Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-10-13
2001-10-16
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S378000, C525S379000, C525S380000
Reexamination Certificate
active
06303703
ABSTRACT:
FIELD OF INVENTION
The present invention concerns novel methods for making oligomeric olefin monoamines. More particularly, the present invention concerns novel methods for making a specific type of halogen-free oligomeric olefin monoamine for use as fuel additives.
BACKGROUND
Deposit control fuel additives are well-known in the prior art. Such additives serve to limit the formation of unwanted deposits in engine intake systems. U.S. Pat. No. 5,810,894 provides a halogen-free additive comprising an oligomeric olefin monoamine. Halogen-free additives are desirable because of today's concerns regarding the use of halogen containing compounds.
Unfortunately, the methods disclosed in U.S. Pat. No. 5,810,894 for producing oligomeric olefin monoamines require the use of high-pressures and elevated temperatures which in turn require expensive equipment and high cost facilities. The present invention, however, provides methods for producing a specific type of oligomeric olefin monoamine that do not require the use of high-pressures and elevated temperatures.
SUMMARY OF THE INVENTION
The present invention provides a new and improved method of producing halogen-free oligomeric olefin monoamines having an end group structure of
using temperatures of less than about 150° C. and pressures less than about 200 psi comprising epoxidizing a specific class of oligomeric olefins to provide an oligomeric olefin epoxide, and then converting the oligomeric olefin epoxide to an oligomeric olefin aldehyde. In one preferred embodiment the aldehyde is converted to an oxime followed by converting the oxime to a monoamine. Alternatively, the aldehyde may be formed directly from the oligomeric olefin, and then converted to an oxime, and finally to a monoamine. In an alternative embodiment, the method comprises converting the aldehyde to a formamide intermediate, and then using hydrolysis to convert the formamide to the monoamine. In yet another embodiment, the method comprises the conversion of the epoxide to the oxime and then the oxime is converted to the monoamine. All of these methods avoid the use of costly high-pressure and high-temperature reactions.
The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the present invention may be employed.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
The present invention provides novel methods of forming a specific class of oligomeric olefin monoamines that avoids the use of high-pressure and high-temperature reactions. The specific class of oligomeric olefin monoamines to which the present invention is directed are disclosed in Dever et al. U.S. Pat. No. 5,810,894. The disclosure of U.S. Pat. No. 5,810,894 is incorporated by reference herein in its entirety.
Oligomeric olefin monoamines that are produced by the methods of the present invention are useful as additives for fuels and oils. Fuels include, for example, gasoline or motor fuels, aviation fuels, marine fuels and diesel fuels. Oils include, for example, crankcase oils, transmission oils and gear oils.
In one preferred embodiment the method includes epoxidizing an oligomeric olefin to provide an epoxidized oligomeric olefin, converting the epoxidized oligomeric olefin to an aldehyde and then converting the aldehyde to an oxime, and then reducing the oxime to provide the oligomeric olefin monoamine.
In another preferred embodiment the method includes converting the aldehyde to a formamide intermediate and converting the formamide by hydrolysis to an amine.
In another preferred embodiment the method includes converting an epoxidized oligomeric olefin to an oxime, followed by reducing the oxime to provide the oligomeric olefin monoamine.
In another preferred embodiment the method includes converting an oligomeric olefin directly to an aldehyde, converting the aldehyde to an oxime and then reducing the oxime to provide the oligomeric olefin monoamine.
The oligomeric olefin utilized in the method of the present invention is preferably a reactive polybutene. A reactive polybutene for use in the present invention is an unsaturated polymer, wherein more than 50% of the double bonds are in the a position. One method of preparing such polybutenes is described in German Patent No. 2,702,604. Applicants hereby incorporate by reference the teachings of German Patent No. 2,702,604 and U.S. Pat. No. 4,832,702.
Commercial polybutene that contains a high level of terminal vinylidene unsaturation suitable for use in the present invention provides a material having the following chemical structure in its terminal monomer unit:
Additional end group structures may also be present in commercial polybutenes, but such end group structures are not preferred for use in the method of the present invention.
The average molecular weight of commercial polybutenes of interest in the present method is generally greater than about 400, preferably from about 400 to about 3,000, more preferably from about 600 to about 2,200 and most preferably from about 800 to about 1,600. Notwithstanding the foregoing ranges, it is understood that the practice of the present invention is possible with any commercially available reactive polybutene oligomers having any number average molecular weight between about 400 and 3,000, and having terminal unsaturation.
Typical useful polybutenes that are commercially available today include, for example, INDOPOL H-100HR® (Mn 1000), Ultravis® 10 (Mn 950) or Ultravis® 30 (Mn 1300) all from BP Amoco Chemicals and Glissopal® ES 3250 (Mn 1000) from BASF.
The initial step in one embodiment of the method of the present invention is epoxidation of the unsaturation in the oligomeric olefin. Preferably, the epoxidation reaction occurs by reacting the oligomeric olefin with hydrogen peroxide in the presence of an organic carboxylic acid and a mineral acid catalyst. Due to the high viscosity of the starting oligomeric olefins, the epoxidation reaction is desirably carried out in a hydrocarbon solvent.
The amount of the hydrogen peroxide is generally from about 0.5 to about 2.5, and preferably from about 1.5 to about 2.0 moles per mole of olefin based upon the number average molecular weight of the olefin. The organic carboxylic acid is generally a monocarboxylic acid having a total of from 2 to 4 carbon atoms with acetic acid being preferred. The amount of the organic carboxylic acid is generally from about 0.15 to about 0.5 moles, and preferably from 0.25 to about 0.40 moles per mole of oligomeric olefin based upon the number average molecular weight of the olefin. In addition to this organic carboxylic acid, an acid catalyst is also required. The acid catalyst can be one or more organic acids, or one or more inorganic acids, or combinations thereof which are utilized to effect the epoxide reaction. Examples of specific acid catalysts include methanesulfonic acid, toluenesulfonic acid, sulfuric acid, phosphoric acid and the like and are utilized in small amounts as from about 0.0025 to about 0.40 moles per mole of the olefin based upon the number average molecular weight thereof.
The hydrocarbon solvent utilized in the epoxidation reaction can generally be any inert organic solvent, that is a solvent which does not enter into reaction with any of the reactants. Such solvents include aromatic solvents having a total of from about 6 to about 14 carbon atoms with specific examples including xylene, toluene, C
10
, C
9
, A100, A150 aromatics and the like, an aliphatic solvent having from about 6 to about 14 carbon atoms with specific examples including isooctane, heptane, cyclohexane and the like, or various aliphatic substituted aromatic compounds and the like, as well as combinations thereof.
The temperature of the epoxidation reaction will depend on the organic acid used and is a function of the stability of the intermediate peracid and the reaction
Baldwin Larry J.
Dever James L.
Kinder James D.
Sonby Kevin M.
Taylor Daniel P.
Ferro Corporation
Lipman Bernard
Rankin, Hill Porter & Clark LLP
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