EP-4735273-A1 - HYDROCARBON RESIN FROM BIO-BASED AND/OR RECYCLED MATERIALS, AND RUBBER COMPOSITION COMPRISING SAID HYDROCARBON RESIN

Abstract

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

Inventors

• LECOQ, Aurélie
• SUTTER, MARC
• TOULEMONDE, Paul-Aymé

Assignees

• COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN

Dates

Publication Date

20260506

Application Date

20240625

Claims (1)

1. CLAIMS [Claim 1] Hydrocarbon resin based on an aromatic distillation cut T150°C-220°C originating from the separation of the pyrolysis effluent of a styrenic feedstock, called a "stream rich in heavy compounds", and an aliphatic stream of biosourced origin, said resin having the following characteristics: ^ a glass transition temperature (denoted Tg) ranging from 20°C to 140°C; ^ a number-average molar mass of less than 5000 g/mol; ^ a dispersity Đ of less than 3; ^ A level of aromatic protons, determined by 1H NMR, of between 0.5% mol and 50% mol; ^ A level of aliphatic protons, determined by 1H NMR, of between 50% mol and 99.5% mol; ^ A level of ethylenic protons, determined by 1H NMR, less than or equal to 10 mol%; the sum of the levels of aromatic, aliphatic and ethylenic protons being equal to 100%. [Claim 2] Hydrocarbon resin according to the preceding claim in which the level of aromatic protons, determined by 1H NMR, is between 1 mol% and 40 mol%, preferably between 2 mol% and 30 mol%. [Claim 3] Hydrocarbon resin according to any one of the preceding claims, in which the charge of styrenic compounds comprises at least 90% by weight of polystyrene, preferably at least 93% by weight of polystyrene, and preferably at least 95% by weight of polystyrene. [Claim 4] Hydrocarbon resin according to any one of the preceding claims obtained by a process comprising at least: a. A step of preparing the charge of styrenic compounds so as to be able to feed this charge into the pyrolysis step; b. A step of pyrolysis of the charge of styrenic compounds making it possible to obtain at least one gaseous effluent and one pyrolysis oil, said gaseous effluent comprising at least 20% by weight of aromatic compounds; c. A step of separating the gaseous effluent into at least one stream rich in heavy compounds whose bubble point and dew point measured at atmospheric pressure are in the temperature range from 150°C to 220°C; d. A step of synthesizing resins comprising a polymerization section supplied with the stream rich in heavy compounds from step c) and with a stream of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, followed by a finishing section and producing a polymerized effluent; e. A treatment step comprising a section for separating the polymerized effluent from step d) into a solvent-rich effluent and a resin-rich effluent, and a drying section supplied with the resin-rich effluent in order to produce a stream of hydrocarbon resins. [Claim 5] Rubber composition based on at least one elastomer and a hydrocarbon resin according to any one of the preceding claims. [Claim 6] Rubber composition according to the preceding claim comprising a reinforcing filler and a crosslinking system. [Claim 7] Rubber composition according to any one of claims 5 to 6 comprising from 10 to 150 phr, preferably from 50 to 130 phr of silica. [Claim 8] Rubber composition according to any one of claims 5 to 7 in which the elastomer is a diene elastomer. [Claim 9] Rubber composition according to any one of claims 5 to 8 in which the elastomer mainly comprises a diene elastomer having a glass transition temperature Tg of less than -20°C, preferably between -20°C and -110°C. [Claim 10] Rubber composition according to any one of claims 5 to 9 comprising at least 60 phr, preferably at least 70 phr, more preferably at least 80 phr of at least one diene elastomer chosen from the group consisting of polybutadiene, butadiene copolymers and mixtures of these elastomers. [Claim 11] A rubber composition according to the preceding claim, wherein the butadiene copolymer is a butadiene-styrene copolymer. [Claim 12] A vehicle tire comprising a rubber composition according to any one of claims 5 to 11 or a resin according to any one of claims 1 to 4. [Claim 13] A vehicle tire according to the preceding claim, wherein the tread comprises a hydrocarbon resin according to any one of claims 1 to 4 or a rubber composition according to any one of claims 5 to 11.

Description

HYDROCARBON RESIN FROM BIOSOURCED AND/OR RECYCLED MATERIALS AND RUBBER COMPOSITION COMPRISING THIS HYDROCARBON RESIN Technical field of the invention The present invention relates to the field of hydrocarbon resins, rubber compositions comprising such resins, as well as vehicle tires comprising such rubber compositions. Prior art It is known from the prior art that elastomers having a low glass transition temperature ("Tg") allow an improvement in terms of abrasion performance (WO 2015/043902) and are therefore very useful when seeking to obtain the best compromise between performance properties that are difficult to reconcile simultaneously, such as wear resistance and grip, which must be high, and rolling resistance, which must be low in order to minimize fuel consumption. These low Tg elastomers have poor compatibility with hydrocarbon-based plasticizing resins typically used in vehicle tires. However, the compatibility of the resins with the elastomeric matrix, and in particular their ability to disperse correctly in the mixture, is essential for them to play their role correctly. The compatibility of the resin with an elastomeric matrix depends, among other things, on properties such as the glass transition temperature and the softening point of the resin, these properties being dependent on the molar mass, the nature and the ratio of aromatic units to aliphatic units of the resin (see for example J. Appl Polym. Sci 2022139(15) 51950). Resins comprising aliphatic and aromatic units and having high Tgs make it possible, in particular, to modify the Tg of the mixture. Such resins are well known in the state of the art. Document EP 0936229 teaches for example the manufacture of hydrocarbon resins from aliphatic and aromatic monomers in cationic polymerization, from petroleum-based flows. Documents WO2016/043851, US9139721 or FR2968006 describe hydrocarbon resins having high Tg. Document FR 3099166 describes a tire comprising a rubber composition comprising a specific hydrocarbon resin from petroleum fractions having improved road behavior at different temperatures. While the performance of tires such as rolling resistance and wear resistance are key to limiting their environmental impact, it is also important to limit the use of fossil resources as much as possible when manufacturing rubber articles. Documents WO2022/101562 and WO2022/101563 describe the production of hydrocarbon resins from residues from the pyrolysis of rubber chips. These documents do not address the impact of these resins on the performance of rubber compositions. Continuing its research, the applicant discovered that a resin derived from bio-sourced and/or recycled resources made it possible to maintain, or even improve, key performances of rubber compositions usable in vehicle tires, thus being able to advantageously replace petroleum-based hydrocarbon resins. Detailed description of the invention The invention relates to a hydrocarbon resin based on an aromatic distillation cut T150°C-220°C originating from the separation of the pyrolysis effluent of a styrenic feedstock, called a "stream rich in heavy compounds", and an aliphatic stream of biosourced origin, said resin having the following characteristics: • a glass transition temperature (denoted Tg) ranging from 20°C to 140°C; • a number-average molar mass of less than 5000 g/mol; • a dispersity Đ of less than 3; • an aromatic proton content, determined by 1H NMR, of between 0.5 mol% and 50 mol%; • an aliphatic proton content, determined by 1H NMR, of between 50 mol% and 99.5 mol%; • an ethylenic proton content, determined by 1H NMR, of less than or equal to 10 mol%; The sum of the aromatic, aliphatic and ethylenic proton levels being equal to 100%. Preferably, the aromatic proton level, determined by 1H NMR, is between 1 mol% and 40 mol%, preferably between 2 mol% and 30 mol%. Preferably, the charge of styrenic compounds comprises at least 90% by weight of polystyrene, preferably at least 93% by weight of polystyrene, and preferably at least 95% by weight of polystyrene. Preferably, the hydrocarbon resin according to the invention is obtained by a process comprising at least: a. A step of preparing the charge of styrenic compounds so as to be able to feed this charge into the pyrolysis step; b. A step of pyrolysis of the charge of styrenic compounds making it possible to obtain at least one gaseous effluent and one pyrolysis oil, said gaseous effluent comprising at least 20% by weight of aromatic compounds; c. A step of separating the gaseous effluent into at least one stream rich in heavy compounds whose bubble point and dew point measured at atmospheric pressure are included in the temperature range from 150°C to 220°C; d. A resin synthesis step comprising a polymerization section supplied with the stream rich in heavy compounds from step c) and with a stream of aliphatic compounds comprising at least 5% by weight of terpene compounds of biosourced origin, followed by a fin