Hydrocarbon compositions containing polyolefin graft polymers

Fuel oils and lubricants of improved properties contain ethylene-propylene copolymers bearing units derived from N-vinyl pyrrolidone and phenothiazine.

DESCRIPTION OF PREFERRED EMBODIMENTS 
EXAMPLE I 
In this example which describes the best mode presently known, the charge 
EPM polymer is the polymer of molecular weight M.sub.n of 140,000 of 
M.sub.w /M.sub.n ratio of 1.6, and containing 60 mole % of units derived 
from ethylene and 40 mole % of units derived from propylene. 100 parts of 
this polymer are dissolved in 300 parts of commercial hexane and added to 
a reaction vessel. 
In the first step, the mixture is heated to 155.degree. C. with agitation 
under nitrogen atmosphere at 200 psig. N-vinyl pyrrolidone (5 parts 
dissolved in 15 parts of hexane) is added followed by 5 parts of 25 w % 
dicumyl peroxide in hexane. The reaction mixture is stirred for one hour. 
In the second step, phenothiazine (4 parts) dissolved in 16 parts of 
tetrahydrofuran is added followed by a solution of 2 part of dicumyl 
peroxide initiator in 6 parts of commercial hexane. The mixture is stirred 
at 155.degree. C. and 200 psig for 1 hour. Solvent Neutral Oil (SUS 100) 
(1076 parts) is then added; and the hexane is distilled off at 
90-.degree.120.degree. C. The resulting solution contains about 8.5 w % 
polymer. 
The product polymer contains (per 1000 carbon atoms of polymer backbone) 
about 6 units derived from N-vinyl pyrollidone and 3 units derived from 
phenothiazine. 
The process of Example I may be carried out using the charge polymers of 
Examples II-IV: 
EXAMPLE II 
The Epsyn 4006 brand of EPT marketed by Copolymer containing 58 mole % of 
units derived from ethylene, 40 mole % of units derived from propylene, 
and 2 mole % of units derived from ethylidene norbornene and having a 
M.sub.n of 120,000 and a M.sub.w /M.sub.n of 2.2. 
EXAMPLE III 
The Ortholeum 2052 brand of EPT marketed by DuPont containing 62 mole % of 
units derived from ethylene, 36 mole % of units derived from propylene, 
and 2 mole % of units derived from 1,4-hexadiene and having a M.sub.n of 
35,000 and a M.sub.w /M.sub.n of 2. 
EXAMPLE IV 
The Royalene brand of EPT marketed by Uniroyal containing 60 mole % of 
units derived from ethylene, 37 mole % of units derived from propylene and 
3 mole % of units derived from dicyclopentadiene and having a M.sub.n of 
100,000 and a M.sub.w /M.sub.n of 2.5. 
EXAMPLE V* 
In this control Example, the N-vinylpyrrolidone grafted EPM (as a 25 w % 
solution in hexane) is prepared as in Example I. Solvent hexane is 
exchanged for SNO-100 oil (1076 parts) to give a solution containing 8.5 w 
% polymer. 
There are then added 4 parts of phenothiazine dissolved in 16 parts of 
tetrahydrofuran; and the mixture maintained at 70.degree. C.-80.degree. C. 
under nitrogen for one hour. 
This mixture contains the same quantity of N-vinyl pyrrolidone and of 
phenothiazine as does the product of Example I. In this Example V*, the 
phenothiazine is merely admixed. 
EXAMPLE VI* 
In this control example, the procedure of Example V* is followed except 
that the phenothiazine in tetrahydrofuran is not added. 
EXAMPLE VII 
In this experimental Example, the procedure of Example I is followed except 
that the first graft monomer is (instead of N-vinylpyrrolidone) a monomer 
(8 parts) prepared by heating, for one hour at 100.degree. C.-120.degree. 
C., a mixture of equimolar amounts of allyl glycidyl ether and morpholine. 
The polymer product contains (per 1000 carbon atoms in the polymer 
backbone) 5 units derived from the reaction product of allyl glycidyl 
ether and morpholine and 3 units derived from phenothiazine. It is 
recovered as a 8.5 wt. % solution in SNO-100 oil. 
EXAMPLE VIII* 
In this control Example, the procedure of Example V* is followed except 
that the first graft monomer is the reaction product of allyl glycidyl 
ether and morpholine--prepared as in Example VII. 
EXAMPLE IX 
In this control Example, the procedure of Example VI* is followed except 
that the first graft monomer is the reaction product of allyl glycidyl 
ether and morpholine--prepared as in Example VIII . 
EXAMPLE X 
In this experimental example, the procedure of Example I is followed except 
that the first functional monomer is (instead of N-vinyl pyrrolidone) a 
monomer (6 parts) prepared by heating for one hour at 100.degree. 
C.-120.degree. C., a mixture of equimolar amounts of allyl glycidyl ether 
and N-methylpiperazine. The polymer product contains (per 1000 carbons of 
polymeric chain) 4 units derived from the reaction product of allyl 
glycidyl ether and N-methyl piperazine and 3 units derived from 
phenothiazine. It is recovered as a 8.5 wt. % polymer solution is SNO-100 
oil. 
EXAMPLE XI 
In this experimental example, the procedure of Example I is followed except 
that the first functional monomer is (instead of N-vinyl pyrrolidone) a 
monomer (8 parts) prepared by heating for one hour at 90-100.degree. C., a 
mixture of equimolar amounts of croton aldehyde and 
N-(3-aminopropyl)morpholine. The polymer product contains (per 1000 
carbons of polymeric chain) 4.5 units derived from the reaction product of 
croton aldehyde and N-(3-aminopropyl) morpholine, and 3 units derived from 
phenothiazine. It is recovered as a 8.5 wt. % solution in SNO-100 oil. 
EXAMPLE XII 
In this experimental example, the charge EPM polymer has a molecular weight 
M.sub.n of 140,000, M.sub.w /M.sub.n ratio of 1.6, and contains 60 mole % 
of units derived from ethylene and 40 mole % of units derived from 
propylene. 100 parts of this polymer are dissolved in 300 parts of 
commercial hexane and added to a reaction vessel. 
The mixture is heated to 155.degree. C. with agitation under nitrogen at 
200 psig. There are added (i) 5 parts of N-vinylpyrrolidone, dissolved in 
15 parts of hexane, (ii) 2 parts of phenothiazine, dissolved in 8 parts of 
tetrahydrofuran, and (iii) 6.0 parts of dicumyl peroxide dissolved in 18 
parts of hexane. 
The mixture is stirred at 155.degree. C. and 200 psig for one hour under 
nitrogen. Solvent Neutral Oil (SUS 100) is then added (1076 parts); and 
the hexane is distilled off at 90.degree. C.-120.degree. C. The resulting 
solution contains about 8.5 w % polymer. 
The product polymer contains (per 1000 carbon atoms in the polymer 
backbone) about 6 units derived from N-vinyl pyrrolidone and 1.5 units 
derived from phenothiazine. 
Each of the products of Examples I and V*-XII is formulated with a fully 
formulated base blend to yield a composition containing 0.85 wt. % 
polymer; and these compositions are subjected to the Bench VC Test (BVCT). 
The fully formulated base blend contains the following components: 
TABLE 
______________________________________ 
Components W % 
______________________________________ 
SNO-130 Oil 75.25 
SNO-320 Oil 21.64 
Zinc dithiophosphate (anti-wear) 
1.12 
Naugalube 438 Brand of 0.39 
4,4'-di-nonyl-di-phenyl amine 
(anti-oxidant) 
Surchem 521 Brand of Mg Sulfonate 
1.50 
(detergent) 
Silicone polymer (anti-foamant) 
150 ppm 
______________________________________ 
TABLE 
______________________________________ 
Property Value 
______________________________________ 
Viscosity Kin 40.degree. C. CS 
31.50 
100.degree. C. CS 5.36 
Pour Point .degree.F. 
+5 
Ash sulfated % (ASTM D-874) 
0.93 
Phosphorus % (X-ray) 0.11 
Sulfur % (X-ray) total 
0.40 
Zinc % (X-ray) 0.12 
Magnesium % 0.33 
Cold Cranking Simulator 
1660 
(cP @ -18.degree. C.) 
______________________________________ 
The products of Examples I and V*-XII are subjected to the Bench Oxidation 
Test to determine whether the additive is a satisfactory anti-oxidant. In 
this test, products of Examples I and V*-XII are formulated with SNO-130 
Oil to yield a solution containing 1.5 wt. % polymer. The solution is 
heated with stirring and air agitation. Samples are withdrawn periodically 
and analyzed by Differential Infrared Absorption (DIR) to observe changes 
in the intensity of the carbonyl vibration based on 1710 cm.sup.-1. They 
are also tested in the Clarity Test and the Lumetron Turbidity Test. 
The Oxidation Index is reported as the Carbonyl Group Absorbance in the 
Differential Infrared Spectra after 144 hours of oxidation. The Oxidation 
Index may range from 0 up to 100 and a low rating is desired. A rating 
below 4 is considered excellent. 
The Clarity of the samples is also reported visually and by the Lumetron 
Turbidity Test after 144 hours. In the Lumetron Turbidity Test, product 
turbidity is determined by a Lumetron Photoelectric Colorimeter. 
The Lumetron Turbidity is reported on a scale of 0-100. A rating of below 
about 20 is satisfactory; higher ratings are less satisfactory. 
TABLE 
______________________________________ 
Clarity at 144 hours 
Standards 
Oxidation Lumetron Excellent 
Example 
Index Visual Turbidity 
BVCT Good/Fair 
______________________________________ 
I 1.8 Clear 16 32.1 9.1/31.0/61.0 
V* 2.5 Turbid 100 -- 
VI* 9.5 Turbid 100 36.0 10.1/27.7/51.9 
VII 2.5 Clear 20 34.8 9.1/31.0/61.0 
VIII* 3.0 Turbid 100 -- 
IX* 13.0 Turbid 100 38.5 15.8/31.8/64.6 
X 1.8 Clear 16 23.1 11.1/25.2/65.3 
XI 1.7 Clear 14 37.1 13.7/25.8/68.2 
XII 2.2 Clear 18 36.0 10.2/28.3/52.1 
______________________________________ 
From the above Table, it is apparent that the experimental Examples I, VII, 
and X-XII are characterized by a desirably low Oxidation Index (i.e, 
freedom from oxidation), by a visually clear reading, and by a desirably 
low Lumetron Turbidity rating. Control Examples VI*, and IX* which fall 
outside the scope of this invention are characterized by undesirably 
higher oxidation indices, by a visually turbid reading, and by undesirably 
high Lumetron Turbidity rating. Control Examples V* and VIII* are 
unsatisfactory by the latter two criteria. 
Experimental Examples I, VII, and X-XII are also characterized by 
satisfactory BVCT ratings. 
It is clear from these tests that the products of the instant invention 
which contain polymers bearing first dispersant graft monomers and second 
anti-oxidant monomers possess the ability to form lubricating oils 
characterized by desirable properties including high dispersancy, 
anti-oxidant activity, and desirable viscosity index. 
EXAMPLE XIII* 
In this control Example, a base diesel fuel having the following properties 
is tested in the Potential Deposit Test and found to have an 
unsatisfactory rating of 4+. 
TABLE 
______________________________________ 
Property Value 
______________________________________ 
Lumetron Turbidity 8 
Sp. Gr. 60/60F 0.8606 
Color ASTM 3.0 
Kin. Vis. (cSt @ 100.degree. C.) 
805.5 
Flash Point (COC) 415 
Ash % 0.02 
______________________________________ 
EXAMPLE XIV 
In this experimental Example, there is added to the base fuel of Example 
XIII*, 8.5 w % of the polymer of Example I to yield a mix containing 25 
PTB (corresponding to 0.01 wt. % or alternatively to a nitrogen content of 
0.054 w %). 
The modified diesel fuel is found to have a PDT rating of 1 which is 
satisfactory. 
EXAMPLE XV* 
In this control Example, a commercial olefin copolymer dispersant VI 
improver is blended into formulated oil not containing a VI improver. The 
blend is subjected to the single cylinder MWM-B Diesel Engine Test. In 
this test, results are presented in merits which correlate with amount of 
deposits. Higher merits correspond to lower deposits. 
EXAMPLES XVI-XVII 
In these experimental Examples, the procedure of Example XV* is followed 
except that the product of Example I is added in Example XVI and the 
product of Example X is added in Example XVII (instead of the commercial 
olefin copolymer dispersant VI improver) to a formulated oil not 
containing a VI improver. 
TABLE 
______________________________________ 
Polymer Product MWM-B 
Example Example Merits 
______________________________________ 
XV* Commercial DOCP VII 
53 
XVI I 64 
XVII X 63 
______________________________________ 
From the above table, it is apparent that the experimental Examples XVI and 
XVII are characterized by a better deposit protection (higher merits) than 
the commercial dispersant olefin copolymer VI improver of Example XV*. 
Although this invention has been illustrated by reference to specific 
embodiments, it will be apparent to those skilled in the art that various 
changes and modifications may be made which clearly fall within the scope 
of this invention.