EP0327559A1 - Titanium and zirconium complexes, and fuel compositions. - Google Patents

Titanium and zirconium complexes, and fuel compositions.

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Publication number
EP0327559A1
EP0327559A1 EP87906884A EP87906884A EP0327559A1 EP 0327559 A1 EP0327559 A1 EP 0327559A1 EP 87906884 A EP87906884 A EP 87906884A EP 87906884 A EP87906884 A EP 87906884A EP 0327559 A1 EP0327559 A1 EP 0327559A1
Authority
EP
European Patent Office
Prior art keywords
group
carbon atoms
formula
hydrocarbyl
fuel composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87906884A
Other languages
German (de)
French (fr)
Other versions
EP0327559B1 (en
Inventor
George Robert Hill
Biase Stephen A Di
Marvin Bradford Detar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
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Lubrizol Corp
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Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Priority to AT87906884T priority Critical patent/ATE80175T1/en
Publication of EP0327559A1 publication Critical patent/EP0327559A1/en
Application granted granted Critical
Publication of EP0327559B1 publication Critical patent/EP0327559B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • Priority Country US tent
  • NL European patent
  • SE European pat
  • a method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up o haust particles collected in said trap comprises operating said diesel engine with a fuel containing at least compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust ticulates collected in said trap.
  • Fuel compositions which are useful particularly in the operation of diesel engines equi with exhaust particluate traps wherein the fuel contains at least one titanium or zirconium complex, and certain novel nium and zirconium complexes are described and claimed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in said trap. The method comprises operating said diesel engine with a fuel containing at least one compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust particulates collected in said trap. Fuel compositions which are useful particularly in the operation of diesel engines equipped with exhaust particluate traps wherein the fuel contains at least one titanium or zirconium complex, and certain novel titanium and zirconium complexes are described and claimed.

Description

PCT WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau
INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PC
(51) International Patent Classification 4 (11) International Publication Number : WO 88/ 0
C10L 1/18, 1/26, 1/30 A3 C07F 7/00, C10L 10/06 (43) International Publication Date: 7 April 1988 (07.
(21) International Application Number: PCT/US87/02495 (74) Agents: POLYN, Denis, A. et al.; The Lubrizol poration, 29400 Lakeland Blvd., Wickliffe, OH
(22) International Filing Date: 25 September 1987 (25.09.87) (US).
(31) Priority Application Number : 914,382 (81) Designated States: AT (European patent), AU, B ropean patent), CH (European patent), DE (
(32) Priority Date: 2 October 1986 (02.10.86) pean patent), FR (European patent), GB (Eur patent), IT (European patent), JP, LU (Europea
(33) Priority Country: US tent), NL (European patent), SE (European pat
(71) Applicant: THE LUBRIZOL CORPORATION [US/
US]; 29400 Lakeland Blvd., Wickliffe, OH 44092 Published (US). With international search report
(72) Inventors: HILL, George, Robert ; 104 Countryside With amended claims .
Drive, Chagrin Falls, OH 44022 (US). DI BIASE, Stephen, A. ; 504 East 266th Street, Euclid, OH 44132 (US). DETAR, Marvin, Bradford ; 1880 Ridgewick, (88) Date of publication of the international search report Wickliffe, OH 44092 (US). 21 April 1988 (21.0
Date of publication of the amended claims:
05 May 1988 (05.05.8
(54) Title: TITANIUM AND ZIRCONIUM COMPLEXES, AND FUEL COMPOSITIONS
(57) Abstract
A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up o haust particles collected in said trap. The method comprises operating said diesel engine with a fuel containing at least compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust ticulates collected in said trap. Fuel compositions which are useful particularly in the operation of diesel engines equi with exhaust particluate traps wherein the fuel contains at least one titanium or zirconium complex, and certain novel nium and zirconium complexes are described and claimed.
FOR THE PURPOSES OFINFORMAπON ONLY
Codes used to identify States party to the PCT on the front pages of pamphlets publishing international applications under the PCT.
AT Austria FR France ML Mali
AU Australia GA Gabon MR Mauritania
BB Barbados GB United Kingdom M Malawi
BE Belgium HU Hungary NL Netherlands
BG Bulgaria IT Italy NO Norway
BJ Benin JP Japan RO Romania
BR Brazil KP Democratic People's Republic SD Sudan
CF Centra] African Republic ofKorea SE Sweden
CG Congo KR Republic ofKorea SN Senegal
CH Switzerland LI Liecbtenstein SU Soviet Union
CM Cameroon LK Sri anJca TD Chad
DE Germany, Federal Republic or LU Luxembourg TG Togo
DE Denmark MC Monaco US United States of America
Fl Finland MG Madagascar

Claims

Claims
1. A method of operating a diesel engine equipped with an exhaust system particulate trap to reduce the build-up of exhaust particles collected in said trap comprising operating said diesel engine with a fuel containing at least one compound selected from titanium or zirconium compounds effective to lower the ignition temperature of the exhaust particulates collected in said trap.
2. The method of claim 1 wherein the titanium and zirconium compounds are dispersible or soluble in the diesel fuel.
3. The method of claim 1 wherein the titanium and zirconium compounds are organo-titanium or organo-zirconium compounds.
4. The method of claim 1 wherein the titanium and zirconium compounds are titanium and zirconium salts of at least one organic acid, said organic acid being selected from the group consisting of carboxylic acids, phosphoric acids, sulfonic acids, and mixtures thereof.
5. The method of claim 4 wherein the salts are basic metal salts.
6. The method of claim 4 wherein the metal salts are salts of carboxylic acids, sulfonic acids, or mixtures thereof.
7. The method of claim 4 wherein the metal salts are titanium salts.
8. The method of claim 1 wherein the titanium and zirconium compounds are titanium and zirconium complexes characterized by the formula
(RO)xM(Ch)y (I) wherein R is hydrogen or a hydrocarbyl group containing from 1 to about 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from at least one metal chelating agent.
9. The method of claim 8 wherein the metal chelating agent contains a hydrocarbon linkage and at least two functional groups on different carbon atoms.
10. The method of claim 9 wherein the chelating agent contains at least two functional groups which are in vicinal or beta-position to each other on the hydrocarbon linkage.
11. The method of claim 9 wherein the functional groups are selected from hydroxy, carboxy, carbonyl, amino or mercapto groups.
12. The method of claim 8 wherein the chelating agent (Ch) is a diol, a dithiol, a mercapto alcohol, a diamine, an amino alcohol, an amino thiol, a dicarboxylic acid, a hydroxy carboxylic acid, a mercapto carboxylic acid, an amino carboxylic acid, a diketone, a ketocarboxylic acid, or ester, or mixtures thereof.
13. The method of claim 8 wherein the complex is a titanium complex.
14. The method of claim 8 wherein R in Formula I is an aliphatic group containing from about 1 to about 30 carbon atoms.
15. The method of claim 8 wherein x and y in Formula I are each 2.
16. The method of claim 8 wherein the metal chelating agent (Ch) is selected from the group consisting of:
(A) aromatic Mannich bases, (B) amino acid compounds of the formula
(VI) wherein R1 is hydrogen or a hydrocarbyl group; R2 is R1 or an acyl group; R3 and R4 are each independently hydrogen or lower alkyl groups; and z is 0 or 1,
(C) beta diketones,
(D) phenolic compounds of the structure
(VIII)
wherein each R is a hydrocarbyl group; and X is CH2, S, or CH2OCH2, and
(E) an aromatic difunctional compound of the formula
(IX) wherein R1 is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta-position relative to X, and X and Y are each independently OH, NH2, NHR, COOR, SH or C(O)H groups wherein R is hydrogen or a. hydrocarbyl group.
17. The method of claim 16 wherein the aromatic Mannich base (A) is the reaction product of (A-1) a hydrocarbon-substituted aromatic phenol or thiol phenol, (A-2) an aldehyde or ketone, and (A-3) an amine which contains at least one primary or secondary amino group.
18. The method of claim 17 wherein the aromatic phenol or thiophenol compound (A-1) is represented by the formula
(R1)n (XH)m (II)
wherein Ar is an aromatic group or a coupled aromatic group, m is 1, 2 or 3, n is an integer from 1 to 4, R1, independently, is hydrogen or a hydrocarbyl group having from 1 to about 100 carbon atoms, R° is hydrogen, amino, or carboxy1, and X is 0, S, or both when m is 2 or greater.
19. The method of claim 17 wherein the aldehyde or ketone (A-2) is characterized by the formula
(III)
or a precursor thereof wherein R2 and R3, independently, are hydrogen, a hydrocarbyl group having from 1 to about 18 carbon atoms, or R3 is a carbonyl containing hydrocarbon group having from 1 to 18 carbon atoms.
20. The method of claim 18 wherein R1 of said (A-1) compound is hydrogen, an alkyl group having from 1 up to an average of about 70 carbon atoms, a cycloalkyl group having from 4 to about 10 carbon atoms, an alkenyl group having from 2 to about 30 carbon atoms. an aromatic or an alkyl-substituted aromatic having from about 7 to about 30 carbon atoms, an aromatic-substituted alkyl group having from about 7 to about 30 carbon atoms, and said coupling agent of said coupled Ar group is O, S, NH or a lower alkylene group.
21. The method of claim 17 wherein said (A-3) compound is a hydrocarbyl amine containing from zero to about 10 hydroxyl and thiol groups and from 1 to about 10 amine groups.
22. The method of claim 17 wherein the amine (A-3) is characterized by the structural formula
(IV)
wherein R1 is a hydrocarbyl, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy- substituted hydrocarbyl group, and R2 is hydrogen or R1.
23. The method of claim 17 wherein the amine (A-3) is at least one aliphatic or aromatic monoamine or polyamine containing at least one primary and/or secondary amino group, polyalkylene polyamine, or heterocyclic amine or polyamine.
24. The method of claim 17 wherein the amine (A-3) is a polyalkylene polyamine.
25. The method of claim 17 wherein (A-3) is a hydroxylhydrocarbyl amine having the formula
(V) wherein each of R1 is independently a hydrogen atom or a hydrocarbyl, hydroxyhydrocarbyl, aminohydrocarbyl, or hydroxyaminohydrocarbyl group, provided that at least one of R1 is a hydroxyhydrocarbyl or hydroxyaminohydrocarbyl group, R2 is an alkylene group, and x is an integer from 0 to about 5.
26. The method of claim 18 wherein Ar of said (A-1) compound is phenyl, m is 1 or 2, n is 1 or 2, R° is H, R1 is an alkyl group containing from about 4 to about 20 carbon atoms, a cycloalkyl group having from about 5 to 7 carbon atoms, an alkenyl group having from about 8 to about 20 carbon atoms or an alkyl-substituted aromatic group containing from 7 to about 12 carbon atoms.
27. The method of claim 26 wherein m of said (A-1) compound is 1, n is 1 or 2, R1 is an alkyl group containing from about 4 to about 20 carbon atoms, X is 0, and R2 and R3 of said (A-2) compound is hydrogen.
28. The method of claim 16 wherein Ch of Formula I is
(B) at least one amino acid compound of the formula
(VI) wherein R1 is a hydrocarbyl group; R2 is an acyl group; R3 and R4 are each independently hydrogen or lower alkyl; and z is 0 or 1.
29. The method of claim 28 wherein R1 is an alkyl, cycloalkyl, phenyl, alkyl-substituted phenyl, benzyl or alkyl-substituted benzyl group.
30. The method of claim 28 wherein R3 and R4 are hydrogen.
31. The method of claim 28 wherein z is 0.
32. The method of claim 28 wherein R2 is an acyl group represented by the formula
R2'C(O)-
wherein R2' is an aliphatic group containing up to about 30 carbon atoms.
33. The method of claim 32 wherein R2' contains from about 12 to about 24 carbon atoms.
34. The method of claim 16 wherein Ch is
(C) at least one beta-diketone characterized by the formula
R-C(O)-CH2-C(O)-R1 (VII)
wherein R and R1 are each independently hydrogen or hydrocarbyl groups.
35. The method of claim 34 wherein R and R1 are lower hydrocarbyl groups.
36. The method of claim 16 wherein Ch is
(D) at least one phenolic compound of the formula
(VIII)
wherein each R is independently a hydrocarbyl group; and X is CH2, S, or CH2OCH2.
37. The method of claim 36 wherein X is CH2.
38. The method of claim 36 wherein each R is a hydrocarbyl group containing from about 4 to about 20 carbon atoms.
39. The method of claim 8 wherein Ch is at least one aromatic Mannich base
(A) which is the reaction product of (A-1) a compound of the formula
wherein R1 is an alkyl group containing from about 4 to about 20 carbon atoms,
(A-2) formaldehyde or a precursor of formaldehyde, and
(A-3) a polyalkylene polyamine.
40. The method of claim 8 wherein Ch is a beta-diketone characterized by the formula
R-C(O)-CH2-C(O)-R1 (VII)
wherein R and R1 are each independently lower alkyl groups.
41. The method of claim 40 wherein the diketone is 2,4-pentanedione.
42. The method of claim 16 wherein Ch is (E) an amino phenol.
43. The method of claim 42 wherein Ch is ortho-aminophenol.
44. A fuel composition comprising a major amount of a normally liquid fuel and a minor, property- improving amount of at least one titanium or zirconium complex charaxterized by the formula
(RO)xM(Ch)y (I)
wherein R is an aliphatic group containing from 1 tp about 30 carbon atoms; M is titanium or zirconium; x is 1 ot 2; y is 2 or 3; x + y is 4; and Ch is derived from at least one metal chelating agent.
45. The fuel composition of claim 44 wherein the metal chelating agent contains a hydrocarbon linkage and at least two functional groups on different carobn atoms.
46. The fuel composition of claim 45 wherein the chelating agent contains at least two functional groups which are in vicinal or beta-position to each other on the hydrocarbon linkage.
47. The fuel composition of claim 45 wherein the functional groups are selected from hydroxy, carboxy, carbonyl, amino or mercapto groups.
48. The fuel composition of claim 42 wherein the chelating agent (Ch) is a diol, a dithiol, a mercapto alcohol, a diamine, an amino alcohol, an amino thiol, an ortho-aminophenol, a dicarboxylic acid, a hydroxy carboxylic acid, a mercapto carboxylic acid, an amino carboxylic acid, a diketone, a ketocarboxylic acid, or ester, or mixtures thereof.
49. The fuel composition of claim 44 wherein the complex is a titanium complex.
50. The fuel composition of claim 44 wherein R in Formula I is an aliphatic group containing from about 1 to about 30 carbon atoms.
51. The fuel composition of claim 44 wherein x and y in Formula I are each 2.
52. The fuel composition of claim 44 wherein the metal chelating agent (Ch) is selected from the group consisting of:
(A) aromatic Mannich bases,
(B) amino acid compounds of the formula
(VI) wherein R1 is hydrogen or a hydrocarbyl group; R2 is R1 or an acyl group; R3 and R4 are each independently hydrogen or lower alkyl groups; and z is 0 or 1, (C) beta diketones,
(D) phenolic compounds of the structure
(VIII)
wherein each R is a hydrocarbyl group; and X is CH2, S, or CH2OCH2, and
(E) an aromatic difunctional compound of the formula
(IX) wherein R1 is a hydrocarbyl group containing 1 to about 100 carbon atoms, n is an integer from 0 to 4, Y is in the ortho or meta-position relative to X, and X and Y are each independently OH, NR2, COOR, SH or C(O)H groups wherein R is hydrogen or a hydrocarbyl group.
53. The fuel composition of claim 52 wherein the aromatic Mannich base (A) is the reaction product of (A-1) a hydrocarbon-substituted aromatic phenol or thiol phenol, (A-2) an aldehyde or ketone, and (A-3) an amine which contains at least one primary or secondary amino group.
54. The fuel composition of claim 53 wherein the aromatic phenol or thiophenol compound (A-1) is represented by the formula
(II)
wherein Ar is an aromatic group or a coupled aromatic group, m is 1, 2 or 3, n is an integer from 1 to 4, R1, independently, is hydrogen cr a hydrocarbyl group having from 1 to about 100 carbon atoms, R° is hydrogen, amino, or carboxyl, and X is 0, S, or both when m is 2 or greater.
55. The fuel composition of claim 53 wherein the aldehyde or ketone (A-2) is characterized by the formula
(III)
or a precursor thereof wherein R2 and R3, independently, are hydrogen, a hydrocarbyl group having from 1 to about 18 carbon atoms, or R3 is a carbonyl containing hydrocarbon group having from 1 to 18 carbon atoms.
56. The fuel composition of claim 52 wherein R1 of said (A-1) compound is hydrogen, an alkyl group having from 1 to an average of about 70 carbon atoms, a cycloalkyl group having from 4 to about 10 carbon atoms, an alkenyl group having from 2 to about 30 carbon atoms, an aromatic or an alkyl-substituted aromatic having from about 7 to about 30 carbon atoms, an aromatic-substituted alkyl group having from about 7 to about 30 carbon atoms, and said coupling agent of said coupled Ar group is 0, S, NH or a lower alkylene group.
57. The fuel composition of claim 53 wherein said (A-3) compound is a hydrocarbyl amine containing from zero to about 10 hydroxyl and thiol groups and from 1 to about 10 amine groups.
58. The fuel composition of claim 53 wherein the amine (A-3) is characterized by the structural formula
(IV) wherein R1 is a hydrocarbyl, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxysubstituted hydrocarbyl group, and R2 is hydrogen or R1.
59. The fuel composition of claim 53 wherein the amine (A-3) is at least one aliphatic or aromatic monoamine or polyamine containing at least one primary and/or secondary amino group, polyalkylene polyamine, or heterocyclic amine or polyamine.
60. The fuel composition of claim 53 wherein the amine (A-3) is a polyalkylene polyamine.
61. The fuel composition of claim 53 wherein (A-3) is a hydroxylhydrocarbyl amine having the formula
(V) wherein each of R1 is independently a hydrogen atom or a hydrocarbyl, hydroxyhydrocarbyl, aminohydrocarbyl, or hydroxyaminohydrocarbyl group, provided that at least one of R1 is a hydroxyhydrocarbyl or hydroxyaminohydrocarbyl group, R2 is an alkylene group, and x is an integer from 0 to about 5.
62. The fuel composition of claim 54 wherein Ar of said (A-1) compound is phenyl, m is 1 or 2, n is 1 or 2, R° is H, R1 is an alkyl group containing from about 4 to about 20 carbon atoms, a cycloalkyl group having from about 5 to 7 carbon atoms, an alkenyl group having from about 8 to about 20 carbon atoms or an alkyl-substituted aromatic group containing from 7 to about 12 carbon atoms.
63. The fuel composition of claim 62 wherein m of said (A-1) compound is 1, n is 1 or 2, R1 is an alkyl group containing from about 4 to about 20 carbon atoms, X is 0, and R2 and R3 of said (A-2) compound is hydrogen.
64. The fuel composition of claim 52 wherein Ch of Formula I is
(B) at least one amino acid compound of the formula
(VI) wherein R1 is a hydrocarbyl group; R2 is an acyl group; R3 and R4 are each independently hydrogen or lower alkyl; and z is 0 or 1.
65. The fuel composition of claim 64 wherein R1 is an alkyl, cycloalkyl, phenyl, alkyl-substituted phenyl, benzyl or alkyl-substituted benzyl group.
66. The fuel composition of claim 64 wherein R3 and R4 are hydrogen.
67. The fuel composition of claim 64 wherein z is 0.
68. The fuel composition of claim 64 wherein R2 is an acyl group represented by the formula
R2'C(O)-
wherein R2' is an aliphatic group containing up to about 30 carbon atoms.
69. The fuel composition of claim 68 wherein R2' contains from about 12 to about 24 carbon atoms.
70. The fuel composition of claim 52 wherein Ch is
(C) at least one beta-diketone characterized by the formula
R-C(O)-CH2-C(O)-R1 (VII)
wherein R and R1 are each independently hydrocarbyl groups.
71. The fuel composition of claim 70 wherein R and R1 are lower hydrocarbyl groups.
72. The fuel composition of claim 52 wherein Ch is (D) at least one phenolic compound of the formula
(VIII)
wherein each R is independently a hydrocarbyl group; and X is CH2, S, or CH2OCH2.
73. The fuel composition of claim 72 wherein X is CH2.
74. The fuel composition of claim 72 wherein each R is a hydrocarbyl group containing from about 4 to about 20 carbon atoms.
75. The fuel composition of claim 44 wherein Ch is an aminophenol.
76. The fuel composition of claim 44 wherein Ch is ortho-aminophenol.
77. The fuel composition of claim 44 wherein Ch is at least one
(A) aromatic Mannich base which is the reaction product of
(A-1) a compound of the formula
wherein R1 is an alkyl group containing from about 4 to about 20 carbon atoms,
(A-2) formaldehyde or a precursor of formaldehyde, and (A-3) a polyalkylene polyamine.
78. The fuel composition of claim 44 wherein Ch is a beta-diketone characterized by the formula
R-C(O)-CH2-C(O)-R1 (VII)
wherein R and R1 are each independently lower alkyl groups.
79. The fuel composition of claim 78 wherein the diketone is 2,4-pentanedione.
80. A titanium or zirconium complex characterized by the formula
(RO)χM(Ch)y (I)
wherein R is a hydrocarbyl group containing from 1 to about 30 carbon atoms; M is titanium or zirconium; x is 1 or 2; y is 2 or 3; x + y is 4; and Ch is derived from a metal chelating agent selected from the group consisting of:
(A) aromatic Mannich bases,
(B) at least one amino acid compound of the formula
(VI) wherein R1 is hydrogen or a hydrocarbyl group; R2 is R1 or an acyl group; R3 and R4 are each independently hydrogen or lower alkyl groups; and z is 0 or 1, (D) phenolic compounds of the structure (VIII)
wherein each R is a hydrocarbyl group, and X is CH2, S, or CH2OCH2, and
(E) an ortho-aminophenol.
81. The complex of claim 80 wherein M is titanium.
82. The complex of claim 80 wherein R in Formula I is an aliphatic group containing from about 1 to about 30 carbon atoms.
83. The complex of claim 80 wherein x and y in Formula I are each 2.
84. The complex of claim 80 wherein Ch of Formula I is (A) is the reaction product of (A-1) a hydrocarbon-substituted aromatic phenol or thiol phenol, (A-2) an aldehyde or ketone, and (A-3) an amine which contains at least one primary or secondary amino group.
85. The complex of claim 84 wherein (A-1) is represented by the formula
m (II)
wherein Ar is an aromatic group or a coupled aromatic group, m is 1, 2 or 3, n is an integer from 1 to 4, R1, independently, is hydrogen or a hydrocarbyl group having from 1 to about 100 carbon atoms R° is hydrogen, amino, or carboxyl, and X is 0, S, or both when m is 2 or greater.
86. The complex of claim 84 wherein (A-2) is characterized by the formula
R (III)
or a precursor thereof wherein R2 and R3, independently, are hydrogen, a hydrocarbyl group having from 1 to about 18 carbon atoms, or R3 is a carbonyl containing hydrocarbon group having from 1 to 18 carbon atoms.
87. The complex of claim 84 wherein (A-3) is characterized by the formula
(IV)
wherein R1 is a hydrocarbyl, amino-substituted hydrocarbyl, hydroxy-substituted hydrocarbyl, or alkoxy- substituted hydrocarbyl group, and R2 is hydrogen or R1.
88. The complex of claim 80 wherein Ch of Formula I is
(B) at least one amino acid compound of the formula
(VI) wherein R1 is a hydrocarbyl group; R2 is an acyl group; R3 and R4 are each independently hydrogen or lower alkyl; and z is 0 or 1.
89. The complex of claim 88 wherein R1 in Formula VI is an alkyl, cycloalkyl, phenyl, alkyl- substituted phenyl, benzyl or alkyl-substituted benzyl group.
90. The complex of claim 88 wherein R3 and R4 in Formula VI are hydrogen.
91. The complex of claim 88 wherein z in Formula VI is 0.
92. The complex of claim 88 wherein R2 in Formula VI is an acyl group represented by the formula
R2'C(O)-
wherein R2' is an aliphatic group containing up to about 30 carbon atoms.
93. The complex of claim 92 wherein R2' contains from about 12 to about 24 carbon atoms.
94. The complex of claim 80 wherein Ch in Formula I is
(D) at least one phenolic compound of the formula
(VIII)
wherein each R is independently a hydrocarbyl group; and X is CH2, S, or CH2OCH2.
95. The complex of claim 94 wherein X is CH2.
96. The complex of claim 94 wherein each R is a hydrocarbyl group containing from about 4 to about 20 carbon atoms.
97. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 80.
98. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 84.
99. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 88.
100. A fuel additive concentrate comprising a normally liquid organic diluent and from about 10% to about 99% by weight of the complex of claim 94.
EP87906884A 1986-10-02 1987-09-25 Titanium and zirconium complexes, and fuel compositions Expired - Lifetime EP0327559B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87906884T ATE80175T1 (en) 1986-10-02 1987-09-25 TATANIUM AND ZIRCONIUM COMPLEXES AND FUEL COMPOSITIONS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US91438286A 1986-10-02 1986-10-02
US914382 1986-10-02

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EP0327559B1 EP0327559B1 (en) 1992-09-02

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WO1988002392A2 (en) 1988-04-07
ATE80175T1 (en) 1992-09-15
EP0327559B1 (en) 1992-09-02
AU8078687A (en) 1988-04-21
DE3781557D1 (en) 1992-10-08
ZA877370B (en) 1988-06-29
WO1988002392A3 (en) 1988-04-21
CA1324151C (en) 1993-11-09
JPH02504645A (en) 1990-12-27
DE3781557T2 (en) 1993-03-18
AU605193B2 (en) 1991-01-10

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