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Patent US5696067 - Hydroxy-group containing acylated nitrogen compounds useful as additives for ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsCompositions comprising hydroxyl group containing acylated nitrogen compounds, a process for reacting certain carboxylic reactants with olefinic compounds then reacting the product prepared thereby with ammonia, a hydrazine or an amine, products prepared thereby and lubricating oil and fuel composit...http://www.google.com/patents/US5696067?utm_source=gb-gplus-sharePatent US5696067 - Hydroxy-group containing acylated nitrogen compounds useful as additives for lubricating oil and fuel compositionsAdvanced Patent SearchPublication numberUS5696067 APublication typeGrantApplication numberUS 08/632,570Publication dateDec 9, 1997Filing dateApr 15, 1996Priority dateApr 15, 1996Fee statusLapsedAlso published asCA2202448A1, DE69708961D1, DE69708961T2, EP0802255A2, EP0802255A3, EP0802255B1Publication number08632570, 632570, US 5696067 A, US 5696067A, US-A-5696067, US5696067 A, US5696067AInventorsPaul E. Adams, Mark R. Baker, Jeffry G. DietzOriginal AssigneeThe Lubrizol CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (26), Non-Patent Citations (4), Referenced by (30), Classifications (88), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetHydroxy-group containing acylated nitrogen compounds useful as additives for lubricating oil and fuel compositions
38. The process of claim 33 wherein the olefinic compound has the general formula (R1)(R2)C&#9552;C(R6)(CH(R7)(R8))   (III) wherein each of R1 and R2 is, independently, hydrogen or a hydrocarbon based group and each of R6, R7 and R8 is, independently, hydrogen or a hydrocarbon based group. 39. The process of claim 38 wherein each of R1 and R2 is hydrogen and R6 is H or a lower alkyl group and the group (CH(R7)(R8)) is a hydrocarbyl group containing from 7 to about 5000 carbon atoms.
40. The process of claim 39 wherein the olefinic compound has Mn ranging from about 100 to about 70,000.
41. The process of claim 39 wherein the group (CH(R7)(R8)) is an aliphatic group containing from about 30 to about 200 carbon atoms and the olefinic compound is derived from homopolymerized and interpolymerized C2-18 olefins.
42. The process of claim 41 wherein the group (CH(R7)(R8)) contains from about 50 to about 100 carbon atoms.
43. The process of claim 40 wherein the olefinic compound has Mn ranging from about 400 to about 3,000.
44. The process of claim 40 wherein the olefinic compound has Mn ranging from about 1,300 to about 5,000.
45. The process of claim 41 wherein the olefinic compound is a polyolefin comprising a mixture of isomers, at least about 50% by weight of the mixture comprising isomers of the formula H2 C&#9552;C(R6)(CH(R7)(R8)) wherein R6 is H or lower alkyl. 46. The process of claim 45 wherein the polyolefin is a polybutene.
47. The process of claim 46 wherein the polybutene is polyisobutylene.
48. The process of claim 45 wherein R6 is methyl.
49. The process of claim 38 wherein the olefinic compound is a polyolefin comprising a mixture of isomers wherein from about 50% to 65% are trisubstituted olefins wherein one substituent contains from 2 to about 5000 carbon atoms and the other two substituents are lower alkyl.
50. The process of claim 49 wherein the trisubstituted olefin comprises a mixture of cis-and trans- 1-lower alkyl, 1-aliphatic hydrocarbyl containing from about 30 to about 100 carbon atoms, 2-lower alkyl ethene and 1,1-di-lower alkyl, 2-(aliphatic hydrocarbyl containing from 30 to about 100 carbon atoms) ethene.
51. The process of claim 49 wherein the polyolefin is a polybutene.
52. The process of claim 51 wherein the polybutene is polyisobutylene.
53. The process of claim 38 wherein the olefinic compound is a linear α-olefin containing from 8 to about 28 carbon atoms.
54. The process of claim 33 wherein the olefinic compound is a ethylene-alpha olefin-diene copolymer.
55. The process of claim 54 wherein the alpha olefin is a lower olefin and the diene is a non-conjugated diene.
56. The process of claim 33 wherein the olefinic compound is a polyolefinic compound.
57. The process of claim 33 wherein the olefinic compound is a polydiene polymer.
58. The process of claim 33 wherein the reaction between (A) and (B) is conducted in the presence of an acid catalyst.
59. The process of claim 58 wherein the acid catalyst is selected from the group consisting of a mineral acid and an organic sulfonic acid.
60. The process of claim 33 wherein the reaction between (A) and (B) is conducted in the absence of an acidic catalyst.
61. The process of claim 33 wherein (C) is an alkylene polyamine.
62. The process of claim 33 wherein (C) is an alkylene polyamine bottoms product.
63. The process of claim 33 wherein (C) is a condensed polyamine derived from at least one hydroxy-containing material and at least one alkylene polyamine or alkylene polyamine bottoms product.
64. The process of claim 61 wherein the alkylene polyamine is at least one member of the group consisting of diethylene triamine, dimethyl aminopropylamine, ethylene aliamine,and aminoethylpiperazine.
65. A composition prepared by the process of claim 33.
66. An additive concentrate for formulating lubricating oil or fuel compositions comprising from about 20% to about 90% by weight of a normally liquid, substantially inert organic solvent/diluent and from about 10% to about 80% by weight of the composition described in claim 1.
67. An additive concentrate for formulating lubricating oil or fuel compositions comprising from about 20% to about 90% by weight of a normally liquid, substantially inert organic solvent/diluent and from about 10% to about 80% by weight of the composition described in claim 65.
68. A lubricating composition comprising a major amount of an oil of lubricating viscosity and a minor amount of the composition described in claim 1.
69. A lubricating composition comprising a major amount of an oil of lubricating viscosity and a minor amount of the composition described in claim 65.
70. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of the composition described in claim 1.
71. A fuel composition comprising a major amount of a normally liquid fuel and a minor amount of the composition described in claim 65.
72. A fuel composition according to claim 70 further comprising a fluidizer.
73. A fuel composition according to claim 71 further comprising a fluidizer.
74. A fuel composition according to claim 72 wherein the fluidizer is selected from the group consisting of mineral oils and synthetic oils having viscosity measured at 100� C. of from about 2 cSt to about 25 cSt.
75. A fuel composition according to claim 73 wherein the fluidizer is selected from the group consisting of mineral oils and synthetic oils having viscosity measured at 100� C. of from about 2 cSt to about 25 cSt.
76. A fuel composition according to claim 74 wherein the fluidizer is a synthetic oil selected from the group consisting of polyoxyalkylene mono- and polyols, ether derivatives thereof and N-vinylpyrrolidinone addition products thereof, polyalphaolefins, and hydrogenated polyalphaolefins.
77. A fuel composition according to claim 75 wherein the fluidizer is a synthetic oil selected from the group consisting of polyoxyalkylene mono- and polyols, ether derivatives thereof and N-vinylpyrrolidinone addition products thereof, polyalphaolefins, and hydrogenated polyalphaolefins.
78. A fuel composition according to claim 70 further comprising an auxiliary dispersant selected from the group consisting of Mannich type dispersants acylated nitrogen dispersants, ester dispersants, aminophenol dispersants, aminocarbamate dispersants, and amine dispersants.
79. A fuel composition according to claim 71 further comprising an auxiliary dispersant selected from the group consisting of Mannich type dispersants, acylated nitrogen dispersants, ester dispersants, aminophenol dispersants, aminocarbamate dispersants, and amine dispersants.
80. A fuel composition according to claim 70 wherein the normally liquid fuel comprises gasoline.
81. A fuel composition according to claim 71 wherein the normally liquid fuel comprises gasoline.
82. A fuel composition according to claim 70 wherein the normally liquid fuel comprises oxygenates.
83. A fuel composition according to claim 71 wherein the normally liquid fuel comprises oxygenates.
84. A fuel composition according to claim 70 wherein the normally liquid fuel is a diesel fuel oil.
85. A fuel composition according to claim 71 wherein the normally liquid fuel is a diesel fuel oil.
This invention relates to hydroxyl group containing acylated nitrogen compounds which are useful as low chlorine containing additives for lubricating oils and normally liquid fuels and a process for preparing the compounds.
Numerous types of additives are used to improve lubricating oil and fuel compositions. Such additives include, but are certainly not limited to dispersants and detergents of the ashless and ash-containing variety, oxidation inhibitors, anti-wear additives, friction modifiers, and the like. Such materials are well known in the art and are described in many publications, for example, Smalheer, et al. "Lubricant Additives", Lezius-Hiles Co., Cleveland. Ohio, USA (1967); M. W. Ranney, Ed., "Lubricant Additives", Noyes Data Corp. Park Ridge. N.J., USA (1973); M. J. Satriana, Ed. "Synthetic Oils and Lubricant Additives, Advances since 1977", Noyes Data Corp., Park Ridge N.J., USA (1982), W. C. Gergel. "Lubricant Additive Chemistry", Publication 694-320-65R1 of the Lubrizol Corp., Wickliffe, Ohio, USA (1994); and W. C. Gergel et ET AL, "Lubrication Theory and Practice" Publication 794-320-59R3 of the Lubrizol Corp., Wickliffe, Ohio, USA (1994); and in numerous United States patents, for example Chamberlin, III. U.S. Pat. No. 4,326,972, Schroeck et al, U.S. Pat. No. 4,904,401, and Ripple et al, U.S. Pat. No. 4,981,602. Many such additives are frequently derived from carboxylic reactants, for example, acids. esters, anhydrides, lactones, and others. Specific examples of commonly used carboxylic compounds used as intermediates for preparing lubricating oil additives include alkyl-and alkenyl substituted succinic acids and anhydrides, polyolefin substituted carboxylic acids, aromatic acids, such as salicylic acids, and others. Illustrative carboxylic compounds are described in Meinhardt. et al, U.S. Pat. No. 4,234,435; Norman et al, U.S. Pat. No. 3,172,872; LeSuer et al, U.S. Pat. No. 3,454,607, and Rense, U.S. Pat. No. 3,215,707.
The present invention provides hydroxy group containing acylated nitrogen compounds which meet this requirement.
The present invention provides a composition comprising a compound of the formula ##STR1## wherein each of R1 and R2 is H or a hydrocarbon based group, R3 is H or hydrocarbyl;
A is a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group; and each of R9 and R10 is independently H, alkoxyhydrocarbyl, hydroxyhydrocarbyl, hydrocarbyl, aminohydrocarbyl, N-alkoxyalkyl- or hydroxyalkyl-substituted aminohydrocarbyl, or a group of the formula .paren open-st.Y.paren close-st.a R11 --B,
wherein each Y is a group of the formula ##STR2## each R11 is a divalent hydrocarbyl group, R12 is as defined above for R9 and R10, and B is H, hydrocarbyl, amino, hydroxyhydrocarbyl, an amide group, an amide-containing group, an acylamino group, an imide group, or an imide-containing group, and a is 0 or a number ranging from 1 to about 100, provided that no more than three R9, R10, and R12 contain amide groups, imide-containing groups, acylamino groups or amide-containing groups; or
R9 and R10 taken together with the adjacent N constitute a nitrogen-containing heterocyclic group optionally, further containing one or more additional heteroatoms selected from the group consisting of N, O and S; or one of R9 and R10 taken together with the adjacent N constitute a N--N group.
In another aspect of this invention, there is provided a process comprising first reacting, optionally in the presence of an acidic catalyst selected from the group consisting of organic sulfonic acids. heteropolyacids, Lewis acids. and mineral acids,
and compounds of the formula ##STR4## wherein each of R3, R5 and R9 is independently H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, and n is 0 or 1; wherein (A) and (B) are reacted in amounts ranging from 0.6 moles (B) per mole of (A) to 1.5 moles (B) per equivalent of (A); then reacting the product formed thereby with from about 0.5 equivalents up to about 2 moles, per mole of (B) of at least one of
In general, no more than about three non-hydrocarbon substituents or hereto atoms, and preferably no more than one, will be present for every 10 carbon atoms in the hydrocarbon, hydrocarbyl or hydrocarbon based groups. Most preferably, the groups are purely hydrocarbon in nature, that is they are essentially free of atoms other than carbon and hydrogen.
As noted hereinabove, provided by this invention are certain hydroxy-containing nitrogen compounds and a process for preparing low chlorine or chlorine free compositions useful as low chlorine or chlorine free additives for lubricating oil and fuel compositions.
In one embodiment, this invention relates to a composition comprising a compound of the formula ##STR5## wherein A is a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group. In one embodiment A is selected from groups of the formula ##STR6## wherein z=0 or 1; X is a divalent hydrocarbyl group selected from the group consisting of ##STR7## when z=0, and ##STR8## when z=1; and each of R5, R6, R7, and R8 is independently H or a hydrocarbon based group.
R5 is H or hydrocarbyl. When R5 is hydrocarbyl, it is usually an aliphatic group, often a group containing from 1 to about 30 carbon atoms, often from 8 to about 18 carbon atoms. In another embodiment, R5 is lower alkyl, wherein "lower alkyl" is defined hereinabove. Most often, R5 is H or lower alkyl.
When at least one of R6, R7 and R8 is a hydrocarbyl group, it preferably contains from 7 to about 5,000 carbon atoms. More often, such hydrocarbon groups are aliphatic groups. In one embodiment R6 is an aliphatic group containing from about 10 to about 300 carbon atoms. In another embodiment, R6 contains from 30 to about 100 carbon atoms and is derived from homopolymerized and interpolymerized C2-18 olefins.
In a further embodiment, at least one of R7 and R8 is an aliphatic group containing from 10 to about 300 carbon atoms. Often, at least one of R7 and R8 contains from about 30 to about 100 carbon atoms and is derived from homopolymerized and interpolymerized C2-18 olefins. The polymerized olefins are frequently 1-olefins, preferably ethylene, propylene, butenes, isobutylene, and mixtures thereof. Polymerized olefins are often referred to herein as polyolefins.
Each of R1 and R2 is H or a hydrocarbon based group. In one particular embodiment, each of R1 and R2 is independently H or a lower alkyl group provided at least one is lower alkyl. In another embodiment, one of R1 and R2 is H and the other is lower alkyl. As used herein, the expression "lower alkyl" refers to alkyl groups containing from 1 to 7 carbon atoms. Examples include methyl, ethyl and the various isomers of propyl, butyl, pentyl, hexyl and heptyl. In one especially preferred embodiment, each of R1 and R2 is H.
The subscript `y` is an integer ranging from 1 to about 200, more often from 1 to about 50 and even more often from 1 to about 20. Frequently y is 1.
Each of R9 and R10 is independently H, alkoxyhydrocarbyl, hydroxyhydrocarbyl, hydrocarbyl, aminohydrocarbyl, N-alkoxyalkyl- or hydroxyalkyl-substituted aminohydrocarbyl, or a group of the formula .paren open-st.Y.paren close-st.a R11 --B, wherein each Y is a group of the formula ##STR9## each R11 is a divalent hydrocarbyl group, R12 is as defined above for R9 and R10, and B is H, hydrocarbyl, amino, hydroxyhydrocarbyl, an amide group, an amide-containing group, an acylamino group, an imide group, or an imide-containing group, and a is 0 or a number ranging from 1 to about 100, provided that no more than three R9, R10, and R12 contain amide groups, imide-containing groups, acylamino groups or amide-containing groups; or
R9 and R10 taken together with the adjacent N constitute a nitrogen-containing heterocyclic group; or
one of R9 and R10 taken together with the adjacent N constitute a N--N group.
In another embodiment, the present invention relates to a process comprising first reacting, optionally in the presence of an acidic catalyst selected from the group consisting of organic sulfonic acids, heteropolyacids, Lewis acids, and mineral acids.
(A) at least one olefinic compound containing at least one group of the formula ##STR10## and (B) at least one carboxylic reactant selected from the group consisting of compounds of the formula
and compounds of the formula ##STR11## wherein each of R3, R5 and R9 is independently H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, and n is 0 or 1: wherein (A) and (B) are reacted in amounts ranging from 0.6 moles (B) per mole of (A) to 1.5 moles (B) per equivalent of (A); then reacting the product formed thereby with from about 0.5 equivalents up to about 2 moles, per mole of (B) of at least one of
With respect to the first step of the process, while both of reactants (A) and (B) may be present at the same time, it has been found that improvements in yield and purity of product are attained when the carboxylic reactant (B) is added, either portionwise or continuously, over an extended period of time, usually up to about 10 hours, more often from 1 hour up to about 6 hours, frequently from about 2-4 hours.
Optionally the first step of the process may be conducted in the presence of an azeotroping solvent. Well known azeotroping solvents include toluene, xylene, cyclohexane, etc. Cyclohexane is preferred. When an azeotroping solvent is used, the mode of combining reactants (A) and (B) does not appear to have an appreciable effect.
The olefinic compound employed as a reactant in the process of this invention contains at least one group of the formula ##STR12## and has the general formula
Virtually any compound containing an olefinic bond may be used provided it meets the general requirements set forth hereinabove for (III) and does not contain any functional groups (e.g., primary or secondary amines) that would interfere with the carboxylic reactant (B). Useful olefinic compounds may be terminal olefins. i.e., olefins having a H2 C═C group, or internal olefins. Useful olefinic compounds may have more than one olefinic bond, i.e., they may be dienes, trienes, etc. Most often they are mono-olefinic. Examples include linear α-olefins, cis- or trans-disubstituted olefins, trisubstituted olefins and tetrasubstituted olefins.
When (A) is monoolefinic, one mole of (A) contains one equivalent of C═C; when (A) is diolefinic, one mole of (A) contains 2 equivalents of C═C bonds; when (A) is triolefinic, one mole of (A) contains 3 equivalents of C═C bonds, and so forth.
In one preferred embodiment, at least one R is derived from polybutene, that is, polymers of C4 olefins, including 1-butene, 2-butene and isobutylene. Those derived from isobutylene, i.e., polyisobutylenes, are especially preferred. In another preferred embodiment, R is derived from polypropylene. In another preferred embodiment, R is derived from ethylene-alpha olefin polymers, including ethylene-propylene-diene polymers. Representative of such polymers are the ethylene-propylene copolymers and ethylene-propylene-diene terpolymers marketed under the Trilene� tradename by the Uniroyal Company. Molecular weights of such polymers may vary over a wide range, but especially preferred are those having number average molecular weights (Mn) ranging from about 300 to about 20,000, preferably 700 to about 10000, often from 900 to 2500. In one preferred embodiment, the olefin is an ethylene-propylene-diene copolymer having Mn ranging from about 900 to about 8000, often up to about 2000. Such materials are included among the Trilene� polymers marketed by the Uniroyal Company. Middlebury, Conn., USA and Orthoeum� 2052, marketed by the DuPont Company.
A preferred source of hydrocarbyl groups R are polybutenes obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75 weight percent and isobutylene content of 15 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than 80% of total repeating units) isobutylene repeating units of the configuration ##STR13## These polybutenes are typically monoolefinic, that is they contain but one olefinic bond per molecule.
When the olefin is a tri-substituted olefin, it frequently comprises a mixture of cis- and trans- 1-lower alkyl, 1-(aliphatic hydrocarbyl containing from 30 to about 100 carbon atoms), 2-lower alkyl ethene and 1,1-di-lower alkyl, 2-(aliphatic hydrocarbyl containing from, 30 to about 100 carbon atoms) ethene.
In one embodiment, the monoolefinic groups are predominantly vinylidene groups, i.e., groups of the formula ##STR14## especially those of the formula ##STR15## although the polybutenes may also comprise other olefinic configurations.
In one embodiment the polybutene is substantially monoolefinic, comprising at least about 30 mole %, preferably at least about 50 mole % vinylidene groups. more often at least about 70 mole % vinylidene groups. Such materials and methods for preparing them are described in U.S. Pat. Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823 and 5,408,018, and in published European patent application EP646103-A1, each of which is expressly incorporated herein by reference. They are commercially available, for example under the tradenames UItravis (BP Chemicals) and Glissopal (BASF).
Specific characterization of olefin reactants (A) used in the processes of this invention can be accomplished by using techniques known to those skilled in the art. These techniques include general qualitative analysis by infrared and determinations of average molecular weight, e.g., Mn, number average molecular weight and Mw, weight average molecular weight. etc. employing vapor phase osmometry (VPO) and gel permeation chromatography (GPC). Structural details can be elucidated employing proton and carbon 13 (C13) nuclear magnetic resonance (NMR) techniques. NMR is useful for determining substitution characteristics about olefinic bonds, and provides some details regarding the nature of the substituents. More specific details regarding substituents about the olefinic bonds can be obtained by cleaving the substituents from the olefin by, for example, ozonolysis, then analyzing the cleaved products, also by NMR, GPC, VPO, and by infra-red analysis and other techniques known to the skilled person.
One mole of olefin is defined as the formula weight or number average molecular weight (Mn) of an olefinic compound. The equivalent weight is defined as the formula weight or Mn of the olefin divided by the number of olefinic bonds present per olefinic compound. To illustrate, one mole of butene is 56.11. The equivalent weight of butene is also 56.11 since the formula weight divided by the number of olefinic bonds (one) equals the formula weight. Butadiene has two olefinic bonds. The formula weight of butadiene is 54.09. The equivalent weight is 54.09/2 or 27.05, one-half of the formula weight.
and compounds of the formula ##STR16## wherein each of R3, R5 and R9 is independently H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, and n is 0 or 1. Specific embodiments of the groups R3 and R5 are set forth hereinabove where corresponding groups in the compound (I) are described. R9 is H or hydrocarbyl, preferably H or lower alkyl.
Examples of carboxylic reactants (B) are glyoxylic acid, and other omegaoxoalkanoic acids, keto alkanoic acids such as pyruvic acid, levulinic acid, ketovaleric acids, ketobutyric acids and numerous others. The skilled worker, having the disclosure before him, will readily recognize the appropriate compound of formula (V) to employ as a reactant to generate a given intermediate. Preferred compounds of formula (V) are those that will lead to preferred compounds of formula (I).
Reactant (B) may be a compound of the formula ##STR17## wherein each of R3 and R5 is independently H or alkyl. Such compounds arise when the carbonyl reactant is hydrated. Glyoxylic acid monohydrate is a representative example.
The intermediate arising from the reaction of (A) and (B) may be a carboxylic acid or a lactone. Often, the intermediate arising from the reaction of (A) and (B) is a mixture comprising both lactone and carboxylic acid. ps (C) Ammonia, Hydrazine and Amine Reactants
Suitable (C) reactants, as defined herein, include ammonia, hydrazines, monoamines or polyamines. The (C) reactants must contain at least one N--H group. The monoamines generally contain from 1 to about 24 carbon atoms, preferably 1 to about 12, and more preferably 1 to about 6. Examples of monoamines useful in the present invention include primary amines, for example methylamine, ethylamine, propylamine, butylamine, octylamine, and dodecylamine. Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine, ethylhexylamine, etc. Tertiary monoamines will not result in formation of an amide.
In another embodiment, the monoamine may be a hydroxyamine. Typically, the hydroxyamines are primary or secondary alkanolamines or mixtures thereof. As stated above, tertiary monoamines will not react to form amides; however tertiary alkanol monoamines sometimes can react to form a tertiary amino group containing ester. Alkanol amines that can react to form amide can be represented, for example, by the formulae:
H2 N--R'--OH,
and ##STR18## wherein each R4 is independently a hydrocarbyl group of one to about 22 carbon atoms or hydroxyhydrocarbyl group of two to about 22 carbon atoms, preferably one to about four, and R' is a divalent hydrocarbyl group of about two to about 18 carbon atoms, preferably two to about four. The group --R'--OH in such formulae represents the hydroxyhydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group. Typically, R' is an acyclic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group. When two R4 groups are present in the same molecule they can be joined by a direct carbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples of such heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and the like. Typically, however, each R4 is independently a methyl, ethyl, propyl, butyl, pentyl or hexyl group.
H2 N--(R'O)x --H, ##STR19## wherein x is a number from about 2 to about 15 and R4 and R' are as described above. R4 may also be a hydroxypoly (hydrocarbyloxy) group.
Alkylene polyamines are represented by the formula ##STR20## wherein n has an average value between about 1 and about 10, preferably about 2 to about 7, more preferably about 2 to about 5, and the "Alkylene" group has from 1 to about 10 carbon atoms, preferably about 2 to about 6, more preferably about 2 to about 4. R5 is independently hydrogen or an aliphatic or hydroxy-substituted aliphatic group of up to about 30 carbon atoms. Preferably R5 is H or lower alkyl, most preferably, H.
Alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, etc. Higher homologs and related heterocyclic amines such as piperazines and N-amino alkyl-substituted piperazines are also included. Specific examples of such polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tris-(2-aminoethyl)amine, propylene diamine, trimethylene diamine, tripropylene tetramine, tetraethylene pentamine, hexaethylene heptamine, pentaethylenehexamine, dimethylaminopropylamine, etc.
Ethylene polyamines, such as some of those mentioned above, are preferred. They are described in detail under the heading Ethylene Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2d Edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965). Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with ammonia or by reaction of an ethylene imine with a ring opening reagent such as water, ammonia. etc. These reactions result in the production of a complex mixture of polyalkylene polyamines including cyclic condensation products such as the aforedescribed piperazines. Ethylene polyamine mixtures are useful.
Other useful types of polyamine mixtures are those resulting from stripping of the above-described polyamine mixtures to leave as residue what is often termed "polyamine bottoms". In general, alkylene polyamine bottoms can be characterized as having less than two, usually less than 1% (by weight) material boiling below about 200� C. A typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport. Tex., designated "E-100" has a specific gravity at 15.6� C. of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40� C. of 121 centistokes. Gas chromatography analysis of such a sample contains about 0.93% "Light Ends" (most probably diethylenetriamine). 0.72% triethylenetetramine, 21.74% tetraethylene pentaamine and 76.61% pentaethylene hexamine and higher by weight). These alkylene polyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like.
Another useful polyamine is a condensation product obtained by reaction of at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group. The hydroxy compounds are preferably polyhydric alcohols and amines. Preferably the hydroxy compounds are polyhydric amines. Polyhydric amines include any of the above-described monoamines reacted with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide. etc.) having two to about 20 carbon atoms, preferably two to about four. Examples of polyhydric mines include tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol, N,N,N',N'-tetrakis(2-hydroxypropyl) ethylenediamine, and N,N,N',N'-tetrakis(2-hydroxyethyl) ethylenediamine.
Specific examples of alkoxylated alkylenepolyamines include N-(2-hydroxyethyl) ethylenediamine, N,N-di-(2-hydroxyethyl)-ethylenediamine, 1 -(2-hydroxyethyl) piperazine, mono-(hydroxypropyl)-substituted tetraethylenepentamine. N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtained by condensation of the above illustrated hydroxy-containing polyamines through amino groups or through hydroxy groups are likewise useful. Condensation through amino groups results in a higher amine accompanied by removal of ammonia while condensation through the hydroxy groups results in products containing ether linkages accompanied by removal of water. Mixtures of two or more of any of the aforesaid polyamines are also useful.
In another embodiment, the polyamine may be a heterocyclic polyamine. The heterocyclic polyamines include aziridines, azetidines, azolidines, tetra- and dihydropyridines, pyrroles, indoles, piperidines, imidazoles. di- and tetrahydroimidazoles, piperazines, isoindoles, purines, N-aminoalkylmorpholines. N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,N'-bisaminoalkyl piperazines, azepines, azocines, azonines, azecines and tetra-, di- and perhydro derivatives of each of the above and mixtures of two or more of these heterocyclic amines. Preferred heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines containing only nitrogen, or nitrogen with oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine, aminoalkylsubstituted piperidines, piperazine. aminoalkylsubstituted piperazines, for example, aminoethylpiperazine, morpholine. aminoalkylsubstituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especially preferred. Usually the aminoalkyl substituents are substituted on a nitrogen atom forming part of the hereto ring. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-diaminoethyl-piperazine. Hydroxy alkyl substituted heterocyclic polyamines are also useful. Examples include N-hydroxyethylpiperazine and the like.
Typically, polyalkene-substituted amines are prepared by reacting halogenated-, preferably chlorinated-, olefins and olefin polymers (polyalkenes) with amines (mono- or polyamines). The amines may be any of the amines described above. Examples of these compounds include poly(propylene)amine; N,N-dimethyl-N-poly (ethylene/propylene)amine, (50:50 mole ratio of monomers); polybutene amine; N,N-di(hydroxyethyl)-N-polybutene amine; N-(2-hydroxypropyl)-N-polybutene amine; N-polybutene-aniline; N-polybutenemorpholine; N-poly(butene) ethylenediamine; N-poly(propylene)trimethylenediamine; N-polybutene)diethylene-triamine; N',N'-polybutene)tetraethylenepentamine; N,N-dimethyl-N'-poly(propylene)-1,3-propylenediamine and the like.
The polyalkene substituted amine is characterized as containing from at least about 8 carbon atoms, preferably at least about 30, more preferably at least about 35 up to about 300 carbon atoms, preferably 200, more preferably 100. In one embodiment, the polyalkene substituted amine is characterized by an n (number average molecular weight) value of at least about 500. Generally, the polyalkene substituted amine is characterized by an n value of about 500 to about 5000. preferably about 800 to about 2500. In another embodiment n varies between about 500 to about 1200 or 1300.
It is generally preferred to utilize sufficient amine reactant (C) to convert substantially all of the intermediate arising from reaction of (A) with (B) to amide; however, conversion of at least 50%, more preferably 75% is often acceptable. Preferably, at least 90%, more preferably 99-100% conversion is effected.
The reaction with the (C) reactant to prepare the products of this invention is conducted at temperatures ranging from about 25� C. to about 230� C. When the amine is an alkanolamine, an alkylene polyamine or a thioalkanol amine, N-containing heterocyclic compounds such as imidazoline, oxazoline, or thiazoline formation may occur. These are frequently obtained by first preparing the amide then continuing the reaction at elevated temperature to generate imidazoline, thiazoline or oxazoline by removal of water.
A mole of any of (C) is its formula weight, for example, 17.03 for ammonia, 60.10 for ethylene diamine, and 189.31 for tetraethylenepentamine. The equivalent weights of these are 17.03, 30.05 and 37.86, respectively, each determined by dividing the formula weight by the number of nitrogen atoms having at least one H bonded thereto. Thus the equivalent weight of (C) is its formula weight divided by the number of nitrogen atoms per molecule having at least one H atom bonded thereto.
The first step of the process of this invention is conducted at temperatures ranging from ambient up to the lowest decomposition temperature of any of the reactants, usually from about 60� C. to about 220� C., more often from about 120� C. to about 180� C., preferably up to about 160� C. The process employs from about 0.6 moles (B) per mole of (A) to 1.5 moles (B) per equivalent of (A), more often from about 0.8 moles (B) per mole of (A) to about 1.2 moles (B) per equivalent of (A), even more often from about 0.95 moles (B) per mole of (A) to about 1.05 moles (B) per equivalent of (A). The product formed in this first step is then reacted, at temperatures ranging from about 25� C. to about 230� C., preferably from about 60� C. to about 150� C., more often from about 100� C. to about 110� C. with (C) ammonia, a hydrazine or an amine characterized by the presence within its structure of at least one N--H group. Reactant (C) is used in amounts ranging from about 0.5 equivalents up to about 2 moles, per mole of (B).
A reactor is charged with 3000 parts of a polyisobutene having a number average molecular weight of about 1000 and which contains about 80 mole % terminal vinylidene groups and 6 parts 70% aqueous methanesulfonic acid. The materials are heated to 160� C. under N2 followed by addition of 577.2 parts 50% aqueous glyoxylic acid over 4 hours while maintaining 155-160� C. Water is removed and is collected in a Dean-Stark trap. The reaction is held at 160� C. for 5 hours, cooled to 140� C. and filtered. The filtrate has total acid no. (ASTM Procedure D-974)=34.7 and saponification no. (ASTM Procedure D-74)=53.2. Mn (Gel permeation chromatography (GPC)) =1476 and Mw (GPC)=3067; unreacted polyisobutene (Thin layer chromatography-Flame ionization detector (TLC-FID))=8.6%.
A reactor is charged with 350 parts of the product of Part A of Example 1, 17.2 parts diethylene triamine and 267.5 parts mineral oil diluent, heated under N2 to 160� C. and held at 160� C. for 5 hours. Filtered 145� C. Filtrate contains 1.02% N.
A reactor is charged with 250 parts of the product of Part A of Example 1 and 29 parts aminoethylpiperazine, heated to 160� C. and held at 160� C for 6 hour, then stripped to 160� C. and 25 millimeters (mm) Hg. The residue is mixed with 93 parts of aromatic hydrocarbon diluent. The product contains 2.19 % N and 0.23% free amine.
A reactor is charged with 350 parts of the product of Part A of Example 1, 20.4 parts of an ethylene polyamine mixture containing, on average, 34% N, and 246.9 parts mineral oil. The materials are mixed whole heating, under N2, to 160� C. and held at 160� C. for 6 hours. The solution is filtered at 140� C. The filtrate contains 1.19% N.
Following essentially the procedure of Example 3, 350 parts of the product of Part A of Example 1, 21.6 parts of an ethylene polyamine bottoms having an equivalent weight of 42 based on % N and 247.7 parts mineral oil diluent are heated and filtered. The filtrate contains 1.21 % N.
A reactor is charged with 425 parts of an intermediate product prepared essentially according to the procedure of Part A of Example 1 and 40.8 parts ethylene diamine. The materials are mixed while heating, under N2, to 135�, are held at temperature for 6 hours, stripped to 130� C. at 35 mm Hg, cooled to 100� C., then mixed with 150.7 parts aromatic hydrocarbon solvent. The solution contains 1.28% N and 0.20% free amine.
A reactor is charged with 300 parts of the intermediate product of Example 5, 9.7 parts of the ethylene polyamine bottoms of Example 4 and 206.5 parts of mineral oil diluent. The materials are mixed and heated, under N2, to 160� C. and held at temperature for 6 hours, then filtered at 140� C. The filtrate contains 0.66% N.
A reactor is charged with 200 parts of the intermediate product of Example 5, 1.6 parts pentaerythritol and 211.6 parts mineral oil diluent, heated to 160� with stirring, under N2, and held at temperature for 6 hours. A small amount of ester is detected. Methane sulfonic acid (1.2 parts) is added and the reaction is heated to 180� C., holding at temperature for 6 hours. Filtered at 120� C. Total acid No=4.6; infrared: 1780 cm-1, 1740 cm31 1. To another reactor are charged 275 parts of the above product and 5 parts of the ethylene polyamine bottoms of Example 4. The materials are heated and mixed, under N2, to 160� C., held at temperature for 6 hours, then filtered at 130� C. The filtrate contains 0.75% N.
A reactor is charged with 250 parts of an intermediate prepared essentially according to the procedure of Part A of Example 1, 18.6 parts of the ethylene polyamine bottoms of Example 4 and 179 parts of mineral oil diluent. The materials are heated to 160� C., under N2, held at temperature for 6 hours the filtered at 140� C. The filtrate contains 1.38% N.
A reactor is charged with 300 parts of the intermediate of Example 8 and 34.1 parts of aminoethylpiperazine. The materials are mixed while heating, under N2, to 160� C. and are held at temperature for 5 hours, stripped to 160� C. and 35 mm Hg, cooled to 100� C., mixed with 143.2 parts aromatic hydrocarbon and filtered. The filtrate contains 2.06% N and 0.28% free amine.
A reactor is charged with 300 parts of the intermediate of Example 8 and 26.95 parts N,N-dimethylaminopropyl amine. The materials are mixed while heating, under N2, to 160� C., held at temperature for 5 hours, stripped to 160� C. and 35 mm Hg, cooled to 100� C., mixed with 140.1 parts aromatic hydrocarbon diluent and is filtered. The filtrate contains 1.28% N and 0.28% free amine.
A reactor is charged with 150 parts of an intermediate prepared essentially according to the procedure of Part A of Example 1 and 9.24 parts aminoethylpiperazine. The materials are mixed while heating, under N2, to 160� C. and are held at temperature for 5 hours, stripped to 160� C. and 25 mm Hg, cooled to 130� C., mixed with 53.1 parts aromatic hydrocarbon diluent and the solution is filtered. The filtrate contains 1.44% N.
The procedure of Example 11 is repeated except 13.9 parts aminoethyl piperazine is employed and the maximum reaction temperature is 180� C. The filtrate contains 1.96% N.
The procedure of Example 12 is repeated employing 250 parts of the intermediate of Example 11, 24.6 parts diethylene triamine and 91.5 parts of aromatic hydrocarbon diluent. The product contains 2.23 % N.
The procedure of Example 13A is repeated except the reaction is conducted at 200� C. The filtrate contains 1.94% N.
The procedure of Example 13A is repeated except the reaction temperature is 160� C. The filtrate contains 2.01% N.
A reactor is charged with 600 parts of an intermediate prepared essentially according to the procedure of Part A of Example 1, 68.2 parts N,N-dimethylaminopropylamine, and 286.4 parts mineral oil. The materials are mixed while heating, under N2, to 160� C., are held at temperature for 6 hours, stripped to 160� C. and 25 mm Hg, and filtered. The filtrate contains 1.18% N.
A reactor is charged with 300 parts of the intermediate of Example 14, 40.9 parts of aminoethylpiperazine and 150 parts 2-ethyl hexanol. The materials are mixed while heating, under N2, to 160� C. and are held at temperature for 5 hours. stripped to 160� C. and 25 mm Hg, cooled to 100� C. whereupon 146.1 parts aromatic hydrocarbon diluent are added and the solution is filtered. The filtrate contains 2.14% N and 0.50% free amine.
A reactor is charged with 1200 parts of the polybutene of Part A of Example A, 2.4 parts 70% aqueous methanesulfonic acid and 0.1 parts of a silicone antifoam agent. The materials are heated, under N2, to 150� C. whereupon 213.1 parts 50% aqueous glyoxylic acid are added dropwise over 1.5 hours. collecting water in a Dean-Stark trap. Heating is continued for 3 hours at 150� C., whereupon 139.3 parts aminoethylpiperazine are added over 8 minutes, while temperature rises exothermically to 153� C. The materials are heated at 150� C. for 3 hours, cooled to 100� C. The materials are mixed with 139.3 parts of aromatic hydrocarbon diluent and filtered. The filtrate contains 1.88% N.
A reactor is charged with 1639 parts of a polyisobutene having a Mn about 1000 and containing about 50 mole % terminal vinylidene groups and 150.8 parts glyoxylic acid monohydrate. The materials are heated, under N2, to 150� C. and are held at temperature for 4 hour, collecting 40 parts aqueous distillate during the first 2.25 hours and a total of 43 parts (about 1 part organic) after 4 hours. The materials are filtered at 140� C. The filtrate contains (by TLC-FID) 39.8% unreacted polyisobutene, has total acid no=16.1 and saponification no=54.8.
A reactor is charged with 250 parts of the product of Part A and 24.9 parts of N,N-Me2 aminopropyl amine, heated under N2 to 200� C. and held at temperature for 6.5 hours. The materials are cooled to 120� C. and stripped to 120� C. and 20 mm Hg the filtrate is diluted with 91.1 parts aromatic hydrocarbon solvent and filtered at 120� C. The solution contains 1.4% N.
A reactor is charged with 450 parts polybutene having Mn, about 2400 and containing about 80 mole % terminal vinylidene groups and 2 parts 70% aqueous methane sulfonic acid. The materials are mixed while heating, under N2, to 160� C. followed by dropwise addition of 44.4 parts 50% aqueous glyoxylic acid over 0.3 hours. The reaction mixture is held at 160� C. for a total of 6 hours, diluted with 318.3 parts mineral oil diluent and filtered at 140� C. The filtrate has (GPC) 65.9% Mn =4712, Mw =10681 and 34.1% Mn =309, Mw =410. Saponification No.=11.8, total acid no=11.7. Product contains 42% polybutene (TLC-FID).
A reactor is charged with 600 parts of the product of Part A, 7.95 parts of the polyamine bottoms of Example 4 and 5.3 parts mineral oil. The materials are mixed while heating, under N2, to 160� C. and are held at temperature for 5 hours. The materials are cooled to 130� C. and filtered. The filtrate contains 0.52% N and 0% Cl.
A reactor is charged with 800 parts of a polybutene having Mn =586 and containing about 80 mole % terminal vinylidene groups and 3 parts 70% aqueous methane sulfonic acid. The materials are mixed while heating, under N2, to 150� C. followed by dropwise addition of 262.7 parts 50% aqueous glyoxylic acid over 2 hours, collecting aqueous distillate in a Dean-Stark trap. The reaction mixture is held at 150� C. for a total of 6 hours and filtered at 145� C. The filtrate has total acid no=55.6 and saponification no=89.45. The product contains (TLC-FID) 7.2% unreacted polyisobutene.
A reactor is charged with 400 parts of the product of Part A and 78.2 parts of aminoethylpiperazine. The reactants are mixed while heating, under N2, to 160� C., held at temperature for 6 hours, stripped to 160� C. 25 mm Hg, cooled to 120� C. and filtered. The filtrate contains 3.49% N.
A reactor is charged with 200 parts of the intermediate product of Part A of Example 19, 31.2 parts diethylene triamine and 57.8 parts mineral oil, 160� C. The materials are mixed while heating, under N2, to 160� C., held at temperature for 5 hours, cooled to 140� C. and filtered. The filtrate contains 4.18% N.
A reactor is charged with 98 parts C12 α-olefin and 63 parts glyoxylic acid monohydrate. The materials are mixed and heated at 180�-210� C. for 10 hours while collecting total of 36 parts distillate containing about 75% water. The residue is filtered at room temperature. The filtrate has saponification no=231. Infra red: strong C═O @1710 cm-1 and 1780 cm-1.
A reactor is charged with 55 parts of the product of Part A of this example, 7.4 parts ethylene diamine and 150 parts toluene. The materials are heated, under N2, for 20 hours at 110� C.; infra red spectrum shows trace of lactone after 8 hours. Stripping is conducted under reduced pressure on a rotary evaporator. The residue contains 6.06% N.
A reactor equipped with stirrer, thermowell, subsurface inlet and Dean-Stark trap is charged with 300 parts polyisobutylene having a number average molecular weight of about 1000 and containing about 50 mole % of terminal vinylidene groups, 44 parts 50% aqueous glyoxylic acid and 1 part sulfuric acid. The materials are heated to 100� C. and are held at 100� C. for 1.5 hours while removing water under a slow N2 purge. The materials are then heated to 125� C. and held at 125� C. for 2.5 hours then heated to 150� C. and held at 150� C. for 3 hours while continuing to remove water under a slow N2 purge. The strong acid (neutralization number, bromphenol blue indicator) is neutralized by sodium hydroxide. At this point the materials contain (TLC-FID) 34.9% unreacted polyisobutylene. The materials are reheated to 110� C. and filtered through a diatomaceous earth filter aid. The filtrate has saponification no.=40 and total acid no.=12.0; Mn =1486, Mw =9133.
To another reactor is charged 150 parts of the product of Part A of this example which is heated to 95� C. under N, followed by addition of 3 parts diethylene triamine. The temperature is held at 95� C. for 1 hour, then increased to 150� C. The reaction is held at temperature for 5 hours then temperature is increased to 200� C. and held for 2 hours followed by addition of 7 parts diethylene triamine and heating for 1 more hour. The materials are cooled to 150� C. and held at that temperature for 3 hours, stripped to 150� C. at 30 mm Hg the filtered. The filtrate contains 1.94% N and 1% free amine.
A reactor equipped as in Example 22, Part A is charged with 300 parts polyisobutylene having a number average molecular weight of about 1000 and containing about 50 mole % of terminal vinylidene groups and 44 parts 50% aqueous glyoxylic acid. The materials are heated to 100� C. and are held at 100� C. for 1 hour while removing water under a slow N2 purge. The materials are then heated to 125� C. and held at 125� C. for 2.5 hours during which 9 parts water are collected, then to 150� C. and held at 150� C. for 3 hours while continuing to remove water under a slow N2 purge, collecting an additional 14 parts water. At this point the materials contain by analysis (TLC-FID) 35.7% unreacted polyisobutylene. The materials are allowed to cool, then are reheated to 150� C. stripped to 150� C. at 10 mm Hg and filtered. The filtrate has saponification no.=48 and total acid no.=14.2. Mn =1408, Mw =2428.
Another reactor is charged with 150 parts of the product of Part A of this example and 31.5 mineral oil diluent. The materials are mixed with heating, under N2, to 90� C., 9.5 parts diethylene triamine are added, then the temperature is increased to 150� C. The reaction is held at temperature for 6 hours, stripped to 150� C. @ 20 mm Hg for 3 hours then filtered. The filtrate contains 1.42% N and 0% free amines.
A reactor charged with 150 parts of the intermediate of Example 11 and 11.1 parts of diethylenetriamine is heated to 160� C. held at temperature for 5 hours, then stripped to 160� C. at 25 mm Hg. The residue is cooled to 130� C., diluted with 53.7 parts aromatic hydrocarbon diluent and filtered. The solution contains 1.75% N.
A reactor is charged with 150 parts of an intermediate prepared essentially according to the procedure of Part A of Example 1 and 18.5 parts aminoethylpiperazine. The materials are mixed while heating, under N2, to 160� C. and are held at temperature for 5 hours, stripped to 160� C. and 25 mm Hg, cooled to 130� C., 56.2 parts aromatic hydrocarbon diluent are added and the solution is filtered. The filtrate contains 2.57% N.
The procedure of Example 25 is repeated except the reaction is conducted at 200� C. and stripping at 190� C. The filtrate contains 2.34% N.
A reactor is charged with 250 parts of the intermediate of Example 1-A. 22.1 parts of a branched polyamine derived from the condensation of tris-hydroxymethyl aminomethane with an ethylene polyamine, and 214.7 parts mineral oil. The materials are heated, under N2, to 160� C. and are held at 160� C. for 6 hours, then filtered at 130� C. The filtrate contains 1.16%.
A reactor is charged with 1000 parts polyisobutylene having a number average molecular weight of about 1000, 207.2 parts 50% aqueous glyoxylic acid. 5 parts 70% aqueous methane sulfonic acid, 0.1 parts silicone antifoam agent and 300 parts cyclohexane. The reaction is heated to 105� C. under N2 and is held there for 6 hours, under N2, collecting water. The temperature is increased to 110� C. and held for 4 hours, collecting water. Cyclohexene is removed by heating at 110� C. for 2 hours. Strip to 120� C. at 25 mm Hg for 2 hours then filter with a diatomaceous earth filter aid. Filtrate shows 15.3% unreacted polyisobutylene (TLC-FID). Saponification no.=58.4.
A reactor is charged with 350 parts of the product of Part A of this Example and 42.3 parts N-aminoethylpiperazine. The materials are heated, under N2, to 170� C. and are held at 170� C. for a total of 8 hours, then stripped to 170� C. at 25 mm Hg for 1 hour. To the residue are added 168.1 parts aromatic hydrocarbon, the materials are mixed then filtered. The filtrate contains 1.66% N.
In one embodiment of this invention, the compositions are lubricating oil compositions. The lubricating compositions employ an oil of lubricating viscosity. including natural or synthetic lubricating oils and mixtures thereof. Mixtures of mineral oil and synthetic oils, particularly polyalphaolefin oils and polyester oils, are often used.
Natural oils include animal oils and vegetable oils (e.g. castor oil, lard oil and other vegetable acid esters) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid treated mineral lubricating oils of the paraffinic. naphthenic or mixed paraffinic-naphthenic types. Hydrotreated or hydrocracked oils are included within the scope of useful oils of lubricating viscosity.
Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins, etc. and mixtures thereof, alkylbenzenes, polyphenyl, (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.). alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof, and those where terminal hydroxyl groups have been modified by esterification, etherification. etc., constitute other classes of known synthetic lubricating oils that can be used.
Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans and the like, silicon-based oils such as the o polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils.
______________________________________3,163,603      3,381,022    3,542,6803,184,474      3,399,141    3,567,6373,215,707      3,415,750    3,574,1O13,219,666      3,433,744    3,576,7433,271,310      3,444,170    3,630,9043,272,746      3,448,048    3,632,5103,281,357      3,448,049    3,632,5113,306,908      3,451,933    3,697,4283,311,558      3,454,607    3,725,4413,316,177      3,467,668    4,194,8863,340,281      3,501,405    4,234,4353,341,542      3,522,179    4,491,5273,346,493      3,541,012    RE 26,4333,351,552      3,541,678______________________________________
The above-illustrated additives may each be present in lubricating compositions at a concentration of as little as 0.001% by weight usually ranging from about 0.01% to about 20% by weight, more often from about 1% to about 12 % by weight.
The various additives described herein can be added directly to the lubricating oil or fuel. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates usually comprise about 0.1 to about 80% by weight, frequently from about 1% to about 10% by weight, more often from about 10% to about 80% by weight, of the compositions of this invention and may contain, in addition, one or more other additives known in the an or described hereinabove. Concentrations such as 15%, 20%, 30% or 50% or higher may be employed.
Additive concentrates used for preparing lubricating oil compositions are illustrated by the following examples. The amounts shown are indicated as parts by weight or parts by volume. Unless indicated otherwise, components are indicated as parts or percentages by weight of chemical present on an oil or diluent free basis. When products of Examples set forth hereinabove are used, the amounts listed are as prepared, including diluent, if any.
Additive concentrates are prepared by blending 6.7 parts of calcium overbased (MR˜1.1) sulfur-coupled alkyl phenate, 8.6 parts of zinc mixed isopropyl-isooctyl (60/40 molar) dithiophosphate, 4.66 parts calcium overbased (Metal Ratio (MR)˜2.3) sulfur-coupled alkyl phenate, 3.76 parts of calcium overbased (MR˜1.2) alkylbenzene sulfonate, 3.06 parts magnesium overbased (MR ˜14.7) alkylbenzene sulfonate, 1.93 parts di-(nonyl phenyl) amine, 0.1 parts of silicone antifoam, 8.69 parts of product obtained by reacting reaction polyisobutene (Mn ˜1000) substituted succinic anhydride with ethylene polyamine then with pentaerythritol and 4.9 parts of the product of the indicated example:
______________________________________Example      I        II     III    IV  V______________________________________Product of Example        4        1-B    18     3   32______________________________________
and sufficient mineral oil to bring the total to 100 parts.
An additive concentrate similar to that of Example I but containing 0.96 parts of di-(nonyl phenyl) amine.
An additive concentrate similar to that of Example I replacing di-(nonyl phenyl) amine with mineral oil.
An additive concentrate is prepared by mixing together 9.7 parts of the reaction product of polyisobutylene (Mn ˜1000) substituted succinic anhydride with an ethylene polyamine mixture containing about 34% N, 8.5 parts of the imidazoline derived from isostearic acid and ethylene polyamine, 1.2 parts di-(nonyl phenyl) amine, 62.78 parts of the product of Example 16 and sufficient mineral oil to bring the total to 100 parts.
An additive concentrate is prepared by mixing together 2.79 parts of the borated reaction product derived from polyisobutylene (Mn ˜1000) substituted succinic anhydride with an ethylene polyamine mixture containing about 34% N. 0.83 parts of dibutyl phosphite, 15.45 parts of styrene-mixed C.sub.(8-10, 12-18) maleate copolymer, 1.75 parts di-(nonyl phenyl) amine, 4.16 parts of dithiocarbamate derived from dibutyl dithiocarbamic acid and methyl acrylate, 6.25 parts of hydroxy propyl tertiary dodecyl sulfide, 29.2 parts of the product of Example 3 and sufficient mineral oil to bring the total to 100 parts.
An additive concentrate is prepared as in Example IX except 29.2 parts of the product of Example 3 are replaced with 29.2 parts of the product of Example 32.
The lubricating compositions of this invention are illustrated by the examples in the following Tables. The lubricating compositions are prepared by combining the specified ingredients, individually or from concentrates, in the indicated amounts and oil of lubricating viscosity to make the total 100 parts by weight. The amounts shown are indicated as parts by weight or parts by volume. Unless indicated otherwise, where components are indicated as parts by weight, they are amounts of chemical present on an oil or diluent free basis. Thus, for example, an additive comprising 50% oil used at 10% by weight in a blend, provides 5% by weight of chemical. Totals are 100% by weight or 100 parts by weight. However, when referring to incorporation of products of Examples set forth herein, amounts are as prepared.
A lubricating oil composition is prepared by mixing together a mineral oil of lubricating viscosity (Exxon ISO 46) and 0.1 parts of the product of Example 20.
A lubricating oil composition as in Example A except 0.5 of the product of Example 20.
Examples C-J
Lubricating oil compositions are prepared by mixing together in a mineral oil of lubricating viscosity (Exxon 15W-40), 7.5 parts of a 91% oil solution of an ethylene-propylene-diene copolymer, and the indicated amounts of the additive concentrates set forth in the following table:
______________________________________Additive Concentrate/Parts by WeightExample______________________________________C                  Example I/13.3D                  Example II/13.3E                  Example III/13.3F                  Example IV/13.3G                  Example VI/13.5H                  Example VII/13.2J                  Example V/13.3______________________________________
A lubricating oil composition is prepared by mixing together in a mineral oil of lubricating viscosity (85% 600N and 15% Bright Stock) 0.15 parts of a polymethacrylate pour point depressant, and 13.5 parts of the additive concentrate of Example VIII.
A lubricating oil composition is prepared by mixing together in a mineral oil basestock (Exxon Dexron III basestock) 0.025 parts of red dye, 0.042 parts of a mixed silicone antifoam, and 12 parts of the additive concentrate of Example IX.
A lubricating oil composition is prepared as in Example L replacing the additive concentrate of Example IX with that of Example X.
The fuels used in the fuel compositions of this invention are well known to those skilled in the an and usually contain a major portion of a normally liquid fuel such as hydrocarbonaceous petroleum distillate fuel (e.g., motor gasoline as defined by ASTM Specifications D-439-89 and D-4814-91 and diesel fuel or fuel oil as defined in ASTM Specifications D-396-90 and D-975-91). Fuels containing non-hydrocarbonaceous materials such a alcohols, ether, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) are also within the scope of this invention as are liquid fuels derived from vegetable or mineral sources. Vegetable or mineral sources include, for example, crude petroleum oil, coal, corn, shale, oilseeds and other sources.
Fluidizers are usually fuel soluble, meaning they are soluble in the fuel in amounts of at least 0.1% by weight, more preferably at least 1% by weight. Certain fluidizers, for example, butylene- and propylene oxide derived fluidizers, are generally soluble in fuels at all levels. These are typically prepared from alcohol, glycol, and phenol initiators under superatmospheric pressure. Basic catalysts are preferred.
Particularly useful synthetic oils are the polyether oils such as those marketed under the UCON tradename by Union Carbide Corporation, poly(oxyalkylene) glycols such as those marketed under the EMKAROX tradename by ICI Chemicals and described in EP 0647700-A1 based on U.S. Ser. No. 133442 filed Oct. 6, 1993 and polyester oils derived from a polyol and one or more monocarboxylic acids such as those marketed by Halco Corporation.
It has been found that fluidizers, particularly when used within the ranges specified herein, together with the compositions of this invention, improve detergency, emissions, and reduce the tendency toward valve sticking. Amounts of the various additives, including individual amounts to be used in the fuel composition, and relative amounts of additives are given hereinafter.
The fuel compositions of this invention may contain auxiliary dispersants. A wide variety of dispersants are known in the art and may be used together with the amide compounds described herein. Preferred auxiliary dispersants are Mannich type dispersants, acylated nitrogen-containing dispersants, aminophenol dispersants. aminocarbamate dispersants, ester dispersants and amine dispersants.
Mannich products are described in the following patents: U.S. Pat. No. 3,980,569: U.S. Pat. No. 3,877,899; and U.S. Pat. No. 4,454,059 (herein incorporated by reference for their disclosure to Mannich products).
The auxiliary dispersant may be a polyalkene-substituted amine. Polyalkene-substituted amines are well known to those skilled in the art. Typically. polyalkene-substituted amines are prepared by reacting olefins and olefin polymers (polyalkenes) and halogenated derivatives thereof with amines (mono- or polyamines). These amines are disclosed in U.S. Pat. No. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; and 3,822,289. These patents are hereby incorporated by reference for their disclosure of hydrocarbyl amines and methods of making the same.
Aminophenols are also included among useful auxiliary dispersants that may be used in the fuel composition of this invention. Typically, such materials are prepared by reducing hydrocarbyl substituted nitrophenols to the corresponding aminophenol. Useful aminophenols include those described in Lange. U.S. Pat. Nos. 4,320,000 and 4,320,021. Aminophenols and methods for preparing are described in U.S. Pat. Nos. 4,100,082 and 4,200,545 to Clason et al. U.S. Pat. No. 4,379,065 (Lange) and U.S. Pat. No. 4,425,138 (Davis). It should be noted that the term "phenol" used in the context of aminophenols is not intended to limit the compounds referred to in that manner as being only hydroxybenzene derivatives. The term "phenol" is intended to encompass hydroxy aromatic compounds, including hydroxybenzene compounds, naphthols, catechols and others as described in the foregoing patents, all of which are incorporated herein by reference for relevant disclosures contained therein.
Treating levels of the additives used in this invention are often described in terms of pounds of additive per thousand barrels (PTB) of fuel. PTB values may be convened to approximate values expressed as parts (by weight) per million parts (by weight) of fuel by multiplying PTB by 4 for gasoline and by 3.3 for diesel oil and fuel oil. To determine precise values it is necessary that the specific gravity of the fuel is known. The skilled person can readily perform the necessary mathematical calculations.
As mentioned hereinabove, the additives for use in fuels may be supplied as additive concentrates which are then diluted with normally liquid fuels. The following Table illustrates additive concentrates for use in fuels.
______________________________________          Concentrate (% by Weight)Component        F-I     F-II    F-III F-IV______________________________________Alkylated aromatic hydrocarbon1            15.76   19.2    15.76 19.2Product of Example 9             33.38 38Product of Example 10            33.38   38Demulsifiers     0.22            0.22Polyether Oil2      42.8          42.8Propoxylated succinic acidMineral oil3            45.94           45.94 21.372-Ethylhexanol   4.54            4.54______________________________________ 1 = HISOL10, Ashland Chemical Co. 2 = EMKAROX AF20, ICI 3 = 800N
The following illustrates several fuel compositions of the instant invention comprising unleaded gasoline and the indicated amounts of additive in percent by weight concentrate in fuel.
______________________________________GASOLINE + % WEIGHT ADDITIVE CONCENTRATE   ExampleConcentrate     F-A       F-B    F-C    F-D   F-E______________________________________F-I       0.08F-II                0.07F-III                      0.08F-IV                              0.0007                                   0.015______________________________________
While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the an upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications that fall within the scope of the appended claims.
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derivatives and use as lubricating oil and fuel additivesUS6054493 *Dec 30, 1998Apr 25, 2000The Lubrizol CorporationEmulsion compositionsUS6147036 *Aug 8, 1997Nov 14, 2000The Lubrizol CorporationProcess for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives and derivatives thereofUS6176893Dec 30, 1998Jan 23, 2001The Lubrizol CorporationControlled release emulsion fertilizer compositionsUS6200398Dec 30, 1998Mar 13, 2001The Lubrizol CorporationEmulsion explosive compositionsUS6211122 *Jul 27, 1998Apr 3, 2001The Lubrizol CorporationCarboxylic compositions and derivatives thereof and use as lubricating oil and fuel additivesUS6265358 *Dec 3, 1997Jul 24, 2001The Lubrizol CorporationNitrogen containing dispersant-viscosity improversUS6288013Dec 3, 1997Sep 11, 2001The Lubrizol CorporationNitrogen containing dispersant-viscosity improversUS6486101Apr 30, 2001Nov 26, 2002The Lubrizol CorporationNitrogen containing dispersant-viscosity improversUS6492306Mar 23, 2001Dec 10, 2002The Lubrizol CorporationNitrogen containing dispersant-viscosity improversUS6827750Aug 24, 2001Dec 7, 2004Dober Chemical CorpControlled release additives in fuel systemsUS6835218Aug 24, 2001Dec 28, 2004Dober Chemical Corp.Fuel additive compositionsUS7883638May 27, 2008Feb 8, 2011Dober Chemical CorporationControlled release cooling additive compositionsUS7938277May 10, 2011Dober Chemical CorporationControlled release of microbiocidesUS8109287Feb 7, 2012Cummins Filtration Ip, Inc.Controlled release of additives in fluid systemsUS8425772Apr 23, 2013Cummins Filtration Ip, Inc.Filtration device with releasable additiveUS8591747May 26, 2009Nov 26, 2013Dober Chemical Corp.Devices and methods for controlled release of additive compositionsUS8702995May 27, 2008Apr 22, 2014Dober Chemical Corp.Controlled release of microbiocidesUS20050090611 *Sep 25, 2002Apr 28, 2005Stephan HufferHydrophilic emulsifiers based on polyisobutyleneEP2292722A1Mar 28, 2003Mar 9, 2011The Lubrizol CorporationMethod of operating internal combustion engine by introducing detergent into combustion chamberWO2000040327A1 *Dec 15, 1999Jul 13, 2000The Lubrizol CorporationEmulsion compositionsWO2000040522A2 *Dec 15, 1999Jul 13, 2000The Lubrizol CorporationEmulsion explosive compositionsWO2000040522A3 *Dec 15, 1999Nov 2, 2000Lubrizol CorpEmulsion explosive compositionsWO2003083020A2Mar 28, 2003Oct 9, 2003The Lubrizol CorporationMethod of operating internal combustion engine by introducing detergent into combustion chamberWO2009045979A1Sep 30, 2008Apr 9, 2009The Lubrizol CorporationLubricants that decrease micropitting for industrial gears* Cited by examinerClassifications U.S. Classification508/476, 508/551, 560/183, 564/201, 44/418, 564/204, 44/391, 508/555, 560/179International ClassificationC10L10/00, C10M133/56, C10L1/14, C10L1/30, C10M133/16, C10L1/222, C10L1/22, C10L1/16, C08F8/32, C10L1/20, C10L10/08, C10M159/12, C07C235/06, C10L1/24, C10L1/26, C10L1/224, C10L1/238, C10L1/18Cooperative ClassificationC10M2215/221, C10L1/238, C10M2215/26, C08F8/32, C10L1/2493, C10M2215/225, C10M2215/28, C10L1/1802, C10L1/1832, C10M2215/082, C10M2217/046, C10M2227/00, C10M2217/06, C10L1/2456, C10M2215/22, C10L1/1641, C10L1/1905, C10L1/19, C10L1/2383, C10M2207/124, C10L1/232, C10M2215/08, C10L1/2387, C10L1/1985, C10M2215/04, C10N2270/02, C10L1/1824, C10L1/1883, C10M2205/02, C10L1/221, C10L1/2475, C10L1/191, C10L1/1616, C10L1/226, C10L1/201, C10L1/2335, C10L1/224, C10L1/198, C10L1/2691, C10L1/143, C10M133/56, C10L1/306, C10M2215/00, C10M159/12, C10M2215/30, C10L1/1608, C10M2215/226, C10L1/22, C10L1/303, C10M2205/00, C10L10/06, C10L10/04European ClassificationC08F8/32, C10L1/224, C10L1/238, C10L1/22W, C10M133/56, C10L1/22, C10L10/00, C10M159/12, C10L1/14BLegal EventsDateCodeEventDescriptionApr 15, 1996ASAssignmentOwner name: LUBRIZOL CORPORATION, THE, OHIOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ADAMS, PAUL E.;BAKER, MARK R.;DIETZ, JEFFRY G.;REEL/FRAME:007982/0283Effective date: 19960415May 22, 2001FPAYFee paymentYear of fee payment: 4Jun 29, 2005REMIMaintenance fee reminder mailedDec 9, 2005LAPSLapse for failure to pay maintenance feesFeb 7, 2006FPExpired due to failure to pay maintenance feeEffective date: 20051209RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services