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Патент USA US2411579

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Patented Nov. 26, 1946'
2,411,579‘
.
UNIT-Bo; , STATES ;
OFFICEf
' . @CONDENSATION rItoDUcrrANnMETHoDoF
,I
II
w-I
,
PREPARING'AND-USING
.
.,
I
Eugene Lieber, New-‘York, N.‘ 56., and Marvin E.- l
Thorner, ~- Corpus‘ ' Christi, Tex., assignors to
Standard 'Oil Development Company, a corpo
'
= ration of Delaware'
No Drawing,“ Original application November'15,
v194:1, Serial N0. 419,314. Divided and thiS‘B/ll
plication September 15, 1944,‘ Serial No. 554,344
7 Claims.
(Cl_.I252—.52)'
I
,
I
1
are still subject to Friedel-Crafts condensation.
This invention relates to a novel type of‘ chem
Speci?c ‘examples - of suitable aromatic com
ical condensation products and to methods of
preparing such products and using them for var
pounds include benzene,_ naphthalenaanthra
cene, phenanthrene, toluene, xylene, amyl bene
ious purposes; more particularly as pour de
pressors in waxy lubricating oils.
.
5 zene, retene,qphenol,~ alpha- or beta-naphthol,
a
cresol, anisole, tertiary'amyl phenol, diphenyl,
It is known that pour idepressors can be ‘made
by condensing an aromatic compound, such. as
naphthalene with .an?aliphatic 'compound,_gbut it
and
- The
*diphenyl
Friedel-Crafts'catalyst
oxide.
,
.
~ to , be used‘
. ‘ inef
has always heretofore been considered necessary
fecting; . this condensation of, the ' lower- aliphatic I
to Y use relatively long: chain. I. or ‘oi-high "molecular,
10 etherrwith :thev aromatic compound, accordingto
this. invention, is preferably anhydrous, aluminum ‘
weight aliphaticicompounds, ‘such. as chlorinated
paraf?n wax' or corresponding ole?ris," for such
chloride,‘ although otherjFrIiedel-Crafts catalysts
can be, used, ‘ such as boron-?uoride, ferric chlo-v
condensation:
One object of
1 rthepresent
i -,=
_. invention
- :- .Iisrto. avoid
I} j
I ride, titanium: tetrachloride',-_boron trichloride,
the use of‘ suchlong-chain. aliphatic compounds, 15 antimony chloride,fzinc chloride, .landin some
3
,
and another object is to vruse ‘aliphatic compounds ' -- ceses'seyenhydrogen ?uoride; 1
The proportions 'of reactants to be used- should
which are saturated in respectito hydrogen (i. e‘., ' I
free from ole?nic linkages) and yet do not con- ,'
tain any reactive halogen atoms as are present in
chlorinated paraf?n wax.
'
I
bev about ‘1/5._to-5;mols, preferably’ 1/2 to 215111015,
of lower aliphatic ether to 1 mol of aromatic
zoycompound and the amount ofcatalyst should be,
‘I for instance in the case of aluminum chloride, -
_Broadly, the invention comprises the produc
about yl/gto 4 mols-preferably 1-3 mols per mol
tion of condensation products having wax-modie
,
fying properties, by' chemically condensing a I _ "of aromatic compound .
The use of an inert diluent or solvent,1espe
lower saturated aliphatic ether with-"Ian'aromat'ic '
compound. This condensationis preferably car; 2'5 cially onewhich'is a good solvent for the result- .
ried out by the use of a Friedel-Crafts catalyst‘ 1“ I ‘ing high‘ molecular weight condensation product,
according to the procedure commonly used for . "is optional but is preferred, and if used,"should
effecting such condensations.
I-I
II
I.
v“be present
-
is one having a low molecular weight and a low
number of carbon atoms. Although some modi
?ed ethers may be used, it is preferred to use
about 1/2 to 10 volumes, preferably. I
f1-5 volumes, per volume of total reactants, and;
The lower saturated aliphatic ether to beused
3O
catalyst;
'
I
'
>
,..In carrying out the invention," the operating
conditions to be used should include a tempera
' 'ture between the approximate limits of room tem-‘
Iethers having the general'formula R'-—O—'R’,
Iperature and Y300" F., preferably mixing the re
where R and R’ are like or unlike alkyl groups
and where the total number of carbon atoms inv 35actants and catalyst at about room temperature
and then after any initial reaction has begun to
subside, heating the reaction mixture to a ?nal
temperature of about 150-250° F., with a reaction
time of about 1/2. to 10;.hours, usually about 1
ether, dipropyl ether, di-isopropyl ether, di-sec- I
ondary butyl ether, methyl isopropyl ether, iso 40 to 5 hours. The .reactants and catalystcan be
propyl tertiary ‘butyl ether, etc, or mixtures of ' mixed in any desired order, for instance,- the ali
R and R.’ together is less than 10, and preferably
less than '7 carbon atoms. Speci?c examples of 7
such ethers include dimethyl ether, di-ethyl
two or more such pure compounds, or commer-v
' cial products of which such ethers represent the
phatic ether and the aromatic compound can be
mixed together first, with or without solvent, and
then ,the catalyst added, or the catalyst may be
The aromatic compound tobe used as the other 45 mixed with the aromatic compound, and then
the aliphatic‘ether subsequently added.
reactant may be composed of asing'le. aromatic
‘After the reactants and’ catalyst have been
ring or polynuclear compounds,_and.in' the latter
mixed togetherv and after the reaction mixture
case the several nuclei maybe separate orcon
has been heated to the desired ?nal temperature‘
densed. Various derivatives of such aromatic
main constituent.
‘
,
.
‘
compounds may also be used, such asthose con
50 ‘fora su?icient time to complete the reaction, the
taining alkyl, hydroxy,'amino, and other substit
"reaction mixture. is, then cooled, diluted with a
uents, or partially hydrogenated aromatic com
pounds, so long as these various derivatives still
convenient volume of kerosene, light chlorinated
hydrocarbon or other suitable diluent,
he;-v
tralized by any of the methods familiar to the
contain at least two replaceablehydrogen, atoms,‘
on the nucleus, or, in other words,‘ so long as they 55 ?riedeléqrafts art, 1, e.,. by adding water, alcohol,
2,411,579
3
4
dilute aqueous caustic soda solution, etc., a mix
ture of alcohol and water being very suitable.
The reaction mixture is then separated, as by
settling, into two layers, the aqueous layer con
are tested in a 2% or 5% concentration in a waxy
mineral lubricating oil base stock having a pour
point of +30° F.
"
taining the aluminous sludge being removed, {and
5
'
‘
j‘ .v
_,
\
Example‘ 1
.1
k
H
v _
_
the kerosene extract, after washing with water, is
Into a 3-liter-4-neck round bottom ?ask ?tted
then distilled under reduced pressure, i. e., with. - with a mechanical stirrer, reflux condenser, ther
?re and steam or with vacuum (e. g. 5-50 mm,‘ 'mometer and dropping funnel were Placed 130
mercury at absolute pressure) to a temperature
,graInS of di-sec. butyl ether, 128 g- of naphthalene
of about 500° or 600° F. to remove solvent and: 10 ‘and 500 cc. of kerosene (heavily treated with sul
low-boiling products
The distillation. residue
,gfuric acid before use) as solvent. Means were
constitutes the desired condensationproduct of 1- Hprovided for cooling and heating the reaction
this invention.
’
-
>
?ask.
This product generally has a consistency rang-
The mechanical stirrer was started and
while maintaining a temperature of 60° F., 300 g.
ing from a viscous oil to a hard resin and has a 15 of anhydrous A1C13 were slowly added to the re
color ranging from green to brown or black. This ‘ ‘action mixture over a period of 45 minutes. After
product is soluble in mineral oils, has a fairly
the addition of the A1013 the reaction mixture was
high molecular weight, e. g., about 500 to 2,000,
heatedlto 150° F., and maintained thereat for 4
and has the property of modifying the crystal
hours, after which time it was diluted with a fur
Structure of Waxes Such as paramn wax when 20 ther quantity of kerosene, cooled to 100° F., and
added to compositions containing such wax. For
the AlCh destroyed by Slowly adding 500 00- 03'
instance, when about 0.5—10.0%, preferably about
Water» After Settling, the kerosene eXtI'act was
1-5%, of this ‘wax modi?er is added to a waxy
Washed free of acid and then distilled with ?re
lubricating oil, such as a Pennsylvania ‘or other
and steam to 540° F‘: in Order to remove Solvent
parai‘?nic type lubricating oil having a relatively 25 and low-boiling products- AbOttOmS residue 60m
high pour point, the resultant blend‘will have a
prising I14’? gramsof afgreen viscous oil was ob~
substantially lower pour point; this condensation
mined as product. ' This Was found 110 be freely
product is therefore an effective pour depressor
soluble. in.lubricating-oil in all 1pI‘0P0Tti0I1S
for'waxy oils. A small amount of this wax modi'When‘ 2% vof this vcondensation product Was
?er is also useful vas a dewaxing aid for removing 30 added to a waxy Oil/the P0111‘ Point Of Which Was
wax from mineral lubricating oils of undesirably
+.30°
the pour pointwas found to be 0° F.
high wax content," and if ‘desired, this wax modiIn all of the seven tests described in the follow
?er may also be incorporated in similarly small
ing table, 300 g. of aluminum chloride were used,
amounts into paraf?n wax or compositions conandin tests land 2 thealuminum chloride was
taining the same to be used for various purposes, 35 added last, whereas‘, inytests 3-7 the aluminum
such as for coatingor' impregnating paper, etc, ' chloride; aromatic: compound and solvent were
or for making various molded products.
?rst mixed together and'then the ether was added
Some of the condensation products of‘ this in-
last.‘
'
'7
>
‘
‘ l
.
Table
Ether
_
Aromatic compound
Solvent v(cc.)
Test No‘
'
Name
G.
Ker,3
Tetra
senel
élglg];
500
______ __
,
This?’ Yéegd’
Name
G.
Di-sec.buty1____
130
Naphthalene____
128
150
4
_____do _________ __
130
_.___do _________ __
128
______ __
500
150
4
128
______ i.
‘ 500
. 200
3
7s
______ -.
500
Di-is0propyl..__
____.do _______
2
Di-sec.butyl____
Di-isopropyl____
_____do _________ __
.250
Diphenyl _____ __
_ 2%
200
128
500 ______ __
100 ______ __
500
100
______ ._
500
Pong goint,
.
v
5%
147
_ 0
____ ._
78
+5
____ __
116 __._‘__
3
43
200
200
‘3
3
107
120
____ >_
0
0
200
3
110
-5
0
0
—10
0
____ __
Greenvviscous oil.
Black resin.
Black resin (green).
Black resin, hard.
Brown resin.
Brown resin, hard.
Brown resin.
1 Made inert by heavy pretreatment with H2804.
ZAdded last.
vention also are good dyes, for instance having
The above table shows that by the Friedel
the property of imparting a green color to a min-
Crafts condensation of lower saturated aliphatic
eral oil even though the condensation product
ethers withv aromatic compounds, high boiling
itself may be a black, hard resin.
condensation products are produced which have
The invention will be better understood from 60 pour-depressing properties, i. e., in 2% concentra
a consideration of the following experimental
tion they reduce the pour point of a waxy 111
data which are given for the sake of illustration
bricating oil base stock from +30° F. to about 0°
‘but without intending to limit the invention to
F., ‘or even lower. It should also be noted that
the particular materials or operating conditions
the condensationproduct of test 3 was a good
used.
v
v
65 green dye for mineral oils.
For the sake of clearness the procedure used
in carrying out the ?rst experiment will'be eX-
This application is va division of Serial No.
419,314, ?led November 15, 1941.
,
plained in detail, and for convenience and brevity,
It is not intended that this invention be limited
the kinds and amounts of materials, as well as
to any of the speci?c examples which were given
operating conditions used in the other tests, will 70 merely for the sake of illustration but only by the
be indicated only in the summary table in which
appended claims in which it is intended to claim
all of the test data are given. This table also.
all novelty inherent in the invention as well as
shows the yield (weight) of product obtained and"
equivalents coming within the scope and spirit
shows the A. S. T. M. pour point data obtained
when the condensation products of this invention 75
of the invention.
‘ It is claimed: ‘
'
2,411,579
5
1. A lubricating composition comprising a ma
jor proportion of a waxy mineral lubricating oil
and a wax-modifying amount of a Friedel-Crafts
condensation product of a lower saturated ali
phatic
ether
having the
general
formula
R—O—R', where R and R’ are alkyl groups having
a total of less than 10 carbon atoms with an aro
6
4. Composition according to claim 1 containing
a condensation product of 1/2 to 2 mols of the ether
and 1 mol of the aromatic compound.
5. Composition according to claim 1 in which
the condensation product is non-volatile up to
500° F. under reduced pressure.
6. A lubricating composition comprising a ma
‘jor proportion of a waxy mineral lubricating oil
matic compound selected from the group consist
and a small but wax-modifying amount of a Frie
ing of aromatic hydrocarbons and alkyl, hydroxy,
amino, and partially hydrogenated derivatives 10 del-Crafts condensation product of a lower satu
rated aliphatic ether having the general formula
thereof, said condensation product being non
R-O—R', where R and R.’ are alkyl groups, each
volatile up to 500° F. under reduced pressure, solu
having 3 to'4 carbon atoms, with an aromatic hy
ble in mineral oil and having wax-modifying prop
drocarbon having 1 to 2 nuclei, said condensation
erties.
2. A lubricant comprising a major proportion of 15 product being soluble in mineral oil and being
non-volatile upto 500° F. under reduced pressure.
a waxy mineral lubricating oil and about 0.5 to
7. A lubricant comprising a major proportion of
10.0% of an oil-soluble, pour-depressing Friedel
Crafts condensation product of di-isopropyl ether ' waxy mineral lubricating oil and a pour depressing
amount of an aluminum chloride condensation
and naphthalene, said condensation product being
non-volatile up to 500? F. under reduced pressure. 20 product of 1/2 to 2 mols of di-isopropyl ether with
1 mol of naphthalene, said condensation product
3. A lubricant comprising a major proportion
being non-volatile under ?re and steam distilla
of waxy mineral lubricating oil and a pour-de
tion up to'500° F. and being soluble in said waxy
pressing amount of a Friedel-Crafts condensa
mineral lubricating oil.
tion product of about 1/2 to 2 mols of di-isopropyl
ether with about 1 mol of aromatic hydrocarbon, 25
EUGENE LIEBER.
said condensation product being non-volatile un
MARVIN E‘. THORNER.
der ?re and steam distillation to a temperature of
at least about 500° F., soluble in mineral oil and
having pour-depressing properties.
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