Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
1997-11-26
2001-07-17
Medley, Margaret (Department: 1714)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S503000
Reexamination Certificate
active
06262310
ABSTRACT:
FIELD OF THE INVENTION
The invention relates generally to deposit-control fuel additives which are free from halogen, and more particularly to hydroxypolyalkene amines, such as hydroxypolybutene amines and hydroxypolypropylene amines, as well as to a generally multiple-step process for their production.
BACKGROUND OF THE INVENTION
Deposit-control fuel additives effectively control deposits in engine intake systems (carburetors, valves, fuel injectors, etc.). A major deposit-control fuel additive used in gasoline today is made by the chlorination of polybutene to produce an intermediate followed by the reaction of this intermediate with an amine compound to produce a polybutene amine. These polybutene amines typically contain from about 0.5 to about 1.0 percent residual chlorine, and seldom less than 0.25 percent chlorine. With today's concerns regarding halogen compounds, it is desirable to reduce or eliminate chlorine from fuel additives.
The present invention relates to halogen-free hydroxypolyalkene amine fuel additives. This fuel additive is produced through the epoxidation of a polyalkene followed by the reaction of the epoxypolyalkene with an amine to produce a hydroxypolyalkene amine.
U.S. Pat. No. 4,302,215 to Lewis relates to hydrocarbyl carbonates and their fuel compositions which are deposit-control additives in gasoline compositions.
U.S. Pat. No. 3,794,586 to Kimura et al. relates to a lubricating oil composition containing a hydroxyalkyl-substituted polyolefin prepared by reacting a polyalkene epoxide with a polyamine at a temperature of from 15 to 180° C.
European Patent Application No. 384,086 to Blackborrow et al. relates to a process for producing long chain alkyl amines from polyolefins by reacting (a) a polyolefin having a molecular weight in the range of 330-2000 with ozone in the presence of a solvent, (b) reacting the ozonolysis product from (a) without separation and/or isolation of the carbonyl compounds formed therein with a primary hydrocarbyl amines to form an imine, (c) hydrogenating the imine from step (b) to give an amine in the presence of a hydrogenation catalyst, and (d) recovering the long chain alkyl amine from the hydrogenation products formed in step (c).
European Patent Application No. 385,039 to Blackborrow relates to a process for producing active carbonyl compounds predominating in aldehyde groups from polybutene having at least 50 percent of the unsaturation in the terminal position. The process has an initial epoxidation of the polybutene followed by isomerization of the epoxide so formed at a relatively higher temperature. The active nature of the carbonyl group enables these compounds to be converted to the corresponding amines or imines which can be used as fuel and lube oil additives.
SUMMARY OF THE INVENTION
The present invention relates to halogen-free hydroxypolyalkene amines such as hydroxypolybutene amines and hydroxypolypropylene amines and to a process for their production, and to a fuel containing such amines as a fuel additive.
The structure of the hydroxypolyalkene amines is generally a function of the end group structure of the polyalkene and generally several such structures exist for each polyalkene compound. The following are examples of some of the end group structures in polybutene and the hydroxypolybutene amines generally derived therefrom.
The following examples are some of the end-group structures of polypropylenes and the hydroxypolypropylene amines generally derived therefrom.
Cationically polymerized polypropylene suitable for use in this invention contains several different end-group structures resulting from extensive rearrangement during manufacturing. These end-group structures are represented as 3 or 4 carbon atom-terminated polypropylenes in the preceding structures. When 4 carbon atom-terminated structures are involved, such is due to alkyl group migration from one of the preceding repeat units.
A generic representation of the hydroxypolyalkene amine is:
where n=3 or 4, where Polyalkene is polypropylene or polybutene, and where, as apparent from the above formulations, the hydroxyl group and the amine group are always attached to adjacent, i.e., an adjoining or contiguous carbon atom.
The hydroxypolyalkene amines of the present invention are produced by a multiple-step process in which a polyalkene is first epoxidized in a suitable solvent using hydrogen peroxide in the presence of an organic acid. The intermediate epoxide is subsequently treated with a primary or secondary amine compound which may be a monoamine, a diamine, or a polyamine causing addition of the amine compound to the polyalkene epoxide intermediate. This addition reaction is run either neat or in a suitable solvent with an excess of amine at a temperature of from about 185° C. to about 300° C. The excess amine and solvent, if present, are removed from the final hydroxypolyalkene amine product by any conventional procedure such as vacuum stripping, wiped film evaporation, or a combination of vacuum stripping and water washing.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention, a process for making a halogen-free hydroxypolyalkene amine product generally of the formula
where n=3 or 4, where Polyalkene is cationically polymerized polypropylene or polybutene, and where the hydroxyl group and the amine group are attached to adjacent carbon atoms. That is, the amine group is attached to one carbon atom which is connected to the next or contiguous carbon atom which has the hydroxyl group thereon. Due to the large number of possible isomers, a single generic formula with amine on one carbon atom and the hydroxyl group on the next carbon atom cannot be drawn, rather specific examples have been set forth hereinabove and below.
The amine substitution is fully described hereinbelow in a multiple-step process comprising an epoxidation step, followed by the addition of an amine compound to the intermediate epoxide thus produced. In the first step, a polyalkene is epoxidized. The polyalkene can be any polyalkene known to the art and to the literature with the initial alkene monomer containing 3 or 4 carbon atoms, with 4 carbon atoms being highly preferred.
Polybutene is the commercial name for polymers manufactured from C
4
olefin refinery streams of catalytic or steam-cracked petroleum. These C
4
fractions consist mainly of isobutylene, but also contain other C
4
olefins. The definition of polybutene is well known to those skilled in the art, and is described in “Carbocationic Polymerization” by J. P. Kennedy and E. Marechal, Wiley-Interscience, New York, N.Y., 1982, pp. 469-475, which is hereby fully incorporated by reference. When the halogen-free hydroxypolyalkene amine product is made from a polybutene, the end product has the general formula
Specific examples of various isomers of such products is set forth hereinabove.
Polypropylene is the commercial name for polymers manufactured from C
3
olefin refinery streams of catalytic or steam-cracked petroleum. In the manufacture of polypropylene utilizing cationic polymerization, there is opportunity for carbon atom rearrangement. Thus, a generic formula cannot be set forth inasmuch as the polypropylene end group structure will contain one unsaturated point within the three or four terminal carbon atoms as set forth above in the various formulas. The definition of polypropylene, as well as the end group structures thereof which are predominantly branched, are set forth and described in “J. Org. Chem. 49,” I. Puskas and S. Meyers, 258 (1984), and “Macromolecules, 12” I. Puskas, E. M. Banas, A. G. Nerheim, and G. J. Ray, 1024 (1979), which are hereby fully incorporated by reference.
The initial step of the preparation of the compositions of the present invention is the epoxidation of a polyalkene. When the polyalkene is polybutene, it desirably has a number average molecular weight of from about 400 or 450 to about 2,200, preferably from about 700 to 1,600, and most preferably from about 800 to about 1,400, and a degree of polymerization of f
Baldwin Larry J.
Dever James L.
Yaggi Cyril J.
Ferro Corporation
Medley Margaret
Renner Kenner Greive Bobak Taylor & Weber
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