AU633481B2 - Lubricating oil compositions and fuel compositions containing substantially straight chain pinwheel alkylphenyl poly(oxypropylene) aminocarbamates - Google Patents

Description

OPI DATE 01/08/90 AOJP DATE 30/08/90 APPLN. ID 32868 89

PCI

PCT NUMBER PCT/US88/04710 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification (11) International Publication Number: WO 90/07564 133/56, C10L 1/22 Al 1/18, C07C 125/06 (43) International Publication Date: 12 July 1990 (12.07.90) (21) International Application Number: PCT/US88/04710 Published With international search report.

(22) International Filing Date: 30 December 1988 (30.12.88) (71)Applicant: CHEVRON RESEARCH/COMPANY [US/ US]; P.O. Box 7141, San Francisco, CA 94120-7141 /X

(US).

(72) Inventor: BUCKLEY, Thomas, III 2232 Redwood i Road, Hercules, CA 94547 (US).

(74) Agents: CAROLI, Claude, J. et al.; Chevron Corporation, T Law Department, P.O. Box 7141, San Francisco, CA 94120-7141 (US).

(81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (European patent), DE (European patent), DK, FI, FR (European patent), GB (European patent), IT (European patent), JP, KR, LU (European patent), NL (European patent), SE (European patent).

633481 (54)Title: LUBRICATING OIL COMPOSITIONS AND FUEL COMPOSITIONS CONTAINING SUBSTANTIALLY STRAIGHT CHAIN PINWHEEL ALKYLPHENYL POLY(OXYPROPYLENE) AMINOCARBAMATES (57) Abstract Disclosed are liquid alkylphenyl poly(oxypropylene) aminocarbamates which do not form a wax when cooled to -400C in a 50 weight percent solution with toluene, said aminocarbamates having at least one basic nitrogen and an average molecular weight of about 600 to 6,000 and wherein the alkyl group is substantially straight-chain of from 25 to 50 carbon atoms. Also disclosed are fuel compositions and concentrates as well as lubricating oil compositions and concentrates containing said alkylrplenyl poly(oxypropylene) aminocarbamates.

IL_ wmffa WO 90/07564 PCT/US88/04710 01 LUBRICATING OIL COMPOSITIONS AND FUEL COMPOSITIONS CONTAINING SUBSTANTIALLY STRAIGHT CHAIN PINWHEEL 03 ALKYLPHENYL POLY(OXYPROPYLENE)

AMINOCARBAMATES

04 BACKGROUND OF THE INVENTION 06 Field of the Invention 07 Numerous deposit-forming substances are inherent in 08 09 hydrocarbon fuels. These substances when used in internal combustion engines tend to form deposits on and around constricted areas of the engine contacted by the fuel.

12 Typical areas commonly and sometimes seriously burdened by the formation of deposits include carburetor ports, the throttle body and venturies, engine intake valves, etc.

16 Deposits adversely affect the operation of the vehicle. For example, deposits on the carburetor throttle body and venturies increase the fuel to air ratio of the gas mixture 18 to the combustion chamber thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the chamber. The high fuel-air ratio also reduces the gas mileage obtainable from the vehicle.

23 24 Deposits on the engine intake valves when they get sufficiently heavy, on the other hand, restrict the gas mixture flow into the combustion chambe.. This restriction, 26 starves the engine of air and fuel and results in a loss of 28 power. Deposits on the valves also increase the probability of valve failure due to burning and improper valve seating.

In addition, these deposits may break off and enter the combustion chamber possibly resulting in mechanical damage to the piston, piston rings, engine head, etc.

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WO 90/07564 PC~/US88/04710 2- 01 The formation of these deposits can be inhibited as well as 02 removed by incorporating an active detergent into the fuel.

03 These detergents function to cleanse these deposit-prone 04 areas of the harmful deposits, thereby enhancing engine performance and longevity. There are numerous 06 detergent-type gasoline additives currently available which, 07 to varying degrees, perform these functions.

08 09 Three factors complicate the use of such detergent-type gasoline additives. First, with regard to automobile 11 engines that require the use of nonleaded gasolines (to 12 prevent disablement of catalytic converters used to reduce 13 emissions), it has been found difficult to provide gasoline 14 of high enough octane to prevent knocking and the concomitant damage which it causes. The chief problem lies 16 in the area of the degree of octane requirement increase, 17 herein called "ORI", which is caused by deposits formed by 18 the commercial gasoline.

19 The basis of the ORI problem is as follows: each engine, 21 when new, requires a certain minimum octane fuel in order to 22 operate satisfactorily without pinging and/or knocking. As 23 the engine is operated on any gasoline, this minimum octane 24 increases and, in most cases, if the engine is operated on the same fuel for a prolonged period, will reach an 26 equilibrium. This is apparently caused by an amount of 27 deposits in the combustion chamber. Equilibrium is 28 typically reached after 5,000 to 15,000 miles of automobile 29 operation.

31 The octane requirement increase in particular engines used 32 with commercial gasolines will vary at equilibrium from 5 to 33 34

M,

WO 90/07564 PCT/US88/04710 01 6 octane units to as high as 12 or 15 units, depending upon 02 the gasoline compositions, engine design and type of op- 03 eration. The seriousness of the problem is thus apparent.

04 A typical automobile with a research octane requirement of 85, when new, may after a few months of operation require 97 06 research octane gasoline for proper operation, and little 07 unleaded gasoline of that octane is available. The ORI 08 problem also exists in some degree with engines operated on 09 leaded fuels. U.S. Patent Nos. 3,144,311; 3,146,203; and 4,247,301 disclose lead-containing fuel compositions having 11 reduced ORI properties.

12 13 The ORI problem is compounded by the fact that the most 14 common method for increasing the octane rating of unleaded gasoline is to increase its aromatic content. This, 16 however, eventually causes an even greater increase in the 17 octane requirement. Moreover, some of presently used 18 nitrogen-containing compounds used as deposit-control 19 additives and their mineral oil or polymer carriers may also significantly contribute to ORI in engines using unleaded 21 fuels.

22 23 It is, therefore, particularly desirable to provide deposit 24 control additives which effectively control the deposits in intake systems of engines, without themselves eventually 26 contributing to the problem.

27 28 In this regard, hydrocarbyl poly(oxyalkylene) amino- 29 carbamates are commercially successful fuel additives which control combustion chamber deposits thus minimizing ORI.

*P /31 32 33 34 WO 90/07564 PCT/US88/04710 01 A second complicating factor relates to the low temperature 02 properties of fuel and lubricating oil additives. Since it 03 is not unusual for solutions of these additives to be 04 subjected to cold temperature extremes, it is important that solids (such as waxes) are not formed during handling, 06 storage, or in actual field use. When formed, these waxy 07 constituents can totally plug the in-line filtering devices 08 normally in service in additive distribution systems and the 09 fuel or lube systems of actual operating engines. Such a plugging would obviously be catastrophic and must be 11 avoided.

12 13 A thir-1 complicating factor relates to the lubricating oil 14 compatibility of the fuel additive. Fuel additives, due to their higher boiling point over gasoline itself, tend to 16 accumulate on surfaces in the combustion chamber of the 17 engine. This accumulation of the additive eventually finds 18 its way into the lubricating oil in the crankcase of the 19 engine via a "blow-by" process and/or via cylinder wall/piston ring "wipe down". In some cases, as much as 21 25%-30% of the non-volatile fuel components, including 22 fuel additives, will eventually accumulate in the 23 lubricating oil. Insofar as the recommended drain interval 24 for some engines may be as much as 7,500 miles or more, such fuel additives can accumulate during this interval to 26 substantial quantities in the lubricating oil. In the case 27 where the fuel additive is not sufficiently lubricating oil 28 compatible, the accumulation of such an oil-incompatible 29 fuel additive may actually contribute to crankcase deposits as measured by a Sequence VD test.

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lii7n3sii(~ WO 90/07564 PCT/US88/04710 01 The incompatibility of certain fuel additives in lubricating 02 oils, oils which contain other additives, arises in 03 spite of the fact that some fuel additives are also known to 04 be lubricating oil dispersants. However, even if employed in a fully formulated lubricating oil as a dispersant rather 06 than as a fuel additive, the incompatibility of these 07 dispersants with other additives in the lubricating oil will 08 result in increased crankcase deposits as measured by a 09 Sequence V-D engine test.

11 Several theories exist as to the cause of the lubricating 12 oil incompatibility of certain fuel/lubricating oil 13 additives. Without being limited to any theory, it is 14 possible that some of these additives when found in the lubricating oil interfere with other additives contained in 16 the lubricating oil and either counterbalance the 17 effectiveness of these additives or actually cause disso- 18 lution of one or more of these additives. In either case, 19 the incompatibility of the additive with other additives in the lubricating oil demonstrates itself in less than 21 desirable crankcase deposits as measured by Sequence VD 22 engine tests.

23 24 In another theory, when used as a fuel additive, it is possible that the accumulation of the additive into the 26 lubricating oil during the drain interval period surpasses 27 its maximum solubility in the lubricating oil. In this 28 theory, this excess amount of additive is insoluble in the 29 lubricating oil and is what causes increased crankcase deposits.

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WO 90/07564 PCT/US88/04710 01 In still another theory, it is possible that the additive 02 will decompose in the lubricating oil during engine 03 operation and the decomposition products are what cause 04 increased crankcase deposits.

06 In any case, lubricating oil incompatible additives are less 07 than desirable insofar as their use during engine operation 08 will result in increased deposits in the crankcase. This 09 problem can be catastrophic.

11 It is recognized that hydrocarbyl poly(oxybutylene) 12 aminocarbamates are substantially more expensive than the 13 hydrocarbyl poly(oxypropylene) aminocarbamates. This is 14 because butylene oxide is much more expensive than propylene oxide. Currently, the price for butylene oxide (BO) is more 16 than four times the price of propylene oxide (PO) on a pound 17 for pound basis. However, because heretofore no known 18 hydrocarbyl poly(oxypropylene) aminocarbamate was found to 19 be sufficiently lubricating oil compatible and non-waxy, it was necessary to employ the more expensive hydrocarbyl 21 poly(oxybutylene) aminocarbamates which are sufficiently 22 lubricating oil compatible. Accordingly, it would be 23 particularly advantageous to develop hydrocarbyl 24 poly(oxypropylene) aminocarbamates which are compatible in lubricating oil compositions and are non-waxy at -40 0

C.

26 27 The instant invention is di.rected to lubricating oil 28 compositions and fuel compositions containing a novel class 29 of hydrocarbyl poly(oxypropylene) aminocarbamates. As a fuel additive, these novel hydrocarbyl poly(oxyalkylene) 31 aminocarbamates control combustion chamber deposits thus 32 minimizing ORI and in lubricating oil are compatible with 33 34 I WO 90/07564 PCT/US88/04710 -7 01 the lubricating oil composition. As a lubricating oil 02 additive, these novel hydrocarbyl poly(oxyalkylene) 03 aminocarbamates provide dispersancy without possessing 04 lubricating oil incompatibility. Significantly, the novel additives of this invention are also liquids which do not 06 form a wax at -40 0 C in a 50 weight percent solution with 07 toluene.

08 09 Relevant Art 11 Numerous references disclose hydrocarbyl poly(oxyalkylene) 12 aminocarbamates as fuel additives. These include the 13 following U.S. Patent Nos.: 14 4,160,648; 4,243,798; 4,521,610; and 16 4,191,537; 4,270,930; 4,568,358 17 4,197,409; 4,274,837; 18 4,236,020; 4,288,612; 19 Of articular relevance is U.S. Patent No. 4,274,837 which 21 discloses that hydrocarbyl poly(oxyalkylene) aminocarba- 22 mates containing certain poly(oxyalkylene) chains, i.e., 23 oxypropylene, when used in fuels employed in combination 24 with certain lubricating oils, produce crankcase varnish.

This reference further discloses that lubricating oil 26 compatible hydrocarbyl poly(oxypropylene) aminocarbamates 27 are improved by employing the poly(oxypropylene) as a 28 copolymer also containing 1 to 5 branched C 9 to C 30 29 oxyalkylene units.

31 U.S. Pazent No. 4,160,648 discloses an intake system 32 deposit control additive for fuels which is a hydrocarbyl 33 34 WO 90/07564 PCT/US88/04710 01 poly(oxyalkylene) aminocarbamate wherein the hydrocarbyl 02 is from 1 to 30 carbon atoms including alkyl or 03 alkylphenyl groups. Specifically disclosed hydrocarbyl 04 groups include tetrapropenylphenyl, olelyl and a mixture of C 16

C

18 and C 20 alkyl groups. Likewise, U.S. Patent 06 No. 4,288,612 discloses deposit control additives for 07 gasoline 4ngines which are hydrocarbyl poly(oxyalkylene) 08 aminocarbamates wherein the hydrocarbyl group contains 09 from 1 to about 30 carbon atoms including alkylphenyl groups wherein the alkyl group is straight or branched 11 chain of from 1 to about 24 carbon atoms. U.S. Patent No.

12 4,568,358 discloses diesel fuel compositions containing an 13 additive such as a hydrocarbyl poly(oxyalkylene) 14 aminocarbamate. This reference discloses hydrocarbyl groups such as alkyl groups of 1 to 30 carbon atoms; aryl 16 groups of 6 to 30 carbon atoms, alkaryl groups of 7 to 17 carbon atoms, etc.

18 19 U.S. Patent No. 4,332,595 discloses hydrocarbyl poly(oxyalkylene) polyamines wherein the hydrocarbyl group 21 is a hydrocarbyl radical of 8 to 18 carbon atoms derived 22 from linear primary alcohols.

23 24 U.S. Patent Nos. 4,233,168 and 4,329,240 among others disclose lubricating oil compositions containing a 26 dispersant amount of a hydrocarbyl poly(oxyalkylene) 27 aminocarbamate.

28 29 While these prior art references disclose fuel compositions containing C 1 to C 30 hydrocarbyl poly(oxy- 31 alkylene) aminocarbamates which include poly(oxypropylene) 32 polymers, none of these references disclose the unique 33 34 L I hydrocarbyl group of this invention nor do any of these references suggest that use of this unique hydrocarbyl group would overcome the art recognized problem of lubricating oil incompatibility arising from using the prior art hydrocarbyl poly(oxypropylene) aminocarbamates, and especially the problem of low temperature wax formation.

SUMMARY OF THE INVENTION The present invention provides a liquid alkylphenyl poly(oxypropylene) aminocarbamate which does not form a wax when cooled to -40 0 C in a 50 weight percent solution with toluene, said aminocarbamate having at least one basic nitrogen and an average molecular weight of about 600 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxypropylene) aminocarbamate is a substantially straight-chain alkyl group of from about 25 to 50 carbon atoms and is attached to the phenyl group at least 6 carbon atoms from the terminus of the longest chain of the alkyl group.

In a composition aspect, the instant invention is directed toward a fuel compsition containing a novel class of hydrocarbyl poly(oxypropylene) aminocarbamates which as a fuel additive controls combustion chamber deposits thus minimizing ORI and in lubricating oil is compatible with the lubricating oil composition. In particular, the instant invention is directed toward a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of the alkylphenyl poly(oxypropylene) aminocarbamate of the present invention.

92112O,p:\oNi i_ .32.spe,9 n .Paa~-~ WO 90/07564 PCT/US88/04710 01 In another composition aspect, the instant invention is 0 directed to a fuel concentrate comprising an inert stable 02 03 oleophilic organic solvent boiling in the range of 1500 to 04 400°F and from 5 to 50 weight percent of an alkylphenyl poly(oxypropylene) aminocarbamate of this invention.

06 07 In still another composition aspect, the instant invention 0 is directed to a lubricating oil composition comprising an 08 0 oil of lubricating viscosity and a dispersant effective 1 amount of an alkylphenyl poly(oxypropylene) aminocarbamate Sof this invention, 11 12 In still another composition aspect, the instant invention 13 Sis directed to a lubricating oil concentrate comprising 14 from about 90 to 50 weight percent of an oil of 16 lubricating viscosity and from about 10 to 50 weight 17 percent of an alkylphenyl poly(oxypropylene) aminocarbamate of this invention.

18 19 The present invention also relates to the novel alkyl- 21 phenol compounds which are employed to prepare the instant 2alkylphenyl poly(oxypropylene) aminocarbamates. These 22 23 novel alkylphenol intermediate compounds are alkylphenols 2wherein the alkyl group is a substantially straight-chain 24 alkyl group of from about 25 to 50 carbon atoms and is 2attached to the phenol ring at least 6 carbon atoms from 26 2the terminus of the longest chain of the alkyl group.

28 Preferably, the alkyl group on the alkylphenol will 2contain from about 28 to 50 carbon atoms, and more 3preferably, from about 30 to 45 carbon atoms. Moreover, 30 the alkyl substituent is preferably derived from a 31 32 substantially straight chain alpha olefin oligomer of Cg 33to

C

20 alpha olefins.

34 WO 90/07564 PCT/US88/04710 I I 01 Among other factors, the present invention is based on the 02 discovery that the "pinwheel" alklphenyl 03 poly(oxypropylene) aminocarbamates of the present 04 invention having a substantially straight chain alkyl substituent do not produce wax when cooled to -40°C in a 06 50 wt% solution of toluene. These non-waxy carbamates do 07 not produce any traces of crystalline wax under these 08 conditions.

09 It is critical that these aminocarbamates are non-waxy at 11 low temperatures. Fuel additives and lubricating oil 12 additives must all be able to be pumped, for example, into 13 fuels, and to operate effectively under cold conditions in 14 such locations as Alaska or Wisconsin in the wintertime.

Even very small amounts of wax, milligrams, will 16 plug the micron-sized filters that these additives 17 commonly come in contact with. For example, there are 18 micron-sized filters in the additive distribution and 19 blending systems which make additive packages and blends prior to the consumer's purchase. There are also 21 micron-sized filters in automobiles and diesel engines 22 where the fuel is filtered prior to combustion.

23 24 DETAILED DESCRIPTION OF THE INVENTION 26 The alkylphenyl poly(oxypropylene) aminocarbamates of the 27 present invention consist of an amino moiety and an 28 alkylphenyl poly(oxypropylene) polymer bonded through a 29 carbamate linkage, The specific alkylphenyl group employed in the instant invention in the 31 alkylphenyl poly(oxypropylene) polymer is critical to 32 achieving lubricating oil compatibility for the 33 34 a.-Iiii~i~ WO 90/07564 PC/US88/04710 01 alkylphenyl poly(oxypropylene) aminocarbamates, while 02 providing excellent low temperature properties. In 03 particular, it has been found that employing the 04 "pinwheel" alkylphenyl group of this invention wherein the alkyl group is substantially straight-chain of from 25 to 06 50 carbon atoms results in an alkylphenyl 07 poly(oxypropylene) aminocarbamate which is lubricating oil 08 compatible and non-waxy at low temperatures.

09 As used herein, the abbreviation "PO" is meant to 11 designate propylene oxide or propylene oxide-derived 12 polymers. Similarly, the abbreviation "BO" is meant to 13 designate butylene oxide or butylene oxide-derived 14 polymers. Also, the term "EDA" is meant to designate ethylene diamine or ethylene diamine-derived carbamates.

16 Further, the term "DETA" is meant to designate diethylene 17 triamine or diethylene triamine-derived carbamates.

18 19 The term "alpha olefin" or "simple alpha olefin" as used herein refers generally to 1-olefins, wherein the double 21 bond is at the terminal position of an alkyl chain. Alpha 22 olefins are almost always mixtures of isomers and often 23 also mixtures of compounds with a range of carbon numbers.

24 Low molecular weight alpha olefins, such as the C6, C8, C10, C12 and C14 alpha olefins, are almost exclusively 26 1-olefins. Higher molecular weight olefin cuts such as 27 C 16 18 or C 20 24 have increasing proportions of the 28 double bond isomerized to an internal or vinylBdene 29 position; nonetheless these higher molecular weight cuts are also called alpha olefins herein.

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WO 90/07564 PC/US8/04710 13 01 The term "alpha olefin oligomer(s)" (AOO), as used herein 02 means olefin dimers, trimers, tetramers and pentamers 03 prepared or derived from C 8 to C 20 alpha olefins. These 04 AOO's have a pinwheel-type structure consisting of primarily internal disubstituted and trisubstituted 06 olefins. The olefin double bond of these AOO's is 07 generally located at least n-2 carbon atoms from the end 08 of the longest continuous carbon chain, where n is the 09 number of carbon atoms in the starting alpha olefin.

11 The Alkyl Substituent 12 13 The alkyl substituent of the alkyphenyl moiety of the 14 present alkylphenyl poly(oxpropylene) carbamates is a substantially straight-chain alkyl group having from about 16 25 to 50 carbon atoms. The term "substantially 17 straight-chain" is meant to designate an alkyl group 18 wherein greater than about 80 number percent of the 19 individual carbon atoms in the alkyl substituent are either primary (CH 3 or secondary (-CH 2 carbon atoms.

21 Preferably, greater than 85 number percent of the carbon 22 atoms in the alkyl substituent are primary or secondary 23 carbons.

24 The alkyl substituent in the alkylphenyl poly- 26 (oxypropylene) aminocarbamates of the present invention is 27 arranged in what will herein be designated as a "pinwheel" 28 configuration. This configuration has been found to be 29 critical to providing aminocarbamates having non-waxy low temperature characteristics.

31 32 33 34 06- WO 90/07564 PCT/US88/04710 01 By "pinwheel" configuration is meant that the alkyl group 02 is attached, for example to an aromatic ring, at a 03 position significantly removed from the terminus of the 04 longest chain of the alkyl group. This results in at least two hydrocarbon tails, or wheels of the pinwheel, 06 emanating from near the attachment point. By 07 "significantly removed from the terminus" is meant at 08 least 6 carbon atoms from the terminus of the longest 09 chain of the alkyl group, preferably at least 8 carbon atoms toward the center of the chain. Thus a "pinwheel" 11 alkyl phenol has an alkyl group comprising at least two 12 tails of at least six carbon atoms in length, preferably 13 at least 8 carbon atoms in length.

14 Preferred "pinwheel" compounds useful in this invention 16 are those wherein the alkyl substituent has tails which 17 are substantially straight-chain hydrocarbon radicals.

18 19 As will be discussed in more detail below, the alkylphenyl substituent of the aminocarbamate of this invention is 21 derived from the corresponding alkylphenol. A preferred 22 type of alkylphenol is that prepared by alkylating phenol 23 with one or more alpha olefin oligomers. Alkylation with 24 alpha olefin oligomers, such as decene trimer or octene tetramer, provides alkylphenols having "pinwheel" 26 configurations. Such configurations can be represented by 27 structure A as an example of decene trimer-derived 28 alkylphenol and structure B as an example of octene 29 tetramer-derived alkylphenol, as shown below. In these structures, the brackets are intended to denote the 31 various manners of attachment of the alkyl group to the 32 phenol.

33 34 nau wn On/n754 PCr/ US88/04710 01 02 HO 03 04 06

A

07 08 09

HO

11 12 13

B

14 16 The alpha olefin oligomers used herein are prepared by 16 1methods well-known in the art. One preferred method of 18 preparing these oligomers is using BF 3 as the 1oligomerization catalyst, as described, for example, in U.S. Patent Nos. 4,238,343 and 4,045,507, and in 21 Onopchenko, et al., BF 3 -Catalyzed Oligomerization of 2Alkenes (Structures, Mechanisms and Properties). 183rd 2ACS Natl. Meet. (Las Vegas, Mar. 1982). Ind. Eng. Chem., 24 Prod. Res. Dev., 22(2), 182-91 (June 1983).

24 26 27 28 29 31 32 33 34 WO 90/07564 PCT/US88/04710 01 These alpha olefin oligomers are 75% or more di or 02 trisubstituted at the olefin site. For example, an alpha 03 olefin trimer has a structure that can be represented by: 04 06 R R R 07 08 09 11 wherein: R n-2, and n is the carbon number of 12 the starting alpha olefin.

13 14 Alpha olefin oligomers are substantially straight-chain with 16 respect to the number of branched tertiary or 17 quarternary) carbons as a percent of the total number of 18 carbon atoms. That is, greater than 80 percent of the 19 carbon atoms in the molecule are primary or secondary carbons, preferably greater than 85 percent.

21 22 Substantially straight-chain alkyl groups are exemplified in 23 Table A below: 24 26 27 28 29 31 32 33 34 MOMMOMEd

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TABLE A

ALKYLPHENOLS

C

0o 0 Starting Olefin Representative Phenol Structure A B (2) Total A B Percent (3) Primary Secondary Propylene Tetramer (Comparative) 0

HO

R R R Decene Trimer HO-(a' C32 Octene Tetramer Where R is linear C 8 R R R R RHRR Where R is linear C 6 A Primary Secondary Alkyl Carbon Atoms B Tertiary Quarternary Alkyl Carbon Atoms

A

A B, 17 r I I

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WO 90/07564 PCTF/US88/04,710 01 Preferred alpha olefin oligomers (AOO's) are derived from C 8 02 to C 20 alpha olefins, more preferably, C 10 to C 16 alpha 03 olefins. Preferred AOO's are dimers, trimers, tetramers and 04 pentamers. Preferably, the alkyl group of the instant carbamates is derived from alpha olefin oligomers selected 06 from the group consisting of: C 8 tetramers, C 10 trimers, C 12 07 trimers, C 14 dimers and trimers, C 16 dimers and trimers, C 1 8 08 dimers and C 20 dimers.

09 As described above, the alkyl substituent of the present 11 alkylphenyl poly(oxypropylene) aminocarbamates is arranged 12 in a so-called "pinwheel" configuration. This "pinwheel" 13 configuration is readily distinguishable from alkyl groups 14 wherein the hydrocarbon chains are attached at or near the terminus of the longest chain of the alkyl group, i.e., 16 within 1 to 5 carbon atoms of a terminus. Thus, 17 aminocarbamates prepared from simple alpha olefins, (as 18 compared to alpha olefin oligomers) as well as their 19 precursors, including the phenols and the alkylphenyl poly(oxypropylene) alcohols, have alkyl groups in a 21 "terminal" configuration. Compounds having an alkyl group 22 in a terminal configuration are herein designated "terminal 23 compounds", for example, C 20 -2 4 terminal alkyl phenols and 24 terminal alkyl carbamates.

26 In terminal compounds such as terminal alkyl phenols, there 27 is only 1 main chain emanating from near the attachment 28 point of the alkyl group to the phenol. Terminal compounds 29 include those prepared by reacting alpha olefins with phenol under typical acidic reaction conditions.

31 32 33 34 M II WO 90/07564 P(7/US88/04710 01 The Preferred Alkyphenyl Group 02 03 The preferred alkylphenyl group of the alkylphenyl 04 poly(oxypropylene) aminocarbamate employed in this invention is derived from the corresponding alkylphenol of Formula I 06 below: 07 08 OH 09 0 11 12 m 1wherein R is a substantially straight-chain alkyl group of 14 from about 25 to 50 carbon atoms and m is an integer from 1 1 to 2.

16 17 Preferably, R is a substantially straight-chain alkyl 18 group of from 28 to 50 carbon atoms. More preferably, R 19 1is a substantially straight-chain alkyl group of from to 45 carbon atoms.

21 22 When m is one, the alkylphenyl is a monoalkylphenyl; 23 whereas when m is two, the alkylphenyl is a dialkylphenyl.

24 The alkylphenols of Formula I above are prepared by 26 2reacting the appropriate olefin or olefin mixture with 27 phenol in the presence of an alkylating catalyst at a 28 2temperature of from about 60 0 C to 200 0 C, and preferably 29 125CC to 180°C either neat or in an essentially inert solvent at atmospheric pressure. A preferred alkylating 31 catalyst is a sulfonic acid catalyst such as Amberlyst 32 available from Rohm and Haas, Philadelphia, Pennsylvania.

33 34 L_ WO 90/07564 PCT/US88/04710 01 Molar ratios of reactants can be employed. When molar 02 ratios are employed, the reaction yields a mixture of 03 dialkylphenol, monoalkylphenol and unreacted phenol. As 04 noted above, dialkylphenol and monoalkylphenol can be used to prepare the additives used in the compositions of this 06 invention whereas the unreacted phenol is preferably 07 removed from the post reaction mixture via conventional 08 techniques. Alternatively, molar excess of phenol can be 09 employed, 2 to 2.5 equivalents of phenol for each equivalent of olefin with unreacted phenol recycled. The 11 latter process maximizes monoalkylphenol. Examples of 12 inert solvents include benzene, toluene, chlorobenzene and 13 250 thinner which is a mixture of aromatics, paraffins and 14 naphthenes.

16 The preferred alkylphenyl group is derived from a pinwheel 17 phenol. Pinwheel phenols may be prepared from alpha 18 olefin oligomers.

19 Useful AOO derived alkylphenols have average molecular 21 weights in the range of 480 to 790, and average alkyl 22 carbon numbers ranging from 25 to 50, and preferably from 23 28 to 50. More preferred average alkyl carbon numbers are 24 in the range of from 30 to 26 Alternative methods of preparing the alkylphenol compounds 27 used herein are also contemplated. "Pinwheel" alkyl 28 Enenols can be synthesized by any number of methods.

29 These methods typically rely upon either preforming the entire alkyl moiety prior to alkylation of the phenol or 31 subsequently elaborating a preformed alkyphenol wherein 32 the alkyl group has the requisite functionality for 33 34 N

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WO 90/07564 P~/US88/04710 01 further development to a pinwheel alkyl phenol. Thus, one 02 could alkylate phenol with either a pinwheel olefin or a 03 corresponding alcohol, or alkyl halide, such as a chloride 04 or bromide.

06 The exact structure of the final alkyl phenol is difficult 07 to predict with certainty. Alkylations using carbonium 08 ions result in rearrangements during carbonium ion 09 formation and reaction. It is also known that the products of such alkylation schemes can also suffer 11 rearrangements, dealkylations, and realkylations under 12 reaction conditions. Thus, a variety of structures are 13 included in the present invention.

14 Particularly preferred monoalkylphenols employed in this 16 invention are either ortho-monoalkylphenols of Formula II 17 below: 18 R II 21 22 23 or para-monoalkylphenols of Formula III below: 24 OH 1

III

26 0 27 28

R

29 Particularly preferred dialkylphenols employed in this 31 invention are generally 2,4-dialkylphenols of Formula IV 32 below: 33 34 L c~ 1 ;P;nrJarr*m*MII WO 90/07564 PCIr/US88/04710 01 OH 02 03 IV 04 06 07 although there may be minor amounts of 2,6-dialkylphenol of 0Formula V below: 08 09 OH RR V 11 12 13 Preferred Poly(oxypropylene) Component 14 The alkylphenyl poly(oxypropylene) polymers which are 16 utilized in preparing the carbamates of the present 17 invention are monohydroxy compounds, alcohols, often 18 termed alkylphenyl "capped" poly(oxypropylene) glycols and 19 are to be distinguished from the poly(oxypropylene) glycols (diols), which are not alkylphenyl terminated, 21 not capped. The alkylphenyl poly(oxypropylene) 22 alcohols are produced by the addition of propylene oxide 23 to the alkylphenol of Formula I, i.e., 24

OH

26 27 28 m 2under polymerization conditions, wherein R and m are as defined above. In general, the poly(oxypropylene) poly- 3mers will vary in chain length but their properties 32 closely approximate those of the polymer represented by 33 34 II -i ii i -~ir-u*l WO 90/07564 PC-/US8/04710 1-3 01 the average composition and molecular weight. Each poly- 02 (oxypropylene) polymer contains at least 1 oxypropylene 03 unit, preferably from 1 to about 100 oxypropylene units, 04 more preferably from about 5 to about 50 oxypropylene units, and most preferably from about 10 to about 25 oxy- 06 propylene units. Methods of production and properties of 07 these polymers are disclosed in U.S. Patent Nos. 2,841,479 08 and 2,782,240, which are incorporated herein by reference, 09 as well as Kirk-Othmer's "Encyclopedia of Chemical Technology", "'lume 19, p. 507. An alternative method for 11 preparing alkylphenyl poly(oxypropylene) polymers having 12 either 1, 2, or 3 oxypropylene units involves employing a 13 compound of Formula VI below 14 16 CH 3 17 17 C1(CH 2 CHO) H VI 18 19 1wherein q is an integer from 1 to 3. When employing the compound of Formula VI, the phenoxide of the alkylphenol, I, 21 is first prepared and then reacted with the compound of 22 22 Formula VI to yield the desired alkylphenyl poly(oxypro- 23 pylene) polymer having from 1 to 3 oxypropylene units.

24 SCompounds of Formula VI are commercially available or can be prepared by art recognized methods.

26 27 Preferred Amine Component 28 29 The amine moiety of the alkylphenyl poly(oxypropylene) aminocarbamate employed in this invention is preferably 3derived from a polyamine having from 2 to about 12 amine 32 nitrogen atoms and from 2 to about 40 carbon atoms. The 33 34

A

WO 90/07564 PCT/US88/04710 01 polyamine is preferably reacted with an alkylphenyl 02 poly(oxypropylene) chloroformate to produce the alkylphenyl 03 poly(oxypropylene) aminocarbamate additives finding use 04 within the scope of the present invention. The chloroformate is itself derived from alkylphenyl 06 poly(oxypropylene) alcohol by reaction with phosgene. The 07 polyamine, encompassing diamines, provides the product 08 alkylphenyl poly(oxypropylene) aminocarbamate with, on 09 average, at least about one basic nitrogen atom per carbamate molecule, a nitrogen atom titratable by a 11 strong acid. The polyamine preferably has a 12 carbon-tonitrogen ratio of from about 1:1 to about 10:1.

13 14 The polyamine may be substituted with substituents selected from hydrogen, hydrocarbyl groups of from 1 to about 16 10 carbon atoms, acyl' groups of from 2 to about 17 carbon atoms, and monoketo, monohydroxy, mononitro, 18 monocyano, lower alkyl and lower alkoxy derivatives of (B) 19 and "Lower", as used in terms like lower alkyl or lower alkoxy, means a group containing from 1 to about 6 21 carbon atoms. At least one of the substituents on one of 22 the basic nitrogen atoms of the polyamine is hydrogen, e.g., 23 at least one of the basic nitrogen atoms of the polyamine is 24 a primary or secondary amino nitrogen atom.

26 Hydrocarbyl, as used in describing all the components of 27 this invention, denotes an organic radical composed of 28 carbon and hydrogen which may be aliphatic, alicyclic, 29 aromatic or combinations thereof, aralkyl. Preferably, the hydrocarbyl group will be relatively free of 31 aliphatic unsaturation, ethylene and acetylenic, 32 particularly acetylenic unsaturation. The substituted 33 34 ~rrslrm~ WO 90/07564 PCT/US88/04710 01 polyamines of the present invention are generally, but not 02 necessarily, N-substituted polyamines. Exemplary hydro- 03 carbyl groups and substituted hydrocarbyl groups include 04 alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hnxyl, octyl, etc., alkenyls such as propenyl, 06 isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 07 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyi, 08 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 09 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 11 2-(2ethoxyethoxy)ethyl, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl, 12 3,6,9,12-tetraoxatetradecyl, 2-(2-ethoxyethoxy)hexyl, etc.

13 The acyl groups of the aforementioned substituents are 14 such as propionyl, acetyl, etc. The more preferred substituents are hydrogen, C 1

-C

4 alkyls and C1-C 4 16 hydroxyalkyls.

17 18 In a substituted polyamine the substituents are found at any 19 atom capable of receiving them. The substituted atoms, substituted nitrogen atoms, are generally geometric- 21 ally inequivalent, and consequently the substituted amines 22 finding use in the present invention can be mixtures of 23 mono- and polysubstituted polyamines with substituent groups 24 situated at equivalent and/or inequivalent atoms.

26 The more preferred polyamine finding use within the scope of 27 the present invention is a polyalkylene polyamine, including 28 alkylene diamine, and including substituted polyamines, 29 alkyl and hydroxyalkyl-substituted polyalkylene polyamine. Preferably, the alkylene group contains from 2 to 6 31 carbon atoms, there being preferably from 2 to 3 carbon 32 atoms between the nitrogen atoms. Such groups are 33 34 C ~C~ WO 90/07564 PCI-/US88/04710 01 exemplified by ethylene, 1,2-propylene, 02 2,2-dimethyl-propylene trimethylene, 1,3,2-hydroxypropylene, 03 etc. Examples of such polyamines include ethylene diamine, 04 diethylene triamine, di(trimethylene)triamine, dipropylene triamine, triethylene tetramine, tripropylene tetramine, 06 tetraethylene pentamine, and pentaethylene hexamine. Such 07 amines encompass isomers such as branched-chain polyamines 08 and the previously mentioned substituted polyamines, 09 including hydroxy- and hydrocarbyl-substituted polyamines.

Among the polyalkylene polyamines, those containing 2-12 11 amine nitrogen atoms and 2-24 carbon atoms are especially 12 preferred, and the C 2

-C

3 alkylene polyamines are most 13 preferred, in particular, the lower polyalkylene polyamines, 14 ethylene diamine, diethylene triamine, propylene diamine, dipropylene triamine, etc.

16 17 The amine component of the alkylphenyl poly(oxypropylene) 18 aminocarbamate also may be derived from heterocyclic 19 polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle comprises 21 one or more 5-6 membered rings containing oxygen and/or 22 nitrogen. Such heterocycles may be saturated or unsaturated 23 and substituted with groups selected from the aforementioned 24 and The heterocycles are exemplified by piperazines, such as 2-methylpiperazine, 26 N-(2-hydroxyethyl)piperazine, 1,2bis-(N-piperazinyl)-ethane, 27 and N,N'bis(N-piperazinyl)piperazine, 2-methylimidazoline, 28 3-aminopiperidine, 2-aminopyridine, 29 2-(3aminoethyl)3-pyrroline, 3-aminopyrrolidine, N-(3aminopropyl)morpholine, etc. Among the heterocyclic 31 compounds, the piperazines are preferred.

32 33 34 WO 90/07564 PCT/US88/04710 01 Another class of suitable polyamines are diaminoethers 02 represented by Formula VII 03 04 H 2 NX 1 +X 2 +r NH 2

VII

06 07 wherein X1and X2are independently alkylene from 2 to 08 about 5 carbon atoms and r is an integer from 1 to about 09 10. Diamines of Formula VII are disclosed in U.S. Patent No. 4,521,610, which is incorporated herein by reference 11 for its teaching of such diamines.

12 13 Typical polyamines that can be used to form the compounds 14 of this invention by reaction with a poly(oxyalkylene)chloroformate include the following: 16 ethylene diamine, 1,2-propylene diamine, 1,3-propylene 17 diamine, diethylene triamine, triethylene tetramine, 18 hexamethylene diamine, tetraethylene pentamine, dimethyl- 19 aminopropylene diamine, N-(beta-aminoethyl)-piperazine, N-(beta-aminoethyl)piperidine, 3-amino-N-ethylpiperidine, 21 N-(beta-aminoethyl)morpholine, N,N'-di(beta-aminoethyl)- 22 piperazine, N,N'-di (beta-aminoethylimidazolidone-2; 23 N-(beta-cyano-ethyl)ethane-1,2-diamine, 24 l-amino-3,6,9-triazaoctadecane, 1-amino-3,6-diaza-9-oxadecane, N-(beta-aimonoethyl)di- 26 ethanol-amine, 27 N'-acetyl-N-methyl-N-(beta-aminoethyl)ethane-l,2-diamine, 28 N-acetonyl-1,2-propanediamine, N-(beta-nitro- 29 ethyl)-l,3-propane diamine, ethyl)hexahydrotriazine, N-(beta-aminoethyl)hexahydrotri- 31 azine, 5-(beta-aminoethyl)-1,3,5-dioxazine, 32 2-(2-aminoethylamino)--ethanol, 33 2[2-(2-aminoethylamino)ethylamino]-ethanol.

34 WO 90/07564 PCT/US88/04710 01 The amine component of the alkylphenyl poly(oxypropylene) 02 aminocarbamate may also be derived from an 03 amine-containing compound which is capable of reacting 04 with an alkylphenyl poly(oxypropylene) alcohol to produce an alkylphenyl poly(oxypropylene) aminocarbamate having at 06 least one basic nitrogen atom. For example, a substituted 07 aminoisocyanate, such as (R) 2

NCH

2

CH

2 NCO, wherein R is, for 08 example, a hydrocarbyl group, reacts with the alcohol to 09 produce the aminocarbamate additive finding use within the scope of the present invention. Typical aminoisocyanates 11 that may be used to form the fuel additive compounds of 12 this invention by reaction with a hydrocarbylpoly(oxy- 13 alkylene) alcohol include the following: N,N-(di- 14 methyl)aminoisocyanatoethane, generally, N,N-(dihydrocarbyl)aminoisocyanatoalkane, more generally, N-(perhydrocar- 16 byl)-isocyanatopol-olyalkylene polyamine, 17 N,N-(dimethyl)aminoisocyanatobenzene, etc.

18 19 In many instances the amine used as a reactant in the production of the carbamate of the present invention is 21 not a single compound but a mixture in which one or 22 several compounds, predominate with the average compo- 23 sition indicated. For example, tetraethylene pentamine 24 prepared by the polymerization of aziridine or the reaction of dichloroethylene and ammonia will have both lower 26 and higher amine members, triethylene tetramine, 27 substituted piperazines and pentaethylene hexamine, but 28 the composition will be mainly tetraethylene pentamine and 29 the empirical formula of the total amine composition will closely approximate that of tetraethylene pentamine.

31 Finally, in preparing the compounds; of this invention, 32 where the various nitrogen atoms of the polyamine are not 33 34 06 WO 90/07564 PCT/US88/04710 01 geometrically equivalent, several substitutional isomers 02 are possible and are encompassed within the final product.

03 Methods of preparation of amines, isocyanates and their 04 reactions are detailed in Sidgewick's "The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; 06 Nollers' "Chemistry of Organic Compounds", Saunders, 07 Philadelphia, 2nd Ed. 1957; and Kirk-Othmer's 08 "Encyclopedia of Chemical Technology", 2nd Ed., especially 09 Volume 2, pp. 99-16.

11 Preferred Alkylphenyl Poly(oxypropylene) Aminocarbamate 12 13 Having described the preferred alkylphenyl 14 poly(oxypropylene) component and the preferred polyamine component, the preferred alkylphenyl poly(oxypropylene) 16 aminocarbamate additive of the present invention is 16 1obtained by linking these components together through a carbamate linkage i.e., 18 19 0 21 -OCN< 22 wherein the ether oxygen may be regarded as the terminal 23 24 hydroxyl oxygen of the alkylphenyl poly(oxypropylene) 2alcohol component, and the carbonyl grqup is pre- 2ferably provided by the coupling agent, phosgene.

26 27 2The alkylphenyl poly(oxypropylene) aminocarbamate employed 28 in the present invention has at least one basic nitrogen 29 atom per molecule. A "basic nitrogen atom" is one that is 30 3titratable by a strong acid, a primary, secondary, 32 33 34

-I'

lllllllil~--. WO 90/07564 PCT/US88/04710 01 or tertiary amino nitrogen, as distinguished from, for 02 example, an amido nitrogen, i.e., 03 04 0 06 (I -CN< 07 08 which is not so titratable. Preferably, the basic nitro- 09 gen is in a primary or secondary amino group.

11 The preferred alkylphenyl poly(oxypropylene) 12 aminocarbamate has an average molecular weight of from 13 about 600 to 6,000; preferably an average molecular weight 14 of from 800 to 3,000; and most preferably an average molecular weight of from 1,000 to 2,500.

16 17 A preferred class of alkylphenyl poly(oxypropylene) 18 Saminocarbamate can be described by the following general 19Sformula: 21 CH 3 0 22 1 I| 22 >O+CH 2 CHO-- CNH-(R 1 NH) -H 23 2 n

P

24 R m 26 wherein R is a substantially straight-chain alkyl group of 27 from about 25 to 50 carbon atoms; R1 is alkylene of 2 to 6 28 carbon atoms; m is an integer from 1 to 2; n is an integer 29 such that the molecular weight of the compound is from 30 about 600 to 6,000; and p is an integer from 1 to about 6; 31 and wherein said compound does not form a wax when cooled 32 to -40 0 C in a 50 weight percent solution with toluene.

33 Preferably, R is attached to the phenyl ring at least 6 34 1 WO 90/07564 PCT/US88/04710 01 carbon atoms from the terminus of the longest chain of 02 said alkyl group R.

03 04 Hydrophilic-Lipophilic Balance 06 It is important that the relatively hydrophilic propylene 07 oxide polymeric back-bone be balanced by the hydrophobic 08 alkyl carbons of the alkyl phenol. The aminocarbamates of 09 this invention must achieve a good hydrophilic-lipophilic balance (HLB) in order to have sufficient hydrocarbon 11 solubility in oil and therefore to not perform 12 detrimentally with regard to crankcase varnish.

13 14 For good lubricant solubility, It has been found that the ratio of the number of carbon atoms in the alkyl group 16 needs to be about twice the number of propylene oxide 17 units. For example, if the average number of propylene 18 oxide units is n, then the alkyl chain attached to the 19 phenoxy radical should have approximately 2n carbon atoms; preferably, between 2n-4 and 2n+4 carbon atoms; most 21 preferably between 2n and 2n+4 carbon atoms.

22 3 Preparation of the Alkylphenyl 23 Poly(oxypropylene) Aminocarbamate 24 2The additives employed in this invention can be most 2conveniently prepared by first reacting the appropriate 26 2alkylphenyl poly(oxypropylene) alcohol with phosgene to 2produce an alkylphenyl poly(oxypropylene) chloroformate.

28 The chloroformate is then reacted with the polyamine to 29 produce the desired alkylphenyl poly(oxypropylene) '31 aminocarbamate.

31 32 33 34

'A

WO 90/07564 PCT/US88/04710 01 Preparation of aminocarbamates are disclosed in U.S.

02 Patent Nos. 4,160,648; 4,191,537; 4,197,409; 4,236,020; 03 4,243,798; 4,270,930; 4,274,837; 4,288,612; 4,512,610; and 04 4,568,358, which are incorporated wherein by reference.

In general, the reaction of the poly(oxypropylene) 06 compound and phosgene is usually carried out on an 07 essentially equimolar basis, although excess phosgene can 08 be used to improve the degree of reaction. The reaction 09 may be carried out a temperatures from -100 to 100 0

C,

preferably in the range of 0° to 50 0 C. The reaction will 11 usually be complete within 1/4 to 5 hours. Times of reac- 12 tion will usually be in the range of from 2 to 4 hours.

13 14 A solvent may be used in the chloroformylation reaction.

Suitable solvents include benzene, toluene, etc.

16 17 The reaction of the resultant chloroformate with the amine 18 may be carried out neat or preferably in solution.

19 Temperatures of from -100 to 200 0 C may be utilized, the desired product may be obtained by water wash and 21 stripping usually be the aid of vacuum, of any residual 22 solvent.

23 24 The mole ratio of polyamine to polyether chloroformate will generally be in the range from about 2 to 20 moles of 26 polyamine per mole of chloroformate, and more usually 5 to 27 15 moles of polyamine per mole of chloroformate. Since 28 suppression of polysubstitution of the polyamino is 29 usually desired, large molar excesses of the polyamine will be used. Additionally, the preferred adduct is the 31 monocarbamate compound, as opposed to the bis(carbamate) 32 or disubstituted aminoether.

33 T~a~-r~yll*-c~LII-U lli i WO 90/07564 PPr/'(JS88/04710 33 01 The reaction or reactions may be conducted with or without 02 the presence of a reaction solvent. A reaction solvent is 03 generally employed whenever necessary to reduce the 04 viscosity of the reaction product. These solvents should be stable and inert to the reactants and reaction product.

06 Depending on the temperature of the reaction, the 07 particular chloroformate used, the mole ratios, as well as 08 the reactant concentrations, the reaction time may vary 09 from less than 1 minute to 3 hours.

11 After the reaction has been carried out for a sufficient 12 length of time, the reaction mixture may be subjected to 13 extraction with a hydrocarbon-water or 14 hydro-carbon-alcohol-water medium to free the product from any low-molecular-weight amine salts which have formed and 16-any unreacted diamine. The product may then be isolated 17 by evaporation of the solvent. Further purification may 18 be effected by column chromatography on silica gel.

19 Depending on the particular application of the composition 21 of this invention, the reaction may be carried out in the 22 medium in which it will ultimately find use, e.g., 23 polyether carriers or an oleophilic organic solvent or 24 mixtures thereof.and be formed at concentrations which provide a concentrate of a detergent composition. Thus, 26 the final mixture may be in a form to be used directly for 27 blending in fuels.

28 29 An alternative process for preparing the alkylphenyl poly(oxypropylene) aminocarbamates employed in this 31 invention involves the use of an arylcarbonate 32 33 34 li -nxr*l- WO 90/07564 PCT/US88/0471 01 intermediate. That is to say, the alkylphenyl poly(oxy- 02 propylene) alcohol is reacted with an aryl chloroformate 03 to form an arylcarbonate which is then reacted with the 04 polyamine to form the aminocarbamate employed in this invention. Particularly useful aryl chloroformates 06 include phenyl chloroformate, p-nitrophenyl chloroformate, 07 2,4-dinitrophenyl chloroformate, p-chlorophenyl chloro- 08 formate, 2,4-dichlorophenyl chloroformate, and 09 p-trifluoromethylphenyl chloroformate. Use of the aryl carbonate intermediate allows for conversion to amino- 11 carbamates containing close to the theoretical basic 12 nitrogen while employing less excess of polyamine, i.e., 13 molar ratios of generally from 1:1 to about 5:1 of 14 polyamine to the arylcarbonate, and additionally avoids the generation of hydrogen chloride in the reaction 16 forming the aminocarbamate. Preparation of hydrocarbyl 17 capped poly(oxyalkylene) aminocarbamates via an 18 arylcarbonate intermediate are disclosed in U.S. Serial 19 Nos. 586,533 and 689,616, which are incorporated herein by reference.

21 22 As will be appreciated by those skilled in the art, the 23 aminocarbamates of this invention are mixtures of many 24 individual compounds.

26 The alkyl group will typically have a variety of carbon 27 numbers since the starting olefins are not generally pure 28 compounds and, for any given carbon number in the alkyl 29 group, there are many structural isomers. Moreover, monoand dialkyl phenols are generally obtained. Also, the S31 number of propylene oxide units is an average number and 32 different molecules will have a somewhat different number 33 of PO units.

34

M--

a~~rt WO 90/07564 PCT/US88/04710 01 Also included within the scope of this invention are fully 02 formulated lubricating oils containing a dispersant 03 effective amount of an alkylphenyl poly(oxyalkylene) amino 04 carbamate.

06 Contained in the fully formulated composition is: 07 08 1. an alkenyl succinimide., O8 09 2. a Group II metal salt of a dihydrocarbyl 1 dithiophosphoric acid, 11 3. a neutral or overbased alkali or alkaline earth metal 1 hydrocarbyl sulfonate or mixtures thereof, and 13 4. a neutral or overbased alkali or alkaline earth metal 14 alkylated phenate or mixtures thereof.

5. A viscosity index (VI) improver.

16 The alkenyl succinimide is present to act as a dispersant and 17 prevent formation of deposits formed during operation of the 18 engine. The alkenyl succinimides are well-known in the art.

19 The alkenyl succinimides are the reaction product of a polyolefin polymer-substituted succinic anhydride with an 21 amine, preferably a polyalkylene polyamine. The polyolefin 22 polymersubstituted succinic anhydrides are obtained by 23 reaction of a polyolefin polymer or a derivative thereof with 24 maleic anhydride. The succinic anhydride thus obtained is reacted with the amine compound. The preparation of the 26 alkenyl succinimides has been described many times in the 27 art. See, for example, U.S. Patent Nos. 3,390,082; 28 3,219,666; and 3,172,892, the disclosure of which are 29 incorporated herein by reference. Reduction of the alkenyl substituted succinic anhydride yields the corresponding alkyl 31 derivative. The alkyl succinimides are intended to be 32 included within the scope of the term "alkenyl succinimide".

33 34 WO 90/07564 PCT/US88/04710 01 A product comprising predominantly mono or bis-succinimide 02 can be prepared by controlling the molar ratios of the 03 reactants. Thus, for example, if one mole of amine is 04 reacted with one mole of the alkenyl or alkyl substituted succinic anhydride, a predominantly mono-succinimide product 06 will be prepared. If two moles of the succinic anhydride are 07 reacted per mole of polyamine, a bis-succinimide will be 08 prepared.

09 Particularly good results are obtained with the lubricating 11 oil compositions of this invention when the alkenyl 12 succinimide is a polyisobutene-substituted succinic anhydride 13 of a polyalkylene polyamine.

14 The polyisobutene from which the polyisobutene-subst.tuted 16 succinic anhydride is obtained by polymerizing isobutene can 17 vary widely in its compositions. The average number of 18 carbon atoms can range from 30 or less to 250 or more, with 19 a resulting number average molecular weight of about 400 or less to 3,000 or more. Preferably, the average number of 21 carbon atoms per polyisobutene molecule will range from 22 about 50 to about 100 with the polyisobutenes having a 23 number average molecular weight of about 600 to about 1,500.

24 More preferably, the average number of carbon atoms per polyisobutene molecule ranges from about 60 to about 90, and 26 the number average molecular weight ranges from about 800 to 27 1,300. The polyisobutene is reacted with maleic anhydride 28 according to well-known procedures to yield the 29 polyisobutene-substituted succinic anhydride.

31 In preparing the alkenyl succinimide, the substituted 32 succinic anhydride i's reacted with a polyalkylene polyamine 33 L L I WO 90/07564 PCT/US88/04710 37 01 to yield the corresponding succinimide. Each alkylene 02 radical of the polyalkylene polyamine usually has up to 03 about 8 carbon atoms. The number of alkylene radicals can 04 range up to about 8. The alkylene radical is exemplified by ethylene, propylene, butylene, trimethylene, tetramethylene, 06 pentamethylene, hexamethylene, octamethylene, etc. The 07 number of amino groups generally, but not necessarily, is 08 one greater than the number of alkylene radicals present in 09 the amine, if a polyalkylene polyamine contains 3 alkylene radicals, it will usually contain 4 amino radicals.

11 The number of amino radicals can range up to about 9.

12 Preferably, the alkylene radical contains from about 2 to 13 about 4 carbon atoms and all amine groups are primary or 14 secondary. In this case, the number of amine groups exceeds the number of alkylene groups by 1. Preferably the 16 polyalkylene polyamine contains from 3 to 5 amine groups.

17 Specific examples of the polyalkylene polyamines include 18 ethylenediamine, diethylenetriamine, triethylenetetramine, 19 propylenediamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, 21 pentaethylenehexamine, di-(trimethylene)triamine, 22 tri(hexamethylene)tetramine, etc.

23 24 Other amines suitable for preparing the alkenyl succinimide useful in this invention include the cyclic amines such as 26 piperazine, morpholine and dipiperazines.

27 28 29 31 32 33 34 WO90/07564 PCT/US88/04710 01 Preferably the alkenyl succinimides used in the compositions 02 of this invention have the following formula: 03 04

CH----C

1 NfAlkyleneN+

H

n 07 09 wherein: 11 a. R 1 represents .an alkenyl group, preferably a substan- 12 tially saturated hydrocarbon prepared by polymerizing 13 aliphatic monoolefins. Preferably R 1 is prepared from 14 isobutene and has an average number of carbon atoms and a number average molecular weight as described above; 16 17 b. the "Alkylene" radical represents a substantially 18 hydrocarbyl group containing up to about 8 carbon atoms 19 and preferably containing from about 2-4 carbon atoms as described hereinabove; 21 22 c. A represents a hydrocarbyl group, an amine-substituted 23 hydrocarbyl group, or hydrogen. The hydrocarbyl group 24 and the amine-substituted hydrocarbyl groups are generally the alkyl and amino-substituted alkyl analogs 26 of the alkylene radicals described above. Preferably A 27 represents hydrogen; 28 29 d. n represents an integer of from about 1 to 10, and preferably from about i p 31 32 33 34 L

C~

WO 90/07564 PCrUS8/04710 3 01 Also, included within the term "alkenyl succinimide" are the 02 modified succinmides which are disclosed in U.S. Patent No.

03 4,612,132 which is incorporated herein by reference.

04 The alkenyl succinimide is present in the lubricating oil 06 compositions of the invention in an amount effective to act 07 as a dispersant and prevent the deposit of contaminants 08 formed in the oil during operation of the engine. The 09 amount of alkenyl succinimide can range from about 1 percent to about 20 percent weight of the total lubricating oil 11 composition. Preferably the amount of alkenyl succinimide 12 present in the lubricating oil composition of the invention 13 ranges from about 1 to about 10 percent by weight of the 14 total composition.

16 The alkali or alkaline earth metal hydrocarbyl sulfonates 17 may be either petroleum sulfonate, synthetically alkylated 18 aromatic sulfonates, or aliphatic sulfonates such as those 19 derived from polyisobutylene. One of the more important functions of the sulfonates is to act as a detergent and 21 dispersant. These sulfonates are well-known in the art.

22 The hydrocarbyl group must have a sufficient number of 23 carbon atoms to render the sulfonate molecule oil soluble.

24 Preferably, the hydrocarbyl portion has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually 26 alkylaromatic. Most preferred for use are calcium, 27 magnesium or barium sulfonates which are aromatic in 28 character.

29 Certain sulfonates are typically prepared by sulfonating a 31 petroleum fraction having aromatic groups, usually mono- or 32 dialkylbenzene groups, and then forming the metal salt of 33 34 WO 90/07564 PCT/US88/04710 01 the sulfonic acid material. Other feedstocks used for 02 preparing these sulfonates include synthetically alkylated 03 benzenes and aliphatic hydrocarbons prepared by polymerizing 04 a mono or diolefin, for example, a polyisobutenyl group prepared by polymerizing isobutene. The metallic salts are 06 formed directly or by metathesis using well-known 07 procedures.

08 09 The sulfonates may be neutral or overbased having base numbers up to about 400 or more. Carbon dioxide and calcium 11 hydroxide or oxide are the most commonly used material to 12 produce the basic or overbased sulfonates. Mixtures of 13 neutral and overbased sulfonates may be used. The sulfo- 14 nates are ordinarily used so as to provide from 0.3% to by weight of the total composition. Preferably, the neutral 16 sulfonates are present from 0.4% to 5% by weight of the 17 total composition and the overbased sulfonates are present 18 from 0.3% to 3% by weight of the total composition.

19 The phenates for use in this invention are those 21 conventional products which are the alkali or alkaline earth 22 metal salts of alkylated phenols. One of the functions of 23 the phenates is to act as a detergent and dispersant. Among 24 other things, it prevents the deposition of contaminants formed during high temperature operation of the engine. The 26 phenols may be mono or polyalkylated.

27 28 The alkyl portion of the alkyl phenate is present to lend 29 oil solubility to the phenate. The alkyl portion can be obtained from naturally occurring or synthetic sources.

31 Naturally occurring sources include petroleum hydrocarbons 32 such as white oil and wax. Being derived from petroleum, 33 34

IL--

i III"~11-- i~-l WO 90/07564 PCT/US88/04710 01 the hydrocarbon moiety is a mixture of different hydrocarbyl 02 groups, the specific composition of which depends upon the 03 particular oil stock which was used as a starting material.

04 Suitable synthetic sources include various commercially available alkenes and alkane derivatives which, when reacted 06 with the phenol, yield an alkylphenol. Suitable radicals 07 obtained include butyl, hexyl, octyl, decyl, dodecyl, 08 hexadecyl, eicosyl, tricontyl, and the like. Other suitable 09 synthetic sources of the alkyl radical include olefin polymers such as polypropylene, polybutylene, 11 polyisobutylene and the like.

12 13 The alkyl group can be straight-chained or branch-chained, 14 saturated or unsaturated (if unsaturated, preferably containing not more than 2 and generally not more than 1 16 site of olefinic unsaturation). The alkyl radicals will 17 generally contain from 4 to 30 carbon atoms. Generally when 18 the phenol is monoalkyl-substituted, the alkyl radical 19 should contain at least 8 carbon atoms. The phenate may be sulfurized if desired. It may be either neutral or 21 overbased and if overbased will have a base number of up to 22 200 to 300 or more. Mixtures of neutral and overbased 23 phenates may be used.

24 The phenates are ordinarily present in the oil to provide 26 from 0.2% to 27% by weight of the total composition.

27 Preferably, the neutral phenates are present from 0.2% to 9% 28 by weight of the total composition and the overbased 29 phenates are present from 0.2 to 13% by weight of the total composition. Most preferably, the overbased phenates are 31 present from 0.2% to 5% by weight of the total composition.

32 Preferred metals are calcium, magnesium, strontium or 33 barium.

34 WO 90/07564 PCT/US88/04710 01 The sulfurized alkaline earth metal alkyl phenates are 02 preferred. These salts are obtained by a variety of 03 processes such as treating the neutralization product of an 04 alkaline earth metal base and an alkylphenol with sulfur.

Conveniently the sulfur, in elemental form, is added to the 06 neutralization product and reacted at elevated temperatures 07 to produce the sulfurized alkaline earth metal alkyl 08 phenate.

09 If more alkaline earth metal base were added during the 11 neutralization reaction than was necessary to neutralize the 12 phenol, a basic sulfurized alkaline earth metal alkyl 13 phenate is obtained. See, for example, the process of 14 Walker et al, U.S. Patent No. 2,680,096. Additional basicity can be obtained by adding carbon dioxide to the 16 basic sulfurized alkaline earth metal alkyl phenate. The 17 excess alkaline earth metal base can be added subsequent to 18 the sulfurization step but is conveniently added at the same 19 time as the alkaline earth metal base is added to neutralize the phenol.

21 22 Carbon dioxide and calcium hydroxide or oxide are the most 23 commonly used material to produce the basic or "overbased" 24 phenates. A process wherein basic sulfurized alkaline earth metal alkylphenates are produced by adding carbon dioxide is 26 shown in Hanneman, U.S. Patent No. 3,178,368.

27 28 The Group II metal salts of dihydrocarbyl dithiophosphoric 29 acids exhibit wear, antioxidant and thermal stability properties. Group II metal salts of phosphorodithioic acids 31 have been described previously. See, for example, U.S.

32 Patent No. 3,390,080, columns 6 and 7, wherein these 33 34 a.

WO 90/07564 PCT/US88/04710 13 01 compounds and their preparation are described generally.

02 Suitably, the Group II metal salts of the dihydrocarbyl 03 dithiophosphoric acids useful in the lubricating oil 04 composition of this invention contain from about- 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may 06 be the same or different and may be aromatic, alkyl or 07 cycloalkyl. Preferred hydrocarbyl groups are alkyl groups 08 containing from 4 to 8 carbon atoms and are represented by 09 butyl, isobutyl, sec.-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. The metals suitable for forming 11 these salts include barium, calcium, strontium, zinc and 12 cadmium, of which zinc is preferred.

13 14 Preferably, the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula: 16 17

R

2 0 S 18

P

19 RO S M 3 2 1 21 22 wherein: 23 24 e. R 2 and R 3 each independently represent hydrocarbyl radicals as described above, and 26 27 28f. M 1 represents a Group II metal cation as described above.

29 31 The dithiophosphoric salt is present in the lubricating oil 31 3compositions of this invention in an amount effective to 33 34 r WO 90/07564 PCT/US88/04710 01 inhibit wear and oxidation of the lubricating oil. The 02 amount ranges from about 0.1 to about 4 percent by weight of 03 the total composition. Preferably, the salt is present in 04 an amount ranging from about 0.2 to about 2.5 percent by weight of the total lubricating oil composition. The final 06 lubricating oil composition will ordinarily contain 0.025 to 07 0.25% by weight phosphorus and preferably 0.05 to 0.15% by 08 weight.

09 Viscosity index (VI) improvers are either non-dispersant or 11 dispersant VI improvers. Non-dispersant VI improvers are 12 typically hydrocarbyl polymers including copolymers and 13 terpolymers. Typically hydrocarbyl copolymers are 14 copolymers of ethylene and propylene. Such non-dispersant VI improvers are disclosed in U.S. Patents Nos. 2,700,633; 16 2,726,231; 2,792,288; 2,933,480; 3,000,866; 3,063,973; and 17 3,093,621 which are incorporated herein by reference for 18 their teaching of non-dispersant VI improvers.

19 Dispersant VI improvers can be prepared by functionalizing 21 non-dispersant VI improvers. For example, non-dispersant 22 hydrocarbyl copolymer and terpolymer VI improvers can be 23 functionalized to produce aminated oxidized VI improvers 24 having dispersant properties and a number average molecular weight of from 1,500 to 20,000. Such functionalized 26 dispersant VI improvers are disclosed in U.S. Patents Nos.

27 3,864,268; 3,769,216; 3,326,804 and 3,316,177 which are 28 incorporated herein by reference for their teaching of such 29 dispersant VI improvers.

31 Other dispersant VI improvers include amine-grafted acrylic 32 polymers and copolymers wherein one monomer contains at 33 34

IL

WO 90/07564 PC/US88/04710 01 least one amino group. Typical compositions are described 92 in British Patent No. 1,488,382; and U.S. Patents Nos.

03 4,89,794 and 4,025,452, which are incorporated herein by 04 reference for their teaching of such dispersant VI improvers.

06 07 Non-dispersant and dispersant VI improvers are generally 08 employed at from 5 to 20 percent by weight in the 09 lubricating oil composition.

11 Ful Compositions 12 13 The alkylphenyl poly(oxypropylene) aminocarbamates of this 14 invention will generally be employed in a hydrocarbon distillate fuel. The proper concentration of this additive 16 necessary in order to achieve the desired detergency and 17 dispersancy varies depending upon the type of fuel employed, 18 the presence of other detergents, dispersants and other 19 additives, etc. Generally, however, from 30 to 5,000 weight parts per million (ppm), and preferably 100 to 500 ppm and 21 more preferably 200 to 300 ppm of alkylphenyl 22 poly(oxypropylene) aminocarbamate per part of base fuel is 23 needed to achieve the best results. When other detergents 24 are present, a less amount of alkylphenyl poly(oxypropylene) aminocarbamate may be used. For performance as a carburetor 26 detergent only, lower concentrations, for example 30 to 27 70 ppm may be preferred. Higher concentrations, 2,000 28 to 5,000 ppm may result in a clean-up effect on combustion 29 chamber deposits.

31 The deposit control additive may also be formulated as a 32 concentrate, using an inert stable oleophilic organic 33 34 WO 90/07564 PCT/US88/04710 01 solvent boiling in the range of about 150 to 4000F.

02 Preferably, an aliphatic or an aromatic hydrocarbon solvent 03 is used, such as benzene, toluene, xylene or higher-boiling 04 aromatics or aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, 06 n-butanol and the like, in combination with hydrocarbon 07 solvents, are also suitable for use with the 08 detergent-dispersant additive. In the concentrate, the 09 amount of the additive will be ordinarily at least 5 percent by weight and generally not exceed 50 percent by weight, 11 preferably from 10 to 30 weight percent.

12 13 When employing certain of the alkylphenyl poly(oxypropylene) 14 aminocarbamates of this invention, particularly those having more than 1 basic nitrogen, it can be desirable to addition- 16 ally add a demulsifier to the gasoline or diesel fuel 17 composition. These demulsifiers are generally added at from 18 1 to 15 ppm in the fuel composition. Suitable demulsifiers 19 include for instance L-1562

R

a high molecular weight glycol capped phenol available from Petrolite Corp., Tretolite 21 Division, St. Louis, Missouri, and OLOA 2503Z available 22 from Chevron Chemical Company, San Francisco, California.

23 24 26 27 28 29 31 32 33 34 Oh-- ~II Pnrc1~-a~ WO 90/07564 PCT/US88/04710 01 In gasoline fuels, other fuel additives may also be included 02 such as antiknock agents, methylcyclopentadienyl man- 03 ganese tricarbonyl, tetramethyl or tetraethyl lead, or other 04 dispersants or detergents such as various substituted succinimides, amines, etc. Also included may be lead scav- 06 engers such as aryl halides, dichlorobenzene or alkyl 07 halides, ethylene dibromide. Additionally, antioxi- 08 dants, metal deactivators -and demulsifiers may be present.

09 In diesel fuels, other well-known additives can be employed 11 such as pour point depressants, flow improvers, cetane 12 improvers, etc.

13 14 Lubricating Oil Compositions 16 The alkylphenyl poly(oxypropylene) aminocarbamates of this i 17 invention are useful as dispersant additives when employed 18 in lubricating oils. When employed in this manner, the 19 additive is usually present in from 0.2 to 10 percent by weight to the total composition, preferably at about 0.5 to 21 8 percent by weight and more preferably at about 1 to 6 22 percent by weight. The lubricating oil used with the addi- 23 tive compositions of this invention may be mineral oil or 24 synthetic oils of lubricating viscosity and preferably suitable for use in the crankcase of an internal combustion 26 engine. Crankcase lubricating oils ordinarily have a 27 viscosity of about 1300 CSt 0 F to 22.7 CSt at 210°F (99 0

C).

28 The lubricating oils may be derived from synthetic or 29 natural sources. Mineral oil for use as the base oil in i 30 this invention includes paraffinic, naphthenic and other 31 oils that are ordinarily used in lubricating oil composi- 32 tions. Synthetic oils include both hydrocarbon synthetic 33 34 Ohl rl WO 90/07564 PCT/US88/04710 01 oils and synthetic esters. Useful synthetic hy ncarbon 02 oils include liquid polymers of alpha olefins having the 03 proper viscosity. Especially useful are the hydrogenated 04 liquid oligomers of C 6 to C 12 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity such 06 as didodecyl benzene, can be used. Useful synthetic esters 07 include the esters of both monocarboxylic acid and polycarb- 08 oxylic acids as well as monohydroxy alkanols and polyols.

09 Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate and 11 the like. Complex esters prepared from mixtures of mono and 12 dicarboxylic acid and mono and dihydroxy alkanols can also 13 be used.

14 Blends of hydrocarbon oils with synthetic oils are also 16 useful. For example', blends of 10 to 25 weight percent 17 hydrogenated 1-decene trimer with 75 to 90 weight percent 18 150 SUS (100°F) mineral oil gives an excellent lubricating 19 oil base.

21 Additive concentrates are also included within the scope of 22 this invention. The concentrates of this invention usually 23 include from about 90 to 50 weight percent of an oil of 24 lubricating viscosity and from about .10 to 50 weight percent of the additive of this invention. Typically, the concen- 26 trates contain sufficient diluent to make them easy to 27 handle during shipping and storage. Suitable diluents for 28 the concentrates include any inert diluent, preferably an 29 oil of lubricating viscosity, so that the concentrate may be readily mixed with lubricating oils to prepare lubricating 31 oil compositions. Suitable lubricating oils which can be 32 used as diluents typically have viscosities in the range 33 34 1 i~il l WO 90/07564 PCT/US88/04710 01 from about 35 to about 500 Saybolt Universal Seconds (SUS) 02 at 100°F (38 although an oil of lubricating viscosity 03 may be used.

04 Other additives which may be present in the formulation 06 include rust inhibitors, foam inhibitors, corrosion 07 inhibitors, metal deactivators, pour point depressants, 08 antioxidants, and a variety of other well-known additives.

09 The following examples are offered to specifically illus- 11 trate this invention. These examples and illustrations are 12 not to be construed in any way as limiting the scope of this 13 invention.

14

EXAMPLES

16 17 18 Example A 19 Preparation of Alpha-Olefin Oligomers (C 1 4-Derived) 21 Using a Sulfonic Acid Catalyst 22 23 24 This example shows alpha-olefin oligomers useful in this invention. Into a dry 500-ml, three-necked round bottom 26 flask, equipped with a heating mantle, a mechanical stirrer, 27 and a condenser were charged 200 grams of C 14 alpha olefin 28 (Chevron Chemical Co., San Francisco) and 10 grams of an 29 experimental alumina-supported fluorosulfonic acid catalyst (DOW XUS 40036.07), available from Dow Chemical Company.

31 These ingredients were heated and stirred under nitrogen for 32 25 hrs. at 185 0 C. At this time, the dark reaction mixture 33 34 t WO 90/07564 PCT/US88/04710 01 was stripped of any residual C 14 impurities by heating under 02 vacuum, filtered. The product was analyzed by SFC, thus 03 revealing a 95/5 ratio of olefin dimer to trimer. This 04 product was used for phenol alkylation without further purification. This product could not be induced to 06 crystallize at very low temperatures, and as such was 07 regarded as wax free.

08 09 Example B Preparation of Alpha-Olefin Oligomers 11

(C

1 4 -Derived) Using BF3 12 13 This example also shows alpha-olefin oligomers useful in 14 this invention. In this example, the C 14 alpha-olefin of Example A was oligomerized using boron trifluoride gas and 16 an alcohol co-catalyst, as described, for example, in U.S.

17 Patent Nos. 4,238,343 and 4,045,507. Approximately 18 2-1/2 gallons of a clear light yellow liquid containing 19 approximately 67% dimer, 25% trimer, and 8% tetramer/pentamer combined were prepared. This mixture, having an 21 average molecular weight of 472, was converted to the 22 pinwheel alkyl phenol without further purification. This 23 product was a nonviscous liquid at room temperature and 24 below and was, as such, regarded as wax free.

26 27 Example C 28 Preparation of Alpha-Olefin Oligomers (C16Derived) 29 31 This example shows oligomers useful in this invention. The 32 procedure of Example A was followed as a C16 as a C 16 alpha 33 34 WO 90/07564 PCT/US88/04710 5-1 01 olefin. The resulting product was an approximately 95/5 02 mixture of dimers to trimers. This product was a nonviscous 03 liquid at room temperature and below and was, as such, 04 regarded as wax free.

06 Example 1A 07 Preparation of Pinwheel Alkyl Phenols from (C -Derived) Oligomers of Example B 08 14 09 Into a one-liter, three-necked flask, equipped with a 11 heating mantle, mechanical stirrer, and condenser was 12 charged 310 grams (0.66 mole) of the BF3 prepared olefin 13 oligomers of Example B. The liquid was heated to 85 0 C at 14 which time 344 grams (3.83 mole) of liquefied phenol was added followed by 65 grams of dry Amberlist 15. The 16 reaction mixture was theni heated for 24 hours at 150 0 C at 17 which time the resin was removed by hot suction filtration.

18 Excess phenol was removed by vacuum distillation thus 19 affording 343 gms of a non-viscous amber colored pinwheel alkyl phenol (343 grams; Hydroxyl no. 105.4). This phenol 21 had an average alkyl carbon content of 36 carbon atoms.

22 This product was converted to polyoxypropylene alcohol 23 without further purification. This phenol was a nonviscous 24 liquid at room temperature and became a thick oil at lower temperature. No waxing was observed.

26 27 28 29 31 32 33 34 Ob.- Lk WO 90/07564 PP/US88/4710 01 Example 1B 02 Preparation of Pinwheel Alkyl Phenols 03 from Oligomers of Example C.

04 06 The C 16 -derived olefin oligomer of Example C was used to 07 alkylate phenol in a manner similar to that described in 08 Example 1A. The resulting pinwheel alkyl phenol had an 09 average alkyl carbon content of 34 carbon atoms.

11 12 Comparative Example 1C 13 Preparation of a C 20

-C

2 4 Terminal Alkylphenol 14 16 To a 5-liter flask, equipped with stirrer, Dean Stark trap, 17 condensor, and nitrogen inlet and outlet was added 500 gm of 18 a substantially straight chain C 20 to C 24 alpha olefin 19 mixture (approximate olefin content C 18 and less-l%;

C

20

C

22

C

24

C

26 and greater-0.1%) wherein in 21 the entire olefin fraction at least 15 mole percent of said 22 olefins contain vinylidine groups (C 20 to C 24 alpha olefins 23 are available from Chevron Chemical Company, San Francisco, 24 CA), 656 grams of phenol and 75 grams of a sulfonic acid cation exchange resin (polystyrene crosslinked with 26 divinylbenzene) catalyst (Amberlyst 1 5 R available from Rohm 27 and Haas, Philadelphia, PA). The reaction mixture was 28 stripped by heating under vacuum and the product was 29 filtered hot over diatomaceous earth to afford 1050 grams of a C 20 to C 24 terminal alkylphenol with a hydroxyl number of 31 120 mg KOH/gm sample) and with approximate 32 para-alkylphenol content. This phenol was a low melting wax 33 at room temperature.

34 WO 90/07564 PCrT/US88/04710 53 01 Comparative Example 2A 02 Preparation of a C20-C28 Terminal Alkylphenol 03 04 To a 2-liter flask, equipped with stirrer, Dean Stark trap, 06 condensor and nitrogen inlet and outlet was added 674 gms of 07 a substantially straight chain C 20 to C 28 alpha olefin 08 mixture (olefin content: C 18

C

20

C

22

C

24 -13%; 09 C 26

C

28 and greater than C 30 wherein in the entire olefin fraction at least 20 mole percent of said 11 olefins contain vinylidine groups (C 2 0

-C

24 alpha olefins and 12 C 24

-C

28 alpha olefins are available from Chevron Chemical 13 Company, San Francisco, CA and are then physically mixed at 14 an equal mole basis to provide a C20-C28 olefin mixture), 211.5 grams of phenol, 43 grams of a sulfonic acid cation 16 exchange resin (polystyrene crosslinked with divinylbenzene) 17 catalyst (Amberlyst 15 available from Rohm and Haas, 18 Philadelphia, PA). The reaction mixture was heated to about 19 140°C for about 8 hours with stirring under a nitrogen atmosphere. The reaction mixture was stripped by heating 21 under vacuum and the product was filtered hot over 22 diatomaceous earth to afford 574 grams of a C 2 0

-C

28 23 alkylphenol with a hydroxyl number of 110 and with 56% 24 para-alkylphenol content. This alkylphenol had approximately 26% dialkyl phenol and had an average alkyl 26 carbon number of 29. This product was a hard wax at room 27 temperature.

28 29 31 32 33 34 WO 90/07564 PCT/US88/04710 01 Comparative Example 2B 02 Preparation of Low Dialkyl C 20 28 Terminal Alkyl Phenol 03 04 The procedure of Example 2A was used except 966 gm C 2 0

-C

28 0alpha olefins and 211.5 gm of phenol were used. The 06 0resulting alkyl phenol had approximately 6% dialkyl phenol and an average alkyl carbon number of 24. This product was 08 a wax at room temperature.

09 11 12 Comparative Example 2C 13 Preparation of a C 26 -Average Terminal Alkyl Phenol 14 In a separate procedure, the low dialkyl C 20 28 phenol of 16 Example 28 was realkylated using an additional 10% C20-C24 17 alpha Chevron olefin (per conditions described in Example 18 1C). This reaction thus afforded an alkylphenol composed of 19 approximately 16% dialkyl phenol species. The average alkyl carbon number was 26. This product was a wax at room 21 temperature.

22 23 Comparative Example 3 24 Preparation of Tetrapropenylphenol 26 27 To a 2-liter flask, equipped with stirrer, Dean Stark trap, 28 condensor, and nitrogen inlet and outlet was added 567 grams 29 of tetrapropylene, 540 grams of phenol, 72 grams of a sulfonic acid cation exchange resin (polystyrene crosslinked 31 with divinylbenzene) catalyst (Amberlyst 15 available from 32 Rohm and Haas, Philadelphia, PA). The reaction mixture was 33 34 a.

WO 90/07564 PCT/US88/04710 01 heated to about 110*C for about 3 hours with stirring under 02 a nitrogen atmosphere.

03 04 The reaction mixture was stripped by heating under vacuum and the resulting product filtered hot over diatomaceous 06 earth to afford 626 grams of tetrapropenylphenol and with a 07 hydroxyl number of 205 and with 96% para-alkylphenol 08 content.

09 11 Comparative Example 4 12 Preparation of C 2 0 to C 28 Terminal Alkylphenol 13 Poly(oxypropylene) Alcohol 14 To a dried 12-liter 3-necked flask under a nitrogen atmo- 16 sphere was added 3.5 liter of toluene and 2020.5 grams (4.61 17 moles) of a C 20 to C 28 terminal alkylphenol prepared in a 18 manner similar to Example 2A. The system was warmed to 19 approximately 60°C and 60 grams (1.54 moles) of metallic potassium cut into small pieces was slowly added with 21 vigorous stirring. The temperature of the reaction system 22 was allowed to increase during this addition and reached 23 approximately 100°C. After 2-1/2 hours, all of the metallic 24 potassium was dissolved. The reaction system was then allowed to cool to 60 0 C. Afterwards, 4552 grams (78.37 26 moles) of propylene oxide was added to the system by an 27 addition funnel at an addition rate slow enough to avoid 28 flooding of the vapor condensing system. The system was 29 then gently refluxed for 72 hours at which point the temperature increased to 110 0 C and was held there for an addi- 31 tional 3 hours. The system was then cooled to 60°C and the 32 reaction quenched by the addition of 0.54 liter of 3N HCl 33 34 WO 90/07564 PCT/US88/04710 01 solution. The system was then dried by azeotropic distill- 02 ation. The system was then diluted with 10 liters of hexane 03 which was afterwards extracted three times with a slightly 04 basic brine solution (pH 8 to In each extraction, a cuff between the aqueous solution and the hexane solution 06 was formed. The cuff as well as the aqueous solution was 07 discarded after each extraction. The resulting hexane 08 solution was stripped and dried under elevated temperature 09 and high vacuum to afford 4450 grams of the title compound as a light weight oil having a molecular weight of approxi- 11 mately 1435 and a hydroxyl number of 39. The product had an 12 average of 17 PO units. This procedure was repeated to give 13 the product listed as Example 13 below. This product was a 14 waxy paste at room temperature.

16 17 Comparative Example 18 Preparation of C 20 to C 28 Terminal Alkylphenyl 19 Poly(oxypropylene) Chloroformate_ 2To a 12-liter 3-necked flask under a nitrogen atmosphere was 22 added 3 liters of anhydrous toluene and 3042 grams (2.6 23 moles) of C 2 0 to C 2 8 terminal alkylphenyl poly(oxypropylene) 24 alcohol prepared as in Example 4 above. The system was cooled to 5°C with stirring. While stirring, 297 grams 26 moles) of liquid phosgene was added all at once to the 27 reaction system. The reaction system was allowed to warm to 28 room temperature and stirred gently for 24 hours. In order 29 to remove excess phosgene as well as HCl formed during the reaction, the system was vigorously sparged with nitrogen.

31 Infrared analysis of an aliquot revealed a strong chloro- 32 formate absorption at 1785 cm 1 and no detectable alcohol 33 34 i II~__LIILII LIL_____LIII_~1- WO 90/07564 P~T/US88/04710 57 01 absorption at 3450 cm- 1 This product was a waxy paste at 02 room temperature.

03 04 Example 06 Preparation of a Pinwheel Alkylphenyl Poly(oxypropylene) 07 Chloroformate from the Poly(oxypropylene) 08 Alcohol of Example 32 09 11 To a cooled (5 0 C) mechanically stirred solution of the 12 pinwheel poly(oxypropylene) alcohol (440 gr, 0.26 moles) of 13 Example 32, derived from C 14 oligomer, in 1 liter of dry 14 toluene under a nitrogen atmosphere was added all at once 254 ml of a 20% solution of phosgene in toluene (242 gr).

16 The reaction mixture was allowed to warm to room temperature 17 and stirred gently for 24 hours to remove excess phosgene 18 and the HC1 formed during the reaction period. Infrared 19 analysis of an aliquot revealed a strong chloroformate absorption at 1785 cm- and no detectable alcohol -l 21 (3450 cm This product was a liquid at room temperature.

22 23 24 Comparative Example 6 Preparation of C 20 to C 28 Alkylphenyl 26 Poly(oxypropylene) Ethylene Diamine (EDA) Carbamate 27 28 The entire chloroformate/toluene solution of Example 29 Swas diluted with 4 liters of dry toluene. In a separate flask, 2565 grams (42.7 moles) ethylene diamine (EDA) was 31 also diluted with 4 liters of dry toluene. At room 32 temperature, these two solution were rapidly mixed using 33 34 1 i 1 WO 90/07564 PCI/US88/04710 01 two variable apccd teflon gear pumps and a 10 inch Kcnica 02 static mixer. After fifteen minutes, the crude reaction 03 mixture was stripped, diluted with 12 liters of hexane, 04 washed successively once with water and three times with a slightly basic (pH a 9) brine solution. Phase separation 06 of the aqueous brine solution and the hexane solution was 07 improved by adding brine as needed. The hexane solution 08 was separated, dried over anhydrous sodium sulfate, fil- 09 tered and stripped to afford the title product as a light yellow liquid which solidified to a loose paste upon 11 cooling and having an alkalinity value of 30 and 0.75 12 weight percent basic nitrogen. This preparation was 13 repeated to give the product listed as example 23 below.

14 This product was a waxy paste at room temperature and did not pass the wax test as described in Example 16 17 18 Comparative Example 7 19 Preparation of C 20 to C 28 Terminal Alkylphenyl Poly(oxypropylene) Diethylene Triamine Carbamate 21 I22 n the manner described in Example 6 above, 2256 grams (1.53 23 moles) of C 20 to C 28 terminal alkylphenyl poly(oxypropylene) 24 chloroformate prepared similarly to method described in Example 5A above was treated with 2654 grams (25.8 moles) of 26 diethylene triamine (DETA) to afford the title compound 27 having an alkalinity value of 56 and 1.4 weight percent 28 basic nitrogen. This preparation was repeated to give the 29 product listed as Example 27 below. This product was a waxy 30 paste at room temperature and failed the wax test of 31 Example 32 33 34 a.- ~-Cpi ~;Tlx~ar-- WO 90/07564 PCT/US88/04710 51 01 Comparative Example 8 02 Preparation of n-Butyl 03 Poly(oxypropylene) Ethylene Diamine Carbamate 04 2000 grams (0.91 moles) of n-butyl poly(oxypropylene) 06 al.cohol was prepared in the manner of Example 4 by 07 substituting n-butanol for the C 20 to C 28 alkylphenol. The 08 n-butyl poly(oxypropylene) alcohol was then treated with 09 phosgene in the manner of Example 5A to yield the n-butyl poly(oxypropylene) chloroformate which was reacted with 1093 11 grams (18.2 moles) of ethylene diamine in the manner of 12 Example 6 to yield the title compound as a light yellow 13 liquid having an alkalinity value of 22.5 and 0.56 weight 14 percent basic nitrogen. This product was a liquid at room temperature and passed the wax test of Example 16 17 18 Comparative Examples 9-17 19 21 Other hydrocarbyl poly(oxyalkylene) alcohols were prepared 22 by employing different hydrocarbyl groups including those of 23 Examples 2A and 3; by employing different poly(oxyalkylene) 24 groups of different chain lengths. Examples 9 through 17 found below in Table I summarizes the different hydrocarbyl 26 poly(oxyalkylene) alcohols so prepared.

27 28 29 31 ,2 :33 34 WO 90/07564 PCT/US88/0471 0 01 TABLE I 02 03 POLY(OXYALKYLENE) ALCOHOLS OF THE FORMULA 04R 1 3

OC

2

CO~

06 07 Phenol Avg. No.

Source of Alkyl 08 E.R 3Ex. No. R 1rn Carbons 09 9 n-butyl CH 3 -37 4 1110 n-buty. -CH 3 -23 4 12 11 tetrapropenylpheny. 3 -CH 3 -20 12 13 12 tetrapropenyiphenyl 3 -CH 2 CH 3 17 12 14 13 C 20-28 terminal alkylphenyl 2A -CH 3 -17 29 14 C 2 0 2 8 terminal alkyiphenyl 2A -CH 3 -14 29 161 02 em'nlaklhnl A-H3-0 2 17 165 2028 terminal alkylphenyl 2A -CH 3 -6 29 17 17 C 20-28 terminal alkyiphenyl 2A -CH2H 3 1 29 18 17 C 20 28 terminal alkylphenyl 2A -CH 2

C

3 -17 29 19 29 C 20 28 terminal alkyiphenyl 2B -CH 3 -13 24 30 C 20-28 terminal alkylphenyl 2B -CH 3 -14 24 22 32 M-C 14 derived pinwheel 23 alkylphenyl 1A -CH 3 -20 36 24 33 a-C 14 oligomer alkylphenyl alkylphenyl IA -CH 3 -16 36 26 34 a-C 16 oligomer alkylphenyl 27 alkylphenyl lB -CH 3 -17 34 28 29 31 32 33 34 Ek.- WO 90/07564 WO 9007564PCr/US88/04710 TABLE II Carbamates of the Formula R 0 1 1 R 3 +CH 2 CHO+ nCNH+CH 2 -CH 2 -NH+ p H Ex.

n-butyl n-butyl te trapropenylphenyl tetrapropenylphenyl te trapropenylphenyl C 20-28 terminal alkyiphenyl C 20-28 terminal alkylphenyl C 20-28 terminal alkylphenyl C 20-28 terminal alkyiphenyl C 20-28 terminal alkylphenyl C 20 28 terminal alkyiphenyl C 20-28 terminal alkyiphenyl C 20-28 terminal alkyiphenyl C 20-28 terminal alkyiphenyl C 20-28 terminal alkyiphenyl a- 4derived pinwheel alkylphenyl XC14derived pinwheel alkylphenyl M- 6derived pinwheel alkylphenyl Phenol Source Ex. No. R1 -C 1 -CH 3 3 -CH 3 3 -C2H 5 3 C 2 H 3A -CH5 2A -CH 3 2A -CH 3 2A -CH 3 2A -CH 3 2A -CH 3 2AB -CH 3 2 B -CH 3 2 B -CH 3 2 C -CH 3 1A -CH 3 1A -CH 3 1A -CH 3 Avg. No.

of Alkyl Carbons n p -37 -23 -17 -17 -14 -17 -17 -13 -13 -14 20 2 -16 2 -17 2 .1 WO 90/07564 PCT/US88/04710 01 Comparative Examples 18-28 02 03 04 Other hydrocarbyl poly(oxyalkylene) aminocarbamates were prepared by employing different hydrocarbyl groups including 06 those of Examples 2 and 3 and by employing poly(oxyalkylene) 07 groups of different chain lengths. Examples 18 through 28 08 are found in Table II, which summarizes the different 09 hydrocarbyl poly(oxyalkylene) aminocarbamates so prepared.

11 12 Comparative Example 29 13 Preparation of a C 24 Terminal AlkylPhenyl 14 Poly(oxypropylene) Alcohol 16 17 In a manner similar to that described in Example 4, 622 gm 18 (1.45 moles) of the terminal low dialkyl terminal phenol 19 derived from the C 20 to C 28 alpha olefin (Example 2B) was converted to 2048 gm of the poly(oxypropylene) alcohol 21 (Hydroxyl 40.0; MW, 1402) by reaction with approximately 22 17 moles of propylene oxide. This product was a waxy paste 23 at room temperature.

24 26 Comparative Example 27 Preparation of a C24 Average Terminal Alkylphenyl 28 Poly(oxypropylene) Alcohol 29 31 The alkyl phenol of Example 2B was reacted with 13 moles of 32 PO in the manner of Example 4 to give the alkylphenyl 33 poly(oxypropylene) alcohol of the example.

WO 90/07564 PC~/US8/04710 (p3 01 Comparative Example 31 02 Preparation of a C 26 Terminal Alkyl Phenyl 03 Poly(oxypropylene) Alcohol 04 06 The alkyl phenol of Example 2C was converted to a 14 PO 07 polymer (as determined by Nmr) in a manner similar to that 08 described in Example 4, but using 14 moles of PO per mole of 09 phenol. This product was a waxy paste at room temperature.

11 12 Example 32 13 Preparation of Pinwheel Poly(oxypropylene) Alcohols 14 from C 14 Oligomer Derived Phenol of Example 1A 16 This experiment was carried out in dry 2-liter, three-necked 17 flask, equipped with a heating mantle, mechanical stirrer, 18 and a dry ice condenser fitted to maintain an inert nitrogen 19 atmosphere. To a warm solution of dry toluene (250 ml) and 203 grams (0.36 moles) of the pinwheel alkylrhenol of 21 Example 1A was slowly added potassium metal (5.4 gr) in 22 small pieces with vigorous mechanical stirring. The pot 23 temperature increased to approximately 100 0 C during the 24 addition, and after 2-1/2 hours, all of the potassium was dissolved. After cooling to 60 0 C, 585 mls of propylene 26 oxide (486 grams, 8.36 moles) was added in such a way as to 27 avoid flooding of the vapor condensing system. The reaction 28 solution was gently refluxed for 72 hours at which point the 29 temperature rose to 110°C and was held at temperature for an additional 3 hours. After cooling to 60 0 C, the reaction was 31 quenched with 60 ml of 3N HCl (a slight excess) and dried by 32 azeotropic distillation. The crude product was then diluted 33 34 WO 90/07564 PCT/US88/04710 01 with hexane (3 liter), extracted three times with slightly 02 basic brine. In each case, a cuff was formed and discarded.

03 The resulting hexane solution was then stripped and dried 04 under high vacuum to afford 670 gr of a light yellow oil having a molecular weight of approximately 1725 (by hydroxyl 06 number determination). Spectroscopic analysis (1H and 13C 07 Nmr) revealed that this alcohol contained an average of 08 propylene oxide monomer units. This product was a non- 09 viscous liquid at room temperature and could not be induced to crystallize at low temperature.

11 12 13 Example 33 14 Preparation of Pinwheel Alkylphenyl Poly(oxypropylene) Alcohols 16 17 18 The pinwheel alkyl phenol of example 1A (C 14 -derived) was 19 converted to the poly(oxypropylene) alcohol by reaction with 16 mole equivalents of propylene oxide in a manner similar 21 to that described in Example 32.

22 23 24 Example 14 Preparation of Pinwheel Alkylphenyl 26 Poly(oxypropylene) Alcohols 27 28 29 The pinwheel alkyl phenol of example 1B (C 16 -derived) was converted to the poly(oxypropylene) alcohol by reaction with 31 17 mole equivalents of propylene oxide in a manner similar 32 to that described in Example 32.

33 34

WOMMOM"

-ULSILI~ I~IIIIIIP DI~P I~ I~ WO 90/07564 PCT/US88/04710 01 Comparative Example 02 Preparation of the Terminal Low Dialkyl C 20 24 Carbamate EDA 03 04 Without further purification, the terminal alkylphenol 06 alcohol of Example 29 was converted to the chloroformate as 06 described in Example 5A, except that a 20 weight percent 07 solution of phosgene in toluene was employed rather than 08 condensed phosgene liquid (for handling convenience and 09 safety). After reaction, the chloroformate was then 11 vigorously sparged to remove excess phosgene and the HC1 12 reaction by-product.

13 14 The resulting chloroformate was then converted to the corre- 14 sponding EDA carbamate by reaction with ethylene diamine as 16 described in Example 6. The average alkyl carbon number was S24; alkalinity value 34; basic nitrogen was 0.85%. This 18 product did not pass the wax test of Example 19 2 Sequence V-D engine testing as described in Example 43 21 revealed that varnish control was exceedingly poor (4.4, 22 average of three separate tests). In an effort to improve 23 this performance aspect, a similar molecule was synthesized, 2but with less PO. This is shown in Example 36.

26 27 28 29 I 31 32 33 34

A

WO 90/07564 PP/US88/04710 01 Comparative Example 36 02 Preparation of a Terminal C 24 -Average Alkyl Phenyl 03 Poly(oxypropylene) 2.,A Carbamate 04 06 In a separate procedure, the terminal "low" dialkylphenol of 07 Example 2B was converted to a phenol-capped 08 poly(oxypropylene) alcohol containing 13 PO units using a 09 procedure similar to that described in Example 4. This alcohol was converted to the corresponding chloroformate, as 11 in Example 5A using a phosgene/toluene solution. The 12 chloroformate was degassed and used without further 13 purification.

14 One portion of this chloroformate was converted to an EDA 16 carbamate as in Example 6 (alkalinity value 37, 0.93% 17 basic nitrogen). This product did not pass the wax test of 18 Example 19 21 Comparative Example 37 22 Preparation of a C 24 Terminal Alkylphenyl 23 Poly(oxypropylene) DETA Carbamate 24 26 The remainder of the chloroformate of Example 36 was 27 converted to the corresponding DETA carbamate (alkalinity 28 value -67.4, 1.69% basic nitrogen) as in Example 7. This 29 product did not pass the wax test of Example 31 32 33 34 l i WO 90/07564 PM1US88/44710 17 01 Comparative Example 38 02 Preparation of a C 24 -Average Terminal Alkylphenyl 03 Poly(oxypropylene) EDA Carbamate 04 06 The poly(oxypropylene) alcohol of Example 31 was converted 07 to the corresponding chloroformate as in Example 5A and 08 reached with EDA to afford the desired ethylene diamine 09 carbamate in a manner similar to that of Example 6 (alkalinity value 34.0, 0.85% basic nitrogen). This 11 product did not pass the wax test of Example 12 13 As demonstrated by Examples 24, 35, 36, 37, and 38, reducing 14 the number of propylene oxide units in the additive backbone does not improve varnish performance nearly as significantly 16 as does increasing the number of alkyl carbons in the alkyl 17 phenol. As can be seen in Example 35, an average alkyl 18 carbon content of 24 carbon atoms with PO formulations is 19 insufficient to provide the required varnish and sludge control. Neither by reducing the PO content (Example 36) nor 21 by switching to DETA carbamates (Example 37) can varnish 22 performance be restored to the level exemplified by Example 23 24. However, by increasing the dialkyl content to a higher 24 level (Example 38) performance is restored to base case values. None of these examples, however, represents a total 26 solution to the overall problem which additionally requires 27 these additives to be nonwaxy at low temperatures, thus 28 passing the test of Example 29 31 32 33 34

-A

I i WO 90/07564 pCr/US8/04710 01 Example 39 02 Preparation of Alkylphenyl Poly(oxypropylene) 03 Diethylenetriamine Carbamate 04 06 The chloroformate/toluene solution of Example SB was diluted 07 to 2 liters with dry toluene. In a separate flask, 08 530 grams of diethylene triamine (5.2 moles) was also 09 diluted to 2 liters with dry toluene. These two solutions were rapidly mixed using two variable speed teflon gear 11 pumps and a 10-inch Kenics static mixer. The crude reaction 12 mixture was then stripped, diluted with 6 liters of hexane, 13 and washed successively with water basic (pH-9) water 14 and water Phase separation was improved by adding isopropanol as needed. The organic layer was then 16 dried (NaSO 4 filtered and stripped to afford a light 17 orange product which remained a liquid at -40 0 C (alkalinity 18 value 50, 1.25% basic nitrogen). As such, this product 19 was regarded as non-waxy by virtue of passing the wax test of Example 45. This carbamate does not produce detrimental 21 varnish and sludge relative to the base oil.

22 23 24 Examples 40-41 Preparation of Aminocarbamates of the Present Invention 26 27 28 The pinwheel alcohols 33 and 34 were reacted in a manner 29 similar to Examples 5 and 7 to give a C 1 4-derived DETA pinwheel carbamate having 16 oxypropylene units and an 31 average alkyl carbon number of 34 (Example 40) and a 32 C 16 -derived DETA pinwheel carbamate having 17 oxypropylene 33 34

I

WO 90/07564 PCT/US88/04710 01 units and an average alkyl carbon number of 36 (Example 41).

02 These products pass the wax test at -40 0 C and do not produce 03 detrimental sludge or varnish relative to base oil.

04 06 Example 42 07 Oil Solubility Bench Test 08 09 This procedure was designed to determine the oil 11 solubility/compatibility of different additives in a fully 12 formulated lubricating oil. Insofar as as much as 25-30% of 13 a gasoline additive can enter into the crankcase via blow-by 14 and/or cylinder wall/piston ring "wipe down", this is an important performance criteria.

16 17 The lubricating oil composition was formulated to contain: 18 6 percent by weight of a monopolyisobutenyl succinimide; 19 millimoles per kilogram of a highly overbased sulfurized calcium phenate; 30 millimoles per kilogram of a highly 21 overbased sulfurized calcium hydrocarbyl sulfonate; 22.5 22 millimoles per kilogram of a zinc dithiophosphate; 13 weight 23 percent of a commercial non-dispersant viscosity index 24 improver; 5 parts per million of a foam inhibitor in 150N Exxon base oil to give a 10 W 40 formulated oil.

26 27 The oil solubility of the additive was determined as 28 follows: 29 To a heated solution (50 grams) of the above-described lube 31 oil was added 50 grams of the neat additive. The mixture 32 33 34 I WO 90/07564 PCT/US88/04710 01 was then heated with constant stirring to 170°F and main- 02 tained at that temperature for 15 minutes. Dilutions were 03 then prepared according to the desired solubility test range 04 using fresh hot reference oil as the diluent. In each case, the diluted samples were stirred to 170 0 F for 10 minutes to 06 insure complete mixing. The solutions were then sealed and 07 left to cool undisturbed for from 1-5 days typically at room 08 temperature. Each sample was then rated visually for oil 09 continuity.

11 Additives that were marginally soluble in this blend 12 separated as a denser secondary phase, and were clearly 13 visible as such without the need for centrifugation.

14 Additives which gave rise to oil incompatibility problems were inherently oil soluble, however, they tended to 16 displace what appears to be the VI (viscosity index) 17 improver. This phenomenon resulted in the separation of the 18 VI improver which is less dense than the bulk oil forming a 19 clear thick upper layer. The solubility/compatibility of a gasoline additive was thereby defined as the highest con- 21 centration (on a weight basis) which did not result in the 22 formation of either an insoluble lower additive phase or an 23 insoluble uppe. VI improver phase.

24 The oil solubility (or insolubility) of the hydrocarbyl 26 poly(oxyalkylene) aminocarbamates including the alkylphenyl 27 poly(oxypropylene) aminocarbamates of this invention is 28 believed to correlate well to the oil solubility of the 29 precursor hydrocarbyl poly(oxyalkylene) alcohol. Accordingly, Table III below contains solubility data for the 31 hydrocarbyl poly(oxyalkylene) alcohols. Oil solubility is 32 reported in weight percent of additive in the lubricating 33 oil composition.

34 WO 90/07564 PCT/US88/04710 -1 1 TABLE III Example No 9 11 12 13 14 16 17 Oil Solubility 8 18 27 The oil solubility of the amino carbamates is reported in Table IV.

Example 43 Sequence V-D Test Method Formulated oils containing alkylphenyl poly(oxypropylene) aminocarbamate were tested in a Sequence V-D test method as well as formulated oils containing comparative hydrocarbyl poly(oxyalkylene) aminocarbamates. This procedure utilizes a Ford 2.3-liter, four-cylinder Pinto engine. The test method simulates a type of severe field test service characterized by a combination of low speed, low temperature "stop and go" city driving and moderate turnpike operation.

The effectiveness of the additives in the oil is measured in a- WO 90/07564 PCT/US88/04710 01 terms of the protection against sludge and varnish deposits 02 on a 0 to 10 scale with 0 being black and 10 indicating no 03 varnish or sludge deposits. The results of these tests are 04 found in Table IV below.

06 The reference composition was formulated to contain: 07 6 percent by weight of a mono-polyisobutenyl succinimide; 08 millimoles per kilogram of a highly overbased sulfurized 09 calcium phenate; 30 millimoles per kilogram of a highly overbased calcium hydrocarbyl sulfonate; 22.5 millimoles per 11 kilogram of a zinc dithiophosphate; 13 weight percent of a 12 commercial non-dispersant viscosity index improver; 5 parts 13 per million of a foam inhibitor in 150N Exxon base oil to 14 give a 10 W 40 formulated oil.

16 Comparisons against this reference were made by employing an 17 oil formulated identically as the reference except for the 18 additional amount of the additive as shown in Table IV 19 below: 21 22 23 24 26 27 28 29 31 32 33 34 ~1 WO 90/07564 PCT/US88/04710 173 TABLE IV Carbamate Performance and Properties Ex.

Oil (1) Compatibility 1 7 16 16 16 Crankcase (3) Wax Av. Varnish -40 0 C 2.5 5.5 no 4.4 Crankcase Av. Sludge 2.5 5.4 HC 9.2 5.7 5.5 9.5 yes yes yes yes yes yes yes yes yes yes 12 9.55 12 12 29 9.35 29 29 29 29 29 6.4 7.5 9.6 4.4 5.4 7.4 6.2 (6) (6) (6) 9.4 9.2 9.4 34 36 34 21 22 23 24 26 27 28 29 31 32 33 34 See Ex. 42 See Ex. See Ex. 43 Rating scale 1-10, with 10 meaning no varnish or sludge.

Weight percent additive.

Average alkyl carbon number in alkyl phenyl group These carbamates are not detrimental relative to the base oil of Example Ir WO 90/07564 PCT/US88/04710 01 Examples 18 through 22 represent prior art hydrocarbyl 02 poly(oxyalkylene) aminocarbamates. This Table establishes 03 that the alkylphenyl poly(oxypropylene) aminocarbamates of 04 this invention (Examples 39-41) were less detrimental, i.e.

gave decreased crankcase deposits, as measured by average 06 varnish in the Sequence V-D results.

07 08 The table also establishes that the additives of this 09 invention possess lubricating oil compatibility. This is particularly surprising in view of the fact that prior art 11 hydrocarbyl poly(oxypropylene) aminocarbamates are not 12 lubricating oil compatible, Examples 18, 19 and 13 14 Example 44 1,6 TGA Stability of Amino Carbamates 17 18 19 The thermal oxidative stability of fuel additives can be measured by thermogravimetric analysis (TGA). The TGA 21 procedure employed Du Pont 951 TGA instrumentation coupled 22 with a microcomputer for data analysis. Samples of the fuel 23 additives, approximately 25 milligrams, were heated isother- 24 mally at 200 0 C under air flowing at 100 cubic centimeters per minute. The weight of the sample was monitored as a 26 function of time. Incremental weight loss is considered to 27 be a first order process. Kinetic data, rate 28 constants and half-lives, were readily determined from the 29 accumulated TGA data. The half-life measured by this procedure represents the time it takes for half of the additive 31 to decompose and evaporate. Half-life data for a fuel 32 additive correlates to the likelihood that that additive 33 34 WO 90/07564 PCT/US88/04710 01 will contribute to ORI. Lower half-lives represent a more 02 easily decomposable product one which will not as likely 03 accumulate and form deposits in the combustion chamber. All 04 of the comparative carbamate examples and the carbamate examples of the present invention have good TGA performance, 06 i.e. half lives of less than about 4 hours, and therefore 07 will contribute minimally to ORI.

08 09 Example 11 Determination of Additive Waxiness 12 I 13 14 Since it is not unusual for solutions of these additives to be subjected to cold temperature extremes, it is important 16 that solids (typically waxy) are not formed during handling, 17 storage, or in actual field use. When formed, these waxy 18 constituents can totally plug the in-line filtering devices 19 normally in service in additive distribution systems and the fuel or lube systems of actual operating engines. Such a 21 plugging would obviously be catastrophic and must be 22 avoided. The following test procedure constitutes a reason- 23 able evaluation of this low temperature tendency and serves 24 as the critical distinguishing feature of this invention whereby PO oligomers are to be employed as 26 dispersants/detergents.

27 28 The test additive (30 gr) is dissolved in an equivalent 29 weight of reagent grade toluene, cooled to -40 0 C, and held at that temperature for four weeks. The sample solution is 31 then inspected for visual clarity ("brightness"). If any 32 sedimented solids appear or the sample is hazy, the sample 33 34 L WO 90/07564 PCT/US88/04710 -7( 01 has failed the test. A sample which passes this test is one 02 described as "clear and bright", a well-known 03 industry-designated standard.

04 06 Example 46 07 Measuring the Epoxide Content 08 09 Nmr spectroscopy provides a method for measuring the 11 backbone "epoxide content" of these additives. The ether 12 carbons and their associated protons are segregated and 13 easily "counted".

14 The "epoxide count", independently determined from carbon 16 and proton Nmr spectra is averaged and gives good repeat- 17 ability and consistent agreement with our experimental 18 charge mole ratios and reaction mass balance data. Analysis 19 of the polyethers can be done at the alcohol stage or later on in the products.

21 22 Analyses were performed using a Varian VXR 300. The 23 polyethers were dissolved "as is" in deuteromethylene 24 chloride (30 mg/ml), and the proton FT Nmr spectra was determined according to the instrument parameters detailed 26 below.

27 28 For carbon FT Nmr spectra, the polyethers were also 29 dissolved in deuteromethylene chloride (400 mg/ml) which contained approximately 5 mg of a relaxation agent 31 Cr(III)-tris-acetylacetonate, Cr(III)(AcAc) 3 32 All spectra were determined using high performance 5 mm Nmr 33 t'ibes.

34 ~zn WO 90/07564 PCT/US88/04710 1-7 01 Instrument Conditions 02 To Observe Proton To Observe Carbon Frequency Spectral Width Acq. Time Relax. Delay Pulse Width Temperature No. Repetitions Spin Rate FT Size 299.944MHz 5000 Hz 1.6 Sec 2.0 Sec 140 Ambient 16 20 Hz 16K 75.429 MHz 20492 Hz 0.4 Sec 2.0 Sec Ambient 2048 24 Hz 32K Determination of Inteqral Values Proton Nmr Spectra The aromatic protons (6.5 to 7.5 ppm) serve as the internal standard for this evaluation. When dealing with products derived from "high dialkylation" phenols (20 to the integral value for this region of the spectra is divided by 3.75. This signal value per proton is then used to evaluate ether carbon proton content. Otherwise, this signal is attributed to four aryl protons (for phenols having dialkylation).

The ether protons of interest lie in the region between 3.2 and 4.0 ppm. Here we see the mass of methylene and methine protons which include the separated multiplets observed for the first and the last epoxide units assembled in these polyethers. One-half of the total number of PO related WO 90/07564 PCT/US88/04710 01 protons are observed in this region, whereas only 02 three-eighths of the BO-related protons are represented 03 here.

04 Carbon Nmr Spectra 06 07 The six aromatic carbons (105 to 160 ppm) serve as the 08 internal standard for this evaluation. This is no need to 09 make any allowances for the presence of dialkyl phenol in this case.

11 12 The ether carbons of interest lie in the region between 13 and 80 ppm. Bearing in mind that only two-thirds of the 14 observable PO-related carbons are counted in this region (one-half for BO polymers), the calculation to determine 16 epoxide units is straightforward.

17 18 19 Example 47 Determination of the Nature of the Alkylphenyl Group 21 22 23 Analytical methods for determining the general nature of the 24 alkylphenyl substituent of the aminocarbamates can be accomplished in the following manner: 26 27 A sample of an alkylphenyl poly(oxyalkylene) aminocarbamate 28 identified by Infrared and Nmr spectroscopy) is hydrolyzed 29 using strong base to afford the corresponding polyoxyalkylene alcohol. Further nonoxidative thermal 31 degradation strips away the polyether portions leaving 32 behind the alkyl phenol. This residue can then be examined 33 34 L I LC jri WO 90/07564 PCT/US88/04710 01 by Mass Spectroscopy for the appearance of the tropylium ion 02 species. Alkyl phenols tend to fragment in such a way that 03 the larger of the two (or three) benzylic substituents will 04 be eliminated in the formation of the observed phenol ion species. Thus, the tropylium ions generated from simple 06 alpha olefins will typically contain from 1-3 carbon atoms 07 more than those accounted for by the aromatic ring itself.

08 By comparison, the same ionized species generated from the 09 pinwheel alkyl phenols employed in the invention, such as those derived from an alpha olefin oligomer, will contain 11 many more carbon atoms due to fragmentation at the benzylic 12 positions.

13 14 It is important to recognize that such tropylium ion species are readily formed from alkyl phenols, and high energy 16 impact ionization may be too severe a technique for all 17 cases. As a result, under forcing conditions, more detailed 18 information concerning the structure of the alkyl portion 19 may be lost. In these cases, it is possible to examine "low energy" impact ionization which may be useful for observing 21 these tropylium ions. In any event, tropylium ions are 22 noted for their relative stability and more often than not 23 appear as the base ion peak (peak of highest relative 24 intensity). See: Silverstein, Bassler, and Morril, Spectrometric Identification of Organic Compounds. Wiley 26 and Sons (New York, 1974) pp. 19-22.

27 28 Another less preferred but supporting analysis can be per- 29 formed by conducting carefully controlled oxidations of the alkyl phenol side chains. This is typically done via 31 aqueous potassium permanganate oxidation under pH conditions 32 designed to control the extent of the oxidative chain 33 34 SWO 90/07564 PCT/US88/04710

.I

01 cleavage reactions desired. If the alkyl phenol has been 02 derived by alkylation with, for example, linear alpha ole- 03 fins, then a bimodal distribution of low and high molecular 04 weight alkanoic acids will result. However, if the phenol in question is a pinwheel alkyl phenol and the phenyl ring 06 is.attached toward the center of the alkyl chain, then 07 higher molecular weight alkanoic acids will be observed, 08 although they may not comprise the majority of oxidation 09 reaction products. Hence, for a pinwheel alkyl phenol derived from a C 1 0 a-olefin oligomer one would expect to 11 observe the corresponding C 7

-C

9 alkanoic acids after 12 degradation. On the other hand, when 13 the phenol derived from simple C 20 alpha olefin alkylation 14 is examined, high molecular weight acid fragments will also be produced and observed which will reflect the existence of 16 these longer chains in the original phenol.

17 18 It should be noted that due to the general severity of these 19 reaction conditions, one may observe only small quantities of these heavier acids. However, by derivatization they may 21 be observed chromatographically. In concert with other 22 general data such as phenol MW, dialkylation level, etc.

23 this method can be informative.

24 i 26 27 28 29 31 32 33 34 SWO 90/07564 PCT/US88/04710 i 01 Example 48 02 Determination of Average Alkyl Hydrocarbon 03 Content of Alkylphenols 04 06 Chemical Method 07 08 After determining the hydroxyl number (mg KOH/gr sample) for 09 a given phenol, the molecular weight is calculated: MW 56,100/hydroxyl number, wherein 56,100 is the meg. wt. of 11 KOH.

12 13 Since the phenol portion of these products accounts for 91 14 mass units, the balance (MW 91) is due to the average alkyl hydrocarbon content.

16 17 As these alkyl groups.are saturated hydrocarbons, dividing 18 the balance portion by 14 (the mass units for a -CH 2 19 moiety) gives the average number of alkyl hydrocarbon atoms in the phenol.

21 22 Spectroscopic Method 23 24 Alternatively, Nmr analysis can be used to determine the average alkyl hydrocarbon content. Nmr analysis of 26 integrated H spectra indicate the relative balance of aryl 27 to aliphatic hydrogens which can be used to approximate the 28 average hydrocarbon content of the phenol.

29 This information may also be obtained by using integrated 31 13C Nmr spectra of these products. Thus, the number of 32 aromatic carbons can be used as an internal standard for 33 S34

I

IPIYL~C

WO 90/07564 P~/US880410 01 gauging the average number of saturated carbons in the 02 phenol. Typically, the H and 13C Nmr results are averaged 03 and are in good agreement with the chemical determination.

04 It is assumed that the average alkyl hydrocarbon content of 06 the phenols does not change during the reaction to make the 07 alcohols, chloroforinates and carbamates.

08 09 11 12 13 14 16 17 18 19 21 22 23 24 26 27 28 29 31 32 33 34

Claims (18)

1. A liquid alkylphenyl poly(oxyproplene) aminocarbamate which does not form a wax when cooled to -40 °C in a 50 weight percent solution with toluene, said amino carbamate having at least one basic nitrogen and an average molecular weight of 600 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxypropylene) aminocarbamate is a substantially straight-chain alkyl group of from 25 to 50 carbon atoms and is attached to the phenyl group at least 6 carbon atoms from the terminus of the longest chain of the alkyl group.

2. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 1, wherein the alkyl group of said alkylphenyl poly(oxypropylene) aminocarbamate is a substantially straight-chain alkyl group of from about 28 to about 50 carbon atoms.

3. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 2, wherein the alkyl group of said alkylphenyl poly(oxypropylene) aminocarbamate is a substantially straight-chain alkyl group of from about 30 to 45 carbon atoms. 20 4. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 1, wherein the alkyl group of said alkylphenyl poly(oxypropylene) aminocarbamate I is derived from a substantially straight-chain alpha olefin oligomer of C 8 to C 2 0 alpha olefins. j 25 5. An alkylphenylpoly(oxypropylene) aminocarbamate according to Claim 1, wherein said alkylphenyl poly(oxypropylene) aminocarbamate contains from 1 to about 100 oxypropylene units.

6. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 5, wherein the poly(oxypropylene) group of said alkylphenyl poly(oxypropylene) aminocarbamate contains from about 5 to about 50 oxypropylene units. S921120,p:\oper\dab,32868.spe,83 -84-

7. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 6, wherein said alkylphenyl poly(oxypropylene) aminocarbamate contains from about to 25 oxypropylene units.

8. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 1, wherein the aminocarbamate group of said alcylphenyl poly(oxypropylene) aminocarbamate is derived from a polyamine having 2 to 12 amino nitrogen atoms and 2 to 40 carbon atoms.

9. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 8, wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms.

10. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 9, wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, diethylene triamine and dipropylene triamine.

11. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.

12. An alkylphenyl poly(oxypropylene) aminocarbamate according to Claim 1, wherein said alkylphenyl poly(oxypropylene) aminocarbamate has an average molecular weight of from about 1,000 to about 2,500.

13. A compound of the Formula 303 o+CH2CHC+ C-NH+RlNH+ P R m 921120,p:\oper\dab,3268sp*,84 i 1. wherein R is a substantially straight-chain alkyl group of from 25 to 50 carbon atoms and is attached to the phenyl ring at least 6 carbon atoms from the terminus of the longest chain of said group R; R 1 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from 600 to 6,000; and p is an integer from 1 to 6; and wherein said compound does not form a wax when cooled to -40 0 C in a 50 weight percent solution with toluene.

14. A compound according to Claim 13, wherein R is a substantially straight-chain alkyl group of from about 28 to about 50 carbon atoms. A compound according to Claim 14, wherein R is a substantially straight-chain alkyl group of from about 30 to 45 carbon atoms.

16. A compound according to Claim 13, wherein R is a substantially straight-chain alkyl group derived from a substantially straight-chain alpha olefin oligomer of C 8 to C 2 0 alpha olefins.

17. A compound according to Claim 13, wherein n is an integer from about 1 to about 100.

18. A compound according to Claim 17, wherein n is an integer from about 5 to about

19. A compound according to Claim 18, wherein n is an integer from about to about A compound according to Claim 13, wherein the compound has an average molecular weight of from about 1,000 to 2,500. I d r 921120,p:\oper\dab,32868.spe,85 ~E nr~raanrr~:

86- 21. A fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from 30 to 5,000 parts per million of a compound as defined in any one of the preceding claims. 22. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of 150 C to 400 °F and from 5 to 50 weight percent of a compound as defined in any one of claims 1 to 23. A lubricating oil composition comprising an oil of lubricating viscosity and a dispersant effective amount of a compound as defined in any one of claims 1 to 24. A lubricating oil concentrate comprising from 90 to 50 weight percent of an oil lubricating viscosity and from 10 to 50 weight percent of a compound as defined in any one of claims 1 to S: 25. An alkylphenol wherein the alkyl group is a substantially straight-chain alkyl group of from 25 to 50 carbon atoms and is attached to the phenol ring at least 6 carbon atoms from the terminus of the longest chain of the alkyl group. 26. An alkylphenol according to Claim 25, wherein the alkyl group contains .from about 28 to 50 carbon atoms. 27. An alkylphenol according to Claim 26, wherein the alkyl group contains from about 30 to 45 carbon atoms. 28. An alkylphenol according to Claim 25, wherein the alkyl group is Sderived from a substantially straight-chain alpha olefin oligomer of C 8 to C20 alpha olefins. 921120,poper\dab,32868.s 86 921120,p:\oper\ dab,32868.spe,86 -I I i-i- I -87- 29. Liquid alkylphenyl poly(oxypropylene) aminocarbamates or fuel compositions, fuel concentrates or lubricating oil concentrates containing them, substantially as hereinbefore described with reference to the Examples. Compounds according to Claim 13 or fuel compositions, fuel concentrates or lubricating oil concentrates containing them, substantially as hereinbefore described with reference to the Examples. 31. Alkylphenols according to Claim 25, substantially as hereinbefore described with reference to the Examples. i: i; I r DATED this 20th day of November 1992 20 Chevron Research and Technology Company By Its Patent Attorneys DAVIES COLLISON CAVE V* 921120,p:\oper\d~ib,32868.spe,87 i i r s i i ii i-i .:I ii i;i -i INTERNATIONAL SEARCH REPORT International Application No. PCT/US88/04710 1. CLASSIFICATION OF SUBJECT MATTER (if several classrfication symbols apply, indicate all) 6 According to International Patent Classification (IPC) or to both National Classification and IPC INT. CL C1OM 133/56; ClOL 1/22, 1/18; C07C 125/06 TIT. CT, 252/51.5A: 44/71: 560/137. 159 II. FIELDS SEARCHED II. FIELDS SEARCHED I Minimum Documentalon Searched 7 Classification System Classification Symbols US 252/51.A; 44/71; 560/137, 159 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched B

111. DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category Citation of Document, with indication, where appropriate. of the relevant passages 12 Relevant to Claim No.13 Y US, A, 4,568,358, (Courtney), 1-24 04 February 1986, See entire document. 27-30 Y US, A, 4,288,612, (Lewis et al), 1-30 08 September 1981, See entire document. Y US, A, 4,270,930, (Campbell et al), 1-24 02 June 1981, See entire document. 7- 27-30 Y US, A, 4,236,020, (Lewis et al), 1-30 November 1980, See entire document. Y US, A, 4,233,168, (Lewis et al), 1-22, 11 November 1980, See entire document. 25-30 Special categories of cited documents: 10 later document published after the international iGling date document defining the general sate ofthe art which is not or priority date and not in confict with the application but cited to understand the principle or theory underlying the considered to be ol particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason las specified) cannot be considered to involve an inventive steo when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search i Date of Mailing of this International Search Report May 16, 1989 0 7 JUN 198 International Searching Authority Sgnatle It Authori d Officer ISA/US Elen McAvoy FonrPCTASMtO (wond shee) (Rev.11.87) International Applicaion No, PCT/US 88 /04710 111, DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category *I Citation of Document, with indication, where appropriate. of tie relevant passages IRelevant to Claim No Y YI A A A A US, A, 4,191,537, (Lewis et al), 04 March 1980, See entire document. US, A, 4,160,648, (Lewis et al), July 1979, See entire document. us, A, 4,329,240, (Lilburn), 11 May 1982, See entire document. US, A, 4,289,634, (Lewis et al), September 1981, See entire document. US, A, 4,274,837, (Lilburn), 23 June 1981, See entire doi.ui.tent. US, A, 4,197,409, (Lilburn), 08 April 1980, See entire document. I 1-30 1-24 1-30 1-30 1-30 1-30 PUTW CflSD2tO(Wa Imu (Puw.1 147)