DD153844A1 - PROCESS FOR THE PREPARATION OF 0,0'-DIALKYL DITHIOPHOSPHORA SURES - Google Patents

Abstract

The invention relates to a process for the targeted production of dialkyldithiophosphorus acids having an increased proportion of unsymmetrical alkyl group arrangement, wherein available and inexpensive alcohols are to be used. The invention is based on the object by combination of suitable alkyl groups and by suitable synthesis parameters in the alcoholysis of tetra phosphorus disulfide on the formation of 0,0'-Dialkyldithiophosphorsaeuren influence with asymmetric alkyl group arrangement in order to obtain suitable starting materials for high quality lubricants. According to the invention reaction products are obtained with an increased proportion of compounds with asymmetric alkyl group arrangement, by the implementation of Tetraphosphordekasulfid with alcohol mixtures containing at most 5 alcohol components, the C number of alcohol components and the position of the OH groups are crucial, the molar ratio between the alcohol components of 1: 1 to 1: 5 and carried out at temperatures of 313.15 to 383.15 K.

Description

- «- 223 8 3

4 · VIII. 1980

(Title of the invention

Process for the preparation of O _s O * dialkyldithiophosphoric acids

Field of application of the invention,

The invention relates to a process for the targeted production of O _f O ^f -Dialkyldithiophosphorsäuren asymmetrical Alkylgrupponanordnung "Neutralization of such compounds are lubricant additive produced with a high utility value *

Characteristic of the known technical solutions

For the preparation of 0,0 * -Dialkyl- or, OyO'-Diaryldithiophosphorsäuren and derivatives of these compounds a variety of syntheses are known «They are based principle principle on the implementation of Tetraphosphordekasulfid with alcohols or phenols corresponding to the general reaction P ₄ S ₁₀ + 8 EOH -s * 4 (RO) ₂ PSSH * 2H ₂ S and differ in addition to the desired end product mainly in the synthesis parameters.

For the synthesis parameters, eg, the reaction temperature, which in most cases is between 313 »and 423.15 K , is primarily the reactivity of the alcohol component. As alcohols find unbranched and branched primary and secondary, aliphatic and cyclische Alkoho3.e with a preferred carbon number of

«" 2

4 to 12 carbon atoms, alkylated phenols and substituted HydroxyIverbindungen use. They can exist as pure defined or technical products and are used both as Einzelvex compounds and as mixtures »

When using individual alcohols bsw. phenols become O, O ^f -dialkyl- or O _? O ^f -dialedithiophosphoric acids with symmetrical alkyl or aryl group arrangement of the all-. common formula

receive,'

In US Patent 2,680,123, DE-P 832 030 S and 323-AS i 097 are 0 ^ 0 * -dialkyl "bsw _e O, O ⁱ ~ Diaryldithiophosphorsäuren and derivatives from G? Yp

at the

^H 1 "R ₂ - 0

or with a mixed or unsymmetrical _e alkyl, "penanordnung led Arylgrup-. They are useful as lubricant additives much more effective than those with the same or syrnmetriseher alkyl bsw _e Arylgruppenanordnung _β The preparation of these compounds is carried out by dafeach 'Tetrephosphordekasulfid reacting with a mixture of Two different alcohols, for example, phenols or an alcohol and a phenol. The mixture used is, for example, an aliphatic alcohol E 1 CH 3 with 4 carbon atoms and an aliphatic alcohol SpOH with 6 carbon atoms in a mixture ratio of 1: 2 to 5 ^s -1., Characteristic door these syntheses is that _f as Umsetsungsprodufet always Einse connections _$! for example, metal salts of the type

^K 1 "" O ^ ps! = SS ^ pO ^H 2 ~ ⁰ ^ ^ ^S " ^Μθ ~ ^S ^ ^ ⁰ "

to be obtained. "

The mentioned possibilities of variation with regard to the qualitative and quantitative composition of the alcohol mixtures as well as the different synthesis parameters, especially the reaction temperature, suggest that they exert no influence on the formation of such compounds.

Some authors, U ₉ a. However, SUDEK's argue that in the reaction product of alcohol mixtures, compounds having symmetrical and asymmetric alkyl or aryl group arrangements can coexist. About their percentage ratio, however, no-information is made

In synthetic-alcohol syntheses, which are, for example, an inevitable result of isobutanol synthesis and are used in additive production, multi-component mixtures of O, O ^t -dialkyldithiophosphoric acids with symmetrical and unsymmetrical alkyl groups may be obtained. However, their composition is also indefinite. Derivatives produced therefrom, Zt, B. the zinc salts, reach as. Lubricant additive in terms of effectiveness is not or conditional on the determining technical condition "The reason for this must u, a _e also a too small proportion

25 'be considered for compounds with asymmetric alkyl group arrangement.

The factors which determine the material composition of the reaction products in the synthesis with defined or technical alcohol mixtures, and the conditions in which the highest possible proportion of O-dialkyl- Bsw, OjO ^f ~ Diaryldithophosphorsäuren unsymmetrical alkyl or _e Ärylgruppenanordmxng or whose derivatives can be achieved are so far unknown.

1) SUDEE ₅ Vi KAU, Λ5 (1973) 686. ,

Object of the invention

The aim of the invention is it _? a method for the production of 0 ₉ O ^f -Dialkyldithiophosphorsäuren with a höchstmögliehen proportion of compounds with asymmetric Alkylgruppenanordnung to develop using available and inexpensive alcohols can be used and improve the derivatives, especially the zinc algae, used as high-quality lubricant additive, the power level alloyed lubricant © are '

Explanation of the essence of the invention

In technical solutions known per se, 0.0 ^s -bialkyldithiophosphoric acids and unsymmetric alkyl group arrangement derivatives can be prepared by reacting alcohol mixtures with tetraphosphorus decasulfide as a single compound _o A targeted preparation of conversion products having asymmetrical alkyl group arrangements as an input product for the preparation-substantially more effective However, effective lubricant additive is not possible with the known processes.

, The invention has for its object to develop a process werdenβ formed with the ^f by combining suitable means and synthesis parameters in the alcoholysis of tetra • phQsphordekasulfid O _s O -Dialkyldithiophosphorsäuren having an increased proportion of unsymmetrical Alkylgruppenanordnung

It has been found that bsi the implementation of Tetraphosphordekasulfid with alcohol mixtures are not Einzelverb indungen, but always mixtures of 0.0 ⁵ -Dialkyläithiophosphorsäuren with symmetrical and asymmetric alkyl group arrangement., For example, from "binary Aiko" ho! Mixtures the compositions

E / λ CJ τ> f »C * U rv R ₁ - O ^ ^ SH, R ₂ -O->" SH, R ₂ -O '

and that reaction products are obtained with an increased proportion of compounds with asymmetric alkyl group arrangement by the implementation of Tetraphosphordekasulfid with Alkoho3jD.ischungen containing at most 5 alcohol components, wherein the C number of alcohol components in the same position of the OE groups in binary mixtures between 2 and 6 is different and with more than 2 alcohol components the difference of the highest and lowest component 2 to 16j is preferably 4 to 12 C atoms and that in alcohol components with different position of the QH group in binary mixtures, the number of C atoms by at most 2 different and in particular primary am / 5-C atom branched alcohols are used in admixture with secondary alcohols, the molar ratio between the alcohol components of 1 ί 1 to 1: 5 and the reaction takes place at temperatures of 313 »15 to 383.15 K. ,

According to the invention, alcohol mixtures containing not more than 5 $, preferably 2 to 3, alcohol components are suitable. Suitable compounds are unbranched and free-radical primary and secondary aliphatic alcohols having 2 to 24, preferably 3 to 18, carbon atoms and cyclic alcohols mixed with aliphatic alcohols with 5 ^ iS 9 carbon atoms, for example cyclopenta- nol and cyclohexanol, the mixtures or mixtures can be used both pure and technical single alcohols having an alcohol content of at least 70 % or corresponding products already present as an alcohol mixture.

If R ^ OH and B _P OH are not in the position of the hydroxyl group (eg exclusively primary or exclusively secondary alcohols)

then the carbon number of the alcohols should differ by at least 2, preferably by 4 to 6. For mixtures containing more than 2 alcohol components, the difference in the number of carbon atoms between the lowest carbon and the highest carbon number alcohol should be 2 to 16, preferably 4 to 12, depending on the number and structure of the compounds.

Differ Β ,, ΟΗ and EP ⁰ ** case of binary mixtures in the position of the hydroxyl group (e.g., "B _s primary and secondary alcohol mixtures), the number of carbon atoms should be equal or differ by no more than. 2 It is advantageous if, for alcohols having different steric ratios, the odor is the less sterically hindered alcohols 1 bäw. Have 2 more carbon atoms "Especially primary am / S- carbon atom branched alcohols in a mixture with secondary alcohols are suitable,

The alcohol mixtures or mixtures, in each case the highest yields of 0,0 »-Dialkyldithiophosphorsäuren be achieved with asymmetric alkyl group arrangement, have a molar ratio between 1: 1 and 1 t 5. For alcohols, due to their carbon number or, chemical Structure differ not or only slightly in the reactivity, a äquimoL-ekulares mixing ratio is advantageous. On the other hand, for alcohols with different reactivity, a mixing ratio is advantageous in which the one or less less reactive alcohols have a higher molar fraction. The size of the ratio depends on the reactivity.

In the case of mixtures or mixtures containing more than 2 alcohols, the molar proportions of all or only individual components may vary. "This depends above all on the extent to which the alcohols differ from one another in their reactivity.

Reaction patterns for the synthesis of unsymmetrical alkyl group O, Ο -dialkyldithiophosphoric acids range from 313 »15 to 393 * 15 K and are also governed by the chemical structure and chain length of the ethereal alcohols. Regarding the share of 0 _? O ^t -Diallcyldithiophosphorsäuren with unsymmetrical Al ~ kylgruppenanordnung prove to be the following reaction temperatures as appropriate:

Un * 313 »15 t> ^is 333» 15 K for mixtures of branched or branched secondary alcohols. ⁹ 323 15 to 343 15 E for mixtures of unbranched or branched primary and unbranched or branched secondary alcohols.

· 333 »15 to 353 * 15 E for mixtures of branched primary alcohols.

• 343 »15" to 363 »15 E 'for mixtures of unbranched and branched primary alcohols.

• 353> 15 "to 373 * 15 E for mixtures of unbranched · primary alcohols.

•> 363 »15 K for mixtures containing cyclic alcohols *

With the proposed procedure, 0 _s 0 ^f -Dialkyldithiophosphorsäuren unsymmetrical alkyl group arrangement can be prepared with maximum yield «The synthesized 0, O ^f -Dialkyldithiophosphorsäuren are starting materials for high-quality lubricant additives _t These are both metal salts and other, metal 'free derivatives of these compounds consideration. The processes for their preparation are well known. Thereafter, metal salts are obtained by reacting the acids with metal compounds, for example with metal oxides. The metal used is, inter alia, lead, bismuth, cadmium, antimony, nickel and, above all, zinc. The zinc salts of the reaction products which are according to the invention

- 8 ~ 223 8 30!

have a high proportion of compounds with unsymmetrical alkyl group arrangement, "have particularly favorable ge properties for effectively acting lubricant additives.

embodiments

The invention will be explained in more detail below with reference to some embodiments:

Example 1:

Ο, 5 moles of copanol-2 and 0.5 mol of octanol-2 are heated in a supersonic flask to 333 ° C. Thereafter, with stirring, the portionwise addition of 0.12 mol of tetraphosphorodecasulfide is carried out. After the end of the reaction, the percentage ratio of the formed OjO'-dialkyldithiophosphoric acids with symmetrical or asymmetric Alkylgruppenanorä- »tion determined for the unsymmetrical O3rfcyl ~ 2-, Propyl-2 ~ dithiophosphorsäure aer proportion 74-% by mass and for <3ie symme- tri-di-propyl-2- and di-octyl-2-dithiophosphoric acids 26% by mass,

Example 2:

2i? Oj5 mol of an unbranched and 0.5 mol of a branched primary alcohol are reacted as in Example 1 at 353 K. * It is the mixture of hexanol-1/3 ~ methyl biolecanol-1 and octanol-1/2 ~ methylpropanol ~ 1 , While the proportion of OjO'-dialkyldithiophosphoric acid with unsymmetrical Alkylgruppenanordnung the first alcohol mixture with a difference of 1 carbon atom 46 _s is 5% by mass j was the second alcohol mixture with a difference of 4 carbon atoms, 63% by mass of O, Ö ^f -di ~ alkyldithiopiiosphorsäuren found with unsymmetrical alkyl group attachment »

•. -9- 2

Example 3 ^:

0.5 mol of 2-ethylhexanol-1 and 0.5 mol of butanol-2 and 0.5 mol of 2-ethylhexanol-1 and 0.5 mol of octanol-2 are reacted as in Example 1 at 3 ^ 3 K. The play "be at 52 Ma -% 2-Äthylhe: ^ l-1-butyl-2-dithiophosphoric acid and 69% by mass of 2-ithylhe:.> QYL-1 ~ 0ld; yi-DithiQphosphorsäure ₀

Example 4-s

0.5 mol of Rückoktanol (90 ™ Ma-% 2-lthylhexanol-1) and 0.5 mol of hexanol technically (7Q ~ Ma-% 2-lthylbutanol-1) are reacted as technical alcohols as in Example 1 "at 353 K. The proportion of 2-Alkylbuty1-1-2-1thylhexyΙα ithiophosphorsäure "is 46% by mass,

Example 5:

Butanol-1 and Eeptanol-1 are reacted in the "ratio 0.5 i 0.5 as in Example 1" at 363 K. The proportions "are 56 mole percent butyl-1-heptyl-i-bithiophosphoric acid and each 22 mole percent dibutyl-1 and diheptyl-1-dithiophosphoric acid _e

Example 6;

2-methylpropanol-1 and octanol-2 are reacted once in the ratio 0.5: 0.5 mol and once in the ratio 0.33 * 0.66 mol as in Example 1 "at 3 ^ 3 E. At the first mixing ratio becomes Proportion of 2-methylpropyl-i-octyl-2-dithiophosphoric acid of 54% by mass and obtained at the second mixing ratio of 65% by mass,

Example 7- '

0.5 mol of butanol-1, 0.5 mol of 2-methylprop3jD.ol-1 and 0.5 mol

Butanol-2 are in each case reacted with 0.5 mol of hexanol-1 "at 333 and at 353 K as in Example 1. Of the reaction products, the neutralization rate NZ was determined, which, based on the average molecular weight in theory, amounts to approx _e would have been found for the mixture of butanol-1 / hexanol ~ 1 184 at 333 and 191 at 353 K, for the composition 2-Methylpropenol-i / Höxaaol-T 199 at 333 and 179 at 353 K and the mixture • butanol 2 / hexanol-1 186 at 333 and 116 at 353K.

Claims (2)

invention claim 1. A process for the preparation of OjO ^ Dialkyldithiophosphorsäuren with an increased proportion of asymmetrically arranged alkyl groups by reacting Tetrap hosphordekasulfid with alcohols at temperatures between 313.15 "to 4-23.15 * C», characterized in that the implementation of Tetraphosphordekasulfid with alcohol mixtures not more than 5 alcohol components 1Q, the C number of the Aikoho components differing in the same position of the OH groups for binary mixtures between 2 and 6 and for more than 2 alcohol components the difference between the highest and lowest component 2 to 16, preferably 4 to 12 C Atoms is and that in alcohol components with different position of the OH group in binary mixtures, the number of carbon atoms differs by at most 2 and in particular primary am / 3 -C atom branched alcohols are used in admixture with secondary alcohols _s the molar ratio between the Alcohol components from 1 ί to 1 ί 5 and the reaction takes place at temperatures of 313.15 to 383.15 E. , 2 · Method according to item 1, characterized in that the reaction of tetraphosphorus decasulfide with mixtures of unbranched or or _c . and branched secondary alcohols boi 313.15 to 333.15 K takes place. Method according to item 1, characterized in that the reaction of tetraphosphorus decasulfide with mixtures of unbranched or branched primary and branched or branched "secondary alcohols takes place at 323.15 to 34-3.15 K." 4 * method according to item Ij, characterized in that the reaction of tetra phosphorus disulfide with mixtures of branched primary alcohols at 333.15 to 353 * 15 E occurs. '' Process according to item 1, characterized in that the conversion of tetraphosphorus decasulfide with mixtures of unbranched and branched primary alcohols takes place at 343 s 15 Ms 363.15 K. 6. The method according to item 1, characterized in that the reaction of Tetraphosphordekasulfid with mixtures of unbranched primary alcohols "at 353" to 373s15 K occurs. ,
10 7 · The method of item 1, characterized in that the reaction of tetra phosphorus sulfide with Deka mixtures contain / equal © alcohols "at _363? 15" to .383 * 15 K © rfolgt. ,