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Патент USA US2407087

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Patented Sept. 3, 1946
Eugene Lieber, Staten Island, N. Y., and Aloysius
F. Cashman, Bayonne, N. J ., assignors to Stand
ard Oil Development Company, a corporation
of Delaware
'No Drawing. Application December 26, 1940,
Serial No. 371,788
6 Claims. (Cl. 252-52)
This invention relates to a novel type of chemi
cal condensation product and. to methods of pre
paring such products and using themfor various
purposes, more particularly as pour depressors in
waxy lubricating oils.
It has been known for some time that substances
which reduce the A. S. T. M. pour point of waxy
mineral lubricating oils can be made by various
FeCla, ZnClz, BF3, etc. The Friedel-Crafts type
of catalyst is preferred. Auto-condensation in
the presence of catalysts of the above types re
sults in the substantial removal of oxygen and
the formation of a high molecular weight essen
tially hydrocarbon product.
wax with naphthalene. However, a new method
has now been discovered for preparing condensa
The amount of condensation agent to be used
will, of course, vary with the particular type of
‘condensing agent used. Generally about .01 to
‘.10, preferably .02 to .05, mols of a Friedel-Crafts
catalyst should be used per mol of ketone. .With
activated clays or mineral acids, larger amounts
of the condensing agent should be used. It is not
tion products having pour-depressing properties
necessary to use a solvent or diluent in carrying
sired to use a solvent, a re?ned kerosene or naph
chemical condensation reactions involving organic
compounds containing long aliphatic hydrocarbon
chains, such as by reacting chlorinated para?in
from a class of organic compounds containing 15 out the condensation, especially with the lower
molecular weight ketones; however, if it isde
low molecular weight aliphatic hydrocarbon
tha, which has been pretreated with strong sul
furic acid or A1013 to make it inert, will serve as
tion of wax modifying agents by subjecting low
molecular weight aliphatic ketones to auto-con 20 a suitable solvent. If a solvent or diluent is used,
generally a slightly larger amount of catalyst is
densation. Such ketones may be represented by
the general formula R--CO-—R’, where R and
The temperature for carrying out the conden
R’ are aliphatic hydrocarbon groups having a
combined total of less than 12 carbon atoms, , sation should be between the approximate limits
of room temperature and about 300° F. It is pre
preferably less than 8 carbon atoms. More
ferred to add the catalyst to the ketone at low
broadly the invention comprises the auto-condene
temperatures and then heat the reaction mass to
sation of ketones having the general formula
the desired maximum temperature, usually be
X—R—CO--R'-X', where X may be hydrogen,
tween about 100° F. and 200° F. A reaction time
hydroxyl, or halogen, and X and X’ may be the
same or different, and where R and R’ are ali 30 of about 1/2 hour to 20 hours, preferably 1 to 5
hours, may be used. The temperature and time
phatic hydrocarbon groups which maybe either
should be adjusted for the desired combination
saturated or may contain an ole?nic linkage and
Broadly, ‘the invention comprises the produc
R and R.’ may be the same or different.
of yield and‘ potency of pour depressor.
After the reaction has been completed, which
having the formula R-CO-R', where Rand R’
are alkyl radicals having each less than 6 carbon 35 may be judged by testing small samples of the
product, the condensing agent is separated from
atoms are preferred.
the reaction mass according to known methods.
Speci?c examples of these ketones include
For instance if a Friedel-Crafts catalyst was used,
acetone, methyl ethyl ketone, diethyl ketone,
the reaction mixture is preferably cooled and
methyl propyl ketone, dipropyl ketone, methyl
butyl ketone, dibutyl ketone, methyl amyl ketone,
diamyl ketone, ethyl propyl ketone, ethyl butyl
ketone, ethyl amyl ketone, methyl isobutyl ketone,
methyl tertiary butyl ketone, methyl isoamyl
ketone, phorone (di-iso propylidene acetone),
40 diluted with an inert diluent, such as a re?ned
kerosene and then neutralized by adding to it, or
pouring it into, water, an aqueous solution of
caustic soda, or an alcohol, or a mixture thereof
such as a mixture of water and alcohol. The
acetonyl acetone, and others. Mixtures of two 45 keroseneextract is then allowed to settle and the
catalyst-sludge layer is drawn off. The kerosene
extract is then ?ltered, if necessary, to remove
cial products consisting essentially of. one or more
any insoluble material and then distilled to re
ketones of theclass described, together with minor
move the solvent and low boiling products, this
amounts of substances which are either inert or
do notinterfere with the desired auto-condensa 50 distillation being preferably carried out under
or more ketones may be used, as well as commer
tion of the ketones.
To effect the auto-condensation-it is preferred
to use a condensation agent or catalyst, such as
vacuum or with ?re and steam, in the latter case
carrying the temperature up to about 600° F.
The ketone auto-condensation product of this
activated clay, alumina, silica gel, and various - invention generally has a colorand ‘texture-rang
catalysts of the Friedel-Crafts type, c.‘ g., A1012, 55 ing from a green viscous oil to a brown,‘britt1e
1 .1
A‘ ‘v
resin. It is soluble in hydrocarbon oils. It has
a fairly high molecular weight and is substantially
non-volatile at temperatures below about 600° F.
Although the chemical structure of these auto—
kerosene extract containing the desired product
tainty, itvis believed that they are composed
green cast was obtained as product. The pour
was washed further with water and then distilled
with ?re and steam to 600° F. to remove solvent
and low boiling products. A bottoms residue com
condensation products is not known with cer- 5 prising 14 grams of a very viscous oil of dark
essentially of very highly branched linear chains
depressing potency of this condensation product
and are composed essentially of hydrocarbons,
especially when made from unsubstituted ketones.
was determined by dissolving 2% of it in a waxy
mineral lubricating oil base stock having a pour
The product of this invention has the property 10
of modifying the crystal structure of waxes such
as para?in wax present when added to compositions containing the same. For instance, when
about .05-l0.0%, preferably .2-5.0%, of this wax
point of +30° F. and then testing the resultant
blend for pour point according to the standard
A. S. T. M. method.
A number of other 'condensations were carried
out in the same manner, except that di?erent
' modi?er is added to a waxy lubricating oil such 15 amounts and types of catalyst were used to effect
as a Pennsylvania type lubricating oil having a
the condensation and various ketones and reac
relatively high pour point, the resultant blend
tion conditions were used. The proportions of
will have a substantially lower pour point; in .
materials used as well as the operating conditions,
other words, this wax modi?er is an effective pour
yield of product and pour-depressing potency of
depressor for waxy oil. A small amount of this 20 the product are summarized in the following
wax modi?er is also useful as a dewaxing aid for
Raw materials
N .
Phorone _________ __
ethyl keon .
Acetoiie _________ _. 100gm_. HsP041-_._
T2??? Thlfgf’" Yield ° §Pgfplglleliid
(2- conc')
Dark green visc. oil.
Brown resin.
Brown brittle resin.
Brown resin.
Black resin.
Brown resin. -
8 _________ ._do ___________ __
9 ____ __ Mtethyl ethyl ke-
100E111" resou...~
l0 ........ “d2 ___________ .. 100 5111.. HaPOUM-
1l___._ Methyl isobutyl
300gm_. H2S044..._
Red resin.
1 85% strength.
I Followed by re?ux at ISO-200° F. for 1 hour.
a Dry pellets.
‘ 96.5% strength.
removing wax from mineral lubricating oils of 45
This table shows that the auto-condensation
undesirably high wax content. In similarly small
products of the low molecular weight ketones,
amounts, this wax modi?er may also be incor
lowered, i. e., depressed, the +30° F. pour point
porated into paraffin wax or compositions con
of a waxy mineral lubricating oil by at least 20°
taining the same to be used for various purposes
F. and in some cases by as much as 65° F. (i. e.
such as for coating or impregnating paper, etc., 50 down to _—35°F.) , thus indicating that the prod
or for making various molded products.
ucts of this invention are potent pour depressors.
If desired, the yield of potent pour depressor
obtained in these auto-condensation reactions
can be increased by subjecting some of the in
One liter of acetone was placed in a suitable 55 termediate condensation products which have
reactor equipped with a mechanical stirrer, ther- . been recovered overhead when subjecting the
mometer and re?ux condenser open to the atmos
condensation products to the ?re and steam dis
phere. The reactor was cooled by an external
tillation up to 600° F., to a further condensation
bath of cold running water. 100 grams of an
with an additional quantity of aluminum chloride
hydrous aluminum chloride was now slowly added 60 or othercatalyst, and then subjecting the result
while agitating the acetone and maintaining the
ant condensation product to a catalyst-removal
temperature at 65° F. 30 minutes were required
treatment and ?nal ?re and steam distillation,
for the addition of the A1C13. After the addition
the same as described above.
of the A1C13 the reaction temperature was raised
The condensation products of the low molec-'
to re?ux and maintained thereat for 3 hours. As 65 ular weight aliphatic ketones not only are pour
the condensation of the acetone by the AlCla pro- e ‘I depressors but also impart other valuable prop
gressed, the temperature of the reaction mixture
erties to mineral lubricating oil when added
gradually increased until at the end of 3 hours a
thereto, such as resistance to oxidation, decreased
reaction temperature of 140° F. was attained.
sludge formation and enhanced oiliness.
The reaction mixture was then diluted with 500 70
It is not intended that this invention be lim
cc. of kerosene and cooled below 80° F. The cata—
» ited to any of the speci?c examples which we're
lyst was then decomposed by slowly adding 1000
given merely for the sake of "illustration nor to
cc. of water to the reactor while stirring. After
any theory as to the mechanism- of the oper
For the sake of illustration, but without limit
ing the invention to the particular materials used,
the following experimental data are given:
settling, the aqueouslayer containing the alumi:
nous sludge was drawn off and discarded. The
ation of the invention but only by the appended
claims ‘in which itvis intended‘ to claim all nov
elty inherent in the invention as broadly as the
prior art permits.
6 carbon atoms, said wax modifier being substan
tially non-volatile under ?re and steam distilla
tion conditions at temperatures below 600° F.
We claim:
1. A composition comprising as a base a hydro
carbon product containing hydrocarbon wax and
a small amount of an auto-condensation prod
uct of an aliphatic ketone having less than 12
carbon atoms, said condensation product being
substantially non-volatile under ?re and steam
distillation conditions at temperatures below 10
4. A lubricating oil composition comprising a
waxy mineral lubricating oil base containing dis
solved therein a pour-depressing amount of an
oil-soluble high molecular ‘Weight auto-condensa
tion product of acetone substantially non-vola
tile at temperatures up to about 600° F.
5. A lubricating oil composition comprising a
waxy mineral lubricating oil base containing dis
600° F.
solved therein a pour-depressing amount of an
2. A composition comprising a hydrocarbon
auto-condensation product of methyl ethyl ke
product containing a hydrocarbon wax and asso
ciated therewith a high molecular weight auto
6. A composition according to claim 3 in which
condensation product of a ketone having less 15
than 12 carbon atoms and having the general
formula X—R—CO—R'—-X', where X and X’
the auto-condensation product has been derived
by subjecting the ketone to auto-condensation in
the presence of .01—l.0 mols of aluminum chlo
are either hydrogen, hydroxyl or halogen, X and
ride as a catalyst per mol of ketone, at a tem
X’ are the same or different, R and R’ are ali
phatic hydrocarbon groups and R and R’ ‘are 20 perature between the approximate limits of room
temperature and 300° F., for about Me hour to
either the same or different, said auto-condensa
tion product being substantially non-volatile
under ?re and steam distillation conditions at
temperatures below 600° F.
3. A composition comprising a waxy mineral
lubricating oil base and a small amount of a wax
modi?er consisting essentially of ,an auto-con
densation product of a ketone having the general
formula R--CO—R’, where R and R’ are the
same or different alkyl groups having less than 30
20 hours, hydrolyzing and removing the catalyst,
and distilling the condensation product in the
presence of an inert volatile hydrocarbon solvent
with ?re and. steam to about 600° F. to obtain
the desired high molecular weight product as dis
tillation residue.
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