Hydrocarbon resin from bio-based material and / or recycled material, and rubber composition comprising same

Abstract

The invention relates to a hydrocarbon resin based on an aromatic distillation fraction of T150 DEG C to 220 DEG C obtained by separation of the pyrolysis effluent of the styrene feedstock and referred to as a "stream rich in heavy compounds", and an aliphatic stream of bio-based source.

Description

TECHNICAL FIELD

[0001] The present invention relates to the field of hydrocarbon resins, to rubber compositions comprising such resins, and to vehicle tires comprising such rubber compositions. BACKGROUND

[0002] It is known from the prior art that elastomers having a low glass transition temperature (“Tg”) are able to improve the wear resistance of tires (WO 2015 / 043902) and are therefore very useful when seeking to obtain the best compromise between performance characteristics that are difficult to reconcile, such as a necessarily high wear resistance and adhesion, and a necessarily low rolling resistance in order to minimize fuel consumption.

[0003] These low Tg elastomers have a low compatibility with the hydrocarbon plasticizing resins usually used in vehicle tires.

[0004] However, the compatibility of the resins with the elastomer matrix, and in particular their ability to disperse correctly in the mixture, is essential for them to perform their role correctly. The compatibility of the resins with the elastomer matrix depends, among other factors, on properties such as the glass transition temperature and softening point of the resins, which depend on the molar mass, nature and proportion of aromatic units to aliphatic units of the resins (see, for example, J. Appl. Polym. Sci. 2022 139 (15) 51950). Resins comprising aliphatic and aromatic units and having a high Tg value are in particular able to modify the Tg of the mixture.

[0005] Such resins are well known in the prior art. For example, document EP 0 936 229 teaches the preparation of hydrocarbon resins by cationic polymerization of aliphatic and aromatic monomers from a petroleum-based stream. Documents WO 2016 / 043851, US 91 / 39721 or FR 2 968 006 describe hydrocarbon resins having a high Tg value. Document FR 3 099 166 describes a tire comprising a rubber composition comprising a specific hydrocarbon resin derived from a petroleum distillate, which enables the tire to have an improved road behavior at different temperatures.

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

[0007] Documents WO 2022 / 101562 and WO 2022 / 101563 describe the production of hydrocarbon resins from the pyrolysis residues of rubber chips. The said documents do not address the impact of these resins on the performance of rubber compositions.

[0008] Continuing its research, the Applicant has found that resins deriving from bio-based and / or recycled resources are able to maintain or even improve key performance characteristics of rubber compositions useful for vehicle tyres, thus advantageously replacing petroleum-based hydrocarbon resins. SUMMARY

[0009] The present application relates to a hydrocarbon resin based on an aromatic distillation fraction T150°C to 220°C obtained by separation of the pyrolysis effluent of a styrene compound feedstock and an aliphatic stream of bio-based origin, said aromatic distillation fraction being referred to as "heavy compound-enriched stream", said resin having the following characteristics: • a glass transition temperature (expressed as Tg) of 20°C to 140°C; • a number average molar mass of less than 5000 g / mol; • a polydispersity of less than 3; • an aromatic proton content of between 0.5 mol% and 50 mol% as determined by 1 H NMR; • an aliphatic proton content of between 50 mol% and 99.5 mol% as determined by 1 H NMR; • an olefinic proton content of less than or equal to 10 mol% as determined by 1 H NMR; the sum of the contents of aromatic, aliphatic and olefinic protons being equal to 100%.

[0010] Preferably, the aromatic proton content as determined by 1 H NMR is between 1 mol% and 40 mol%, preferably between 2 mol% and 30 mol%.

[0011] Preferably, the styrene compound feedstock comprises at least 90% by weight of polystyrene, preferably at least 93% by weight of polystyrene, preferably at least 95% by weight of polystyrene.

[0012] Preferably, the hydrocarbon resin according to the present application is obtained by a process comprising at least the following steps: a. a step of preparing a styrene compound feedstock so as to be able to feed this feedstock to a pyrolysis step; b. a pyrolysis step of the styrene compound feedstock, so that at least one gaseous effluent comprising at least 20% by weight of aromatic compounds and a pyrolysis oil can be obtained; c. a step of separating the gaseous effluent into at least one heavy compound-enriched stream having a bubble point and a dew point measured at atmospheric pressure in the temperature range of 150°C to 220°C; d. a resin synthesis step comprising a polymerization section fed with a heavy compound-enriched stream from step c) and an aliphatic compound stream comprising at least 5 wt% of terpene compounds of biological origin, followed by a finishing section and producing a polymerization effluent; e. a treatment step comprising a section for separating the polymerization effluent from step d) into a solvent-enriched effluent and a resin-enriched effluent, and a drying section fed with the resin-enriched effluent to produce a hydrocarbon resin stream.

[0013] The present application also relates to a rubber composition based on at least one elastomer and a hydrocarbon resin according to the present application.

[0014] Preferably, the rubber composition according to the present application comprises a reinforcing filler and a crosslinking system.

[0015] Preferably, the rubber composition according to the present application comprises from 10 to 150 phr, preferably from 50 to 130 phr, of silica.

[0016] Preferably, the elastomer of the rubber composition according to the present application is a diene elastomer.

[0017] Preferably, the elastomer of the rubber composition according to the present application mainly comprises a diene elastomer having a glass transition temperature Tg lower than -20°C, preferably between -20°C and -110°C.

[0018] Preferably, the rubber composition according to the present application comprises at least 60 phr, preferably at least 70 phr, preferably at least 80 phr, of at least one diene elastomer selected from the group consisting of polybutadiene, butadiene copolymers and mixtures of these elastomers.

[0019] In a preferred manner, the butadiene copolymer is a butadiene / styrene copolymer.

[0020] The present application also relates to a vehicle tire comprising a rubber composition according to the present application or a resin according to the present application.

[0021] Preferably, the tread of the pneumatic tire according to the present application comprises a hydrocarbon resin according to the present application or a rubber composition according to the present application.

[0022] Definitions The carbon-containing compounds mentioned in the description can be of fossil origin or of biological origin. In the latter case, they can be derived, partially or completely, from biomass, or from renewable raw materials derived from biomass. This particularly concerns polymers, plasticizers, fillers, etc.

[0023] The term "composition based on" means that the composition comprises a mixture of the various base ingredients used and / or the in situ reaction products, some of which are able to react with each other at least partially during the various stages of manufacture of the composition or during the subsequent curing and / or are intended to react with each other, which can modify the constitution of the composition as it is initially prepared. Thus, the composition described below can be different in the uncrosslinked state and in the crosslinked state.

[0024] All percentages (%) shown are percentages by weight ("wt%") unless explicitly otherwise mentioned. Furthermore, any numerical interval denoted by the expression "between a and b" means a range of values extending from more than a to less than b (i.e. excluding the limits a and b), while any numerical interval denoted by the expression "from a to b" means a range of values extending from a up to b (i.e. including the strict limits a and b).

[0025] The term "C n The term "C n The term "C m The term "C

[0026] The term "heteroatom" means an atom other than carbon or hydrogen, such as nitrogen, sulfur or oxygen.

[0027] A compound is considered major when it represents more than 50% by weight of the compounds of the same nature. Thus, a major elastomer is an elastomer representing more than 50% by weight relative to the total weight of elastomers present.

[0028] hydrocarbon resin The present invention relates to a hydrocarbon resin obtained from a feedstock of styrene compounds and a stream of aliphatic compounds of biological origin, said resin having the following characteristics: a glass transition temperature (expressed as Tg) of between 20°C and 140°C; a number average molar mass of less than 5000 g / mol, preferably less than 4000 g / mol, preferably less than 3000 g / mol; a polydispersity index less than 3, preferably less than 2.5, preferably less than 2; by 1 an aromatic proton content of between 0.5 mol% and 50 mol%, preferably between 1 mol% and 40 mol%, preferably between 2 mol% and 30 mol%, preferably between 5 mol% and 30 mol% determined by H NMR; By 1 The aliphatic proton content measured by H NMR is between 50 mol% and 99.5 mol%, preferably between 70 mol% and 99 mol%, preferably between 70 mol% and 98 mol%; By 1 The olefinic proton content measured by H NMR is less than or equal to 10 mol%, preferably less than or equal to 5 mol%, more preferably less than or equal to 4 mol%, The sum of the contents of aromatic, aliphatic and olefinic protons is equal to 100%.

[0029] The hydrocarbon resin according to the application is based on an aromatic distillation fraction T150°C to 220°C from the separation of the pyrolysis effluent of a styrene compound feedstock and a bio-based derived aliphatic stream, said aromatic distillation fraction being referred to as "heavy compounds enriched stream".

[0030] The term "styrene compound feedstock" means a feedstock comprising styrene-based polymers such as styrene rubber and polystyrene.

[0031] Preferably, the styrene compound feedstock is a styrene compound feedstock derived from waste plastic. Such a feedstock preferably comprises at least 90 wt% of polystyrene, preferably at least 93 wt% of polystyrene, more preferably at least 95 wt% of polystyrene. The feedstock of polystyrene compounds can comprise other compounds, in particular if it is derived from plastic waste. These other compounds can include but are not limited to plastic compounds such as polyethylene, polypropylene, elastomers, organic materials such as paper, food, or inorganic materials such as glass, metal or sand.

[0032] The aliphatic compound stream comprises at least 5 wt% of bio-based derived terpene compounds.

[0033] The aliphatic compound stream is bio-based derived. In other words, it is derived from biomass or from a product derived from biomass.

[0034] The term "derived from biomass" means that the compound is derived from a plant, animal, fungal or microbial organism and has undergone possible treatments. Preferably, the aliphatic compound stream is derived from a plant organism. The term "product derived from biomass" means that the biomass used to obtain the aliphatic compound stream can undergo treatments, for example biological treatments (for example based on the function of plants, animals or microorganisms), chemical treatments (for example in the presence of an acid, a base treatment, a treatment in the presence or absence of a catalyst), and / or physical treatments (for example pressurization, heat treatment, electromagnetic or microwave treatment).

[0035] Production of the resin The hydrocarbon resin according to the present application can be obtained by the process described hereinafter.

[0036] Preparation step a) In the preparation step a) the styrene compound feedstock is conditioned so that it can be fed to the pyrolysis step b). This preparation step can include chopping, degassing and temperature collection operations in order to melt the plastic compound, for example in an extrusion device, where the temperature is gradually increased and the steam effluent (water, light compounds resulting from the partial decomposition of the polystyrene feedstock) and the solid effluent (non-melted fragments such as metal fragments, glass) are separated.

[0037] Preferably, the styrene compound feedstock is gradually heated to a temperature between 100°C and 300°C, preferably between 150°C and 300°C, more preferably between 200°C and 300°C, which temperature results in the melting of the polystyrene (when such compound is present) while limiting its thermal decomposition.

[0038] Pyrolysis step b) The styrene compound feedstock is fed to a pyrolysis step which results in at least one gaseous effluent and a pyrolysis oil comprising at least 20 wt% of aromatic compounds.

[0039] The term "pyrolysis" means thermal decomposition of a compound under inert atmosphere.

[0040] The feedstock is fed to a pyrolysis step which is carried out at a temperature and a pressure such that the styrene compound depolymerizes into styrene oligomers and styrene monomers. Preferably, the pyrolysis step is carried out at a temperature between 300°C and 900°C, preferably between 300°C and 800°C.

[0041] The pyrolysis step is preferably carried out at a pressure between 0.8 bar and 7.5 bar, preferably between 1 bar and 6 bar, more preferably between 1 bar and 4.5 bar.

[0042] The pyrolysis step preferably comprises a microwave pyrolysis step. Such microwave pyrolysis which can be used for the pyrolysis of the styrene compound feedstock is described for example in WO 2020 / 202089.

[0043] The use of a microwave-assisted pyrolysis step enables higher heat transfer rates and higher reaction temperatures which are beneficial for the chain-end scission reactions and minimize the formation of styrene oligomers. The microwave pyrolysis step is further characterized by a lower temperature in the reaction mass than in a conventional pyrolysis section. The lower temperature in the reaction mass results in a lower amount of styrene oligomers being vaporized and avoids the production of "over-cracked" styrene. The use of a microwave pyrolysis step enables to reduce the formation of styrene oligomers relative to a conventional pyrolysis step.

[0044] The pyrolysis step produces at least a gaseous effluent and a pyrolysis oil. The gaseous effluent can also contain entrained liquid droplets. In addition to the styrene oligomers, the gaseous effluent comprises most of the styrene monomers produced in the pyrolysis step, as well as light aromatic compounds which are gaseous under the operating conditions, such as a-methylstyrene, ethylbenzene, cumene and toluene.

[0045] The gaseous effluent comprises at least 20% by weight of aromatic compounds, preferably at least 20% by weight of styrene.

[0046] Preferably, the gaseous effluent comprises not more than 10% by weight of ethylbenzene, preferably not more than 5% by weight of ethylbenzene, more preferably not more than 3% by weight of ethylbenzene.

[0047] Preferably, the gaseous effluent comprises at least 10% by weight of compounds having a boiling point higher than styrene.

[0048] The pyrolysis oil can also comprise solid components, un-melted polymers produced during the pyrolysis process or fragments not separated in the feedstock preparation step. This stream is preferably fed to a separation section, where any solid fraction is separated from the liquid fraction, which can be recycled as a mixture with the feed to the pyrolysis step or used in the resin synthesis step d).

[0049] The pyrolysis step can be carried out in a pyrolysis reactor and can be carried out continuously, semi-continuously or in batch. Such reactors are well known to the person skilled in the art.

[0050] Separation step c) To the separation step c) is fed at least the gaseous effluent from step b) and produces at least one stream enriched in light compounds, one stream enriched in styrene and one stream enriched in heavy compounds.

[0051] The stream enriched in light compounds mainly comprises compounds lighter than styrene, in particular toluene and ethylbenzene compounds.

[0052] The stream enriched in light compounds is a T100°C to 140°C fraction, preferably a T110°C to 140°C fraction. The term "T a °C to b °C fraction" means that the bubble point and the dew point of the fraction, measured at atmospheric pressure, are in the temperature range a °C to b °C. Thus, the stream enriched in light compounds has a bubble point and a dew point, measured at atmospheric pressure, in the temperature range 100 to 140 °C, preferably 110 to 140 °C.

[0053] Preferably, the cumulative content of toluene and ethylbenzene in the stream enriched in light compounds is at least equal to 60 mass%, preferably at least equal to 70 mass%, preferably at least equal to 75 mass%.

[0054] The styrene-rich stream mainly comprises aromatic compounds comprising from 6 to 9 carbon atoms. The separation step c) is performed so that the styrene-rich stream comprises at least 99 mass% of styrene and so that the styrene recovery (i.e. the ratio of the styrene flow rate in the aromatic compounds-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%, preferably at least equal to 97%.

[0055] Preferably, the aromatic compounds-rich stream is a fraction T140°C to 150°C, preferably a fraction T144°C to 146°C.

[0056] The heavy compounds-rich stream mainly comprises compounds heavier than styrene, as well as undepolymerized styrene compounds, and in particular styrene oligomers when the feedstock comprises polystyrene.

[0057] The heavy compounds-rich stream is a fraction T150°C to 220°C, preferably a fraction T160°C to 210°C.

[0058] Preferably, the content of a-methylstyrene in the heavy compounds-rich stream is at least equal to 60 mass%, preferably at least equal to 70 mass%, more preferably at least equal to 80 mass%, very preferably at least equal to 90 mass%.

[0059] In a preferred manner, the separation step c) is performed by distillation.

[0060] In a first variant of this preferred arrangement, the first column fed with the gaseous effluent from step b) separates this effluent into a light compounds-rich stream and a residual liquid, which is separated by a second column into a styrene-rich stream and a heavy compounds-rich stream.

[0061] In a second variant of this preferred arrangement, the separation is performed in a single distillation column. In this variant, the vapour effluent at the top of the column is cooled to a temperature between 30°C and 50°C, preferably to a temperature between 35°C and 45°C. The condensed liquid fraction is returned as reflux to the top of the column, while the vapour fraction is then subcooled to a temperature between -5°C and 10°C, preferably to a temperature between -5°C and 5°C, in order to condense any styrene entraining light compounds. The subcooled condensed stream is returned as reflux at the top of the column. The residual vapour fraction constitutes the light compounds-rich stream. This stream can then be used, for example, in the form of energy. The primary cooling enables the use of cooling water at ambient temperature as cold utility to the maximum, and the use of specific cold utility for achieving the subcooling to the minimum, which advantageously impacts the life cycle analysis of the process.

[0062] In this variant, the distillation column is operated at a pressure between 0.1 and 2.0 bara, preferably between 0.5 and 1.5 bara, more preferably between 0.5 and 1.1 bara, the operating pressure being understood to mean the pressure measured at the top of the column. The term "bara" is understood to mean absolute bar, and not a pressure expressed in relative bar, usually expressed as "barg" according to the notation "bar gauge".

[0063] In this variant and preferably, the distillation column is fed at the bottom with at least the gaseous effluent from step b), and produces at the top a stream rich in light compounds, at the bottom a stream rich in heavy compounds, and through a side line a stream rich in styrene, the only thermal input into said column being the gaseous effluent from step b).

[0064] The gaseous effluent from step b) is at a high temperature, preferably at a temperature higher than 300°C. This temperature is sufficient for the column to not require any other thermal input.

[0065] By supplying the feedstock at the bottom of the column, the feedstock is rapidly cooled, thus enabling to limit the potential polymerization of styrene. This form of supply also enables to better manage the "heavy" compounds. This is because the bottom of the column is not provided with a recycling system which is usually used to maintain the temperature of the distillation column, which greatly limits the risk of fouling of the "heavy" compounds which are particularly viscous.

[0066] The distillation column used in this variant of step c) of the process comprises between 5 and 20 theoretical stages, preferably no more than 15 theoretical stages, more preferably between 8 and 12 theoretical stages.

[0067] The stream rich in styrene is withdrawn on an intermediate plate. This withdrawal plate is located in the lower third of the distillation column, preferably at 1 to 3 theoretical stages from the bottom plate. Carrying out this withdrawal at a lower position in the column, slightly further from the bottom plate, enables to limit the entrainment of heavy compounds in the stream rich in styrene, and accordingly to limit the risk of fouling of the subsequent equipment.

[0068] Preferably, and in order to further limit the risk of polymerization, an inhibitor of the polymerization of styrene into polystyrene, such as 2,2,6,6-tetramethyl-4-oxopiperidinyloxy, can be supplied to the distillation column, preferably to the top of the column, in step c) of the process.

[0069] Toluene and ethylbenzene type compounds which are not reacted in the step d) of the synthesis of the resin can be used as solvents in this synthesis step, thus avoiding the addition of an external source of solvent to the process.

[0070] Step d) of the synthesis of the resin The resin synthesis step mainly consists in oligomerizing the monomers contained in the heavies-enriched stream from step c) and in the aliphatic compound stream comprising at least 5 wt% of terpene compounds of biological origin, in particular the styrene and the compounds heavier than styrene contained in the heavies-enriched stream, by controlling the macrostructure, in particular by limiting the content of low molecular weight compounds (e.g. monomers, dimers and trimers) and high molecular weight compounds (i.e. those having a molecular weight greater than 5000 g / mol) and the microstructure, and thus in producing a new oligomeric material of the resin type. The term "dimer" means a compound comprising two monomers linked by a covalent bond. The dimer can be a homo-dimer (i.e. a combination of two identical monomers), a hetero-dimer (i.e. a combination of two different monomers), or a mixture of homo-dimers and hetero-dimers. The term "trimer" means a compound comprising three monomers linked by a covalent bond. The trimer can be a homo-trimer (i.e. a combination of three identical monomers), a hetero-trimer (i.e. a combination of at least two different monomers), or a mixture of homo-trimers and hetero-trimers.

[0071] The resin synthesis step mainly consists in oligomerizing the monomers contained in the heavies-enriched stream from step c) and in the aliphatic compound stream comprising at least 5 wt% of terpene compounds of biological origin, in particular the styrene and the compounds heavier than styrene contained in the heavies-enriched stream, by controlling the macrostructure, in particular by limiting the content of low molecular weight compounds (e.g. monomers, dimers and trimers) and high molecular weight compounds (i.e. those having a molecular weight greater than 5000 g / mol) and the microstructure, and thus in producing a new oligomeric material of the resin type. The term "dimer" means a compound comprising two monomers linked by a covalent bond. The dimer can be a homo-dimer (i.e. a combination of two identical monomers), a hetero-dimer (i.e. a combination of two different monomers), or a mixture of homo-dimers and hetero-dimers. The term "trimer" means a compound comprising three monomers linked by a covalent bond. The trimer can be a homo-trimer (i.e. a combination of three identical monomers), a hetero-trimer (i.e. a combination of at least two different monomers), or a mixture of homo-trimers and hetero-trimers.

[0072] The term "terpene compound of biological origin" means a compound of the terpene family, which is an unsaturated hydrocarbon of plant origin. The terpene compound useful for the purposes of the present application is preferably selected from terpenes comprising not more than 20 carbon atoms, preferably from the compounds limonene, a-pinene, b-pinene, myrcene, farnesene and mixtures thereof, preferably from the compounds limonene, a-pinene, b-pinene and mixtures thereof, and preferably is limonene.

[0073] Limonene is a terpene hydrocarbon which can be obtained in particular from citrus peels or by microbial fermentation.

[0074] By feeding the heavies-enriched stream from step c) and the aliphatic compound stream into the resin synthesis step, it is possible to control the ratio between aromatic units and aliphatic units in the resin produced, thus adapting the resin to the polymer matrix into which it is intended to be introduced. Thus, it is possible to obtain resins with excellent compatibility derived from renewable and / or recycled resources.

[0075] Thus, the process is able to use the heavies-enriched stream according to the parameters required for the resin produced, thus providing great versatility. Preferably, when the heavies-enriched stream is produced by distillation in step c), no further treatment is required before using this stream for resin production.

[0076] The mass ratio of the stream from step c) to the stream of aliphatic compounds fed to step d) is adjusted to control the ratio of aliphatic protons and aromatic protons in the resin.

[0077] In a preferred way, also a solvent stream is fed to the polymerization section, said solvent stream being selected from the group consisting of aliphatic solvents, aromatic solvents and halogenated solvents and mixtures thereof.

[0078] In a preferred way, the solvent selected from the group consisting of aliphatic solvents, aromatic solvents, halogenated solvents and mixtures thereof is selected from the group consisting of C7-C10 aromatic solvents, C6-C8 aliphatic solvents and C1-C2 chlorinated solvents and mixtures thereof, preferably from the group consisting of toluene, methylcyclohexane and dichloromethane.

[0079] Preferably, a part of the pyrolysis oil obtained in step b) is used as solvent stream. Preferably, the process is fed only with a styrene compound feedstock and a stream of aliphatic compounds comprising at least 5 wt% of terpene compounds of biological origin, the solvent required in step d) being provided by at least one stream obtained in step c) and / or at least a part of the pyrolysis oil obtained in step b), preferably at least a part of the pyrolysis oil obtained in step b) is fed to step d).

[0080] Preferably, to the synthesis step d) a stream obtained in step c) and a stream of aliphatic compounds comprising at least 5 wt% of terpene compounds and a solvent stream are fed, so that the monomer content is between 50 wt% and 75 wt%. Thus, the solvent flow can be adjusted to adjust the monomer content in step d). This content enables to limit the exotherm in step d) while providing a polymerization effluent whose viscosity allows its transport to the downstream steps of the process.

[0081] Preferably, the resin obtained by the process comprises less than 1 wt% of compounds having a molecular weight greater than 5000 g / mol. Preferably, the resin obtained comprises not more than 50 wt% of dimer and trimer compounds.

[0082] The polymerization section is operated in the absence of catalyst or in the presence of an acid catalyst of Bronsted, Lewis or Friedel-Crafts type, which can be homogeneous or heterogeneous. Preferably, the polymerization section is operated in the presence of an acid catalyst of Bronsted or Lewis type. The polymerization section can also be operated in the presence of a ligand, a co-catalyst and / or a cationic polymerization initiator of the type proton generating or of the type carbon cation generating.

[0083] Preferably, the catalyst is a Lewis acid comprising a ligand of the family of halogenated aluminum. In a preferred manner, these ligands are chosen from aluminum chlorides, such as aluminum trichloride, alkyl aluminum chlorides, such as diethyl aluminum chloride and ethyl aluminum dichloride, and aryl aluminum chlorides, such as phenyl aluminum chloride. Preferably, the catalyst also comprises a co-ligand having Lewis base characteristics, capable of modulating the acid characteristics of the Lewis acid ligand, which can be of the aliphatic ether type (such as diethyl ether, dibutyl ether), of the aromatic ether type (diphenyl ether) or of the ester type (ethyl acetate) or even of the alkyl amine (triethylamine) or aryl amine (diphenylamine, triphenylamine) type. The polymerization section can also be operated with ligands containing phosphorus, sulfur or any other heteroatom.

[0084] The polymerization section is preferably operated at a temperature of between -60°C and +300°C, preferably between -60°C and +120°C, very preferably between -50°C and +100°C, preferably between -40°C and +90°C, very preferably between +20°C and +90°C.

[0085] 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 volumetric flow rate of the feed entering into this section.

[0086] The amount of catalyst (including any ligand and co-ligand) relative to the weight of olefin monomer entering into the polymerization section is preferably between 0.05% and 5% by weight, and in a preferred manner between 0.1% and 2% by weight relative to the weight of olefin monomer entering into the polymerization section.

[0087] The stream from the polymerization section is then treated in a finishing section, resulting in a polymerization effluent.

[0088] The finishing section can be operated by adding a compound that quenches the polymerization reaction, which deactivates the catalyst and terminates the chains that are still growing. The finishing section is preferably operated by contacting a stream comprising a quenching compound chosen from water, C1-C3 alcohols and mixtures thereof, preferably chosen from water, methanol, ethanol and mixtures thereof, very preferably water, at a temperature of between 5°C and 80°C, preferably at a temperature of between 15°C and 30°C (for example at room temperature), then separating the polymerization effluent and the effluent comprising mainly the quenching compound by phase decantation.

[0089] The molar ratio of quenching compound to polymerization catalyst in the finishing section is at least equal to 1.1, preferably at least equal to 2.

[0090] When the quenching compound is water, the volume ratio of the reaction medium to water in the finishing section is preferably between 20:1 and 10:1, preferably between 10:1 and 5:1, and preferably between 5:1 and 1:1.

[0091] The stream coming from the polymerization section and the stream comprising the quenching compound are contacted under stirring for a period of time, preferably comprised between 5 min and 2 h, preferably comprised between 15 min and 45 min, to promote the contact of the quenching compound with the reaction medium.

[0092] At the end of this stirring phase, a decanting phase is carried out in order to separate, on the one hand, an organic phase consisting of a polymerization effluent mainly comprising resin, solvent, unconverted monomers, dimers, trimers and low molecular weight oligomers, and, on the other hand, a phase mainly comprising the quenching compound, catalytic residues and organic residues soluble in the quenching compound.

[0093] The decanting phase is preferably carried out for a period of time comprised between 5 min and 4 h, preferably comprised between 15 min and 2 h.

[0094] The phase mainly comprising the quenching compound can then be treated in order to recover the quenching compound into the finishing section.

[0095] The polymerization effluent is then fed into a treatment step.

[0096] Step e) of treating the polymerization effluent The process comprises a step of treating the polymerization effluent coming from step d), this step comprising a section for separating a solvent-rich effluent from a resin-rich effluent, and a drying section feeding the resin-rich effluent to produce a resin.

[0097] The implementation of the polymerization effluent treatment step in the process makes it possible to adjust the characteristics of the resin, in particular by eliminating low molecular weight oligomers (such as dimers, trimers and tetramers) and reducing the dispersity, in order to control the properties of the resin obtained (such as the glass transition temperature).

[0098] The section for separating a solvent-rich effluent from a resin-rich effluent makes it possible, on the one hand, to recover a large part of the solvent and unconverted monomers for subsequent use, preferably in the resin synthesis step of the process, and, on the other hand, to concentrate the resin in the resin-rich effluent.

[0099] The separation section can be operated by any method known to the person skilled in the art, in particular preferably by evaporation, distillation, resin coagulation, liquid-liquid extraction or a combination of these methods.

[0100] In a preferred arrangement, the separation section is operated by distillation in at least one distillation column, so as to produce at the top a solvent-rich effluent and at the bottom a resin-rich effluent. This section is able to eliminate the residual monomers and oligomers at the top and most of the solvent used in the resin synthesis step, and thus to adjust the macrostructure of the resin and its properties, such as the glass transition temperature (denoted Tg), in particular by eliminating low-molecular-weight compounds to reduce the dispersibility. The resin-rich effluent comprises most of the resin fed to the separation section. The resin recovery corresponds to the ratio of the resin flow in the resin-rich effluent to the resin flow fed to the separation section, preferably greater than 80%, preferably greater than 90%. This recovery can be adjusted by increasing the number of separation stages in the separation section, or by adjusting the operating parameters of said section, such as the reflux ratio.

[0101] In another preferred arrangement, the separation section is operated by coacervation of the resin. In this arrangement, the polymerization effluent from step d) is contacted with a coacervation solvent in which the resin is insoluble, so as to precipitate them. The coacervation solvent dissolves the residual monomers, the solvent used in the resin synthesis step and the low-molecular-weight oligomers.

[0102] The coacervation 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 such as tetrahydrofuran (THF) and dioxane.

[0103] The coacervation separation section is preferably operated with a volume ratio of coacervation solvent to medium to be coacervated of between 1 : 1 and 10: 1, preferably between 2: 1 and 5: 1. The coacervation separation section is preferably operated at a temperature of between 5°C and 40°C.

[0104] The stream comprising the coacervation solvent constituting the solvent-rich effluent can then be recovered, if necessary, to the resin synthesis step, for example, first by carrying out a purification treatment step.

[0105] In another preferred arrangement, the separation section is operated by liquid-liquid extraction. In this arrangement, the polymerization effluent from step d) is washed with a stream comprising mainly water. This extraction can be carried out in one or more steps, preferably in one to three steps.

[0106] The liquid-liquid extraction can also be carried out upstream of the separation by distillation or by resin coacervation as described previously.

[0107] In another preferred arrangement, the separation section is implemented by evaporation, for example by evaporation in a wiped-film evaporator.

[0108] The viscosity of the resin-rich effluent depends on the resin content in the effluent and its temperature. These contents and temperatures are thus adjusted so that the effluent can be transported to the drying section. It can be sought to maintain a high temperature to have a high resin content, while maintaining the viscosity of the effluent to enable its transport, while taking care to remain below the temperature of thermal degradation of the resin.

[0109] The resin-rich effluent is then fed to a drying section, in which it is filtered and then dried. At the end of the drying step, the dried resin has a content of residual solvent (comprising the solvent used in the synthesis step and any solvent used in the separation section) of less than 3% by weight, preferably less than 1.5% by weight, more preferably less than 0.8% by weight, relative to the mass of the resin. The dried resin has a residual free monomer content of less than 5% by weight, preferably less than 2% by weight, preferably less than 1% by weight, relative to the mass of the resin.

[0110] The hydrocarbon resin content in the rubber composition can be in the 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 hydrocarbon resin of the present invention, the effect of the hydrocarbon resin of the present invention becomes insufficient and the rubber composition can have adhesion problems. Above 150 phr, the composition can have manufacturing difficulties in terms of ease of incorporation of the hydrocarbon resin of the present invention into the composition.

[0111] Rubber composition The present invention also relates to a rubber composition based on at least one elastomer and the hydrocarbon resin according to the present invention. The rubber composition can also comprise various optional components well known to the person skilled in the art. Some of them are also described below.

[0112] Elastomer The rubber composition according to the present invention comprises at least one elastomer, preferably a diene elastomer. It should be borne in mind that the term "diene type elastomer" is understood to mean an elastomer of which at least part (i.e. a homopolymer or a copolymer) is produced from diene monomers (monomers bearing two conjugated or non-conjugated carbon-carbon double bonds).

[0113] These diene elastomers can be classified into two categories: "substantially unsaturated" or "substantially saturated". The term "substantially unsaturated" generally means a diene elastomer obtained at least in part from conjugated diene monomers having a diene-derived unit (conjugated diene) content greater than 15% (mol%); thus, diene elastomers such as butyl rubbers or EPDM-type copolymers of a diene and an alpha-olefin do not fall under the foregoing definition and can be particularly described as "substantially saturated" diene elastomers (low or very low content of diene-derived units, always less than 15% (mol%)). The diene elastomers comprised in the rubber composition of the application are preferably substantially unsaturated.

[0114] The term "diene elastomer usable in the rubber composition according to the application" particularly means: a) any homopolymer of a conjugated or non-conjugated diene monomer having 4 to 18 carbon atoms; b) any copolymer of a conjugated or non-conjugated diene having 4 to 18 carbon atoms with at least one other monomer.

[0115] The other monomer can be ethylene, an olefin or a conjugated or non-conjugated diene.

[0116] Suitable as conjugated dienes are conjugated dienes having 4 to 12 carbon atoms, especially 1,3-dienes, such as in particular 1,3-butadiene and isoprene.

[0117] Suitable as olefins are vinyl aromatic compounds having 8 to 20 carbon atoms and aliphatic alpha-mono-olefins having 3 to 12 carbon atoms.

[0118] Suitable vinyl aromatic compounds include, for example, styrene, o-methylstyrene, m-methylstyrene or p-methylstyrene, the "vinyltoluene" commercial mixture or p-(tert-butyl)styrene.

[0119] Suitable as aliphatic alpha-mono-olefins are in particular acyclic aliphatic alpha-mono-olefins having 3 to 18 carbon atoms.

[0120] The diene elastomer is preferably a diene elastomer of the highly unsaturated type, in particular a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably selected 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 mixtures of these copolymers.

[0121] The above diene elastomers can be, for example, block, random, sequential or microsequential elastomers, and can be prepared in dispersion or in solution; they can be coupled and / or star-branched or functionalized, for example epoxidized, with a coupling agent and / or a star-branched or functionalizing agent.

[0122] The term "isoprene elastomer" means a diene elastomer chosen from natural rubber (NR) which can be plasticized or plasticized, synthetic polyisoprene (IR), various isoprene copolymers, in particular isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR) copolymers, and mixtures of these elastomers.

[0123] According to a particularly preferred embodiment of the application, the elastomer is a diene elastomer having a glass transition temperature Tg lower 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 the person skilled in the art, for example described in WO 2015 / 185394 and WO 2017 / 168099.

[0124] Preferably, the main diene elastomer is chosen from polybutadienes, butadiene copolymers and mixtures of these elastomers, more preferably from polybutadienes, butadiene-styrene copolymers and mixtures of these elastomers.

[0125] The butadiene copolymers are preferably copolymers of butadiene and of a vinyl aromatic monomer. As vinyl aromatic compounds, the following are suitable, for example: styrene, o-methylstyrene, m-methylstyrene or p-methylstyrene, the "vinyltoluene" commercial mixture, p-(tert-butyl)styrene, methoxystyrene, chlorostyrene, vinylmesitylene, divinylbenzene or vinyl naphthalene. Preferably, the vinyl aromatic monomer of the copolymers of butadiene and of a vinyl aromatic monomer is styrene.

[0126] According to this embodiment, the main elastomer, preferably a diene elastomer, having a very low Tg is present in the composition in a content preferably greater than or equal to 60 phr, more preferably greater than or equal to 70 phr, even more preferably greater than or equal to 80 phr. More preferably, the composition comprises 100 phr of an elastomer having a very low Tg as described above.

[0127] Reinforcing filler The rubber composition according to the application preferably comprises a reinforcing filler. Any type of reinforcing filler known to be able to reinforce an elastomer composition that can be used to manufacture a tire can be used, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, or a blend of these two fillers, in particular a blend of carbon black and silica.

[0128] All carbon blacks generally used for tires ("tire-grade" carbon blacks), in particular of HAF, ISAF or SAF type, are suitable as carbon black. Among the latter, reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades) will be mentioned more particularly, such as N115, N134, N234, N326, N330, N339, N347 or N375 carbon black, or, depending on the targeted application, carbon blacks of higher series can also be mentioned (such as N660, N683 or N772). The carbon black can for example have been introduced into the isoprene elastomer in the form of a masterbatch (see for example applications WO 97 / 36724 and WO 99 / 16600). The BET specific surface area of the carbon black is measured according to standard D6556-10 [multipoint (minimum 5 points) method - gas: nitrogen - relative pressure p / p0 range: 0.1 to 0.3].

[0129] In the present patent application, the term "reinforcing inorganic filler" is understood, by definition, to mean any inorganic or mineral filler (whatever its color and origin (natural or synthetic)), also called "white filler", "transparent filler" or even "non-black filler" as opposed to carbon black, which is itself capable of reinforcing the rubber composition used to manufacture tires without the need for an intermediate coupling agent, in other words, which is capable of replacing a conventional tire-grade carbon black in terms of reinforcing action; such a filler is generally characterized, in a known manner, by the presence of hydroxyl (-OH) groups on the surface.

[0130] Mineral fillers of siliceous type, in particular silica (Si02), or of aluminous type, in particular alumina (AI2O3), are particularly suitable as reinforcing inorganic fillers. The silica used can be any reinforcing silica known to the person skilled in the art, in particular any precipitated or fumed silica having a BET specific surface area and a CTAB specific surface area both less than 450 m 2 / g, preferably between 30 and 400 m 2 / g. As high-dispersion precipitated silica (HDS), one can mention for example Ultrasil 7000 and Ultrasil 7005 silicas from the company Degussa, Zeosil 1165MP, 1135MP and 1115MP silicas from the company Rhodia, Hi-Sil EZ150G silica from the company PPG, Zeopol 8715, 8745 and 8755 silicas from the company Huber or a silica having a high specific surface area as described in patent application WO 03 / 16837.

[0131] The physical state of the reinforcing inorganic filler provided is not important, whether it is a powder, microbeads, granules, beads or any other suitable compact form. Needless to say, the term "reinforcing inorganic filler" also refers to a mixture of different reinforcing inorganic fillers, in particular a mixture of highly dispersible siliceous and / or aluminous fillers.

[0132] The reinforcing inorganic filler used, in particular if it is silica, preferably has a BET specific surface area of between 45 and 400 m 2 / g, more preferentially between 60 and 300 m 2 / g.

[0133] Preferably, the rubber composition according to the application comprises from 1 to 100 phr, more preferentially from 1 to 80 phr and preferentially from 1 to 60 phr of carbon black, the optimal value depending in a known manner on the specific application targeted: for example, the level of reinforcement desired for a bicycle pneumatic tyre is of course less than that required for a pneumatic tyre capable of travelling at a sustained high speed (for example a motorbike tyre, a passenger car tyre or a tyre for a utility vehicle such as a heavy goods vehicle). In a preferred arrangement, the reinforcing filler comprises mainly carbon black and preferably consists of carbon black.

[0134] Preferably, the rubber composition according to the application comprises from 10 to 150 phr, preferentially from 50 to 130 phr of silica. In a preferred arrangement, the reinforcing filler comprises mainly silica and preferably consists of silica.

[0135] In order to couple the reinforcing inorganic filler to the elastomer, at least a bifunctional coupling agent (or bonding agent) can optionally be used in a known manner, which aims to provide a satisfactory link of chemical and / or physical nature between the inorganic filler (the surface of the particles thereof) and the elastomer, in particular a bifunctional organosilane or polyorganosiloxane.

[0136] In particular, silane polysulphides can be used, referred to as "symmetrical" or "asymmetrical" according to their specific structure, for example as described in applications WO 03 / 002648 (or US 2005 / 016651) and WO 03 / 002649 (or US 2005 / 016650).

[0137] As examples of silane polysulfides, mention can be made more particularly of polysulfides (in particular disulfides, trisulfides or tetrasulfides) of bis((Ci-C4)alkoxy(Ci-C4)alkyl)silyl(Ci-C4)alkyl), for example bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides. Among these compounds, use is made in particular of bis(3-triethoxysilylpropyl) tetrasulfide of formula [(C2H50)3Si(CH2)3S2]2, abbreviated TESPT, or of bis(triethoxysilylpropyl) disulfide of formula [(C2H50)3Si(CH2)3S]2, abbreviated TESPD. As a preferred example, mention will also be made of bis(mono(Ci-C4)alkoxydi(Ci-C4)alkylsilylpropyl) polysulfides (in particular disulfides, trisulfides or tetrasulfides), more particularly of bis(monoethoxydimethylsilylpropyl) tetrasulfide, as described in patent application US 2004 / 132880.

[0138] As examples of coupling agents other than alkoxy silane polysulfides, mention will be made in particular of bifunctional POSs (polyorganosiloxanes) or hydroxyl silane polysulfides as described in patent applications WO 02 / 30939 and WO 02 / 31041, or silanes or POSs bearing an azodicarbonyl function as described for example in patent applications WO 2006 / 125532, WO 2006 / 125533 and WO 2006 / 125534.

[0139] In the rubber composition according to the application, the content of coupling agent is preferably between 5 and 18% by weight relative to the amount of silica, preferably between 8 and 12% by weight relative to the amount of silica.

[0140] The person skilled in the art understands that it is possible to use another reinforcing filler of organic nature, in particular, as an equivalent to the reinforcing inorganic filler described in this part, provided that this reinforcing filler is covered with an inorganic layer such as silica, or comprises functionalization sites, in particular hydroxyl sites, on its surface, making it possible to establish a bond between the filler and the elastomer, in the presence or absence of covering agent or coupling agent.

[0141] Crosslinking system The rubber composition according to the application comprises a sulfur-based crosslinking system comprising a metal oxide, a stearic acid derivative and a vulcanization accelerator. It is then called a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur or a sulfur donor.

[0142] The sulfur is used in a content of between 1 and 20 phr, preferably between 1 and 10 phr.

[0143] The vulcanization accelerator is used in a preferred content such that the sulfur / vulcanization accelerator mass ratio is less than or equal to 4.

[0144] As accelerators, any compound capable of acting as a diene elastomer vulcanization accelerator in the presence of sulfur can be used, in particular thiazole-type accelerators and derivatives thereof, or sulfenamides, thiurams, dithiocarbamates, dithiophosphates, thioureas and xanthates-type accelerators. As examples of such accelerators, mention can be made in particular of the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviation 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 dibenzyl dithiocarbamate (ZBEC) and mixtures of these compounds.

[0145] The mass ratio of metal oxide to stearic acid derivative in the crosslinking system is less than 4, preferably less than 3. The metal oxide is preferably zinc oxide.

[0146] The crosslinking system can also optionally comprise a vulcanization retarder.

[0147] The rubber composition can preferably comprise additives that are usually used in elastomer compositions intended in particular for the manufacture of vehicle tires, such as pigments, protective agents such as anti-ozone waxes, chemical anti-ozone agents or antioxidants, plasticizers other than those mentioned above, anti-fatigue agents, reinforcing resins or methylene acceptors (such as novolac resins) or methylene donors (such as HMT or H3M).

[0148] The rubber composition can also comprise a plasticizing system. This plasticizing system can consist of a hydrocarbon resin having a Tg higher than 20°C and / or a plasticizing oil, in addition to the specific hydrocarbon resins mentioned above.

[0149] Preparation of the rubber composition The rubber composition according to the application is manufactured in a suitable mixer using preparation stages well known to those skilled in the art: - a thermomechanical working or kneading stage, which can be carried out in a single thermomechanical step, during which all the necessary ingredients, in particular the elastomer matrix, the hydrocarbon resin, the filler and optionally various other additives, are introduced into a suitable mixer, for example a standard internal mixer (for example of the "Banbury" type). The introduction of the filler into the elastomer can be carried out in one or more times simultaneously with the thermomechanical kneading. In the case where the filler, in particular carbon black or silica, has been introduced into the elastomer, totally or partially, in the form of a masterbatch, as described for example in patent applications WO 97 / 36724 or WO 99 / 16600, it is the masterbatch which is directly kneaded and, if appropriate, other elastomers or fillers not present in the form of a masterbatch in the composition, as well as various other optional additives, are introduced.

[0150] The thermomechanical kneading is carried out at high temperature, the maximum temperature being between 110°C and 200°C, preferably between 130°C and 185°C, for a period of time generally between 2 and 10 minutes.

[0151] - Then, after cooling the mixture obtained during the first stage to a lower temperature, generally below 120°C, for example between 40°C and 100°C, a second stage of mechanical working is carried out in an open mixer, for example a roll mill.

[0152] The optional crosslinking system is added during the second stage. For example, a polyacid-based or polydienophile-based crosslinking system is generally added during the first stage. A peroxide- or sulphur-based crosslinking system is generally added during the second stage.

[0153] The final composition thus obtained can then be calendered, for example in the form of a sheet or a plate, in particular for laboratory characterisation, or extruded in the form of a rubber semi-finished product (or shaped piece).

[0154] The composition can be in the raw state (before crosslinking or vulcanisation) or in the cured state (after crosslinking or vulcanisation), can be a semi-finished product which can be used in a tyre.

[0155] The curing can be carried out in a manner known to the person skilled in the art, generally at a temperature between 130°C and 200°C, under pressure, for a sufficient time which can vary for example between 5 and 90 min, in particular as a function of the curing temperature, the crosslinking system employed, the crosslinking kinetics of the composition considered or the size of the tyre.

[0156] Tyre for vehicle The application also relates to a tyre for vehicle comprising a rubber composition based on at least one elastomer and a hydrocarbon resin according to the application.

[0157] The vehicle tire can be a pneumatic tire or a non-pneumatic tire. The term "non-pneumatic tire" means that the tire is able to support the load of the vehicle by means other than pressurized gas, for example by a load bearing cover.

[0158] The vehicle tire according to the application is chosen from, but not limited to, a tire for a two-wheeled vehicle, a passenger vehicle, a "heavy" vehicle (i.e. a subway, a bus, an off-road vehicle, a heavy transport vehicle such as a truck, a tractor or a trailer), an airplane, construction equipment, a heavy agricultural vehicle or a material handling vehicle.

[0159] In a preferred manner, the tire according to the application comprises a tread comprising the rubber composition according to the application or the hydrocarbon resin according to the application. In a manner known to the person skilled in the art, the tread is the part of the tire that circumferentially surrounds the tire and ensures contact with the rolling surface. BRIEF DESCRIPTION OF DRAWINGS

[0160] [ Figure 1 ] Figure 1 schematic representation of the process according to the application. DETAILED DESCRIPTION

[0161] A styrene compound feedstock (1) is fed to a step a) of preparing a styrene compound feedstock, so as to be able to feed this feedstock (2) to a pyrolysis step b). The pyrolysis step b) of the styrene compound feedstock makes it possible to obtain at least one gaseous effluent (3) comprising at least 20% by weight of aromatic compounds and a pyrolysis oil (4).

[0162] The gaseous effluent (3) is then treated in a separation step c) in which it is separated into at least one stream (5) rich in heavy compounds, the bubble point and dew point of which, measured at atmospheric pressure, are in the temperature range of 100°C to 140°C.

[0163] The stream (5) is fed to a resin synthesis step d) comprising a polymerization section, which is also fed at least with a stream (6) of aliphatic compounds comprising at least 5% by weight of terpene compounds of biological origin, and optionally with a solvent stream (7), the polymerization section being followed by a finishing section producing a polymerization effluent (8).

[0164] The polymerization effluent (8) is fed to a treatment step e) comprising a section of separation of the polymerization 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 to produce a hydrocarbon resin stream (10).

[0165] MEASURING METHODS Glass transition temperature The glass transition temperature Tg is generally measured by differential scanning calorimetry (DSC), for example, according to the standard ISO 11357-2 of 2014, unless otherwise specifically mentioned.

[0166] Macrostructure (Mw, Mn, Mz and ) The macrostructure (mass average molar mass, number average molar mass, centrifugal molar mass and polydispersity index, denoted Mw, Mn, Mz and respectively) is determined by size exclusion chromatography (SEC) as described below. Mz reflects the thermodynamic equilibrium between sedimentation and diffusion and depends on its size. This high order average is used as an indication of the proportion of high molar mass present in the sample.

[0167] As a reminder, the SEC analysis comprises, for example, the separation of macromolecules in solution according to their size by passing through a column filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the largest volume molecules being eluted first. The sample to be analysed is simply previously dissolved in an appropriate solvent, tetrahydrofuran, at a concentration of 1.5 g / litre. The solution is then filtered through a filter with a porosity of 0.45 μm before being injected into the device at a flow rate of 1 mL / min and a temperature of 35°C. The device used is, for example, a "Waters Alliance" chromatography chain.

[0168] Molar calibration is carried out with a series of commercial polystyrene standards having low polydispersity (less than 1.2) with known molar masses covering the range of masses to be analysed. The data recorded (mass distribution curve of the molar masses) are used to deduce Mw and Mn, and = Mw / Mn.

[0169] All the molar mass values indicated in this patent application are therefore relative to the calibration curve produced with polystyrene standards.

[0170] Molar distribution1H 脂族 / 1H 烯属 / 1H 芳族 The molar distribution of the aliphatic protons, olefinic protons and aromatic protons is measured using a spectrometer, in this case a Brucker Avance III 400 MHz spectrometer, and is expressed as a ratio of the total peak area. The solvent used is CDCl3 solvent (deuterated chloroform), 25°C, 120 scans.

[0171] The NMR data of the hydrocarbon resins were measured by dissolving 20 ± 1 mg of sample in 0.7 ml of solvent. The sample was dissolved in a 5 mm NMR tube at 25°C until the sample was dissolved. CDC13 in the form of a singlet at 7.20 ppm was used as the reference peak for the sample. The aromatic protons 1 The H NMR signal is located between 8.5 ppm and 6.2 ppm. The olefinic protons give a signal between 6.2 ppm and 4.5 ppm. Finally, the signal corresponding to the aliphatic protons is located between 4.5 ppm and 0 ppm. When the signals of the resins are integrated, the signals corresponding to the solvent, water and any other impurities are subtracted.

[0172] The areas of each type of proton are taken relative to the sum of these areas, giving the distribution of the percentage of area of each type of proton.

[0173] Dynamic properties The dynamic properties tan (delta) were measured at 23°C and 100°C on a viscoanalyzer (Metravib VA4000) according to standard ASTM D 5992-96. The response of a sample of crosslinked composition (cylindrical test specimen of 4 mm thickness and 400 mm 2 of simple alternating sinusoidal shear stress at a frequency of 10 Hz under defined temperature conditions (at 23°C and 100°C). The strain amplitude sweep was performed from 0.1% to 50% (outward cycle) and then from 50% to 1% (return cycle). The result used is the loss factor tan (delta). For the return cycle, the maximum value of tan (delta) observed is indicated. The tan (delta) value measured at 100°C is an indicator of dry grip. A high value indicates an improvement in grip. The tan (delta) value measured at 23°C is an indicator of rolling resistance. A low value indicates a lower rolling resistance.

[0174] The dynamic properties tan (delta) were measured on a viscoanalyzer (Metravib VA4000) according to standard ASTM D 5992-96. The response of a sample of crosslinked composition (cylindrical test specimen of 4 mm thickness and 10 mm diameter) to simple alternating sinusoidal shear stress at a frequency of 10 Hz was recorded at a temperature gradient of +1.5°C / min in the temperature range from -80°C to +100°C under a maximum stress of 0.7 MPa. The tan delta value was then measured at 0°C. The tan (delta) value measured at 0°C is an indicator of wet grip. A high value indicates an improvement in grip.

[0175] Examples of resins The feedstock of styrene compound (1), in this case polystyrene, is fed to the preparation step a), in this case an extruder, where it is heated to a temperature of 250°C. The liquid fraction of feedstock (2) is fed to the pyrolysis step b), in this case microwave pyrolysis, which is operated at a temperature of 340°C and a pressure of 1.1 bar. The gaseous effluent from the pyrolysis step (3) is separated by distillation in the separation step c) into a stream rich in light compounds, a stream rich in styrene and a stream rich in heavy compounds (5).

[0176] The stream rich in heavy compounds (5) consisting of 77.6 wt% of a-methylstyrene, 17.6 wt% of styrene, 1.7 wt% of cumene and 1.2 wt% of ethylbenzene is fed to the resin synthesis step. This step is also fed with a bio-based limonene stream containing 99 wt% of limonene and a toluene stream, both streams coming from sources external to the process. The mass ratio of limonene stream / stream rich in heavy compounds is equal to 0.5. The flow rate of the toluene stream is such that the concentration of monomers (a-methylstyrene + styrene + limonene) at the inlet of the reactor is 30 wt%.

[0177] Aluminium chloride (2 mol% with respect to the content of limonene, a-methylstyrene and styrene monomers) is introduced into the reactor under inert atmosphere. The reactor is then kept under inert atmosphere throughout the reaction. The medium is stirred and operated at a temperature of 50°C for 1 h 30 min. The reaction is then quenched by adding water.

[0178] The reaction medium constituting the polymerization effluent is separated into a stream rich in solvent and a stream rich in resin by washing with water and coagulating the resin with methanol. The stream rich in resin is then dried in an oven at 180°C for 16 hours. The resin is recovered in the form of a translucent orange solid.

[0179] These steps are repeated, varying the mass ratio of limonene stream to stream rich in heavy compounds at the beginning of the resin synthesis step, the other parameters remaining unchanged. The resins obtained have the characteristics shown below: [Table 1] Table 2 shows commercial hydrocarbon resins. Resin T1 is a bio-based resin resulting from the polymerization of limonene, the trade name of which is Dercolyte L120 from the company DRT. Resin T2 is a resin resulting from the polymerization of dicyclopentadiene (DCPD) of petroleum origin, the trade name of which is Escorez 5600 from the company Exxon.

[0180] [Table 2] Examples of rubber compositions The rubber compositions were manufactured by introducing all the ingredients except the vulcanization system into an internal mixer. The vulcanizing agents (sulfur and accelerators) were introduced into an open mixer at low temperature (the constituent rollers of the mixer were at 30°C). The compositions were cured under pressure at 150°C for 40 minutes.

[0181] Table 3 shows various rubber compositions using the resins shown in Tables 1 and 2, and some of their properties.

[0182] [Table 3] Table 3 reference (1 b) SBR with Tg = -48°C as described in the examples of WO2015 / 185394 (2) Carbon black, ASTM N234 grade (3) Silica, Zeosil 1165MP, HDS type from Solvay (4) N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (Santoflex 6-PPD) and 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) from Flexsys (5) Coupling agent: Si69 from Evonik - Degussa (6) Diphenyl guanidine, Perkacit DPG from Flexsys (7) Stearic acid, Pristerene 4931 from Uniqema (8) Zinc oxide, technical grade - Umicore (9) N-cyclohexyl-2-benzothiazylsulfenamide (Santocure CBS from Flexsys) The results are expressed on a scale of 100, the value 100 being attributed to the control CT1. Values greater than 100 indicate that the corresponding property value is greater than that of the control. Values lower than 100 indicate that the corresponding property value is lower than that of the control.

[0183] With respect to compositions based on petroleum-based hydrocarbon resins or on bio-based poly-limonene-based resins, it was observed that the compositions according to the application have similar performances in terms of dry and wet grip, and an improved rolling resistance.

Claims

1. A hydrocarbon resin based on an aromatic distillation fraction T150°C to 220°C and an aliphatic stream of biobased origin, said aromatic distillation fraction being obtained by separation of the pyrolysis effluent of a styrene compound feedstock and being referred to as "heavy compounds rich stream", said resin having the following characteristics: • a glass transition temperature (expressed as Tg) of 20°C to 140°C; • a number average molar mass of less than 5000 g / mol; • polydispersity less than 3; • by 1 The aromatic proton content determined by1H NMR is between 0.5 mol% and 50 mol%; • by 1 The aliphatic proton content determined by1H NMR is between 50 mol% and 99.5 mol%; • by 1 H NMR determined olefinic proton content less than or equal to 10 mol%; the sum of the contents of aromatic protons, aliphatic protons and olefinic protons being equal to 100%.

2. The hydrocarbon resin according to the preceding claim, wherein the aromatic proton content determined by1H NMR is between 1 and 40 mol%, preferably between 2 and 30 mol%. 1 H NMR determined aromatic proton content is between 1 and 40 mol%, preferably between 2 and 30 mol%.

3. The hydrocarbon resin according to any one of the preceding claims, wherein the styrene compound feedstock comprises at least 90 wt% of polystyrene, preferably at least 93 wt% of polystyrene, preferably at least 95 wt% of polystyrene.

4. The hydrocarbon resin according to any one of the preceding claims, obtained by a process comprising at least the following steps: a. a step of preparing a styrene compound feedstock so as to be able to feed this feedstock to a pyrolysis step; b. a pyrolysis step of the styrene compound feedstock, thereby being able to obtain at least one gaseous effluent comprising at least 20 wt% of aromatic compounds and a pyrolysis oil; c. a step of separating the gaseous effluent into at least one heavy compounds rich stream having a bubble point and a dew point measured at atmospheric pressure in the temperature range of 150°C to 220°C; d. a resin synthesis step comprising a polymerization section fed with the heavy compounds rich stream from step c) and an aliphatic compound stream comprising at least 5 wt% of biobased origin terpene compounds, followed by a finishing section and producing a polymerization effluent; e. a processing step comprising a section for separating the polymerization effluent from step d) into a solvent rich effluent and a resin rich effluent, and a drying section feeding the resin rich effluent to produce a hydrocarbon resin stream.

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

6. The rubber composition according to the preceding claim, comprising a reinforcing filler and a crosslinking system.

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

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

9. The rubber composition according to any one of claims 5 to 8, wherein the elastomer comprises mainly diene elastomers having a glass transition temperature Tg lower than -20°C, preferably between -20°C and -110°C.

10. The 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 selected from the group consisting of polybutadiene, butadiene copolymers and mixtures of these elastomers.

11. The rubber composition according to the preceding claim, wherein the butadiene copolymer is a butadiene / styrene copolymer.

12. Vehicle tire comprising the rubber composition according to any one of claims 5 to 11 or the resin according to any one of claims 1 to 4.

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

Images