Tire incorporating a rubber composition comprising a specific hydrocarbon resin

Abstract

This article describes a tire comprising a rubber composition based at least on an elastomer matrix and a hydrocarbon resin, the elastomer matrix comprising 50 phr to 100 phr of at least one copolymer of butadiene and a vinyl aromatic monomer, the at least one copolymer of butadiene and a vinyl aromatic monomer having a vinyl aromatic unit content between 0 and 5 wt% and a Tg in the range of -110°C to -70°C, wherein the hydrocarbon resin is based on a cyclic monomer selected from petroleum refining stream fractions, C4, C5 and C6 cyclic olefins and mixtures thereof, wherein the hydrocarbon resin has an aromatic proton content (H Ar, in mol%), a glass transition temperature (Tg, in °C) and a number-average molecular weight (Mn, in g / mol) as expressed by: (1) 12 mol% ≤ H Ar ≤ 19 mol%, (2) Tg ≥ 95 - 2.2 * (H Ar), (3) Tg ≥ -53 + (0.265 * Mn) and (4) 300 g / mol ≤ Mn ≤ 450 g / mol.

Description

Technical Field

[0001] This invention relates to tires comprising a rubber composition containing a specific hydrocarbon resin. Background Technology

[0002] It is known from the prior art that elastomers with low glass transition temperatures (“Tg”) can improve wear performance (WO 2015 / 043902). However, these low-Tg elastomers have poor compatibility with hydrocarbon plasticizers commonly used in tires, making them unsuitable for easy and optimal use in tire compositions where the best compromise between performance characteristics that are difficult to reconcile simultaneously (i.e., the need for high wear resistance and grip versus the need for low rolling resistance to minimize fuel consumption) is achieved.

[0003] Therefore, it is currently advantageous for tire manufacturers to find formulations that enable an improved balance between all these performance characteristics, particularly by improving the compatibility between the elastomer and the hydrocarbon plasticizer.

[0004] Document WO2013 / 176712 describes various resins of the cyclopentadiene / dicyclopentadiene / methylcyclopentadiene type with specific molecular weights and softening points. In this document, these resins are used in the disclosed examples to improve wet grip.

[0005] Documents WO2017 / 064235 and WO2017 / 168099 also describe various resins of the cyclopentadiene / dicyclopentadiene / methylcyclopentadiene type and their use in tires with high grip and low rolling resistance. Summary of the Invention

[0006] The applicant has demonstrated that specific compositions containing specific hydrocarbon resins enable tires with improved road performance at various temperatures. This invention relates to such tires, as further described below.

[0007] This article describes a tire comprising a rubber composition based at least on an elastomer matrix and a hydrocarbon resin, the elastomer matrix comprising 50 phr to 100 phr of at least one copolymer of butadiene and a vinyl aromatic monomer, the at least one copolymer of butadiene and a vinyl aromatic monomer having a vinyl aromatic unit content between 0 and 5 wt% and a Tg in the range of -110°C to -70°C, wherein the hydrocarbon resin is based on a cyclic monomer selected from fractions of petroleum refining streams, C4, C5 and C6 cyclic olefins and mixtures thereof, wherein the hydrocarbon resin has an aromatic proton content (HAr, in mol%), a glass transition temperature (Tg, in °C) and a number-average molecular weight (Mn, in g / mol) as expressed by: (1) 12 mol% ≤ H Ar ≤ 19 mol%, (2) Tg ≥ 95 - 2.2 * (H Ar), (3) Tg ≥ -53 + (0.265 * Mn) and (4) 300 g / mol ≤ Mn ≤ 450 g / mol.

[0008] The tires according to the invention will be selected, without limitation, from tires intended for mounting two-wheeled vehicles, passenger vehicles, or “heavy” vehicles (i.e., subways, buses, off-road vehicles, heavy road transport vehicles (e.g., trucks, tractors or trailers)), or aircraft, construction equipment, heavy agricultural vehicles or transport vehicles. Attached Figure Description

[0009] Figure 1 This is a graph showing the relationship between Tg and H / Ar for the hydrocarbon resin of the present invention, the comparative resin, and the prior art elastomer composition.

[0010] Figure 2 The Tg and M of the hydrocarbon resins of the present invention, the prior art comparative hydrocarbon additives, and the prior art comparative elastomer compositions are described. n A diagram of relationships.

[0011] Figure 3 This is a graph showing the relationship between Tg and Mz for hydrocarbon resins of the present invention, prior art hydrocarbon additives, and prior art elastomer compositions. Detailed Implementation

[0012] This document provides tires comprising a rubber composition based at least on an elastomer matrix and a hydrocarbon resin, the elastomer matrix comprising 50 phr to 100 phr of one or more copolymers of butadiene and vinyl aromatic monomers having a vinyl aromatic unit content between 0 and 5 wt% and a Tg in the range of -110°C to -70°C, wherein the hydrocarbon resin is based on cyclic monomers selected from fractions of petroleum refining streams, C4, C5 and C6 cyclic olefins and mixtures thereof, wherein the hydrocarbon resin has an aromatic proton content (H Ar, in mol%), a glass transition temperature (Tg, in °C) and a number-average molecular weight (Mn, in g / mol) as expressed by: (1) 12 mol% ≤ H Ar ≤ 19 mol%, (2) Tg ≥ 95 - 2.2 * (H Ar), (3) Tg ≥ -53 + (0.265 * Mn) and (4) 300 g / mol ≤ Mn ≤ 450 g / mol.

[0013] definition

[0014] For the purposes of this disclosure, unless otherwise stated, the following definitions will be used:

[0015] Unless otherwise stated, the singular forms of “a,” “an,” and “the” as used herein include the plural referent.

[0016] The term "dominant compound" refers to the compound that is dominant among similar compounds in the composition. For example, the dominant compound is the compound that accounts for the largest weight among similar compounds in the composition. Thus, for example, the dominant polymer is the polymer that accounts for the largest weight in the total weight of the polymers in the composition.

[0017] The term "dominant unit" refers to the unit that constitutes the majority of the units forming the same compound (or polymer), representing the largest weight fraction among all the units forming the compound (or polymer). For example, a hydrocarbon resin may contain a dominant cyclopentadiene unit, wherein the cyclopentadiene unit constitutes the largest weight among all the units constituting the resin. Similarly, as described herein, a hydrocarbon resin may contain a dominant unit selected from cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, and mixtures thereof, wherein the sum of units selected from cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, and mixtures thereof constitutes the largest weight among all the units.

[0018] The term "major monomer" refers to the monomer that constitutes the largest weight fraction in the total polymer. Conversely, "minor" monomers are those that do not constitute the largest molar fraction in the polymer.

[0019] The term "composition-based" means that a composition comprises a mixture of various basic components used and / or in-situ reaction products, some of which are capable of and / or intended to react at least partially with each other during various stages of the manufacture of the composition or during subsequent curing (which may modify the originally prepared composition). Therefore, the compositions described below differ in their non-crosslinked and crosslinked states.

[0020] Unless otherwise expressly stated, all percentages (%) shown are weight percentages (“weight %”). Furthermore, any range of values ​​expressed as “between a and b” represents a range from greater than a to less than b (i.e., excluding the endpoints a and b), while any range of values ​​expressed as “a to b” means a range from a to b (i.e., including the strictly defined endpoints a and b).

[0021] rubber composition

[0022] The tire of the present invention comprises a rubber composition based at least on a specific elastomeric matrix and a specific hydrocarbon resin, as described below. The rubber composition may also contain various optional components known to those skilled in the art. Some of these are also described below.

[0023] Hydrocarbon resins

[0024] The hydrocarbon resins are based on cyclic monomers selected from petroleum refining streams, C4, C5 and C6 cyclic olefins and mixtures thereof, wherein the hydrocarbon resins have aromatic proton content (H Ar, in mol%), glass transition temperature (Tg, in °C) and number average molecular weight (Mn, in g / mol) as expressed by: (1) 12 mol% ≤ H Ar ≤ 19 mol%, (2) Tg ≥ 95 - 2.2 * (H Ar), (3) Tg ≥ -53 + (0.265 * Mn) and (4) 300 g / mol ≤ Mn ≤ 450 g / mol.

[0025] The term "hydrocarbon resin-based" refers to the polymerization of polymers derived from proposed monomers (i.e., cyclic monomers and / or aromatic monomers), which, after polymerization, become their respective units in the polymer. Such polymerization of cyclic and / or aromatic monomers will produce hydrocarbon resins containing the corresponding cyclic and / or aromatic units.

[0026] As used herein, the term "cyclic monomer" refers to fractions and / or synthetic mixtures of C5 and C6 cyclic olefins, dienes, dimers, codimers, and trimers. More specifically, cyclic monomers include (but are not limited to) cyclopentene, cyclopentadiene ("CPD"), dicyclopentadiene ("DCPD"), cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylcyclopentadiene ("MCPD"), di(methylcyclopentadiene) ("MCPD dimer"), and codimers of CPD and / or MCPD with C4 cyclic compounds (e.g., butadiene) and C5 cyclic compounds (e.g., pentadiene). An exemplary cyclic monomer is cyclopentadiene. Optionally, the cyclic monomer may be substituted. Dicyclopentadiene may be endo- or exo-type.

[0027] Substituted cyclic monomers include those derived from C1 to C2. 40 Linear, branched, or cyclic alkyl-substituted cyclopentadienes and dicyclopentadienes. In one aspect, the substituted cyclic monomer may have one or more methyl groups. In another aspect, the cyclic monomer is selected from: cyclopentadiene, cyclopentadiene dimers, cyclopentadiene-C4 codimers, cyclopentadiene-C5 codimers, cyclopentadiene-methylcyclopentadiene codimers, methylcyclopentadiene-C4 codimers, methylcyclopentadiene-C5 codimers, methylcyclopentadiene dimers, cyclopentadiene and methylcyclopentadiene trimers and cotrimers, and / or mixtures thereof.

[0028] In one aspect, the cyclic monomer is selected from cyclopentene, cyclopentadiene, dicyclopentadiene, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylcyclopentadiene, di(methylcyclopentadiene), and mixtures thereof. In another aspect, the cyclic monomer is selected from dicyclopentadiene, cyclopentadiene, and methylcyclopentadiene. In yet another aspect, the cyclic monomer is cyclopentadiene.

[0029] In one aspect, the hydrocarbon resin contains cyclic monomers in an amount between 10% and 90% by weight. In another aspect, the hydrocarbon resin contains cyclic monomers in an amount between 25% and 80% by weight.

[0030] In one aspect, the hydrocarbon resin contains between 10% and 90% by weight of dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene. In another aspect, the hydrocarbon resin contains between 25% and 80% by weight of dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene. In another aspect, the hydrocarbon resin contains between 0.1% and 15% by weight of methylcyclopentadiene. In yet another aspect, the hydrocarbon resin contains between 0.1% and 5% by weight of methylcyclopentadiene.

[0031] The hydrocarbon resins of this invention contain one or more cyclic monomers for preparing one or more complex copolymers as described herein. The composition of the complex copolymer can be controlled by the type and amount of monomers contained in the resin (i.e., the microstructure of the copolymer). However, the monomer positions in the polymer chain are random, further complicating the polymer microstructure.

[0032] In one aspect, hydrocarbon resins further comprise aromatic monomers. In another aspect, aromatic monomers are selected from olefin-aromatic compounds, aromatic fractions, and mixtures thereof.

[0033] In one aspect, the hydrocarbon resin contains aromatic monomers in an amount between 10% and 90% by weight. In another aspect, the hydrocarbon resin contains aromatic monomers in an amount between 20% and 75% by weight.

[0034] In one aspect, the aromatic monomer is an aromatic fraction. In another aspect, the hydrocarbon resin comprises an aromatic fraction from a petroleum refining stream, for example, an aromatic fraction obtained by separating a fraction with a boiling point in the range of 135°C to 220°C from a steam cracking stream by fractionation. In one aspect, the aromatic fraction comprises at least one of styrene, alkyl-substituted styrene derivatives, indene, alkyl-substituted indene derivatives, and mixtures thereof. In another aspect, the aromatic fraction comprises 4% to 7% by weight of styrene, 20% to 30% by weight of alkyl-substituted styrene derivatives, 10% to 25% by weight of indene, 5% to 10% by weight of alkyl-substituted indene derivatives, and 35% to 45% by weight of non-reactive aromatic compounds.

[0035] On one hand, aromatic monomers include olefin-aromatic compounds selected from indene derivatives, vinyl aromatic compounds, and mixtures thereof.

[0036] On the one hand, aromatic monomers include indene derivatives represented by formula (I):

[0037] [Chemical Formula 1]

[0038]

[0039] R1 and R2 independently represent hydrogen atoms, alkyl, alkenyl, cycloalkyl, aryl, or arylalkyl. For example, such compounds can be 1H-indene, 1-methyl-1H-indene, alkylindene, 5-(2-methylbut-2-enyl)-1H-indene, 5,6,7,8-tetrahydro-1H-cyclopentane, 4H-indene-5-but-1 alcohol, or derivatives thereof.

[0040] On the one hand, aromatic monomers include vinyl aromatic compounds represented by formula (II):

[0041] [Chemical Formula 2]

[0042]

[0043] R3 and R4 independently represent hydrogen atoms, alkyl, alkenyl, cycloalkyl, aryl, or arylalkyl groups. α-Methylstyrene or substituted α-methylstyrene having one or more substituents on the aromatic ring is suitable, particularly when the substituents are selected from alkyl, cycloalkyl, aryl, or combined groups, each substituent having 1 to 8 carbon atoms. Non-limiting examples include α-methylstyrene, α-methyl-4-butylstyrene, α-methyl-3,5-di-tert-benzylstyrene, α-methyl-3,4,5-trimethylstyrene, α-methyl-4-benzylstyrene, α-methyl-4-chlorohexylstyrene, and / or mixtures thereof. The hydrocarbon resins of the present invention can be prepared using various methods. For example, thermal polymerization can be used with a feed stream of olefin-aromatic compounds, substituted benzene, and aromatic fractions combined or uncombined cyclic compounds. Different resins are prepared to achieve desired molecular weights and specific tackifier cloud points, as described in the following examples. Specifically, Tables 2A, 2B, 3A and 3B below describe the feed stream, polymerization conditions and final properties of the hydrocarbon resins of the present invention.

[0044] Incompatibility with the base polymer limits the application of high-Tg resins in situations requiring low molecular weight and ease of processing. The hydrocarbon resins of this invention overcome this limitation through a novel combination of Tg and Mn not previously described.

[0045] Specifically, the hydrocarbon resin has an aromatic proton content (“H Ar”) between 12 mol% and 19 mol%, expressed as a percentage. Furthermore, the hydrocarbon resin is defined by its glass transition temperature (“Tg”) and aromatic proton content (“H Ar”), as well as its glass transition temperature (“Tg”) and number-average molecular weight (“Mn”). More specifically, the hydrocarbon resin of the present invention is defined as follows: Tg ≥ 95 - 2.2 * (H Ar); Tg ≥ -53 + (0.265 * Mn), and 300 g / mol ≤ Mn ≤ 450 g / mol, where Tg is the glass transition temperature of the resin expressed in °C, H Ar represents the aromatic proton content in the resin, and Mn represents the number-average molecular weight of the resin.

[0046] On the one hand, the glass transition temperature (Tg) of the hydrocarbon resin is 70°C to 95°C, preferably 70°C to 90°C.

[0047] On the one hand, the z-average molecular weight (Mz) of hydrocarbon resins is less than 1000 g / mol.

[0048] In one respect, hydrocarbon resins have at least one of the following additional characteristics, preferably all of them:

[0049] - Number-average molecular weight (Mn) is between 350 g / mol and 420 g / mol.

[0050] - The glass transition temperature (Tg) is expressed as Tg≥100-2.2*(H Ar),

[0051] - The glass transition temperature (Tg) is expressed as Tg≥-32+(0.265*Mn).

[0052] As described above, the rubber composition of the present invention comprises one or more of the hydrocarbon resins of the present invention.

[0053] The content of hydrocarbon resin in the rubber composition can be in the ranges 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. If the content of hydrocarbon resin in the present invention is below 15 phr, the effect of the hydrocarbon resin becomes insufficient and the rubber composition will have grip problems. If the content is above 150 phr, the composition will have manufacturing difficulties in easily incorporating the hydrocarbon resin of the present invention into the composition.

[0054] elastomer

[0055] The tire of the present invention comprises a rubber composition based at least on an elastomer matrix and a specific hydrocarbon resin as described above. The elastomer will be further described below. The composition of the tire according to the present invention may comprise one elastomer or a mixture of multiple elastomers, referred to as the elastomer matrix.

[0056] As used herein, the terms “elastomer” and “rubber” are used interchangeably. They are well known to those skilled in the art.

[0057] "Dienes elastomers" refer to elastomers that are at least partially (i.e., homopolymers or copolymers) derived from diene monomers (monomers having two carbon-carbon double bonds, regardless of whether they are conjugated or not). Diene elastomers can be "highly unsaturated" and derived from conjugated diene monomers, with the molar content of the conjugated diene monomers being greater than 50%.

[0058] Diene elastomers can be divided into two categories: "substantially unsaturated" or "substantially saturated." "Substantially unsaturated" is generally understood to mean diene elastomers that are at least partially derived from conjugated diene monomers and have a diene source (conjugated diene) unit content greater than 15% (mol%). Therefore, diene elastomers such as butyl rubber or EPDM-type copolymers of dienes and α-olefins do not fall into the aforementioned definition but can be specifically referred to as "substantially saturated" diene elastomers (low or very low diene source unit content, always less than 15%). Within the category of "substantially unsaturated" diene elastomers, "highly unsaturated" diene elastomers are specifically understood to mean diene elastomers with a diene source (conjugated diene) unit content greater than 50%.

[0059] In light of these definitions, as is known to those skilled in the art, diene elastomers are more specifically understood to mean:

[0060] (a) Any homopolymer obtained by polymerization of conjugated diene monomers having 4 to 12 carbon atoms;

[0061] (b) Any copolymer obtained by copolymerization of one or more conjugated dienes with each other or by copolymerization of one or more conjugated dienes with one or more vinyl aromatic compounds having 8 to 20 carbon atoms;

[0062] (c) Terpolymers obtained by copolymerization of ethylene and α-olefins having 3 to 6 carbon atoms with non-conjugated diene monomers having 6 to 12 carbon atoms, for example, elastomers obtained by copolymerization of ethylene and propylene with non-conjugated diene monomers of the type described above (e.g., particularly 1,4-hexadiene, ethylidene norbornene or dicyclopentadiene).

[0063] (d) Copolymers of isobutylene and isoprene (butyl rubber), and halogenated forms of such copolymers, particularly chlorinated or brominated forms.

[0064] For the purposes of this invention, a tire composition comprises an elastomer matrix comprising 50 to 100 phr of at least one copolymer of butadiene and a vinyl aromatic monomer, the at least one copolymer of butadiene and the vinyl aromatic monomer having a vinyl aromatic unit content between 0 and 5% by weight and a Tg in the range of -110°C to -70°C. Therefore, the copolymer of butadiene and the vinyl aromatic monomer may contain 95% to less than 100% by weight of butadiene units and more than 0 to 5% by weight of vinyl aromatic units.

[0065] For example, the following are suitable as vinyl aromatic compounds: styrene, (o-, m-, or p-)methylstyrene, commercially available "vinyltoluene" mixtures, p-(tert-butyl)styrene, methoxystyrene, chlorostyrene, vinyltrimethylbenzene, divinylbenzene, or vinylnaphthalene. Preferably, the vinyl aromatic monomer of the copolymer of butadiene and the vinyl aromatic monomer is styrene.

[0066] Elastomers can possess any microstructure, which depends on the polymerization conditions used, particularly the presence or absence of modifiers and / or atacticizers and the amount of modifiers and / or atacticizers used. Elastomers can be, for example, block, atactic, sequential, or microsequential elastomers, and can be prepared in dispersions or solutions. In the case of copolymers based on dienes and vinyl aromatic compounds, particularly copolymers containing butadiene and styrene, the two monomers are preferably randomly distributed.

[0067] Copolymers of butadiene and vinyl aromatic monomers can be coupled and / or star-branched or functionalized by groups introduced via coupling agents and / or star-branching agents or functionalizing agents known to those skilled in the art. Such groups can be located at the ends of the linear host elastomer chain. Thus, the butadiene elastomer can be described as chain-end functionalized. It is typically an elastomer obtained by reacting an active elastomer with a functionalizing agent, i.e., any molecule with at least one monofunctional group, the functional group being any type of chemical group known to those skilled in the art that reacts with the ends of an active chain.

[0068] Such groups can be located within the linear host elastomer chain. Although the groups are not precisely located in the middle of the elastomer chain, it can be said that the diene elastomer is coupled or functionalized in the middle of the chain compared to the "chain ends" position. It is typically an elastomer obtained by reacting the two chains of an active elastomer with a coupling agent, i.e., any molecule that is at least bifunctional, whose functional group is any type of chemical group known to those skilled in the art that reacts with the ends of the active chain.

[0069] This group can be located at the center, with n elastomer chains (n>2) bonded to it, thus forming a star-branched structure. Therefore, the diene elastomer can be described as star-branched. It is typically an elastomer obtained by reacting n chains of an active elastomer with a star-branching agent, which is any multifunctional molecule whose functional group is any type of chemical group known to those skilled in the art that reacts with the ends of the active chain.

[0070] Those skilled in the art will understand that functionalization reactions with reagents containing more than one functional group reactive with the active elastomer produce a mixture of entities functionalized at the chain ends and in the middle of the chain (which constitute the linear chains of the functionalized elastomer) and, where appropriate, star-branched entities. Depending on the operating conditions, primarily the molar ratio of the functionalizing agent to the active chain, some entities are dominant in the mixture.

[0071] Preferably, for the purposes of this invention, the copolymer of butadiene and vinyl aromatic monomers has a Tg in the range of -110°C to -80°C, preferably -95°C to -80°C.

[0072] Preferably, the copolymer of butadiene and vinyl aromatic monomers has a Mooney viscosity in the range of 50 to 80. In this specification, Mooney viscosity is intended to mean the ML(1+4) Mooney viscosity of the compound, particularly the copolymer of butadiene and vinyl aromatic monomers used in this invention, at 100°C, as measured according to standard ASTM D1646.

[0073] According to a preferred embodiment, the copolymer of butadiene and vinyl aromatic monomers has a vinyl aromatic unit content of 1% to 4% by weight based on the total weight of the copolymer, and a vinyl unit content involving the diene portion ranging from 8% to 15% by weight, preferably from 10% to 15% by weight.

[0074] Preferably, at least 70% by weight of the copolymer of butadiene and vinyl aromatic monomers is functionalized, preferably by alkoxysilyl groups, which are optionally partially or completely hydrolyzed to produce silanols. The alkoxysilyl groups may or may not contain another functional group capable of interacting with reinforcing fillers, and are bonded to the diene elastomer via silicon atoms. Preferably, the copolymer of butadiene and vinyl aromatic monomers is functionalized primarily in the middle of the chain. The microstructure of these elastomers can be determined by the presence or absence of a polar agent and the amount of polar agent used during the anionic polymerization step. Preferably, when the diene elastomer is based on diene and styrene, the amount of polar agent used during the polymerization step is such that the polar agent promotes the random distribution of styrene along the polymer chain, while maintaining the 1,2-bond content between preferably 8% and 15%, preferably 10% to 15%.

[0075] The terms "alkoxysilyl group that interacts advantageously with reinforcing filler" or "functional group capable of interacting with reinforcing filler" are understood to mean any other alkoxysilyl group or functional group, preferably amine, capable of forming a physical or chemical bond with the filler within the rubber composition reinforced by the filler. Such interaction can be established, for example, through covalent bonds, hydrogen bonds, ionic bonds, and / or electrostatic bonds between the functional group and functional groups present on the filler.

[0076] The alkoxy group of the alkoxysilyl group may have the formula R'O-, where R' represents a substituted or unsubstituted C1-C10 or even C1-C8 alkyl group, preferably a C1-C4 alkyl group, and more preferably methyl and ethyl.

[0077] Other functional groups as described above can be, for example, amine, thiol, polyoxyethylene, or polyether groups. Most preferably, other functional groups capable of interacting with the reinforcing filler are primary, secondary, or tertiary amines. This variant of the invention is particularly advantageous due to its improved hysteresis properties.

[0078] In this specification, primary or secondary amines are intended to refer to primary or secondary amines that are protected or unprotected by protecting groups known to those skilled in the art.

[0079] As secondary or tertiary amine functional groups, amines substituted with C1-C10, preferably C1-C4 alkyl groups, more preferably methyl or ethyl groups, or cyclic amines forming a heterocycle containing a nitrogen atom and at least one carbon atom (preferably 2 to 6 carbon atoms) are suitable. For example, suitable groups are methylamino-, dimethylamino-, ethylamino-, diethylamino-, propylamino-, dipropylamino-, butylamino-, dibutylamino-, pentylamino-, dipentylamino-, hexylamino-, dihexylamino-, or hexamethyleneamino- groups, preferably diethylamino- and dimethylamino- groups.

[0080] Preferably, the functional group that can interact with the reinforcing filler is a tertiary amine functional group, preferably diethylamine or dimethylamine.

[0081] According to a variant of the invention, functional groups (preferably primary, secondary, or tertiary amines) that can interact with reinforcing fillers can be directly bonded to silicon atoms that are themselves directly bonded to the diene elastomer.

[0082] According to another variant of the invention, functional groups (preferably primary, secondary, or tertiary amines) capable of interacting with reinforcing fillers are linked to silicon atoms bound to the diene elastomer via spacer groups, which can be atoms or groups of atoms. The spacer groups can be saturated or unsaturated cyclic or acyclic linear or branched divalent C1-C18 aliphatic hydrocarbon groups or divalent C6-C18 aromatic hydrocarbon groups, and may contain one or more aromatic groups and / or one or more heteroatoms. The hydrocarbon groups may optionally be substituted.

[0083] Preferably, the copolymer of butadiene and vinyl aromatic monomers comprises, by weight, more than 0 and at most 30% by weight (more preferably between 0 and 20%) of star-branched copolymer of butadiene and vinyl aromatic monomers.

[0084] Preferably, the copolymer of butadiene and vinyl aromatic monomers exists in the elastomer matrix in a total content of 75 phr to 100 phr, more preferably 90 phr to 100 phr, and even more preferably 100 phr.

[0085] When the elastomer matrix comprises a supplementary elastomer of a copolymer of butadiene and vinyl aromatic monomers, the supplementary elastomer can be any elastomer known to those skilled in the art, particularly elastomers selected from polybutadiene, natural or synthetic polyisoprene, isoprene copolymers, butadiene copolymers other than those claimed in this invention, and mixtures thereof. Preferably, these supplementary elastomers are selected from polybutadiene, natural or synthetic polyisoprene, copolymers of isoprene and vinyl aromatic monomers, copolymers of butadiene and vinyl aromatic monomers with a Tg greater than -70°C, and mixtures thereof.

[0086] Reinforced packing

[0087] The composition may contain reinforcing fillers. Any type of reinforcing filler known to be able to reinforce rubber compositions that can be used to manufacture tires may be used, such as organic fillers like carbon black, reinforcing inorganic fillers like silica or alumina, or blends of both.

[0088] As described in this article, reinforcing fillers can be selected from silica, carbon black, and mixtures thereof.

[0089] The content of reinforcing filler can range from 5 phr to 200 phr and from 40 to 160 phr. In one aspect, the reinforcing filler is silica, and in another aspect, its content ranges from 40 phr to 150 phr. The compositions provided herein may contain a small amount of carbon black, wherein in one aspect, the content ranges from 0.1 phr to 10 phr.

[0090] All carbon blacks, especially "tire-grade" carbon black, are suitable as carbon blacks. More specifically, within tire-grade carbon blacks, reinforcing carbon blacks of the 100, 200, or 300 series (ASTM grades), such as N115, N134, N234, N326, N330, N339, N347, or N375, or higher series carbon blacks depending on the target application (e.g., N660, N683, or N772). Carbon blacks may, for example, be incorporated into isoprene elastomers in masterbatch form (see, for example, applications WO 97 / 36724 or WO 99 / 16600).

[0091] The rubber composition of the present invention may contain one type of silica or a blend of multiple silicas. The silica used may be any reinforcing silica, particularly those with a BET surface area and a CTAB specific surface area each less than 450 m². 2 / g, for example, 30m 2 / g to 400m 2 Any precipitated or pyrolytic silica per gram. Highly dispersible precipitated silica (“HDS”) will be referred to, for example, “Ultrasil 7000” and “Ultrasil 7005” silica from Degussa, “Zeosil 1165MP”, “1135MP” and “1115MP” silica from Rhodia, “Hi-Sil EZ150G” silica from PPG, and “Zeopol 8715”, “8745” and “8755” silica from Huber. Processed precipitated silica, such as aluminum-doped silica as described in application EP-A-0735088, or silica with a high specific surface area as described in application WO03 / 16837. The silica may have a surface area of ​​45 μm. 2 / g to 400m 2 Between / g, preferably 60m 2 / g to 300m 2 BET specific surface area between / g.

[0092] In addition to coupling agents, these compositions may optionally contain coupling activators, agents for coating inorganic fillers, and any other processing aids that, by improving the dispersion of fillers in the rubber matrix and reducing the viscosity of the composition, can improve the processability of the composition in its untreated state in a known manner. These agents are, for example, hydrolyzable silanes such as alkylalkoxysilanes, polyols, fatty acids, polyethers, primary, secondary, or tertiary amines, or hydroxylated or hydrolyzable polyorganosiloxanes.

[0093] In particular, silane polysulfides can be used, which are referred to as “symmetric” or “asymmetric” according to their specific structures, as described in, for example, applications WO 03 / 002648 (or US2005 / 016651) and WO 03 / 002649 (or US2005 / 016650).

[0094] Moreover, not limited to the following definition, it is particularly suitable to refer to the silane polysulfides corresponding to the following general formula III as "symmetrical":

[0095] (III) ZA-Sx-AZ, where:

[0096] -x is an integer from 2 to 8 (e.g., 2 to 5);

[0097] -A is a divalent hydrocarbon group (e.g., C1-C). 18 Alkylene or C6-C 12 Aspartic acid, especially for C1-C 10 Alkylenes, especially C1-C4 alkylenes, particularly propylenes;

[0098] -Z corresponds to one of the following formulas:

[0099] [Chemical Formula 3]

[0100]

[0101] in:

[0102] -R 1 The groups are substituted or unsubstituted and are either the same as or different from each other, indicating C1-C. 18 Alkyl, C5-C 18 cycloalkyl or C6-C 18 Aryl (e.g., C1-C6 alkyl, cyclohexyl or phenyl, especially C1-C4 alkyl, more particularly methyl and / or ethyl);

[0103] -R 2 The groups are substituted or unsubstituted and are either the same as or different from each other, indicating C1-C. 18 Alkoxy or C5-C 18 Cycloalkoxy groups (e.g., groups selected from C1-C8 alkoxy and C5-C8 cycloalkoxy groups, such as groups selected from C1-C4 alkoxy, especially methoxy and ethoxy groups).

[0104] In the case of mixtures of alkoxysilane polysulfides corresponding to formula (III) above, especially in the case of commercially available conventional mixtures, the average value of the "x" index is, for example, a fraction between 2 and 5 (approximately 4). However, advantageously, the mixture can be implemented with alkoxysilane disulfides (x = 2). Examples include silane polysulfides of bis((C1-C4)alkoxy(C1-C4)alkylsilyl(C1-C4)alkyl) polysulfides (especially disulfides, trisulfides, or tetrasulfides), such as bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides. Among these compounds, bis(3-triethoxysilylpropyl)tetrasulfide of the formula [(C2H5O)3Si(CH2)3S2]2, abbreviated as TESPT, or bis(3-triethoxysilylpropyl)disulfide of the formula [(C2H5O)3Si(CH2)3S]2, abbreviated as TESPD, may be used in particular. Other examples include bis(mono(C1-C4)alkoxybis(C1-C4)alkylsilylpropyl)polysulfides (especially disulfides, trisulfides, or tetrasulfides), and more particularly bis(monoethoxydimethylsilylpropyl)tetrasulfide, as described in patent application WO 02 / 083782 (or US2004 / 132880). As coupling agents other than alkoxysilane polysulfides, bifunctional POS (polyorganosiloxanes) will also be mentioned, or hydroxysilane polysulfides (R2=OH in Formula III) as described in published patent applications WO 02 / 30939 (or US 6 774 255) and WO 02 / 31041 (or US2004 / 051210), or silanes or POS with azodicarbonyl functional groups as described in published patent applications WO 2006 / 125532, WO 2006 / 125533 and WO 2006 / 125534.

[0105] The content of coupling agent in the composition of the present invention can be between 1 phr and 15 phr and between 3 phr and 14 phr.

[0106] In addition, the filler can consist of a reinforcing filler having another property (especially organic properties), provided that the reinforcing filler is covered with a silica layer or contains functional sites, especially hydroxyl sites, on its surface that require the use of a coupling agent to form a connection between the filler and the elastomer.

[0107] It does not matter what physical state the reinforcing filler is provided in, whether it is in the form of powder, microspheres, granules, beads or any other suitable densification form.

[0108] Crosslinking system

[0109] In the rubber compositions provided herein, any type of crosslinking system for the rubber composition can be used.

[0110] The crosslinking system can be a vulcanization system, i.e., a vulcanization system based on sulfur (or based on a sulfur donor) and a primary vulcanization accelerator. Various known secondary vulcanization accelerators or vulcanization activators, such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (especially diphenylguanidine), can be added to this basic vulcanization system, introduced in the first non-production stage and / or during the production stage, as described below.

[0111] The sulfur content used can be between 0.5 phr and 10 phr, between 0.5 phr and 5 phr, and especially between 0.5 phr and 3 phr.

[0112] The vulcanization system of the composition may also contain one or more other accelerators, such as thiuram, zinc dithiocarbamate derivatives, sulfenamides, guanidines, or compounds of the thiophosphate family. Any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur can be used, particularly thiazole-type accelerators and their derivatives, thiuram-type accelerators, and zinc dithiocarbamate. These accelerators are selected from 2-mercaptobenzothiazole disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazole sulfenamide (abbreviated "CBS"), N,N-dicyclohexyl-2-benzothiazole sulfenamide (abbreviated "DCBS"), N-(tert-butyl)-2-benzothiazole sulfenamide (abbreviated "TBBS"), N-(tert-butyl)-2-benzothiazole sulfenimide (abbreviated "TBSI"), zinc dibenzyl dithiocarbamate (abbreviated "ZBEC"), and mixtures of these compounds. Use sulfenamide-type main accelerator.

[0113] The rubber composition may optionally contain all or part of conventional additives typically used in elastomer compositions specifically intended for the manufacture of treads, such as pigments, protective agents (e.g., anti-ozone waxes, chemical anti-ozone agents, or antioxidants), plasticizers, fatigue inhibitors, reinforcing resins, or methylene acceptors (e.g., linear phenolic resins) or donors (e.g., HMT or H3M).

[0114] The rubber composition may also contain a plasticizing system. In addition to the specific hydrocarbon resins mentioned above, such a plasticizing system may also consist of hydrocarbon resins with a Tg greater than 20°C and / or plasticizing oils.

[0115] Of course, the composition can be used alone or blended (i.e., mixed) with any other rubber composition that can be used to manufacture tires.

[0116] The rubber composition described herein can be in two states: "uncured" or non-crosslinked (i.e., before curing) and "cured" or crosslinked or vulcanized (i.e., after crosslinking or vulcanization).

[0117] Preparation of rubber composition

[0118] The rubber composition is manufactured using two consecutive preparation stages in a suitable mixer: a first stage (sometimes referred to as the “non-production” stage) of thermomechanical processing or kneading at high temperatures (up to between 110°C and 200°C, for example, a maximum temperature between 130°C and 180°C), followed by a second stage (sometimes referred to as the “production” stage) of mechanical processing at lower temperatures, typically below 110°C, for example, between 60°C and 100°C, during which a crosslinking or vulcanization system is introduced; such stages have been described, for example, in applications EP-A-0501227, EP-A-0735088, EP-A-0810258, WO 00 / 05300, or WO 00 / 05301.

[0119] The first (non-production) stage is carried out in multiple thermomechanical steps. During this first step, the elastomer, reinforcing filler, and hydrocarbon resin (and optionally coupling agents and / or other components besides the crosslinking system) are introduced into a suitable mixer (e.g., a conventional closed mixer) at a temperature between 20°C and 100°C, preferably between 25°C and 100°C. After several minutes (0.5 to 2 minutes) and after the temperature rises to 90°C or 100°C, the other components besides the crosslinking system (i.e., those remaining if not all were added initially) are added in batches or all at once during a mixing process of 20 seconds to several minutes. The overall duration of kneading in this non-production stage at a temperature less than or equal to 180°C, preferably less than or equal to 170°C, is between 2 and 10 minutes.

[0120] After cooling the resulting mixture, the crosslinking system is then typically introduced into an open mixer (e.g., a two-roll mill) at a low temperature (usually below 100°C). The combined mixture is then mixed (in the production stage) for several minutes, for example, between 5 and 15 minutes.

[0121] The resulting final composition is then calendered, for example, into sheets or plates for laboratory characterization, or extruded to form rubber molded parts, for example, used in the manufacture of tires. These products can then be used to manufacture tires, with the advantage of good adhesion between the layers before the tire cures.

[0122] Crosslinking (or curing) can be carried out for a sufficient time at temperatures and pressures typically between 130°C and 200°C, said time being, for example, between 5 minutes and 90 minutes, depending in particular on the curing temperature, the crosslinking system used, the crosslinking kinetics of the composition under consideration, or the size of the tire.

[0123] Test methods for invention

[0124] The characteristics of the hydrocarbon resins and compositions containing hydrocarbon resins of the present invention are demonstrated in the following non-limiting examples. The test methods and experimental procedures used in the examples are described directly below.

[0125] Molecular weight distribution (“MWD”) corresponds to the expression M w / M n Expression M w / M n It is the weight-average molecular weight (M w ) and number-average molecular weight (M n The ratio of ).

[0126] The weight-average molecular weight is given by the following formula.

[0127] [Mathematical Expression 1]

[0128]

[0129] The number-average molecular weight is given by the following formula.

[0130] [Mathematical Expression 2]

[0131]

[0132] The z-average molecular weight is given by the following formula.

[0133] [Mathematical Expression 3]

[0134]

[0135] Where n in the above equation i For having a molecular weight M i The number fraction of molecules. M w M z and M n The measured values ​​were determined by gel permeation chromatography as described further below.

[0136] Gel permeation chromatography (GPC). Molecular weight distribution and moments (Mw, Mn, Mw / Mn, etc.) were determined using room temperature (20°C) gel permeation chromatography. The GPC employed a Tosoh EcoSEC HLC-8320GPC equipped with a blocked refractive index (RI) and ultraviolet (UV) detector. Four Agilent PLgels were used in tandem: 5 μm. 5μm 5μm 5 μm Mixed-D. Aldrich reagent-grade tetrahydrofuran (THF) was used as the mobile phase. The polymer mixture was filtered through a 0.45 μm Teflon filter and degassed using an online degasser before entering the GPC instrument. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 200 μL. Molecular weight analysis was performed using EcoSEC software.

[0137] The concentration (c) at each point in the chromatogram is calculated using the following equation by subtracting the baseline IR5 broadband signal intensity (I): c = βI, where “β” is a mass constant determined using a polystyrene standard. The mass recovery is calculated as the ratio of the integrated area of ​​the concentration chromatogram relative to the elution volume to the injection mass equal to the predetermined concentration multiplied by the injection cycle volume.

[0138] Molecular weight. The molecular weight was determined using a polystyrene calibration relationship calibrated with a column of monodisperse polystyrene (PS) standards: 162, 370, 580, 935, 1860, 2980, 4900, 6940, 9960, 18340, 30230, 47190, and 66000 kg / mol. The molecular weight “M” per elution volume was calculated using the following equation:

[0139] [Mathematical Expression 4]

[0140]

[0141] Variables with the subscript "PS" represent polystyrene, while those without subscripts correspond to the test sample. In this method, aPS = 0.67 and KPS = 0.000175, where "a" and "K" are calculated using a series of empirical formulas (T. Sun, P. Brant, R.R. Chance, and W.W. Graessley, 34(19) MACROMOLECULES 6812-6820(2001)). Specifically, a / K for polyethylene = 0.695 / 0.000579, and a / K for polypropylene = 0.705 / 0.0002288. Unless otherwise stated, all concentrations are expressed in g / cm3, molecular weight in g / mol, and intrinsic viscosity in dL / g.

[0142] DSC Measurement. The following DSC procedure was used to determine the glass transition temperature (Tg) of hydrocarbon resins. Approximately 6 mg of material was placed in a microliter aluminum sample pan. The sample was placed in a differential scanning calorimeter (Perkin Elmer or TA Instrument thermal analysis system) and heated from 23 °C to 200 °C at 10 °C / min, and held at 200 °C for 3 minutes. The sample was then cooled to -50 °C at 10 °C / min. The sample was held at -50 °C for 3 minutes, and then heated from -50 °C to 200 °C at 10 °C / min for a second heating cycle. Tg was determined in TA Universal Analysis during the second heating cycle using the inflection point method. The Glass Transition menu item on the TA Universal Analysis device was used to calculate the start point, end point, inflection point, and signal change of Tg in the DSC. The program determines the starting point, which is the intersection of the first and second tangents. The inflection point is the portion of the curve with the steepest slope between the first and third tangents. The ending point is the intersection of the second and third tangents. The Tg of the hydrocarbon resin is the inflection temperature of the curve.

[0143] Aromatic proton (HA) percentage: 120 scans were performed at 25 °C using a 500 MHz NMR instrument in either TCE-d2 (1,2-dichloroethane) or CDCl3 (chloroform) solvent. NMR data for hydrocarbon resins were measured by dissolving 20 ± 1 mg of sample in 0.7 ml of d-solvent. Samples were dissolved in TCE-d2 in 5 mm NMR tubes at 25 °C until dissolved. No standards were used. Peaks at 5.98 ppm or 7.24 ppm for TCE-d2 / CDCl3 were observed and used as reference peaks for the samples. Aromatic proton percentage. 1The H NMR signal ranges from 8.5 ppm to 6.2 ppm. Alkene protons produce signals between 6.2 ppm and 4.5 ppm. Finally, the signal corresponding to aliphatic protons ranges from 4.5 ppm to 0 ppm. The area of ​​each proton class is correlated with the sum of these areas to obtain the distribution of the area % of each proton class.

[0144] Softening point. The "softening point" is the temperature at which a material will flow, measured in °C, determined using the ring and sphere method, such as by ASTM E-28. Empirically, the relationship between Tg and softening point is approximately: Tg = softening point - 50 °C.

[0145] Kinetic properties of the composition (after curing)

[0146] Kinetic properties G* and tan(δ)max were measured on a viscosity analyzer (Metravib VA4000) according to standard ASTM D 5992-96. The responses of vulcanized composition samples (cylindrical test specimens with a thickness of 4 mm and a diameter of 10 mm) subjected to simple alternating sinusoidal shear stress at a frequency of 10 Hz were recorded according to standard ASTM D 1349-99 under temperature conditions (23 °C), or at different temperatures. Deformation scans were performed from 0.1% to 50% (forward cycle) and then from 50% to 0.1% (return cycle). For the return cycle, the stiffness value at 10% deformation was then recorded.

[0147] A higher stiffness value at 10% deformation and 23°C indicates better road handling provided by the composition. Results are expressed based on a performance baseline of 100, meaning a value of 100 is arbitrarily assigned to a control so that the various tested configurations can be compared at 23°C with G*10% (i.e., stiffness and therefore road handling). The value based on the baseline of 100 is calculated as (sample's G*10% value at 23°C / control's G*10% value at 23°C)*100. Therefore, a higher value indicates improved road handling performance, while a lower value indicates reduced road handling performance.

[0148] A higher stiffness value at 10% deformation and 40°C indicates better road handling provided by the composition. Results are expressed based on a performance baseline of 100, meaning a value of 100 is arbitrarily assigned to a control so that the various tested configurations can be compared at 40°C with G*10% (i.e., stiffness and therefore road handling). The value based on the baseline of 100 is calculated as (sample's G*10% value at 40°C / control's G*10% value at 40°C)*100. Therefore, a higher value indicates improved road handling performance, while a lower value indicates reduced road handling performance.

[0149] The following examples are intended to highlight various aspects of certain embodiments of the invention. However, it should be understood that, unless explicitly stated otherwise, these examples are included for illustrative purposes only and are not intended to limit the scope of the invention.

[0150] Example 1

[0151] Methods for preparing prior art hydrocarbon resins involve thermal polymerization of a mixture consisting essentially of (e.g., see U.S. Patent No. 6,825,291) 5% to 25% by weight of styrene or aliphatic or aromatic substituted styrene, and 95% to 75% by weight, based on the total monomer content, of a cyclic diene component containing at least 50% by weight of dicyclopentadiene. This sequential addition of monomers has been used to control the molecular weight of hydrocarbon resins. This method is not only cumbersome but also results in a wide polydispersity of hydrocarbon resins. Table 1 below summarizes the comparative results obtained.

[0152] [Table 1]

[0153]

[0154]

[0155] Example 2: Analysis of specific hydrocarbon resins of the present invention

[0156] Hydrocarbon resins (HR) samples B, C, D, E, G, and H were prepared by altering the feed stream in a known thermal polymerization unit to achieve a specific tackifier softening point or Tg and molecular weight. After treatment in the thermal polymerization unit, the tackifier was nitrogen stripped at 200 °C. The properties of the hydrocarbon resins are provided in Tables 2A, 2B, 3A, and 3B below. The resins described herein can be prepared by known methods (e.g., see Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 13, pp. 717-744). One method is the thermal polymerization of petroleum fractions. Polymerization can be batch, semi-batch, or continuous. Thermal polymerization is typically carried out at temperatures between 160 °C and 320 °C (e.g., between 260 °C and 280 °C) for a time of 0.5 to 9 hours (typically 1.0 to 4 hours). Thermal polymerization is typically carried out with or without an inert solvent.

[0157] The inert solvent can have a boiling point range of 60°C to 260°C and can be selected from 2% to 50% by weight of isopropanol, toluene, heptane, and Exxsol. TM or Varsol TM Or basic "petroleum solvents". These solvents can be used alone or in combination.

[0158] The resulting hydrocarbon resin can optionally be dissolved in an inert, dearomatized, or non-dearomatized hydrocarbon solvent (e.g., Exxsol) in the following proportions. TM or Varsol TM In a base "petroleum solvent", the proportion is 10% to 60% by weight of the polymer, for example, around 30%. Hydrogenation is then carried out in a fixed-bed continuous reactor, wherein the feed stream is an upflow or downflow liquid phase or a trickle bed operation is performed.

[0159] Hydrogenation conditions typically involve reactions within temperature ranges of 100°C to 350°C, 150°C to 300°C, and 160°C to 270°C. The hydrogen pressure within the reactor should not exceed 2000 psi, for example, not exceeding 1500 psi, and / or not exceeding 1000 psi. Hydrogenation pressure varies with hydrogen purity; if the hydrogen contains impurities to provide the required hydrogen pressure, the total reaction pressure should be higher. Typically, the optimal pressure used is between 750 psi and 1500 psi, and / or between 800 psi and 1000 psi. Under standard conditions (25°C, 1 atm), the hydrogen-to-reactor feed volume ratio can typically range from 20 to 200. Other exemplary methods for preparing the hydrocarbon resins described herein are generally found in U.S. Patent No. 6,433,104.

[0160] Tables 2 and 3 below include comparisons of the feed streams, polymerization conditions, and resulting properties of hydrocarbon resins.

[0161] [Table 2]

[0162] Feed flow HR B HR C HR D HRE HRG HR H Cyclic compounds (wt%) 27.9 35.9 35.9 27.9 27.9 39.9 Olefin aromatic compounds (wt%) 58 44 44 58 58 50 Substituted benzene (wt%) 0 0 0 0 0 0 Aromatic fraction (wt%) 0 0 0 0 0 0 MCPD (weight %) 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (wt%) 14 20 20 14 14 10 Reaction temperature (°C) 275 275 273 275 265 275 Reaction time (min) 65 65 70 65 75 65

[0163] [Table 3]

[0164] HR B C D E G H HR softening point (°C) 126 124 137 133 133 133 HR Tg (°C) 75 76 89 80 87 88 Mn(g / mol) 372 354 379 386 384 389 Mz(g / mol) 720 600 637 800 700 667 Mw / Mn(MWD) 1.25 1.23 1.25 1.30 1.25 1.27 Argon H (%H Ar) 18 15 15 18 18 16

[0165] Comparative Examples B*, C*, and D* were prepared by a feed stream of vinyl aromatic compounds consisting of styrene and vinyltoluene, as provided in Tables 4 and 5. Comparative Example E* was prepared by a substituted benzene stream and aromatic fraction, but under conditions of low Tg and high % H Ar. Comparative Examples A and F were prepared by an olefinic aromatic compound stream, but under conditions of high % H Ar or high Tg. Under the reaction conditions of the present invention, the relative reaction rate of homopolymerization and oligomerization of vinyl aromatic compounds is higher than that of copolymerization of cyclic compounds with vinyl aromatic compounds. The resulting homopolymer oligomers have a higher Mn than required for the optimal HR. It is preferable to react substantially all theoretical amounts of vinyl aromatic compound monomers with the cyclic compound feed stream to minimize the homopolymerization reaction that forms undesirable high molecular weight polymers.

[0166] HR can be hydrogenated cyclopentadiene or a hydrogenated cyclopentadiene derivative, with or without aromatic components (olefin-aromatic compounds, substituted benzene, and aromatic fractions).

[0167] [Table 4]

[0168]

[0169]

[0170] [Table 5]

[0171] Comparative Example B* C* D* E* A F HR softening point (°C) 113 128 92 90 123 147 HR Tg (°C) 60 78 42 40 73 99 Mn(g / mol) 565 591 512 535 345 394 Mz (grams per mole) 1886 4659 3010 2550 600 700 Mw / Mn(MWD) 1.9 1.5 2.0 1.8 1.23 1.27 Argon H (%H Ar) 18 15 29 28 20.8 16

[0172] Figure 1 A graph illustrating the Tg and H / Ar relationship of the hydrocarbon resin of the present invention, the comparative resin, and the prior art elastomer composition. Figure 2 A graph showing the relationship between Tg and Mn for the HR of the present invention, the comparative resin, and the prior art comparative elastomer compositions. Figure 3 A graph illustrating the Tg and Mz relationship of the hydrocarbon resin of the present invention, the comparative resin, and the prior art elastomer composition.

[0173] Example 3: Preparation of SBR with a Tg of -88℃ and functionalized with aminoalkoxysilane in the middle of the chain.

[0174] Assuming thorough stirring is performed according to those skilled in the art, methylcyclohexane, butadiene, styrene, and tetrahydrofurfuryl ethyl ether are continuously introduced into a 32-liter reactor with a continuously stirred feed in the following proportions: butadiene flow rate = 4.013 kg·h⁻¹ (by weight), styrene flow rate = 0.122 kg·h⁻¹ (by weight), monomer weight concentration = 9.75 wt%, and 15 ppm of tetrahydrofurfuryl ethyl ether. Sufficient amounts of n-butyllithium (n-BuLi) are introduced to neutralize protonated impurities introduced from the different components present at the inlet of the first reactor; 850 μmol of n-BuLi / 100 g monomer is introduced.

[0175] Different flow rates were calculated to achieve an average residence time of 35 minutes in the reactor. The temperature was maintained at 95°C. A sample of the polymer solution was taken from the outlet of the polymerization reactor. The resulting polymer was subjected to antioxidant treatment by adding 0.4 pr of 2,2'-methylenebis(4-methyl-6-(tert-butyl)phenol) and 0.2 pr of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine. The treated polymer was then separated from its solution by steam stripping and dried on a two-roll mill at 100°C. The measured "initial" intrinsic viscosity was 1.98 dl·g⁻¹. The number-average molar mass Mn, determined by SEC, was 90,000 g·mol⁻¹, and the polydispersity index (PI) was 1.90. At the outlet of the polymerization reactor, a solution of 440 μmol / 100 g monomer of (3-N,N-dimethylaminopropyl)trimethoxysilane (coupling and star branching agent CA) in methylcyclohexane was added to the solution of the active polymer (CA / Li = 0.52).

[0176] The resulting polymer was subjected to antioxidant treatment by adding 0.4 phr of 2,2'-methylenebis(4-methyl-6-(tert-butyl)phenol) and 0.2 phr of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine. The treated polymer was then separated from its solution by steam stripping and dried on a two-roll mill at 100 °C.

[0177] The measured "final" intrinsic viscosity was 2.52 dl·g⁻¹. In this case, the viscosity jump (defined as the ratio of the "final" viscosity to the "initial" viscosity) was 1.27. The Mooney viscosity of polymer A was 70. The number-average molar mass Mn, determined by SEC techniques, was 168,600 g·mol⁻¹, and the polydispersity index PI was 1.68. The microstructure of the polymer was determined by NIR methods. The content of 1,2-units, based on butadiene units, was 12.7%. The styrene content was 2.1% by weight. The glass transition temperature of the polymer was -88 °C. The cold flow CF(1+6) of the polymer at 100 °C was 0.52. Using the above modeling methods, the distribution of the functionalized entity was given: 86% functionalized chains (77% of which were functionalized in the middle of the chain) and 14% star-branched unfunctionalized chains.

[0178] Example 4: Exemplary Rubber Composition

[0179] Rubber compositions are prepared by introducing all components except the vulcanization system into a closed mixer. The vulcanizing agents (sulfur and accelerators) are introduced into a low-temperature open mixer (the component rollers of the mixer are at 30°C).

[0180] The examples shown in Table 6 are intended to compare the different rubber properties of the control composition (T1) with those of the composition (C1) having the hydrocarbon resin H of the present invention. The components in Table 6 are indicated by phr. The properties measured before and after curing are shown in Table 8.

[0181] [Table 6]

[0182]

[0183]

[0184] (1) The SBR of Example 3, a functionalized SBR, has 2.1 wt% styrene units and 12.7 mol% butadiene units 1,2 relating to the butadiene moiety, based on the total weight of the copolymer, and has a glass transition temperature Tg of -88°C.

[0185] (2) Carbon black, ASTM N234 grade

[0186] (3) Silica, from Solvay's "Zeosil 1165MP", HDS type

[0187] (4) Hydrocarbon resins disclosed in Table 7 below

[0188] [Table 7]

[0189] Mn Mz H Ar Tg E5615 509 1400 10％ 68 E5600 484 1450 10％ 51 HR-H 389 667 16％ 88

[0190] (5) N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (“Santoflex 6-PPD”) and 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) from Flexsys.

[0191] (6) Coupling agent: "Si69" from Evonik-Degussa

[0192] (7) Diphenylguanidine: from Flexsys' "Perkacit DPG"

[0193] (8) Stearin, from Uniqema's "Pristerene 4931"

[0194] (9) Zinc oxide, industrial grade - Umicore

[0195] (10) N-cyclohexyl-2-phenylthiazole sulfenamide (from Flexsys' "Santocure CBS").

[0196] [Table 8]

[0197] T1 C1 G*10% (base 100) at 23℃ 100％ 121％ G*10% (base 100) at 40℃ 100％ 111％

[0198] Regarding the control compositions, it can be noted that composition T1, which does not conform to the hydrocarbon resins described herein, serves as the base number 100 for comparing the performance of other compositions. It can be noted that composition C1 can improve road handling performance by more than 10%.

Claims

1. A tire comprising a rubber composition, said rubber composition being at least based on an elastomer matrix and a hydrocarbon resin, said elastomer matrix comprising 50 phr to 100 phr of at least one copolymer of butadiene and a vinyl aromatic monomer, said at least one copolymer of butadiene and a vinyl aromatic monomer having a vinyl aromatic unit content between 0 and 5 wt% and a Tg in the range of -110°C to -70°C, said hydrocarbon resin being based on a cyclic monomer selected from petroleum refining stream fractions, C4, C5 and C6 cyclic olefins and mixtures thereof, said hydrocarbon resin having an aromatic proton content HAr in mol% as expressed by the following formula, a glass transition temperature Tg in °C as expressed by the following formula, and a number-average molecular weight Mn in g / mol as expressed by the following formula: (1) 12 mol% ≤ H Ar ≤ 19 mol% (2)Tg ≥ 95 - 2.2 * (H Ar), (3) Tg ≥ -53 + (0.265 * Mn) and (4) 300 g / mol ≤ Mn ≤ 450 g / mol.

2. Tyre according to the preceding claim, wherein, The hydrocarbon resin is further characterized by a Tg of 70°C to 95°C.

3. Tyre according to any one of the preceding claims, wherein, The hydrocarbon resin is further characterized by a Z-average molecular weight M z less than 1000 g / mole.

4. The tire of claim 1, wherein, The hydrocarbon resin contains cyclic monomer units in amounts between 10% and 90% by weight.

5. The tire of claim 1, wherein, The cyclic monomers are selected from cyclopentene, cyclopentadiene, dicyclopentadiene, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylcyclopentadiene, di(methylcyclopentadiene), and mixtures thereof.

6. The tire of claim 1, wherein, The hydrocarbon resin contains methylcyclopentadiene units in amounts ranging from 0.1% to 15% by weight.

7. The tire of claim 1, wherein, The resin is further based on aromatic monomers.

8. Tyre according to the preceding claim, wherein, The aromatic monomers are selected from olefin-aromatic compounds, aromatic fractions, and mixtures thereof.

9. The tire according to the preceding claim, wherein, The aromatic monomer is an aromatic fraction; or the aromatic monomer comprises an olefin-aromatic compound selected from indene derivatives, vinyl aromatic compounds, and mixtures thereof.

10. The tire according to the preceding claim, wherein, The aromatic monomers include indene derivatives of formula (I) or vinyl aromatic compounds of formula (II): [Chemical Formula 1] （I） R1 and R2 independently represent hydrogen atoms, alkyl, alkenyl, cycloalkyl, aryl, or arylalkyl. [Chemical Formula 2] (II) R3 and R4 independently represent hydrogen atoms, alkyl, alkenyl, cycloalkyl, aryl, or arylalkyl.

11. The tire according to claim 1, wherein, The hydrocarbon resin has at least one of the following additional characteristics: - The number-average molecular weight Mn is between 350 g / mol and 420 g / mol. - The glass transition temperature Tg is expressed as Tg ≥ 100 - 2.2 * (H Ar). - The glass transition temperature Tg is expressed as Tg ≥ -32 + (0.265 * Mn).

12. The tire according to claim 1, wherein, The content of the hydrocarbon resin is in the range of 15 phr to 150 phr.

13. The tire according to claim 1, wherein, The copolymer of butadiene and vinyl aromatic monomers has a Tg in the range of -110°C to -80°C.

14. The tire according to claim 1, wherein, The copolymer of butadiene and vinyl aromatic monomers has a vinyl aromatic unit content of 1% to 4% by weight based on the total weight of the copolymer, and a vinyl aromatic unit content involving the diene portion of 8% to 15% by weight.

15. The tire according to claim 1, wherein, At least 70% by weight of the copolymer of butadiene and vinyl aromatic monomers is functionalized.

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