Novel resins as asphaltene dispersant in petroleum products

Abstract

The present invention deals with novel amine-modified substi tuted phenol-aldehyde resins, their synthesis method and their use as asphaltene inhibitor, especially in petroleum products. The instant invention further pertains to an additive composition comprising said resins as well as its use as an additive in a petroleum product such as a crude oil or any product which results therefrom by any refining and / or extraction process. The additive composition of the invention is especially useful for dispersing asphaltenes in petroleum products.

Description

[0001] DESCRIPTION

[0002] TITRE : Novel resins as asphaltene dispersant in petroleum products

[0003] The present invention deals with novel amine-modified substituted phenol-aldehyde resins, as defined hereafter, a method for preparing these resins, and their use as asphaltene inhibitor, especially in petroleum products.

[0004] The instant invention further pertains to an additive composition compri sing said resins as well as its use as an additive in a petroleum product such as a crude oil or any product which results therefrom by any refining and / or extraction process. The additive composition of the invention is especially useful for dispersing asphaltenes in petroleum products.

[0005] In addition, the inventi on aims at providing a petroleum product compri sing such an additive composition, as well as a method for preventing the precipitation of asphaltenes present in a petroleum product, wherein an additive composition as defined herein is added.

[0006] PRIOR ART AND BACKGROUND OF THE INVENTION

[0007] Crude oils mainly contain two categories of products: maltenes and asphaltenes. The maltenes mainly contain oils (saturated hydrocarbon compounds and aromatics) and resins. The asphaltenes compri se highly polar entities which have a tendency to combine together to form agglomerates. They constitute the heaviest component of crude oil s. Asphaltenes are composed of molecules comprising fragments of polycycles, polyaromatics, short aliphatic chains, heteroatoms, such as N, O or S, and m etals (for example Ni, V or Fe). They are insoluble in alkanes, such as n-pentane or n-heptane, but they are soluble in aromatic solvents, such as toluene or xylene. The interaction of asphaltenes with their environment is a complex phenomenon which i s difficult to control .

[0008] The asphaltenes are generally present in crude oils as well as in many products derived from the refining thereof, such as in particular heavy oils and residues. They have a high tendency to precipitate in petroleum production wells, in pipelines and more generally on the surface of any installation in contact with a product containing them.

[0009] The precipitation of asphaltenes shall be avoided all the more that it can lead to problems of cl ogging of filters and plugging of pipes. This phenomenon results in a loss of productivity and a reduction in the transportation flows. Without a treatment which makes it possible to prevent such precipitati ons, the frequency of the operations for the maintenance of the production sites of crude oils as well as of the transportation equipment and handling plants represents a maj or economic burden.

[0010] Several factors can promote the precipitation of asphaltenes in a petroleum product, such as a rise in pressure, a rise in temperature, variations in composition, especially due to inj ection of material into the crude oil or into the derived product, for example the arrival of a drilling mud in the reservoir, a mixture of crude oils or an inj ection of gas or of another fluid.

[0011] The composition of the crude oils and of the derived products also influences the phenomenon of precipitation of the asphaltenes: light oils, exhibiting a low content of asphaltenes, are rich in alkanes in which asphaltenes are not very soluble, and the latter have a tendency to precipitate from this medium. Heavy oils, rich in asphaltenes, comprise high amounts of intermediate compounds which are good solvents for asphaltenes and delay or prevent their precipitation. However, in crude oils, the precipitation of asphaltenes often brings about the coprecipitation of other components, such as resins or waxes.

[0012] In underground formations, the inj ection of fluids and the application of high pressures result in the adsorption of residues on the rock and a decrease in the permeability which can trigger reservoir blockage. During the refining operations, the rise in temperature applied to the crude oils causes problems of coking and of fouling in the distillation columns and on the heat exchangers, and also deactivation of catalysts. During the transportation of the oil products (crude and refined), the pressure applied to the fluid can lead to the sealing of the pipes. These phenomena are largely attributable to the precipitation of the asphaltenes. The losses in production and the remediable operations which result therefrom represent significant costs.

[0013] Several attempts related in the art have been developed to address this issue. For instance, alkylphenol-based asphaltene inhibitors, especially nonylphenol formaldehyde resins and amine modified nonylphenol formaldehyde resins have been di sclosed for example in WO 2016 / 162392 to prevent the precipitation of asphaltenes in crude oil .

[0014] However, the implementation of these alkylphenol-based asphaltene di spersant, especially nonylphenol-based asphaltene dispersant, remains to be improved. In particular, the use of nonylphenol poses problems in terms of toxicity.

[0015] Accordingly, it remains a real need to provide novel additives which are effective in dispersing asphaltenes in crude oil s as well as in products deriving therefrom and which therefore makes it possible to avoid the drawbacks described above.

[0016] Indeed, one of the purposes of the present invention is to provide novel additives with lasting effectiveness in dispersing the various types of asphaltene compounds which can be present in all kinds of crude oils and products derived therefrom such as heavy oils and residues, while having a better impact on the environment, especially no toxicity problems.

[0017] OBJECT OF THE INVENTION

[0018] The present invention namely results from the unexpected findings, by the inventors, that novel amine-modified substituted phenol-aldehyde resins, as defined below, which are obtained from biobased substances, are particularly efficient for dispersing asphaltenes and preventing the precipitation thereof in crude oils whatever their origin, as well as in petroleum products derived from such crude oils, even over a long period of time.

[0019] Therefore, the present invention relates to an amine-modified substituted phenol-aldehyde resin chosen from : (i) an amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ) obtainable by a Mannich reaction of:

[0020] - a 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ), with

[0021] - at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms; and

[0022] - at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms; said 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ) being itself obtainable by condensation of: o at least one 4-(2-alkoxyethyl)phenol compound having the following formula (I) :

[0023] Formula (I) wherein X denotes :

[0024] • a linear or branched, saturated or unsaturated, hydrocarbon group containing from 1 to 24 carbon atoms, optionally interrupted with one or more heteroatoms, especially one or more heteroatoms chosen among oxygen, nitrogen, sulfur and / or phosphorous atoms,

[0025] • a saturated or unsaturated, aromatic or non-aromatic, heterocyclic or cyclic moiety, o with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms; (ii) an amine-modified alkenylphenol-aldehyde resin (A-MR2) obtainable by a Mannich reaction of:

[0026] - an alkenylphenol-aldehyde condensation resin (R2) with

[0027] - at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms; and

[0028] - at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms; said alkenylphenol-aldehyde condensation resin (R2) being itself obtainable by condensation of: o at least one phenol substituted by a linear or branched alkenyl group having from 12 to 24 carbon atoms, o with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms, and

[0029] (iii) a mixture thereof.

[0030] The amine-modified sub stituted phenol-aldehyde resins (A- MR1 ) and (A-MR2) according to the present invention overcome the issues rai sed in the prior art as they are effective as asphaltene inhibitors, even over a long period of time, while exhibiting very good ecotoxicological results.

[0031] Indeed, both amine-modified substituted phenol-aldehyde resins according to the invention are synthesized from bio-based compounds derived from renewable sources, for instance renewable feedstocks and biomass, allowing the preparation of asphaltene dispersant resins having a low impact on environment, including towards aquatic ecosystems, such as marine environment and aquatic life.

[0032] Indeed, said amine-modified substituted phenol-aldehyde resins according to the invention display the asset of not releasing any toxic substance during their implementation, ensuring that they can be widely used in many countries, including its widespread and sustainable use in marine environment.

[0033] In other words, amine-modified substituted phenol-aldehyde resins according to the invention display the asset of being based on bio-based phenols, especially on renewable compounds, leading to asphaltene dispersant resins that are environment friendly. Both amine-modified substituted phenol-aldehyde resins according to the invention are biodegradable and reduce CO2 emi ssion allowing the preparation of asphaltene di spersant resins having a low carbon footprint.

[0034] Especially, resin (A-MR1 ) displays the asset of being based on bio-based phenols, especially on a renewable compound, namely on Tyrosol which is a natural occurring nontoxic phenol, and resin (A- MR2) is based on a bio-based phenol, especially on cardanol which is a bio-based phenol obtained from cashew nutshell liquid.

[0035] It bespeaks that both resins (A-MR1 ) and (A-MR2) are biodegradable and reduce CO2 emission allowing the preparation of an additive composition having a low carbon footprint.

[0036] Hence, resins (A-MR1 ) and / or (A-MR2) are asphaltene inhibitors that are more environment friendly than the additives already known in the prior art for dispersing asphaltenes, while being at least as effective.

[0037] As a result, these resins can be handled more safely and present fewer health risks for the workforce.

[0038] The instant invention also relates to a method for preparing said amine-modified substituted phenol-aldehyde resins as defined hereabove, said method comprising at least a step of reacting by a Mannich reaction at least: a 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ) as defined hereabove or an alkenylphenol-aldehyde condensation resin (R2) as defined hereabove, with at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms; and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms.

[0039] In one embodiment, said process comprises, prior to the Mannich reaction of said 4-(2-alkoxyethyl)phenol-aldehyde condensation resin resin (Rl ) with said aldehyde / ketone and said hydrocarbon compound, a step of preparing said resin (Rl ) by condensation of at least one 4-(2- alkoxyethyl)phenol compound of formula (I) as specified above with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms.

[0040] In another embodiment, said process comprises prior to the Mannich reaction of said alkenylphenol-aldehyde condensation resin (R2) with said aldehyde / ketone and said hydrocarbon compound, a step of preparing said resin (R2) by condensation of at least one phenol substituted by a linear or branched alkenyl group having 12 to 24 carbon atoms with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms.

[0041] The instant invention is also directed to the use of said amine- modified substituted phenol-aldehyde resins as asphaltene inhibitor.

[0042] In particular, the present invention deals with the use of at least one modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ), as previously defined, or at least one modified alkenylphenol-aldehyde resin (A-MR2), as previously defined, as an asphaltene inhibitor, especially in a petroleum product.

[0043] Another subj ect-matter of the present invention pertains to an additive composition comprising at least one modified 4-(2- alkoxyethyljphenol-aldehyde resin (A-MR1 ), as previously defined, and / or at least one modified alkenylphenol-aldehyde resin (A-MR2), as previously defined.

[0044] The additive composition has an excellent solubility in crude oils as well as in petroleum products and i s not harmful to human beings and to the environment. It does not give ri se to corrosive or other aggressive products, or to solid products which may plug lines or deposit in storage vessel s.

[0045] Such additive composition is very effective in keeping asphaltenes di spersed in a hydrocarbon matrix and in avoiding or delaying the phenomena of agglomeration and precipitation of asphaltenes, even over a long period of time.

[0046] The composition is more effective than many additives already known in the prior art for dispersing asphaltenes. They are effective even when used at low treatment rates and over a great variety of crude oils whatever their compositions. The present invention pertains to the use of such a composition as an additive in a petroleum product, as well as a petroleum product compri sing such an additive composition.

[0047] Another subj ect-matter of the present invention also aims at a method for preventing the precipitation of asphaltenes present in a petroleum product, comprising a step of adding an additive composition as defined herein to said product.

[0048] Other obj ects, features, aspects and advantages of the invention will become more apparent upon reading the following description and examples.

[0049] In the following, and at least one other indication, the limits of a value range are included within this range, particularly in the expressions "between" and "ranging from ... to ... " .

[0050] Moreover, the expressions " at least one" and " at least" used in the present description are respectively equivalent to the expressions "one or more" and "more than or equal to" .

[0051] Finally, in a manner known per se, Cncompound or group designates a compound or a group containing in its chemical structure n carbon atoms.

[0052] DETAILED DESCRIPTION

[0053] As previously mentioned, the amine-modified substituted phenol-aldehyde resins of the present invention are obtainable by a Mannich reaction between the corresponding substituted phenolaldehyde condensation resin with at least one aldehyde and / or ketone having from 1 to 8 carbon atoms and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms.

[0054] The substituted phenol-aldehyde condensation resins can be:

[0055] - a 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ) (also named O-alkylated tyrosol aldehyde resin), as defined hereafter; or

[0056] - an alkenylphenol-aldehyde condensation resin (R2), in particular a cardanol-aldehyde resin, as defined hereafter.

[0057] The amine-modified substituted phenol-aldehyde resins of the present invention are thus chosen among: (i) an amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ) (also named amine-modified O-alkylated tyrosol aldehyde resin), as defined hereafter,

[0058] (ii) an amine-modified alkenylphenol-aldehyde resin (A-MR2), as defined hereafter, in particular an amine-modified cardanol-aldehyde resin; and

[0059] (iii) mixtures thereof.

[0060] Resin (A-MR1)

[0061] As previously mentioned, said resin (A-MR1 ) is obtainable by a Mannich reaction of:

[0062] - a 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ) (also named O-alkylated tyrosol aldehyde resins), with

[0063] - at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms; and

[0064] - at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms.

[0065] Resin (Rl ): 4-(2-alkoxyethyl)phenol-aldehvde condensation resin

[0066] Said resin (Rl ) is obtainable by condensation of: o at least one 4-(2-alkoxyethyl)phenol compound (also named O-alkylated tyrosol) having the following formula (I) :

[0067] Formula (I) wherein X denotes :

[0068] • a linear or branched, saturated or unsaturated, hydrocarbon group containing from 1 to 24 carbon atoms, optionally interrupted with one or more heteroatoms, especially one or more heteroatoms chosen among oxygen, nitrogen, sulfur and / or phosphorous atoms,

[0069] • a saturated or unsaturated, aromatic or non-aromatic, heterocyclic or cyclic moiety, o with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms.

[0070] According to the present invention, an aromatic or non-aromatic moiety may represent a mono- or polycyclic, fused or not fused, radical compri sing 6- to 24-membered groups, especially comprising from 6 to 24 carbon atoms, preferably from 6 to 12 carbon atoms.

[0071] According to one embodiment of the present invention, the cyclic moiety i s aromatic and may represent a mono- or polycyclic, fused or not fused, comprising from 6 to 24 carbon atoms, preferably from 6 to 12 carbon atoms.

[0072] Preferably, an aromatic cyclic moiety may be chosen among the group consisting of phenyl, biphenyl or naphthyl, indenyl, anthracenyl, preferably phenyl .

[0073] According to one embodiment of the present invention, the cyclic moiety is non-aromatic and may represent a mono- or polycyclic, fused or not fused, comprising from 6 to 24 carbon atoms, preferably from 6 to 12 carbon atoms, and may comprise one or more unsaturations.

[0074] According to the present invention, an aromatic or non-aromatic heterocyclic moiety may represent a mono- or polycyclic, fused or not fused, saturated or unsaturated, radical comprising 6- to 24-membered groups, including one or more heteroatoms chosen from nitrogen, oxygen, phosphorous and / or sulfur atoms, preferably chosen from oxygen and / or nitrogen atoms.

[0075] Preferably, the heterocyclic moiety is aromatic and may be chosen among the group consisting of morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, azepanyl, thioazepanyl; preferably pyrrolidinyl and morpholinyl . Preferably, in formula (I), X represents a linear or branched, saturated or unsaturated, hydrocarbon group containing from 1 to 24 carbon atoms optionally interrupted with one or more heteroatoms, in particular chosen from nitrogen, oxygen or sulfur atom, especially one or several oxygen atoms.

[0076] Preferably, in formula (I), X represents a linear or branched, saturated or unsaturated, hydrocarbon group containing from 1 to 24 carbon atoms.

[0077] Preferably, in formula (I), X represents a linear or branched, saturated or unsaturated, hydrocarbon group containing 2 to 14 carbon atoms, more preferably from 2 to 12 carbon atoms.

[0078] More preferably, in formula (I), X is a linear or branched saturated hydrocarbon group containing 2 to 14 carbon atoms, even more preferably from 2 to 12 carbon atoms, especially from 2 to 10 carbon atoms.

[0079] Preferably, the compound of formula (I) is selected among the group constituted of the following compounds : 4-(2- butoxyethyl)phenol; 4-(2-i sobutoxyethyl)phenol; 4-(2-

[0080] (pentyloxy)ethyl)phenol; 4-(2-(hexyloxy)ethyl)phenol; 4-(2-((4- methylpentyl)oxy)ethyl)phenol; 4-(2-((2-ethylhexyl)oxy)ethyl)phenol; 4-(2-(octyloxy)ethyl)phenol; 4-(2-(decyloxy)ethyl)phenol; 4-(2-((2- ethyloctyl)oxy)ethyl)phenol; 4-(2-(dodecyloxy)ethyl)phenol ; 4-(2- ((ethyloxy)ethyl)phenol; and mixtures thereof.

[0081] More preferably, the compound of formula (I) is selected from the group constituted of 4-(2-((ethyloxy)ethyl)phenol, 4-(2- butoxyethyl)phenol, 4-(2-isobutoxyethyl)phenol, 4-(2-((2- ethylhexyl)oxy)ethyl)phenol, 4-(2-(hexyloxy)ethyl)phenol, 4-(2- (octyloxy)ethyl)phenol, 4-(2-(decyloxy)ethyl)phenol, 4-(2- (dodecyloxy)ethyl)phenol or mixtures thereof.

[0082] Even more preferably, the compound of formula (I) is selected from the group constituted of:

[0083] 4-(2-butoxyethyl)phenol,

[0084] 4-(2-(hexyloxy)ethyl)phenol, 4-(2-((ethyloxy)ethyl)phenol, 4-(2-(octyloxy)ethyl)phenol, or mixtures thereof.

[0085] Said at least one aldehyde has from 1 to 8 carbon atoms, especially from 1 to 4 carbon atoms, more preferably from 1 to 2 carbon atoms, specifi cally 1 carbon atom.

[0086] Said aldehyde is preferably chosen from the group constituted of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2- ethylhexanal, benzaldehyde and mixtures thereof.

[0087] More preferably, said aldehyde is chosen among the group constituted of formaldehyde, acetaldehyde and mixtures thereof.

[0088] Most preferably, said aldehyde is formaldehyde.

[0089] In other words, resin (Rl ) i s advantageously a 4-(2- alkoxyethyl)phenol - formaldehyde resin (also named O-alkylated tyrosol formaldehyde resin).

[0090] In still other words, resin (Rl ) is advantageously a 4-(2- alkoxyethyl)phenol - formaldehyde resin having the following formula wherein X has the same meaning as in formula (I) and n is an integer ranging from 1 to 14, especially ranging from 12 to 14.

[0091] Preferably, X represents a linear or branched, saturated or unsaturated, hydrocarbon group containing 2 to 14 carbon atoms, more preferably from 2 to 12 carbon atoms, even more preferably from 2 to 10 carbon atoms.

[0092] Resin (Rl ) is preferably selected among the group constituted of the following compounds:

[0093] 4-(2-((ethyloxy)ethyl)phenol - formaldehyde resin, 4-(2-butoxyethyl)phenol - formaldehyde resin,

[0094] 4-(2-isobutoxyethyl)phenol - formaldehyde resin, 4-(2-((2-ethylhexyl)oxy)ethyl)phenol - formaldehyde resin, 4-(2-(hexyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(octyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(decyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(dodecyloxy)ethyl)phenol - formaldehyde resin, or mixtures thereof.

[0095] Resin (Rl ) is advantageously selected among the group constituted of:

[0096] 4-(2-butoxyethyl)phenol - formaldehyde resin, 4-(2-isobutoxyethyl)phenol - formaldehyde resin, 4-(2-(hexyloxy)ethyl)phenol - formaldehyde resin, 4-(2-((ethyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(octyloxy)ethyl)phenol - formaldehyde resin, or mixtures thereof.

[0097] In particular, resin (Rl ) can be obtainable by condensation of: at least one 4-(2-alkoxyethyl)phenol compounds, as previously defined in formula (I),

[0098] - with at least one aldehyde having from 1 to 8 carbon atoms, as previously defined, preferably in the presence of at least one acidic catalyst, such as p-toluenesulfonic acid (pTSA), which may be dissolved in at least one solvent, preferably in at least one organic solvent such as an aromatic solvent, for example toluene.

[0099] Resin (A-MR1 ) : amine-modified 4-(2-alkoxyethyl)phenol- aldehyde resin

[0100] As mentioned above, an amine-modified 4-(2- alkoxyethyl)phenol-aldehyde resin according to the invention is obtained by a Mannich reaction between a 4-(2-alkoxyethyl)phenol- aldehyde condensation resin with at least one aldehyde and / or ketone having from 1 to 8 carbon atoms and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms. The at least one aldehyde and / or ketone having from 1 to 8 carbon atoms is more particularly chosen from aldehydes and ketones having from 1 to 4 carbon atoms.

[0101] According to a preferred embodiment, said resin (A-MR1 ) is obtained by employing one and the same aldehyde used for preparing said 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ), as defined hereabove.

[0102] According to a preferred embodiment, said resin (A-MR1 ) is thus obtained from at least one aldehyde chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde and mixtures thereof. More preferably, said aldehyde i s chosen among the group constituted of formaldehyde, acetaldehyde and mixtures thereof.

[0103] Most preferably, said aldehyde is formaldehyde.

[0104] The at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms can be a hydrocarbon compound having at least one alkylmonoamine or alkylpolyamine (alkylamine) group having between 1 and 30 carbon atoms, preferably between 4 and 30 carbon atoms.

[0105] Said alkylamine may compri se at least one primary and / or secondary amine group.

[0106] In particular, the alkylamine is advantageously chosen from primary or secondary amines respectively sub stituted by one or two alkyl groups preferably comprising from 12 to 24 carbon atoms, more preferably from 12 to 22 carbon atoms.

[0107] According to a preferred embodiment, the amine-modified 4-(2- alkoxyethyl)phenol-aldehyde resin (A-MR1 ) is obtainable by a Mannich reaction of:

[0108] - a resin (Rl ) as previously defined, with

[0109] - at least one aldehyde having from 1 to 8 carbon atoms, preferably formaldehyde; and

[0110] - at least one alkylmonoamine or from at least one alkylpolyamine having at least one primary amine group . Preferably, resin (A-MR1 ) can advantageously be obtained from at least one alkylmonoamine or from at least one alkylpolyamine, all the amine groups of which are primary amines.

[0111] The alkylamine is preferably an alkylmonoamine or an alkylpolyamine comprising a fatty chain having from 12 to 24 carbon atoms, preferably from 12 to 22 carbon atoms. Use is more preferably made of an alkylpolyamine having at least one primary amine group, preferably at least two primary amine groups and more preferably three primary amine groups, and comprising a fatty chain having from 12 to 24 carbon atoms, preferably from 12 to 22 carbon atoms.

[0112] Preferably, the alkylamine is an alkylpolyamine having at least two primary amine groups and comprising a fatty chain having from 12 to 22 carbon atoms.

[0113] The commerci al alkylamines are generally not pure compounds but mixtures. Mention may in particular be made, among the marketed alkylamines which are suitable, of the alkylamines comprising a fatty chain sold under the Noram®, Trinoram®, Duomeen®, Dinoram®, Triameen® T, Armeen®, Polyram®, Lilamin® and Cemulcat® names.

[0114] In a particular embodiment, the alkylamine is a tallow di ropylenetri amine.

[0115] Mention may be made, as preferred example, of Triameen® T, which is a tallow dipropylenetriamine.

[0116] According to a particularly preferred embodiment, the amine- modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ) is obtainable by a Mannich reaction of a 4-(2-alkoxyethyl)phenol- formaldehyde condensation resin (also named O-alkylated tyrosol formaldehyde condensation resin), as previously defined, with formaldehyde and at least one alkylpolyamine having at least two primary amine groups and comprising a fatty chain having from 12 to 22 carbon atoms.

[0117] Synthesis of resin (A-MR1 )

[0118] The method for preparing a resin (A-MR1 ) comprises at least a step of reacting by a Mannich reaction at least a 4-(2- alkoxyethyl)phenol-aldehyde condensation resin (Rl ), in particular as described hereabove, with at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms as defined hereabove, preferably the same aldehyde as the one used for condensation resin (Rl ), and more particularly formaldehyde, and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms, in particular as described hereabove.

[0119] The Mannich reacti on is preferably conducted in an aromatic solvent, preferably selected from toluene, xylenes and Heavy Aromatic Naphta (HAN) solvents and more preferably from Heavy Aromatic Naphta (HAN) solvents.

[0120] HAN are known solvents which consist in a mixture of hydrocarbons generally obtained by the distillation of a hydrocarbon fraction containing a substantial amount of aromatic hydrocarbons. HAN consists predominantly of, preferably consists of, aromatic hydrocarbons having a carbon number between 9 and 16, preferably between 9 and 1 1 . Such aromatic hydrocarbons preferably have a boiling point, measured at atmospheric pressure ( 1 ,013. 105Pa), comprised between 165°C and 290°C, more preferably between 181 and 205°C.

[0121] Preferably, the Mannich reaction is conducted in the presence of at least one acidic catalyst, such as an alkyl benzene sulfonic acid, for example p-toluenesulfonic acid (pTSA).

[0122] The Mannich reaction is preferably carried out at a temperature ranging from 80°C to 140°C . In a particular embodiment, temperature is set at around 100°C.

[0123] In particular, the method for preparing a resin (A-MR1 ) compri ses:

[0124] (1 ) reacting by condensation at least one O-alkylated tyrosol compound of formula (I) : with at least one aldehyde having from 1 to 8 carbon atoms as previously defined, in particular formaldehyde, to obtain at least one resin (Rl ),

[0125] (2) reacting said resin (Rl ) with at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms as defined hereabove, and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms as previously defined, preferably in an aromatic solvent, in the presence of a catalyst.

[0126] Said O-alkylated tyrosol compound of formula (I) can previously obtained by reacting 4-(2-hydroxyethyl)phenol with at least one alkanol of formula X-OH, preferably in a solvent free continuous process in the presence of at least one heterogeneous catalyst, namely a cation exchange resin.

[0127] Advantageously, thi s step is a cross-etherification of 4-(2- hydroxyethyl)phenol with at least one alkanol corresponding to formula X-OH.

[0128] In other words, the 4-(2-alcoxyethyl)phenol compounds (also named O-alkylated tyrosol) as previously defined in formula (I) can be obtained in step ( 1 ) by cross-etherification of 4-(2-hydroxyethyl)phenol and at least one alkanol having the formula X-OH.

[0129] The alkanol X-OH may be used in such method in an equimolar amount to 4-(2-hydroxyethyl)phenol or in excess, preferably in excess.

[0130] In a particular embodiment, the cross-etherification is preferably implemented in a solvent free continuous flow process.

[0131] Preferably, it is operated in the presence of at least one heterogeneous acid catalyst. The heterogenous catalyst may namely be at least one cation exchange resin, preferably at least one sulfonic resin such as Amberlyst- 15 as catalyst.

[0132] The cross-etherification of 4-(2-hydroxyethyl)phenol with at least one alkanol is namely carried out in one step.

[0133] The completion of the reaction may be monitored by a thin layer chromatography.

[0134] This step for obtaining said O-alkylated tyrosol compound of formula (I) may be performed at atmospheric pressure and at a temperature ranging from 20°C to 200°C, preferably from 80°C to 150°C, more preferably from 100°C to 140°C, especially occurs at 120°C .

[0135] The condensation step (1 ) for obtaining said resin (Rl ) may be performed in the presence of at least one an acidic catalyst, such as an alkyl benzene sulfonic acid, for example p-toluenesulfonic acid (pTSA), which may be dissolved in at least one solvent, in particular in an aromatic solvent such as toluene, xylenes or Heavy Aromatic Naphta (HAN) solvents and more preferably in an Heavy Aromatic Naphta (HAN) solvent.

[0136] The condensation may be performed at a temperature ranging from 90 to 200°C and more preferably from 100°C to 180°C.

[0137] Step ( 1 ) of said method may be performed one or several times.

[0138] On completion of step(s) ( 1 ), the i ssued reaction mixture may be cooled and said at least aforementioned solvent can be removed, preferably under high vacuum .

[0139] In other embodiment, step (2) is carried out directly in the reaction medium of synthesis of resin (Rl ).

[0140] Step (2) is carried out between resin (Rl ) issued from step ( 1 ) and at least at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms as defined hereabove, preferably the same aldehyde as the one used for condensation resin (Rl ), and more particularly formaldehyde, and at least one alkylamine, such as the marketed alkylamines previously described.

[0141] Step (2) may be carried out in the conditions as detailed hereabove, preferably in an aromatic solvent, in the presence of a catalyst and in a temperature ranging from 80°C to 140°C, in particular at 100°C. In particular, it is carried out at atmospheric pressure.

[0142] Said catalyst is preferably the same as the one used in step (1 ) for obtaining the resin (Rl ).

[0143] In particular, in the case wherein step (2) is carried out in the reaction medium of synthesis of resin (Rl ), the solvent and catalyst for the synthesis of the amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ) are the same as the ones used for prior synthesis of resin (Rl ).

[0144] Resin (A-MR2)

[0145] As previously mentioned, said resin (A-MR2) is obtainable by a Mannich reaction of:

[0146] - an alkenylphenol-aldehyde condensation resin (R2) as defined hereafter, in a particular cardanol-aldehyde condensation resin, with

[0147] - at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms; and

[0148] - at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms.

[0149] Resin (R2) : alkenylphenol-aldehyde condensation resin

[0150] Said resin (R2) is obtainable by condensation of: o at least one phenol substituted by a linear or branched alkenyl group having from 12 to 24 carbon atoms, o with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms.

[0151] Said phenol is preferably substituted in meta position, and more preferably corresponds to formula (I I ) below: wherein Xi denotes a linear of branched, alkenyl group containing from 12 to 24 carbon atoms, preferably from 12 to 18 carbon atoms and more preferably from 14 to 16 carbon atoms.

[0152] In particular, in formula (Ii), Xi represents a linear alkenyl group containing from 12 to 24 carbon atoms, preferably from 12 to 18 carbon atoms and more preferably from 14 to 16 carbon atoms, and having 1 to 3 double bonds, in particular 2 double bonds.

[0153] A particularly preferred compound is cardanol, which i s a compound of formula (Ii) wherein Xi denotes an alkenyl group with an average number of 15 carbon atoms and 1 to 3 double bonds.

[0154] Cardanol can be obtained in a known manner from an oil that i s itself obtained from the shell of cashew kernels also known as cashew nutshell liquid.

[0155] The aldehyde used for obtaining said resin (R2) preferably contains from 1 to 4 carbon atoms. Said aldehyde is preferably chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2- ethylhexanal, benzaldehyde and mixtures thereof, and more preferably from formaldehyde.

[0156] Preferably, resin (R2) is a cardanol-formaldehyde resin.

[0157] Resin (A-MR2) : amine-modified alkenylphenol-aldehyde resin

[0158] As mentioned above, an amine-modified alkenylphenol-aldehyde resin according to the invention, in particular an amine-modified cardanol-aldehyde resin is obtained by a Mannich reaction between an alkenylphenol-aldehyde condensation resin with at least one aldehyde and / or ketone having from 1 to 8 carbon atoms and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms.

[0159] The at least one aldehyde and / or ketone having from 1 to 8 carbon atoms is more particularly chosen from aldehydes and ketones having from 1 to 4 carbon atoms.

[0160] According to a preferred embodiment, said resin (A-MR2) is obtained by employing one and the same aldehyde used for preparing said 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ), as defined hereabove. According to a preferred embodiment, said resin (A-MR2) is thus obtained from at least one aldehyde chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde and mixtures thereof. More preferably, said aldehyde i s chosen among the group constituted of formaldehyde, acetaldehyde and mixtures thereof.

[0161] Most preferably, said aldehyde is formaldehyde.

[0162] The at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms) can be as disclosed hereabove for the resin (A-MR1 ).

[0163] The at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms can be a hydrocarbon compound having at least one alkylmonoamine or alkylpolyamine (alkylamine) group having between 1 and 30 carbon atoms, preferably between 4 and 30 carbon atoms.

[0164] Said alkylamine may compri se at least one primary and / or secondary amine group.

[0165] In particular, the alkylamine is advantageously chosen from primary or secondary amines respectively sub stituted by one or two alkyl groups preferably comprising from 12 to 24 carbon atoms, more preferably from 12 to 22 carbon atoms.

[0166] According to a preferred embodiment, the amine-modified alkenylphenol-aldehyde resin (A-MR2) is obtainable by a Mannich reaction of:

[0167] - a resin (R2) as previously defined, with

[0168] - at least one aldehyde having from 1 to 8 carbon atoms, preferably formaldehyde; and

[0169] - at least one alkylmonoamine or from at least one alkylpolyamine having at least one primary amine group .

[0170] Preferably, resin (A-MR2) can advantageously be obtained from at least one alkylmonoamine or from at least one alkylpolyamine, all the amine groups of which are primary amines.

[0171] The alkylamine is preferably an alkylmonoamine or an alkylpolyamine comprising a fatty chain having from 12 to 24 carbon atoms, preferably from 12 to 22 carbon atoms. Use is more preferably made of an alkylpolyamine having at least one primary amine group, preferably at least two primary amine groups and more preferably three primary amine groups, and comprising a fatty chain having from 12 to 24 carbon atoms, preferably from 12 to 22 carbon atoms.

[0172] Preferably, the alkylamine is an alkylpolyamine having at least two primary amine groups and comprising a fatty chain having from 12 to 22 carbon atoms.

[0173] The commercial alkylamines are generally not pure compounds but mixtures. Mention may in particular be made, among the marketed alkylamines whi ch are suitable, of the alkylamines comprising a fatty chain sold under the Noram®, Trinoram®, Duomeen®, Dinoram®, Triameen® T, Armeen®, Polyram®, Lilamin® and Cemulcat® names.

[0174] In a parti cular embodiment, the alkylamine is a tallow dipropylenetri amine.

[0175] Mention may be made, as preferred exampl e, of Triameen® T, which is a tallow dipropylenetriamine.

[0176] According to a particularly preferred embodiment, the amine- modified alkenylphenol-aldehyde resin (A-MR2) is obtainable by a Mannich reaction of a cardanol-formaldehyde resin, with formaldehyde and at least one alkylpolyamine having at least two primary amine groups and compri sing a fatty chain having from 12 to 22 carbon atoms.

[0177] Synthesis of resin (A-MR2)

[0178] The method for preparing a resin (A-MR2) comprises at least a step of reacting by a Mannich reaction at least an alkenylphenol- aldehyde resin (R2), in particular as described hereabove, with at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms as defined hereabove, preferably the same aldehyde as the one used for condensation resin (Rl ), and more particularly formaldehyde, and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms, in particular as described hereabove.

[0179] The Mannich reaction is preferably conducted in an aromatic solvent, preferably selected from toluene, xylenes and Heavy Aromatic Naphta (HAN) solvents and more preferably from Heavy Aromatic Naphta (HAN) solvents. HAN are known solvents which consist in a mixture of hydrocarbons generally obtained by the distillation of a hydrocarbon fraction containing a substantial amount of aromatic hydrocarbons. HAN consists predominantly of, preferably consists of, aromatic hydrocarbons having a carbon number between 9 and 16, preferably between 9 and 1 1 . Such aromatic hydrocarbons preferably have a boiling point, measured at atmospheric pressure ( 1 ,013. 105Pa), comprised between 165°C and 290°C, more preferably between 181 and 205°C.

[0180] Preferably, the Mannich reaction is conducted in the presence of at least one acidic catalyst, such as an alkyl benzene sulfonic acid, for example p-toluenesulfonic acid (pTSA).

[0181] The Mannich reaction is preferably carried out at a temperature ranging from 80°C to 140°C . In a particular embodiment, temperature is set at 100°C.

[0182] In particular, the method for preparing a resin (A-MR2) compri ses:

[0183] (1 ’) reacting by condensation at least one phenol substituted by an alkenyl group having from 12 to 24 carbon atoms, as previously defined, with at least one aldehyde having from 1 to 8 carbon atoms as previously defined, in particular formaldehyde, to obtain at least one resin (R2),

[0184] (2 ’) reacting said resin (R2) with at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms as defined hereabove, and at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms as previously defined, preferably in an aromatic solvent, in the presence of a catalyst.

[0185] Step (2’ ) is carried out between resin (R2) issued from step (1 ’) and at least at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms as defined hereabove, preferably the same aldehyde as the one used for condensation resin (Rl ), and more particularly formaldehyde and at least one alkylamine, such as the marketed alkylamines previously described.

[0186] Step (2 ’) may be carried out in in the conditions as detailed hereabove, preferably in an aromatic solvent, in the presence of a catalyst and in a temperature ranging from 80°C to 140°C, in particular at 100°C. In particular, it is carried out at atmospheric pressure.

[0187] In a particular embodiment, step (2’ ) is carried out directly in the reaction medium of synthesis of resin (R2).

[0188] Use

[0189] As previously indicated, the present invention also encompasses the use of at least one amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ), as previously defined, or at least one amine-modified alkenylphenol-aldehyde resin (A-MR2), as previously defined, as an asphaltene inhibitor.

[0190] Preferably, the present invention deals with the use of at least one amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ), as previously defined, as an asphaltene inhibitor.

[0191] Preferably, the present invention deals with the use of at l east one amine-modified alkenylphenol-aldehyde resin (A-MR2), as previously defined, as an asphaltene inhibitor.

[0192] Especially, the instant inventi on concerns the use of at least one resin, as previ ously defined, especially at least one resin (A-MR1 ) or at least one resin (A-MR2), as an asphaltene inhibitor in petroleum products.

[0193] Advantageously, a further subj ect-matter of the present invention is the use of at least one resin, as previously defined, especially at least one resin (A-MR1 ) or at least one resin (A-MR2), for preventing or reducing the precipitation of asphaltenes present in a petroleum product.

[0194] In one embodiment, the instant invention is the use of at least one resin (A-MR1 ), as previously di sclosed, for preventing or reducing the precipitation of asphaltenes present in a petroleum product.

[0195] In one embodiment, the instant invention is the use of at least one resin (A-MR2), as previously di sclosed, for preventing or reducing the precipitation of asphaltenes present in a petroleum product. The additive composition

[0196] Another subj ect-matter of the present invention pertains to an additive composition comprising at least one modified 4-(2- alkoxyethyljphenol-aldehyde resin (A-MR1 ), as previously defined, and / or at least one modified alkenylphenol-aldehyde resin (A-MR2), as previously defined.

[0197] Preferably, the additive composition comprises at least one modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ), as previously defined, or at least one modified alkenylphenol-aldehyde resin (A-MR2), as previously defined.

[0198] According to a preferred embodiment, the additive composition comprises at least one modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ) as previously defined.

[0199] According to a preferred embodiment, the additive composition comprises at least one modified alkenylphenol-aldehyde resin (A-MR2) as previously defined.

[0200] According to a preferred embodiment, the additive composition of the present invention further contains one or more liquid organic solvent(s). By liquid, it is meant a solvent which is in liquid form at ambient temperature (20°C) and atmospheric pressure ( 1 ,013. 105Pa).

[0201] Such solvents may in particular be chosen from poly alkyl ethers, aliphatic hydrocarbons such as alkanes, aromatic solvents such as aromatic hydrocarbons and aromatic hetero-compounds, and mixtures thereof.

[0202] Preferred organic solvents are chosen from aromatic solvents, such as N-methylpyrrolidone, xylene, toluene, benzene; and poly alkyl ethers such as butyl carbitol (diethylene glycol monobutyl ether); as well as mixtures thereof.

[0203] Other preferred organic solvents include those derived from biomass, such as oils of vegetable origin. A particularly preferred solvent is cashew nutshell liquid, also known as CSNL, which is a widely available vegetable oil derived from cashew nutshell . CNSL can be used as a mixture with any other solvent such as those described herein. Preferably, the additive composition comprises one or more organic solvent chosen among the group constituted of oils of vegetable origin, especially cashew nutshell liquid.

[0204] The composition of the invention may contain an amount of solvent ranging from 25 to 95% by weight, preferably from 40 to 90%wt of the composition, more preferably from 50 to 80%wt, relative to the total weight of the composition.

[0205] When it contains a solvent, the composition advantageously contains said resins (A-MR1 ) and / or (A-MR2) as previously defined, in a total amount ranging from 5 to 75% by weight, preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, relative to the total weight of the composition.

[0206] According to a preferred embodiment, when it contains a solvent, the composition advantageously contains said resin (A-MR1 ) as previously defined, in a total amount ranging from 5 to 75% by weight, preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, relative to the total weight of the composition.

[0207] According to a preferred embodiment, when it contains a solvent, the composition advantageously contains said resin (A-MR2) as previously defined, in a total amount ranging from 5 to 75% by weight, preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, relative to the total weight of the composition.

[0208] The additive composition may further contain one or more additi onal additives, different(s) from resins (A-MR 1 ) and / or (A-MR2) previously defined.

[0209] Mention may be made, as additional optional additives, of: dispersants / detergents, metal passivators, antioxidants, corrosion inhibitors, biocides, demulsifiers, antifoam agents, paraffin deposition inhibitors, pour point lowering agents, paraffin anti-settling additives, wax inhibitors, scale inhibitors, foamers, anti-foulant, H2S scavengers, organic deposit inhibitors, such as naphthenic acids, mineral deposit inhibitors, heat stabilizers, emulsifiers, friction reducers, surfactants, reodorants and their mixtures.

[0210] Preferred additional additives are: i) antifoam additives, in particular (but non limitatively) chosen from polysiloxanes, oxyalkylated poly siloxanes and amides of fatty acids resulting from vegetable or animal oils; ii) detergent additives and / or corrosion inhibitors, in particular

[0211] (but non limitatively) chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylpolyamines, polyetheramines and imidazolines; iii) lubricating additives or antiwear agents, in particular (but non limitatively) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and polycyclic carboxylic acid; iv) crystallization-modifying additives, additives which inhibit paraffin deposits, additives which lower the pour point; modifiers of the rheology at low temperature, such as ethylene / vinyl acetate (EVA) and / or ethylene / vinyl propionate (EVP) copolymers, ethylene / vinyl acetate / vinyl versatate (E / VA / VeoVA) terpolymers; ethylene / vinyl acetate / alkyl acrylate terpolymers; EVA copolymers modified by grafting; polyacrylates; acrylates / vinyl acetate / maleic anhydride terpolymers; amidated maleic anhydride / alkyl (meth)acrylate copolymers capable of being obtained by reaction of a maleic anhydride / alkyl (meth)acrylate copolymer and of an alkylamine or polyalkylamine having a hydrocarbon chain of 4 to 30 carbon atoms, preferably of 12 to 24 carbon atoms; amidated a-olefin / maleic anhydride copolymers capable of being obtained by reaction of an a-olefin / maleic anhydride copolymer and of an alkylamine or polyalkylamine, it being possible for the a-olefin to be chosen from C 10-C50 a-olefins, preferably from C 16-C20 a-olefins, and the alkylamine or the polyalkylamine advantageously having a hydrocarbon chain of 4 to 30 carbon atoms, preferably of 12 to 24 carbon atoms. Mention may be made, as examples of terpolymers, of those which are described in EP01692196, W02009 / 106743 , W02009 / 106744, U. S . Pat. No. 4,758,365 and U. S . Pat. No. 4, 178,951 ; v) antioxidants, for example of hindered phenolic type or aminated of alkylated para-phenylenediamine type; vi) metal passivators; vii) acidity neutralizers.

[0212] Use of the additive composition

[0213] The additive composition as described above is particularly useful for dispersing asphaltenes in petroleum products. Said composition can especially be used for preventing or reducing the precipitation of asphaltenes present in a petroleum product.

[0214] According to a preferred embodiment, the composition of invention is used as an additive in a petrol eum product which is handled in an equipment chosen from a tank, a refining plant, a pipeline, a drilling well, a storage vessel, a transportation equipment or a filter.

[0215] The petroleum product may be a crude oil or any product which derives therefrom by any refi ning and / or extraction process. The petroleum product may also be a bitumen, such as bitumens of natural origin such as those present in natural bitumen or natural asphalt deposits, or bituminous sands, the bitumens origi nating from the refining of crude oil, in particular from the atmospheric and / or vacuum distillation of oil, it being possible for these bitumens to optionally be blown, visbroken and / or deasphalted and / or mixed.

[0216] The petroleum product is especially selected from crude petroleum oils; hydrocarbon fractions and residues deriving from the distillation thereof such as in heavy fuel oils, heavy residues; and bitumens.

[0217] The additive composition is advantageously used in an amount ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resins (A-MR1 ) and / or (A- MR2) with respect to the total weight of the petroleum product.

[0218] According to a preferred embodiment, the additive composition is advantageously used in an amount ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resins (A-MR1 ) with respect to the total weight of the petroleum product.

[0219] According to a preferred embodiment, the additive composition is advantageously used in an amount ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resins (A-MR2) with respect to the total weight of the petroleum product.

[0220] The petroleum product

[0221] The petroleum product contains a crude oil or a product which results therefrom by any refining and / or extraction process, and an additive composition as described above.

[0222] The petroleum product may also contain a bitumen, such as bitumen of natural origin such as those present in natural bitumen or natural asphalt deposits, or bituminous sands, the bitumen originating from the refining of crude oil, in particular from the atmospheric and / or vacuum distillation of oil, it being possible for these bitumen to optionally be blown, visbroken and / or deasphalted and / or mixed.

[0223] The petroleum product preferably contains a crude petroleum oil and / or at least one hydrocarbon fraction or at least one residue deriving from the distillation of crude petroleum oil, such as heavy fuel oil s, heavy residues and / or at least one bitumen.

[0224] The petroleum product advantageously contains a total amount of said resins (A-MR1 ) and / or (A-MR2) ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resins (A-MR1 ) and / or (A-MR2) with respect to the total weight of the petroleum product.

[0225] The petroleum product advantageously contains a total amount of said resin (A-MR1 ) ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resin (A-MR1 ) with respect to the total weight of the petroleum product.

[0226] The petroleum product advantageously contains a total amount of said resin (A-MR2) ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resin (A-MR2) with respect to the total weight of the petroleum product.

[0227] The method

[0228] The method of the invention for preventing the precipitation of asphaltenes present in a petroleum product comprises a step of adding an additive composition as defined herein to said product.

[0229] The petroleum product i s advantageously chosen from those described above.

[0230] The additive composition is preferably added in an amount ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resins (A-MR1 ) and / or (A- MR2) with respect to the total weight of the petroleum product.

[0231] Preferably, the additive composition is preferably added in an amount ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resin (A- MR1 ) with respect to the total weight of the petroleum product.

[0232] Preferably, the additive composition is preferably added in an amount ranging from 1 to 5000 ppm by weight, preferably from 5 to 2000 ppm, more preferably from 10 to 1000 ppm and more preferably still from 15 to 500 ppm, expressed as total weight of said resin (A- MR2) with respect to the total weight of the petroleum product.

[0233] According to a preferred embodiment, the method of the invention compri ses at least two steps :

[0234] (A) the introduction of an additive composition as described above into the petroleum product, and

[0235] (B) a treatment step chosen from : a ri se in pressure, a rise in temperature and a mixing with at least one other fluid.

[0236] According to a most preferred embodiment, steps (A) and (B) are carried out successively (step A and then step B).

[0237] According to a preferred variant, step (B) is chosen from : an extraction of a crude oil from a reservoir, a stage of refining a crude oil or a derived product, a transportation of a crude oil or of a derived product, a filtration of a crude oil or of a derived product, an inj ection of gas into a crude oil or into a derived product, a mixing of crude oils or of derived products, and a mixing of a crude oil or of a derived product with a solvent.

[0238] Step (B) can for example correspond to a pressurization, for example in a pipeline or any type of pipe, or through a filter; it can compri se a heating in a refining plant, an inj ection of a gas or a mixing with another variety of crude oil or with another grade of heavy oil resulting from the refining.

[0239] Conventionally, such treatments result in a precipitation of asphaltenes and a fouling and / or a clogging of the equipment. The method of the invention makes it possible to keep the asphaltenes in dispersion during these treatments and to improve the compatibility of the asphaltenes with the non-asphaltenic part of the petroleum product.

[0240] The method of the invention is advantageously carried out in an equipment chosen from : a tank, a drilling well, a refining plant, a pipeline, a storage vessel, a transportation equipment or a filter.

[0241] The method can be carried out at any stage from the recovery of crude oil s from a reservoir up to the refining and the use of the hydrocarbon fractions, via the transportation of the different petroleum products deriving therefrom. The invention is targeted at keeping the asphaltenes in, di spersion in the medium, so as to improve the recovery of the crude oils, to stop, prevent, decrease or delay the precipitation of the asphaltenes, the formation of asphaltene deposits, the fouling in the tanks, treatment and transportation plants, such as the extraction or refining equipment, the pipelines, the pipes of all types, the filters, the storage vessels.

[0242] The example hereafter only aims at illustrating the present invention and shall not be interpreted so as to limit its scope.

[0243] EXAMPLES

[0244] Example 1 : Synthesis examples of resins (A-MR1)

[0245] A. Preparation of O-alkylated tyrosol formaldehyde resins A. 1 . 4-(2-butoxyethyl)phenol - formaldehyde resin (IA)

[0246] 4-(2-butoxyethyl)phenol formaldehyde resin (IA) was prepared by condensation of 4-(2-butoxyethyl)phenol and formaldehyde in the presence of at least one acidic catalyst:

[0247] A three-neck 500ml round bottom flask was equipped with a magnetic stirrer and Dean Stark trap with a reflux condenser along with a Schlenk line for maintaining the nitrogen atmosphere. In the initial step, 4-(2-butoxyethyl)phenol was taken along with acid catalyst such / -TSA in 10 mL of toluene.

[0248] The mixture was then stirred under a nitrogen blanket at 120°C, and a solution of trioxane in toluene (20 mL) was taken in a syringe and added drop wise over a period of about I hr by using syringe pump repeatedly for three times.

[0249] After the addition of trioxane, the temperature increased to 165°C, and the reaction continued for 10 hours. The procedure was then repeated for l Ohrs using same amount of p-TSA, trioxane. When the collection of water stopped, the reaction mixture was cooled, and the toluene was removed under a high vacuum. The crude precipitated by the methanol (approx. 50 mL), DCM (approx. 20 mL) and found the polymer as an insoluble gel . The solvent was evaporated by rotary evaporator.

[0250] The pure gel was dried under vacuum which afforded a solid polymer. The 4-(2-butoxyethyl)phenol - formaldehyde resin (IA) exhibits a good ecotoxicity profile.

[0251] A.2. 4-(2-(hexyloxy)ethyl)phenol formaldehyde resin (IB)

[0252] 4-(2-(hexyloxy)ethyl)phenol formaldehyde resin was prepared from 4-(2-(hexyloxy)ethyl)phenol using a similar protocol as the one previously described for resin (IA).

[0253] The end product 4-(2-(hexyloxy)ethyl)phenol formaldehyde resin was characterized by NMR analysis.

[0254] XH NMR (CDCh, 400 MHz) 3 = 9.41 (s, 1H, -OH), 7.03-6.98 (m, 2H, Ar-H), 3.81 (s, 2H, Ar-CH2-Ar), 3.57 - 3.50 (t, 2H, -OCH2-), 3.44 -3.39 (t, 2H, -OCH2-),2.80 - 2.76 (t, 2H, Ar-CH2-CH2-O-), 1.59 - 1.18 (m, 8H, Alkyl) and 0.88 - 0.87 (t, 3H, -CH3) ppm;

[0255] 13C NMR (CDCh, 101 MHz) 3 = 147.33, 129.88, 129.16, 128.84, 72.15, 71.77, 35.59, 31.73, 29.77, 25.93, 22.66 and 14.07 ppm;

[0256] DEPT 135 NMR (CDCh, 101 MHz) 3 = 129.81 , 129.16, 72.15, 71.17, 35.51 , 31.73 , 29.77, 25.93, 22.66 and 14.07 ppm.

[0257] A.3 . 4-(2-((2-ethylhexyl)oxy)ethyl)phenol formaldehyde resin

[0258] (IQ

[0259]

[0260] 4-(2-((2-ethylhexyl)oxy)ethyl)phenol formaldehyde resin was prepared from 4-(2-((2-ethylhexyl)oxy)ethyl)phenol, using a similar protocol as the one previously described for resin (IA).

[0261] A.4. 4-(2-octyloxy)ethyl)phenol formaldehyde resin (ID)

[0262] 4-(2-octyloxy)ethyl)phenol formaldehyde resin was prepared from 4-(2-octyloxy)ethyl)phenol, using a similar protocol as the one previously described for resin (IA).

[0263] B . Preparation of amine-modified O-alkylated tyrosol formaldehyde resin The following amine-modified O-alkylated tyrosol formaldehyde resins can be prepared as follows.

[0264] Tallow dipropylenetriamine sold under the commercial name Triameen® T and formaldehyde are both added to O-alkylated tyrosol formaldehyde resin in a C I O aromatic solvent in the presence of a catalyst (p-toluenesulfonic acid). The reaction medium is maintained under reflux at a temperature of 100°C between 30 minutes and 1 hour. Water distillation is then performed to remove water. B . 1 . Amine-modified O-butyl-Tyrosol formaldehyde Resin wherein R’ is based on tallow moiety (2% of C 14; 30% of C 16; 40% of C 18 and 3% of C20). Said amine-modified O-butyl-Tyrosol formaldehyde has a number average molecular weight, Mn, ranging from 4000 g / mol and 12000 g / mol .

[0265] B .2. Amine-modified 4-(2-(hexyloxy)ethyl)phenol formaldehyde resin wherein R’ is based on tallow moiety (2% of C 14; 30% of C 16;

[0266] 40% of C 18 and 3 % of C20). Said amine-modified O-hexyl-Tyrosol formaldehyde has a number average molecular weight, Mn, ranging from 4000 g / mol and 12000 g / mol .

[0267] B .3 . Amine-modified 4 -(2 -((2 -ethyl hexyl) oxy) ethyl )phenol formaldehyde resin wherein R’ is based on tallow moiety (2% of C 14; 30% of C 16; 40% of C 18 and 3 % of C20). Said amine-modified O-2-ethylhexyl-

[0268] Tyrosol formaldehyde has a number average molecular weight, Mn ranging from 4000 g / mol and 12000 g / mol .

[0269] B .4. Amine-modified 4-(2-octyloxy)ethyl)phenol formaldehyde resin wherein R’ i s based on tallow moiety (2% of C 14; 30% of C 16; 40% of C 18 and 3% of C20). Said amine-modified O-2-octyl-Tyrosol formaldehyde has a number average molecular weight, Mn, ranging from 4000 g / mol and 12000 g / mol .

[0270] Example 2: Synthesis examples of resins (A-MR2)

[0271] C. Preparation of a resin (R2)

[0272] As resin (R2), use was made of the cardanol-formaldehyde condensation resin marketed by the company Cardolite under trade name NX-4009.

[0273] D. Preparation of amine-modified cardanol formaldehyde resin

[0274] The following amine-modified cardanol formaldehyde resin can be prepared as follows.

[0275] Tallow dipropylenetriamine sold under the commercial name Triameen® T and formaldehyde are both added to cardanol formaldehyde condensation resin in a C I O aromatic solvent in the presence of a catalyst (p-toluenesulfonic acid). The reaction medium is maintained under reflux at a temperature of 100°C between 30 minutes and 1 hour. Water di stillation is then performed to remove water.

[0276] Example 3: Evaluation of the effectiveness of additive compositions (Al) to (A4)

[0277] Asphaltene Dispersancy Test (APT) protocol on crude oil:

[0278] The performance in terms of preventing asphaltene precipitation was assessed on crude oil, using an asphaltene di spersancy test (ATD) described below. The ADT provides a rapid test method which allows to assess the performance of an additive composition in preventing asphaltene precipitation in a crude oil . The test allows to compare the relative effectiveness of additive compositions in keeping asphaltene dispersed in a non-solvent medium. The ADT takes advantage of the insolubility of asphaltenes in an alkane diluent (n-hexane). Dilution of a fixed volume of crude oil in a fixed volume of alkane diluent results in precipitation of asphaltenes. Dilution of the same fixed volume of crude oil properly dosed with an effective additive composition in the same fixed volume of alkane diluent results in minimal precipitation of asphaltenes during a controlled testing period. An effective additive composition will prevent the agglomeration and eventual precipitation of asphaltenes when the crude oil sample is diluted in the alkane diluent.

[0279] 1 . Preparation of a 10% diluted crude oil sample

[0280] Crude oil was heated uniformly to a temperature above 20°C, at which point wax appears, for a period ranging from 30 minutes to 1 hour, then mixed homogeneously and subj ected to sampling.

[0281] 8 grams of this crude oil were then taken and made up to 80 grams by adding toluene, resulting in a 10% diluted crude oil sample.

[0282] The sample was then kept at a temperature of 60°C for an hour before performing the ADT test.

[0283] 2. Preparation of additive compositions (Al ) to (A4)

[0284] The following resins were used to prepare additive compositions (Al ) to (A4).

[0285] - The resin A-MR2 synthesized in Example 2 - Section D was used to prepare additive composition (A l ) according to the present invention,

[0286] - A modified alkylphenol-aldehyde resin synthesized according to the protocol described below was used to prepare a comparative additive composition (A2):

[0287] Synthesis of the modified alkylphenol-aldehyde resin:

[0288] • stage 1 : in a first stage, an alkylphenol-aldehyde condensation resin was prepared by condensation of para- nonylphenol and formaldehyde (for example according to the procedure described in EP 857 776), with a viscosity at 50° C . of between 1800 and 4800 mPa s (viscosity measured at 50° C . using a dynamic rheometer with a shear rate of 10 s'1on the resin diluted with 30% by weight of aromati c solvent (Solvesso 150 ®)),

[0289] * stage 2 : in a second stage, the alkylphenol-aldehyde condensation resin resulting from the first stage was modified by a Mannich reaction by addition of 2 molar equivalents of formaldehyde and 2 molar equivalents of tallow dipropylenetriamine, known under the name N- (tallowalkyl)dipropylenetriamine and sold under the name Trinoram S®

[0290] The features of the modified alkylphenol-aldehyde resin obtained at the end of stage 2 are detailed in Table 1 below:

[0291] Table 1

[0292] (*) viscosity at 50° C : measured on the resin diluted with 70% by weight of Solvesso 150®, shear rate of 10 s’1, using a Haake RheoWin ® rheometer.

[0293] (* *) evaluation of the mean number of phenol nuclei per resin molecule or Nphe: measured by proton nuclear magnetic resonance;

[0294] - A cardanol-formaldehyde condensation resin sold by the company Cardolite under the trade name NX-4009 was used to prepare a comparative additive composition (A3 ),

[0295] - The amine-modified O-butyl-Tyrosol formaldehyde resin corresponding to the resin A-MR1 synthesized in Example 1 - Section B . l was used to prepare additive composition (A4) according to the present invention . Each composition (Al ) to (A4) was prepared by dissolving the corresponding resin with C I O Naphtha / heavy aromatic naphtha as solvent, the total amount of resin was 50% by weight.

[0296] 3 . Preparation of solutions containing 1 % by weight of additive composition

[0297] Four solutions S I to S4 were respectively prepared as follows: in a 100 ml storage j ar, 0.5g of each additive composition A l to A4 was mixed with 50g toluene. Each mixture was thoroughly agitated to ensure complete dissolution.

[0298] 4. Evaluation of additive efficiency at 10 ppm, 25 ppm and 50 ppm treatment rate

[0299] The efficiency in terms of preventing asphaltene dispersion of the additive compositions was assessed by mixing each solution (S I ) to (S4) in the diluted crude oil sample, at respective treatment rates (corresponding to the amount of active resin) of 50 ppm, 25 ppm and 10 ppm by weight.

[0300] For each treatment rate of 50 ppm, 25 ppm and 10 ppm by weight (amount of active resin), four centrifugation tubes were prepared by mixing 500 l of each formulation with 10 ml of n-hexane.

[0301] Each tube was vortexed for 30 seconds, and the tubes were then stored at room temperature for 360 hours.

[0302] The presence of sediments was assessed by comparing with a blank sample compri sing 500 pl of the diluted crude oil sample mixed with 10 ml of n-hexane (no additives), immediately after preparation and after storage thereof at room temperature for a duration detailed in table below.

[0303] The results obtained are detailed in Table 2 below, in terms of percentage of asphaltene dispersion which was calculated according to the equation below:

[0304] Percentage of asphaltene dispersed = 100 x (1 - Sa / S0) wherein: Sa is the sediment level from a tube dosed with additive compositions (Al ) to (A4) (active sample = 500 l of a formulation, which is obtained by mixing a solution of the corresponding additive composition (A l ) to (A4) with the diluted crude oil, mixed with 10 ml of n-hexane), Formulation resulting from mixing a solution of additive composition with the diluted crude oil sample

[0305] So is the sediment level from a tube with no additive (blank sample = 500 pl of the diluted crude oil sample mixed with 10 ml of n-hexane).

[0306] Table 2 :

[0307] The results detailed in Table 2 highlight that the additive compositions (Al ) and (A4) according to the present invention provide an effective prevention of asphaltene precipitation which is better and last longer than the one obtained with comparative compositions (A2) and (A3 ).

[0308] Especially, the additive composition (Al ) according to the present invention provides an effective prevention of asphaltene precipitation on long term-storage, as all compositions remained fully dispersed without any apparition of sediments.

Claims

CLAIMS1. Amine-modified substituted phenol-aldehyde resin chosen from :(i) an amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ) obtainable by a Mannich reaction of:- a 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ), with- at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms; and- at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms;- said 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ) being itself obtainable by condensation of: o at least one 4-(2-alkoxyethyl)phenol compound having the following formula (I) :Formula (I) wherein X denotes :• a linear or branched, saturated or unsaturated, hydrocarbon group containing from 1 to 24 carbon atoms, optionally interrupted with one or more heteroatoms, especially one or more heteroatoms chosen among oxygen, nitrogen, sulfur and / or phosphorous atoms,• a saturated or unsaturated, aromatic or non-aromatic, heterocyclic or cyclic moiety,o with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms,(ii) an amine-modified alkenylphenol-aldehyde resin (A-MR2) obtainable by a Mannich reaction of:- an alkenylphenol-aldehyde condensation resin (R2) with- at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms; and- at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms;- said alkenylphenol-aldehyde condensation resin (R2) being itself obtainable by condensation of: o at least one phenol substituted by a linear or branched alkenyl group having from 12 to 24 carbon atoms, o with at least one aldehyde having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms,(iii) and a mixture thereof.

2. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to claim 1 , wherein in said formula (I), X denotes a linear or branched, saturated or unsaturated, hydrocarbon group containing from 2 to 14 carbon atoms, more preferably from 2 to 12 carbon atoms, more preferably a linear or branched saturated hydrocarbon group containing from 2 to 14 carbon atoms, even more preferably from 2 to 12 carbon atoms.

3. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to claim 1 or 2, wherein said 4-(2-alkoxyethyl)phenol compound, corresponding to formula (I), is selected among the group consisted of: 4-(2-butoxyethyl)phenol; 4-(2-isobutoxyethyl)phenol; 4- (2 -(pentyl oxy )ethyl)phenol; 4-(2-(hexyloxy)ethyl)phenol; 4-(2-((4- methylpentyl)oxy)ethyl)phenol; 4-(2-((2-ethylhexyl)oxy)ethyl)phenol; 4-(2-(octyloxy)ethyl)phenol; 4-(2-(decyloxy)ethyl)phenol; 4-(2-((2- ethyloctyl)oxy)ethyl)phenol; 4-(2-(dodecyloxy)ethyl)phenol ; 4-(2-((ethyloxy)ethyl)phenol, and mixtures thereof, preferably selected among the group consisted of 4-(2-butoxyethyl)phenol; 4-(2- (hexyloxy)ethyl)phenol; 4-(2-((2-ethylhexyl)oxy)ethyl)phenol; 4-(2- (octyloxy)ethyl)phenol; and mixtures thereof.

4. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to any of the preceding claims, wherein said aldehyde used for obtaining said resin (Rl ) contains from 1 to 4 carbon atoms, preferably said aldehyde is chosen among the group constituted of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2- ethylhexanal, benzaldehyde and mixtures thereof, and more preferably said aldehyde is formaldehyde.

5. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to any of the preceding claims, wherein said resin (Rl ) is a 4-(2-(alkoxy)ethyl)phenol formaldehyde resin having the following formula (II) :wherein X has the same meaning as in formula (I) and n is an integer ranging from 1 to 14.

6. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to any of the preceding claims, wherein said resin (Rl ) is selected among the group constituted of:4-(2-butoxyethyl)phenol - formaldehyde resin, 4-(2-isobutoxyethyl)phenol - formaldehyde resin, 4-(2-((ethyloxy)ethyl)phenol - formaldehyde resin, 4-(2-((2-ethylhexyl)oxy)ethyl)phenol - formaldehyde resin, 4-(2-(hexyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(octyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(decyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(dodecyloxy)ethyl)phenol - formaldehyde resin, or mixtures thereof,preferably selected among the group constituted of: 4-(2-butoxyethyl)phenol - formaldehyde resin, 4-(2-((ethyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(hexyloxy)ethyl)phenol - formaldehyde resin, 4-(2-(octyloxy)ethyl)phenol - formaldehyde resin, or mixtures thereof.

7. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to any of the preceding claims, wherein said resin (Rl ) is obtainable by condensation of at least one 4-(2-(alkoxy)ethyl)phenol compound, as defined in any of claims 1 to 3 , with at least one aldehyde having from 1 to 8 carbon atoms, as defined in any of claims 1 and 4, in the presence of at least one acidic catalyst.

8. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to any of the preceding claims, wherein said at least one hydrocarbon compound having at least one alkylamine group is chosen from alkylpolyamines having at least one primary amine group, preferably at least two primary amine groups and more preferably three primary amine groups, and compri sing a fatty chain having from 12 to 24 carbon atoms, preferably from 12 to 22 carbon atoms.

9. Amine-modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A- MR1 ) according to any of the preceding claims, wherein said at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms used in the Mannich reaction is the same aldehyde as the one used for condensation resin (Rl ), in particular as defined in claim 4.

10. Amine-modified alkenylphenol-aldehyde resin (A-MR2) according to claim 1 , wherein said at least one phenol substituted by a hydrocarbon group corresponds to formula (Ii) below:wherein Xi denotes a linear of branched, alkenyl group containing from 12 to 24 carbon atoms, preferably from 12 to 18carbon atoms and more preferably from 14 to 16 carbon atoms, preferably containing 1 to 3 double bonds, in particular 2 double bonds.1 1 . Amine-modified alkenylphenol-aldehyde resin (A-MR2) according to claim 1 or 10, wherein said at least one phenol substituted by a hydrocarbon group having from 12 to 24 carbon atoms is cardanol .

12. Amine-modified alkenylphenol-aldehyde resin (A-MR2) according to any of claims 1 , 10 or 1 1 , wherein the aldehyde used for obtaining said resin (R2) contains from 1 to 4 carbon atoms, preferably said aldehyde is chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde and mixtures thereof, and more preferably said aldehyde is formaldehyde.13 . Amine-modified alkenylphenol-aldehyde resin (A-MR2) according to any of claims 1 , 10 to 12, wherein said at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms used in the Mannich reaction i s the same aldehyde as the one used for condensation resin (Rl ), in particular as defined in claim 12.

14. Amine-modified alkenylphenol-aldehyde resin (A-MR2) according to any of claims 1 , 10 to 13 , wherein said at least one hydrocarbon compound having at least one alkylamine group i s chosen from alkylpolyamines having at least one primary amine group, preferably at least two primary amine groups and more preferably three primary amine groups, and comprising a fatty chain having from 12 to 24 carbon atoms, preferably from 12 to 22 carbon atoms.

15. A method for preparing an amine-modified substituted phenol-aldehyde resin as define in any of claims 1 to 14, said method compri sing at least a step of reacting by a Mannich reaction at least:- a 4-(2-alkoxyethyl)phenol-aldehyde condensation resin (Rl ) as defined in any of claims 1 to 7 or an alkenylphenol-aldehyde condensation resin (R2) as defined in any of claims 1 and 10 to 12, with- at least one aldehyde and / or one ketone having from 1 to 8 carbon atoms, in particular as defined in claim 9 or 13 ; and- at least one hydrocarbon compound having at least one alkylamine group having from 1 to 30 carbon atoms, in particular as defined in claim 8 or 14.

16. The method as defined in claim 15, wherein said Mannich reaction i s conducted in an aromatic solvent, preferably selected from toluene, xylenes and Heavy Aromatic Naphta (HAN) solvents, and in the presence of at least one acid catalyst, in particular an alkyl benzene sulfonic acid, for example p-toluenesulfonic acid.

17. The method as defined in claim 15 or 16, wherein the Mannich reaction is carried out at a temperature ranging from 80°C to 140°C, in particular at a temperature of around 100°C.

18. Use of at least one amine-modified 4-(2-alkoxyethyl)phenol- aldehyde resin (A-MR1 ) as defined in any of claims 1 to 9 or as obtained by the method as defined in any of claims 15 to 17, and / or at least one modified alkenylphenol-aldehyde resin (A-MR2), as defined in any of claims 1 , 10 to 14 or as obtained by the method as defined in any of claims 15 to 17, as an asphaltene inhibitor, especially in petroleum products.

19. An additive composition comprising at least one amine- modified 4-(2-alkoxyethyl)phenol-aldehyde resin (A-MR1 ) as defined in any of claims 1 to 9 or as obtained by the method as defined in any of claims 15 to 17, and / or at least one modified alkylphenol-aldehyde resin (A-MR2) as defined in any of claims 1 , 10 to 14 or as obtained by the method as defined in any of claims 15 to 17.

20. The composition as defined in the preceding claim, wherein it further comprises one or more liquid organic solvent(s) chosen in the group constituted of: poly alkyl ethers, aliphatic hydrocarbons such as alkanes, aromatic solvents such as aromatic hydrocarbons and aromatic hetero-compounds, organic solvents derived from biomass, in particular oil s of vegetable origin and more preferably cashew nutshell liquid, and mixtures thereof.

21. A petroleum product containing:- a crude oil and / or at least one hydrocarbon fraction or at least one residue deriving from the distillation of a crude petroleum oil, and / or at least one bitumen; and- an additive composition as defined in any of claims 19 and 20.

22. Use of at least one composition as defined in any of claims 19 and 20 as an additive in a petroleum product, preferably for preventing or reducing the precipitation of asphaltenes.

23. A method for preventing the precipitation of asphaltenes present in a petroleum product, comprising a step of adding to said product an additive composition as defined in any of claims 19 and 20.

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