FR2786490A1 - POLYBUTYL- OR POLYISOBUTYLAMINES, -HYDRAZINES OR -AZIDES, PROCESS FOR PREPARING THEM AND USES THEREOF AS DETERGENTS IN FUELS - Google Patents

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

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POLYBUTYL- OR POLYISOBUTYLAMINES, -HYDRAZINES OR -AZIDES,
THEIR PROCESS OF PREPARATION 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 carburettors of internal combustion engines running on gasoline clean.

 US Pat. No. 3,275,554 describes the preparation of apolyisobutylallylamines and p-polyisobutyl methallylamines according to a process consisting in chlorinating / dehydrochlorinating polyisobutene in a solvent medium (CCl4) and in the presence of iodine, and then reacting the chloride obtained with an amine.

 The product obtained has the disadvantage of containing allyl unsaturations capable of forming tar, that is to say undesirable products which are likely to limit their use as detergents in fuels.

contenant une poly(iso)butylamine de formule Ra # CH2 # N(Rb)(Rc) dans laquelle Ra représente un radical poly(iso)butyle dérivé de l'isobutène (et, jusqu'à 20 % en poids de n-butène), Rb et Rc, qui peuvent être identiques ou différents, représentent notamment chacun un atome d'hydrogène un radical hydrocarboné aliphatique ou aromatique, un radical polyaminoalkylène ou un radical aminoalkylène. EP 0 244 616 discloses a fuel composition

containing a poly (iso) butylamine of the formula Ra # CH2 # N (Rb) (Rc) in which Ra represents a poly (iso) butyl radical derived from isobutene (and, up to 20% by weight of n-butene ), Rb and Rc, which may be identical or different, each represent in particular a hydrogen atom, an aliphatic or aromatic hydrocarbon radical, a polyaminoalkylene radical or an 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 of between 80 ° C. and 200 ° C. and under CO / H 2 pressures of up to 600 bars, and 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 at hydrogen pressures of up to 600 bar, preferably between 80 and 300 bar.

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 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 high temperatures).

Compounds of general formula (I) have now been found: 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, isobutene derivative and, for a proportion of up to 20% by weight, n-butene, and - A represents an azido -N 3 radical; a radical hydrazino --NH-
N (R 2) (R 3) in which R 2 and R 3, which are 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 (R4) (R5) in which R4 and R5, which are 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 - [R6] - N (R7) (R8) in which R6 represents a radical having a number of carbon atoms ranging from 1 to 10 and, R7 and R8, identical or different, each represents 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 [-R6-NR7] -m R8 in which the radicals R6 and R7 are each identical or different, the radicals R6, R7 and R8 have the meanings given above and m is an integer ranging from 2 to 8, or wherein R4 and R5 of the amino radical -N (R4) (R5) together form, with the nitrogen atom to which they are attached, an A2-imidazolinyl, imidazolidinyl, A2-pyrrolinyl, pyrrolidinyl, pyrazolidinyl, 3-pyrazolinyl, piperidyl, piperazinyl, morpholinyl, 1,2,4-triazolyl, piperazyl radical.

 The invention also relates to a process for preparing the compounds of formula (I).

 This process consists in hydrobromiding a polybutene or a polyisobutene in the presence of oxygen, in aprotic apolar solvent medium, at temperatures of between -10 ° C. and 60 ° C., and preferably between 0 ° C. and 25 ° C., and then in a second step,

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 the obtained poly (iso) butyl bromide is subjected to amination, to obtain a poly (iso) butylamine, or to a reaction with a compound of formula H 2 N -N (R 2) (R 3) to obtain a poly (iso) butyl hydrazine or alternatively to a reaction with an alkaline azide to obtain a poly (iso) butyl azide.

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

 Oxygen can be supplied as it is or by air, air enriched with oxygen or even by any gas inert to the reagents, enriched with oxygen.

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

 Cyclohexane will preferably be used.

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

 Generally, one operates with a weight ratio poly (iso) butene / solvent at most equal to 100% and preferably between 10% and 40%.

 It is preferably carried out with a slight excess of HBr, the molar ratio HBr / poly (iso) butene 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 of between 50 ° C. and 200 ° C., and preferably between 90 ° C. and 150 ° C., under pressures at most equal to 80 bar and, preferably, between 1 bar and 50 bar, and optionally in the presence of an alkaline iodide.

 As the usable solvent, for the amination reaction, there may be mentioned aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as heptane, dodecane, cycloaliphatic hydrocarbons such as cyclohexane.

 In the amination reaction the weight content of the solvent is a function of the viscosity of the polyisobutyl bromide; it is between 0% and 70%.

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It is also possible for the amination reaction to use an aprotic polar co-solvent 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 KI, in an amount by weight at most equal to
10% and preferably between 1% and 5% relative to the poly (iso) butyl bromide used.

 When ammonia is used as an amination reagent, [R4 = R5 = H in the -N (R4) (R5)] radical, it is preferred to use it in liquid form.

 By way of illustration of amines, polyamines or nitrogenous heterocycles which can be used according to the present invention (as amination reagent), mention may be made of: 3-dimethylaminopropylamine (CH 3) 2 N- (CH 2) 3 -NH 2, tetraethylene pentamine HN (CH2CH2NHCH2CH2NH2) 2, diethylenetriamine, triethylenetetramine, pentaethylene hexamine, hexaethyleneheptamine, isopropylamine, pentylamine, 2-imidazoline, morpholine, 1,2,4-triazole, piperazine.

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

 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.

 The poly (iso) butyl hydrazines R 1 NH-N (R 2) (R 3) can be prepared by subjecting the poly (iso) butyl bromide to a reaction with hydrazine hydrate or with a compound of formula H 2 N -N ( R2) (R3), R2 and R3 having been previously defined. The hydrazination reaction may be carried out in a solvent medium, at temperatures of between 20 ° C. and 150 ° C., and preferably between 80 ° C. and 120 ° C., using a molar ratio of H2N-N (R2) (R3) or hydrate. hydrazine / poly (iso) butyl bromide ranging from 1 to 20 and preferably from 5 to 15.

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

 As solvents usable for the hydrazination reaction according to the present invention, mention will be made of DMF, DMSO, NMP, toluene or a mixture of at least two of the abovementioned solvents.

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 The poly (iso) butyl azides R 1 -N 3 can be prepared by subjecting the poly (iso) butyl bromide to a reaction with an alkaline azide.

 Preferably, sodium azide will be used.

The azidation reaction can be carried out in a solvent medium, at temperatures of between 20 ° C. and 150 ° C., and preferably between
50 C and 120 C, using an alkali metal azide / poly (iso) butyl bromide molar ratio of 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 that can be used for the azidation reaction according to the present invention, mention may be made of DMF, DMSO, NMP, alcohols such as CH 3 OH, CH 3 (CH 2) nOH with n ranging from 1 to 4, aromatic compounds, such as benzene, toluene, xylenes or the mixture of at least 2 of the aforementioned solvents.

 The poly (iso) butyl hydrazines and the poly (iso) butyl azides are isolated from the reaction media and then purified by known methods.

 The compounds of the general formula (I) of the present invention may be used as maintenance additives or valve cleaners of gasoline internal combustion engines.

 The weight amounts of the polyisobutylamines of general formula (1) used as fuel additives, especially 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 marketed by BASF under the designation Glissopal ES 3250, hereinafter referred to as PIB, and having the following characteristics: average molecular weight weight Mw = 1300 number-average molecular mass Mn = 940 polydispersity Mw / Mn = 1.38 weight content of α-olefin: 85% weight content in ss olefin: 7%
0.105 moles of double bonds per 100 g determined by bromine index
Operating conditions:

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In a reactor of safelight glass of 1 I, provided with a mechanical stirrer, a thermometer, arrivals of hydrogen bromide (HBr gas) and air and a condenser coupled to a washing bottle for To reduce the excess of HBr (or non-consumed HBr), 150 g of PIB (0.158 mol) dissolved in 500 g of cyclohexane (ie a PIB / cyclohexane weight ratio = 30%) are introduced. At room temperature (25 ° C.), with stirring and in the presence of a stream of air having a flow rate of 0.45 l / h, 24.3 g of HBrgaz, ie 0.30 mol, are introduced over 90 minutes ( flow rate: 4.5 l / h).

 The introduction of HBr gas ended, the reaction medium is left stirring for 4 hours at room temperature.

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

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

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

The resulting PIB-Br has the following characteristics: bromine content: 94 mmol / 100g
By NMR analysis of the proton on a Bruker AC300 apparatus, using CDCl3 as the solvent, there is a complete disappearance of the signals of the terminal double bonds of the PIB which were 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 AMMONIA LIQUID TEST 1
In a 100 ml stainless steel autoclave equipped with stirring, 10 g of PIB-Br (# 9.4 mmol of Br) dissolved in 15 g of toluene are introduced. 0.5 g of KI is added. The autoclave is closed and 17 g of liquid ammonia are charged. Under vigorous stirring (800 rpm), the temperature is raised to 110 ° C (45 bar) and the reaction is continued for 12 hours. At the end of the reaction, the autoclave is brought back to ambient temperature and the excess ammonia is degassed. The reaction mixture is washed with water until neutral (4 x 100 ml), dried over magnesium sulphate and the toluene is evaporated under reduced pressure.

 The conversion of the calculated polyisobutyl bromide by residual bromine mineral assay in the amine product thus obtained amounts to

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 90%. The nitrogen content in the product, determined by the Kjeldahl method, is 69 mmol / 100 g, which corresponds to a yield of 73%.

 The following tests 2 and 3 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 initially:
10 g of GDP-Br,
17 g of ammonia,
0.5 from KI
The temperature is 110 C.

<Tb>
<Tb>

Nitrogen
<tb> Test <SEP> Solvent <SEP> Time <SEP> Pressure <SEP> Bromine <SEP> NH3 / Br <SEP> Conver <SEP> (mmol <SEP> Render-
<tb> -sion <SEP> 1100 <SEP> g) <SEP> ment
<tb> Nature <SEP> Qty <SEP> (hours) <SEP> (bar) <SEP> initial <SEP> final <SEP> mol / mol <SEP> (%) <SEP> (%)
<tb> (in <SEP> g) <SEP> (mmol / 100g)
<tb> 2 <SEP> toluene <SEP> 15 <SEP> 24 <SEP> 45 <SEP> 88 <SEP> 8 <SEP> 110 <SEP> 91 <SEP> 70 <SEP> 80
<tb> 3 <SEP> toluene <SEP> 15 <SEP> 3 <SEP> 35 <SEP> 94 <SEP> 9 <SEP> 110 <SEP> 90 <SE> 64 <SEP> 68
<tb> NMP5
<Tb>

TABLE 1
On the products obtained analyzed by proton NMR according to the conditions previously described, a total disappearance of the signal corresponding to the methylenic protons of -CH2Br at 3.2 ppm and the appearance of the signal corresponding to the methylenic protons of CH2NH2 at 2.4 are observed. 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 (CH3) 2
100 g of PIB-Br (8.5 mmol of Br), 4.3 of DMPPA (42 mmol), 0.5 g are introduced into a 100 ml glass reactor equipped with stirring, with a condenser. of KI, 10 g of toluene and 10 g of N-methylpyrrolidinone. With stirring (800 rpm), the temperature is raised to 110 C, then allowed to react for 24 hours. The

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 The reaction mixture is recovered, washed with 5% potassium bicarbonate solution and then washed with water until neutral. The organic phase is dried over magnesium sulphate and the solvent is then evaporated off under reduced pressure. The conversion of the PIB-Br, determined by mineral determination of the residual bromine, is 98%. The nitrogen content of the product, determined by the Kjeldahl method, is 116 mmol / 100 g, which corresponds to a yield of 68%.

Préparation du produit de formule : PIB - N - N N il
Dans un réacteur en verre de 500 ml muni d'un réfrigérant et d'une agitation mécanique, on introduit 108 g de PIB-Br (0,081 mole de Br), 19,6 g de triazolate de sodium (0,21 mole), 72 g de cycohexane, 100 g de DMF ainsi que 6,5 g d'iodure de potassium. TEST 5:
USE OF 1,2,4-TRIAZOLE IN THE FORM OF SODIUM SALT

Preparation of the formula product: PIB - N - NN il
500 g of Br-PIB (0.081 moles of Br), 19.6 g of sodium triazolate (0.21 moles) are introduced into a 500 ml glass reactor equipped with a condenser and a mechanical stirrer. 72 g of cyclohexane, 100 g of DMF and 6.5 g of potassium iodide.

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

 The conversion of the PIB-Br, determined by determination of the residual Br, is 98%.

Préparation du produit de formule : PI \O
Dans un réacteur en verre de 1 I, muni d'un réfrigérant et d'une agitation mécanique, on introduit 130 g de PIB-Br (0,102 mole), 36 g de morpholine (0,410 mole), 130 g de cyclohexane et 130 g de NMP. TEST 6:
USE OF MORPHOLINE

Preparation of the product of formula: PI \ O
In a 1 liter glass reactor equipped with a condenser and a mechanical stirrer, 130 g of PIB-Br (0.102 mol), 36 g of morpholine (0.40 mol), 130 g of cyclohexane and 130 g are introduced. of NMP.

 With stirring, the reaction mixture is heated until reflux (100 ° C. in the reactor) is obtained. It is left to act for 24 hours. The reaction mixture is filtered and decanted.

 The organic phase is washed with water saturated with NaCl, dried over magnesium sulfate, and the solvent is evaporated.

 The conversion of the PIB-Br, determined by determination of residual bromine, is 91%.

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uans un réacteur en verre de 250 ml, muni d'un réfrigérant et d'une agitation mécanique, on introduit 10 g de PIB-Br (7,5 mmol), 6,9 g de pipérazine (80 mmol), 0,5 g de KI (3 mmol), 10 g de cyclohexane et
10 g de N-méthylpyrrolidinone. Sous agitation, on chauffe le mélange réactionnel jusqu'à l'obtention du reflux et on laisse réagir 24 heures. En fin de réaction, le mélange réactionnel est lavé à l'eau. La phase organique est séchée sur sulfate de magnésium, puis le solvant est évaporé. La teneur en brome résiduel est inférieure à 500 ppm. La teneur en azote déterminée par la méthode Kjeldahl est de 115 mmol/100 g. TEST 7: @ USE OF PIPERAZINE

250 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 of KI (3 mmol), 10 g of cyclohexane and
10 g of N-methylpyrrolidinone. With stirring, the reaction mixture is heated to reflux and allowed 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 and the solvent is evaporated. The residual bromine content is less than 500 ppm. The nitrogen content determined by the Kjeldahl method is 115 mmol / 100 g.

Preparation of a poly (iso) butylhydrazine of formula PIB-NHNH2
In a glass reactor of 11, equipped with stirring and a condenser, is introduced 100 g of PIB-Br prepared as indicated above and having 0.085 mol of Br, 40 g of hydrazine hydrate (0.8 mol), 5 g of KI (0.03 mol), 350 g of toluene and 50 g of N-methylpyrrolidinone. With stirring (800 rpm), the temperature is raised to 110 C, then allowed to react for 24 hours. The reaction mixture is recovered and decanted. The organic phase is washed with water, dried over magnesium sulfate and the solvent is evaporated. The conversion of the PIB-Br, determined by assaying residual bromine, is 80%.

Preparation of a poly (iso) butylazide of formula PIB-N3
1 g of a glass reactor equipped with a condenser and a mechanical stirrer are charged with 100 g of PIB-Br prepared as indicated above and having 0.081 mol of Br, 15 g of sodium azide (0, 23 mol), 100 g of toluene and 400 g of DMF. With stirring, the temperature is raised to 1 10 C, and allowed to react for 72 hours. The reaction mixture is filtered and decanted. The organic phase is washed with water, dried over magnesium sulfate and the solvent is evaporated. The conversion of the PIB-Br, determined by determination of the residual bromine, is greater than 98%. Infrared analysis shows the azide band at 2097 cm -1.

Evaluation of compounds of formula 1 obtained according to the invention as additives for gasoline.

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 The motor performance of the polyisobutylamines (PIBA) obtained according to our invention were evaluated.

 The tests were conducted on Honda test engines, over a period of 80 hours, with unleaded gasoline 95 (SP 95), additivated to 300 ppm of PIBA or not.

 The test consists of measurements of clogging of the valves (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 the test 2, the PIBA referenced B comes from the test 4 (PIB-DMAPA), the product referenced C is a PIBA having undergone the debromination treatment and containing 850 ppm bromine.

<Tb>
<Tb>

Valve <SEP> Admissions
<tb> Gasoline <SEP> Additive <SEP> Reference <SEP> Deposit <SEP> (mg) <SEP> Cleanliness
<tb> (quotation
<tb> visual <SEP> on <SEP> 10)
<tb> SP <SEP> 95 <SEP> without <SEP> 120 <SEP> 3,2
<tb> SP <SEP> 95 <SEP> PIBA <SEP> A <SEP> 1 <SEP> 9.9 <SEP>
<tb> SP <SEP> 95 <SEP> PIB <SEP> - <SEP> DMAPA <SEP> B <SEP> 3 <SEP> 9.9
<tb> SP <SEP> 95 <SEP> PIBA <SEP> C <SEP> 5 <SEP> 9.9
<Tb>

TABLE 1
Both for the low deposition on the valves and for the cleanliness of the intake manifolds, the tested additives appear excellent.

Claims (15)

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 [-R6-NR7] -mR8 in which the radicals R6 and R7 are each When identical or different, the radicals R6, R7 and R8 have the meanings given above and m is an integer ranging from 2 to 8, or in which R4 and R5 of the amino radical -N (R4) (R5) together with the nitrogen atom to which they are attached, a 2-imidazolinyl, imidazolidinyl, 2-pyrrolinyl, pyrrolidinyl, pyrazolidinyl, 3-pyrazolinyl, piperidyl, piperazinyl, morpholinyl, 1,2,4-triazolyl, piperazyl radical.  of formula [R6] -N (R) (R $) in which R6 represents a radical having a number of carbon atoms ranging from 1 to 10 and R7 and R8, which are identical or different, each represent an atom of hydrogen, an alkyl radical having a number of carbon atoms ranging from 1 to

6; or an amino-N (R 4) (R 5) radical in which R 4 and R 5, which may be identical or different, each represent a hydrogen atom or a linear or branched aliphatic hydrocarbon radical having a number of carbon atoms ranging from 1 to 10, a phenyl radical, an aminoalkyl radical N (R 2) (R 3) in which R 2 and R 3, which are 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  1. Compounds of general formula: R1-A in which: R1 represents a polybutyl or polyisobutyl radical having a number of carbon atoms ranging from 20 to 400 and preferably from 35 to 200, derived from isobutene; and, for a proportion of up to 20% by weight, n-butene, and - A represents an azido-N3 radical; a radical hydrazino -NH- 2. Compounds according to claim 1, characterized in that in their formula R1-A, A is an azido-N3 or hydrazino-NHNH2 radical. 3. Compounds according to claim 1, characterized in that in their formula R1-A, A is a radical -NH2, -NH (CH2) 3N (CH3) 2, morpholinyl, 1,2,4-triazolyl, piperazyl. <Desc / Clms Page number 12>  4. Process for the preparation of the compounds of formula R1-A according to one of revendicaitons 1 to 3, characterized in that hydrobromure a polybutene or a polyisobutene in the presence of oxygen in aprotic apolar solvent medium at temperatures between - 10 C and 60 C, and then the poly (iso) butyl bromide is subjected to amination, hydrazination or azidation. 5. Process according to claim 4, characterized in that a polybutene or a polyisobutene is hydrobrominated at a temperature of between 0 ° C. and 25 ° C. 6. Method according to one of claims 4 or 5, characterized in that the apolar aprotic solvent is cyclohexane. 7. Process according to claim 4, characterized in that the amination of the brominated compound is carried out at temperatures between 50 C and 200 C under pressures at most equal to 80 bar. 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 an aprotic polar co-solvent.  11. The method of claim 10, characterized in that the aprotic polar co-solvent is N-methylpyrrolidone (NMP). 20 C and 150 C, using a molar ratio of H2N-N (R2) (R3) or hydrazine hydrate / poly (iso) butyl bromide ranging from 1 to 20.  12, Process according to claim 4, characterized in that the hydrazination is carried out by contacting the poly (iso) butyl bromide with a compound of formula H2N-N (R2) (R3) or with the hydrate d hydrazine, in a solvent medium at temperatures between <Desc / Clms Page number 13>  13. The method of claim 4, characterized in that the azidation is carried out by contacting the poly (iso) butyl bromide with an alkaline azide, in a solvent medium, at temperatures between 20 ° C. and 150 ° C., using a molar ratio of alkali azide to poly (iso) butyl bromide of between 1 and 5. 14. The method of claim 13, characterized in that the alkaline azide is sodium azide. 15. Use of compounds of formula R1-A according to one of claims 1 to 3, as maintenance additives or cleaning valves of internal combustion engines running on gasoline.