NON-CROSS LINKED PRODUCTS OF HYDROCARBON POLYMERS WITH OLEFINIC POLAR COMPOUNDS AND PROCESSES FOR MAKING SAME

PROCEDES D'OBTENTION DE PRODUITS SANS RETICULATION CROISEE DE POLYMERES D'HYDROCARBURES ET DE COMPOSES POLAIRES OLEFINIQUES

English Abstract

ABSTRACT OF THE DISCLOSURE
This invention discloses novel, reaction products of ethylene-
propylene copolymers, or ethylene-propylene nonconjugated diene terpolymers,
with polar olefinic compounds, such reaction products being useful as deter-
gent-dispersant-viscosity index improvers. Also disclosed are processes for
their preparation and lubricating compositions containing such products.

Claims

The embodiments of the invention in which an ex-
clusive property or privilege is claimed are defined as follows:
1. A multipurpose lubricant additive comprising reac-
tion products selected from a hydrocarbon polymer substrate of
the group consisting of an ethylene-propylene copolymer, an
ethylene-propylene diene terpolymer and mixtures thereof, with
the terpolymer having an iodine number of about 1 to about 30,
and the propylene content of said ethylene-propylene copolymer
and terpolymer being in the range of 20 to 76.5% by weight; and
of a basic polar olefinic compound characterized by having an unsaturated
portion capable of reacting with a hydrocarbon polymer, as above
defined, when catalyzed by a free radical initiator, with the
ratio of polar olefinic compound to initiator being from 1:1 to
8:1, said polar olefinic compound being incorporated in said ad-
ditive to the extent of at least 1 to 40 moles per 100,000 grams
of hydrocarbon polymer; said olefinic compound having the
formula:
<IMG> wherein X is:
<IMG> or
a polynuclear aromatic amine and Y is oxygen or NR5; with R1,
R3, R4 and R5 being hydrogen or alkyl; andR2 being methylene or
polymethylene having from 1 to 16 carbon atoms in the chain;
said olefinic compound being attached to said substrate in the
form of single units and in the form of chains of multiple
units; said chains being too short, in the aggregate, to be
considered polymeric in the sense that they do not cause an
increase in the viscosity of a solution of the modified polymer
relative to the viscosity obtained with a solution of the
unmodified polymer substrate.
-25-

2. The additive of Claim 1, wherein said hydro-
carbon is derived from ethylene propylene and a non-con-
jugated diene.
3. The additive of Claim 1, wherein said polar
olefinic compound is selected from the group consisting of dimethyl-
aminoethyl acrylate, dimethylaminoethyl methacrylate, di-
methylaminopropyl acrylamide, dimethylaminopropyl methacry-
lamide, 2-vinylpyridine, 4-vinylpyridine; 2-dimethylamino-2-
methylpropyl acrylate, dimethylamino-2-methylpropyl methac-
rylate, 2-vinylquinoline, 4-vinylquinoline; 2-aminoethyl
acrylate, 2-aminoethyl methacrylate, t-butylaminoethyl
acrylate, t-butylaminoethyl methacrylate, N-vinylmorpholine,
2-ethylpyridinyl acrylate, 2-ethylpyridinyl methacrylate, N
vinylindole and mixtures thereof.
4. The additive of Claim 1, wherein said ter-
polymer is selected from the group consisting of ethylene/
propylene/1,4-hexadiene; ethylene/propylene/1,4-dodecadiene;
ethylene/propylene/1,4-heptadiene; ethylene/propylene/6-
methyl-1,4-decadiene; ethylene/propylene/1,4-tridecadiene;
ethylene/propylene/7,7-dimethyl-1,4-octadiene; ethylene/
propylene/5-methylidene-2-norbornene; ethylene/propylene 5-
ethylidene-2-norbornene; ethylene/propylene/5-isobutyl-
idene-2-norbornene; ethylene/propylene/5-n-heptylidene-2
norbornene; ethylene/propylene/5-n-decylidene-2-norbornene;
ethylene/propylene/5-n-dodecylidene-2-norbornene; ethylene/
propylene/5-n tridecylidene-2-norbornene; ethylene/propylene/
5-n-tetradecylidene-2-norbornene; ethylene/propylene/5-
hexadecylidene-2-norbornene, and mixtures thereof.
-26-

5. The additive of Claim 1, wherein said hydro
carbon polymer is an ethylene-propylene copolymer having a
molecular weight of 20,000 to 50,000 and said olefinic com-
pound is dimethylaminoethyl methacrylate.
6. The additive of Claim 1, wherein said polymer
has a reduced solution viscosity of about 0.6 to 1.15 in
decalin at 135°C.
7. The additive of Claim 1, wherein said hydro-
carbon polymer is an ethylene propylene-5-ethylidene-2-
norbornene terpolymer and said olefinic compound is dimethyl-
aminoethyl methacrylate.
8. The additive of Claim 1, wherein said hydro-
carbon is an ethylene-propylene copolymer having a reduced
solution viscosity of about 0.6 in decalin at 135°C and said
olefinic compound is 4-vinylpyridine.
9. The additive of Claim 1, wherein said hydro-
carbon is an ethylene-propylene copolymer having a reduced
solution viscosity of about 0.6 in decalin at 135°C and
said olefinic compound is dimethylaminopropyl methacrylamide.
10. The additive of Claim 1, wherein said hydro-
carbon is an ethylene-propylene copolymer having a reduced
solution viscosity of about 0.6 in decalin at 135°C and
said olefinic compound is 2-(dimethylamino)-2-methyl-propyl
methacrylate.
11. The additive of Claim 7, wherein said ter-
polymer has a molecular weight of around 76,000 a reduced
solution viscosity of about 2.15 in decalin at 135°C and
an iodine number of 6.
-27-

12. The additive of Claim 1, wherein said hydrocarbon is an ethylene-
propylene-1,4-hexadiene terpolymer and said olefinic compound is dimethyl-
aminoethyl methacrylate.
13. A process for making a multipurpose lubricating oil additive
which comprises adding to a solvent, a hydrocarbon polymer substrate selected
from the group consisting of ethylene-propylene copolymers, ethylene-propyl-
ene-diene terpolymers and mixtures thereof, with the terpolymers having an
iodine number of about 1 to about 30, and the propylene content of said
ethylene-propylene copolymer and terpolymer being in the range of 20 to 76.4%
by weight; adding to the resulting solution a free radical initiator and a
basic polar olefinic compound characterized by having an unsaturated portion
capable of undergoing an addition reaction with a hydrocarbon polymer, as
above defined, when catalyzed by said free radical initiator at a temperature
of about 50 to 200°C the ratio of polar olefinic compound to initiator being
from 1:1 to 8:1; said polar olefinic compound being incorporated in said ad-
ditive to the extent of at least 1 to 40 moles per 100,000 grams of hydro-
carbon polymer, said olefinic compound having the formula:
<IMG> wherein X is:
<IMG> or
28

a polynuclear aromatic amine and Y is oxygen or NR5; with
R1, R3, R4 and R5 being hydrogen or alkyl; and
R being methylene or polymethylene having from 1 to 16
carbon atoms in the chain.
14. The process of Claim 13, wherein said hydro-
carbon is derived from ethylene, propylene and a noncon-
jugated diene.
15. The process of Claim 13, wherein said polar
olefinic compound is selected from the group consisting of dimethyl-
aminoethyl acrylate, dimethylaminoethyl methacrylate; di-
methylaminopropyl acrylamide, dimethylaminopropyl methacry-
lamide, 2-vinylpyridine, 4-vinylpyridine, 2-dimethylamino-2-
methylpropyl acrylate, 2-dimethylamino-2-methylpropyl
methacrylate; 2-vinylquinoline, 4-vinylquinoline; 2-amino-
ethyl acrylate, 2-aminoethyl methacrylate; t-butylaminoethyl
acrylate, t-butylaminoethyl methacrylate; N-vinylmorpholine,
2-ethylpyridinyl acrylate, 2-ethylpyridinyl methacrylate; N-
vinylindole, and mixtures thereof.
16. The process of Claim 13, wherein said ter-
polymer is selected from the group consisting of ethylene/
propylene/1,4-hexadiene; ethylene/propylene/1,4-dodecadiene;
ethylene/propylene/1,4-heptadiene; ethylene/propylene/6-
methyl-1,4-decadiene; ethylene/propylene/1,4-tridecadiene;
ethylene/propylene/7,7-dimethyl-1,4-octadiene; ethylene/
propylene/5-methylidene-2-norbornene; ethylene/propylene 5-
ethylidene-2-norbornene; ethylene/propylene/5-isobutyl-
idene-2-norbornene; ethylene/propylene/5-n-heptylidene-2
norbornene; ethylene/propylene/5-n-decylidene-2-norbornene;
ethylene/propylene/5-n- dodecylidene-2-norbornene; ethylene/
-29-

propylene/5-n-tridecylidene-2-norbornene; ethylene/pro-
pylene/5-n-tetradecylidene-2-norbornene; ethylene/pro-
pylene/5-hexadecylidene-2-norbornene, and mixtures thereof.
17. The process of Claim 15, carried out in the
presence of an acrylate-type ester of the formula:
<IMG>
wherein R is hydrogen or lower alkyl and Rd is an alkyl
group having from 1 to 30 carbon atoms in the chain.
18. The process of Claim 13, carried out in the
presence of a solvent of the group of benzene, chloroben-
zene; n-heptane, dodecane and hydrocarbon mixtures having a
viscosity at 100°F of about 10 to 200 SUS.
19. The process of Claim 13, further including
the steps of isolating the polymeric product and dissolving
same in a mineral oil having a viscosity at 100°F of about
10 to 200 SUS to form a solution containing from about 2% to
about 60% by weight of polymer.
20. The process of Claim 13, comprising adding to
the reaction mixture a mineral oil having a viscosity at
100°F of about 10 to 200 SUS and isolating a polymer-oil
solution by stripping said reaction solvent from said
mixture.
21. The process which comprises dissolving under
a nitrogen atmosphere an ethylene/propylene/5-ethylidene-2-
norbornene terpolymer having a molecular weight of about
76,000 and an iodine number of 6 in a mineral oil having a
viscosity of about 100 SUS at 100°F; adding to the resulting
solution dicumyl peroxide and dimethylaminoethyl
methacrylate; with the ratio of said methacrylate to said
peroxide being from 1.1 to 8:1; heating the resulting
reaction mixture at about 140°C for about 4 hours, then
adding to the resultant mass a solvent neutral oil having a
viscosity of about 123 to 133 SUS at 100°F.
-30-

22. A lubricating composition comprising a major proportion of a
petroleum base lubricating oil and admixed therewith 2-25 parts of an addi-
tive according to Claim 1 per 100 parts of lubricating composition.
23. The composition according to Claim 22, wherein said additive is
prepared by a reaction of an ethylene/propylene/5-ethylidene-2-norbornene
terpolymer having a molecular weight of about 76,000 and an iodine number of
6 with dimethylaminoethyl methacrylate.
24. A multipurpose lubricating oil additive prepared by the process
which comprises adding in a solvent, a hydrocarbon polymer substrate se-
lected from the group consisting of ethylene-propylene copolymers, ethylene-
propylene-diene terpolymers having an iodine number of about 1 to about 30,
and mixtures of said substrates; the propylene content of said copolymer and
terpolymer being in the range of 20 to 76.4% by weight; adding to the result-
ing solution a free radical initiator and a basic polar olefinic compound
characterized by having an unsaturated portion capable of undergoing an addi-
tion reaction with a hydrocarbon polymer, as above defined, when catalyzed by
said free radical initiator at a temperature of about 50° to 200°C the ratio
of polar olefinic compound to initiator being from 1:1 to 8:1; said polar
olefinic compound being incorporated in said additive to the extent of at
least 1 to 40 moles per 100,000 grams of hydrocarbon polymer, said olefinic
compound having the formula:
31

<IMG> wherein X is:
<IMG> ; <IMG> or
a polynuclear aromatic amine and Y is oxygen or NR5; with
R1, R3, R4 and R5 being hydrogen or alkyl; and R2 being
methylene or polymethylene having from 1 to 16 carbon atoms
in the chain.
25. A multipurpose lubricant additive consisting of
the reaction product in the presence of dicumyl peroxide of
an ethylene-propylene-1,4 hexadiene terpolymer having a
molecular weight of 20,000 to 50,000 and an iodine number
ranging from about 1 to about 30 and dimethylaminoethyl
methacrylate, wherein the ratio of said methacrylate to said
peroxide ranges from 1:1 to 8:1; said dimethylaminoethyl
methacrylate being attached to said terpolymer in the form
of single units and in the form of chains of multiple units;
said chains being too short, in the aggregate, to be
considered polymeric in the sense that they do not cause an
increase in the viscosity of a solution of the modified
terpolymer relative to the viscosity obtained with a
solution of the unmodified terpolymer.
-32-

Description

PIELD OF T~!E ~NVENTION
This invention discloses novel polymers of ethylene-propylene co-
polymers, or ethylene-propylene nonconjugated diene terpolymers with polar
olefinic compounds, such reaction products being useful as detergent-dispers-
ant, viscosity index improvers. Also disclosed are processes for their prep-
aration and lubricating compositions containing such products.
BACK_ROUND OF THE INVENTION
The rate of change of viscosity of lubricating oil wi~h temperature
is called -the viscosity index or V.I. Oils having a high viscosity index ex-
hibit a smaller change in viscosity with temperature variation than those
with a low V.I. In such applications as automobile and aircraft engine lub-
rications, where a wide range of temperature is encountered, lubricating oils
having high viscosity indices are highly desirable and often critically nec-
essary.
It is known that small quantities of long chain polymers of such
hydrocarbons as isobutylene and similar aliphatic hydrocarbons, and of acryl-
ates and methacrylates esters, will substantially increase the V.I. of pet-
roleum lubricants. In particular, homopolymers and copolymers of methacrylic
acid esters have been used extensively as "`V.I. improvers". These polymeric
additives are usually prepared by the free radical polymerization of a mon-
omer or a mixture of monomers. Polymers and copolymers of such esters as
butyl methacrylate, hexyl methacrylate, dodecyl methacrylate and octadecyl
; methacrylate have been prepared by this method. Polymers of the lower alkyl
methacrylates are generally good viscosity index lmprovers but are relative-
ly insoluble in oil; the higher alkyl esters produce polymers which are more
oil soluble but generally inferior
'
i '
.,
-1-
' ~

~3~0~
V.I. improvers. A copolymer of a lower alkyl methacrylate and a higher alkyl
me-thacrylate will combine the desirable properties of its constituents, one
portion providing the necessary oil solubility and the other contributing
V.I. improvement to the oil. Copolymers with these properties are utilized
extensively as V.I. improvers in lubricating oil.
Another type of additive commonly used in lubricating oils is the
detergent-dispersant type. In the course of operating an internal combustion
engine, products of oxidation of fuel and lubricant components are produced
in the engine. These deleterious products tend to form sludge and varnish
`` 10 deposits within the engine and generally have an adverse effect on engine
operating efficiency; ultimately the build-up of such products can cause the
engine to fail.
The purpose of the detergent-dispersant additives is to keep the
deleterious material suspended in the oil, thus preventing deposit formation.
Examples of such detergent dispersants are the reaction products of low mol~
ecular weight (200-2000) polyolefins with ~a) P2S5, subsequently reacted with
ethylene oxide, and ~b) maleic anhydride, subsecluently reacted with poly-
ethyleneamines; these additives do not have the ability to improve viscosity
index. The present invention relates to the preparation of novel additives
having detergent-dispersant as well ~lS viscosity index-improving properties
~dual-purpose additives).
A previously proposed dual-purpose additive, described in United
` States Patent 3,7~5,980, is prepared by oxidation ~or hydroperoxidation) of
an ethylene-propylene copolymer followed by subsequent reaction with an '
~ amine. This additive suffers from disadvantages in that ~a) its preparation
-~ requires two reaction steps which ~for commercial purposes) add processing
,; costs, compared with the one-step
! ~
-- 2 --

~3~
reaction required for the present invention; (b~ the
flrst ~tep of the patented process i.~corporates oxygen
functionq on~o ~he polymer bac~bone, making it more
susceptible to participation in ~he delet~rious deposit-
~orming proce~ses occurring under automotive engine opera~
tion than the additive of the p~esent in~ntion, which has
only carbon and hydrogen attached to the polymer bac~one;
and (c) the product o the patented process tends to have
an undesirably dark color. Anothe~ ~ual-purpose additive,
10 described in U~S. patent 3,40~,0gl, is made by oxidation
of an ethylene~propylene-diene terpolymer and subsequent
gra t polymer~zation reactia~ with acrylonitrile; this
additi~e suffer~ ~rom the same above-men~ianed draw~acks
as the additlve described in U.S. Pa~nt 3,785,980. This
~.
is ~lso ~he case for the additi~e d~scribed in U.S. Patent
3,687,849 or which, additionally, all examples must utilize
an ethylene-propylene-diene terpolymer. The process of
this invention is not so restricted and can use a saturated
polymer such a~ an ethylene-propylene copolymer.
: 20 The products of the pr~sent invention re~uixe
a sis~iicantly lower prOportiQn of polar olefinic compound
for ~fec~ive detergent-dispersant properties ~han i5
de~cribed in the examples o U.S. Pate~ 3,687,849. Fur~her-
mora, ~he weight ratios of polar ole~inic compound to fr~e
radical iMitiator employed in the patent are relativ~ly high
at about 11:1 and higher. By contra~t, the present inven-
~ tion disclo~es the unexpected result that detergent~dispersant
J effectivene~s is signific~ntly i roved whon much lower
weight ratios of polar oleLinic ~ompound to initiator (less
than about 7:1) are employed.
Unexpectedly, and ~uxprisingly,the products of
~his i~ention show no evidence of crosslinking which
--3--

~3~
would be expect~d when heati.ng the polymers in the presence of these initi-
tiators. Such evidence, absent here, includes higher viscosity in solutions
of the product or insolubility of the polymer in oil.
Other previously proposed dual-purpose additives are described and
claimed in United States Patent 3,923,930. These additives comprise substan-
tially linear hydrocarbon terpolymer backbone having grafted thereon poly-
methacrylate polymers which are prepared by metallation techniques using
alkyl lithium. In the absence of the unsaturated function, provided by the
diene in the substrate polymer, the process of patent 3,923,930 is inoper-
ative with a saturated ethylene-propylene copolymer (see D.P. Tate et al.,
"Metallation of Unsaturated Polymers and Formation of Graft Copolymers",
J. Polymer Science, Part A-l, Vol. 9, 139-145 ~1971); referred to in the
patent).
Additionally, there are several differences between the products
of the patent and those of the present invention. Unsaturation is present
in all products of the patent, but not in all products of this invention.
The patent discloses only alkyl methacrylate and dialkylaminoalkyl meth-
acrylate moieties; the products of this invention have these and other ex-
amples of unsaturated polar compounds. ~,
In comparing the respective products, it should be noted that the
unpurified patented product would never be considered for use because of the
detrimental effects expected from the impurities, lithium compounds and the
tetraalkylalkylene diamine. Advantageously, the present products can be
used without purification.
This invention represents several substantial improvements, and
otherwise differs from United States Patent 3,879,304. The patent requires
utilization of an ethylene-propylene-diene terpolymer (having olefinic
groups) while
, ~ .
- 4 - .

-the present invention is not so restricted and can be
carried out with ethylene-propylene copolymers (i.e., no
third monomer included to incorporate unsaturation). The
patent requires two separate reaction which (for commercial
pruposes) adds processing costs, compared with the present
invention which requires only one reaction. The above
patent utilizes a lithium compound and a N,N,N'N'-tetra-
alkylalkylene diamine. In addition to their relatively high
cost, the use of these materials requires that the xeaction
product must be purified before use to remove the diamine
and by-product lithium compound which would be deleterious
in the applications of the product. No such purification
steps are required here in the present invention.
In Belgian Patent No. 844,761 filed July 30, 1976
and issued January 31, 1977 and German offenlegunsschrift
No. 634,033 filed on July 29, 1976, corresponding to U. S.
Patent No.4,146,489, is disclosed a process for the
preparation of a graft polymer of a co-polymeric hydrocarbon
substrate and a nitrogen containing monomer characterized in
that a liquid mixture of the hydrocarbon polymer, a polar
nitrogen-containing monomer and a free-radical forming
initiator is prepared under temperature conditions that
prevent decomposition of the inltiator followed by raising
of the temperature to decompose the initiator, and graft
copolymers prepared by that process.
Examination of Offenlegunsschrift No. 643,033,
hereinafter "No. 643,033", reveals several differences and
deficiencies of that work compared with the present
invention. Firstly, the graft copolymerization reaction of
No. 634,033 led to increased thickening power of the
product, and with it, a deterioration of the products shear
stability (i.e., ability
'~3
1. . I

to withstand mechanical shearing). Number 634,033 noted that this effect
can be avoided~ but not without degradation of the desired dispersing abil-
ity; it was found preferable to degrade, to a lower molecular weight, either
the polymer substrate or the product graft copolymer. In the case of the
present invention, on the other hand, no increase in thickening power~ or
deterioration of shear stability, was observed. Second, all examples of
No. 634,033 graft copolymer preparation were carried out with a weight ratio
of monomer (or olefinic polar compound) to initiator of about 10:1. Lower
ratios of these reagents were employed in the present invention, and the
olefinic polar organic groups that become attached to the hydrocarbon poly-
mer apparently do not constitute polymeric moieties, and the product is not
considered a graft copolymer, in the sense that an increase in thickening
power, through an increase of the polymer chain length, was not observed.
Further, reducing the ratio of olefinic polar compound to initiator caused ,,
improvement in dispersing ability. Third, the products of No. 634,033 re-
quire a higher nitrogen level for satisfactory dispersancy than those of the
present invention. Material reported in No. 634,033 containing G.08% nitro-
gen was described therein as a failed grafting product, while the products
of the present invention are not so limited (i.e., higher or lower levels of
nitrogen are satisfactory). Finally, No. G34~033 specifies that, in the
preparation of the graft copolymer product, the liquid mixture of hydro-
carbon polymer, olefinic polar organic compound, and initiator is prepared
under temperature conditions which prevent decomposition of the initiator.
The process of the present invention is not so limited, and may be carried
out either above or below the decomposition temperature of the
,
.~

i n i t i a t o r .
SUMMARY OF T~IE INVENT.ION
In accordance with this invention, there is pro- i
vided a multipurpose lubricant additive comprising reaction
products selected from a hydrocarbon polymer substrate of
~, the group consisting of an e-thylene~propylene copolymer, and1
,1 an ethylene-propylene-diene terpolymer and mixtures thereof,¦
il with the terpolymer having an iodine number of about l to
,1 about 30, with the propylene content of the ethylene-propy-
¦f lene copolymer and terpolymer being in the range of 20 to
76.5% by weight; and of a basic polar olefinic compound cha-
il racterized by having an unsaturated portion capable of re-
11 acting with a hydro-carbon polymer, as above defined, when
il catalyzed by a free radical initiator, with the ratio of po-
~lar ole~inic compound to initiator being from l:l to 8
the polar olefinic compound being incorporated in the addi-
tive to the extent of at least l to 40 moles per lO0,000
grams of hydrocarbon po].ymer, the olefinic compound having
the ~ormula
/x
¦1 32C=c~ whereiD X is:
_R2 NR3R4 ~ ~ N ~ or
a polynuclear aromatic amine and Y is 0 or NR5; Rl, R3, R
and R5 being hydrogen or alkyl; R2 being methylene or poly-
methylene having from l to l6 carbon atoms in the chain; the
Il olefinic compound being attached to the substrate in the
I form of single units and in the form of chains of multiple
¦ units; these chains being too short, in the aggregate, to be
considered polymeric in the sense that they do not cause an
¦ increase in the viscosity of a solution of the modified
polymer relative to the viscosity obtained with a solution
of the unmodified polymer substrate.
7-
1l .

The products of this invention are viscosity indeximprovers useful as an additive for internal combustion
engines or for other automotive parts, such as automotive
-transmissions. This invention also relates to produc-ts made
by this process and to lubricating compositions containing
such products.
DETAILED DISCLOSURE OF THE INVENTION
Hydrocarbon polymers found to be useful for the
purposes of this invention include ethylene-propylene co-
polymers and ethylene-propylene-diene terpolymers having a
reduced solution viscosity of about 0.3-4.0 or higher in
decalin at 135C as well as hydrogenated styrene-conjugated
diene copolymers in which examples of the conjugated diene
include l,3-butadiene and isoprene. In the case of the
terpolymers, the latter may have an iodine number of from l-
30 and the diene monomer incorporated therein include, for
example, either 5-alkylidene-2-norbornene or 1,4-alkadiene
present at about 1.8-10 percent by weight of terpolymer.
Propylene content of either the ethylene-propylene copolymer
or the ethylene-propylene-diene terpolymer may be in the
range of 20-76~4 percent by weight.
Representative examples of terpolymers made with
1,4-alkadienes include: ethylene/propylene/1,4-hexadiene;
ethylene/propylene/1,4-dodecadiene; ethylene/propylene/-1,4-
heptadiene; ethylene/propylene/6-mthyl-1,4-decadiene;
-7a
~,

~L~3~90
ethylene/propylene/1,4~tridecadiene; ethylene/propylene/7~7-dimethyl-1,4-
octadiene.
Representative examples of terpolymers made with 5-alkylidene-2-
norbornenes include: ethylene/propylene-5-methylidene-2-norbornene; ethyl-
ene/propylene/5-ethylidene 2-norbornene; ethylene/propylene/5-isobutylidene-
2-norbornene; ethylene/propylene/5-n-heptylidene-2-norbornene, ethylene/
propylene/5-n-decylidene-2-norbornene; ethylene/propylene-5-n-dodecylidene-
2-norbornene, ethylene/propylene/5-n-tridecylidene-2-norbornene; ethylene/
propylene/5-n-tetradecylidene-2-norbornene; and ethylene/propylene/5-hexa-
decylidene-2-norbornene. Mixtures of two or more polymers chosen from among
both ethylene-propylene and ethylene-propylene-diene polymers may be used if
desired. A particularly preferred starting material is a commercially avail-
able ethylene-propylene-5-ethylidene-2-norbornene terpolymer.
Preparation of the above-described terpolymers can be accomplished
as set forth in United States Patent 3,151,173 by contacting ethylene, at
least one alpha-olefin, and at least one S-alkylidene-2-norbornene in solu-
tion in inert solvents with coordination catalysts, at temperatures between
-20C and 70C, at atmospheric, subatmospheric or superatmospheric pressure
and in the absence of catalyst poisons such as oxygen, water and carbon
dioxide.
Examples of polar olefinic compounds suitable for reaction with
the above-described polymers include dimethylamino ethyl acrylate and meth-
acrylate, dimethylaminopropyl acrylamide and methacrylamide, 2- and 4-vinyl-
pyridine, 2-dimethylamino-2-methylpropyl acrylate and methacrylate, 2- and
4-vinylquinoline, 2-aminoethyl acrylate and methacrylate, t-butylaminoethyl
acrylate and methacrylate,

N-vinyl morpholine, 2-ethylpyridinyl acrylate and methacrylate, and N-vinylin-
dole. Reactions may be carried out with mixtures o~ polar olefinic compounds.
Principal requirements of such polar olefinic compounds are the
presence of a basic primary, secondary or tertiary amine function and an un-
saturated portion capable of undergoing an addition reaction with a hydrocar- `
bon when catalyzed by a free radical initiator:
~ I
R-H ~ C - C-~ R-C-C-H (R - alkyl or alkenyl). The polar olefinic com-
pounds of this invention are included in, though not limited by, the following
general formula: X
CH2 = C
wherein: X = -C-Y-R2-NR3R4; ~3 ; ~ ); and
polynuclear aromatic amines
Y = 0 or NR
R', R , R and R = H or alkyl
R2 = methylene or polymethylene (Cl-C.16)
The reaction with polar olefinic compou~ds (as described above) also
may be carried out in the presence of acrylate-type esters of the type:
Rlc
CH2 = C-C02R
wherein Rc is hydrogen or alkyl of from 1 to 3 inclusive carbon atoms as exem-
plified by methyl, ethyl, propyl and isomers thereof, and Rd is alXyl of from
1 to 30 inclusive carbon atoms exemplified by methyl, ethyl, propyl, butyl,
pentyl, hexyl, octyl~ nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl,
eicosyl, docosyl, pentacosyl and

~3~
isomers and mixtures thereof. Inclusion of such acrylate-
type esters in the reaction provides a product capable of
improving the low temperature properties, .e~g., lowering
the pour point, of lubricating oil formulations. .. :
Any of the typical free radical initiators, such
as dicumyl peroxide, dibanzoyl peroxide, di-t-butyl peroxide,
azobisisobutyronitrile, diacetyl peroxide, t-butyl-perace-
tate and diisopropyl peroxidicarbonate may be employed in
this invention.
Solvents for this reaction may include such inert
.solvents as benzene, chlorobenzene and carbon tetrachloride,
as well as hydrocarbon soIvents such as n-heptane, dodecane
and hydrocarbon mixtures including mineral oils having a
viscosity at lOOQF of about 10 to 200 SUS. Polymer concentra-
tions in such solvents may range from about 2% to 60~ or
higher.
Reactions typically are carried out under an inert
atmosphere (e.g., nitrogen) at about 50 to 200~C, prefer-
ably 60 to 160C, for periods of about 1-18 hours; re-
action temperature and time are chosen according to thereactivity of the free radical initiator, lower reaction
tempexatures or shorter reaction times being allowed for
the more reactive initiators. Reactions may be carried out
at a~mospheric pressure or above or below atmospheric.
The polymeric portion of the reaction mixture may
be separated and isolated by any of the usual methods, such
as precipitation with nonsolvents (e.g., acetone and iso-
propyl alcohol) or stripp.ing solvent and other volatiles
from the reaction mixture, and the polymeric product thus
isolated may be used as the detergent-dispersant V~I.
improver (dual-purpose) additive; if convenient for blending
purposes, the isolated polymeric product may be subsequently
--10--

~ ~ 3~1~9~
dissolved in a mineral oil, having a viscosity at 100F of about 10 to 100
SUS, to obtain a solutlon containing from about 2% to 60% polymer. Alternat-
ively, such a polymer-oil solution may be obtained by either (a) using the
oil as the reaction solvent, or (b) using a lower boiling reaction solvent
~such as benzene, chlorobenzene, heptane or decane), adding the oil to the
reaction mixture, and isolating the polymer-oil solution by stripping the
more volatile reaction solvent. Polymer-oil solutions thus prepared can be
used without further purification as the dual-purpose additive.
The nitrogen content of the polymeric portion (after isolation by
precipitation with acetone) of the dual-purpose additive of this invention
generally is at least 0.01% to 0.4%, from which it is seen that the polar
olefinic compound is incorporated to the extent of at least 1-40 mole per
100,000 g of hydrocarbon polymer, or higher. In addition to single units of
olefinic polar compo~mds attached to the hydrocarbon polymer backbone, the
latter also may have attached chains of multiple units; these chains being
too short to be considered polymeric in the sense that, in the aggregate,
they do not cause an increase in the viscosity of a solution of the modified
polymer relative to the viscosity obtained with unmodified hydrocarbon poly-
mer substrate, and thereby do not cause a degraclation of the polymer's shear
stability (i.e., ability to withstand mechanical shearing) which would other-
wise diminish the polymer's effectiveness as a VI improver.
In the finished lubricating oil compositions of the invention, there
may be added also additional additives such as supplementary detergent dis-
persants and V.I. improvers, oxidation inhibitors, corrosion inhibitors, anti-
foamants, etc.
- 11 -
.~

~L3~
Examples of the supplementary de-tergent dispersants contemplated
herein are alkylsuccinimide, the ethylene oxide derivatives of inorganic
phosphorus, acid-free, steam-hydrolyzed polyisobutene ~having a molecular
weight of (700-5000) -P2S5 reaction product; and overbased calcium alkyl aro-
matic sulfonate having a total base number at least abollt 300; and sulfurized
normal calcium alkylphenolate. These supplementary detergent dispersants are
disclosed in United States Patents 3,087,956, 3,549,534 and 3,537,966.
Examples of suitable antioxidants contemplated herein are zinc and
calcium dialkyl dithiophosphate and diaryl dithiophosphates, the alkylated
diphenyl amines, sulfurized alkylated diphenylamines, unsulfurized and sul-
furized alkylphenols, phenolates and hindered phenols.
Examples of suitable corrosion inhibitors are zinc dialkyl dithio-
phosphates, zinc diaryl dithiophqsphates, basic calcium, barium and magnesium
sulfonates; calcium, barium and magnesium phenolates.
A widely used antifoamant can be included in the finished composi-
tions of the invention; namely; the dimethylsilicone polymers, which are em-
ployed in amounts of between about 1 and 1,000 ppm.
The various procedures for making the compositions of the invention
are described in Exa~ples A-Z below.
EXAMPLE A
Into a round bottom flask equipped with mechanical stirrer, ther-
mometer, gas inlet and reflux condenser were placed 25.0 g of ethylene propyl-
ene copolymer having a molecular weight of 20,000 to 50,000 and 100 ml of
chlorobenzene. The polymer was allowed to dissolve and the system was placed
under a nitrogen
,J
,~,,~

~L3~L~
atmosphere. 1.57 g of dimethyl amino ethyl methacrylate (DMAEMA) and the
initiator, dicumyl peroxide ~0.20 g), were added to the reaction flask and
the mixture was heated, with stirring, at 130C for 6 hours. Samples were
removed at various times to follow the progress of the reaction by nitrogen
and infrared analyses of the polymer, which had been isolated by precipita-
tion with hot acetone.
At the end of the six-hour reaction period most of the remaining
reaction solution was added to 600 ml of hot acetone to precipitate the poly-
mer. The latter was taken up in 150 ml of ben~ene and reprecipitated in 600
ml of hot acetone; this process was repeated to give a total of three precip-
itations. After drying at 100C with full pump vacuum, the product (12.1) g
had a nitrogen content of 0.025%. A Bench VC Test (BVCT) on a blend of the
product at 1.5 wt % (net polymer) in oil showed that the product provided
very good dispersancy. The BVCT rating for the blend was 8.5 (references:
4,52,62), compared with 97.0 (references: 4, 18, 40) for a like blend of the
unreacted polymer. (The numerical~ parenthetical references are BVCT ratings
of three standard dispersants; the mlmerical value of ratings decrease with
increase in effectiveness). The Bench VC Test, above-mentioned, measures
turbidity, the lower the turbidity values indicated below, the better dis-
persancy. This test is carried out as follows:
Exact volumes of the test oil, a synthetic blowby, and a mineraloil diluent are mixed together in a test bottle. The bottle is then placed
on a rocker and rocked for four hours at 280F. After heating, the sample is
diluted with more mineral oil, cooled to room temperature, and the sample's
turbidity is measured with a Lumetron turbidimeter equipped with a 700 milli-
micron filter.

3~
Syn~hetic blowby is a hydrocar~on frac:tiorl which has been
oxldiz~d under pecific conditions~ This material s:imulates
the oxidized compounds w~ich find their way p st the piston
rings and in~o the crankç:ase o~ a~ internal combus~ior
e~gine ~
EX~DLE B
13.65 pounds of an ~thvlene/~ropvlene~5-
ethylidene-2-norbornene te~polymer tor EPDM) available
from Copolym~r Rubber and Chemical Corp), having a molecular
weight o~ around 76,00~, were diss~lved ~n 92.0 pounds of
a ~ineral oil having a viscosity of 145 SUS at 100F under
a ni~rogen a~mosphere in a stainless steel reac~io~ ~essel.
To the solution was add~d DMAEMA (0.874 lbs) and dicumyl
pero~ide tO.436 lb), and the mixture was heated at 140C
for 4 houxs ~der nitrogen at S psig in t}le sealed reactor.
105 pounds of a solvent neutral oil having ~ viscosity of
123-133 at 100F was added and t~e reaction mixture was
stElpped under vacuum; a portion of the pxoduc~ was flltered
through a 5-~cron car~ridge filter (63. 2 lb. recovered)
20 and the re~t was filtered through filter aid (125 . 8 lb.
ree::over~d ) .
The lat~er portion of the product was evalua~ed
in th~ Bench ~C Test as the only ashle~s dispersant-det rgenl:
com~?onent at 12.0 w~. % in a fully fo~mulate~ lubricant
oil and recaived a rating of 6~0 (re~er~nc~s: 2, 32,.76~.
The same pro~uct was also e~luated in a VC engine test
at 18.0 wt. % in a fully formul~tPd lubricant oil which
also contained a minor amount of a s~pplemental ashless
detergent-dispersant ~alXenyl ~uccinimid~) at 3.5 wt. %;
resul~ing V~ engine ~est ra~ings were as follows: average
sludge, 9.5; average ~arnish, a . 40; piston skirt varnish~
8.46. Corresponding minima ~o meet SE quali~y standards
in this te~t are 8.5, 8.0 and 7.9 respectively. The product
thus exceeded the sE standards.
-14-

EX~MPLE C-I
The procedure of these runs (summarized in Table I) was generally
the same as that used in the previous Example A except that ~a) reactant
ratios were varied, and ~b) instead of isolating the polymer, oil was added
to the reaction mix~ure at the end of the reaction time, and solvent and any
unreacted DMAEMA were stripped from the mixture with vacuum to yield a poly-
mer-in-oil concen~rate (containing 10.0-17.5 wt % polymer). The latter con-
centrate was filtered to improve clarity and then used to make blends in oil
to contain 1.5 wt % neat polymer. The BVCT and thickening power data were
obtained from these blends. The polymer was precipitated from small samples
of the concentrates (using hot acetone to precipitate) for determination of
polymer nitrogen content.
Examples A and C-H show reaction carried out in benzene of chloro-
benzene solvents. In Examples J-~ an oil was used as the solvent. These ex-
amples have an advantage over processes involving other solvents ~including
processes of existing patents) in that the polymer-oil product mixture can be
used as a lubricant without the added step of solvent exchange ~e.g., re-
placement of benzene with oil).
EXAMPLE J
~0 Into a roun~ bottom flask equipped with mechanical stirrer, ther-
mometer, gas inlet tube and reflux condenser were placed 60 g of mineral oil
~123-133 SUS at 100F) and 50 g of E-P copolymer having a reduced solution
viscosity of about 0.6 in decalin at 135 C. The polymer was allowed to dis-
solve and the system was placed under a nitrogen atmosphere. DMAEMA (2.0 g)
rinsed in with 2.0 g of mineral oil (100 SUS at 100F) and the initiator,
dicumyl peroxide
- 15 -

~L~L 3 ~a~
(l.0 g), were added to the reaction flask and the mixture was heated, with
stirring, at 130C for 1~ hours. The reaction solution was diluted with the
same mineral oil (138 g), and volatiles were stripped from the diluted solu-
tion at lO0 C using a rotary evaporator and a vacuum pump. The solution was
filtered to improve clarity. Nitrogen contents of the product solution, and
of polymer isolated by precipitation, were analyzed to be 0.12 and 0.057%,
respectively. The product solution blended at 12.5 wt % (2.5 wt % neat poly-
mer basis) in mineral oil (123-133 SUS at 100F) had a thickening power of
23.0 SUS. The BVCT rating for the blend was 9.0 (references 2, 23, 69).
EXAMPLE K
The procedure of Example J was repeated except that lauroyl peroxide
was substituted for dicumyl peroxide and the reaction was run at 75C instead
of 130C.
EXAMPLE L
The procedure of Example J was repeated except that 4-vinylpyridine
was substituted for DMAE~A.
EXAMPLE M
.
The procedure of Example J was repeated except that the mineral oil
used as reaction solvent had a viscosity SUS of 145 at 100F.
EXAMPLE N
The procedure was the same as Example J except dimethylaminopropyl
methacrylamide was substituted for DMAEMA.
EXAMPLE 0
The procedure was the same as Example J except that the reaction
solvent was a mineral oil having a viscosity SUS of 100 at 100 F.
- 16 -
~.

~3~
EXAMPLE P
Same as ExamPle J except 2-(dimethylamino).2-
methylpropyl methacrylate was substituted for D~AEMA.
EXAMPLE Q
The procedure used was the same as Example J
except that the E-P copolymer ~25.0 g) had a reduced solu-
tion viscosity of about 1.15 in decalin at 135C, and the
mineral oil solvent was incr~ased to 85.0 g.
EX~PLE R
Same as Example J except th~t 46.8 g of an.
ethylene/propylene/5-ethylidene-2-norbornene terpolymer
(a) having a molecular weight of around 76,000 and a reduced
solution viscosity of about 2.15 in decalin at 135C;
iodine number of 6 was used, (b) the amounts of mineral oil
solvent, dicumyl peroxide and DMAEMA were increased to
313.2, 3.0 and 6.0 g, respectively, (c~ the reaction was
r~l at 140C for 4 hours, (d) dilution was with 358 g
mineral oil (100 SUS at 100~).
Test data for compositions C to $ are given in
Table I and for compositions K to S in Table II.
These data show im~roved dispersancy as a result
of the presence of the products of the invention.
EXAMPLE S
The pxocedure of Example J was repeated except
for the following modifications: 360 g of a commercially
available ethylene-propylene 1,4-hexadiene terpolymer
dissolved in 1260 g of a mineral oil having a viscosity
of 145 SUS at 100F was reacted in a round bottom flask
under a nitrogen atmosphere at about 140C for 4 hours
wi~h 16.0 g of DMAEMA rinsed in with 20 g of mineral oil,
100 SUS at 100F, and 8.0 g of dicumyl peroxide. The re-
action solution was diluted with 1600 g of mineral oil

~3~
(100 SUS at 100F), s-tripped at about 140C in the reaction vessel with full
pump vacuum, and filtered.
EXAMPLE T
Into a round bottom flask equipped with mechanical stirrer, ther-
mometer, gas inlet tube and reflux condenser were placed 290 g of a commercial
VI improver, consisting of about 13~ by weight of an E-P copolymer having a
reduced solution viscosity of about 1~15 (in decalin at 135C) dissolved in a
mineral oil solvent ~about 100 SUS at 100F), 6.0 g of DMAEMA, the latter
rinsed in with 2.0 g of mineral oil solvent ~about 100 SUS at 100F), and 3.0
g of dicumyl peroxide. The stirred solution was placed under a nitrogen
atmosphere and heated to about 140C. After maintaining this temperature for
4 hours, the solution was stripped at about 100C at full pump vacuum using
a rotary evaporator and the solution was filtered.
EXAMPLE U
The procedure of Example T was repeated except that the amounts of
DMAEMA and dicumyl peroxide used were 4.8 and 2.4 g, respectively.
EXAMPLE V
The procedure of Example T was repeated except that the amounts of
DMAEMA and dicumyl peroxide used were 4.2 and 1.4 g, respectively.
EXAMPLE W
The procedure of Example T was used except that the amount of DMAEMA
and dicumyl peroxide used were 4.2 g and 0.6 g, respectively.
EXAMPLE X
The procedure of Example T was used except that the amounts of
DMAEMA and dicumyl peroxide used were 3.2
- 18 -
.~.,.~

~L~3~
and 1.2 g, respectively, and the reaction was run at about 130C for 18
hours.
EXAMPLE Y
The procedure of Example R was used except that (a) the mineral oil
reaction solvent had a viscosity of 145 SUS at 100F, (b) 3.0 g of DMAEMA and
1.5 g of dicumyl peroxide (the latter dissolved in 4.5 g of mineral oil, 100
SUS at 100F) were added to the polymer solution at the reaction temperature
of about 140C and rinsed with 2.0 and 2.5 g respectively, of mineral oil
(100 SUS at 100F), and (c) after heating at about 140C for 4 hours from the
time of dicumyl peroxide addition, the reaction solution was diluted with
351 g of mineral oil (100 SUS at 100 F). After stripping and filtering, the
product was tested in the BVCT at 12.0 and 6.0 wt % as the only ashless deter-
gent-dispersant in a formulated motor oil test blend having a mineral oil
(123-133 SUS at 100F) as the predominant component and minor amounts of an
overbased calcium sulfonate detergent (1.53 wt %) a ~inc dialkyldithiophos-
phate antioxidant (1.35 wt %), an alkyl diaryl amine antioxidant (0.25 wt %),
a poly-(alkyl methacrylate) pour point depressant, (0.05 wt %), and a dialkyl
silicone polymer anti-foamant (150 ppm). The BVCT ratings with 12.0 and
6.0 wt % product were 5.0 and 10.5, respectively, references for both tests
were: 2.5, 17, 67. :
EXAMPLE Y-1
The procedure of Example Y was used except that 4.68 g of DMAEMA
and 0.26 g of dicumyl peroxide (dissolved in 1.0 g of mineral oil, 100 SUS at
100F) were added to the polymer solution at about 90 C, and rinsed with 3 g
and 1 g, respectively, of mineral oil (100 SUS at 100F). After stirring at
about 90C for 30 minutes, the temperature
- 19 -
.~

~3~
o~ the reaction solution was increased to 150C over a 43
minute period. After 40 minutes at 1~0C, an additional
solution of 0.26 g of dicumyl peroxide in 1.0 g of the
same mineral oil was added and rinsed with l.0 g more of
the mineral oil. After heating at 150C for l hour from
the time fo the second addition of dicumyl peroxide solution,
the reaction solution was diluted with 353 g of the same
mineral oil ~lO0 ~US at 100F). After stripping and
filtering, the product was tested in the BVCT at 12.0 and
6.0 wt. % as the only ashless detergent-dispersznt in the
same test blend used in Example Y. The BVCT ratings with
12.0 nd 6.0 wt. ~ product were 13.0 and 32.0, respectively;
references for both tests were: 2.5, 17, 67.
''r~ EXAMPLE Z
The procedure of Example Y wals used except that
84.0 g of a commercially available hydrogenated styrene-
butadiene copolymer (molecular weight of about 57,400;
styrene & butadiene mole ratio of aboul 48:52; iodine
number of 6.7) was used in place of the ethylene/propylene/
~ S-ethylidene-2-norbornene terpolymer. The amounts of other
materials were changed to the following: mineral oil
solvent (145 SUS at lOO~F), 266 g; DMAEMA, 4.0 g; mineral
oil to rinse latter~ 2.0 g; dicumyl peroxide, 2.0 g; mineral
oil to make solution of latter, 6.0 g; mineral oil to rinse
the peroxide solution, 4.0 g; mineral oil diluent (100 SUS
at 100F), 338 g. After stripping and filtering, the product
is tested in the BVCT at 20.0 wt. ~ as the only ashless
detergent dispersant in the same test blend used in Example
Y. The BVCT rating was 19.5j the references were Z, 16,
and 59.5.
The test data for Examples T-X are tabulated in
Table III, below.
-20-

Among the advantageous features of this invention
are the s.implicity and economy of the process and the
fact that the reaction product are suitable for use without
any purification treatment. Tllere is no need even for ,~.
stripping or filtration.
-21-

L3~
~ ~ .~
u~ 5 h
~ E~ ~ ~0
~_ h a> ~ rO
U~ 41
'-- ~d ~d ~ ~ ~ ~ ~ r1 0 0 ~ u~ ~H ~ 0 ~1
h ~ ~ oo ,; o ,; ~ ,; ~ . ,~ o o\O
0 ~0 r1 r~ 5 a) ~ c\
'r~ O ~1 ~ C) r~ 0 3
~) o
h ,s: r~ r~
~ ~ O
3 `~ u~ . ~ r~ O
~ ~ O ~ O h ~ ha)h d ,~ `
u~ h t~ r-~
~ ~ ~r~ 0 ~rl v~
O E~ t~ ) ~ 0~ C
O ~ C~ ~ ~ ~ d ~ ~ r` ~ ~ h ~ ~
.~ o o o o Ir) o o o , ~1 ~ O h ~ ~ h
I LI ~ r U~ O1~ o o1~ ~ ~ o
~I r lr ~ r~ r~ r 1 ~ H r~
~, m ~ h O ~ ~~ O r1 h ~
Ul tO~ ~ S~ ~rl ~ a~ o o
Z: O\o ~ h
O ; ~ rl .rl r
a~ ~ o o o o o ~rl O
h a~~ ~ ~~I ~r~ h ~ ~ h O
CC E3 R o o o O O O o I C h o O
H :4 ~ o . . . . . . . I ~~ ~ R ~ o ::s ~: h ~::
rl ~ O O O O O O O ~rl rl rl rl ~rl O
Z ~ ~ R ~~ O ,~
oo ~ R
~ri ~ ~ ;Ll O h~. )
U.l ~ ^ r10 0 0 0 ~ O ~ ~ O~: ¢ ,9 p~
o ~ ~ v ~ '~ I h ~ h ~ ~ R a o
a~,~ o ~u7,~ o ~>,~
0 ~d o\O ~ q ~ ~ ~ ,c 3 O
æ I h r~ cd ~rl 4~ ~:a~ ~ t"l
--, 3 h 3 h 3 4~ Rs: ~ ~ a~ ~S I
o o o o o o o O Q~ rl ~ R
Oo ~D~D ~ ~ o ~ ~ R R~ ~,1 c)~ ~d
¢ ~ X o o o o o ,; O , Ro ~ ,; ,,u~ u~
O h ~rl a~ ~ rJ ~ ~ O ~d ~> r I
~,~ ~ R a~ ~ ~ h h ~
E~ ,~ ~ ~ ,~u~ ~ G h ~ rl ~rl h ,RI3 ~ d ~ r I
r l o ~ rl ~ h h C~R
:~ ~~ O t~ r~S7 ~ ~ O R ~ ~ ~ a~
c~ ¢ ~i R o ~
~; ~ ~ I O Ei ~ ~ .~~ :: R
,~ o u~ R ~ ~ a~ 3 ~,1 o o~ ~> ~
R ~ ~ p, ~,,~.c~ ~ ~, R
,~ ,~ ~ u, ~ a~ o o ~ ~ 3: o
0 h a~ 30 ~ h ~ D h r~
E~ O O O h 1~ R ~ ~d h ,QI I
r--l r1 r 1 ~1 r~ rl O ~ 1 ~ r~ rl
r1 r1 r-~~1 rt r~ ~ R 4~ R ~
o 1l ~> o o a~ R O
R ~ O ~, ~a ~
o ~ ~ ~ h ~ ~ u) ~ ~
,~ ,~ E~ ~ h E~ ~ N Rl c~ h
~)r_ ~_ r~ O
~D 1~ ~ r~ ~ ~ ~ ~ ~ ~ o
- 22 -

e~
X
0 Z ~ 3
~o
~ .
l_ :
:D
o
~ a~ Y ~ S: 3
O ~ O o ~ o c:~ ~
t
~r
tn d~
o ~ o o ~ o ~ o o ~ o
~, . , . . . . ... . ~ CL~ ..
o ~ o o o ~-- ~ ~ o ~ :
o ~ CO ~- ~ ~
o . ~ . .
,t ~:
o c~ o o o o o o o 0~ 3 ,~
. . . . . . . , .
O ~ O 1~ ~ ~5 W
5A W.P Ul ~ ~ J ~I Ul N
O ," N tt' t~l
O :'
H~ C;J o
1~ ~ a ~ 3
W~1 U- ~n Ul UlUl ~ ~n ~ ~D
~ ~ ~
O ~
~ ~ ~ P~
O o ~.n o ul o o C
O ~-
~D
y ~ N ~ ~ ~ ~ ~ ~D
O ~ ~ tD ~
c~ 7 ~n cn ~ a'~ O g
p~ Ul ~ U~ ~ ~ ~
Ul O lD
U~ o ~ " 01
O G~ Ul
~- . ~3
~ ~,
.' ~
~ ~ I_ ~ I_ I_ O ~'
O C) ~ N I O 5
, . . . . . ~q~
w ~ ~ c~ w
U~ ~
U~ ~

~3~
,_ X
~, ~
C C ~ ~
, tD ~'
,-- ~o
U2 ~
~3
X
.
o o
.
o
. . (~ Q
1-- 1--
1-- W `I 1~ 1-- Ul
:b oP
O
~o ~ 00 ~
t~ . O O O O O ~ 1-- H
a o o o o o
r~ ~ o
P~ .,
C~P
o

~--
c~ ~ W ~ ~I ~I r~
O . . . .
o ~ ~ o o ~
U~ ~3
~ Ul
nl ~ .
t,q ~ ~ I-- ~ ~ ~
u~ n ~ _
(D o ~ " ~D I_
1-- ` ~ ~ ~.
CD ~ ~ ~
co ~D
~ ut U~
--24 -