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Патент USA US2406549

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Patented Aug. 27, 1946
Eugene Lieber, West New Brighton, Staten Island,
N. Y., assignor to Standard Oil Development
Company, a corporation of Delaware
No Drawing. Application October 28, 1941,
Serial No. 416,825
7 Claims. (01. 252-57)
This invention relates to a novel type of chem
,ical' condensation products and to methods of
preparing such products and using them for vari—
ous purposes, more particularly as pour depres
Where R and R’ are saturated hydrocarbon radi
cals or unsaturated or chlorinated derivatives
sors in Waxy lubricating oils, and as dyes, etc.
Heretofore pour depressors have generally been
made by chemical condensation of long-chain
aliphatic substances, such as chlorinated para?in
thereof, at least one, preferably R’, being ali
phatic and the other being. aliphatic or cyclic in
structure, and n being an integer of 1, 2, 3, or
more. Speci?c examples of esters coming with
in .the general formulas described above include:
wax or corresponding long chain cle?ns, with an
aromatic compound, such as naphthalene. Such
pour depressors are high molecular weight com
pounds with a complex chemical structure not
well understood, but it has always been ‘consid
ered necessary in the preparation of pour de
pressors, to use some materials containing long-'
chain aliphatic groups. Attempts have also been
made in the past to produce pour depressors from
aliphatic materials containing oxygen, such as
‘ Methyl acetate
Propyl acetate
Butyl acetate
Amyl acetate
Methyl. butyrate
Isjopropyl butyrate
esters, but successful pour-depressor results
could only be obtained by using esters contain 20
ing long-chain aliphatic groups, such as at least
10 or 12 carbon atoms and preferably more, such
as 16, 18, 22, and the like.
' >
It has now been‘ found possible to make pour
' depressors from esters’containing less than 10
carbon atoms by selecting special conditions for
reacting them with a suitablearomatic com
pound, such as naphthalene.
Broadly, the invention comprises the chemical
Di-isopropyl phthalate
Di-ethyl carbonate
Ethyl silicate
‘ Ethyl phosphate
Amyl borate
Methyl ester of monochloracetic acid
I ‘Amyl ester of propenoic acid
Di-allyl phthalate.
Ally] acetate
'Also, if desired, mixtures of various esters may
be used, especially commercial mixtures of ma
which are isomeric or very similar in
condensation of lower esters, i. e., those having 30 terials
structure, as, for example, the product known
less than 10 carbon atoms with aromatic com
pounds in the presence of a Friedell-Crafts cata
lyst, using a sufliciently large amount of catalyst
to e?ect the desired condensation.
The esters to be used according to the present
invention contain less than 10 carbon atoms and
preferably less than 8 carbon atoms. ' The hy
drocarbon groups in such esters should contain
as “Pent-acetate,” which is the acetic acid ester
of a commercial mixture of amyl alcohols made
from mixed amylenes, It is indeed very surpris
ing that such condensation can be effected With
outhaving in the ester any. reactive group, such
as an o-le?nic linkage or a replaceable halogen
atom, as is necessary in order to combine a par
a?in wax » molecule with naphthalene.
less than '7 carbon atoms. The acid radicals of.
The aromatic‘ compounds to be "used as the
these esters may originate from either'organic or 40 other primary raw material according to this in
inorganic acids, but the remaining portion of the
vention may be of various types with the primary
requisite that they contain one or more replace
ester should originate from organic hydroxy
able hydrogen» atoms on‘ the aromatic nucleus.
compounds, such as alkyl alcohols or phenols or
9f the-various types > ofv aromatic compounds
substituted derivatives of such hydroxy com
compounds. When the esters ,are entirely or-_ 45 available,'the hydrocarbons are preferred, such
as ‘naphthalene, benzene, diphenyl, phenan
ganic they should contain at least one -—CO0-R"
group in which R’ is an aliphatic-hydrocarbon,
preferably an alkyl radical, and they may have
various general formulas such as the following:
threne, toluene, amyl'benzene, retene (which is
l-methyle'7-isopropyl phenanthrene), ?uorene
(diphenylene methane); chrysene \(CIBHIZ), etc.
lflrornaticvcompounds which may be considered
' 4
shade. The product is soluble in mineral oils
as aromatic hydrocarbons containing substituent
and is very useful therein for reducing pour point
groups containing one or more nonhydrocarbon
and at least in some cases it is also very useful as >
elements, such as oxygen, nitrogen, etc., may also
be used, for instance, the following hydroxy aro
matic hydrocarbons:
a green dye suitable as a lubricating oil dye, i. e.,
having a red through color and a green ?uores- '
Amyl phenol
Suitable nitrogen derivatives include aniline, tol
uidine, naphthyl amine, etc.
Bil-10.0%, preferably 0.2-5.0%," of this wax mod
i?er is added to a waxy lubricating oil such as a
Of the condensing agents to be used Friedel
Crafts catalysts are preferred, and of these an
Pennsylvania type or other parai?nic lubricating
hydrous aluminum chloride is preferred, but‘ 15
others may be used, such as ferric chloride, boron
?uoride, antimony chloride, stannic chloride, and
zinc chloride. Other condensation catalysts or
condensing agents include sulfuric acid, hydro
gen ?uoride, activated clays, silica gels, semi-d1»
vided metals, such as zinc, aluminum, etc.
The pour-depressing value of this novel con
densation product is due to its property of mod
ifying the crystal structure of paraffin wax pres
10 ent in lubricating oils, for instance, when about
use of ita issolvent
to be preferred,
is optionaland
of the various materials suitable, hydrocarbon
solvents, such as a re?ned kerosene, high-boiling
oil having a relatively high pour point, the re-._
sultant blend will have a substantially lower pour
point; A small amount of this wax modi?er is
also useful as a dewaxing aid for removing wax
from mineral lubricating oils of undesirably high
wax content. In similarly small amounts, this
wax modi?er may also be incorporated into par
a?in wax or compositions containing the same to
" be used for various purposes, such as coating or
impregnating papers or for making various mold
ed products.
For the sake of illustration but without in
tending to limit the invention to the particular
materials used, some experimental data are given.
The procedure used in the ?rst test will be‘ dis-,
dichloro benzene, etc.
The proportions of the reactants to be used in
in detail and then the materials, proper
carrying out this invention may be varied over a 30 tions, and reaction conditions used in all of the
fairly wide range, as for instance, 0.2-5.0 mols,
tests, as well as the results obtained thereby, are
preferably 0.5-2.0‘ mols, of an ester for one mol
outlined in a table, it being understood that. the ‘
of aromatic compound, the amount of catalyst of
process used for allof the tests is the same as
the Friedel-Crafts type, such as aluminum chlo
that used in the ?rst one,except when otherwise _
ride, should vbe about 0.‘5—5.0 mols, preferably 1-3
noted in they table.
Incarrying out the ?rst “test, 118 grams of
mols, per mol of ester. If a solvent is used, the amount thereof should be about 1/,2-5 volumes per
di-ethyl carbonate havingthe formula
volume of mixed reactants. The temperature
naphtha, etc., may be mentioned, and various
halogenated hydrocarbon solvents, such as tetra
chlorethane, ethylene dichloride, lvchlorobenzene,
used for carrying out the reaction should notibe 40
(Cal-I50) 200
permitted to exceed 300° F., and preferably should
and 128 grams of naphthalene were dissolved
be betweenthe approximate limits of room tem
in 300 cc.~of kerosene (which had been highly
perature and about 250° F. A convenient meth
pretreated with aluminum chloride‘before use
od of carrying out the reaction is to start the re
action at room temperature'until all of the mate
rials have been added, and as the reaction begins
in order to make it inert), contained in a suit-'
able-reaction vessel ?tted with a mechanical
to subside, to start the application of heat until
means for heating and cooling. The stirrer was
a suitable elevated temperature, such as 150°’ F.
or 250° F. or more is‘reached and then to main- '
_ tain such reaction temperature until the reaction
has been completed, which will usually not take
longer than 5 hours or so.
After the reaction
has been completed, the reaction mixture is pref
erably cooled and diluted with some solvent ‘such
as kerosene, or a halogenated solvent, preferably
the same kind as was usedduring the reaction,
if any was used then.
After such cooling and
dilution, the catalyst is hydrolyzed by contact
'- ing the reaction mass with water, dilute caustic
soda, alcohol, and mixtures of such suitable me
stirrer, thermometer, reflux condenser and
started and while ‘maintaining’ the reaction mix
ture at 90-100° F. .266’ grams of aluminum »
chloride were slowly added to the reaction mixg
ture over a period’ of one hour. v"After'the addi~
tion of the aluminum chloride, the reaction-mix
ture was heated to 200°- F; and _ maintained
thereat for three hours. 'At?the conclusion of
this time, the reaction mixture was cooled’and'
' diluted with a further quantity of'kerosene. The
aluminum chloride wasdecomposed by'the addi"v
tion of water and the resulting kerosene extract
Was washed free ‘of acid. It was-‘then distilled
dia, and the resulting catalyst sludge is settled 60 with ?re and steam'to 600° F. in order to fremove ,
solvent and low-boiling products. 132 grams
of a bottoms residue comprising a brownv resin
are then distilled either with ?re and steam or
out and removed. The condensation products
ous substance was obtained as product. . When
with vacuum distillation, e. g., under an absolute
2% of this condensation product was added to
pressure of 100 mm., 50 mm., 20 mm., or even
' less of mercury, to a suitable temperature such 65 a waxy lubricating oil base stock having a pour
point’ of>+30° F., the, pour point was-lowered
as about 600° F. in order to remove solvent and.
low boiling products and to obtain asdistillation
residue the desired high molecular'weight con
to '-15° F., thereby showing that this condensa
tionproduct is an effective pour depressor.
It should be noted that in this ?rst test, the
densation product having pourédepressing' and
70 aluminum chloride was added last to the ‘reac
other valuable properties.
tion vessel, whereas, as indicated, in the table, "
- This novel condensation product has a physical
in many of the other'tests the aluminum chloride
consistencyortemperature range'from a viscous
oil .to a resinous solid which may in some cases
be very hard and brittle. Its color is usually
was mixed?with the naphthalene or other aro
matic compound, and the solvent,- and ?nally the
green, brown, or #black, or some intermediate 75 ester was addedlast. In all the tests the reac4
tion was started at 90° F. and the ?nal heating
temperature was 200° F.
aromatic compound and a saturated ester havi
ing less than 10 carbon atoms, said condensa
1"..- Diethylcarbonate_____ ' 118
2"... Amy] acetates (mixed)
1 98
.--..d0 ______________ .._
Solvent (300 cc.
C1oHs_.__ ‘128
Kercglsene2 ______ ._
o ______________ _
Sec. but. acetate ____ __ 1116
Metéi. aceto acetate
1 266
266 ‘iiéioseh'éIIIII
o ......... __
266 Tetréichlorethane?
o __________ __
Keroisene 5 ______ _.
3 154
o __________ __
Brown resinous.
o __________ __
_____do _________ __
Yie1d, point in
Green oil.
Black oil green dye.
Brown viscous oil.
7 170
Green viscous oil.
Brown resinous green dye.
Red-brown resinous. ,
—10 Brdittle
black resinous green
Brown resinous.
5%/-10° F. resinous.
Brown viscous oil.
32 ........ __ 5%/—10° F. black resinous
green dye.
1 Added last.
1 Made inert by heavy pretreatment with AlCla.
I Distillation stopped at 500° F.
The above table of data shows that good pour 25 tion product being soluble in mineral oils, and
’ depressors can be made from many diiTerent
types of lower esters, such as diethyl carbonate,‘
substantially non-volatile at temperatures up to
600° F. under ?re and steam distillation.
2. A lubricant according'to claim 1 containing
a condensation product of an aromatic hydro
carbon and a saturated ester having less than
can be obtained by using a number of other
10 carbon atoms containing at least one —COOR
di?erent aromatic compounds and using'a sub
group in which R represents an alkyl radical.
stantially wide range of proportions of ester to
3. Lubricant according to claim 1 containing
aromatic compound. Good results were ob
the condensation product of an aromatic hydro
tained both with a highly re?ned and inert kero 35 carbon and an ester of an alkyl alcohol and an
sene as well as with tetrachlorethane as sol
acid selected from the group consisting of organic
vent. A number of the products not only were
carboxylic acids and inorganic polybasic acids.
good pour depressors but also had the additional
4. A lubricant comprising a major proportion
valuable property of being effective dyes suitable
of a waxy mineral lubricating oil and a small
for imparting to the oil a green ?uorescence or 40 but pour-depressing amount of an anluminum
enhancing such property if it is already present
chloride condensation product of about 1 mol of
to some degree. The most important pour de
aromatic hydrocarbon and about 0.5 to 2 mols of
pressor obtained was that produced in test 11 by ' saturated ester having less than 10 carbon atoms
reacting '75 grams of methyl aceto acetate with
of an alkyl alcohol having less than 7 carbon
128 grams of naphthalene using 266 grams of 45 atoms and a fatty acid having less than '7 carbon
aluminum chloride (added last) in the presence
atoms, said condensation product being soluble
of 300 cc. of tetrachlorethane, the materials being
in mineral oils and being substantially non
?rst mixed slowly at about 90° F. and then heated
volatile at temperatures up to 600° F. under ?re
to about 200° F. for 3 hours, resulting in 52
and steam distillation.
grams of brown, resinous product, 2% of which 50
5. A lubricant comprising a major proportion
reduced the pour point of a waxy mineral lubri
of waxy mineral lubricating oil and a small but
ethyl acetate, amyl acetate, secondary butyl
acetate, and methyl aceto acetate, and they also
show that these unexpectedly satisfactory results
cating oil stock from +30° F. to -30° F. ‘
pour-depressing amount of a Friedel-Crafts con
The novel condensation products of this inven
densation product of an aromatic compound and
tion may, if desired, be added to other types of
a saturated acetoacetate ester having less than
lubricating oil base stocks, such as those derived 55 10 carbon atoms, said condensation product befrom naphtheni'c or mixed naphthenic-parali‘lnic
ing soluble in mineral oils and being substantially
base crudes, and may also be added to other
non-volatile at temperatures up to 600° F. under
types of petroleum fractions, such as naphtha,
?re and steam distillation.
gasoline, kerosene, fuel oil, Diesel oil, etc.
6. Lubricant according to claim 5 containing
It is not intended that this invention be limited 60 a condensation product of naphthalene and
to any of the speci?c examples, which have
methyl acetoacetate.
been given merely for the sake of illustration, but
7. A lubricant comprising a major proportion
only by the appended claims in which it is in
of a waxy mineral lubricating oil and a small but
tended to claim all novelty inherent in the in
pour-depressing amount of a Friedel-Crafts con-r
vention as well as any equivalents coming with- 65 densation product of an aromatic hydrocarbon
in the scope and spirit of the invention.
and ethyl acetate, said condensation product be
I claim:
ing soluble in mineral voils and substantially non—‘
1. A lubricant comprising a major proportion
volatile at temperatures up to 600° F.; under ?re
of lubricating oil and a pour-depressing amount
and steam distillation.
of a Friedel-Crafts condensation product of an 70
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