CA1105030A - Lactone oxazolines as oleaginous additives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Hydrocarbyl lactone oxazolines respresented by the formula:

Description

The present application is directed to hydrocarbyl lactone oxazolines and their preparation and use whexeas divisional appl.icatlon serial number ~s-G ~3 f.iled ~ J~ly ~ is directed to hydrocarbon or hetero substituted lactone acids, amides and esters used to prepare the oxazolines.
The present invention concerns hydrocarbon-soluble alkyl lactone oxazolines, their method o~ preparation and the use o said lactone oxazolines in hydrocarbon fuel and lubricating compositions as highly stable anti-rust agents and/or sludge dispersan-ts.
U.S. Patent 3,261,782 teaches that alkylbutyro-lactone-alpha-acetic acids are use~ul rust inhibitors in lubricating oil compositions which acids are derived from long-chain dicarboxylic acids.
United Kingdom Specification 809,001 teaches corrc~sion inhibitors compris-ing a multiple salt complex derived from the reackion produc-t of hydrocarbyl-sub-stituted dicarboxylic acids and hydroxy amines (including 2-amino-2-methyl-1,3-propanediol and tris-hydroxymethylam.inomethane (THAM) further complexed with mono-and polycarboxylic acids (see Examples 17-19).
U.S. Patent 3,576,7~3 teaches reacting polyisobutenylsucci.nic anhydride with a polyol, such as pentaerythritol, followed by reaction with T~AM, tsee Example 1). U.S. Patent 3,632,511 teaches reacting polyisobutenylsuccinic anhydride with ~0 ~ both a polyamine and a polyhydric alcohol including THAM. U.S. Patent 3,697,428 (Example 11) teaches:reacting polyisobutenyl succinic anhydride with a mi.xture of pentaerythritol and T~I~M. United Kinydom Specification 98A,409 teaches ashless, amide/imide~ester type lubricant additives prepared by reacting an alkenyl succinic anhydride, said alkenyl ~roup having 30 to 700 carbon atoms, w.ith a hydroxy amine including T~AM.
German Published Application DOS 2S12201 teaches reacting long chain hydroaarbon substituted succin.tc anhy-.

..

. '~' : , ~ .3~

1 dride with 232'-disubstituted~2-amino-l alkanol to produce

2 mono- and bis-oxazoline products ~see also DOS 2534921/2

3 for similar reac~ion produr~s which can also be modiied by

4 reaction with phosphorus, boron or oxygen compounds).
The above dicarbo~ylic acid lactone type products 6 have also been provided with anti-rust and/or dispersan~
7 properties by reaction with hydroxy amines such as ethanol- :
8 a~,ine and diethanolamine (see U.SO 3~248,187 and 3,620,977).
9 As noted above, the prior art teaches oil-soluble additives formed from hydrocarbyl-substituted dicarboxylic ll acid material which has been converted into a lactone and 12 reacted with various amino or hydroxy compounds ei~her l3 t~rough an amide, imide or es~er linkage, and that theæe ad-4 ditives are stated to be useful or var~ou~ func~ion~, such as anti~rust agen~s, detergents or dispersants for oleagin-16 OU5 composi~ions incLuding l.ube oil, gasollne, turbine oils 17 and oils for drilling applications.
18 It has now been dlscovered tha~ long-chain hydro-19 carbon structures which ~eature vicinal lactone and oxazo-line ring systems can be so cons~ructed using novel synthe~ic 21 methods whereby a highly sta~le additive o enhanced dis-22 persancy, enhanced viscosity properties, andlor anti-rus~
23 properties i8 obtained. Moreover, further functionallzation .
24 of this dual he~erocyclic system with vicinal hydroxyl3 thiyl and sulfo- groups can give other desirable properties, 2~ such as anti-oxidation and anti-corrosion activity, This 27 novel class o~ additives can be represented in part by the 28 ~ormula .

:~ .

.

~` H /~ ~ ~2 5f CjHR ~ C~ / 5 6~ \ ~ C~ C~2 1~ .

9 whereln R is selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 400 or more carbons, 1~ X is selected from the group consisting of an aLkyl or hy~
1~ droxy alkyL group and at least one of the`X substituents and 13 preferably both of the X substituents being a hydroxy alkyl ~4 group o the structure -~C~2)nOH where n is 1 to 3 and Y ls selected from the group consisting of hydrogen, hydroxyl, 16 sulfoa alkylthio (TS-), alkyldithio ~TSS-~, and a sulfur 17 bridge, e~g., -S- and -S-S-, jolning ~wo lactone oxazoline 18 unl~.s toget~e~ as depicted below wher~ln z ls a number rang-~9 ing ~rom 1 to 4 and T is defined hereafter as contalning l to 50, preferably 2 to 20 carbons.
~1 O
I ~.
22 : -23 :~ \
24~, ~ CHR \ ~N \ / x 26CHR ~ ~`x Z7 / ~ ~ ~Hz 28 ~
~H~ H2~X
3~ qHR ~
33 ~f Preerred~herein is polylsobutyl Lactone oxazoline of num-6 ber average molecular weight~ranging ~rom about 400 to 37 100,000 prepared by the reaction of equlmolar proportions 38 of polyis~batyl lactone carboxylic acid wl~h tris-[hydroxy-: . .

, 3 ~

methyl] aminomethane at a temperature from about 100-240C, 2 preferably 150~180Co until two moles of H2O per mole of 3 reactant is removed from the reaction~
4 These hydrocarbon-soluble compounds have at least 8 carbons in the substantially saturated aliphatic hydro~
6 carbyl group and a carboxylic acid group of th~ dicarboxylic 7 acid material co~verted into a lactone ring and another 8 carboxylic acid group converted.intQ an oxazoline ring as a 9 result of the reaction o at le~t equimolar amounts of sald hydrocarbon substituted dicarboxylic acid lactone material 11 and a 2~2-disubstituted-2-amino-~ kanol having 1 to 3 12 hydroxy groups and containlng a total o 4 to 8 carbons.
13 These novel alkyl lactone oxazolines of the pres-14 ent invention can be prepared by heating together alkyl lactone aclds, esters or amides with a 2,2-disubstituted-2-16 amino~l-aLcohol, such as tris-(hydroxymethyl) aminome~hane, 17 as expressed in ~he fol~owi~g equation.
18 ~H2OH-19 R\ /Y NH2C-- CH2OH \ /
21 ~ &U o ~H2~H ~ ~ CH ~ \2/ CH2OH
23 C ~HR C- Q ~ G~ ~HR ,C~ C~
24 / \ ~ N / ~ CH2OH
2S O\ ~ H-~H2 ~H-CH2.
~6 C
~, U

28 where Q - OH, OR or NHR.
29 The prepara~io~ o~ the requisi~e reactan~s in-~olve~ a lactoniza~ion of an alkenyl succinic acid analog 31 obtained via the Ene reaction of an olefin wlth an alpha-32 beta unsaturated C4 to Clo dicarbox~lic acid, or anhydrides 33 or es~ers thereof~ such as ~maric aeid, itaconic acid, 34 maleic acid, maleic anhydride~ dimethyl fumarate, etc. The dicarbo~yl~c ~cid;material can b~ illustra~ed by an alkenyl-~: .
: - 5 ~

. ~ - .

1 substituted anhydride which may contain a single alkenyl 2 radical or ~ mixture of alkenyl radicals variously bonded to 3 the cyclic succinic anhydride group, and is understood ~o 4 comprise such ~tructures as:
R R
6 R \ ~ CH2 R \ /~ H

HzC ~ ~ H~C~ C~

1~ 0 0 15 wherein R may be hydrogen or hydrocarbyl or substituted 16 hydrocarbyl each having from 1 to about 400 and more car-17 bons, and preferably from 1 to about 200 carbon atoms. The 18 anhydride~ can be obtained by well~known methods, such as the 19 reaction be~ween an olefin and maleic anhydride or halosuc-cinic anhydride or succinic es~er ~U S. Pat.No.23568,876).
~ In branched ole~lns, par~icularly branched polyolefins, R
22 may be hydrogen~ methyl or a long-chain hydrocarbyl group.
23 ~ultable olefins include bu~ene, ~sobutene~ pen-24 tene, decene, ~odecene, tetr~decene3 hexadecene; octadecene, ~icosene, and polymers of propylene, butene, isobu~ene, pen-26 tene, decene and the like~and halogen-containing olefins.
27 The olefins may also contain cycloalkyl and aromatic groups.
28 The most preferred alkenyl succinic anhydrides are those in 29 which the alkenyl group contains a total of from 4 to 400 30 carbon at~ms; rom ~ to ~bout 20 carbon atoms for aqueous 31 systems; and at leas~ 8 to 400 and more preferably 10 to300 32 for hydrocarbon systems.
33 Prefesred olefin polymers fos seaction with the .

unsaturated dicar.boxylic ac:ids are polymers comprising a 2 major molar amount o:E C~ to Cs monoolefin, e .g. 9 ethylene, 3 propylene, butylene 9 isobutylene and pentene . The polymers 4 can be homopolymers, such as polyisobutylene, as well as copolymers of two or more of such oleins such as copolymers 6 of ethylene and propylene~ butylene and lsobutylene or of 7 propylene and isobutylensO Other copolymers include those 8 in which a minor molar amount of the copolymer monomers, 9 e.g., 1 to 20 mole % is a C4 to Clg non-conjugated diolefin, e.g. 3 a copolymer of isobutylene and butadien~ or a copoly-11 mer of ethylene, propylene and 1,4-hexadiene, etc.
12 'rhe olefin polymers will usually h~ve number aver-13 a~e molecular weight~ within ~he. range o abou~ 750 and 14 about 200,000, more usually betweerl about 1000 and a~ut 20,000. particularly useful olefin polymers have number 16 average molecular weights within the range o~ about 900 and 17 about 3000 with approximately one ter~inal double bond per 18 polymer chain. An especially valuable startlng material 19 for a highly potent dispersant additive ls polyalkenPs, e.g. polyisobutylene, havi~g up to 109000 carbonsO
21 E~peci~lly use~ul when it is desired ~hat the 22 dispersant addi~ives also possess viscosity index improving 23 properties are S,000 to 200,000, eOg., 25,000 to 100,000 24 number averaga molecular weight polymers. An especially preerred example of such a V~lo improving polymer is a 26 copolymer of about 30 to 85 mole % ethylene~ about 15 to 70 27 mole % C3 to C5 mono-alpha-012~in~ preferably propylene, and 28 0 to 20 mole % of ~ C~ to Cl~ non-conjugat2d diene.
29 Unsubstituted or simple lactone rea~tant~ (Y-H) are readLLy obtained b~ the acld~cataly~ed lactonization Qf - 7 ~

.

1 an alkenyl dicarboxylic acid analo~9 the latter belng de-2 rived from the ring scission of an alkenyl succinic an-3 hydride wi~h water, an alcohol or an amine as shown below 4 whPrein HQ represents water, alcohols containing ~rom 1 to 10 carbons and dialkyl amines con~aining from 2 to 10 car~
6 bons and R is as previously defined.

O ~ H2R

l3 R ~ O ~ R ~ ~ H f OH ~ R ~
14 H2~ H ~ ~ C
16 ~ 2 ~ C ~Q 2 ~ ~Q

18 The reaction with HQ is assumed to open the an-19 hydride at the least congested carbonyl group and form a succinic acid, hemi-ester or amic acld product which in the 21 presence of aa acid catalyst cyclizes mostly ~o the 5-ring 22 lactone product as shown aboveO
23 It is possible to use alkenyl substituents with 24 the double bond in the 1, 2, or 3-posi~ion or even double 25 bonds ~r~her out on ~he hydrocarbyl chain since the acid 26 catalyst is capable at moving i~ i~to a position suitable 27 ~or lactone formatlon. In general, the siæe of the lac~one `~
28 ring formed wilL depend upon, inter alla, the position of 29 ~he double bond, and which carbo~ylic acid group partic~-p~es in the lactone forming reaction. As a consequence, 31 both 5- and 6-ring (or Larger ring) lactones can be en-32 vi~sged as illustrated below:

,~

.

. : . , .
- , ~

3 ~ ~0 R~ R

R~) o ~ CH2~-Q

9 For convenience, the product~ o:f the present invention are 10 usually shown as 5 ring lactones although l~rger ring 11 lactone prod~cts can also be present.
1~ The intramolecular cyc lization step involved in 13 the proce~s of this invention must be carried out in the 14 presence of an acid-type catalyst in order to e ffect orma-15 tion of the lactoneO Suitable c~talysts include the miner-16 al acid~ ~uch a~ hydrochloric acid,sulfuric acid, perchloric 17 acid, and phosphoric acid; ~he sulfonic acids such as the 18 alkanesulfonic aclds and the arylsulfonic acids; the Lewis 1~ type acids such as aluminum chloride boron trlfluoride, 20 antimony trichloride, and ~itanium tetrachloride and low 21 molecular weight suIfonic acid~type ion exchange resin 22 materials, such as cross-linked sulfonated polystyrene9 23 whlch is co~nercially available a~ Dowex~50. The alkane-24 sulfonic ~cid catalysts are preerably ~he lower alksnesul-25 fonic acids con~aining from 1 to 12 carbon atoms, :~or 26 exampLe, methane6ulfonic acid, ethanesulfonic acid, propane-27 sulfon~c acid~ and butanesulfonic acid. If desired, a mix-.28 ture o~ lower alkanesulfonic acid~ can be used and such a 29 mixture contaLning methane, ethane, and propanesul~onic acids is commercially available. Ordinarily, the alkane-31 sulfonic acld will comprlse ~rom 92% to 95% sulfonic acid, from 1 to 2% sulfurlc acld, and from 3 to 6~/o wa~er. The 3~ .
33 arylsulfo~ic acid catalys~ which can b~ used in the process 3~ ~nclude~ the benzenesulfonic acids, toluenesulfonlc acid, ~ ~ h~rk . . .

~ .3'~

1 and chlorobenzenesulfonic acids~ with p-toluenesulfonic 2 acid and 4-chloro~benzenesulfonic acid being preferred.
3 The amount of catalyst used is determined to a considerable 4 extent by the ~emperature selected for cvnducting ~he reao-tion. Thus, at higher ~emperatures the amount of catalyst 6 required in the reaction is less than w~en lower tempera~
7 tures are usPd and the use of excessive amounts of catalyst 8 at the more eleva~ed ~emperatures wil1 promote the forma~ion 9 of undesired side prod~cts~ Ordinarily, the amount of catalyst used will be be~ween about 0.1~/~ up to 10% by 11 weight o the amount of the alkenyl succinic anhydride re-12 actant.
13 The presence of certain heteroa~oms adjacent to 14 the novel lactone oxazoline ring combination oftimes endows the novel lac~one oxaæoline system with o:ther desirable 16 properties such as antioxidation and an~icorrosion activity.
17 Hydroxyl-containing lactone reactants are prepared 18 Yia the addi~ion of peracids~ hydrocarbyl peroxides or aque-19 ous hydrog~n peroxide to alkenyl succinic acid, hemiester or amide reagents as shown belowo 21 R R\
22 R~ ~H R~ ~ C~0O~

R ~ \ HlC ~ ~ H H30 ~ R~ ~ HC ~
226 ~2C~ ~ Q 2 ~ C

28 ~ Il 29 wherein Q is as previously defined and Rl represents hydro-gen, acyl group conta~ning from 2 to 20 carbons or alkyl 31 group containing from 2 to 20 carbons, As an al~ernate, the - 10 ~

~$ ~

epoxidation of alkenyl succinic anhydride, with peracids 2 gives epoxy anhydrides which can react with (1) water, alco-3 hols or amines to generate the desired hydroxy-substitllted 4 lactone reactants or (2) directly with THAM to give ~he lactone oxazoline end-produ~ts.
6 The thiyl-su~stituted lactones can be conveniently 7 prepared via (1) thiol-induced sci~sion of epoxy anhydrides 8 a5 shown below wher~n T represen~ alkyl, aryl or hetero-g cy lic groups containing rom 1 to 50 carbons.
0 ~R ~ C~ - S
12 ~ CH R ~ /
13 I" ~ 5 14 R ~ ~H~ R'~ \Hf ~ o 16 H2 \ / H2C~ ", OH
17 ~ ~
18 or via (2) sulfenyl halide addition ~o the double bond in 19 alkenyl ~uccinic acids or esters followed by lactonization via an internal displacement of halide as shown below:

22 R~ H i C/- O

23 HC ~ C ~ _~Q~ H ~ , C~
24 ~ H~ ~ OH
26 H2C~ ~ Q H~ ~ Q

29 wherei~ T i9 defined as above~
The ~yp~ of thiyl sub~tituted lactone product 31 will depend upo~ (i) the mode of ring cleavage by the thiol 32 reagent ~nd ~ he mode of addition of th2 sulfenyl chlor-33 ide ~o ~he double bond in ~he alkenyl succin~c acid, es~er ' ~
- ' .

l vr amide reactant~
2 With sulfur halides (SXC12~ where ~ is 1-43, thio, 3 dithio and polythio bls-lactones are formed. Subsequent 4 reaction of the latter with THAM gives the corresponding thio-bis~lactone o~azoline products.
6 Oxidation of the mono-~hio-bis~lactones wi~h pe~-7 oxides can yield both sulfoxides and sulfonesO In the case 8 of the dithio-bis-lactones, oxidati~n gives sulfo~containing 9 lactones.
In another approach thiyl lactones can also be ll prepared by addition of the sulfenyl chloride reagent ~o 12 the alkenyl succinic anhydride. Lactonization o~ the adduct l3 can ~hen be effected by either reacting ti) the sulfenyl l4 chloride adduct per se, or ~ he dehydrohalogenated ad-duct with An alcohol.~ water or an amine. L~ctonization of 16 the dehydrohalogenated thiyl ~ubstituted anhydride via op-17 tlon (ii) is preferably conducted in the presence of an acid 18 catalyst.
19 Examples of useful thiol~ in preparing thiyl lac-tones via epoxide cleavage include alkyl and aryl thiols 21 and he~erocyclic thiols such as 2-mercapto-benzothiazole.
22 Dithlophosphoric acids e.g. (RO)2P(-S)-SH, are also useful 23 in preparing phosphorus-containing produc~sO In an alter-24 na~e approach, the sulenyl chloride analogs o~ the above-described thlols can be added to alkenyl s~ccinic acid ana-26 I.ogs to giYe the desired thiyl-substituted lactone reage~ts.
~7 In another embodime~t of the present in~ention~
28 the reactlon o~ chloro~ulonic acid or its equivalent, e.g.
29 ~ 5~3 and its complexes~ with alkenylsuccinic anhydrides gives adduc~s which upon hydra~ion yield sulfo lac~one acids.

1 Treatment of the latter with THAM can under suitable condi-2 tions generate sulfo lactone oxazoline end;products.
3 In still another embodiment, lactam carboxylic 4 acids are used in ~he prepara~ion of lactam oxazoline addi-tives.
6 The amino alcohol used to react with ~he lactone 7 to provide the oxazoline ring is a 2~2 disubstituted-2-amino~
8 l-alkanol containing a total o~ 4 to 8 carbon atoms 9 and 9 which can be repre~ented by ~he formuLa:
X
ll N~2 - C - CH2O~

l3 wherein X is ~ an alkyl, or hydroxy alkyl group9 14 with at least one of the X subs~ltuents3 and pre~erably both of the X sub~tituents, be~ng a h~droxy alkyl group, with at 16 least one o the X subs~i~uents9 and preferably both o the 17 X substituents being a h~droxy alkyl group of the structur~
l8 -(CH2)nOH, wherein n is 1 to~3 1~ Examples of such 2, 2-d~ subs~ci tuted arnino alkanols, include 2-amino 2-methyl 1,3-propanediolg 2-amino~2-(hydroxy-21 methyl~-1,3-propanediol (also known as ~ri~-hydroxyaminometh-2~ ane or T~A~), 2-amino-2-ethyl-1~3-propanediol, etc. Because 23 of it~ effectiveness,avallability~ and cost, THAM is pax~icu-24 larly preferred.
~y sharp contrast, we have found tha~ o~her amino 26 alcohols such ag ethanolamine, propanolamine and butanolamine 27 which lack ~ disubstl~ution, do not give oxazoline prQducts, 28 Similarly, ~he prior~ar~ (British Pa~en~ 1,420~962) clearly 29 teaches tha~ ethanolamine reacts with lactone aclds~to giV2 amide derivatives via cleava~e of the lactone ~ing. We have ; .

~ 13 ' .. ~

3~ $ ~ ~

l discovered that interaction of lactone aci~s, esters and 2 amides with 2,2-disu~stituted amino alcohols is unique9 in 3 that the lactone ring of the reactant remaîns intact and 4 novel lactone oxazoline products are formed exclusively.
The formation of the novel oxazoline materials in 6 a very high yield can be effected by adding at least about 7 1 molar equivalent of the aforesaid 2j2~disubstituted-2 8 amino-l-alkanol per mole equivaLent o the polyalkyl lactone 9 acid, ester or amide with or without an inert diluent, and o heating the mixture at 100~240~C., preferably 170-220C. un-ll til reaction is complete by infra~red analy~is of the pro~
12 duct showing maxim~l absorption ~or o~azoline.
13 Inert solvents which may be used in the above re-4 ac~ion include hydrocarbon oils, e.g. mineral lubricating oil, kerosene, neutral mirleral oils~ xylene or halogenated 16 h~drocarbons.
17 Although n~t necessary, the presence of small 18 amounts~ such a~ .01 to 2 wt. %, preferably 0.1 ~o 1 wt. %, 19 b~sed on ~he weight of the reactants~ of a metal sal~ can be used in the reac~ion mixture as a ca~alyst.
21 The me~al salt can be left in the reaction mixture9 22 as it appears to become s~ably dispersed, or dissolved, in 23 the reactio~ product, and depending on the metal9 it may 24 even contribute perormance benefits to the oil or gasoline.
Thls is believed to occur with the use o~ zlnc ca~alysts in 26 lubricarlts-27 Metal salts that may be used a~ catalys~s in the 28 invention include carboxylic acid ~al~s of Zn, Co~ Mn and Fe.
29 The carboxylic acidg used ~o prepa~e the desired catalysts, in~lu~e ~1 to C18- e.g.~ C8 acids, such as the sat~r-~ . . ~ : . , t~

1 ated or unsaturated mono- and dicarboxylic aliphatic hydro-2 carbon acids, par~icularly fatty acids. Specific examples 3 of such desired carboxylic acid salts include zinc acetate5 4 zinc formate3 zinc propionate~ zinc stearate, manganese(ou~) acetate, iron tartrate, cobalt~ous3 acetate3 e~cO Complet-6 ion o~ the oxazoline reac~ion can be readily ascertained by 7 using periodic infrared spectral analysis for ollowing ox 8 azoline forma~ion (C--N absorptiQn band at 6~0 microns) until 9 maximized relative to lactone absorption or by the cessation o of water evolution.
11 The oil-soluble lactone oxa~oline reac~ion pro-12 ducts of the im7ention can be incorpora1:ed in a wide variety 13 of oleaginous compositions~ They can be used in lubrica~ing 14 oil compositions~ such as automotive crankcase lubricating oils, automatic transm~ssion ~luids~ etc, in concentrations 16 generally within the range of about 0.01 to 20 weig~t per-17 cent, e.g~ 0,1 to 10 weight percent~ preferably .3 to 3O0 18 weight percent~ of the ~otal composition~ The lubricants to 19 which the lacto~e~oxazoline products can be added include not only hydrocarbon oils derived from petroleum but also i~clude 21 synthe~lc lubricating oils such as polyethylene oils~ alkyl 22 esters o~ dicarboxylic acid, complex este~s o~ dica~bo~ylic 23 aclds, polyglycols and alcohols, and mixtures of mineral ~4 lubricating oil and synthe~ic oils in any proportion.
When the prod~cts o ~his invention are used as 26 ~ulti~mctional additives having detergentcy and anti-rust 27 properties~in petroleum fuels such as gasoline, kero~ene, 28 diesel ~uels 3 u~1 oil and other middle distillate~ a con~
29 centration of the additive in the ~uel in ~he range of 0.001 to 0.5 weight percent~ based on the weight of the total com-1 posi~ion, will usually be employed.
2 When used as an antlfoulan~ in oil streams in re-3 ~inery opera~ions to preven~ fouling of process equipment, 4 such as heat exchangers, or in turbine oils~ about 0.001 to 2 wt. % will generally be used.
6 The additive may b~ conveniently dispensed as a 7 concentrate comprising 20 to 90 parts by weight of the addi-8 tive dlssolved in 10 ~o ~0 parts of a mineral lubricating 9 oi.l.
EXAMPLE 1 (DIBSALAC) 11 Thirty grams (0.143 mole) of diisobutenyl succinic 12 anhydride ~DIBSA), which can be a mi~ure of three isomers 13 (A9 B and C) depending on the mode of synthesis, were mixed.
14RC ~ 4 CH~ RCH~ , CH3RCH~ ~ CH3 16 C~ O C ~ Ch~

19 ' : ~o '''' A s C
20 R - t-Butyl ~1 with 2.6 g of water and ~hre0 drops of concentrated suluric 22 acid. The mixture was heated ~o 110-120C. for one hour.
23 I~frared anal~sis of t~e reaction mix~ure showad that lac-24 tone formation was virtually complete. The addition of 200 ml of ether and subsequent cooling of the resulting ether 26 801ution caused ~olids to separa~e from solu~ion. Three 27 crop~ of white solid amounting to 27,1 g were collected and 28 r~cry~allized ~rom e~her-acetone solution. The product, 29 m.p. 141-142C.~ ~eatured an IR spectrum wi.th intense car-bonyl absorption bands at 5.70 (lactone) and 5.82 (carboxyl-, ~ - 16 -'~ - . : ' ' ;?3!~

1 ic acid) microns and analyzed for 62.78% C and 9.14% H
2 (Theory: 63.13% C and 8,86% H). The product, DIBSALAC, 3 presumably could be one or more of the isomeric lactones de-4 picted belowO The proton and IR spectral da~a suggest tha~

5 the 5-ring lactone acld products

6 ~H3 HO-C ~ O ~ O ~ O
11 0 H2C-OH CH2C~ OH

13 Rl 1~ CH3 ~ CH ~
16 ~b 19 R - neo-pent~l; Rl - t-butyl 20 predominate when reactant ~ is employed in the lactonization ~1 process.
~: 22 EXAMPLE 2 (NOSAL~C) 23 One mole (210 g) of n-2-octenylsuccinic anhydride 24 (NOSA) and 1.1 mole (20 g) of water were combined and hea~ed at 100-110C. ~or about a hal hour. A quantitative conver-26 sion to n~2-octen~l~uccillic acid occurred. Five drops of 27 concentra~ed sulfuric acid were added ~o the la~ter, and the 28 mixtur~ wa~ ~hen heated for 16 hours at about 155C. Upon 29 cooling, the liquid produc~ graduaLly crystallized. The 30 whi~e solids, m,p. 94^95C~ were lsolated in high yield and 3~ ea~ured an IR spectrum with strong absorptlon bands at 5.65 32 and 5.82 microns.~ The lac~one acid analyzed or 63.49% C and . : ..
. '' " .

- ' 1 8.35% H, and jud~ing rom its IR spec~rum (carbony~ absorp-2 ti.on at 5.65 microns) is mainly a 5-ring lactone although 3 some 6-ring lactone products can also orm depending upon 4 reaction conditions.
EXAMPLE 3 ~TPSALAC) 6 A mlxture o~ 405 g (1.52 moles) of tetrapropenylsuc-

7 cini a~hydride (TPSA~ and 30 g (1.66 moles) of water were

8 heated to 100-110C, for a half hour. Infrared analysis of

9 the reac~ion mixture indicated complete conversion of the Q anhydride to tetr~propenylsuccinic acid~ The mix~ure was ll treated with 40 g o Amberlyst L5 catalyst and heated to 12 125-130C. overnight. Infrared analysis indicated ~ha~ lac-13 ~onization was complete~
14 ~XAMPLE 4 (OSA~AC~
____ ~ hal mole (175 g) of 2-octadecenyl succinic anhy-6 dride (OSA) and 0.55 mole (10 g) of water were mixed and 17 heated in a reaction flask or a half hour at 80C. Infrared 18 analysis showed tha~ complete conversion of the anhydride to 19 succinic acid had occurred. While stirring at 80G.~ 0.5 g Of concentrated sulfuric acld was added, and the reaction 21 tempera~ure WAS increased to 130~ 0C. Heating a~ 140C.
22 ~or 1.5 hours comple~ely converted the dicarboxylic acid to 23 the desired lactone acid produc~s. When the cooled mixture ~4 was dilu~ed with etherJa whi~e. solid separated from solution.
~5 Infrared analysis of the isolated solids revealed the pres-26 ence of a S-ring lactone acid (strong bands at 5.67 and 5.82 27 microns). Cooling the supernatant liquid gave more solids.
28 Further fractional crystallization of later crops gave 6-ring 29 lac~one acid prodacts. The combined weight of all crops re-veaLed ~hat the yield o~ lactone acid product was quantLta-~ 18 -.
-. : . . . -. : . .
.
,. :.. . .

1 tlveO A recrystallized sample o~ S ring lactone product 2 melted at 112C:, and analyzed for 71~507O carbon, 10~77% H
3 and 16067% oxygen. Theory requires 71.49% C, 11.18% H, and 4 17.32% o.
EXAMPLE 5 (PIBSALAC) 6 One hundred twenty grams of polyisobu~enyl succinic 7 anhydride (PTBSA) o~ MW about 960 and have a saponification 8 number (Sap. No,) of 92 were diluted in 100 ml of tetrahydro-9 fur n (THF~ Two grams of wa~er were added and ~he result-0 ing mixture was heated to reflux tem~erature for about two ll hours. Infrared analyses of the mi~ture showed that the an~
12 hydride was fully converte~ to the suscinic acid analogO
13 The THF solvent was boiled o~f and 1 ml of concen~rated sul-14 ~uric acid was added to the mixture at about 110Co Heating lS for two hours at 120C~ ef~ected the converslon of the poly-16 isobutenyl succinlc acid to ~he desired lactone acîd produet.
l7 Infrared analyses showed the presence of strong absorption l8 bands at about 6~5-8.5 micronsO
19 The mixture was diluted in 200 ml of hexane, washed twice with 200 ml of wa-ter and subsequently concentrated by 21 ro~oevaporation for two hours at 80Cc Infrared analysis o 22 the lactone acid product trea~ed with diethylamine featured 23 an intense absorption band at. 5,64 microns ~5~ri~g lactone 24 carbonyl stretching3 2s ~XAMPLE 6 (PIBSAL~C~
26 A mixture of one hundre~ grams of polyisobu~enyl 27 succinic acid as prepared in Examp~e 5 and lO g o~ Amberlys~
28 15 ca~al~st were heated at about lOO~Co or about 8 hours, 29 and ~hen at 120C, for a half hour~ Infrared analysis showed the presence of lactone ac~d.

- 19;

~ r~

1 EXAMP1E 7 (PI~SALAC) 2 A mix~ure o~ 140 g (0.1 mole) o polyisobutenyl 3 succinic anhydride (MW about 960 and having a saponification 4 number ~Sap. No.) o~ 92), 3 g of water and 1 g of concen~
trated sulfuric acid were heated for about three hours at 6 105Co Infrared analysis indicated that the anhydride was - -7 directly and completely converted ~o the desired lacto~e 8 acid as evidenced by the s~ro~g carbonyl absorption bands at 9 5.63 to 5.84 microns, The reacti~n product was treated with 0.02 mole of Na~H (dissolved in ~etrahydrofuran), ~ ered 11 and rotoevaporated at 80C. for ~our hoursO The IR spectrum 12 of ~he amber concentrate ~reated with arl excess o diethyl-13 amine showed a strong lactone carbonyl absorption at S,65 14 microns ~ (NOSALAC ESTER) 6 A half~mole (105 g) of n-octenylsuccinic anhydride 17 and 23 g of absolute ethanol were combined and gradually 18 hea~ed ~o 100C~ over a half~hour period~ A mi~liliter o 19 concen~rated sulfuric acid was added and heating at 120C.
was continu~d or 30 hours. Infrared analysis ind~cated vir-21 tually complete conversi~n to lac~one es~er. Upon s~and~n~, 22 the product p~r~ially solidifled~ Recrystallization of the 23 crude solld from he~ane gav0 a crystalline material, mOp~
~4 83Co~ which feat~red an infrared spec~rum with intense lac-tone and ~ster carbonyl absorption bands at 5.63 and 5.80 26 m~crons~
27 EXAMPLE 9 (DIBSALAC AMID~) 28 rrhe dropwise addition of a tenth mole (703 g) o 29 diethylamine to 0,l mole (21 g~ of diisobutenylsuccirlic an-h~dride in 100 ml of ether ~av~ the amic acid direc~ly.
' .
.
- 20 ~

.. . . . . . . .
- . . . . . . . .

-3~

Three drops of concentra~ed sulfuric acid was added to the 2 reac~ion mixture which was reed of e~her solvent and heated 3 to about ~00C. for lO hours. Infrared analysis revealed the 4 presence of lactone amide. The pro~uct was diluted in ether and washed with aqueous Na2C03. The ether solution was dried 6 over solid Na2C03 and rotoevaporatedO
7 Distillation of a portion o ~he concentrated pro-8 duct gave a fraction~ b.p. 170C a (0~1 mm~ ~ which featured 9 an infrared spec~rum with very s~rong a~sorp~ion bands at 0 5.62 (lactone~ and 6.08 (amide~ microns, and analyzed for 11 4~90% nl~rogen, Theory required 4094% nitrogen.
12 E~AMPLE lO (NOSALAC AMIDE) ___ 13 Twenty~eight grams o~ the lactone acid product 14 prepared in Example 2 (mainly n~hexyl bu~yrolac~.one~alpha-acetic acid) were treated wlth an excess of gaseous`ammonia 16 at 1~0C. for abou~ ~wo hours, The produc~ was di~solved in 17 hot ~ylene and filtered. Upon cooling the solutlon9 a solid 18 product precipitated. The dried produc~ (lS ~) melted at 19 ll7-ll9C~? showed an IR spectrum with dominant ba~s at 5.65 and 6,0 mlc~ons and analyzed for 62.75% C, 9.~% H and 6.18%
21 N. Theor~ for the lactone amide requires 63.40% C~ 9.31% H
22 and 6.l8% N~
23 ~ (EPOXY-~IBSA) 24 Gram portlons of 0.05 mole of me~a-chlo*operbenzoic acid (70% purity) were added over a half~hour period ~o 0.05 26 mole (lO.l g) of diisobutenylsuccinic anhydride diqsolved in 27 300 ml of methylene chloride mnintained at 0C~ As ~he mix~
28 ture warmed ~o room temperature, it became clear and then 29 clouded~as m-chlorobenzoic acid byproduc eparated rom the , 30 solution~ The mia~ure was s~irred overnight at room tempera~

: ' '.: . . . ~ . . . ' 1 ture. The. mixture was filtered~ and the supernatant was 2 washed with a 5~/0 aqueous Na2C03 solution twice, dried over 3 Na2S04, and concentrated by rotoevaporation. During evapor-4 ation~ a solid separa~ed from solu~ion. The white solid (9.4 g) melted at 94-97C. and analyzed for 7.9% oxygen 6 (theor~ required 8.01% oxygen). The spectral data were 7 consistent with 8 ~ ~ CH2 1~ \ C
11 ~' 1 ' 12 ~ 2 ~ R - t~Bu 1$ EXAMPLE 12 (EPOXY PIBSA) 16 Appro~ima~ely 0.2 mole ~240 g) of polyisobutenyl-~7 succlnic anhydride (MW about 960) having a saponiica~ion 18 number of approximately 84 was dissolved in one liter of 19 C~Clz at 25~C, the well stirred solution wa~ treated 2~ with 5 g portions of 002 mole (40.6 g) of m-chloroperbenzoic 21 acid over an hour period. kl exo~hermic reac~ion ensued, 22 and raised th~ temperature of the reaction mixture to 34C.
23 Upon s~anding overnight, m-chlorobenzoic acid separated 24 from solution. FiLtratlon gave a clear CH2C12 solution 25 which was washed with aqueous 5% Na2C03 solution, and dis-26 tilled water~ and then dried over CaC12. Rotoevaporatîon 27 at 70C. for two hours af:l~ rded 242 g. of epoxy PIBSA as an 28 amber oil.
~9 ExAMpLE 13 (EPO~Y PIBSA) Two hundred grams of polyi~obutenylsuccinic an-31 hydride of MW about 1300 having a saponification number of ..

~. . .

f~

about 100 were dissolved in a liter of CH2C12 and 4û .5 g 2 g (0.2 mole) of m-chloroperbenzoic acid (85%) were added 3 portionwise over an hour period to the well stirred reac-4 tion mixture at room ~emperature, The clear solu~ion was S allowed to s~ir at ambien~ temperature for fiv~ hours.
6 During this period, white solids ~eparated from solution.
7 The solids were removed by filtra~ion, and ~he superna~ant 8 was freed of CH2Cl29 and diluted in he~ane and filtered.
9 Rotoevaporation at 80C. for two hours gave a concentrate (1~0 g) which was diluted in 90 g of neu~ral oil.
11 EXAMPLE 14 (HYDROXY DIB~ALAC) 12 A mixture of ca. 0.01 mole (2.76 g~ of epoxy 13 DIBSA as described ln Example 11 and 0;2 g af H20 wa~ dis--14 solved in S ml of te~rahydrofuran ~TH~) and heated to re-flux for an hour. IR analysl~ indicates complete conversion 16 of the epoxy anhydride to S- and 6-ring hydroxy lactone 17 ~arboxylic acids:
18 ~H2H HQ

~ o ~ V
21 ~2" ~C~H
2~ ~ O
23 R - neo-pentyl 24 The synthesis of the la~ter was also achieved by simply comblning equimolar amount~ C0.1 mole) of ~IBSA9 26 hydrogen p0roxi.de (30/O3 and a catalytic amount o sulfuric 27 acid (1 drop) in 100 ml tetrahydrouran ~THF~ and re~luxing 28 the mix~ure for several hours.
29 A~di tion of ether to the reac tion mix~ure in-30 duced ~he separation of solid product. Filtration gave a - ~3 -1 solid which featured an infrared spectrum with intense lac-2 tone and carbonyl absorption bandsO Recrystalllzation from 3 e~her gave a solid whlch melted a~ 180C. and analyzed 4 for 59.29% carbon, 8.28% hydrogen and 32~57~/o oxygen.
Theory for the hydroxy lactone carboxylic acid requires 6 59.00% C, 8.25% H and 32.75~ 0.
7 EXAMPLE 15 ~HYDROXY PIBSALAC ) 8 A mix~ure eomprising 0~32 mole (410 g) of PIBSA
9 (MW about 960~ wi~h a ~aponif1ca~:lon number of 833 0.32 mole (36.3 g) hydrogen per~xide ~30~/O aqueous solution) and 11 0~4 g (Ool wt. % of coneentra~ed sulfuric acid was heated 12 wi~h s~irring at abou~ 120C~ or appro~imately five hours~
13 Infrared analysls showed the presence of carbonyl band~ as-14 cribable ~o lactone acld, The product was diluted with an equal volume of neutral. oil.
16 EX~LE L6 (HYDROXY DIBSAI~C ESTl~R~ ~
17 A ~enth mole (22.6 g~ of monomethyl diisobutenyl 18 succinate and 0.1 mGle ~ 4 g~ of 30% hydrogen peroxide 19 were combined wlth 4.6 g of formie acid and heated to about 20 50C. with stirring. Infrared analy~is of the reaction mix-21 ture after two hours reac~ion a~ 50 reveale~ ~hat the hemi-22 ester was completely co~verted to the desired hydroxy~ con-23 taining lactone e~ter. The ~ame est.er was also obtained by 24 (i) epo~idation of mono~methyl diisobutenyl succinate w~th m-chloroperbenzoic aoid or (ii~ me~hanolysls of epoxy DIBSA
26 prepared in Example 11. The proposed structure for the 27 ma~or hydroxyl-containing lactone e~er generated via the 28 three syn~hetic schemes ls methyl ~- neo-pentyl- ~-hy-29 dro~methylbutyrolactone~ ~-acetate O

`p`~

1 (CH3~ C-CH2 C~20H
2 ~ ~
3 V ~
OC~3 6 Treatment of the latter with an equimolar portion 7 of morpholine gave a product ~hich featured an IR spectrum 8 identical to that for the hydro~y lactone amide obtained 9 in Example 19.
EX~MPLE 17 (H~DROXY PXBSALAC ESTER~
___ 11 A tenth mole (1~1 g) of epoxy PIBSA prepared in 12 Example 12 and 0.1 mole ~134 g~ of n-oc~anol were heated 13 together for about 12 hours~ The pr~duct was diluted with 14 an equ~l weight of neutral oil and filtered, The infrared spectrum of the oil-diLuted produc~ eatured the expected 16 lacton~ and ester carbonyl absorptions a~ 5062 and 5.7b~
17 microns, 18 EXAMPLE 18 (9YDROXY DIRSALAC AMIDE) 19 An e~her solution of O~Ol mole (0.87 g~ o morpho-line was ~dded dropw~se ~ an ether ~olution of 0,01 mole 21 (2.26 g) of epox~ DIBSA (Example 11~ at about ~SC. The 22 addition was exothermic and caused the e~her to reflux dur-23 ing addition. Upon cooling, solids formed, Inrared anflly-24 ~ 5iS of the~isolated solid (0~4 g~ showed sharp bands at 3,03 (hydroxyl)~, 5o80 ~lac~.one) and 6008 (amide) microns 26 indica~ive of the hydroxyl-containing 6-ring la¢tone amide.
27 The residue from the ~uperna~a~t (ca~ 2,4 g) featured an~IR
2~ spectrum consistent wi~h the 5-ring lac~one product. The 2g solid product m.pO 94-97 analyzed for 62007% C, 8,60% H, a~d 4,74~/~ N,~Theory for the hydro~ lactone amide requires 31 61,32% C, 8.69~/~ H,:~and 4047~/~ N, :;; 25 -. - - , : ~

r EXAMPLE 19 ~HYDROXY PIB~LAC AMIDE) 2 A tenth mole (121 g) of epo~y PIBSA prepared in 3 Example 12 was dissolved in 100 ml o CH2C12, and 0.1 mole 4 (9.0 g) of morpholine was added to it dropwise. The addition was exothermic. The mixture was then heated at 80C. for 6 12 hours, and at 130C. for an additional 6 hours. The 7 product analyzed for 0.83% N~ and featur~dan IR spectrum 8 with prominent bands at 5 . 61 and 6 . 02 microns as expected 9 for a lactone amide.
0 ~XAMP1E 20 (ADDUCT OF SC12 and n-OCTENYLSUCCINIC ANHY~RIDE) ll Three moles (630 g) of n-octenylsuccinic anhy-~2 dride were diluted in a liter of CH~C12 and stirred at room temperatur~. Then l.S moles (154 g) of SC12 in 500 14 ml. of CH2C12 were added dropwise. The exo~hermic reaction peaked to 50C. initially and external cooling was applied 16 to maintain reaction temperature at about 25C. No HCl 17 evolution oc.curred. After stirring the reaction mixture 18 for an hour after the SC12 addition, the solvent was re-19 moved by evaporation with a mild stream of nitrogen. The solid ~ha~ separa~ed rom solution during solven~ evapora-21 tion was isolated (40 g) and after being recrystallized 22 from CH2C12, melted at 149-150C. and analyzed for 55~4$~
23 C, 7~17% H, $~73~/o S and 11.4% Cl. The adduct~ C24H26O6SC12 24 requires 55.06% C, 6.93% H, 6.13% S, and 13.SS% Cl. The infrared spectrum eatured an intense anhydride absorption 26 at 5.67 microns, and a proton spec~rum was consis~ent with 27 the .s~ructure shown ~elow.
28 The concentrate obtained rom the supernatant wei~hed 745 g and ~eatured an IR spectrum similar to that 8ho&~n for the solid. The yield of adduct was vlr~ually .

1 quantitative. One possible structure shown below.

3 f ~H2 ~ ~ C~ CH ~ /
6 ~ ~ o ~ Cl Cl Or~O
7 R ~ n~pentyl EXAMPLE 21 (S Cl -n~OCTENYLSUCCINIC ANHYDRIDE ADDUCT) ~ 2 2 9 A mole (210 g) of n~octenylsuccinlc anhydride was dissolved in a liter of ether and a half mole ~67.5 ~) 11 of-sulfur monochloride (S~C12~ was added dropwise to the 12 ~tirred s~lution at room temperature. An exothermic reac-13 tion occurred and ~he addition was completed under reflux-14 ing condition~. The reaction mixtura wa~ stirred overnight and ~hen concen~rated by rotoevaporation at 50C. for 2 hours. The product featured an IR spectrum with a promin-17 ent anhydride carbonyl band at 5.65 microns, and analyzed 18 ~or 49.33% C, 6.04% Hs 10.7% S and 12.6% Cl. Theory for 19 the S2G12-n~octenyl~uccinic anhydride adduct (C24H36C120~S2) requires 51~88~/o C~ 6.53~/~ H, 11.54% S5 and 12.7~% Cl.
21 EXAMPLE 22 :
22 Two-tenths (30.4 g) mole of cis-1,2,3,6-~e~rahy-23 drophthalic anh~dride (ci~-4-cyclohe~ene-1j2-dicarboxyLic 24 anhydrlde) was dis~oLved in chloroorm (200 ml) and 0.1 mole (10.3 g~ of SCl~ were added dropwise to the well s~irred 26 solutiQn at room temperature. The SC12 addition increased 27 ~he ~emperatuYe ~o 53C. and the addition wa~ co~pleted at 28 abou~ 53C. Midway during SC12 addition the solution turned 2g hazy and som~ ~olids separated from 901u~ion~. A~ter addi-tion, the~mixt~re was allowed ~o cool and ~hé solids (20 g) 31 were i~olated by iltration. The solld product fea~ured an - 2~7 -.

r 3~

IR spectrum wi~h strong anhydride carbonyl absorption, 2 melted at 177-178C, and analyzed for 46.88% C9 4.22% ~, -3 7.68% S, and 14.93% Cl. Theory for ~he adduct 4 (ClsHl6Cl206S3 requires 47.1~% Cg 3.96% ~9 7.87% S, and 17.4~% Cl.
6 EXAMPLE 23 (THIO-BIS-OSALAC) __ _ 7 Two-tenths mole (73.6 g~ of octadecenyl succinic acid was dissolved in 500 ml ether and a ~en~h mole (1~o3 g g) of SC12 w~s added dropwise to the stlrred ether solu- -~ion at about 25C~ The addition was exothermic (ether 11 refluxed) and HCl evolu~ion occurred. The mixture was re- :
12 fluxed for about 8 hours. Upon cooling solids sep~rated ~ .
13 ~rom solution. The solid product fea~ured an infrared 14 spectrum with prominent lactone and carboxylic acid car-bonyl absorptions at 5.62 and 5.82 microns, melted at 158-16 163, and analyzed for 69.01% C, 10.17% H, 4.37% S and 17 16.74% O. Theory for the lactone ~cid (C44H7gO~S) requires 18 68.88% Cj 10.25% H, 4.18% S and 1~69~/o 0~
19 Further re1~xing ~he supernatant liquid gave four more crops of product with a combined welght of 50 g~
21 The yields were ~uantitative. The proposed structure for 22 thio- bls-OSAL~C is illustrated below:

24 C~ - S - CH
26O~C~ ~ H / H~ ~'C~O
27HC\ ~ 2 C~2~ CH
28 pC~I2 CH2 32R ClSH31 : - 28 -.

1 EXAMPLE 24 (DITHIO-BIS-OSALAC) ~ Two hundred grams (0.54 mole) of n-octadecenyl 3 succinic aoid were dissolved in a liter of CHC13 and 36~7 4 g (0.272 mole) o sulfur monochloride (S2C12) were added dropwise to the stirred solution at roQm temperature~ The 6 exothermic process was accompanied by vigorous HCl evol~-7 ~ion~ After refluxing ~he mixture for about eight hours, 8 the solution was cooled and solid5 separated~ Filtration 9 gave 19 g of solid ~m.p. 131~136C.) w~ich e~tured an IR
spectrum wi~h intense carbonyl bands a~ 5.62 and 5.72 11 microns~ and ~nalyzed or 66.42% C, 9.63% H, and 8.22% S.
1~ Thèory for the adduct (C44H7gOgS2) requires 66~12% C, 9.84%
13 H, and 8.02% S~ Rotoevaporation of ~he supernatan~ gave 14 a solid product in high yield~ The proposed structure for 15 di~hio-bis-OSAl~C is given below.
:L6 R R
17 fO CH\ "~ CH~
180~ H:-- S-S HC~ C-O
19H~ C~12 CH2~CH

22 R ' ~C15H31 23 ~ PLE 25 (TNIO-BIS-DIBSALAC) 24 ~ Two tenths mole (42.0 g) of DIBSA was dissolved ~n 100 ml. o THF and 0.1 mole (10.3 g`) of SG12 were added.
26 During addi~ion the reaction temperature climbed to about 27 35C. and HCl evolution occurred. The mixture was refluxed ~8 for four hours and then heated to 100 (THF dlstilled of~) :
2g ~or two ~ore hours to effec~ complete dehydrohalogena~ion.
The resldue was cooled and dissolved in T~F and 31 0.2 mole o~ wa~er and two drops of concentrated sulfurlc . .

.

. . . . . . .

r r; ~

1 acid were added. The mixture was re1uxed for several 2 hour~. Infrared analysis revealed complete conversion to 3 the de~ired thio-bis-lactone acid.
4 EXAMPLE 26 (THIO-~IS-PIBSALAC) Appro~im~tely 130 g of polyisobutenylsuecinic acid 6 ~MW about 960) (prepared via hydrolysis of PIBSA having a 7 saponification number of about 84) were dissolved in 400 ml 8 Mf chloroorm and 0.05 mole (5.3 g3 of SC12 was a~ded drop-9 wise ~o the stirred solution. Af~er re1uxing the mixture overnight, ~wo drops of sulfuric acid were added~ the sol~
11 vent was ~tripped off~ and the mixture heated at about 100C.
12 overnigh~. The produc~ featured an in~rared spectrum with 13 strong absorption bands in the 5.6 5.8 micron region and 14 analyzed for 1.69% sulfur and 0.09% chlorine. The IR spec trum of the diethylamine-treated product revealed a strong 16 lactone carbonyl band at 5,63 microns.
: 17 EXAMPLE 27 (THI0-BIS-PIBSALAC~
18 ~ ten~h mole tl30 g) of polyisobutenylsuccinlc 19 anhydride (MW ~bou~ 960) having a saponification number of approximately 84 was dissolved in 100 ml of ~oxane and 0.05 21 mole (5.3 g) of SC12 were added dropwise to the wel]~-stirred 22 solution at ca 25C. The mi~ture was then refluxed for four 23 hour~ (HCl evolution no~ed3. At this point, 4 g of water 24 acidiied with ~hree drop~ o~ concentrated sulfuric acid wers added and the mixt-tre was furt~er refluxed for 24 hours.
26 The mi~ture was filtered through.basic celite and rotoevap-27 orated at 90QC- for several hours. The concentrate fea~ured 28 an IR spectrum with strong absorption band~ in the 5.6-5.8 29 micron regioD~ and analyzed or 1~55% sulfur and 0.09%
chl~rine , . .

, ..

~ ~lt~ 3 1 EXAMPLE 28 (THIO-BIS-NOSALAC ESTER) 2 A half mole of the adduct o SCl2 and n-octenyl-3 succini anhydride described in Example 20 was added ~o 4 500 ml of xylene containing 32 g of methanol. The mixture wa~ allowed to stîr overnight and heated to reflux for about 6 four hours. The product was then rotoevaporated for three 7 hours at 70-80C. The final product featured an IR spec-8 tr~m with intense lactone and ester carbonyl absorp~ion at 9 5.63 and 5078 microns, and analyzed or 60.4~% carbon, ~;30~/O hydrogen, and 6.48% sulfur. The thio-bis lactone ester ll (C26H4~ 85) requires 60.67% C, 8.23% H and 6.~3% S.
12 The same ester lactone was easily prepared via l3 the addition of SC12 ~o mono-methyl ester of n-octenyl suc-l4 cinic acid.
EXAM LE 29 ~DITHIO-~S-NOSALAC ESTER) 16 Four tenths mole o the adduct of S2C12 and n-17 octenylsuccinlc anhydride described in Example 21 and 0.8 l8 mole (25.6 g) o~ methanol were dissolved in 200 ml o l9 chloroform and stirred at room temperature for four days, refluxad for 16 hours, and roto-evapora~ed at 80C. for 2l three hours~ The product showed an IR spec~rum with in-22 t~n~e lactone and ester carbonyl bands and analy~ed ~or 23 S7.19% carbon~ 7.93% hydrogen, and 10.54% sulfur. Theory 24 for the dithio-NOSAI~C methyl ester (C~6H4208S2) requires 57.11% carbon, 7.7~O hydrogen and 11.73% sulfur.
26 XA~PL~ 30 ~HIO~BIS-DIBSALAC ESTER) ~7 A tenth mole of mono-methyl dlisobutenylsuccinate ?8 was dissolved in 100 ml o xyleRe and 0.05 mole of SC12 was added dropwise to~ the stirred xylene solu~ion. The mix~ure was refloxed overnight and rotoe~aporated ~or ~hree hours ~ 31 ~

1 at 90C. IR analysis revesled that the hemi-ester/SC12 2 adduc~ was completely conver~ed to the des~red thio-bis-3 lactone methyl ester. A plausible structure for the sulfur-4 bridged bis~Lactone is shown below:
~ ~ / CH2 , CH2C-O
l3 O=CCH2 OCH3 14 O~H3 R = neo pentyl ~ `
16 ~ (THIO-BIS-~OSALAC ~MIDE) 17 A ~enth mole ~51.3 g) of the adduct o~ SCl~ and 13 n-octenyl ~uccinic anhydride described in Example 20 was 19 dissolved in 100 ml chloroform, and 0.2 mole (14.6 ~) of diethylamine wa~ added dropwise to the well stirred solu-21 tio~ at room temperature. The exothermlc reaction caused 22 ~he reac~lon ~empera~ure ~o pe~k to about 50C.~ and ex-23 ternal cooling was applied to main~ain reaction tempera-24 ture at about 10C. The cooling bath was removed, and the rea~ion mix~ure was re1uxed for two hours. The evolution 26 of HCl gas occurred. The mixture was rotoevapQrated ~nr ~7 an hour a~ 80~C. and diluted with 200 ml o~ ether. Filtra~
28 tion removed the Et2NH~HCl salt that ~ormed. The filtrate 29 was washed with aqueous Na2CO3 ~5% soln.) and dried over Na2CO3. Rotoevaporation of the ether solu~lon gave a resid-31 ue which ~eatured an IR spectrum with prominent lactone ~nd 32 amide carbonyl absorption bands at 5.62 and 6.10 microns~
33 ~nd analyzed for 63~73~/o C~ 9.36% H, 4~69~/o N and 5.37% S.
34 Theory Eor ~he thio bis-La~one amide ~C32~S~N2O6S~ re~

, . -~ ~t~

1 quires 64.39% C, 9.45% H~ 4.69% N and 5.37% S.

3 A tenth mole of mono~me~hyl diisobutenyl succin-4 a~e was dissolved in 100 ml of xylene and a tenth mole (23.5 g~ of 2,4-dinitrobenæenesulfenyl chloride (dissolved 6 in 100 ml xylene) was added dropwiseO The reaction mixture 7 was then refluxed overnight (HCl evolution occurred)~ The 8 mi~ture was ~otoevaporated using high vacuum at 90C. or 9 four hours. The re~idue, featured an IR ~pectrum with lo strong lactone and est~r carbonyl absorption bands a~ 5.63 11 and 5.73 microns.
12 ~XAMPLE 33 ~DIBMALAC ESTER) 13 0.05 mole (10.4 g) o diisobutenyl maleic anhy-4 dride (from diisobutylene and 2-chloro maleic anhydride) and O.OS mole (2.4 g) of absolute ethanol were combined and 16 heated to 95C. to generate the hemi-ester. ~t this point, 17 a drop of sulfurlc acid (95%? was added and the stirred 18 mixture heated at 100C. for about an hourc The product : 19 (in ether) was washed with aqueous Na2C03 (5% solu~lon) and dried over Na~C03, Vacuum distilla~ion of ~he crude product 21 af~orded 7.0 g of distilla~,e, b.p. 118-119C. ~0.15 mm) 22 which f~a~ured an IR spectrum with Ln~ense lac~one and 23 ester carbonyl absorption bands at 5.63 and 5.7 microns.
24 The distilled product analyzed ~or 66~07% carbon and 8.73%
hydrogen. Theory for the DIBMA lactone es~er (C~H2204) re-26 quires 66.11% carbon and 8~72% hydrogen.
27 EXoMPL~ 34 - (DIBSALAC O~AZOLI~
28 Eleven grams (0.045 mole~ of DIBSALAC described 29 in E~ample 1 was dissolved in 20 ml of xylene and 4.65 g i 30 (0.048 mole) of 2-amino-2-methyl-1-propanol was added drop-:~ :

~ 33 - -l wise. The reaction mixture was heated to re1ux in a flask 2 equipped with a Dean-Stark moisture trap. After 16 hour&, 3 1.5 ml of water were collected and the xylene was removed b~
4 rotoevaporation. Vacuum distillation of the residue af-forded a colorless liquid, b.p. 135C. (0.3 mm) in about 85%
6 yield. The liquid gradually crystallized on standing. The 7 crystalline product featured an infrared spectrum with prom-8 inent lactone and oxazoline ~bsorption bands at about SD68 9 and 6.02 micron~, and analyzed for 68.15% carbon, 9.48%
hydrogen, 4.93% nitrogen and 16.54% oxygen. Theory for the ll lactone oxazoline (C16H27NO3) requires 68.2~% carbon, 9.~%
12 hydrogen, 4.59% ni~rogen and 17.06% oxygen. The proposed l3 structure is shown below.
l4 R ~ H3 ~ 0 ~ ~2 CH
~ - ~ 2 ~ C~ - ~ C~3 16 0 \ CH - 2 l7 C
18 o R ~ neo--pentyl 19 E~AMPLE 35 (D~BSALAC OXAZOLINE?
DIBSALAC (0.05 mole, 11.4 g) described in Example 1 and 0.05 mole (6.2 g) o tris;(hydroxymethyl)-aminome~hane 22 (THAM) were added to 25 ml of xylene in a reactor equipped 23 wlth a Dean~Stark mois~ure trap. The mi~ture was reflu~ed 24 until ca. 1.6 ml of water were collec~ed in the moisture ~rap (approximately 5 hours). Infrared anaLysis indicated 26 cornplete conversion to lactone oxazoline product. Upon 27 coollng to room tempera~ure, the clear solutlon became cloudy 28 and whlte solid separated ~rom soLution. The solid product 29 was filtered off, washed several times with ether, and dried.
The firs~ crop weighed 6.0 grams a~d melted at 82~88C. Re-3~

1 crys~allization from xylene g~ve a white solid which mel~ed 2 at 97-103C " and featured an IR spectrum with prominent 3 lactone carbonyl and oxazoline (C=N) absorption bands at 4 5~66 and 6.0 micronsO The recrys~allized solid analyzed ~or 59.87% C, 8046% H and 4026% N. Theory for the lactone 6 oxazoline hemi-hydrate ~Cl6~24NO501/2 H20) requires 60~15~/o 7 C, 7.89% N, and 4038% No The product can be represented 8 by the following structureo ~3 / \ ~CH20~
11 ~ C/~ ~ 2 f ~ N~- \ C~20H
13 ~ ~CH- CH2 16 ~ - neo-pentyl 17 F,XAMPLE 36 (NOSA~AC OXAZOLINE) 18 NOSALAC amide (0.025 mole, 5.67 g) described in 19 Example 10 and 00025 mole (300 g) of THAM were added to 10 ml of xylene and the mixturP was refluxed overnight. The 21 solvent was stripped off and the mi~ture was hea~ed to 200 22 for two hours, then cooled and dissolved in ben~ene. The 23 addition of ether to the benzene solution caused the gradual 24 precipitation of solid rom solution4 Tha IR spectrum of the solid9 m-p. 108-109C., featured characteristic lactone car-26 bonyl and oxazoline (C~N) absorptioxl bands at 5,63 and 6.0 27 microns, and analyzed or 61.5-1% C, 8~38~r/o H and 4~69% N.
28 Theor~ for the adduct (CL~H~705N) requires 61.32% C, 8.69%
29 H and 4.47% N.
EXA~PLE 37 ~OS~LAC OXAZOLINE) 31 Two tenths mole (73.6 g) of OSALAC described in 32 Example 4 and 002 mole (24.2 g) of tris-hydroxymethyl amino-.

: ~ 3S -; :
': ' ' ': , 1 methane (THAM) were added to 100 ml of xylene contained in 2 a reactor equipped with a Dean-Stark moisture trap. The 3 mi~ture was refluxed until 5 ml of wa~er were collected 4 (about three hours) and the xylene solvent was then removed by rotoevaporation. The product was diluted in ether and 6 two crops amounting to 71 g were isolated by filtration.
7 The product melted at 121-122C. and featured an IR spectrum 8 with prominent lactone carbonyl and oxazoline (C--N~ absorp-9 tion bands. Elemental analyses shvwed 66,86% C, 10.61% H, 3.45% N and 12.01% O. Theory for the OSALA~ ox zoline ll (C26H47NOs) required 66.86% C, 10.44% H, 3.09% N a~d 12.63%

13 EXAMPLE 38 (PIBSALAC OXAZOLINE) 14 Si~ty grams (ca. O.05 mole) o PIBSALAC described in Example 5 and 6.1 g (0.05 mole) o tris-(hydroxymethyl) 16 aminomethane (T~AM) were added to 50 ml of tetrahydro~uran 17 (THF). The stirred mixture was gradually heated to dissolve 18 t~e reactants.
19 The THF solvent was then boiled off, and the reac-tion tempersture was raised to 170 and kep~ there for about 21 an hour. The residue wa~ dissolved in hexane~ fiLtered and 22 rotoevaporated at 90C. for four hours~ and diluted with an 23 equal weight of neutral oil. The in~rared spectrum of the 24 product featured prominent Lactone carbon~l and oxazoline (C~N) absorption bands at .5.63 and 6.0 microns.
26 The diluted produc~ (50% a.i.) showed a hydroxyl ; 27 n~mber of 43.1:and analyzed for 0.69% nitrogen (by Kjeldahl).
: ~ 28 The basic ni~rogen conten~, determined by non-aqueous titra-29 tion with perchloric acid was 0.56%.

, ~
: ,, .
~ 36 ~

: . ~ ' , : ' . .... - . . .

1 EXAMPLE 39 (PIBSALAC OXAZOLINE~
2 The PIBSALAC prepared in Ex~mple 7 and 0.1 mole 3 (12.0 g) o ~ris ~hydro~ylme~hyl) aminomethane (THAM) were 4 comblned and h~ated at 180C. for about four hours, The product was diluted in 200 ml hexane~ filtered and rotoevap-6 orated at 90C~ for four hours. The residue w~s diluted in 7 an equal weight of neutral oil (S-150N~. IR analysis o the ~ product showed strong absorption bands a~ 5.65 and 6.0 mierons 9 ascribable ~o lac~one and o~azoline func~ionality. Analyses revealed that the polyisobutyl lactone o~azoline product ll contained 0.63% nitrogen by Kjeldahl's method and 0056 basie 12 ni~rogen as determined by non-aqueous titration with per- :
13 chloric acid. The hydrc)~yl number o the diluted product 14 (50% a.i.), as determined accordlng to AM-S 240.10-1~ was 51 . 2 .
16 EXAMPLE 40 (HYDROXY-DIBSALAC OXAZOLINE ) 7 Epoxy PIBSA ~0 . 01 mole, 2 . 26 g) described in 1~ E~cample 11 and THAM (~.019 1.21 g~ was dissolved in 10 ml ::
14 of xylene and reflua~ed overnight. Removal o~ ~he xylene solvent by rotoevaporation gave a concentra~e which featured 21 an IR spectrum with the c~rac~eri~tic lac~one carbonyl and 22 oxazoline (C~N) ab~orption band~ at 5.70 and 6.01 microns.
23 EXAU!?LE 41 (HYDRO~Y-PIBSALAC OXAZOLINE) 24 The hydroxy ~IBSA Lactone acid (ca. 0,05 mole1 ~5 130 g o:~ 50/0 a.i.) described in Example lS and 0.05 mole 26 (6.05 g) of T~M were mixed and heated ~o 180C. for about 27 four hours. The product was diluted in 100 ml h~xane, fll-28 tered sn~ concentrated by rv~oevapora~ion. ~he diluted pro-29 ~uc~ (50% a.~.) ~atured an IR spec~rum with lacton~e carbonyl and oxazoline (C~ ab30rptlon bands at 5,7 and 6.03 micrnns - ~ . :

r~ r~3~

1 and analyzed for 0.57% ni~rogen (Kjeldahl).
2 EXAMPLE 42 (THIO-BIS-OSALAC OXAZOLINE) 3 Thio~bis-OSALAC (0.05 mole, 38.4 g) described in 4 Exampl~ 23 and THAM (0.1 mole~ 12.1 g) were added to xylene (200 ml) in a reactor fitted with a moisture trap. The mix-6 ture wa~ refluxed until abou~ 3 ml of water were collected 7 in the mQistUre trap (three hours). The hazy xylene solu-8 tion was ~iltered, and diluted with ace~one to the cloud 9 po~nt. T he solids that separated fr~m solution were recovered by filtration. Four crops amounting to 47.5 g were collected.
11 The solid product~ m.p. 171~175C. ~eatured an IR spectrum 12 with prominent absorption bands a~ 5.63 and 6.0 microns, and 13 analyzed for 64.95% C, 9.07% H, 3.03% N and 2.92% S. Theory 14 for the thio-bis-lactone o~cazol~ne (C52H92N2010S~ requires 66.63% C, 9.89% H, 3.00% N and ~3.42% S. A plausible struc-16 tu~e is shown belowo L8: ,C~
19' ~ C~

21 ~ 2 ~ C~ ~ C ~ 2 23 ~ O ~ ~H2 24 ~\
~HR / ~ 2 CH20H
27 H~ ~ ~ 2 ~ C ~ N ~' - CH20H
28 ~ ~,CH-~9 C

31 R ~ C15~31 3~ E~AMPLE 43 (THIO~BIS-PIBSALAC OX~ZOLINE
.
33 Thio-bis PIBSALAC (0.01 mole, 26~3 g) described 34 in E*ampl~ 26, THAY ~0.02 mole, 2.42), and 0.01 g. of zinc 3~

1 acetate were added to 26 g of neutral oil (S-150N) and heated 2 to 180C. for about two hours. The IR spectrum of ~he pro-3 duct showed absorption bands at 5055 (lactone~ and 6,0 (oxa-4 zoli.ne~ micronsO The diluted produot (50~/0 a.i,) analyzed for 0.54% N.
6 EXAMPLE 44 - Chemical St~bility of PIBSA~AC O~AZOLIN~.
7 Fi~teen grams of the produc~ of Example 38 and 1 8 gram of THAM were combined and heated at 195C~ for six hoursO
9 The in~rared spectrum o the reaction mix~ure was vir~ually ~o identical ~o th~t of ~he PIBSALAC O~AZOLINE reactan~ indi- : -11 eating ~hat the lac~one oxazoline was re~istant to further 12 aminolysl~ by THAMc By way of contrast, trea~.ment of poly-3 butenyl succinic anhydride/mono~THAM ester (formed by reac 14 ting polybutenyl succinic anhydride with one mole of T~AM
lS at 170 for several hours) with THAM under similar conditions 16 converted the mono-oxazoline ester completely to the bis-17 oxazoline produc~ in ~es~ than an hourO
18 ~ @~ Thermal Stability of PIBSALAC OXAZOLIN~
19 Heating ~he product of ~.xample 38 at 200CO for About 20 hour$ caused no ob~ervabIe changes in its infrared 21 spectrum, Under similar thermolysi3 collditions, polybutenyl-22 bis~oxazoline (prepared from poly~u~enyl succinic anhydride 23 and 2 moles of THAM a~ 180 for 2 hours) showed dis~inct 24 changes ~n its infrared spectrum. Heating caused the dom-inant absorption band at 6.0 microns ~C-N s~re~ching) (char 26 acteristlc o~ oxazolines) ~o gradual.ly diminish and become 27 less inten~e than the imide~ype absorption band (at about 28 5085 micr3ns) which event~ally dominated the spectrum of the 29 thermalized material ater 20 hours, `

- 3g -1 EXAMPLE 46 - Sludge Inhibition B~nch (SIB) Test 2 The product of Example 38 and two other dispersant 3 additives were subjected to a Sludge Inhibitioll Bench (5IB) 4 Test which has been found after a large number o evaluations~
to be an excellen~ test for asses~îng the dispersing power 6 of lubricating oil dispersant additiv~s~
7 The medium chosen for the Slud~e Inhibition Bench 8 Test was a used crankcase mineral lubr~cating oil composi-9 tion having an original viscosity of about 325 SUS at 100F.
~hat had been used in a ~axicab that was driven generally for ll ~hort ~rip~ only, thereby causing a buildup of a high concen~
12 tration o sludge prectlrsorso The oil ~hat was used con~
13 tained only a reined base mineral lubricating oil, a vis-14 cosity index improver, a pour point depres~ant and zinc di-alkyldithiophosphate antlwear additiveO The oil contained 16 no sludge dispersants. A quan~i~y o~ such used oil was ac-17 quired by draining and refillin~ the taxicab crankcase at ~8 1000-~000 mile lntervalsO
19 The Sludge Inhibition Bench Test is conducted in the following manner. The aforesaid used crankcase oil, 21 which is miLky brown in color~ ic freed o sludge by centri-22 fuging ~or 1l2 ~our at about 3~000 gravities (gs~). The 23 resulting clear brigh~ red supexnatant oil is then decanted ~4 from the lnsoluble sludge particles thereby separated out.
Ho~ever, the supernatant oil still contains oil-soluble 26 ~ludge precursors which on hea~ing under the condltions 27 employed by this test will ~eDd to form addit:ional oil-in-28 soluble deposits of sludge. The slud~e inhibi.tin~ properties 29 o~ the addi~ives being tested are de~ermined by adding to portionæ o~ ~he supernatant used oil) a small amount, such ~ - 40 ~

~ 3~

1 as 0.5, 1.0 or 1.5 weight percent~ on an ac~ive îngredient 2 b~sis, of ~he particular additlve being tested~ Ten grams 3 of each blend being tested is placed in a stainless steel 4 cen~rifuge tube and is heated a~ 280F, for 16 hours in ~he - -presence of airO Following the heating~ ~he tube containing 6 ~he oil being tes~ed is cooled and then ce~triuged for 30 7 minutes at about 39jO00 gs~ Any deposits of new ~ludge that 8 form in ~his step are separ~ted from the oil by decanting 9 the supernatant oil and then carefully washing the sludge deposits wi~h 15 ml, of pen~ne ~o remove all remaining oil 11 fram ~he sludge~ Then the weight of the new solid sludge 12 that has been formed in the test, in mllligrams, is deter-13 mined by drying the residue and weighing i~. The result~
14 are reported as mllligrams of slud~e per 10 ~rams of oil, thus measuring differences a~ small as 1 part per lO~OOOo 16 The less ~ew sludge ~ormed the more eff0ctive is the addi-7 ~ive as a sludge dispersantO In other words, if the addi-18 tive is effec~ive, it will hold at least a portion of the 19 ne~ sludge ~hat forms on heating and oxidation, stably sus~
pended 1~ the oil 90 it doe.s not precipitate down during 21 the centrifuging4 ~2 Usi~g the a~ove described test, t.he dispersant 23 ~c~ion of the lac~one-oxazoline addi~ives o~ ~he presen~ in-24 vention wa~ compared with ~he dispersing power o a eo~mer-2s cial dispersant referred ~o as PIBSA/TEPAJ The PIBSA/TEPA
26 was prepared by reaction of 1 mole of tetraethylene pent-27 amine with 1,5 moles of polyisobutenyl ~uccinlc anhydride 28 (Sap. ~o. 80) obtai~ed rom polyisobutylene of about 1000 29 num~er average molecuLar weight. The PIBSA/TEPA dispersan~
30 was u~d i.n the orm of ~n add~tive con~:entrate containing - 41 - :

- . - , . . . ..
. .

1 about 50 weight percent PIBSA/TEPA in 50 wt. % mineral lubri-2 cating oil. This PIBSA/TEPA additive concentrate analyzed 3 about 1.8% nitrogen~ indica~ing that the active ingredient, 4 i.eO, PIBSA¦TEPA per se9 contained about 3.6% nitrogenO
In addition, ~he lacton0-oxazoline product of the 6 present invention was also compared with polyisobutenylsuc 7 cinic anhy~rided-bis-oxazoline material prepared in accord-8 ance with the ~eachings of German Se~ial DOS 2512201 in the 9 Sludge Inhibition Bench Test. The bis oxazoline designated PIBSA/Bis-T~AM dlspersant was prepared vi~ the react~on of ~1 2 molar proportions of trls (hydroxymethyl) aminomethane 12 wi~h polyisobutenylsuccinic anhydride according to ~he 13 procedure, stoichiome~,ry and react~ion condi~ions specified 14 in ~.his patent application. The tes~ results are given in the table below.

18 RESULTS _ l9Milli rams Sludge/10 . Oil at Additive _ 21 o Example 38 0.69 7.70 4037 0.0 22 Blank lO~O 10~0 lO.O
Z3 PIBSA/Bl3THAM 1.0 7.61 4~17 0.56 24 PIBSAlTEPA 1.2 7.78 3.44 2.22 25The data~of this Table illustrates the outstanding 26 dispersan~ activi~y o the additive products o~ the inven-27 tion when compared with a known commercial dispersant re-28 ferred ~o as PIBSA-TEP~
29 The oxidation resistance is illus~ra~ed by a test 30 in which air is bubbled through lubricant samples maintained 31 at sbout 160C. over a 48-hour perlodO Each 30û gram sample ~I

:
~ 42 -. ~ : . .
. ~ , ~ 3 ~

1 ls modified by the addition o about 5.5 volume percent 2 (50% a,i.) dispersant to measure its respective effect ln 3 reducing ~hickening. Twen~y parts per million of iron acetyl-4 acetonate is added to each sample at the beginning ~n~ agaln at the end of 24 hoursO At the end of the tes~ thë result 6 were as ~ollows:
7 ~ L~ DisE~rs nt Added ~ O
8 l none 46 9 2 E~ample 38 addi~ive 68

10 3 PIBSA-TEPA 80

11 The preparation of the heterosubs~ituted hydro~

12 carbyl lactone acid materials are produced as noted earller

13 by reactlon with a .~unctionalizing agent of the class con-

14 ~is~ing of an oxidizing agent or a thiylating age~t a~ a temperature of from -20C7 to l00C, until functionalization 16 is complete. The preferred oxidizing agent i9 of the class 17 consi~ting of peracids~ alkyl hydroperoxides and hydrogen 18 peroxide and pref0rably used w~en the temperature is from 19 ~20C, to 50C~ The preferred thiyla~ing agents consis~ o hydrocarbyl sulenyl halides, a sulfur chlorl~e o the 21 ~ormula S~Cl2 wherein x i~ an lnteger of rom l to 4 and 22 chlorosulon1c acl~. The ~liiylating agents are usefully re~
23 acted over ~he en~ire range of -20C, to 100C., though pre~
24 erably a~ from about 20C, to 80C, ~5 ~XAMPLE 47 - SVLFO PIBSALAC O~ZOLIWE
______ ~ 26 Seventy grams (0O05 mole) of PIBSA (M~ about 960 ; 27 with a Sap~ No, of about 83) were di~solved in l00 ml of 28 ~etrahydrofuran (THF) and 6 g, (0O05 g) o~ chlorosul~onic ~ acid were added dropwise to the stirred THF ~olution at abou~
25C. The addi~ion was exothermic and external cooling was i .

:

~ 5~b3~

1 necessary to maintain the reaction temperature at about 25C.
2 After addi~ion the reaction mixture was stirred at room temper-3 ature for an hour, and then 1.0 g of wa~er was added and the 4 mixture was heated at reflux for 2 hours. The THF was 5 stripped of and the. residue dissolved in 200 ml. of hexane.
6 The hexane solution was washed twice with 100 ml. of water, 7 dried, and rotoevaporated at 80C. for 4 hoursO The concen 8 ~rate featured an I~ spec rum wi~h strong lactone absorption 9 bands at 5.6~5.71 microns indicating a mixture of 5- and 6 ring lactones, and analyzed for 1.92% sulfur.
11 Twenty-~ix grams of the sulfo PIBSALAC were d-ls-12 solved in 26 g, of neutral oil, and combined with 5 ~rams 13 of THAM9 and 0.01 g. of ZnAc2. The mixture was he~ted to 14 180C. for abou~ 4 hours, diluted in hexane, filtered and rotoavaporated at 80C. for 2 hours. Inrared snalysis 16 of the product showed the presence of lactone and oxazoline 17 ~unction~llty.

Claims (9)

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

1. Hydrocarbyl lactone oxazoline represented by the formula:

wherein R is selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 400 carbon atoms, X is selected from the group consisting of alkyl and hydroxyl alkyl and Y is selected from the group consisting of hydrogen, hydroxyl, sulfo, alkylthio, alkyldithio and a sulfur bridge containing 1 to 4 sulfur atoms joining two lactone oxazoline units together.

2. A hydrocarbyl lactone oxazoline according to claim 1 wherein X is a hydroxy alkyl group of the structure -(CH2)nOH
wherein n is 1 to 3.

3. A hydrocarbyl lactone oxazoline according to claim 1 wherein Y is a sulfur bridge containing 1 to 4 carbon atoms joining two lactone oxazoline units together, so that the oxazoline has the structure:

wherein S represents sulfur and z is an integer ranging from 1 to 4.

4. A hydrocarbyl lactone oxazoline according to claim 1 wherein R is derived from polyisobutylene and said oxazoline is polyisobutyl lactone [5,5-bis-(hydroxymethyl)oxazoline-2].

5. A lubricating oil composition comprising a major amount of lubricating oil and 0.01 to 20 wt. % of the oil-soluble lactone oxazoline of claims 1-3.

6. An additive concentrate comprising an amount of mineral lubricating oil in the range of 10 to 80 parts by weight and 20 to 90 parts by weight of the lactone oxazoline of claims 1-3.

7. A process for preparing a lactone oxazoline by heating together an equimolar mixture of a hydrocarbon-substituted lactone acid material selected from the group consisting of acids, amides and esters, with a 2,2-disubstitute 2-amino-1-alkanol having 1 to 3 hydroxy groups and containing a total of 4 to 8 carbons at a temperature of from 100 to 240°C until infra-red absorption for oxazoline is maximal indicating completion of the oxazoline reaction.

8. The process according to claim 7 wherein said amino-alkanol has the formula wherein X is alkyl or hydroxyl alkyl, 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.

9. The process according to claims 7 or 8 wherein said hydrocarbon-substituted lactone acid material is polyisobutyl lactone carboxylic acid, said amino-alkanol is tris-(hydroxymethyl) aminomethane and said heating is continued until about 2 molar equivalents of water have evolved.