DE1278053B - Process for the preparation of basic alkaline earth alkylthiophenolates - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .: '

ClOm

German KI .: 23c -1/01

Number: 1 278 053

File number: P 12 78 053.9-43 (C 29934)

Filing date: May 14, 1963

Opening day: September 19, 1968

Basic alkaline earth alkylthiophenolates are used as binders in lubricating oils to prevent harmful To neutralize acids, prevent corrosion and deposits on the piston rings and to avoid the formation of resin in internal combustion engines, which occurs as a result of the oxidation of the Lubricating oil and the oxidation polymerization of the fuel residues in the machine.

For many years, metal phenolates, in particular alkali and alkaline earth metal phenolates, have been used as additives used for mineral oils that are used for the lubrication of internal combustion engines. In combination with many other additives, the metal phenates improve the cleaning properties of lubricating oil, reduce machine wear, put the formation of harmful ones Deposits to a minimum and improve the oil's resistance to oxidation. the end British Patent 744,534 also discloses the use of oil-soluble alkaline earth alkylthiophenolates to the above Known purposes.

Numerous attempts have now been made to produce oil-soluble alkaline earth alkylthiophenolates, which have the advantageous properties of the known phenates and, moreover, are capable of are able to neutralize larger amounts of materials than the known products. According to the invention Process it is possible to produce "overbased" alkaline earth alkylthiophenolates, which can neutralize larger amounts of acid than the products previously available.

The "normal" alkaline earth thiophenolates mentioned above are metal phenolates, in which the molar ratio of metal to phenolic nucleus is about 1: 2, e.g. B. in the following structural formula:

where R is an alkyl substituent on the benzene ring and M is an alkaline earth metal. The sulfur atom (- S -) is attached to two benzene rings. The expression "basic carbonized alkaline earth thiophenolates" refers to alkaline earth thiophenolates with a base ratio of more than 1.2, d. In other words, the percentage of alkaline earth metal is more than 20% higher than that of "normal" alkaline earth thiophenolates. A metal phenate with a base

Process for the preparation of basic
Alkaline earth alkylthiophenolates

Applicant:

California Research Corporation,

San Francisco, Calif. (V. St. A.)

Representative:

Dr. W. Beil, A. Hoeppener

and Dr. H. J. Wolff, lawyers,

6230 Frankfurt-Höchst, Adelonstr. 58

Named as inventor:

Walter William Hanneman, El Cerrito, Calif.

(V. St. A.)

Claimed priority:

V. St. v. America May 15, 1962 (194 996)

ratio of "1" is a neutral (normal) phenolate.

Such "basic" carbonized alkaline earth metal thiophenolates can be prepared using the process of the present invention with metal contents of more than 20% above the content of the metal present in the corresponding normal alkaline earth thiophenolates easily and simply obtained. The values for the base ratio are the basic ones obtainable in this way Phenates between 1.2 and 4.5 or higher. The strongly basic alkaline earth thiophenolates according to the invention are particularly suitable as additives for diesel oils.

The present invention thus provides a process for the preparation of oil-soluble basic alkaline earth thiophenolates from an alkylphenol, an alkaline earth sulfonate, sulfur and alkaline earth oxide or hydroxide in lubricating oils, which is characterized in that an alkylphenol with 4 to 30 carbon atoms in the alkyl radical, an alkaline earth sulfonate and a monohydric alcohol with 8 to 18 carbon atoms in a lubricating oil ^{heated to 66 to 88 0} C, then the sulfur, the alkaline earth hydroxide or oxide and additionally ethylene glycol at 121 to 149 ° C, then into the mixture after removing the water of reaction initiates carbon dioxide at 121 to 177 ^{0 C and then}

M »617/517

the mixture under reduced pressure again heated to about 199 ⁰ C for Äbdestillieren of Äthylenglycols.

Alkylphenols which can be used as starting material in the present process, are represented by the following formula:

(R) "AOH

in which A is an aromatic hydrocarbon radical, preferably a benzene radical, R is a straight-chain or branched-chain, saturated or unsaturated hydrocarbon radical having 4 to 30 carbon atoms and α is an integer from 1 to 2. The total number of carbon atoms for R is a minimum of 8. Therefore, when α is 1, the minimum number of carbon atoms in R is 8.

Examples of suitable hydrocarbon radicals are alkyl radicals, such as butyl, hexyl, octyl, decyl, Dodecyl, hexadecyl, eicosyl, tricontyl residues, residues of petroleum hydrocarbons, such as white oil, Wax, olefin polymers (e.g. polypropylene and polybutylene).

The basic sulfonates used herein contain 0 to 300% metal in excess on the amount of metal used in normal, i.e. H. contain essentially neutral metal sulfonates is. The basic sulfonates used here are derived from neutral sulfonates, which are derived from the following Formula can be represented:

[(R) ₀ ASOg] ₂ M

from, in which R is a high molecular weight, straight-chain or branched-chain, saturated or unsaturated hydrocarbon radical with a molecular weight of about 150 to about 800, A is an aromatic radical, such as. B. benzene, naphthalene, anthracene, etc., α is an integer from 1 to 4 and M is an alkaline earth metal.

Metals that fall under the term "alkaline earth metals" include calcium, barium and Strontium, with calcium being preferred.

Examples of suitable hydrocarbon radicals are: dodecane, hexadecane, eicosane, triacontane, Residues of petroleum hydrocarbons such as white oil, wax, olefin polymers (e.g. polypropylene and polybutylene, etc.). Those used in the preparation of the basic thiophenolates of the invention Sulphonic acids can also be oil-soluble sulphonic acids obtained from petroleum, like the "Mahogany" acids and the synthetic sulfonic acids, which are produced by various synthetic processes can be obtained (e.g. sulfonic acids, which are obtained by reacting a chlorinated white oil with Benzene using hydrofluoric acid as a catalyst and subsequent treatment of the white oil alkylated benzene obtained with chlorosulfonic acid or fuming sulfuric acid to form a white oil benzenesulfonic acid will).

Examples of the metal sulfonates are: calcium white oil benzene sulfonate, Barium white oil benzene sulfonate, calcium dipolypropylene benzene sulfonate, barium dipolypropylene benzene sulfonate, Calcium mahogany petroleum sulfonate, barium mahogany petroleum sulfonate, calcium triacontylbenzenesulfonate, barium triacontylbenzenesulfonate etc.

The monohydric alcohol with 8 to 18 carbon atoms is expedient in amounts of no more used as 75 percent by weight, based on the alkylphenol used. Suitable alcohols are e.g. B. Octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol and cetyl alcohol. By using a lubricating oil as the reaction medium, oil concentrates are directly produced obtained basic alkylated metal thiophenolates. Suitable lubricating oils are, for example, the lubricating oils based on napthen or paraffin and mixtures thereof, other hydrocarbon lubricants, e.g. B. Lubricating oils made from coal products and synthetic oils, e.g. B. Alkylene polymers (such as the polymers of Propylene, butylene and their mixtures), alkylene oxide polymers, e.g. B. those produced by polymerization the alkylene oxides, e.g. B. propylene oxide, in the presence of water or alcohols, (e.g. ethyl alcohol) are obtained, carboxylic acid esters, for example those obtained by esterifying carboxylic acids, for example adipic acid, azelaic acid, subaric acid, sebacic acid, alkenyl succinic acid, fumaric acid, Maleic acid with alcohols such as butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol and pentaerythritol, obtained, alkylbenzenes, polyphenyls, polymers of silicone.

The various components used in the methods are discussed with respect to one another in used in certain proportions. Per mole of alkylphenol, 0.01 to 1 mole of sulfonate is preferred 0.01 to 0.05 mol and 0.1 mol to 1.5 mol of the high molecular weight alcohol, preferably tridecyl alcohol, used.

The amount of elemental sulfur present in the reaction mixture is adjusted so that the molar ratio of sulfur to the alkaline earth metal of the basic substance is between 0.25 and 4.0 lies. The molar ratio is preferably between 0.5 and 1.5.

The amount of alkaline earth metal oxide or hydroxide used should be sufficient to provide a base ratio from 1.2 to 4.5, preferably 1.5 to 3.5, to be added. The amount of used in the implementation Alkaline earth metal oxides or hydroxides depend on the amount of that desired in the product Metal excess compared to the normal phenolate. Usually used in the production of basic, alkylated sulfur phenolates a slight excess (z. B. 5 mol percent) calcium oxide or hydroxide used over the amount that is desired in the finished basic phenate.

Carbon dioxide is used in an amount of 300 to 10 mole percent, preferably 150 to 10 mole percent, based on the alkylphenol used.

In the method according to the invention, ethylene glycol is preferably used. The amount of Glycol used depends on the amount of calcium oxide or hydroxide used.

The amount of glycol used should be sufficient to provide a portion of each of the reactants solve so that the implementation can take place in a relatively short time. To that end is it is advantageous to have certain weight ratios of alkaline earth metal oxide or hydroxide to the glycol apply. The molar ratio of alkaline earth metal to glycol can be between 2: 1 and about 0.25: 1, preferably 1: 1 and about 0.5: 1.

In the last stage of the process, the reaction mixture is z. B. 2 to 10 hours at 149 to 199 ° C heated, the absolute pressure being 40 to 50 torr

is lowered to remove the glycol. In certain cases, some of the Ce to 'Cj 8 alcohols can be removed along with the ethylene glycol. Regardless of whether all of the alcohol or only a part thereof is removed, the resulting lubricating oil is for the intended use extremely suitable. When the particularly preferred high molecular weight alcohol, i.e. tridecyl alcohol, is used, then it is advantageous that at least 50% by weight of it in the finished lubricating oil preparation remains. With this preferred alcohol, the finished lubricating oil preparation but also contain only 30 to 50 percent by weight of the original tridecyl alcohol. The high molecular weight alcohol can also be removed completely, or it can be up to 100% of the amount used remains in the finished preparation.

In the process for the production of alkaline earth alkylthiophenolates according to the British patent 744 534 · first the appropriate ethers and disulfides and the thiophenolates are formed therefrom with alkaline earth metal, while according to the invention the implementation takes place in one stage. In addition, the carbonization takes place according to the invention in the presence of ethylene glycol; through this and through the simultaneous presence of a Ce-bis Ci8 alcohol becomes an alkalization and suspension of alkaline earth metal that was previously unattainable achieved with minimal precipitation.

example 1

Production of basic carbonized
Calcium alkyl sulfur phenate

A mixture of 1893 kg of an alkylphenol with a hydroxyl number of 184, in which the alkyl radical comes from a polypropylene with an average of 12 carbon atoms, 19211 of a refined oil from California with a viscosity of 130 SSU at 38 ^° C., 198 kg of a basic calcium sulfonate with a content of 40% calcium in excess of the amount required for a neutral sulfonate (ie the base ratio was 1.4: 1) and 587 kg of tridecyl alcohol were heated at 82 ° C. with stirring. 398 kg of sulfur were added to the vessel and the temperature was kept at 82 to 88 ^° C. Hydrated lime was added to the mixture in an amount of 896 kg. The temperature of the reaction mixture was increased to 127 ⁰ C. 5071 unheated ethylene glycol was slowly added to the reaction mixture which was maintained during the Glycolzugabe at 127-132 ⁰ C. The reaction mixture was then ^{heated to 171 °} C. in order to remove water.

With rapid stirring of the reaction mixture, 261 kg of CO2 were introduced in a ratio of 45.4 kg per hour at an initial temperature of 166 ^° C. Unbound CO2 was removed. The mixture was heated to 199 ⁰ C at an absolute pressure of about 40 Torr, to distill off water, ethylene glycol and tridecyl alcohol. The resulting lubricating oil mixture contained 9.72 percent by weight calcium.

As explained above, it is desirable that the finished lubricating oil preparation have a has high basicity. The starting amount of alkylphenol should be 20 to 45 percent by weight, based on the finished preparation, preferably 25 to 35 percent by weight be. The lubricating oil reaction medium is used in amounts of 15 to 50 percent by weight, based on the finished preparation, preferably 20 to 30 percent by weight, used.

The metal sulfonate used in the previous example was a concentrate made up of 46.4 percent by weight of a mineral lubricating oil and 53.6 weight percent of a calcium petroleum sulfonate, the petroleum residue being a mineral oil with a viscosity of 500 SSU at 38 ° C. The calcium content of the ulcer concentrate was 11.4 percent by weight, and the base ratio was 1.4.

To compare the method of the invention with the method of the British patent 744 534 was prepared under the conditions of the previous example with those from the following table apparent quantities worked:

Table I.

Dodecylphenol *)
Ca (OH) ₂

sulfur

Tridecyl alcohol
Ethylene glycol
Calcium sulfonates
Basic Ca _
Sulfonate Ca ~
Neutral oil

CO ₂

All in all

1186.5

*) Hydroxyl number 205 mg KOH / g.

According to the invention

Mole

0.022 (Ca)

Molar ratio

1.75
1.79.
0.42
1.28

0.017 (Ca)

(25.5% task)
1.18 0.93

Dodecylphenol *)
Ca (OH) ₂

sulfur

Tridecyl alcohol
Ethylene glycol ..
Calcium sulfonates

Basic approx
Sulfonate approx
Neutral oil
CO ₂

All in all .

= 0.42

1006

*) Hydroxy number 205 versus KOH / g.

British patent 744 534

Mole

Molar ratio

1.08
1.89
1.92
0.46
1.38

0.018 (Ca)

1.0

1.75.
1.78
0.43
1.28

0.017 (Ca)

(25.5% task)
0.95 0.88

After all of these materials were heated as shown in the example, the ethylene glycol became distilled off. The conditions under which the glycol was distilled off were both. Preparations are the same with the exception of the order chosen for distilling off. That

Distilling off took place such that the mixture was heated while IV2 hours at a pressure of 506 mm Hg to 182 ° C and for ¹ ^ hour at a pressure of 40 Torr to 198 ° C.

The production process was then continued by carbonizing the two mixtures, with carbon dioxide being introduced at a temperature of 162 to 165 ^° C. ^{in the course of 2 × / 2 hours.} The product obtained after this time by the process according to the invention showed only 1.0 volume percent precipitate, while the preparation from which the glycol had been distilled off showed 15.5 volume percent precipitate, which is largely due to the presence of undispersed calcium compounds . According to the method according to the invention, the glycol was then distilled off from the carbonized preparation.

The following table provides a comparative overview of the composition and the Properties of the products of the two processes and shows the superiority of the according to the invention. available products:

Table II

viscosity

after S ayb ο 1 d 210
Compatibility test ¹ )

Precipitation,

Volume percentage

CaO conversion,% ² )

According to the invention
product

681

0.04
97

Product according to the method of

British
Patent 744,534

566

1.9

68

Alkalinity, mgKOH / g
Calcium,
Weight percent

CO2, percent by weight

Sulfur,
Weight percent ...

243

3.6

3.8

Product after
Procedure of the

British
Patent 744,534

195

6.9
1.9

4.1

35 ¹ J Adjusted for a calcium content of 400 mM / kg

in SAE 50 base oil.
² ) The calculation was based on the assumption of a specific gravity of the precipitation of 1.0.

Claims (1)

Claim: 1. Process for the production of basic alkaline earth alkylthiophenolates from an alkylphenol, an earth alkyl sulfonate, sulfur and earth alkyl oxide or hydroxide in lubricating oils, characterized in that an alkylphenol having 4 to 30 carbon atoms is first used in the alkyl radical, an alkaline earth sulfonate and a monohydric alcohol having 8 to 18 carbon atoms Heated in a lubricating oil to 66 to 88 ° C, then the sulfur, the alkaline earth hydroxide or oxide and additionally ethylene glycol at 121 to 149 ° C, then into the mixture after removing the water of reaction at 121 to 177 ° C carbon dioxide is introduced and then the mixture under reduced pressure again to distill off the ethylene glycol to about 199 ° C heated. Considered publications:
British Patent No. 744 534.