Fuel and related compositions – Liquid fuels – Boron containing
Reexamination Certificate
1995-05-25
2002-03-12
Medley, Margaret (Department: 1714)
Fuel and related compositions
Liquid fuels
Boron containing
C044S330000, C044S331000, C044S347000, C044S351000
Reexamination Certificate
active
06355074
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to oil soluble dispersant additives useful in fuel and lubricating oil compositions, including concentrates containing said additives, and methods for their manufacture and use. The dispersant additives are dicarboxylic acids, anhydrides, esters, etc., substituted with a high molecular weight hydrocarbon group, and derivatives thereof such as salts, amides, imides, esters, oxazolines, etc. formed by further reaction with amine, alcohol, amino alcohols, and which may be further treated, e.g. borated. The high molecular weight hydrocarbon group has a number average molecular weight ({overscore (M)}
n
) of about 1500 to 5000. The additives will have a ratio (functionality) of about 1.05 to 1.25 dicarboxylic acid producing moieties per said high molecular weight hydrocarbon used in the reaction.
2. Prior Disclosures
U.S. 4,234,435 discloses as oil additives, polyalkene substituted dicarboxylic acids derived from polyalkenes having a {overscore (M)}
n
of 1300 to 5,000 and containing at least 1.3 dicarboxylic acid groups per polyalkene.
Canadian Patent 895,398 discloses reacting a mole of an unsaturated hydrocarbon group of 700 to 10,000 mol. wt. with 1 to 1.5 moles of chloro-substituted maleic or fumaric acid, which material can then be further reacted with alcohol.
U.S. Pat. No. 3,927,041 discloses a mole of polybutene of 300 to 3,000 mol. wt. containing 5 to 200 ppm 1,3 dibromo-5.5-dialkylhydantoin as a catalyst reacted with 0.8 to 5, generally 1.05 to 1.15 moles of dicarboxylic acid or anhydride, to form materials which can be used per se, or as esters, amides, imides, amidines, in petroleum products.
U.S. Pat. No. 3,215,707 discloses reacting chlorine with a mixture of polyolefin up to 50,000 molecular weight, especially of 250 to 3,000 molecular weight with one or more moles of maleic anhydride depending upon whether one or more succinic anhydride radicals are to be in each polymer molecule.
U.S. Pat. Nos. 4,113,639 and 4,116,876 disclose an example of alkenyl succinic anhydride having a molecular weight of the alkenyl group of 1300 and a Saponification Number of 103 (about 1.3 succinic anhydride units per hydrocarbon molecule. This alkenyl succinic anhydride may be reacted with polyamine and then boric acid (U.S. 4,113,639), or may be reacted with an amino alcohol to form an oxazoline (4,116,876) which is then borated by reaction with boric acid.
U.S. Pat. No. 4,062,786 in Example 13 shows a polyisobutenylsuccinic anhydride of molecular weight of about 1300 and a Saponification Number of about 100 (about 1.25 succinic anhydride units per alkenyl group).
U.S. Pat. No. 4,123,373 in Example 3 shows a polyisobutenylsuccinic anhydride of about 1400 molecular weight having a Saponification Number of 80 (about 1.07 succinic anhydride units per polyisobutylene units.
Further related prior disclosures, which are expressly incorporated herein by reference in their entirety are U.S. Pat. Nos.: 3,087,936; 3,131,150; 3,154,560; 3,172,892; 3,198,736; 3,219,666; 3,231,587; 3,235,484; 3,269,946; 3,272,743; 3,272,746; 3,278,550; 3,284,409; 3,284,410; 3,288,714; 3,403,102; 3,562,159; 3,576,743; 3,632,510; 3,836,470; 3,836,471; 3,838,050; 3,838,052; 3,879,308; 3,912,764; 3,927,041; Re. 26,330; 4,110,349; 4,113,639; 4,151,173; 4,195,976; and U.K. Patents 1,368,277 and 1,398,008.
SUMMARY OF THE INVENTION
The present invention is directed to a dispersant additive comprising a polyolefin of 1500 to 5,000 number average molecular weight substituted with 1.05 to 1.25, preferably 1.06 to 1.20, e.g. 1.10 to 1.20 dicarboxylic acid producing moieties, preferably acid or anhydride moieties, per polyolefin molecule. This acid or anhydride material is useful per se as an additive, e.g. a dispersant additive, for example in the same manner as previously known polyolefin substituted dicarboxylic acid or anhydride acylating agents as disclosed in U.S. Pat. No. 3,288,714 where prior acylating agents are used as dispersant/detergents and U.S. Pat. No. 3,714,042 where prior acylating agents are used to treat overbased metal complexes. Also, the material of the invention can be used in the manner described in U.S. Pat. No. 3,965,017 wherein overbased detergents are treated with acylating agents. The dicarboxylic acid producing materials of the invention can also be further reacted with amines, alcohols, including polyols, amino-alcohols, etc. to form other useful dispersant additives. Thus, if the acid producing material is to be further reacted, e.g. neutralized, then generally a major proportion of at least 50% of the acid units up to all the acid units will be reacted.
The materials of the invention are different from the prior art because of their effectiveness coupled with their low degree of interaction with other additives, as compared to those prior disclosures mentioned above which have a functionality of 1.3 or more dicarboxylic acid producing groups per hydrocarbon moiety used in the reaction.
Lubricating oil compositions, e.g. automatic transmission fluids, heavy duty oils suitable for gasoline and diesel engines, etc., can be prepared with the additives of the invention. Universal type crankcase oils wherein the same lubricating oil compositions can be used for both gasoline and diesel engine can also be prepared. These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations. Among these types of additives are included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, etc.
In the preparation of lubricating oil formulations it is common practice to introduce the additives in the form of 10 to 80 wt. %, e.g. 20 to 80 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually these concentrates may be diluted with 3 to 40, e.g. 5 to 20 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g. crankcase motor oils. The purpose of concentrates, is of course, to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend. Thus, a metal hydrocarbyl sulfonate or a metal alkyl phenate would be usually employed in the form of a 40 to 50 wt. % concentrate, for example, in a lubricating oil fraction. Ordinarily when preparing a lubricating oil blend that contains several types of additives no problems arise where each additive is incorporated separately in the form of a concentrate in oil. In many instances, however, the additive supplier will want to make available an additive “package” comprising a number of additives in a single concentrate in a hydrocarbon oil or other suitable solvent. Some additives tend to react with each other in an oil concentrate. Dispersants having a functionality (ratio) of 1.3 or higher, of the dicarboxylic acid moieties per hydrocarbon molecule have been found to interact with various other additives in packages, particularly overbased metal detergents to cause a viscosity increase upon blending, which may be followed by a subsequent growth or increase of viscosity with time in some instances resulting in gellation of the blend. This viscosity increase can hamper pumping, blending and handling of the concentrate. While the package can be further diluted with more diluent oil to reduce the viscosity to offset the interaction effect, this dilution reduces the economy of using the package by increasing shipping, storage and other handling costs. The materials of the present invention with a functionality below 1.25:1 minimize this viscosity interaction while achieving an effective additive. The composition described represents an additional improvement in that the hydrocarbon polymer required to maintain the oil solubility of the dispersant during engine operation can be provided with fewer acylating units per polyamine. For exam
Emert Jacob
Lundberg Robert D.
Waddoups Malcolm
Exxon Chemical Patents INC
Medley Margaret
LandOfFree
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