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Патент USA US3079349

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ilnited grates
Patented Feb. 26, 1953
C14 alkylcarboxylic acid, e.g., methylthioacetic acid,
ethylthioacetic acid, ethylthiopro-pionic acid, methyldi
Thomas E. Reamer, El Cerrito, Cali?, assignor to Shell
Oil Company, a corporation of Delaware
thioacctic acid, ethyldithioacetic acid; sulfur-containing di
carboxylic acids, e.g., thiodiacetic acid, thiodipropionic
No Drawing. Filed Get. 5, 1959, Ser. No. 844,211
9 Claims. (Cl. 252—33.6)
are preferred are sodium mercaptoacetate, mercaptosuc~
acid, dithiodiacetic acid, and the like. The salts which
cinate, thiodiacetate, thiodipropionate, dithiodiacetate and
This invention relates to aqueous base metal-working
lubricating compositions.
mixtures thereof.
More particularly, it relates
The water-soluble hydroxy-containing reducing agent
to a water-base metal cutting ?uid.
It is well known in the art that water base ?uids possess
includes inorganic compounds such as hydroxylamine and
good cooling properties for processing metals, but that
pounds such as phenyl hydrozine hydrochloride, phenyl
hydroxylamine, aliphatic or aromatic polyhydroxyl-con
taining compounds such as carbohydrates, e.g., glucose,
lactose; aromatic polyhydroxyl-containing compounds
organic compounds such as water-soluble amino com
they lack the lubricity and extreme pressure properties
of oil base lubricants and usually cause corrosion. On
the other hand, oil base lubricants are inferior coolants
and are costly.
The art discloses various means of imparting rust in
hibiting and extreme pressure properties to water, base
such as resorcinol, pyrogallol, phloroglucinol and the like.
i In cases'where the-metal being worked is extremely
susceptible to corrosion or extremely di?icult frictional
metal-working lubricants, but with little success. Among
conditions are encountered, the addition of from 0.5% to
the materials commonly used for this purpose are water 20 10%, preferably 1% to 5% each of an alkanolamine cor
soluble non-ionic compounds, such as alkyl phenol
rosion inhibitor such as mono, di or triethanolamine,
~ ethylene ox'de reaction products, tallow, fatty acids, soaps,
mono-, di-, or tripropanolamine, etc, or the like; and as
such as sodium or potassium oleate or sulfonate, in com
an antifriction agent a water-soluble hetero copolymeric
bination with water-soluble alkali metal compounds and
alkylene, glycol, ether or e or thereof, wherein the dif
mixtures thereof, such as the nitrites, phosphates, car
ferent oxyalkylene units are substantially randomly dis
bonates, or chromates, e.g., mixtures of sodium nitrite‘
tributed throughout the entire polyoxyalkylene chain.
and sodium phosphate, or mixtures of sodium nitrite‘and
5 The water-soluble hetero copolymer improves the anti
sodium carbonate. Water-oil emulsions additionally pre
frictional properties of compositions of the present inven
sent a dermatitis and stability problem upon use and are
tion, particularly under slow sliding conditions. On the
generally undesirable because of their opaqueness thus 30 other hand, other non-ionic polymeric compounds such
making it difficult to observe the machining process.
as alkyl phenol-ethylene oxide reaction products, block
It is an object of this invention to provide a cutting
copolymers of dissimilar alkylene oxides and their deriva
fluid having both good cooling and good lubricating
tives such as are commercially available under the trade
name of “Pluronics” and the like produce undesirable
frictional problems, foaming, instability and the like. I
The water-miscible hetero-copolymer polyalkylene ox
properties. Another object of the invention is to provide
a non-corrosive aqueous cutting solution. Still another
object of the invention is to provide a stable, non-corro
sive, aqueous cutting composition free of ingredients capa—
ide ?uids also enhance the load carrying properties of the
composition of the present invention. The above oxides
the invention is to provide a multi-functional metal work
are hetero-copolymers of dissimilar alkylene oxides such
ing lubricant useful at high speeds, heavy loads, high 40 as copolymer ethylene oxide and 1,2-propylene oxide
pressures and high temperatures.
(poly(oxyethylene-1,2-oxypropylene)glycol), as well as
ble of causing dermatitis infections. Another object of
The above and other objects are attained in accordance
with the present invention by an aqueous medium, such
as water containing from about 0.05 to about 5 moles per
liter (molar=l\/i), preferably from 0.1 to 1 mole each of
(l) a water-soluble alkali metal compound containIng
at least one sulfur atom in the molecule, preferably in
an oxidized state, and (2) a water-soluble reducing agent
containing at least a group selected from hydroxyl and
amino groups, a preferred class of compounds being
I monoethers and monoesters thereof, preferably at oxide
ratios of from 75:25 to 10:90 ethylene oxide to 1,2
, propylene oxide, and molecular weight of from about 250
to about 1500.
By a ratio of from 75:25 to 10:90 is meant that, in
the formation of copolymer the amount of 1,2-propylene
oxide is from 1/2, to 9 times the amount of ethylene oxide
present, by Weight, the parts of proportion of the 1,2
oxide being given last. These materials are
' amino and hydroxy-containing compounds, for example," 50 described in U.S. Patents 2,425,755 and 2,425,845. The
hydroxylamine. The ?nal water-base ?uid should have
copolymer diols may be employed in a modi?ed form as
a pH of at least 7, preferably between 8 and 11.
the monoethers or monoesters of monohydric alcohols
The combination of the above additives functions in a
or monobasic acids with the diols. The alcohols pref
particular manner to produce an outstanding extreme pres
' erably have from 1 to about 10 carbon atoms, While the
sure water base metal-working ?uid.
monocarboxylic acids preferably have from 1 to 12 car
The water-soluble alkali metal compounds which must
contain sulfur in the molecule include sodium, lithium or
bon atoms.
potassium sulfur-containing salts, the anionic portion
being either an inorganic sulfur-containing anion, pref
erably in an oxidized state, such as a sulfate, persulfate,
thiosulfate, sulfoxylate, dithionate, as well as sul?de or
hydrosul?de or an organic sulfur-containing anion such
The following compositions are representative of the
invention, which can be used neat or diluted with from
1 to 10, preferably 1 to 10 parts of water, as metal
as mercaptocarboxylate, thiocarboxylate and mixtures
thereof. The water-soluble alkali metal organic sulfur
containing salts include, sodium, lithium or potassium salts
of mercapto mono- and poly-carboxylic acids such as so
working lubricants for cutting, drilling and the like. The
concentrations are molar.
Composition A:
Sodium thiosulfate __________________ __
Hydroxylamine ____________________ __
0.1 M
0.1 M
Composition B:
dium, lithium or potassium mercaptoacetate, mercapto
Sodium hydrosul?te _________________ __
0.1 M
proprionate, mercaptosuccinate, mercaptoglutarate and
Hydroxylamine ____________________ __
0.1 M
mercaptoadipate; sodium, lithium or potassium salts of
mono~ or polysul?de-containing carboxylic acids such 70
as sodium, lithium or potassium salts of C1“,, alkyl thio
Composition C:
Potassium pcrsulfate _________________ __
0.1 M
Hydroxylamine ____________________ __
0.1 M
Composition D:
compositions may be applied with excellent results to
Sodium thiosulfate __________________ __
0.1 M
general cutting operations Where cooling and lubricat~
Glucose ___________________________ __
0.1 M
ing of the tool and work piece under adverse conditions
Composition E:
Sodium thiosulfate __________________ __
0.1 M
Hydroxylamine ____________________ __
___________________ __
are encountered.
Metals machined with the aid of ?uids
of this invention have good surface ?nish, are free from
rust and the cutting tool life is excellent.
0.1 M
I claim as my invention:
2% wt.
Hetero-copolymer of ethylene oxide-1,2
propylene oxide (75/25), visc. 450/
1. An aqueous metal-working lubricant consisting
essentially of a major amount of water and from about
100° F __________________________ __ 10% wt.
10 0.05 to about 5 moles per liter of water each of (1) a
Oil M
0.1 M
water-soluble sulfur-containing alkali metal salt selected
from the group consisting of alkali metal thiosulfate,
alkali metal hydrosul?te, alkali metal persulfate, alkali
Sodium thiodiacetate ________________ __
0.1 M
15 ducing agent selected from the group consisting of
Phenyl hydrazine hydrochloride _______ __
0.1 M
'hydroxylamine, glucose, lactose, resorcinol, pyrogallol
Composition F:
Sodium thiodiacetate ________________ __
Hydroxylamine ____________________ __
Composition G:
Composition H:
metal thiodiacetate and (2) a hydroxyl-containing re
and phloroglucinol.
2. An aqueous metal-working lubricant consisting
thiodiacetate ____ __, __________ _..
0.1 M
Pyrogallol _______________________ __,_
Composition 1:
Sodium thiodiacetate ________________ __
0 1 M
Phenyl hydroxylamine _______________ _-
0.3 M
and hydroxylamine.
3. An aqueous metal-working lubricant consisting
Potassium thiosulfate ________________ __
0.2 M
essentially of a major amount of water and from about
0.1 to 1 mole per liter of Water each of sodium thiodi
Hydroxylamine ____________________ __
0.1 M
acetate and hydroxylamine.
0.1 M
0.1 M
essentially of a major amount of water and from about
0.1 to 1 mole per liter of water each of sodium thiodi
The outstanding properties of compositions of this
acetate and phenyl hydroxylamine.
5. An aqueous metal-Working lubricant consisting
essentially of a major amount of ‘Water and from about
20 0.1 to 1 mole per liter of Water each of sodium thiosulfate
0.1 M
Composition '1 :
Composition K:
Lithium dithiodiacetate ______________ __
lydroxylamine ____________________ __
4. An aqueous metal-working lubricant consisting
invention were demonstrated by subjecting them to the 30
following tests:
(1) Four-ball machine test as described in the Journal
of the Institute of Petroleum Technology, pages 206—229,
April 1946.
essentially of a major amount of water and from about
0.1 to 1 mole per liter of water each of sodium thiodi~
acetate and pyrogallol.
6. The lubricant composition of ‘claim 2 containing
35 from about 2% to about 10% by weight each of Water
(2) Tool life test.--The compositions were used as
lubricants in drilling 1” holes in A181 4340 steel and
the number of holes drilled to failure of tool was noted.
(3) Rust test.-—Cast iron strips were immersed in the
miscible hetero-copolymer of ethylene oxide and 1,2-pro
pylene glycol, and an ethanolamine.
7. The lubricant composition of claim 3 containing
from about 2% to about 10% by weight each of water—
test lubricant for 24 hours and the strips were then re 40
miscible hetero-copolymer of ethylene oxide and 1,2-pro
moved and assigned a rust rating of A=none, B=trace,
pylene glycol, and an ethanolamine.
8. The lubricant composition of claim 4 containing
Compositions A-K in the four-ball test gave average
about 2% to about 10% by weight each of water
weld load (kg) values of between 600 and 800, averaged
around 175 holes drilled in the tool life test and in the 45 miscible hetero-copolymer of ethylene oxide and 1,2-pro
pylenc glycol, and an ethanolamine.
rust test gave a rating of A. When the reducing agents
9. The lubricant composition of claim 5 containing
were omitted from compositions A-K and the salt con
about 2% to about 10% by weight each of water
centration increased to 0.2 M, the average weld load (kg)
miscible hetero-copolymer of ethylene oxide and 1,2-pro
varied between 300-400 kg. Also, when the salts were
omitted from compositions A-K and the amount of 50 pylene glycol, and an ethanolamine.
reducing agent adjusted to 0.2 M the average weld load
References Cited in the ?le of this patent
(kg) was reduced to 100-200 kg. Also, in each case
when one or the other of the two essential additives were
omitted from compositions A—K the tool life was re
Crabtree et al. , ________ __ Dec. 8, 1936
duced to approximately 30-35 holes drilled.
Henricks ____________ __ Mar. 4, 1952
Compositions of this invention may contain additional
Reamer ____________ __ Apr. 25, 1961
additives, such as water-soluble corrosion inhibitor, e.g.,
C=moderate, Dzheavy.
sodium mercaptobenzothiazole, anti-foaming agents such
as silicone polymer, perfuming agents, and dyes. The
Great Britain ________ __ Jan. 21, 1959
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