DE1912515A1 - Process for the production of adducts from esters of high molecular weight carboxylic acids with epoxides and use of the adducts as additives in lubricants as well as in fuels and fuels - Google Patents

Description

· .. DR. ELISABETH JUNG, DR. VÖLKER VÖSSiÜS, DIPL-ING.

PATENT LAWYERS 8 MONKS 23. S I E G ES STRASSE 28 TEL EFON 348087. TELEGRAM ADDRESS: INVENT / MONCHEN

UoZo: D 979 (Pi / Vo / kä) * 1 2nd MffZ.

LF-1051-WG

THE LUBRIZOL CORPORATION
Cleveland, Ohio, V ₀ St.A.

it process for the production of adducts from esters of high molecular weight carboxylic acids with epoxides and use of the adducts as Additives in lubricants, as well as in fuels »and fuels"

Priority: March 13, 1968, V ₀ St ₀ A ₀₈ No. * 712 606

From the French patent specification 1 396 64-5 »the British Patents 981 850 and 1 055 337 as well as the USA patents 3 255 108p 3 311 558, 3 331 776 and 3 346 354 is di « Use of esters of high molecular weight carboxylic acids as additives in lubricants and in fuels and fuels known

The object of the invention is to provide new adducts of esterification products of high molecular weight carboxylic acids with epoxides which are suitable as additives in lubricants, as well as in power and fuels

909845/1565

Q35GINAL IHSPECTED

111 ι · C A · β

ι s »J ι. nt ι ι

* j ·· s * ij j · «*

11 · JJ i »} *

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This task is solved by

(A) at least one ester of a high molecular weight mono- or polyoarboxylic acid of the general formula I.

Ri-COOH) _n (I)

in which R is a hydrocarbon radical containing at least about 50 aliphatic C atoms with an average molecular weight of about 700 to about ICO 000, _{B is} the at least 80 % saturated. Has bonds, and η is an integer from 1 to 6, with a polyhydric alcohol which has 2 to 10 hydroxyl groups and up to about 40 aliphatic carbon atoms with

(b) at least one 2 to about 40 aliphatic carbon atoms tendon epoxy of the general formula II

R ¹ - CH - CH - R ² (II)

1 2

in which R and R are hydrogen atoms or optionally substituted, mean aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, according to methods known per se in such proportions that 1 equivalent of the alcohol component of the prayers is 0.05 to 5 equivalents Epoxy equivalent.

The aforementioned esters are either known or they can be prepared by customary processes «. Since the aforementioned Patents describing numerous esterification products of this type and various processes for their preparation is available on they referencedο

These patents describe for the most part

909345 / 1SSS

* ♦ · r ftf ι rc «

r * · c r f r r

products of substituted succinic acids with aliphatic poly-

also / hydric alcohols «The invention relates, however, to / the production of adducts of similar _P from monocarboxylic acids or other polycarboxylic acids derived from esters derived from succinic acid. Such later can be produced according to the general production process for succinic acid esters described in the aforementioned patents by reacting mono and polycarboxylic acids serving as acylating agents with the corresponding aliphatic alcohols.

BXe acid component of the esters "from which the adducts of the invention are produced" derives from a, high-molecular! -! © no "or polycarboxylic acid ( general formula)

EC-OOOH) _n (I)

A particularly important characteristic of the rest of E is his

· The remainder R should contain at least about 50 aliphatic carbon atoms. Fuels * Another important Gesichtepunkt in the training ι choice of the radical E is _s that it preferably should be substantially saturated, i.e., _Q h _O9 least about 80 # "is preferably 95 # of the total number of carbon-carbon bonds to be saturated" Particularly preferably bind high molecular weight. Carboxylic acids _t whose remainder R has at least about 98 $> saturated bonds ■ „, Sin a greater degree of unsaturation makes the esters more sensitive to oxidation, degradation and polymerization processes _v whereby the effectiveness of the end products as additives in lubricants ρ fuels and fuels is reduced will. \

909845/1565

·· «1 9 * ί% as. -Ι *

Furthermore, the remainder R should be essentially free of oil-soluble
the branches, doho groups with more than about 6 aliphatic carbon atoms, although some such branches may be present, their proportion should preferably not exceed one
such a remainder for every 25 aliphatic G "" atoites of the main hydrocarbon chain of the remainder R "

The radical R can contain polar substituents with the
that these are not present in proportions and ₀ the one © w
Change of the hydrocarbon character d @ s best E b
Typical suitable polar substituents are S ₀ B
such as chlorine or bromine atoms, oxo- ,, .oxy-j. ForayX- _p
Sulfinyl-3 thio and nitro groups The Aateil äiseer
Substituents should preferably be 10 $ of the total weight
Coal water et off rest it R not over very ©! ten «.

High molecular weight carboxylic acids, of which the esters are the
derive dung can be prepared by known processes, such as those for "Be in'den USA patents 3,087 936"
3 163 605 _B 3 172 892, 3 189 544, 3 219 666, 3 272 746,
3 288 714s 3 306 907 _f 3 331 776, 3 340 28I ₈ 3 341 542 and
3,346,354 are described ₀

As in the aforementioned patent specifications erlaix-fcart _f there are various processes for the preparation of these high molecular weight carboxylic acids olefinically unsaturated hydrocarbon or a chlorinated hydrocarbon which contains at least about 50 oJipliat-ical carbon atoms

90 984 5/158 5

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hold, at temperatures of about 100 to about 30O ⁰ Co The chlorinated hydrocarbon or olefinically unsaturated hydrocarbon, in consideration of the abovementioned general limitations polar substituents or "oil-soluble solubilizing contain branches, as well as unsaturated ₀ From these reaction components zunmindest approximately as are to address hydrocarbons , the majority of the aliphatic carbon atoms in the hydrocarbon free R come from the end products ₀

For the production of the high molecular weight carboxylic acids according to one of these In both processes, a lower carboxylic acid of the general formula III

R ⁵ (-COOH) _n (III)

3
used “in which R contains at least one olefinically unsaturated bond and η is an integer between 1 and 6 _0, preferably between 1 and 2. Instead of the lower carboxylic acid, 2, B _{0 can} also be the corresponding halide, anhydride, an ester or a mixture of these compounds The lower carboxylic acid usually contains a maximum of 10, preferably a maximum of 6 carbon atoms "and it should preferably have at least one double bond in the CK position to at least one carboxyl group", examples of lower carboxylic acids or their derivatives are acrylic acid ρ methacrylic acid, maleic acid , maleic anhydride, fumaric acid, itaconic acid _3-8 itaconic anhydride, citraconic acid _P citraconic anhydride Masaconsäure, glutaconic acid, ChI> rmaleinsäure, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, hexene ~ and decene ~ 10-oic acid ₀ Aue economic reasons vsrwendet is preferably acrylic acid, methacrylic acid, Maleic acid, and maleic anhydride <>

909845/1565

»» I J · i * J ft φ

* 2 * i J J J J # ♦

* J · J it · l · «·

* J 4 ι J J 1 ·

From the above it can be seen that the high molecular weight carboxylic acids of the general formula B (* OOOH) _n can contain cyclic and / or aromatic radicals. However, these carboxylic acids are essentially aliphatic in nature. The preferred high molecular carboxylic acids R (-COOH) _n are aliphatic · »Table mono- and polycarboxylic acids, their anhydrides and halides,

The succinic acids substituted by an essentially saturated aliphatic hydrocarbon radical and their anhydrides are particularly preferred acylating agents for the preparation of esterification products which are used as starting materials according to the invention. These succinic acid ^ uwä their derivatives can easily by reacting Maleinsäureasliydrid mini-! · A high molecular weight olefin or a chlorinated hydrocarbon such as a chlorinated polyolefin are produced "The beid © it reaction components are preferably heated to a temperature of about 100 to 30O ⁰ C ₉ heated from 100 to 200 ^° C. “As explained in the aforementioned patents, a substituted succinic anhydride is obtained, the substituent of which is derived from the olefin or chlorinated hydrocarbon. If necessary, the product can be hydrogenated by a conventional hydrogenation process to remove all of a portion of the unsaturated bonds. The substituted succinic anhydrides can be hydrolyzed to the corresponding acids by treatment with water or steam, and either the anhydride or the acid can be a phosphorus halide or an alcohol converted to the corresponding acid halide or ester "

909845/1565

t · rr

• · ♦ r c ff r • · f r r

The olefinically unsaturated hydrocarbons used for the production of the high molecular weight carboxylic acids or the chlorinated hydrocarbons are mainly the high molecular weight "in%? Eeen, saturated petroleum fractions or the essentially saturated olefin polymers and the corresponding chlorinated compounds" The polymers and chlorinated polymers, oils see from Mon © © lefte @ n with 2 to ®about 30 (Derive Kitomen, preferred! © foraugt verweii ^ © ^ ® ^ © Ijmerisat® derive

_t isobutene _v -1 _s as well as with medium @ t © a-4i elsafails

, © £ ia © wa.tQE'Siinander and Olefins, cy as olefi-

aiseh uageeättigis © ifehloa ^ aiusesatoff © ii @ ia @ ii ₀ Such copoly «· asrieate ^ g ^ ten S ₀ B ₀ dmsefe OepolyiaesiEatioa ^ on leobuten with Sty E ¹ Sl ₈ ! © © buten with Biataäi © a ₀ lropyl @ a with Is © pr @ a ₈ propylene with! © © buten, litfeflea ® £ t Sip © ^ l © a ₈ Is @ lsiat © a with Ofeloropi'en, Isobut @ a ait p- & i®thylstyrol _ß H © 2e © h. «~! with Hezadiene «»!,? ,, Octene «l with Hexen-1, Heptene« ° l © it Pentene lp 3- = Ethylbutea ° l with Octene-1 »3,3-Dimethylpentene-l with Hexene-1 and isobutene made with styrene and piperylene

With regard to the oil solubility and stability, the fü:? the preparation of the high molecular weight carboxylic acids R (COOH) _n copolymers used substantially aliphatiecher nature and saturated 8oin _f d "h _e they are at least about 80 and vorzugo-

9098A5 / 1565

T »It

wise contain about 95 Gewo- # units »which are derived from aliphatic echen monoolefins.» Preferably, they should not contain more than about 5 i> olefinic linkages based on the total number of carbon-carbon bonds.

The chlorinated hydrocarbons and olefinically unsaturated hydrocarbons, which are used to prepare the high molecular weight carboxylic acids have molecular weights can range from. about 700 to about 100 000 to have higher "is preferred to have the above polyolefins and chlorinated polyolefins having a Durchechnittsmolekulargewicht of about 700 to about 500Oo If the high molecular weight carboxylic acids Rt-COOH) _n has a molecular weight above about 10,000, have the ester when they contain nitrogen, also properties that improve the viscosity index.

Instead of the aforementioned high molecular weight hydrocarbons and chlorinated hydrocarbons, it is also possible to use hydrocarbons which contain polar radicals that activate the reaction with the olefinically unsaturated lower carboxylic acid and are sulfide and disulfide groups, as well as nitro, mercapto, carbonyl and Formyl groups ₀ Examples of these hydrocarbons substituted by polar radicals are polypropylene sulfide, dipolyisobutene disulfide, nitrated mineral oils, dipolyethylene sulfide and brominated polyethylene

You high molecular weight carboxylic acids can also be prepared by halogenation of high molecular weight hydrocarbons such as the eiiannten before ^ olefin Polymeri8ate _p anechliesßende implementation of halogenate polymer. a polynitrile and subsequent hydrolytic: the

909845/1565

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Cleavage can be produced <> They can also be produced by oxidizing a high molecular weight polyhydric alcohol with potassium permanganate, nitric acid or a similar oxidizing agent. Another method for preparing the polycarboxylic acids beateht therein "that an olefin or substituted by polar residues * hydrocarbon, such as _p chloropolyisobutene with an unsaturated Polyoarbonsäur9, such as pentene-2-1,3,5-tricarbonBäurep prepared by dehydration of citric acid, transposed high molecular © monocarboxylic acids can be obtained with ketenes ₀ Sin also by oxidation of monohydric alcohols with potassium permanganate or duroh reaction halogenated _c hoohmolekularer olefin polymers another common method for preparing the high molecular weight monocarboxylic acids consists of the reaction of sodium metal with an acetoacetic ester or a Malonester and condensation of the sodium derivative of the ester with a halogen-! Erten _c high molecular weight hydrocarbon, Z ₀ as a brominated wax or brominated polyisobutene ·

High molecular weight mono- and polycarboxylic acids can also be converted ZoBo of chlorinated mono- and polycarboxylic acids »their Anhydrides and halides with optionally substituted, olefinically unsaturated hydrocarbons »ZoB» the aforementioned Polyolefins and substituted polyolefins according to USAo Patent 3,340,281 can be obtained.

Die.Anhydride mono "and polycarboxylic acids can be easily SiOH duroh heating to temperatures of at least about 70 ° C, preferably in the presence of a dehydrating agent," such as acetic anhydride produced, ₀ Cyclic anhydrides are usually obtained from polycarboxylic acids whose carboxyl groups

909845/15 ^ 5

i J < 1, I JI ₍

separated from each other by at most 3 carbon atoms "like subsetic or glutaric acid, while linear ones are obtained from polycarboxylic acids, whose separated by at least 4 carbon atoms

3® &

The acid halides can be prepared by reaction d @ r mono- or polycarboxylic acids or their anhydride with © genierungsraittel as are produced Phosphortriteosiid _s or thionyl chloride '"

The ate used for the production of the adducts? © is preferably divided by adding the high molecular weight chlorides or anhydrides with an ali] alcohol with up to about 40 carbon atoms. These alcohols contain 2 Ms lekül · Suitable® polyhydric alcohol ^ e © pos © 3it @ n ia The esters used in accordance with the invention are airnd g _e B _ö Hkylsagljk ©! © Ethylene glycol 2 & opyl @ nglykol, friiiefl22r2 © 2>., gljliQl _D Bü ^ üaäiol Polyglycols, such as diethylene aglycol, üfeiäthylesgljr ^ lgropylenglycol, xetylene glycol glycol glycol © llkylenglykois like glycols, in which the alkylene radical 2 bi @ holds about S G-Ato © 3 ο other polyvalent alcohol components simd ^ cBo QIyg © mim. <Glycerinmonomethylather, pentaerythritol _s acid, 9,10-Dihyaroxystearinßäureäthylest®r 3 _g ^ <3U! M ^ l ₃ l diel, 1,2-butanediol, 1,4-butanediol, 2 _{g of} 3 pinacol, erythritol, arabitol, sorbitol " mannitol _θ 1,4-Cyclohexandiolj, l, 4- (2-hydroxyethyl) - 'fl Sy0l © © xan ₉ 1 ₀ <xy-nitro butane-2, 1,4-di- (2-hydroxyethyl) -h @ nzoi

909845 / 1SiS

· Tr 'f
· Ι c
# fr
· · «F

- 11 -

such as Gluooee «rhamnose, mannose, glyceraldehyde and galactose, amino alcohols such as di (2-hydroxyethyl) amine, tri- (3-hydroxypropyl) amine and N, H ^f -di (hydroxyethyl) - äthylencLiamine as well as that Oopolyester from allyl alcohol and styrene

With aliphatiecher in this group alcohols, the polyhydric alcohols include having at least 3 hydroxyl groups, of which at least one with a monocarboxylic acid having from 8 to about 30 carbon atoms, such as caprylic acid, oleic acid ₉ stearic acid, linoleic acid, lauric acid or tall oil fatty acid is esterified. Examples of such partially esterified polyhydric alcohols are sorbitol monooleate, glycerol monooleate, glycerol monostarate, sorbitol diet ear at and erytliritol dilaurato

A preferred class of the esters of the invention is derived from polyhydric alcohols having up to 10 _5, preferably 3 to 10 carbon atoms. Specific examples of these alcohols are glycerol, erythritol »pentaerythritol, gluconic acid, glyceraldehyde, glucose« arabinose, 1,7-heptanediol, 2,4-heptanediol, 1,2,3-hezanetriol, 1,2,4-hexautriol, 1, 2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,6-tetrakis hydroxymethylcyelohexanolp l ₉ lO-decanediol and digitalose « Particularly preferred are the esters which are derived from aliphatic alcohols with at least 3 hydroxyl groups and with up to 10 carbon atoms

A particularly preferred class of polyhydric alcohols from which the esters of the invention are derived are the polyhydric alcohols having 3 to 6 carbon atoms _P and at least 3 hydroxyl groups. Specific examples of these alcohols are glycerol,

909845/1565

1 *

f I
f 1

- 12 erythritol, pentaerythritol, mannitol, sorbitol and 1,2,4-hexanetriol

The epoxides used to produce the adducts can contain 2 to about 40 carbon atoms and correspond to the general formula

R ¹ - OH - OH- R ² (II)

1 2
in which R and R have the meaning given above «

1 2
livable, the radicals R and R Wasserstoffatoiae or alkyl-C-p haloalkyl, cycloalkyl, halocycloalkyl, aryl or HaIogenarylreste, wherein 3 carbon atoms than 1 halogen atom kommtο Special be preferred are the lower alkylene and haloalkylene-epoxides, including the Cycloalkylene epoxides _p the arylene and haloarylene epoxides containing 2 to 8 carbon atoms have radicals with one to two resonance ring structures _p Z ₀ B.

. Phenyl ,, _S naphthyl or substituted phenyl and Haphthyl- as alkylphenyl "- or halophenyl-j, ZOB" tolyl, Kreeyl-, xylyl, p-chlorophenyl and methylnaphthyl _e The preferred aryl epoxides have phenyl and halophenyl as leftovers

1 2

R and R c epoxides are particularly preferably _p in which at least one of the carbon atoms linked to the oxygen atom in the oxirane ring is also connected to two Wasaerstoffatomen ₀ lists These epoxides man "terminal epoxides"<.

Specific examples of usable according to the method of the invention epoxides are ethylene oxide "propylene oxide, 1,2-epoxybutane _s 1,2-epoxypentane, l" 2 ~ epoxyheptane, 1,2-Epoxyciodekan, 2 _S 3-epoxybutane _p l _f 2-epoxycyclohexane _s 2 _S 3-epoxyheptane _p 1,2-epoxyoctane ,. Epichlorohydrin, l _r 2 ^ epoxy = 4 - = - chlorobutane _p styrene oxide, p-methylst3'-ro5, oxide _s r ^ chlorostyrgloxyd, epoxidized soybean oil,

•" does

- 13 -

O / pIO-epoxy-atearic acid methyl ester, and epoxidized fatty acid esters » whose. Fatty acid residues up to about 30 aliphatic carbon atoms and whose alcohol residue is from an aliphatic alcohol with up to about 8 G-Al; omen derives »Special preferred Ethylene oxide, propylene oxide and epichlorohydrin are used to produce the ester adducts >

BaB process for the preparation of the adducts of the invention consists in the reaction of the esters or the Estergemisohs with an epoxy or a Epoxydgemisch at temperatures of about 25 ⁰ C up to the decomposition temperature of the ester used or "epoxide, preferably at temperatures of about 50 to 25O ⁰ C , usually in the presence of an inert diluent, "Good results are obtained _p when the reaction at temperatures of about 70 is carried out to 200 C · the esters and epoxies can arbitrarily be blended ₀ Preferably turning to any mechanical Mischniethode on to to achieve a thorough mixing of the ester and the epoxy »

Solvents, any substantially inert organic liquids can be used _a such as aliphatic, cycloaliphatic and aromatic hydrocarbons and their chlorinated derivatives such as pentane _p hexane, heptane, cyclohexane, benzene ο toluene, xylene, chlorobenzene and the chlorhexaneo petroleum distillates such as mineral oils, benzines and ligroin the esters may also be used as a 'solvent wordene In many instances prepared ala Üllösungen, which are used then in the preparation of the adducts of the invention, wherein oil-ice dae solvent used.

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■ - 14 -

The exact chemistry by which the properties of the esters as dispersants are improved in accordance with the process of the invention is not known. It is believed that the epoxides react with unesterified hydroxyl groups, although reaction with any free carboxyl group present is also possible. In a preferred one embodiment of the invention should be substantially free from unesterified carboxyl groups, such as the Berneiteinsäurediester unlike the Monoestern the esters .. they are obtained by the stoichiometric amount or an excess of alcohol is used in the _o preparation of the ester is an ester will be substantially free viewed by free Garboxylgruppen when more than about 10 # of Carboxylfunk "functions free carboxyl groups, are usually is the number of free carboxyl groups in this preferred embodiment of the invention less than about 5 fi _B based on the prenamed © Gesamtzahlο are free carboxyl groups present? s The proportion of epoxy can be increased so that up to about 1 equivalent of epoxy is added for each equivalent of the free carboxyl groups in addition to the amount that is used to prepare the ester adducts.

The esters and spoxyde should be converted in proportions such that 1 equivalent de? The alcohol component of the EstOTS corresponds to about 0.05 to about 5 and preferably O ₉ I to about 2 equivalents of spoxide ο Here, nan is the equivalent weight of the alcohol divided by the number of hydroxyl groups present, regardless of whether they are esterified or not. Similarly, the equivalent of an epoxy is chosen as that by the number of mole-

909845/15 * 1

kttl contained oxirane rings divided molecular weight dee Spoxyds accepted. For example, the Beter contains 4 equivalents of alcohol if it contains 1 mole of pentaerythritol as an alcohol component if the method of the invention includes such a Beter with 0.2 hie 20, preferably 0.4 to 8 equivalents of epoxy d are reacted. This equivalent ratio is only used as a guideline for the cheapest proportions of the meter and The epoxies given and does not mean that the total amount of the epoxies used reacts with the ester. Ee iet possible, however, routinely within the aforementioned range to determine the optimal ratio of each meter or ester mixture on the one hand to each epoxy or epoxy mixture on the other hand O

The invention further relates to use of the aforesaid ^dia Eeteraddukte as additives in Sohmiermitteln and fuels mentioned ₀ How are suitable calibration Eeteraddukte the like serving as Ausgangeprodukte esterification itself for these purposes ,, in which they act as detergents or Dispersante ₀ When using of the ester adducts as additives in lubricating oils, they are usually used in proportions of about opi to about 50 percent by weight, based on the lubricant, usually about 0.5 to about 10 percent by weight; under very unfavorable operating conditions, such as the operation of certain engines, it can reach up to about $ 30> the lubricant weight.

909845/1565

When used in lubricating oils, the Eeter adducts can be used for calibration or together with other diepersants or detergents. The lubricants can additionally for "B _e rust inhibitors, öxydationsinhibitoren ,, Viecoßitäte index Verfcesßerer and extreme pressure additives Examples included for these other additives are described in the aforementioned patents specified X) Ie ester adducts, both in lubricants based on mineral oils" doh ", petroleum distillates a viscosity »the. their use as lubricants allowed to be used »as well as in those based on synthetic oils» Since the lubricants based on mineral oils predominate, this is where the main area of application of the ester adducts lies.

In power "and fuels, the Bster adducts of the invention make it easier to keep the engine clean by reducing or preventing harmful deposits in the fuel system, in the engine and in the exhaust system." They are primarily intended for use in petroleum distillate fuels and fuels that are liquid under normal conditions, doh, those petroleum distillates that _{boil in the range characteristic of fuels such as gasoline, heating oils 9,} diesel fuels, aviation fuels and kerosene. and fuels, the esters are usually used in lower concentrations than in lubricants; B z ₀ are "in proportions of from about 0.001 to about 2 contained 6 © w _o -56 and preferably from about 0.01 to about 1 percent ₀ ~ # _o The fuels may contain other commonly used additives examples of lead cleaner Enteisungsmlttel , Means to prevent clogging of oil filters and demulsifiers,

9 09845/156 5

The examples explain the invention · ropes and percentages are trained on the weightο

example 1

Bin ester is prepared by reacting 600 Teil® © ines by a polyisobutenyl group substituted with a Bernsteinsäureashydrids Durchschnittsraolekulargewieht of 1100 in nitrogen flow over 17 hours at 150 to 16O ⁰ O 230 Pro ^ropes! 'Pylenglykol with a Durchschnittsmolekulargewieht of 425 g the presence of 547 parts of a mineral oil transposed 32.8 feile a commercially available acidified clay adds the mixture in a nitrogen stream a further 11 hours around 200 ⁰ C © rhitzt "ad filtered The filtrate is an öllösimg of desired ester.

This Flltrat be incorporated 43 _B 2 T © ile propylene oxide, the mixture heated 17 hours at 85 bie 90 ⁰ G and up au 85 ^Q 0/80 Torr of volatile content © *! Tb © f £ © ite The obtained © ßeiileeh is an oil solution of the propyleno2qrd & ddukts d®e ester ₀

Example 2 ⁽

(A) 3240 parts of a high molecular weight carboxylic acid ®it a Durchschnittsmolekulargewieht of 982, dmroli prepared reacting 1 equivalent of chlorinated polyisobutene ^ 1! Equivalent of acrylic acid ρ within ron 90 minutes © iner temperature b®i 115-125 ° C in a mixture from 200 ropes sorbitol and 1000 parts of a solvent serving oil eing © · »tragenο then the mixture further 400 cable © oil as solvent incorporated the mixture is heated in a nitrogen stream 16 hours approximately 195-205 ⁰ C, and then with 155 parts of oil verse did cooled to 140 ⁰ C and filtered "This is a FiItrat

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- 18 oil solution of the ester ₀

(B) The abovementioned ester is incorporated with Propylenosyd MEges @ "& st _f " ind @ i man 108 parts of propylene oxide at a temperature of 80 fei a 90 ⁰ Q 5 105 parts of the filtrate and 25 parts of Pyriiisi, the mixture for 2 to 3 hours 110 -to 12O ⁰ G 17O ⁰ G / 15 Torr contains volatile components «Mixture is the epoxy compound of the ester»

(A) Am mixture of 658 parts of a GaElboasatiye with © ia © n average molecular weight produced from 1 .018 ₈ äusQh uaee of chlorinated polyisobutene with Acrylaäwre _s wad 22 parts of pentaerythritol 18 hours in Stio & substance Troy to 20§ ° G heated to about 180 ο on afegeküiilt about 90 ⁰ C and 14 ieile Ifhjlenoxyä slowly over 2 hours at 90 to XOO ⁰ G © ~ eing bear ₀ then be the Geaiscsii, within 4 1/2 hours at about 190 to 200 ⁰ C more © 16 parts With the ethylene oxide slowly incorporated, keep this temperature for a further 2 hours, the mixture is freed of volatile components up to 150 ° C / 18 Torr and then filtered. The filtrate is an oil solution of the ethylene oxide adduct of the ester »

(B) The ester is geiaäes 5 (A) with Epiohlorhydrin coll © _s SetAt said Ithylenoxyü is replaced by the equivalent amount of epichlorohydrin "

Example 4

(A) An ester is prepared by reacting 3518 parts of a substituted succinic anhydride by a polyisobutenyl

909845/1565

* t

f V f

- 19 ~

with. a Durohsohnittamelekulargewioht of 1. 100, 408 parts of pentaerythritol and 2445 ropes Ul ale solvent S hours to ISO ⁰ O and aneohliessend weitexe 5 hours at 200 ° to 210 ⁰ C erhitet · The mixture is filtered, dae Piltrat iet a · öllöaung the petitioner.

(B) The ester of 4 (A) is reacted with an epoxide by heating the filtrate to about 8O ⁰ O, within 4 hours up to 80 to 90 ⁰ C 123 ropes of propylene oxide, since @ Qenieoh after the addition is complete the Propylenoxyds further 3 hours at 80 to 9O ⁰ C. and freed schlieselich to eu 150 ⁰ C / 20 Torr of volatile .Anteilen gives a Ölluaung of propyl © nexydaädi & i3 © s · dee-Saters

Example 5

According to example 1 always m @ a 1! ^! "Gmlent @ in © s by a polyisopropenyl group with an average molecular weight of 750 substituted muartinic anhydride with 3 equivalents Mannitol to »Sine oil solution containing 1,000 parts of the ester, is reacted with 145 ropes of butylenozyme

Example 6

According to Example 3 (A), the ester is used in an equivalent amount Styrene oxide instead of ethylene oxide

Example 7

Sin ester of Example 4 by the simultaneous reaction of 1 mole of a polyisobutenyl substituted by a © BernBteinsäureanhydride with an average molecular weight of 3 0 _s 2OC with 5 moles of glycerol and 0.5 mole of pentaerythritol manufactured

909845/1565

represents and the obtained chandelier »from the 1,000 ropes in one 40 jk-igen oil solution are contained, is converted with 58 ropes of propylenozyd. ,

Example 8

An ester is prepared by reacting 2,000 ropes of the '... · carboxylic acid from Example 2 (A) and 1,200 ropes of the anhydride from Example 1 with 300 parts of sorbitol in 1,400 parts of oil according to by -. Game 2 (A) produced. The filtrate is then made up of 300 parts Propylene oxide is added and the procedure is followed according to Example 2 (B)

Example 9

An ester is aue 1000 parts of the. Carboxylic acid of example 2 (A) and 92 parts of glycerol hergeetellt and then reacted with 180 parts of propylene oxide according to Example 2 (A)

Example 10 The ester of Example 4 (A) is mixed with 100 parts of propylene oxide

and 25 parts of epichlorohydrin according to Example 4 reacted

Example 11

A mixture of 340 g (0.3 Hol) of an alcohol, prepared by copolymerizing equimolar proportions of styrene and allyl alcohol to form a copolymer with a molecular weight of 1,150 and an average content of 5 hydroxyl groups per molecule, 1.5 mol of the succinic anhydride, which is substituted by a polyisobutenyl group according to Example 1 and 500 g of xylene is heated to 80 to 115 ° C, diluted with mineral oil, heated further to remove the xylene and filtered. The filtrate is Bückflusß at 70 to 15O ⁰ C and about 1 equivalent of propylene oxide

909845/1565

per equivalent of the alcohol component and diluted with oil to form a solution with an oil content of $ 40

Examples A to I describe the use of the ester adducts the invention in lubricants "as well as fuels and fuels",

Example A.

SAE 20 mineral oil with a content of $ 1> of the product of Example I ₀

Example B.

SAB 30 mineral oil containing Oj 4 ί> of the product of Example 2 (B) and 0.15 # of the zinc salt of an equimolar mixture of dicyclohexyldithiophosphate and diisobutyldithiophosphate

Example C

SAS IOW-30 mineral lubricating oil containing 4 # of the product of Example 3 (A) ₀

Example D '^

SAE 10W-30 mineral lubricating oil with a content of 1.5 J * of the product of Example 4 (B) ₉ 0.075 & phosphorus in the form of the adduct, as obtained by heating dinonyldithiophosphate with 0.25 moles of hexene-1,2-oxide 100 ⁰ C is obtained, 6 i » a viscosity index improver based on polyisobutene ait an average molecular weight of about 100,000, 0.005 # polyalkyl methacrylate as antifoam, 0.5 & Speok oil and with the addition of a sulfonated methyl ester of tall oil fatty acid with a Sulfur content of 15 3 »o

909845/1565

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Example p

SAE 20 mineral lubricating oil with a content of 2.5 of the product of Example 4 "0.75 i" phosphorus as Diootyldithiophoephat, 2 fi of a barium Detergents prepared by neutralization aine β hydrolyze the reaction product of polypropylene having a molecular weight of 2,000 with 1 Hol phosphorus pentasulfide and 1 pint of sulfur through barium hydroxide. 3 fi of a barium-Detergents, prepared by treating a mixture of a mineral W ralöllösung mahogany acid and a 5 ^ strength stöehiometrischen excess of barium hydroxide with carbon dioxide at 180 ⁰ C in the presence of octyl phenol as an accelerator, and 3 # of additional ashless Uispersants, produced by copolymerization of a mixture of 95% by weight of deeyl methaorylate and 5% by weight of diethylaminoethyl aorylate.

Example P

Sin lubricant based on di-2-ethylhexyl sebacate containing £ 0.25 of the product of Example 2 (B).

Example G

Diesel fuel with a content of 0.2 56 of the product of

Example 4 « Example H

Kerosene containing 0.15 # of the product of Example 1

Example I.

Benain with a content of 0 »003 36 of the product of Example 4»

90 9845/1505

Claims (1)

Claims Process for the preparation of adducts from esters of high molecular weight Carboxylic acids with epoxides, characterized by i ο h η e t that one (a). at least one ester of a high molecular weight mono- or polycarboxylic acid of the general formula I. R (-QOOH) _n (I) containing in which R is an at least about 30 aliphatic "C-atoms Kohlenwasseret> Z frest with a Durohsohnittemoleku ^ largewioht of about 700 to about 100,000, which has at least 80 i> saturated bonds, and η is an integer from 1 to 6 , with a polyhydric alcohol that has 2 to 10 hydroxyl groups and up to 40 aliphatic carbon atoms, with (b) contains at least one 2 to about 40 aliphatic carbon atoms epoxy of the general formula II R ¹ - CH - CH - R ² . (II) 1 2 in which B and R, hydrogen atoms or optionally substituted, aliphatic, cycloaliphatic or aromatic Hydrocarbon radicals are converted by methods known per se in proportions such that 1 equivalent the alcohol component of the ester corresponds to 0.05 to 5 equivalents of Ep « Method according to claim 1 _f, characterized in that the epoxy used is an aliphatic epoxy with 2 to 8 carbon atoms 9098 ^ 5/1565 3c method according to claim 1 and 2, characterized in that an ester is used, its The radical R of the high molecular weight carboxylic acid has a Durohsohnittsmolecular weight of about 700 to about 5,000 · 4ο method according to claim 1 to 3 _t daduroh characterized in that an ester is used, its Best R of the high molecular weight carboxylic acid has at least 95 i » saturated bonds o 5 «The method according to claim 1 to 4, characterized in that the ester used is an esterification product of a monocarboxylic acid 6. The method according to claim 1 to 5 »characterized in that the ester used is an esterification product of a polyhydric aliphatic alcohol with up to 10 carbon atoms and with at least 3 hydroxyl groups. 7 «A method according to claim 6, characterized in that reacting an ester whose polyhydric alcohol component up to 6 carbon atoms derived from a polyhydric alkenol with, and used as the aliphatic epoxide ethylene oxide or propylene oxide _t and so dimensioned play esters having epoxy, that 1 equivalent of the alcohol component of the ester corresponds to about 0.1 to about 2 equivalents of epoxide. β ο A method according to claim 7, characterized geke η η -zeichnet "that as polyhydric aliphatic alcohol glycerol, erythritol, pentaerythritol, mannitol or sorbitol used _c O 909845/1565 9 »Process according to claims 1 to 4 _S, characterized in that the ester οin esterification product of a dicarboxylic acid is used« Method according to claim 9 »characterized in that that the ester is an esterification product of a substantially saturated ,, at least about 50 substituted hydrocarbon radical containing aliphatic carbon atoms Used succinic acid 11 »The method according to claim 10, characterized in that the ester is a diester of a polyolefin radical containing no more than about 5 ° unsaturated bonds and having a molecular weight of about 700 to about 5,000 substituted succinic acid used. 12 ο method according to claim 11, characterized in that that the ester is an esterification product of a polyhydric aliphatic alcohol with up to 10 carbon atoms and at least 3 hydroxyl groups are used. 13 ο Method according to claim 12, characterized in that one is an ester, its polyhydric alcohol component from a polyhydric alkanol with up to 6 carbon atoms, and ethylene oxide or propylene oxide is used as the aliphatic epoxy, and so many proportions of ester are reacted with epoxy that 1 equivalent of the alcohol component corresponds to about 0.1 to about 2 equivalents of epoxy « 909845/1565 ■ - 26 - Η "The method according to claim 13, -. T ge characterized characterizing, daQB * the ester is a diester of a substituted by a polyisobutenyl succinic acid with Glyoerinj erythritol" pentaerythritol mannitol or sorbitol is ₀ 15 «Use of the process products according to claims 1 to 14 as additives in lubricants, as well as in fuels and fuels, 90II4I / 1SII