HYDROCARBON RESIN DERIVED FROM BIO-BASED AND / OR RECYCLED MATERIALS AND RUBBER COMPOSITION COMPRISING THIS HYDROCARBON RESIN

Abstract

The invention relates to a hydrocarbon resin based on an aromatic distillation cut (T100°C-140°C) obtained from the separation of the pyrolysis effluent from a styrenic feedstock, referred to as the "light compound-rich stream," and an aliphatic stream of bio-based origin. Fig 1

Description

Title of the invention: HYDROCARBON RESIN DERIVED FROM BIOSOURCED AND / OR RECYCLED MATERIALS AND RUBBER COMPOSITION COMPRISING THIS RESIN HYDROCARBON Technical field of the invention

[0001] The present invention relates to the field of hydrocarbon resins, rubber compositions comprising such resins, as well as vehicle tires comprising such rubber compositions. Prior art

[0002] It is known from the prior art that elastomers having a low glass transition temperature ("Tg") allow an improvement in terms of abrasion performance (WO 2015 / 043902) and are therefore very useful when seeking to obtain the best compromise between performance properties that are difficult to reconcile simultaneously, such as wear resistance and grip, which must be high, and rolling resistance, which must be low in order to minimize fuel consumption.

[0003] These low Tg elastomers have poor compatibility with hydrocarbon-based plasticizing resins typically used in vehicle tires.

[0004] However, the compatibility of the resins with the elastomeric matrix, and in particular their ability to disperse correctly in the mixture, is essential for them to play their role correctly. The compatibility of the resin with an elastomeric matrix depends, among other things, on properties such as the glass transition temperature and the softening point of the resin, these properties being dependent on the molar mass, the nature and the ratio of aromatic units to aliphatic units of the resin (see for example J. Appl Polym. Sci 2022 139(15) 51950). Resins comprising aliphatic and aromatic units and having high Tg make it possible, in particular, to modify the Tg of the mixture.

[0005] Such resins are well known in the state of the art. Document EP 0 936 229 teaches, for example, the manufacture of hydrocarbon resins from aliphatic and aromatic monomers in cationic polymerization, from petroleum-sourced streams. Documents WO2016 / 043851, US9139721 or FR2968006 describe hydrocarbon resins having high Tg. Document FR 3 099 166 describes a tire comprising a rubber composition comprising a specific hydrocarbon resin derived from petroleum fractions with improved road behavior at different temperatures.

[0006] If the performance of tires such as rolling resistance and wear resistance are key to limiting their environmental impact, it is also important to limit as much as possible the use of fossil resources during the manufacture of rubber articles.

[0007] Documents WO2022 / 101562 and WO2022 / 101563 describe the production of hydrocarbon resins from residues from the pyrolysis of rubber chips. These documents do not address the impact of these resins on the performance of the rubber compositions.

[0008] Continuing its research, the applicant discovered that a resin derived from bio-sourced and / or recycled resources made it possible to maintain, or even improve, key performances of rubber compositions usable in vehicle tires, thus being able to advantageously replace petro-sourced hydrocarbon resins. Detailed description of the invention

[0009] The invention relates to a hydrocarbon resin based on an aromatic distillation cut T100°C-140°C originating from the separation of the pyrolysis effluent of a styrenic feedstock, called “stream rich in light compounds”, and an aliphatic stream of biosourced origin, said resin having the following characteristics:

[0010] • a glass transition temperature (denoted Tg) ranging from 20°C to 140°C;

[0011] • a number-average molar mass of less than 5000 g / mol;

[0012] • a dispersity D less than 3;

[0013] • A rate of aromatic protons, determined by 1H NMR, between 0.5% mol and 20%mol;

[0014] • A rate of aliphatic protons, determined by 1H NMR, between 80% mol and 99.5%mol;

[0015] • A rate of ethylenic protons, determined by 1H NMR, less than or equal to 10%mol;

[0016] The sum of the aromatic, aliphatic and ethylenic proton levels being equal to 100%.

[0017] Preferably, the level of aromatic protons, determined by 1H NMR, is between 2 mol% and 20 mol%, preferably between 5 mol% and 20 mol%.

[0018] Preferably, the charge of styrenic compounds comprises at least 90% by weight of polystyrene, preferably at least 93% by weight of polystyrene, and preferably at least 95% by weight of polystyrene.

[0019] Preferably, the hydrocarbon resin according to the invention is obtained by a method comprising at least:

[0020] a. A step of preparing the charge of styrenic compounds so as to be able to feed this charge into the pyrolysis step;

[0021] b. A step of pyrolysis of the charge of styrenic compounds making it possible to obtain at least one gaseous effluent and one pyrolysis oil, said gaseous effluent comprising at least 20% by weight of aromatic compounds;

[0022] c. A step of separating the gaseous effluent into at least one stream rich in light compounds whose bubble point and dew point measured at atmospheric pressure are within the temperature range from 100°C to 140°C;

[0023] d. A resin synthesis step comprising a polymerization section supplied with the flow rich in light compounds from step c) and with a flow of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, followed by a finishing section and producing a polymerized effluent;

[0024] e. A treatment step comprising a section for separating the polymerized effluent from step d) into a solvent-rich effluent and a resin-rich effluent, and a drying section fed with the resin-rich effluent in order to produce a stream of hydrocarbon resins.

[0025] The invention also relates to a rubber composition based on at least one elastomer and one hydrocarbon resin according to the invention.

[0026] The rubber composition according to the invention preferably comprises a reinforcing filler and a crosslinking system.

[0027] The rubber composition according to the invention preferably comprises from 10 to 150 pce, preferably from 50 to 130 pce of silica.

[0028] The elastomer of the rubber composition according to the invention is preferably a diene elastomer.

[0029] The rubber composition according to the invention preferably comprises mainly a diene elastomer having a glass transition temperature Tg of less than -20°C, preferably between -20°C and -110°C.

[0030] The rubber composition according to the invention comprises at least 60 phr, preferably at least 70 phr, more preferably at least 80 phr of at least one diene elastomer chosen from the group consisting of polybutadiene, butadiene copolymers and mixtures of these elastomers.

[0031] Preferably, the butadiene copolymer is a butadiene-styrene copolymer.

[0032] The invention also relates to a vehicle tire comprising a rubber composition according to the invention or a resin according to the invention.

[0033] The vehicle bandage according to the invention preferably comprises a strip bearing comprising a hydrocarbon resin according to the invention or a rubber composition according to the invention. Definitions

[0034] The carbon-containing compounds mentioned in the description may be of fossil or bio-sourced origin. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This includes in particular polymers, plasticizers, fillers, etc.

[0035] The term "composition based on" designates a composition comprising the mixture and / or the product of the in situ reaction of the different basic constituents used, some of these constituents being able to react and / or being intended to react with each other, at least partially, during the different phases of manufacture of the composition or during the subsequent curing, which may modify the composition as it is initially prepared. Consequently, the compositions described below may be different in the uncrosslinked state and in the crosslinked state.

[0036] Unless expressly stated otherwise, all percentages (%) indicated are percentages by weight ("wt. %). Furthermore, any range of values ​​referred to as "between a and b" represents the range of values ​​extending from more than a to less than b (i.e., the limits a and b are excluded), while any range of values ​​referred to as "from a to b" refers to the range of values ​​extending from a to b (i.e., including the strict limits a and b).

[0037] By Cn compound is meant a compound comprising n carbon atoms. Similarly, by Cn-Cm compounds is meant a set of compounds comprising from n to m carbon atoms.

[0038] By heteroatom is meant an atom other than carbon or hydrogen, for example nitrogen, sulfur, oxygen.

[0039] A compound is said to be predominant when it represents more than 50% by weight of the compounds of the same nature. Thus, a predominant elastomer is an elastomer which represents more than 50% by weight relative to the total weight of the elastomers present. Hydrocarbon resin

[0040] The present invention relates to a hydrocarbon resin obtained from a charge of styrenic compounds and a flow of aliphatic compounds of biosourced origin, said resin having the following characteristics: • a glass transition temperature (noted Tg) ranging from 20°C to 140°C; • a number-average molar mass of less than 5000 g / mol, preferably in less than 4000 g / mol and preferably less than 3000 g / mol; • a dispersity D of less than 3, preferably less than 2.5 and in a manner preferred less than 2; • A rate of aromatic protons, determined by 1H NMR, between 0.5% mol and 20% mol, and preferably between 2% mol and 20% mol, preferably between 5% mol and 20% mol; • A level of aliphatic protons, determined by 1H NMR, between 80% mol and 99.5% mol, preferably between 80% mol and 98% mol, preferably between 80% mol and 95% mol; • A level of ethylenic protons, determined by 1H NMR, less than or equal to 10% mol, preferably less than or equal to 5% mol, preferably less than or equal to 4% mol,

[0041] the sum of the aromatic, aliphatic and ethylenic proton levels being equal to 100%.

[0042] The hydrocarbon resin according to the invention is based on an aromatic distillation cut T100°C-140°C originating from the separation of the pyrolysis effluent from a styrenic feedstock, called “stream rich in light compounds”, and an aliphatic stream of biosourced origin.

[0043] By styrenic compound filler is meant a filler which comprises styrene-based polymers, such as styrenic rubbers and polystyrene.

[0044] Preferably, the filler of styrenic compounds is a filler of styrenic compounds derived from plastic waste. Such a filler preferably comprises at least 90% by weight of polystyrene, preferably at least 93% by weight of polystyrene, and more preferably at least 95% by weight of polystyrene. The filler of styrenic compounds may comprise other compounds, in particular if it is derived from plastic waste. These other compounds may be, in a non-limiting manner, plastic compounds such as polyethylene, polypropylene, elastomers, organic materials such as paper, food, or inorganic materials such as glass, metal, sand.

[0045] The flow of aliphatic compounds comprises at least 5% by weight of terpene compounds, of biosourced origin.

[0046] The flow of aliphatic compounds is of biosourced origin. That is to say, it comes from biomass or is derived from products derived from biomass.

[0047] By derived from biomass, it is meant that the compounds are derived, after possible treatment, from plant, animal, fungal or microbe organisms. Preferably, the stream of aliphatic compounds is derived from plant organisms. By derived from products derived from biomass, it is meant that the biomass used to obtain the stream of aliphatic compounds may have undergone a treatment such as a biological treatment, based for example on the functioning of plants, animals, or microorganisms, a chemical treatment, such as for example a treatment in the presence acid, alkaline treatment, in the presence or absence of a catalyst, and / or physical treatment such as pressurization, heat treatment, electromagnetic treatment or microwave treatment. Obtaining the resin

[0048] The hydrocarbon resin according to the invention can be obtained by the process described below. Step a) of preparation

[0049] The charge of styrenic compounds is conditioned in a preparation step a) in order to be able to feed the pyrolysis step b). This preparation step may comprise grinding, degassing and heating operations in order to cause the plastic compounds to melt, for example in an extrusion device during which the temperature is gradually increased, the vapor effluents (water, light compounds generated by the partial decomposition of the polystyrenic charge) and the solid effluents (non-fusible debris such as metal debris, glass) are separated.

[0050] Preferably, the charge of styrenic compounds is gradually heated to a temperature between 100°C and 300°C, preferably between 150°C and 300°C and more preferably between 200°C and 300°C, this temperature making it possible to obtain the melting of the polystyrene, when such a compound is present, by limiting its thermal decomposition. Step b) of pyrolysis

[0051] The charge of styrenic compounds feeds a pyrolysis step making it possible to obtain at least one gaseous effluent and one pyrolysis oil, said pyrolysis oil comprising at least 20% by weight of aromatic compounds.

[0052] Pyrolysis means the thermal decomposition of compounds in an inert atmosphere.

[0053] The feedstock feeds a pyrolysis step, carried out at a temperature and pressure such that the depolymerization of the styrenic compounds into styrene oligomers and styrene monomer takes place. Preferably, the pyrolysis step is carried out at a temperature ranging from 300 to 900°C, preferably ranging from 300°C to 800°C.

[0054] The pyrolysis step is preferably carried out at a pressure ranging from 0.8 bar to 7.5 bar, preferably ranging from 1 bar to 6 bar and more preferably ranging from 1 bar to 4.5 bar.

[0055] Preferably, the pyrolysis step implements a microwave pyrolysis step. Such microwave pyrolysis usable for the pyrolysis of a charge of styrenic compounds is for example described in document WO 2020 / 202089.

[0056] The use of a microwave-assisted pyrolysis step makes it possible to achieve Higher heat transfer rates and reaction temperatures, which promote end-of-chain scission reactions and minimize the formation of styrene oligomers. A microwave pyrolysis step is also characterized by a lower temperature in the reaction mass than a conventional pyrolysis section. The lower temperatures in the reaction mass result in lower styrene oligomer evaporation rates and help avoid over-cracking the styrene product. Using a microwave pyrolysis step will reduce the formation of styrene oligomers compared to a conventional pyrolysis step.

[0057] The pyrolysis step produces at least a gaseous effluent and a pyrolysis oil. The gaseous effluent may also contain entrained liquid droplets. In addition to styrene oligomers, the gaseous effluent comprises the majority of the styrene monomer produced in the pyrolysis step, as well as gaseous light aromatic compounds under the operating conditions such as alpha-methyl-styrene, ethylbenzene, cumene and toluene.

[0058] The gaseous effluent comprises at least 20% by weight of aromatic compounds, preferably at least 20% by weight of styrene.

[0059] Preferably, the gaseous effluent comprises at most 10% by weight of ethylbenzene, preferably at most 5% by weight of ethylbenzene and preferably at most 3% by weight of ethylbenzene.

[0060] Preferably, the gaseous effluent comprises at least 10% by weight of compounds whose boiling point is higher than that of styrene.

[0061] The pyrolysis oil may also comprise solid elements, unfused polymers, produced during pyrolysis, or debris not separated in the feedstock preparation step. This flow preferably feeds a separation section in which the possible solid fraction is separated from the liquid fraction, the latter being able to be recycled in a mixture with the feed for the pyrolysis step or used in step d) of resin synthesis.

[0062] The pyrolysis step can be carried out in a pyrolysis reactor, and can be operated continuously, semi-continuously or in batch processing. Such reactors are well known to those skilled in the art. Step c) of separation

[0063] A separation step c) is fed at least with the gaseous effluent from step b) and produces at least one stream rich in light compounds, one stream rich in styrene and one stream rich in heavy compounds.

[0064] The stream rich in light compounds mainly comprises compounds lighter than styrene, in particular toluene and ethylbenzene compounds.

[0065] The flow rich in light compounds is a T100°C-140°C cut, preferably a Tl cut 10°C-140°C. By "Ta°Cb°C Cut" is meant that the bubble point and dew point of the cut, measured at atmospheric pressure, are in the temperature range from a°C to b°C. The stream rich in light compounds therefore has a bubble point and a dew point measured at atmospheric pressure in the temperature range from 100 to 140°C, preferably from 110 to 140°C.

[0066] Preferably, the cumulative content of toluene and ethylbenzene in the stream rich in light compounds is at least equal to 60% by mass, preferably is at least equal to 70% by mass, and preferably is at least equal to 75% by mass.

[0067] The styrene-rich stream comprises predominantly aromatic compounds comprising from 6 to 9 carbon atoms. The separation step c) is carried out so that the styrene-rich stream comprises at least 99% by mass of styrene and the styrene recovery rate, i.e. the ratio of the styrene flow rate in the aromatic-rich stream to the styrene flow rate in the gaseous effluent from step b) is at least equal to 90%, preferably at least equal to 95% and more preferably at least equal to 97%.

[0068] Preferably, the stream rich in aromatic compounds is a T140°C-150°C cut, preferably a T144°C-146°C cut.

[0069] The flow rich in heavy compounds mainly comprises compounds heavier than styrene, as well as non-depolymerized styrenic compounds, and in particular styrene oligomers when the feed comprises polystyrene.

[0070] The stream rich in heavy compounds is a T150°C-220°C cut, preferably a T160°C-210°C cut.

[0071] Preferably, the alpha-methylstyrene content in the stream rich in heavy compounds is at least equal to 60% by mass, preferably is at least equal to 70% by mass, preferably is at least equal to 80% by mass and very preferably is at least equal to 90% by mass.

[0072] Preferably, separation step c) is carried out by distillation.

[0073] In a first variant of this preferred arrangement, a first column fed with the gaseous effluent from step b) separates this effluent into a stream rich in light compounds and a raffinate, the latter being separated by means of a second column into a stream rich in styrene and a stream rich in heavy compounds.

[0074] In a second variant of this preferred arrangement, the separation is carried out in a single distillation column. In this variant, at the top of the column, the vapor effluent is cooled to a temperature between 30°C and 50°C, preferably between 35°C and 45°C. The condensed liquid fraction is returned to the top of the column as reflux, while the vapor fraction is then subcooled to a temperature between -5°C and 10°C, preferably between -5°C and 5°C in order to condense any styrene entrained with the light compounds. The condensed stream after subcooling is returned to the top of the column as reflux. The residual vapor fraction constitutes the stream rich in light compounds. This stream can then be recovered, for example in the form of energy. An initial cooling allows maximum use of cooling water at ambient temperature as cold utility and minimizes the use of specific cold utility to obtain subcooling, which has a favorable impact on the life cycle analysis of the process.

[0075] In this variant, the distillation column is operated at a pressure of between 0.1 and 2.0 bara, preferably between 0.5 and 1.5 bara and more preferably between 0.5 and 1.1 bar, the operating pressure being understood as the pressure measured at the top of the column. By "bara" is meant absolute bar, as opposed to a pressure expressed in relative bar, commonly noted "barg" according to the English notation "bar gauge".

[0076] In this variant and preferably, the distillation column is fed at the bottom of the column with at least the gaseous effluent from step b) and produces at the top of the column a flow rich in light compounds, at the bottom a flow rich in heavy compounds, and by a lateral withdrawal a flow rich in styrene, said column having as its only heat input said gaseous effluent from step b).

[0077] The gaseous effluent from step b) is at high temperature, preferably at a temperature above 300°C. This temperature is sufficient so that the column does not require any further heat input.

[0078] By feeding the feedstock at the bottom of the column, the feedstock is rapidly cooled, thus limiting any potential styrene polymerization reactions. This feedstock also allows for better management of so-called heavy compounds. Indeed, the absence of a recirculation system at the bottom of the column, usually used to maintain the temperature of the distillation column, greatly limits the risk of fouling by so-called heavy compounds, which are particularly viscous.

[0079] The distillation column implemented in this variant of step c) of the process comprises from 5 to 20 theoretical stages, preferably at most 15 theoretical stages, preferably from 8 to 12 theoretical stages.

[0080] A styrene-rich stream is withdrawn onto an intermediate tray. This withdrawal tray is located in the lower third of the distillation column, preferably 1 to 3 theoretical stages from the bottom tray. This withdrawal at a low position in the column, slightly removed from the bottom tray, limits the entrainment of heavy compounds in the styrene-rich stream and thus limits the risk of fouling subsequent equipment.

[0081] Preferably, and in order to further limit the risk of polymerization, an inhibitor of polymerization of styrene into polystyrene, such as 2,2,6,6-tetramethyl-4-oxopiperidinooxy, may be fed into the distillation column of step c), or the distillation columns of step c) of the process, preferably at the column head.

[0082] Toluene and ethylbenzene type compounds, which do not react in step d) of resin synthesis, can be used as solvent in this synthesis step, which makes it possible to avoid the addition of a solvent of external origin to the process. Step d) of resin synthesis

[0083] A step d) of resin synthesis comprising a polymerization section is fed by the flow rich in light compounds from step c) and by a flow of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, followed by a finishing section and producing a polymerized effluent.

[0084] The resin synthesis step mainly consists of oligomerizing the monomers included in the stream rich in light compounds from step c), in particular styrene and compounds lighter than styrene included in the stream rich in light compounds, and the stream of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, and thus of preparing new oligomeric materials of resin type, by controlling the macrostructure, in particular by limiting the content of low molecular weight compounds, such as monomers, dimers and trimers, and high molecular weight compounds, i.e. whose molecular weight is greater than 5000 g / mol, as well as the microstructure. By dimer is meant a compound comprising two monomers linked by a covalent bond.A dimer can be a homodimer, i.e., the combination of two identical monomers, a heterodimer, i.e., the combination of two different monomers, or a mixture of homodimer and heterodimer. A trimer means a compound comprising three monomers linked by a covalent bond. A trimer can be a homotrimer, i.e., the combination of three identical monomers, a heterotrimer, i.e., the combination of at least two different monomers, or a mixture of homotrimer and heterotrimer.

[0085] By terpene compounds of biosourced origin is meant compounds of the terpene family which are unsaturated hydrocarbons of plant origin. The terpene compounds useful for the purposes of the invention are preferably chosen from terpenes comprising at most 20 carbon atoms, preferably chosen from the compounds limonene, alpha-pinene, beta-pinene, myrcene, farnesene and their mixtures, preferably chosen from the compounds limonene, alpha-pinene, beta-pinene and their mixtures and preferably are limonene.

[0086] Limonene is a terpene hydrocarbon which can be obtained, in particular, from citrus peels or by microbial fermentation.

[0087] By feeding the resin synthesis step with the stream rich in light compounds from step c) and a stream of aliphatic compounds, it is possible to control the ratio of aromatic and aliphatic units in the resin produced and thus adapt the resin to the polymer matrix in which this resin is intended to be incorporated. It is thus possible to obtain a resin having excellent compatibility derived from renewable and / or recycled resources.

[0088] Thus, the method makes it possible to use the stream rich in light compounds according to the parameters sought for the resin produced, which allows great versatility. Preferably, when the stream rich in light compounds is produced by distillation in step c), no other treatment is required before using this stream for the production of resin.

[0089] The mass ratio of the flow from step c) to the flow of aliphatic compounds feeding step d) is adjusted to regulate the proportion of aliphatic and aromatic protons in the resin.

[0090] Preferably, the polymerization section is also supplied with a stream of solvent chosen from aliphatic, aromatic, halogenated solvents and their mixtures.

[0091] Preferably, the solvent chosen from aliphatic, aromatic, halogenated solvents and their mixtures is chosen from C7-C10 aromatic solvents, C6-C8 aliphatic solvents and C1-C2 chlorinated solvents and their mixtures, preferentially from toluene, methylcyclohexane and dichloromethane.

[0092] Preferably, a fraction of the pyrolysis oil from step b) is used as solvent stream. Preferably, the process is fed only with the feedstock of styrenic compounds and the stream of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, the solvent required in step d) being provided by at least one stream from step c) and / or at least one fraction of the pyrolysis oil from step b), preferably at least one fraction of the pyrolysis oil from step b) feeding step d).

[0093] Preferably, synthesis step d) is fed by the flow from step c) and by a flow of aliphatic compounds comprising at least 5% by weight of terpene compounds and by a flow of solvent such that the monomer content is between 50 and 75% by weight. Thus, the solvent flow rate can be adapted so as to adjust the monomer content in step d). This content makes it possible to limit the exothermicity within step d), while making it possible to obtain a polymerized effluent whose viscosity allows it to be conveyed to the downstream steps of the process.

[0094] Preferably, the resin obtained by the process comprises less than 1% by weight of compounds whose molecular mass is greater than 5000 g / mol. Preferably Typically, the resin obtained comprises at most 50% by weight of dimeric and trimeric compounds.

[0095] The polymerization section is operated in the absence of catalyst, or in the presence of an acid catalyst, of the Bronsted acid, Lewis acid or Friedel-Crafts type, said catalyst being able to be homogeneous or heterogeneous. Preferably, said polymerization section is operated in the presence of an acid catalyst, of the Bronsted acid or Lewis acid type. Said polymerization section can also be operated in the presence of ligands, a co-catalyst, and / or a cationic polymerization initiator, for example of the proton or carbocation generator type.

[0096] Preferably, the catalyst is a Lewis acid comprising ligands from the aluminum halide family. Preferably, these ligands are chosen from aluminum chlorides, for example aluminum trichloride, alkylaluminum chlorides, such as diethylaluminum chloride and ethylaluminum dichloride, and arylaluminum chlorides, such as phenylaluminum chloride. Preferably, the catalyst also comprises a co-ligand with Lewis base character, making it possible to modulate the acid character of the Lewis acid ligand, of the aliphatic ether type (for example diethyl ether, dibutyl ether), aromatic ether (diphenyl ether), or ester (ethyl acetate) or alkyl amines (triethylamine) or arylamines (diphenylamine, triphenylamine). The polymerization section can also be operated with ligands containing phosphorus, sulfur or any other heteroatom.

[0097] The polymerization section is preferably operated at a temperature ranging from -60°C to +300°C, preferably ranging from -60°C to +120°C, very preferably ranging from -50°C to +100°C and preferably ranging from -40°C to +90°C and very preferably ranging from +20 to +90°C.

[0098] The average residence time in the polymerization section is preferably between 0.25 h and 7 h, preferably between 0.5 h and 4 h. When the polymerization section is operated continuously, the average residence time in said section is the ratio of the reaction volume of said section to the volume flow rate of the feeds of the section.

[0099] The quantity of catalyst, including the possible ligands and co-ligands, is preferably within a range from 0.05% to 5% by weight relative to the weight of olefinic monomers entering the polymerization section, and preferably ranges from 0.1% to 2% by weight relative to the weight of olefinic monomers entering the polymerization section.

[0100] The stream from the polymerization section is then treated in a finishing section producing a polymerized effluent.

[0101] This finishing section allows the polymerization reaction to be stopped by the addition of a compound which deactivates the catalyst and stops the chains still growing. The finishing section is preferably implemented by contacting with a flow comprising a stopper compound chosen from water, a C1-C3 alcohol and their mixtures, preferably chosen from water, methanol, ethanol and their mixture, very preferably water at a temperature between 5 and 80°C, preferably at a temperature between 15 and 30°C (for example at room temperature), followed by separation by phase decantation of a polymerized effluent and an effluent mainly comprising the stopper compound.

[0102] The molar ratio of stopper compound to polymerization catalyst in the finishing section is at least 1.1, preferably at least 2.

[0103] When the stopper compound is water, the volume ratio of reaction medium to water in the finishing section is preferably between 20:1 and 10:1, preferably between 10:1 and 5:1 and more preferably between 5:1 and 1:1.

[0104] The flow from the polymerization section and the flow comprising the stopper compound are brought into contact with stirring for a period preferably ranging from 5 min to 2 h, preferably ranging from 15 min to 45 min, in order to promote contact between the stopper compound and the reaction medium.

[0105] At the end of this stirring phase, a decantation phase is carried out in order to separate on the one hand an organic phase constituting the polymerized effluent containing mainly the resins, the solvent, the unconverted monomers, dimers, trimers and oligomers of low molecular weight and a phase containing mainly the stopper compound, the catalytic residues and organic residues soluble in the stopper compound.

[0106] The decantation phase is preferably carried out for a period ranging from 5 min to 4 h, preferably ranging from 15 min to 2 h.

[0107] The phase containing mainly the stopper compound can then be treated in order to recycle the stopper compound in the finishing section.

[0108] The polymerized effluent then feeds the treatment stage. Step e) treatment of the polymerized effluent

[0109] The method comprises a step of treating the polymerized effluent from step d) comprising a section for separating a solvent-rich effluent and a resin-rich effluent, and a drying section fed with the resin-rich effluent in order to produce the resins.

[0110] The implementation of the polymerized effluent treatment step in the process makes it possible to adjust the characteristics of the resins, in particular by eliminating low molecular mass oligomers (dimers, trimers, tetramers for example) and by reducing the dispersity, in order to control the properties of the resins obtained (glass transition temperature for example).

[0111] The separation section of a solvent-rich effluent and a resin-rich effluent makes it possible, on the one hand, to recover a majority of the solvent and unconverted monomers for subsequent use, preferably for recycling them in the resin synthesis stage of the process, and on the other hand to concentrate the resins in the resin-rich effluent.

[0112] The separation section can be carried out by any method known to those skilled in the art, in particular and preferably by evaporation, distillation, coagulation of resins, liquid-liquid extraction or a combination of these methods.

[0113] In a preferred arrangement, the separation section is carried out by distillation in at least one distillation column so as to produce a solvent-rich effluent at the top and a resin-rich effluent at the bottom. This section makes it possible to eliminate the residual monomers and oligomers at the top as well as the majority of the solvent used in the resin synthesis step and thus to adjust the macrostructure of the resins as well as its properties, for example the glass transition temperature noted Tg, in particular by reducing the dispersity by eliminating the low molecular weight compounds. The resin-rich effluent comprises the majority of the resins feeding the separation section. The resin recovery rate, corresponding to the ratio of the flow rate of resins in the resin-rich effluent to the flow rate of resins in the feed of the separation section, is preferably greater than 80%, preferably greater than 90%.This recovery rate can be adjusted by increasing the number of separation stages in the separation section, or by adjusting the operating parameters of said section, for example the reflux rate.

[0114] In another preferred arrangement, the separation section is carried out by coagulation of the resins. In this arrangement, the polymerized effluent from step d) is brought into contact with a coagulation solvent in which the resins are not soluble in order to precipitate them. The coagulation solvent solubilizes the residual monomers, the solvent used in the resin synthesis step and the low molecular weight oligomers.

[0115] The coagulation solvent is preferably chosen from polar protic or aprotic solvents with a low boiling point such as alcohols, for example methanol, ethanol and isopropanol, acetone, ethers, for example tetrahydrofuran (denoted THF) and dioxane.

[0116] The coagulation separation section is preferably operated with a coagulation solvent / medium to be coagulated volume ratio ranging from 1:1 to 10:1, preferably ranging from 2:1 to 5:1. The coagulation separation section is preferably operated at a temperature ranging from 5°C to 40°C.

[0117] The stream comprising the coagulation solvent, constituting the solvent-rich effluent, can then be recycled, for example to the resin synthesis stage, by undergoing beforehand, if necessary, a purification treatment step.

[0118] In another preferred arrangement, the separation section is carried out by liquid-liquid extraction. In this arrangement, the polymerized effluent from step d) is washed with a stream comprising mainly water. This extraction can be carried out in one or more stages, preferably in one to three stages.

[0119] Liquid-liquid extraction can also be carried out upstream of a separation by distillation or by coagulation of the resins as described previously.

[0120] In another preferred arrangement, the separation section is carried out by evaporation, for example by evaporation in a wiped film evaporator.

[0121] The viscosity of the resin-rich effluent depends on the resin content in this effluent and its temperature. These contents and temperatures are therefore adjusted so that this effluent can be transported to the drying section. One can seek to maintain a high temperature to have a high resin content while maintaining a viscosity of the effluent allowing its transport, taking care to remain below the temperatures at which the resins degrade thermally.

[0122] The resin-rich effluent then feeds a drying section in which it is filtered and then dried. At the end of the drying step, the dried resins have a residual solvent content (grouping together the solvent(s) used in the synthesis step as well as the solvent(s) optionally used in the separation section) of less than 3% by weight, preferably less than 1.5% by weight and preferably less than 0.8% by weight relative to the mass of resins. The dried resins have a residual content of free monomers of less than 5% by weight, preferably less than 2% by weight and preferably less than 1% by weight relative to the mass of resins.

[0123] The content of the hydrocarbon resin in the rubber composition may be in a range of 15 phr to 150 phr, 25 phr to 120 phr, 40 phr to 115 phr, 50 phr to 110 phr, and 65 phr to 110 phr. Below 15 phr of the present hydrocarbon resin, the effect of the present hydrocarbon resin becomes insufficient and the rubber composition may have adhesion problems. Above 150 phr, the composition may have manufacturing difficulties in terms of easily incorporating the present hydrocarbon resin into the composition. Rubber composition

[0124] The present invention also relates to a rubber composition based on at least one elastomer and a hydrocarbon resin according to the invention. Said rubber composition may further comprise various optional components, well known to those skilled in the art. Some of them are also described below. Elastomer

[0125] The rubber composition according to the invention comprises at least one elastomer, preferably diene. By diene type elastomer, it is recalled that it should be understood that an elastomer is derived at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers carrying two carbon-carbon double bonds, conjugated or not).

[0126] These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". "Essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a content of units or patterns of diene origin (conjugated dienes) which is greater than 15% (mol %); thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins such as EPDM do not fall within the preceding definition and can in particular be described as "essentially saturated" diene elastomers (low or very low content of patterns of diene origin, always less than 15% (mol %)). The diene elastomers included in the rubber composition according to the invention are preferably essentially unsaturated.

[0127] The term diene elastomer capable of being used in the rubber compositions in accordance with the invention is particularly understood to mean: a. any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms; b. any copolymer of a diene, conjugated or not, having from 4 to 18 carbon atoms and at least one other monomer.

[0128] The other monomer may be ethylene, an olefin or a diene, conjugated or not.

[0129] Suitable conjugated dienes are conjugated dienes having from 4 to 12 atoms. of carbon, in particular 1,3-dienes, such as 1,3-butadiene and isoprene.

[0130] Suitable olefins are vinylaromatic compounds having from 8 to 20 carbon atoms and aliphatic α-monoolefins having from 3 to 12 carbon atoms.

[0131] Suitable vinylaromatic compounds include, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyl-toluene", para-tert-butylstyrene.

[0132] Suitable aliphatic α-monoolefins include α-monoolefins acyclic aliphatics having from 3 to 18 carbon atoms.

[0133] The diene elastomer is preferably a diene elastomer of the highly unsaturated type, in particular a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably chosen from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-butadiene-styrene copolymers (SBIR), ethylene-butadiene copolymers (EBR) and blends of such copolymers.

[0134] The above diene elastomers may, for example, be block, random, sequenced, microsequenced, and may be prepared in dispersion or in solution; they may be coupled and / or star-shaped or even functionalized with a coupling and / or star-shaped or functionalizing agent, for example epoxidized.

[0135] By "isoprene elastomer" is meant a homopolymer or a copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR) which can be plasticized or peptized, synthetic polyisoprenes (IR), the various copolymers of isoprene, in particular copolymers of isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR), and mixtures of these elastomers.

[0136] According to a particularly preferred embodiment of the invention, the elastomer is a diene elastomer having a glass transition temperature Tg of less than -20°C, preferably between -20°C and -110°C, more preferably between -60°C and -110°C, more preferably between -60°C and -90°C. Such elastomers are known to those skilled in the art and described for example in documents WO2015 / 185394 and WO2017 / 168099.

[0137] Preferably, the predominant diene elastomer is selected from the group consisting of polybutadiene, butadiene copolymers and blends of these elastomers, and more preferably from the group consisting of polybutadiene, butadiene and styrene copolymers and blends of these elastomers.

[0138] The butadiene copolymer is preferably a copolymer of butadiene and a vinylaromatic monomer. Suitable vinylaromatic compounds include, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyl-toluene", para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinyl-mesitylene, divinylbenzene, vinylnaphthalene. Preferably, the vinylaromatic monomer of the copolymer of butadiene and vinylaromatic monomer is styrene.

[0139] According to this embodiment, the predominant elastomer, preferably diene, having a very low Tg, is present in the composition at a content preferably greater than or equal to 60 phr, more preferably greater than or equal to 70 phr and even more preferably greater than or equal to 80 phr. More preferably, the composition comprises 100 phr of elastomer having a very low Tg as defined above. Reinforcing filler

[0140] The rubber composition according to the invention preferably comprises a reinforcing filler. Any type of reinforcing filler known for its ability to reinforce an elastomeric composition suitable for the manufacture of tires may be used, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, or a blend of these two types of filler, in particular a blend of carbon black and silica.

[0141] Suitable carbon blacks are all carbon blacks, in particular HAF, ISAF, SAF type blacks conventionally used in tires (so-called tire grade blacks). Among the latter, mention will be made more particularly of reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), such as for example blacks NI 15, N134, N234, N326, N330, N339, N347, N375, or even, depending on the intended applications, blacks of higher series (for example N660, N683, N772). The carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example applications WO 97 / 36724 or WO 99 / 16600). The BET specific surface area of ​​carbon blacks is measured according to standard D6556-10 [multi-point method (minimum 5 points) - gas: nitrogen - relative pressure range P / P0: 0.1 to 0.3].

[0142] By "reinforcing inorganic filler" is meant in the present application, by definition, any inorganic or mineral filler (whatever its color and its natural or synthetic origin), also called "white" filler, "light" filler or even "non-black filler" as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other words capable of replacing, in its reinforcing function, a conventional pneumatic grade carbon black; such a filler is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface.

[0143] Suitable inorganic reinforcing fillers are, in particular, mineral fillers of the siliceous type, in particular silica (SiO2), or of the aluminous type, in particular alumina (A12O3). The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface area and a CTAB specific surface area both of less than 450 m2 / g, preferably from 30 to 400 m2 / g. Examples of highly dispersible precipitated silicas (known as "HDS") include "Ultrasil 7000" and "Ultrasil 7005" silicas from Degussa, "Zeosil 1165MP", "1135MP" and "1115MP" silicas from Rhodia, "Hi-Sil EZ150G" silica from PPG, "Zeopol 8715", "8745" and "8755" silicas from Huber, and high specific surface area silicas as described in application WO 03 / 16837.

[0144] The physical state in which the reinforcing inorganic filler is present is in different, whether in the form of powder, microbeads, granules, beads or any other suitable densified form. Of course, reinforcing inorganic filler also means mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers.

[0145] The reinforcing inorganic filler used, in particular if it is silica, preferably has a BET surface area of ​​between 45 and 400 m2 / g, more preferably between 60 and 300 m2 / g.

[0146] Preferably, the rubber composition according to the invention comprises from 1 to 100 phr, more preferably from 1 to 80 phr and more preferably from 1 to 60 phr of carbon black, the optimum being, in a known manner, different depending on the particular applications targeted: the level of reinforcement expected on a bicycle tire, for example, is of course lower than that required on a tire capable of rolling at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for a utility vehicle such as a heavy goods vehicle. In a preferred arrangement, the reinforcing filler mainly comprises carbon black, and preferably consists of carbon black.

[0147] Preferably, the rubber composition according to the invention comprises from 10 to 150 phr, preferably from 50 to 130 phr of silica. In a preferred arrangement, the reinforcing filler mainly comprises silica and preferably consists of silica.

[0148] To couple the reinforcing inorganic filler to the elastomer, it is possible optionally to use in a known manner an at least bifunctional coupling agent (or bonding agent) intended to ensure a sufficient connection, of a chemical and / or physical nature, between the inorganic filler (surface of its particles) and the elastomer, in particular organosilanes, or bifunctional polyorganosiloxanes.

[0149] It is possible to use in particular polysulfurized silanes, called "symmetrical" or "asymmetrical" depending on their particular structure, as described for example in applications WO03 / 002648 (or US 2005 / 016651) and WO03 / 002649 (or US 2005 / 016650).

[0150] Examples of polysulfurized silanes that may be mentioned include more particularly bis-(alkoxyl(Cl-C4)-alkyl(Cl-C4)silyl-alkyl(Cl-C4)) polysulfides (in particular disulfides, trisulfides or tetrasulfides), such as bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides. Among these compounds, bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C2H5O)3Si(CH2)3S2]2 or bis-(triethoxysilylpropyl) disulfide, abbreviated to TESPD, of formula [(C2H5O)3Si(CH2)3S]2. Preferred examples include polysulfides (especially di sulfides, trisulfides or tetrasulfides) of bis-(monoalkoxyl(Cl-C4)-dialkyl(Cl-C4)silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide as described in patent application US 2004 / 132880.

[0151] As coupling agent other than polysulfurized alkoxysilane, mention will be made in particular of bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides as described in patent applications WO 02 / 30939 and WO 02 / 31041, or silanes or POS carrying azo-dicarbonyl functional groups, as described for example in patent applications WO 2006 / 125532, WO 2006 / 125533, WO 2006 / 125534.

[0152] In the rubber compositions in accordance with the invention, the content of coupling agent is preferably in a range from 5 to 18% by weight relative to the quantity of silica, preferably in a range from 8 to 12% by weight relative to the quantity of silica.

[0153] Those skilled in the art will understand that, as a filler equivalent to the reinforcing inorganic filler described in this paragraph, a reinforcing filler of another nature, in particular organic, could be used, provided that this reinforcing filler is covered with an inorganic layer such as silica, or else comprises functional sites on its surface, in particular hydroxyl sites, making it possible to establish the bond between the filler and the elastomer in the presence or absence of a covering or coupling agent. Crosslinking system

[0154] The rubber composition according to the invention comprises a sulfur-based crosslinking system comprising a metal oxide, a stearic acid derivative and a vulcanization accelerator. This is then referred to as a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or a sulfur-donating agent.

[0155] Sulphur is used at a rate ranging from 1 to 20 pce, preferably ranging from 1 to 10 pce.

[0156] The vulcanization accelerator is used at a preferential rate such that the sulfur / vulcanization accelerator mass ratio is less than or equal to 4.

[0157] Any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur may be used as an accelerator, in particular accelerators of the thiazole type and their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate types. Examples of such accelerators include the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N,N-dicyclohexyl-2-benzothiazyl sulfenamide ("DCBS"), N-tert-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-tert-butyl-2-benzothiazyl sulfenimide ("TBSI"), tetrabenzylthiuram disulfide ("TBZTD"), zinc dibenzyldithiocarbamate ("ZBEC") and mixtures of these compounds.

[0158] The mass ratio of metal oxide to stearic acid derivative in the crosslinking system is less than 4, and preferably less than 3. The metal oxide is preferably zinc oxide.

[0159] The crosslinking system may also optionally comprise a vulcanization retarder.

[0160] The rubber compositions may preferably comprise additives commonly used in elastomeric compositions particularly intended for the manufacture of vehicle tires, such as, for example, pigments, protective agents, such as antiozonant waxes, chemical antiozonants or antioxidants, plasticizing agents other than those described above, antifatigue agents, reinforcing resins, or acceptors (for example, a phenolic novolak resin) or donors (for example HMT or H3M) of methylene.

[0161] The rubber compositions may further comprise a plasticizer system. This plasticizer system may be composed of a hydrocarbon-based resin having a Tg greater than 20°C, in addition to the specific hydrocarbon resin described above, and / or a plasticizer oil. Preparation of rubber compositions

[0162] The rubber composition in accordance with the invention is manufactured in suitable mixers, using preparation phases well known to those skilled in the art: - a thermomechanical working or mixing phase, which can be carried out in a single thermomechanical step during which all the necessary constituents, in particular the elastomeric matrix, the hydrocarbon resin, the fillers, and any other various additives, are introduced into a suitable mixer such as a conventional internal mixer (for example of the 'Banbury' type). The incorporation of the filler into the elastomer can be carried out in one or more stages by thermomechanical mixing. In the case where the filler, in particular carbon black or silica, is already incorporated in whole or in part into the elastomer in the form of a masterbatch as described, for example, in the applications WO 97 / 36724 or WO 99 / 16600, it is the masterbatch which is directly mixed and where appropriate the other elastomers or fillers present in the composition which are not in the form of masterbatch are incorporated, as well as any other various additives.

[0163] Thermomechanical mixing is carried out at high temperature, up to a maximum temperature of between 110°C and 200°C, preferably between 130°C and 185°C, for a duration generally of between 2 and 10 minutes. - a second phase of mechanical work is then carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first phase to a lower temperature, typically below 120°C, for example between 40°C and 100°C.

[0164] The possible crosslinking system will be added during the second phase. For example, a crosslinking system based on polyacids or polydienophiles will typically be added during the first phase. A crosslinking system based on peroxides or sulfur will typically be added during the second phase.

[0165] The final composition thus obtained can then be calendered, for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or even extruded in the form of a semi-finished (or profiled) rubber product.

[0166] The composition may be either in the raw state (before crosslinking or vulcanization), or in the cured state (after crosslinking or vulcanization), and may be a semi-finished product which may be used in a tire.

[0167] The curing can be carried out, in a manner known to those skilled in the art, at a temperature generally between 130°C and 200°C, under pressure, for a sufficient time which can vary for example between 5 and 90 min depending in particular on the curing temperature, the crosslinking system adopted, the crosslinking kinetics of the composition considered or even the size of the tire. Vehicle bandage

[0168] The present invention also relates to vehicle tires comprising a rubber composition based on at least one elastomer and a hydrocarbon resin according to the invention.

[0169] The vehicle tire may be a pneumatic or non-pneumatic tire. By non-pneumatic, it is meant that this tire is capable of supporting the load of the vehicle by a means other than a pressurized inflation gas, for example by means of stays.

[0170] The vehicle tire according to the invention will be chosen from, without limitation, tires intended to equip a two-wheeled vehicle, a passenger vehicle, a “heavy load” vehicle (i.e., a subway, a bus, off-road vehicles, heavy load transport vehicles, such as trucks, tractors or trailers), an aircraft, construction equipment, a heavy agricultural vehicle or a handling vehicle.

[0171] Preferably, the pneumatic tire according to the invention comprises a strip tread comprising a rubber composition according to the invention or a hydrocarbon resin according to the invention. In a manner known to those skilled in the art, the tread is the part of the pneumatic tire which circumferentially surrounds this tire and ensures contact with the rolling surface. Description of figures

[0172] [Fig.l] [Fig.l] represents a schematic view of the method according to the invention.

[0173] A charge of styrenic compounds (1) feeds a step a) of preparation of the charge of styrenic compounds so as to be able to feed (2) this charge in step b) of pyrolysis. Step b) of pyrolysis of the charge of styrenic compounds makes it possible to obtain at least one gaseous effluent (3) and one pyrolysis oil (4), said gaseous effluent (3) comprising at least 20% by weight of aromatic compounds.

[0174] The gaseous effluent (3) is then treated in a separation step c) in which it is separated into at least one stream rich in light compounds (5) whose bubble point and dew point measured at atmospheric pressure are within the temperature range from 100°C to 140°C.

[0175] The flow (5) feeds a step d) of resin synthesis comprising a polymerization section also fed at least by a flow (6) of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, and optionally by a flow of solvent (7), the polymerization section being followed by a finishing section producing a polymerized effluent (8).

[0176] The polymerized effluent (8) feeds a treatment step e) comprising a section for separating the polymerized effluent (8) from step d) into a solvent-rich effluent (9) and a resin-rich effluent, and a drying section fed with the resin-rich effluent in order to produce a stream of hydrocarbon resins (10). Measurement methods Glass transition temperature

[0177] The glass transition temperature Tg is measured in a known manner by differential scanning calorimetry, or DSC (Differential Scanning Calorimetry), for example and unless otherwise specified, according to ISO 11357-2 of 2014. Macrostructure (Mw, Mn, Mz and D)

[0178] The macro structure (mass-average molar mass, number-average molar mass, centrifugation average molar mass and polydispersity index, respectively denoted Mw, Mn, Mz and D) is determined by size exclusion chromatography (SEC) as indicated below. The Mz reflects the thermodynamic equilibrium between sedimentation and diffusion and depends on its size. This higher-order average is used as an indication of the proportion of high molar masses present in the sample.

[0179] As a reminder, SEC analysis, for example, consists of separating macromolecules into solution according to their size through columns filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the largest being eluted first. The sample to be analyzed is simply previously solubilized in an appropriate solvent, tetrahydrofuran at a concentration of 1.5 g / liter. Then the solution is filtered through a 0.45 μm porosity filter, before injection into the apparatus at a flow rate of 1 ml / min and a temperature of 35°C. The apparatus used is, for example, a "Waters alliance" chromatographic chain.

[0180] A Moore calibration is carried out with a series of commercial standards of low D polystyrene (less than 1.2), of known molar masses, covering the range of masses to be analyzed. From the recorded data (molar mass distribution curve) Mw, Mn, as well as D = Mw / Mn, are deduced.

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187] All molar mass values ​​indicated in this application are therefore relative to calibration curves produced with polystyrene standards. Molar distribution: Haliphatic / Ethylene / Aromatic The molar distribution of aliphatic, ethylenic and aromatic protons is measured using a spectrometer, here a Brucker AVANCE III 400 MHz spectrometer and is expressed as raw peak area ratios. The solvent used is CDC13 (deuterated chloroform) at 25°C and 120 scans. Hydrocarbon resin NMR data are measured by dissolving 20+1 mg of sample in 0.7 ml of solvents. The samples are dissolved in a 5 mm NMR tube at 25 °C until the sample is dissolved. CDCl3 appears as a peak at 7.20 ppm and is used as a reference peak for the samples. 1H NMR signals of aromatic protons are located between 8.5 ppm and 6.2 ppm. Ethylene protons lead to signals between 6.2 ppm and 4.5 ppm. Finally, signals corresponding to aliphatic protons are located between 4.5 ppm and 0 ppm. Signals corresponding to solvent, water and other possible impurities are subtracted when integrating the resin signals. The areas of each category of protons are reported to the sum of these areas to give a distribution in % of area of ​​each category of protons. Dynamic properties The dynamic properties of tan(ô) are measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D 5992-96 standard. The response of a sample of crosslinked composition (cylindrical specimen 4 mm thick and 400 mm2 in cross section) is recorded, subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, under the defined temperature conditions, for example at 23°C and 100°C according to the ASTM D 1349-99 standard. A strain amplitude sweep is carried out from 0.1 to 50% (forward cycle), then from 50% to 1% (return cycle). The results used are the loss factor tan(ô). For the return cycle, the maximum value of tan(ô) observed is indicated. The value of tan(ô) measured at 100°C is an indicator of grip on dry ground. A high value denotes improved grip. The value of tan(ô) measured at 23°C is an indicator of rolling resistance. A low value denotes lower rolling resistance. Tensile tests

[0188] The tests were carried out in accordance with French standard NF T 46-002 of September 1988. All tensile measurements were carried out under normal temperature (23±2°C) and hygrometry (50+5% relative humidity) conditions, according to French standard NF T 40-101 (December 1979).

[0189] The breaking stresses (in MPa) and the elongations at break (AR in %) are measured, at 23°C ± 2°C, according to standard NF T 46-002, on samples cooked for 40 minutes at 150°C. The breaking energy is equal to the product of the breaking elongation and the breaking stress. Examples of resins

[0190] A charge of styrenic compounds (1), here polystyrene, feeds a preparation step a), here an extruder, in which it is heated to a temperature of 250°C. The liquid part of the charge (2) feeds a pyrolysis step b), here a microwave pyrolysis, carried out at a temperature of 340°C and at a pressure of 1.1 bar. The gaseous effluent (3) from the pyrolysis step is separated by distillation in a separation step c) into a stream rich in light compounds (4), a stream rich in styrene (5) comprising 99.2% by weight of styrene and a stream rich in heavy compounds (6).

[0191] The stream rich in light compounds (4) of composition 34% by weight of toluene, 45% by weight of ethylbenzene, 0.3% by weight of cumene, 19.9% ​​by weight of styrene, 0.8% by weight of alphamethylstyrene feeds a resin synthesis step. This step is also fed by a stream of biosourced limonene comprising 99% by weight of limonene. No solvent stream is added, the compounds present in the stream of light compounds, and in particular ethylbenzene and toluene, being in sufficient quantity to ensure this role.

[0192] Aluminum chloride (1.5 mol% relative to the content of limonene, alpha-methylstyrene and styrene monomers) is introduced into the reactor under an inert atmosphere. The reactor is then kept under an inert atmosphere throughout the reaction. The medium is stirred and operated at a temperature of 30°C for 1 h. The reaction is then stopped by adding water.

[0193] The reaction medium, constituting the polymerized effluent, is separated into a solvent-rich effluent and a resin-rich effluent by coagulation of the resins with water. The resin-rich effluent is then dried in an oven at 150°C for 48 h. A resin is recovered in the form of a translucent orange solid.

[0194] These steps are reproduced by varying the mass ratio of the limonene flow to the flow rich in light compounds at the inlet of the resin synthesis step, the other parameters remaining unchanged. The resins obtained have the characteristics presented below:

[0195] [Tableauxl] Example 1b Mass ratio of limonene stream / light-rich stream 90 / 10 80 / 20 50 / 50 Glass transition temperature (Tg, °C) 56 53 57 Number-average molar mass (Mn, g / mol) 640 680 900 Z-average molar mass (Mz, g / mol) 2100 1900 4200 Polydispersity index (D) 1.8 1.8 2.2 Molar distribution of lH-Iphatic / l-Ethylene / l-Aromatic H 94 / 2 / 4 89 / 2 / 9 75 / 1 / 24

[0196] Table 2 presents commercial hydrocarbon resins. Resin T1 is a bio-sourced resin resulting from the polymerization of limonene “Dercolyte L120” from the company DRT. Resin T2 is a resin resulting from the polymerization of dicyclopentadiene (DCPD) of petro-sourced origin, whose commercial name is “Escorez 5600” from the company Exxon.

[0197] [Tables2] Example Tl T2 Glass transition temperature (Tg, °C) 72-76°C 51 Number-average molar mass (Mn, g / mol) 690 488 Weight-average molar mass (Mz, g / mol) 1186 784 Polydispersity index (D) 1.7 1.6 Molar distribution 1 Haliphatic / 1 Ethylethylene / 1 Aromatic 97 / 2 / 1 90 / 0 / 10 Examples of rubber compositions

[0198] Rubber compositions are manufactured with the introduction of all the constituents on an internal mixer, with the exception of the vulcanization system. The vulcanization agents (sulfur and accelerator) are introduced on an external mixer at low temperature (the rollers constituting the mixer being at 30°C). The compositions are cooked under pressure at 150°C for 40 minutes.

[0199] Table 3 shows different rubber compositions using the resins presented in Tables 1 and 2 as well as some of their properties.

[0200] [Tables3] CTI CT2 Cl C2 C3 CT 3 CT4 C4 C5 C6 SBR (la) 100 100 100 100 100 SBR (1b) 100 100 100 100 100 Carbon black (2) 4 4 4 4 4 3 3 3 3 3 Silica (3) 130 130 130 130 130 60 60 60 60 60 Resin Tl 88 - - - - 30 - - - - Resin T2 - 88 - - - - 30 - - - Resin la - - 88 - - - - 30 - - Resin 1b - - - 88 - - - - 30 - Resin le - - - - 88 - - - - 30 Antioxidant (4) 6 6 6 6 6 2.7 2.7 2.7 2.7 2.7 Coupling agent (5) 13 13 13 13 13 6.4 6.4 6.4 6.4 6.4 DPG (6) 2.5 2.5 2.5 2.5 2.5 2 2 2 2 2 Stearic acid (7) 3 3 3 3 3 2 2 2 2 2 ZnO (8) 0.9 0.9 0.9 0.9 0.9 1 1 1 1 1 Accelerator (9) 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 Soluble sulfur 0.7 0.7 0.7 0.7 0.7 1 1 1 1 1 Results (base 100) Tan(ô) at 100°C 100 93 107 97 103 100 93 99 100 94 Tan(ô) at 23°C 100 83 91 86 111 100 96 94 93 102 Energy at failure at 23°C 100 123 102 100 128 100 105 109 115 84

[0201] References of Table 3(la) SBR of Tg = -88 °C as described in the examples of WO2017 / 168099

[0202] (1b) SBR of Tg = -48°C as described in the examples of WO2015 / 185394

[0203] (2) Carbon black, grade ASTM N234 (3) Silica, “Zeosil 1165 MP” from Solvay, HDS type(4) N-(l,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (“Santoflex 6-PPD”) from Flexsys and 2,2,4-trimethyl-l,2-dihydroquinoline (TMQ)(5) Coupling agent: “Si69” from Evonik - Degussa(6) Diphenylguanidine, “Perkacit DPG” from Flexsys(7) Stearin, “Pristerene 4931” from Uniqema (8) Zinc oxide, industrial grade - Umicore(9) N-Cyclohexyl-2-benzothiazolesulfenamide (“Santocure CBS” from Flexsys)

[0204] The results are expressed in base 100, the value of 100 being assigned to the CTL witness. A value greater than 100 indicates that the value of the corresponding property is greater than that of the witness. A value less than 100 indicates that the value of the corresponding property is less than that of the witness.

[0205] Compared to compositions based on a petro-sourced hydrocarbon resin or based on a bio-sourced poly-limonene resin, it is observed that the compositions in accordance with the invention have similar performances in terms of grip on dry ground, improved rolling resistance and breaking energy.

Claims

Claims

1. Hydrocarbon resin based on an aromatic distillation cut T100°C-140°C originating from the separation of the pyrolysis effluent of a styrenic feedstock, called “stream rich in light compounds”, and an aliphatic stream of biosourced origin, said resin having the following characteristics: • a glass transition temperature (denoted Tg) ranging from 20°C to 140°C; • a number-average molar mass of less than 5000 g / mol; • a dispersity D of less than 3; • A level of aromatic protons, determined by 1H NMR, of between 0.5% mol and 20% mol; • A level of aliphatic protons, determined by 1H NMR, of between 80% mol and 99.5% mol; • A level of ethylenic protons, determined by 1H NMR, of less than or equal to 10% mol; The sum of the aromatic, aliphatic and ethylenic proton rates being equal to 100%.

2. Hydrocarbon resin according to the preceding claim in which the level of aromatic protons, determined by 1H NMR, is between 2 mol% and 20 mol%, preferably between 5 mol% and 20 mol%.

3. A hydrocarbon resin according to any preceding claim, wherein the styrenic compound filler comprises at least 90% by weight of polystyrene, preferably at least 93% by weight of polystyrene, and most preferably at least 95% by weight of polystyrene.

4. Hydrocarbon resin according to any one of the preceding claims obtained by a process comprising at least: a. A step of preparing the charge of styrene compounds so as to be able to feed this charge in the pyrolysis step; b. A step of pyrolysis of the charge of styrene compounds making it possible to obtain at least one gaseous effluent and one pyrolysis oil, said gaseous effluent comprising at least 20% by weight of aromatic compounds; c. A step of separating the gaseous effluent into at least one stream rich in light compounds whose bubble point and dew point, measured at atmospheric pressure, are in the temperature range from 100°C to 140°C; d. A resin synthesis step comprising a polymerization section fed by the stream rich in light compounds from step c) and by a stream of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, followed by a finishing section and producing a polymerized effluent; e. A treatment step comprising a section for separating the polymerized effluent from step d) into a solvent-rich effluent and a resin-rich effluent, and a drying section fed by the resin-rich effluent in order to produce a stream of hydrocarbon resins.

5. Rubber composition based on at least one elastomer and one hydrocarbon resin according to any one of the preceding claims.

6. Rubber composition according to the preceding claim comprising a reinforcing filler and a crosslinking system.

7. Rubber composition according to any one of claims 5 to 6 comprising from 10 to 150 phr, preferably from 50 to 130 phr of silica.

8. A rubber composition according to any one of claims 5 to 7 wherein the elastomer is a diene elastomer.

9. Rubber composition according to any one of claims 5 to 8 in which the elastomer predominantly comprises a diene elastomer having a glass transition temperature Tg of less than -20°C, preferably between -20°C and -110°C.

10. Rubber composition according to any one of claims 5 to 9 comprising at least 60 phr, preferably at least 70 phr, more preferably at least 80 phr of at least one diene elastomer chosen from the group consisting of polybutadiene, butadiene copolymers and mixtures of these elastomers.

11. A rubber composition according to the preceding claim wherein the butadiene copolymer is a butadiene-styrene copolymer.

12. A vehicle tire comprising a rubber composition according to any one of claims 5 to 11 or a resin according to any one of claims 1 to 4.

13. A vehicle tire according to the preceding claim, wherein the tread comprises a hydrocarbon resin according to any one of claims 1 to 4 or a rubber composition according to any one of claims 5 to 11.

Images