CA1050991A - Additive useful in oleaginous compositions - Google Patents

Abstract

ABSTRACT
A process fro preparing oxazolines and compositions thereof with metal salts, which comprises reacting a substantially saturated hydrocarbyl-substituted C4-C10 dicarboxylic acid or anhydride or ester thereof having at least 50 carbon atoms in said hydrocarbyl group with a 2,2-disubstituted-2-amino-1-alkanol having 2 to 3 hydroxy groups and contain-ing a total of 4 to 8 carbon atoms of the formula

Description

This is a division of application serial No.
222,577,filed March l9, 1975.

l During the past decade, ashless sludge dispersants

2 have become increasingly lmportant, primarily in improving

3 the performance of lubricants and gasoline in keeping the

4 engine clean of deposits and permitting extended crankcase ~ .
oil drain periods Most commercial ashless dispersants fall .
6 into several general categorles. Xn one category, an amine 7 or polyamine is attached to a long chain hydrocarbon 8 polymer, usually polyisobutylene, directly by reaction o~
9 halogenated olefin polymer with polyamine as in U.S Patents 3,275,554; 3,565,592; 3,565,B04. In another cate~.ory, a 11 polyamine is linked to the polyisobutylene through an acid 12 .group, such as long chain monocarboxylic acid, e.g, see 13 U~S. Patent 3,444,170 or long chain dicarboxyl~c acid such 14 as polyisobu~enylsuccinic anhydride, by forming amide or ~mide linkages, such as described in U.S Patents 3,172,892;
16 3,219,666; e~c~ More recently,.non-nitrogen ashless di~- .
17 persants have been formed by es~erifying long chain dicar-18 boxylic acids; such as the polyisobutenylsuccinic anhydride, 19 with polyols, such as pentaerythritol~ as in tJ.S. Patent 3,381,022.
21 Reactlon products of hydrocaxbon substituted suc-22 cinic anhydrlde, e,g,) ~he afore~aid polyisobutenylsuccinic 23 anhydride, with compounds containing both an amine group 24 and a hydroxy group have been suggested or invèstigated in ~he prlor:art. For ex~mple, U S Pa~ent 3,272,746 teaches 26 ~he reaction of ethanolamine and diethanolamine, as well as 27 various hydroxyalkyl substituted alkylene amine~ 7 such as 28 N~ hydroxyethyl) ethylene diamine, ~N'-bis(2-hydroxy-29 e~hyl) ethylene diamine, witll allcenyl s~ceinic anhydride 3~ to obtain ~shless dispersants for lube oil A hydroxy~ ~
~5~g9~

.

9 ~ ~
1 amine, such as diethanolamine~ is reacted with a long chain 2 alkenylsuccinic anhydride in U~S. Patent 3,3249033 to orm 3 a mixture of esters and amides, w~erein some of the di~
4 ethanolamine reacts through a hydroxy group to give an ester linkage, while another portion of the diethanolamine ~orms 6 an amide linkage. U.S. Patent 3J364~001 teaches a ter~iary 7 a1kanolamine reac~ed with an alkenyl succinic anhydride to 8 form an ester useful a~ a gasoline additi~e. U.S. Patent 9 3,448,049 teaches dispersant~, corroslon inhibltors and antiwear agents in lubricants and fuels by es~erifying al-11 kenyl succ~nic anhydride with a hydroxy compound made by 12 reacting an alkanolamine with an unsaturated e~ter, amide 13 or nitrile. U.S. P~tent 3,630,904 teaches reacting a 1~ hydroxy amine with both short and long chain dicarboxylic acid. U.S, Patent 3,484,374 teaches the polymeric conden-16 sation product of polycarbox~lic acid or anhydride with 17 variou$ alkanolamines ~uch as aminoethy1 ethanola~ine, 18 N-methyldiethanolamine, etc.
19 U.S. Patent 3,576,743 teaches reacting polyiso-butenylsuccinic anhyd~ide with a polyol, such as pentaery-21 thritol, followed by reaction with tris-methylolaminomethane 22 (~), (see Example 1). U.S. Patent 3 9 632,511 ~eaches re-23 ac~i~g polyisobutenylsuccinic anhydride with both a poly~
24 amine and a polyhydric alcohol including THAM. U S~ Patent 3,697,428 (Example 11) teaches reacting polyisobutenyl-~6 suceinic anhydrlde with a mixture of pentaerythritol and 27 THAM.
28 As noted above9 the prior art teaches dispersants 29 formed from long ehain hydrocarbyl sub~tituted dicarboxylic acid material, usually alkenyl succinic anhydride, reacted l wlth ~arious amlno vr hydroxy compounds, elther through a~
2 amide, imide, or ester linkage~ In contrast to the prior 3 art, ,he present invention is based upon the discovery that 4 reactlon of long chaln hydrocarbyl dicarboxyllc acld mater-

5 ial, i.e., acid, or anhydri.de, or e~ter, wl~h certain : 6 classes of amino alcohols, under certain conditlons, will 7 result in a d~ferent type of linkage, namely an oxazoline 8 linkage, and that materlals with this oxazoline linkage 9 appear very effective as detergents or dispersan~s for 10 oleaginou~ compositions such as lubrica~ing oil and gaso-11 llne.
12 The long chain hydrocarbyl-sub~tituted dicarboxyl-13 ic acid ma~erial, i e , aci~ or anhydride, or ester, used 14 in the invention ~e prep~red :~rom alpha-beta unsaturated C~ to C10 dicarboxylic acids,.ox anhydrides or esters thereof, such a~
16 fumaric acid, itaconic acid, maleic acid, m~leic anhydride, 17 chloromaleic acid9 dimethyl ~umara~e, etc., which are sub-18 stituted wlth a long hydrocarbon chain~ .generally a olefin 19 polymer cha in .
In general, these hydrocarbyl substituted dicar 21 boxylic acid material~ and their prepara~ion arc well known ~2 in the art~ for example see U.SO Patents 3,219,666; 3~172,892;
23 3,272~746; a~ well as the afGrementioned prlor art patents~
24 m e hydrocarbyl portion should average at least 50 ~ :
aliphatlc carbon ~toms per dicarboxylic acid group and b~
26 sub~tan~lally ~aturated ~sually no more than 10 mole %, 27 and pre~erably 5 mole % or less of the total carbon to car-28 bon linkage will be unsaturated, as excessive unsaturation 29 in the final product will tend to oxidi~e and unduly form gU~ ~nd resins in the engine. Further d~er~p~.ion~ an* -999~
exampleQ of the hydrocarbyl substituent portion are set 2 forth in U.S. Patent 3,272,746, column 2, line 35 to column 3 4 ~ line 10.
4 Frequently ~chese hydroc~rbyl ~ubstituted dicar~
boxyllc ac~d materials are prepared by reacting the unsat

6 ura~ed d~carboxylic acid material9 usu~lly m~leic anhydride,

7 with an olefin, usually an olein polymer still retaining a

8 terminal unsatura~ion. The olefin pol.ymer can, if desired,

9 be ~irst halogenated~ for example, chlcrinated or brom~nated

10 to about 2 to 5 wt. % chlorine, or about 4 to ~ Wto % bro-

11 mine, based on the we~ght of polymer, and then reacted with

12 the maleic anhydride (see U.S. Patent 3,444,170).

13 In some case~, the ole~in polymer m~y be complete~

14 ly ~a~urated, for example ~n ~thylene-propylene copolymer made by a Ziegler-Natta s~nthesi~ u~ing hydrogen as a mod-16 er~tor to co~rol molecular weight. In the case of such 17 ~atura~ed polymers, the polymer can then be halogenated to 18 m~ke ~t reactive ~o i~ can be conden~ed with ~he unsatur-19 ated d~carboxylic acid materlal which is then randomly added along th~ polymer chaln, 21 . Preferred olefin polymers for reaction wi~h ~he 22 un~a~urated dicarboxylic ac~ds are polymers comprising a 23 ma~or molar amount af ~2 to Cs monoolefin, e.g., ethyLene, 24 propylene, bu~ylene, isobu~ylene and pentene, The polymers can be homopolymers ~uch as poly~sobutylen~9 as well a~
26 copolymer~ of two or more of such olef~ns such as co~
27 polymer~ of: e~hylene and propylene; butylene and isobu~yl~
28 ene; propylene and i~obutylene; etc. Other copolymers in~
29 clude tho~e ~ which a min~ molar amount of the copolymer monomer~, e.g., 1 to 20 mole % is a C4 to C18 nonccon-~ 5 =~

~5~9~9~L
jugated diol.efin, e. g., a copolymer of isobutylene and 2 bu~adiene; or a copolyrner of ethyleneg propylene and 1,4a 3 hexad~ ene; etc ~
4 The olefin polymers will u~ lly have number aver-age molecular weights within the r~nge of about 750 and 6 about 200,000, more usu~lly between sbout 1000 and about 7 20~000. Particularly useful olefin po]Lgloers h~ve number 8 average molecular weights with~n the r~mge of about 900 and 9 about 3000 wi~h approxim~tely one termiLn~l double bond per polymer chain~ An especially valu~ble starting ma~erial 11 ~or a highly potent dispersant additive m~de in accordance 12 with this invention i~ polyisobutylene.
13 ~pecially useul when it is desired that the dis~
14 persan~ additives also po~se~s viscosity index lmproving properties are 10J0OO to 200,000, e~g., ~59000 ~0 100~000 16 number average molecular weight polymer~. An especially 17 preerred ex~mple of such a V.I. improving polymer is a 18 copolymer of about 30 to 85 mole % ethylene~ about lS to 19 70 mole % C3 to C5 mono-alpha~olef~n, preerably propylene9 and 0 to 20 moIe % o a C4 ~o Cl~; nonoconjugated diene.
21 These ethylene-propylene V.I. improving copol~mer~
22 or ~erpolymer~ are usually prepared by ~iegler-Natta syn~
23 the~is, e.g., see U,S. P~tent 3,5$1,336. Some o~ these co-24 polymers and terpolymers a~e commerc~ally available, ~uch as an elastomeric terpolymer o~ ethylene, propylene and 5~
26 ethylidene norbornene and a ~erpolymer of ethylene, propyl--27 ene and 19 4-hexadiene O .
28 O~her halogenation technique~ for attaching the 29 dicarboxylic acid ~er~al to a long hydrocarbon chain, in~
volve irs~ halogenating the un~at:urated dicarboxyllc acid . . . . . . .
. . , ., . ~ . .. .

0 5~ ~ 9 ~ :
1 material and then reacting with the olef~n polymer~ or by 2 blowing halogen gas, e~g., ~hlorine, through a mixture of 3 the polyolefin and unsaturated dlcarboxylic acid material, 4 then heating to 150 ~o 220C. in order to remove HCl gas, e.g.9 see U.S. Patents 3,381,022 and 3~565,804.
6 The amino alcohol used to make the oxazoline dis-~ persan~ is a 2,2-disubstitu~ed~2-amino~ alkanol3 having 2 8 to 3 hydroxy groups, containing a total of 4 to 8 carbon 9 a~om~, and which can be represented by ~he formula:
X
11 NH2 ~ C ~ CH20H

13 w~erein X is an alkyl, or hydroxy alkyl group, with at 14 least one o the X sub~tituents, and pr~ferably bo~h of ~he X sub~tltuent~, belng a hydroxy alkyl group o the struc-16 ture -(~12)nOH, wherein n i~ 1 to 3.
17 Examples of such 2,2~disubstitu~ed amino alkanols9 18 include 2-amino-2-meth~1- 1,3~propanediol, 2~amlnoc2- ~y- :
19 droxy-methyl)-1,3-propanediol (also known a$ trie-(hydroxy~
methy~ a~o methane or THAM), 2~amino~2-ethyl-1,3-propane-21 diol, etc. Because of its effectivene~, availabil~ty, and 22 cost, ~he THAM is particularly preferred.
23 The formation of ~he novel oxazol~ne disper~ants9 24 in a f~irly high yield, can be efected by adding about 1 to 2 mole equlvalen~ of the aforesaid 2,2~disubstituted--2 26 amino~l-alkanol per mole equ~valent of the dicarboxylic 27 ~cid material, with or without an lnert diluent, and heat-28 in the mixture at 140-240Co i preferably 180-220C. or 1/2 2~ ~o 24, more u~u~lly 2 to 8 hours Although not necessary, the presence of ~mall a-~ 7 ~ :

~ 0s~g~
l mounts, such as .01 to 2 wt. V/o, preferably 0.1 to 1 wt. %, 2 based on the weight 3f the reactants, of a metal salt can 3 be used in the reaction mixture as catalyst to shorten the 4 reaction times. The metal catalyst can later be removed by filtration or by washing a hydrocarbon solution of the pro-6 duct with ~ lower alcohol, such as methanol, ethanol, iso~
7 propanol~ etcO 9 Qr an alco~ol/w~ter ~olutionO
8 Al~ernatlvely~ the metal ~alt can be lef~ in ~he 9 reaction mix~ure, as 1~ appears to become stably di~per~ed, 10 or dissolved9 in the reaction product, and~ depending on the 11 metal~ it may even contribute performance bene~its to the 12 oil or ga~oline. This is believed to oceur with the use of 13 zinc ca~alysts.
14 Inert solvents which may be u~ed in the above re-lS action include hydrocarbon ollsl e.g., mineral lubricating 16 o~l, kerosene, neutral mineral oils, xylene, halogenated 17 hydrorarbons, e~g., carbon tetrachloride, dichloroben~ene, 18 tetrahydrofuran, etcO
19 Metal salts that may be used as catalysts in the 20 invention include carboxylic acid salts of Zn, C:o, Mn and 21 Fe~ Metal catalysts derived from strong acids (HCl, ~ul-22 ~onic acid, H2SO~, HN03, e~c.) and bases tend to dlm~nish 23 the yield of the oxazoline products and in~ead avor lmlde 24 or ester formation. For this rea~on, these strong acid cat-25 alysts or basic catalys~cs are not pre~erred and usually 26 wlll be Rvoided. The carboxylic ac ids used to prep~re the 27 desired cat~lysts9 include Cl to C18, e.~0 9 ~1 to C~9 acids, 28 such a~ the saturated or unsaturated mono and dicarboxylic 29 al~pha~ic hydrocarbon ~cids, particularly fat~y acids.
30 Speciic example~ of such desired carboxylic ac.Ld salts .

. ~ 8 ~

:. ,, , , - .- . ,, " ~;,,, -9 9 ~
1 include zinc acetate, zinc forma~e, zinc propionate, zinc 2 steara~e, manganese (ous) ace~ate, iron tartrate, cobalt 3 (ous) acetate~ etc, Completlon of the oxazoline reaction 4 can be readily ascerta~ned by using periodic infr~red spectral analysis for following the oxa~oline formation 6 (oxazoline peak forms at 6.0 micron~), or by the ce~sat~on 7 o~ water evolution.
8 While not Icnown with complete certainty, but based 9 on experlmental evi~ence, it is bel~eved that the reaction of the hydrocarbyl-substituted dicarboxylic acid materlal, 11 e . g~, a hydrocarbyl substituted succinic anhydride, with the 12 amlno alcohol o the invention9 e.gO, two equivalents of 29 13 2-disubstituted~2-aminoetharlol ~uch as tris-hydroxymethyl~
14 amlno meth~ne (~AM), give~ oxaæoline, e.g " bie-oxaæolines, via the intermediacy of several discrete reaction species.
16 If an acid anhydride i~ used9 the initial trans~ormation 17 appears to involve the scis~ion of the anhydride by the 18 amino function of one mole of the amino alcohol to yield ~n 19 ~mic acid. Addition of another mole equi~alent of amino al~
cohol is believed to form the ~mic acid amine salt, which 21 then upon fur~her hea~ingj undergo2s cyclo~dehydration to 22 the inal b~s-oxazolin~ prDduct. The catalyst effect of 23 metal salts, such as zinc acetate (Zn~c2~ on ox~$oline 24 forma~ion i~ very likely ascribable to the favor~ble pola~-i~ation of the amide group by the ~nc ion ~owards a~tack 26 bq the hydroxy func~ion of ~he amino alcohol reac~antO ~he~e 27 reactions can be typified ~s follows in the ea~e o~ b~so 28 oxazolineo 3509g~

3 R~+ 2NH2C-CH20U ~ HO\
6 O X ~ X
7 --o,,&OH ~ NH 2CCH20H

X, 2 ~ ~ X
\ ~ A

17 N ~

19 where R is ~he hydrocarbyl group of the succlnic anhydride, and e~ch X in thi~ case of uqing tris-hydrox~methylamino-21 methane (~M) represents a ~CH20H group.
22 In contrast to the above oxazoline ormatlon u~ing 23 the disubstituted amino alcohol, 1 ~he amino alcohol has no 24 substituents as in 2-aminoethanol, or has only one. sub-stituent in the 1- or 2-position as in 2-amino-1-p~op~nol, 26 2-amino-1-butanol, and related monoosubstituted 2-amino~
27 ethanoLs~ the amino alcohol fails ~o undergo the aforesaid 28 oxaæoline reaction. Instead, the~e other amino ~lcohols ~9 will react with the succinic anhydr~de to give almost ex-30 clusively ~uccinimide products as illustrated in ~he follow~
31 ing reactlion.

33 R~ + NHzCHCH20H~~\NCHCH20~l `6 36 R~
~ o + NH2CH~CH~H~NCH~CHOH

~ ~0 ~

~051999~
1 wherein R and X are as previously defined. In experiments 2 on the above reac~ons, in no instance were dis~ernible a-3 mounts of bi~-oxazoline product~ foundD
4 Th~ oil-solu~le oxazoline reaction products o~
S this ~nvention can be incorporated in a wide variety of 6 oleaginou3 compositions. They can be used in lubricating 7 oil compo~itions 5, such as automot~ve crankcase lubricating 8 oil8; automatic tran~mission fluids, etc. in conce~trat~on~
9 generally within the range of abou~ 0.01 to 20 wei~ht per~
cent, e,g.g 0~1 ~o 10 we~ght percent, preferably 0.3 to 11 3.0 weight percent, of the total composition. The lubri-12 cants to which the oxazollne products can be added include 13 no~ only hydrocarbon oil~ der~ved from petroleum, but also 14 include synthetic lubricating oils ~uch as polyethylene oil8; alkyl ester~ of dlcarboxylic acid; complex es~ers o~
16 dicarboxylic acld7 polyglycol and alcohol; alkyl esters o:E
17 carbonic or pho~phoric ac~ds; polysilicones; fluorchydro-18 earbon oil~, m~x~ures of mineral lubricating oil and ~yn-19 thetic oils in any proportion, etc.
When the products of th~s inventlon are used as 21 detergents or dlsper~ants ~n fuels such as ga~oline, kero-22 sene, diesel fuel~, No, 2 fuel oll and other middle dis~
23 ~illateg, a concentration of the additive in the fuel in 24 the range of 0.001 to 0.5 weight percent, based on the weight of the total composition, will usually be employed.
26 When u~ed a~ an anti~oulant in oil stream~ in re-27 finery operations ~o prevent fouling of process equipment 28 ~uch a~ heat exchangers, ~bout 0,001 to 2 wt. % will ge~-29 er~lly be used, The addit~ve may be convenien~ly dispen$ed as a ~ ~ 9 9 ~

1 concentrate comprising ~ mlnor proportion of the addltiveg 2 e.g., 2 to 45 parts by weight, dissolved in a major pro-3 portion of a mlneral lubricating oil, e.g., 98 ~o 55 par~s 4 by weight, with or without other addit:Lve~ being present.
In the above compositions or concentrates, other 6 conventional additives m~y al50 be pre~ent, including dyes, 7 pour point depressants, antiwear agents such as tricresyl 8 phosphate or ~inc dialkyl dithiophosphates of 3 ~o 8 carbon 9 atoms in each alkyl group, antioxidants, such as N-phenyl alpha-naphthylamine, tert-octylphenol sulfide, 4,4'~methyl-11 ene bis(2,6-dl~tert-butylphenol~, viscosity lndex improvers 12 such as ethylene-propy~ene copolymers, polymethacrylates, 13 polylsobutylene, alkyl ~umarate-vinyl acetate copolymers 14 and the like, as well as other ashless dispersan~s, deter-gen~s and viscoslty index improver3, etc.
16 ~
17 A bis oxazoline of polyisobutenyl~ucclnlc anhy-L8 dride and ~ hydroxymethylaminomethane was prepared 19 ~ollows:
280 gms. (0.5 equi~fllent) of polyisobutenylsuccinic 21 anhydride (PIBSA) was charged into a laboratory glass 1 22 liter reaction 1ask, e~uipped with a bottom draw~of, a 23 thermometer, a charging ~unnel, a nitrogen bleed, and an 24 overhead condenser equipped with a Deane Starlcè water trnp.
-25 The flask was heated in an oil bath. The anhydride was 26 then heated to about 200~C. under a blanket o nitrogen.
27 While ~tirring at this temperature, 0 5 mole (60.5 g.3 of ~8 tris-hydroxymethylaminomethane (THAM) was added in a series 29 o portion~ o~ about 5 grams each, over an hour perlod with 3~ rlng~ Thereafter, the reaction was continued with ~2 .

.. :. ., ~ .. . . . . . .

~ ~ 50 9 1 stirring at 200C. for 2 hours while collectlng water from 2 the condenser. The flask was then allowed to cool and a 3 liter of hexane was added to the flask to dissolve the re-4 action product, which was then dralned from the flask and filtered through filter paper to remove any solids, The 6 hexane solution was then washed three times with 250 ml.
7 portions of methanol. Thereafter the hexane layer was 8 placed in a rotoevaporator at 90C. for about 2 hours to 9 e~aporate o~f the hexaneO Then an equal weight of a neutral mineral lubricating oll havlng a viscosity of abou~ 150 11 SUS at 100F. (Solvent 150 Neutral) was added with stirring 12 to give ~n oil concentrnte consisting o~ about 50 wt. % of 13 ~he oxa~oline reaction product in about 50 wt, % mineral 14 lubricating oll. The lnErared spectrum of this concentrate product ~eatured a strong absorption band at abou~ 6.0 16 microns ~s expected ~or the bis-oxazoline. The product .
17 (50% active ingredient in Solvent 150 Neutral Oil) analyzed 18 for 0,78 wt. % nitrogen and 2.30 wt. % oxygen. The ob-19 served oxygen to nitrogen (0/~) ra~io o~ 2.95 is in excel-lent agreemen~ with the theoretical O/N ratlo of 3. The 21 product showed a to~Ql asid number (A~'~M D664) o~ 0~03.
22 The polyisobu~enylsuccinic anhydride used ~bove 23 had been prepared by conventlonal techniques, namel~ the 24 reac~ion o~ chlorinated polyl~obutylene having a chlorine content oE about 3.8 wt. ~/0, based on the weight of chlorina~
26 ted polyisobutylene, and an average o~ 70 carbon a~oms in 27 the polyisobutylene group, wlth maleic anhydride at about 28 200C. The resulting polyisob-l~enylsuccinic anhydride 29 ~h~e~ ~ saponification number (Sap. No.~ o~ 80 mg KOH/gm.

- l3 ~

319~

2 A mixture of 500 gm. (0.78 equivalent) o polyiso~
3 butenylsuccinic anhydride, wherein the polyisobu~enyl group 4 ~veraged about 70 carbon atoms~ having a Sap. No. o 87, 500 ml. of tetrahydrofuran (m F~ as solven~, 4 gm. o~ zinc 6 acetate dihydrate (ZnAc2~2H20) as a catalyst Qnd 96.8 gm.
7 ~0.8 mole~ o tris-hydroxymethylaminomethane (THAM) was 8 charged into the pre~iously de~cribed glas~ reactor and 9 heated. When the reaction temperature h~d risen to 72C., the THF solvent distilled off. Further heating at about 11 200C. ~or four hour~ gave the expected quan~ity of water, ..
12 i.e., about 1.1 moles of water in the trap. After filtra-13 tion, the reaction product analyzed ~or 1.99 wt. % nitrogen, 14 and 0,12 wt. ~/0 zinc~ The product was drawn from the flask . and diluted with ~n equal weight o the So~vent lS0 Neutral 16 mineral lubricating oil for tes~ng in th2 Sludge Inhibition 17 Bench (SIB) test ~o be ~a~er described.

lg A mixture o~ 500 gm. (0.78 equ-Lvalent) o~ the polyisobutenylsuccinic anhydride of Example 2, 96.8 gm.
21 (0~8 mole~) of tris-hydroxymethylaminomethane and 4.0 gms.
2~ o~ zinc acetate dihydrate were charged into the glass reactor 23 previously descr~bedJ The mixture was heated in the oil 24 bath at about 200w220C. or about three hours, until water 2S ceased to evol~e from the reactorO Approxim~ely 18.0 gm~
26 (1 mole) of water collected in the trap. The lnfrared 27 spectrum of the re~c~ion product drawn rom ~he flask showed 28 a strong absorption band at 6.0 microns showing the oxaæo~
~9 lina struc~ure had formed. Elemental analysis showed that 30 the final product o~ 50 wto % o:~ the reac~ion product dis-.. . . .. . . . . . . . ..

1~ 5~ 9 ~ ~
1 solved ln 50 wt % Solvent 150 Neutral Oil, contain~d 1.08%
2 nitrogen and 0.058% zinc.

4 A mixture of 60.57 pounds (27 5 moles~ of polyiso-butenylsuccinic anhydride o~ Example 2J 11. 73 pounds (27 5 6 moles) of ~HAM, and 0.48 pounds (1 mole) of zlnc acetate 7 dihydrate as catalyst, were charged into a small pllot 8 plant stlrred reactor equipped wi~h a nltrogen purgle, stir-9 rer, and overhead condenser wlth a water trap. The reaction mlxture was heated to 220C. at a rate of 50C. per hour 11 and held on temperature until 3.35 pounds (ca. 84.49 moles) 12 o~ wa~er o~ reaction was produced. Thereafter, the reac-13 tion contents were cooled and d~.lu~ed with the a~oresaid 14 Solvent 150 Neutral oll to give a 50 wt. % soLutlon of ~he reaction product ln 50 wt. % oil. l~is oil concen~rate 16 showed a Hydroxyl Number o~ 37.0 and contalned 0.92 wt. %
17 ni~rogen and 0.05 wt. % zinc, based on the weight o~ the 18 concentrate.
19 ~XA ~5_ 5~æ
U~i.ng the same general procedure as descrlbed ln 21 Example 3, various polyisobutenyl~uccinic anhydrides (PIBSA) 22 of polylsobutylene havlng number average molecular weights 2~ of 930 and 18,000 were reacted with 2 mole equivalents 24 of va~lous amlno alcohol~ to form bi~-oxazolinès; including 2-amlno-2~methyl~1-propanol ~AMP), 2~amino~2-methyl-1,3 26 propane-d~ol ~AMPD) and 2-amlno-2-hydroxymethyl-1,3~pro~
27 panediol (THAM~, 28 The reactants7 proportion~, and ~nalyse3 of ~he 29 products formed in Examples 1 tv 23 are summarlzed in Table ~0 ~, , ~s~

¦ ~ o o o ~ ~I r~

pj ¦ C ~ ¦ 3 5Z ~ ~ ~ ~ N
¢ ,_~
~ O ~
t"~ `
ol ~ ¦ o NO t ~ C O ~t ~I` o O O O ':S

C~l t`~
~ ~ t~
u~ u~ o c~l o o~ oo u~ u~ ~ ,~ ~ .
~3 o to ~D ~i O ~ o o o p ¢

~O~ ' .~ _ O ~ ¦ S ¦ O O O O O OO O O O O O O O ~ ~

~1: æ ~ ::
~:4 1~ O 00 $ co C`J ~ o C`3 C~l N ~1 ~1 o o o o o o~ o 00 Co ~Co O
~,t ~ ~ ~ U~ O ~ C~t ~'t G

.. . . ... ... . . ~ ..

~s~9:~
o ~ol ~ ~
--~ ~ ~ o ~ ~ o~
o~ ~;~o~l ~ I ~ I 1 8 ~ ~ ~

n æ l '' ~`I ~ '' ~ '~ vc 1 ~
~ ~ ~ . o ~ o X
~ o ~ ~ ~
.~!9~ o~ ~~ P~ ~o ~o ~

c~ 1 ~ ~ o ~ ~ æ
H ~ 3 ~ o o ~3 O ~ ~
¢ ~ D
~ . ~

h ~ o ~I ~ o C~ o U
P
O ~ ~, ~ ~ C~

~ O c~ ~ DI ~

~ O O O ;d 11 ~I 11 1:4~ O O O O O $ $
~1 3 oo ` 00 0~ `
~ æ a~ ~
~!~ ~
..

~ 17 ~

y, ~L~S~9~
1 A number of the additives of this invention were 2 subjected to a Sludge Inhibition Bench ~SIB) Test which has 3 been found, after a large number of evaluations, to be an 4 excellent test for assessing the dispersing power of lub-ric~ting oil dispersant additives.
6 The medium chosen for the Sludge Inhibition Bench 7 Test was a used crankcase mineral lubricating oil composi-8 tion having an original viscosity of about 325 SUS at 100F.
9 that had been used in a taxicab that was driven generally for short trlps only, thereby causing a buildup of a high 11 concentration of sludge precu~sors. The oil that was used 12 contained only a refined base mineral lubricating oil, a 13 viscosity index improver, a pour point depressant and zinc 14 dialkyldithiophosphate antiwear additLve. The oil contained no sludge dispersan~. A quantity of such used oil was ac-16 quired by draining and refilling the taxicab crankcase at 17 100002000 mile interv~ls, 18 The Sludge Inhibition Bench Test is conducted in 19 the following manner. The aforesaid used crankcase oil, which is milky brown in color, i5 ~reed of sludge by cen-21 trifuging ~or 1 hour at ~bout 39,000 gravities ~gs.). The 22 resul~ing clear bright red supernatant oil is then decanted 23 from the insoluble sludge particles thereby separated out.
24 However, the supernatant oil still contains oi.l~soluble sludge precursors which on heating under the condltions em-26 ploy~d by this test will tend to form additional oil~in~
27 soluble deposits of sludge. The sludge inhibi~ing proper~
28 ties of the additives belng te~ted are determined by adding 2~ to porEions of the supernatan~ used oil, a small amount, such ~s 0,3 9 OJ 5 9 1 or 2 weigh~ psrcent, on an active in~

~ 18 S~9~
1 gredien~ basis, of ~he par~icular additive being tested.
2 Ten grams of each blend being tested is placed in a stain-3 less steel centri~uge tube and is heated at ~80F. for 16 4 hours in the presence of air. Following the heating, the tube containing the oil being tested is cooled and then 6 centrifuged for 30 minutes at about 39,000 gs. Any de-7 posits of new sludge that form in this step are separated 8 from the oil by decanting the supernatant oil and then 9 carefully washing the sludge deposits with 25 ml. of pentane to remove all rem~ining oil ~rom the sludge. Then the 11 weight of ~he new solid sludge that has been formed in the 12 test, in milligrams, is ~etermined by drying the residue 13 and weighlng it. The results are reported as milligrams of 14 sludge per 1~ grams of oil, thus measuring dif~erences as small as 1 part per 10,000. The less new sludge ormed 16 the more effective i9 the addltive as a sludge dispersant.
17 In other words, if the additive is effectlve~ it will hold ~i lB at least a portion of the new sludge that ~orms on heating 19 and oxidation, stably suspended ln the oil so it does not precipitate down during the centriuging 21 Using the above described test, the disper~ant ac-22 tion of oxazoline additives of the presen~ invention was com-23 pared with the dispersing power of a commerclal dispersant 24 referred to as PIBSA/TEPA. The PIBSA/TEPA was prepared by-reaction of l mole of tetraethylene pen~amine wlth 2.8 moles 26 o~ polyisobutenylsuccinic anhydride obtained frotn polyiso 27 butylene of about 1000 number average molecular weigllt The 28 PIBSA/TEPA dispersant w~s used in the form of an additi~e 29 concentrate containing about 50 weight percent PIBSA/TEPA
ln 50 wt. % min2ral lubricating oil. This PIBSAtTEPA ad~

, .. .. .,,, . , .. ' : :

~5~D9 ~ 1 -1 ditive concentrate analyzed about 1.14% nitrogen, indicating 2 tha~ ~he active ingredient, i.e~, PIBSA/TEPA per se, con-3 ~ained abou~ 2.28% nitrogen. Suffic~ent quantities of all 4 the additive concentrates tested below were used in making the test blends to furnish the 1.0 3 0.5, and 0.3 weight 6 percent of actual addit~ve. The test results are g~ven in 7 T~ble II.
8 laBL~ II
9 ~ ' .

Example 12 10 1.6 6.6 -13 lS 3.5 14 ~4 3.8 - ~
12 ~.9 5.9 7.3 16 11 2.7 6.1 7.3 17 21 2.6 5,9 18 22 2.8 6.3 19 23 2.0 PIBSA~TEPA 5.2 7,5 7.7 21 It will be noted from Table II that ~he dispersants 22 of the inven~ion were more effective than the commercial 23 PIBSA/TEPA dispersant which is ~n widespread use ~n crank-24 cese lubricating formulation~. Speeifically 1.0 wt. % of PIBSA!TEPA per se (i.e., 2 wt. % of its 50 wt.~% concentrate~ :
26 ga~e 5.2 mg. of new sludge precipitated, per 10 gms. of crank~
27 case oil~ On ~he other hand~ the bis-oxa201ine products of .
28 ~he invention shown in Table II, were more effective as 29 slud~e dispersants ~ince they stably suspended a larger pro~
por~ion of the new sludge ~s shown by the f~et tha~ less ,,, :

l~SQ~
1 sludge precipitated down during the centrifugation. Simi~
2 lar result~ are shown at the 0.5 wt, %, and 0,3 wt~ % ac-3 tive ingredient levels.
4 LubricaDt A ~ This was a SAE Grade 30 crankcase lubricant formulation for automotive crankcase applicatlon 6 that was used as a reerence. The reference formulation con-7 tained mineral lubricating oil, 4068 wt. % o the PIBSA/
TEPA ashless dispersant concentrate, and a series of conven~
9 tional additive~, nam~ly, a P2S5~treated alpha-pinene as an oxid~tion and corrosion inhibitor, a zinc dialkyl dithiophos-11 phate, and as detergent inh~bitor additives, barium sulfon~
12 ate and an overba~ed barium detergent conprising barium car-13 bonate formed in the presence of P2S5~treated polyisobu~ylene 14 and alkyl phenol as surfac~nts;along wlth an an~i~rust additl~s.
16 _u Lanc~ B ~ E W These lubricants were identi-17 cal wlth Lubric~nt A described above, except that the 4068 18 wt. % of the 50 wto % concentrate of the PIBSA~TEPA ashless 19 disper~ant was omitted, and the inventive oxazoline disper~
sant of ExampLe 4 was used in varying amounts as follows~
21 Lubricant B - 4.68 wt.~k; Lubricant C ~ 3076 wt. %, Lubri~
22 cant D 3.25 wt. % and Lubricant E 0 20 75 wt~ % of the 50 23 wt. % concentrate of oxazoline of E~ample 40 24 Lubricants A to E described above were tested in a MS Se~uence VC Engine Test, which is well known in the auto~
26 motive lndustry9 be~ng described ln the public~tion entitled 27 "Multicylinder Test Sequence~ for Evaluatlng Automotive Eno 28 gine Oils" w~ich is ASTM SpeciaL Publication 315-Eo At the 29 end of each test 9 various parts of the engine are rated on ~ merit basis of 0 to 109 wherein 10 repre~ent~ a perfectly ~ 21 ~

S~9~
1 clean part whlle the lesser numbers represent increasing de-2 grees of deposit form~tion. The various ratings are then 3 totaled and averaged on a b~sis of 10 as a perect rating, 4 The results obtained with the compositions described above are glven in Table III, 6TABLE I[I
7 M ~ LTS
_~, 8Merit Ratings (Basis 0 to 10 9Lubricant B --~F-----D-~ E
11 Sludge Merit 9~2/9,2 9.5 9,2 9,0 8,~
12 Varnish ~erit 8~2/7,7 8.8 8,2 804 8,0 13 Pi~ton Skirt Var-14 nish Merit 8.4/7.9 8.8 8.7 8,4 8,6 PIBSA-TEP~ (50% a.i.
16 i.e., acti~e in-L7 gredient) 4.68%
18 Example 4 (50% a,i, i e., active in- 4,68% 3.76% 3,25% 2.75%
21 A~ seen by Table III, two engine runs were made on 22 the PIBSA~TEPA containing formulation. H~wever, taking the 23 better of the two runs on Lubricant A, it is seen that the 24 bis-oxazoline di~persant of Example 4 wa~ superior at the 4,68 and the 3,76 wt, % concentration~, indirating the higher 26 e~ectiveness of ~he o~azoline, Considering varnlsh, the 27 ox~zol-lne was as effecti~e afi the P~BSA~TEP~ even a~ the 28 3.25 wt, % level, and almost as effective a~ the 2.75 wt, %
29 level ($.e,, 1.38 wt, V/o actual ingredlent)~ Th~s, in an 30 importan~ ~ndustry test, the ox~oline dispersants were very 31 effective. l~ese engine test results show that the oxazoline 32 additi~e of this invention, was no~ only a good ~ludge dis-33 persant a~ shown by Sludge Merit, but also possesses good 34 oxidation control~ as shown by the reduction in varnish ~ ~ .

5~
1 deposits ~Varnish Merit~ on ~he various engine par~, and 2 par~icularly on the piston ~kirts ~Piston Skirt Varnish 3 Merit). Thi~ favorable ~ntioxidant property of the oxazo~
4 line dispersant additive dimini~hes the need or addi~ional conventional antioxidants.
6Lubric~nts A and B were tested in the Caterpillar 7 l~H test (MILoL-2104B~. Follow~ng in Table IV are the re-8 su1ts of two such engine test~ on each Lubricant9 showing 9 the p~ston cleanliness.
10 ~ABLE IV
11CATERPILLAR 1 H TEST ~ 480 HOURS
12 Lubricant 13 A _ 1~ Requirements(l?
14 TGF (%) 13128 18/4 30 max.
~nd groove 24/3 0/10 30 snax.
16 1st Land 16/16 7¦3 60 max.
17 Below 0/0 6/0 0 18 R~ting Pass/P~s B~Pas~/Pass 19 ~ e estim~tes, actually certi~ication of a piston is done by inspection and some varia-21 tion~ from the limit shown are allowed based on the 22 total condition of the pi~ton.
23 As ~een by Table IV, Lubricant B eontaining the 24 oxazoline dispers~nt gave exceptlonally low deposits as in-25 dicated by the % top groove :Eill (rJLIG~)9 the amount o~ deo ~6 posit in the second ring groove~ and the depo~ts on the 27 first land area, although one of the two runs waq a border~
28 liae p~s (B~L pa~ due to deposlts below the second groove 29 (Below3. Thi~, however9 can be ~vercome by changes in the ormulation~

32 Part A ~ 350 gms. tO,328 moles~ of polyisobutenyl-.

: ~ 23 -, . . . . ~ .

5~99~l succinic anhydride having an ASTM s~ponification number of 2 about 105 and a molecular weight o about 1067 w~s reacted 3 with 79.4 gms. (0.656 moles) of 2~amino 2-hydroxymethyl~l, 4 3~propanediol (THAM) a8 follows- the polyisobutenylsuccinic S anhydride and THAM were dissolved in ~50 ml. xylene in a 6 2 liter 4-neck flask equipped with the!rmometer, stirrer, dropping fur~nel, a condenser includin~, a Deane-Starke 8 water trap, and having a nitrogen bleed ~o provide a nltro-9 gen blanket. The heat wa~ raised to about 145 to 152C. and 10 over a period of one hour and 45 minutes~ about 9 cc water 11 collected ~n the trap. The heat wa~ ~hen turned off over-12 night and the following day ~he reaction mix~ure was re-13 fluxed another hour at 1S3C. whereupon 10 cc o~ water had 14 now collec~ed ln the tr~p. The reac~ion mixtur~e was then sparged with nitrogen ~o evaporate the xylene during which 16 time ~he temperature rose to 193C. Then the sy~tem was 17 connected to a racuum pump and heated to about 182~193C.
18 for 3 hours under a pre~ure of about 20-30 mm. Hg~ The 19 heat was then turned off ovPrnight. The following day the mi~ture, which was not free of xylene, was warmed to 93C.
~1 and 489 cc ~419 gm.) xylene was ~dded to make ~ concentrate 22 containing 50 wt. % of the bi~oxa~oline reaction prod~ct 23 dlssolved in the xylene to give a concentrate having a 24 nitrogen content of 1~23 wt. % against a calculated nitro-gen content of 1.1 wt. %.
26 Part B ~ A ~ample of the concentrate product of 27 Part A above was added to a g~soline in an amount equivalent 28 to 25 lbs. of the concentrate (S0% a.i.~ per 1000 barrels o 29 gasoline. Thl9 addi~ive ~re~ed gasoline was th~n tested for its effe¢t~venes~ in a carburetor detcrgen~ ~e$t de~-. . .

. .

~ 24 -.

.. . .. . . ..

cribed as follows:
2 The test gasoline was a MS~08 gai~oline which con 3 tained about 0. 8 wt. % sulfur and which acceler~ted the for-4 r~tion of earburetor depositisi. The ~est was carrled out by opera~lng a specially fitted 280 cublc inch dlsplacement V
6 teisit engine fitted wi~h ~wo iseparate carburetors le~ding to 7 opposite mani:Eolds on either side of the engine. The com-8 bustion products from the engine which leaked around the 9 pi~ton rings were cycled back to the in~ake of the carbure-10 tor~. In each carburetor was a metal sleeve wh~ch could 11 be readily removed ~nd weighed to determine the amount of 12 depoisitis that had accumulated on the sleeve The engine was 13 operated for 24 hours under no load through a te~t cycle of 14 8 minute idle at 700 rpm, and then 30 seconds at 2500 rpm, ~ollowed by repeating the cycle. During the ir~t 12 hours 16 o~ ~he teist, the. one curburetor (hereinafter called the 17 irst carburetor~ was operated on the untrea~ed gasoline, 18 while the other carburetor (hereinafter called the isiecond 19 carburetor) wai3 opera~ed on the g~sol~ne cont~ining the ad~
ditive. At the end of thls 12 hour perlod, the ~leeves were 21 removed, weighed, cleaned and then replaced. During the 22 next twel.ve hours o oper~tion the feed to the two carburet 23 orsiwas reversed so that the ~irs~ carburetor now operated 24 on the additive treated gasoline, while the second carburet-or operated on the non-~dditive gasoline. ~he 31eeves were 26 again removed and weighed. The % c~rbure~or cleanup due ~o 27 the addltive was ealculated as foll~w~o the ch~nge ~n 28 weight of the two sleeves during ~helr run w~th ~he un~
29 treated gasoline were added ~ogether ~f~rst ~o~al~ and rom this value was subtracted the sum of ~he change in weight of ,. , . , : :

~5~99~
.~
1 thc two sleeves during their cleanup period while oper-2 ating on the additive treated gasoline (~econd total). The 3 % carburetor cleanup ~s then calculated as follows:
~/0 cle~nupm ~ x 100 6 In this ca~e, ~he carbuetor cleanup was 55% in-7 dicating that the addltive wa~ very efecti~e ~ a carburet-8 or detergent when added to gasoline~
9 Part C - A SIB Test was carried out on the product o~ Part A, above, ko determin~ its efectiveness as a sludge 11 dispersant in lubricating oil. A set of two blanks, ~e., 12 the SIB oil without additi~e, was run fir~t~ The bLanks 13 gave 17.1 and 2.7 mg, sludge per 10 grams of oil re~pect- -14 ively. A second set of blanks gave 16,3 and 16~6 mg. sludge per 10 grams o~ oi:L, thus clearly indicating that ~he afore-16 said 2.7 reading wa~ ~n error, and could be dlsregarded, 17 Blends ~n the SIB Te~t oil o 0025 wt. %~ 0.50 wt. % and lB 0~75 wt. ~/0 of the concentrate (50% oxs~ollne) of Part A9 l9 gave sludge readings of 9.6, 0.3, and 0,1 mg, $1udge/10 gm.
o~ oil, respectively. Since the oil without additive gave 21 readings of 16-17, ~he treated oll showed tha~ the oxa~oline 22 concentrate was ef~ective a~ a dispersan~ and extremely ef-23 fective at ~he 0.50 and 0.75 wt. % concentrations.
24 The SIB Te~ts were repeated again at a later ~ime.
Here a se~ of 4 blanks, i.e~, untreated oil, gave r~adings 26 of 16.4, 17.2, 18.1 and 17.8 mg. sludge/10 gmO of oil, re~
27 ~pectively~ Two tests of the SIB oil con~aining 0.25 wt~ %
28 of the concentra~e of Part A gave readlngs of 12.2 and 12Ø
29 Two tests of the SIB oil containing 0,50 w~. % of said con-centrate gave readings o~ 3~1 and 6.1. Te~s at 0.75 wt. %

- ~6 ~

~_J ~ ~ ~ 9 9 ~
1 and 1.0 wt~ % c~ncentrata levels each gave a reading of 0.1.
2 1,5 wt. % concentrate gave a reading of 0.7, and 2.0 wt. ~/O
3 concentrate gave a reading of 0.6. All of sai~ preceding 4 readings are in term~ of mg. sludge per 10 grams of ths test oil. This test data confirm~ the precelling SIB te~t data - 6 on the bls-oxazoline product of Par~ A above showing ~hat 7 it is an extremely effecti~e sludge dispersant, particular-8 ly at about the 0.75 wt. % concentration level, i.e, about 9 0.375 wt. % active ingredient.

ll 32 gm. (0~03 moles) o~ polyisobutenylsucc:Lnie an-12 hydride having a molecular weight of ~bout 1067 was reacted 13 .with 7.2 gms. ~0.06 moles~ of 2~amino~2~hydroxymethyl~1,3 14 propanediol by combining the reactants together in 100 ml.
3-neck 8tirred flask along with 25 ml. xylene. The temper-16 ature W~8 raised to 93C. for 1 hour, then the heat was 17 turned off and the mixture wa.s allowed to stir over a week-18 end~ Following thi8 the mixture was again heated to 93C.
19 with 3 hours of stirring, The temperature was then rai~ed to 191C. and the content~ were blown with nitrogen to re~
21 move the xylene. After comple~ion of the xylene rem~all ~he 22 ~ixture wa~ t~en vacuum ~tripped at 2 mmO ~g~ pressllre at 23 191C, ~or 3 hour~ to remove water that had Eormed. The 24 reaction mixture was allowed ~o cool overnight while the vacuum wa~ maintained. The ~ollowing day the produc~ wa~ re-26 mo~ed from the flask. The product analyzed 2D22 Wto % n~ro~
27 gen ~s against a c~lculated value o abou~ 2~20 Wto % n~ro~
2~ gen for the bis~oxazoline~
29 The product of Example 25 wa~ tested for its ef~
fectiveness as a gasoline anti~rust agent. Since ~h~ ox~

~ 27 ~ :

1 ~ 5~ 9 1 zoline product was not directly soluble in gasoline, it wa~
2 first dissolved in xylene, and sufficient xylene solution 3 was then added to the gasoline to incorporate the additlve 4 at a tre~t rate of 10 pounds of oxazol:ine additive per thou-~and barrels of gasoline, i.e., about 0.024 wt. %. The 6 gasoline so trea~ed was then tested for rust according to 7 ASTM D~665M rus~ test. In brief, this test is carried out 8 by observing the amount of rust that forms on a s~eel 9 spindle after ro~ating for an hour in a water-g~soline mix-ture. In this case, the oxazoline treated gasoline gave 11 no ru~t ~ndicating that i~ was very effective as an anti-12 rus~ additive since the untreated ga~oline will g~ve rust 13 over ~he entlre surface of the spindle.
14 Several mono-o~azolitle di~per~ants were prepared as follows:
16 EXA~PL~ 26 17 Approximately 0.2 mole of polyisobutenylsuccinic 18 anhydrlde (Sap. ~o. 803 was charged into a reactor and 19 heated to 205C. u~der a nitrogen blanket. To ~he st~rred reactant were added 0.2 mole (24.2 g.) of tris~hydroxy~
~1 methylaminometh~ne, in portion~, over ~n hour periodO
22 Therea~er, the mixture was sti.rred at 205~C. for ~bout 3 23 hours while water dis~illed from the reactor. Upon cDoling, ~4 hal~ of the reac~ion mixture was di~solved in an equ~l weight percent cf Solvent 150 Neutral o~l. Thè resulting 26 oil solution was then dilu~ed with 500 ml. of hexane-and 27 the resulting hexana solution was washed three t~mesj each 28 with a 250 ml, portion of me~hanol. Rotoevapor~tion of the 29 hexane Layer aforded a concent~a~e w~ich ~naly~e~d for 0~50 wti % ni~rogen and 2.37 wt. % oxygen, and fe~ture~d a T~N

- 28 ~

~_J ~ S~ 9 9 ~
1 (total acid number) of 0.16. The experimentally ~ound 0/N
2 ratlo of 4.7 was in excellent agreement with the theoreti-3 cal 0/N ratio of 4t 6. Furthermore, a strong absorption 4 band ~t 6.0 microns in infrared spectrum of the product indicated a mono-oxazoline s~ructure formedO Another 6 ~trsng absorption band at 5375 mieron indica~ed an ester 7 structure had al80 formed; which is believed to be between 8 one of the hydroxy groups extending from the oxazoline ring 9 with a carboxy group of the polyisobutenyl~uccin~c anhy-dride.

__ 12 1335 grams o polyisQbutenyl~uccinic anhydride13 havlng a Sap. No. o about 80 wa~ charged into a 1 l~ter 4-14 neck~d flask, and heated to 205~. The reactant was stir-red under a nitrogen sparge and blanket and 121 grams of 16 tri~-hydroxymethylaminomethane were added o~er a 1 hour 17 period, being ca~eul to avoid foaming. The course o re~18 action was monitored by infrared spectro~c~py, which ~n-19 dicated that the reaction was essentially complete after eight hoursr The neat product analyæed or 1.12 wt. % ni~
21 troge~ and featured a number average molecular weight of 22 3034 (by vapor pre~ure osmometry)O The inra~ed ~pectrum 23 o~ the product showed the expected ester and oxa~oline bands 24 at 5.75 and 6.02 microns, re~pecti~ely.
EX~MPIE 28 __ 26 53.4 pounds of polyisobutenylsuccinic anhydride27 (PIBSA~ w~th a S~p. Not of about 80 w~ charged in~o a re-28 aetor and heated ~o 435Fo The P~BSA reactant was stirred29 and ~parged wi~h ni~rogen, and 4.84 pound~ of trishydroxy-methylaminomethane were added over an hour period. Reac~

.
. ~ 2~ ~ .

.. ,. , . , . ~ . . . . ... .; - -. -9 ~
1 tion was continued until water evolution had ceased. The 2 product was diluted with an equal weight of Solvent 150 3 Neutral oil and showed ester and oxazoline absorptions in 4 the infrared. The oil solution analyzed or 0.51 wt. %
nitrogen.
6 Also there should be 50 to 1400, preferably about 7 60 to 300 carbon atoms per moiety o~ d:Lcarboxylic acid mate-8 rial. Thus, in the case of very h~gh molecular weight poly-9 mers, they will be generally chlorin~ted to permit adding on a number of dicarboxylic acid groups along the chain.
11 For example, using a polymer with 10,000 carbon atoms, one 12 could chlorinate and ~hen react wlth maleic anhydride so as 13 to distribute about 50 malelc anhydride units randomly along 14 the polymer chain, and then convert ~hese maleic anhydride unit~ lnto mono or bis-oxazoline units, or mixtures of mono-16 and bis-oxazoline units, 17 ~n summary, effective additives for oleaginous 18 compositionfi can be prepared by reaction of a hydrocarbon 19 substituted dicarboxylic acid material wlth a 292~disub~
stituted-2-amino l-alkanol under conditions such that forma-21 tLon of ~imple ester3, imides or amides is eliminated, or 22 a~ leas~ minimizecl, so ~hat a substantlal proportion of the 23 amino~alkanol is converted into oxaæoline rings. Infrared 24 analysi6 of some of the aforesald Examples indicate that a m~or proportion9 and in some cases essentially all9 of the 26 amino~a~kanol was converted to oxa~oline ring~.

~ 30 -.

Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of oxazolines and compositions thereof with metal salts, which comprises reacting a substantially saturated hydrocarbyl-substituted C4 - C10 dicarboxylic acid or anhydride or ester thereof having at least 50 carbon atoms in said hydrocarbyl group with a 2,2-disubstituted-2-amino-1-alkanol having 2 to 3 hydroxy groups and contain-ing a total of 4 to 8 carbon atoms of the formula wherein S is alkyl or hydroxyalkyl, said alkyl groups having 1 to 3 carbon atoms, and at least one of said X is a hydroxyalkyl group of the structure -(CH2)nOH where n is 1 to 3, said reaction being carried out in the presence of a small amount of a metal salt.

2. A process according to claim 1 in which one molar portion of the substantially saturated hydrocarbyl-substituted C4 - C10 dicarboxylic acid or anhydride or ester thereof is reacted with 1 to 2 molar portions of the 2,2-disubstituted-2-amino-1-alkanol.

3. A process according to claim 1 in which one molar portion of the substantially saturated hydrocarbyl-substituted C4 - C10 dicarboxylic acid or anhydride or ester thereof is reacted with 2 molar portions of the 2,2-disubstituted-2-amino-1-alkanol.

4. A process according to claim 1 in which one molar portion of the substantially saturated hydrocarbyl-substituted C4 - C10 dicarboxylic acid or anhydride or ester thereof is reacted with one molar portion of the 2,2-disubstituted-2-amino-1-alkanol.

5. A process according to any of claims 1, 2 and 3, in which the substantially saturated hydrocarbyl-substituted C4 - C10 dicarboxylic an-hydride is an alkenyl succinic anhydride.

6. A process according to any of claims 1, 2 and 3, in which the 2,2-disubstituted-2-amino-1-alkanol is tris-hydroxy methyl amino methane.

7. A process according to any of claims 1, 2 and 3 comprising heating a mixture of the substantially saturated hydrocarbyl-substituted C4 - C10 dicarboxylic acid or anhydride or ester thereof and the 2,2,-di-substituted-2-amino-1-alkanol at a temperature of 140° to 240°C. in the presence of a small amount of a metal salt and removing the water formed.

8. A process for the preparation of oxazolines and compositions thereof with metal salts, which comprises reacting a substantially sat-urated hydrocarbyl-substituted C4 - C10 dicarboxylic acid or anhydride or ester thereof having at least 50 carbon atoms in said hydrocarbyl group with 2,2-disubstituted-2-amino-1-alkanol having 2 to 3 hydroxy groups and containing a total of 4 to 8 carbon atoms of the formula wherein X is alkyl or hydroxyalkyl said alkyl groups having 1 to 3 carbon atoms, and at least one of said X is a hydroxyalkyl group of the structure -(CH2)nOH where n is 1 to 3, said reaction being carried out in the presence of a small amount of a metal salt at a temperature in the range of 180-200°C.
for 1/2 to 24 hours.

9. A process according to claim 8 in which the reaction mixture is heated for 2 to 8 hours.

10. A process according to any of claims 1, 2 and 3 wherein said metal salt is a carboxylic acid salt of zinc, cobalt, manganese or iron.

11. A process according to claims 1, 2 and 3 wherein said metal salt is a zinc salt present in an amount of from 0.01 to 2 weight percent, based on the combined total weight of the reactants.

12. A process according to claim 8 wherein said metal salt is a zinc salt present in an amount of from 0.01 to 2 weight percent, based on the combined total weight of the reactants.

13. An oxazoline composition prepared by reacting a substantially saturated hydrocarbyl-substituted C4 - C10 dicarboxylic acid or anhydride or ester thereof having at least 50 carbon atoms in said hydrocarbyl group with a 2,2-disubstituted-2-amino-1-alkanol having 2 to 3 hydroxy groups and containing a total of 4 to 8 carbon atoms of the formula wherein X is alkyl or hydroxyalkyl, said alkyl groups having 1 to 3 carbon atoms, and at least one of said X is a hydroxyl alkyl group of the structure -(CH2)nOH where n is 1 to 3, said reaction being carried out in the presence of a small amount of a metal salt.

14. The oxazoline composition according to claim 13, characterized in that the oxazoline is primarily a bis-oxazoline.

15. The oxazoline according to claim 13, characterized in that the oxazoline is primarily a mono-oxazoline.

16. An oil composition containing a major amount of a lubricating oil and 0.01 to 20 wt. % based on the total weight, of the oxazoline composition of any of claims 13, 14 and 15.

17. An oil composition containing a major amount of a lubricating oil and 2-45 wt. % of the oxazoline composition of any of claims 13, 14 and 15 to form a concentrate.