DE1668973A1 - Sulphonic acid salts and their use as lubricating oil additives - Google Patents

Description

• MDNCHEN 2i · 81 EQ ES8TRA88E 2 «· TELEPHONE 34 · 0β7. TELEGRAM ADDRESS: INVENT / MONCHEN

SHELL IITERNATIOIALE RESEARCH MAAT3CHAPPIJ N.T. Pen Haag, the Netherlands

"Sulphonic acid salts and their use as a Sohmierölatz"

Priority: March 17, 1967, Y.St.A. Registration no. 623 837

The invention relates to sulfonic acid salts of the formula A.

Pfe ₃ ) _n [H ² OO ₂ O) _n ] J ₁ I

in the A either

a τοη a fatty acid and a polyalkylene polyamine of the formula

HH ₂ ^ ¹ HH - ^ R ¹ HH ₂ II

In which R is a C1-alkylene group and -η O or a whole number

is, derived AnId or

a condensation product of such an amide with a Cg, «-

Represents alkylphenol and an aldehyde,

2 "

R is an organ-flat group, m an integer and χ a ganee

Number τοη 1-10 means, which corresponds to the number of τοη moles of sulfonic acid of the formula R (SO ₂ OH) _B required for salt formation »

Pi sulfonic acid salts of the invention can be used as ash-free terburning

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en additives are used that prevent rust formation and have dispersant properties · They are that is, as additives for lubricating oils of interest, which and must have a cleaning effect, e.g. for gear owls and Two-stroke lubricating oils or two-stroke mixtures.

The amide A can be prepared by shredding 1-4 moles of fatty acid with 1 pint of polyalkylenepolyamine at an elevated temperature.The amide preferably contains 1 or 2 amide groups in the molecule, in which case χ in the sulfonic acid salaryζ must be 1 or 2 accordingly.

Straight-chain or branched-chain fatty acids or mixtures of such fatty acids are suitable for producing the antide, for example straight-chain, iso-, neo-, dimerized or trimerized fatty acids. Commercially available mixtures of such fatty acids can be used to produce the amides, for example a mixture of C ^ ₀ ... fatty acids, a mixture of straight-chain and Ieo fatty acids or a mixture of mono-, dimerized and trimerized fatty acids, e.g. the one under the trade name "Eapol 1014 "Fatty acid mixture sold. Preference is given to aliphatic fatty acids of the general formula HCOOH, in which R is a saturated or unsaturated aliphatic group with 4-30 C atoms, preferably a C ₈ JT ₀ - expediently ⁰ Q _- ^? ^or ^ ₁₂ - _p ) -alkyl group. Examples of suitable saturated aliphatic fatty acids are lauric, caproic, olfCt-dimethyleapronic, caprylic, isocaprylic, myristic, palmitic, stearic, isostearic and arachidic acids. Iso-tearic acid is particularly preferred. Examples of unsaturated aliphatic ·!

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BATH ORIGINAL

Acids are oleic, linoleic, linolenic and elaostearic acids. Suitable Fatty acids preferably have 8-22 carbon atoms Examples of dmerized and trimerized fatty acids are Dimers and trimers of linoleic, linolenic and eicosa-8,12-diene-1,20-dlic acid.

The group R in the polyalkylene polyamine is preferably one Ethylene or propylene group. η is preferably 0 or an integer from 1-8. The polyalkylene polyamine can be a mixture of isomers be. For example, it can be 10-30% by weight of branched and a cyclic polyalkylene polyamines, e.g.

^C 2 ^H 4

Sulfonic acid salts derived from these isomers can be used in one Sulfonic acid salt of the invention may be included. Examples of straight-chain polyalkylenepolyamines are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, fentaethylenhexamine, dipropylenetriamine, tripropylenetetramine and tetrapropylenepentamine. Special Tetraethylene pentamine is preferred.

To prepare the condensation product of the amide with an aldehyde and a phenol, one mole of the amide with each React 1-4 moles of the Cg ^ g-alkylphenols and the aldehyde. Examples of suitable phenols are octylphenol, decylphenol, lauryphenol and ootadecylphenol. Dodecylphenol is special preferred. As the aldehyde, an aliphatic aldehyde, e.g.

Acetaldehyde, an aromatic aldehyde, e.g. benzaldehyde, or

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• AD ORiGfNAk

a heterocyclic aldehyde, e.g. furfural, can be used. Aliphatic aldehydes are preferred, in particular formaldehyde, which is expediently used in the form of paraforraaldehyde.

To prepare the sulfonic acid salts of the invention from the amide or its condensation product and the organic sulfonic acid, 1 mole of the amide or the condensation product is reacted with 1-10 moles of sulfonic acid. The reaction can be carried out at a temperature of 0-100 ^° C., if desired under a nitrogen atmosphere at atmospheric pressure.

As the organic sulfonic acid, a petroleum sulfonic acid or a synthetic sulfonic acid can be used. Suitable sulfone

2 2

acids correspond to the formula R (SOgOH7 _m , in which R denotes an organic group, for example an aliphatic, cycloaliphatic or aromatic group and m is an integer.

Under ⁿ petroleum sulfonic "is meant any sulfonic acid which is produced from a petroleum product, such as a mineral lubricating oil. The mineral lubricating oil made of a naphthene-paraffinic or gemischtbasischen crude oil can be used. Preferably, a neutral lubricating oil, eg a lubricating oil having a molecular weight of 250 - 1000 or more and a viscosity of 60 to 2000 SUS (Saybolt Universal seconds) at 37.8 ⁰ C. another preferred lubricating oil is a bright stock, a bright stock is a viscous petroleum product 'by refining by means of solvent extraction, hydrogenation and. Dewaxed.

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product can be sulfonated with any sulfonating agent e.g. with sulfur trioxide, chlorosulfonic acid or preferably with oleum (fuming sulfuric acid). The petroleum sulfonic acids can optionally be substituted and e.g. 8ticketoff, Contain sulfur, oxygen or chlorine atoms *

A "synthetic sulfonic acid ¹¹ " is to be understood as meaning any organic sulfonic acid that is not petroleum sulfonic acid. A synthetic sulfonic acid can, for example, be a sulfonic acid of a lubricating oil which is produced by liquefaction of coal or by a synthetic process, e.g. polymerizing an alkylene, has been manufactured, e.g. e in polyethylene, polypropylene or polybutylene sealing oil *

The synthetic sulfonic acids can be cyclic as well be aliphatic. Suitable synthetic sulfonic acids are described, for example, in Canadian Patent 733 142 and US Patent 3,250,710. The synthetic suIfon

• Ζ Λ

acids can have the general formulas R -T (SO, H) _b or R (SO-B). correspond, in which a and b are 1 or higher integers, B * and R * aliphatic «groups, 2.B. Alkyl, alkenyl, alkoxy, alkoxyalkyl or carboalkoxyalkyl groups, and T is a sykliaoher learn, e.g. a benzene, naphthalene, anthraoene, diphenylene sulfide, phenothiazine, diphenyl oxy d, diphenyl sulfide,

Diphenylamine cyclohexene, decahydronaphthalene or cyclopentane

3 4 ring · The groups Rg-? and R preferably contain at least

15 carbon atoms. Specific examples of R * are derived from saturated or unsaturated paraffin wax · and polyolefin hydrocarbons, including polymerized C-olefins ·

2— ο

109844/1856

Groups. R, R and S know organic or inorganic substituents, see B. Hydroxyl, mercapto, litroso, nitro, Amino, sulfide or di-sulfide groups or halogens.

Specific examples of suitable oil-soluble synthetic sulfone · acids are mono- or poly-water-substituted τοη naphthol, Diphenylither, laphthalene disulfide, diphenylamine, thiophene or

-Chlonaphthalene-derived sulfonic and polysulfonic acids. Other suitable sulfonic acids are e.g. CetyIchlorbenzenesulfonic acids, Getylphenol monosulfide sulfonic acids, cetoxycaprylbenzenesulfonic acids, Dicetylthianthrendisulfide sulfonic acids, dilauryl-ß-naphthylsulfonic acids, dicaprylnitronaphthalenesulfonic acids and alkarylsulfonic acids, such as dodecylbenzenesulfonic acids, i.e. sulfonic acids,

which are derived from benzene alkylation products produced in Alkylation of benzene with propylene tetramers or isobutene trimers for the introduction of 1, 2, 3 or more C ^ substituents in the Benzene nucleus were obtained (Bodecylbenzolnachlauf exists in essentially from mixtures of mono- and didodecyl benzene), and Mono- or polytridecylbenzenesulfonic acids, aliphatic sulfonic acids, such as paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted "paraffin wax sulfonic acids, Hezapropylenesulfonic acids, tetraamylenesulfonic acids, polysobutylenesulfonic acids, chlorine-substituted paraffin wax sulfonic acids and Hitroparaffin waxesulphonic acids, cycloaliphatic sulphonic acids, such as Zardulnaphthensulfonsäuren, Bie (diisobutyl) cyclohexylsulfonsäuren and mono- or polywax-substituted cyclohexylsulfonic acids.

The invention furthermore relates to the use of sulfonelureaaleen of the formula I as a lubricating oil additive. Sulfoneture

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acid salt of the formula I as a Sehmier oil additive. The sulfonic acid salts of the invention can be added to natural or synthetic lubricating oils or mixtures of natural and synthetic lubricating oils. Examples of synthetic B&SiseohalerQle are polyolefins, polyesters and polyethers. The sulfonic acid salts of the invention are preferably used as an additive for mineral lubricating oils. Suitable base oils are mineral oils which come from a naphthenic, paraffinic or mixed-basic crude oil and have a low, medium or high viscosity index fall (SAE means Society of Automotive Engineers), e.g. SAE 10 - SAE 50 MotorschmierSle. The suif on acid salts of the invention can be used in amounts from 0.01 to 40 parts by weight jf, preferably 0.1 to 20 wt .- ^, in particular 1-15 wt .- ^ used.

An example of sulfonic acid salts of the invention are salts of general formula

SO ₂ R ² J

C-O C = O

R i

2 in which R and R are as defined above.

The nitrogen atoms can also be linked to the acyl radicals RCO or the sulfonic acid esters H SO-O in other ways.

The production of various sulfonic acid salts is revengeful the invention explained by means of examples.

1 09844/1856

1. Production of amides or condensation products suitable for all starting materials

2 moles of leoetearic acid and 1 hol of tetraethylene pentamine are used

76.7 - 98.9 C in a reaction vessel reacted with one another The product obtained is the diisoetearamide of tetraethylene pentamine (I (a)).

The following amides are prepared in an analogous manner: Isostearamide of tetraethylene pentamine (I (b)) j

Lauramide of tetraethylene pentamine (I (c)); Stearaid of Ethylenediamine (Kd)) { Dipalmitamide of polyethylene triamine (I (e)); Diisostearamide of dipropylenetriamine (I (f)); DliaoBtearamide of tetrapropylene pentamine (I (g)) j Condensation product of 1 mole of I (a) with 1.5 Hol of formaldehyde and dodecylphenol (I (h)) each.

2. Production of earth sulfonic acids suitable as starting material

Bin 3 liter equipped with a stirrer, a dropping funnel, a thermometer and a vent-equipped three-necked flask is charged with 1 kg Ellenburger Brightstook from West Texas, the following properties: viscosity at 37.8 ⁰ C, SUS 2812

Viscosity at 98.9 ⁰ C, SUS 116.1 Viscosity index 99 Sulfur, wt .- ^ 0.07 Molecular weight 77O Total aromatics 40 Light aromatics 28.1

109 84 Ul 18 56

105% by weight of sulfuric acid (200 g, 20% by weight of oleum) are added dropwise to the Brightatock over the course of 1 stand, while stirring vigorously. Until temperature of the mixture thereby ateigt from 25 to 45 ⁰ O. The mixture is stirred for a further 30 minutes and then added under stirring with 15 ml of water. Then the mixture is mixed with a volume of hexane (1132 ml) corresponding to the volume of the brightstock used and left to stand overhead.A small amount (86 ml, 149 g) of used, dark brown, fairly liquid and easy to handle acid separates out ab · The supernatant hexane layer is separated off and washed with a clay mixture of 500 ml of water and 750 ml of methanol. The clear, yellow, lower layer which separates out is discarded, while the upper layer is shaken out with 750 ml of absolute methanol. Two phases are formed which separate completely from one another within 2 hours. The upper layer is discarded · The solvent is stripped off the lower layer, which contains the desired petroleum sulfone structure. The residue is a petroleum sulfonic acid, hereinafter referred to as II (a), with an average molecular weight of 850 and an acid number of 5.0.

Using the lubricating oils listed below anateil · of the Brightstock, further petroleum sulfonic acids are based on analogs Way made:

Neutral oil with a viscosity of 1250 SUS at 37.8 ⁰ C and 82.5 SUS at 98.9 ⁰ C, a flash point of 210 ⁰ C according to COC and a viscosity index of 55 · This lubricating oil results in petroleum sulfonic acid II (b) .

109844/1886

ErdöleulfoneÄure II (c) from a neutral oil having a viscosity of 1080 old SDS at 37.8 ⁰ C and 71.2 SUS at 98.9 ⁰ O, a flash point of 226.7 to ⁰ C and a COC Tiakoait & teindex τοη 25 t

Petroleum sulfonic acid II (d) aue a neutral oil with a viscosity · ▼ on 106 80S at 37.8 ⁰ C and 38.2 SUS at 98.9 ⁰ C and a flash point of 162.8 ⁰ C according to COCj

& Srdölsulfona acid II (e) of a neutral oil having a Viskoaitat of 557 SITS at 37.8 ⁰ C and 55.8 SDS at 98.9 ° C, a flash point of 212.8 C after COC and a viscosity index of

ErdSlsulfonaftare II (f) of a neutral oil having a SUS at 37.8 Yiskoaität of 265 ⁰ C and 50 SUS at 98.9 ° C, a flash point of 221.1 to ⁰ C and a COC Tiskositätsindex of 93rd

3. Manufacture of sulfonic acid salts !! the invention; 1 mole of dea amide I (a) is reacted at room temperature with 2 ha of petroleum-sulfonic acid II (a) to form the dieulfonic acid alkali according to the invention III (a). This sulfonic acid salt contains 0.44% by weight of basic nitrogen and 1.19% by weight of total nitrogen.

In an analogous Yeiee "following sulfonic acid salts of the invention made ^ground:;

III (b) from 1 mole ICa) and 2 moles II (b); (Disulfonic acid alkali) III (o) aue 1 mol 10>) and 2 mol H (a); (Disulfonic acid alkali) III (d) from 1 mol of Kd) and 2 mol of II (e); (Disulfonic acid aals) III (e) au «1 mole I (g) and 2 moles II (d); (Disulfonic acid eels)

III (f) from 1 mol I (a) and 1 mol II (a) t (Monosulfomäuresale)

109844 / 18S6

III (g) from 1 mol kg) and 2 mol II (a); (Diaulfoneäureeal ") III (h) from 1 mol I (h) and 2 mol II {a); (Diaulfona acid eels) 111 (1) from 1 mole I (h) and 1 Hol II (a); (ttonosulfone & ureeale) ZII (j) aua 1 mol I (a) and 2 mol β ine 3 from dodecylbenzo3tnaehlauf sulfona acid mixture obtained; (Sisulffonic acid salt) III (k) aua 1 mol Ka) and 1 mol one from dodecylbenzene follow-up prepared sulfonic acid mixture; (Monosulfonic acid as) 111 (1) from 1 mole l (a) and 2 moles of one from dodecylbeneol follow-up prepared gulfona acid mixture; (üisulfonsäuraeala) .-

Manufacture of Seamier81sn under 7srwenduns the above - »-

level Sulfo-Acid Salts of the Invention: Lot, Oew.-jC 7.86
rest SohalerOl Beatand parts 8.00
rest IV (a) SaIs III (a)
Mineral oil (SAE 30) 7.5
3.4 IV (b) SaIa III (b)
Mineral oil (SAE 30) IV (c) Sal «Ill (a)
Zinc bis (octylphenyl) dithiophosphate

"Acryloid 150 * (trade name for a Polymerization product of a methacrylate) - 0.5

Mineral oil (SAE 30) rest

IT (d) Sale III (c) 9.0

Folyieobutylauccinlfflid of tetraethy-

lenpentaain 1.0

Zinc bie- (ootylphenyl) dithiophoaphate 3.0

"Aorylold 150 · · 0.5

Mineral oil (SAE 10W) _m ^ Reat 109844/1856

Lubricating oil Components Amount, wt .- ^ ΙΤ (β) Salt III (d)
Mineral oil (SAB 30) 9.5
Heat IV (f) Salt UK ©)
Mineral oil (SAE 10 / 20W) 5.0:
rest

Salt Ill (f)

4,4 ^l -Methylene-bis (3,6-di-tert-buty! Phenol)

"Acryloid 150" mineral oil (SAE IOW)

8.5

5.0 0.5 Heat

IT (h) salt III (h) 8.5 Mineral oil (SAE 20) rest IV (i) Salt III (3) 9.0 Mineral oil (SAE 30) ' rest IY (I) salt 111 (1) 9.3 Mineral oil (SAE 30) rest

Motor set of sulfop & fcureaalzen of the invention included

The lubricating oil IV (a) is tested in a 196Oiger Oldemotele engine such as that used for the Sequence I dee AMA-MS-Teate (described in ASTM-Technical Publication 315, copyright 1962, under the heading "Reference Sequences I, II, III ") is used. To carry out the test, the. ClSseobile-Moter Jtdooh so modified, jg.B. duroh increase Uer "" blcwby-Geemenge "atuf

I BITE

O, 0425 m ⁵ / min., That prevail conditions during dee tests in the engine which promote the formation of rust strongly * This Teatlauf sets calibration composed of 30 cycles to give the engine in each case 10 minutes with a eeschwindigkedt run of 2500 rpm without load 18JJt and then turn off for 20 minutes. The Olsunpftemperatur is at each cycle during start-up each 54-, 5 ⁰ G and when the engine respectively 79.5 ⁰ C. to a host rating said rating 10 receives clay 9.5 "In the examination of the lubricating oil IV (a) complete prevention of rust formation means "

The sulfonic acid salt III (a) is thus an extremely effective rust inhibitor and moreover does not contribute to the deposits in the engine, since it burns free of ash.

The sulfonic acid salts III (b) to HI (I) according to the invention result in a mixture with engine oils lubricating oils, which in the above Test with that of the lubricating oil I7 (a) give comparable ratings.

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Claims (1)

a tentanaprttche 1. Sulphonic acid salts of the formula in the A either one of a fatty acid and a polyalkylene polyamine the formula NH ₂ in which R is a C «, alkylene group and η O or an integer means derived amide or a condensation product of such an amide with a ^ 8-18 "' phenol and an aldehyde, R is an organic group, η is an integer and χ is a number from 1 to 10, which corresponds to the _{number of moles of sulfonic acid of the formula R (SO 2} OH) _{m required for salt formation.} 2 · sulfonic acid sal according to claim 1, characterized in that £ Ä is a condensation product obtained by reacting 1 mole of amide with 1-4 moles of alkylphenol and aldehyde each 3 · sulfonic acid salt according to claim 2, characterized in that A is a condensation product of dodecylphenol. 4 ·· Sulphonic acid sal ζ according to one of claims 2 and 3 »thereby characterized in that A is a condensation product of an aliphatic aldehyde, in particular formaldehyde. 109844/1856 ■ "■ '-.- 15 - 5. sulfonic acid salts according to any one of claims 1 to 6, characterized characterized in that the amide is a degradation product of 1 * 4 Hol Fatty acid with 1 mole of polyalkylenepolyamine. 6. SuIfonaSureaale according to one of claims 1 to 5, characterized characterized in that the amide has one or two amide groups. 7. sulfonic acid salt according to any one of claims 1 to S _t, characterized in that the amide is derived from an aliphatic ¹ en fatty acid of the formula RCOOH, in which E is an aliphatic (group with 4-30 carbon atoms, in particular a C ₈ * ₀ -Alkyl group, mean 6. sulfonic acid salt according to claim 7, characterized in that that the amide is derived from isostearic acid. 9. Sulphona acid alkali according to any one of claims 1-8, characterized in that the amide is from a polyalkylene polyamine of the formula II, in which R is an ethylene or propylene group and η is 0 or an integer from 1-8. 10. sulfonic acid salt according to claim 9, characterized in that that the amide is derived from tetraethylspentamine. 11. sulfonic acid salt according to any one of claims 1 to 10, characterized characterized in that the organic sulfonic acid is a petroleum sulfone acid, which is preferably a neutral one Lubricating oil or a ribbon stick. ". ■: .. * ■ 12. Use of sulfonic acid salts!} According to one of the claims ■ * - '· -ν- 109844/1856 ~ 16 - 1 to 11, ale lubricating oil additive, especially for Mineral Eohmier-Sie lind voraugeweiee in an amount of 0.01 - 40 wt .- ^, get onto the finished lubricating oil gasket. 1 O 9 β