JP2002146371A - Colorless petroleum marker dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To find a colorless maker dye having improved solubility in petroleum products. SOLUTION: A composition comprising a liquid petroleum product and a colorless marker compound which has the formula [wherein R1 is a 1-18C alkyl, a 1-18C alkenyl, aryl or aralkyl; R2, R3 and R4 are each independently hydrogen, a 1-12C alkyl, chloro or bromo; R5 is hydrogen, chloro or bromo] and is present in an amount that is not visually detectable is disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates generally to compositions comprising a colorless marker dye and a liquid petroleum product, as well as a method for marking petroleum products. Certain phthalein derivatives are known as markers in petroleum applications and other industrial applications, including paints and plastics,
It is used. For example, US Pat. No. 6,020,056 discloses the use of thymolphthalein, cresolphthalein and related compounds as markers for petroleum products. However, this reference only discloses compounds having two phenolic hydroxyl groups and does not suggest the use of phthalein esters as markers.

[0002] The disadvantages of phthalein derivatives result from the typically low solubility of the phthalein derivatives in petroleum products. As a result of this property, the phthalein marker can be used to deliberately mark the petroleum that has been marked by extraction with water, either deliberately when it is desired to remove the marking, or as a result of the marked petroleum product contacting the underlying water in the storage tank. Can be removed from the product. The problem addressed by the present invention is to find colorless marker dyes with improved solubility in petroleum products.

[0003] The present invention relates to liquid petroleum products and compositions comprising a compound of formula I in an amount which is not visually detectable.

[0004]

Embedded image

In formula I, R¹Is C₁-C₁₈Al
Kill, C₁-C₁₈Alkenyl, aryl or arua
Luquil; R², R³And R⁴Independently of the water
Elementary, C ₁-C₁₂Alkyl, chloro or bromo
R;⁵Is hydrogen, chloro or bromo. Book
The invention provides a method for producing visually undetectable amounts of a compound of Formula I.
The car is added to petroleum products as a car, and the marker contacts the developer.
Marking liquid petroleum products, including touching to develop color
How to do it.

[0006] An "alkyl" group refers to a hydrocarbon group having from 1 to 18 carbon atoms in a straight, branched or cyclic arrangement. Alkyl groups can be substituted with one or more halo, alkoxy, alkanoyl or amide groups, and alkoxy, alkanoyl and amide groups can be similarly substituted with one or more halo substituents. Preferably, the alkyl groups are unsubstituted. An “alkenyl” group is one in which at least one single bond in the “alkyl group” has been replaced with a double bond. An “aryl group” is a substituent derived from an aromatic compound, and includes a heterocyclic aromatic compound having a heteroatom selected from nitrogen, oxygen, and sulfur. Aryl groups have a total of 5 to 20 ring atoms and have one or more separate or fused rings. An aryl group can be substituted with one or more halo, alkyl, alkenyl, alkoxy, alkanoyl, or amide groups, and an alkyl, alkenyl, alkoxy, alkanoyl, or amide group can be substituted with one or more halo groups. it can. Preferably, the aryl groups are unsubstituted or substituted only with halo or alkyl groups. An “aralkyl” group is an “alkyl” group substituted with an “aryl” group.

R ² , R ³ and R ⁴ are hydrogen or 1
Preferably, it is an alkyl having up to 4 carbon atoms. Also, R ¹ is preferably an alkyl having 1 to 4 carbon atoms. Preferably, R ⁵ is hydrogen. Liquid petroleum products include gasoline, diesel fuel, jet fuel, fuel oil, kerosene or kerosene (lamp o
il). The compound of formula I has 0.5 p
preferably present in an amount of from pm to 100 ppm,
More preferably, it is present in an amount of 0.5 ppm to 10 ppm. The compounds of formula I are preferably prepared as a mixture with a high boiling hydrocarbon soluble solvent. Preferred solvents include 1-octyl-2-pyrrolidone, mixed methylnaphthalenes (Exxon Corporation)
n, sold as AROMATIC 200), or aromatic hydrocarbon solvents. The preferred concentration of the marker in the solvent is between 20% and 30%. The developer is a strongly basic drug, for example, a hydroxide of an alkali metal or quaternary ammonium ion.
Preferably, the agent is a quaternary ammonium hydroxide. The invention further relates to compounds of formula I, wherein R ¹ is propyl, R ² is methyl and R ³ , R ⁴ and R ⁵ are hydrogen. The method for preparing this compound is described in Example 1.
Is disclosed.

EXAMPLES Example 1 Preparation of di-n-butyl ester of o-cresolphthalein 10 equipped with a stirrer, thermocouple and condenser
The following starting materials were added to a 0 mL three neck round bottom flask: (1) o-cresolphthalein, 1.73 g
(0.005 mol); (2) water, 30 mL; (3) 50
% NaOH, 0.8 g; (4) Na ₂ CO ₃ , 0.6
g; and (5) xylene, 8 g. The mixture is 20-25
Stirred at 1 ° C. for 1 hour, during which 2 g of butyric anhydride was added. The mixture was then heated to 50-55 C until TLC indicated that the esterification reaction was complete. The upper xylene layer was separated and to it was added 2.5 g of 1-octyl-2-pyrrolidone. Xylene and water were removed azeotropically under vacuum. 6.6 g of residue were obtained.

The residue 10 is dissolved in xylene (100 mL).
0 mg, dissolve 1 mL of the residue solution with kerosene
By making 10 mL solution to make 00 mL,
A marker solution was prepared. The developer was made by dissolving 1 g of a 40% solution of benzyltrimethylammonium hydroxide in methanol in 99 g of 2-ethyl-1-hexanol. To 10 mL of the 10 ppm marker solution prepared as described above, 2.5 mL of the developer was added. The mixture turned blue-purple after shaking for a few seconds. If desired, a quantitative determination of the marker concentration can be made by measuring the absorbance of the solution at a wavelength of 581 nm. 10 mL of the 10 ppm solution prepared as described above
Stirred with mL of water for 1/2 hour and separated the layers. 2 mL of the developer solution was added to the organic layer and a blue-purple color developed. No color was formed even when 2 mL of the color former solution was added to the aqueous layer. This indicates that the marker was not extracted in the aqueous layer.

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Claims (10)

[Claims] 1. A liquid petroleum product and formula [In the formulas, ^{R 1} is _C 1 _{-C 18 alkyl,} C 1 _{-C 18} alkenyl, aryl or ^{aralkyl; R} 2,
R ³ and R ⁴ are independently hydrogen, C ₁ -C ₁₂ alkyl, chloro or bromo; and R ⁵ is hydrogen, chloro or bromo. Wherein the compound is present in an amount that is not visually detectable. 2. The method according to claim 1, wherein the compound is 0.5 ppm to 100 pp.
The composition of claim 1, wherein the composition is present in an amount of m. 3. The composition according to claim 2, wherein the liquid petroleum product is gasoline, diesel fuel, jet fuel, fuel oil, kerosene or kerosene. 4. R ² , R ³ and R ⁴ are hydrogen, or 1
The composition of claim 3 which is an alkyl having from 4 to 4 carbon atoms. 5. The composition according to claim 4, wherein R ¹ is alkyl having ¹ to 4 carbon atoms and R ⁵ is hydrogen. 6. The formula A compound having the formula: 7. A compound of the formula [In the formulas, ^{R 1} is _C 1 _{-C 18 alkyl,} C 1 _{-C 18} alkenyl, aryl or ^{aralkyl; R} 2,
R ³ and R ⁴ are independently hydrogen, C ₁ -C ₁₂ alkyl, chloro or bromo; and R ⁵ is hydrogen, chloro or bromo. A method for marking a liquid petroleum product, comprising adding the compound of the formula (1) as a marker to a petroleum product, wherein the compound is not visually detectable, and the compound is colored by contact with a developer. 8. The method according to claim 1, wherein the compound is 0.5 ppm to 100 pp.
8. The method of claim 7, wherein the method is present in an amount of m. 9. The method according to claim 8, wherein the liquid petroleum product is gasoline, diesel fuel, jet fuel, fuel oil, kerosene or kerosene. 10. R², R³And R⁴Is hydrogen, or
Alkyl having 1-4 carbon atoms, R¹Is 1
Alkyl having up to 4 carbon atoms; ⁵Is hydrogen
The method according to claim 9, wherein