WO1998012284A1 - Method of synthesizing pure additives and the improved compositions thereby produced - Google Patents

Method of synthesizing pure additives and the improved compositions thereby produced

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Publication number
WO1998012284A1
WO1998012284A1 PCT/US1997/016648 US9716648W WO1998012284A1 WO 1998012284 A1 WO1998012284 A1 WO 1998012284A1 US 9716648 W US9716648 W US 9716648W WO 1998012284 A1 WO1998012284 A1 WO 1998012284A1
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WO
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Patent type
Prior art keywords
amine
polyolefinic
nitrogen
amines
reaction
Prior art date
Application number
PCT/US1997/016648
Other languages
French (fr)
Inventor
Donald E. Koehler
William J. Claffey
Original Assignee
Petrokleen, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date

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    • CCHEMISTRY; METALLURGY
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/16Reaction products obtained by Mannich reactions
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/30Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33306Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
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    • C10L1/14Organic compounds
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    • C10L1/234Macromolecular compounds
    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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    • C10L1/1985Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
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    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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Abstract

An improved process of synthesizing gasoline soluble polyolefinic amines or polyether amines comprising the steps of reacting polyolefinic halides or polyether halides with amines in a specific sequence of reactions; distilling off non-reactive amines; neutralizing the reaction mixture; recovering amine(s) and water; and separating polyolefinic amines from the solids with simple filtration or centrifuge or decanting. The gasoline soluble products are used in blended fuels to improve intake valve deposit control in automotive engines.

Description

METHOD OF SYNTHESIZING PURE ADDITIVES AND THE IMPROVED COMPOSITIONS THEREBY PRODUCED

Background of the Invention

This is a continuation-in-part of Serial No.

08/356,700 filed December 15, 1994. The polyolefin amines or polyether amines synthesized according to the process of said parent application are used in blended fuels as described herein.

The present invention relates to an improved method of synthesizing polyolefinic-amines containing a maximum of one polyolefinic chain per amine unit. It concerns the improved fuel additives thereby produced, and the improved fuel composition which comprises an admixture of said fuel additive and gasoline.

Previous patent work focused on the processing and use of oil soluble polyolefinic-amines containing a single type of amine. The prior art identifies the use of blended amines of the same type to improve raw material economics. Numerous nitrogen containing components have been identified, but combining nitrogen components containing specific and different characteristics is not described. It is known that the most desirable polyisobutene- amines are monomeric and contain primary nitrogen. The least desirable contain "over-reaction" components where the nitrogen is sterically hindered by over reaction components . The literature identifies chemical yield limitation due to unreacted components and the formation of undesirable over reaction products identified as dimers and trimers . The limitations exist because previous work has not controlled the type of reaction (monomeric versus dimer/trimer) throughout the reaction sequence.

In processes where nitrogen containing components are limited to only one reactive nitrogen (i.e., N' N' dimethylamine , N' N ' -dimethylamino ropylamine , aminoethylethanolamine) the resulting polyisobutene- polyamine is monomeric but does not contain primary nitrogen.

Described in this patent are three classes of polyolefinic-amines : 1) those synthesized by reacting polyolefinic halide with amines containing only one reactive nitrogen, where the main reaction component is monomeric, the nitrogen moiety being limited to secondary and tertiary, and a low concentration of unreacted polyolefin; 2) those synthesized by reacting polyolefinic halide with amines containing more than one reactive nitrogen, the main reaction components being monomeric and undesirable dimerized components (i.e., polyolefinic-amine-polyolefin) . The nitrogen moiety include primary, secondary and tertiary, and a low concentration of unreacted polyolefines ; and 3) those synthesized by reacting polyolefinic halide with amines containing only one reactive nitrogen and amines containing more than one reactive nitrogen, the main reaction components being monomeric containing primary, secondary and tertiary nitrogen, a low concentration of unreacted polyolefin, but no dimer (less than 5% prior to the addition of any diluent) . The first two classes are described throughout the literature. The third class is new and is the subject of this invention. Differences between the amine classes described are demonstrated by example using Gel Permeation Chromatography, an analytical technique for measuring molecular weight .

One of the primary indicators of deposit control performance is the concentration of basic nitrogen in the polyolefin-amine . For a given polymer amine combination, the most effective polyolefin-amine is a monomer where the nitrogen groups (s) are not sterically hindered. The calculated polymer-to-amine molar ratio will be 1 or less (i.e. one mole polymer to one mole amine) . This assumes that the average number of reaction sites contained in the polyolefin is 1 and the reactivity is 100%. This is not always the case. Typical polyolefins do not contain 100% reactive sites. This is the primary reason for the low concentration of unreacted material in all products of this type. Polyolefines containing multiple reaction sites, for example, BP Chemical Limited' s Ultra Vis polymers, the average number of allylic reaction sites is greater than one (1.1 to 1.5), and the opportunity exists to further reduce the polymer-to-amine ratio and thus increase the basicity of the reaction product. Therefore, if conventional polymer is used, the ideal polymer-to-amine ratio would be about 1.1 or less to account for the unreacted material. If a highly reactive polymer is used, the ratio would be significantly less than 1.

Throughout the literature, reference is made to the ratio of polymer to amine groups, as at least one polymer per amine group (i.e., U.S. Patent Nos. 5,006,130; and 4,728,340). The molar ratio of polymer units to amine units calculated from available examples ranges up to 2, supporting the statement that there are, on average, up to two polymer groups per amine group. These represent classes one and two.

It is recognized throughout the literature that reaction components contained in a polyolefin-amine cannot be represented by a single structure due to the complexity of the reaction; however, use of average values is accepted.

The invention describes the synthesizing of polyolefin-amines using amines containing multiple primary nitrogen to create a monomeric reaction point containing primary nitrogen and the highest concentration of basic nitrogen of any polyolefin-amine class. This invention describes this new class of polyolefine amines (class "3") as "High Yield" polyolefinic-amines, where the molar ratio of polymer to amine is 1.1 or less, and over reaction components are less than 5%. This invention specifically identifies the reacting of nitrogen containing components with precise characteristics in a sequence to maintain a precise ratio of reactive nitrogen sites to polyolefin reactive sites.

It is known that oil soluble polyolefin amines containing at least one olefinic polymer chain or oil soluble polyether can be employed to improve the detergent properties of fuel and lubricant compositions. The use of such compositions, their utility in providing a fuel with significantly reduced octane requirement increase (ORI) characteristics; removal and/or beneficial modification of deposits in the combustion chamber, intake valves and the like; as well as potential improvement in fuel efficiency are taught by a number of prior patents including U.S. Patent Nos. 3,275,554; 4,438,757; 3,565,804; 3,574,576; 3,898,056; 3,960,515; 4,022,589; 4,357,148; 4,846,848; and, 4,039,300, the disclosures and claims of all of which are specifically incorporated herein by reference. Such polyolefinic-amines have been used both alone and in combination with other additives, particularly polymeric additives .

The polyolefinic-amines described in this invention contain a maximum of one olefinic polymer derived from alkanes or alkenes with straight or branched chains, which may or may not have aromatic or cycloaliphatic substituents, for instance, groups derived from polymers or copolymers of olefins which may or may not have a double bond. This new class of polyolefinic-amines has been demonstrated to be effective in the control of induction system deposits. It is recognized that the reduced ratio polymer to amine will further improve performance beyond the other classes of polyolefinic- amines in the performance area identified. Examples of non-substituted alkenyl and alkyl groups are polyethylene groups, polypropylene groups, polybutylene groups, polyisobutylene groups, polyethylene- polypropylene groups, polyethylene-poly-alpha-methyl styrene groups and the corresponding groups without double bonds. Particularly preferred are polypropylene and especially polyisobutylene groups, or oil soluble polyethers such as copolymers of ethylene oxide and propylene oxide .

The amines used to form the polyolefinic-amine compounds of this invention include primary, secondary, and tertiary low molecular weight amines such as ethylene diamine, d i e t hy 1 e n e t r I a m i n e , triethylenetetramine , dimethy1a inopropy1amine , propylene diamine, butylene diamine, trimethyl trimethylene diamine, tetramethylene diamine, diaminopentane or pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, diaminooctane, decamethylene diamine, and higher homologues up to about 18 carbon atoms. In the preparation of these compounds, the same amines can be used or substituted amines can be used such as N-methyl ethylene diamine, N-propyl ethylene diamine, N,N-dιmethyl 1,3 -propane diamine, N-2- hydroxypropyl ethylene diamine, penta- (1- methylpropylene) hexamine, tetrabutylene-pentamine, hexa- (1, 1-dimethylethylene) heptane, di- (1-methylamylene) - tria ine, tetra- (1, 3-dimethylpropylene) pentamine, penta- (1, 5-dimethylamylene) hexamine, di (1 -methyl - 4 - ethylbutylene) triamine, penta- (1 , 2 -dimethyl- 1-isopropyl ethylene) hexamine, tetraoctylenepentamine and the like. Ammonia and other non-polyamines are also effective as used in the process described.

Compounds possessing triamine as well as tetramine and pentamine groups are applicable for use because these can be prepared from technical mixtures of amines, which could offer economic advantages.

The amine can be a cyclic, for instance, the cyclic polyamines formed when aliphatic polyamines with nitrogen atoms separated by ethylene groups were heated in the presence of hydrogen chloride . The polymeric components are well known in the art and numerous patents exist which relate to their manufacture, such as U.S. Patent Nos. 3,275,554 3,513,093; 3,753,670; 3,008,993; 3,275,554; 3,573,001 3,574,576; 3,576,743; 3,578,422; 3,597,174; 3,639,110 3,652,240; 3,655,351; 3,658,494; 3,658,495; 3,676,089 3,701,640; 3,711,255; 3,717,447; 3,728,091; 3,746,520 3,751,225; 3,756,793; 3,762,889; 3,764,281; 3,765,850 3,773,479; 3,752,657; 3,753,670; 3,779,724; 3,782,912; 4,039,300 and others.

It should be noted that reference to amines does not mean they are made solely of carbon, hydrogen and amino nitrogen. For example the compounds may contain minor amounts of oxygen, sulfur, non-amino nitrogen, etc. and may include small amounts of halogen.

As previously stated, the efficacy of the additive is primarily a function of the nitrogen content, and/or the presence of a reactive amine moiety. When terminal amine contains a primary or tertiary or a sterically hindered secondary nitrogen, there is no di erization, and the efficacy of such additive is greater than those containing dimers . The dimers significantly reduce the nitrogen concentration of the product and reduces and eliminate the benefits of the dimerized nitrogen, increases molecular weight, and increases viscosity. This requires a higher concentration of additive in order to achieve the same overall effect.

Until now, polyolefinic-amines synthesized using amines containing multiple primary nitrogen manufactured to maximize monomer concentration have generally been produced by reacting a polyolefinic halide with a substantial stoichiometric excess of amine to reduce the over reaction components to about 40% (US patent No. 5,346,965) , though not totally eliminating the formation of dimers and trimers . The use of such a stoichiometric excess of amine, however, results in a substantial negative impact to the manufacturing costs due to the significant quantity of excess amine that must be continuously purified and recycled, and the reduction in effective reactor volume.

Summary of the Invention The present invention provides a method of synthesizing polyolefinic amines, virtually eliminating the concentration of dimers and/or trimers. It comprises the steps of:

(a) forming a polyolefinic halide;

(b) reacting the halide with less than one molar equivalent (i.e. from about 0.99 to about 0.01 molar equivalent) of a amine having only one reactive nitrogen, for a period of from about 0.5 to about 15.0 hours at a temperature of from about 75 °F to about 410 °F and a pressure of from about 0 to about 6 atmospheres;

(c) adding to the reaction mass at least one additional amine having at least two reactive nitrogen moieties, in an amount equal to from 1 to about 10 times the molar quantity of polyolefinic halide employed to form the first reaction mass and reacting the second reaction mass for a period of from about 0.5 to about 15 hours at a temperature of from about 75 °F to about 410°F and a pressure of from about 0 to about 6 atmospheres;

(d) distilling off any unreacted amine at a distillation temperature below about 400 °F; and, (e) treating the second reaction mass to recover polyolefinic or polyether amine products.

The present invention also encompasses the fuel additive product produced by the foregoing process, and the novel motor fuel composition containing an amount of this additive of up to 8 ppmw, preferably about 2-6 ppmw, most preferably about 2.5 - 3.5 ppmw, expressed as basic nitrogen. This will inhibit octane requirement increase (ORI) and clean up the induction system. This invention claims the use of the high yield polyolefinic- amines manufactured by this process in gasoline, such as that disclosed in Patent No. 5,006,130 and incorporated herein by reference. Based on the results and general knowledge available in the literature, it is concluded that the polyolefinic-amine described herein will be effective with numerous carrier fluids tested in various vehicles and engines identified throughout the literature .

The present invention is further directed to an unleaded fuel or gasoline composition comprising a major amount of a hydrocarbon based fuel of the gasoline boiling range, reformulated or conventional with or without oxygenates. The fuel contains an effective amount of a component which reduces intake valve deposits in carburetted and/or electronic port fuel injected engines. The composition of the component comprises a mixture of (a) up to 8 ppmw preferably 1 to 6 ppmw, basic nitrogen including primary and secondary and terminally bound tertiary nitrogen and less than 5% dimerized polymer based on the fuel composition in the form of polyolefinic-amine containing one polymer chain attached to one nitrogen atom, the polymer having a molecular weight in the range of from about 600 to about 10,000; and (b) from 0 to about 800 ppmw based on the fuel composition of at least one component selected from (I) a polymer of a C2 to C4 onoolefin, (ii) a copolymer of a C2 to C. monoolefin, (iii) the corresponding hydrogenated polymer of copolymer, (iv) an oil soluble poly (oxyalkylene) alcohol, glycol or polyol or a mono or diether thereof, which has the formula R-^O- (R20) n-R3 wherein R-_ and R3 each independently is a hydrogen atom or an aliphatic, cycloaliphatic or mononuclear aromatic hydrocarbon group of up to 40, preferably 20, carbon atoms, R2 represents an alkylene group, preferably containing 2 to 8 carbon atoms, but not limited to 2 to 8 carbon atoms, and n is an integer of at least 7, (v) a naphthenic or paraffinic oil having a visocity of 100°C of from about 2 to about 15 centistokes. The molecular weight of (b ) is in the range of from about 600 to 10,000.

The fuel may also contain additional components such as demulsifiers, corrosion inhibitors and/or fuel stabilizers. The composition may also include other detergent based systems such as polyalkyl amines, polyether amines, po lya 1 ky 1 s uc c i n i m i de , polyalkylaminophenol, and/or low molecular weight amines . These may be added to enhance cleanliness, performance or economics .

The polyolefinic -amine component (a) has one polymer chain having a molecular weight in the range from about 500 to about 9,900 and preferably from about 550 to about 4,900, and particularly from 600 to 1,300, and which may be saturated or unsaturated and straight or branch chain and attached to a nitrogen atom.

Preferred polyolefin-substituted polyolefinic- amines have the structural formula:

H R"

R-N I-R' - (N-R' )X-NI-R" where R is a polyolefin having a molecular weight from about 500 to about 9,800, R' is an alkylene radical having from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, R" is hydrogen or lower alkyl, and x is 0 to 5, preferably 0 to 3. The molecular weight range of

R is preferably 550 to 4,900, with a molecular weight range of 600-1,330 being particularly preferred. The ratio of the polyolefinic-amine groups containing primary and terminal secondary and/or terminal tertiary nitrogen to groups containing non- terminal nitrogen groups is greater than three. The olefinic polymers (R) which are reacted with amines to form the additive of the present invention include olefinic polymers derived from alkanes or alkenes with straight or branched chains, which may or may not have aromatic or cycloaliphatic substituents, for instance, groups derived from polymers or copolymers of olefins which may or may not have a double bond. Examples of non- substituted alkenyl and alkyl groups are polyethylene groups, polypropylene groups, polybutylene groups, polyisobutylene groups, polyethylene- polypropylene groups, polyethylene-polyalpha-methyl styrene groups and the corresponding groups without double bonds. Particularly preferred are polypropylene and especially polyisobutylene groups. The preference is when both R" groups are hydrogen; however, alkyls, containing up to 7 carbon atoms, preferably selected from methyl, ethyl, propyl and butyl groups, are effective and are considered included in the invention. For simplification, except as otherwise clear from the context, the term "polymeric halide" shall be understood to include both polyolefin halides, polyether halides, and/or mixtures of such halides. "Amines" shall be understood to include both polyamines and monoamines .

Still further, the present invention encompasses a method of producing polyolefinic amine or polyether amine which facilitates separation of amine hydrochloride from polyolefinic amine or polyether amine product without the use of a plurality of aqueous washing steps. This is possible because of improved amine hydrochloride crystal size and morphology which facilitate the separation of any amine hydrochloride salts from the product.

The Preferred Embodiment In the preferred process of the present invention, the preferred polymer is a polyolefin halide, such as polyisobutylenechloride, the first amine, having only a single reactive nitrogen, is an amine in which all other nitrogen moieties are hindered, such as for example dimethylaminoproplylamine (DMAPA) , and the second amine is one having at least two primary amine moieties such as for example ethylenediamine (EDA) or tetraethylenepentamine .

There are, of course, any number of equally suitable materials which may be utilized in the practice of the present invention; however, the remaining discussion will center primarily on the use of polyisobutylene, EDA, and DMAPA, because these reactants are readily commercially available. Again, the various United States patents previously incorporated herein by reference all list a number of suitable amines for use in the synthesis of additives such as those contemplated by the present invention.

Proper selection of amines and processing sequences and reaction times are important to control the ratio of amine to polyolefin reaction sites and to control the amine-amine and a ine-salt exchange reactions. As specific illustrations of the preparation of products by the process in the present invention, the following examples are presented by way of illustration and not by way of limitation.

Preparation of Polymeric Halides

In a flask, 1000 grams of the desired polyolefin having an average molecular weight of 950 was contacted with about 97 grams of chlorine gas. The temperature was maintained between 95 and 105°C for about 4 hours. A 30 minute nitrogen purge was used to remove suspended chlorine and HCl from the polyolefinic halide (the chlorine analysis was determined to be 4.7%) .

Example 1

Into a 4 liter high pressure autoclave, 1,147 grams of polyolefinic halide (produced as described) was transferred via a pressure bomb. Immediately following this, 692 grams of ethylene diamine was added to the autoclave via a second pressure bomb. The autoclave was sealed and pressurized to about 60 PSIG and the temperature increased to 170°C with constant stirring. This temperature was maintained for about 5 hours . A portion of the material was transferred to a flask where the free amine was distilled. Aqueous sodium hydroxide was added to free the amine reacted with the amine -HCl salts. Following this, water and free amine were distilled. A portion of the mixture was transferred to a high pressure filter for separation of the solids. Several attempts were made to filter the solids: Attempt A: #1 Watman filter paper, no filter aid, 75 PSIG, unable to filter

Attempt B: #1 Watman filter paper, with filter aid #1, 75 PSIG, unable to filter Attempt C: #1 Watman filter paper, with filter aid #2, 40 PSIG, able to filter 30 ml after % hour.

Analysis of filtered material showed: 2.3% nitrogen, 1300 ppm of ionic chloride.

Significance: The nitrogen analysis demonstrates that the process is effective at reacting polyolefinic halide with ethylene diamine; however, the solids produced during the reaction could not be easily filtered. The molar ratio of polyolefin to amine is 1.2 to 1. The 1300 ppm of ionic chloride in the polyolefinic amine is unacceptable. This experiment demonstrates the reason most polyolefinic amine manufacturing relies upon a series of water/butanol wash steps to remove the finely dispersed solids.

Example 2

In a flask, 99 grams of polyolefinic halide (produced as previously described) were reacted with 3.5 grams of di ethylaminopropylamine at a temperature of

125°C for about 100 minutes with constant stirring; 15 grams of ethylene diamine plus 25 grams of dimethylaminopropylamine were added to the polyolefinic halide mixture. The flask temperature was increased to about 145°C over a period of 200 minutes with stirring and reflux. The total reaction time was 300 minutes. Following the reaction, the reflux equipment was replaced with distillation equipment and the free amine removed as the temperature was increased to about 160°C. The flask was cooled to 70°C and aqueous sodium hydroxide was added at a stoichiometric excess of 1.1 to 1.2 relative to the initial polyolefinic halide. The mixture was stirred as the temperature was increased to 160 °C as the water and free amine (amine freed from the amine -HCl salts) were distilled. The material in the flask was clear and bright, with a dark straw color, with a layer of solids at the bottom. A sample was decanted from the flask and analyzed for nitrogen and chlorine and found to contain 2.60% nitrogen (polymer to amine ratio less than 1.1) and 90 ppm ionic chloride. A portion of the sample was filtered through '#1 Watman filter paper without filter aid. A portion was centrifuged. The filtered and centrifuge samples contained the same concentration of ionic chloride and nitrogen. Significance: The results demonstrate that the process described in this example effectively reacts polyolefinic halide with ethylene diamine and the solids can be easily filtered from the polyolefinic amine. Additional analysis was conducted to verify that the sample described by Example 2 was free of dimers and trimers. Gel permeation chromatography (GPC) analysis was conducted. For reference, unreacted polyolefin and a commercial polyolefinic amine are presented. The number average molecular wt . , Mn was selected as the characteristic most descriptive for these samples.

Sample Mn ,

"b Di .fference

A. Unreacted polyolefin 1, 097 N.A.

B. Example 2 sample 1, 071 -2.4

C. Commercial sample 1, 952 +77.9

Significance: The results demonstrate that the sample from Example 2 did not increase Mn, verifying that crosslinking producing dimers and trimers did not occur. The 2.4% difference between A and B is within experimental variability. The commercial sample C showed a 77.9% increase relative to the unreacted polyolefin.

Further analysis combining the GPC results with nitrogen analysis for the polyolefinic amines (B and C) demonstrates that sample B contains about 65% more reacted nitrogen than sample C. This difference is due to the reduced number of polyolefinic halide reaction sites in "B" resulting from the formation of dimers and trimers during the manufacturing. Exampl e 3

In a flask, 95 grams of polyolefinic halide (produced as previously described) was reacted with 24 grams of dimethylamino propylamine (2.5 molar ratio of PIB-chloride to DMAPA) at a temperature of 125°C for 100 minutes with stirring and reflux; 45 grams of tetraethylenepentamine was added to the polyolefinic halide dimethylaminopropylene mixture. The flask temperature was increased to about 145°C over a period of 200 minutes with stirring and reflux. The total reaction time was 300 minutes. Following the reaction, the reflux equipment was replaced with distillation equipment and the free dimethylaminopropylamine was removed. The contents of the flask were contacted with HCL to convert unreacted amine to amine HCL. The contents were transferred to a pressure funnel with #1 Watman filter paper and the amine -HCl crystals were separated from the polyolefinic amine. The amine -HCl crystals were transferred to a clean flask and aqueous NaOH was added at a stoichiometric excess to recover the amine . The water and dimethylaminopropylamine was distilled and the tetraethylenepentamine was filtered from the solids. Analysis of the polyolefinic amine after simple filtration through #1 Watman filter paper without filter aid and less than 5 PSIG pressure showed 3.1% nitrogen and about 100 ppm of ionic chloride.

One of the significant advantages of the process of the present invention is the manner in which it facilitates the recovery of unreacted amine. When PIB- Cl is reacted with EDA, excess EDA formed EDA -HCl crystals during the reaction which are too small to filter, and it is necessary to employ a series of water wash steps for product purification. The sequential reaction steps provided by the process of the present invention promote first the growth of large, easily filterable DMAPA -HCl crystals and then later formed EDA -HCl crystals which grow epitaxially upon those crystals already present, providing amine -HCl crystals which are much easier to filter and remove, thereby substantially simplifying product purification.

It is commonly accepted in the art that liquid hydrocarbon distillate fuel compositions containing polyolefinic-amines such as those produced according to the present invention effectively counteract, nullify and/or inhibit fouling of vital parts of internal combustion engines.

Example 4 Intake valve deposits tests were conducted in a Ford 2.3 -liter naturally aspirated engine. The test sequence included 100 hours of stepped steady state operation. The specific test procedure was developed by the Coordinating Research Council as a replacement for the industry recognized BMW vehicle tests. This industry engine test was specifically designed to characterize intake valve deposit of both gasoline and gasoline additives.

The test fuel was a commercially available unleaded premium.

The table identifies selected results demonstrating the effectiveness of the polyolefinic-amine manufactured by the process described herein.

The polyolefinic-amine manufactured by this process was tested separately and blended with both polyisobutene and paraffinic mineral oil to demonstrate intake valve deposit control.

Basic N, as Ratio of Ford

Tests delivered by Component Component (B+C) to 2.3L,

Component A, B, ppmw C, ppmw A (A as avg.IVD, ppmw basic N) mg

1 0 0 0 NA 275-438

2 3 0 0 NA 108

3 4 0 0 NA 31

4 2 103 26 64 23

5 3 150 37 62 5

Component :

A - polyolefinic-polyamines .

B - Polyisobutene added as carrier fluid.

C - Paraffinic mineral oil, approximate viscosity, 600 SUS @ 100°F.

The results demonstrate that the gasoline compositions of the invention effectively control intake deposit formation. It is also demonstrated that the addition of components B and C increased deposit control at the same concentration of component A.

The process of the present invention will carry out the objects set forth hereinabove. It is, therefore, to be understood that any variations evident fall within the scope of the claimed invention and thus, the selection of specific reactants as well as processing conditions can be determined without departing from the spirit of the invention herein disclosed and described. In particular, deposit control fuel additives according to the present invention are not necessarily limited to those having the amines exemplified herein or the mole ratios employed. Moreover, as noted hereinabove, other reaction temperatures can be substituted for those disclosed herein. Thus, the scope of the invention shall include all modifications and variations that may fall within the scope of the attached claims.

Claims

We claim :
1. An unleaded gasoline composition,
(conventional or reformulated) , containing up to 8 ppmw of an additive which is formed from an oil soluble polyolefinic polymer reacted with an amine, with a maximum of one polymer unit per amine unit and the molecular weight of the polymer ranging from about 600 to 10,000, whereby the additive is used to control and reduce carburetor, fuel injector, intake valve and combustion chamber deposits in gasoline engines.
2. The composition according to claim 1 wherein the basic structural formula is:
H R" R-N I-R' - (N-R' )X-NI-R" where R is a polyolefinic polymer having a molecular weight from about 500 to about 9,800, R' is an alkyl radical having from 1 to 8 carbon atoms, R" is hydrogen and/or lower alkyl and x is 0 to 5 and the ratio of polymer-amine units containing terminal primary and terminal secondary or terminal tertiary nitrogen to polymer-amine units containing non-terminal nitrogen is greater than three.
3. The composition according to claim 1 wherein the additive is present from about greater than 2 ppmw to about 6 ppmw basic nitrogen.
4. The composition according to claim 1 wherein the additive is present from about 2.5 to about 3.5 ppmw basic nitrogen.
5. The composition according to claim 2 wherein in said structural formula, R is selected from the group consisting of polypropylene and polyisobutylene and has a molecular weight from about 600 to 1,300.
6. The composition according to claim 2 where R is a polyisobutylene group.
7. The composition according to claim 2 where each R' is independently an alkyl group containing from 1 to 4 carbon atoms, and x is 0 to 3.
8. A composition according to claim 1 wherein a structure of the polyolefinic polymer contains multiple allylic reaction sites available for reacting with an amine, such that the additive is a polyolefinic-amine product containing multiple amine units each containing terminal primary and secondary or tertiary nitrogen.
9. The composition according to claim 1 where up to 600 ppmw of any of the following are also added: (i) a polymer of a C2 to C4 monoolefin, (ii) a copolymer of a C2 to C. monoolefin, (iii) the corresponding hydrogenated polymer or copolymer, (iv) an oil soluble poly (oxyalkylene) alcohol, glycol or polyol or a mono or di ether thereof, which has the formula Rx-0- (R20) n-R3 wherein R1 and R3 each independently is a hydrogen atom or an aliphatic, cycloaliphatic or mononuclear aromatic hydrocarbon group of up to 40 carbon atoms, R2 represents an alkylene group and n is an integer of at least 7, (v) a naphthenic or paraffinic oil having a viscosity of 100 C of from about 2 to about 15 centistokes.
10. The composition according to claim 1 where additional components such as demulsifiers and corrosion inhibitors, and fuel stabilizers are included in the composition.
11. The composition according to claim 1 where other detergent based systems (i.e. polyalkyl amines, polyether amines, po 1 y a 1 ky 1 s uc c i n i m i d e , polyalkylammophenol , low molecular weight amines) are included in the composition to enhance cleanliness, performance or economics .
12. A composition according to claim 1 where class 1 polyolefinic amines which are synthesized by reacting polyolefinic halide with amines containing only one reactive nitrogen where the main reaction component is monomeric and the nitrogen moiety being secondary or tertiary, and/or class 2 polyolefinic amines which are synthesized by reacting polyolefinic halide with amines containing more than one reactive nitrogen, the main reaction components being monomerized and dimerized components, are added in combination with the polyolefinic-amine additive.
13. The composition according to claim 9 where the added polymer is a C3 or C4 monoolefin having a molecular weight in the range from about 600 to about 950.
14. The composition according to claim 9 where an oil soluble poly (oxyalkylene) alcohol, a glycol or polyol or mono or di ether is added.
15. The composition according to claim 9 where, in the polyoxyalkylene chain -(R20)n-, R2 is an alkyene group containing 2 to 8 carbon atoms.
16. The composition according to claim 9 where R2 is an ethylene or 1 , 2 -propylene group.
17. The composition according to claim 9 where R2 is a 1,2 propylene group .
18. The composition according to claim 9 where at least one of Rx and R3 is an alkyl or alkylphenyl group containing up to 20 carbon atoms.
19. The composition according to claim 18 where R is hydrogen and R3 is an alkyl group.
20. The composition according to claim 18 where R3 is dodecyl or a mixture of alkyls from C12 to C15.
21. The composition according to claim 18 where R2 is an ethylene or 1 , 2 -propylene group.
22. The composition according to claim 9 where a naphthenic or paraffinic oil is added.
23. The composition according to claim 1 where the additive is present from about greater than 2 ppmw to about 6 ppmw basic nitrogen.
24. The composition according to claim 9 wherein the additive is present from about greater than 2 ppmw to about 6 ppmw basic nitrogen and the additional component is present in about 50 ppmw to about 600 ppmw.
25. A composition according to claim 1 where the additive is present from about 2.5 to about 4.0 ppmw basic nitrogen and the additional component is present in about 100 to about 400 ppmw.
26. A composition according to claim 1 where the additive is present at about 3.0 ppmw basic nitrogen and the additional component is present at about 185 ppmw.
27. A composition of matter for fueling an internal combustion engine equipped with at least one carburetor or electronic fuel injector, which comprises a major amount of hydrocarbons boiling in the gasoline boiling range and a minor amount of a polyolefinic amine or polyether amine synthesized according to the steps Of: a. forming a polymeric halide; b. reacting said polymeric halide with from about 0.01 to about 0.99 molar equivalent of an amine having only one reactive amine site, for a period of from about 0.5 to about 15.0 hours at a temperature of from about 75 *F to about 410 *F at a pressure of from about 0 to about 6 atmospheres; c. adding to said reaction mass at least one additional amine having at least two reactive amine moieties, in an amount equal to from 0.01 to about 10 times the molar quantity of polyolefinic halide employed to form the first reaction mass and reacting said second reaction mass for a period of from about 1 to about 15 hours at a temperature of from about 75'F to about 410 °F at a pressure of from about 0 to about 6 atmospheres; d. distilling off any unreacted amine at a distillation temperature below about 400 "F; and, e. treating said second reaction mass to recover polyolefinic amine products.
28. A composition of matter for fueling a diesel internal combustion engine equipped with fuel injection which comprises a major amount of hydrocarbons boiling in the diesel boiling range including conventional and low aromatic and or low sulfur fuels and a minor amount of a polyolefinic amine or polyether amine synthesized according to the steps of: a. forming a polymeric halide; b. reacting said polymeric halide with from about 0.01 to about 0.99 molar equivalent of an amine having only one reactive amine site, for a period of from about 0.5 to about 15.0 hours at a temperature of from about 75 *F to about 410 *F at a pressure of from about 0 to about 6 atmospheres; c. adding to said reaction mass at least one additional amine having at least two reactive amine moieties, in an amount equal to from 0.01 to about 10 times the molar quantity of polyolefinic halide employed to form the first reaction mass and reacting said second reaction mass for a period of from about 1 to about 15 hours at a temperature of from about 75 ° F to about 410 °F at a pressure of from about 0 to about 6 atmospheres; d. distilling off any unreacted amine at a distillation temperature below about 400 "F; and, e. treating said second reaction mass to recover polyolefinic amine products .
29. A composition of matter for lubricating an internal combustion engine which comprises a major amount of hydrocarbon or synthetic oil soluble component boiling in the gasoline lubricant boiling range and a minor amount of a polyolefinic amine or polyether amine synthesized according to the steps of : a. forming a polymeric halide,- b. reacting said polymeric halide with from about 0.01 to about 0.99 molar equivalent of an amine having only one reactive amine site, for a period of from about 0.5 to about 15.0 hours at a temperature of from about 75 'F to about 410 *F at a pressure of from about 0 to about 6 atmospheres ; c. adding to said reaction mass at least one additional amine having at least two reactive amine moieties, in an amount equal to from 0.01 to about 10 times the molar quantity of polyolefinic halide employed to form the first reaction mass and reacting said second reaction mass for a period of from about 1 to about 15 hours at a temperature of from about 75 *F to about 410 "F at a pressure of from about 0 to about 6 atmospheres ; d. distilling off any unreacted amine at a distillation temperature below about 400 "F; and, e. treating said second reaction mass to recover polyolefinic amine products.
30. The composition of claim 29 wherein the synthesis of the polyolefinic amine or polyether amine calls for the use of low temperature chlorination in the range of 110°C and below to selectively activate allylic hydrogen on a polyolefinic polymer to promote a nitrogen substitution reaction without significant chlorination of the polymer backbone.
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WO2003078553A3 (en) * 2002-03-12 2004-02-19 Lubrizol Corp Method of operating a direct injection spark-ignited engine with a fuel composition
KR100727363B1 (en) * 2000-05-05 2007-06-13 바스프 악티엔게젤샤프트 Fuel additive compositions for fuels for internal combustion engines with improved viscosity properties and good ivd performance

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