DE1940801A1 - Process for the preparation of aromatic dialkyl compounds of high molecular weight - Google Patents

Description

Patent attorneys

Dlpl.-Ing> A. Grünecker 11, / JlW WßQ

Dr. -Ing. H. Kinkeldey *

Dr.-Ing, W. Stockmair

*, Maximilian * ». 43 1 ^ 4030]

P 2618

COSTIHEBTAL OIL COMPANY
Ponca City, Oklahoma 74601, V.St.A.

Process for the preparation of aromatic dialkyl compounds of high molecular weight

"The present invention" relates to a method of making synthetic hydrocarbon compositions that have properties that make them particularly useful as lubricants in extremely low temperature applications.

Various fractions of petroleum have been used as lubricants for many years. Although different from

- 1 009814/196 ^

Petroleum derived lubricants for most applications are satisfactory, there are applications such as jet engine lubricants and arctic oil which, due to the requirements, uses conventional petroleum-derived lubricants either unsatisfactory or marginally useful. Synthetic ones are used to solve this problem Lubricants (e.g. diesters) with improved properties, especially with improved viscose! ' tat and improved flow point properties ^ been. The already known synthetic lubricants ^ are, however, disadvantageously relatively expensive. For this Reason is interest in the development of synthetic hydrocarbon lubricants. The goal was In the development of lubricants with the same or better properties than the diester-type lubricants, the however, are less expensive.

US Pat. No. 3,288,716 describes a synthetic hydrocarbon mixture with properties because of which they are alο lubricants particularly satisfactory is. This composition contains 50 to 95 parts by volume of alkylbenzenes and 5 to 50 parts by volume of diphenyl alkylene tie. In addition, other substances, for example Tetrahydrocaphthaiine, to be available.

Mn process for the production of a hydrocarbon composition, which contains substantial amounts, for example over $ 75, of high molecular weight dialkylbenzenes, consists in the disproportionation of monoalkylbenzenes However, commercially available monoalkylbenzenes having the desired alkyl groups are usually of complex compositions before using other materials, such as tetrahydronaphthalenes, contain. Because an increase in the amount of tetrahydronaphthalenes reduces the temperature

0098U / 1966

BATH ORIGINAL

increased of compositions containing dialkylbenzenes and tetrahydronaphthalenes are desirable possibilities to have available to the amount of tetrahydronaphthalenes produced in a disproportionation process to keep it minimal.

The present invention provides a process for the preparation of dialkylbenzenes from honoalkylbenzenes without significantly increasing the tetrahydronaphthalene content.

From the USA patent specification 2 753 384- the disproportionation of monoalkylbeneols to dialkylbeneols using application of HF-BF * as a catalyst. The alkyl groups "

are limited to propyl and butyl. From the patent mentioned BU it can be seen that n-butylbenzenes Craokung. and other lifting reactions more easily than the n-propylbene brines · In view of this finding would be too expect that there will be very little, if any, disproportionation of Cg monoalkylbenzenes.

The German patent application P 15 68 268.5 of the applicants relates to the disproportionation of mono-n-alkyl (C _Q _ ^ g) benzene sols to di-n-alkyl benzene sols, it being stated that Friedel-Crafts catalysts can be used, aluminum chloride being used is the preferred catalyst.

It has now been found that the use of HF-BF as a Catalyst for the disproportionation of honoalkylbeneols to dialkylbeneols in the presence of tetrahydronaphthalenes without increasing the amount of the latter. This is not the case with aluminum chloride the catalyst 1st.

It has also been found that not all Friedel-Crafts catalysts, especially the weaker catalysts,

0098U / 1966

like Eieen-III-chlorld, BF, alone and aluminum chloride / Nltrobensol, a disproportionation of monoalkylCCoig) benzenes to the corresponding dialkylbenzenes.

The present invention thus relates to a method for Production of aromatic dialkyl compounds with at least 8 carbon atoms in the alkyl groups by contacting aromatic monoalkyl compounds having the corresponding Contains alkyl groups, with HF-BF * catalyst and recovering the desired product from the reaction product

The present invention relates in a preferred embodiment a process for the preparation of dialkylbenzenes with at least θ carbon atoms in the alkyl groups by contacting a hydrocarbon compound, the Moooalkylbenzenes with alkyl groups with the same number of carbon atoms such as dialkylbeneols and tetrahydronaphthalenes contains, with HF-BF ^ catalyst and the recovery of the dialcylbenzenes from the reaction product.

An excellent feature of the process according to the invention is the use of HF-BF ~, which is used for disproportionation of monoalkylbenzenes to dialkylbenzenes in the presence of P Tetrahydronaphthallnen leads without doing any significant Increasing the amount of tetr & hydronaphthalenes occurs "

The invention is described in detail below.

Suitable materials for use as starting materials in the inventive method are alkyl aromatic Compounds with at least 8 carbon atoms in the alkyl group. The alkyl group suitably contains 8 to 18 carbon atoms, with 10 to 15 carbon atoms preferred

- 4 -00981 kl 1966

are. The aromatic part can be derived from benaol, toluene, xylene or naphthalene, but is preferably derived from it from Benaoi from »

A particularly suitable material is a composition containing a substantial amount of mono-n-alkylbene oils made according to the method of U.S. Patent 3,516,294. These mono-n-alkylfeenzenes are characterized by the fact that the Aikyleubeti « They contain 8 to 18 carbon atoms and contain at least 95 £ of the alkyl substituents through a secondary Carbon atom of the respective alkyl group on the benzene nucleus are bound.

She U.S. Patent 3,316,294 relates to a method for Preparation of a detergent alkylate, according to which one (a) a Fraction of essentially straight-chain Og to C ^ g hydrocarbons separated from a petroleum distillate which is essentially free of olefins and the straight-chain hydrocarbons together with non-straight-chain hydrocarbons Contains hydrocarbons, (b) this traction is chlorinated to the extent that between about 10 and about 35 mol-jG of the straight-chain hydrocarbons present are essentially only monochlorinated, and (o) an aromatic one Compound, e.g. benzene, with the chlorination product of step (b) in the presence of an alkylation catalyst alkylated.

In the context of the description of the present invention, express reference is made to said US Pat. No. 3,316,294 Referenced.

The suspension composition containing monoalkylbenzene may be a smaller henge (less than 25 ^, preferably less ale

0098U / 1966

11/0 contain tetrahydronaphthalenes.

The term used in the description of the present invention includes ^{n n} tetrahydronaphthalenes tetrahydronaphthalenes with alkyl substituents containing up to 8 Kohlenetoffabome. .

In the method according to the invention, a mixture of anhydrous liquid hydrogen fluoride and boron trifluoride is used used. Interestingly, it has been found that BF «alone does not lead to any product at all. The usage HF alone provides a product with properties that make it suitable for use as a jet engine lubricant or make it unsuitable as an arctic lubricant.

The HF-BiU catalyst should have at least 2 sewing parts H? per part Bl \ included. The catalyst preferably contains about 10 parts by weight of EF per part of ΒΪ ,. Larger amounts of H? can be used with no apparent benefit, while of course adding to the cost.

The amount of HP-BF * used in the method according to the invention should be about 20 to about 80 wt .- ^, based on the Feedstock containing monoalkyl aromatics. Based to the same level, the amount of EF-BF should preferably be from about 40 to about 60 weight percent.

Suitable Seaktionsbedingungen for the inventive process are a temperature in the range of about 0 to about 70 ⁰ C Mt a reaction time of about 0.5 to about 6 hours. More suitable reaction conditions are a temperature in the range from about 15 to about 35 ^° C. with a reaction time of about 1 to about 2.5 hours. In the case of the above temperatures and times, the longer time corresponds to the lower temperature. The preferred reaction

0098U / 1966

The conditions for the process according to the invention are 25 ^° C. and 1.5 hours.

The recovery of the dialkylbenzene fraction from the reaction - failure. can be done using conventional means. Recovery is usually accomplished by first allowing the reaction mixture to drain and then withdrawing the catalyst. The reaction mixture is then washed with a basic solution. In addition to the washing process, the reaction dissolution βατ removal of unreacted monoalkylate and lighter materials is distilled. The point of intersection depends on the ffolekularge * wioht of the Konoalkylat-Besohiokungsmateriale "If the mono" · alkylBt is predominantly Oo-Monoalkylbenöl, "o the intersection point of 145 ⁰ C at 1OnHg Brück is suitable · If the Honoalkylat is predominantly O-jj-Monoalkylbenol , Β is an intersection of 197 ⁰ O at IO m Hg pressure suitable

If the beechiocing material is the approved koa alkylate fraction produced by USUL-PÄt "ntsohrift 3 316 294, the product contains at least 80% by weight" 4 (dialkylbenaol and not more than 20 H xetrahydronaphthalenes. The product preferably contains at least 85 % dialkylbeneols and not more than £ 15 letrahydronaphthalene.

The inventive method provides at least one 20% by weight conversion of aromatic monoalkyl compounds into aromatic dialkyl compounds. The procedure Usually delivers at least a 30 year update and usually at least a forty-year-old transformation.

In the conversion of monoalkylbenzenes according to the invention in dialkylbene sols there is a disproportioni * - reaction.

*. 7 -
0098U / 1966

In describing the present invention, the term "no significant increase" is used with respect to the amount of tetrahydronaphthalene produced in the reaction. This term "pressure" used here does not mean any significant increase, "let it be defined" in such a way that it is no longer around 30 t, preferably around 15 +% , based on the tetrahydronaphthalenes originally present in the Beeohiokungeoisohune.

The product according to the invention, as already mentioned above, particularly suitable for the use of all lubricants, those as DUsenjet thruster soothing and arctic Oils are usable. The product is usually used as a base material combined with conventional additives such as Oxidation-corrosion inhibitors and the like. In the worst case, the product can be used with other urundV materials are mixed in order to create a composition with special properties.

The product according to the invention is also used as a sulfonation starting material for the production of oleosulfonates high quality suitable.

The following examples are intended to further illustrate the present invention, but not to limit it.

example 1

The present example illustrates the precautionary conditions of the method of the invention. The monoalkylate solution is produced according to the procedure of the USA-Petentechrlft 5 316 294 and results in the following analysis:

0098U / 1 966

Monoalkylbenzene * 89.5 #

Tetrahydronaphthalenes 10.5 #

⁰ II " ^D * ⁸ Ci", «- alkyl groups ₉ where C ^ predominates

900 g of the monoalkylate composition are placed in an autoclave, after which. 50 g BF «and 500 g HF are added to the autoclave. This reaction mixture is stirred at a temperature of 25 ⁰ O for 1 hour. The reaction mixture is then allowed to settle and the catalyst is stripped off. The reaction product is washed with an aqueous baee. Thereafter, the R # is fractionated aktionsproaukt _distilled} being an intersection point of 197 ⁰ C at 10 cm Hg used. The desired product (residue fraction) is clear as water. It contains 87 »7 % dialkylbenzenes * and 12.1 #! Detrahydronaphthalenes and has the following physical properties:

Pour point, - ⁰ C ( ⁰ F) -51.1 (-60)

Viscosity at -40 ° 0 (-4O ⁰ P), es 6795

Viscosity at 38 ⁰ C (100 ⁰ F), it. 27.05

Viscosity, at 99 ⁰ C (210 ⁰ F) _s it. 4.93

Viscosity index 119

* Bar D'3i'.vo: a! I3.ii; igsprogeiatsat2! of Honoalkylbenzenes in Dile is 56 #.

E e I ₁₁ S ₁ ρ ie 1- 2

The present example is a comparative example »that the effect of using AlCl * as a catalyst shows. The mono-aluminum used as feed material

is the same as in example 1.

1500 g of the monoalkyl & t composition are poured into one

0098U / 1966

Introduced into the autoclave. 20 g of AlCl ₅ (1.3% by weight, based on Mcnoalkylat) and 0.3 g of water are added. The contents of the autoclave are stirred for 2 hours while the temperature is kept at HO ⁰ C. The reaction mixture is then allowed to settle and the catalyst is stripped off. The reaction product is washed with an aqueous base. The reaction product is then fractionally distilled, an intersection of X97 ° 0 at 10 ram Hg being used. The product (residue fraction) is yellow to brown in color. Ee contains 67.1 % dialkyl-Hlbenzenes and 24.4% tetrahydronaphthalenes, while the remaining 8.5% are a mixture of naphthalenes, hydronaphtholines and diphenylalkanes. The product has the following physical properties

PlieSpunkt, ⁰ C ( ⁰ P) -53.9 (-65)

Viscosity at -40 ° 0 (-40 ⁰ J) 12 066

Viscosity at 38 ⁰ O (10O ⁰ I ¹ ) 32.84

Viscosity at 99 ° O (210 ° P) 5.41

Viscosity index 110

* The conversion percentage of Mcnoalkylbenzenes in Dlalkylbeszöle is 45 ί>.

Example 3

The present example is a comparative example and shows the effect of using other catalysts as dsm HF-BF ^ complex, in all experiments the monoal " The catalyst composition is the same as in Example 1. The various catalysts tested and the results obtained are shown below.

- 10 -

009314/1966

Catalyst result Iron III chloride no disproportionation

Β ?, (alone) no disproportionation

ΑΙΟΙ, -nitrobenzene no disproportionation

H? (alone) the product has a very high Vis

viscosity at -4O ⁰ O (-40 ⁰ I)

BF, + water no disproportionation AlCl - Hitromethane no disproportionation

The present invention is not limited to the specific embodiments described, since many modifications can be carried out without departing from the path of the invention.

The present invention also relates to the disproportionation of aromatic monoalkyl compounds to aromatic ones Dialkyl compounds using EI-Bf. ale catalyst. The alkyl groups contain at least 8 carbon atoms. A preferred embodiment of the present invention relates to the disproportionation of nonoalkylbeneols to dialkylbenzenes using Hf-BP. as a catalyst. The monoalkylbenzenes subjected to disproportionation are present in a composition which Contains tetrahydronaphthalene. The use of the Hf-Bf * Catalyst gives dialkylbenzenes without oine significant Increase in! Detrahydronaphthalenes.

- 11 -

0098U / 1 966

Claims (1)

Claims asssBSssssasssssssasssassssss Process for the preparation of aromatic dialkyl compounds with at least β carbon atoms In the alkyl groups, wherein the aromatic part is benzene, toluene, xylene or naphthalene, characterized in that aas (A) aromatic monoalkyl compounds, the alkyl group and the aromatic part of which correspond to the specifications for the aromatic dialkyl compounds, with HF-BF ^ catalyst for about 0.5 to about 6 hours at a temperature in the range from about O ⁰ C to about 7O ⁰ C contacted and (b) the aromatic dialkyl compounds are obtained from the reaction product of step (a) 2. The method according to claim 1, characterized in that that the conversion of Honoalkylbenzenes in Dialkylbenzenes is at least 20 wt .- ^. 3. The method according to claim 2, characterized in that the amount of HF-BF, catalyst about 20 to e «wa 80 Gev. ^r . ~ £, based on the aromatic monoalkyl compounds, and the catalyst contains at least 2 parts by weight of HF per part of BF ^. 4. The method according to claim 3, characterized in that the Kenge of HF-BF, -Xatalyeator about 40 to about 60 wt. - $> and the catalyst contains at least about 10 parts _{by weight of HF per part of BF 5} . 5. The method according to claim 4 »characterized in that - 12 - 0098U / 1966 CIA y SAO ORIGlNAt that the temperature is about 15 to about 35 ⁰ C and the reaction time about 1 to about 2.5 hours. 6 »Method according to claim 5» characterized in that that the aromatic rope is derived from benzene and the alkyl group contains from about 10 to about 15 carbon atoms. 7. Process for the disproportionation of monoalkylbenzenes in a mixture which contains monoalkylbenzene «and tetrahydronaphthalenes without simultaneously meaning« en increasing the amount of tetrahydronaphthalenes in the. Cause reaction product, .With the alkyl group of Monoalkylbenzenes and the dialkylbenzenes contains at least 8 carbon atoms, characterized in that one (a) a mixture of monoalkylbenzenes and letrahydro- "naphthalenes about 0.5 to about .6 hours at a temperature of about 0 ⁰ C to about 70 ⁰ C with HF-Bf-z-contacted catalyst and (b) the! »! alkylbenzenes from the reaction product of Stage (a) wins. 8. The method according to claim 7 characterized in that ate the amount of HF-BSy catalyst from about 20 to about 80 wt .- ^, based on the mixture of Mcnoalkylbenolen and tetrahydronaphthalenes, and the catalyst is at least 2 parts by weight of H? per Sell BF. 9 · A method NaOH claim S _9, characterized in that the amount of H-B, -? Katalyeator about 40 to about 60 (3ew.- £ by weight and the catalyst at least · about 10 parts by weight per SJf XeIl BF ₃ contains . 10. The method according to claim 9, characterized in that - 13 - 0098U / 1966 BATH ORIGINAL that the temperature is about 15 ⁰ O to about 35 ⁰ C and the reaction time about 1 to about 2.5 hours. 11. The method according to claim 10, characterized in that that the alkyl group has about 10 to about 15 carbon atoms contains. 12. The method according to claim 11, characterized in that the temperature is a
1.5 hours. that the temperature is about 25 ⁰ C and the reaction time about - 14 - 0098U / 1966 0AOOHHJJNAt