Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Organic -co- compound
Reexamination Certificate
2001-05-01
2002-11-05
McAvoy, Ellen M. (Department: 1764)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Organic -co- compound
C508S468000, C508S591000
Reexamination Certificate
active
06475963
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to additives for improving the flow properties of certain oleaginous composition, particularly lubricating oil compositions in which are used lubricating oil basestocks characterized as “Group II” and “Group III” according to the American Petroleum Institute. More particularly, the present invention relates to additives for improving at least the low temperature flow properties of lubricating oil compositions, and more particularly lubricating oil compositions that include lubricating oil flow improvers in combination with high ethylene content ethylene alpha-olefin copolymer (EAO) viscosity index improvers. Still more particularly, the present invention relates to improved lubricating oil compositions including such additives for improving the flow properties thereof. The present invention relates also to methods for improving the flow properties of oleaginous compositions, particularly engine crankcase lubricating compositions.
A wide variety of compounds for use as lubricating oil or fuel oil additives are known. These include compounds variously referred to as pour point depressants (PPD), viscosity index improver (VII) or viscosity modifier (VM) compositions, wax crystal modifiers, and the like. In particular, Cashman et al, U.S. Pat. No. 2,825,717, discloses the preparation of certain lubricating oil additives by the copolymerization of polycarboxylic acid esters with other polymerizable monomeric materials, including vinyl compounds such as vinyl acetate. The preferred unsaturated polycarboxylic acid esters therein are fumaric acid esters produced from C
1
through C
18
aliphatic alcohols.
Bartlett, U.S. Pat. No. 2,618,602, discloses pour point depressing and/or viscosity index improving materials obtained by polymerizing certain specified alkyl fumarate esters. In particular this patentee discloses the use of polymerized fumarate esters of C
12
to C
14
alcohols for such purposes. This patent specifically discloses that the C
12
alcohol was more effective than the C
14
alcohol, although both polymerized esters exhibited pour point depressing properties.
Rossi et al, U.S. Pat. No. 4,088,589, discloses the use of specified mixtures of lubricating oil pour point depressants which include polyesters consisting of a polymeric ester of acrylic acid or methacrylic acid and a monohydric alcohol containing from 10 to 18 carbon atoms, and/or interpolymers of a vinyl alcohol ester of a C
2
to C
18
alkanoic acid (e.g., vinyl acetate) and a di- (C
6
-C
18
alkyl) fumarate as one of the components thereof for improving the viscosity index of high wax content lubricating oils which also include viscosity index improving ethylene copolymers. Also, Wyman, U.S. Pat. No. 3,250,715, discloses terpolymers of dialkyl fumarates, vinyl esters, and alkyl vinyl ethers for improving the pour point of lubricating oils, and most particularly in which the dialkyl fumarates are prepared from various C
10
through C
18
alcohols including tetradecyl alcohol alone as well as alcohol mixtures averaging from 12 to 14 carbon atoms.
There has also been disclosed in U.S. Pat. Nos. 4,713,088 and 4,863,486 (R. D. Tack et al.) the use of specific dialkyl fumarate vinyl acetate polymers and copolymers in various middle distillate fuel compositions for lowering the pour point and controlling the size of wax crystals in these fuel composition products. Most specifically, these patent applications disclose the use of such compounds in which the average number of carbon atoms in the alkyl groups in the polymer or copolymer must be from 12 to 14. In addition these additives are also disclosed as being useful in combination with the polyoxyalkylene esters, ethers, esters/ethers and mixtures thereof, as well as with various other additives. Furthermore, British Pat. No. 2,023,645 discloses, for use in treating distillate fuel oils, various three-component systems which include as a first component flow improvers having an ethylene backbone, such as various ethylene polymers including ethylene polymerized with various mono- or diesters (e.g., vinyl acetate; and C
13
fumarates), as a second component a lube oil pour depressant such as various oil soluble esters and/or higher olefin polymers (e.g., dialkyl fumarate, vinyl acetate copolymers), and as a third component various polar oil-soluble compounds (e.g., phenates, sulfonates, phosphates, and carboxylates).
It is also disclosed in U.S. Pat. Nos. 4,661,121 and 4,661,122 (K. Lewtas) that the size of wax crystals forming in fuels boiling in the range of 120° C. to 500° C. can be controlled by an additive which includes the polymers and copolymers of mono- and di-n-alkyl esters of mono-ethylenically unsaturated C
4
to C
8
mono- or dicarboxylic acids, in which the average number of carbon atoms in the n-alkyl groups is from 14 to 18. These patents show a preference for copolymers of di-n-alkyl fumarates and vinyl acetate, and specifically state that the fumarates can be made from single alcohols or mixtures of alcohols, and when mixtures are used they are mixed prior to esterification. Furthermore, these patents disclose the use of various ethylene unsaturated ester copolymer flow improvers as co-additives therewith, but do not specify that these additives are produced from alcohol mixtures. Finally, in U.S. Pat. No. 4,956,492, which is a divisional of U.S. Pat. No. 4,670,130 (A. R. Dekraker et al.), there is disclosed as a dewaxing aid a copolymer of dialkyl fumarate and vinyl acetate in which a large proportion of the alkyl groups are C
20
to C
24
alkyl groups.
U.S. Pat. No. 5,330,545 (K. Lewtas et al.) discloses narrow boiling or sharply fractionated middle distillate fuel compositions with improved low temperature properties by the addition of a copolymer such as dialkyl fumarate-vinyl acetate. The copolymers are directed to those having specifically limited branching characteristics and limited amounts of ester monomers having greater than 20 carbon atoms and fewer than 12 carbon atoms. Furthermore, use of copolymer mixtures as taught in the prior art (GB 1,469,016) is specifically discouraged (column 2, lines 41-43) for the middle distillate fuels of interest.
GB 1,469,016 discloses a combination of pour point depressants for use in middle distillate, high end point fuels. The additives are based on an ethylene copolymer such as ethylene vinyl acetate and a polymer that is a polymer of an olefin or unsaturated dicarboxylic acid ester, such as dialkyl fumarate-vinyl acetate. Neither ethylene alphaolefin viscosity index improvers nor mixed dialkyl fumarate-vinyl acetate copolymers having controlled structures are suggested.
GB 1,080,910 discloses light oil additives of fumarate-vinyl acetate copolymer pour point depressants in combination with fumarate vinyl acetate copolymer viscosity index improvers; ethylene alphaolefin copolymer viscosity index improvers are not disclosed. Dual pour point depressants in combination with a viscosity index improver are not disclosed. The average side-chain carbon number for the reference pour point depressant is 8.8 to 10.6 and for the viscosity index improver, 7.6 to 8.6. The products for which the reference combination of additives is intended do not include high viscosity index lubricating oil basestocks having high saturates and low sulfur content.
Four Romanian patents disclose work with various additive combinations for use in diesel fuel, and “medium” and crude oils. RO 67487 discloses an additive of vinyl acetate-fumarate esters in a toluene-diesel oil mixture for use with paraffinic crude oils and heavy petroleum products. The fumarate esters used to prepare the vinyl acetate copolymers consist of a mixture of C
18
, C
20
, C
22
and C
34
esters. Consequently, all of the copolymers are distinguished from the present invention. RO 111108 discloses low temperature additives for use in medium oils based on a C
12
or C
14
fumarate vinyl acetate copolymer; or mixed copolymers based on C
8
and C
16
that provide an average of C
12
or C
14
. RO 113057 disc
Bloch Ricardo A.
Martella David J.
Infineum International Ltd.
McAvoy Ellen M.
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