FUEL ADDITIVE COMPOUNDS AND PROCESS FOR PRODUCING THE SAME.

专利摘要:
The present application relates to detergent base products and methods for forming the detergent base products. One embodiment of the process comprises forming a bis-Mannich-type intermediate by reacting (i) at least one hydroxyl-substituted aromatic ring compound having, on the ring, an aliphatic hydrocarbyl substituent from a polyolefin of average molecular weight in nobre in a range from about 500 to about 3000; (ii) at least one primary amine; and (iii) at least one aldehyde. The resulting bis-Mannich intermediate compound is then reacted with at least a second amine compound selected from primary and secondary amines to form the detergent base product.
公开号:BE1018138A5
申请号:E2007/0201
申请日:2007-04-26
公开日:2010-06-01
发明作者:Dennis J Malfer；Abbas Kadkhodayan；May Thomas
申请人:Afton Chemical Corp；
IPC主号:

专利说明:

Fuel additive compounds and method of making such compounds
Disclosure Description Domain of Disclosure
The present application relates to a novel process for the manufacture of detergents and fuel compositions comprising detergents.
Background of the disclosure
For several years, considerable work has been devoted to additives to combat (prevent or reduce) the formation of deposits in fuel injection systems of spark-ignition internal combustion engines. In particular, the additives that can effectively fight against deposits in fuel injectors, deposits in the intake valves and against deposits in the combustion chamber, represent the focal point of considerable research activities in the field, but, in spite of these efforts, further improvements are desired.
Conventional Per Port Fuel Injection (IFP) engines form a homogenous pre-mix of gasoline and air by injecting gasoline into the intake port. Direct injection gasoline (DIG) engines operate by direct injection of gasoline into the combustion chamber, similar to a diesel engine, so that it becomes possible to form a stratified fuel mixture. , which contains a greater amount of fuel than the stoichiometric amount near the spark plug, but a very lean amount throughout the combustion chamber.
The main areas that are subject to the problem of fuel-related deposits for PFI and DIG engines are the injectors, the intake valves and the combustion chamber. Mannich base type fuel additives in the petroleum industry are well known for solving these deposition problems. However, while these Mannich base additives are traditionally excellent in the control of intake valve deposits, they can not combat deposits to a desired degree for PFI and / or DIG type engine injectors. There is a need in the petroleum industry to produce fuel additives that are suitable for use in PFI and / or DIG engines, which can more effectively combat engine deposits, and to develop processes for the production of fuel additives. these fuel additives.
Summary of Disclosure
According to the disclosure, an embodiment of the present application relates to a method of forming a detergent base product. The process comprises forming a bis-Mannich-type intermediate by reacting together (i) at least one hydroxyl-substituted aromatic ring compound having, on the ring, an aliphatic hydrocarbyl substituent derived from a polyolefin of a number average molecular weight in the range of about 500 to about 3000, (ii) at least one primary amine and (iii) at least one aldehyde. The bis-Mannich intermediate compound is then reacted with at least a second amine compound selected from primary and secondary amines to form the detergent base product.
Another embodiment of the present application relates to a method of forming a product of a Mannich reaction. The process comprises reacting at least one amine compound, selected from primary and secondary amines, with a bis-Mannich compound of formula III:
wherein R 1 is selected from hydrogen and C 1-6 alkyl; R3 represents a hydroxyaromatic compound having, on the ring, an aliphatic hydrocarbyl substituent from a polyolefin of number average molecular weight in the range of about 500 to about 3000, and R4 represents a linear, branched or cyclic substituted alkylamine group or unsubstituted, saturated or unsaturated.
Another embodiment of the present application relates to a fuel composition comprising a base fuel and a detergent base product comprising a mixture of compounds of formulas (VI) and (VII):
wherein R 1 and R 3 are substituents independently selected from hydrogen, C 1-6 alkyls and hydrocarbyl substituents having a number average molecular weight in the range of about 500 to about 3000, provided that at least one of one of the radicals R 1 and R 3 is a hydrocarbyl substituent; R4 represents a substituent selected from alkyl, aryl, alkenyl, alkylamino, dialkylamino, alkylaminoalkyl and dialkylaminoalkyl groups; R5 and R6 are independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkaryl and aralkyl, provided that at least one of R5 and R6 is not hydrogen.
Other purposes and advantages of the disclosure will be partly set forth in the following description, and may be learned by practicing this disclosure. The objects and advantages of the description will be attained and achieved by means of the elements and combinations reported, particularly in the appended claims.
It will be appreciated that both the foregoing general description and the following detailed description are provided by way of example and explanation only, and do not limit the disclosure as claimed.
Description of the embodiments
The process of the present application involves the formation of a detergent base product using a bis-Mannich type intermediate. In the embodiments, the reaction mechanism may comprise a two-step process, wherein the bis-Mannich intermediate is formed in the first step, and then reacted with an amine in the second step to obtain a detergent base product. The reactions of the first and second steps will now be described.
Formation of bis-Mannich intermediate compound
In the embodiments of the present application, bis-Mannich-type intermediates can be formed by reacting (i) at least one hydroxyl-substituted aromatic ring compound having, on the ring, an aliphatic hydrocarbyl substituent derived from a polyolefin of number average molecular weight in the range of about 500 to about 3000, (ii) at least one primary amine and (iii) at least one aldehyde. Any hydroxyl-substituted aromatic ring compound which is readily reactive in a Mannich condensation reaction can be used. Hydroxyl substituted aromatic ring compounds used in the formation of bis-Mannich type intermediates of the present application are represented by the following Formula I:
wherein R 1, R 2 and R 3 can be each independently selected from hydrogen, C 1-6 alkyl, or hydrocarbyl substituent having a number average molecular weight in the range of about 500 to about 3000, provided that at least one of the radicals R1, R2 and R3 is a hydrocarbyl substituent. Representative C1-C6 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.
Representative hydrocarbyl substituents may include polypropylene moieties, polybutene moieties, polyisobutylene moieties, poly (alpha-olefin) moieties, such as poly-1-octene moieties, and ethylene / alpha-olefin copolymer moieties. Other similar long chain hydrocarbyl substituents may also be used. Examples that may be mentioned are copolymer groups having at least one monomer chosen from butylene, isobutylene and propylene, and at least one monomer chosen from copolymerizable mono-olefinic comonomers, such as ethylene and 1-pentene. , 1-hexene, i-octene, i-decene, etc., wherein the copolymer molecule contains at least 50% by weight of butylene and / or isobutylene and / or propylene units. Comonomers polymerized with propylene, such as butenes, may be aliphatic and may also contain non-aliphatic groups, for example, styrene, o-methylstyrene, p-methylstyrene, divinylbenzene and the like. The polymers and copolymers obtained used to form the compound of formula (I) are substantially aliphatic hydrocarbon polymers. In certain embodiments, the hydrocarbyl substituents may be substantially saturated and contain only residual unsaturation.
In one embodiment, the hydrocarbyl substituent is a polybutylene group. Unless otherwise indicated, the term "polybutylene" is used herein in the generic sense to include polymers obtained from "pure" or "substantially pure" 1-butene or isobutene and polymers obtained from mixtures of two or three of the monomers 1-butene, 2-butene and isobutene. The commercial grades of these polymers may also contain insignificant amounts of other olefins.
In some embodiments, high reactivity polyisobutenes, having relatively high proportions of polymer molecules with a terminal vinylidene moiety, can be used to form the hydrocarbyl substituent. In certain embodiments, at least 20% of all terminal olefinic double bonds of these high reactivity polyisobutenes may comprise an alkyl vinylidene isomer. For example, at least 50% and, in other examples, at least 70% of all terminal olefinic double bonds may include an alkylvinylidene isomer. Suitable high reactivity polyisobutenes are disclosed, for example, in U.S. Patent No. 4,152,499 and West German Published Application 29,04,314, the disclosures of which are hereby incorporated by reference in their entirety. In other embodiments, copolymers of ethylene and alpha-olefin having a number average molecular weight of 500 to 3000, wherein at least about 30% of the polymer chains contain terminal unsaturation can be used. of ethylidene type, to form the hydrocarbyl substituent.
In one embodiment, the compound of formula (I) can be obtained by alkylating o-cresol with the high molecular weight hydrocarbyl polymers described above. For example, an o-cresol, such as ortho-methylphenol, can be reacted with polyisobutylene (PIS) to obtain an ortho-methylphenol substituted with a PIS group in the para position. Suitable methods for alkylating the hydroxy aromatic compounds of the present disclosure are well known in the art. Examples of some suitable methods well known for forming hydroxyl-substituted aromatic ring compounds are taught in GS No. 1,159,368 and US Pat. Nos. 4,238,628; Nos. 5,300,701, 5,876,468 and 6,800,103, all of which are incorporated by reference herein in their entirety.
In one embodiment, the radical R 1 of the hydroxy substituted aromatic ring compound of formula I may be C 1-4 alkyl, R 2 may be hydrogen and R 3 may be hydrocarbyl substituted, selected from hydrocarbyl substituents described above. For example, R 1 may be methyl, R 2 may be a hydrogen radical and R 3 may be a polyisobutylene group. In other embodiments, R 1 and R 2 are both hydrogen radicals and R 3 is a hydrocarbyl substituent selected from the hydrocarbyl substituents described above.
The amines that can be used in the first step of the reaction include any primary amine suitable for use in Mannich reactions to form the bis-Mannich intermediate compound. In embodiments, the primary amine can meet the following formula (II);
II
wherein R4 may be any substituent selected from alkyl, aryl, alkenyl, alkylamine, dialkylamine, alkylaminoalkyl and diakylaminoalkyl.
Representative examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine and dipentylamine. Representative examples of suitable primary amines include cyclohexane-amine, 1,3-propanediamine; 1,2-ethanediamine, 1,4-butanediamine; 1,6-hexanediamine; 1,2-cyclohexanediamine; 1,2-diamino-3-methylcyclohexane; 1,2-diamino-4-methylcyclohexane; N-aminomethyl-1,1-methanediamine and 3,3-dimethylamino-propylamine.
In some embodiments, the amine of formula (II) may be a hydrocarbon chain substituted at one end by a primary amino group and substituted at the other end by a primary, secondary or tertiary amino group. For example, the radical R 4 of the compound of formula (II) may be -C 1 -6 NR 'R ", wherein the C 1-6 portion of the substituent is a straight-chain or branched alkyl and R' and R" may be independently selected from H, methyl, ethyl, propyl and butyl substituents. Examples of such compounds include dialkylaminoalkylamine3, such as dimethylaminopropylamine, diethylaminopropylamine and dimethylaminobutylamine.
Any aldehyde suitable for a Mannich reaction can be used to prepare the bis-Mannich type intermediate. Non-limiting examples of suitable aldehydes include aliphatic aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde and stearaldehyde. Aromatic aldehydes that can be employed include benzaldehyde and salicylaldehyde. Heterocyclic aldehydes that can be used herein are, by way of illustration, furfural and thiophene-aldehyde, etc. Also useful are formaldehyde-producing reagents, such as paraformaldehyde. In one embodiment, the aldehyde selected is formaldehyde.
Any suitable proportion of reactants can be used, which will result in the formation of the bis-Mannich intermediate. In one embodiment, the reactants can be mixed in the following ratio: about 1 mole of hydroxyl-substituted aromatic ring compound; about 0.3 to about 0.7 moles of primary amine; and about 0.8 to about 1.5 moles of aldehyde. For example, the reactants can be mixed in the following ratio: about 1 mole of hydroxyl-substituted aromatic ring compound, about 0.5 mole of primary amine and about 1 mole of aldehyde.
The condensation reaction between the hydroxyl-substituted aromatic ring compounds, the primary amines and the aldehydes is carried out at a temperature in the range of 40 ° C to about 200 ° C. The reaction can be carried out with or without a diluent or solvent. Examples of suitable solvents include aromatic solvents, such as xylenes, toluene, mesitylene, Aromatic 100 and heptane or mixtures thereof. There is a release of water during the reaction, which can be removed by azeotropic distillation during the reaction. Typical reaction times are in the range of 2 to 4 hours, although longer or shorter times may be used if necessary.
The bis-Mannich type intermediate obtained is a compound of formula (III):
III
wherein R1, R3 and R4 are as defined above. As can be seen from formula (III), the bis-Mannich type intermediate comprises two hydroxyl-substituted aromatic ring groups, formed from the above-mentioned reactive compounds of formula (I), which are joined by bridging with a tertiary amine group. The bis-Mannich type intermediate can be used to form the desired detergent base products in a second reaction step, which will be described hereinafter.
Formation of a detergent base from a bis-Mannich type intermediate
In the second step of the reaction process, the bis-Mannich intermediate of formula (III) can be reacted with a primary or secondary amine to form a desired detergent base product. The primary or secondary amine may be an amine of
formula (IV):
IV
wherein R5 and R6 are each independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkaryl and aralkyl, provided that at least one of R5 and R6 is not a hydrogen radical; . The alkyl, cycloalkyl, aryl, alkaryl and aralkyl groups may be unsubstituted or substituted by suitable functional groups, such as carbonyl groups, hydroxyl groups and amino groups. The alkyl, cycloalkyl, aryl, alkaryl and aralkyl groups may have, for example, 1 to 30 carbon atoms, especially 1 to 18 carbon atoms or, in other examples, 1 to 6 carbon atoms.
In some embodiments, R6 is selected to represent a hydrogen radical and R5 is an alkyl group substituted with a primary amine. The amine obtained is a diamine of formula (V):
V
wherein R7 is a linear, branched or cyclic alkyl group having from 1 to 10 carbon atoms. For example, R7 may represent a straight saturated hydrocarbon chain having 1 to 6 carbon atoms. In another embodiment, R7 may be a substituted or unsubstituted cycloalkane having 4 to 8 carbon atoms as ring members, which may optionally be substituted by one or more methyl, ethyl or propyl groups.
Representative examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine and dipentylamine. Representative examples of suitable primary amines include cyclohexane-amine, 1,3-propanediamine; 1,2-ethanediamine; 1,4-butanediamine; 1,6-hexanediamine; 1,2-cyclohexanediamine; 1,2-diamino-3-methylcyclohexane; 1,2-diamino-4-methylcyclohexane; N-aminomethyl-1,1-methanediamine and 3,3-dimethylamino-propylamine.
The bis-Mannich intermediate of formula (III) is reacted with the primary or secondary amines of formula (IV). Any suitable proportion of reagents can be used which will allow the formation of the desired end products. In one embodiment, the reactants can be mixed in a ratio of about 1 mole of primary or secondary amine for each mole of bis-Mannich type intermediate.
The reaction can be carried out in the temperature range of about 125 ° C to about 200 ° C, for example, at about 150 ° C. Typical reaction times are in the range of 2 to 4 hours, although longer or shorter times may be used if necessary. Solvents from the first stage of the reaction may be present during the second stage of the reaction and / or additional appropriate solvents may be added in the second stage, if necessary.
The second stage of the reaction gives the products of formulas (VI) and (VII) below:
wherein R1, R3, R4, R5 and R6 are defined as indicated above. As can be seen from formulas (VI) and (VII), the reaction cleaves the bis-Mannich intermediate of formula (III) to give two hydroxyl-substituted aromatic ring compounds which are substituted, each, by an amine group, in addition to the substituents R1, R3 and hydroxyl. The compound of formula (VI) is substituted by an amine group formed from the primary amine reagent of the first stage of the reaction, while the compound of formula (VII) is substituted by an amine group formed from the reactant of primary or secondary amine of the second stage of the reaction.
In one embodiment in which a primary amine of formula (V) is used as amine in the second step, the products of the reaction comprise an amine-substituted compound of formula (IV), as indicated above. But in this embodiment, the product also comprises a primary amine substituent on one of the hydroxyl-substituted aromatic ring compounds, as set forth below in formula (VIII):
wherein R1, R3, R4 and R7 are defined as indicated above. The ratio of the compound of formula VI to the compound of formula VIII in the product mixture may vary depending on certain parameters, such as the reaction conditions and / or reagents used. For example, the ratio of the compound of formula VI to the compound of formula VIII may vary from about 1: 4 to about 4: 1. In some embodiments, the ratio may be about 1: 1.
The amine substituted products of the present application can be used as a detergent base in fuel compositions. In some embodiments, the detergent base can be used in fuel additive concentrates, which can be packaged and sold to consumers in a form separate from the base fuel. The additive concentrates of the present invention may contain, for example, from about 12 to about 69% by weight and, more preferably, from about 22 to about 50% by weight of the detergent on an active ingredient basis. The additive concentrates may also contain a carrier fluid, the level of which is determined by the desired carrier / detergent base ratio.
The carrier fluid may be of various types, for example, liquid poly-α-olefin oligomers, liquid polyalkene hydrocarbons (e.g., polypropene, polybutene, polyisobutene or the like), hydrotreated polyalkene hydrocarbons (eg for example, hydrotreated polypropene, hydrotreated polybutene, hydrotreated polyisobutene or the like) mineral oils, hydrotreated mineral oils, liquid poly (oxyalkylene) compounds, liquid alcohols or polyols, liquid esters and liquid carriers or similar solvents. Mixtures of two or even more carriers or solvents can be used.
When formulating fuel compositions according to the present application, the detergent base and the carrier fluid (with or without additive) are used in amounts sufficient to reduce or inhibit the formation of deposits in an internal combustion engine. . As a result, the fuels may contain minor amounts of the detergent base and the liquid carrier fluid, in the proportions indicated above, which combat the formation of deposits in the engine or reduce it, such as deposits in a valve intake or in an injector.
In some embodiments, the fuels of this description may contain, on an active ingredient basis, a quantity of Mannich base detergent in a range of about 2.27 kg (5 pounds) to about 136 kg (300 pounds). pounds) (kg per weight of additive per thousand barrels of fuel volume), for example, in the range of about 4.5 kg to 90 kg (10 to about 200 pounds). The active ingredient base excludes the weight (i) of unreacted components, such as product-associated polyalkylene compounds remaining in the product as it is produced and used, and (ii) diluents and solvents, if present, used during the manufacture of the detergent during its formation or after it, but before adding a support, in the case where a support is used.
Other optional additives, for example, one or more fuel-soluble antioxidants, demulsifying agents, antioxidants, such as phenols and hindered amines; rust inhibitors or corrosion inhibitors, metal deactivators; combustion modifiers, alcohol co-solvents, octane promoters, emission reducers, friction modifiers, lubricating additives, ancillary detergent / dispersant additives, labels, dyes and multifunctional additives (e.g., methylcyclopentadienyl manganese tricarbonyl compounds and / or other cyclopentadienyl manganese tricarbonyl compounds) can also be included in the fuels and additive concentrates. These components may be present in the composition in any desired concentration. For example, each component may be present in an amount at least sufficient to perform its function (s) in the finished fuel composition.
The base fuels used to formulate the fuels of the present application may be any of the basic fuels suitable for use in the operation of spark ignition internal combustion engines, such as kerosene or gasolines. lead-free engines for aircraft and car engines, and so-called reformulated gasolines, which often contain both hydrocarbons boiling in the range of boiling temperatures of gasolines and oxygenated mixture compounds soluble in fuel ("referred to as oxygenates"). Examples of suitable oxygenates that may be used include alcohols, such as methanol and ethanol, fuel-soluble ethers, such as methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether; and mixtures of these materials. When used, the oxygenates may be present in the base fuel in any desired amount. The choice of an effective amount of oxygenates is within the skill of the skilled person.
EXAMPLES
Example 1 - Preparation Process for the Intermediate
Exact amounts of starting materials were determined and calculated based on a 2: 1: 2 molar ratio of 2-methyl-4-polyisobutylphenol, dimethylaminopropylamine (DMAPA) and formaldehyde, respectively. The 2-methyl-4-polyisobutylphenol is introduced into a round-bottomed vessel, and about 75% of the total calculated amount of Aromatic 100 solvent, which is to be used in the process, is then added. The mixture is stirred under a blanket of nitrogen. Once the mixture is homogeneous, the calculated amount of DMAPA is added. The temperature of the mixture is about 40 to 45 ° C. Formaldehyde is added and the temperature of the mixture increases to a value of about 45 to 50 ° C. The mixture was heated and distilled under nitrogen using a Dean Stark trap system set at 150 ° C. During distillation, the temperature is maintained at 150 ° C over a period of about 2 to 2.5 hours. After distillation, sufficient Aromatic 100 solvent is added to the intermediate to bring the final conditioning composition to 25% solvent, taking into account the loss of water.
The procedure mentioned above makes it possible, in theory, to obtain the product BIS represented in the reaction below:
Example 2 - Process for the preparation of the final product
Using the intermediate BIS product of Example 1 as a starting material, 1,2-diaminocyclohexane (DACH) was added in the molar ratio of 1: 1, while stirring at room temperature under a blanket of nitrogen. The temperature is set at 90 ° C and held for 2 hours. The temperature is then set at 145 ° C, while increasing the nitrogen stream, and maintained as is for 2.5 hours. The process is theoretically translated by the following reaction:
Example 3
The gasoline fuel compositions using the final product of Example 2 are subjected to engine tests, during which the substantial effectiveness of these compositions in reducing the weight of the deposits formed in intake valves is demonstrated. The reaction products of Example 2, mentioned above, are compared with several other detergent compounds, in particular a first comparative compound obtained by a Mannich reaction in the 1: 1: 1 molar ratio of the 4-polyisobutylphenol, dibutylamine and formaldehyde ("Mannich additive 1"); a second comparative compound obtained by a Mannich reaction in the molar ratio 1: 1: 1 of the compounds 2-methyl-4-polyisobutylphenol, DMAPA, and formaldehyde ("Mannich additive 2) and a third comparative compound which is a amine PIS Each of the compounds of Example 2 and the comparative compounds are mixed with a base fuel to form fuel compositions, which are designated in Tables I and II depending on the additive compound used (compounds of the Example 2, Mannich compounds 1, Mannich 2 and amine PIS).
A first comparative engine IVD test was carried out with the compounds of Example 1, the Mannich 1, Mannich 2 compounds and the additive-free base fuel, using a bench-mounted 2.3 liter Ford engine. test under standard operating conditions, to determine the formation of deposition on the intake valves. The results are shown in Table I below.
Table I
2.3L IVD Test Results
Composition of Example IVD (mq)
Fuel without additive 478 to 527 mg
Mannich 1 53 to 56 mg
Mannich 2 67.9 mg
Compound of Example 2 64.6
Example 4
A second comparative motor IVD test was carried out with the compounds of Example 2, Mannich 1, Mannich 2, amine PIB and the additive-free base fuel, using an IVD simulator. on bench (model L-2), which can be used to test the IVD performance of gasoline detergent. The test simulates IVD deposition in an engine. In the test, the fuel compositions containing detergent additives are delivered via an injector. A separate air flow is injected via an air flow line. The air flow and the gasoline flow are mixed at the end of the injector and the mixture is directed onto a hot metal plate. The temperatures of the plates are set at about 174 ° C. The essence evaporates on the surface of the hot plate, leaving behind a deposit and a stain.
At the end of the bench IVD simulator test, the deposit is weighed on the metal plate. The results are shown in Table II below.
Table II
IVD bench test from China
Composition of Example IVD (mg)
Fuel free additive 14 to 15 mg
Comparative Example 1 7.7 mg
Comparative Example 2 1.3 mg
Example 2 1.0
Amine GDP 1.4 mg
It is clear from studying Tables I and II above that the reaction products of Example 2 exhibit improved performance compared to an additive-free base fuel, and performance comparable to that of the additives of the examples. Comparatives 1 and 2, as demonstrated by the reduced amount of deposits in the Ford 2.3L engine test. In addition, the reaction product of Example 2 exhibits improved performance compared to the base fuel free of additive and additives of Comparative Examples 1 and 2, as evidenced by the reduced amount of deposits in the bench IVD test from China.
For the purposes of this specification and the appended claims and unless otherwise indicated, it is understood that all numbers expressing quantities, percentages or proportions, as well as the other numerical values used in the description and in the claims, may be modified in any circumstances by the term "about". Therefore, unless otherwise indicated, the numerical parameters indicated in the following description and appended claims are approximations which may vary depending on the desired properties sought in the present disclosure. Finally, without seeking to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter will at least be interpreted in light of the number of important figures mentioned and by applying ordinary rounding techniques.
Note that, as used in this description and in the appended claims, the singular forms "a (e)" and "the (la)" imply plural referents, unless the limitation expressly and specifically unequivocal on a single referent. As a result, referring to, for example, "an acid" means two or more different acids. As used here, the term "includes", as well as its grammatical variants, is not meant to be limiting; for example, the enumeration of the elements of a list does not exclude other related elements, which may be substituted or added to the enumerated elements.
Although particular embodiments, variations, modifications, changes, improvements and sensible equivalents, which are or may be presently unforeseen, have been disclosed to the Applicant or other skilled persons . As a result, the appended claims, as filed and modifiable, are intended to encompass all such forms of variations, modifications, changes, improvements, and sensible equivalents.

权利要求:
Claims (19)
[1]
A process for forming a detergent base product, the process comprising: forming a bis-Mannich intermediate compound by reacting: (i) at least one hydroxyl-substituted aromatic ring compound having on the ring an aliphatic hydrocarbyl substituent from a polyolefin of number average molecular weight from about 500 to about 3000; (ii) at least one first amine which is a primary amine of formula II

[2]
The process according to claim 1, wherein at least one hydroxyl-substituted aromatic ring compound has formula I

[3]
3. A process according to claim 2 wherein one of R1, R2 and R3 is C1-6 alkyl selected from methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
[4]
4. Process according to claim 2, in which the hydrocarbyl substituent is a group chosen from polypropylene groups, polybutylene groups, poly (alpha-olefin) groups and ethylene / alpha-olefin type copolymer groups.
[5]
5. The process according to claim 2, wherein the hydrocarbyl substituent is a copolymer group, having at least one monomer selected from butylene, isobutylene and propylene, and at least one monomer selected from the mono-olefinic comonomers.
[6]
The process of claim 2 wherein the hydrocarbyl substituent is a polyisobutylene moiety.
[7]
7. The process according to claim 2, wherein R1 is methyl, R2 is a hydrogen radical and R3 is a polyisobutylene group.
[8]
8. The process according to claim 1, wherein R4 is -C1-6NR'R ", wherein the C1-6 moiety of the moiety is straight or branched chain alkyl, and R 'and R" are independently selected from hydrogen radical and methyl, ethyl, propyl and butyl groups.
[9]
9. The process according to claim 1, wherein at least one primary amine is selected from dimethylaminopropylamine, diethylaminopropylamine and dimethylaminobutylamine.
[10]
10. Process according to claim 1, wherein said at least one aldehyde is chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde, benzaldehyde, salicylaldehyde, furfuraldehyde, thiophene-aldehyl and paraformaldehyde.
[11]
The process of claim 1, wherein at least one hydroxyl-substituted aromatic ring compound; said at least one primary amine and said at least one aldehyde are mixed in a ratio of about 1 mole of hydroxyl-substituted aromatic ring compound, from about 0.3 to about 0.7 mole of primary amine; and from about 0.8 to about 1.5 moles of aldehyde.
[12]
The process according to claim 1, wherein at least one second amine is a compound of formula V

[13]
13. The process according to claim 12, wherein R7 is a saturated straight hydrocarbon chain having 1 to 6 carbon atoms.
[14]
The process according to claim 12, wherein R 7 represents a substituted or unsubstituted cycloalkane having 4 to 8 carbon atoms as ring members, which is optionally substituted with one or more methyl, ethyl or propyl groups.
[15]
The process according to claim 1, wherein said at least one second amine is selected from dimethylamine, diethylamine, dipropylamine, dibutylamine and dipentylamine.
[16]
The process of claim 1, wherein said at least one second amine is selected from cyclohexanediamine; 1,3-propanediamine; 1,2-ethanediamine; 1,4-butanediamine; 1,6-hexanediamine; 1,2-diaminocyclohexane; 1-, 2-diamino-3-methylcyclohexane; 1,2-diamino-4-methylcyclohexane; N-methylaminomethanediamine and 3-3-diamethylamino-propylamine.
[17]
A detergent base product formed according to the process of claim 1.
[18]
18. A method of forming a product of a Mannich reaction, the process comprising: - reacting at least one amine compound, selected from primary and secondary amines, with a bis compound -Mannich of formula III

[19]
19. Fuel composition comprising: -. a basic fuel; and a detergent base product comprising a mixture of compounds of formulas VI and VII

wherein R 1 and R 3 'are substituents independently selected from hydrogen, C 1-6 alkyls and hydrocarbyl substituents having a number average molecular weight in the range of about 500 to about 3000, provided that at least one of the radicals R1 and R3 is a hydrocarbyl subsistent, R4 is a substituent selected from alkyl, aryl, alkenyl, alkylamino, dialkylamino, alkylaminoalkyl and dialkylaminoalkyl; R5 and R6 are each independently selected from hydrogen, substituted or unsubstituted alkylamine, alkyl, cycloalkyl, aryl, alkaryl, and aralkyl, provided that at least one of R5 and R6 is not a hydrogen radical.

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JPH10503226A|1998-03-24|Reaction products of polyisobutene with nitrogen oxides or mixtures of nitrogen oxides and oxygen and the use of said compounds as additives for fuels and lubricating oils

---

BE1018138A5|2010-06-01|FUEL ADDITIVE COMPOUNDS AND PROCESS FOR PRODUCING THE SAME.

---

EP3110928A1|2017-01-04|Composition of additives and performance fuel comprising such a composition

---

FR2486538A1|1982-01-15|DETERGENT COMPOSITIONS, THEIR PREPARATION AND THEIR USE AS FUEL ADDITIVES

---

CA1173045A|1984-08-21|N-substituted succinimides, process forpreparing the same and their use as additives infuels

---

FR2910018A1|2008-06-20|MANNICH DETERGENTS FOR HYDROCARBON FUELS

---

EP3110927A1|2017-01-04|Composition of additives and performance fuel comprising such a composition

---

EP0353116B1|1992-04-15|Recipes of nitrogenous additives for engine fuels, and engine fuels containing them

---

FR2890078A1|2007-03-02|Fluid additive composition for lubricating composition, comprises dispersant| obtained by reacting hydrocarbyl substituted acylating agent| and amine|, and containing terminal vinylidene

---

EP0530094B1|1997-05-21|Motor fuel additive formulation comprising ester products and a detergent-dispersant agent

---

US9981958B2|2018-05-29|Oxazolidines derived from polyalkyl or polyalkenyl n-hydroxyalkyl succinimides, obtainment process and use

---

EP0349369B1|1992-05-20|Composition obtained from hydroxy-imidazolines and polyamines, and their use as fuel additives

---

FR3041362A1|2017-03-24|DETERGENT ADDITIVE FOR FUEL

---

EP0627483B1|1998-12-23|Additives formulated for motor-fuels containing at least one alkoxylated imidazo-oxazole compound

---

BE1021686B1|2016-01-08|FUEL ADDITIVES FOR TREATING INTERNAL DEPOSITS OF FUEL INJECTORS.

---

WO2021240116A1|2021-12-02|Additive composition for motor fuel

---

FR3103815A1|2021-06-04|Use of diols as detergency additives

---

WO2019110912A1|2019-06-13|Additive composition for fuel

---

WO2021105268A1|2021-06-03|Use of alkyl phenol compounds as detergent additives for petrols

同族专利:

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公开号 | 公开日

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US20080040968A1|2008-02-21|

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SG170040A1|2011-04-29|

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CN101126039B|2010-12-01|

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CN101126039A|2008-02-20|

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SG140542A1|2008-03-28|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

US4038043A|1975-09-12|1977-07-26|E. I. Du Pont De Nemours And Company|Gasoline additive compositions comprising a combination of monoamine and polyamine mannich bases|

---

US4334085A|1978-09-14|1982-06-08|Standard Oil Company |Transamination process for Mannich products|

---

EP0042617A1|1980-06-24|1981-12-30|Hoechst Aktiengesellschaft|Process for the production of shaped articles and coatings|

---

WO1990010051A1|1989-02-21|1990-09-07|Union Oil Company Of California|Fuel composition for control of intake valve deposits|

---

EP0870819A2|1997-04-10|1998-10-14|Ethyl Corporation|Additives for minimizing intake valve deposits, and their use|

---

EP1081209A1|1999-08-31|2001-03-07|Ethyl Corporation|Mannich dispersants with enhanced lubricity|

---

EP1229100A2|2001-02-02|2002-08-07|Ethyl Corporation|Secondary amine mannich detergents|

---

WO2002090471A2|2001-05-04|2002-11-14|The Lubrizol Corporation|Ortho-alkylphenol derived mannich detergent composition and concentrate, fuel and method thereof|

---

WO2004050806A2|2002-12-02|2004-06-17|Basf Aktiengesellschaft|Use of amines and/or mannich adducts in fuel and lubricant compositions for direct injection spark ignition engines|

---

EP1475411A1|2003-05-05|2004-11-10|Sika Technology AG|Mannich bases and Preparation of Mannich bases|

---

US3985802A|1965-10-22|1976-10-12|Standard Oil Company |Lubricating oils containing high molecular weight Mannich condensation products|

---

US3649229A|1969-12-17|1972-03-14|Mobil Oil Corp|Liquid hydrocarbon fuels containing high molecular weight mannich bases|

---

US3809648A|1972-07-12|1974-05-07|Chevron Res|Magnesium phenoxides and lubricants containing the same|

---

US3980569A|1974-03-15|1976-09-14|The Lubrizol Corporation|Dispersants and process for their preparation|

---

US4787996A|1986-05-21|1988-11-29|Mobil Oil Corporation|Mannich base oil additives|

---

US4913830A|1987-07-24|1990-04-03|Exxon Chemical Patents Inc.|Lactone-modified, mannich base dispersant additives useful in oleaginous compositions|

---

US5241003A|1990-05-17|1993-08-31|Ethyl Petroleum Additives, Inc.|Ashless dispersants formed from substituted acylating agents and their production and use|

---

US5107299A|1990-09-28|1992-04-21|Xerox Corporation|Printer job recovery of complete or partially complete jobs in an electronic reprographic printing system|

---

US5109062A|1990-11-15|1992-04-28|Exxon Chemical Patents Inc.|Stabilized Mannich emulsions|

---

US5697988A|1991-11-18|1997-12-16|Ethyl Corporation|Fuel compositions|

---

US5385588A|1992-06-02|1995-01-31|Ethyl Petroleum Additives, Inc.|Enhanced hydrocarbonaceous additive concentrate|

---

US5279626A|1992-06-02|1994-01-18|Ethyl Petroleum Additives Inc.|Enhanced fuel additive concentrate|

---

US5354453A|1993-04-13|1994-10-11|Exxon Chemical Patents Inc.|Removal of H2 S hydrocarbon liquid|

---

US5558683A|1995-03-20|1996-09-24|Ethyl Corporation|Mannich base derivatives, and the production and uses thereof|

---

US5634951A|1996-06-07|1997-06-03|Ethyl Corporation|Additives for minimizing intake valve deposits, and their use|

---

US6821307B2|1997-05-15|2004-11-23|Infineum International Ltd.|Oil composition|

---

US6048373A|1998-11-30|2000-04-11|Ethyl Corporation|Fuels compositions containing polybutenes of narrow molecular weight distribution|

---

CA2288387A1|1998-12-18|2000-06-18|Ethyl Corporation|High-amine mannich dispersants for compression-ignition fuels|

---

CN1098345C|1999-03-30|2003-01-08|中国石油化工集团公司|Antioxidative succinimide dustless dispersing agent|

---

US6509303B1|2000-03-23|2003-01-21|Ethyl Corporation|Oil soluble molybdenum additives from the reaction product of fatty oils and monosubstituted alkylene diamines|

---

JP2001316361A|2000-05-01|2001-11-13|Ethyl Corp|Succinimide acid compound and its derivative|

---

US20040118035A1|2001-05-15|2004-06-24|Saleem Al-Ahmad|Olefin polymerization catalyst and process and polymer, polymer derivatives, lubricants and fuels thereof|

---

US20030131527A1|2002-01-17|2003-07-17|Ethyl Corporation|Alkyl-substituted aryl polyalkoxylates and their use in fuels|

---

US6852679B2|2002-02-20|2005-02-08|Infineum International Ltd.|Lubricating oil composition|

---

US6866690B2|2002-04-24|2005-03-15|Ethyl Corporation|Friction modifier additives for fuel compositions and methods of use thereof|

---

US7049273B2|2002-07-17|2006-05-23|Afton Chemical Intangibles Llc|Hybridized olefin copolymer additives|

---

US20040198615A1|2003-04-04|2004-10-07|The Lubrizol Corporation|Di-secondary alkyl hindered phenol antioxidants|

---

CA2496100A1|2004-03-10|2005-09-10|Afton Chemical Corporation|Power transmission fluids with enhanced extreme pressure characteristics|

---

US7384434B2|2004-06-03|2008-06-10|Afton Chemical Corporation|Reaction of phenols with intermediate triazines|GB2493377A|2011-08-03|2013-02-06|Innospec Ltd|Gasoline composition comprising Mannich additive|

---

US9587198B2|2012-04-26|2017-03-07|China Petroleum & Chemical Corporation|Mannich base, production and use thereof|

---

CN103666563B|2012-09-26|2015-05-20|中国石油化工股份有限公司|Antiscale composition and application thereof|

---

CN103666564B|2012-09-26|2015-07-01|中国石油化工股份有限公司|Antiscale composition and application thereof|

---

CA2919739A1|2015-02-13|2016-08-13|Chevron Oronite Technology Bv|Lubricating oil compositions with enhanced piston cleanliness|

法律状态:
2012-10-31| RE| Patent lapsed|Effective date: 20120430 |

优先权:

---

申请号 | 申请日 | 专利标题

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US46527806|2006-08-17|

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US11/465,278|US20080040968A1|2006-08-17|2006-08-17|Fuel additive compounds and method of making the compounds|

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