US2071521A

US2071521A - Production of fluorescence producing substances soluble in hydrocarbon oils

Info

Publication number: US2071521A
Application number: US628365A
Authority: US
Inventors: Hartmann Hans; Rabe Hans
Original assignee: IG Farbenindustrie AG
Current assignee: IG Farbenindustrie AG
Priority date: 1930-02-03
Filing date: 1932-08-11
Publication date: 1937-02-23
Anticipated expiration: 1954-02-23

Description

Feb. 23, 1937. HARTMANN ET AL 2,071,521

, PRODUCTION 0F FLUORESCENCE PRODUCING SUBSTANCES SOLUBLE IN HYDROCARBON OILS Filed Aug. 1l, 1932 VESSEL V533 EL F02 Co MPL/57E /PGL rfv/E22 /zA 77o WA TER /NLE 7' Se PA 2A r/bfv v.s.s El.

Maw@ @www Patented Feb. 23, 1931 PATENT OFFICE PRODUCTION OF FLUORESCENCE PRO- DUCING vSUBSTANCES SOLUBLE IN HYDROCABBON OILS Hans Hartmann and Hans Rabe, Mannheim,

Germany, assignors Aktiengesellschaft,

Germany to I. G. Farhenindustrie Frankforton -the-Maln,

Application August 11, 1932, Serial No. 628,365

In Germany February 3, 1930 (Cl. ISB-78) 5 Claims.`

consistency, may be dissolved in lubricating oils while warming and have the disadvantage that the greater part of them is precipitated again, after allowing the solution to stand and cool for some time, and that in many cases they give only a slight opalescence. These products furthermore are not soluble in benzines but are precipitated by them. c

We have now found that fluorescence producing substances which are readily soluble, even at low temperatures, in hydrocarbon oils`(by which expression we understand heavy oils or middle oils or lubricating oils or liquid motor fuels, such as benzines, or' other liquid hydrocarbon fractions-Whether they be of `naphthenic or paratflnic base-) 4are obtained, if oleiines of purely aliphatic constitution, which are liquid at ordinary temperature, are subjected tdcondensation with polynuclear organic -substances in which none of the nuclei is saturated with hydrogen, said condensation being carried out at an elevated temperature in the presence of condensing catalysts of the Friedel-Crafts-type, in particular aluminium chloride. Of particular advantage are those of the aforesaid polynuclear substances whose aromatic nuclei are devoid of substituents. Examples of such substances are unsubstituted polynuclear aromatic hydrocarbons.' such as naphthalene or anthraceneor phenanthrene, or polynuclearhetero'cyclic compounds, such as carbazol. As olenes suitable as initial materials for this conversion may be mentioned the liquid products obtained by cracking paraillnic hydrocarbons, such as hard or vsoft parailin wax, petrolatum, or oils entirely or mainly consisting of paramnic hydrocarbons; or oleflnes obtained by;

dehydration `of alcohols, such as from octodecyl alcohol.

The, said condensation of oleiines and polynuclear aromatic hydrocarbons is effected at temperatures between and 250 C., preferably between and 200 C. In order to carry off the great heat evolved by the said condensation, the

treated materials are preferably diluted with an indifferent diluent, such as, :for example, a' benzine fraction boiling between and 200 C., or another oil boiling at the same or higher temperatures, and simultaneously externally cooled.

plus does not take part in the reaction, but acts only as a diluent and would have to be distilled from the resulting condensation. product. The intensity ofthe iiuorescence caused by a deiinite amount ofthe condensation product is the greater the greater is the amount of aluminium chloride employed.l Preferably from 20 to 60 per cent of aluminiumchloride with reference to the amount. ofthe initial oleilnes to be condensed are employed With larger amounts oialuminium chloride the resulting condensation products produce a uorescence having a slightly blue tinge. The products` obtained according to the presentinvention ordinarily have a mean molecular weight of between 600 and 8 00.

.The accompanying drawing shows a schematic layout of equipment suitable for carrying out the process, and the drawing is provided with appropriate legends to equipment.

The fluorescence producing substances thus obtained are thickly liquid, viscdus products which explain the functioning of the at ordinary temperature may be dissolved in hydrocarbon oils of naphthenic or paramn base,

- such as in lubricating oils or in benzine. No

'precipitation or resiniflcation occurs in the oils mixed with the said substances. 'I'he oils conrtaining these substances are" entirely clear in transparent light. An addition of from 0.1 to 0.2 per cent is sumcient for imparting to the oil a red colrin transmitted light and agreen color in reilected light, so that this'oil, in its appearance, is inl no way different from that of a Pennsylvanian oil. Th'e following examples will further illustrate how the present invention may be carried out in practice; the invention is, however, not restricted to these examples.

' f Example 1 i 1 kilogram of a fraction mainly consisting of oleilnes which boils between 90 and 150 C under a pressure 012 millimeters mercury gauge and which has been obtained by cracking soft.

paraiiin wax is subjected to condensation with 1,

kilogram of naphthalene in the presence of 0.4 kilogram af aluminium chloride. The reaction product having attained a temperature of 180 C.. is allowed to cool down, then stirred with water and thereupon freed from the solid matter mainly consisting of the aluminium hydroxide formed. 'I'he reaction product is then heated to 150 C. under a pressure of 2 millimeters mercury gauge, 0.05 kilogram of oil thereby being distilled as iirst runnings. The liquid residue amounting to 1.9 kilograms represents an excellent fluorescence producing substance soluble in lubricating oils and benzine. If a mineral oil having a yellow color is mixed with 0.15 per cent of its Weight of the said liquid residue the mineral oil obtains a. remarkable green fluorescence and appears red in transmitted light.

' Example 2 4 kilograms of a product obtained by cracking petrolatum, which boils above 100 C. under a pressure of 2 millimeters mercury-gauge are polymer-ized with 1 kilogram of naphthalene, 0.5 kilogram of anthracene oil and 0.5 kilogram of carbazol in the presence of 1.2 kilograms of aluminium chloride at a temperature of 200 C. while stirring. The resulting products are worked up as described in Example 1. An oil is thus obtained in a nearly quantitative yield representing a iiuorescence producing substance which when added to an oil causes that the latter appears red in transmitted light and green in reected light.

Example 3 10 kilograms of a product obtained by 'crack- 1 ing hard parailin wax and which boils between 20 and 300 C. at atmospheric pressure is diluted with 5 kilograms of rst runnings as obtained for example in the process described in Examplel 1. After adding 6 kilograms of naphthalene and 10 kilograms of aluminium chloridel to the mixture the whole is` polymerized for 2 hours at about 125 C. Theresulting product is worked up as described in Example 1. In addition to 6 kilograms of rst runnings 14.5 kilograms of a viscous product are obtained which when added to an oil showing no fluorescence in an amount of 0.2 per cent of the amount of oil, imparts to the oil a iluorescence which is in no way diilerent from that of a Pennsylvanian oil.

Example 4 20 kilograms of a product obtained by cracking paraflin wax which has been diluted with 8 kilograms of a high boiling benzine fraction, are mixed with 5 kilograms of naphthalene and 7.5 kilograms of aluminium chloride added to the mixture in 3 portions amounting each to 2.5 kilograms, the second and third portions being added only after the reaction set up by the last preceding portion is nished (which may easily be determined by the decrease of the tempera'- ture). The whole of the aluminium chloride having been added to the reaction mixture, the latter is maintained for about 1 hour at 150 C. The reaction product, when worked up as described in Example 1 represents a uorescence producing substance which when added to an oil in an amount vof 0.1 per cent imparts to the latter a green uorescence and a red appearance in transmitted light.

Example 5 10 kilograms of a product obtained by cracking paraiiin wax are diluted with 10 kilograms of rst runnings as obtained for example in the process described in Example 1 and,4 after an addition of 5 kilograms of aluminium chloride, polymerized while simultaneously introducing the cracking gases obtained in the cracking of paraffin wax. After the reaction temperature E has attained about C., 8 kilograms of naph` thalene, 1 kilogram of anthracene and 0.5 kilogram of phenanthrene are added. The Whole mixture is then heated to 150 C, and maintained at this temperature for one hour. The resulting products are subjected to distillation at 150 C. under a pressure of 1 millimeter mercury gauge, 18 kilograms of a substance vbeing obtained as residue which when added to oils imparts to them a fluorescence as intensive as do the products obtained as described in the foregoing examples. v

The addition of the said cracking gases does not materially increase the yield of the uorescence producing substance but the amount of the portions which are separated by the distillation Vof the condensation products and which constitute oils having lubricating properties is considerably increased. In this manner the cracking gases are made use of at the same time for the preparation of lubricating oils.

In the appended claims by the term condensation (or condensing) it is intended to include both condensation and polymerization.

1. A process for the production of a uorescence producing substance which is soluble in hydrocarbon oils which comprises subjecting a mixture of an oleiine of purely aliphatic constitution and liquid at ordinary room temperature with from 20 to 70 per cent with reference to said oleiine of a polynuclear aromatic'substance in which none of the nuclei is saturated with hydrogen to condensation at a temperature between '70 and 250 C. and in the presence of at least 20% with reference to said olei'ine of a condensing agent of the Friedel-Crafts type for a reaction time such as to produce uorescence producing substances, soluble in hydrocarbon oils, and having a mean molecular weight of between 600 and 800.

2. A process for the production of a fluorescence producing substance which is soluble in hydrocarbon oils which comprises subjecting a mixture of an olene of purely aliphatic constitution and liquid at ordinary room temperature with from 20 to :70 per cent with reference to said olefine of a polynuclear aromatic substance in which none of the nuclei is saturated with hydrogen to condensation at a temperature between and 200 C. and in the presence of at least 20% with reference to said olene of a condensing agent of the Friedel-Crafts type for a reaction time such as to produce fluorescence producing substances, soluble in hydrocarbon oils, and having a mean molecular weight of between 600 and 800.

3. A process for the production of a uorescence producing substance which is soluble in hydrocarbon oils which comprises subjecting a mixture of a liquid at least mainly consisting of olenes liquid at ordinary temperature, which is obtained by cracking parain wax with from 20 to 70 per cent, with reference to the olefines contained in said liquid of naphthalene to condensation at a temperature between 70 and 250 C. and in the presence of at least 20% with reference to said olefln'e of aluminium chloride rescence producing substances,

as to produce uosoluble in hydrocarbon oils, and having a mean molecular weight of between 600 and 800.

4. A process for the for a reaction time such production o! a. uo

i rescence producing substance which is soluble in hydrocarbon oils which comprises subjecting a mixture of a liquid consisting at least mainly of oleiines of purely aliphatic constitution and liquid at ordinary room temperature with from 20 to '70 per cent with reference to the olenes contained in said liquid of a polynuclear aromatic substance in which none ot the nuclei is saturated with hydrogen and which is devoid of substituents to condensation at a temperature between 70 and 250 C. and in the presence of from 20 to 60 per cent by weight oi said mix= ture of #um chloride for a reaction time hydrocarbon oils,

such as to produce iiuorescence producing substances, soluble in hydrocarbon oils, and having,

a mean molecular weight of between 600 and 800.

5. A process for the production of a iiuorescence producing substance which is soluble in which comprises subjectingr a mixture of a liquid oleilne of purely aliphatic constitution with more than 20 per cent with reference to said olene of a polynuclear aromatic substance in which none of the nuclei is saturated with hydrogen, to condensation at a condensing temperature 'and in the presence of at least 20% with reference to said olene of a condensing agent of the Friedel-Crafts type.