PL237262B1 - Composition of anti-oxidant and stabilizing additives for engine fuels - Google Patents

Description

Description of the invention

TECHNICAL FIELD

The subject of the invention is a composition of antioxidant-stabilizing additives for motor fuels.

STATE OF THE ART

Oxidation stability is one of the basic operational properties determined for fuels intended for engines and heating fuels, which determines the fuel's tendency to degradation. The fuel oxidation process leads to the formation of various types of deposits, resins and acids. Products resulting from the oxidation process can damage fuel pumps and block filters and fuel lines. By settling on the tips of the injectors, they disrupt the fuel injection process. Acid oxidation products degrade engine components, causing increased corrosion and rapid deterioration of seals. The oxidation resistance of fuels can be increased by using antioxidants, which can be introduced as additives.

US 8,110,532 discloses the composition of an additive composition to prevent the oxidation of a fuel, for example diesel fuel, Fischer Tropsch fuel, GTL (gas-to-liquid) fuel, BTL (biomass-to-liquid) fuel. The antioxidant composition consists of a diarylamine with no more than four butylene groups and the reaction product p-cresol, dicyclopentadiene and isobutylene.

The authors of the patent specification US 6,303,052 presented a composition of antioxidant additives, applicable in various types of liquid hydrocarbons, including gasoline-type fuels, diesel oils, containing transesterification products of phenolic esters with 2-alkyl-1-alkanols containing from 4 to 24 carbon atoms in the alkyl chain .

Patent application US 2002/0142923 describes a composition of antioxidants containing in its composition the reaction products of ortho-tert-butylphenol (OTBP), 2,6-di-tert-butylphenol (DTBP) with formaldehyde in an organic solvent in the presence of a catalyst. This composition is further characterized by a low level of 2,6-di-tert-butylphenol and ortho-tert-butylphenol, a trace level of 2,4,6-tri-tert-butylphenol. The composition can be used for jet fuels, gasoline, heating oils and diesel fuels.

The authors of patent application US 2007/0154608 have disclosed a polymer in the chain of at least two aromatic ring monomers substituted with at least one tert-butyl group or a substituted or unsubstituted n-alkoxycarbonyl group. This substance has excellent antioxidant properties when used in petroleum products (e.g. gasoline, kerosene, diesel, heating oil, propane, jet fuel).

In US Patent 5,534,039, the authors disclose a composition of organometallic antioxidants for use in diesel fuel in cars with compression ignition engines equipped with diesel particulate filters. 2,6-di-tert-butyl-4-methylphenol, 4,4-methylenebis (2,6-di-tert-butylphenol), 4,4'-thiobis (2-methyl-6 -tert-butylphenol), N-phenyl-α-naphthylamine, N-phenyl-3-naphthylamine, tetramethyldiaminodiphenylmethane, anthranilic acid and phenothiazines and their alkyl derivatives.

The authors of the patent application US 2007/0106059 presented a method of obtaining a macromolecular substance (hexyl ether - 1,6-bis [N- (4-hydroxyphenyl) -3- (2,6-di-tert-butyl-4-hydroxy-phenyl) amide ]) with excellent antioxidant properties and high thermal resistance, as well as polymers based on them. Also presented are antioxidant additives for liquid hydrocarbon fuels containing products of these syntheses.

In U.S. Patent No. 7,964,002, the authors disclose a composition of antioxidants, the combination of which produces a synergistic effect, containing a mixture of at least one aromatic diamine selected from the group consisting of N- (1,4-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1 , 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine and N, N'-di-sec-butyl-p-phenylenediamine and at least one trisubstituted phenol selected from the group consisting of 2,4-dimethyl-6-tert -butylphenol, 2-methyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol and 1,2,3-trihydroxybenzene in a weight ratio of about 1: 1.

In patent application US 2012/0124896, the authors presented the composition of an antioxidant additive package for biodiesel, which included substituted naphthylamines such as phenyl-α-naphthylamine, phenyl-3-naphthylamine, N-p-methoxyphenyl-α-naphthylamine, substituted diphenylamines

PL 237 262 B1 containing substituents having from 4 to 10 carbon atoms and substituted quinolines from the group consisting of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-phenyl-2,2,4-trimethyl-1 , 2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline and 2,2,4-trimethyl-1,2-dihydroquinoline.

The authors of the patent application US 2015/0033617 disclosed the composition of a package of additives for diesel oil and biodiesel of a higher category, in which compounds such as: di-t-butyl-2,6-4-methyl-phenol (BHT), t- butylhydroquinone (TBHQ), 2,6- and 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, pyrogallol, tocopherol, 4,4'-methylene bis (2,6-di -t-butylphenol) singly or as mixtures thereof.

Also in the patent applications US 2009/0300974, WO 2013/007738, US 2007/0197412, additive compositions containing di-t-butyl-2,6-4-methyl-phenol (BHT) and / or t-butylhydroquinone (TBHQ) in nature of antioxidant additives.

The authors of patent application EP 2173838 describe the use of a nitrogen-containing dispersant additive to improve the oxidative stability of biodiesel-containing fuel compositions. This additive includes products obtained by reaction of polyisobutylene succinic acid derivatives containing 12 to 200 carbon atoms in the polyisobutylene chain and molecular weight from 500 to 2800 with polyethyleneamines containing from 1 to 8 amine groups in the chain.

The authors of the invention according to patent EP 2302020 (WO 2009/016400) disclosed that the use of a dispersing-stabilizing additive in the amount of 500 to 20,000 ppm ensures excellent thermo-oxidative stability of such hydrocarbon fuels as: biodiesel, diesel oil, gasoline, aviation fuel, marine fuel, heating oil , heavy fuel oil, GTL (gas-to-liquid) fuel, CTL (coal-toliquid) fuel, BTL (biomass-to-liquid) fuel and OTL (oil sands-to-liquid) fuel. The described dispersing-stabilizing additive is the reaction product of a substituted succinic acid derivative (e.g. a substituted acid, anhydride or ester), with a molecular weight from 500 to 1500, and polyamines from the group: ethylene diamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, pentaethylenehexamine, hexaethylene, dimethyleneheptamine, aminoethylethanolamine and mixtures thereof.

The authors of the patent application WO2009016400 describe the use of a nitrogen containing dispersant additive to improve the oxidative stability of fuel compositions containing fatty acid methyl esters (biodiesel). This additive includes products obtained by reaction of polyisobutylene succinic acid derivatives containing 12 to 200 carbon atoms in the polyisobutylene chain and molecular weight from 500 to 2800 with polyethyleneamines containing from 1 to 8 amine groups in the chain. The obtained additive was added to the fuel in an amount of 190 to 250 mg / kg as the sole component or in a composition additionally containing one of the antioxidants: BHT, TBHQ, pyrogallol, pyrocatechol.

The authors of the patent application US 2005/0223627 describe the use of the reaction product of an alkylated succinic anhydride with a primary amine in which the alkyl chain contains 4 to 29 carbon atoms as an additive increasing the thermo-oxidative stability of hydrocarbon fuels, in particular for gasoline and jet fractions.

The aim of the present invention is to obtain a composition of antioxidant-stabilizing additives for motor fuels, which is characterized by a high antioxidant and stabilizing effect in relation to motor fuels.

It has surprisingly been found that such properties are possessed by the composition of antioxidant-stabilizing additives for motor fuels according to the present invention.

SUMMARY OF THE INVENTION

The antioxidant-stabilizing additive composition for motor fuels according to the present invention, containing acylation products of polyalkylene polyamines with alkenyl succinic anhydride and an antioxidant selected from the group consisting of an alkylphenol derivative and a hydroquinone derivative, is characterized by containing, based on the total weight of the composition: I. from 92, 0% (m / m) to 99.99% (m / m) of controlled imide and amide alkenyl succinimide amides obtained by a process comprising the following steps:

A. a step of acylating a linear or branched polyalkylene polyamine with alkenyl succinic anhydride with a molecular weight of 750 to 2500 Daltons, the acylation step being carried out with a ratio of reagents such that 1.0 to 3.0 mol per 1.0 mol of polyalkylene polyamine is alkenyl succinic anhydride, the acylation reaction being carried out in a hydrocarbon solvent for 2 to 5 hours, in the temperature range from 80 to 95 ° C, under reduced pressure, in an atmosphere

Nitrogen or other inert gas to oxalic acid or acetic acid or acetic acid anhydride as imidization catalyst, collecting reaction water;

B. the thermal conditioning stage of the post-reaction mixture obtained after the completion of stage A, which stage B is carried out in the temperature range from 50 to 130 ° C, in the presence of 0.5% (m / m) to 5% (m / m), based on the weight of the reaction mixture obtained after the completion of Step A, of an inorganic or organic compound containing at least one hydroxyl group, wherein said inorganic or organic compound containing at least one hydroxyl group is one compound selected from the groups a) to c ), or any mixture of them:

(a) aqueous solutions of alkali metal hydroxides, alkaline earth metal hydroxides, amphoteric hydroxides;

b) water;

c) linear or cyclic alcohols, monohydroxy or polyhydroxy alcohols with the number of carbon atoms in the molecule from 2 to 18 and the content of hydroxyl groups in the molecule from 1 to 4;

where step B is carried out until the integration of proton signals in the ¹ HNMR spectrum, in the range of 3.0-4.0 ppm derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, in the ratio for the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration), ranging from 2.0 to 3.5, and at the same time maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3, 30 ppm, ranging from 1: 1.5 to 1: 3.5;

II. from 0.01% (m / m) to 8.0% (m / m), an antioxidant in the form of tert-butylalkylphenol or tertalkylhydroquinone or a mixture of tert-butylalkylphenol and tert-alkylhydroquinone, in which the mass ratio of tert-butylalkylphenol to tert -alkyl-hydroquinone ranges from 4: 1 to 1: 4.

Preferably the composition according to the invention comprises:

I. from 94.0% (m / m) to 99.90% (m / m) of alkenyl succinimide-amides with a controlled content of imide and amide groups,

II. from 0.10% (m / m) to 6.0% (m / m) of the antioxidant in the form of tert-butylalkylphenol or tertalkylhydroquinone or a mixture of tert-butylalkylphenol and tertalkylhydroquinone, in which the mass ratio of tert-butylalkylphenol to tert- the alkyl hydroquinone ranges from 4: 1 to 1: 4.

Preferably, in the composition according to the invention, in the mixture of tert-butylalkylphenol and tert-alkyl-hydroquinone, the mass ratio of tert-butylalkylphenol to tert-alkyl-hydroquinone is in the range from 3: 2 to 2: 3.

Preference is given to a composition according to the invention in which alkenyl succinimide amides with controlled imide and amide groups are prepared by a process wherein the polyalkylene polyamine is diethylenetriamine or triethylene tetraamine or tetraethylene pentamine or pentaethylene hexa-amides as an anhydride or an anhydride mixture thereof in step A, being the product of the reaction of ene polybutene and / or polyisobutene with maleic anhydride, the alkenyl succinic anhydride thus produced having a molar ratio of polybutene and / or polyisobutene to succinic anhydride of 1.0: 1.2 and used for the production of highly alkenyl succinic anhydride reactive ene polybutene and / or polyisobutene is obtained by a method without the use of a chlorine-containing catalyst.

The composition according to the invention is also preferred, in which alkenyl succinimide amides with a controlled content of imide and amide groups are prepared by a method in which in step A, 1.0 to 1.2 moles of alkenyl succinic anhydride are per 1.0 mole of the polyalkylene polyamine, and the acylation reaction is carried out by in toluene for 3 to 4 hours, in the temperature range from 80-90 ° C, with the concentration of the imidization catalyst from 0.0075 to 0.015 mol per 1 mol of alkenylsuccinic anhydride.

A composition according to the invention is preferred in which alkenyl succinimide amides with a controlled content of imide and amide groups are prepared by a process in which step B of the thermal conditioning of the post-reaction mixture obtained after completion of step A is carried out at a temperature range of 70 to 100 ° C in the presence of from 1.5% (m / m) to 2.5% (m / m) of an inorganic or organic compound containing at least one hydroxyl group, whereby step B is carried out until the integration of proton signals in the 1HNMR spectrum, in the range 3, 0-4.0 ppm

PL 237 262 B1 derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, in relation to the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration), ranging from 2.5 to 3.0 and simultaneously maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm, being from 1: 2.0 to 1: 2.5.

Preferably the composition according to the invention contains as tert-butylalkylphenol at least one compound selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol. -butylphenol, 2,6-ditert-butyl-4-isobutylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tritert-butylphenol, 2,6-ditert-butylphenol, 2,4-ditert -butylphenol, 2,6-ditert-butyl-4-nonylphenol, 2,6-di-tert-butyl-4-octylphenol, 4,4'-methylene-bis-2,6-ditert-butylphenol, 2,2'-ethylidene-bis -4,6-di-tert-butylphenol, and as the tertalkyl-hydroquinone it contains at least one compound selected from 2,5-di-tert-butyl-hydroquinone and 2,5-di-tert-amyl-hydroquinone.

The term "inorganic or organic compound containing at least one hydroxyl group" as used herein means a chemical compound containing at least one hydroxyl group or an aqueous solution of a chemical compound containing at least one hydroxyl group.

It turned out during the research that the tert-butylalkylphenols or tertalkyl-hydroquinones or their mixtures used in the above composition and alkenylsuccinimide-amides with a controlled content of imide and amide groups show synergism of action, improving the oxidative stability of fuels from a few to even over 60% more effectively (in research according to PN-EN 15751 and PN-EN 16091) than known antioxidant additives, such as tert-butylalkylphenols or tert-alkyl-hydroquinones, used in fuels as the only antioxidant agents.

The present invention is illustrated in Examples 1 to 27 illustrating the evaluation of the performance properties of an antioxidant stabilizing additive composition for motor fuels, containing tert-butylalkylphenols or tertalkylhydroquinones or mixtures thereof and alkenyl succinimide-amides with controlled content of imide and amide groups in tests Thus, they cannot be considered as limiting the essence of the invention, since they are merely illustrative.

EXAMPLES

Example 1 - preparation of alkenyl succinimide-amides with a controlled content of imide and amide groups

59.5 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals), 10.4 g of tetraethylene pentaamine with a boiling point of 190-240 ° C (at a pressure of 20 ° C) were introduced into a glass reactor equipped with a mechanical stirrer, a condenser with an azeotropic cap and a heating mantle. mbar), 30 cm ^{3 of} toluene and 0.1 g of oxalic acid. The reaction mixture was heated to 90 ° C and stirred for 3 hours under reduced pressure. The water evolving from the reaction was azeotroped away. The obtained reaction product, with an acid number of 0.89 mg KOH / g and a total base number of 119.42 mg KOH / g, contained about 70% (m / m) of alkenyl succinic acid imide with a characteristic band in the infrared spectrum resulting from vibrations of stretching bonds C = About the imide at 1703 cm ^-1 .

Hexyl alcohol was introduced into the reaction product obtained above in a weight ratio of the product to the alcohol of 40: 1. The mixture was homogenized by vigorously mixing in an ultrasonic bath. The mixture was thermally conditioned at 100 ° C. The process was monitored by recording spectra by 1HNMR spectroscopy. The process was completed after 24 hours, when the expected integration of signals in the range of 3.0-4.0 ppm, derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, was achieved, in relation to the integration of vinyl proton signals , of 2.51 and a ratio of the signal intensity at 3.60 ppm to the signal intensity at 3.30 ppm of 1: 2.1. The product, i.e. alkenyl succinimide amides with controlled imide and amide groups, was purified by distilling off the alcohol under reduced pressure. During distillation, toluene was also distilled, the loss of which was supplemented with a fresh portion in order to obtain the appropriate viscosity of the product, resulting in easy handling.

Example 2 - preparation of alkenyl succinimide-amides with a controlled content of imide and amide groups

59.5 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals), 10.4 g of tetraethylene pentaamine with a boiling point of 190-240 ° C were introduced into a glass reactor equipped with a mechanical stirrer, a condenser with an azeotropic cap and a heating mantle.

(At a pressure of 20 mbar), 30 cm ^{3 of} toluene and 0.1 g of oxalic acid. The reaction mixture was heated to 90 ° C and stirred for 3 hours under reduced pressure. The water evolving from the reaction was azeotroped away. The obtained reaction product, with an acid number of 0.89 mg KOH / g and a total base number of 119.42 mg KOH / g, contained about 70% (m / m) of alkenyl succinic acid imide with a characteristic band in the infrared spectrum resulting from vibrations of stretching bonds C = About the imide at 1703 cm ^-1 .

Demineralized water was introduced into the reaction product obtained above in a weight ratio of product to water equal to 40: 1. The mixture was homogenized by vigorously mixing in an ultrasonic bath. The mixture was thermally conditioned at 85 ° C. The process was monitored by recording spectra by 1HNMR spectroscopy. The process was completed after 48 hours, when the expected integration of signals in the range of 3.0-4.0 ppm from imide (CH2-N-imide) and amide (CH2-NH-amide) groups was achieved, compared to the integration of vinyl proton signals of 2.79 and the ratio of the signal intensity at 3.60 ppm to the signal intensity at 3.30 ppm of 1: 2.1. The product, ie alkenyl succinimide amides with controlled content of imide and amide groups, was purified by washing three times with distilled water and then distilling off the residual water under reduced pressure. During distillation, toluene was also distilled, the loss of which was supplemented with a fresh portion in order to obtain the appropriate viscosity of the product, resulting in easy handling.

Example 3 - preparation of alkenyl succinimide-amides with a controlled content of imide and amide groups

59.5 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals), 10.4 g of tetraethylene pentaamine with a boiling point of 190-240 ° C (at a pressure of 20 ° C) were introduced into a glass reactor equipped with a mechanical stirrer, a condenser with an azeotropic cap and a heating mantle. mbar), 30 cm ^{3 of} toluene and 0.1 g of oxalic acid. The reaction mixture was heated to 90 ° C and stirred for 3 hours under reduced pressure. The water evolving from the reaction was azeotroped away. The obtained reaction product, with an acid number of 0.89 mg KOH / g and a total base number of 119.42 mg KOH / g, contained about 70% (m / m) of alkenyl succinic acid imide with a characteristic band in the infrared spectrum resulting from the vibration of stretching bonds C = About the imide at 1703 cm-1.

A 3% (m / m) aqueous sodium hydroxide solution was introduced into the above-obtained reaction product in a weight ratio of the product to sodium hydroxide solution equal to 65: 1. The mixture was homogenized by vigorously mixing in an ultrasonic bath. The mixture was thermally conditioned at 70 ° C. The process was monitored by recording spectra by 1HNMR spectroscopy. The process was completed after 52 hours, when the expected integration of signals in the range of 3.0-4.0 ppm from imide (CH2-N-imide) and amide (CH2-NH-amide) groups was achieved, compared to the integration of vinyl proton signals of 2.83 and the ratio of the signal intensity at 3.60 ppm to the signal intensity at 3.30 ppm of 1: 2.2. The product, i.e. alkenyl succinimide amides with controlled imide and amide groups, was purified by washing three times with distilled water and then distilling off the residual water under reduced pressure. During distillation, toluene was also distilled, the loss of which was supplemented with a fresh portion in order to obtain the appropriate viscosity of the product, resulting in easy handling.

P r z k ł a d 4

Structure studies were carried out by 1HNMR spectroscopy for the products of Examples 1, 2 and 3. The spectra were recorded on a Bruker Avance III 600 MHz spectrometer, in solutions in chloroform-D6. The processing of the spectra included the Fourier transform FID (Free Induction Decay signal of free precession decay), manual phasing of spectra, baseline correction using the Whittaker algorithm and calibration of the spectra for the residual solvent signal (due to the low content of TMS [tetramethylsilane] in the used solvent), taking the position of the u signal from chloroform-D6 in the 1HNMR spectra to be 7.26 ppm.

The analysis included the integration of signals from imide (CH2-N-imide) and amide (CH2-NH-amide) groups (3.0-4.0 ppm) in relation to the integration of vinyl proton signals in the range of 4.4-5.6 ppm (unit integration) and the ratio of the signal intensity at 3.60 ppm to the signal intensity at about 3.30 ppm. The test results are presented in Table 1.

PL 237 262 Β1

Table 1. Results of the analysis of signal integration in ¹ HNMR spectra.

A sample Integration of signals in the range of 3.0 - 4.0 ppm in relation to the integration of signals of vinyl protons in the range of 4.4 - 5.6 ppm Ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm The product of example 1 2.51 1: 2,1 The product of example 2 2.79 1: 2,1 The product of example 3 2.83 1: 2.2

Example 5 (comparative)

An alkenyl succinimide was prepared by the method of the invention covered by patent PL 147691 for the purpose of comparative studies.

1000 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals) was introduced into a glass reactor equipped with a mechanical stirrer, a condenser with an azeotropic cap and a heating mantle and heated to 90 ° C, admitted a small stream of nitrogen and dosed 49 g of tetraethylene pentaamine, then increased the temperature of the reaction mixture to 120 ° C and 2 g of oxalic acid were added, the pressure in the reaction system was reduced to 53.2 kPa and the temperature was raised to 160 ° C and the temperature was maintained for 3.5 hours, the water evolving in the reaction was collected with a nitrogen stream. After the reaction was added 500 g of mineral oil having a viscosity of 10 mm ² / s at 100 ° C. The obtained reaction product contained 1.2% (m / m) of nitrogen.

Example 6

49.95 g of the product obtained as in Example 1 were introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to 40 ° C, then 0.05 g of 2,6-di-tert-butyl-4-methylphenol was added with vigorous stirring. After the second component was introduced, the composition was stirred at 40 ° C for 1 hour.

Example 7

48.5 g of the product obtained as in Example 1 were introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to a temperature of 40 ° C, then 1.5 g of 2,5-di-tert-butyl-hydroquinone were added with vigorous stirring. After the second component was introduced, the composition was stirred at 40 ° C for 1 hour.

Example 8

56.5 g of the product obtained as in Example 2 were introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to a temperature of 40 ° C, then 3.5 g of 2,4,6-tritert-butylphenol were added with vigorous stirring. After the second component was introduced, the composition was stirred at 40 ° C for 1 hour.

Example 9

48.5 g of the product obtained as in Example 2 were introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to a temperature of 40 ° C, then 1.5 g of 2,5-di-tert-amyl-hydroquinone were added with vigorous stirring. After the second component was introduced, the composition was stirred at 40 ° C for 1 hour.

Example 10

99.90 g of the product obtained as in Example 2 were introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to a temperature of 40 ° C, then 0.025 g of 2,6-di-tert-butyl-4-methylphenol, 0.025 g of 2 , 6-di-tert-butyl-4-ethylphenol, 0.025 g of 2,5-diitert-butyl-hydroquinone, and 0.025 g of 2,5-di-tert-amylhydroquinone. After the last component was charged, the composition was stirred at 40 ° C for 1 hour.

Example 11

113.0 g of the product obtained as in Example 3 was introduced into the flask placed on a magnetic stirrer.

3.5 g of 2,6-di-tert-butyl-4-methylphenol and 3.5 g of 2,5-di-tert-butyl-hydroquinone were added with vigorous stirring. After the last component was charged, the composition was stirred at 40 ° C for 1 hour.

Example 12 (comparative)

49.95 g of the product obtained as in Example 5 were introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to a temperature of 40 ° C, then 0.05 g of 2,4,6-tritert-butylphenol was added with intense stirring. After the second component was introduced, the composition was stirred at 40 ° C for 1 hour.

Example 13 (comparative)

97.0 g of the product obtained as in example 5 was introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to a temperature of 40 ° C, then 1.5 g of 2,6-di-tert-butyl-4-methylphenol and 1 5 g 2,5-di-tert-butyl hydroquinone. After the last component was charged, the composition was stirred at 40 ° C for 1 hour.

Example 14 (comparative)

113.0 g of the product obtained as in Example 5 were introduced into the flask placed on a magnetic stirrer. The contents of the vessel were heated to a temperature of 40 ° C, then 3.5 g of 2,6-di-tert-butyl-4-methylphenol and 3 5 g 2,5-di-tert-butyl hydroquinone. After the last component was charged, the composition was stirred at 40 ° C for 1 hour.

Example 15

The product of Example 6 was introduced in an amount of 50 mg / kg into diesel fuel containing 7% (WV) FAMA with the properties shown in Table 2, determined by standard tests.

Table 2. Characteristics of the test fuel oil.

No. Property Unit Findings 1 Cetane number - 53.4 2 Fractional composition distils to 250 ° C %(IN 35.1 distills to 350 ° C %(in 94.3 95% (ITT) distills to temperature ^D C 352.6 3 Density at 15 ° C kg / m ³ 840.3 4 Sulfur content mg / kg 7.1

Example 16

The product of Example 7 was introduced in an amount of 50 mg / kg into diesel fuel containing 7% (WV) FAMA with the properties shown in Table 2, determined by standard tests.

Example 17

The product of Example 8 was introduced in an amount of 50 mg / kg into diesel fuel containing 7% (WV) FAMA with the properties shown in Table 2, determined by standard tests.

Example 18

The product of Example 9 was introduced in an amount of 50 mg / kg into diesel fuel containing 7% (WV) FAMA with the properties shown in Table 2, determined by standard tests.

Example 19

The product of Example 10 was introduced in an amount of 50 mg / kg into diesel fuel containing 7% (WV) FAMA with the properties shown in Table 2, determined by standard tests.

PL 237 262 B1

P r z k ł a d 20

The product of Example 11 was introduced in an amount of 50 mg / kg into diesel fuel containing 7% (V / V) FAME with the properties shown in Table 2, determined by standard tests.

P r z k ł a d 21 (comparative)

The product of example 12 was introduced in an amount of 50 mg / kg, based on the content of alkenyl succinic acid imide, into a diesel fuel containing 7% (V / V) FAME with the properties shown in Table 2 determined by standard tests.

P r z k ł a d 22 (comparative)

The product of example 13 was introduced in an amount of 50 mg / kg, based on the alkenyl succinic acid imide content, into a diesel fuel containing 7% (V / V) FAME with the properties shown in Table 2, determined by standard tests.

P r z k ł a d 23 (comparative)

The product of example 14 was introduced in an amount of 50 mg / kg, based on the alkenyl succinic acid imide content, into a diesel fuel containing 7% (V / V) FAME with the properties shown in Table 2, determined by standard tests.

P r z k ł a d 24 (comparative)

To the diesel oil containing 7% (V / V) FAME with the properties presented in Table 2, 2,6-di-tert-butyl-4-methylphenol was introduced in the amount of 50 mg / kg.

P r z k ł a d 25 (comparative)

To the diesel fuel containing 1% (V / V) FAME with the properties presented in Table 2, 2,5-di-tert-butyl-hydroquinone was introduced in the amount of 50 mg / kg.

P r z k ł a d 26

The refined diesel oil as in the examples 15-25 and the base diesel oil with the properties from Table 2 were tested for oxidative stability according to PN-EN 15751 "Motor fuels - fatty acid methyl esters (FAME) as fuel or fuel component for diesel engines - Determination of oxidative stability) in the accelerated oxidation test ”. The test consisted in the absorption of volatile products of fuel oxidation in water and measurement of its specific conductivity. The fuel sample was placed in a test tube which was heated to a temperature of 110 ° C and air was passed through it in the amount of 10 dm ³ / h. Volatile oxidation products of the sample were absorbed in a measuring vessel filled with distilled water. The conductivity of the water was measured during the test. The time needed to achieve a sharp increase in conductivity was a measure of the resistance of the fuel sample to oxidation. The test results are presented in Table 3.

PL 237 262 Β1

Table 3. Results of oxidation stability tests according to PN-EN 15751.

A sample Product content in fuel, mg / kg Test result according to PN-EN 15751, h Change in relation to the fuel in Table 2,% Fuel with properties shown in Table 2 - 31.1 - Upgraded fuel as in example 15 50 53.4 71.7 Upgraded fuel as in example 16 50.2 61.4 Upgraded fuel as in example 17 48.4 55.6 Upgraded fuel as in example 18 49.3 58.5 Upgraded fuel as in example 19 47.7 53.4 Upgraded fuel as in example 20 54.3 74.6 Upgraded fuel as in example 21 (comparative) 33.2 6.7 Upgraded fuel as in example 22 (comparative) 30.3 2.6 Upgraded fuel as in example 23 (comparative) 31.5 1.3 Upgraded fuel as in example 24 (comparative) 45.5 46.3 Upgraded fuel as in example 25 (comparative) 43.5 39.9

The obtained compositions of the present invention, used at a dosage level of 50 mg / kg of fuel, containing alkenyl succinimide-amides with a controlled content of imide and amide groups, improve the oxidative stability of the fuel (test according to PN-EN 15751) in the range from about 45 to about 75%, while the compositions polyalkylene polyamines containing acylation products with alkenyl succinic anhydride, obtained by the process according to the invention covered by patent PL 147691, improve this parameter by no more than 7%.

Compared to commercial additives such as tert-butylalkylphenols or tert-alkyl-hydroquinones improving the oxidative stability according to PN-EN 15751 from the value of 31.1 h for the base fuel to the value of 45.5 h and 43.5 h, respectively, the compositions being the subject of the invention improve this parameter in the range from 53.4 h to 74.6 h.

PL 237 262 Β1

Example 27

The refined diesel oil as in the examples 15-25 and the base diesel oil with the properties from Table 2 were subjected to the oxidation stability test according to PN-EN 16091 "Liquid petroleum products - middle distillates, fatty acid methyl esters (FAMA) and their blends - Oxidative stability determination in small-scale accelerated oxidation test ”. The test consisted in measuring the pressure changes in a tightly closed test vessel, into which 5 ml of the tested sample was introduced, and then oxygen to obtain a pressure of 700 kPa ± 5 kPa (at ambient temperature). The pressure vessel with the sample was heated to a temperature of 140 ° C. The pressure in the vessel was recorded at 1 s intervals until the end point was reached, i.e. the pressure dropped by 10% from its highest value. The result of the test was the time that elapsed from the beginning of the test, i.e. from the moment the sample reaches the temperature of 140 ° C until the pressure inside the test vessel drops by 10%. The test results are presented in Table 4.

Table 4. Results of oxidation stability tests according to PN-EN 16091.

A sample Product content in fuel, mg / kg Test result according to PN-EN 16091, min. Change compared to fuel from Tabhcy 2,% Fuel with properties shown in Table 2 - 57 - Upgraded fuel as in example 15 50 89 56.1 Upgraded fuel as in example 16 86 50.9 Upgraded fuel as in example 17 78 36.8 Upgraded fuel as in example 18 80 40.4 Upgraded fuel as in example 19 82 43.9 Upgraded fuel as in example 20 86 50.9 Upgraded fuel as in example 21 (comparative) 58 1.8 Upgraded fuel as in example 22 (comparative) 57 0.0 Upgraded fuel as in example 23 (comparative) 61 7.0 Upgraded fuel as in example 24 (comparative) 72 26.3 Upgraded fuel as in example 25 (comparative) 73 28.1

PL 237 262 B1

The obtained compositions of the present invention, used at a dosage level of 50 mg / kg of fuel, containing alkenyl succinimide-amides with a controlled content of imide and amide groups, improve the oxidative stability of the fuel (test according to PN-EN 16091) in the range from about 30 to about 50%, while the compositions The acylation products containing polyalkylene polyamines with alkenyl succinic anhydride obtained by the process according to the invention covered by patent PL 147691 improve this parameter by no more than a few percent.

Compared to commercial additives such as tert-butylalkylphenols or tert-alkyl-hydroquinones, improving the oxidation stability according to PN-EN 16091 with a value of 57 min. for the base fuel to the value of 26.3 min, respectively. and 28.1 min. the compositions according to the invention improve this parameter within a value range of 36.8 min. up to 56.1 min.

In the above examples, the action of the composition according to the invention in improving the oxidation stability of motor fuels has been demonstrated and its industrial applicability has been proven.

Claims (7)

A composition of antioxidant-stabilizing additives for motor fuels, containing acylation products of polyalkylene polyamines with alkenyl succinic anhydride and an antioxidant selected from the group consisting of an alkylphenol derivative and a hydroquinone derivative, characterized in that it contains, based on the total weight of the composition: I. from 92.0% (m / m) to 99.99% (m / m) of alkenyl succinimide-amides with controlled content of imide and amide groups, obtained by a process comprising the following steps: A. a step of acylating a linear or branched polyalkylene polyamine with alkenyl succinic anhydride with a molecular weight of 750 to 2500 Daltons, this step being carried out with a ratio of reagents such that 1.0 to 3.0 moles of polyalkylene polyamine per 1.0 mole of polyalkylene polyamine are alkenyl succinic anhydride, the acylation reaction being carried out in a hydrocarbon solvent for 2 to 5 hours, at a temperature of 80 to 95 ° C, under reduced pressure, under nitrogen or other inert gas, in the presence of oxalic acid or acetic acid or acetic anhydride as imidization catalyst, receiving reaction water; B. the thermal conditioning stage of the post-reaction mixture obtained after the completion of stage A, which stage B is carried out in the temperature range from 50 to 130 ° C, in the presence of 0.5% (m / m) to 5% (m / m), based on the weight of the reaction mixture obtained after the completion of Step A, of an inorganic or organic compound containing at least one hydroxyl group, wherein said inorganic or organic compound containing at least one hydroxyl group is one compound selected from the groups a) to c ), or any mixture of them: (a) aqueous solutions of alkali metal hydroxides, alkaline earth metal hydroxides, amphoteric hydroxides; b) water; c) linear or cyclic, monohydroxy or polyhydroxy alcohols with the number of carbon atoms in the molecule from 2 to 18, and the content of hydroxyl groups in the molecule from 1 to 4, whereby step B is carried out until the integration of proton signals in the 1HNMR spectrum, in the range 3.0-4.0 ppm derived from imide (CH2N-imide) and amide (CH2-NH-amide) groups, in relation to the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration), between 2.0 and 3.5 and simultaneously maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm, being from 1: 1.5 to 1: 3.5; II. from 0.01% (m / m) to 8.0% (m / m) of the antioxidant in the form of tert-butylalkylphenol or tertalkylhydroquinone or a mixture of tert-butylalkylphenol and tertalkylhydroquinone, in which the mass ratio of tert-butylalkylphenol to tert- the alkyl hydroquinone ranges from 4: 1 to 1: 4. PL 237 262 B1 2. A composition according to claim 1 1, characterized in that it comprises: I. from 94.0% (m / m) to 99.90% (m / m) of alkenyl succinimide-amides with a controlled content of imide and amide groups, II. from 0.10% (m / m) to 6.0% (m / m) of the antioxidant in the form of tert-butylalkylphenol or tertalkylhydroquinone or a mixture of tert-butylalkylphenol and tertalkylhydroquinone, in which the mass ratio of tert-butylalkylphenol to tert- the alkyl hydroquinone ranges from 4: 1 to 1: 4. 3. A composition according to p. The method of claim 1 or 2, characterized in that in the mixture of tert-butylalkylphenol and tertalkyl-hydroquinone, the mass ratio of tert-butylalkylphenol to tert-alkyl-hydroquinone ranges from 3: 2 to 2: 3. 4. A composition according to p. A process according to claim 1, characterized in that the alkenyl succinimide amides with a controlled content of imide and amide groups are prepared by a process in which in step A the polyalkylene polyamine is diethylenetriamine or triethylene tetramine or tetraethylene pentaamine or pentaethylene hexaamine, or an alkene anhydride mixture thereof, and an anhydride-anhydride mixture thereof is used as the polyalkylene polyamine. the reaction of the ene polybutene and / or polyisobutene with maleic anhydride, the alkenyl succinic anhydride thus produced having a molar ratio of polybutene and / or polyisobutene to succinic anhydride of 1.0: 1.2, and highly reactive enoic anhydride used in the preparation of alkenyl succinic anhydride polybutene and / or polyisobutene is obtained by a method without the use of a chlorine-containing catalyst. 5. A composition according to p. A method according to claim 1, characterized in that alkenyl succinimide-amides with a controlled content of imide and amide groups are prepared by a process in which in step A, 1.0 to 1.2 moles of alkenylsuccinic anhydride per 1.0 mole of polyalkylene polyamine are present, the acylation reaction is carried out in toluene for 3 to 4 hours, in the temperature range from 80-90 ° C, with the concentration of the imidization catalyst from 0.0075 to 0.015 moles per 1 mole of alkenyl succinic anhydride. 6. A composition according to p. A process according to claim 1, characterized in that alkenyl succinimide-amides with a controlled content of imide and amide groups are prepared by a process in which step B of the thermal conditioning of the post-reaction mixture obtained after completion of step A is carried out at a temperature range of 70 to 100 ° C, in the presence of 1 5% (m / m) to 2.5% (m / m) of an inorganic or organic compound containing at least one hydroxyl group, whereby step B is carried out until the integration of proton signals in the 1HNMR spectrum, in the range of 3.0- 4.0 ppm derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, compared to the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration), ranging from 2.5 to 3.0 and simultaneously maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm, being from 1: 2.0 to 1: 2.5. 7. The composition according to p. The tert-butylalkylphenol of claim 1, wherein the tert-butylalkylphenol is at least one compound selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol. -butylphenol, 2,6-ditert-butyl-4-isobutylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tritert-butylphenol, 2,6-ditert-butylphenol, 2,4-ditert -butylphenol, 2,6-ditert-butyl-4-nonylphenol, 2,6-ditert-butyl-4-octylphenol, 4,4'-methylene-bis-2,6-ditert-butylphenol, 2,2'-ethylidene -bis-4,6-di-tert-butylphenol, and as the tertalkyl-hydroquinone it contains at least one compound selected from 2,5-di-tert-butyl-hydroquinone and 2,5-di-tert-amyl-hydroquinone.