DE1807924A1 - Flowable compositions containing organophosphorus compounds and such compounds - Google Patents

Description

PATENT ADVOCATE

DR. £. WIEGAND DIPL-ING. W. NIEMANN. ',, _n , ^ _r

DR. M. KÖHLER DIPUNG, C. GERNHARDT ™ - ~ _: - ^ '_; ·

MÖNCHEN HAMBURG 1 8 U / 3 2

Nov 8, 1968

TELEPHONE: 555476 8000 Mü N CH EN 15,

TELEGRAMS: KARPATENT NUSS3AUMSTRASSE IS

W. 13 933/68 Ko / G

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

Or ^ anophosphorus compounds and such compounds containing flowable masses

The invention relates to new 0r _; ; Phosphorus compounds, their use as additives and their application in liquid or flowable compositions.

Organophosphorus compounds as additives for various Liquids, especially lubricants or lubricants, are known for a long time · For example, in U.S. Patent 2,957,931 phosphorus compounds which contain carbon-phosphorus bonds and which are used as hydraulic fluids and additives are useful for mineral oils. The compounds described there include Älkanphosphonatester, which by Implementation of a phosphite ester with an olefin. In US Pat. No. 2,724,718 it is a similar process for making organophosphonates described. However, none of these patents indicate that certain specific alkane phosphonates as a friction modifier to reduce corrosion are valuable.

Friction modifiers are, of course, used in automatic transmission fluids wherever their property is most necessary to modify the surface finish

909823/1172

6AD ORIGINAL

are "The Importance of Achieving Good Frictional Properties is given below in which the evaluation of the Allcanphosphonate as a paragraph dealing with friction modifiers.

It has now been found that certain alkane phosphonates have extremely favorable properties for modifying friction. These alkane phosphonates are the hydrocarbon esters of alkane phosphonates with C ^ ₂ to ρο * ^ ⁶ A ^mmon; i- ^umsa l ^{z; e of} these compounds have similarly good properties. Some ammonium salts are new compounds *

According to the invention, there are therefore liquid or flowable masses which contain a larger proportion of a base liquid or a base superplasticizer and a smaller proportion of a hydrocarbon ester of an alkane phosphonate with C ^ ₂ to C ₂₀ or an ammonium salt thereof.

The alkane phosphonates have the formula:

OR

f
OX

wherein R is a hydrocarbon group »for example a Alkyl · »Cycloalkyl, aralkyl, alkenyl, aryl or Al-k-.aryl groups having 1 to about 30 carbon atoms, R 'is an alkyl group having 12 to about 20 carbon atoms and X is Hydrogen atom or a residue from the same group

909823/1172

ORIGINAL

of the hydrocarbon radicals such as R, an aramonium group or an alkylammonium group or alkenylammoniura group with 1 to about 50 carbon atoms mean

The compositions according to the invention give excellent flow agents or liquids when they are used as sliding or lubricating oils, for example as gear oil or as automatic transmission fluids # For the compositions of particular interest are those additives in which R ^{1 contains} 16 to 18 carbon atoms and is not branched , R is an alkyl group with 1 to about 5 carbon atoms and X is a hydrogen atom or an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group with 1 to about JQ carbon atoms, which can be the same as the radical R or different or the ammonium group R ¹¹ UH ₂ R ¹ "mean, in which R" and R ¹ "represent hydrogen atoms or alkyl or alkenyl groups with preferably 1 to about JO carbon atoms and can be the same or different ·

The additives to be used in the context of the invention can be prepared from known intermediates · One of the most common reactions is the preparation of the as Dialkylphosphonates, which are used as intermediates, consist of the reaction of an alcohol with phosphorus trichloride. To the Production of the alkani) hosp3ionates to be used in the context of the invention the dialkyl phosphonates are reacted with an olefin according to the following equation:

H IIP (O) (OR) _p + C - C - ^ - CGP (O) (OR) ₀

909823/1172

BATH

wherein R has the above meaning. This reaction was generally carried out in the presence of a free radical initiator, for example an organic peroxide. Suitable peroxydones include di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, and the like. About 3 mol % of the peroxide catalyst gives the best products, since an excess of initiator can cause highly exothermic reactions leading to products with incorporated olefin / phosphite ratios greater than 1. The reaction temperatures can be between 10 C and about 30O ⁰ C and are preferably 125 ° C to 175 ° C. Other initiators that can be used include ultraviolet light and azobisisobutyronitrile 3 * 1 are preferred. If desired, the reaction mixture can contain an inert organic solvent, including, for example, hexane, benzene, ether, ethyl acetate and other common organic solvents. Palis the 'reactants are miscible, the presence of an additional solvent is not necessary.

The olefins to be used in the context of the invention contain 12 to 20 carbon atoms and are preferably composed from straight-chain 1-olefins. Hexadecene-1 and Octadecone-1 are of paramount importance because the products made with these olefins are unexpectedly excellent Rubbing properties of the base fluids or base " result in fluids.

909823/1 1 72

BATH ORIGINAL

Si «Qruppe R can have 1 to 30 carbon tones on * show * But it was found »that Aücylseete pit 1 to 5 carbon atoms are excluded * Doohalb In the Utasetsung, the olefin is also a high phosphonate, like dirnethylphoaphonate, diethylphoephonate »Dipropylphoe» phonate, dibutylphoephonat and dianylplioBphonet are the beneficial • part of the reaction toilnehotor. Other ßoeignote Fboephonate can Diootylphoaphonatit Dinonylphoaphonat »Dideoylphoephonfttf Dioyclohexylphoephonat, Diphenylphoephonat und Unlike

woitexe Auebildunßefom dear Äcfindung concerned • ion with de * Heretellung of Honoelkyl-0 ₁₂ ^{h ± m} Ο ^^ πΟΙφ »» phoephonaten and ede their AnaoniuaeAlmen "Amin Galaen" Of the Alkmnphoephonaten "ββ eißte to _t that they ait a besrenete TeiliiydroIjrBe in the treatment a »Baoe and anaoMieBendew AneAuesn

(D mm

X ₉ R ^f PCo) C0R) _a Ca) Heg _y r * Ko> (i ») C3b

The Honoalkylphoephoaet received can then be made with / Itwmnlek or a · AaIn ₉ S ⁹⁴ HHK ^{9 tf} _# under Bildune de · correolie »· the Salsee uaeesetst

II «R ^f ? CO) (OB) 0ß ♦ R ^#t iaiR ··· -> R ^ PCo) (CR) Cr 4 · R ⁹ WWL

Both the ionoalkylphosphonate and the anine derivatives hiorron are specially selected as defined in the invention * The groups R ₉ R% R ^9t and R *** have the same meaning as above

909823/1172

8AO LOCAL

The sequence I of the hydrolysis conversion is carried out under conditions known per se. The reaction mixture containing the alkanolephonate and the base is heated with stirring for a period of a few minutes up to two or three hours der Boss * preferably 10 to 20 % excess should be used · The Oeraiach is "acidified until a pH value of 1 is reached" by slowly stirring it into the acid. The organic Hisse is then separated from the aqueous! Alcohols or solvents are removed by distillation. The solvents that can be used in this reaction sequence include alcohols and ethers "like" methanol _for ethanol and ethyl ether.

Bas receive · product is then optionally reacted with ammonia or an amine "Pas thereby sais formed could be of predominantly ionic structure * Bas molar ratio of ammonia or amine amounts to Phoaphonat b" before "UGT 1 t1 _t although an excess serving as the reaction partner compounds Ammonia or Ami can be used "for full" ifase solution. The "tempera-tures" can be set at about 10 ° 0 to about 100 ° 0.

In the hydrolysis solution X, any "inorganic" base ", for example alkali metal hydroxide, such as the above-mentioned" sodium hydroxide or alkaline earth metal hydroxide, can be used. -hydroxyd «wi« calcium oxide, or mixtures of Al « and its alkaline earth bases. The "acid" is common

909823/1172

8AD ORIGINAL

• m Π m,

from an organic acid »such as hydrochloric acid» sulfuric acid, Phosphoric acid and the like «On the other hand, can also Ammonium hydroxide or aqueous amine solutions are used for the direct production of the corresponding salts or these can be used as inorganic bases prior to acidification in hydrolysis reaction I

In the new implementation II below, ammonia or amines of the formula R ¹¹ IiHR ¹ * 'with 1 to 30 carbon atoms are used «methylamine, ethylamine, propylarain, octylamine, decylarain, dodecylamine, tetradecylarain, hexadecylarain, octadecylamine, eicosylamine and similar compounds can be used. Mixtures of amines are also of interest. Aliphatics derived from natural oils, such as soybean oil, amines with CLq to C * o, which can be present both as alkyl groups and as alkenyl groups, give very favorable products. Secondary amines can also be used in the reaction can be used with the monoalkylphosphonates, such as dimothylamine, diethylamine, dipropylamine and the like.Tertiary amines can also be used, for example trimothylarain, in which case the N-hydrogen atom becomes an aliphatic radical.Cyclic amines such as piperidine or pyrrolidine are also suitable The primary amines are preferred, especially those with 12 to 20 carbon atoms *

The Alkanphosplionate are according to the invention in lubricants or Air-conditioning oil bases applied, for what purpose Mineral oils, both paraffinic and naphthenic

909823/1172

SAD ORtQ (NAt

See belong "and are used in synthetic oils, ie · hydrocarbon oils" such as polyolefins, polyglycolic oils and esters of mono- and polyhydric alcohols with 1 to 10 carbon atoms and mono- and polybasic carboxylic acids with 2 to 30 carbon atoms "Such esters include, for example, the Biestert Di -2- * äthylhexylsebacat, dihexyl, Neopentylglycoldipentanoat and similar "the Triesteri trimethylolpropane ^ riöctanoat and the like and the Tetraester and Hexaesten Pentaerythrittetrahexanoat, Penta> rerythrittetraoctanoat _f pentaerythritol te tradecanoat, Ponta ^ erythritdihexanoatdioctanoat" Dipentaerythrithexabutyrat and similar compounds *

The alkane phosphonates yield according to the invention not only have superior frictional properties, but also ensure that the metal surfaces do not corrode · An important aspect of transmission fluids and gear oils is that the »superplasticizers does not adversely affect the parts of the transmission system. The new masses according to the invention] are non-corrosive «, the concentrations of the additive can in the range of 0, Qj? up to about 10 percent by weight

In the following examples various features of the invention are explained without the invention being limited thereby «

example 1

A mixture of 330 g of dimethyl phosphonate and 2j? 2 g 1-octadecene was heated to 45 ⁰ C to 50 ° C. and stirred while 4.5 g di-tert-butyl peroxide over one hour

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8AD ORIGINAL

■■ ;; 'i' ¹ " ¹ - '' Ij ϊ ¹ !!!!!!!! ¹ ''!!""!!!!!!!!!!!!!!!!!! ¹ ! '!! ¹¹ !! ^111111881 : ' ¹ '! ¹¹

were added Maintained for a further hour, whereupon the excess of Diinethylphosphonat distilled off under reduced pressure became. The yield of dimethyl n-ocbadecylphosphonate was 548 g (over 99 #) ♦

Analyzer

ber.i C 66.26 $ H 11.95i

GOf .: G 66.66; H 11.95 i P 8.28

Example 2

To Giner solution of 2,900 g of dimethyl n-octadecylphosphonate in 4 l of methanol there were 4150 g of sodium hydroxide added · The equipment was heated to reflux with stirring for 2 hours · It became sufficient Amount of concentrated hydrochloric acid added * to adjust the pH to bring the solution to 1. 1 ml v / water and 2,000 ml benzene were added to the solution with stirring. The organic layer was decanted and washed with a few portions of 1 liter of water - benzene and the last Acid water and methanol were removed by distillation removed under vacuum · The yield of methyl n -oetadecylphosphonate was 2,680 g (96 #)

Example.fr

A quantity of 15 g of methyl n-octadecyl phosphonate was dissolved in anhydrous ether and ammonia as a gas was blown through the solution for 20 minutes

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BATH ORIGINAL

evaporate the ether and received about 15 g dos ammonium salt

Analysis:
ber: N 3.84-gof .: N 2.03

Example 4-

A mixture of 10.0 g of methyl n-octadecyl phosphonate and 7.66 S oleylamine was heated until a homogeneous yellow oil was obtained »When the mixture was cooled, a waxy solid resulted»

Example 5

550 g of Djjaethyl-n-hexadecylphosphonate were added to a solution of 120 g of sodium hydroxide in methanol. the Solution was heated to reflux for 3 hours and then acidified to pH 1 with concentrated hydrochloric acid. To the solution 1 1 of water and 1.5 1 of benzene were added · After all of the solid was dissolved, the benaol was removed and washed with 3 portions of 500 ml of water, The benzene was removed in vacuo (1 mm) while nitrogen was passed through. The yield of mebhyl n-hoxadocylphosphonate was 510 g (97 ^),

Analysis »(C

ber · »C 67.71t H 11.64 \ P 9.67 found ·» C 64.79 | H 11 _f 65 | P 9.1?

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SAD ORIGINAL

valuation

You products used in the present invention were divided into two test series evaluated _y the Off · wet * the Reibungemodifizierung automatic Trans "determined miseionsflüssigkeiten was · Sin excellent modifier for friction following characteristics must ^ have At a curve" in the coefficient of friction against the If the friction speed of the plates of the transmission is plotted, a positive friction curve must be obtained at a temperature range of 38 to 155 ° 0 (100 to 275 ° ϊ) · This means "that the dynamic coefficient of friction is higher than the static coefficient of friction at any speed" This property must also be maintained at all speed heights * "Liquids or release agents without friction modifiers or with poor modifiers have flat or negative curves * The flow agent must not damage the friction material on the clutch plate surface and the flow agent" has a high resistance t against oxidation and. have thermal stability.

In the friction device test at low speed, a mineral oil wet base material »which contained small amounts of antioxidants and cleaning agents» which contribute nothing to the desired friction properties , ejsa transmission fluid using alkyl phosphonates as a friction modifier was investigated. The device consisted of a container »

909823/1172

BAD ORIGINAI.

- 12 -

wherein dlo Versuchaflüsoislceit housed "In the KLüßsicIcoit öiiia Stahlringseheibe is immersed, the oboro surface with phenol ifcpior impregnated by a Reibiiiißsraatorial, oinori available in trade, bodockt" The disc is of oinan Doiinunissnesoor / ίο-dependent on "A second St & hlseheibe _f tor can be set before by oinon Γιο in threat _t viird on top of the first disk in Borülirung ⁿ ^ AEEN Roibunssnaterlal Housed that Gatnzflücliö oodaß in the Eüissi _(, iceit atoht * Dor 3) Rpt to the surface dos Iteibuiißsnatorials botruß 8.4 lig / cn ² (120 psi) · Bio upper jaw was nit vorschiodenen Geschv / indigköiten (1 »5» ^ 9 ¹ J * G _t 1 _# 9 »1t 12,2 κϊ / Hin or, ^, 15, 20 iindjjO, W feot / rain) rotiort and the retained losses are registered on the span plate. The friction effiaionton v / urdon from diosen Ableountjen boreclmet, the experiments were carried out at 38 ° C, 93 ° G and Λ33 ⁰ C (100, 200, 275 ° F) and a friction Geachwindiijkoitslcurve at each temperature, v / o the experiments were carried out, recorded * 2> The Masrsoii ßonäß the discovery were »also examined in the Reibungsnaocliine SAüi IIr # 2 taid älinliciie Roibun {* skurvon horopstolö;» The Iiaijcliine suspects the typical Kupi>lunf;3Gin,; riff in the i'ransnission, woboi svtol steel plates in touch ait oinor nittisson disc brought before, dio to Jedor Soito nit don {the same first caution to {; ewondten Roibunßsnatorial botiockt. The middle disk is rotated by an oinon motor ₉ so that the friction between the disk and Jedor outer hat takes place

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SAD OWG (NAL

180792

knife connected «The tests were carried out during 4,000 cycles at 104 ° C with energy absorption of 1,416 mkp (10 2 ^ 0 foot / lb) during ^ each Ganges · The fluid was determined based on the condition of the friction material after the test and of the friction curves.

The results of these two verses are below summarized in the table ι

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BATH ORIGINAL

Ge
weight
percent 0.50 X-ammonium 0.50 • Friction advantage
directional
never look
driger ge
speed O Status
scher Un <»
difference SAE No. 2 Ver
search State
the
plates additive - R'eOcta-
decyl i ^H 55 Type * 0.04 Type of friction ⁺ out
draws Without
ReMethyl Xi * vJas. ~: Or- 0.25
material R »methyl 37
0.50 0.50 A. 0.05 A. η R'srOcta-
decyl 0.50 R * -Octa-
decyl D. C. 0.06 E. ti R-methyl R-MethyJ C. C. X «methyl A— WJrww ^ c R'-octa-
decyl R'-octa-
decyl 0.02 • R-methyl D. E. 0.04 It C. O 0.04 η C. 0.07 Well O

909823/1172

BATH ORIGINAL

R-methyl
X-methyl

R'-hexa-

decyl 0.50 D 0.03 E.

⁺ Ar Like the basic fluid, 38 ° C curve negative; B: all curves narrow and flat j Gi all gate valve curves positive or with a positive static end, variation between the coefficients boi of the static temperature above 0.03} Dj all curves positive, with the exception of a maximum temperature variation of 0.03 j E: all curves positive, maximum static temperature variation of 0.02.

⁺⁺ Difference between the static friction of both the 38 ° C coefficient and the 135 ° G coefficient

The results of the automatic transmission tests show that the additives of the invention are excellent Result in superplasticizers. These liquids can also contain additives such as antioxidants, pour point depressants and similar received. Other commonly used additives can also be used.

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SAD

Claims (1)

- 16 batent claims 1 * Flowable mass, which is a basic liquid, for example a lubricating or sliding oil and an alkane phosphonate derivative in the base fluid that acts as a friction modifier by the content of an alkanephosphonate derivative of the formula “OR
I. R ¹ - P = O
I.
OX wherein R is a hydrocarbon group from 1 to 50 Carbon atoms, R 'is an alkyl group having 12 to 20 carbon atoms and X is a hydrogen atom or mean a hydrocarbon, ammonium, alkylammonium or allcenylammonium group, the organic Groups X contain 1 to 30 carbon atoms 2, mass according to claim 1, characterized in that where radical X ^{denotes the group R 11} HH ₂ R ¹¹ *, in which R ^f * P and R * * · denote hydrogen atoms, alkyl or alkenyl groups, with 1 to 30 carbon atoms. 3 · Composition according to claim 2, characterized in that the radical R * ^{1 contains} 12 to 20 carbon atoms and the radical R · * · is a hydrogen atom * 909823/1172 BATH ORIGINAL 1607924 4 * Cash box naoh claim 1 _V, characterized in that the AlkanphoapaonatderiYat from an alkyleeter of Hexadeoylphösphonats or Ootadeoylphoephonats. before "* suggests of methyl or dimethylocbadecylphoaphonate, or the ammonium or octadecylamine salts of methyloetadecylphosphonate .ode? Dinothylhexadeoylphoaphonat consists of » Alkanphoephonate of the general formula IF where R and R * have the meaning given in claim 1 and R ^M and R * ^f * have the meaning given in claim 2 6 «Alkanphoephonate according to claim 5, characterized in that R ^{M is} a hydrogen atom or an · alkyl group · and R ' ^{M is} a hydrogen atom» 9823/1172 BAD OBIGlNM.