WO2000032650A1

WO2000032650A1 - Polybutyl-or polyisobuzylamines,hydrazines or hydrazides, method for preparing same and use as detergents in fuels

Info

Publication number: WO2000032650A1
Application number: PCT/FR1999/002892
Authority: WO
Inventors: Jean-Luc Couturier; Jacques Kervennal; Laurent Germanaud; Paul Maldonado
Original assignee: Atofina
Priority date: 1998-11-30
Filing date: 1999-11-24
Publication date: 2000-06-08
Also published as: NO20012528D0; KR20010075722A; NO20012528L; CA2352983A1; EP1141037A1; JP2003517044A; FR2786490A1; ID29932A; BR9915794A; AU1279800A

Abstract

The invention concerns polybutyl-or polyisobutylamines-hydrazines or hydrazides, a method for obtaining them which consists in subjecting to hydrohalogenation a polybutene or polyisobutene in the presence of oxygen and in aminating the resulting brominated compound or subjecting it to a reaction with hydrazine or still with an alkaline metal azide. The invention also concerns their use as detergents in fuels.

Description

POLYBUTYL- OR POLYISOBUTYLAMINES- HYDRAZINES OR -AZIDES, THEIR PREPARATION PROCESS AND THEIR USES AS DETERGENTS IN FUELS.

The present invention relates to poly (iso) butylamines, - hydrazines or -azides, a process for obtaining them and their application as detergents in fuels.

Poly (iso) butylamines have been used for a long time to keep the valves and carburetors of internal combustion engines running on petrol clean.

US Patent 3,275,554 describes the preparation of α-polyisobutylallylamines and β-polyisobutyl methallylamines according to a process which consists in carrying out the chlorination / dehydrochlorination of polyisobutene in a solvent medium (CCI4) and in the presence of iodine, then in reacting the chloride obtained with an amine.

The product obtained has the drawback of containing unsaturations of the allylic type capable of forming tars, that is to say undesirable products which are of a nature to limit their use as detergents in fuels.

Patent EP 0 244 616 describes a fuel composition containing a poly (iso) butylamine of formula R ^a - CH2 - N (R ^D ) (R ^C ) in which R ^a represents a poly (iso) butyl radical derived from isobutene (and, up to 20% by weight of n-butene), R ^b and R ^c , which may be identical or different, each in particular represent a hydrogen atom, an aliphatic or aromatic hydrocarbon radical, a polyaminoalkylene radical or a aminoalkylene radical.

These compounds can be prepared by an aminomethylation reaction of a poly (iso) butene according to a process described in said patent which consists in hydroformylating a poly (iso) butene with a rhodium or cobalt catalyst, in the presence of CO and of H2, at temperatures between 80 ° C and 200 ° C and under CO / H2 pressures up to 600 bars, then the oxo product is subjected to a hydrogenating amination. The amination reaction is preferably carried out at a temperature ranging from 80 ° C to 200 ° C and under hydrogen pressures ranging up to 600 bars, preferably between 80 and 300 bars. According to this way of operating, the conversion of poly (iso) butene is at most equal to 80%. In addition, this process uses drastic operating conditions (high pressures and temperatures). We have now found compounds of general formula (I): R ¹ - A in which:

R ¹ represents a polybutyl or polyisobutyl radical having a number of carbon atoms ranging from 20 to 400 and preferably ranging from 35 to 200, derived from isobutene and, for a proportion ranging up to 20% by weight, of n-butene, and - A represents an azido radical -N3; a hydrazino - NH - N (R ² ) (R ³ ) radical in which R ² and R ³ , identical or different, each represent a hydrogen atom, a linear or branched aliphatic hydrocarbon radical having a number of carbon atoms ranging from 1 to 6; or an amino radical - N (R) (R ⁵ ) in which R ⁴ and R ⁵ , identical or different, each represent a hydrogen atom, a linear or branched aliphatic hydrocarbon radical having a number of carbon atoms ranging from 1 to 10, a phenyl radical, an aminoalkyl radical of formula - [R ⁶ ] - N (R ⁷ ) (R ⁸ ) in which R ⁶ represents a radical having a number of carbon atoms ranging from 1 to 1 0 and , R ⁷ and R ⁸ , identical or different, each represent a hydrogen atom, an alkyl radical having a number of carbon atoms ranging from 1 to 1 0, a phenyl or naphthyl radical, a polybutyl or polyisobutyl radical having a number of carbon atoms ranging from 20 to 400 each, a polyaminoalkyl radical of formula [- R ⁶ - NR ⁷ ] - _m R ⁸ in which the radicals R ^ and R ⁷ are each identical or different, the radicals R ⁶ , R ⁷ and R ⁸ have the meanings given above and m is an integer ranging from 2 to 8, or da ns which R ⁴ and R ^ of the amino radical -N (R ⁴ ) (R ⁵ ) together form, with the nitrogen atom to which they are attached, a Δ2-imidazolinyl, imidazolidinyl, Δ2-pyrrolinyl, pyrrolidinyl, pyrazolidinyl radical , Δ3- pyrazolinyl, piperidyl, piperazinyl, morpholinyl, 1,2,4-triazolyl, piperazyl.

The invention also relates to a process for the preparation of the compounds of formula (I). This process consists in hydrobromiding a polybutene or a polyisobutene in the presence of oxygen, in an aprotic apolar solvent medium, at temperatures between -10 ° C and 60 ° C and, preferably, between 0 ° C and 25 ° C, then in a second step, the poly (iso) butyl bromide obtained is subjected to an amination, to obtain a poly (iso) butylamine, or to a reaction with a compound of formula H2N - N (R ² ) (R ³ ) to obtain a poly (iso ) butylhydrazine or else to a reaction with an alkali metal azide to obtain a poly (iso) butyi azide.

According to the present invention, the hydrobromination of poly (iso) butene is carried out with hydrogen bromide in the presence of oxygen.

Oxygen can be supplied as such or by air, air enriched with oxygen or even by any inert gas with respect to the reactants, enriched with oxygen.

As aprotic apolar solvents which can be used for the hydrobromination reaction according to the present invention, mention will be made of aromatic hydrocarbons such as benzene, toluene; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane; aliphatic hydrocarbons such as heptane, dodecane; phenylcyclohexane or a mixture of at least two of the above-mentioned solvents.

Cyclohexane is preferably used.

The aprotic apolar solvent is used in an amount such that the reaction medium is easily agitated.

Generally, the operation is carried out with a poly (iso) butene / solvent weight ratio at most equal to 100% and, preferably between 10% and 40%.

The operation is preferably carried out with a slight excess of HBr, the HBr / poly (iso) butene molar ratio is at most equal to 2 and, preferably, between 1.2 and 1.8.

The amination reaction is carried out, optionally in a solvent medium, at temperatures between 50 ° C and 200 ° C and, preferably, between 90 ° C and 150 ° C, under pressures at most equal to 80 bars and preferably between 1 bar and 50 bars, and optionally in the presence of an alkali metal iodide.

As solvent which can be used for the amination reaction, mention will be made of aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as heptane, dodecane, cycloaliphatic hydrocarbons such as cyclohexane.

In the amination reaction the weight content of solvent is a function of the viscosity of the polyisobutyl bromide; it is between 0% and 70%. It is also possible to use for the amination reaction an aprotic polar cosolvent such as N-methylpyrrolidone, DMF, DMSO, 1,3-dimethyl-2-imidazolinone (DMI) or sulfolane.

The amination reaction can also be carried out in the presence of an alkaline iodide such as K1, in an amount by weight at most equal to 10% and, preferably between 1% and 5% relative to the poly (iso bromide) ) butyl used.

When ammonia is used as amination reagent, [R ⁴ = R ⁵ = H in the radical-N (R ⁴ ) (R ⁵ )], it is preferred to use it in liquid form.

By way of illustration of amines, polyamines or nitrogen heterocycles which can be used according to the present invention (as amination reagent), there may be mentioned: 3-dimethylaminopropylamine (CH3) 2N- (CH2) 3 - NH2, tetraethylenepentamine HN (CH ₂ CH2NHCH2CH ₂ NH2) 2, diethylenetriamine, triethylenetetramine, pentaethylene hexamine, hexaethyleneheptamine, isopropylamine, pentylamine, ^ 52-imidazoline, morpholine, 1,2,4-triazole, piperazine .

Preferably, ammonia, 3-dimethylamino-1-propylamine, morpholine, 1, 2,4-triazole, piperazine will be used.

The product obtained after amination can undergo an alkaline treatment according to known methods in order to reduce the possible presence of residual bromine.

The sodium bromide formed can be removed by washing with water. Poly (iso) butylhydrazines R ¹ NH - N (R) (R ³ ) may be prepared by subjecting poly (iso) butyl bromide to a reaction with hydrazine hydrate or with a compound of formula H2N - N (R ² ) (R ³ ), R ^ and R ^ having been defined previously. The hydrazination reaction can be carried out in a solvent medium, at temperatures between 20 ° C and 150 ° C and, preferably, between 80 ° C and 120 ° C, using a H2N - N (R molar ratio) ² ) (R ³ ) or hydrazine hydrate / poly (iso) butyl bromide ranging from 1 to 20 and, preferably, between 5 and 1 5.

The reaction is preferably carried out at atmospheric pressure and with stirring.

As solvents which can be used for the hydrazination reaction according to the present invention, mention will be made of DMF, DMSO, NMP, toluene or the mixture of at least two of the above-mentioned solvents. The poly (iso) butylazides R ¹ - N can be prepared by subjecting the poly (iso) butyl bromide to a reaction with an alkali azide.

Preferably, sodium azide will be used. The azidation reaction can be carried out in a solvent medium, at temperatures between 20 ° C and 150 ° C and, preferably, between 50 ° C and 120 ° C, using an alkali azide / bromide molar ratio. poly (iso) butyl between 1 and 5 and preferably ranging from 2 to 4. The reaction is preferably carried out at atmospheric pressure and with stirring.

As solvents which can be used for the azidation reaction according to the present invention, mention will be made of DMF, DMSO, NMP, alcohols such as CH3OH, CH3 (CH2) nOH with n of between 1 and 4, aromatic compounds, such as benzene, toluene, xylenes or the mixture of at least 2 of the above-mentioned solvents.

The poly (iso) butylhydrazines and the poly (iso) butylazides are isolated from the reaction media and then purified according to known methods.

The compounds of general formula (I) of the present invention can be used as maintenance or cleaning additives for the valves of internal combustion engines operating on petrol.

The weight amounts of the polyisobutylamines of general formula (I) used as fuel additives, in particular gasolines, is between 10 and 5000 ppm and, preferably, between 50 and 1000 ppm. The following examples illustrate the invention.

PREPARATION OF A POLYISOBUTYLAMINE: Hydrobromination of a polyisobutene polyisobutene sold by the company BASF under the designation Glissopal ES 3250 hereinafter designated by PIB and having the following characteristics: average molecular mass weight Mw = 1,300 average molecular mass in number Mn = 940 polydispersity Mw / Mn = 1.38 weight content of α olefin: 85% weight content of β olefin: 7%

0.10 05 mole of double bonds per 1 00 g determined by bromine index

Operating conditions: In a 1 l inactinic glass reactor, fitted with mechanical stirring, a thermometer, hydrogen bromide (HBr gas) and air inlets and a coolant coupled to a washing flask for cut down the excess HBr (or HBr not consumed), 150 g of GDP (0.158 mole) dissolved in 500 g of cyclohexane (ie a weight ratio of GDP / cyclohexane = 30%) are introduced. At room temperature (25 ° C), with stirring and in the presence of an air stream having a flow rate of 0.45 l / h, 24.3 g of Brgaz, or 0.30 mole, are introduced in 90 minutes (flow rate: 4.5 l / h).

When the introduction of HBr gas is complete, the reaction medium is left under stirring for 4 hours at room temperature.

The excess of HBr gas is removed by stripping in air and then the cyclohexane is evaporated under reduced pressure.

The product obtained - hereinafter referred to as PIB-Br is in the form of yellow honey. It is obtained with a yield of 90% determined by mineral dosage of bromine in the PIB-Br obtained.

The GDP conversion - calculated by bromine index - is 90%.

The GDP-Br obtained has the following characteristics: bromine content: 94 mmol / 1 00g

By NMR analysis of the proton on a Bruker AC300 device, using CDCI3 as solvent, there is a total disappearance of the signals of the terminal double bond of the PIB which were located at 4.65 and 4.85 ppm.

The signal corresponding to the protons of -CH2-Br appears at 3.2 ppm (multiplet). Amination of polyisobutyl bromide PIB-Br

TEST 1 TO 3: USE OF LIQUID AMMONIA

TEST 1

10 g of PIB-Br (≈9.4 mmol of Br) dissolved in 15 g of toluene are introduced into a 100 ml stainless steel autoclave provided with stirring. 0.5 g of Kl are added. The autoclave is closed and 17 g of liquid ammonia are charged. With vigorous stirring (800 revolutions / minute), the temperature is raised to 110 ° C. (P≈45 bars) and the reaction is continued for 12 hours. At the end of the reaction, the autoclave is brought to room temperature, then the excess ammonia is degassed. The reaction mixture is washed with water until neutral (4 x 100 ml), dried over magnesium sulfate and the toluene is evaporated under reduced pressure.

The conversion of polyisobutyl bromide calculated by mineral determination of the residual bromine in the amino product thus obtained amounts to 90%. The nitrogen level in the product, determined by the Kjeldahl method, is 69 mmol / 100 g, which corresponds to a yield of 73%.

Tests 2 and 3 which follow were carried out in the same apparatus using certain quantities of reagents and certain different operating conditions. These quantities and conditions, as well as the results obtained are reported in Table 1.

For tests 2 and 3, we use at the start:

10 g of GDP-Br,

17 g of ammonia,

0.5 Kl

The temperature is 1 10 ° C.

TABLE 1

On the products obtained analyzed by proton NMR according to the conditions described above, there is a total disappearance of the signal corresponding to the methylene protons of -CH2Br at 3.2 ppm and the appearance of the signal corresponding to the methylene protons of - CH2NH2 at 2, 4 - 2.5 ppm as a multiplet. The stability of the polyisobutylamines obtained was studied by

Differential Scanning Calorimetry (DSC).

There is a beginning of degradation from about 310 ° C. TEST 4:

USE OF 3-DIMETHYLAMINOPROPYLAMINE - DMAPA Preparation of the product of formula: PIB - NH - (CH2> 3 N (CH ₃ ) ₂

10 g of PIB-Br (8.5 mmol of Br), 4.3 of DMPPA are introduced into a 100 ml glass reactor fitted with a stirrer and a condenser.

(42 mmol), 0.5 g of Kl, 10 g of toluene and 10 g of N-methylpyrrolidinone. With stirring (800 revolutions / min), the temperature is brought to 110 ° C., then left to react for 24 hours. The reaction mixture is recovered, washed with a 5% potassium bicarbonate solution, then washed with water until neutral. The organic phase is dried over magnesium sulfate, then the solvent is evaporated under reduced pressure. The conversion of GDP-Br, determined by mineral determination of the residual bromine, is 98%. The nitrogen content of the product, determined by the Kjeldahl method, is 1116 mmol / 1.00 g, which corresponds to a yield of 68%.

TEST 5:

USE OF 1,2,4-TRIAZOLE IN THE FORM OF SODIUM SALT Preparation of the product of formula: PIB - N - N

N 1 08 g of PIB-Br (0.081 mole of Br), 1 9.6 g of sodium triazolate (0.21) are introduced into a 500 ml glass reactor equipped with a condenser and mechanical stirring. mole), 72 g of cycohexane, 1 00 g of DMF as well as 6.5 g of potassium iodide.

With stirring, the reaction mixture is heated until reflux is obtained (93 ° C. in the reactor). Leave to act for 72 hours. The reaction mixture is filtered and then decanted. The organic phase is washed with water, then dried over magnesium sulfate. Finally, the solvent is evaporated.

The conversion of GDP-Br, determined by measuring the residual Br, is 98%. TEST 6: USE OF MORPHOLINE - \

Preparation of the product of formula: PIB - N O

1 30 g of PIB-Br (0.102 mole), 36 g of morpholine (0.41 0 mole), 1 30 g are introduced into a 1 I glass reactor, fitted with a condenser and mechanical stirring. of cyclohexane and 130 g of NMP.

With stirring, the reaction mixture is heated until reflux is obtained (100 ° C. in the reactor). Leave to act for 24 hours. The reaction mixture is filtered and then decanted. The organic phase is washed with water saturated with NaCl, dried over magnesium sulfate, then the solvent is evaporated.

The conversion of the GDP-Br, determined by determination of the residual bromine amounts to 91%. TEST 7: USE OF PIPERAZINE

Preparation of the product of formula: - H

10 g of PIB-Br (7.5 mmol), 6.9 g of piperazine (80 mmol), 0.5 g are introduced into a 250 ml glass reactor equipped with a condenser and mechanical stirring. g Kl (3 mmol), 10 g cyclohexane and 10 g N-methylpyrrolidinone. With stirring, the reaction mixture is heated until reflux is obtained and it is left to react for 24 hours. At the end of the reaction, the reaction mixture is washed with water. The organic phase is dried over magnesium sulfate, then the solvent is evaporated. The residual bromine content is less than 500 ppm. The nitrogen content determined by the Kjeldahl method is 11.5 mmol / 1.00 g. Preparation of a poly (iso) butylhydrazine of formula PIB - H H2

100 g of PIB-Br, prepared as indicated above and having 0.085 mol of Br, 40 g of hydrazine hydrate (0, 0) are introduced into a 1 l glass reactor, equipped with stirring and a condenser. 8 mol), 5 g of Kl (0.03 mol), 350 g of toluene and 50 g of N-methylpyrrolidinone. With stirring (800 revolutions / min), the temperature is brought to 110 ° C., then left to react for 24 hours. The reaction mixture is recovered and decanted. The organic phase is washed with water, dried over magnesium sulfate, then the solvent is evaporated. The conversion of the GDP-Br, determined by determination of the residual bromine amounts to 80%.

Preparation of a poly (iso) buty! Azide of formula PIB - IM3

100 g of PIB-Br, prepared as indicated above and having 0.081 mol of Br, 1.5 g of sodium azide (0 g) are introduced into a 1 I glass reactor, fitted with a condenser and mechanical stirring. , 23 mol), 100 g of toluene and 400 g of DMF. With stirring, the temperature is brought to 110 ° C. and allowed to react for 72 hours. The reaction mixture is filtered and then decanted. The organic phase is washed with water, dried over magnesium sulfate, then the solvent is evaporated. The conversion of GDP-Br, determined by assaying residual bromine rises, is greater than 98%. The infrared analysis shows the azide band at 2097 cm- ¹ .

Evaluation of the compounds of formula 1 obtained according to the invention as additives for petrol. The motor performances of the polyisobutylamines (PIBA) obtained according to our invention were evaluated.

The tests were carried out on Honda test engines, over a period of 80 hours, with unleaded petrol 95 (SP 95), added to 300 ppm of PIBA or not.

The test consists of valve fouling (deposit mass) and cleanliness of the intake manifolds (visual rating out of 10).

The results are recorded in the following table 1:

In this table 1:

- the PIBA referenced A comes from test 2,

- the PIBA referenced B comes from test 4 (PIB - DMAPA),

- the product referenced C is a PIBA having undergone the debromination treatment and containing 850 ppm of bromine.

TABLE 1

Both for the low deposit on the valves and for the cleanliness of the intake manifolds, the additives tested appear excellent.

Claims

REVEN DI CATI ONS

1. Compounds of general formula: R ¹ - A in which: - R ¹ represents a polybutyl or polyisobutyl radical having a number of carbon atoms ranging from 20 to 400 and, preferably ranging from 35 to 200, derived from isobutene and, for a proportion of up to 20% by weight, of n-butene, and

- A represents an azido radical -N3; a hydrazino - NH - N (R ² ) (R ³ ) radical in which R ² and R ³ , which are identical or different, each represents a hydrogen atom, a linear or branched aliphatic hydrocarbon radical having a number of carbon atoms ranging from 1 to 6; or an amino radical - N (R ⁴ ) (R ⁵ ) in which R ⁴ and R ⁵ , identical or different, each represent a hydrogen atom, a linear or branched aliphatic hydrocarbon radical having a number of carbon atoms ranging from 1 to 10, a phenyl radical, an aminoalkyl radical of formula— [R ⁶ ] - N (R ⁷ ) (R ⁸ ) in which R ⁶ represents a radical having a number of carbon atoms ranging from 1 to 1 0 and, R ⁷ and R ⁸ , identical or different, each represent a hydrogen atom, an alkyl radical having a number of carbon atoms ranging from 1 to 10, a phenyl or naphthyl radical, a polybutyl or polyisobutyl radical having a number of carbon atoms ranging from 20 to 400 each, a polyaminoalkyl radical of formula [- R ⁶ - NR ⁷ ] - _m R ⁸ in which the radicals R ⁶ and R ⁷ are each identical or different, the radicals R ⁶ , R ⁷ and R ⁸ have the meanings given above and m is an integer ranging from 2 to 8, or in which R ⁴ and R ⁵ of the amino radical - N (R ⁴ ) (R ⁵ ) together form, with the nitrogen atom to which they are attached, a Δ2-imidazolinyl, imidazolidinyl, Δ2-pyrrolinyl, pyrrolidinyl, pyrazolidinyl radical , Δ3-pyrazolinyl, piperidyl, piperazinyl, morpholinyl, 1,2,4-triazolyl, piperazyl.

2. Compounds according to claim 1, characterized in that in their formula R ¹ - A, A is an azido-N ₃ or hydrazino-NHNH ₂ radical.

3. Compounds according to claim 1, characterized in that in their formula R ¹ -A, A is a radical -NH ₂ , -NH (CH ₂ ) ₃ N (CH ₃ ) ₂ , morpholinyl, 1, 2,

4-triazolyl, piperazyl

. Process for the preparation of the compounds of formula R ¹ —A according to one of claims 1 to 3, characterized in that a polybutene or a polyisobutene is hydrobrominated in the presence of oxygen in an aprotic non-polar solvent medium at temperatures between -10 ° C and 60 ° C, then the poly (iso) butyl bromide is subjected to amination, hydrazination or azidation.

5. Method according to claim 4, characterized in that one hydrobromides a polybutene or a polyisobutene at a temperature between 0 ° C and 25 ° C.

6. Method according to one of claims 4 or 5, characterized in that the aprotic apolar solvent is cyclohexane.

7. Method according to claim 4, characterized in that the amination of the bromine compound is carried out at temperatures between 50 ° C and 200 ° C under pressures at most equal to 80 bars.

8. Method according to one of claims 4 or 7, characterized in that the amination is carried out in the presence of a solvent.

9. Compounds according to one of claims 4, 7 to 8, characterized in that, in addition, the amination is carried out in the presence of an alkaline iodide.

10. Method according to one of claims 4 and 7 to 8, characterized in that the amination is carried out in the presence of a polar aprotic co-solvent.

11. Method according to claim 10, characterized in that the aprotic polar co-solvent is N-methylpyrrolidone (NMP).

12. Method according to claim 4, characterized in that the hydrazination is carried out by bringing poly (iso) butyl bromide into contact with a compound of formula H ₂ NN (R ² ) (R ³ ) or else with hydrazine hydrate, in solvent medium at temperatures between

20 ° C and 150 ° C, using a H ₂ NN (R ² ) (R ³ ) or hydrazine hydrate / poly (iso) butyl bromide molar ratio ranging from 1 to 20.

13. Process according to claim 4, characterized in that the azidation is carried out by bringing poly (iso) butyl bromide into contact with an alkali azide, in a solvent medium, at temperatures between 20 ° C and 150 ° C , using an alkali azide / poly (iso) butyl bromide ratio of between 1 and 5.

14. Method according to claim 13, characterized in that the alkali metal azide is sodium azide.

15. Use of the compounds of formula R ¹ - A according to one of claims 1 to 3, as maintenance or cleaning additives for the valves of internal combustion engines running on petrol.