CA1121945A - Method for preparing a lactone reaction product - Google Patents
Method for preparing a lactone reaction productInfo
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- CA1121945A CA1121945A CA000265137A CA265137A CA1121945A CA 1121945 A CA1121945 A CA 1121945A CA 000265137 A CA000265137 A CA 000265137A CA 265137 A CA265137 A CA 265137A CA 1121945 A CA1121945 A CA 1121945A
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Abstract
ABSTRACT OF THE DISCLOSURE
Method for preparing a lactone reaction product comprising reacting an alkenylsuccinic acid under substantially anhydrous conditions in the presence of a protonating agent and at an elevated temperature ranging up to about 100°C., and a motor fuel composition containing said lactone reaction product.
Method for preparing a lactone reaction product comprising reacting an alkenylsuccinic acid under substantially anhydrous conditions in the presence of a protonating agent and at an elevated temperature ranging up to about 100°C., and a motor fuel composition containing said lactone reaction product.
Description
The use of certain lactones or lactone reaction products as rust and corrosion inhibitors in hydrocarbon oil compositions is known. Thus, such a material as tetrapropenylsuccinic acid lactone has exhibited effectiveness as a rust inhibitor in gasoline.
The alkenylsuccinic acid lactones have been prepared by reacting an alkenylsuccinic acid with a hydrating mineral acid, such as 50 percent sulfuric acid, dilute hydrochloric acid or dilute sulfuric or phosphoric acid. In general, the reaction has been conducted at an elevated temper-ature ranging up to about 212F. and in the presence of a nonpolar solvent, such as hydrocarbon i.e. naphtha, kerosene or the like. A feature of the known process is that the catalyst for the reaction has been employed in a hydrating environment, i.e. in an aqueous solution, such as 50 percent aqueous sulfuric acid or other dilute aqueous mineral acids.
The conventional method for preparing a lactone reaction product is relatively inefficient and produces a low yield of the desired product.
In particular, the conventional method gives a poor yield of a lactone reaction product in which the alkenyl radical on the alkenylsuccinic acid reactant is a high molecular weight radical having from about 300 to 3,000 average molecular weight.
United States 3,248,187 discloses a hydrocarbon oil composition which has been inhibited against rust by the addition thereto of a lactone reaction product. This reference discloses the process of reacting an alkenyl succinic acid in the presence of a dilute aqueous mineral acid and a hydrocarbon solvent at an elevated temperature to produce an alkenyl substituted lactone reaction product.
The method of the invention which is effective for preparing a relatively high molecular weight alkenyl substituted lactone reaction product comprises reacting an alkenylsuccinic acid in which the alkenyl radical has an average molecular weight ranging from about 300 to 3,000 in the presence of a protonating agent and under substantially anhydrous ~b ' ~,d'9 reaction conditions at an elevated temperature up to about 100 C. until a substantial proportion of the alkenylsuccinic acid has been converted to the lactone reaction product.
~ lus, the invention provides a method for preparing a high molecular weight alkenyl-substituted lactone reaction product which comprises admixing an alkenylsuccinic acid, said alkenyl radical having an average molecular weight ranging from about 300 to 3,000 with a protonating agent or electron pair acceptor in a concentration sufficient to provide from about 0.25 to 1.5 moles of protons or electron pair acceptors per mole of said alkenylsuccinic acid to form an essentially anhydrous mixture and reacting said mixture under essentially anhydrous reaction conditions at an elevated temperature up to about 100C. until infrared spectra at about 5.66 and 5.74 micro meters indicates the conversion of said alkenylsuccinic acid to said lactone reaction product.
The invention further provides a motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range containing a minor amountof the lactone reaction product prepared according to the method of the invention.
In carrying out the method of the invention, a high molecular weight alkenylsuccinic acid, in which the alkenyl radical has a molecular weight ranging from about 300 to 3,000, is advantageously admixed with an electron pair acceptor or a protonating agent to form a reaction mixture.
The protonating agent is generally a concentrated mineral acid and can be added next to the alkenylsuccinic acid-containing reaction mixture. The temperature of the reaction mixture is then raised up to about 100 C. to promote lactone formation while maintaining substantially anhydrous reaction conditions. The reaction is continued under these conditions for sufficient time to effect conversion of a substantial portion of the reactant to a laclone reaction product. It is convenient to follow the process of the reaction by withdrawing samples during the reaction and subjecting them ~o , 5, infrared radiation. The formation of alkenyl substituted 5 and 6 membered ring lactone reaction products is shown by infrared radiation at 5.66 and 5.74 micrometer regions. Thus, by utilizing the infrared analysis or correlated reaction times, it is possible to insure conversion of a major portion or substantially all of the alkenylsuccinic acid to a lactone reaction product.
The alkenylsuccinic acid reactant employed in this process is represented by the following formula:
R - CH - COOH
in which R represents an alkenyl radical having an average molecular weight ranging from about 300 to 3,000. A more preferred reactant is an alkenylsuccinic acid in which the alkenyl radical has an average molecular weight from about 700 to 2,000. The most preferred reactants are those al-kenylsuccinic acids in which the alkenyl radical has an average molecular weight ranging from about 800 to 1,200.
It will be understood that the prescribed alkenylsuccinic acid reactant can be prepared from the corresponding alkenylsuccinic anhydride.
Specifically, an alkenylsuccinic anhydride and water can be reacted in equimolar amounts to form the prescribed alkenylsuccinic acid reactant in accordance with known methods. Thus, the present invention contemplates that an alkenylsuccinic anhydride can be employed as a precursor to the reactant in this process by undergoing the hydrolysis reaction noted.
This process is also conveniently conducted by dissolving the prescribed alkenylsuccinic acid in an inert non-hydrating solvent such as a hydrocarbon solvent. A suitable solvent is a mineral oil having an SUS
viscosity at 100F. ranging from about 50 to about 1,000. Other suitable hydrocarbon solvents for this process include kerosene, benzene, ~ylene and the like.
The interesterification reaction or formation of a lactone , ~ , 11'~1945 reaction product in the present invention is conducted in the presence of an acid catalyst. The catalyst may be any protonating agent or electron pair acceptor i.e. any material which can provide a hydrogen ion or accept a pair of electrons to catalyze the reaction. The protonating agent or electron pair acceptor employed should provide from about 0.25 to 1.5 moles of protons or electron acceptors per mole of the alkenylsuccinic acid being reacted although smaller or larger amounts can be employed with compromises in efficiency and/or economy. It is preferred to employ a protonating agent or electron pair acceptor which provides from about 0.5 to 1 moles of proton or electron pair per mole of alkenylsuccinic acid. These ranges can be also expressed as 0.25 to 1.5 or 0.5 to 1 equivalents of acid per mole of the alkenylsuccinic acid moiety.
A variety of protonating agents or electron pair acceptors can be employed in the present process. Included among these are the mineral acids such as sulfuric acid and perchloric acid. Organic acids including p-toluene sulfonic acid hydrate, electron pair acceptors such as boron trifluoride etherate, and solid acid catalysts such as sulfonic acid ion exchange resins are suitable. There appears to be criticality in the catalyst since formic acid, oxalic acid and aqueous hydrochloric acid are either inoperative or have little effect on the process.
The reaction is normally conducted at a temperature ranging from about 25C. up to about 100C. with a range from about 60 to ~100 C. being especially suitable. A preferred temperature range for this process is from about /0 to 98C. Highly efficient conversions have been realized e~mploying a temperature in a preferred range, namely from about 85 to 95C.
A temperature of 100C. or above should be avoided because these temperatures tend to decrease conversion and lead to the production of undesirable reaction products.
A critical feature of the process of this invention for the production of a high molecular weight alkenyl substituted lactone reaction product is that it be conducted under substantially anhydrous conditions.
The reactant, solvent and the catalyst or the protonating agent must all be selected so as to insure substantially anhydrous and preferably essentially anhydrous reaction conditions. By substantially anhydrous reaction conditions is meant that the reaction mixture should contain no more than about 5 percent water. It is preferred that this mixture contain no more than about 2 percent water with the most preferred situation being an essentially anhydrous reaction mixture. The surprising improvement in yield of high molecular weight alkenyl substituted lactone reaction product is attributed to the use of the described substantially anhydrous reaction conditions.
The following example illustrates a known lactone process employing an unconventional high molecular weight polyisobutenylsuccinic acid:
EXAMPLE I
POLYISOBUTENYLSUCCINIC ANHYDRIDE REACTION
USING AQUEOUS MINERAL ACID
To a solution of 126 g. of a 50 wt.% oil solution of crude polyisobutenylsuccinic acid (prepared from polyisobutene of 1300 molecular weight and maleic anhydride by thermal alkenylation with about 50% unreacted polyisobutene) in 125 ml. of hexane, 100 g. of 50 wt.% sulfuric acid in water was added. The mixture contained about 0.025 moles of polyisobutenylsuccinic acid and about 0.5 moles of sulfuric acid or about 1.0 moles of available protons. After stirring one hour at about 25C. an aliquot is diluted with water, extracted with hexane, and the hexane extract separated. Infrared analysis of the residue obtained by evaporation of the hexane under nitrogen with mild heating shows lactone and anhydride formation to an incomplete degree. After four hours the temperature of the mixture was 29C. and an infrared analysis as above showed much less anhydride and lactone formation compared to the one-hour sample.
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The mixture was then heated to reflux. The mixture temperature was about 74C. Infrared analysis after 80 minutes of refluxing (method as above) indicated small amounts of lactone and anhydride were formed, but that the starting material, polyisobutenylsuccinic acid was predominately unchanged. After 17 hours and 20 minutes of refluxing, infrared analysis indicated relatively little change in reaction mixture composition as compared to the 80-minute reaction mixture composition.
The mixture was cooled to room temperature and washed with water and co-solvents until the wash water was about a pH of 5. The organic phase was separated and flash evaporated. The residue was held at 95C. at about 20 mm Hg pressure for about 12 hours to remove solvent traces. By infrared analysis the final product appears to be largely polyisobutenyl succinic acid with a small amount of anhydride present and little if any lactones. The amount of lactones present cannot be greater than 15 mole % and are probably less than 5 mole %.
Upon repeating this ex~mple, no change was noted in the starting material by infrared analyscs at 15, 30 60 and 90 minutes in the initial phase (25C) described above and this work was discontinued.
The following examples illustrate the novel process of this invention:
EXAMPLE II
A mixture of 126 g. (0.025 mole) of crude polyisobutenylsuccinic acid (containing about 50% unreacted polyisobutene of about 1300 average mole-cular weight) in a 50 wt.% mineral oil solution and 1.25 g. (0.0125 mole) of sulfuric acid is mixed at 90C~ for three hours. The infrared spectrum of the product indicates high conversion to five and six membered lactones.
The yield of lactones is greater than 85 mole %.
EXAMPLE III
A mixture of 2,570 g. (1.0 mole) of crude polyisobutenyl succinic anhydride (containing about 50% unreacted polyisobutene of about 1300 ~,, ~
9 ~5 average molecular weight) and 25 g. (0.25 mole) of about 96% aqueous sulfuric acid and 18 g. (1.0 mole) of water were heated and stirred at 90C.
for about one hour and then allowed to cool to room temperature. The mineral acidity can be removed by extraction but the product can be used without further purification. Infrared analysis indicates high conversion to lactones as in Example II.
EXAMPLE IV
A mixture of 1058 g. (0.5 mole) of crude polypropenylsuccinic anhydride (containing about 50% unreacted polypropene of about 850 average molecular weight) were heated to about 90C. with stirring. Over a period of about four minutes, 21.5 g. of a solution consisting of 12.5 g. of about 96% sulfuric acid and 9.0 g. (0.5 mole) of water were added dropwise. After four hours the mixture was allowed to cool. This product has similar strong lactone absorptions in its infrared spectrum to Example I and gave the following analysis.
ASTM D-94 Saponification Number 94.5 ASTM D-974 Total Acid Neut. Number 55.0 Iodine Number 7.8 Average Molecular Weight (by vapor pressure osmometry) 955 EXAMPLE V
A mixture of 270 g. (1.0 mole) of tetrapropenylsuccinic anhydride, 18.0 g. (1.0 mole) of water, and 51.5 g. (0.5 mole) of about 96% sulfuric acid and 100 ml. of xylene were heated to reflux at atmospheric pressure for two hours and allowed to coo~. The product was mixed with ethyl ether and hexane and the organic phase extensively washed with water until the pH
of the aqueous extract was repeatably between 4 and 5. The organic raffinate was filtered through diatomaceous earth, flash evaporated, and stripped of traces of solvent in a vacuum oven to obtain 260.1 g. of product. The infrared spectrum of the product indicated high conversion to ~ ,~
9~S
five and six membered lactones by strong absorptions at 5.66 and 5.74 micrometers.
EXAMPI,E_VI
A mixture of 377.5 g. (0.05 mole) of crude polyisobutenylsuccinic anhydride (containing about 31% unreacted polyisobutene of about 400 average molecular weight) 12.5 g. (0.125 mole) of about 96% sulfuric acid, and 9.0 g. (0.5 mole) of water were heated to about 90C. with stirring for one hour and allowed to cool. The product was washed free of mineral acidity by extraction and weighed 360.9 g. after handling-solvent evaporation. The product exhibited the same strong lactone absorptions in its infrared spectrum as the product of Example II.
Examples II through VI illustrate the effectiveness of the novel process of this invention for providing a substantial yield of high molecular weight alkenyl substituted lactone reacticn products in contrast to prior methods. The lactone reaction products of this process are particularly effective as dispersants in motor fuel compositions.
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The alkenylsuccinic acid lactones have been prepared by reacting an alkenylsuccinic acid with a hydrating mineral acid, such as 50 percent sulfuric acid, dilute hydrochloric acid or dilute sulfuric or phosphoric acid. In general, the reaction has been conducted at an elevated temper-ature ranging up to about 212F. and in the presence of a nonpolar solvent, such as hydrocarbon i.e. naphtha, kerosene or the like. A feature of the known process is that the catalyst for the reaction has been employed in a hydrating environment, i.e. in an aqueous solution, such as 50 percent aqueous sulfuric acid or other dilute aqueous mineral acids.
The conventional method for preparing a lactone reaction product is relatively inefficient and produces a low yield of the desired product.
In particular, the conventional method gives a poor yield of a lactone reaction product in which the alkenyl radical on the alkenylsuccinic acid reactant is a high molecular weight radical having from about 300 to 3,000 average molecular weight.
United States 3,248,187 discloses a hydrocarbon oil composition which has been inhibited against rust by the addition thereto of a lactone reaction product. This reference discloses the process of reacting an alkenyl succinic acid in the presence of a dilute aqueous mineral acid and a hydrocarbon solvent at an elevated temperature to produce an alkenyl substituted lactone reaction product.
The method of the invention which is effective for preparing a relatively high molecular weight alkenyl substituted lactone reaction product comprises reacting an alkenylsuccinic acid in which the alkenyl radical has an average molecular weight ranging from about 300 to 3,000 in the presence of a protonating agent and under substantially anhydrous ~b ' ~,d'9 reaction conditions at an elevated temperature up to about 100 C. until a substantial proportion of the alkenylsuccinic acid has been converted to the lactone reaction product.
~ lus, the invention provides a method for preparing a high molecular weight alkenyl-substituted lactone reaction product which comprises admixing an alkenylsuccinic acid, said alkenyl radical having an average molecular weight ranging from about 300 to 3,000 with a protonating agent or electron pair acceptor in a concentration sufficient to provide from about 0.25 to 1.5 moles of protons or electron pair acceptors per mole of said alkenylsuccinic acid to form an essentially anhydrous mixture and reacting said mixture under essentially anhydrous reaction conditions at an elevated temperature up to about 100C. until infrared spectra at about 5.66 and 5.74 micro meters indicates the conversion of said alkenylsuccinic acid to said lactone reaction product.
The invention further provides a motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range containing a minor amountof the lactone reaction product prepared according to the method of the invention.
In carrying out the method of the invention, a high molecular weight alkenylsuccinic acid, in which the alkenyl radical has a molecular weight ranging from about 300 to 3,000, is advantageously admixed with an electron pair acceptor or a protonating agent to form a reaction mixture.
The protonating agent is generally a concentrated mineral acid and can be added next to the alkenylsuccinic acid-containing reaction mixture. The temperature of the reaction mixture is then raised up to about 100 C. to promote lactone formation while maintaining substantially anhydrous reaction conditions. The reaction is continued under these conditions for sufficient time to effect conversion of a substantial portion of the reactant to a laclone reaction product. It is convenient to follow the process of the reaction by withdrawing samples during the reaction and subjecting them ~o , 5, infrared radiation. The formation of alkenyl substituted 5 and 6 membered ring lactone reaction products is shown by infrared radiation at 5.66 and 5.74 micrometer regions. Thus, by utilizing the infrared analysis or correlated reaction times, it is possible to insure conversion of a major portion or substantially all of the alkenylsuccinic acid to a lactone reaction product.
The alkenylsuccinic acid reactant employed in this process is represented by the following formula:
R - CH - COOH
in which R represents an alkenyl radical having an average molecular weight ranging from about 300 to 3,000. A more preferred reactant is an alkenylsuccinic acid in which the alkenyl radical has an average molecular weight from about 700 to 2,000. The most preferred reactants are those al-kenylsuccinic acids in which the alkenyl radical has an average molecular weight ranging from about 800 to 1,200.
It will be understood that the prescribed alkenylsuccinic acid reactant can be prepared from the corresponding alkenylsuccinic anhydride.
Specifically, an alkenylsuccinic anhydride and water can be reacted in equimolar amounts to form the prescribed alkenylsuccinic acid reactant in accordance with known methods. Thus, the present invention contemplates that an alkenylsuccinic anhydride can be employed as a precursor to the reactant in this process by undergoing the hydrolysis reaction noted.
This process is also conveniently conducted by dissolving the prescribed alkenylsuccinic acid in an inert non-hydrating solvent such as a hydrocarbon solvent. A suitable solvent is a mineral oil having an SUS
viscosity at 100F. ranging from about 50 to about 1,000. Other suitable hydrocarbon solvents for this process include kerosene, benzene, ~ylene and the like.
The interesterification reaction or formation of a lactone , ~ , 11'~1945 reaction product in the present invention is conducted in the presence of an acid catalyst. The catalyst may be any protonating agent or electron pair acceptor i.e. any material which can provide a hydrogen ion or accept a pair of electrons to catalyze the reaction. The protonating agent or electron pair acceptor employed should provide from about 0.25 to 1.5 moles of protons or electron acceptors per mole of the alkenylsuccinic acid being reacted although smaller or larger amounts can be employed with compromises in efficiency and/or economy. It is preferred to employ a protonating agent or electron pair acceptor which provides from about 0.5 to 1 moles of proton or electron pair per mole of alkenylsuccinic acid. These ranges can be also expressed as 0.25 to 1.5 or 0.5 to 1 equivalents of acid per mole of the alkenylsuccinic acid moiety.
A variety of protonating agents or electron pair acceptors can be employed in the present process. Included among these are the mineral acids such as sulfuric acid and perchloric acid. Organic acids including p-toluene sulfonic acid hydrate, electron pair acceptors such as boron trifluoride etherate, and solid acid catalysts such as sulfonic acid ion exchange resins are suitable. There appears to be criticality in the catalyst since formic acid, oxalic acid and aqueous hydrochloric acid are either inoperative or have little effect on the process.
The reaction is normally conducted at a temperature ranging from about 25C. up to about 100C. with a range from about 60 to ~100 C. being especially suitable. A preferred temperature range for this process is from about /0 to 98C. Highly efficient conversions have been realized e~mploying a temperature in a preferred range, namely from about 85 to 95C.
A temperature of 100C. or above should be avoided because these temperatures tend to decrease conversion and lead to the production of undesirable reaction products.
A critical feature of the process of this invention for the production of a high molecular weight alkenyl substituted lactone reaction product is that it be conducted under substantially anhydrous conditions.
The reactant, solvent and the catalyst or the protonating agent must all be selected so as to insure substantially anhydrous and preferably essentially anhydrous reaction conditions. By substantially anhydrous reaction conditions is meant that the reaction mixture should contain no more than about 5 percent water. It is preferred that this mixture contain no more than about 2 percent water with the most preferred situation being an essentially anhydrous reaction mixture. The surprising improvement in yield of high molecular weight alkenyl substituted lactone reaction product is attributed to the use of the described substantially anhydrous reaction conditions.
The following example illustrates a known lactone process employing an unconventional high molecular weight polyisobutenylsuccinic acid:
EXAMPLE I
POLYISOBUTENYLSUCCINIC ANHYDRIDE REACTION
USING AQUEOUS MINERAL ACID
To a solution of 126 g. of a 50 wt.% oil solution of crude polyisobutenylsuccinic acid (prepared from polyisobutene of 1300 molecular weight and maleic anhydride by thermal alkenylation with about 50% unreacted polyisobutene) in 125 ml. of hexane, 100 g. of 50 wt.% sulfuric acid in water was added. The mixture contained about 0.025 moles of polyisobutenylsuccinic acid and about 0.5 moles of sulfuric acid or about 1.0 moles of available protons. After stirring one hour at about 25C. an aliquot is diluted with water, extracted with hexane, and the hexane extract separated. Infrared analysis of the residue obtained by evaporation of the hexane under nitrogen with mild heating shows lactone and anhydride formation to an incomplete degree. After four hours the temperature of the mixture was 29C. and an infrared analysis as above showed much less anhydride and lactone formation compared to the one-hour sample.
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The mixture was then heated to reflux. The mixture temperature was about 74C. Infrared analysis after 80 minutes of refluxing (method as above) indicated small amounts of lactone and anhydride were formed, but that the starting material, polyisobutenylsuccinic acid was predominately unchanged. After 17 hours and 20 minutes of refluxing, infrared analysis indicated relatively little change in reaction mixture composition as compared to the 80-minute reaction mixture composition.
The mixture was cooled to room temperature and washed with water and co-solvents until the wash water was about a pH of 5. The organic phase was separated and flash evaporated. The residue was held at 95C. at about 20 mm Hg pressure for about 12 hours to remove solvent traces. By infrared analysis the final product appears to be largely polyisobutenyl succinic acid with a small amount of anhydride present and little if any lactones. The amount of lactones present cannot be greater than 15 mole % and are probably less than 5 mole %.
Upon repeating this ex~mple, no change was noted in the starting material by infrared analyscs at 15, 30 60 and 90 minutes in the initial phase (25C) described above and this work was discontinued.
The following examples illustrate the novel process of this invention:
EXAMPLE II
A mixture of 126 g. (0.025 mole) of crude polyisobutenylsuccinic acid (containing about 50% unreacted polyisobutene of about 1300 average mole-cular weight) in a 50 wt.% mineral oil solution and 1.25 g. (0.0125 mole) of sulfuric acid is mixed at 90C~ for three hours. The infrared spectrum of the product indicates high conversion to five and six membered lactones.
The yield of lactones is greater than 85 mole %.
EXAMPLE III
A mixture of 2,570 g. (1.0 mole) of crude polyisobutenyl succinic anhydride (containing about 50% unreacted polyisobutene of about 1300 ~,, ~
9 ~5 average molecular weight) and 25 g. (0.25 mole) of about 96% aqueous sulfuric acid and 18 g. (1.0 mole) of water were heated and stirred at 90C.
for about one hour and then allowed to cool to room temperature. The mineral acidity can be removed by extraction but the product can be used without further purification. Infrared analysis indicates high conversion to lactones as in Example II.
EXAMPLE IV
A mixture of 1058 g. (0.5 mole) of crude polypropenylsuccinic anhydride (containing about 50% unreacted polypropene of about 850 average molecular weight) were heated to about 90C. with stirring. Over a period of about four minutes, 21.5 g. of a solution consisting of 12.5 g. of about 96% sulfuric acid and 9.0 g. (0.5 mole) of water were added dropwise. After four hours the mixture was allowed to cool. This product has similar strong lactone absorptions in its infrared spectrum to Example I and gave the following analysis.
ASTM D-94 Saponification Number 94.5 ASTM D-974 Total Acid Neut. Number 55.0 Iodine Number 7.8 Average Molecular Weight (by vapor pressure osmometry) 955 EXAMPLE V
A mixture of 270 g. (1.0 mole) of tetrapropenylsuccinic anhydride, 18.0 g. (1.0 mole) of water, and 51.5 g. (0.5 mole) of about 96% sulfuric acid and 100 ml. of xylene were heated to reflux at atmospheric pressure for two hours and allowed to coo~. The product was mixed with ethyl ether and hexane and the organic phase extensively washed with water until the pH
of the aqueous extract was repeatably between 4 and 5. The organic raffinate was filtered through diatomaceous earth, flash evaporated, and stripped of traces of solvent in a vacuum oven to obtain 260.1 g. of product. The infrared spectrum of the product indicated high conversion to ~ ,~
9~S
five and six membered lactones by strong absorptions at 5.66 and 5.74 micrometers.
EXAMPI,E_VI
A mixture of 377.5 g. (0.05 mole) of crude polyisobutenylsuccinic anhydride (containing about 31% unreacted polyisobutene of about 400 average molecular weight) 12.5 g. (0.125 mole) of about 96% sulfuric acid, and 9.0 g. (0.5 mole) of water were heated to about 90C. with stirring for one hour and allowed to cool. The product was washed free of mineral acidity by extraction and weighed 360.9 g. after handling-solvent evaporation. The product exhibited the same strong lactone absorptions in its infrared spectrum as the product of Example II.
Examples II through VI illustrate the effectiveness of the novel process of this invention for providing a substantial yield of high molecular weight alkenyl substituted lactone reacticn products in contrast to prior methods. The lactone reaction products of this process are particularly effective as dispersants in motor fuel compositions.
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Claims (36)
1. A method for preparing a high molecular weight alkenyl-substituted lactone reaction product which comprises admixing an alkenylsuccinic acid, said alkenyl radical hav-ing an average molecular weight ranging from about 300 to 3,000, with a protonating agent or electron pair acceptor in a concentration sufficient to provide from about 0.25 to 1.5 moles of protons or electron pair acceptors per mole of said alkenylsuccinic acid to form an essentially anhydrous mix-ture and reacting said mixture under essentially anhydrous reaction conditions at an elevated temperature up to about 100°C. until infrared spectra at about 5.66 and 5.74 micro-meters indicates the conversion of said alkenylsuccinic acid to said lactone reaction product.
2. A method according to Claim 1 in which the concentration of said protonating agent or electron pair acceptors is sufficient to provide from about 0.5 to 1 moles of proton or electron pair acceptor per mole of said alkenyl-succinic acid.
3. A method according to Claim 1 in which the average molecular weight of said alkenyl radical ranges from about 700 to 2,000.
4. A method according to Claim 1 in which the average molecular weight of said alkenyl radical ranges from about 800 to 1200.
5. A method according to Claim 1 in which said protonating agent is a concentrated mineral acid.
6. A method according to Claim 1 in which said protonating agent is concentrated sulfuric acid.
7. A method according to Claim 6 in which said protonating agent is 96 percent sulfuric acid.
8. A method according to Claim 1 in which said reaction is conducted at a temperature ranging from about 60 to 100°C.
9. A method according to Claim 1 in which said reaction is conducted at a temperature ranging from about 90 to 99°C.
10. A method according to Claim 1 in which equi-molar amounts of an alkenyl succinic anhydride and water are reacted to form said alkenylsuccinic acid.
11. A method according to Claim 1 in which said reaction mixture is dissolved in an inert hydrocarbon sol-vent.
12. A method according to Claim 11 in which said solvent is a mineral oil.
13. A method according to Claim 1 in which infra-red radiation absorption characteristics of lactone at about 5.66 and 5.74 micrometers indicates the conversion of at least 50 percent of said alkenylsuccinic acid to said lac-tone reaction product.
14. A method according to Claim 1 in which said reaction mixture contains less than about 2 percent water.
15. A method according to Claim 1 in which said alkenyl radical has an average molecular weight ranging from about 1,000 to 3,000.
16. A method according to Claim 13 in which the yield of lactones from said alkenylsuccinic acid is greater than 85 mole percent.
17. A high molecular weight alkenyl-substituted lactone reaction product prepared by the steps comprising admixing an alkenylsuccinic acid, said alkenyl radical hav-ing an average molecular weight ranging from about 300 to 3,000, with a protonating agent or electron pair acceptor selected from the group consisting of sulfuric acid, per-chloric acid, p-toluene sulfonic acid, boron trifluoride etherate and sulfonic acid ion exchange resins in a concen-tration sufficient to provide from about 0.25 to 1.5 moles of protons or electron pair acceptor per mole of said alkenyl-succinic acid to form an essentially anhydrous reaction mix-ture and reacting said mixture under essentially anhydrous reaction conditions at an elevated temperature up to about 100°C. until infrared spectra at about 5.66 and 5.74 micro-meters indicates the conversion of said alkenyl-succinic acid to said lactone reaction product.
18. A reaction product according to Claim 17 in which the concentration of said protonating agent or elec-tron pair acceptors is sufficient to provide from about 0.5 to 1 moles of protons or electron pair acceptors per mole of said alkenyl-succinic acid.
19. A reaction product according to Claim 17 in which the average molecular weight of said alkenyl radical ranges from about 700 to 2,000.
20. A reaction product according to Claim 17 in which the average molecular weight of said alkenyl radical ranges from about 800 to 1200.
21. A reaction product according to Claim 17 in which said protonating agent is concentrated sulfuric acid.
22. A reaction product according to Claim 21 in which said protonating agent is about 96 percent sulfuric acid.
23. A reaction product according to Claim 17 in which said reaction is conducted at a temperature ranging from about 60 to 100°C.
24. A reaction product according to Claim 17 in which said reaction is conducted at a temperature ranging from about 90 to 99°C.
25. A reaction product according to Claim 17 in which infrared radiation absorption characteristics of lac-tone at about 5.66 and 5.74 micrometers indicates the con-version of at least 50 percent of said alkenylsuccinic acid to said lactone reaction product.
26. A motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range containing from about 0.003 to 0.5 volume percent of a high molecular weight alkenyl-substituted lactone reaction product prepared by the steps comprising admixing an alkenylsuccinic acid, said alkenyl radical having an average molecular weight ranging from about 300 to 3,000, with a protonating agent or electron pair acceptor selected from the group consisting of sulfuric acid, perchloric acid, p-toluene sulfonic acid, boron trifluoride etherate and sulfonic acid ion exchange resins in a concentration sufficient to provide from about 0.25 to 1.50 moles of protons or electron pair acceptor per mole of said alkenylsuccinic acid to form an essentially anhydrous reaction mixture and reacting said mixture under essentially anhydrous reaction conditions at an elevated temperature up to about 100°C. until infrared spectra at about 5.66 and 5.74 micrometers indicates the conversion of said alkenylsuccinic acid to said lactone reaction product.
27. A motor fuel composition according to Claim 26 in which the concentration of said protonating agent or electron pair acceptors is sufficient to provide from about 0.5 to 1 moles of protons or electron pair acceptors per mole of said alkenyl succinic acid.
28. A motor fuel composition according to Claim 26 in which the average molecular weight of said alkenyl radical ranges from about 700 to 2,000.
29. A motor fuel composition according to Claim 25 in which the average molecular weight of said alkenyl radical ranges from about 700 to 1200.
30. A motor fuel composition according to Claim 26 in which said protonating agent is concetrated sulfuric acid.
31. A motor fuel composition according to Claim 30 in which said protonating agent is 96 percent sulfuric acid.
32. A motor fuel composition according to Claim 26 in which said reaction product is prepared at a tempera-ture ranging from about 60 to 100°C.
33. A motor fuel composition according to Claim 26 in which said reaction product is prepared at a tempera-ture ranging from about 90 to 99°C.
34. A motor fuel composition according to Claim 26 in which the infrared radiation absorption characteris-tics of said reaction product at about 5.66 and 5.74 micro meters indicates the conversion of at least 50 percent of said alkenylsuccinic acid to said lactone reaction product.
35. A motor fuel composition according to Claim 26 containing from about 0.005 to 0.20 volume percent of said reaction product.
36. A motor fuel composition according to Claim 26 containing from about 0.01 to 0.10 volume percent of said reaction product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000265137A CA1121945A (en) | 1976-11-08 | 1976-11-08 | Method for preparing a lactone reaction product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000265137A CA1121945A (en) | 1976-11-08 | 1976-11-08 | Method for preparing a lactone reaction product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121945A true CA1121945A (en) | 1982-04-13 |
Family
ID=4107224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000265137A Expired CA1121945A (en) | 1976-11-08 | 1976-11-08 | Method for preparing a lactone reaction product |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1121945A (en) |
-
1976
- 1976-11-08 CA CA000265137A patent/CA1121945A/en not_active Expired
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