CA1341045C - Lubricating oil compositions and fuel compositions containing substantially straight chain pinwheel alkylphenyl poly(oxypropylene) amino carbamates - Google Patents

Abstract

Disclosed are liquid alkylphenyl poly(oxypropylene) aminocarbamates which do not form a wax when cooled to -40°C
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 alkylphenyl poly(oxypropylene) aminocarbamates.

Description

1341 p45 O1 LUBRI(:ATING OIL COMPOSITIONS AND
02 FUEh COMPOSITIONS CONTAINING
SUHSTANTI:ALLY STRAIGHT CHAIN PINWHEEL
03 ALKYLPHENYL fOLY(OXYPROPYLENE) AMINOCARBAMATES
04 BACF:GROUND OF THE INVENTION

06 field of the Invention 08 Numerous deposit-foaming substances are inherent in 9 hydrocarbon fuels. These substances when used in internal combustion engines tend to form deposits on and around 11 Constricted areas of: the engine contacted by the fuel.
12 Typical areas commonly and sometimes seriously burdened by 13 the formation of deposits include carburetor ports, the 14 throttle body and ve~nturies, engine intake valves, etc.
16 Deposits adversely affect the operation of the vehicle. For 17 example, deposits on. the carburetor throttle body and 18 venturies increase the fuel to air ratio of the gas mixture 19 to the combustion chamber thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the 21 Chamber. The high fuel-air ratio also reduces the gas 22 mileage obtainable from the vehicle.

24 Deposits on the engine intake valves when they get sufficiently heavy, on the other hand, restrict the gas 26 mixture flow into the combustion chamber. This restriction, 27 starves the en~~ine of air and fuel and results in a loss of 28 power. Deposits on the valves also increase the probability 29 of valve failure due to burning and improper valve seating.
In addition, these deposits may break off and enter the 31 combustion chamber possibly resulting in mechanical damage 32 to the piston, piston rings, engine head, etc.

1 341 p4 5 O1 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 05 performance and longevity. There are numerous 06 detergent-type gasoline additives currently available which, p7 to varying degrees, perform these functions.

Og 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, 1~ herein called "ORI", which is caused by deposits formed by lg the commercial gasoline.

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 :Eor a prolonged period, will reach an 26 equilibrium. '.Chis is apparently caused by an amount of 2~ deposits in thE~ combustion chamber. Equilibrium is 2g typically rea died after 5,000 to 15,000 miles of automobile 2g operation.
31 The octane requirement increase in particular engines used 32 with commercial gasolines will vary at equilibrium from 5 to O1 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 05 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.

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.

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 t~~ the problem.

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

1341 p45 O1 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 05 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 pg normally in service in additive distribution systems and the p9 fuel or lube system:. of actual operating engines. Such a plugging would obviously be catastrophic and must be 11 avoided.

13 A third complicating factor relates to the lubricating oil 14 compatibility of t:he~ fuel additive. Fuel additives, due to their higher boili:ng~ 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 lg its way into the lubricating oil in the crankcase of the lg engine via a "blow-b~y" 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, i.e., 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 2~ where the fuel additive is not sufficiently lubricating oil 28 compatible, the accumulation of such an oil-incompatible 2g fuel additive :may actually contribute to crankcase deposits as measured by a Sequence VD test.

1341 p4~
O1 The incompatibility of certain fuel additives in lubricating 02 oils, i.e., 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 05 in a fully formulated lubricating oil as a dispersant rather 06 than as a fuel additive, the incompatibility of these 0'7 dispersants with other additives in the lubricating oil will 08 result in increased crankcase deposits as measured by a O9 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, 1g 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.

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 2g theory, this excess amount of additive is insoluble in the 2g lubricating oi.l and is what causes increased crankcase deposits.

O1 In still another thE~ory, 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 cata:ctrophic.
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°C.

27 The instant invention is directed to lubricating oil 28 compositions a:nd fuel compositions containing a novel class 29 of hydrocarbyl poly(axypropylene) 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 O1 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 05 additives of this invention are also liquids which do not 06 form a wax at -40°C in a 50 weight percent solution with 07 toluene.

09 Relevant Art 11 Numerous references disclose hydrocarbyl poly(oxyalkylene) 12 aminocarbamates as fuel additives. These include the 13 following U.S. Patent Nos.:

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;

Of particular 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 b:y employing the poly(oxypropylene) as a 28 copolymer also containing 1 to 5 branched C9 to C30 29 oxyalkylene units.
31 U.S. Patent No. 4,160,648 discloses an intake system 32 deposit control additive for fuels which is a hydrocarbyl _7_ O1 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 05 of C16. C18 and C20 alkyl groups. Likewise, U.S. Patent 06 No. 4,288,612 discloses deposit control additives for 07 gasoline engines which are hydrocarbyl poly(oxyalkylene) 08 aminocarbamates wherein the hydrocarbyl group contains O9 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 30 1'7 carbon atoms, etc.

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

24 U.S. Patent Noes. 4,233,168 and 4,329,240 among others disclose lubri~~ating oil compositions containing a 26 dispersant amount of a hydrocarbyl poly(oxyalkylene) 2~ aminocarbamate.

2g While these prior art references disclose fuel compositions containing C1 to C30 hydrocarbyl poly(oxy-31 alkylene) aminc~carbamates which include poly(oxypropylene) 32 polymers, none of these references disclose the unique _g_ 1341045, _ .
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.
SLfMI!~iARY OF THH INVHNTION
The present invention provides a liquid alkylphenyl poly(oxypropylene) aminocarbamate which does not form a wax when cooled to -40°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 sub:~tantially straight-chain alkyl group of from about 30 to 95 carbon atoms derived from a substantially straight-chain al~~ha olefin oligomer of C8 to C20 alpha olefins, and further wherein the alkyl group is attached to the phenyl group at least 6 carbon atoms from the terminus of the longest chain of the alkyl group.
In a composit:Lon aspect, the instant invention is directed toward a fuel composition containing a novel class of hydrocarbyl poly(c~xypropylene) aminocarbamates which as a fuel additive controls combustion chamber deposits thus minimizing ORI and in lubrics~ting oal is compatible with the lubricating oil composition. In particular, the instant invention is directed toward a fuel <:omposition comprising a hydrocarbon boiling in the ga~~oline or diesel range and from about 30 to C

about 5,000 parts per million of the alkylphenyl poly(oxypropylene) aminocarbamate of the present invention.
9a O1 In another composition aspect, the instant invention is 02 directed to a i:uel concentrate comprising an inert stable 03 oleophilic organic solvent boiling in the range of 150° to 04 400°F and from 5 to 50 weight percent of an alkylphenyl 05 poly(oxypropyle~ne) arninocarbamate of this invention.

In still another composition aspect, the instant invention 08 is directed to a lubricating oil composition comprising an O9 oil of lubricating viscosity and a dispersant effective amount of an alkylphernyl poly(oxypropylene) aminocarbamate 11 of this invention.

13 In still another composition aspect, the instant invention 14 is directed to a lubricating oil concentrate comprising from about 90 to 50 weight percent of an oil of 16 lubricating viscosity and from about 10 to 50 weight 1~ percent of an alkylphenyl poly(oxypropylene) 18 aminocarbamate ~~f this invention.

The present invention also relates to the novel alkyl-21 phenol compound; which are employed to prepare the instant 22 alkylphenyl poly(oxypropylene) aminocarbamates. These 23 novel alkylphenol intermediate compounds are alkylphenols 24 wherein the alk~rl group is a substantially straight-chain alkyl group of i:rom albout 25 to 50 Carbon atoms and is 26 attached to the pheno:L ring at least 6 carbon atoms from 2~ the terminus of the longest chain of the alkyl group.
28 Preferably, the alkyl group on the alkylphenol will 29 contain from about 28 to 50 carbon atoms, and more preferably, from about= 30 to 45 carbon atoms. Moreover, 31 the alkyl substituent is preferably derived from a 32 substantially straight. chain alpha olefin oligomer of C8 33 to C20 alpha olefins.

O1 Among other factors, the present invention is based on the 02 discovery that t:he "p:inwheel" alklphenyl 03 poly(oxypropylene) am:inocarbamates of the present 04 invention having a substantially straight chain alkyl 05 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 0$ conditions.

It is critical that these aminocarbamates are non-waxy at 11 low temperature:. 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, e.g., milligrams, will 16 plug the micron--sized filters that these additives 17 commonly come in contact with. For example, there are lg micron-sized fiT.ters in the additive distribution and 19 blending system;> whiclh make additive packages and blends prior to the consumer's purchase. There are also 21 micron-sized fi7Lters in automobiles and diesel engines 22 where the fuel 'Ls filtered prior to combustion.

24 DETAI1~ED DESCRIPTION OF TIDE INVENTION
26 The alkylphenyl poly(oxypropylene) aminocarbamates of the 27 present invention consist of an amino moiety and an 28 alkylphenyl pol~t(oxypropylene) polymer bonded through a 29 carbamate linkage, i.e., -OC(O)N<. The specific alkylphenyl group employed in the instant invention in the 31 alkylphenyl pol~l(oxypropylene) polymer is critical to 32 achieving lubricating oil compatibility for the 1341 p45 O1 alkylphenyl pol~~(oxypropylene) aminocarbamates, while 02 providing excellent low temperature properties. In 03 particular, it has been found that employing the 04 "pinwheel" alky:lphenyl group of this invention wherein the 05 alkyl group is o~ubstantially 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.

As used herein, the abbreviation "PO" is meant to 11 designate propylene oxide or propylene oxide-derived 12 polymers. Simi:Larly, 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 team "DETA" is meant to designate diethylene 17 triamine or dieithylene triamine-derived carbamates.

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 o:E compounds with a range of carbon numbers.
24 Low molecular weight alpha olefins, such as the C6, C8, C10, C12 and C1~~ alpha olefins, are almost exclusively 26 1-olefins. Higher molecular weight olefin cuts such as 27 C16-18' or C20-:Z4 have increasing proportions of the 28 double bond isomerized to an internal or vinylidene 29 position; nonetheless these higher molecular weight cuts are also called alpha olefins herein.

O1 The term "alpha olefin oligomer(s)" (A00), as used herein 02 means olefin diners, trimers, tetramers and pentamers 03 prepared or derived from C8 to C20 alpha olefins. These 04 A00's have a pinwheel-type structure consisting of 05 primarily internal disubstituted and trisubstituted 06 olefins. The o:Lefin double bond of these A00's is p7 generally located at least n-2 carbon atoms from the end pg of the longest continuous carbon chain, where n is the Og number of carbon atoms in the starting alpha olefin.
11 The Alkyl Substituent 13 The alkyl subst:ituent of the alkyphenyl moiety of the 14 present alkylph~~nyl poly(oxpropylene) carbamates is a substantially sitraight-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 lg individual carbon atoms in the alkyl substituent are either primary (CH3-) or secondary (,-CH2-) carbon atoms.
21 Preferably, greeter than 85 number percent of the carbon 22 atoms in the alltyl substituent are primary or secondary 23 carbons.

The alkyl substituent in the alkylphenyl poly-26 (oxypropylene) ;~minocarbamates of the present invention is 2~ arranged in what will herein be designated as a "pinwheel"
28 configuration. This configuration has been found to be 2g critical to providing aminocarbamates having non-waxy low temperature characteristics.

O1 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 oi: the alkyl group. This results in at 05 least two hydrocarbon tails, or wheels of the pinwheel, 06 emanating from near tlae 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 alb;yl 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.

Preferred "pinwheel" compounds useful in this invention 16 are those wherep_n the alkyl substituent has tails which 17 are substantial~Ly straight-chain hydrocarbon radicals.

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

134~p45 of B

16 The alpha olefin oligomers used herein are prepared by 17 methods well-kn~~wn in the art. One preferred method of 18 preparing these oligomers is using BF3 as the 19 oligomerization catalyst, as described, for example, in U~S. Patent Nos. 4,238,343 and 4,045,507, and in 21 Onopchenko, et al., BF3-Catalyzed Oligomerization of 22 Alkenes (Structures, Mechanisms and Properties). 183rd 23 ACS Natl. Meet. (Las Vegas, Mar. 1982). Ind. Eng. Chem., 24 Prod. Res. Dev., 22(2), 182-91 (June 1983).

, 1 34 ~ ~4 5 ~:. .
O1 These alpha olei:in ol:igomers are 75% or more di or 02 trisubstituted zit the olefin site. ~'or example, an alpha 03 olefin trimer hz~s a structure that can be represented by:

11 wherein: R = n-2, and n is the carbon number of 12 the starting alpha olefin.

Alpha olefin ol:igomers are substantially straight-chain with 16 respect to the number of branched (i..e., 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, prefer~~bly greater than 85 percent.

22 Substantially straight-chain alkyl groups are exemplified in 23 Table A below:

~34~ 045 M
1a l~ ',?~ (~
'(~," N '~f N ft5 G ~D O M
U E~ O
1-a ..i V
N ~ V

t~
~J W N O N
O ,~ M M
H ~
N
cp ~ M d' »
a w ,-~ E ~
w x -- o r C~1 a ~' ~ O N N ~Q', O
..Ca 1 H x o a .~ U
U ~
x U ~ U ~r ~t,' x a4 _ s~ N .-~ ?~
O rcS P4 a ~ o it a~ ~ a o ~ +~ G4 _ .~ .~ sa -.-~ U .-1 pa r--1 rtf fly 'b .t~
(a 1.a U! N 1~"
1.J .IJ L1a _~ ~.~ ~r-1 O rt3 p ~ Ri. U
x rx a~ a °a O % O ~ Q a ~ ~ts N ,~ \ O O .~ O
rx w x x 3 x 3 O ~ 11 eW
,, cu a~ a a~
v .~.~ c~ o w H ao tr, o a it cu a~ a .,o~ ~ ~ ~ ~ iu s~ v ~ a n ~C ~s a u.i p?~., a ~ Ga ~ O ~ FC CO
its v O .1.~ O O -.a N
JJ r-i 1-r ~ CJ M f.-~ M ~ '-1 N M
U1 O C~ E~ v U H U E-~ ~.- _. ...

13~,~Q45_ 01 Preferred alpha olefin oligomers (A00's) are derived from Ca 02 to C2~ alpha olefins, more preferably, C1~ to C16 alpha 03 olefins. Preferred AOO's are dimers, trimers, tetramers and 04 pentamers. Prei_erabl:y, the alkyl group of the instant 05 carbamates is derived from alpha olefin oligomers selected 06 from the group consisting of: Ca tetramers, C1~ trimers, C12 0'7 trimers, C14 dirners a:nd trimers, C16 dimers and trimers, Cla Og dimers and C2~ dimers.
As described above, t:he alkyl substituent of the present 11 alkylphenyl pol~t(oxypropylene) aminocarbamates is arranged 12 in a so-called "pinwheel" configuration. This "pinwheel"
13 configuration is readily distinguishable from alkyl groups 14 wherein the hyd~_ocarbon chains are attached at or near the terminus of the longest chain of the alkyl group, i.e., 16 within l to 5 c<~rbon atoms of a terminus. Thus, 1~ aminocarbamates prepared from simple alpha olefins, (as lg 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, C20-24 terminal alkyl phenols and 24 terminal alkyl ~~arbamates.
26 In terminal compounds such as terminal alkyl phenols, there 2~ is only 1 main chain emanating from near the attachment 2g point of the alkyl group to the phenol. Terminal compounds 2g include those prepared by reacting alpha olefins with phenol under typical acidic reaction conditions.

-la-1341 045-_ O1 The Preferred Alkyphenyl Group 03 The preferred a_~Lkylph~enyl group of the alkylphenyl 04 poly(oxypropylene) aminocarbamate employed in this invention 05 is derived from the corresponding al.kylphenol of Formula I
06 below:

12 m 13 wherein R is a substantially straight-chain alkyl group of 14 from about 25 to 50 carbon atoms and m is an integer from 1 to 2.

17 Preferably, R is a substantially straight-chain alkyl 18 group of from 28 to 50 carbon atoms. More preferably, R
19 is a substantia:Lly straight-chain alkyl group of from 30 to 45 carbon atoms.

22 yJhen m is one, i~he alkylphenyl is a monoalkylphenyl;
23 whereas when m :is two, the alkylphenyl is a dialkylphenyl.

The alkylphenols of Formula I above are prepared by 26 reacting the appropriate olefin or olefin mixture with 27 phenol in the p~:esence of an alkylating catalyst at a 28 temperature of :From about 60°C to 2U0°C, and preferably 29 125°C 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 15R
32 available from l~ohm and Haas, Philadelphia, Pennsylvania.

O1 Molar ratios of reactants can be employed. When molar 02 ratios are employed, t:he reaction yields a mixture of 03 dialkylphenol, n~onoal~;ylphenol and unreacted phenol. As 04 noted above, dia~lkylphenol and monoalkylphenol can be used 05 to prepare the additives used in the compositions of this 06 invention whereas the unreacted phenol is preferably removed from then post reaction mixture via conventional Og techniques. Alt:ernat:ively, molar excess of phenol can be Og employed, i.e., 2 to 2.5 equivalents of phenol for each equivalent of olefin with unreacted phenol recycled. The 11 latter process maximi;~es 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 a7~kylph~enyl group is derived from a pinwheel 1~ phenol. Pinwheel phenols may be prepared from alpha lg olefin oligomer:~.

Useful A00 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 45.
26 Alternative metlhods of preparing the alkylphenol compounds 2~ used herein are also contemplated. "Pinwheel" alkyl 2g phenols can be synthesized by any number of methods.
2g 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 1 341 ~4 5 O1 further development to a pinwheel alkyl phenol. Thus, one 02 could alkylate phenol with either a pinwheel olefin or a 03 corresponding a:Lcohol, or alkyl halide, such as a chloride 04 or bromide.

06 The exact struci:ure of the final alkyl phenol is difficult 07 to predict with certainty. Alkylations using carbonium p8 ions result in rearrangements during carbonium ion O9 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.

Particularly prc~ferre~d monoalkylphenols employed in this 16 invention are either ortho-monoalkyl.phenols of Formula II
17 below:

19 ~H
R II

23 or para-monoalkylphenols of Formula III below:

I III

R

Particularly preferred dialkylphenols employed in this , 31 invention are generally 2,4-dialkylphenols of Formula IV
32 below:

02 , ~ R

07 although there rnay be minor amounts of 2,6-dialkylphenol of ~8 Formula V below.:

R. R V

13 PrefE~rred Poly(oxypropylene) Component The alkylphenyl poly(~oxypropylene) polymers which are 16 utilized in preparing the carbamates of the present 17 invention are monohydroxy compounds, i.e., 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 i.e., 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., OH

I

2g Rm 29 under polymerization conditions, wherein R and m are as defined above. In general, the poly(oxypropylene) poly-31 mers will vary :in chain length but their properties 32 closely approximate those of the polymer represented by the average composition and molecular weight. Each poly-(oxypropylene) polymer contains at least 1 oxypropylene unit, preferably from 1 to about.100 oxypropylene units, more preferably from about 5 to about 50 oxypropylene units, and most preferably from about 10 to about 25 oxy-pcopylene units. Method's of production and properties of these polymers are disclosed in U.S. Patent Nos. 2,841,479 and 2,782,240, as well as Kirk-Othmer's~ "Encyclopedia of Chemical Technology", Volume 19, p. 507. An alternative method for preparing alkylphenyl poly(oxypropylene) polymers having either 1, 2, or 3 oxypropylene units involves employing a compound of Formula VI below C:l ( CH2CH0 ) qH VI
wherein q is an integer from 1 to 3. When employing the ~'0 compound of Formula VI, the phenoxide of the alkylphenol, I, is first prepared and then reacted with the compound of Formula VI to yield the desired alkylphenyl poly(oxypro-pylene) polymer having from 1 to 3 oxypropylene units.
Compounds of Formula VI are commercially available or can be prepared by art recognized methods.
Preferred Amine Component The amine moiety of the alkylphenyl poly(oxypropylene) v0 aminocarbamate employed, in this invention is preferably derived from a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.. The ,. , 1341 p45 O1 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 05 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 car-bamate molecule, i.e., 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.

14 The polyamine ma.y be substituted with substituents selected from (A) hydrogen, (B:! hydrocarbyl groups of from 1 to about 16 10 carbon atoms, (C) acyl groups of from 2 to about 10 17 carbon atoms, and (D) monoketo, monohydroxy, mononitro, 18 monocyano, lower alkyl and lower alkoxy derivatives of (B) 19 and (C). "Lower", as used in terms like lower alkyl or lower alkoxy, means a group containing from 1 to about 6 21 carbon atoms. ~~t 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 ar sec:ondary 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 hydr~~gen which may be aliphatic, alicyclic, 29 aromatic or combinations thereof, e.g., aralkyl. Prefer-ably, the hydrocarbyl group will be relatively free of 31 aliphatic unsaturation, i.e., ethylene and acetylenic, 32 particularly acetylenic unsaturation. The substituted 1 341 0.4 5 _ Ol polyamines of the present invention are generally, but not 02 necessarily, N-substituted polyamines. Exemplary hydro-03 carbyl groups anal substituted hydrocarbyl groups include 04 alkyls such as methyl,, ethyl, propyl, butyl, isobutyl, 05 pentyl, hexyl, octyl, etc., alkenyls such as propenyl, 06 isobutenyl, hexe~nyl, octenyl, etc., hydroxyalkyls, such as 07 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 08 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 09 6-ketooctyl, etc., allcoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 11 2-(2ethoxyethox~~)ethy:L, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl, 12 3,6,9,12-tetrao}:atetradecyl, 2-(2-ethoxyethoxy)hexyl, etc.
13 The acyl groups of t:he aforementioned (C) substituents are 14 such as propion5il, acetyl, etc. The more preferred substituents are' hydrogen, Cl-C4 alkyls and Cl-C4 16 hydroxyalkyls.

18 In a substituted polyamine the substituents are found at any 19 atom capable of receiving them. The substituted atoms, e.g., 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, 2g e.g., alkyl and hydroxyalkyl-substituted polyalkylene poly-amine. 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 ~34~ 045 exemplified by ethylene, 1.,2-propylene 2,2-dimethyl-propylene trimethylene, 1,3,2-hydroxypropylene, etc. Examples of such polyamines include ethylene diamine, diethylene triamine, di(trimethylene)triamine, dipropylene triamine, triethylene tetramine, tripropylene tetramine, tetraethylene pentamine, pentaethylene hexamine, butylene diamine and pentylene dis~mine. Such amines encompass isomers such as branched-chain palyamines and the previously mentioned substituted polyamines, including hydroxy- and hydrocarbyl-substituted polyamines. Among the polyalkylene polyamines, those containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially preferred, and the C2-C3 alkylene polyamines are most preferred, in particular, the lower polyalkylene polyamines, e.g., ethylene diamine, diethylene triamine, propylene diamine, dipropylene triamine, etc.
The amine component of the alkylphenyl poly(oxypropylene) aminocarbamate also may be derived from heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle comprises one or mare 5-E> membered rings containing oxygen and/or nitrogen. ~~uch heterocycles may be saturated or unsaturated and substituted with groups selected from the aforementioned (A), (B) (C) and (D). The heterocycles are exemplified by pips~razlnE?s, such as 2-methylpiperazine, N-(2-hydroxyethyl)yiperazine, l,2bis-(N-piperazinyl)-ethane, and N,N'bis(N-piperaziny7L)piperazine, 2-methylimadazoline, 3-aminopiperidine, 2-aminopyridlne,2-(3-aminoethyl)3-pyrroline, 3-aminopyrrolidine, N-(3-aminopropyl)morpholine, etc. Among the heterocyclic compounds, the piperazines are preferred.
26a Another class of .suitable polyamines are diaminoethers represented by Formula VII
H2WX1fOX2~rNH2 VII
wherein X1 and X2 are independently alkylene from 2 to about 5 carbon atoms and r is an integer from 1 to about 10. Diamines of Formu la VII are disclosed in U.S. Patent No. 4,521,610.
Typical polyamine:a that can be used to form the compounds of this invention by reaction with a poly(oxyalkylene)chloroformate include the following:
ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, diethylen~e triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, dimethyl-aminopropylene di,amine, N-(beta-aminoethyl)-piperazine, N-(beta-aminoethy.l)piperidine, 3-amino-N-ethylpiperidine, N-(beta-aminoethyl)morpholine, N,N'-di(beta-aminoethyl)-piperazine, N,N'-~~i(beta-aminoethylimidazolidone-2;
N-(beta-cyano-eth;yl)ethane-1,2-diamine, 1-amino-3,6,9-triazaoctadecane, 1-amino-3,6-diaza-9-oxadecane, N-(beta-aimonoethyl)di-ethanol-amine, N'-acetyl-N-methyl-N-(beta-aminoethyl)ethane-1,2-diamine, N-acetonyl-1,2-propanediamine, N-(beta-nitro-ethyl)-1,3-propane diam,ine, 1,3-dimethyl-5(beta-amino-ethyl)hexahydrotriazine, N-(beta-aminoethyl)hexahydrotri-azine, 5-lbeta-aminoethyl)-1,3,5-dioxazine, 2-(2-aminoethylamino)-ethanol, 2[2-(2-aminoethylamino)ethylamino)-ethanol.

tA, ~ ~ 41 04 5 O1 The amine component oi: the alkylphenyl poly(oxypropylene) 02 aminocarbamate may alao be derived from an 03 amine-containing compound which is capable of reacting 04 with an alkylphenyl poly(oxypropylene) alcohol to produce 05 an alkylphenyl ~~oly(oxypropylene) aminocarbamate having at 06 least one basic nitrogen atom. For example, a substituted 07 aminoisocyanate, such as (R)2NCH2CH2NC0, wherein R is, for 08 example, a hydrocarby7l 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-(dihydrocar-byl)aminoisocyanatoallcane, more generally, N-(perhydrocar-16 byl)-isocyanato~>ol-olyalkylene polyamine, 17 N,N-(dimethyl)aminoisocyanatobenzene, etc.

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 reac-tion of dichloroethylene and ammonia will have both lower 26 and higher amine members, e.g., triethylene tetramine, 27 substituted pipE~razines and pentaethylene hexamine, but 28 the composition will. Ibe mainly tetraethylene pentamine and 29 the empirical formula of the total amine composition will closely approxirnate t'.hat of tetraethylene pentamine.
31 Finally, in preparing the compounds of this invention, 32 where the various nitrogen atoms of the polyamine are not O1 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 05 Chemistry of Nitrogen", Clarendon Press, Oxford, 1966;
06 Nollers' "Chemistry of. Organic Compounds", Saunders, p7 Philadelphia, 2nd Ed. 1957; and Kirk-Othmer's pg "Encyclopedia of Chemical Technology", 2nd Ed., especially p9 Volume 2, pp. 99-16.
11 Prei=erred Alkylphenyl Polyy ox ropylene) Aminocarbamate 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 17 obtained by linking these components together through a 18 carbamate linkage i.e., O
II
21 -OCN<

23 wherein the ethErr oxygen may be regarded as the terminal 24 hydroxyl oxygen of the alkylphenyl poly(oxypropylene) alcohol component, and the carbonyl group -C(0)- is pre-26 ferably provided by tlhe coupling agent, e.g., phosgene.

28 The alkylphenyl poly(~oxypropylene) aminocarbamate employed 29 in the present :W vention has at least one basic nitrogen atom per molecu:Le. A "basic nitrogen atom" is one that is 31 titratable by a strong acid, e.g., a primary, secondary, or tertiary amino nitrogen., as distinguished from, for example, an amido nitrogen, i.e., O
-CN< , 'which is not so titratable. Preferably, the basic nitrogen is in a primary or secondary amino group.
The preferred alkylphenyl poly(oxypropylene) aminocarbamate has an average molecular weight of from about 600 to 6,000; preferably an average molecular weight of from 800 to 3,000= and most preferably an average molecular weight of from 1,000 to 2,500.
A preferred class of alkylphenyl poly(oxypropylene) ,3minocarbamate can be described by the following general Eormula~

O'~O~CH2CH0 n C'NH-(R1NH) -H
P
R
m wherein R is a substantially straight-chain alkyl group of from ,about 30 to 45 carbon atoms derived from a substantially ;straight-chain alpha olefin oligomer of C8 to C20 alpha olefins ~3nd R is attached to the phenyl ring at least 6 atoms from the 'terminus of the longest chain of said group R; R1 is alkylene of 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 about 600 to 6,000= and p is an integer from 1 to about 6; and wherein said compound does not form a wax when cooled to -40oC
in a 50 weight percent solution with toluene.
C

Ci4 Hydro hilic-Lipophilic Balance C~ 5 C~6 It is important that the relatively hydrophilic propylene (~7 oxide polymeric back-bone be balanced by the hydrophobic (fig alkyl carbons of the alkyl phenol. The aminocarbamates of (19 this invention must achieve a good hydrophilic-lipophilic ~.p balance (HLB) in order to have sufficient hydrocarbon ~.1 solubility in oil and therefore to not perform ~.2 detrimentally with regard to crankcase varnish.
1. 3 ~.4 For good lubricant solubility, It has been found that the ~-5 ratio of the number of carbon atoms in the alkyl group ~_( needs to be about twice the number of propylene oxide ~_7 units. For example, if: the average number of propylene ~~g oxide units is n, then the alkyl chain attached to the ~~g phenoxy radical should have approximately 2n carbon atoms;
;p preferably, between 2n--4 and 2n+4 carbon atoms; most preferably between 2n and 2n+4 carbon atoms.
:? 2 Preparation of the Alkylphenyl ~~3 Poly(oxypropylene) Aminocarbamate :? 4 %5 The additives employed in this invention can be most conveniently prepared by first reacting the appropriate alkylphenyl poly(oxypropylene) alcohol with phosgene to a7 produce an alkylphenyl poly(oxypropylene) chloroformate.
a8 The chloroformate~ is then reacted with the polyamine to :Z 9 .3~ produce the desired allcylphenyl poly(oxypropylene) aminocarbamate.
:31 :32 :33 :34 ~341p45-Preparation of aminocarbamates are disclosed in U.S.
Patent Nos. 4,160,648; 4,191,537; 4,197,409; 4,236,020;
4,243,798; 4,270,930; 4"274,837;.4,288,612; 4,512,610; and 4,568,358.
In general, the re~actiorl of the poly(oxypropylene) compound and phosgene i;s usually carried out on an essentially equimolar basis, although excess phosgene can be used to improves the degree of reaction. The reaction may be carried oui: a temperatures from -10° to 100°C, 1.0 preferably in the range of 0° to 50°C. The reaction will usually be compleite within 1/4 to 5 hours. Times of reac-tion will usually be in the range of from 2 to 4 hours.
A solvent may be Bused in the chloroformylation reaction.
Suitable solvents include benzene, toluene, etc.
The reaction of the resultant chloroformate with the amine may be carried out neat or preferably in solution.
Temperatures of from -10° to 200°C may be utilized, the a0 desired product may be obtained by water wash and stripping usually be the aid of vacuum, of any. residual solvent.
The mole ratio of polyamine to polyether chloroformate will generally be in tire range from about 2 to 20 moles of polyamine per mole of c;hloroformate, and more usually 5 to 15 moles of polya.mine per mole of chloroformate. Since suppression of polysubstitution of the polyamino is usually desired, large molar excesses of the polyamine 30 will be used. Additionally, the preferred adduct is the , monocarbamate compound,, as opposed to the bis(carbamate) oc disubstituted aminoether.

C

O1 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 05 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 p8 the reactant concentrations, the reaction time may vary pg from less than 1. minui~e to 3 hours.
11 After the reaction ha;s 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 d:~amine. The product may then be isolated 1'7 by evaporation of the solvent. Further purification may lg be effected by column chromatography on silica gel.

Depending on the particular application of the composition 21 of this inventi~~n, 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 2~ blending in fuels.

2g An alternative proce:;s for preparing the alkylphenyl poly(oxypropylene) aminocarbamates employed in this 31 invention involves the use of an arylcarbonate intermediate. That is to~ say, the alkylphenyl poly(oxy-propylene) alcohol is reacted with an aryl chloroformate to form an arylcarbonate~ which is then reacted with the polyamine to form the aminocarbamate employed in this invention. Particularly useful aryl chloroformates include phenyl chloroformate, p-nitrophenyl chloroformate, 2,4-dinitrophenyl chloroformate, p-chlorophenyl chloro-formate, 2,4-dichlorophesnyl chloroformate, and p-trifluoromethylphenyl chloroformate. Use of the aryl carbonate intermedliate allows for conversion to amino-carbamates containing close to the theoretical basic nitrogen while em~~loyinc~ less excess of polyamine, i.e., molar ratios of ge~neral:ly from 1:1 to about 5:1 of polyamine to the e~rylcarbonate, and additionally avoids the generation of hydrogen chloride in the reaction forming the aminoc:arbamate. Preparation of hydrocarbyl capped poly(oxyal):ylene) aminocarbamates via an arylcarbonate intE~rmedi~ate have been previously disclosed.
2, 0 As will be appreciated by those skilled in the art, the aminocarbamates o:E this invention are mixtures of many individual compounds.
The alkyl group will typically have a variety of carbon numbers since the starting olefins are not generally pure compounds and, for any given carbon number in the alkyl group, there are many structural isomers. Moreover, mono-:l0 and dialkyl phenols are generally obtained. Also, the ., number of propylene oxide units is an average number and different molecules will have a somewhat different number of PO units.

S

Also included within the scope of this invention are fully formulated lubricating oils containing a dispersant effective amount o,E an alkylphenyl poly(oxyalkylene) amino carbamate.
Contained in the fully formulated composition is:
1. an alkenyl succinimide, 2. a Group ii metal salt of a dihydrocarbyl dithiophosphoric acid, 3. a neutral or overbased alkali or alkaline earth metal hydrocarbyl sulfonate or mixtures thereof, and 4. a neutral or overbased alkali or alkaline earth metal alkylated phenate or mixtures thereof.
5. A viscosity index (V'I) improver.
The alkenyl succinimide is present to act as a dispersant and prevent formation of deposits formed during operation of the engine. The alkenyl suc:cinimides are well-known in the art.
The alkenyl succinimides~ are the reaction,product of a 2.0 polyolefin polymer-substituted succinic anhydride with an amine, preferably a polyalkylene polyamine. The polyolefin polymersubstitutedl succi~nic anhydrides are obtained by reaction of a polyolefin polymer or a derivative thereof with maleic anhydride. The succinic anhydride thus obtained is reacted with the amine compound. The preparation of the alkenyl succinimides has been described many times in the art. See, for example, U.S. Patent Nos. 3,390,082;
3,219,666; and 3,1.72,89:2.
Reduction of the alkenyl ';0 substituted succinic anhydride yields the corresponding alkyl derivative. The <:lkyl succinimides are intended to be included within the scope of the term "alkenyl succinimide".
_35_ ,Au O1 A product comprising predominantly mono or bis-succinimide 02 can be prepared by controlling the molar ratios of the 03 reactants. Thu:;, for example, if one mole of amine is 04 reacted with one mole of the alkenyl or alkyl substituted 05 succinic anhydride, a predominantly mono-succinimide product 06 will be prepared. If two moles of the succinic anhydride are p7 reacted per mole of polyamine, a bis-succinimide will be Og prepared.

Particularly good results are obtained with the lubricating 11 oil composition:; of this invention when the alkenyl 12 succinimide is a poly:isobutene-substituted succinic anhydride 13 of a polyalkylene polyamine.

The polyisobutene from which the polyisobutene-substituted 16 succinic anhydride is obtained by polymerizing isobutene can 17 vary widely in i.ts compositions. The average number of lg carbon atoms can ran ge 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. pol.yisobutene 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 pol~tisobutene is reacted with malefic anhydride 28 according to well-known procedures to yield the 2g polyisobutene-substituted succinic anhydride.
w 31 In preparing the alkenyl succinimide, the substituted 32 succinic anhydride is reacted with a polyalkylene polyamine O1 to yield the corresponding succinimide. Each alkylene 02 radical of the ~olyal~;ylene 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 05 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, i.e., if a polyalkylene polyamine contains 3 alkylene radicals, it will usually contain 4 amino radicals.
11 The number of amino r<~dicals can range up to about 9.
12 Preferably, the alkylc~ne radical contains from about 2 to 13 about 4 carbon atoms and all amine groups are primary or 14 secondary. In this c<~se, the number of amine groups exceeds the number of al.kylene groups by 1. Preferably the 16 polyalkylene pol.yamine contains from 3 to 5 amine groups.
17 Specific examples of 'the polyalkylene polyamines include 18 ethylenediamine, dietlhylenetriamine, triethylenetetramine, 19 propylenediamine~, tri~propylenetetramine, tetraethylenepentamin~e, trimethylenediamine, 21 pentaethylenehe~~amirie, di-(trimethylene)triamine, 22 tri(hexamethylene)tetramine, etc.

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

O1 Preferably the alkenyl. succinimides used in the compositions 02 of this invention have' the following formula:

~''NfAlkyleneN~ H
06 ~H2--~~ I n ~0 A

O9 wherein:
11 a. R1 represents an <~lkenyl group, preferably a substan-12 tially saturated hydrocarbon prepared by polymerizing 13 aliphatic monoolefins. Preferably R1 is prepared from 14 isobutene and has an average number of carbon atoms and a number average mo:Lecular weight as described above;

17 b, the "Alkylene" radical represents a substantially 18 hydrocarbyl group containing up to about 8 carbon atoms lg and preferably containing from about 2-4 carbon atoms as described hE~reinabove;

22 c. A represent:> 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 alkyT~.ene radicals described above. Preferably A
27 represents hydrag~en;

2g d. n represents an integer of from about 1 to 10, and preferably i=rom about 3-5.

Also, included within the term "alkenyl succinimide" are the modified succinmid~es which are disclosed in U.S. Patent No.
4,612,132.
The alkenyl succinimide is present in the lubricating oil compositions of the invention in an amount effective to act as a dispersant and prevent the deposit of contaminants formed in the oil during operation of the engine. The amount of alkenyl succinimide can range from about 1 percent to about 20 percent weight of the total lubricating oil composition. Preferably the amount of alkenyl succinimide present in the lubricating oil composition of the invention ranges from about 1 to about 10 percent by weight of the total composition.
The alkali or alkaline earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonate~s, or aliphatic sulfonates such as those derived from polyi.sobutylene. One of the more important ~;p functions of the .~ulfonates is to act as a detergent and dispersant. Theses sulfonates are well-known in the art.
The hydrocarbyl group must have a sufficient number of carbon atoms to reender the sulfonate molecule oil soluble.
Preferably, the h~rdrocarbyl portion has at least 20 carbon atoms and may be aroma tic or aliphatic, but is usually alkylaromatic. Most p referred for use are calcium, magnesium or barium sulfonates which are aromatic in character.
:30 Certain sulfonate;s are typically prepared by sulfonating a petroleum fraction having aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of O1 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 05 prepared by polymerizing :isobutene. The metallic salts are 06 formed directly or by metathesis using well-known 07 procedures.

09 The sulfonates may be neutral or overbased having base numbers up to at~out 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 ordin~~rily used so as to provide from 0.3% to 10%
by weight of the tot.a:l 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 lg from 0.3% to 3% by weight of the total composition.

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, iii prevents the deposition of contaminants formed during high temperature operation of the engine. The 26 phenols may be mono or polyalkylated.

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 n;~turally occurring or synthetic sources.
31 Naturally occurring sources include petroleum hydrocarbons 32 such as white oil and wax. Being derived from petroleum, 1 341 p4 5 O1 the hydrocarbon rnoiety is a mixture of different hydrocarbyl 02 groups, the specific composition of which depends upon the 03 particular oil si;.ock which was used as a starting material.
04 Suitable synthetic sources include various commercially 05 available alkene;s and alkane derivatives which, when reacted 06 with the phenol, yield an alkylphenol. Suitable radicals 07 obtained include butyl, hexyl, octyl, decyl, dodecyl, O8 hexadecyl, eicosyl, tricontyl, and the like. Other suitable pg synthetic sources of the alkyl radical include olefin polymers such as polypropylene, polybutylene, 11 polyisobutylene and the like.

13 The alkyl group can beg 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 unsat:uration). The alkyl radicals will 17 generally contain from 4 to 30 carbon atoms. Generally when lg 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 ii. over!based will have a base number of up to 22 200 to 300 or more. Mixtures of neutral and overbased 23 phenates may be used.

The phenates ar~~ ordinarily present in the oil to provide 26 from 0.2% to 27's by weight of the total composition.
27 Preferably, the neutral phenates are present from 0.2% to 9%
2g by weight of the total composition and the overbased 2g 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.

1341 p45 O1 The sulfurized alkaline earth metal alkyl phenates are 02 preferred. The~;e 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.
05 Conveniently the sulfur, in elemental form, is added to the 06 neutralization product and reacted at elevated temperatures 07 to produce the :~ulfur:ized alkaline earth metal alkyl p8 phenate.

If more alkaline' eartlh 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 obtaLned. 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.

22 Carbon dioxide ~~nd calcium hydroxide or oxide are the most 23 commonly used material to produce the basic or "overbased"
24 phenates. A pr~~cess wherein basic sulfurized alkaline earth metal alkylphen~ates are produced by adding carbon dioxide is 26 shown in Hannem~an, U.S. Patent No. 3,178,368.

28 The Group II metal salts of dihydrocarbyl dithiophosphoric 2g 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 Ol 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 05 12 carbon atoms in each of the hydrocarbyl radicals and may 06 be the same or c~iffer~ent and may be aromatic, alkyl or 07 cycloalkyl. Preferred hydrocarbyl groups are alkyl groups OS containing from 4 to ~B carbon atoms and are represented by Og butyl, isobutyl,, sec.-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. The metals suitable for forming 11 these salts incT.ude barium, calcium, strontium, zinc and 12 cadmium, of which zinc is preferred.

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

17 R2 ~ ~S

R30/ ~ M1 23 wherein:

e' R2 and R3 each independently represent hydrocarbyl radicals as described above, and 28 f. M1 represen~:.s a Group II metal cation as described above.
2 9w 31 The dithiophosphoric salt is present in the lubricating oil 32 compositions of this invention in an amount effective to inhibit wear and oxidation of the lubricating oil. The amount ranges from about 0.1 to about 4 percent by weight of the total composition. preferably, the salt is present in an amount ranging from about 0.2 to about 2.5 percent by weight of the total lubricating oil composition. The final lubricating oil composition will ordinarily contain 0.025 to 0.25% by weight phosphorus and preferably 0.05 to 0.15% by weight.
~,p Viscosity index (~~I? im;provers are either non-dispersant or dispersant VI improvers. Non-dispersant VI improvers are typically hydrocarbyl polymers including copolymers and terpolymers. Typically hydrocarbyl copolymers are copolymers of ethylene and propylene. Such non-dispersant VI improvers are disclosed in U.S. Patents Nos. 2,700,633;
2,726,231; 2,792,288; 2,933,480; 3,000,866; 3,063,973; and 3,093,621.
a0 Dispersant VI improvers can be prepared by functionalizing non-dispersant VI improwers. For example, non-dispersant hydrocarbyl copolymer and terpolymer VI improvers can be functionalized to produce aminated oxidized VI improvers having dispersant properrties and a number average molecular weight of from 1,500 to 20,000. Such functionalized dispersant VI improvers are disclosed in U.S. Patents Nos.
3,864,268; 3,769,216; :!,326,804 and 3,316,177.
Other dispersant VI improvers include amine-grafted acrylic polymers and copolymers wherein one monomer contains at least one amino group. Typical compositions are described in British Patent No. 1"488,382; and U.S. Patents Nos.
4,89,794 and 4,025,452.
Non-dispersant an<i dispersant VI improvers are generally employed at from !i to 20 percent by weight in the lubricating oil composition.
:l 0 Fuel Compositions The alkylphenyl poly(oxypropylene) aminocarbamates of this invention will generally be employed in a hydrocarbon distillate fuel. The proper concentration of this additive necessary in order to achieve the desired detergency and dispersancy varies depending upon the type of fuel employed, the presence of other detergents, dispersants and other additives, etc. Generally, however, from 30 to 5,000 weight ?.p parts per million (ppm), and preferably 100 to 500 ppm and more preferably 200 to 300 ppm of alkylphenyl poly(oxypropylene) aminocarbamate per part of base fuel is needed to achieves the best results. when other detergents are present, a less amount of alkylphenyl poly(oxypropylene) aminocarbamate may be used. For performance as a carburetor detergent only, lower concentrations, for example 30 to 70 ppm may be prE:ferred. Higher concentrations, f.e., 2,000 to 5,000 ppm may result in a clean-up effect on combustion chamber deposits..
The deposit control additive may also be formulated as a concentrate, using an inert stable oleophilic organic A

O1 solvent boiling in the range of about 150 to 400°F.
02 Preferably, an aliphatic or an aromatic hydrocarbon solvent 03 is used, such a:~ benzene, toluene, xylene or higher-boiling 04 aromatics or aromatic thinners. Aliphatic alcohols of about OS 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.

13 When employing ~~ertain 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 1g include for instance L-15628, a high molecular weight glycol capped phenol available from Petrolite Corp., Tretolite 21 Division, St. Louis, Missouri, and OLOA 2503ZR, available 22 from Chevron Chemical Company, San Francisco, California.

O1 In gasoline fuels, other fuel additives may also be included 02 such as antiknock agents, e.g., methylcyclopentadienyl man-03 ganese tricarbonyl, tetramethyl or tetraethyl lead, or other 04 dispersants or detergents such as various substituted 05 succinimides, amines, etc. Also included may be lead scav-06 engers such as aryl halides, e.g., dichlorobenzene or alkyl 07 halides, e.g., erthylene dibromide. Additionally, antioxi-08 dants, metal deactivai;.ors and demulsifiers may be present.

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

14 Lubricating Oil Compositions 16 The alkylphenyl poly(oxypropylene) aminocarbamates of this invention are u:~eful .as dispersant additives when employed 18 in lubricating oils. When employed in this manner, the lg 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 five 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 2~ viscosity of ab~~ut 1300 CSt 0°F to 22.7 CSt at 210°F
(99°C).
28 The lubricating oils may be derived from synthetic or 2g natural sources. Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other , 31 oils that are ordinarily used in lubricating oil composi-32 Lions. Synthetic oils include both hydrocarbon synthetic 1341 n45 O1 oils and synthetic esi~ers. Useful synthetic hydrocarbon 02 oils include liquid polymers of alpha olefins having the 03 proper viscosit~~. Especially useful are the hydrogenated 04 liquid oligomer:~ of Ci~ to C12 alpha olefins such as 1-decene 05 trimer. Likewi:>e, alltyl 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-0g oxylic acids as well ;as monohydroxy alkanols and polyols.
O9 Typical examples are didodecyl adipate, pentaerythritol tetracaproate, cii-2-ethylhexyl adipate, dilaurylsebacate and 11 the like. Comp:Lex esters prepared from mixtures of mono and 12 dicarboxylic acid and mono and dihydroxy alkanols can also 13 be used.

Blends of hydro~~arbon oils with synthetic oils are also 16 useful. For ex~~mple, blends of 10 to 25 weight percent 17 hydrogenated 1-decene trimer with 75 to 90 weight percent lg 150 SUS (100°F) mineral oil gives an excellent lubricating 1g 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 2g the concentrates include any inert diluent, preferably an 2g 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 from about 35 to about 500 Saybolt Universal Seconds (SUS) at 100°F (38°C), although an oil of lubricating viscosity may be used.
Other additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, pour point depressants, antioxidants, and a variety of other well-known additives.
;~0 The following examples ace offered to specifically illus-trate this invention. These examples and illustrations are not to be construed in any way as limiting the scope of this invention.
EXAMPLES
Example A
20 Preparation of Alpha-Olefin Oligomers (C14-Derived) Using a Sulfonic Acid Catalyst This example shows alpha-olefin oligomers useful in this invention. Into a dry 500-ml, three-necked round bottom flask, equipped with a heating mantle, a mechanical stirrer, and a condenser were charged 200 grams of C14 alpha olefin (Chevron Chemical. Co., San Francisco) and 10 grams of an experimental alunnina-supported fluorosulfonic acid catalyst 30 (DOW XUS'~40036.0'1), available from Dow Chemical Company. .
These ingredient~a were heated and stirred under nitrogen for 25 hrs. at 185°C. At this time, the dark reaction mixture Trade mark -4 fA

f 341 p4 5 O1 was stripped of any residual C14 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 05 purification. This product could not be induced to 06 crystallize at very low temperatures, and as such was 07 regarded as wax free.

p9 Example B
Preparation of Alpha-Olefin Oligomers 11 (~~14-Derived) Using BF3 13 This example al:;o shows alpha-olefin oligomers useful in 14 this invention. In this example, the C14 alpha-olefin of Example A was oligomerized using boron trifluoride gas and 16 an alcohol co-ca,talysi=, as described, for example, in U.S.
1~ Patent Nos. 4,238,343 and 4,045,507. Approximately 18 2_1/2 gallons of a clear light yellow liquid containing 19 approximately 6T% dimE~r, 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 ~~henol.without further purification. This 23 product was a nonviscous liquid at room temperature and 24 below and was, as such, regarded as wax free.

2~ Example C
28 Preparation of Alpha-Olefin Oligomers (C16-Derived) 31 This example shows oli.gomers useful in this invention. The 32 Procedure of Example A was followed as a C16 as a C16 alpha 1341 p45 O1 olefin. The re:~ulting product was an approximately 95/5 02 mixture of dimers to trimers. This product was a nonviscous 03 liquid at room i~emperature and below and was, as such, 04 regarded as wax free.

06 Example lA
07 Preparation ~of Pinwheel Alkyl Phenols from 08 (C1~)-Derived) Oligomers of Example B

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 1B. The liquid was heated to 85°C at 14 which time 344 crams (3.83 mole) of liquefied phenol was added followed by 65 grams of dry Amberlist 15. The 16 reaction mixture' was 'then heated for 24 hours at 150°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 <~ non-viscous amber colored pinwheel alkyl phenol (313 grams; Hydroxyl no. - 105.4). This phenol 21 had an average alkyl carbon content of 36 carbon atoms.
22 This product wa:c 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.

~341n45 O1 Example is 02 Preparation of Pinwheel Alkyl Phenols 03 from Oligomers of Example C.

06 The C16-derived olefin. oligomer of Example C was used to 07 alkylate phenol in a manner similar to that described in 08 Example lA. The resulting pinwheel alkyl phenol had an O9 average alkyl carbon cantent of 34 carbon atoms.

12 Comparative Example 1C
13 Preparation of a C20-C24 Terminal Alkylphenol 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 C20 to C24 alpha olefin 19 mixture (approximate olefin content C18 and less-1%;
C20 49%; C22-42%; C24--8%; C26 and greater-0.1%) wherein in 21 the entire olefin fraction at least 15 mole percent of said 22 olefins contain vinyli.dine groups (C20 to C24 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 15R available from Rohm 27 and Haas, Philadelphia, PA). The reaction mixture was 2g stripped by heating under vacuum and the product was 2g filtered hot over diai~omaceous earth to afford 1050 grams of a C20 to C24 terminal alkylphenol with a hydroxyl number of 31 120 ( i . a . mg KO~:I/gm s<~mple ) and with approximate 45%
32 para-alkylphenol content. This phenol was a low melting wax 33 at room temperature.

134~~45 O1 Comparative Example 2A
02 Preparat:lon of a C20-C28 Terminal Alkylphenol 05 To a 2-liter flask, equipped with stirrer, Dean Stark trap, 06 condensor and np_trogen inlet and outlet was added 674 gms of 07 a substantially straight chain C20 to C28 alpha olefin 08 mixture (olefin content: C18-2%; C20-28%; C22-19%; C24-13%;
Og C26-21%; C28-11;x; and greater than C30-6%) wherein in the entire olefin fraction at least 20 mole percent of said 11 olefins contain vinyl:idine groups (C20-C24 alpha olefins and 12 C24 C28 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 (polysityrene crosslinked with divinylbenzene) 17 catalyst (Amberl.yst 15R available from Rohm and Haas, 18 Philadelphia, P~~). The reaction mixture was heated to about lg 140°C for about 8 hours with stirring under a nitrogen atmosphere. They 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 C20-C28 23 alkylphenol with a hydroxyl number of 110 and with 56%
24 Para-alkylphenol contE~nt. This alkylphenol had approximately 26% dia_lkyl phenol and had an average alkyl 26 carbon number of~ 29. This product was a hard wax at room 2~ temperature.

1341 p45 O1 Comparative Example 2B
02 Preparation of Low I)ialkyl C20-28 Terminal Alkyl Phenol 05 The procedure of Example 2A was used except 966 gm C20-C28 06 alpha olefins and 211..5 gm of phenol were used. The resulting alkyl pheno:L had approximately 6% dialkyl phenol 08 and an average alkyl carbon number of 24. This product was 09 a wax at room te~mperai:ure.

12 Comparative Example 2C
Preparation of a C26-Average Terminal Alkyl Phenol In a separate procedure, the low dialkyl C20-28 phenol of 16 Example 2B was realky:Lated using an additional 10% C20-C24 1~ alpha Chevron olefin (per conditions described in Example 18 1C). This reaction thus afforded an alkylphenol composed of 19 approximately lE~% dia:Lkyl phenol species. The average alkyl carbon number ways 26. This product was a wax at room 21 temperature.

23 Cornparative Example 3 24 pre~parat_Lon of Tetrapropenylphenol 2~ To a 2-liter flask, eduipped with stirrer, Dean Stark trap, 28 condensor, and nitrogen inlet and outlet was added 567 grams 29 of tetrapropylene, 541) grams of phenol, 72 grams of a sul-Tonic acid cation exchange resin (polystyrene crosslinked w 31 with divinylbenz;ene) catalyst (Amberlyst 15R available from 32 Rohm and Haas, F~hiladelphia, PA). The reaction mixture was O1 heated to about 110°C for about 3 hours with stirring under 02 a nitrogen atmosphere.

04 The reaction mi:Kture was stripped by heating under vacuum 05 and the resulting product filtered hot over diatomaceous 06 earth to afford 626 grams of tetrapropenylphenol and with a p7 hydroxyl number of 205 and with 96~ para-alkylphenol 08 content.

11 Comparative Example 4 12 Preparation of C20 to C28 Terminal Alkylphenol 13 Poly(oxypropylene) Alcohol 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 1~ moles) of a C20 to C28 terminal alkylphenol prepared in a lg manner similar i.o Exa:mple 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. T:he 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 di.ssolv~ed. The reaction system was then allowed to cool to 60°C. Afterwards, 4552 grams (78.37 26 moles) of propylene oatide was added to the system by an 2~ addition funnel at an addition rate slow enough to avoid 2s flooding of the vapor condensing system. The system was 29 then gently refl.uxed Eor 72 hours at which point the temper-ature increased to 110°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 HC1 1 341 d4 5 O1 solution. The system was then dried by azeotropic distill-02 ation. The system wa:c then diluted with 10 liters of hexane 03 which was afterwards extracted three times with a slightly 04 basic brine solution (pH - 8 to 9). In each extraction, a 05 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 O9 and high vacuum to afi:ard 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 PCB 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.

1~ Cornparative Example 5A
lg Preparaticm of c:20 to C28 Terminal Alkylphenyl 1g Pol~~(oxy~:opylene) Chlorvformate 21 To 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 C20 to C28 iterminal alkylphenyl poly(oxypropylene) 24 alcohol prepared as in Example 4 above. The system was cooled to 5°C with starring. While stirring, 297 grams (3.0 26 moles) of liquid phosgene was added all at once to the 2~ reaction system. The reaction system was allowed to warm to 28 room temperatures and ;stirred gently for 24 hours. In order 2g to remove exces:~ phosgene as well as HC1 formed during the reaction, the system was vigorously sparged with nitrogen.
31 Infrared analysis of ,gin aliquot revealed a strong chloro-32 formate absorption at 1785 cm 1 and no detectable alcohol 134~~45 O1 absorption at 3150 cm~l. This product was a waxy paste at 02 room temperaturE~.

05 Example 5B
06 Preparation oi: a Pinwheel Alkylphenyl Poly(oxypropylene) 07 Chloroi:ormat~e from the Poly(oxypropylene) 08 Alcohol of Example 32 11 To a cooled (5°(:) mecihanically stirred solution of the 12 pinwheel poly(oxyprop:ylene) alcohol (440 gr, 0.26 moles) of 13 Example 32, derived from C14 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 mi~cture was allowed to warm to room temperature 17 and stirred geni:ly for 24 hours to remove excess phosgene lg and the HC1 forrned during the reaction period. Infrared 19 analysis of an aliquot revealed a strong chloroformate absorption at 1'l85 cm l and no detectable alcohol 21 (3450 cm 1). This product was a liquid at room temperature.

24 Comparative Example 6 Prep<~ration of C20 to C28 Alkylphenyl 26 Poly(oxypropylene) Ethylene Diamine (EDA) Carbamate 28 The entire chlon:oformate/toluene solution of Example 5A
29 was diluted with 4 liters of dry toluene. In a separate flask, 2565 grams (42.7 moles) ethylene diamine (EDA) was 31 also diluted wii:,h 4 liters of dry toluene. At room 32 temperature, thE~se two solution were rapidly mixed using O1 two variable speed tef:lon gear pumps and a 10 inch Kenics 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 05 slightly basic (pH - 9) brine solution. Phase separation 06 of the aqueous trine solution and the hexane solution was p7 improved by adding brine as needed. The hexane solution Og was separated, dried over anhydrous sodium sulfate, fil-O9 tered and stripped to afford the title product as a light yellow liquid wr~ich solidified to a loose paste upon 11 cooling and having an alkalinity value of 30 and 0.75 12 weight percent x>asic nitrogen. This preparation was 13 repeated to give the product listed as Example 23 below.
14 This product wa:~ a wa:~cy paste at room temperature and did not pass the wa}: test as described in Example 45.

lg Comparative Example 7 lg Preparati.on of C20 to C28 Terminal Alkylphenyl Poly(oxypropyle:ne) Diethylene Triamine Carbamate 22 In the manner dE~scribed in Example 6 above, 2256 grams (1.53 23 moles) of C20 to C28 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 2a basic nitrogen. This preparation was repeated to give the 2g product listed ~~s Example 27 below. This product was a waxy paste at room temperature and failed the wax test of , 31 Example 45.

O1 Comparative Example 8 02 Preparation of _n-Butyl 03 Poly(oxypropylf~ne) Ethylene Diamine Carbamate 05 2000 grams (0.91. moles) of n-butyl poly(oxypropylene) 06 alcohol was preFrared :Ln the manner of Example 4 by 07 substituting n-butano:L for the C20 to C28 alkylphenol. The 08 n-butyl poly(ox~~propy:Lene) alcohol was then treated with 09 phosgene in the manner of Example 5A to yield the n-butyl poly(oxypropylene) ch:loroformate 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 45.

18 Comparative Examples 9-17 21 Other hydrocarbyl poly(oxyalkylene) alcohols were prepared 22 by employing dii=ferent 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 '.Cable I summarizes the different hydrocarbyl 26 poly(oxyalkylene) alcohols so prepared.

03 POLY(O:KYALKYLENE) ALCOHO LS OF THE FORMULA

05 R3-Of CH2CHO~ nH

07 Phenol Avg. No.

08 Source of Alkyl Ex. R,3 Ex. No. R1 n Carbons -g n-butyl - -CH3 "37 4 11 10 n-butyl - -CH3 "23 4 12 11 tetrapropenylphenyl 3 -CH3 "20 12 13 12 tetrapropenylphenyl 3 -CH2CH3 "17 12 14 13 X20-28 terminal alkylphenyl 2A -CH3 "17 29 14 X20-28 terminal alkylphenyl 2A -CH3 "14 29 16 15 C20-28 terminal alkylphenyl 2A -CH3 "10 29 17 16 C20-28 terminal alkylphenyl 2A -CH3 "6 29 18 17 X20-28 terminal alkylphenyl 2A -CH2CH3 "17 29 19 29 C20-28 terminal alkylphenyl 2B -CH3 "17 24 30 C20-28 terminal alkylphenyl 2B -CH3 "13 24 21 31 C20-28 terminal alkylphenyl 2C -CH3 "14 26 22 32 a-C14 deri~red pinwheel 23 alkylphenyl lA -CH3 "20 36 24 33 a-C14 oligomer alkylphenyl alkylphenyl lA -CH3 "16 36 26 34 a-C16 oligomer alkylphenyl 27 alkylphenyl 1B -CH3 "17 34 1341 04 ~

03 Carbamates of the Formula 06 R30f CH2CH0-~nC~N Hf CH2-CH2-NH~
H

p 08 Phenol Avg. No.

O9 Source of Alkyl Ex. R3 Ex. No. R1 n p Carbons 12 18 n-butyl - -CH3 "37 1 4 13 19 n-butyl - -CH3 "23 1 4 14 20 tetrapropenylphenyl 3 -CH3 "20 1 12 21 tetrapropenylphenyl 3 -C2H5 "17 1 12 16 22 tetrapropenylphenyl 3 -C2H5 "17 2 12 17 23 C20-28 terminal alkylphenyl 2A -CH3 "17 1 29 18 24 C20-28 terminal alkylphenyl 2A -CH3 "14 1 29 19 25 C20-28 terminal alkylphenyl 2A -CH3 "10 1 29 26 C20-28 terminal alkylphenyl 2A -CH3 "6 1 29 21 27 C20-28 terminal alkylphenyl 2A -CH3 "17 2 29 22 28 C20-28 terminal alkylphenyl 2A -CH3 "17 1 29 23 35 C20-28 terminal alkylphenyl 2B -CH3 "17 1 24 24 36 C20-28 terminal alkylphenyl 2B -CH3 "13 1 24 37 C20-28 terminal alkylphenyl 2B -CH3 "13 2 24 26 38 C20-28 terminal alkylphenyl 2C -CH3 "14 1 26 27 39 a-C14 deri~~ed pinwheel 28 alkylphenyl lA -CH3 "'20 2 36 29 40 a-C14 deri~~ed pinwheel alkylphenyl lA -CH3 "16 2 36 31 41 a-C16 deri~~ed pinwhee 1 32 alkylphenyl lA -CH3 ~17 2 34 O1 Comparative Examples 18-28 04 Other hydrocarb:yl poly(oxyalkylene) aminocarbamates were 05 prepared by employing different hydrocarbyl groups including 06 those of Examples 2 and 3 and by employing poly(oxyalkylene) p7 groups of different chain lengths. Examples 18 through 28 08 are found in Table II, which summarizes the different Og hydrocarbyl pol:y(oxyalkylene) aminocarbamates so prepared.

12 Comparative Example 29 13 Prepa ration of a C24 Terminal AlkylPhenyl 14 Poly(oxypropylene) Alcohol 17 In a manner similar to that described in Example 4, 622 gm 18 (1.45 moles) of the terminal low dialkyl terminal phenol lg derived from th~~ C20 to C28 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 1~ moles of pro~~ylene oxide. This product was a waxy paste 23 at room temperature.

26 Comparative Example 30 2~ Preparation of a C24 Average Terminal Alkylphenyl 2g Poly(oxypropylene) Alcohol 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.

1341 p45 O1 Comparative Example 31 02 Prepar,~tion of a C26 Terminal Alkyl Phenyl 03 Poly(oxypropylene) Alcohol 06 The alkyl pheno:L of Example 2C was converted to a 14 PO
07 polymer (as determined by Nmr) in a manner similar to that Og described in Ex~~mple 4, but using 14 moles of PO per mole of Og phenol. This product was a waxy paste at room temperature.

12 Example 32 13 Preparation of Pinwheel Poly(oxypropylene) Alcohols 14 from C14 Oligo:mer Derived Phenol of Example lA
16 This experiment was carried out in dry 2-liter, three-necked 1~ 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 alkylphenol of 21 Example lA was slowly added potassium metal (5.4 gr) in 22 small pieces with vigorous mechanical stirring. The pot 23 temperature increased to approximately 100°C during the 24 addition, and ai:ter 2~-1/2 hours, all of the potassium was dissolved. AftE~r cooling to 60°C, 585 mls of propylene 26 oxide (486 gram:, 8.36 moles) was added in such a way as to 2~ 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 1:10°C and was held at temperature for an additional 3 hours. After cooling to 60°C, the reaction was ' 31 quenched with 6C1 ml of 3N HC1 (a slight excess) and dried by 32 azeotropic distillation. The crude product was then diluted O1 with hexane (3 Liter),, extracted three times with slightly 02 basic brine. Ire 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 05 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 20 08 propylene oxide monomer units. This product was a non-p9 viscous liquid apt room temperature and could not be induced to crystallize apt low temperature.

13 Example 33 14 Preparation of Pinwheel Alkylphenyl Poly(oxypropylene) Alcohols 18 The pinwheel alkyl phenol of example lA (C14-derived) was 19 converted to they poly(oxypropylene) alcohol by reaction with 16 mole equivalents o~E propylene oxide in a manner similar 21 to that described in Example 32.

24 Example 34 Preparation of Pinwheel Alkylphenyl 26 Poly( c~-xypropylene ) Alcohols 29 The pinwheel alkyl phenol of example 1B (C16-derived) was converted to they poly(oxypropylene) alcohol by reaction with , 31 17 mole equivalents o:E propylene oxide in a manner similar 32 to that described in Example 32.

1341 p45 O1 Comparative Example 35 02 Preparation of i:he Terminal Low Dialkyl C20-24 Carbamate EDA

05 Without further purification, the terminal alkylphenol 06 alcohol of Example 29 was converted to the chloroformate as 07 described in Example 5A, except that a 20 weight percent 08 solution of pho:~gene in toluene was employed rather than condensed phvsgE~ne li~~uid (for handling convenience and safety). After reaction, the chloroformate was then 11 rigorously sparcled to remove excess phosgene and the HC1 12 reaction by-product.

14 The resulting chloroformate was then converted to the corre-sponding EDA carbamatcs by reaction with ethylene diamine as 16 described in Example ti. The average alkyl carbon number was 17 24; alkalinity value =- 34; basic nitrogen was 0.85. This 18 product did not pass the wax test of Example 45.

Sequence V-D engine tasting 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 performances aspect, a similar molecule was synthesized, 24 but with less PCi. This is shown in Example 36.

O1 Cornparative Example 36 02 Preparation of a Terminal C24-Average Alkyl Phenyl 03 Poly(ox~roropylene) EDA Carbamate 06 In a separate procedure, the terminal "low" dialkylphenol of Example 2B was c~onveri:ed to a phenol-capped 08 Poly(oxypropylene) alcohol containing 13 PO units using a Og procedure similar to i:hat 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.

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 lg Example 45.

21 Cor~aarative Example 37 22 Preparation of a C24 Terminal Alkylphenyl 23 Pol. (y oxypropylene) DETA Carbamate 26 The remainder of the chloroformate of Example 36 was converted to the corresponding DETA carbamate (alkalinity 2g value =67.4, 1.E~9% basic nitrogen) as in Example 7. This 2g product did not pass i~he wax test of Example 45.

1 341 p4 5 O1 Comparative Example 38 02 Preparation of a C24-Average Terminal Alkylphenyl 03 Poly(oxypropylene) EDA Carbamate 06 The poly(oxypropylene) alcohol of Example 31 was converted 07 to the corresponding chloroformate as in Example 5A and Og reached with EDA to afford the desired ethylene diamine p9 carbamate in a manner similar to that of Example 6 (alkalinity value = 39.0, 0.85% basic nitrogen). This 11 product did not pass the wax test of Example 45.

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 they number of alkyl carbons in the alkyl 17 phenol. As can be seen in Example 35, an average alkyl lg carbon content of 24 carbon atoms with PO formulations is 1g insufficient to provide the required varnish and sludge control. Neither by reducing the PO content (Example 36) nor 21 bY switching to DETA c:arbamates (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 ESCample 45.

1341 p45 O1 Example 39 02 Preparation of Alkylphenyl Poly(oxypropylene) 03 Dieth lenetriamine Carbamate 06 The chloroformate/tolu.ene solution of Example 5B was diluted 07 to 2 liters with dry t.aluene. In a separate flask, 08 530 grams of diethylene triamine (5.-2 moles) was also Og 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 Ke~nics static mixer. The crude reaction 12 mixture was then stripped, diluted with 6 liters of hexane, 13 and washed successively with water (4X), basic (pH=9) water 14 (2X), and water (4X). Phase separation was improved by adding isopropanol as needed. The organic layer was then 16 dried (NaS04), filtered and stripped to afford a light 17 orange product which remained a liquid at -40°C (alkalinity lg value = 50, 1.25% basic nitrogen). As such, this product lg was regarded as non-waxy by virtue of passing the wax test of Example 45. This c:arbamate does not produce detrimental 21 varnish and sludge relLative to the base oil.

24 Examples 40-41 Preparation of: Aminocarbamates of the Present Invention 28 The pinwheel alc:ohols 33 and 34 were reacted in a manner 2g similar to Examples 5 and 7 to give a C14-derived DETA
pinwheel carbamate having 16 oxypropylene units and an .
31 average alkyl carbon number of 34 (Example 40) and a 32 C16 derived DETA pinwheel carbamate having 17 oxypropylene ~ 341 04 5 O1 units and an average alkyl carbon number of 36 (Example 41).
02 These products pass the wax test at -40°C and do not produce 03 detrimental sludge or varnish relative to base oil.

06 Example 42 07 Oil solubility Bench Test This procedure was designed to determine the oil 11 solubility/compatibili.ty 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.

17 The lubricating oil composition was formulated to contain:
lg 6 percent by weight oi° a monopolyisobutenyl succinimide; 20 19 millimoles per k.ilogr<~m of a highly overbased sulfurized calcium phenate; 30 m'illimoles 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 t:o give a 10 W 40 formulated oil.

2~ The oil solubility of the additive was determined as 2g follows:

To a heated solution (50 grams) of the above-described lube 31 oil was added 5C1 gram:a of the neat additive. The mixture 1341 p45 O1 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, 05 the diluted samples were stirred to 170°F for 10 minutes to 06 insure complete mixing. The solutions were then sealed and p7 left to cool undisturt>ed for from 1-5 days typically at room OS 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) 1'7 improver. This phenonnenon resulted in the separation of the 18 VI improver which is less dense than the bulk oil forming a 1g 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 upper VI improver phase.

The oil solubility (or insolubility) of the hydrocarbyl 26 poly(oxyalkylene~) aminocarbamates including the alkylphenyl 2~ poly(oxypropylene) am:inocarbamates of this invention is 2g believed to correlate well to the oil solubility of the 2g precursor hydroc:arbyl poly(oxyalkylene) alcohol. Accord-ingly, Table II7: below contains solubility data for the 31 hydrocarbyl poly(oxya:lkylene) alcohols. Oil solubility is 32 reported in weight percent of additive in the lubricating 33 oil composition..

1 341 p4 5 Ol TA8LE III

03 Example No Oil Solubility 08 1:L 18 1:3 40 11 l~l 50 13 lEi 50 14 1'l 50 16 The oil solubil:Lty of the amino carbamates is reported in 17 Table IV.

Example 43 21 Sequence V-D Test Method 24 Formulated oils containing alkylphenyl poly(oxypropylene) aminocarbamate were tested in a Sequence V-D test method as 26 well as formulai:.ed oils containing comparative hydrocarbyl 27 poly(oxyalkylenc~) aminocarbamates. This procedure utilizes 28 a Ford 2.3-liter:, four-cylinder Pinto engine. The test 29 method simulates a type of severe field test service characterized bbl a combination of low speed, low temperature 31 "stop and go" city driving and moderate turnpike operation.
32 The effectiveness of the additives in the oil is measured in 1~~1045 O1 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 sludcie deposits. The results of these tests are 04 found in Table 7:V below.

06 The reference composition was formulated to contain:
07 6 percent by weight of a mono-polyisobutenyl succinimide; 20 08 millimoles per i;ilogr.am 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 i:ormul,ated oil.
16 Comparisons against tlhis 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:

~34~045 02 Carbamate Performance and Properties 04 Crankcase (3) Crankcase Oil (1) Wax (2) Av. Varnish Av. Sludge (5) Av.

05 Ex. Compatibility @ -40C 2.5 (4) 5.5 2.5 5.4 HC #

18 0.5 no 4.4 9.2 4 19 1 no 4 08 20 7 no 12 21 15 no 5.7 5.5 9.5 9.55 12 O9 22 15 no 12 11 23 16 yes 29 24 20 yes 6.4 7.5 9.6 9.35 29 12 25 45 yes 29 13 26 50 yes 29 27 16 yes 29 14 28 16 yes 29 35 18 yes 4.4 9.5 24 16 36 20 yes 5.4 9.4 24 37 18 yes 7.4 9.2 24 1~ 38 22 yes 6.2 9.4 26 39 18 no (6) (6) 34 19 40 18 no (6) (6) 36 41 18 no (6) (6) 34 (1) See Ex. 42 22 (2) See Ex. 45 (3) See Ex. 43 -- ng scale 1-10, with 10 meaning no varn ish Rati =

23 or sludge.

24 (4) Weight percent ditive.
ad (5) Average alkyl bon number in alkyl phenyl group car (6) These carbamates are not the baseoil detrimental relative to 26 of Example :30.

, ~ 341 p4 5 O1 Examples 18 thro~igh 22 represent prior art hydrocarbyl 02 poly(oxyalkylene) aminocarbamates. This Table establishes 03 that the alkylph~enyl poly(oxypropylene) aminocarbamates of 04 this invention (Examples 39-41) were less detrimental, i.e.
05 gave decreased crankcase deposits, as measured by average 06 varnish in the Sequence V-D results.

OS The table also establishes that the additives of this p9 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, i.e., Examples 18, 19 and 20.

Example 44 16 TGP. Stability of Amino Carbamates 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°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, i.e., rate 2g constants and h~~lf-lives, were readily determined from the 29 accumulated TGA data. The half-life measured by this pro-cedure 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 O1 will contribute to ORI. Lower half-lives represent a more 02 easily decomposable product one which will not as likely 03 accumulate and i'orm deposits in the combustion chamber. All 04 of the comparatW a carbamate examples and the carbamate 05 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.

Example 45 11 Dei=ermination of Additive Waxiness 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 i9 normally in ser~~ice in additive distribution systems and the fuel or lube sy;~tems 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.

28 The test additive (30 gr) is dissolved in an equivalent 2g weight of reagent grade toluene, cooled to -40°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 O1 has failed the test. A sample which passes this test is one 02 described as "c7.ear and bright", a well-known 03 industry-designated standard.

06 Example 46 07 rZeasuring the Epoxide Content Nmr spectroscopy provides a method for measuring the 11 backbone "epoxic~e content" of these additives. The ether 12 carbons and thei~.r associated protons are segregated and 13 easily "counted".

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

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.

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-acE~tylacetonate, i.e., Cr(III)(AcAc)3.
32 All spectra werE~ determined using high performance 5 mm Nmr 33 tubes.

_ 1341 045 O1 Instrument Conditions 03 To Observe Proton To Observe Carbon 05 Frequency 299.944MHz 75.429 MHz 06 Spectral Width 5000 Hz 20492 Hz 07 Acq. Time 1.6 Sec 0.4 Sec 08 Relax. Delay 2.0 Sec 2.0 Sec 09 Pulse Width 14° 90°
Temperature Ambient Ambient 11 No. Repetitions 16 2048 12 Spin Rate 20 Hz 24 Hz 13 FT Size 16R 32K

Determination oi= Integral Values 17 Proton Nmr Specl:ra 19 The aromatic protons (6.5 to 7.5 ppm) serve as the internal standard for this evaluation. When dealing with products 21 derived from "h:igh dialkylation" phenols (20 to 25%), the 22 integral value :Eor this region of the spectra is divided by 23 3.75. This signal value per proton is then used to evaluate 24 ether carbon proton content. Otherwise, this signal is attributed to four aryl protons (for phenols having <10%
26 dialkylation).

28 The ether protons of interest lie in the region between 3.2 29 and 4.0 ppm. Here we see the mass of methylene and methine protons which include the separated multiplets observed for 31 the first and the last epoxide units assembled in these 32 polyethers. One-half of the total number of PO related _77_ O1 protons are observed :in this region, whereas only 02 three-eighths of: the BO-related protons are represented 03 here.

05 Carbon Nmr Spectra 07 The six aromatic; carbons (105 to 160 ppm) serve as the 08 internal standai:d for this evaluation. This is no need to O9 make any allowances for the presence of dialkyl phenol in this case.

12 The ether carbons of interest lie in the region between 60 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 i;~ straightforward.

lg Example 47 Determination of the Nature of the Alkylphenyl Group 23 Analytical methods for determining the general nature of the 24 alkylphenyl substituent of the aminocarbamates can be accom-plished in the following manner:

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 phen.al. This residue can then be examined O1 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 05 species. Thus, the tropylium ions generated from simple 06 alpha olefins wall typically contain from 1-3 carbon atoms 07 more than those accounted for by the aromatic ring itself.
0g By comparison, i:he same ionized species generated from the Og 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.

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 lg information concerning the structure of the alkyl portion 19 may be lost. Iz 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 b,~se ion peak (peak of highest relative 24 intensity). Se~e: Silverstein, Bassler, and Morril, Spectrometric Identification of Organic Compounds. Wiley 26 and Sons (New Y~crk, 1974) pp. 19-22.

2g Another less p referred but supporting analysis can be per-2g formed by conducting carefully controlled oxidations of the alkyl phenol si~3e chains. This is typically done via , 31 aqueous potassium permanganate oxidation under pH conditions 32 designed to control the extent of the oxidative chain _79_ O1 cleavage reactions desired. If the alkyl phenol has been 02 derived by alky7_ation 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 05 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, Og although they may not comprise the majority of oxidation Og reaction products. Hence, for a pinwheel alkyl phenol derived from a C:10 a-olefin oligomer one would expect to 11 observe the corresponding C7-C9 alkanoic acids after 12 degradation. On the other hand, when 13 the phenol derived from simple C20 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.

lg 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 in:Eormative.

Ol Example 48 02 Determination of Average Alkyl Hydrocarbon 03 Content of Alkylphenols 06 Chemical Method 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.

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.

17 As these alkyl groups are saturated hydrocarbons, dividing 18 the balance portion by 14 (the mass units for a -CH2-19 moiety) gives the average number of alkyl hydrocarbon atoms in the phenol.

22 Spectroscopic Method 24 Alternatively, Dlmr an<~lysis can be used to determine the average alkyl hydrocarbon content. Nmr analysis of 26 integrated 1H 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.

This information may <~lso be obtained by using integrated 31 13C Nmr spectra of these products. Thus, the number of 32 aromatic carbonic can be used as an internal standard for O1 gauging the average number of saturated carbons in the 02 phenol. TypicaJ.ly, the 1H and 13C Nmr results are averaged 03 and are in good agreement with the chemical determination.

05 It is assumed that the average alkyl hydrocarbon content of 06 the phenols doe:c not change during the reaction to make the 07 alcohols, chloroformates and carbamates.

w

Claims (22)

1. A liquid alkylphenyl poly(oxypropylene) 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 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 30 to 45 carbon atoms derived from a substantially straight-chain alpha olefin oligomer of C8 to C20 alpha olefins, and further wherein the alkyl group 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 said alkylphenyl poly(oxypropylene) aminocarbamate contains from 1 to about 100 oxypropylene units.

3. An alkylphenyl poly(oxypropylene) aminocarbamate according to claim 2, wherein the poly(oxypropylene) group of said alkylphenyl poly(oxypropylene) aminocarbamate contains from about 5 to about 50 oxypropylene units.

4. An alkylphenyl poly(oxypropylene) aminocarbamate according to claim 3, wherein said alkylphenyl poly(oxypropylene) aminocarbamate contains from about 10 to 25 oxypropylene units.

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

6. An alkylphenyl poly(oxypropylene) aminocarbamate according to claim 5, wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms.

7. An alkylphenyl poly(oxypropylene) aminocarbamate according to claim 6, 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.

8. An alkylphenyl poly(oxypropylene) aminocarbamate according to claim 7, wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.

9. 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.

10. A compound of the Formula wherein R is a substantially straight-chain alkyl group of from about 30 to 45 carbon atoms derived from a substantially straight-chain alpha olefin oligomer of C8 to C20 alpha olefins and R is attached to the phenyl ring at least 6 atoms from the terminus of the longest chain of said group R; R1 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 about 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°C in a 50 weight percent solution with toluene.

11. A compound according to claim 10, wherein n is an integer from about 1 to about 100.

12. A compound according to claim 11, wherein n is an integer from about 5 to about 50.

13. A compound according to claim 12, wherein n is an integer from about 10 to about 25.

14. A compound according to claim 10, wherein the compound has an average molecular weight of from about 1,000 to 2,500.

15. A fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to 5,000 parts per million of a compound as defined in any one of claims 1 to 14.

16. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of 150° to 400°F
and from 5 to 50 weight percent of a compound as defined in any one of claims 1 to 14.

17. A lubricating oil composition comprising an oil of lubricating viscosity ands a dispersant effective amount of a compound as defined in any one of claims 1 to 14.

18. A lubricating oil concentrate comprising from about 90 to 50 weight percent of a.n oil of lubricating viscosity and from about 10 to 50 weight percent of a compound as defined in any one of claims 1 to 14.

19. An alkylphenol wherein the alkyl group is a substantially straight-chain alkyl group of from about 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.

20. An alkylphenol according to claim 19, wherein the alkyl group contains from about 28 to 50 carbon atoms.

21. An alkylphenol according to claim 20, wherein the alkyl group contains from about 30 to 45 carbon atoms.

22. An alkylphenol according to claim 21, wherein the alkyl group is derived from a substantially straight-chain alpha olefin oligomer of C8 to C20 alpha olefins.