hydrocarbon substituents or
heteroatoms, and preferably no more than one, will be present for every 10
carbon
atoms in the hydrocarbon or hydrocarbon based groups. Most preferably, the
groups
are purely hydrocarbon in nature, that is, they are essentially free of atoms
other than
carbon and hydrogen.
It must be noted that as used in this specification and in the appended
claims,
the singular forms also include the plural unless the context clearly dictates
otherwise. Thus the singular forms "a", "an", and "the" include the plural;
for
example "an amine" includes mixtures of amines of the same type. As another
example the singular form "amine" is intended to include both singular and
plural
unless the context clearly indicates otherwise.
The Oil
The quenching oil compositions of this invention comprise at least one oil
having kinematic viscosity (ASTM Test Method D-445) at 40°C ranging
from about
4 to about 45 mm2sec ~ (40 to about 210 SUS) and having a saturated content
from
about 80% to about 100%. Both mineral oils and synthetic oils are useful.
Mixtures
of these oils are useful. In one preferred embodiment, the oil is a paraffinic
mineral
oil, particularly a solvent refined paraffinic oil. In another preferred
embodiment, the
oil is a hydrotreated mineral oil having kinematic viscosity of about 60 to
about 90
SUS. In yet another preferred embodiment, the oil is a poly-alphaolefin
oligomer,
preferably a polyoctene or polydecene oligomer.
Examples of useful oils include Excel/Paralube 70N, Excel/Paralube 75HC,
(both from Pennzoil/Conoco) and Ergon° Hygold P70N.
The Polyolefin
The quenching oil compositions of this invention contain (2) a polyolefin
having Mn ranging from about 300 to about 10,000, preferably from about 500 to
about 5,000 and more often from about 1,000 to about 3,000 and often ranging
from
about 1,500 to about 3,000.
In one preferred embodiment, the polyolefin is an aliphatic polyolefin
derived from at least one alpha olefin containing from 3 to about 8 carbon
atoms.
Polyolefins derived from more than one olefin, for example ethylene-propylene
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
7
copolymers, are useful. Polypropylene and polybutenes, especially
polyisobutylene,
are preferred. Polyisobutylene is particularly preferred.
In another preferred embodiment, the polyolefin is an olefin-polyene,
preferably dime, -especially preferred non-conjugated dime, copolymer, derived
from at least one olefin, preferably an alpha olefin containing from about 3
to about
8 carbon atoms and the ratio of total number of moles of olefin to moles of
polyene
ranges from about 100:1 to about 1:1, preferably 25:1 to 1:2 and most
preferably,
15:1 to 1:1. In a preferred embodiment, the olefin is isobutylene. Useful
polymers of
this type are commercially available, for example from BASF and BP Chemicals.
In one embodiment, the polyolefin is an olefin-dime copolymer comprising
from about 0.5 to about 5 moles of units derived from dime per mole of
copolymer
based on M~ of copolymer. In another embodiment, the polyolefin is an olefin-
polyene copolymer, wherein the olefin contains from 3 to about 8 carbon atoms
and
weight ratio of olefin to polyene ranges from about 250:1 to about 1:4,
preferably
25:1 to 1:2 and most preferably 15:1 to 1:1. In each of these embodiments, the
olefin
comprises isobutylene. Examples of olefin-dime copolymers include butyl
rubbers
(isobutylene-isoprene) and commercially available ethylene-propylene-dime
terpolymers sold by Uniroyal Chemicals under the tradename TRILENE~.
The Metal Salt
The quenching oil compositions of this invention contain at least one
member selected from the group consisting of a metal salt of hydrocarbyl
substituted
phenols, salicylic acids, carboxylic acids, and sulfonic acids and alkaline
earth metal
salts of hydrocarbyl substituted saligenin derivatives. The metal salts may be
acidic,
neutral or basic, often referred to as 'overbased'.
The relative amount of metal present in "basic salts" is frequently indicated
by the expression "metal ratio" (abbreviated MR), which is defined as the
number of
equivalents of metal present compared to a "normal", stoichiometric amount.
Thus,
for example, a basic salt containing twice the amount of metal compared to the
stoichiometric amount, has a metal ratio (MR) of 2. For the purposes of this
invention, the metal ratio of metal salts of phenols and salicylic acids
ranges from
about 0.5 to about S, preferably from about 0.5 to about 2 and the metal ratio
of
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
8
metal salts of sulfonic acids ranges from about 1 to about 20, preferably from
about
1 to about 3.
The basicity of the metal salts used in the present invention generally is
expressed in terms of a total base number TBN). TBN is the amount of acid
(perchloric or hydrochloric) needed to neutralize all of the metal salt's
basicity.
The amount of acid is expressed as potassium hydroxide equivalents. Total
base number is determined by the procedure described in ASTM D-2896.
Typically, the metal salt has TBN ranging from about 45 to about 900,
preferably
from about 100 to about 800.
Metal salts and techniques for preparing them are well known to those
skilled in the art. Neutral and acidic salts are generally prepared by
contacting the
acidic reactant with a metal reactant to form the salt. Overbased materials
are
prepared by reacting an acidic material (typically an inorganic acid or lower
carboxylic acid, preferably carbon dioxide) with a mixture comprising an
acidic
organic compound, a reaction medium comprising at least one inert, organic
solvent for said acidic organic material, a stoichiometric excess of a metal
base,
and a promoter.
The acidic organic compounds useful in making the metal salts of the
present invention include carboxylic acids, sulfonic acids, phenols and
hydrocarbyl substituted saligenin derivatives or mixtures of two or more
thereof.
Salicylic acids are considered as both phenols and carboxylic acids.
Salicylic acids can be aliphatic hydrocarbon-substituted salicylic acids
wherein
each aliphatic hydrocarbon substituent contains an average of at least about 8
carbon atoms per substituent.
Sulfonic acids useful in the invention include the sulfonic and
thiosulfonic acids. The sulfonic acids include the mono- or polynuclear
aromatic or cycloaliphatic compounds. Illustrative examples of sulfonic acids
include hydrocarbyl substituted naphthalene sulfonic acids, hydrocarbyl
substituted benzene sulfonic acids. petroleum sulfonic acid and the like.
Phenols useful in making the metal salts used in this the invention can
be represented by the formula (R,)a Ar-(OH)b, wherein R, is a hydrocarbon
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
9
group; Ar is an aromatic group; a and b are independently numbers of at least
one, the sum of a and b being in the range of two up to the number of
displaceable hydrogens on the aromatic nucleus or nuclei of Ar.
While the term "phenol" is used herein, it is to be understood that this
term refers to both mononuclear and polynuclear aromatic compounds.
Polynuclear groups can be of the fused type wherein an aromatic nucleus is
fused at two points to another nucleus or of the linked type wherein at least
two
nuclei (either mononuclear or polynuclear) are linked through bridging
linkages
to each other.
Saligenin, also known as salicyl alcohol and o-hydroxybenzyl alcohol
and derivatives thereof are useful for preparing metal salts used in this
invention.
The alkaline earth metal salts of saligenin derivatives of the present
invention can be represented by the formula
X
RW L R~ J m
P
where M is a valence of an alkaline earth metal, and the identity,
description,
and amounts of other symbols are as set forth hereinbelow.
The subscript "m" can be 0 to 10. This means that the number of rings
can be 1 to 1 l, although it is to be understood that the upper limit of "m"
is not
a critical variable. Preferably, m is 2 to 9, more preferably 3 to 6.
At least one ring, and preferably most of the rings contain at least one R1
substituent, which is a hydrocarbyl group, preferably an alkyl group,
containing
1 to 60 carbon atoms, more preferably 7 to 18 carbon atoms. The R~ groups
will normally comprise a mixture of various chain lengths, so that the
foregoing
numbers usually represent an average number of carbon atoms in the R1 groups
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
(number average). Each ring in the structure will be substituted with 0, 1, 2,
or
3 such R~ groups (that is, each p is independently 0, l, 2, or 3, most
typically 1,
and different rings in a given molecule may contain different numbers of such
substituents. At least one aromatic ring in the molecule must contain at least
5 one R' group, and the total number of carbon atoms in all the R' groups in
the
molecule should be at least 7, preferably at least 12.
In the above structure the X and Y groups may be seen as groups
derived from formaldehyde or a formaldehyde source, by condensative reaction
with the aromatic molecule. While various species of X and Y may be present
10 in the molecules in question, the commonest species comprising X are CHO
(aldehyde functionality) and CHZOH (hydroxymethyl functionality); similarly
the commonest species comprising Y are CHZ (methylene bridge) and
CHZOCH2 (ether bridge). The relative molar amounts of these species in a
sample of the above material can be determined by ~H/~3C NMR as each carbon
and hydrogen nucleus has a distinctive environment and produces a distinctive
signal.
Alkaline earth metal salts of hydrocarbyl substituted saligenin
derivatives are described in detail in U.S. Patent 6,310,009 which is hereby
incorporated herein by reference.
The metal compounds useful in making the metal salts are generally any
Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the
Elements). including alkali metals (sodium, potassium, lithium, etc.) and
Group lb
metals such as copper. Group 2 metals of the metal base include the Group 2a
alkaline earth metals (magnesium, calcium, barium, etc.) as well as the Group
2b
metals such as zinc or cadmium
An acidic material is used to accomplish the formation of the basic metal
salt. A promoter is a chemical employed to facilitate the incorporation of
metal into
the basic metal compositions. A particularly comprehensive discussion of
suitable
promoters is found in U.S. Patents 2,777,874, 2,695,910, and 2,616,904.
As noted hereinabove, the metal of the metal salt comprises at least one of
Group 1 and Group 2 metal, preferably, an alkali and/or an alkaline earth
metal. In
one preferred embodiment, the metal salt is an alkaline earth metal salt.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
11
In one preferred embodiment, the metal salt comprises a metal salt of sulfur
or methylene coupled hydrocarbyl substituted phenols or salicylic acids. In
one
preferred embodiment, the composition comprises a metal salt of a hydrocarbyl
substituted phenol. In another preferred embodiment, the composition comprises
a
metal salt of a Mg or Ca methylene coupled C~_15 aliphatic group substituted
phenate. In yet another preferred embodiment the composition comprises an
alkaline earth metal salt of hydrocarbyl substituted saligenin derivatives.
In one preferred embodiment, the composition comprises a metal salt of a
hydrocarbyl substituted salicylic acid. In another embodiment, the composition
comprises a metal salt of a hydrocarbyl substituted sulfonic acid. In yet
another
embodiment, the composition comprises a metal salt of a hydrocarbyl
substituted
carboxylic acid.
Mixtures of two or more of these metal salts may be used.
Hydrocarbyl Substituted Succinic Derivatives
The quenching oil compositions of this invention may, in an optional
embodiment, also contain hydrocarbyl substituted succinic derivatives selected
from
the group consisting of esters, amides, ester-amides, imides, amine salts,
acid-esters,
acid-amides ester-amine salts, amide-amine-salts and acid-amine salts. The
hydrocarbyl substituent typically has M~ ranging from about 500 to about 5000,
preferably from about 900 to about 2500.
These succinic derivatives are well known to those skilled in the art.
The quenching oil compositions of this invention typically comprise from
about 0.2% to about IO%, preferably to about 5% by weight of the aliphatic
polyolefin (2), and a total of from 0.2% to about 10% by weight of a metal
salt of
hydrocarbyl substituted phenols, salicylic acids and sulfonic acids and
alkaline earth
metal salts of hydrocarbyl substituted saligenin derivatives, and optionally
at least
one of hydrocarbyl substituted succinic esters, amides, ester-amides, imides,
amine
salts, acid-esters, acid-amides, ester-amine salts, amide-amine salts and acid-
amine
salts, provided that the composition comprises at least one of a metal salt
and a
succinic derivative. When used, the succinic derivatives are present in
amounts
ranging from about O.I% to about S% by weight.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
12
In one preferred embodiment, the composition comprises from about 0.2% to
about 5% by weight of the aliphatic polyolefin (2), and (3)(a) from about 0.2%
to
about 5% by weight of at least one metal salt wherein the weight ratio of
(2):(3)(a)
ranges from about 10: 1 to about 1: 10.
In another preferred embodiment, the composition comprises from about
0.2% to about 5% by weight of the aliphatic polyolefin (2), a total of from
about
0.2% to about 4% by weight of (3)(a) at least one metal salt; and a total of
from
about 0.1 % to about 4% by weight of at least one hydrocarbyl substituted
succinic
derivative selected from the group consisting of amides, imides, amine salts,
acid-
amides and acid-amine salts wherein the weight ratio of polyolefin : metal
salt
succinic. derivative ranges from about (20-40) : (40-70) : (10-20).
This invention also relates to a method of heat treating metals comprising
heating the metal to a temperature above its critical temperature and
thereafter
cooling the metal by immersion thereof into a quenching oil bath comprising
the
quenching oil composition of this invention.
The additive components may be incorporated into the base oil as individual
components, added thereto in any order. Alternatively, and preferably, the
additive
components are added to the base oil as a concentrate which comprises the
desired
additives in appropriate ratios which, when incorporated into the base oil,
provide a
finished quenching oil composition containing the desired amount of each
additive.
The following examples illustrate additive concentrates uses to prepare
quenching oil compositions of this invention. All parts are parts by weight
and
unless indicated otherwise, are on a neat chemical, i.e., oil and diluent
free, basis.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
13
TABLE 1
Example # 1 2 3 4 5 6 7 8 9
Parts by Weight
Polyisobutylene ( M., 25 25 25 25 30 30 30 30 30
~ 1700)
Ca (MR 0.8~) Me C12- Phenol. 50 60
(55% oil)
Mg (MR<1) Me Ci2- Saligenin 50 50 50 55 50 60
(50% oil)
Ca (MR 0.8) Me C~- Phenol50
(69%
oil)
Polyisobutenyl ( Mn ~ 25 25 15 15 10 10
1700)
Succinimide (SS% oil)
Ca (MR 1.4) Petroleum 10
Sulfonate
(57% oil)
Ca (MR 2.4) Petroleum 10 15 10 10 10 10
Sulfonate
(53% oil)
Me : methylene coupled
The following examples illustrate compositions of this invention:
A series of quenching oil compositions is prepared, each member of the
series containing 2% by weight of one of additive concentrates 1-5 in
Pennzoil/Conoco Excel Paralube 75-HC (75N) oil. A second series is prepared,
each member of the series containing 4% by weight of one of additive
concentrates
1-2 and 4-5 in the same oil. A third series is prepared, each member
containing 6%
by weight of additive concentrates 1-2, and 4-5 in the same oil.
Two additional series of quenching oil compositions are prepared, each
member of the f rst series containing 2% by weight of one of additive
concentrates
6-9 and each member of the second series containing 4% by weight of one of
additive concentrates 6-9 in Ergon Hygold P70N oil.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
14
A portion of each of these oils as well as commercial quench oils is heat
stressed by heating at 170°C for 22 hours while aerating at 10 liters
per hour and
tested with respect to the non-stressed quench oil samples.
Each sample is subjected to a one-minute quench test and a 3 hour panel
coker test. The quench test quantifies the cooling characteristics of the
quench oil
sample and the panel coker test measures the tendency of the quench oil sample
to
stain and/or form deposits on hot metal surfaces. Similar results between
corresponding heat stressed and unstressed oils samples provide an indication
of
durability and consistency of the test oils.
It is known that some of the materials described above may interact in the
final formulation, so that the components of the final formulation may be
different
from those that are initially added. For instance, metal ions (of, e.g., a
detergent)
can migrate to other acidic sites of other molecules. The products formed
thereby,
including the products formed upon employing the composition of the present
invention in its intended use, may not susceptible of easy description.
Nevertheless,
all such modifications and reaction products are included within the scope of
the
present invention; the present invention encompasses the composition prepared
by
admixing the components described above.
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 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 that may be customarily present in the
commercial material, unless otherwise indicated. It is to be understood that
the
upper and lower amount, range, and ratio limits set forth herein may be
independently combined. As used herein, the expression "consisting essentially
of
permits the inclusion of substances that do not materially affect the basic
and novel
characteristics of the composition under consideration.
CA 02470953 2004-06-18
WO 03/052145 PCT/US02/40160
While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof will
become
apparent to those skilled in the art upon reading the specification.
Therefore, it is to
be understood that the invention disclosed herein is intended to cover such
5 modifications that fall within the scope of the appended claims.
