DE2325675A1 - STABLE, OIL-SOLUBLE METAL SULFONATE PREPARATION - Google Patents

Description

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CONOIIMEITTAL OIL COMPANY

P.O. Box 1267

Ponca City, Oklahoma 74601

U S-JL

Stable, oil-soluble metal sulfonate preparation

The invention relates to an oil-soluble metal sulfonate preparation with an improved stability, which consists of an oil-soluble metal sulfonate and an oil-soluble amine compound consists.

In recent years it has been found that oil-soluble metal sulfonates and dispersions of metals in these sulfonates can be used to prepare better standards for spectrographic equipment by dissolving these materials in predetermined solvents in a suitable solvent. These standards have an indefinite shelf life and any combination of metals can be used without filling out the metal parts. Moreover Ii i.al from the en se ₅ starry öllösliehe Ke! Sulfonate contains on-J. in dispersions are of considerable importance as additives in fuels and fuel

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oil obtained. These dispersions have also proven to be very suitable additives for other materials. Suspend of insoluble waste generated during the use of the material and to prevent corrosion proven. When the oil-soluble metal sulfonates are used as additives for engine lubricants, they serve these additives to, those in fuel combustion, oil oxidation or similar processes occurring during "the operation of the engine," insoluble constituents formed to disperse or peptize effectively.

Although the use of oil-soluble metal sulfonates is general known and recognized, certain occur in the manufacture of oil-soluble metal sulfonate preparations Metals such as molybdenum, vanadium, one, boron, and silver face difficulties. There are also problems with the mixing stability of these metal sulfonates at low Metal concentrations in the range of about 100 ppm and fewer. One has therefore been on the prowl after a lance more stable oil-soluble metal sulfonate preparation.

Certain of the previously known oil-soluble metal sulfonate preparations have the disadvantage that, after prolonged storage, an acidic odor occurs which is similar to the odor of HgS, SO ^ and HCl. In addition, the previously known metal sulfonate preparations show poor mixing stability when stored for a long time at low metal concentrations and a visible precipitate can be observed, while with other known metal sulfonate preparations, in which the problem of mixing stability was not visible, this problem could be determined by instrumental analysis methods.

The aim of the present invention is therefore on new öllösliehy Metallsulfonatzubereitungen with improved stability

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indicate those made from readily available starting compounds in an economical and effective manner »The aim of the invention is also to develop new, indicate stable 5 oil-soluble metal sulfonate preparations, the metals from the group molybdenum, vanadium, iron, boron, barium, beryllium, tin, silver, titanium, copper, magnesium, Contain sodium and mixtures thereof, which give them improved stability «

Other objects, features and advantages of the invention go on from the following description «

It has now been found that the above aims can be achieved by using certain oil-soluble amine compounds from the group of amines, aminesulfonates. Amine salts of fatty acids, Aiamoniumsulfonate and the reaction products of amines with alkyl succinic anhydrideri to oil-soluble sulfonates of metals from the group molybdenum, vanadium, iron, boron, barium, beryllium, tin, silver ^ Titanium ₉ copper, magnesium, sodium and mixtures thereof adds to form Oil-soluble metal sulfonate preparations which do not have the disadvantages of the previously known metal sulfonate preparations, ie with which no odor and stability problems arise «,

The invention therefore relates to a stable, oil-soluble Me »-, allsulfonate preparation, which is characterized in that is that it consists of

(a) an oil-soluble ßulfonat a metal from the group - molybdenum, vanadium, iron, boron, barium, beryllium, tin _s, silver, titanium, copper, magnesium, sodium and mixtures thereof and

(b) an oil-soluble amine compound from de3? Group of amines, Amine sulfonates, amine salts of fatty acids, the ammonium sulfonate

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fonates and the reaction products of amines with alkyl succinic anhydrides.

The improved oil-soluble metal sulfonate preparation of the Invention can be prepared by combining the oil-soluble metal sulfonate and the oil-soluble amine compound mixes with each other and stirs the mixture until a uniform mixture of the compounds is achieved, to form the desired metal sulfonate formulation. It has also been found that it is useful if in the Preparation according to the invention the metal sulfonate and the Amine compound in a ratio of about 1: 0.3 to about 1: 8, based on the metal content of the metal sulfonate and the amine content of the amine compound.

A method for producing the preparation according to the invention is that the oil-soluble sulforate and the oil-soluble amine compound in one with a stirring device equipped vessel are introduced. The amount of the components may vary depending on the one used Components may be varied, but the oil-soluble sulfonate and the oil-soluble amine compound should be preferred are present in a ratio of from about 1: 0.4 to about 1: 1.5.

Once the components have been introduced into the vessel, v / she ground thoroughly stirred, and the mixture is heated to a temperature which is generally within the range of about 60 to about 150 ⁰ C. When the mixture has reached this temperature range, it is held at that temperature for a period of time sufficient to allow the metal sulfonate and the amine compound to mix together sufficiently. The v; irki; ar ^: ie time period is generally within a range of about 0.25 to about 12 hours.

After "the steps described above have been carried out,"

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if necessary, the mixture is suitably "for example by yakuum stripping or by. stripping the mixture with a gas, such as nitrogen, carbon dioxide, Luft'und the like., Over a period of .etwa 0.25 to about Freed from volatile components for 12 hours. The stripped product is usually obtained by filtering the stripped product by a suitable inert solvent, such as aluminum oxide, diatomaceous earth, pumice stone and the like., clarified.

In other ELillen a convenient method is that the two components are mixed together at a temperature between 20 and 90 ⁰ C with good mixing to ensure a uniform mixture of the two components. Also, the metal sulfonate and the amine compound can be mixed simultaneously at ambient temperature and diluted with a solvent such as an oil or isooctane. In addition, the amine compound can be mixed first with the solvent and then with the metal sulfonate.

Examples of suitable oil-soluble amine compounds are Amines, amine sulfonates, amine salts of fatty acids, ammonium sulfonates and the reaction products of amines with alkyl acid anhydrides. Particularly good results are achieved when the alkyl radical of the alkylborn stone anhydride is from one. Polybutene with a molecular weight of 600 to 2000 is derived. With the amine and ammonium sulfonates used here they are those that can be derived from oil-soluble sulfonic acids, such as those in the US patent application No. 240 273 are described.

Preferred oil-soluble amino compounds according to the invention For example, (1) amine salts of fatty acids (Dioleates), (2) diamines, (2) diamine monosulfonate precursors and (4-) diamine disulfonate precursors, especially beneficial results are obtained when the

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SAD ORIGINAL

Amine compound is the diamine 1,3-diaminopropane with an alkyl radical from the group n-coconut, η-tallow, η-soy and n-oleyl. The compound 1,3-diaminopropane can be represented by the general formula E-KH (G ^ HgMIp), in which R is an alkyl group that represents the coconut, tallow _? Soy or oleyl radical. These diamines are commercially available under the tradenames DUOMEEIT G, T, 0 and S.

Examples of other suitable amine compounds are tetraethylene pentamine and similar amino compounds which contain primary and / or secondary amino groups. Suitable amines are also those of the general formulas R (Mip) o ^{un <} i R (KH-G ₇ HgIiEp) ρ, in which R denotes an alkyl radical which is derived from the dinating of an unsaturated C 1-6 fatty acid. Another group of suitable anine compounds are those of the general formula RH- (C ₇ HgKHp) OJ in which R is an alkyl radical derived from tallow, oleyl and lauryl fatty acids.

In the case of the oil-soluble metal sulfonates, the ST according to the invention can be used, it concerns those sulfonates in which the metal from the group molybdenum, vanadium, iron, Boron, barium, beryllium, tin, silver, titanium, copper, magnesium, and sodium is selected. The metal sulfonate component the preparation according to the invention should preferably contain less than 100 ppm metal. Regarding closer For details, see US Pat. No. 3,250,710 and US Pat U.S. Patent Applications Nos. 14-8,263, 148,264, 148,267 and 240 273 referenced. According to the in this patent specification and "processes described in these patent applications Oil-soluble metal sulfonates can be used as an oil-soluble metal sulfonate component in the preparation according to the invention be verified.

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η _

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto. In each of the experiments described in the following examples, ₉ unless otherwise stated, ₉ the metal sulfonate was one which was derived from a sulfonic acid of an alkyl aromatic compound, which was mainly composed of di ~ n ~ alkyl benzene sols with a molecular weight of about 420 existed.

Example 1

100.0 g of molybdenum sulfonate (prepared according to the process described in US patent application Mr. 143,264) and 1.0 g of distilled n-coconut-1,3-diaminopropane were introduced into a flanged reaction flask ⁰ G heated, held for 15 minutes at this temperature, then heated to 150 ° 0 and stripped for 15 minutes with Hp-GaS «The reaction product was then ^{cooled to 100 to 110 0} G and filtered through Hyflo« After 5 non-period storage of the product at ambient temperature was only a trace of a smell ₉ during a comparison sample from the same Molybdänsulfonat without the addition of the amine compound to ^ -no month period of storage a severe sharp ,, had ₅ offensive odor, the smell of SO DER ₀ resembled ''

A 1% solution of the product in methyl isobutylketoii remained clear for about 5 weeks »

Example 2

75 g molybdenum sulfonate (as in Example 1) and 1.5 C distilled n-coconut 1,3-diaminopropane were placed in a beaker. The components were heated over a period of about 1 Dtunde in an oven at about 100 ⁰ G and mixed. The mixture was then mechanically mixed and

by. Diatomaceous earth filtered.

10.0 g portions of the product were stored for about 4 weeks at ambient temperature and at 70 ° C. and compared with a comparative sample of molybdenum sulfonate without the added diamine, which had been stored under the same conditions. At 70 ⁰ C, the inventive product after a week was odorless and thereafter only a trace of a smell was detected at the end of the 4-week storage period. At 70 ⁰ C, the comparison sample had after 2 days a sharp, SOP smell disgusting, and the smell took place during the 4-week lag eruiigsp eri ο de intensity too.

A 2% solution of the product according to the invention in methyl isobutyl ketone remained clear for about 3 weeks.

Example 3

(a) Two amine sulfonates of the following composition were prepared from a sulfonic acid (as described in US patent application 711 920) and n-coconut-1 _{5 3 -diaminopropane:}

JL JL

Sulfonic acid * (g) 200.0 200.0

H-Eokos-1 ₅ 3-diaminopropane (g) 63.9 33 »5 approximate excess amine C ^: a). 100 5 Pale Oil 80 thinner (g) 32.4 32.4 isopropyl alcohol (ml) 50x50

* Total acid content 1.101 milliequivalents (mAq of sulfonic acid 1.0p4 meq / g ₅ non-volatile constituents GQ 56.84% by weight

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All reactants except the oil were placed in a flanged flask, heated to reflux temperature and refluxed for one hour ⁰ C away. The reaction wet was stripped with IT gas for 15 minutes, then filtered through diatomaceous earth. Both products A and B were clear and fluid.

(b) Using products A and B above and iron sulfonate5 that of the US patent application 711 92O described sulfonic acid has been prepared v / ar, "were mixtures of the compositions given below made in IsoQctane:

Iron sulfonate (g) Product A (g) Product B (g) Isooctane (ml)

Make mixing of each mixture in a 0.55 1 (1pint) ~ Plasche this was done by means of a mechanical chute! Shaken for 5 minutes and then stored at ambient temperature and daylight. After 2 v / o storage no visible sediment was observed, while one Comparative sample with the same ice concentration (approx 100 ppm) a visible sediment appeared after 10 days under the same conditions.

A solution was prepared in isooctane _s containing about 1000 ppm of the above-identified product A contained "From Variadinsulfonat iron and standards (prepared from the in U.S. Pate nt aim el dung sulfonic acid 711 920 described), the 5OOO ppm Fe or V, mixtures were made that contain

σ D. 1.0 1.0 1.5 _ 1.5 250 250

50 ppm Fe or V and the solution containing the product A. contained. The mixtures were stored in glass at ambient temperature. Tray, a month was in the mixes no visible sediment observed, while in comparison samples from the Pe- and V-SuIfοnaten. without the product A after 2 v / o a visible sediment appeared.

Example 4

Using the starting materials given below mixtures were made:

(1) DUOMEEH CD monosulfonate

(2) DUOMEEN / CD disulfonate

(3) DUOMEElT CD

(4) DUOMEEF T-Dioleate (TDO)

Each mixture was made up in 250 ml of isooctane. The aainsulfonates were about 80 % active. The DUOI-DvCIi OD can be represented by the general formula R-Mi-CHp-GH ₂ -CiLj-JTiI ₀ , in which E means the coconut residue. TBO can through the

.0

general formula (RNH ₂ -OH ₂ -CHp-Gn ₂ -ISI ₇ ) ⁺⁺ 2 (R ¹ OO) """has been shown, in which R denotes the Calg-Hest and R ¹ denotes the oleate.

Eisensulfο nat-Mischimgeri

Mixture of iron mixed with: it the time to the time during which sulfonate * occurs above the Mi- (g) ^ yP (x) (&) of a pine loop clear

stroke stayed (monthο)

. “_______, (months) .

(a) .1.0 (comparative sample) - 1 -

(b) 1.0 (2) - 1.5 - 7

(c) 1.0 (1) - 1.5 '- 7

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(d) 1 , 0 (D -1.5 (e) 1 ? ° (3) - 1 * 65 (f) 1 , 0 (3) - 0.25 (s) 1 _s o (4) ~ 1 ₉ 65 (H) 1 , 0 (4) - 0.25

6 5 5 5 5

about 100 ppm}? o

Miso hung Vaaadin
fonat *
Ce) 1.0 sul- mixed with that
above type (x)
(s) Time until
Appear
one down
blow
(Months) Time while
the the Wed
schung clear
stayed (Ivlonate) (a) 1.0 (Comparative sample) - 3 00 1.0 (D - 1.2 ti ». 6th (c) 1.0 (2) - 1.2 . «- 6th (d) 1 ₅ 0 (5) - 0.9 o _s 5 (V) 1.0 (3) - 0.25 6th (f) 1.0 W - 1.65 . 6th (ε) (4) - 0.25 = ~ 5

ppm ¥

Example 5

For individual metals warcn been diluted to 5 ° ppm in isooctane ₉ irisuelle observations were made, The dilutions were -and prepared in glass flasks v / ährond of BeobachtunGsseitrauns before a .Fenster asked The dilutions were prepared from 5000 PPIA Standards (from the in the TLS patent application Ur ₀ 711 920) produced without special control of the age or the identity of the standard. An exception was a comparison

between a ^ 0 ppm dilution of vanadium of an old standard with a new 5000 ppm standard. The dilutions of the old standard showed turbidity and precipitation within 4 to 14 days, while the dilution of the new standard after standing for 14 days Iceine Exhibited precipitation or turbidity. The following table shows the results of the tests with the 50 ppm dilutions.

Vanadium

Time until the formation of a cloudiness or precipitation

not treated 4, 11 , 13, 14 • days O r / i Treatment amount. 1/4 g / l JZiLß / i 1.0 r / 1 2, 3 months Plus DUOMEK CD
Monosulfonate ' 16 days 16 days Cook 6.7 _ DUOMEElI CD- ■
Disulfonate 16 " 7 " 3 " 3 .Days. DUOMEEN CD - / IQ Il 4th - DUOKEEN T-
Oleat in order
at 4 mo
naten iron

non-treated treatment amount plus DUQHEElT CD

DUOMEEN CD-Mon no sul f onat

DUOMEEN T-Oleat

Time up to the formation of haze, it od exemplary ällunp;

17 days, 6 weeks, 2 months 1/2 r / 1 I.

ok ok after 3 months * after 3 months

- in order

after 7 months

OK after 3 I ionator?

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untreated treatment amount

Plus I) UOMEEIT CD monosulfonate

molybdenum

Time for turbidity or precipitation to develop

Weeks

okay after 7 months

tin

non-treated treatment amount plus TJUOiIEEK CD

DIIOKEEIi CD-disulfonate

DUOMEEH CD-Mon no sulfonate

Time for turbidity or precipitation to develop

Weeks

months

K / l

ok after 14 weeks

5 months

okay after 6 months

Example 6

In the case of individual mixtures containing 20 met all or β aiii see standards with a metal amount of 20 ppm each, instructive observations were carried out. Each of the mixtures contains .ie It silver, aluminum, boron, barium, beryllium, cadmium, chromium _v Kupier, iron, magnesium, manganese, molybdenum, sodium, ITiclccl, lead, silicon, tin, titanium, vanadium and zinc. Two mixtures containing 190 ppm DUOIuEEN CD monosulfonate and two mixtures without the monosulfonate were prepared.

Dio! -! Were looped after a Ro

vel'iahi-cn a. analyzed for their molybdenum content. This The method is known per se. The sample becomes the gamna

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Radiation exposed to a radioisotope _s which cause the emission of X rays from the metals of the sample. The X-ray energy is maintained over a certain period of time in various detector channels in which the energy for the respective metal is most concentrated. The sum of the counters for four channels at 4000 seconds is used as a measure of the molybdenum concentration. The results of the analysis were as follows:

Mixture after 2 months of aging

Mixture according to 4-moxiatiger Aging

with amine without amine> sulfonate sulfonate

18 952

18 654 16 469

The data show that the 4 month old treated mixture had practically the same numerical value (molybdenum concentration) as the 2 month old untreated mixture, but that the 4 month old untreated mixture compared to the 4 month old treated mixture a uni had about 12 % lower count, indicating a stability problem that did not exist with the treated sample.

Sponsorship application

BATH ORIGINAL

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Claims (1)

Patent application ρ rü che / 1 ») Stable _§ oil-soluble metal sulfonate preparation, thereby marked j that it consists of (A) an oil-soluble sulfonate of a metal from the Group molybdenum, vanadium, 'iron ,. Boron, barium, beryllium, tinj silver, titanium, copper, magnesium, sodium and Mixtures of these and (b) an oil-soluble amine compound from the group of • Amines, the amine sulfonates, the amine salts of fatty acids, the ammonium sulfonates or the reaction products of amines with alkyl succinic anhydrides ₀ 2 »Preparation according to claim 1, characterized in that that they are the metal sulfonate and the amine compound in one Contains a ratio of about 1: 0.5 to etv / a 1: 8. 3. Preparation according to claim 1 and / or 2 _S, characterized in that it is the amine compound 1,3-diaminopropane with an alkyl radical from the group of n-coconut, η-tallow, n-soy and n-oleyl radicals contains. 4-. Preparation according to at least one of claims 1 to 3 » characterized in that the metal sulfonate is less than 100 ppm. Metal contains » 303851/1205.