Process for producing hydrocarbon resins from polystyrene residue and tire residue

Abstract

The present invention relates to a process for producing a hydrocarbon resin from feedstocks including a styrene compound and rubber chips, the resin produced by this process, and a rubber composition containing such a resin.

Description

[Technical Field]

[0001] The present invention relates to a process for producing hydrocarbon resins from recycled residues, resins produced by such a process, and further to compositions containing these resins, in particular in the field of compositions for rubber articles, and especially for vehicle tires. [Background technology]

[0002] Pneumatic tires, and more generally rubber articles, such as conveyor belts and non-pneumatic tires, are complex objects composed of numerous components. For example, tires are made from over 200 different starting materials, including different families of elastomers, reinforcing fillers, oils, and hydrocarbon resins. Among hydrocarbon resins, those with high glass transition temperatures (Tg) that possess both aliphatic and aromatic properties are used to compensate for compromises in the performance of mixtures, such as rolling resistance or grip. In particular, these resins allow for the modification of the Tg of the mixture. Such high-Tg resins are known from the prior art and are described, for example, in WO2016 / 043851, US9139721, or FR2968006. The compatibility of the resin with the elastomer matrix, particularly its ability to properly disperse in the mixture, is essential for the resin to perform its role correctly. The compatibility of the resin with the elastomer matrix depends, in particular, on properties such as the glass transition temperature and softening point of the resin, which in turn depend on the molar mass, properties, and ratio of aromatic to aliphatic units of the resin (see, e.g., J. Appl. Polym. Sci. 2022 139(15)51950). Therefore, it is important that these parameters can be varied to accommodate the diverse elastomers used in rubber compositions. Such resins containing aliphatic and aromatic units are well known in the prior art, e.g., EP0936229, which teaches the production of hydrocarbon resins from aliphatic and aromatic monomers by cationic polymerization from a petroleum-based stream.

[0003] While tire performance, such as rolling resistance and wear resistance, is crucial for limiting the environmental impact of these tires, it is also important to strive to minimize the use of fossil resources in the manufacture of rubber products. US2013 / 0281611 describes a tire rubber composition containing a plasticizer derived from recycled waste, where the plasticizer is used as a substitute for process oil. WO2022 / 101562 and WO2022 / 101563 describe the production of hydrocarbon resins from the pyrolysis residues of rubber chips. However, these documents do not address the issue of adjusting the microstructure of the resin, particularly the issue of adjusting the aromatic and aliphatic monomer content. Therefore, one object of the present invention is to provide a process that enables the production of resins from bio-based and / or recycled resources that can be incorporated into a wide variety of elastomer compositions. [Overview of the Initiative]

[0004] The present invention relates to at least one process for producing a hydrocarbon resin from a feedstock comprising a styrene compound feedstock and rubber chips, wherein at least: a. A step of preparing a feedstock for the styrene compound so that this feedstock can be supplied to the pyrolysis step, b1. A step that enables the thermal decomposition of a styrene compound feedstock to obtain at least one gaseous effluent and a thermal decomposition oil, wherein the gaseous effluent contains at least 20% by mass of an aromatic compound. c1. Separating the gaseous effluent obtained from step b1) into at least one stream rich in light compounds, one stream rich in aromatics, and one stream rich in heavy compounds. b2. A step enabling the thermal decomposition of a feed material including rubber chips at a temperature between 300 and 900°C with an ascending temperature lamp to obtain a gaseous effluent, a pyrolysis oil, and a solid effluent, wherein the pyrolysis oil contains at least 1.5% by mass of C4-C12 olefin monomer. c2. A step of separating the pyrolysis oil obtained from step b2) into at least one raffinate, an intermediate fraction and an extract, wherein the intermediate fraction has a boiling point at atmospheric pressure in the range of 140 to 280°C and contains 10% by mass or less of heteroatoms, d. A resin synthesis step comprising a polymerization section to which at least one stream obtained from step c1) and an intermediate fraction obtained from step c2) are supplied, and a subsequent finishing section, wherein a polymerization efflux is produced. e. A processing step comprising a section for separating the polymerization effluent from step d) into solvent-rich effluent and resin-rich effluent, and a drying section to which the resin-rich effluent is supplied to generate a stream of hydrocarbon resin. This includes processes related to the process.

[0005] Preferably, the styrene compound supply material is derived from waste plastic containing at least 90% by mass of polystyrene. Preferably, the rubber tip comprises a diene elastomer of at least 50 phr, and preferably a diene elastomer of at least 60 phr. Preferably, the raw material supplying the styrene compound 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, during step a). Preferably, the pyrolysis step b1) includes a pyrolysis reactor operated at a temperature in the range of 300°C to 900°C, more preferably 300°C to 800°C, and a pressure in the range of 0.8 bar to 7.5 bar.

[0006] The pyrolysis step b1) preferably includes a microwave pyrolysis step. In a preferred embodiment, separation step c1) is carried out by distillation. In a preferred embodiment, the mass ratio of the stream obtained from step c1) supplied to step d) and the intermediate fraction obtained from step c2) is adjusted so that the resulting resin has an aliphatic H / aromatic H molar ratio in the range of 40 / 60 to 95 / 5, preferably in the range of 50 / 50 to 90 / 10, and more preferably in the range of 55 / 45 to 90 / 10. In a preferred embodiment, the polymerization section of resin synthesis step d) is also supplied with a solvent stream selected from aliphatic, aromatic, and halogenated solvents and mixtures thereof. In a preferred configuration, the process according to the present invention is supplied only with feedstocks including a styrene compound and rubber chips, and the solvent required in step d) is provided by at least one stream obtained from step c2) and / or at least one fraction of the pyrolysis oil obtained from step b1). In a preferred embodiment of this configuration, at least one fraction of the pyrolysis oil obtained from step b1) is supplied to the resin synthesis step d).

[0007] This invention also has the following features: • Glass transition temperature (denoted as Tg) in the range of 20℃ to 140℃. • Number average molar mass of less than 5000 g / mol, preferably less than 4000 g / mol, preferably less than 3000 g / mol. • A variance of D less than 3, preferably less than 2.5, preferably less than 2. · 1 The aromatic proton content is between 0.5 mol% and 50 mol%, preferably between 2 mol% and 30 mol%, preferably between 2 mol% and 20 mol%, as determined by 1H NMR. · 1 The aliphatic proton content is between 50 mol% and 99.5 mol%, preferably between 70 mol% and 98 mol%, and more preferably between 80 mol% and 98 mol%, as determined by 1H NMR. · 1 The ethylene proton content is determined by 1H NMR to be 0 mol% or less, preferably 5 mol% or less, and more preferably 4 mol% or less. It relates to a resin prepared by a process according to any one of the preceding embodiments, having and the total content of aromatic, aliphatic and ethylene protons being equal to 100%. Preferably, 1 The ethylene proton content determined by 1H NMR is 0.5 mol% or more, preferably 1 mol% or more.

[0008] The present invention also relates to a rubber composition based on at least one elastomeric matrix, comprising at least 50 phr of a butadiene copolymer, a reinforcing filler, a crosslinking system, and a hydrocarbon resin according to the present invention or prepared by a process according to the present invention. Preferably, the butadiene copolymer of the rubber composition according to the present invention has a glass transition temperature Tg below 20 °C, preferably between 20 °C and 110 °C. The present invention also relates to a vehicle tire, the tread of which comprises the rubber composition according to the present invention. Definitions The carbon-containing compounds referred to herein may be of fossil or biobased origin. In the latter case, the compounds may be partially or completely derived from biomass or obtained from renewable raw materials derived from biomass. "C n compound" means a compound containing n carbon atoms. Similarly, "C n -C m compound" means a set of compounds containing from n to m carbon atoms. The term "heteroatom" means an atom other than carbon or hydrogen, such as nitrogen, sulfur or oxygen. The term "hydrocarbon compound" means a compound consisting of carbon and hydrogen.

[0009] Process feedstock The process according to the present invention is a process for producing a hydrocarbon resin from a feedstock comprising a styrene compound feedstock and a rubber chip. These two feedstocks are derived from materials such as the recycling of polystyrene objects and used vehicle tires, or unused manufacturing residues or residues not suitable for intended use. The term "feedstock for styrene compounds" means a feedstock containing styrene-based polymers such as styrene rubber and polystyrene. Preferably, the feedstock for styrene compounds is a feedstock for styrene compounds derived from waste plastics. Such a feedstock preferably contains at least 90% by mass of polystyrene, preferably at least 93% by mass of polystyrene, more preferably at least 95% by mass of polystyrene. The feedstock for polystyrene compounds may contain other compounds, especially when derived from plastic waste. These other compounds can include, but are not limited to, plastic compounds such as polyethylene, polypropylene, and elastomers, organic materials such as paper and food, or inorganic materials such as glass, metal, or sand.

[0010] The term "chip" means a small element obtained by shredding a rubber article, preferably a used rubber article. The rubber article preferably has non-rubber components, such as textile fibers or metal wires, removed therefrom. The rubber chip preferably has a maximum length in the range of 1 to 100 mm, preferably in the range of 1 to 50 mm, preferably in the range of 1 to 30 mm. The chip can be of any shape, but chips having a relatively homogeneous size and shape are preferred to facilitate the thermal decomposition step. Control of size and shape is well known to those skilled in the art. Preferably, the rubber chip contains at least 50 phr of a diene elastomer. The term "diene" elastomer (or rubber, without distinction) should be understood to mean an elastomer that is at least partially (i.e., a homopolymer or copolymer) composed of diene monomer units (monomers having two conjugated or non-conjugated carbon-carbon double bonds), whether natural or synthetic, as is well known.

[0011] Preferably, the diene elastomer is selected from the group consisting of polybutadiene (BR), natural rubber (NR), synthetic polyisoprene (IR), butadiene copolymer, isoprene copolymer, and mixtures thereof of elastomers. The butadiene copolymer is selected from the group consisting of styrene / butadiene copolymer (SBR) in particular. Preferably, the diene elastomer is an isoprene elastomer. The term "isoprene elastomer" in known embodiments means a diene elastomer selected from the group consisting of isoprene homopolymers or copolymers, in other words, natural rubber (NR), synthetic polyisoprene (IR), various isoprene copolymers, and mixtures thereof. Among the isoprene copolymers, isobutene / isoprene (butyl rubber, IIR), isoprene / styrene (SIR), isoprene / butadiene (BIR), or isoprene / butadiene / styrene (SBIR) copolymers are particularly mentioned. This isoprene elastomer is preferably selected from the group consisting of natural rubber, synthetic cis-1,4-polyisoprene, and mixtures thereof, and among these synthetic polyisoprenes, polyisoprene having a cis-1,4-bond content (mol%) of more than 90%, and more preferably more than 98%, is used. Preferably, according to any one of the configurations of this document, the diene elastomer is natural rubber. A high content of diene elastomer promotes the formation of the target monomer, particularly limonene, at the end of thermal decomposition. Preferably, the rubber chips are obtained from pneumatic tire treads, particularly from large pneumatic tire treads, the latter having a high content of diene elastomer, preferably isoprene elastomer, typically 60-100 phr of isoprene elastomer.

[0012] Preparation step a) The process according to the present invention includes a step of preparing a feedstock for the styrene compound. During this step, the feedstock for the styrene compound is prepared to be supplied to step b) pyrolysis. This preparation step may include, for example, crushing, degassing and temperature acquisition operations to melt the plastic compound in an extrusion device, during which the temperature is gradually increased and vapor effluents (water, light compounds generated by the partial decomposition of the polystyrene feedstock) and solid effluents (metal debris, non-molten debris such as glass) are separated. Preferably, the feedstock for the styrene compound 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, where this temperature limits its thermal decomposition while causing fusion of polystyrene if such a compound is present.

[0013] Step b1) of thermal decomposition of the raw material for the styrene compound The styrene compound feedstock is supplied to a pyrolysis step that produces at least one gaseous effluent and a pyrolysis oil, the pyrolysis oil containing at least 20% by mass of an aromatic compound. The term "thermal decomposition" means the thermal decomposition of a compound in an inert or low-oxygen atmosphere, i.e., in an atmosphere containing less than 5% by volume of oxygen, preferably less than 3% by volume, more preferably less than 2% by volume, and preferably in an inert atmosphere. The raw materials are supplied to a thermal decomposition step carried out at a temperature and pressure such that depolymerization of the styrene compound into styrene oligomers and styrene monomers occurs. Preferably, the thermal decomposition step is carried out at a temperature in the range of 300°C to 900°C, preferably in the range of 300°C to 800°C. The pyrolysis step is carried out at a pressure preferably in the range of 0.8 bar to 7.5 bar, preferably in the range of 1 bar to 6 bar, and more preferably in the range of 1 bar to 4.5 bar.

[0014] The pyrolysis step preferably includes a microwave pyrolysis step. Such microwave pyrolysis, which can be used for the pyrolysis of feedstocks for styrene compounds, is described, for example, in WO2020 / 202089. The use of a microwave-assisted pyrolysis step allows for the achievement of higher heat transfer coefficients and higher reaction temperatures, which is advantageous for chain end cleavage reactions and minimizes the formation of styrene oligomers. The microwave pyrolysis step is also characterized by a lower reactant temperature than that of the conventional pyrolysis section. Lower reactant temperatures result in lower evaporation levels of styrene oligomers, avoiding "over-cracking" of the generated styrene. The use of a microwave pyrolysis step reduces styrene oligomer formation compared to the conventional pyrolysis step. The pyrolysis step produces at least a gaseous effluent and pyrolysis oil. The gaseous effluent may also contain entrained droplets. In addition to the styrene oligomer, the gaseous effluent contains most of the styrene monomer produced in the pyrolysis step, as well as light aromatic compounds that are gaseous under the operating conditions, such as α-methylstyrene, ethylbenzene, cumene, and toluene.

[0015] The gaseous effluent contains at least 20% by mass of aromatic compounds, preferably at least 20% by mass of styrene. Preferably, the gaseous effluent contains 10% by mass or less of ethylbenzene, preferably 5% by mass or less of ethylbenzene, and more preferably 3% by mass or less of ethylbenzene. Preferably, the gaseous effluent contains at least 10% by mass of a compound having a boiling point higher than that of styrene. The pyrolysis oil may also contain solid elements, unmelted polymers generated during pyrolysis, or debris not separated in the feed preparation step. This stream is preferably fed into a separation section where any solid fractions are separated from the liquid fraction, the latter of which can be reused as a mixture with the feed for the pyrolysis step or used in the resin synthesis step d). The pyrolysis step may be carried out in a pyrolysis reactor, and may be carried out continuously, semi-continuously, or in batches. Such reactors are well known to those skilled in the art.

[0016] Step c1) Separating the gaseous effluent obtained from step b1) The process according to the present invention includes a separation step in which gaseous effluent obtained from at least step b1) is supplied to produce at least one stream rich in light compounds, one stream rich in aromatics, and one stream rich in heavy compounds. The stream rich in light compounds mainly contains compounds lighter than benzene, particularly compounds of hydrogen, methane, ethane, ethylene, propane, propylene, butane, butene, and isobutane. The aromatic-rich stream mainly contains aromatic compounds with 6 to 9 carbon atoms. Separation step c1) is performed so that the aromatic-rich stream contains at least 99% by mass of styrene. Streams rich in heavy compounds mainly contain non-depolymerized styrene compounds, particularly styrene oligomers when the raw material contains polystyrene. In a preferred embodiment, separation step c1) is carried out by distillation.

[0017] In a first modification of this preferred configuration, a first column supplied with the gaseous effluent from step b1) separates the effluent into a stream rich in light compounds and a raffinate, the latter of which is separated by a second column into an aromatic-rich stream and a stream rich in heavy compounds. In a second modification of this preferred configuration, separation is performed in a single distillation column. In this modification, the vapor effluent at the column head 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 column head as reflux, while the vapor fraction is subsequently supercooled to a temperature between -5°C and 10°C, preferably between -5°C and 5°C, to condense any styrene encompassed with the light compounds. The stream condensed after supercooling is returned to the top of the column as reflux. The residual vapor fraction constitutes a stream rich in light compounds, which can then be utilized, for example, in the form of energy. The first cooling allows for maximum use of ambient temperature cooling water as a cooling source and minimizes the use of a specific cooling source to achieve supercooling, thereby favorably impacting the lifecycle analysis of the process according to the present invention. In this modification, the distillation column is operated at a pressure 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, where the operating pressure is understood to mean the pressure measured at the column head. The term "bara" is understood to mean absolute bar, as opposed to relative bar, which is generally indicated as "barg" according to the notation "bar gauge".

[0018] In this modified example, preferably, the distillation column is supplied with gaseous effluent from at least step b1) at the bottom of the column, generating a stream rich in light compounds at the top of the column, a stream rich in heavy compounds at the bottom, and an aromatic-rich stream by lateral withdrawal, the sole heat input to the column being the gaseous effluent from step b1). The gaseous effluent from step b1) is at a high temperature, preferably above 300°C. This temperature is sufficient so that the column does not require any other heat input. By supplying the feedstock to the bottom of the column, the feedstock is rapidly cooled, thus limiting the potential polymerization reaction of styrene. This method of supply also allows for better control of "heavy" compounds. This is because the risk of fouling, especially with highly viscous "heavy" compounds, is significantly reduced because there is no recirculation system at the bottom of the column, which is generally used to maintain the temperature of distillation columns. The distillation column used in this modification of step c1) of the process according to the present invention comprises 5 to 20 theoretical plates, preferably 15 theoretical plates or less, and more preferably 8 to 12 theoretical plates.

[0019] The aromatic stream is drawn off at an intermediate plate. This drawing plate is located in the lower third of the distillation column, preferably one to three theoretical plates from the bottom plate. This drawing off at a low position in the column, slightly away from the bottom plate, makes it possible to limit the entrainment of heavy compounds in the aromatic stream, and consequently, the risk of fouling of subsequent equipment. Preferably, to further limit the risk of polymerization, a styrene polymerization inhibitor that produces polystyrene, such as 2,2,6,6-tetramethyl-4-oxopiperidinooxy, can be provided to the distillation column, preferably at the top of the column, in step c) of the process. Toluene and ethylbenzene-type compounds that do not react in resin synthesis step d) can be used as solvents in this synthesis step, thus avoiding the addition of solvents of external origin to the process.

[0020] Step b2) Thermal decomposition of the supply material, including rubber chips. The feedstock, including rubber chips, is supplied to a step of thermal decomposition of rubber chips, carried out at a temperature between 300 and 900°C with an increasing temperature ramp, making it possible to obtain gaseous effluent, thermal decomposition oil, and solid effluent, the thermal decomposition oil containing at least 1.5% by mass of C4-C 12 Contains olefin monomers. The pyrolysis step is carried out at a temperature preferably between 350 and 800°C, more preferably between 350 and 650°C, a pressure of less than 1 bar, and a ratio of solid residence time to gas residence time in the range of 10 to 240, preferably 10 to 120, and very preferably 10 to 60. A shorter residence time for the gas fraction relative to the residence time for the solid fraction can improve the yield of the target monomer. The residence time of the gas fraction can be shortened by supplying an inert gas to the pyrolysis step. This preferential supply also improves the desorption of volatile materials bound to the solid fraction. The residence time for the solid fraction in the pyrolysis step is preferably in the range of 3 to 180 minutes, and more preferably in the range of 3 to 120 minutes. The residence time for the gas fraction is less than 3 minutes. These specific conditions make it possible to maximize the production of the target compound, particularly monomers such as limonene, as well as gaseous fractions that can be improved for fuel use, and heavy liquid fractions that can be used to produce carbon black.

[0021] In particular, by using a rising temperature ramp, it becomes possible to optimize the yield and selectivity of the pyrolysis reaction to the advantage of the target monomer. Preferably, the pyrolysis step is carried out using a temperature ramp between 1 and 10°C / min. The pyrolysis step may be carried out in a pyrolysis reactor, and may be carried out continuously, semi-continuously, or in batches. Such reactors are well known to those skilled in the art. The pyrolysis reactor may be any device in which the reaction can be carried out via the addition of heat, and the addition of heat may be carried out in any way known to those skilled in the art, for example by combustion, electrical means or radiation. If the pyrolysis step is carried out continuously or semi-continuously, it may be carried out in multiple zones operated by heating, so that the stream passing through these zones is subjected to a temperature increase between 1 and 10°C / min. The pyrolysis effluent is cooled to condense the volatile fraction. Once the condensation is complete, three effluents are obtained: a gaseous effluent containing non-condensable gases (i.e., gases that are gaseous under normal temperature and pressure conditions, i.e., at 0 °C and 1 atm), a liquid effluent designated "pyrolysis oil", and a solid effluent. The pyrolysis oil mainly consists of a mixture of hydrocarbons having a wide range of boiling points. Most of these compounds belong to the families of alkanes, olefins, naphthenes (cycloalkanes), and aromatics. Some species containing heteroatoms are also present.

[0022] The operating conditions of the pyrolysis step of the process according to the invention are such that a pyrolysis oil containing at least 1.5% by mass of C4-C 12 olefin monomers, preferably at least 2% by mass of C4-C 12 olefin monomers, preferably at least 4% by mass, can be obtained. The term "olefin monomer" means a hydrocarbon compound containing an unsaturated carbon-carbon bond that can be polymerized under suitable conditions. Among these olefin monomers, mention may be made of limonene, terpenes, aromatic olefins such as styrene, α-methylstyrene, indene, coumarone, linear olefins or cyclic olefins such as dicyclopentadiene. The pyrolysis oil preferably contains at least 70% by mass, preferably at least 74% by mass, and preferentially at least 78% by mass of elemental carbon. The pyrolysis oil preferably contains at most 5% by mass, preferably at most 3% by mass, and preferentially at most 1.5% by mass of elemental nitrogen. The pyrolysis oil preferably contains at most 2% by mass, preferably at most 1.5% by mass, and preferentially at most 1% by mass of elemental sulfur.

[0023] Step c2) of separating the oil obtained from step b² The process according to the invention includes the step of separating the pyrolysis oil from step b² into at least one raffinate, an intermediate fraction, and an extract, the intermediate fraction having a boiling point at atmospheric pressure in the range of 140 to 280 °C and containing at most 10% by mass of heteroatoms. The boiling point at atmospheric pressure can be determined by methods known to those skilled in the art, for example, in accordance with the provisions of the standard ASTM D86-23. The term "extract" refers to a lighter fraction than the intermediate fraction, i.e., a fraction with a lower final boiling point (or cut point in distillation terminology). The term "raffinate" refers to a heavier fraction, i.e., a fraction with a higher final boiling point than the intermediate fraction. The separation step allows for the removal of components from the pyrolysis oil that may be detrimental to the proper operation of the resin synthesis step, particularly in terms of catalyst activity. In a preferred embodiment, the intermediate fraction obtained from step b2) is a cut having a boiling point at atmospheric pressure in the range of 150 to 280°C, preferably 150 to 260°C. This cut concentrates most of the desired olefin monomer while simultaneously removing most of the compounds that may adversely affect the resin synthesis step.

[0024] The aforementioned intermediate fraction contains 10% by mass or less of heteroatoms. In particular, it includes limonene and other compounds of the terpene family, such as α-pinene, β-pinene, carene, myrcene, farnesene, other oxidized or non-oxidized terpenes, aromatic olefins, such as styrene, α-methylstyrene, indene, coumarone, linear and cyclic olefins, such as dicyclopentadiene, as well as compounds that are inert with respect to the resin synthesis step, such as aliphatic and aromatic hydrocarbons. Preferably, the intermediate fraction obtained from step b2) contains 2% by mass or less, preferably 1.5% by mass or less, preferably less than 1% by mass, and very preferably less than 0.8% by mass of sulfur, and less than 0.8% by mass of sulfur is particularly detrimental to the subsequent resin synthesis step. The step of separating the pyrolysis oil into at least a raffinate, an intermediate fraction, and an extract is C4-C 12 This may be done by any means known to those skilled in the art, which can increase the concentration of olefin monomers and limit the heteroatom content. Particularly preferably, the separation step b2) is carried out by distillation, which may be carried out sequentially (in batches) or continuously in one or more intermediate steps. Therefore, in a preferred configuration, separation step b2) is carried out by distillation, and the intermediate fraction is obtained by a tailing operation following a topping operation.

[0025] The term "topping operation" refers to the removal of the light fraction with a cut point at atmospheric pressure below 140°C, preferably below 150°C. The term "tailing operation" refers to the removal of the heavy fraction with a cut point above 280°C, preferably above 260°C. In another preferred configuration, separation step b2) is performed in a single distillation step, and the intermediate fraction is obtained by lateral drawing from the distillation step. A particularly preferred implementation of this configuration is in an "inner wall" column. If separation step b2) is preferably carried out by distillation, this is preferably carried out at a pressure below atmospheric pressure, preferably below 0.5 bar, and preferably below 0.250 bar.

[0026] In a preferred embodiment, the intermediate fraction from step c2) is purified before being supplied to step d). This purification process can, in particular, reduce the content of compounds such as sulfur or carbonyl compounds before supplying the intermediate fraction to step d) resin synthesis, where appropriate. Preferably, the purification process is carried out by passing the intermediate fraction through a fixed bed of silica, alumina, activated carbon, ion exchange resin, or a mixture of these components. More preferably, the purification process is carried out by passing the intermediate fraction through a fixed bed of alumina beads, particularly to remove polar impurities. In configurations where purification is performed, the heteroatom content in the intermediate fraction at the end of the purification process is less than 2% by mass, preferably less than 1% by mass, more preferably less than 0.9% by mass, and in a preferred embodiment less than 0.8% by mass. Polyaromatically rich raffinates may be modified, for example, by a "blast furnace" process for the production of carbon black, whose properties and specifications are equivalent to those of carbon black produced from conventional starting materials. This may be used in the manufacture of new rubber products such as tires, conveyor belts, or any rubber articles. The extract of the target compound for the resin synthesis step of the process according to the present invention may preferably be used as a solvent, fuel, or plasticizer, or may be treated in a refining process to recover light aromatic hydrocarbons (benzene, toluene, xylene).

[0027] Resin synthesis step d) The process according to the present invention includes a resin synthesis step comprising a polymerization section supplied with at least a stream from step c1) and an intermediate fraction from step c2), followed by a finishing section, to produce a polymerization effluent. The resin synthesis step mainly consists of oligomerizing monomers contained in the stream obtained from step c1), particularly styrene and α-methylstyrene, and monomers contained in the intermediate fraction obtained from step c2), and thus controlling the macrostructure, thereby further controlling the microstructure by limiting the content of low molecular weight compounds, particularly monomers, dimers, and trimers, and high molecular weight compounds, i.e., compounds with a molecular weight greater than 5000 g / mol, in order to prepare a new oligomeric material of resin type. The term "dimer" means a compound containing two monomers linked via a covalent bond. A dimer may be a homodimer, i.e., a combination of two identical monomers, a heterodimer, i.e., a combination of two different monomers, or a mixture of homodimers and heterodimers. The term "trimer" means a compound containing three monomers linked via a covalent bond. A trimer may be a homotrimer, i.e., a combination of three identical monomers, a heterotrimer, i.e., a combination of at least two different monomers, or a mixture of homotrimers and heterotrimers.

[0028] By supplying at least one stream obtained from step c1) and the intermediate fraction obtained from step c2) to the resin synthesis step, the ratio of aromatic units to aliphatic units in the resulting resin can be controlled, thereby allowing the resin to be adapted to the polymer matrix into which it is intended to be incorporated. In this way, a resin with excellent compatibility derived from recycled resources can be obtained. Therefore, the process according to the present invention allows the use of a stream rich in light compounds, a stream rich in aromatic compounds, or a stream rich in heavy compounds, depending on the parameters required for the resin to be produced, which enables great versatility. Preferably, if a stream rich in light compounds, a stream rich in heavy compounds, or a stream rich in aromatic compounds is produced by distillation in step c1), no further processing is required before using one of these streams for resin production. In a preferred embodiment, the mass ratio of the stream obtained from step c1) supplied to step d) and the intermediate fraction obtained from step c2) is adjusted so that the resulting resin has an aliphatic H / aromatic H molar ratio in the range of 40 / 60 to 95 / 5, preferably in the range of 50 / 50 to 90 / 10, and more preferably in the range of 55 / 45 to 90 / 10.

[0029] In a preferred embodiment, the polymerization section is also supplied with a solvent stream selected from aliphatic, aromatic, and halogenated solvents and mixtures thereof. In a preferred embodiment, the solvent selected from aliphatic, aromatic, halogenated solvents and mixtures thereof is preferably selected from C7-C10 aromatic solvents, C6-C8 aliphatic solvents, and C1-C2 chlorinated solvents and mixtures thereof, with a preference being toluene, methylcyclohexane, and dichloromethane. Preferably, the fraction of pyrolysis oil obtained from step b1) is used as a solvent stream. Preferably, the process according to the present invention is supplied with only the feedstock of the styrene compound and the intermediate fraction obtained from step c2), and the solvent required in step d) is provided by at least one stream obtained from step c1) and / or at least one fraction of pyrolysis oil obtained from step b), preferably only at least one fraction of pyrolysis oil obtained from step b) is supplied to step d).

[0030] Preferably, in synthesis step d), a stream obtained from step b), an intermediate fraction obtained from step c2), and a solvent stream are supplied such that the monomer content is between 50% and 75% by mass. Therefore, the solvent flow rate may be adapted to adjust the monomer content in step d). This content makes it possible to limit the exothermic activity in step d), and at the same time, a polymerization effluent is obtained that, due to its viscosity, can be sent to the downstream steps of the process of the present invention. Preferably, the resin obtained by the process according to the present invention contains less than 1% by mass of compounds with a molecular mass greater than 5000 g / mol. Preferably, the obtained resin contains 50% by mass or less of dimer and trimer compounds. The polymerization section is operated in the absence of a catalyst, or in the presence of a Brønsted acid, Lewis acid, or Friedel-Crafts type acid catalyst, which may be homogeneous or heterogeneous. Preferably, the polymerization section is operated in the presence of a Brønsted acid or Lewis acid type acid catalyst. The polymerization section may also be operated in the presence of ligands, co-catalysts, and / or cationic polymerization initiators, such as protons or carbocation-generating types.

[0031] Preferably, the catalyst is a Lewis acid containing ligands from the aluminum halide family. In preferred embodiments, these ligands are selected from aluminum chloride, e.g., aluminum trichloride; alkylaluminum chloride, e.g., diethylaluminum chloride and ethylaluminum dichloride; and arylaluminum chloride, e.g., phenylaluminum chloride. Preferably, the catalyst also includes Lewis basic auxiliary ligands that can adjust the acidity of the Lewis acid ligand, such as aliphatic ether type (e.g., diethyl ether, dibutyl ether), aromatic ether type (diphenyl ether), or ester type (ethyl acetate), or alkylamine (triethylamine) or arylamine (diphenylamine, triphenylamine). The polymerization section may also be operated with ligands containing phosphorus, sulfur, or other heteroatoms. The polymerization section is operated at temperatures preferably in the range of -60°C to +300°C, more preferably in the range of -60°C to +120°C, very preferably in the range of -50°C to +100°C, more preferably in the range of -40°C to +90°C, and very preferably in the range of +20°C to +90°C. The average residence time of the polymerization section is preferably between 0.25 hours and 7 hours, and more preferably between 0.5 hours and 4 hours. When the polymerization section is operated continuously, the average residence time of the section is the ratio of the reaction volume of the section to the volumetric flow rate of the feed to the section.

[0032] The amount of catalyst containing optional ligands and auxiliary ligands is preferably in the range of 0.05% to 5% by mass relative to the mass of olefin monomers entering the polymerization section, and in a preferred embodiment, it is 0.1% to 2% by mass relative to the mass of olefin monomers (styrene, α-methylstyrene, limonene, indene) entering the polymerization section. The stream from the polymerization section is then processed in the finishing section to produce polymerization effluent. In this finishing section, the polymerization reaction can be quenched by adding a compound that deactivates the catalyst and stops the still-growing chain. The finishing section is operated by contacting a stream containing a quenching compound, preferably selected from water, C1-C3 alcohols and mixtures thereof, preferably selected from water, methanol, ethanol and mixtures thereof, and very preferably water, at a temperature between 5 and 80°C, preferably between 15 and 30°C (e.g., room temperature), and then separating the polymerization effluent from the effluent mainly containing the quenching compound by phase decantation. The molar ratio of the quenching compound to the polymerization catalyst in the finishing section is at least equal to 1.1, and preferably at least equal to 2. 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, more preferably between 10:1 and 5:1, and more preferably between 5:1 and 1:1.

[0033] The stream from the polymerization section and the stream containing the quenching compound are brought into contact with the reaction medium with stirring, preferably for a period ranging from 5 minutes to 2 hours, and more preferably from 15 minutes to 45 minutes. At the end of this stirring stage, a decantation step is performed to separate the organic phase, which mainly consists of the polymerization effluent containing resin, solvent, unconverted monomers, dimers, trimers, and low molecular weight oligomers, from the other phase, which mainly consists of the quenching compound, catalyst residue, and organic residue soluble in the quenching compound. The decantation phase is preferably conducted for a period ranging from 5 minutes to 4 hours, and more preferably from 15 minutes to 2 hours. Subsequently, the phase, which mainly contains the quenching compound, may be treated to reuse the quenching compound in the finishing section. The polymerization effluent is then supplied to the processing step.

[0034] Step e) to treat polymerization spills. The process according to the present invention includes a step of processing polymerization effluent from step d), which includes a section for separating solvent-rich effluent from resin-rich effluent and a drying section into which the resin-rich effluent is supplied to produce resin. By performing the polymerization effluent treatment step in the process according to the present invention, it is possible to adjust the characteristics of the resin and control the properties of the resulting resin (e.g., glass transition temperature) by removing low molecular weight oligomers (e.g., dimers, trimers, and tetramers) and reducing the degree of dispersion. The section for separating the solvent-rich effluent from the resin-rich effluent allows, on the one hand, the recovery of the majority of the solvent and unconverted monomer for subsequent use, preferably for reuse in the resin synthesis step of the process according to the present invention, and on the other hand, the concentration of the resin in the resin-rich effluent. The separation section may be operated by any method known to those skilled in the art, particularly preferably by evaporation, distillation, resin coagulation, liquid-liquid extraction, or a combination thereof.

[0035] In a preferred configuration, the separation section is operated by distillation in at least one distillation column to produce a solvent-rich effluent at the top and a resin-rich effluent at the bottom. This section allows for the removal of monomers and oligomers remaining at the top, as well as most of the solvent used in the resin synthesis steps, and thus the reduction in dispersion, particularly by the removal of low molecular weight compounds, thereby enabling the adjustment of the resin's macrostructure and properties, such as its glass transition temperature (indicated as Tg). The resin-rich effluent contains most of the resin supplied to the separation section. The resin recovery rate, which corresponds to the ratio of the resin flow rate in the resin-rich effluent to the resin flow rate in the feed to the separation section, is preferably higher than 80%, and more preferably higher 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 the section, such as the reflux ratio.

[0036] In another preferred configuration, the separation section is operated by resin coagulation. In this configuration, the polymerization effluent from step d) is brought into contact with a coagulation solvent in which the resin is insoluble to precipitate the resin. The coagulation solvent dissolves the residual monomers, the solvent used in the resin synthesis step, and the low molecular weight oligomers. The solidification solvent is preferably selected from low-boiling polar protic or aprotic solvents such as alcohols, e.g., methanol, ethanol, and isopropanol, acetone, ethers, e.g., tetrahydrofuran (THF), and dioxane. The coagulation separation section is operated using a volume ratio of coagulation solvent to the medium to coagulate, preferably in the range of 1:1 to 10:1, and more preferably in the range of 2:1 to 5:1. The coagulation separation section is operated at a temperature preferably in the range of 5°C to 40°C. The stream containing the solidification solvent that constitutes the solvent-rich effluent may then be reused, for example, in a resin synthesis step, after undergoing a purification step as needed. In another preferred configuration, the separation section is operated by liquid-liquid extraction. In this configuration, the polymerization effluent from step d) is washed with a stream mainly containing water. This extraction may be carried out in one or more steps, preferably one to three steps. Liquid-liquid extraction may also be performed upstream of the separation by distillation or the aforementioned resin coagulation. In another preferred configuration, the separation section is carried out by evaporation, for example, evaporation in a wiped film evaporator.

[0037] The viscosity of resin-rich spills depends on the resin content and temperature of the spill. Therefore, these content and temperature are adjusted so that the spill can be transported to a drying section. Sometimes, it is necessary to maintain a high temperature to achieve a high resin content while simultaneously maintaining the viscosity of the spill for transport, while taking care to keep the temperature below the point at which the resin degrades due to heat. The resin-rich effluent is then supplied to a drying section, where it is filtered and then dried. Upon completion of the drying step, the dried resin has a residual solvent content of less than 3% by mass, preferably less than 1.5% by mass, and more preferably less than 0.8% by mass, relative to the mass of the resin (including the solvent used in the synthesis step and the solvent used in the separation section). The dried resin has a residual free monomer content of less than 5% by mass, preferably less than 2% by mass, and more preferably less than 1% by mass, relative to the mass of the resin.

[0038] resin The present invention also relates to a hydrocarbon resin obtained by the process according to the present invention, characterized by the following: • Glass transition temperature (denoted as Tg) in the range of 20℃ to 140℃. • Number average molar mass of less than 5000 g / mol, preferably less than 4000 g / mol, preferably less than 3000 g / mol. • A variance of D less than 3, preferably less than 2.5, preferably less than 2. · 1 The aromatic proton content is between 0.5 mol% and 50 mol%, preferably between 2 mol% and 30 mol%, preferably between 2 mol% and 20 mol%, as determined by 1H NMR. · 1 The aliphatic proton content is between 50 mol% and 99.5 mol%, preferably between 70 mol% and 98 mol%, and more preferably between 80 mol% and 98 mol%, as determined by 1H NMR. · 1 Having an ethylene proton content of 10 mol% or less, preferably 5 mol% or less, and more preferably 4 mol% or less, as determined by 1H NMR, The present invention relates to a hydrocarbon resin in which the total content of aromatic, aliphatic, and ethylene protons is equal to 100%. Preferably, 1 The ethylene proton content, as determined by 1H NMR, is 0.5 mol% or more, preferably 1 mol% or more.

[0039] The dried resin may then be formed into shape according to any method known to those skilled in the art, depending on the subsequent use of the resin. This shaping may be carried out, for example, by granulation. The method used to produce the resin will give the rubber composition properties that differ from those of similar resins in terms of structure. rubber composition The present invention also relates to a rubber composition based on at least one elastomer matrix, comprising at least 50 phr of butadiene copolymer, a reinforcing filler, a crosslinking system, and a hydrocarbon resin according to the present invention.

[0040] Elastomer The rubber composition according to the present invention contains at least 50 phr of butadiene copolymer. Butadiene copolymers are preferably copolymers of butadiene and vinyl aromatic monomers. For example, suitable vinyl aromatic compounds include: styrene, ortho-, meta-, or para-methylstyrene, commercially available mixtures of "vinyltoluene," para-(tert-butyl)styrene, methoxystyrene, chlorostyrene, vinylmesitylene, divinylbenzene, or vinylnaphthalene. Preferably, the vinyl aromatic monomer in the butadiene-vinyl aromatic monomer copolymer is styrene. Preferably, the rubber composition according to the present invention contains at least 70 phr, preferably at least 90 phr, of at least one butadiene copolymer, preferably butadiene-styrene copolymer. According to a particularly preferred embodiment of the present invention, the butadiene copolymer has 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, and more preferably between -60°C and -90°C. Such elastomers are known to those skilled in the art and are described, for example, in WO2015 / 185394 and WO2017 / 168099.

[0041] The tire rubber composition according to the present invention may also contain at least one other elastomer, preferably at least one other diene elastomer. It should be remembered that the term "diene elastomer" should be understood to mean an elastomer that is at least partially derived (i.e., a homopolymer or copolymer) from a diene monomer (a monomer having two conjugated or non-conjugated carbon-carbon double bonds). These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated." The term "essentially unsaturated" is generally understood to mean a diene elastomer that at least partially arises from a conjugated diene monomer having a content of more than 15% (mol%) of diene-derived units (conjugated dienes). Therefore, diene elastomers such as butyl rubber or EPDM-type dienes and α-olefin copolymers do not fit the above definition and can be described in particular as "essentially saturated" diene elastomers (having a low or very low content of diene-derived units, always less than 15% (mol%)). The diene elastomers contained in the rubber compositions according to the present invention are preferentially essentially unsaturated.

[0042] The diene elastomer is preferably an essentially unsaturated diene elastomer, and is particularly selected from the group consisting of natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR), isoprene copolymers, and mixtures thereof. Such copolymers are more preferably selected from the group consisting of isoprene / styrene copolymers (SIR) and mixtures thereof. The above diene elastomer may be, for example, a block, random, sequential, or microsequential elastomer, and may be prepared in a dispersion or in solution, and may be coupled and / or star-branched with a coupling agent and / or star-branching agent or functionalizing agent, or functionalized, for example, epoxidized.

[0043] Reinforcing filler The rubber composition according to the present invention preferably comprises a reinforcing filler. Any type of reinforcing filler known for its ability to reinforce an elastomer composition, which can be used in the manufacture of pneumatic tires, can be used, such as an organic filler such as carbon black, a reinforcing inorganic filler such as silica, or a blend of these two types of fillers, particularly a blend of carbon black and silica. All carbon blacks, particularly HAF, ISAF, or SAF type blacks ("tire grade" blacks) conventionally used in tires, are suitable as carbon blacks. More specifically, reinforced carbon blacks of the 100, 200, or 300 series (ASTM grade), such as N115, N134, N234, N326, N330, N339, N347, or N375 blacks, or even higher series blacks (e.g., N660, N683, or N772) depending on the target application, are mentioned. Carbon black may already be incorporated into isoprene elastomers, for example, in the form of a masterbatch (see, for example, patent applications WO97 / 36724 and WO99 / 16600). The BET specific surface area of ​​carbon black is measured according to standard D6556-10 [multi-point (minimum 5 points) method, gas: nitrogen, relative pressure range p / p0: 0.1~0.3].

[0044] In this patent application, the term “reinforcing inorganic filler” should be understood, by definition, to mean any inorganic or mineral filler (regardless of its color and origin (natural or synthetic)) also referred to as “white filler,” “transparent filler,” or “non-black filler,” in contrast to carbon black, which can reinforce rubber compositions for tire manufacturing on its own without the use of means other than intermediate coupling agents, in other words, it can replace conventional tire-grade carbon black in its reinforcing role. Such fillers are generally characterized by the presence of hydroxyl (-OH) groups on their surface in known ways. Silica-type, particularly silica (SiO2), or alumina-type, particularly alumina (Al2O3), mineral fillers are especially suitable as reinforcing inorganic fillers. Any reinforcing silica known to those skilled in the art, especially those of 450m, can be used. 2 Less than 30-400mg / g 2 Any precipitate or fumed silica having a BET specific surface area and CTAB specific surface area of ​​ / g may be used. Examples of highly dispersible precipitate silica (HDS) include Ultrasil 7000 and Ultrasil 7005 silica from company Degussa, Zeosil 1165MP, 1135MP and 1115MP silica from company Rhodia, Hi-Sil EZ150G silica from company PPG, Zeopol 8715, 8745 and 8755 silica from company Huber, or silica having a high specific surface area as described in patent application WO03 / 16837.

[0045] The physical state in which the reinforcing inorganic filler is provided, whether in the form of powder, micropearls, granules, beads, or any other suitable high-densification form, is not important. Needless to say, the term “reinforcing inorganic filler” also refers to mixtures of different reinforcing inorganic fillers, particularly highly dispersible silica and / or alumina fillers. The reinforcing inorganic filler used, especially if it is silica, is preferably 45 and 400 m 2 Between / g, 60 and 300m are preferred. 2 It has a BET specific surface area between / g. Preferably, the rubber composition according to the present invention comprises 1 to 100 phr, more preferably 1 to 80 phr, and most preferably 1 to 60 phr of carbon black, and the optimal amount varies depending on the specific application to be targeted, as is known. For example, the level of reinforcement expected for a bicycle pneumatic tire is naturally lower than the level of reinforcement required for a pneumatic tire that can travel at high speeds for extended periods, such as a motorcycle tire, a passenger car tire, or a tire for a utility vehicle such as a heavy vehicle. In a preferred configuration, the reinforcing filler mainly comprises, and preferably consists of, carbon black. Preferably, the rubber composition according to the present invention contains 10 to 150 phr, preferably 50 to 130 phr of silica. In a preferred configuration, the reinforcing filler mainly contains silica, preferably consisting of silica.

[0046] To couple a reinforcing inorganic filler to an elastomer, at least a bifunctional coupling agent (or binder), particularly a bifunctional organosilane or polyorganosiloxane, may be used in known ways, intended to provide a connection between the inorganic filler (the surface of its particles) and the elastomer that is satisfactory in terms of chemical and / or physical properties. In particular, silane polysulfides that are referred to as "symmetrical" or "asymmetrical" depending on the specific structure can be used, for example, as described in patent applications WO03 / 002648 (or US2005 / 016651) and WO03 / 002649 (or US2005 / 016650). Examples of silane polysulfides include bis((C1-C4)alkoxyl(C1-C4)alkylsilyl(C1-C4)alkyl) polysulfides (especially disulfides, or trisulfides or tetrasulfides), such as bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides, which can be mentioned in more detail. Among these compounds, bis(3-triethoxysilylpropyl)tetrasulfide of formula [(C2H5O)3Si(CH2)3S2]2, abbreviated as TESPT, or bis(triethoxysilylpropyl)disulfide of formula [(C2H5O)3Si(CH2)3S]2, abbreviated as TESPD, are particularly used. Furthermore, preferred examples include bis(mono(C1-C4)alkoxydi(C1-C4)alkylsilylpropyl) polysulfides (particularly disulfides, trisulfides, or tetrasulfides), as described in patent application US2004 / 132880, and more specifically bis(monoethoxydimethylsilylpropyl)tetrasulfide.

[0047] Other coupling agents besides alkoxysilane polysulfides include, in particular, difunctional POS (polyorganosiloxane) or hydroxysilane polysulfides described in patent applications WO02 / 30939 and WO02 / 31041, or silanes or POS having an azodicarbonyl functional group as described in, for example, patent applications WO2006 / 125532, WO2006 / 125533 and WO2006 / 125534. In the rubber composition according to the present invention, the content of the coupling agent is preferably in the range of 5% to 18% by mass relative to the amount of silica, and preferably in the range of 8% to 12% by mass relative to the amount of silica. Those skilled in the art will understand that reinforcing fillers of different properties, particularly organic properties, can be used as equivalent fillers to the reinforcing inorganic fillers described in this section, provided that these reinforcing fillers are covered with an inorganic layer such as silica, or contain functional moieties, particularly hydroxyl moieties, on their surface, and can establish a bond between the filler and the elastomer, with or without the presence of a coating or coupling agent.

[0048] Crosslinked system The rubber composition according to the present invention comprises a sulfur-based crosslinking system containing a metal oxide, a stearic acid derivative, and a vulcanization accelerator. This is collectively referred to as the vulcanization system. The sulfur may be provided in any form, particularly in the form of molecular sulfur or a sulfur donor. Sulfur is used in concentrations ranging from 1 to 20 phr, preferably in the range of 1 to 10 phr. The vulcanization accelerator is used in a preferential concentration such that the sulfur / vulcanization accelerator mass ratio is 4 or less. As accelerators, any compound that can act as a vulcanization accelerator for diene elastomers in the presence of sulfur, particularly thiazole-type accelerators, their derivatives, or sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea, and xanthate-type accelerators can be used. Examples of such accelerators include, in particular, the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated as MBTS), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N,N-dicyclohexyl-2-benzothiazole sulfenamide (DCBS), N-(tert-butyl)-2-benzothiazole sulfenamide (TBBS), N-(tert-butyl)-2-benzothiazole sulfenimide (TBSI), tetrabenzyl thiuram disulfide (TBZTD), zinc dibenzyl dithiocarbamate (ZBEC), and mixtures of these compounds.

[0049] The mass ratio of the metal oxide to the stearic acid derivative in the crosslinking system is less than 4, preferably less than 3. The metal oxide is preferably zinc oxide. The crosslinking system may also contain a vulcanization retarder. The rubber composition may preferably contain additives commonly used in elastomer compositions, especially those intended for the manufacture of vehicle tires, such as pigments, protective agents, such as ozone-degrading-preventing waxes, chemical ozone-degrading-preventing agents or antioxidants, plasticizers other than those mentioned above, anti-fatigue agents, reinforcing resins, or methylene acceptors (e.g., novolacphenol resins) or methylene donors (e.g., HMT or H3M). The rubber composition may also include a plasticizer. This plasticizer may consist of a hydrocarbon-based resin having a Tg greater than 20°C, in addition to the specific hydrocarbon resins described above, and / or a plasticizing oil.

[0050] Preparation of rubber composition The rubber composition according to the present invention is manufactured in a suitable mixer using preparation steps well known to those skilled in the art: - The thermomechanical processing or mixing stage may be carried out in a single thermomechanical step in which all necessary components, in particular the elastomer matrix, hydrocarbon resin, filler, and various other optional additives are introduced into a suitable mixer, such as a standard closed mixer (e.g., a "Bunbury" type). The incorporation of filler into the elastomer may be carried out in one or more separate stages while thermomechanically mixing. If the filler, in particular carbon black or silica, is already incorporated into the elastomer, either whole or partially, in the form of a masterbatch, as described, for example, in patent applications WO97 / 36724 or WO99 / 16600, then it is the masterbatch that is directly mixed, and where appropriate, other elastomers or fillers present in the composition that are not in the form of a masterbatch, as well as various other optional additives, are also incorporated. Thermomechanical kneading is generally carried out at high temperatures between 110°C and 200°C, preferably between 130°C and 185°C, for a period of 2 to 10 minutes. - The second stage of mechanical processing is then carried out in an external mixer such as an open mill, after the mixture obtained in the first stage has been cooled to a lower temperature, typically below 120°C, for example, between 40°C and 100°C.

[0051] Optional crosslinking systems are added in the second step. For example, crosslinking systems based on polyacids or polydienophiles are typically added in the first step. Crosslinking systems based on peroxides or sulfur are typically added in the second step. The final composition thus obtained can then be calendered, for example, in the form of a sheet or plaque, or extruded in the form of a rubber semi-(or profile) product, particularly for laboratory characterization. The composition may be in an uncured state (before crosslinking or vulcanization) or a cured state (after crosslinking or vulcanization), and may be a semi-finished product that can be used in tires. Curing can be carried out by methods known to those skilled in the art, generally at a temperature between 130°C and 200°C, under pressure, for a sufficient amount of time, which may be in the range of, for example, between 5 and 90 minutes, as a function of the curing temperature, the crosslinking system employed, the crosslinking kinetics of the composition under consideration, or the size of the vehicle tire.

[0052] Vehicle tires The present invention also relates to a vehicle tire in which the tread comprises the rubber composition according to the present invention. Vehicle tires may be pneumatic or non-pneumatic. The term "non-pneumatic tire" means that the tire can support the vehicle's load by means other than pressurized gas, such as a shroud. The vehicle tires according to the present invention are selected from, but are not limited to, tires intended for use on motorcycles, passenger cars, "large" vehicles (i.e., large transport vehicles such as subways, buses, off-road vehicles, trucks, tractors or trailers), aircraft, construction equipment, large agricultural vehicles or material transport vehicles. In embodiments known to those skilled in the art, the tread is the portion of a vehicle tire that surrounds the tire circumferentially and provides contact between the tire and a rolling surface, such as the road.

[0053] Measurement method glass transition temperature The glass transition temperature Tg is conventionally measured by differential scanning calorimetry (DSC) according to the 2014 standard ISO 11357-2, unless otherwise specifically indicated. Macrostructure (Mw, Mn, Mz, and D) The macrostructure (mass-average molar mass, number-average molar mass, centrifugal molar mass, and polydispersity index, denoted as Mw, Mn, Mz, and D, respectively) is determined by size exclusion chromatography (SEC), as shown below. Mz reflects the thermodynamic equilibrium between sedimentation and diffusion and depends on its size. This higher-order average is used as an indicator of the proportion of high molar mass present in the sample. As a precaution, for example, SEC analysis involves separating polymers in a solution according to their size through a column packed with a porous gel. Molecules are separated according to their hydrodynamic volume, with the bulkiest elute first. The sample to be analyzed is simply dissolved beforehand in a suitable solvent, tetrahydrofuran, at a concentration of 1.5 g / liter. The solution is then filtered through a 0.45 μm pore size filter and injected into the instrument at a flow rate of 1 mL / min and a temperature of 35°C. The instrument used is, for example, a "Waters Alliance" chromatography chain. Moore calibration is performed with a set of commercial polystyrene standards with known molar masses and low D (less than 1.2) covering the range of masses to be analyzed. The recorded data (mass distribution curve of molar masses) is used to estimate Mw and Mn, where D = Mw / Mn. Therefore, all molar mass values ​​presented in this patent application are for calibration curves prepared using polystyrene standard materials.

[0054] 1H 脂肪族 / 1H エチレン / 1H 芳香族 molar distribution The molar distributions of aliphatic, ethylene, and aromatic protons are measured using a spectrometer, in this case a Brucker Avance III 400 MHz spectrometer, and expressed as the total peak area ratio. The solvent used is CDCl3 solvent (deuterated chloroform) at 25°C, with 120 scans. NMR data for hydrocarbon resins are measured by dissolving 20 ± 1 mg of the sample in 0.7 mL of solvent. The sample is dissolved in a 5 mm NMR tube at 25°C until dissolved. CDCl3 is present as a peak at 7.20 ppm and is used as the reference peak for the sample. Aromatic protons... 1 The 1H NMR signal is located between 8.5 ppm and 6.2 ppm. Ethylene protons produce a signal between 6.2 ppm and 4.5 ppm. Finally, the signal corresponding to aliphatic protons is located between 4.5 ppm and 0 ppm. Signals corresponding to the solvent, water, and any other impurities are subtracted when integrating the resin signal. The area of ​​each category of protons is obtained for the sum of these areas, and thus the area distribution percentage of each category of protons is obtained.

[0055] Dynamic characteristics The tan(δ) dynamic properties at 23°C and 100°C are measured using a viscometer (Metravib VA4000) in accordance with standard ASTM D 5992-96. Samples of the crosslinked composition (4 mm thick and 400 mm cross-sectional area) are subjected to simple alternating sinusoidal shear stress at a frequency of 10 Hz under specified temperature conditions of 23°C and 100°C in accordance with standard ASTM D 1349-99. 2 The response of a cylindrical specimen is recorded. Strain amplitude sweeps are performed from 0.1% to 50% (forward cycle), then from 50% to 1% (return cycle). The results used are the loss factor tan(δ) and the complex modulus G * In the return cycle, the maximum value of tan(δ) and G were observed. * The values ​​shown are as follows: The tan(δ) value measured at 100°C is an indicator of dry grip. A higher value indicates improved grip. The tan(δ) value measured at 23°C is an indicator of rolling resistance. A lower value indicates lower rolling resistance. [Brief explanation of the drawing]

[0056] [Figure 1] This diagram shows a schematic representation of the process according to the present invention. [Modes for carrying out the invention]

[0057] A feedstock (1) of the styrene compound is supplied in step a) for preparing the feedstock of the styrene compound so that it can be supplied (2) to step b1). Step b1) of thermal decomposition of the feedstock of the styrene compound makes it possible to obtain at least one gaseous effluent (3) and a pyrolysis oil (4), the gaseous effluent (3) containing at least 20% by mass of an aromatic compound. The gaseous effluent (3) is then treated in separation step c1), where it is separated into at least one stream (7) rich in light compounds, one stream (6) rich in aromatics, and one stream (5) rich in heavy compounds. The feed material (8) containing rubber chips is supplied to the pyrolysis step b2). The pyrolysis step b2) of the feed material containing rubber chips produces at least one gaseous effluent (11), pyrolysis oil (9), and solid effluent (10). The pyrolysis oil (9) is then treated in a separation step c2), where it is separated into at least an extract (14), an intermediate fraction (13), and a raffinate (12). At least one of streams (5), (6), or (7) and the intermediate fraction (13) are supplied to a resin synthesis step d) which includes a polymerization section to which these streams are supplied and which may also include a solvent stream (15), the polymerization section being followed by a finishing section to which polymerization effluent (16) is produced. The polymerization effluent (16) is supplied to a processing step e), which includes a section for separating the polymerization effluent (16) from step d) into solvent-rich effluent (18) and resin-rich effluent, and a drying section to which the resin-rich effluent is supplied to generate a stream of hydrocarbon resin (17). [Examples]

[0058] Examples of the process according to the present invention and the resin produced by this process This example demonstrates the production of hydrocarbon resins from feedstocks including styrene and rubber chips. The feedstock for the styrene compound (1), in this case polystyrene, is fed into preparation step a), in this case an extruder, where it is heated to a temperature of 250°C. The liquid portion of the feedstock (2) is fed into thermal decomposition step b1), in this case microwave thermal decomposition operated at a temperature of 340°C and a pressure of 1.1 bar. The gaseous effluent (3) from the thermal decomposition step is separated by distillation in separation step c1) into a stream rich in light compounds (4), an aromatic-rich stream (5) containing 99.2% by mass of styrene, and a stream rich in heavy compounds (5). The heavy compound-rich stream (5) has the following composition: 77.6% by mass of α-methylstyrene, 17.6% by mass of styrene, 1.7% by mass of cumene, and 1.2% by mass of ethylbenzene.

[0059] The feedstock (8), which includes rubber chips, in this case pneumatic tire tread chips with an average diameter of approximately 1 mm and containing 65% by mass of isoprene elastomer, is supplied to the pyrolysis step b2). This step is carried out in a reactor consisting of three sections, which are independently heated to temperatures of 425°C, 550°C, and 775°C, respectively, under an inert atmosphere of nitrogen. At the reactor outlet, the gaseous effluent (11), liquid pyrolysis oil (9), and solid effluent (10) are separated in the following respective yields (effluent flow rate / feed flow rate): 13.5%, 44.5%, and 42%. The pyrolysis oil (9) contains approximately 4% by mass of several monomers of interest, including styrene, methylstyrene, indene, β-pinene, and limonene. The pyrolysis oil (9) is supplied to separation step c2) by distillation carried out in two sections at atmospheric pressure. In the first section, a light cut with an initial boiling point of less than 160°C is separated, which constitutes the extract (14). The heavier fraction is supplied to a second section, which allows for the generation of an intermediate cut that constitutes an intermediate fraction (13), with a cut point of 280°C, i.e., an initial boiling temperature of 280°C at atmospheric pressure, and an intermediate cut. The olefin monomer content in this fraction is approximately 33% by mass, including 24.3% by mass of limonene, 2.8% by mass of styrene, and 3% by mass of indene. The intermediate fraction (13) is passed through a bed of alumina beads to remove polar impurities.

[0060] The intermediate fraction (13) is supplied to the resin synthesis step d) along with the heavy compound-rich stream (5). In this step, a solvent stream (15), in this case toluene, is also supplied, and its flow rate is adjusted so that the total content of limonene, styrene, indene, methylstyrene, and β-pinene monomer is 30% by mass in the mixture of the heavy compound-rich stream (5), intermediate fraction (13), and solvent stream (15). Aluminum chloride (2 mol% relative to the content of limonene, styrene, indene, methylstyrene, and β-pinene monomers) is introduced into the reactor under an inert atmosphere. The reactor is maintained under an inert atmosphere throughout the reaction. The medium is stirred and operated at 50°C for 2 hours. Then, the reaction is stopped by adding water. The reaction medium constituting the polymerization effluent (16) is washed with water, and the resin is solidified with methanol to separate it into solvent-rich effluent (18) and resin-rich effluent. The resin-rich effluent is then dried in an oven at 180°C for 16 hours. The resin (17) is recovered in the form of a translucent orange solid.

[0061] This resin C1 has the following characteristics: [Table 1]

[0062] Table 2 shows commercially available hydrocarbon resins derived from bio-based materials. Resin T1 is a bio-based resin, and its reference commercially available product is Dercolyte L120 manufactured by Company DRT, which is obtained from the polymerization of limonene. [Table 2]

[0063] Examples of rubber compositions The rubber composition is produced by introducing all components except the vulcanizing system into a closed-loop mixer. The vulcanizing agent (sulfur and accelerator) is introduced into a low-temperature external mixer (the rollers of the mixer are at 30°C). The composition is cured under pressure at 150°C for 40 minutes. Table 3 shows various rubber compositions using the resins shown in Tables 1 and 2, as well as some of their properties. [Table 3] See Table 3 (1a) Tg of SBR = -88°C as described in the example WO2017 / 168099 (1b) Tg of SBR = -48°C as described in the example of WO2015 / 185394 (2) Carbon Black, ASTM N234 grade (3) Silica, Solvay Zeosil 1165 MP, HDS type (4) N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (Santoflex 6-PPD) and 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) manufactured by Flexsys (5) Coupling agent: Si69 manufactured by Evonik-Degussa (6) Diphenylguanidine, Perkacit DPG manufactured by Flexsys (7) Uniqema Pristerene 4931 stearin (8) Umicore zinc oxide, industrial grade (9) N-cyclohexyl-2-benzothiazole sulfenamide (Santocure CBS, manufactured by Flexsys)

[0064] The results are expressed with 100 as the baseline, where a value of 100 belongs to the control values ​​CT1 and CT2. A value greater than 100 indicates that the value of the corresponding characteristic is greater than the control value. A value less than 100 indicates that the value of the corresponding characteristic is lower than the control value. Compared to compositions based on bio-based polylimonene resin, compositions according to the present invention exhibit dry grip, rolling resistance, and rigidity G.* Performance improvements are observed in these respects. These performance shifts are particularly advantageous for vehicle tire treads.

Claims

1. A process for producing hydrocarbon resins from feedstocks including styrene compounds and rubber chips, comprising at least: a. A step of preparing a feedstock for the styrene compound so that this feedstock can be supplied to the pyrolysis step, b1. A step that enables the thermal decomposition of a styrene compound feedstock to obtain at least one gaseous effluent and a thermal decomposition oil, wherein the gaseous effluent contains at least 20% by mass of an aromatic compound. c1. Separating the gaseous effluent obtained from step b1) into at least one stream rich in light compounds, one stream rich in aromatics, and one stream rich in heavy compounds. b2. A step enabling the thermal decomposition of a feed material including rubber chips at a temperature between 300 and 900°C with an increasing temperature lamp to obtain a gaseous effluent, a pyrolysis oil, and a solid effluent, wherein the pyrolysis oil contains at least 1.5% by mass of C4-C12 olefin monomer. c2. A step of separating the pyrolysis oil obtained from step b2) into at least one raffinate, an intermediate fraction and an extract, wherein the intermediate fraction has a boiling point at atmospheric pressure in the range of 140 to 280°C and contains 10% by mass or less of heteroatoms, d. A resin synthesis step comprising a polymerization section to which at least one stream obtained from step c1) and an intermediate fraction obtained from step c2) are supplied, and a subsequent finishing section, wherein a polymerization efflux is produced. e. A processing step comprising a section for separating the polymerization effluent from step d) into solvent-rich effluent and resin-rich effluent, and a drying section to which the resin-rich effluent is supplied to generate a stream of hydrocarbon resin. A process that includes this.

2. The process according to claim 1, wherein the raw material for supplying the styrene compound is a raw material for supplying the styrene compound derived from waste plastic containing at least 90% by mass of polystyrene.

3. The process according to claim 1 or 2, wherein the rubber chip comprises at least 50 phr of diene elastomer, preferably at least 60 phr of diene elastomer.

4. The process according to any one of claims 1 to 3, wherein the supply material for the styrene compound 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, during step a).

5. The process according to any one of claims 1 to 4, wherein the pyrolysis step b1) includes a pyrolysis reactor operated at a temperature in the range of 300°C to 900°C, more preferably 300 to 800°C, and a pressure in the range of 0.8 bar to 7.5 bar.

6. The process according to any one of claims 1 to 5, wherein step b1) includes a microwave pyrolysis step.

7. The process according to any one of claims 1 to 6, wherein the separation step c1) is carried out by distillation.

8. The process according to any one of claims 1 to 7, wherein the mass ratio of the stream obtained from step c1) supplied to step d) and the intermediate fraction obtained from step c2) supplied to step d) is adjusted so that the resulting resin has an aliphatic H / aromatic H molar ratio in the range of 40 / 60 to 95 / 5, preferably in the range of 50 / 50 to 90 / 10, and more preferably in the range of 55 / 45 to 90 / 10.

9. The process according to any one of claims 1 to 8, wherein the polymerization section of resin synthesis step d) is also supplied with a solvent stream selected from aliphatic, aromatic and halogenated solvents and mixtures thereof.

10. The process according to any one of claims 1 to 8, wherein only feedstocks including a styrene compound and rubber chips are supplied, and the solvent required in step d) is provided by at least one stream obtained from step c2) and / or at least one fraction of the pyrolysis oil obtained from step b1).

11. The process according to claim 10, wherein at least one fraction of the pyrolysis oil obtained from step b1) is supplied to the resin synthesis step d).

12. The following features: • Glass transition temperature (Tg) in the range of 20°C to 140°C. - Number average molar mass of less than 5000 g / mol, preferably less than 4000 g / mol, preferably less than 3000 g / mol. • A dispersion degree D of less than 3, preferably less than 2.5, preferably less than 2. ・ 1 Aromatic proton content between 0.5 mol% and 50 mol%, preferably between 2 mol% and 30 mol%, preferably between 2 mol% and 20 mol%, as determined by 1H NMR. ・ 1 The aliphatic proton content is between 50 mol% and 99.5 mol%, preferably between 70 mol% and 98 mol%, and more preferably between 80 mol% and 98 mol%, as determined by 1H NMR. ・ 1 Having an ethylene proton content of 10 mol% or less, preferably 5 mol% or less, and more preferably 4 mol% or less, as determined by ¹H NMR, The total content of aromatic protons, aliphatic protons, and ethylene protons is equal to 100%, preferably. 1 A resin prepared by a process according to any one of claims 1 to 11, wherein the ethylene proton content determined by 1H NMR is 0.5 mol% or more, preferably 1 mol% or more.

13. A rubber composition based on at least one elastomer matrix, comprising at least 50 phr of butadiene copolymer, a reinforcing filler, a crosslinking system, and a hydrocarbon resin according to claim 12 or a hydrocarbon resin prepared by a process according to any one of claims 1 to 11.

14. The rubber composition according to claim 13, wherein the butadiene copolymer has a glass transition temperature Tg of less than -20°C, preferably between -20°C and -110°C.

15. A vehicle tire having a tread comprising the rubber composition described in claim 13 or 14.

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