DE2418514A1 - METHOD OF MANUFACTURING LACTONE ACID SALT OR SOAP AND USE OF THE SAME - Google Patents

Description

»ATE M TA N WXlTi

DR. E. WIEGAND DiPL-NG W. NIE / AANN

DR. M. KÖHLER DIPL-INO. C. 3ERNHARDT 24 1 85

MÖNCHEN HAMBURG TELEPHONE: 35547 «8000 M Π N C H E N 2, TEtEGRAMS. KARPATENT MATH I ID ENST * ASEF 12 TElEX: 5: ϊΟ48 ΚΑΧΓ D

April 17, 1974

W 4-1 935/74 3 / fcr

Mobil Oil Corporation New York, N.Y. (V.St.A.)

Process for the production of lactone acetic acid salts or soaps and the use thereof

Addition to the patent

(Patent application P 22 63 W-8)

The invention relates to lactone acetic acid compounds derived from alkenyl succinic anhydrides.

In the patent application P 22 63 547.8 were Lactone acetic acid compounds described by reacting lactone acetic acids with an amine or an alkali or both. Depending on the amine or alkali used and Various products can be obtained under the conditions used. It can be opening the Lactons occur and in certain cases a conversion to a lactam can occur through reaction between the lactone and an amine.

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The lactone acetic acids used as starting materials are obtained by hydrolysis of an alkenyl succinic anhydride produced under acidic conditions.

It has now been found that the esters or thioesters of lactone acetic acids instead of the Acids themselves, can be used.

The present invention is therefore directed to the reaction product of a hydrocarbon- substituted V ~ -butyrolactone acetic acid ester or thioester and an alkali metal compound, an amine or both.

As in the patent application P 22 63 54-7.8 described ^ the reaction products may include two different types, namely those in which the ß-carbon atom of the lactone ring is not organic Bears substituents (type 1), and those in which it is substituted by an organic radical (type 2). The low molecular weight type 1 carboxylates are exceptional as hard water soaps or detergents effective »while the high molecular weight Type 2 products or their metal complexes in organic industrial liquids as dispersants or detergents are used.

According to patent application P 22 63 547.8 the alkenylsuccinic anhydrides under acidic conditions with the formation of free lactone acetic acid hydrolyzed. According to the present working method

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the anhydrides react with an alcohol or a mercaptan in the presence of an acidic Catalyst implemented. The product obtained is an ester or thioester of lactone acetic acid. This reaction is described in patent application P 22 63 547.8.

The reaction between the alkenyl succinic anhydride and the alcohol or mercaptan is an acid catalyzed esterification and lactonic acidification. This reaction is preferably carried out under reflux conditions for about 1 to 15 hours. It can be specified as follows:

R - CH =

+ R "« I XH

R '

R-CH ₂ -C

R "

CH

CH - CH -

C-X

- * P

In the general formulas above, R, R ¹ and R "denote hydrogen atoms or hydrocarbon groups with 1 to about 300 carbon atoms (see patent application P 22 63 547.8), X oxygen or sulfur, R" ¹ hydrocarbon groups

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and ρ is 1 or more, preferably 1 to 4. When ρ is larger than 1, R " ^{1 is} correspondingly multivalent.

R " ¹ [xsl can be a simple alcohol or a simple mercaptan, such as methanol, ethanol, propanol, butanol, pentanol, neopentyl alcohol, hexanol, decanol, tetradecanol, fiexadecanol, eicosanol, benzyl alcohol, cyclopentanol, cyclohexanol, methyl mercaptan, ethyl mercaptan , Propyl mercaptan, halogen-substituted alcohols such as chloroethanol or iodoethanol, polyhydroxy alcohols are also suitable Butane, 2,2, 1-trihydric oxymethyl butane, 2,2-dihydroxymethy_butanol-1 (also referred to as trimethylolpropane), pentaerythritol, ether alcohols (where R " ¹ contains ether bonds), such as cellosolve or methyl cellosolve.

Any highly dissociated anhydrous acid can be used as an acidic catalyst for the reaction such as phosphoric acid, polyphosphoric acid, sulfonic acid, arylsulfonic acid (p-toluenesulfonic acid), Phosphonic acid and hydrogen halides ·. The heterogeneous However, liquid catalysts are preferred. Cationic exchange resins are particularly used preferred as they are very effective and convenient to separate from the reaction mixture allow. Also suitable are crystalline aluminosilicates which are at least partially in the hydrogen form are present, as well as zeolites and synthetic ones

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IGIHAL INSPECTED

241S5H

Aluminosilicates, especially with such carriers as aluminum oxide, vanadium oxide, titanium oxide, chromium oxide, Comium oxide-aluminum oxide and zinc oxide; as other oxides and sulphides, such as phosphorus pentoxide, Iron sulfide and nickel sulfide.

Of the preferred ion exchange resin catalysts, the strongly acidic resins are, in particular the sulfonic acid resins, but also the phenol sulfonic acid resins and phosphonic acid resins very effective. These acidic functional groups are bound to a resin matrix, like a Phenolic resin, a crosslinked styrene-polymer among Use of any crosslinking agent, e.g. a polyfunctional monomer or partial polymer, like a styrene-divinylbenzene copolymer. Other Matrices such as acrylates, polystyrene, chlorinated styrene polymers and the like are also suitable. Sulphonated charcoal can even be used.

In a simplified representation, the esters or thioesters can be represented as follows:

R 'R "

RCH ₀ - C - CH O

^d '' Il

- (0R _£

W.
O

wherein R is the Eest derived from the alcohol or the mercaptan with normally 1 to 20 Eohlen-

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ORIGINAL SWSPECTtD

2 ^ 18514

material atoms, preferably 1 to 6 carbon atoms, represents.

The conversion of the anhydride to the ester or thioester becomes the conversion to the free acid
preferred because the anhydride is converted to the lactonic acid compound in only one step with a yield which can be as high as 90% or more. The ester or thioester can be used directly with the alkali
or amine can be reacted to form the desired products, or they can first be hydrolyzed back to the lactonic acid.

The reaction of the two types of lactonic acid ester or thioester with the alkali or amine or both are discussed below.

Type 1 products (unsubstituted on the β-carbon atom of the lactone ring)

The lactone acetic acid ester or thioester
can be reacted with a mild alkali metal compound or an amine that does not open the lactone ring. A strong alkali, such as sodium hydroxide, can open the lactone ring. The obtained urodium soap, which is produced by hydrolysis of the ester group, can, while having soap properties, in hard water by calcium or
Magnesium will be precipitated. For this reason, it is preferred to first treat the esters or thioesters of Type 1 with an amine to form a lactone amine salt or upon further heating of a lactone

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amids to implement. A strong alkali, preferably sodium hydroxide or another alkali hydroxide, can then be reacted with the intermediate to open the ring, wherein a metal carboxyl group on the 3-carbon atom of the carboxylate is arranged as in the general formula below

_ ^Rt

R-CH ₂ -C - CH ₂ -CjH ₂ -CH ₂ -C-ITH-

OH

where the free valence is the remainder of the amine reactant and M is an alkali metal. Becomes a secondary amine is used as a seactant, the amino hydrogen is replaced by an organic group, generally alkyl. Products of this type are used as detergents in aqueous systems very suitable.

Furthermore, those products are important in which the metal or amine salt or amide (by further heating of the amine salt) followed by ring opening with an amine in place of the metal reactant. The alkali metal component is used as the initial reactant in this variation preferred. The most suitable alkali reactants include alkali carbonates and bicarbonates, e.g.

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ORIGINAL SMSPECTED

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bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate and lithium carbonate, and also metal hydrides, like lithium hydride. The initial reaction with the alkali neutralizes the acetic acid part of the molecule without opening the lactone ring.

This reaction can be carried out in the presence of polar solvents such as water, monohydric and polyhydric alcohols and ethers with about Λ to 6 carbon atoms such as methanol, ethanol, propanol and dirnethoxyethane, inert hydrocarbons such as toluene or benzene, and tetrahydrofuran and mixtures thereof will. Lithium hydride is preferably used in tetrahydrofuran. A water-methanol mixture is a suitable solvent system. ' The products obtained have cleaning properties and form foams in water, although they are also precipitated by calcium.

The amines that are useful at this stage of the reaction sequence include both primary and secondary amines also secondary alkylamines, cycloalkylamines and aralkylamines, ethylene polyamines and alkanolamines and Ethyl oxy Ii er te alkanolamines (which are first with ethylene oxide implemented). The amine reactants can have 1 to about 20 carbon atoms and between 1 and 'have about 10 nitrogen atoms.

The soaps or amides produced by the initial reaction between the ester (or thioester) and the mild alkali have the following

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general formula:

R '

R-CHp-C CH

O CH-CH ₂ -C- (OM) or, (χ)

wherein M represents an alkali metal or substituted ammonium of the amine reactant. Under Under certain conditions the amine reactant yields a lactonamide, where X is the amino group.

The soaps or amides can then be reacted with an amine to open the lactone ring. The carbonyl group of the lactone forms an amide with the amine.

The amines that are suitable for this stage of the reaction can be any amines containing a -KH group have, be, such as an alkyl, cycloalkyl, aralkylamine and the like with between 1 and about 20 carbon atoms, e.g. methylamine, ethylamine, diethylamine, Propylamine, dipropylamine, hexylamine, dodecylamine, Cyclohexylamine, benzylamine and polyamines, in particular Ethylenepolyamines, such as ethylenediamine, diethylenetriamine, Triethylene tetramine and tetraethylene pentamine. This second amine can be the same as that used in the previous step. Of particular interest are the alkanolamines, such as

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ORIGIN ¹ - INSPECTED

Dietbanolamine and Monoethanolamine, which is the most preferred reactant for making aqueous soaps and detergents. This second reaction can be carried out in the presence of any solvent used in the previous reaction or in a non-polar solvent, depending on the reaction temperature desired. The reaction mixture may preferably be boiled to about 175 C at reflux at temperatures in the range of above room temperature, about 30 C, up to 250 ⁰ C. The reaction with monoethanolamine allows an equimolar reaction, ie one mole of amine per mole of metal salt or amine salt.

The product of this reaction sequence is a 5-hydroxycarboxylate of the general formula:

R ^!

R-CH ₂ -

C - CH ₂ -CE-CH ₂ -C- (CM) or- (X) OH C

-L

in which M and X have the meaning given above. One of the most preferred compounds of the! Type is

R-CH ₂ -CH-CH-Ch-CH ₂ -C-OM OH C = O

HN-CH ₂ -CH-OH

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GMM- I5MSPE

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in which E is an alkyl group with 5 to 25 carbon atoms, E 'are hydrogen and M are sodium. the Metal hydroxyamides are so effective in hard water that they are not precipitated in the presence of high concentrations of calcium or magnesium.

The preferred reaction product can be further ethoxylated with ethylene oxide to form ethoxylated Connections are implemented. Ether groups attach to the ethanolamine part of the molecule and give the soap additional hydrophilic properties. 1 to 20 moles of ethylene oxide per mole of hydroxy-_ amide soap can be deposited. The reaction can be carried out at low temperatures, using a liquefied ethylene oxide feed. The ethano1amine reactant can also be used before Eeaktion mit.der Metal 1 actonic acid soap pre-ethoxylated be.

Type 2 products (organic substituent on the ß-carbon atom of the lactone ring)

The second type of product according to the invention is in organic industrial liquids suitable as lubricating oils, greases, fuels and transfer fluids. The lactone ring of the ester • and thioester of type 2 is produced by the subsequent reaction with amines or alkalis to form the 5-hydroxycarboxylate product does not open easily.

The preferred Type 2 products are those

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241 351

in which the lactone ester or thioester with an amine with at least one -ITH group in one Temperature between 125 and 300 G, preferably between 175 and 275 ° C to form a lactonamide or lactamamide of the following general Formula is implemented.

R 'R "

R-CH ₂ -C -CH

C-CH -C-NH- ^or

R 'R "

I I

R-CHr, -C-CH

] ι

». C-CHp-C,

/ N ₃ / I

^ C-CH ₀ -C-NH-C- "

In the above formulas, E "denotes a hydrocarbon group, preferably an alkyl group, R and R ¹ can be hydrogen or hydrocarbon groups, R, R ¹ and R" containing a total of about 30 to about 300 carbon atoms. The product (a) is obtained by reacting one -KHo group per mole of lactonic acid or ester. That

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241SGU

Product (b) is produced by the reaction of two -IiHp groups per Hol lactonic acid or ester formed.

The preferred amine reactant used to make from. Dispersants or detergents used for organic compositions is alkylene polyamine of the formula HoN- (C HoJSH) -H, in which m one integer from 2 to 4 and η an integer from 1 to 10, preferably 1 to 6, are. Preferably is m 2 and the amines are ethylenediamine, diethylenetriamine, Trietbylene tetramine, tetraethylene pentamine, Pentaethylene hexamine and the like. However, it can also Monoamines with between 1 and about 30 carbon atoms are used, such as alkylamines, e.g. methylamine, Ethylamine, butylamine, cyclohexylamine and the like., and aralkylamines, e.g., benzylamine.

When the preferred polyamines are used, the final reaction product may contain the above structures and the polymers thereof, poly (lac tarn) amidomolecules having up to above 3000 carbon atoms. When P is the divalent polyamino group - (C _1n H ₂₁₁₁ WH) _n-1 -C ₁₁₁ H ₂₁₁₁ -, LA is a divalent lactamamido group

R 'R "

R-CH-C CH

I LJL

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ORIGINAL INSPECTED

24185U

and AL is a divalent amidolactam

I »Ot

C - CH ₂ -R

mean, then the following products can be present in the reaction mixture: P-LA-P-AL-, -P-LA-P-LA-, -P-AL-P-LA-, -P-AL-P-AL-, -P-AL-P-LA-P-AL-P-AL-, -P-LA-P-LA-P-AL and the like. The lactonamides of the polyamines can under the conditions according to the invention with the formation of bis (lactone) amides react. If the same amine is used to form both the amide and the lactam, the Addition of the amine to the lactonic acid or ester can be carried out in a single stage. Both the lactone and the lactamamide are in organic compositions effective.

The metal actamäuresalze can also by reacting the lactone ester or thioester with an alkali metal compound and subsequent reaction with an amine. Will e.g. tetraethylene pentamine as an amine and a sodium salt the lactonic acid is used, the reaction products can have the following structures.

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2413514

R »R"

I I

R-CH ₀ -C -CH

² II

".. and

c /

CH - C-CH ₀ -R R-CH ₀ -C -CH NaO-C-CH ₂ -CH N- (C ₂ H ₄ NH) C ₂ H ₄ -IT J ^ H-CH ₂ -C-ONa

Il Ύ

. -ο ο

These monomeric and polymeric lactones and lactam products and the above-mentioned high molecular weight salts also have detergent and dispersant properties in lubricating oils and other organic liquids. The preferred amine for the preparation of the high molecular weight lactone and lactamamides is, as stated above, tetraethylene pentamine.

The lactone and lactamamides can form complexes with metal compounds, in particular with metals from Group IIB and VIII of the Periodic Table of the Elements, such as zinc. Of particular interest are zinc salts of organic acids and

409846/108 ORIGINAL INSPECTED

24'O

Phenates, such as zinc arboxylates with 1 to 20 carbon atoms, Zinc methanesulfonate, zinc hydroquinones and zinc phenates. Alkyl substituted phenates and Hydroquinones in which the alkyl groups contain 1 to about 25 carbon atoms can also be used be used. The complexes can be obtained by adding the zinc salt to the reaction mixture Containing lactone or lactamamide, or the amide can be added to the organic medium, such as a lubricating oil, mixed in first and then the zinc salt added. The amide and that Salts are warmed gently with stirring until the solution occurs.

It should be mentioned that the initial reaction between the ester or thioester and the Amine (as opposed to the alkali metal compound) usually has a substituted ammonium salt result in both types of lactonic esters (or thioesters) would. However, under high temperature conditions, the amide forms on the acetic acid portion of the Molecule. Both simpler and more complicated polymer molecules can also be used in the reaction mixture are present.

The invention is explained in more detail below using examples.

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ORIGINAL INSPECTED

example 1
Production of lactone acetic acid ester

In one with a reflux condenser, stirrer and Thermometer-equipped 5-liter flask were installed 1220 g of a reaction product between polybutene with a molecular weight of about 1300 (about 93 Carbon atoms) and maleic anhydride introduced. About 700 g (0.5 mol) of the amount introduced is alkeny / succinic anhydride, with the remainder being unreacted Is polybutene. 1200 ml of n-octane were added over low heat (about 50 ° C.) and stirring for formation a solution was added, followed by 46 g (1.5 moles) of methanol and 150 g of an ion exchange resin Sulphonic acid on a vinyl divinylbenzene copolymer matrix in pearl form. The mixture was refluxed with stirring for 12 hours. The received Solution was separated from the beads and filtered.

When the solution was distilled under atmospheric conditions, 32 g of methanol and the n-octane withdrawn. The remaining 1,236 grams consisted of 520 grams of polybutene and approximately 71 grams of the methyl ester the corresponding lactone acetic acid. The infrared spectrum showed about 90% gamma-butyrolactone ester . and about 10% of a delta-lactone ester.

Example 2

Preparation of lactone acetic acid ester 100 g (0.34 mol) were added to a 500 ml flask.

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η-Tetradeceny / succinic anhydride, 16.3 g Introduced (0.5 ^ mol) methanol and 250 ml of n-octane. The reaction mixture was taking at about 70 G Stirring heated to reflux. The temperature rose to 80 C and was at this value for two hours held. Octane and excess methanol were stripped off, whereby IO5 g of the half-ester of the n-tetradeceny! succinic acid remained.

In a sealed pressure vessel, which 47 g of said hemiester, I5 of the SuIfonsäureharzkatalysators g of Example 1, 50 ml n-0ctan and 10 drops containing methanol, the reaction mixture was stirred for 3 hours and heated to 125 ⁰ C. The mixture was then cooled, diluted with ethanol and the catalyst filtered off. Ethanol and octane were evaporated, 41.6 g of the methyl ester of the corresponding lactonic acid remaining.

Example 3 Preparation of lactone acetic acid ester

A mixture of 16.5 g of a lactone ester obtained by reacting methanol with a polyisobutenyl succinic anhydride with an average molecular weight of 1400 under similar conditions as in Example was, and 12.3 g of polyisobutene, which was used to make the anhydride, was in 40 cm ^ n-octane in a reaction flask which is equipped with a

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2A185U - 19 -

Reflux condenser and a Dean-Stark trap equipped; was solved. 0.53 grams of trimethylol propane and 2.0 grams of the sulfonic acid resin catalyst were added.

The reaction mixture was stirred and refluxed. Infrared analysis showed that all of the hydroxyl groups of the trimethylolpropane had reacted . The octane-polyester solution obtained was washed three times with water and the octane was distilled off .

Example 4
Production of lactone acetic acid ester

A mixture of 69.5 S of the lactone ester of Example 3 and about 36.1 g of polyisobutene was placed in a reaction flask. To the mixture 2.3 g Irimethylolpropan and 1.0 g of p-toluenesulfonic acid were added. The reaction mixture was stirred and heated to 125 ° C for 4-1 hours. An additional 0.77 grams of trimethylol propane was added. The reaction was carried out for an additional 29 hours. The InfrarotanaIyse showed that all the hydroxyl groups had reacted to form the polyester exchange product and also that part of the lactone rings a reaction to form Esterbindungen was received. The polyester was then treated like the polyester solution of Example 3.

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2 A 1 rj 1

Example 5
Production of lactone acetic acid thioester

In a reactor similar to that of Example 3, 35 g (0.0235 mol) of polyisobutenylsuccinic anhydride prepared from a polyisobutene having a molecular weight of 1,300 and 17 g of unreacted polyisobutene and 25 ml of n-octane were charged. The anhydride was dissolved in the octane with stirring with moderate heating. To this solution were added 3.62 g (0.0247 mole) of 1-octanethiol (5% excess) and 7.5 % of the sulfonic acid resin catalyst used in the previous examples. The mixture was stirred for 8 hours under nitrogen and heated to 120 ° C. Octane and excess thiol were stripped off in vacuo, leaving 53 g of full product (including 17 g of olefin). The presence of the thioester was confirmed by infrared spectrum.

Example 6
Production of lactone acetic acid ester

Put into a reaction flask equipped with a water trap and a condenser 105 g (0.075 mole) of an alkenyl succinic anhydride with an average molecular weight of 1400, 12.4 g (0.095 mol) of n-octyl alcohol, 100 ml of n-octane and 15 g introduced a sulfonic acid resin catalyst. The reaction mixture was stirred for 3 hours and on Boiled under reflux. Additional 6.2 g (0.047 moles)

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ORIGINAL INSPECTED

2Λ1 r ^s "Γ. 1

n-Octyl alcohol was added and the boil the reflux was continued for a further 4 hours. The reaction mixture was cooled, filtered and the octane solvent evaporated. The infrared analysis of the product showed complete conversion of the anhydride to the octyl ester corresponding lactonic acid.

Example 7 Preparation of lactone acetic acid ester

Using a procedure similar to that of Example 1, 20 g (0.068 mole) n-Tetradeceny! succinic anhydride in n-octane dissolved with heating and stirring, and 7.35 S (0.072 mol or 6% excess) n-hexyl alcohol were added followed by 15 S sulfonic acid resin catalyst. The reaction mixture was refluxed at 120 to 125 ° C. To The infrared spectrum showed no for 3 1/2 hours remaining anhydride. Heating continued overnight. The conversion was complete. The product was filtered off through the KatyIysators and evaporating off the n-octane isolated.

Example 8 Hydrolysis of the Ester to Lactone Acetic Acid

In a 250 ml flask with a air-cooled Vigreux column and a condenser, 50 g of lactonic ester, similar

409846/1081 ORIGINAL INSPECTED

that of Example 2 (prepared by reacting the semi-methyl ester of n-tetradeceny / succinic acid with a sulfonic acid resin catalyst ) and 100 cwP of Gn-hydrochloric acid. The reaction mixture was stirred and refluxed until 70 ml of distillate was collected. The residue was dissolved in chloroform, dried with anhydrous sodium sulfate and the solvent was evaporated. Infrared analysis of the product indicated that the ester had been completely hydrolyzed to form the lactonic acid.

Example 9
Hydrolysis of lactone acetic acid

The ester of Example 2 was hydrolyzed with hydrochloric acid and the lactonic acid obtained in in the same way as in Example 4 of patent application P 22 63 547.8 with formation of sodium-3-hydroxyethylamido-5-hydroxy-heptadecanoic acid implemented.

Example 10 Conversion of lactone acetic acid ester with 1 min

In a 4-neck flask equipped with a Dean-Stark trap under a cooler, thermometer, The stirrer and nitrogen inlet tube were 1620 g of a reaction product, which was prepared in a similar manner as was prepared according to Example 1, of which about 58% by weight is the methyl ester of alkyl-gamma-butyrolactone acetic acid (0.648 mol) and the rest of the polybutene

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O / ^Λ - ο '. "1 / / As. Jj

and 122.7 S (0.64-8 moles) of tetraethylene pentamine were introduced. The reactor was purged with nitrogen and sealed under a nitrogen atmosphere. The contents of the flask were stirred and heated at 14-0 ⁰ C. After 4 hours at this temperature, the temperature was increased to 220 ^° C., methanol being collected in the trap. The mixture was held at this temperature for 20 hours. The yield of the reaction product was 1720 g.

Example 11
Implementation of Lactonessigsaureester with amine

Using the apparatus and procedure similar to that of Example 10, a mixture consisting of 74-7 g of a reaction product (1) prepared in a manner similar to that of Example 1 except that the alkyl groups contained about 64 carbon atoms, wherein this product consists of 81% by weight of the methyl ester of alkylgamma-butyrolactone acetic acid (0.575 mol) and the remainder of polybutene, and 851 g of a reaction product (2), prepared as described in Example 8, except that the alkyl groups of the lactone ring "are approximately 190 carbon atoms, this product containing about 4-7.5% by weight of the methyl ester (0.144 moles). To this mixture was added 136 g (0.719 moles) of tetraethylene pentamine and the reaction mixture was allowed to run under nitrogen for 4 hours 140 ⁰ C heated and 20 hours

409846/108 V. INSPECTED

241R5H

heated to 220 ° C. with stirring. The yield of the reaction mixture was 1710 g.

Example 12

Implementation of lactone acetic acid thioester with amine

The thioester of Example 5 was with a equimolar amount of tetraethylene pentamine in the Implemented device described in Example 10, using the same procedure and the same Reaction conditions were applied.

Example 15

Conversion of lactone acetic acid ester with mild alkali and amine

A solution of the ester of Example 1 was in a 1 liter round bottom flask containing 500 ml of methanol contained, manufactured. A 20% aqueous solution of sodium carbonate was added and the mixture was refluxed under nitrogen for 48 hours. Thereafter, the solvent was removed by evaporation, leaving the sodium salt of polybutenyllactone acetic acid was obtained.

The sodium salt (0.05 mol) was then added in 100 ml Tetrahydrofuran dissolved in a 500 ml round bottom flask and an equimolar amount of ethanolamine was added. The mixture was then under for 48 hours

40984 67 108

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Nitrogen refluxed to the sodium salt of I-hydroxyethylamido ^ -bydroxypolybutenic acid to give in moderate yield.

Example 14

Conversion of Lactonessxgsaureester with mild alkali and amine

The methyl ester of Example 2 was used neutralized with an aqueous sodium carbonate solution, the procedure described in Example 13 was used to prepare the sodium salt of the corresponding To give lactone acetic acid in high yield.

The sodium salt (0.05 mol) was then added in 500 ml Tetrahydrofuran, as described in Example 13, added and an equimolar amount of ethanolamine added and heated under reflux for 48 hours under nitrogen to remove the sodium 3-hydro: xyäthylafflido-5-hydroxyüonadeca.noat to surrender.

Example 15 Preparation of the metal complex

A zinc complex was prepared by mixing the lactamamide, which was prepared in a manner similar to that described in Example 10, into a mineral lubricant mixture at a concentration of about 5% by weight. The oil mixture was heated with stirring to about 60 ⁰ C and the zinc salt was added in an amount sufficient for a suitable entration Konz

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of zinc to worry about. The zinc salts used were (a) monozinc di (dodecyl) hydroquinone, (b) Dizinc-2,2-methylene-bis- (6-octadecylhydroquinone) and (c) monozinc tri- (octadecyl) phenol.

The zinc complexes of the lactonamides were then tested in the carbon removal test described in US Pat Patent application P 22 63 547.8 (mode of operation b) is described, examined. Same way of working To prepare the complexes, the same bis-alkenyl succinimides were used to form complexes Used for comparison purposes, the same base materials being used in each comparison. The concentration of the nitrogen-containing material, 5%, was used for the lactamamide and succinimide. The following results were obtained:

Detergent, 5% Zinc-
salt Zinc conc.
in oil
(Wt%) Distant
Deposits) Example 12 product (a) 0.062 4-8 Succinimide Ca) 0.062 25th Example 12 product 0>) 0.021 37 Succinimide 00 0.021 21 Example 12 product (C) 0.062 24 Succinimide (C) 0.062 17th

409846/1081

Claims (11)

Claim e 1. Process for the preparation of lactone acetic acid salts or soaps, characterized in that a hydrocarbon-substituted gamma-butyrolactone acetic acid ester or thioester with an amine and optionally an alkali implements. 2. The method according to claim 1, characterized in that that the Laetonessigsäureester or thioester first with a mild alkali Formation of a lactone acetate salt and then optionally reacts with an amine to open the lactone ring and an alkali metal carboxylate salt 3-amido-5-hydroxy-carboxylic acid. $. Method according to claim 1, characterized in that that the Laetonessigsäureester or thioester first with an amine to form a Amine lactone acetate salt reacts, which then optionally is further reacted with an amine to open the lactone ring and an amine carboxylate salt 3-amido-5-hydroxy-carboxylic acid to form that then optionally heating to form an amine group from the amine salt group. 4. The method according to claim 1, characterized in that that the Laetonessigsäureester or thioester first with an amine to form a 6/1081 INSPECTED 24185H Aminlactonacetatsalzes is implemented, which then is dehydrated to form the lactonamide, which is then optionally reacted with an amine to form the lactone ring with the formation of an amide group open from the amine salt group. 5. The method according to claim 4, characterized in that reacting the lactonamide with an alkali to form the lactone ring to form an amide alkali metal carboxylate salt to open. 6. The method according to any one of claims 1 to 5 » characterized in that the amine is an alkylamine, cycloalkylamine or aralkylamine having 1 to 20 carbon atoms or is an alkylene polyamine having 2 to 10 nitrogen atoms. 7- Method according to one of claims Λ to 5 »characterized in that the amine is alkanolamine, preferably ethanolamine or diethanolamine or an ethoxylated alkanolamine. 8. The method according to any one of claims 1 to 7 » characterized in that the hydrocarbon group of the lactone acetic acid ester or thioester 5 bis Has 25 carbon atoms. 9. The method according to any one of claims 1 to 8, characterized in that the lactone acetic acid ester or thioester has at least one hydrocarbon substituent in the gamma position. 409846/1081 24185H 10. The method according to claim 4, characterized in, that the lactonamide is reacted with an amine to form a lactamamide. 11. The method according to claim 10, characterized in that the "amine" which is used to form the aniide groups and the lactam group is girl polyamine, preferably an alkylene polyamine and in particular tetraethylene pentamine. 12 · The method according to any one of claims 10 or 11, characterized in that the xactone acetic acid ester or thioesters in the B-position by hydrocarbon groups with 25 to 300, preferably 3P up to 150 carbon atoms, substituted is. 13- Use of the products made according to the method according to any one of claims 1 to 12 as a detergent or dispersant in lubricating oils and other liquid hydrocarbons. 409846/1081