MXPA98005485A - Procedure for the preparation of multifunctional additive for combustib polialfaolefinsuccinimidas and composition - Google Patents

Procedure for the preparation of multifunctional additive for combustib polialfaolefinsuccinimidas and composition

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Publication number
MXPA98005485A
MXPA98005485A MXPA/A/1998/005485A MX9805485A MXPA98005485A MX PA98005485 A MXPA98005485 A MX PA98005485A MX 9805485 A MX9805485 A MX 9805485A MX PA98005485 A MXPA98005485 A MX PA98005485A
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MX
Mexico
Prior art keywords
reaction
carried out
alkenylation
composition
amination
Prior art date
Application number
MXPA/A/1998/005485A
Other languages
Spanish (es)
Inventor
Pie Contijoch Olga
Aguirre Carbajal David
Hernandez Mu Oz Agustin
Original Assignee
Instituto Mexicano Del Petroleo
Filing date
Publication date
Application filed by Instituto Mexicano Del Petroleo filed Critical Instituto Mexicano Del Petroleo
Publication of MXPA98005485A publication Critical patent/MXPA98005485A/en

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Abstract

This invention relates to a process for preparing polyalphaolephinsuccionimides from polyaphalephins, maleic derivatives and polyamines as well as the composition of a multifunctional additive based on these chemical species, which incorporated into automotive fuels improves its detergent and anti-rust detergent properties. The product (polyaphalephinsuccinimides) is obtained in two stages: in the first step a polyaphaolefin is reacted with a maleic derivative (preferably maleic anhydride), obtaining an alkenyl succinic anhydride as an intermediate chemical species. In the second stage, this intermediate (alkenyl succinic anhydride) is reacted with a polyamine (preferably triethylenetetramine) to obtain a condensed product of the polyalphaolephinsuccinimide type.

Description

PROCEDURE FOR THE PREPARATION OF POLYALFAOLEINSINSCYCLES AND COMPOSITION OF MULTIFUNCTIONAL ADDITIVE FOR COMBUSTIBLES DESCRIPTION.
TECHNICAL FIELD OF THE INVENTION This invention relates to a process for preparing polyalphaolephinsuccinimides from polyalphaoleophins, maleic derivatives and polyamines as well as the composition of a multifunctional additive based on these chemical species, which incorporated into automotive fuels improves its detergent-dispersant and anti-rust properties.
The product (polyalphaolephinsuccinimides) is obtained in two stages: in the first step a polyalphaolefin is reacted with a maleic derivative (preferably maleic anhydride), obtaining an alkenyl succinic anhydride as intermediate chemical species.
In the second step, this intermediate (alkenyl succinic anhydride) is reacted with a polyamine (preferably triethylenetetramine) to obtain a condensate product of the polyalphaolephinsuccinimide type.
The reaction product is combined with other ingredients such as "carriers", solvents, demulsifiers and corrosion inhibitors to integrate a multifunctional additive for use in internal combustion engines whose main function is to reduce the formation of deposits in intake systems.
BACKGROUND OF THE INVENTION The patent literature describes various classes of alkenyl succinimide compounds and the use thereof as dispersant additives and detergents in fuels and lubricants, for example the following patents may be cited: USES. 4,548,724; USES. 4 048 080; USES. 379 877; USES. 3 717 446.
EP-A-0.299119 and EP 0393769B1 disclose reaction products of alkenylsuccinic acids or anhydrides with amines as additives that provide detergent, dispersant and anti-rust properties in fuels and lubricating oils.
DETAILED DESCRIPTION OF THE INVENTION This invention provides a process for preparing a detergent-dispersant additive for automotive liquid fuels, which may also be used for lubricating oils and obtained in two stages of reaction in an intermittent process.
I.- FORMATION OF ALKENILSUCCINIC ANHYDRIDE In this step polyalphaolefins of the general formula CH3 CH3 CH3 I I I CH3- (CH2) n-CH = CH2 or CH3-C- (CH2-C-) n-CH2-C = CH2 I I CH3 CH3 (A) (B) react with maleic anhydride of the formula: OR CH-C \ O CH-C / O (C) to obtain alkenylsuccinic anhydrides of the formulas CH3- (CH2) n-CH-CH = CH2 i ^ or (D) CH-C \ I O CH2-C / O CH3 I CH; CH3 C = CH2 O CH3-C- (CH2- C-) n-CH-CH-C \ I I or (E) CH3 CH3 CH2-C / O The polyalphaolefins used for this purpose can have molecular weights of 112 (1 octene) to 3000 but preferably 159 (1 decene) to 1500 and are usually oligomers of ethylene, propylene, butene, isobutylene or copolymers.
II.- AMINATION OF THE ALKENILSUCCINIC ANHYDRIDE In this step, the alkenyl succinic intermediate (D) or (E) reacts with a polyamine of the formula: H2N- (CH2-CH2-NH) n-H (F) Preferentially triethylenetetramine resulting in the reaction end product the polyalphaolephinsuccinimide structures indicated CH3- (CH2) n-CH-CH = CH2 CH3- (CH2) n-CH-CH = CH2 I ^ O 0. 1 CH-C? ^ / C-CH | N - (- CH2-CH2-NH) 2-CH2-CH2-N | CH2-C / \ C-CH2 O O (G) CH3 CH3 I I CH3 CH3 C = CH2 CH2 = C CH3 CH3 I I I I I CH3-C- (CH2-C-) n-CH CH- (C-CH2) nC-CH3 IIIOO ^ 1 1 I CH3 CH3 CH-C \ / C-CH CH3 CH3 I N - (- CH2-CH2-NH ) 2-CH2-CH2-N | CH2-C / \ C-CH2 O O (H) The operating conditions for the two reaction stages are indicated in the following table: TABLE 1 ALKENILAC1ON AMINATION Temperature, ° C 80 - 200 80 - 200 Reaction time (hours) 0.5-12 0.5-12 Agitation R.P.M. 50 - 500 50 - 500 Pressure, Kg / cm2 1 -25 1 -25 Molar ratio Olefin / anhydride 0.5 - 50 Molar ratio Anhydride / amine 0.5-20 The product obtained (polyalphaolephinsuccinimides G or H) is used as an active detergent ingredient of formulations or compositions and together with other components it integrates a multifunctional additive package in the proportions described below: % WEIGHT Paos (detergent) 5-100 Carrier or fluidizer 0-60 Hydrocarbon solvent 0-60 Corrosion inhibitor 0-5 Demulsifier 0-5 EXAMPLES EXAMPLE 1 In a glass reactor equipped with heating elements and stirring device was charged 100 ml of polyalphaolefin called 1 tetradecene (molecular weight 196) equivalent to 0.388 moles, to maintain an olefin / anhydride ratio of 0.0155 moles of maleic anhydride ( 1.52 grams), the reaction mixture was heated from room temperature to 180 ° C in the absence of solvents and polymerization inhibitors; this first stage of alkenylation reaction was conducted for 3 hours at a temperature of 180 ° C + 10 ° C at atmospheric pressure and stirring at 180-240 rpm. at this point 0.0155 mol of triethylene tetramine (2.26 grams) was incorporated into the reaction mixture and in the same temperature range of 180 ° C + 10 ° C, same conditions of agitation and pressure the amination reaction was carried out also for 3 hours.
The reaction product was filtered for the separation of impurities and the polyalphaolephinsuccinimide (paos) thus obtained was used as a detergent active ingredient in the following formulation: % WEIGHT Paos (detergent) 36 Polyether type synthetic carrier 20 Aromatic solvent 40 Corrosion inhibitor 2 uTsemuisiopapie 2 100 The formulated product was subjected to several functional tests including: a) deposits in admission systems (ISD). b) reduction of deposits in inlet valves (IVD) in single-cylinder engine of 4 hp b) Reactivity of fuels to water (ASTM-D-1094) d) Anti-rust properties of petroleum products The incorporation of this formulation in the base fuel (see characteristics table II) was carried out in a concentration of 200 ppm.
TABLE II FUEL CHARACTERISTICS: PEMEX-MAGNA UNIT METHOD ASTM VALUE Property Specific weight D-1298 0.7324 VISUAL color Light green Test doctor D-235 Negative Atmospheric distillation Ibp ° C D-86 32.5 50% bp ° C D-86 88.3 90% bp ° C D-86 161.3 Tfe ° C D-86 199 Residues% V D-86 1.1 Steam pressure reid Ib / in2 D-323 8.6 Mercaptanic Sulfur% PESO D-3227 0.0003 Total sulfur% WEIGHT D-1266 / D-2622 0.081 Copper corrosion STD D-130 1a 3h? - @ 50 ° C Preformed rubber mg / 100 D-381 0.4 Induction period minutes D-525 > 300 Lead content g / Gal D-3116 / D-3137 < 0.001 Octane number Ron D-2699 91.4 Mon D-2700 81.6 index 86.5 Phosphorus content g / Gal D-3231 < 0.2 Composition Paraffins% V CHROMATOGRAPHY 11.79 Isoparaffins% V CHROMATOGRAPHY 42.18 Olefins% V CHROMATOGRAPHY 5.84 Naphthenics% V CHROMATOGRAPHY 4.14 Aromatics% V CHROMATOGRAPHY 26.27 Unidentified% V CHROMATOGRAPHY 0.23 Mtbe% V CHROMATOGRAPHY 6.05 Tame% V CHROMATOGRAPHY 1.24 Ferrous corrosion STD NACE-TM-01 E The results of the functionality tests are indicated in Table III.
EXAMPLE 2 In the same laboratory equipment described in Example 1, 100 ml of polyalphaolefin was charged but now composed of a mixture of C-12 and C-14-I dodecene and Itetradecene-with an approximate molecular weight of 177 equivalent to 0.429 moles, to work at an olefin / anhydride ratio of 0.0172 moles of maleic anhydride (1.68 grams) were added, the alkenylation reaction was conducted under the same conditions of pressure, temperature, time, agitation, etc. described above, 0.0172 moles of triethylene tetramine (2.51 grams) were then incorporated into the reaction mixture, the amination reaction also being carried out at the aforementioned operating conditions.
The reaction product was formulated in the same proportions of ingredients indicated in the previous example. The composition was subjected to the corresponding functional tests and the results are indicated in Table III.
EXAMPLE 3 In the same laboratory equipment described in example i, 100 ml of a polyalphaolefin, isobutene polymer with an approximate molecular weight of 500 equivalent to 0.168 mol was charged, maintaining the olefin / anhydride ratio of 25. 0.0067 moles (0.66 grams) were added. of maleic anhydride. the reaction of Alkenylation was carried out at the conditions described in Example 1. Subsequently, 0.0067 moles of triethylene tetramine (0.98 grams) were added, and the amination reaction was also carried out under the operating conditions already described.
The polyalphaolephinsuccinimide reaction product was used in preparing a formulation similar to that indicated in Example 1 and the functionality results are shown in Table III.
EXAMPLE 4 in the same laboratory equipment described in example 1, 100 ml of polalfaolefin with an approximate molecular weight of 530 equivalent to 0.156 mol was charged, maintaining the olefin / anhydride ratio of 0.000624 moles (0.61 grams) of maleic anhydride were added. The alkenylation reaction was carried out under the same operating conditions described in Example 1. Subsequently, 0.00624 moles of triethylene tetramine (0.91 grams) were added, and the amination reaction was also carried out under the operating conditions already described in the example.
The polyalphaolephinsuccinimide reaction product was used in preparing a formulation similar to that described in Example 1 and the functionality results are shown in Table III.
EXAMPLE 5 In the same laboratory equipment described in example 1, 100 ml of a polyalphaolefin with an approximate molecular weight of 1400 equivalent to 0.0603 mol was charged, maintaining the olefin / anhydride ratio of 25, 0.00242 (0.237 grams) of maleic anhydride was added. The alkenylation reaction was carried out under the same conditions described in Example 1. Subsequently, 0.00242 moles (0.353 grams) of triethylene tetramine were added, and amination was also carried out in accordance with the provisions of the aforementioned example.
THE RESULTS OF FUNCTIONALITY ARE INDICATED IN TABLE III.
EXAMPLE 6 In the laboratory equipment described in example 1, 100 ml of itetradecene equivalent to 0.388 moles were charged. To maintain an olefin / anhydride ratio of 12, 0.0323 moles of maleic anhydride (3.16 grams) was added. The first reaction step (alkenylation) was carried out at the conditions indicated in example 1. the second reaction step (amination) started with the incorporation of 0.0323 moles of triethylene tetramine (4.71 grams) and was carried out according to the conditions described in same example.
After filtration, the final product polyalphaolephinsuccinimide was used as a detergent active ingredient in the following formulation: % WEIGHT Paos (detergent) 50 Polyether type synthetic carrier 20 Aromatic solvent 26 Corrosion inhibitor 2 Demulsifier 2 100 The incorporation of this formulation into the base fuel was carried out in a concentration of 300 ppm, and the results of the functionality tests are shown in Table III.
EXAMPLE 7 In the laboratory equipment described in Examples 1 and 6, 100 ml of a polyalphaolefin with an approximate molecular weight of 530 equivalent to 0.156 mol was charged. In order to maintain an olefin / anhydride ratio of 12, 0.0130 moles of maleic anhydride (1.28 grams) were charged. The first reaction stage (alkenylation) was carried out at the conditions mentioned in examples 1 and 6. the second reaction stage (amination) with the addition of 0.0130 mol of triethylene tetramine (1.9 grams) and was carried out in accordance with the conditions described in the same examples.
The product obtained -polyalphaolephinsuccinimide- was used in the same formulation indicated in Example 6 and the results of functionality are indicated in Table III 5 for a dosage level of 300 ppm.
TABLE III 10 RESULTS OF THE EVALUATION OF FORMULATIONS BASED ON DETERGENTS POLIALFAOLEFINSUCCINIMIDAS EXAMPLE LEVEL ISD IVD ASTM-D-1094 NACE TM-01 ppm mg mg% reduction EMULSIONABILITY PREV. RUST 1 200 0.3 9.1 -78.4 1 b (1), 1 min A 2 200 0.1 8.0 -82.5 1b (1), 1, min B ++ 3 200 0.2 8.3 -84.3 1 b (2), 1 min A 4 200 0.3 8.5 -79.9 1 b (1), 1 min B ++ 200 0.4 14.3 -68.7 1b (2), 1 min B ++ 6 300 0.6 10.1 -77.9 1 b (1), min B ++ 7 300 0.5 18.1 -55.6 1 b (1), min B ++ GASOLINE OF 2.4 45.8 +100 1b (1), 1 min E REFERENCE fifteen twenty

Claims (7)

NOVELTY OF THE INVENTION Having described the invention, it is considered as a novelty and therefore the content of the following clauses is claimed as property:
1. - A process for the preparation of polyalfasuccinimides which act as multifunctional additives detergent, dispersant and rust prevention agents, which can be incorporated into liquid fuels mainly gasoline and lubricating oils, characterized in that it is carried out in two reaction stages: alkenylation and amination, in the alkenylation a polyalphaolefin with a molecular weight in the range of 112 (C-8) -3,000 either polyethylenes, polypropylenes, polybutenes or polyisobutylenes, is reacted with maleic anhydride or some of its derivatives, to obtain an intermediate product called alkenyl succinic anhydride , of the general formulas: CH3- (CH2) n-CH-CH = CH2 CH-C \ I O CH2-C / O CH3 I CH3 CH3 C = CH2 O CH3-C- (CH2-C-) n-CH-CH-C \ O In the amination reaction the alkenyl succinic anhydride is reacted with a polyamine of the general formula: H2N- (CH2-CH2-NH) n-H preferably triethylenetetramine.
2. - A procedure according to that described in clause 1, characterized in that the alkenylation reaction is carried out in the temperature range of 80-200 ° C, reaction time of 0.5 to 12 hours, pressure of 1 to 25 kg / cm2 and polyolefin / maleic anhydride molar ratio of 0.5 to 50, and that the amination reaction is carried out in the temperature range of 80-200 ° C, reaction time of 0.5 to 12 hours, pressure of 1 to 25 kg / cm2 and maleic anhydride / tetramine molar ratio of 0.5 to 20.
3- a procedure according to what is described in clauses 1 and 2, characterized in that the alkenylation and amination reactions are carried out in the presence or absence of solvents derived from paraffinic, nephthenic or aromatic hydrocarbons.
4. - A process according to what is described in clauses 1 to 3, characterized in that the alkenylation reaction is carried out in the presence or absence of polymerization inhibitors of the hydroquinone, catechols, phenothiazines and quinones type.
5. - A composition of multifunctional additive for fuels based on polyalphaolefininsuccinimides, as an active detergent ingredient in formulation with other components to integrate a package of multifunctional additives, the composition is among the following% weight ranges: Polyalphaolefinsuccinimides 5 A 100 Carrier or fluidizer 0 A 60 Hydrocarbon solvent 0 A 60 Corrosion inhibitor 0 A 5 Demulsifier 0 A 5
6. - A composition according to clause 5, characterized in that the fluidizer is derived from the distillation of the oil and / or other sources of hydrocarbons or can also be of the synthetic type such as polyethers, ethoxylated and propoxylated polymer alcohols.
7. - A composition according to clauses 5 and 6, characterized in that the multifunctional package is used in fuels or lubricants in the range of 25 to 2500 ppm, but preferably in the range of 50 to 500 ppm.
MXPA/A/1998/005485A 1998-07-06 Procedure for the preparation of multifunctional additive for combustib polialfaolefinsuccinimidas and composition MXPA98005485A (en)

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