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Watented Jan. 7, 1947
_ 2,414,028
Melvin A. Dietrich, Claymont, and James E.
Kirby, Wilmington, Del., asslgnors to E.‘ I.
du Pont de Nemours 84 Company, Wilmington,
lilel, a‘corporatlon of Delaware
No Drawing. Application November 3, 1942, _
Serial No. 464,390
(Cl. 260-42)
2 Claims.
This invention relates to polymeric products
and more particularly to polymeric aromatic
The acylated product when the initial polymer
is made with alkali metal or catalyst is of the
formula -
Monomeric compounds containing long chain
acyl groups on an aromatic nucleous are well
known in the art and have been recommended
for a number of purposes, notably'as additives
for lubricating oils to increase the oiliness chars
acteristics of these materials. They are not
and ‘when made with ‘sodium sulfide is o! the
polymeric _in character and generally have a 10
molecular weightebelow 500. Their e?ects on
properties of lubricants other than oiliness are
The acylation of the aromatic hydrocarbon
This invention has an object a new composi
tion of matter whichis highly effective in im
proving the lubricating properties of oils. A
further object is the manufacture of new syn
polymer is best accomplished by reacting at 20’
thetic waxes valuable for impregnating purposes
which have a high solubility, ‘a marked resistance
I to 150° C. in the presence of aFriedeL-Crafts
catalyst with an aliphatic monocarboxyllc acid
chloride containing- at least 12 carbon atoms.
Inert. solvents have been found to be particularly
to crystal formation, and a melting point suffi 20 useful in this Friedel-Crafts reaction. In gen
ciently low for use under normal operating con“v v eral, one mol of acyl chloride per» aromatic nu
ditions. Other ‘objects will appear hereinafter.
The new polymeric products‘described herein
' _ are made by’acylatlng in the presence of a Frie
cleus 'is employed in this acylation.
. the‘ exact position of the substituents on the arc
matic' nuclei has not been determined, the ratio
del-Crafts catalyst the hydrocarbon polymers
25 of the aliphatic acyl groups to benzenoid groups
obtained by reacting a. mono-aromatic methyl
halide or alcohol with a polymerization catalyst.
is approximately unity in the acylated polymer.
The invention is further illustrated by the iol~
lowing examples in which the parts are by Weight.
These acylated polymeric materials have a mo
lecular weight of at least 2000 and are composed
Example I '
of non-condensed ring aromatic nuclei separated 30
Thirty parts of benzyl chloride and 0.5 part of
by aliphatic groups containing not more than
‘tin tetrachloride’ were mixed and allowed to
two carbon atoms with or without an interven
stand at room temperature, approximately 20° C.,
ins sulfur atom and containing long chain ali
for 24 hours. Hydrochloric acid gas was given
phatic acyl groups as substituents on the aromatic nuclei in the proportion of one acyl group to one 35 off and a. brittle resin formed which weighed 23
parts. Nine and one-tenth parts of this resin
aromatic nucleus, the aliphatic acyl substituent
were mixed with 80' parts of cyclohexane as a
having a total of at least 12 carbon atoms.
solvent-and 30.2 parts of acylating agent con
The initial polybenzyl condensation product is
slsting of stearoyl» chloride. This mixture was
obtained by polymerizing the mono-aromatic‘
agitated at 80°. C. and 5 parts of aluminum chlo
methyl halide or alcohol with various polymer
ride added slowly.‘ Vigorous evolution of gas
izatlon catalysts. In the case of the benzyl chlo
occurred and the resulting mixture was agitated
ride or alcohol the catalyst can be the Friedel
5 hours. The solution was filtered, dumped into
Crafts catalyst used in the subsequent acylation,
cold water, thoroughly washed, and dried over
namely, aluminum chloride or tin tetrachloride.
After acylation the polymer is of the formula
iii anhydrous sodium sulfate. The solvent was re“
moved by evaporation and 15 parts of a was
obtained which was liquid at steam bath temper
atures (80° C. or above) and readily soluble in
where R is the long chain acyl substituent de
fined above and x is an integer denoting the
number of units in the polymer. When xylylene
dihalide orlthe corresponding alcohol is used in .
making the initial polymer,=suitable polymeriza
tion catalysts are alkali metals or sodium sul?de.
various mineral lubricating‘ oils as well as 'fuel
50 and gas oils. In 0.5 %-concentration in an SAE 30
para?ln base oil it lowered the pour point from
25° F. to 5°-F.
Example 11
Nine parts of benzyl chloride polymer obtained
as described in Example I, 30 parts or stearoyl
of aluminum chloride were '
For ‘example, ortho-isopropyl-p-xylylene di
chloride, and 10 parts
mixed and heated with agitation to ‘130° C. for 1
hour. Eighty parts of cyclohexalne were added,
the mixture heated for 15 hours at 40° C.,. and
then poured into 100 parts. of 15% hydrochloric
acid. .After working up in the usual fashion 33
partsof a dark wax-like materialwas obtained
which when used in 0.3% concentration in the
chloride may be used vfor polymer preparation
prior to acylation.
such as the bromide may be used as well as
' the alcohol, for example, benzyl ‘alcohol. The ini
tial polymer is best obtained from the chloride
since it has been found that the reaction is more
readily controlled. Catalysts other than those
para?in base SAE 30 oil lowered the pour point, '
frrom 25° F. to —-l5° F. v _
In place of the benzyl chlorides other halides
mentioned in the examples can be usedv for prep‘
arati'on of the polymers.‘ Thus, aluminum chlo
, .ride can be used with benzyl chloride instead of '
. Thirty-one parts benzyl chloride polymer, 102 I‘ tin tetrachloride and potassium or calcium. may
‘parts stearoyl chloride, and. 100 parts carbon
be used on the xylylene dichloride.
bisul?de were mixed and 31- parts aluminum 15, Suitable acid chlorides useful in the acylation '
chloride added gradually with vigorous agitation.
of the polymer are lauroyl, myristoyl, palm'itolyl,
The reactionproduct was worked up according to
hexadecyleicosanoyl, dodecyloxylacetyl, octa
well known methods and'92 parts of'a soft brown _.
wax obtained, melting below 80° C. When used in
0.1% concentration by weight in the pazaii‘ln base 20
SAE 30 oil the pour point was lowered from 25°
F. to '-5° F.-
decyloxyacetyl, dodecylthioacetyl, hexadecylthio~
acetyl, p- (dodecyloxy) benzoyl, p-(pentadecyl-
oxy)benzoyl, 'l0-phenylstearoyl, 12,-ketostearoyl; '
4-ketostearoyl, and oleyl. Mixed acid chlorides
containing an average of atleast 12 carbon atoms
may be used such as those derived from saponi
These polymers obtained by the above examples
were very‘ soluble in ‘mineral oils, solutions con
?cation of coconut oil, fish oils, castoroil, olive
taining 25% and 30% by weight of polymer be 25 oil, acids derived from oxidation of paraffin wax,
ing readily prepared. The effectiveness- of the -' and naphthenic acids.‘
polymer as a pour point depressant is further
These products are valuable as lubricant and
demonstrated by the tests given below on two
hydrocarbon fuel additives to depress pour point
and improve stability, as aids in re?ning of pe
SAE 30 oils, one of Mid-Continent and one of -
Pennsylvania stock.
nent oil _
his oil
troleum products during dewaxing operations, as
coatings for protection of metallic surfaces such
as steel and‘ iron, as impregnating agents for
'P-our point, —‘_’ F.
I Per cent of polymer added
fabrics and ?bers such as cotton, burlap. Jute,
as ingredients of coating materials suchas paints
and varnishes, and as a component in furniture
polishes. They are also useful as components of >
varnish removers'as well as coatings forpaper
or other surfaces subject to sticking dueito static
friction e?ects. v.Th'ey are suitable for use in
The polymers previously mentioned containing ,
greases which areappliedto roller bearings, rail
road rolling stock, or gears in heavy duty en
a sulfur atom between two methylene groups
attachedvto the aromatic nuclei‘likewise exert a . .
As many apparently widely di?erent embodi
ments of this invention may be made without de
substantial stabilizing action on mineral oils. 45 parting from the spirit and scope thereof," it is
These polymers were prepared from xylylene
to be understood that we do not limit ourselves
dichloride andsodium sul?de followed by acyla
to the speci?c embodiments thereof except as
tion withstearoyl chloride.
Thus twenty-?ve
grams of a solvent extracted Mid-Continent SAE
20 oil containing v60 parts per million of dissolved 50
iron (as oleate) were placed in an oxygen ab
sorption apparatus operating at 150° C_., using
air asthe oxygen carrier.'. This oil, containing
I de?ned in the appended claims.
1. A process for making polymers which com
' prises heating. in the presence of a Friedel-Crafts
catalyst'a polymer in which the recurring units
0.5% of the stearoylated xylylene sul?de polymer, '
absorbed in 690 minutes an amount of oxygen 55
equivalent to 3.4_inches,of mercury (asmeas
ured on the manometer) compared to an ab
sorption of 4.2 inches for a control sample.
= ' (Gone)
and stearoyl chloride- in the ratio of one moi of
said chloride to each of said recurring units. f ' ‘I
Similar wax-like polymeric products contain
2. A wax-like polymerization product obtained ‘
ing no sulfur can be prepared by re?uxing xylyl 60 by heatingv in the presence ‘of’ a Friedel-Crafts
ene dichloride with sodium'in a suitable solvent
catalyst a polymer in which the recurring units
such as xylene followed by acylation with 'a long
chain acyl chloride such as stearoyl chloride.
A benzyl chloride containing aliphatic sub
I ' ({
stituents in the ortho- and meta-positions may 65
be used inv the preparation of a polymer suit
and stearoyl chloride in the ratio of one mol of
able for acylation. Thus, ortho- or meta-methyl,
said chloride to each of'said recurring units.‘ '
ethyl isopropyl benzyl chlorides are suitable.
Similar substituents may be present on a xylylene
dichloride used inpreparation of the polymer.
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