DE1645260A1 - Process for the preparation of ashless lubricating oil additives and lubricants containing such additives - Google Patents

Description

P. 5892 J / V Munich, March 17, 1965

V ..

Shell Internationale Research Maatschappij UV, The Hague

¹¹ Process for the production of asofce-free soaking oil additives and lubricants containing such additives'

Priority 19th March 1964 / Netherlands Registration no. 6 402 969

The present invention relates to a method from the core division of SCiMierülsarsatas'ioffeii, welelis seim 'burn or a decomposer does not leave any ashes ϊΐηά

According to the invention, these newen? UeatäBa's; openly by reacting a polyolefin, which has as a substituent little attene 2 BernateinsäV-regruppan, Eerneteiasä ^ yeaal ^ rS ^ i di groups or succinic acid halide groups ₉ with an aliphatic aryl group , which contains at least one Älteyl in. which vmn ± g »-hmm sia Wu- ^ eg-rg-äoffa ^ iWa has been replaced by a hydroxyl group *

The polyolefin can contain a _{keti © f} welch® ®t * c monomeric units of the fleieliea -Olefiua or composed of m & nemer & n units of different olefins isl-c.

009820/1 ^ 88

Examples of these are polyethylene, polypropylene, polybutene and PclyisobuterJeetten, as well as polyolefinic chains, which are composed of units of ethylene and propylene, for example, propylene and Xiuiien, b? _e \ *. vo: i 3ivt3n and isoprene build up, aöwiö folyolefin chains, which contain structural units derived from substituted olefins, such as styrene

3s.ibstverstaru21i-.3h au3 the iln &afc'i of. Kohlenstoffatoüi is Polyol8firik-3tt3 selected such w®rdeii _g Cass of Susatzatoif is "Söhsiia ^ ölftii laudable: La ^ ₄ DIs this oyfnriorliolio .Katt'-mXSage Iä3t" I spawns ^ xperiinöiiteli Is-uetianien "Ee can gelsen as Hegel ^ tHe in general such a chain a © longitudinal feat, weim si · «im Xntrchschnitt · 30 coals - tfzt ^ m ^ f-te jo'lo;> οΙ? ϊ. ^? * ϊ ^ -ri ^ pe shows Woim this rela« ? Ks'Hsn.laage <> r! Iöhi w?. ^ "', Revbesöcrt" I the Lüeliclikeit. ieti wfeiterii Ei ^s böLeK the feb & üliitcr ^ Xettonlönge is reached however StaßivM- j where the J * ößl: iühkfcit ^; to fall off again

e gi'fissäe abeolut »? Kt tteniänge, which ge.rt.ae are still kftiw.i _f depends, among other things. Factors τοκ Yei ^l zweigunga- grf% ä d © K Kett aiii! their degree of criticality. A Yer connection with a fully ataktieohen polypropylene chain is generally better Sm tt löolich seia as a- compound ".gleicher chain length _y which has ^ eiloeh eleventh isotactic Polyath ^ lenketto.

BAD ORiG) NAL

Pure compounds with a hydrocarbon chain of more than 50,000 carbon atoms, poor solubility in the lubricant must usually be expected.

From the foregoing it was evident that the The number of polar groups also influences the solubility. With regard to the hydrophilic character of a polar group it is understandable that with an increase in the number of such groups in the molecule of the additive the oil solubility eventually becomes very bad. It was already it should be noted that it is preferred to use compounds which have at least 50 carbon atoms for each have polar group in der.Polyolefinkette.

A very suitable ratio of chain length to the number of polar groups is a polar group to an average hnm®hl VOB 100 to 400 Kohlenetoffatomen in the polyolefin chain.

The new additives are preferably made from polyolefins made with succinic anhydride groups. Suitable for this Polyolefins can be made from polyolefins with active sites that react with maleic anhydride make possible so that a polyolefin ait succinic anhydride groups is formed.

009820/1689

Such polyolefins are, for example, compounds with several double bonds or with several Halogen atoms, in the form of a Wasseratoffhalogenidea can be split off with the formation of double bonds. For example, a copolymer can be used as the starting material from isobutene and isoprene to which maleic anhydride has been added. Another example is the reaction of a chlorinated copolymer of ethylene and propylene with maleic anhydride. In this implementation hydrogen chloride is split off and the maleic anhydride reacts with the unsaturated copolymer formed in the process with the formation of new succinic anhydride groups which are bound to the chain of the copolymer.

In both of the above-mentioned processes for the preparation of a polyolefin having succinic anhydride groups, the Reaction of the unsaturated copolymer with the maleic anhydride to form a reaction product in which the number of the double bonds of the main hydrocarbon chain has remained unchanged. If desired, these double bonds be converted into single bonds by subsequent hydrogenation, such hydrogenation being preferred carried out before further reaction with the arain.

009820/1689

Examples of amines suitable for this purpose are primary amines such as l-amino-2-hydroxyethane _f l-alino-2-hydroxypropane, 1-amino-3-hydroxypropane, l-amine-2,3-dihydroxypropane and their higher homologues, such as l -Amino-2,3,4,5 "6-pentahydroxyhexane and also primary amines with branched chains, such as bis (hydroxymethyl) arainoinethane and irie ~ (hydroxymethy3,} piiinoinethane. Examples of suitable secondary amines are ethyl-2-hydroxyethylamine, Propyl-2-hydroxypropylandn, propyl-uS ^ hydroxypropylainiii, diethanoi * amine,! Diisopropanolamiß and their higher homologues as well as alkyl C-polyhydroxyalkyljamineo examples for suitable tertiary amines are 2-hydroxyäthyldiätnylamißjbie (2- »bydrosyätfejamin ät their homologs)

In the implementation £ »it äem AmIn , a part of the amberc"'«iregi'uppeja or the gyuppea derived from it, such as amber acid anliydrid group ^ ii«, with the azalnogruFps water image of an Ijüid and mm part MquqbmMb and üum f @ ii Biamiida raa- '* gia? eÄ, while eia asdarc-2 "fall ai'is öiu ^ r Eytiresi ^ Igrappe dee Aaina im-iar Bilda. ** ^ © Ines Meaoea'&sx's odey Biaaisora respond

both Berßatainsä ^ ireiaiiägrtäppen and B eaiergruppe auXwsisar ·. » However, if iorean il is an amidode? * Imidbiiöuag not possible.

§820 / 1889

Products are preferably used which have been obtained by reaction with an amine which has at least 3 -hydroxyl groups, Basoivl ^ ra preferably '-v ^ rden aungsprodukta r _{s with} primary: "" A ^ i> i ^? I _? welüiio weni-getens 3 H jcylgruppe.n entitsitaa «. 8o-vonl Ti'io-vl'i ^ iiroityr.pthyljaisi.aoffie als ausa Glyüolaaiii atwlle / i se-lir geai ^ -icte AU8 £ angf? Matei'lalieii

v & r & B teln ? Xr ^ ePeLa = I ^ irdj seil daa U product, vorstig ^ ^ ur Ilaupt-e & cne eus Imiden.ür. * 3 -stern

Sin se-ehes Fr ^ dvV't. kmin. produced.> by the

-30hßn 130 vmi 250 °

^ gsYi ^ ise «i? d Say An; An Im ÜbsrachuS?« rwaiid2t »miu bsi Aawss-iynn; slaeg priiTÄrea Amins beva &'mü'Z on the Imiäbxl d.iir * g, at Aawend ^ ag eins3 eakii'-idMren AsUi ^ bereelui-at on di © "-" MMimg ä'iB Dis ^ i ^ s and bsi kruiBUä; mg si ^ * ^ ti ?? 3 tiären Amines "böreihnci;. & ui einft the formation of" ^ a Dieste Yonvogeweiee is "iii üb # & ^L verwenaet gchii3 of the amine of 50 öiö 3Ö0 ^.

The irfliiSMBgägeffiäßÄii new additives are in lubricating oils i? soluble.

009820/1683

BATH ORIGINAL

If desired, the reaction product can initially be in one low-boiling solvents such as hexane are dissolved, whereupon any insoluble impurities present are filtered off and then the solution sweeks removing the solvent wiped off, if desired with steam.

A small amount of oil can be added to the reaction product, if desired can be added to form a concentrate which is then used for the production of lubricants can be which the additives in question should contain. Depending on your requirements, this amount of oil can also be given to the reactants even mixed in with the implementation before the Burehead will.

The reaction products can be used as additives for lubricants of the verecfeiedeneteii kind. Ir first and foremost kessen _Mi & eralseks! ieröI © of various viscosities in Afflicted. Ee also know ey & aesthetic selmder oils as well Lubricating oils containing fatty oils can be used. The new ι Additives can also be incorporated into lubricating greases.

The amounts of new additives added to the lubricants can vary within a wide range.

009320/1583 SAD ORIGINAL

In general, the desired improvements in lubricants are achieved by adding their additives in amounts between 0.1 and 5 wt .- #, in particular from 1 to 3% by weight, based on the finished lubricant, depends on the quantities the additives can also be increased, for example in diesel engines, which tend to be very dirty.

The additives according to the invention can be combined with one another and with other additives, for example with antioxidants, cleaning agents, improvers for the viscosity index, anti-corrosion agents, anti-corrosion agents, pour point depressants, the oily-improving agents and, in general, with substances that are usually added to lubricants.

The invention is explained in more detail by the following examples,

Example I.

Ale Auegangenaterial was a Xthylen-propylene rubber with a * molecular weight of 150,000 and a ratio of the monomeric units of 1: 1 (molar) used the up below a chlorine content of 1.72 percent - $> was chlorinated..

009820/1689

BATH ORIGINAL

5-6 parts by weight of maleic anhydride were dissolved in 20 parts by weight of o-chlorobenzene. -Parts of o-dichlorobenzene added, which in a nitrogen atmosphere "was kept at a temperature of 180 °". After heating the mixture for 20 hours at this temperature with constant stirring, the latter was increased to 200 °, whereupon 10 _s β (Jew "- Parts of tria- '(hydroxy-diethyl) aminomethane were added.

After heating for a further 24 hours at this temperature with constant stirring, the solvent was removed by vacuum distillation. The residue was dissolved in an equal volume of toluene by the solution in five times the volume of methanol eiiig8gosaen ₉ which contained 10 § © # .- $ water The insoluble part which separated out became the same; Volume amount of toluene absorbed by this exercise was again poured into the S-faehaVolumeniaeng © Matfeanol, which contained 10% by weight of water. The separating out insoluble portion was removed by vacuum distillation of solvent and water is freed The yield of the Uametzungsprodukt with a nitrogen content iron 0.81 wt. ^ A chlorine content of 42 wt .- 0 _f ^ betryg 93 _t 9 (Jew. Parts by.

009820/168 9

Example II

A commercially available synthetic rubber was used as the starting material, which was built up from monomeric units of isobutene and Iaoprene, was 2.2 ^c f> unsaturated and had a viscosity according to ML-8 at 100 ° of 45 a.

258 parts by weight of this rubber were divided into 1,000 parts by weight Decalin dissolved. After adding 20.3 parts by weight

With maleic anhydride (excess of $ 100) the mixture was heated to 180 ° for 24 hours. After cooling, the reaction odor was poured into 5 times the volume volume of methanol. The insoluble fraction which separated out was separated off and dissolved in 1,000 parts by weight of Secalin. Then 50 parts by weight of triβ- (hydroxyethyl) aminomethane (excess of 300 ml ) were added. After heating to 180 ° for 24 hours, during which 4 parts by weight of water were collected in a cold trap, the reaction mixture was allowed to cool and poured into 5 times the volume of methanol.

w The separating out insoluble portion was isolated and dissolved amount by weight of toluene in the same, and this solution in turn amount by volume of methanol was poured into the 5-faohe. The insoluble part deposited was separated and dissolved in the same amount by weight of toluene.

009820/1689

872 parts by weight of a paraffin were added to this solution Adding lubricating oil distillate tea with a viscosity of 23.3 cS at 37.8 ° and a viscosity of 4.3 cS at 98.9 °. After removing the volatile solvents by vacuum distillation 1152 parts by weight of an oil concentrate remained, which contained 24.3% by weight of the new additive. By titration with perchloric acid, the content of basic nitrogen was found to be 0.026 milliequivalent per gram of blood concentrate certainly.

The additives according to the invention were in Pom 1.5 weight percent solutions in a S®femier oil using a few gardSLer-Dlssel-HctorE! tested In addition, the additive according to Example I was also tested in buckets of Petter gasoline *, a test wagon in the Gardsier engine was ale parßffl-.issisofe © © Sctesdertsldeetlllat with a viscosity of 11.5 sS solid 9 © e9 ^e "rer ^ saietc B © i ü @ r examination in Petter-Mo ^ or «^ rcl © eia S & slsSl dee same fjrpe but fine tissue ψ © ε 1 ₉ 2 sS" is 93 _f 9 ° e

Gardjaer Diesel Hotor

Water-cooled, lin'Bylinder four-stroke engine. Cylinder boring

rungs 108 bub - Hubhtihex 152 "4 mm - Stroke volume .: 1.4 liters - j Power at 1,200 revolutions per minute (60 mg fuel per work stroke): 11 hp - test duration: 17 hours - fuel ι Diesel oil has a sulfur content of 0.9% by weight deo cooling water: 80 °.

009820/1689

This test determines the amount of piston contamination rated.

Petter petrol engine

Water-cooled, single-cylinder four-stroke engine. Cylinder bore: 85 mn · »stroke height 82.5 mm - stroke volume: 468 cnr - compression ratio: 10.0: 1.

The test was carried out under changing working conditions, namely 55 minutes at 1,500 revolutions per minute, a load of 3 # 5 hp and using a propellant air mixture with a ratio of 1.0, and 5 minutes long at 1,200 revolutions per minute, a load of 2 HP and using a fuel-air mixture with a ratio of 1.9. The test duration was 48 hours. A premlum petrol with an addition of 0.4 ml / liter TEL (containing 61.48 wt .- # tetraethyl lead, 17.86 wt .- ^ ethylene dibromide, 18.81 wt .- # ethylene dichloride, 0.06 wt. ?; Dye and 1.79 wt .- # luminous oil and impurities) and a sulfur content of 0.10 wt .- ^ used, which had an F-I octane number of 100. The temperature of the cylinder cooling water was 80 °, the temperature the cooled cover of the control was 25 °.

In this test the extent der'Schlammbildung rated ·

009820/1689

The results obtained in both engine tests are generally summarized in the tables below

EABELLS

Additive ·! Sitotis ^ eiifirtsiH Sel ^ aMsaMl ^ '

(10 * rice) ■ (10 ^ pure)

itz göiaäS
Example L. B = C

Susata acc

Bsiapiei II 8 ₉ ; 3

BATH

Claims (1)

Claims '/ learn about HsrstrfJvag · one aechef for iio.bs'ierinitteli v / sloher sine oXeaphile öf: rkPtte and »d at least two pelar groups fe - * - 3Fί; κ iapiiron ίτβ ^ κίΐίβίίϊ'Ιΐϊϊΐ ¹ 1j öa £ a. Polyolefin, wel- two Berwst ^ inßyuregmp- · oiler Berneteinsäarehalo- sntM2t _f öit * an aliphatic amine converted s which little one has an alkyl group in which ften *? nin ¥ 'fe..pser-etn.ffatom .by a hydroxyl group fshrer * aacJb. Anepracb l _t thereby gelrenn ^ eich- iiv% _; . mii £ i "IMN $ J® the Polyolcfinkttte ^ ix? he average number of Vf ^ ^ ne Nigst 50 carbon atoms each FVR polar (Jruppe '.} ■ - Verftilir ^ ii imefc £ / v / priieh <. _% uanar-zh gelcennseich- li- ⁴ -; ΐ? Γ · -ΐ? : '■; .- ?. longer Myclefialrethe ei ^ .er A ^ 2 <üil op £ 00 Foi? iru £: töff0-fc ^^ ir for j * ae roLet ^ 0-5 90? Ö / ^- fi0t ORIGINAL INSPECTED 1845260 4.) Method according to Anepruch 1 to 3 »characterized in that the polyolefin chain is no longer ala Has 50,000 carbon atoms. 5.) Method according to claim 1 to 4, characterized in that the Arain contains at least three hydroxyl groups. 6.) - Method according to claim 5 »characterized in that that a primary amine is used as a reaction partner will" 7.) method according to claim 6, characterized in that that tri- (hydroxymethyl) aiainoBiethan as reaction partner is used" 3 * 5 method naoli claim 1 feie 7 _S calculated by the fact that the Affin is used in overshoes. 9.) SohffllerEittelmieehung consisting gröSeren a proportion of a lubricant and a minor amount of a aue Schmierb'lzueatzetoffee according to claims 1 bie. 8 009820/1689