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Патент USA US2411578

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V t/Patented Nov, 26,
1 2,411,573
v j I‘
,' ‘I >
“ EugeneiLieber,,WestNewBr-ighton, Staten Island,
and Marvin E. Thorner, Brooklyn, N. Y., assign
"ors to’ Standard Oil Development ?Com'panyya
corporation-o! Delaware
_v v
Application November 15,1941,
'_ ; ,No “Drawing.
Serial No.419,314‘>,
" I
‘16 Claims‘; ‘(C1, aces-671‘)
as they are still subject to jFriedel-crafts con.
type of chemif I
_‘ This invention relates to ‘a novel
cal' condensation products and to methods?of
preparing such products and using them for vari
densation. ' Speci?c examples of suitable aromatic
compounds include benzene,v naphthalene, an-,
ous purposes, more particularly‘; as pour nde- I
pressors in waxy lubricating oils.
It is known that pour ‘jdepressors can be made
thracerle, phenanthrene, toluene,»xylene, amyl
benzene, retene, phenol, alpha-- or beta-naphthol,
cresol, anisole, tertiary amyl- phenol, diphenyl,
andl‘diphenyl oxide.
' by"c'ondensing an aromatic compoundjsuch as
invention, is preferably anhydrous? aluminum '
weight aliphatic‘compounds, such'as chlorinated
chloride, although other .Friedel-Crafts catalysts’
p'araiilnv wax or corresponding ole?ns, for such
ing thiscondensation of the lower'aliphatic ether
with'the aromatic compound, according to this
to» use relatively long chain or high molecular
, : The Friedel-Crafts catalyst to be used in effect
naphthalene with an aliphatic compound, but it
‘has always heretofore been considered'necess'ary
can be used, such as boron ?uoride, ferric chloride, _
titanium tetrachloride, boron trichloride, anti
One objector the present invention is 'to avoid
the use of such long-chain aliphatic compounds, v15 mony chloride, zinc chloride, and in-ysom'e cases
even hydrogen fluoride;
} Thepro‘portions of reactants to be used should
be about 1/5 to 5 mols, preferably 1A to 2 mols,,of
lower aliphatic ether to 1 mol of aromatic com
and another object i's'to use aliphaticcompounds
which are saturated in respect to hydrogen (i. e..
free from ole?nic linkages) and yet do not con
tain any reactivehalogen- atoms as‘are present
in chlorinated para?in wax.
~ ,
20‘ pound and the amount of catalyst should be, for
Broadly, thepinvention comprises the produc
tion ,of condensation products having‘ wax-lrnodi
fying properties, by chemically condensing a.»
lower saturated aliphatic ether with an aromatic
, instance in the case of aluminum chloride, aboutv ‘
:,_{,1/,» ‘to '4 mols, preferably 1-3 mols' per mol of
-' aromatic ‘compound.
I “The use of an inert diluent or'solvent, especially I
, compound. This condensation is preferably car-, 25 one which is a good solvent for the resulting high
molecular ‘weight condensation product, is op
,ried out by the use of :a‘Friedel-Crafts catalyst:
according to the procedure commonly used for . tional but is preferred, and if used, should be
- present in about 1/2 to 10 volumes, preferably l-5
eilfecting such‘condensations.
. The lower saturated aliphatic ether to be ‘used, ' volumes, per volume of total reactants and cata-'
is one having-a low, molecular weight and a low 30
numberv of carbon ‘atoms.
Although some modi-
, u
In'carrying ‘out the invention, the operating
?ed ethers‘ may be used, it is preferred to use ' , conditionsto be used should include a temperae
I Y ethers having the general fOrmula'It-O-R',
ture between theapproximate limits oi room tem
perature and 300° Fgvpreferably mixing the re
actants and catalyst at about room temperature
jfand then afpterany initial reaction has begunyto
where R and R’ are like or unlike alkyl groups '
v and where the total number of carbon; atoms in 35
R and R’ together is less than 10, andpreferably
less than 'l'carbon atoms. Specific‘ examples of
' subside, heating the reaction mixture toa ?nal
temperature of about 150-.-250°7F., with a‘ reaction
dipropyl ether, di-isopi'opyl ether, di-secondary ‘ time of about 1/2 to 10 hours, usually about 1 to 5
butyl ether, methyl isopropyl ether, isopropyl do hours. The reactants and catalyst can'be mixed '
_ vsuch ethers includedimethyl ether,-di-ethyl-ether,'
tertiary butyl ether, etc., or ‘mixtures of two ‘or
more such pure compounds, or commerclalprod- .
nets of which such ethers representv the main
‘in any desired order, for instance, the aliphatic
ether and the aromatic compound can be mixed
together ?rst,with or without solvent, and‘ thenv
the catalyst added, or the catalyst may be mixed
_- ~' The aromatic compound to be used as the other 45 ,with the aromatic compound, and
‘reactant may be composed of a single aromatic ' phatic'ether subsequently added.
ring or polynuclear compounds, and in the-"latter
then the ali
After thevreactants and catalyst have “been
case the several nuclei may be'separate or'con-T __ mixed together and after the ‘reaction mixture
Various derivatives of‘ such aromatic -
compounds may also be used, such‘as thosecon
taining alkyljhydrozty, amino, and other sub;
stituents, or partially hydrogenatedTaromatic
‘ compounds, so long as these various derlvatiyes
still contain at least two replaceable hydrogen
atoms on the nucleus, or, in other words, solong'
has been heated to the desired ?naltemperature
50 fora su?lcient time to complete the reaction, the
reaction mixture is then cooled, diluted witha
convenient volume of kerosene, light chlorinated
hydrocarbon or other suitable diluent, and neu
tralized by anyv of the methods ‘familiar to the
Friedel-Crafts art, i. e., byaddingzwater, alco
centration in a waxy mineral lubricating oil base
stock having a pour point or +30“ F.
ho], dilute aqueous caustic soda solution, etc., a
mixture of alcohol and water being very suitable.
The reaction mixture is then separated, as by
settling, into two layers, the aqueous layer con
taining the aluminous sludge being removed, and
the kerosene extract, after washing with water,
Into a 3-liter-e-neck round bottom ?ask ?tted
with a mechanical stirrer, re?ux condenser,
is then distilled under reduced pressure, 1. e.,
with fire and steam or with vacuum (e. g. 5-50
. thermometer and dropping funnel were placed
.130 grams of di-sec. butyi ether, 128 g. of naph- "
' mm. mercury at absolute pressure) to a tempera
thalene and 500 cc. of kerosene (heavily treated
ture of about 500° or 600° F. to remove solvent 10 with sulfuric acid before use) as solvent. Means
and low-boiling products. The distillation resi
due constitutes the desired condensation product
were provided for cooling and heating the reac
This product generally has a consistency rang
tion ?ask. The mechanical stirrer was started
and while maintaining a temperature of 60° F.,
This product is soluble in mineral oils, has a
fairly high molecular weight, e. g., about 500 to
2,000, and has the property of modifying the
utes. After the addition of the A1013 the reac
tion mixture was heated to 150° F., and main
tained thereat for 4 hours, aftervwhich time it
‘ of this invention.
300 g. of anhydrous AlCla were slowly added
ing from a viscous oil to a hard resin and has a 15 to the reaction mixture over a period of 45 min
color ranging from green to brown or black.
was diluted with a further quantity of kerosene, '
crystal structure of waxes such as paraffin wax 20
cooled to 100° F., and the AlCla destroyed by
slowly adding 500 cc. of water. Aftersettling,
the kerosenevextract was'washed free of acid
about 1-5%, of this wax modi?er is added to a.
and then distilled with ?re and steam to 540° R,
' waxy lubricating oil, such as a Pennsylvania or
to remove solvent and low-boiling prod
other para?lnic type lubricating oil having a rel 25 in order
A bottoms residue comprising 147 grams
.- ucts.
atively high pour point, the resultant blend will
of a green viscous oil was obtained as product.
have a substantially lower pour 'point; this con
This was found to be freely soluble in lubricating
densation product is therefore an effective pour
oil in all proportions.
depressor for waxy oils. A small amount of this
When 2% of this condensation product was
wax modi?er is also useful as a dewaxing ‘aid for 30
added to a waxy oil, the pour point of which
removing wax from mineral lubricating oils of
was +30“ R, the pour point was found to be 0° F.
undesirably high wax content, and if desired, this
In all‘of the seven tests described in the fol
wax modifier may also be incorporated in simi
when added to compositions containing such wax.
For instance, when about 0.5—l0.0%, preferably
lowing ‘table, 300g. ofaluminum chloride were
larly small amounts into paraffin wax or compo
sitions containing the same to be used for vari 35 used, and in tests 1 and 2 the aluminum chlo
‘ride was added last, whereas, in tests 3-7 thev
ous purposes, such as for coating or impregnating
aluminum chloride, aromatic compound and sol
vent were ?rst mixed together and then the ether
paper, etc., or for making various molded prod
Some of the condensation products of this in
was added last.
Aromatic compound
Solvent (ca)
Pong goint,
Tem . Time Yield
Test No.
a me
,1’_________ _l- Di-sec. butyl_.__
Kem- ré?ltm_
0 Sena l ~ ethane
’ hm '
_ __
130 ......... _-
_ _'___. o ......... _.
1 102
1 102
._-__do . . . _ _ _
_ __
Benzene _____ ._,_.
____ __ Di-sec. buty1__._ 2130
Retene ........ -Diphenyl _____ __
_____do_-_ . _ _ .
6 __________ __ Di-isopropyl. _ . .
7 _______________ ..d<>_.._T .... _.
2 50
a 50
0 .... __ Green viscous oil.
____ -.
____ -_
____ __
Black resin.
-Black resin (green dye).
Black resin, hard.
Brown resin.
Brown resin, hard.
Brown resin,
1 Made inert by heavy pretreatment with H1804.
iAdded last.
The above table shows that by the Friedel
vention also are good dyes, for instance having
the property of imparting a green color to a
mineral oil even though the condensation prod
uct itself may be a black, hard resin. .
The invention will be better understood from
a consideration of the following experimental
data which are given for the sake of illustration
but without intending to limit the invention to
Crafts condensation of lower saturated aliphatic
ethers with aromatic compounds, high boiling
condensation products are produced which have
pour-depressing properties, i. e., in 2% concentra
tion they reduce the pour point of a waxy lubri
eating oil base stock from +30” F. to about 0° F.,
or even lower. It should also be noted that the
condensation product of test 3 was a, good green
the particular materials or operating conditions
used. For the sake of clearness the procedure 65 dye for mineral oils.
It is not, intended that this invention be limited
used in carrying out the ?rst experiment will be
to any of the specific examples which were given
explained in detail, and for convenience and
merely for the sake of illustration but only by the
brevity, the kinds and amounts of materials, as
appended claims in which it is intended to claim
well as operating conditions used in the other
tests, will be indicated only in the summary ta 70 all novelty inherent in the invention as well as
equivalents coming within the scope and spirit
ble in which all of the test data are given. This
of theinvention.
table also shows the yield (weight) of product
Lubricating compositions, e. g. comprising a
obtained and shows the A. S. '11 M. pour point
major proportion of waxy mineral lubricating oil,
data obtained when the condensation products
of this invention are tested in a 2% or 5% con 75 containing the novel condensation products de
‘ ‘2,411,578. 1
elected, from thegroupcon'sisting of "aromatic
I scribed‘herein, are claimed in copending applica
vhydrocarbons and alkyLjh'ydroxy, amino and '
tiOn Serial No. 554,344, ?led September 15, 1944. -' ,.
We claim:
; a
partially ‘hydrogenated “derivatives thereof, said
‘condensation product having‘ a. molecular weight
1. The‘ process which comprises, condensing
about 1A, to 5 molspf an ether having the general
of about 500 to- 2,000 being soluble in mineral
oil and' substantially nonlvolatile at tempera;
formula R-O——R’, in which R and R’ are alkyl .
groups having a total of less than 10 carbon atoms,
with about 1 mol of an aromatic compound, in the l
' tures up to about-500° F. under‘ reduced pressure.
7. An aluminum-chloride condensation prod- I
> ‘
not of di-isopropyl ether and naphthalene, said
presence of about 1/2 to 4 mols of a Friedel-Crafts '
condensation product having a molecular weight ;
catalyst‘ and’ in'thepresence of about 1/2 to 10 V10 of " about 500‘ to 2,000 being soluble in mineral
volumes? of inert solvent'per_. volume of total re- _ ~ oil, ‘substantially non-volatile at temperatures up
actants and catalyst, at ‘a temperature ‘between ‘ to about 500° F. under ?re and steam distilla
~ the approximate'limits of room temperature andv j tion, and having the property ‘of reducing the
about 300° F., hydrolyzing and removing the cata-i '
pour‘ point of waxy mineral oils whenv added '
' , lyst and distilling the condensation products un 15
thereto in small amounts.
der reduced pressure ‘to a temperature of at least
500° F. to obtain as distillation residue a high
8. Process according to cla" > 2 in which the
molecular weight condensation product soluble in .a ''
inert solvent is a re?ned kerosene.
mineral oil;
inert solvent istetrachlorethane.
I " I
19. Process according to claimv 2~in which they
2. The process which, comprises condensing
10. Process according toclaim 2 in which about
about 1A» to 2 'mols of an'ether having the general
500cc. of inert solvent are used lfor each gram _
formula R-—O—-R', where R and R.’ arealkyl ,
mol of aromatic compound.
groups having a total of less than 7 carbon atoms,‘
11. Productaccording to claim»6 having the
‘with about lmol of aromatic ‘compound in the
property of reducing the pour point of a waxyv .
presence of about 1 to 3‘mols of aluminum_chlo-; 25 mineral lubricating oil having -a pour ‘point of .
ride and in the presence on to 5 volumesof inert
'+30°- F. v‘down to at least about 0 when added
solvent per volume of reactants and catalyst, said
thereto in 2% concentration.
12. Product according to claim 7 being a green I
reactants and catalyst being mixed'at about room - '
temperature, and then heating to a‘?nal reaction
temperature of 150-250’ F.'for a reaction ‘time of
dye for mineral oils.
1/2 to 10 hours, hydrolyzing and removing the cat
alyst and distilling the condensation product with
aromatic compound used is naphthalene.
3. The process which comprises condensing
about 1/2 to 2 mols of di-isopropyl ether with'about
‘aromatic hydrocarbon used is naphthalene.
15. The process which "comprises chemically. ‘
weight condensation product soluble in“ mineral " 35
14. Process ‘according to claim 3 in which the
?re and steam distillation to at least about 500° F. '
to obtain asv distillation residue a high molecular
oils and having wax-modifying properties;
~13.’ Process'according to claim 2in vwhich the
condensing a halogen free lower dialkyl ether .
, 'with an aromatic compound in‘ the presence oi.’
a substantial amount of inert solvent and a ..
Friedel-Crafts catalyst at_=_a temperature between
1 mol of aromatic hydrocarbon in-the presence of . I
the approximate'limits of room temperature and ~
aboutl to 3 mols of aluminum chloride and'about
about 300° F., to produce a condensationvproduct
non-volatile at 500° F., under reduced pressure,'_
about room‘temperature and about 300° F., hydro-_ I hydrolyzing andremoving the catalyst, and dis
lyzing and removing the‘ catalystand distilling 'v tilling the reaction .product underreduced pres
1 to 5 volumes of solvent per volume ormixed're
actants and catalyst, at a temperature :between
sure to a temperature of atileast 500? F., to ob- _ ,
the condensation product with ?re and steam to a
temperature of atleast about 500° F. to obtain as
distillation residue a condensation product solu-I
ble in=minera1 oil and having pour-depressing,
properties.v >
4. A Friedel-Crafts condensation product ofa‘
lower dialkyl ether‘ and an aromatic compound,
tain the.desired high molecular weight conden
sation product as distillation residue.
‘ 16. The process which comprises condensing a
dialkyl ether having-less than -10 carbon atoms
' with ‘an aromatic compound selected from‘ the
group consistingjof aromatic hydrocarbons; and _,
alkyl, hydroxyamino andpartially hydrogenated
said condensation. product. havinga molecular ‘
weight of about 500 to 2,000, being substantially
non-volatile up to about 500° F. under reduced
derivative thereof, in the presence of a'Friedel
J Crafts catalyst and in the presence of a substan
tial amount of‘inert aliphatic organic solvent at
a. temperature between the approximate limits of
room temperature and about 300" F., to produce.
a. condensation product ‘non-volatile at 500°-1".‘,
under reduced p'ressure’to a temperature of at
5. A condensation productuof a dialkyl ether
'having less than 10 carbon atoms and an, arc
matic compound, said condensation product hav
ing a. molecular weight of about 500 to 2,000
being soluble in mineral oil and substantially 60 least
E, to obtain the
desired high
as distillation
molecular ‘_‘ -' '
non-volatile at temperatures up'to about 500° F.
,6. A condensation product of an ether havingv
the general formula R-O-R', where R. and R’
are alkyl'groups having a ‘total of less than 10
carbon atoms, with an aromatic compound se 65
.MARVIN n. momma.
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