DE1444892B1 - Lubricating oil - Google Patents

Description

1 2

The invention relates to improved lubricating one to five alkyl substituted aryl carbon oils and in particular a lubricating oil composition acid each having 1 to 20 carbon atoms genes that are essentially non-aryl nucleus with respect to silver, from (C) water and from (D) a carbon corrosive works. Hydrogen solvent.

It is known that certain types of 5 in particular have been found to be the above Diesel machines like those that use two types of zinc dithiophosphate salts mentioned on the railroad, Find use, silver bushings as storage areas d. H. normal zinc-bis (aryl) -ditbiophosphate and used on piston pins or journals. A scbwie- normal zinc-bis- (alkyl) -dithiophosphate, which from the Another problem with lubricating these machines is called neo-alcohols or blocked alcohols consists in the corrosion of the silver bearing io or blocked alcohols are made, d. H. to inhibit surfaces. So are known, commercially available alcohols, in which the carbon atom, the available antioxidants and bearing corrosion inhibitors, the carbon atom bearing the hydroxyl group, although it is for use in lube neighborhood, suboil completely with alkyl groups is very suitable for other types of machines, is non-corrosive to silver, not suitable for use in oils that will render 15 when, as described below, for the lubrication of machines with silver bearings can be reacted with zinc carboxylate salts. Turned over will. For example, zinc salts are inverted from it has been found that zinc-bis- (alkyl) -ditbio-dithiophosphoric acids to a large extent as antiphosphates, which are not different from alcohols of the Neoart Oxidizing agents and bearing corrosion inhibitors can not be derived by reacting with zinc carboxylates Machine oils used. However, 20 attempts have been made to be corrosion-free against silver, shown that when using these salts it is believed that the compound of zinc den Oils for machines with silver bearings, such as iron dithiophosphate with the zinc carboxylate salts railway diesel engines, these oils instead of the corro- coordinative bonds made by those to inhibit sion, actually the silver bearing surfaces which are present in the complexes of the Werner kind, attack and corrode. 35 are similar. The salts are therefore hereinafter referred to as

US Pat. No. 2,739,125 discloses lubricant-coordinated zinc carboxylate-zinc dithiophosphate salts agent compositions for use in indoor designated.

Internal combustion engines are described, particularly those contemplated according to the invention

Contain complex salts of sulfonic acids which are added to the lubricating oil as coordinated zinc carboxylate-zinc dithiophosphate detergents. 30 salts were obviously not known up to now and a solution to the problem, the corrosion of silver represent a new group of compounds.
According to the invention, the coordinated

known. Zinc carboxylate - zinc dithiophosphate salts thereby

The object of the invention is therefore the introduction produced that the reaction mixture of new compounds that are not 35 zinc dithiophosphate, zinc carboxylate, water and silver are corrosive, and furthermore the development of lubricating a hydrocarbon solvent on a temperature oil composition, which contain these and are heated to a temperature sufficient to degrade the water Advantageously no corrosion. This creates a coordinated solution sion of silver bearings occurs. Zinc carboxylate zinc dithiophosphate salt, which is about

The lubricating oil according to the invention is characterized by a molar proportion of each salt of the reaction, that it contains a salt in an amount of components in the hydrocarbon-0.01 contains up to 10 percent by weight, which from the solvent. The product mixture then becomes the fil reaction product a reaction mixture from a trated to remove any unreacted salt, Molar fraction (A) of a zinc dithiophosphate salt. Preferably, a solvent is composed of a of the general formula 45 light hydrocarbons, such as xylene, toluene or

Gasoline, used. Water is distilled off as an azeotropic mixture with the solvent. To After the water has been completely removed, a lubricating oil can be added to the solvent mixture

(RO) ₂ P - sj ₂ Zn 50 and the remainder of the solvent are distilled off

(or the solvent can be removed before the oil is added), creating a lubricating oil con-

wherein R is an aryl radical obtained by 1 to 5 alkyl groups in the center of the product salt, which is suitable for mixing with a base lubricating oil substituted with 1 to 20 carbon atoms.
can be or an alkyl radical with 5 to 20 carbon 55. Suitable zinc bis (aryl) dithiophosphates according to atoms of the formula of the invention are those containing aryl radicals, such as phenyl,

Contains naphthyl and the like. If applicable, they are

j ^ substituted by one or more alkyl groups.

ι ¹ Examples are zinc bis (phenyl) dithiophosphate,

'60 zinc bis (naphthyl) dithiophosphate, zinc bis (toluite) -

dithiophosphate, zinc bis (tert-amylphenyl) dithiophosphate, zinc bis (didodecylphenyl) dithiophosphate, R-i zinc bis (wax phenyl) dithiophosphate.

The zinc salts of bis (alkyl) dithiophosphoric acids,

denotes, in which R _{1 represents} an alkyl radical, and from 65 which are improved by the process according to the invention at least one molar fraction (B) of a zinc, derive from aliphatic alcohols salts of an aliphatic carboxylic acid with 1 to, which is a neocarbon atom or a blocked 20 carbon atoms or one optionally by a carbon atom adjacent to the one

ORIGINAL INSPECTED

Have hydroxyl group-bearing carbon atom. at reduced pressure using a These alcohols correspond to the structure removed from water bath as a heat source. The reaction

mixture was added at about 25 percent by weight

I ^emes mineral oil (100 SUS at 38 ° C) diluted on

I 5 heated in a water bath, and through a bed of

Filtered Ri — C — CH ₂ OH ”diatomaceous earth filter aid. The oil solution was

I analyzed as follows: zinc 5.0%, sulfur 7.3% /

R ₁ phosphorus 3.9%.

in which R _{1 is} alkyl. Examples of suitable ° i _"f ² · Preparation of coordinated Zinkdithiophosphatsalze this type are zinc-bis- zinc acetate Zrnk-bis-CnoliylphenylJdithiophosphat

(2,2 - dimethyl -1 - propyl) - dithiophosphate, zinc - bis- In a 5-1-4 neck flask fitted with an i

(2,2,4-trimethyl-1-pentyl) -dithiophosphate, zinc-bis-stirrer, a thermometer and a distillate on - (2,2-dimethyl-1-decyl) -dithiophosphate, Zinc biscuit vessel, which with a reflux condenser, ^^^ - trimethyl-l-hexadecyty-dithiophosphate. 15 protected by a calcium chloride tube

- The zinc carboxylates, with which the zinc dithio was, 792 g (3.6 mol) of nonylphenol, 161.1 g of phosphate salts by the method according to the invention (1.98 mol) of zinc oxide and 1500 ecm of xylene were introduced, which can be coordinated, The mixture under reflux conditions can be aliphatic or aromatic. The aliphatic zinc carbides to entoxylate the device and contents can be straight chain, branched chain or. 2 ° water. The temperature was reduced to 130 ⁰ G, cyclic type, and 1 to 20 carbon atoms and it was 199.8 g (0.9 moles) P ₂ S _{5 contained} during one. Examples of such zinc salts are those for a period of I ¹ J ₄ hours, the temperature of the following acids: acetic acid, formic acid, butyric acid being kept at 130 to 135 ° C., added. The acid, decanoic acid, stearic acid, oleic acid and linoleic acid were raised to the reflux temperature. Zinc naphthenate salts derived from petroleum naphthenic acids and the mixture for 1 hour reflux conditions are also very useful. subjected (144 to 147 ⁰ C). The temperature was ■ the aromatic carboxylate salts include beispiels- to about 9O ⁰ C decreased and from the Tropttrichter, as Ziiikbenzoat, zinc salicylate and such salts are within about 15 minutes, 150 cc of the trains also be one or more alkyl groups with distilled water. The temperature would have 1 to 20 carbon atoms, kept at 90 to 95 ° C for 2 hours, by which the aromatic ring is substituted in each case. normal zinc salt of bis (nonylphenyl) -dithiophos-

■ The invention will be formed below on the basis of the phosphoric acid.

Production rules and Example closer 197.6 g (0 _ä 9 mol) Zn (C ₂ H _s O _{2) 2} · 2H ₂ O, dissolved in

explained. The production of the new zinc complex- 350 ecm hot distilled water were then carried out salts are carried out in a manner similar to that in the USA.- 35 added to the reaction mixture. The temperature

The operation described in U.S. Patent 2,739,125. was thereafter increased to azeotropic the water

" _TT ",, ■ _. ,,, Way to deposit, the final temperature being 146 ° C

1. Production of the normal zinc salt that was fraudulent. A total of 525 ecm

Bis- (nonylphenyl) -dithiophosphorsaure Nasser separated _{in an azeotropic manner} . The product

In a dry 5-1-4 neck flask ,. 40 was then fitted through a bed of filter aid

, filtered with a stirrer, a thermometer, a wide (»Super-Cel«). It would it, such a pipe for introduction of phosphorus pentasulfide and amount of paraffinisehem mineral oil (100 SUS at a distillate receiving flask equipped with a back 38 ⁰ C) was added to a salt product to xylolfreies

■ Create a flow cooler, protected by a calcium chloride tube, which contains about 25 percent by weight oil.

was connected, 792 g (3.6 mol) of nonylphenol, 45 The xylene was under reduced pressure under pressure

161.1 g (1.98 mol) of zinc oxide (i.e. 120% excess, use of a water bath as a heat source detoxifies) a complete conversion of the dithiophosphere. The product was analyzed as follows: zinc ■ ensure phosphoric acid in the normal salt) and 8.85%, sulfur 5.73% and phosphorus 3.24%.

1500 c, cm xylene introduced. The mixture was ",,

dehydrated by returning them IV for ₂ hours. _T " ■ _o . ? - ·. ^ * "™« ™?, ...., '' exposed to flow conditions. The temperature became zinc bis (2,2,4-frimethyl-l-pentyl) dithiophosphate

then reduced to 130-135 ° C and place 199.8 g in a 2-1-4 neck flask fitted with a

(0.9 mol) phosphorus pentasulfide in proportions during stirrer, a thermometer, a reflux condenser,

• added for a period of IY ₂ hours, protected by a calcium chloride tube, and a

the temperature was kept at 130 to 135 ° C. 55 large closable tube for periodic addition

The mixture was then heated to the reflux temperature of P ₂ S ₅ , 676 g (5.2MoI) of 2,2,4-trimethyl-

heated and 1-pentanol refluxed for 1 hour. 288.6 g of P ₂ S ₅ (1.3 mol) were

(144 to 145 ° C). Then the mixture was over a period of 38 minutes at a

cooled to about 9O ⁰ C, and 150 ecm reaction temperature of 68 to 78 ⁰ C were added-

distilled water for 60 hours. The mixture was then stirred for 4 hours

added half an hour. The temperature is heated to a temperature of 89 to 93 ^{0 C for a long time,}

was kept at 88 to 93 ° C for 2 hours, then poured into a dropping funnel

the normal zinc salt of bis- (nonylphenyl) -dithio- filtered to remove _{unreacted P 2} S _5,

to form pbosphates. The mixture was then fitted onto another 2-1-4 neck flask

Heated to reflux temperature to azeotrope the water 65 with a stirrer, a thermometer, a re

: to be deposited. The product was then heated to 10O ⁰ C flow cooler and the aforementioned drip

.cooled and funneled through a diatomaceous earth filter aid, which is protected by a calcium chloride tube

(»Supetoel«) filtered. The xylene was then added successively 158.8 g (1.95 mol) of zinc

5 6

oxide and 465 ecm of distilled water were introduced. a water bath with boiling water as heat

The phosphorodithioic acid was removed from the drip source. The product was largely a

funnel flowable for a period of 2 _^3/4 hour dark yellow liquid. It was

at a reaction temperature of 60 to 67 ° C, analyzed as follows: zinc 12.8%, sulfur 16.6%

given. During this period of time it became 150 ecm 5 and phosphorus was 7.6%.

Benzene added to dilute the mixture. _TT .

The mixture was then 1% hours at ⁶ * the preparation of the coordinated of Zinkacetatsalzes

kept this temperature. The temperature became zinc bis (n-octyl) dithiophosphate

then increased to a maximum value of 110 ° C, In a dry SOO ccm ^ neck flask, from-

to separate the water azeotropically, and 200 ecm io allowed with a thermometer, a stirrer,

more benzene was added to make the reflux a calcium chloride tube

decrease temperature. Then the reflux condenser and a wide closable

Mixture filtered through the filter bilfe (»Super-Cel«). Pipe for the introduction of P ₂ S ₅ were 78.0 g (0.6 mol)

The benzene was introduced under reduced pressure under ver-n-octyl alcohol. 33.3 g of P ₂ S ₆ (0.15 mol)

Turning a water bath with boiling water 15 were then added in small proportions to that of 60 to

removed as a heat source. The product was given a light alcohol held at ^{70 ° C.} The temperature

viscous liquid. The analysis indicated the following was then increased to 90 ° C and for 4 hours

Values: zinc 8.9%, sulfur 15.7% and phosphorus kept at this value. The product was

7.7%. then filtered into a dry dropper.

. _TT . "J-,, . . . ". ,. . , 20 In a 1-1-4 neck flask fitted with a

4. Preparation of the coordinated Zmkacetatsalzes _{Shaker> a TbsmomebBCf ei} ° _{em Tro} pft _r i t _e r _ch,

τ · t t. · S ¹ O T ^ Ti ^ J 'expanses. _{which is the} dithiophosphoric acid prepared above

Zmk-bis- (2,2,4-trimethyl-l-pentyl) dithiophosphate _{contains and a De} stiUationsvorlage, which is sent to a

In a 2-1-4 neck flask fitted with a reflux condenser was placed 18.3 g of a stirrer, a thermometer and a distillate (0.225 mol) of zinc oxide. Thereafter, receiving vessels, which were added to a reflux condenser, 54 ecm of water. The acid was slowly attached, and a dropping funnel, protected to the stirred sludge from zinc oxide and water by a calcium chloride tube, was added and the whole was heated to 60-65 ° C, sequentially 102 g (1.26 moles) Zinc oxide and 300 ecm The thick mixture was given water distilled with 250 ecm benzene. To the stirred 30 thins. The temperature was then increased to 75 ^° C., 593 g (1.68 mol) of dithiophosphorus were increased and kept at this level for 2 hours. It was acid, prepared as described in the first part of 3., 36.3 g of zinc acetate dihydrate (0.16 mol), dissolved, were added. The acid was added within about 2 hours in 100 cc of distilled water. The mixture at a reaction temperature of 60 to 67 ° C. was then added under reflux conditions. During the addition of acid, 100 ecm 35 were thrown in order to separate off the water azeotropically. The benzene added to dilute the mixture. The product was then filtered through a filter filter ("Super-The mixture was additionally ^{1 1} J ₂ hours with Cel"). The benzene was then stirred at 62 to 63 ° C., and 184 g (0.84 mol) of reduced pressure zinc were removed using a water acetate dihydrate dissolved in a 326 ecm distilled bath as a heat source. The product was water was then added. The temperature 40 a largely flowable colorless liquid and was then increased to the water as azeotropes was analyzed as follows: zinc 15.4% sulfur mixture to remove, and 129 ecm benzene were 11.7% and phosphorus 6.3%. added to the temperature during formation _ _{TT x} ,,,,,. . _x ",, ^,,

of the azeotropic mixture (84 to 106 ° C). 7. Production of the coordinated zinc naphthenate salt The whole thing was then filtered through a filter shell _{45 of} ^the zinc bis (mixed, phenol) dithiophosphate ("Super-Cel"). The benzene was then placed in a 1-1-4 neck flask fitted with a

Reduced pressure using a water stirrer, thermometer, and distillation bath with boiling water as the heat source, which is removed to one through a calcium chloride tube. The product was a lightly viscous liquid. protected reflux condenser was connected, as well as the analysis showed the following values: zinc 15.1%, 50 a wide closable tube for the introduction of sulfur 12.7% and phosphorus 6.6% · of P ₂ S ₅ were successively (in turn) 63, 7 g

, _TT "J ₁ j. . . ". ,. , (0.6MoI) of a mixture of 40 percent by weight

5. Preparation of the coordinated zinc acetate salt _{phenol 56 percent by weight per cent of} cresols and 4 percent by weight of zinc-b _1S - (4-methyl-2-pentyl) _{dithiophosphate xylenols> 250 ml of xylene and} 40.5 _g (0.5 Mol) Into a 2-1-4-necked flask, which is introduced with a stirrer, 55 zinc oxide. The mixture was stirred

a thermometer and a still, and at about 144 ° C reflux conditions below the attached to a reflux condenser to remove all water from the system

was allowed, 180 g of the zinc additive were removed. The temperature was raised to about 130 ° C

bis- (4-methyl-2-pentyl) -dithiophosphate introduced. reduced, and 34.3 g (0.15 moles) of phosphorus pentasulfide This material was diluted with 400 ecm of toluene 60 times over a period of 50 minutes

and 65.9 g (0.30 mol) of zinc acetate dihydrate dissolved in at a reaction temperature of 130-135 ⁰ C.

227 ecm warm distilled water was then added. The temperature of the mixture was on

admitted. The mixture was stirred and heated, the reflux temperature (141 to 142 ° C) increased and the

to separate the water azeotropically. The maximum mixture was refluxed for 1 hour. the temperature for azeotropic deposition was 116 ° C. 65 temperature was then reduced to about 90 ° C,

The product was then passed through a bed to give 88.0 grams (0.225 moles) of petroleum naphthenic acid

Filter aid (Super-Cel «») filtered. The toluene and then 50 ml of distilled water were added,

'Then under reduced pressure using -The mixture was stirred and left on for 2 hours

90 to 93 ⁰ C heated. The temperature was then increased to azeotropically separate the water (144 ° C). The mixture was then cooled and filtered through a filter aid (“Super-Cel”). The filtrate was washed with 150 ml of fresh xylene. The xylene was removed from the filtrate under reduced pressure using a water bath as a heat source. The product was a very viscous, dark brown liquid. After it was liquefied by adding 25 percent by weight of mineral oil (100 SUS at 38 ° C), it showed the following analysis: zinc 9.9%, sulfur 6.3% and phosphorus 3.3%. : ■ -. ■ _ ■

example
Silver corrosion test

The non-corrosive effect of the coordinated Zinc carboxylate zinc dithiophosphate salts according to the invention versus silver compared to the uncoordinated zinc dithiophosphate salts is illustrated by the following series of tests, which are made with the additives of the above manufacturing instructions has been. '■ -.- -

The test procedure used was the EMD procedure No. L. 0.201-47 (developed by the Electro-Motive Division of General Motors Corporation) for determining the corrosion effect of a lubricating oil for heavy loads on silver. The procedure consists in that in an oil bath which is kept at 163 ± 1 ° C, 300 ml Lubricating oil contained in a 600 ml jar is heated. The oil will, at 300 revolutions each Minute (RPM) stirred. As soon as the test oil has reached the temperature is reached, a weighed section of a silver-plated bolt (size approx 76.2 χ 25j4 X 6.3mm, the lead plating is in front of the Testing away from the surface) is hung in the oil so that it covers about 75% of its surface area immersed. After 72 hours, the bearing sleeve section is removed from the oil,

ίο Washed with carbon tetrachloride and dried. The corrosion layer is then removed electrolytically, after which the bearing bush is washed with water and alcohol and by rubbing with a cloth and Place in an oven held at 40 ° C for 10 minutes to dry. After cooling down it is weighed again in a desiccator. If the weight loss is not more than 5 mg,

if the exam is assessed as positive, see a

The lubricating oil used in the tests was

a Mid-Continent solvent refined oil, in which all paraffin distillates have a SUV. value of 77 seconds at 98 ⁰ C. In order to enable an accurate comparison between the additives, the percentage of the additive used in the oil was adjusted in each case so that the same percentage of zinc bound to sulfur resulted (except for the zinc which is bound to a zinc carboxylate coordinating agent -. is like. he in 0.44 and 0.89 percent by weight of the normal

3P zinc bis (4-methyl-2-penryl) dithiophosphate additive (Manufacturing instruction 5) is included. The test results are shown in the table.

Used additional

silver Corrosion. At 163 C,
Loss of calves Weight percent. ; mg 1.04-'V VV.
2.07 V; .V: 19.8 ^.;.; = '0.95
· ■ 1.90 - ■■ "- ■■ - ■ ^: - -0.8
^;; 1.3 - 0.47
0.94 18.1
48.1 0.62
1.24 1.8
2.1 0.44
0.89 19.1
38.9 0.48
0.96 25.2
65.4 0.55
1.10 9.1
36.2 0.85
1.69 1.9
3.6

None,.; ....

Zinc bis (nonylphenyl) dithiophosphate (manufacturing instruction 1) the same. .. ..... - .., - .. ",

Coordinated zinc acetate salt from Example 1 (Manufacturing Regulation 2)

Zinc bis (2,2,4-trimethyl-l-pentyl) dithiophosphate (manufacturing instruction 3)

the same ...

Coordinated zinc acetate salt from Example 3 (Preparation 4) the same ...: '

Zinc bis (4-methyl-2-pentyl) dithiophosphate (manufacturing process 15). the same

Coordinated zinc acetate salt from Example 5 (Preparation 5) the same

Coordinated zinc acetate salt of Zmk-bis- (n-octyl) -dithiophosphate

(Manufacturing instruction 6)

the same. ..... .

Coordinated zinc naphthenate salt of zinc bis (mixed phenol) dithio

phosphate (manufacturing specification 7) ......

The table shows that all three non-coordinated salts (preparation instructions 1, 3 and 5) have a highly corrosive effect on silver. The zinc-bis- (aryl) -dithiophosphate and the zinc-bis- (alkyl) -dithiophosphate, derived from blocked aliphatic alcohols can through Formation of the coordination salts according to the invention can be made non-corrosive to silver (see manufacturing instructions 1 or 3 with the manufacturing instructions 2 or 4 and see also manufacturing specification 7). The Zmk-bis- (alkyl) -dithiophosphates, the differs from the non-blocked form aliphatic

009510/170

Deriving alcohols, are not corrosion-free compared to the formation of the coordination salts Made of silver (see manufacturing instructions 5 and 6).

As the analysis shows, the coordinated salts contain about 1 mole of zinc carboxylate per mole of zinc dithiophosphate. It has been found that the coordinated salt fails the silver corrosion test when less than about 1 mole of zinc carboxylate is combined with the zinc dithiophosphate salt. The amount of Zinc carboxylate salt, the. is used in the reaction with the zinc dithiophosphate salt must therefore be at least 1 mole per mole of zinc dithiophosphate. It will be using a moderate excess above this amount of, for example, 10 to about 50%, in order to also achieve the formation ensure a coordinated salt product which contains the required molar proportion.

As mentioned earlier, the presence of water is essential for that. Coordination response essential. The lowest amount required is about 0.5 mole per mole of zinc dithiophosphate reacted with zinc carboxylate. By using larger amounts of, for example, 10 to 50 moles of water each Mole of converted zinc dithiophosphate the reaction however, much easier. In fact, the upper limit of the amount of water is not critical, and practical considerations will therefore largely dictate the amount used.

As shown in the above manufacturing protocols, the coordinated salt products according to the invention are suitably prepared in the form of concentrated oil solutions. These Solutions can easily be mixed with base oils that are intended to be improved by this. For technical Purposes can, to achieve a certain concentration level, which is in the solutions Amount of salt can be standardized. On an oil-free basis, the amount of is in the lubricating oil coordinated salt used in the range of 0.01 to 10 percent by weight being the usual amount Is 0.5 to -5%.

That; Lubricating oil into which the salts are mixed can also contain other additives which serve to improve the properties of the oil in many ways, e.g. B. detergents, pour point depressants, viscosity index improvers,
Extreme pressure agents, additional antioxidants. According to the invention, the salts can be used in mineral oils and synthetic oils of lubricating oil quality.

Claims (1)

Claim: Lubricating oil, characterized . that it contains a salt in an amount of 0.01 to 10 percent by weight, which is obtained from the reaction product of a reaction mixture of one molar Part (A) of a zinc dithiophosphate salt of the general formula : (RO) ' ₂ P-S. ₂ notes wherein R is an aryl radical which is replaced by 1 to 5 alkyl groups may be substituted with in each case 1 to 20 carbon atoms, or an alkyl radical with 5 to 20 carbon atoms of the formula R ₁ - C-XJ-2 denotes in which R _{1 is} an alkyl radical, and from at least a 1 molar fraction (B) of a zinc salt of an aliphatic or alicyclic carboxylic acid with 1 to 20 carbon atoms or an acrylic carboxylic acid optionally substituted by one to five alkyl groups with 1 to. 20 carbon atoms on the aryl nucleus, consists of (C) water and (D) a hydrocarbon solvent.