DE2127175A1 - Process for the production of oil-soluble copper soaps and their use - Google Patents

Description

¹¹ Process for the production of oil-soluble copper tires and their use "

Priority: June 1, 1970, V.St.A. » Mr. 42 536.

Oil-soluble (carbon; water-soluble) copper wires sir.'l saw "? desired compounds and serve to produce l: uvii: rcontaining Hydrocarbon oils. In general, they serve to contain capers Hydrocarbon oils are obtained by dissolving an oleaginous copper soap in the hydrocarbon oil. The common ones Copper soaps are used in particular as additives in Heisrilen sur Removal or prevention of soot deposits when the oil is burned in ovens or other facilities, 2.B. in locomotives and in oil burners. These copper soaps also serve as a source of soluble copper for use as a catalyst various organic-chemical reactions in liquid phase, e.g. in the production of adipic acid. The oil-soluble copper soaps are also used in the manufacture of pun ^ inides for Oils or products that can be mixed with oil are used.

109850/1994

L'e is known j that numerous · XupferseiiOn, ζ.} -, el ie Kvfi'c.rs e if ο Ii of the sulphonic acids of petroleum :; (Mahc- £ onisi ^: .urc: :) i -: "nd the copper Gif en the ITaphthcnG ^ uren are oil-soluble. Di ο iies ^ n copper tubes underlying Sv.uren have ir. Al: <'.;::' .! ei η or, - a relatively high rolling weight, so that one should use a relatively large amount of the copper soap to manage a hydrocarbon oil with a different copper content. L's is therefore desirable to use copper soaps with a lower metallic weight Use in order to obtain a higher copper content in the solution in question for a given amount of copper soap added. In US Pat. No. 2,622,671, copper soaps of certain acids ... with a lower molecular weight

described. These copper soaps are soluble in turpentine oil in these solutions
/ can also be dissolved in heating oils. These copper soaps are derived from branched, acyclic aliphatic carboxylic acids with 5 to 12 carbon atoms, whereby the carboxyl group is not located on the central atom of the longest hydrocarbon chain.

sucks. However, it has been shown that / all of these copper soaps

"are soluble in non-polar hydrocarbons, e.g. in mineral spirits. that the copper soaps are soluble in turpentine oil and that this solution is then mixed with other non-polar solvents could be. Since the latter non-polar solvents are generally much cheaper than turpentine oil and are therefore used more frequently from an economic point of view, remains in high demand for the use of copper soaps In terms of volume, e.g. in heating oils, there is a need to To produce copper soaps with a relatively high copper content,

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so that the smallest possible amount of mongoose in the cupboard soaps warn nut.

öbe the ^ J-fjη dung \ ηιν cd therefore, a method of nuclear division öllöslichi r Electoral c-rr-en eif available bu. parts by, niv not have the abovementioned disadvantages. Dioee Λ υ. f would vrircl duroli solve the invention. ·

The invention thus relates to a method of production Oil-soluble mixed I-cup soap and bsw. or copi'tl-

r: aii zipped Eupf sap, which is characterized by dajju /

(a) Elemental copper in the presence of an oxidizing agent5> or a copper connection with no total number of connections aliphatic and bsw. or olefinically unsaturated, unsubstituted ones or substituted monocarboxylic acids of various structural types or with soluble salsa of these Acid converts, or

(b) a solution of at least two uniform copper ropes, the residues of the acids mentioned in (a) as acid residues of different structure types, produced in a solvent and the copper soaps by removing the Solvent or by simultaneous precipitation

. coprecipitated.

The invention also relates to stable solutions of the invention Copper soaps in non-polar hydrocarbons or in non-polar halogenated hydrocarbons.

It is often not possible to determine the exact structure of the according to the invention Process obtained copper soaps to "certain

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men j & ζζ ho ir rf- to indicate whether the Vorbir.au. λ; // - ~ n r-Λ c £ (, :: ir.ohxc Kupferoeifenj as Gopruzipitat of two uniform Κιΐ}; ΓβΓΓ..ο: 1-fen odor as Cop: " ^: '.zipi1; at a smoked Kupforsodfο raid Ίο: - ¹ both uniform "biscuits are present. Lor liegrii'f" uniform copper soap "in the present patent application means the copper ε eleven ο of a single acid, for example copper 2-ethylhex-iioate. Hit coprecipitated-copper soap The combination of two copper soaps is referred to, which is obtained by removing the solution by means of a solution containing the two copper ciphers or by simultaneous precipitation from such a solution.

According to a preferred embodiment, the two are uniform Copper soaps are soluble in the acids mentioned above, while the mixed and / or coprecipitated copper soaps are oil-soluble are . The invention-made copper soaps are at room temperature Soluble in non-polar, oil-miscible liquids and results in stable solutions at room temperature.

The mixed copper soaps and / or coprecipitated Copper soaps of the invention dissolve in oils, non-polar hydrocarbons and non-polar halogenated hydrocarbons lighter than mixtures of uniform copper soaps of the same acids. Also show solutions that use the dissolved copper soaps of the invention contain a lower viscosity than Ib "solutions, in which only a uniform copper soap of the same acids dissolves and which in the same total proportions in de, r solution is included. In addition, there is generally an improved viscosity of the copper soaps according to the invention containing solution compared to solutions containing a

109850/1994

contain uniform, soluble copper soaps. Via Yj.skoi-ritr-ltsabnahiiie leads to improved products that are easier to handle, mix and otherwise process.

The isolated mixed and baw. or eoprecipitated apple soaps of the invention have other properties alo a Geuisch uniform copper ripen the same acids from different ones Structure type. The copper soaps of the invention are not granular and crystalline as are most uniform copper soaps of the acids mentioned but represent soft, non-crystalline, plastic hatreds. A physical size more uniform In many cases, copper soaps dissolve in a non-polar solvent not as quickly as the corresponding according to the invention Copper soaps. In general, numerous mixtures can be used Uniform copper soap is obtained by dissolving it, e.g. in mineral spirits, while heating, resulting in a stable solution forms. The coprecipitated copper soaps can be obtained from such solutions by evaporation of the solvent.

It is believed that the mixed copper soaps of the invention the following general structural formula

R-COO-Cu-OOG-R ¹

have, in which R and R ^{1 are} aliphatic or olefinically unsaturated hydrocarbon radicals of different structural types. The radicals R-COO and R'-C00 represent the corresponding monocarboxylic acid radicals lengthened by one carbon atom. The radicals R and R ^{1 are} identical in the uniform copper soaps.

109850/1994 BAD OWQfNAL

The I: onoca.rbori5äureresto can be branched odor xzr.vcz-z '.- r ^ i. ^ I r: ^ in the branched monocarboxylic acid residues can be divided into # · ~ 3, :: i.> J 2-.ethylhexanoic acid, in ß-position, like 3 »5> 5-I * 'i': *. fc ^ ylh ^ fii: ^ '. u-.?e, in ^ -position,' ./ic- 4-Athyl-5,5-dinethylho; -: f; iv.; r, .iirc, and in 0 Position, such as 5-ethyl-6-methylhexanoic acid.

It is found that the position and even the presence of additional branches on the chain, which are more than 5 G atony from the carboxyl group, only wrestle an ßc- w or no influence on the formation of an oil - "> 3-lichen Copper silk o ^J e a decrease in viscosity of the solution obtained when mixed with an unbranched hydrocarbon. The acids branched in the (! (- position contain a first branch on the carbon atoms next to the carboxyl group. Positioned branched acids contain a first branch on the 2nd or 3rd carbon atom after the carboxyl group.

The ionocarboxylic acid residues of the copper soaps according to the invention ™ contain at least 5 carbon atoms, preferably 5 to 20 carbon atoms and in particular 6 to 11 carbon atoms. The upper limit of 20 carbon atoms does not represent a limit with regard to the formation of a soluble copper soap. For copper soaps that are more than Containing 20 carbon atoms, however, a point is reached at which the use of such a copper soap as a source of copper is due the low copper content, based on the total molecule, becomes uneconomical.

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■ ^f 4L

The uncuLnti tiri ^ rtcri! ■ ".onoco.rboiioauron of." Ολ ". -" r ^ ai-norr'toff he. and the mostly v · rv.-onuotes Ynrbiriuur.rerj zuv "t.rstollun" C.:iv <::? - findun ^ o / ^ n.ikraoxi luipf erseif ei}, since the ^ e IiGncoriVyonoL ^ iirfin ar; lighter and :; u the lowest prices available .are. ÜJic Kiipfersoifun uor Urfindi; ng can be substituted jodoch r.uch subetituic-rte: Iloriocarboncilurercrta of coals -., ': - r: r; crr; tcfrerj ciithalt.en, ^; oboi the main or side chain /, ami. Such 3 substituents are, for example, the halogen atoms or sulfur which can be contained in the main chain in the form of an ether bridge or in a dtr oo chain. Preferred among the halogen atoms is chlorine.

In the process of the invention, the unconverted saturated fatty acids, -v. ^r ie valeric acid, ^Capronsr: acid, Gaprylsmxre (n-octane acid £), relargonstlure, n-decanoic acid, undecanoic acid and Laur branched in acid, in {c ^ -3tellun saturated fatty acids such as 2-Ithylbutansäure, 2-ethyl-4- methylpentanoic acid, 2-ethylhexanoic acid, 2,2,4 »4- ^ etrEn: ethylpentanoic acid, 2-isopropyl-2,3-dimethylbutanoic acid, 2-propyl-4-ynethylpentanoic acid, 2-propylheptanoic acid, 2-kethylbutanoic acid, 2-eth3 ^r lpentanoic acid, 2,3-diraethylpentanoic acid, 2,2-diirethylpentanoic acid, 2-ethyl-3-methylbutanoic acid, 2,5-dimethylhezanoic acid, 2,2-dimethylheptanoic acid, 2-ethy'-l-5-ethylhexanoic acid, 2- Ethyl nonanoic acid, 2-ethyloctanoic acid, 2-propylhexanoic acid and 2-propyl-5-ynethylhexanoic acid, saturated monocarboxylic acids which are branched in the ß-position, such as 3-l-ethylbutanoic acid, 3,3-diraethylbutanoic acid, 3,3-dimethylpentanoic acid, 3-ethylpentanoic acid, 3,5-Diaethylhexanoic acid, 3-Ethyl-4-iaethylpentan acid, 3-Hethyloctanoic acid, 3-? Ropylhexanoic acid, 3,5 _f 5-Trimethylhexanoic acid and 3-Ethylnonanoic acid,

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and in / - v.nö <ί ™ 3 division vcrzv / cigto gesüttlrto Μοηοοία · 1> οη :: Γ.ΐϊ.ν ·: .η like 4 ~ Hothylpontanoic acid, 4-rIethylhoxanoic acid, S- ^ othylhoranrjin.i: ·. - ·:;, 5-HethylhoptanalVure, 4-A "Vtiyloctane; lure, 4 -λ thyl ~ -ü,! 3 ~ d:".:. Iothyl ~. hexane ^: iuro, 4 --- methyldccanoic acid and 4 _s 8 ~ di ;; ie tbylnonffnruluro, are used. Alq olefinically unsaturated ionocarboxylic acids can be used, for example, 4-pertic acid, j-ilexene acid, 2-eth; / l-2-hexenoic acid and 10-undecenoic acid.

The presence or absence of an olefinic double bond in the monocarboxylic acids is related to the different structure type of the monocarboxylic acids in the copper soaps according to the invention not significant. The structure type is determined by the presence and the position of the branch is determined, if one exists. For example, 10-undecenoic acid has an effect in the compositions of the invention Copper soaps are identical in structure to n-nonanoic acid.

For the production of oil-soluble mixed Piupferooifen are in the process According to the invention, the aliphatic saturated monocarboxylic acids are preferred, since they are the easiest to obtain and the Manufacture of ICupf Soaps using these acids at the most economically carried out.

Copper salts are used as copper compounds in the process of the invention or a copper hydroxide and, as soluble salts of the monocarboxylic acids, preferably their sodium salts. The implementations are preferably carried out in a non-polar, oil-miscible solvent, one directly with oil miscible concentrated solution of copper soap is obtained. The reaction can also be carried out in an alcohol and / or in water be carried out using the mixed copper soap as a pesticide separated from the reaction mixture and then in

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a solvent that can be rinsed with oil is dissolved.

For the production of orfindunssgemüs ^ er copper wafers from element; -: '· ■?: ■: Copper, finely divided copper and at least two / one monocarboxylic acids of various structure types are dispersed in a mixture of lacquer and water. The no resulting mixture is heated to about GO to 9O ⁰ C and to this 1 e :: vp- ~ - temperature kept!. Air or oxygen as an oxidizing agent is passed through the mixture with stirring. When the reaction is complete, the water is distilled off. In this way a solution of the mixed copper soap in enamel is obtained. The conversion described above can be described by the following general reaction equation:

Cu + ~ O ₂ + HA + HB - => CuAB + 'llgO.

in HA and HB the structurally different monocarboxylic acids mean.

The mixed copper soaps can also be produced by reacting copper hydroxide with a mixture of at least two monocarboxylic acids in mineral spirits. Here, too, a solution of the mixed copper soap is obtained directly. To carry out this reaction, the monocarboxylic acids and the copper hydroxide are dispersed in white spirit in such amounts that the desired copper concentration in the form of mixed copper soaps is obtained in the white spirit after the reaction. The reaction / ill be carried out at about 30 to 70 v ⁰ C. After the reaction has ended, the reaction mixture is heated above the boiling point of the water formed during the reaction. The solution obtained in this way can be used directly as a source of dissolved copper.

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the. Instead of copper hydroxide, bs.r::. :: oh ·; - -Iu; . "Carbonate not with the formula

CuC O ₃ . Cu (OH),

be used.

The mixed cure soaps can also be prepared by double pressing of / Zupfersulfat with a scaffold of the iTatriunml 7.- dor both Ronocarboneruren in an aqueous medium. This creates a mixture of sodium sulfate and the mixed copper soap. The sodium sulfate remains in de.-n waccrigen Iledium in solution, v, ^r uring the mixed plucking soap auofällt lind therefore easily separated v. ^{r can} earth.

The mixed copper soaps of the invention can also be manufactured v / ground by adding a saturated solution of copper acetate in hot ethanol is added to hot water. Before a precipitate falls out, the genic is mixed with a warmed solution of the two monocarboxylic acids in alcohol. The solution obtained in this way is about 15 minutes at a slightly elevated temperature held. The resulting mixed copper soap is then separated from the solvent.

In all of the processes mentioned, the hono carboxylic acids are grounded used in an equimolar ratio. Preferably, the process is based on a small excess of acids the copper, and especially with an excess of 5 to 15 mole percent. The presence of higher amounts of acid does not interfere with the reaction, but is uneconomical.

109850/1994

The Καηυο · ^ί -: · ^< ν.οϊΐο: .1 \ .ιτ · οη can ^r , uch in other: £ · "! - in equi ^ olar ^ n quantities crjnr; o £ -: ot;: tv / orden .! Dios leads however «υ a copper? R; eife, the vmx oinori Ge: .. i: joh der ge ^ icchten Xupf err-oife and dor Ku pi" ·.:. · - soap eggs in i-bernchu3S existing orure byr-.teht. "is / vravde festgo ;; tellt, da; T; those Oeminche, which contain an ubersehn sfj bin r, u 200 Ko l} '- rou ent ei nor dor acids, are oil-soluble.! Osr excess of a imten acid, vrird obtained in the NOCl a öllösHichc K \ ipferceifo is ninclerrtens teilvreisc from LOn liciikeit the er.tcrrechenden uniform I'upf'jrseife * in;.. white spirit or oil depending So uniform Kupforseil'en may themselves rr.it Extremely low solubility in one: if there is an excess, since the soaps obviously cause a certain dissolving effect 150 ^ olprozent In general, _self-t Icne CarbonsDuren may whose corresponding uniform copper soaps only rra..c-ors. ^"; : are slightly soluble, up to an excess of about 50 Kolproirent are present. The amount of a uniform copper soap dissolved in mineral spirits, which is formed from the excess ionocarboxylic acid, can be higher than the amount which would dissolve in a non-polar solvent in the absence of a mixed copper soap. The above uniform copper soaps are soluble when the mixed copper soaps of the invention are present in the solution.

The monocarboxylic acids of different structure types can r.it. Copper or a copper compound mixed with copper soaps Mixture of uniform copper soaps or a mixture of one or two uniform copper soaps and a mixed IIup-

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ferscife form. In all dienon P ^:: lXen b'-tr ^ t dan HolYOrrhUltnis of copper: Üäuvetyp A : acid; type B vorsi ^ gcwcipe 1: 0.3: 1.2 b: .fi 1: 1.2: 0.8 . .. 'enn mol'r ρ.Γη; we; i structure:; !! different Iloroearboncöurer .: present that; ; jo <hole only two structure types can be added, e.g. n-octaiyic acid, n-IlGiu & nüä-ure and 2-J.th-jlheiiziirJ'v.ro, :: o v; orden the Cäuron dccrjelbon CtrulrtLir · - typo ::: v .: c Bostir.irr; us dos above denominated behavior nirj ^ er: added. For example, a Genisc !. from 0.5 hol n ~ octaneuure, 0.6 col n-ITonan? i / -ure and 1.1 ilol 2-ethylhexanoic acid a Kolver-ratio of acid type A: acid type B of 1: 1.

It is angenoninen, the mixed Copper daos cn if the invention in P or πι pure Verbiiidungen exist and Cia.cz dieüe copper soaps represent not only a solid solution of two uniform copper soaps. iCs iet However v / ahrocheinlich daao v. ^T egen the equilibrium distribution of the reaction products from such reactions Geraisch the mixed copper soap and the single copper soaps of the two acids is present.

ψ A genicch of uniform copper soaps can be dissolved to make coprecipitated copper soaps. The dissolved copper soaps are then coprecipitated, for example by removing the solvent. In order to dissolve the uniform copper soaps, an intimate mixture, for example by thorough rubbing, of the compounds is preferably produced.

The coprecipitated copper soaps are also soluble in the proportions described for the mixed copper soaps. In general, they become more uniform as they are manufactured Copper soaps in white spirit using the methods described above

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Adhere to unstable solutions. Aue dJesen solutions case 021 di 0 Copper; different times. If the solutions -unit Iieher copper soaps be wicked before the copper soaps are out of the solutions fail, stable solutions are obtained. This is especially true when the copper soaps are in equinolar amounts or if there is an excess of a copper soap in the range given for the mixed copper soaps. UbcIi removal of the solvent can result in the * ' Coprecipitate to be redissolved in a solvent, creating a stable solution.

The mixed and coprecipitated copper soaps of the invention can be made by any known method for making uniform copper soaps. This only becomes the acid used to produce uniform copper soaps through a mixture of two acids of different structural types replaced. The manufacture of uniform copper soaps is described, for example, in US Pat. No. 2,584,111 and US Pat. No. 2,113,496.

In general, the copper soaps have branched in the o (-position and unbranched aliphatic carboxylic acids have the lowest solubility. The copper soaps in ß- and in ^ -position branched monocarboxylic acids are somewhat more soluble in white spirit or other non-polar hydrocarbons »Des-" half the copper soaps of branched in c (-position odei * straight-chain monocarboxylic acids are not present in an oil in such a large excess as the more soluble copper soaps the monocarboxylic acids branched in ß- or ^ -position,

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- IA -

because at lower concentrations I guess at £ --J! .τη. I · - Hupfer «a branched rlono'i & rbonsrairon, which contain a qxv-ix -.- rnMrec D-atom at the opposite end -3c-r carbon hydrogen chain to the carboxyl group, are similarly soluble as the copper soaps of in of-position branched knocarbonüHU-ren. 2s is surprising that mixed copper coifen before. In the o (-position branched and straight-chain aliphatic'or-o-carboxylic acids have practically the same solubility, v.'ic sB the mixed copper soaps of in oi ~ and ß-ote-llur. ^ branched monocarboxylic acids or of in ß- and j 'Position branched ilonocarboxylic acids.

The oil-soluble wiped copper soaps of the invention are disclosed in US Pat non-polar hydrocarbons or non-polar halogenated Soluble in hydrocarbons. Such hydrocarbons are e.g. liquid hydrocarbon fractions, such as mineral spirits, gasoline, Kerosene, diesel fuels ITr. 1, 2 and 3, higher-boiling fractions, which are used as heating oils Ur. 4, 5 and 6 are known, and aromatic hydrocarbon oils. The mixed copper soaps of the invention are also in hydrocarbon fuels soluble, which only become liquid when heated. Such hydrocarbons are e.g. higher-melting, semi-solid residual oils, which have to be heated to temperatures in the range of 82.2 G to increase their pluidity before they can be used as liquid fuels can be used. Other solvents for the oil-soluble copper soaps are e.g. xylene, Turpentine oil, toluene and ethylbenzene. Usable as a solvent chlorinated hydrocarbons are e.g. o-dichlorobenzene, Carbon tetrachloride, 1,2-dichloroethane and tetrachloro

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üthylon.

Vi'io boruitf; noted above, can be used to make mixed Kuj) for; mature you halogerrlerte, ^r z.'3. chloriorte, monocarboxylic acids, can be used. The hfilo ^ c-nierton monocarboxylic acids are up to now not cheap to be used in economical V. ^T ci -; e for the production of additives for 7 / racing tcf ~ - fe. Palis in the future halc;: oi: i; rte Monoearbonrraureii are available cheaply, theGt ger .-. Ä ^ t de · ::. Proposal of US-PS 2,622,671 to improve the! .'enclet v. earthed Chlorinated organic compounds may serve generally as Chlorqucllcin such products the chlorine reacts with copper, and in this ^T "else the soot formation is reduced GICF, oschicht apparently by reducing the Lntsünduncstfi / cratur the Eussablagerungen.... In the said pater. " ¹ letter v.'ird a separate addition of a chlorinated organic compound

suggested, however, l.'emi chlorinated Monocarboxylic acids are available, one can be combined with another halogenated or non-halogenated Honocarboxylic acid of various structure types for production mixed copper soap used. This eliminates the need to add a chlorinated hydrocarbon separately the copper soap.

The solutions of the mixed copper soaps in mineral spirits contain about 6 to 15 percent by weight and preferably about 8 to ' 12 weight percent copper.

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Lie so horgestvlltcn concentratedon Ιοί, us en r; e; v: ir: chtor Κν.ρίΌϊ · - soaps in laekbenzin are suitable π I as to αεί 13 for rinsing for direct mixing with heating oils or other coals · ^ v /f.sser st of f burn «openly. In general, ^{1 1} CiI of a solution containing 8 percent by weight of copper is mixed with 1000 ropes of heating oil. For higher-boiling fuels and for the semi-solid residual oils, which generally have a higher carbon content, somewhat higher amounts of a concentrated solution of a copper soap are required. In the latter batch, the proportions are about 1 part of the above-mentioned solution of a copper soap to 200 to about 800 parts of fuel oil, preferably about 200 to about 2000 parts of heating oil are added to one part of a concentrated solution of a copper soap.

The examples illustrate the invention.

Comparative Examples A to M

The production of uniform copper soaps is subsequently carried out using 2/2-diethylpentanoic acid as the hydrocarboxylic acid deserved.

136 g of 2,2-dimethylpentanoic acid _f 230 g of mineral spirits and 49 g of copper (II) hydroxide are placed in a reaction vessel at room temperature. The mixture is heated and Fäihren to 75 to 8O ⁰ O then held until substantially complete dissolution of the copper (II) hydroxide at this temperature. The mixture is then heated to remove the resulting 'Vassers to 120 ⁰ C. The reaction mixture is then "

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White spirit is diluted to a copper content of about 8 percent by weight, corresponding to a Cei.-antgev / icht of the Gothic of about 398 g. The Gerisch thus obtained is RVR} \ NTJ '':. Riru: ig filtered from unreacted copper (II) hydroxide at ieo to 13.o ⁰ C hot.

For the production of all uniform copper soaps vi 49 g of copper (II) hydroxide with an excess of the corresponding Monocarboxylic acid converted by about 4 percent, as this the solubility of the copper soap is increased somewhat. The solubilities of the uniform copper soaps thus obtained are shown in Table I put together.

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Comparative example

acid

Table I - * β

Uniform copper soaps

Acid, lacquer Solubility of copper soap in lacquer g gasoline. g_ petrol

ο B. CO C. 00 D. cn Ξ ο co P. CO -P- G H I. ro ' J δ K ο -j? L. 0
2 M.

2,2-dimethylpentanoic acid 230

2-ethyl-4-methylpentanoic acid 150 2-ethylhexanoic acid 150

2-propyl-4-methyl-pentane-165

acid

2-propylheρtanoic acid

2-ethyl-2-hexenoic acid 3,5,5-trimethylhexanoic acid 165

4-ethyl-5,5-dimethylhexane-180 acid

4-methylpentanoic acid

n-octanoic acid
n-nonanoic acid
10-undecenoic acid
η-hexanoic acid

216
216
201

1S6

150 216 165 201 180 186 121 245 150 216 165 201 194 17-2 121 245

partially soluble at room temperature (up to a content of 2 percent by weight Copper)

bsi crystallized from 100 to 12O ⁰ C crystallized at 95 to 105 ⁰ C is crystallized at 110 to 12O ⁰ C

crystallizes on cooling to room temperature

crystallized at 100 to 12O ⁰ C

slowly crystallizes at room temperature after 3ti ^; . £ iccin aging

solidifies completely at room temperature

crystallizes when: n cooling to room temperature

completely solidified at room temperature solidifies at Raur.it indignaos door vol: .- ^t: NIIR;? solidifies at room temperature · veLl £ 'L'". n ■ ::!. ■ _"

crystallizes practically completely b & s space tc mόe ratür.

AuG 'iVboilo I i :: t evident, d * u: ö no: d: r a''·; ! 'lich'.n Kupfercoifcn G'iiiii ^ ontl öllönlieh irt, in order to create a stable solution Ή Lacltbensin ir.it one, Κυρ forgohalt of 8 Crev.-ichtr -.- iro ^ cnt hr-r. Only not a ·. ^ iaipforseifc · int eirio Lö:.: u <is rit a ijupfer £ chr.lt available over 1 weight process. Four copper caves egg \ _; tarrcn trntcr image of a GoI i :. T.ackb-.iiiHin.

example 1

1.07 Hol 2-ethylhexanoic acid, 1.07 KoI 3.5.5 - rinfethylhexruin: iure and 1.0 KoI Ku}> fcr (ll) -hydro: cid \ rer <leTi in LackbeiiKin. The mixture is "heated Umsetzuns. The resulting mixture is ansehiiessend to remove the formed in the reaction" by Rauntemperatur to 70 ⁰ C bit cure practically vollstündicen erhitst ater to 120 ⁰ C. The Ge: nisch. Becomes the Tintfernun ^; το »unconverted ci copper (II) -h ' ^r drozid filtered. The solution is then mixed with enough lacquer that a solution with a copper content of 8 percent by weight is obtained.

The clear solution is then made up by distillation concentrated a copper content of 10 percent by weight. The viscosity of this solution is E (I, 25 3t) on the Gardner-Koldt scale. The white spirit used consists of 6.7 percent aromatic hydrocarbons and 91.3 percent aliphatic hydrocarbons and 2 percent olefinically unsaturated hydrocarbons (S ijp 11 mineral spirits 145-66).

The solvent is then distilled off, the solid mixed xupper soap is obtained. This copper soap is colored green and of a soft, plastic texture. the

109850/1994 BAD ORiQi _NAL

Copper soap v.-ird am: chile ü ε end at Eauvitonui -.- r- · "-. Rur i ^ ίοοτϊοΐ White spirit dissolved that a η solution nit ein.i Lupf or / jol-alt of δ Gev / ichtcprozont arises. Dicrje solution let:; tabxl.

Example 2

Since the procedure of Example 1 is repeated, v / o ¹ oil with different I-iolvorhabencen von_ 2-Äthylhsxansüure to 3 "5.5 ~ £ ri ·. methylhcoic acid worked v / ird. After cooling down the solutions of the mixed copper soaps in white spirit, the following results are registered:

Hol ratio of 2 ~ ethylhexanoic acid " zn • j.5« 5-griTnqthr .'-lho xa nsKure

0.388 dAinke Igrüno s granular π

product

0.5 Stable solution

0.612 Stable solution

0.756 etv / as dark green

Product fails

Example 3 50 g of finely divided copper (98 percent can be sieved through a sieve

with a cask width of 44 p) v / earth with 118 g of 2-ethylhexanoic acid and 129.5 g of 3rd »5,5-trimethylhexanoic acid mixed. The genius It is placed in a 1 liter, three-necked round-bottomed flask with a Reflux condenser, a propeller stirrer and an air inlet tube with a glass frit that extends to the bottom of the flask is provided, in the Lackbensin used in Example 1

The dispersion is then heated to 80.degree. dispersed./IT After adding 25 g of water / water to the dispersion, air is blown through the mixture with vigorous stirring. After the reaction is nearly complete, the remaining solid material is filtered off. The Piltrat is used to "remove the water contained in IOO ⁰ C and 25 Torr

109850/1994

dcstilligrt.

By Linda: npfen dos Lackbenzinn v, ^r ird öfie festt --zupfo:. · -? - äthy lhexanoi; .t - 3,5, 5 ~ l'rimothylhe:>: & noat received. Ijic- · prebinding dissolves spawns in Lacktosiizin and can be carried to a ^ ₅ cc of further Lackben ^ in a Kupfergeha.lt of 8 or 10 G-CV ^r ioht.yprosont diluted. The dark green solution has the properties v. ^r ie the solution obtained in Example 1.

Example 4

1.07 mol of urodium-2-ethylhexanoate and 1.0? Mol. "". Itriun-3,5, 5- trimethyl be dissolved in water. 1 mol of copper (II) sulfate is added to this solution. The mixture is heated to 70 ° C., copper 2-ethylhexanoate-3,5,5-trimethylhexanoate precipitates and can easily be separated from the reaction mixture. The soft, plastic cash register obtained is identical to the product produced in Example 1. The cash register is dried and then dissolved in the laek gasoline used in Example 1 to form a stable solution.

Example 5

A saturated solution of 1 mol of copper (II) acetate in hot water is prepared. 200 ml of ethanol at 70 ^° C. are added to this solution. Before a precipitate forms, the solution obtained is treated with a solution of 1.11 mol of 2-ethylhexanoic acid and 1.11 mol of 3> 5,5-trimethylhexanoic acid in alcohol. The mixture is kept about 15 minutes at 70 ⁰ C! Laughing evaporation of the alcohol and the V / ater is obtained the mixed solid copper soap.

109850/1994

BATH ORIGINAL

At γ; j> ic 1 6

] 3a3 Procedure v. ^r ird is carried out accurately Pjispicl 1, v; c'i.oi ji-ucoh & -ii "fchylhc: cansiluro through 2 --'-- thYl-4--""ΐηνίρ ^ ηtorsrjKuj-o ■ rfetzi, v :■■ ird . The mixed copper soap is called ßrcnc p! L r. "Tj;: ohe .lo .; ^: .. ;; ": obtained easily in Lackbenain under Γ-χΊαπηρ; advises a stable solution or a K ^ APF crg -halt can dissolve bnprjzeiit of 8 Oe.vicr..

Examples 7-17

According to the method described in Example 1, the in Table II listed Konocarboxylic acids in the indicatedon Quantities implemented. It v-erden jev / eils 49 g Xupfer (lJ) · hydroxide used. A stable solution is used in each case a copper content of .8 percent by weight.

109850 / 1-994

BAD DRIOSMAL

Acids B) 2,2-dimethylpentanoic acid
3,5,5-trimethylhoxanoic acid n-honanoic acid
3,5,5-trimethylhexanoic acid Table II A, 5 Acid B,
- g Paint-
petrol, ripe en-
solve now /% R -. ♦ § - I. Per
• p. J at
game ^A !
B) 2-ethyl-4-methylpentanoic acid
3,5,5-trimethylhexanoic acid 10-undecenoic acid
3,5,5-trinethylhexanoic acid acid
δ 82.5 215.5 332 Yield, 7th A) 4-A "thyl-5,5-dimethylhexane
acid
B) 3,5,5-trinethylhexanoic acid 2-ethyl-2-hexenoic acid 68 82.5 208.5 385 96.0 8th ^A \
B) 3,5,5-trimethylhexanoic acid 75 82.5 193.5 393 36, c 9 B) 4-ethyl-5,5-diinethylhej: an-
acid
2 ~ ethylhexanoic acid , 90 82.5 201 395 93, G. 10 A) n-nonanoic acid
2-ethylhexanoic acid 82, 5 82.5 136.5 377 99.2 ro
ro 11 B) 4-I ¹ Ie thylpentanoic acid
η-hexanoic acid 97 C. 82.5 203.5 dickilüGnice though
clear solution 94.3 12th A)
3) 4-methylpentanoic acid
3,5,5-2 trimethylhexanoic acid 75 5 never! "* bor.tir
on Ubor 90
2 η γ) + τ Q j-. r> h '^;"I. B) 2-ethylbutanoic acid 5 75 201 395 13th 3) 90 75 208.5 392 99.2 14th Bj 82, 60.5 245 ■ 709 98.5 15th A) 60 82.5 223 381 ' 96, c 16 60, 22.3 233 381 95.7 17th 60, 95.7

B) 3,5,5-trimothylhexanoic acid

- ? Λ

Dig obi-; o-j Tie it .. ν · :, ο I & tend, da «?: go.vjirjchto i: u ;; - ft; r :: o: ii c.?> cc ;;; "- nischer HUuren, üoren corresponding uniformly-- .. L / upforcc-if er. hei i ^ U; do:.: i) Ci-f.tuv are not soluble or dz ο in LacMvriizin. no ctabilon lo fingen "form, surprising? .." wise öllfin'Jich are uiiä at Fcaynt temperature in mineral spirits ütabilo Losiui ^ en. Gomiechte Kupferenifen, the untor Verv / endiuis two lionoccrVoiisäurc-rj of the same structure type hfcrgeatellt, however, they are not oil soluble.

Matching example II

psrnaps Example I.
The method v / ire. / Using 2- ^ tIIyIhCXaITSaUi ¹ O and a mixture of the position in c-branched acids 2,2,4,4 ~ -etramethylpentansäure (56 percent) and 2-isopropyl-2,3-di ! -i'hylbutansäure (27 percent) (Versatic 9) carried out ". the obtained product is immediately in Fora a dark green granular Hanse and results in a stable solution. the precipitation occurs at temperatures of from Reaktionögernisches etv / a 95 to 100 ⁰ C a.

Comparative example 0

The procedure is according to Example 1 using Caprylic acid and pelargonic acid carried out. The product falls immediately turns dark green when it cools down to room temperature and cannot be dissolved in mineral spirits.

109850/199 A

BAD OBiGlNAt

c'lchsboii.-i'iole? am Ti

The method \ rj.rti geiv, U;: - D Example 1 using the Sr / urepuO-re: .n den £.: N /; egolj: 2: ^ ij. Con / re carried out. The S: iuropi! <', Rc belong to the glci.chen ^ trtikturty. The results are shown in Table III.

1 09850/1994

BATH ORIGINAL Table III

Comparative example

acid

Acid, Lackben- Z ain, fl

Solubility of Mixed Copper Soap in Lacivbonsin

2-ethylhexanoic acid 75

2-ethyl-4-ethylpentanoic acid 75

2-ethylhexanoic acid 75

2-ethyl-2-hexenoic acid 75

2 - /. Ethylhexanoic acid 75

2,2-Diinethylpentanoic Acid 68

216 216

225

crystallizes at 100 bic 110 C.

crystallizes at 100 bie HC

Al -L ¹ l, H, lll "^" ^ ι. Ι * \ j ** ^ - J-. \ < U - '. - **

11O ⁰ C; etiirkore Kriat: illi: room temperature

Aue the Vor ™! 'ichcb / icyi · "lon IT bir; R ir; t' .rrir- ^ lioL, represent: -.; /. · ■■ nifichte jlupi'orrf iff?]; before acids that of the. same Siruk'iru. . · I ,. _; belong, nicl.t üllö; 1 I am.

B ci r ρ i ο 1 18

39 ^ £ o.inor gc: "- ■" :: ο Vc-rgleichrrbaij.-piel G fresh Y '- :. ^% r; c -; -: tfj3 lt - ;. n Löcu) ig von Kupf or-3 »! 3,5-trin -.- thy] hezei-nofit in Loc / boiizin nit a ¹ ICupfergeIt of 8 Gev: icht :; prozc :: t ',.' ird at ICO C: r.it 398 g of a gemr.ss comparison abcippiol II h ^ rge: -! "-. llten solidified solution of JCupfer-il-Mthyl-S / j- dincihylhcxcr.ort with oii: ·:;. copper content of 8 Gev / ichtspros ^ nt ver ::: ir.-cht. s -.-. o Ger.i; ch mIvO. heated to 120 C to form a uniform solution ντΛ then kept at this temperature for 5 to 10 minutes. After cooling to low temperature, a clear and titanic solution is obtained. A coprecipitate can be produced from this solution by evaporating the white spirit. The coprecipitate dissolves at Raunte.nperatur quickly in Lackbenniri.

Examples 19 and 20

The method v / ird was enjoyed in Example 13 using the method described in ! The uniform copper soaps listed in Table IV are carried out. The mixtures are dissolved to produce stable solutions at the temperatures given in Table IV.

109850/1 99 ORfGINAL

Table IV

Example copper soap A and (B edi η guru; en)

Copper soap B and (

On lücaings
temperature

Result beirr. Cooling down to the aauritic temperature

19th

ICupf er-3> 5,5-trimethylh exa.no at,

(Solution, comparison example G)

Copper-n-nonanoate,

(solidified solution, comparative example K)

SO ⁰ C

kl ".re and stable

Copper 3, 5,5-triniethylhexanoate

(Solution, comparison example C-)

Copper caprylate nonanoate

(solidified solution, comparative example O)

clear and

Au ο Table IV can be seen, ö.r: sv, in bciiloi. Ink pen. l'Jrio ν.ιζύ stable solutions are obtained «By Yf; .i \ 1- ^r x ~ .vfen dor .. Laekbenzin» are obtained Cora-ilsipiv to _} which are dissolved in Jj-i-olcbo ^ iyl ·) vicder could21.

Example 21

1.07 moles of 2,2-methylpentene-n-acid, 1.07 hol 3, 5, 5 ~ rx ~ cth; _/ lh '·: - Acid and 1.0 hol copper (II) hydroxide are mixed in o-di-ilo-'oen zo-1. The Gomifich v. ^It is heated from building temperature b:> € to 70 until the conversion is practically complete. The solution is then used to remove the dee during the implementation

standenen ', the reader heated to 120 C. The sounding obtained in this way is diluted with o-dichlorobensol, with a clear rüne Lütun ^ doi * copper soap with a copper content of 8 Gov: ichtc-proaent is obtained.

Example 22

The procedure is as in Example 21 using xylene carried out instead of o-dichlorobenzene. From the received Solution of the copper soap, the xylene can be evaporated quickly. The green-colored, solid mixed copper elf is called soft, plastic hatred. This product dissolves rapidly in xylene at room temperature. It will ax a stable solution made a copper content of 8 weight percent.

109850/1994

BATH ORIGINAL

Claims (1)

Process for the production of öllöslic'r.er / --- ^! —Cbter /!^-,fr.rceifen and bsv /. o'ler copräzi ^ Itiertcr I'Inpf-.r;^; : f; j: .-. 'cn, thereby ge 1-: ■ :. η η ze rejects, may; : '- : o (a) elementary KuoTor in the presence of a 0 ·: ·: ν \ ί..ΐ1οη: - ::. νίΐ - !; ί;. "!. Γ.: - or eiriö iiupf ^ rvc-rbirrlurirj nit inor- ^ sant riindor-toiTj z,. 'ei aliphatic and "bzv;. or olefinic unr ^ r '.- tti ^ th, unsubst it'ii ort en O'ier substituted ilonocarloncäuron von different ßtrul-rturtyp or nitlöslici'.eri salts di.ei.; er Acids do not react ^ d ^ r (b) a solution of at least two / one uniform copper cells, the ale Saurerer-rte the Eeste of the acids mentioned in (a) of different structural types contained in a solvent and the icupper siphon by removing the Solvent or coprecipitated by equilateral precipitation. 2. The method according to claim I _1, characterized in that the aliphatic acids used are straight-chain acids or acids branched in the ¹ X, β, / ~ and J position. 3. The method according to claim 1 and 2, characterized in that that acids with at least 5 carbon atoms are used. 4. The method according to claim 1 to 3, characterized in that that acids with 5 to 20 carbon atoms are used. 5. The method according to claim 1 to 4 »characterized in that acids with 6 to 11 carbon atoms are used. 109850/1994 G. V; Vui;. ''. Y-: Y! η: οι: - "- ϊ ι -: ι x'l-ck J. bi :. ^{ι _:} ■"; -: 'r-ci:; ■ ·> --- r :: ·. ,:.; ".-"! 'j! .η ·' t, daos r._ r: :: 1j: ic- ¹ I .; :.: ·. '·:.' / 'Η & ~ c. (. R .-- oicllu;';:vc-r; /. · Οί,. Oo r '' phati 'oh- ^c ' X: V: "k. -.i-iL-f. tf.t. 7. Vc; rf: hrf.vi v · oh Λποΐ-rur-h i bii: 5, thereby _ο · ^ Λί -:;. ::: ·> ichi ^ et, (Ims ::. ΓιΏ r-.ijy -. '. or-t ·: · ■; ■ a' ^ nradkcttiro oJ ^ r oin ^ in (X- ouor 8. Before driving on n: see Ansxriich 1 bd ε 6, thereby rr.]: '-. Rini: "in-: t, that nan 2-Äthylha; · nnsäure and?, 5, ^ - i'rii.;: lh ;, "] L xaiinr'ur-e begins. 9. Ancestors according to claim 1 to 8, characterized in that r >>enriKc; icLnot that one soldering alc copper connection ^ Kup:? Ci '(II) -hydro: -. J ü. 10. The method according to claim 1 to 8, characterized by cakennselehnet, that a water-soluble copper mixture r.:-.t the nati'iu: ..- salts two conocarboxylic acids in aqueous solution u-setst. 11. The method according to claim 1 to 10, characterized in that that nan sv.'ei acids or sv; ei uniform copper soaps in Pick ratio of 2: 1 to 1: 2 is used. 12. The method according to claim 1 to 11, characterized in that a solution of the copper soap: iit a copper content of at least 6 percent by weight into a non-polar hydrocarbon or produces a non-polar chlorinated hydrocarbon. τ, τ, more stable solutions 13. Use / von ^ uprerseifon according to claim 1 to 12 as Additives in hydrocarbon fuels and heating oils. 109850/1994 BATH ORIGINAL