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Патент USA US3087901

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3,087,892
United States Patent O??ce
Patented Apr. 30, 1963
2
1
3,087 ,892
include methyl, ethyl, propyl, butyl, hexyl, vheptyl, octyl,
nonyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.
ETHER-p-XYLYLENES)
by ?rst reacting diphenylether with a,a'-dichloro-p-xylene
The poly(diphenylether-p~xylylenes) can be prepared
LUBRICANTS CONTAINING POLY (DIPHENYL
Donovan R. Wilgus, Richmond, Cali?, assignor to the
United States of America as represented by the United
States Atomic Energy Commission
N0 Drawing. Filed Feb. 16, 1961, Ser. No. 89,648
6 Claims. (Cl. 252-52)
in the presence of a FriedehCrafts catalyst to form a
copolymer as represented by the following equation:
This invention relates to lubricating oil compositions
having improved viscosity index characteristics; in par
ticular, this invention is directed to lubricating oil com
positions containing new compounds which are effective
to improve the viscosity index (V.I.), of lubricating oil 15
compositions.
This application is a continuation-in-part of patent ap
plication Serial No. 773,149, ?led November 12, 1958,
which issued September 18, 1962, as US. Patent No.
3,054,773.
The greater proportion of oils obtainable by re?ning
wherein X is the same as described hereinabove.
Prior to the reaction with a,on'—dlChl0rO- ~xylenc, the
20
processes and useful as base oils for lubricating oil com
positions have wide variations in viscosity characteristics
with changes in temperature. They do not have agents
speci?cally incorporated therein for the purpose of im
parting reduced changes in viscosity with changes in tem
diphenylether may be alkylated. This alkylated diphenyl
ether may be represented by the following formula:
(Rh
(III)
(Rh:
25
wherein R, n, and o are the same as de?ned hereinabove,
perature. That is, at a particular temperature, a lubricat
and n+0 has a value equal to at least 1.
ing oil may be quite viscous, while at higher tempera
In certain instances, it may be desirable to alkylate the
tures the lubricating oil may have a viscosity of a ?uid
poly(diphenylether-p-xylene) to form the compound
such as kerosene. In order that the viscosity of a lubri 30
cating oil composition will not change rapidly with
(IV)
changes in the temperature of an internal combustion
engine, for example, numerous additives have been de
I‘
signed to modify the viscosity-temperature characteristics
of lubricating oils. The changes in the viscosity occur 35
ring with variations in temperature are kept at a mini
(R) u
(R) 0
ti?) :1
L
wherein R, n, 0 and p are the same as de?ned herein
mum.
above, and n+o+p has a value of at least 1.
The polymeric materials described herein can be pre
Polymeric additives in general are used to improve the
viscosity-index characteristics of lubricating oil compo
by bulk or solution Friedel-Crafts polymerization
sitions. Such polymeric additives include, for example, 40 pared
reactions. The Friedebcraits catalysts which can be used
alkyl methacrylate polymers (cg, lpolybutyl methacry
include ferric chloride, aluminum chloride, aluminum
late), and polyole?ns (cg. polybutenes). These additives
bromide, etc. Such catalysts are used in amounts of
are known to improve the viscosity-temperature relation
about 0.01% to about 1.0% by weight. The mol ratio
ships of lubricating oils.
The art is replete with numerous viscosity index im 45 of diphenylether to a,o=’-dichloro-p-xylene can be in the
range of 10:1 to 1:1, preferably from 2:1 to 1:1.
proving agents. However, the known viscosity index im
Alkylation catalysts include aluminum chloride, hydro
proving agents (e.g., polyalkylrnethacrylates) decompose
?uoric acid, etc.
A dipbenylether will react with a,a'—dichloro-p~xylene
Thus, it is a primary object of this invention to set forth
lubricating oil compositions containing new compounds 50 at temperatures ranging from 65° C. to 150° C. For
best results in this reaction, it is preferred to use tempera
which are thermally stable and which improve the vis
tures ranging from 90° C. to 120° C.
cosity-temperature characteristics of lubricating oil com
The various solvents which can be used in the polymeri
positions, including lubricating oil compositions used in
zation reactions include chloroform, o‘dichlorobenzene,
an atmosphere of nuclear radiation.
nitrobenzene, etc.
In accordance with this invention, it has been discov
The molecular weight of the resulting polymeric com
cred that lubricating oil compositions containing diphenyl
pounds ranges from about 10,000 to about 50,000. That
cther-p-xylylenc copolymers i.e., poly(dipl1enyl-ether-p
at high temperatures.
is, the molecular weight of the alkylated diphenylether-p
xylylencs) have improved viscosity index characteristics.
xylylene
copolymers are in the range of about 10,000
The poly('diphenylether-p-xylylenes) of this invention
60 to about 50,000.
are described by the formula:
As V.I. improving agents, the poly(diphenylether-p
(Pl)0
on.
“I
xylylenes) described herein can be used in amounts of
1% to 20%, by weight, in a wide variety of oils, includ
ing mineral oils, such as naphthenic base, paral'?n base,
Jx 65 and mixed base oils derived from petroleum; synthetic
L
oils, such as polymers of alkylene oxides; aromatic-type
wherein R represents branched or straight-chain hydro
oils, such as alkylphenyl diethers, alkylbiphenyls, alkyl
carbon radicals containing from 2 to 20 carbon atoms;
biphenyl others, polyalkyl terephcnyls, polyphenyls, poly
n, 0, and p are numbers from 0 to 3; and X is a number
representing the number of monomeric units in the
polymer.
It is preferred that R is an alkyl radical containing
from 2 to 20 carbon atoms. Examples of R radicals
70
arylalkanes, dialkylbenzenes, aryl esters, etc.
The new viscosity index improving agents described
herein can be prepared by reacting a diphenylether (or
an alkyiated diphenylether) with a,a'-diehloro-p-xylene,
3,087,892
3
4
using, as a catalyst, from 0.01% to 1.0%, by weight, of
anhydrous aluminum chloride, based on the total weight
of diphenylether and a,a'»dichlorop~xylene, at tempera
of 1.2), 200 grams of a propylene tetrarner (the same as
tures from 65° C. to 150° C. for a period of time from
0.5 hour to 30 hours.
The resulting reaction mixtures can be dissolved in
300 cc. of o-dichlorobcnzene and 300 cc. of hydro?uoric
acid were charged to a reaction vessel at 5° C. The
components of the above mixture were agitated for a
used in Example I hereinabove) (the mol ratio of the
tetramer to benzene rings of the copolymer being 3:1),
benzene, followed by ?ltration. An acetone-methanol
period of 4 hours at 5° C., after which the reaction prod~
blend (2 parts by volume of methanol per volume of ace~
not was obtained in a manner similar to that outlined
tone) is added to the benzene solution to precipitate the
hereinabove in Example I.
polymer. The polymers are redissolved in benzene and 10
A 10% solution of the recovered polymer in toluene
reprecipitated with an acetone-methanol blend. The re
had a viscosity (cs.) at 100° F. of 8.58.
sulting products can be dried in a vacuum oven at tem
Table II hereinbelow presents data showing the e?ec~
peratures of about 100° C. The resulting polymeric
tivcness of these polymers of Example II as V.I. improv
compound can then be alkylated with a hydrocarbon con
ing agents in lubricating oils. The base oils was a C1445
taining from 2 to 20 carbon atoms, using hydrofluoric
alkyl diphenyl ether.
acid as a catalyst.
Example I hereinbelow illustrates the preparation of
Table II
the new compounds of this invention.
EXAMPLE I-ALKYLATED POLY
20
(DIPHENYLETHE R~p—XYLYLENE)
100° F.
A mixture of 15 grams (0.086 mol) of a a,rx'-dichloro
pylene to benzene ring of 351, was dissovled in 225 grams
of ferric oxide, and 0.05 gram ferric chloride was heated
on a steam plate at 100° C. to 105° C. for less than 0.5
hour.
210° F.
26. 8
83. 1
221. 0
526. (J
The resulting polymer was dissolved in benzene
and the benzene solution was ?ltered.
Vlscosltlcs (cs.)
Percent alkylated copolymcr
4.
14.
35.
74.
v1.
83
4
3
3
114
145
138
131.
An acetone
methanol blend (2 volumes methanol per volume ‘ace
tone) was added to precipitate the polymer, which was 30
EXAMPLE III.——PREPARATION OF POLY
toluene had a viscosity of 1.81 cs. at 100° F.
(ALKYLATED BIS-(p-PHENOXYPHENYL)
ETHER-p-XYLYLENE
recovered and dried. A 10% solution of this polymer in
A mixture of 10 grams of the above diphenylether-p
xylylene copolymer and 59 grams of a polypropylene
(i.e., a propylene tetramer) in a mol ratio of polypro
pylene to ‘benzene ring of 3:1, was dissolved in 225 grams
of o~dichloro-benzene. This mixture was reacted in the
A mixture of 35 grams of bis(p—phenoxyphenyl)
r ether-p-xylylene copolymer, 200 grams of a propylene
tetramer (the mol ratio of tetramer to benzene ring being
from 3:1), 315 grams of o-dichlorobenzene and 200 cc.
presence of 150 cc. of hydro?uoric acid as a catalyst for
of hydrofluoric acid agitated at 5° C. for a period of 2
a period of 4 hours at 5° C. The reaction mixture was
hours. 100 cc. of hydro?uoric acid Was added to the
poured into cold dilute caustic solution. The reaction 40 above blend, after which the mixture was agitated for an
product was separated and water Washed, and washed
additional 4 hours at 5° C. The reaction product was
with dilute sodium bicarbonate, then dissolved in benzene.
recovered in a manner described hereinabove in Exam
The benzene solution was blended with an acetone-meth
ple I.
A 10% solution of the recovered polymer in toluene
anol blend to precipitate the product. The product
was a tacky, benzene soluble polymeric compound. The
viscosity of a 10% solution of this polymer in toluene
had a viscosity of 1.92 cs. at 100° F.
Table III hereinbelow presents data obtained to show
was 2.55 cs.
the elfectiveness of the alkylated copolymers of Example
Table I hereinbelow presents data to show the etfec
III as V.‘I. improving agents. The base oil was a C14-“
tiveness of the polymeric compound of Example I here
alkyl diphenyl ether.
inabove as a viscosity index improving agent in lubricat
ing oil compositions. The alkylated copolymer was
blended into (A) a C1446 alkyl diphenylether, and (B)
Table III
a California solvent re?ned naphthenic base oil having a
viscosity of 150 SSU at 100° F.
Vlscoslties (05.)
Percent alkylated copolymer
100° F.
Table 1
210° F.
26. 8
Base 011
Percent
alkyl
Viscosities (cs)
ated co
polymcr
(A) ________________________ __
(B) ________________________ __
100° F.
210° F.
60
VI.
0
2G. 8
4. 83
114
5
10
15
50. 7
96. 6
171. 0
8. 87
14. 6
23. 1
136
137
134
0
5
10
150
46. 3
74. 5
4. 8
at)
7. 29
11. 1
124
133
42. 8
66. 6
107.0
4. 83
7. 28
10. 7
16. 0
V. I
114
134
138
137
EXAMPLE IV.—-POLY(ALKYLATED DIPHENYL
ETHERp-XYLYLENE)
A mixture of 70 grams (0.4 mol) of a,tx'-dichloro-p
xylene, 168 grams (0.44 mol) of C1446 sec-alkyl diphenyl
ether, 20 cc. chloroform, 0.01 gram ferric oxide, and 0.05
EXAMPLE II—ALYKLATED POLY
(DIPHENYL ETHER-p-XYLYLENE)
A mixture of 35 grams of a poly(diphcnyl ether-p
xylylene) (wherein the mol ratio of diphenyl ether to
a,a'-dichloro-p-xylene in the initial reaction had a value
ferric chloride was heated at 100 to 105° C. for a period
of about 1.3 hours. During the course of the reaction,
100 cc. of o-dichlorobenzene was added slowly to keep the
reaction mixture ?uid.
The mixture was refluxed with 150 cc. xylene in the
presence of 0.05 gram aluminum chloride for 1.5 hours,
after which the mixture was ?ltered. The polymeric com
3,087,892
5
6
pound was dissolved in benzene, to which was added a
described herein are of greater thermal stability than
prior V.I. improving agents. In order to determine the
methanol-acetone blend to precipitate the product which
thermal stability thereof, the new compounds were in
corporated in a base oil consisting of an alkyl diphenyl
was dried in vacuo.
A 10% solution of this polymer in toluene had a
viscosity of 3.7 cs. at 100° F.
5
base oil.
10 cosities were determined.
Table IV hereinbelow presents data obtained to show
the e?ec?veness of the polymers’ of Example Iv as Vl
improving agents. Base oil (A) was a. C1446 alky1di_
phenylether. Base oil (B) was a California petroleum
p
.
.
I
_
ether’ wheiem the alkyl group was derived from mono
ole?ns having an average of 14 to 16 carbon atoms. The
resulting solution was heated at the temperatures noted
and the P?IlOd 0f tlme dwgnated, after which 111% V15
Table VI
‘
Concen
tratlon
Test
proving
(weight
temp,
time,
agent
percent)
° F.
hours
V.I. lm-
Test
Viscosity
Before test
After test
Per-
100° F. 210° F. 100° F.
(1) ______ ..
4.2
cent
change
Per
‘210° F.
cent
change
500
as
69.0
11.8
56.3
-19.2
9 44
~2u3
600
a
69.6
11.3
48.2
3a.?
7.95
~3as
X Alkylated (Cm) diphenyl ether-p-Xyiylene copolymer.
Table IV
30
T_
Base on
Pprcem
polymer
0
_ _
hmsmesics‘)
o
7
100 F‘ i 210 F‘
g
10
(B) ________________________ __
1S
1. A lubricating oil composition consisting essentially
in an amount sufficient to improve the viscosity index
thereof, a polymeric compound having a molecular weight
"1'
v in the range of 10,000 to about 50,000 obtained by react
—
(A) """""""""""""""""" "
I claim:
of major proportion of an oil of lubricating viscosity, and,
4 3“ ing a diphenyl ether with an u,a'-dichloro-p-xylene in the
221%
112.0
_____
$133
19.1
{:3
1%?
190
5
527
8.5
135
10
92.3
14.9
141
15
1660
presence of a Friedel-Crafts catalyst at temperatures in
the range of 90° C. to 120° 0., and removing the HCl
2543
139
obtained by said reaction.
2. A lubricating oil composition consisting essentially
4g
.
.
.
.
.
.
of a rumor
proportion
of an 011. of lubricating
viscosity,
and, in an amount su?icient to improve the viscosity index
thereof, a polymeric compound having a molecular weight
in the range of 10,000 to about 50,000 obtained by react
ing a diphenylether with an a,a'-dichloro-p-xylene in the
Table V hereinbelow presents further data concerning
the effectiveness of the polymeric compounds described
herein as VxI. improving agents. Base oils (A) and (B)
presence of a Friedel-Crafts catalyst at temperatures in
the range of 90° C. to 120° (1., wherein the moi ratio of
said diphenylether to said xylene is from 10:1 to 1:1 and
were the same as described heremabove.
removing the HCl obtained by said reaction.
3. A lubricating oil composition comprising an oil of
lubricating viscosity in major proportion, and, in an
amount sufficient to improve the viscosity index thereof,
Table V
Viscosity
Percent
Viscosities ((-s.)
Alkylatedd ofin 10?,
sol. alkylated
Base
to none
0
p y}her use
D 0 ymer
01
(1) __________ _-
1.76
(2) __________ _.
3. 45
(3) ______________________ __
(4) .......... ._
1. 29
(5) __________ ._
2. 50
100° F. 210° F.
5
(A)
(A)
(A)
67.9
107. 0
5
(A)
57. 1
10
15
42. 7
7. 25
134
9. 89
143
11.0
16. 3
130
138
10
15
5
10
15
(A)
(A)
(B)
(B)
(B)
115. 0
219
56. 9
105. 0
95. 0
19.0
34. 6
9. 04
16. 3
28. 6
5
5
10
15
5
10
15
(A)
(A)
(A)
(A)
(B)
(B)
(B)
64.5
36. 8
11.0
6. 27
143
128
5
(A)
50.1
S. 62
140
10
15
5
50. 9
71. 0
40.4
52. 1
72. 5
(A)
(A)
(B)
92. 1
168. 0
56. 1
10 £13)
103.0
15
B)
187.0
8.17
10. 7
0. 26
7. T2
10. 1
l5. 3
26. 5
8. 54
15.0
26. 2
143
138
134
139
137
132
133
113
120
124
143
140
128
135
136
1 Poly (n-nonyl, scc-dodecyldiphenylether-p-Xylylene).
2 Poly
[d1(C1B-C1S.
sec alk l)
a resinous condensation product having a molecular
weight in the range of 10,000 to 50,000 obtained by re
acting an alkyl diphenylether with an a,a’-dichloro-p
xylene in the presence of a Friedel-Crafts catalyst at tern
peratures in the range of 90° C. to 120° C., and removing
V1.
d1phenylether'p-xylylene].
the resulting HCl.
4. A lubricating oil composition consisting essentially
of an oil of lubricating viscosity in major proportion, and,
60
in an amount su?icient to improve the viscosity index
thereof, a polymeric compound having a molecular weight
in the range of 10,000 to 50,000 octane by reacting an
alkyl diphenylether with an u,oz'-dichloro-p-xylene in the
presence of a Friedel-Crafts catalyst at temperatures in the
range of 90° C. to 120° C., and removing the resulting
HCl, wherein said alkyl radical contains from 2 to 20
carbon atoms.
5. A lubricating oil composition having incorporated
therein for the purpose of improving the viscosity index
thereof, from 1% to about 20%, by weight, of a poly
70 meric compound having a molecular weight in the range
of about 10,000 to about 50,000 obtained by reacting an
alkyl diphenylether with an a,a’-dichloro-p-xylylene in the
‘ Poly d?n-nonyll1 (liphenylether-p-xylylene].
presence
of a Friedel-Crafts catalyst at temperatures in
a Potytdodecyldip enyletherp-xylylene) wherein there were
the range of 90° C. to 120° C., and removing the resulting
at least 3 dodecyl radicals per benzene ring.
75 HCl, and wherein said diphenylether contains from 1 to 3
As stated hereinabove, the new V1. improving agents
wherein the mol ratio of Cm to (,1B was 32 2 08.
3Poly n-nonyl diphenylether-p-xylylene),
3,087,892
7
alkyl radicals on each phenyl ring, and wherein said alkyl
radical contains from 2 to 20 carbon atoms.
6. A lubricating composition consisting essentially of
a major proportion of an oil of lubricating viscosity, and
from about 1% to about 20%, by weight, of a polymeric
compound having a molecular Weight in the range of
about 10,000 to about 50,000 obtained by reacting an
alkyl diphenylether with an u,ot'-dichloro-p-xylene in the
presence of a Friedel-Crafts catalyst at temperatures in
the range of 90° C. to 120° C., and removing the result
ing HCl, wherein the mol ratio of said diphenyl-ether
to said xylylene is from 10:1 to 1:1, and said diphenyl
8
ether contains from 1 to 3 alkyl radicals on each phenyl
ring, and wherein said alkyl radical contains ‘from 2 to 20
carbon atoms.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,060,715
2,355,616
2,542,111
2,911,380
2,965,607
3,006,852
Arvin _______________ __ Nov. 10,
Barker ______________ __ Aug. 15,
Bloch ________________ __ Feb. 20,
Doedens ______________ __ Nov. 3,
Martin et al. __________ __ Dec. 20,
Barnum et al. _________ __ Oct. 31,
1936
1944
1951
1959
1960
1961
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