U.S. patent application number 10/498638 was filed with the patent office on 2005-01-20 for quenching oil compositions.
Invention is credited to Sivik, Matthew R., Sweet, William R.
Application Number | 20050011597 10/498638 |
Document ID | / |
Family ID | 23338280 |
Filed Date | 2005-01-20 |
United States Patent
Application |
20050011597 |
Kind Code |
A1 |
Sweet, William R ; et
al. |
January 20, 2005 |
Quenching oil compositions
Abstract
Quenching oil composition comprising (1) an oil having kinematic
viscosity (ASTM Test Method D-445) at 40.degree. C. ranging from
about 4 to about 45 mm.sup.2sec.sup.-1 (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.
Inventors: |
Sweet, William R;
(Willoughby, OH) ; Sivik, Matthew R.; (Broadview
Hts., OH) |
Correspondence
Address: |
The Lubrizol Corporation
Patent Dept-Mail Drop 022B
29400 Lakeland Blvd
Wickliffe
OH
44092-2298
US
|
Family ID: |
23338280 |
Appl. No.: |
10/498638 |
Filed: |
June 14, 2004 |
PCT Filed: |
December 16, 2002 |
PCT NO: |
PCT/US02/40160 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60341612 |
Dec 18, 2001 |
|
|
|
Current U.S.
Class: |
148/713 |
Current CPC
Class: |
C10M 2209/101 20130101;
C10M 2205/02 20130101; C10M 2219/044 20130101; C10N 2020/02
20130101; C10N 2020/067 20200501; C10M 2203/1025 20130101; C10M
2207/028 20130101; C10M 169/044 20130101; C10N 2040/20 20130101;
C10M 2207/023 20130101; C10M 2215/086 20130101; C10M 2215/28
20130101; C10M 2219/046 20130101; C10M 2203/1006 20130101; C10N
2030/52 20200501; C10M 2205/026 20130101; C10M 169/048 20130101;
C10M 2205/06 20130101; C21D 1/58 20130101; C10N 2040/242
20200501 |
Class at
Publication: |
148/713 |
International
Class: |
C21D 001/58 |
Claims
What is claimed is:
1. A quenching oil composition comprising (1) an oil having
kinematic viscosity at 40.degree. C. ranging from about 40 to about
200 SUS and having a saturated content from about 80% to about
100%; (2) an aliphatic polyolefin having {overscore (M)}.sub.n
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 (b)
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.
2. The composition of claim 1 wherein (1) the oil is a mineral oil
and/or synthetic oil.
3-8 (canceled)
9. The composition of claim 1 wherein said aliphatic polyolefin
comprises polyisobutylene.
10. The composition of claim 1 wherein (2) the polyolefin is an
olefin-polyene copolymer, wherein the olefin contains from about 3
to about 8 carbon atoms and the ratio of moles of olefin to moles
of polyene ranges from about 100:1 to about 1:1.
11. (canceled)
12. The composition of claim 1 wherein (2) the polyolefin is an
isobutylene-diene copolymer comprising from about 0.5 to about 5
moles of units derived from diene per mole of copolymer based on
{overscore (M)}.sub.n of copolymer.
13. The composition of claim 1 wherein (2) 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.
14-15 (canceled).
16. The composition of claim 1 comprising at least one member
selected from the group consisting of (3)(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.
17. The composition of claim 16 wherein (3)(a) comprises a metal
salt of sulfur or methylene coupled hydrocarbyl substituted phenols
or salicylic acids.
18. The composition of claim 16 wherein the metal ratio of metal
salts of phenols, saligenin derivatives and salicylic acids ranges
from about 0.5 to about 5 and the metal ratio of metal salts of
sulfonic acids ranges from about 1 to about 20.
19. The composition of claim 16 wherein the metal salt (3)(a) has
TBN ranging from about 45 to about 900.
20. The composition of claim 16 wherein the metal salt is an
alkaline earth metal salt.
21. The composition of claim 16 comprising a metal salt of a
hydrocarbyl substituted phenol.
22. The composition of claim 21 wherein the metal salt is a Mg or
Ca methylene coupled C.sub.7-15 aliphatic group substituted
phenate.
23. The composition of claim 16 comprising a metal salt of a
hydrocarbyl substituted salicylic acid.
24. The composition of claim 16 comprising a metal salt of a
hydrocarbyl substituted sulfonic acid.
25. The composition of claim 16 comprising a metal salt of a
hydrocarbyl substituted carboxylic acid.
26. The composition of claim 16 comprising an alkaline earth metal
salt of a hydrocarbyl substituted saligenin derivative.
27. The composition of claim 1 further comprising at least one
member selected from the group consisting of (3)(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.
28. (canceled)
29. The composition of claim 27 comprising hydrocarbyl substituted
succinic imides.
30. The composition of claim 1 comprising from about 0.2% to about
10% by weight of the aliphatic polyolefin (2), and from 0.2% to
about 10% by weight of (3)(a) a metal salt of hydrocarbyl
substituted phenols, salicylic acids and sulfonic acids and
alkaline earth metal salts of hydrocarbyl substituted saligenin
derivatives; and from 0 to about 5% by weight of (3)(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.
31-34 (canceled)
35. 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 claim 1.
Description
FIELD OF THE INVENTION
[0001] 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
[0002] 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.
[0003] 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.
[0004] 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.
[0005] It is also desirable to provide quench oils that possess
sufficient durability, cleanliness and consistency. Durability
refers to additive lifetime after being exposed to thermal
stressing while consistency relates to constant additive
performance over time. Cleanliness is measured using a coker
test.
[0006] 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, Ohio,
USA (1998). A discussion of quenching appears at pages 973-975 of
that text.
[0007] U.S. Pat. No. 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 5-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.
[0008] U.S. Pat. No. 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.
[0009] U.S. Pat. No. 3,567,640 describes a quenching oil
composition comprised of a major portion of a petroleum oil having
a viscosity within the range of about 40 to about 300 SUS at
100.degree. F. and a flash point in excess of 250.degree. 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.degree. C.
and an aniline point value of less than 50.degree. C.
[0010] U.S. Pat. No. 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.
[0011] U.S. Pat. No. 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.degree. C., a
hydrocarbon obtained by catalytically cracking petroleum and having
a boiling point of not lower than 200.degree. C., a hydrocarbon
obtained by catalytically reforming petroleum and having a boiling
point of not lower than 200.degree. 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.degree. C.
[0012] U.S. Pat. No. 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.
[0013] U.S. Pat. No. 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.
[0014] U.S. Pat. No. 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).
[0015] U.S. Pat. No. 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.
[0016] U.S. Pat. No. 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.degree. 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.degree. C. and a
combination of poly(iso)alkylene and poly(iso)alkylene succinic
anhydride or succinic acid.
[0017] 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
lower cooling rate (6-8.degree. C.) after the workpiece has reached
300.degree. C. to prevent thermal distortion/cracking.
SUMMARY OF THE INVENTION
[0018] The instant invention is directed to a quenching oil
composition comprising
[0019] (1) an oil having kinematic viscosity (ASTM Test Method
D-445) at 40.degree. C. ranging from about 4 to about 45
mm.sup.2sec.sup.-1 (about 40 to about 210 Saybolt Universal Seconds
(SUS)) and having a saturated content from about 80% to about
100%;
[0020] (2) an aliphatic polyolefin having {overscore (M)}.sub.n
ranging from about 300 to about 10,000; and
[0021] (3) at least one member selected from members of the groups
consisting of
[0022] (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
[0023] (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
[0024] 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.
[0025] 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.
[0026] 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.
[0027] The Oil
[0028] The quenching oil compositions of this invention comprise at
least one oil having kinematic viscosity (ASTM Test Method D-445)
at 40.degree. C. ranging from about 4 to about 45
mm.sup.2sec.sup.-1 (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.
[0029] Examples of useful oils include Excel/Paralube 70N,
Excel/Paralube 75HC, (both from Pennzoil/Conoco) and Ergon.RTM.
Hygold P70N.
[0030] The Polyolefin
[0031] The quenching oil compositions of this invention contain (2)
a polyolefin having {overscore (M)}.sub.n 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.
[0032] 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 copolymers, are useful.
Polypropylene and polybutenes, especially polyisobutylene, are
preferred. Polyisobutylene is particularly preferred.
[0033] In another preferred embodiment, the polyolefin is an
olefin-polyene, preferably diene, especially preferred
non-conjugated diene, 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.
[0034] In one embodiment, the polyolefin is an olefin-diene
copolymer comprising from about 0.5 to about 5 moles of units
derived from diene per mole of copolymer based on {overscore
(M)}.sub.n 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-diene copolymers include
butyl rubbers (isobutylene-isoprene) and commercially available
ethylene-propylene-diene terpolymers sold by Uniroyal Chemicals
under the tradename TRILENE.RTM..
[0035] The Metal Salt
[0036] 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`.
[0037] 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 5,
preferably from about 0.5 to about 2 and the metal ratio of metal
salts of sulfonic acids ranges from about 1 to about 20, preferably
from about 1 to about 3.
[0038] 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.
[0039] 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.
[0040] 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.
[0041] 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.
[0042] 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.
[0043] Phenols useful in making the metal salts used in this the
invention can be represented by the formula
(R.sub.1).sub.a--Ar--(OH).sub.b, wherein R.sub.1 is a hydrocarbon
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.
[0044] 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.
[0045] Saligenin, also known as salicyl alcohol and o-hydroxybenzyl
alcohol and derivatives thereof are useful for preparing metal
salts used in this invention.
[0046] The alkaline earth metal salts of saligenin derivatives of
the present invention can be represented by the formula 1
[0047] where M is a valence of an alkaline earth metal, and the
identity, description, and amounts of other symbols are as set
forth hereinbelow.
[0048] The subscript "m" can be 0 to 10. This means that the number
of rings can be 1 to 11, 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.
[0049] 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 R1 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
R.sup.1 groups (number average). Each ring in the structure will be
substituted with 0, 1, 2, or 3 such R.sup.1 groups (that is, each p
is independently 0, 1, 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 one R.sup.1 group, and the total number of carbon
atoms in all the R.sup.1 groups in the molecule should be at least
7, preferably at least 12.
[0050] 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 in the molecules in question, the
commonest species comprising X are CHO (aldehyde functionality) and
CH.sub.2OH (hydroxymethyl functionality); similarly the commonest
species comprising Y are CH.sub.2 (methylene bridge) and
CH.sub.2OCH.sub.2 (ether bridge). The relative molar amounts of
these species in a sample of the above material can be determined
by .sup.1H/.sup.13C NMR as each carbon and hydrogen nucleus has a
distinctive environment and produces a distinctive signal.
[0051] Alkaline earth metal salts of hydrocarbyl substituted
saligenin derivatives are described in detail in U.S. Pat. No.
6,310,009 which is hereby incorporated herein by reference.
[0052] 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 1b 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
[0053] 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. Pat. Nos. 2,777,874, 2,695,910, and
2,616,904.
[0054] 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.
[0055] 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.sub.7-15 aliphatic
group substituted phenate. In yet another preferred embodiment the
composition comprises an alkaline earth metal salt of hydrocarbyl
substituted saligenin derivatives.
[0056] 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.
[0057] Mixtures of two or more of these metal salts may be
used.
[0058] Hydrocarbyl Substituted Succinic Derivatives
[0059] 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 {overscore (M)}.sub.n ranging
from about 500 to about 5000, preferably from about 900 to about
2500.
[0060] These succinic derivatives are well known to those skilled
in the art.
[0061] The quenching oil compositions of this invention typically
comprise from about 0.2% to about 10%, 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 0.1% to about
5% by weight.
[0062] 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.
[0063] 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).
[0064] 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.
[0065] 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.
[0066] 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.
1TABLE 1 Example # 1 2 3 4 5 6 7 8 9 Parts by weight
Polyisobutylene ({overscore (M)}.sub.n .about.1700) 25 25 25 25 30
30 30 30 30 Ca (MR 0.85) Me C.sub.12- Phenol 50 60 (55% oil) Mg (MR
<1) Me Cp.sub.12- 50 50 50 55 50 60 Saligenin (50% oil) Ca (MR
0.8) Me C.sub.7- Phenol 50 (69% oil) Polyisobutenyl ({overscore
(M)}.sub.n .about.1700) 25 25 15 15 10 10 Succinimide (55% oil) Ca
(MR 1.4) Petroleum Sulf- 10 onate (57% oil) Ca (MR 2.4) Petroleum
Sulf- 10 15 10 10 10 10 onate (53% oil) Me: methylene coupled
[0067] The following examples illustrate compositions of this
invention:
[0068] 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.
[0069] Two additional series of quenching oil compositions are
prepared, each member of the first 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.
[0070] A portion of each of these oils as well as commercial quench
oils is heat stressed by heating at 170.degree. C. for 22 hours
while aerating at 10 liters per hour and tested with respect to the
non-stressed quench oil samples.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 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 modifications that fall within the scope of the appended
claims.
* * * * *