• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a copolymer of ethylene and butadiene comprising, statistically distributed, ethylene units, butadiene units, trans-1,2-cyclohexane units, the mole fraction of ethylene units in said copolymer being equal to or greater than 50%, relative to the number of total moles of ethylene, butadiene and trans-12-cyclohexane units, characterized in that the microstructure of the copolymer is homogeneous. The present invention relates to a process for the preparation of such a copolymer as well as to the uses of this copolymer, in particular in tire rubber compositions.
    公开号:FR3045612A1
    申请号:FR1562573
    申请日:2015-12-17
    公开日:2017-06-23
    发明作者:Julien Thuilliez；Nuno Pacheco
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE
    The present invention relates to copolymers of ethylene and butadiene for which the microstructure is controlled and homogeneous throughout the copolymer chain. The present invention also relates to a process for preparing such a copolymer as well as uses of this copolymer, in particular in tire rubber compositions.
    Copolymers based on ethylene and conjugated diene have interesting properties for a pneumatic application according to the characteristics of the targeted materials, as described for example in patent applications WO2014082919 A1 or WO 2014114607 A1.
    Another advantage of these copolymers is the use of ethylene which is a current monomer and available on the market, and accessible by fossil or biological route.
    Another advantage of these copolymers is the presence of ethylene units along the polymer backbone, which units are much less sensitive to oxidative or thermooxidative degradation mechanisms, which gives the materials a better stability and longer life.
    The synthesis of copolymers based on ethylene and butadiene is described for example in US Patents 3,9101,862, EP 0 526 955, WO 2004/035639. In the application WO 2004/035639, the synthesis of copolymers based on ethylene and conjugated diene makes it possible to obtain an ethylene-based elastomer with a low degree of crystallinity (less than 15%), despite the higher ethylene content. at 70 mol%.
    Industrial solution polymerization processes often consist of three main steps: 1) Preparation of reaction mixtures; 2) Polymerization of the monomers in solution in contact with a catalytic system; 3) Recovery of elastomer and recycling of solvents, unreacted reagents and reaction by-products. The preparation step 1) consists of preparing the monomer and catalytic system solutions for their subsequent introduction into the reactor (s) of the polymerization stage. The polymerization step 2) consists in mixing the various monomer and catalytic system solutions to carry out the polymerization reaction of the monomers. The recovery step 3) consists of separating the polymer from solvents and unreacted chemicals (such as monomers). Solvents and unreacted chemicals are preferably recycled to the preparation stage. However, under certain conditions recycling may not be possible.
    In the polymerization processes known to date, the microstructure of the copolymer obtained is undergone or at best the average microstructure is controlled. However, this microstructure is not homogeneous all along the polymer chain and depends in particular on the mode of conducting the polymerization and the reactivity ratios of the catalyst system with respect to each of the monomers. A composition gradient is observed, in particular due to the fact that the ethylene and butadiene monomers have different insertion rates in the growing polymer chain for the existing catalytic systems. The invention particularly relates to copolymers based on ethylene and butadiene also comprising trans-λ, 2-cyclohexane units. Copolymers based on ethylene and butadiene comprising cyclohexane units are for example described in applications WO 2004/35639, EP 1 829 901 and WO 2004/035639. The copolymers obtained by the processes described in these applications have not only a concentration gradient in ethylene units, in butadiene units but also in trans-1, 2-cyclohexane units.
    Surprisingly, it has been discovered that it is possible to control the incorporation rate of ethylene and butadiene and the homogeneity of the different units all along the chain to access copolymers of low crystallinity . The invention relates to copolymers of ethylene and butadiene also comprising trans-1,2-cyclohexane units. The various units that can be found in these copolymers are ethylene units, butadiene units and frans-1,2-cyclohexane units.
    BRIEF DESCRIPTION OF THE INVENTION The invention relates to novel copolymers of ethylene and butadiene. Each copolymer of ethylene and butadiene comprises, statistically distributed, ethylene units, butadiene units, trans-1,2-cyclohexane units, the molar fraction of ethylene units in said copolymer being equal to or greater than 50%, relative to the total number of moles of ethylene, butadiene and trans-1,2-cyclohexane units, characterized in that the microstructure of the copolymer is homogeneous and thus the molar concentration in each of the units is constant all along the copolymer chain .
    The molar fraction of ethylene units advantageously varies from 50 mol% to 95 mol%, relative to the total number of moles of ethylene, butadiene and trans-1,2-cyclohexane units.
    The mole fraction of trans-1,2-cyclohexane units is advantageously between 0 mol% and 25 mol%, relative to the total number of moles of ethylene, butadiene and trans-1,2-cyclohexane units.
    The ethylene-butadiene copolymer advantageously has a crystallinity of less than 20%, advantageously less than 10%. The subject of the invention is also a semi-continuous process for the preparation of a copolymer of ethylene and butadiene according to the invention, comprising the solution polymerization in a hydrocarbon solvent at a temperature of between 0 ° C. and 200 ° C. ° C, ethylene and butadiene in the presence of a catalytic system allowing the formation of trans-1,2-cyclohexane cyclic units in the polymer chain, in a stirred reactor, characterized in that the polymerization is conducted at temperature constant and at constant ethylene pressure and butadiene pressure, in that ethylene and butadiene are injected continuously into the reactor and that in the reaction medium, at each instant of the polymerization, the concentrations of ethylene and butadiene are constant.
    In a variant, the composition of the reaction medium is analyzed continuously and the injection rates of ethylene and butadiene are adjusted to maintain in the reaction medium constant ethylene and butadiene concentrations.
    The temperature is kept constant.
    In another variant, the injection rates of ethylene and butadiene are adjusted to maintain a constant ethylene pressure and butadiene pressure in the reactor.
    In particular, ethylene and butadiene are injected in a predetermined flow ratio.
    In particular, a composition comprising ethylene and butadiene is injected at constant ethylene and butadiene concentrations.
    The catalyst system advantageously comprises at least two constituents, on the one hand, a metallocene corresponding to the formula (I): [P (Cp1) (Cp2) Met] (I) - with:
    Met is a group comprising: o at least one scandium, yttrium or lanthanide atom, the atomic number of which is from 57 to 71, o at least one monovalent ligand belonging to the group of halogens, such as chlorine, iodine, bromine, fluorine, to the group of amides, alkyls or borohydrides o optionally other constituents such as complexing molecules, belonging to the group of ethers or amines, P being a group, based on minus one silicon or carbon atom, bridging the two groups Cp1 and Cp2
    Cp1 and Cp2, are identical to each other or different from each other o when Cp1 and Cp2 are identical to each other, they are chosen from indenyls substituted in the 2-position, such as 2-methylindene, 2-phenylindene, among the fluorenyls, substituted or unsubstituted, such as fluorenyl, 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl, o when Cp1 and Cp2 are different from each other, Cp1 is chosen from fluorenyls, substituted or non, such as fluorenyl, 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl, Cp2 is chosen from cyclopentadienyls substituted at the 2-position and 5-position, such as tetramethylcyclopentadiene, among the indenyls substituted in the 2-position such as 2-methylindene, 2-phenylindene, among substituted fluorenyls, such as 2,7-ditertiobutyl-fluorenyl, 3,6-di-tert-butyl-fluorenyl. on the other hand a co-catalyst is an alkyl magnesium, an alkyl lithium, an alkyl aluminum, a Grignard reagent, or a mixture of these constituents. The subject of the invention is also a copolymer of ethylene and butadiene obtained by the process according to the invention, characterized in that the microstructure of the copolymer is homogeneous.
    Advantageously, the copolymer of ethylene and butadiene according to the invention is an elastomer. The invention also relates to a composition, in particular a rubber composition, comprising a copolymer according to the invention. The invention also relates to a tire of which one of the constituent elements comprises a composition according to the invention.
    In the present description, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., terminals a and b excluded) while any range of values designated by the expression "from a to b" means the range from a to b (i.e., including the strict limits a and b).
    For the purposes of the present invention, the term "ethylene unit" denotes the units of formula - (CH 2 -CH 2) -.
    For the purpose of the present invention, the term "butadiene unit" denotes the 1,4 units of formula - (CH2-CH = CH-CH2) - and the 1,2 units of formula - (CH2-C (CH = CH2)) -. The 1,4 units of formula - (CH 2 -CH = CH-CH 2) - may be of trans or cis configuration.
    By "1,2-cyclohexane trans unit" is meant for the purposes of the present invention, the units of formula:
    In the expression "significantly free of composition gradient", "significantly" means, within the meaning of the present invention, a variation of less than 2 mol%.
    In the expression "the concentration is identical or almost identical to", "quasi-identical" means, within the meaning of the present invention, a variation of less than 2 mol%.
    For the purpose of the present invention, the "reaction medium" designates the solution within the reactor.
    For the purposes of the present invention, the expression "constant temperature" means a temperature variation of less than 5 ° C. within the reactor.
    For the purposes of the present invention, the expression "ethylene pressure" denotes the partial pressure of ethylene within the reactor.
    For the purposes of the present invention, the expression "butadiene pressure" means the butadiene partial pressure within the reactor.
    For the purposes of the present invention, the expression "monomer pressure" denotes the sum of the "ethylene pressure" and "butadiene pressure" pressures, that is to say the sum of the partial pressures of the monomers to be polymerized at within the reactor. The expression "pressure" without any other specific indication indicates the total pressure within the reactor and is the resultant of the "ethylene pressures", "butadiene pressure" and the contribution of the other constituents of the reaction medium, such as the solvent (s), or still the inert gas according to the case (for example: nitrogen).
    For the purposes of the present invention, the term "constant" pressure means a pressure variation of less than 0.5 bar.
    The expression "constant ethylene and butadiene concentrations" means, within the meaning of the present invention, variations of less than 0.1 mol / L.
    BRIEF DESCRIPTION OF THE DRAWINGS
    FIG. 1: Schematic diagram for a polymerization according to the first mode of operation of the invention
    FIG. 2: Schematic diagram for a polymerization according to the second mode of operation, first variant, of the invention
    Figure 3: schematic diagram for a polymerization according to the second mode of operation, second variant of the invention.
    Acronyms used in these figures: CIC: Concentration Indicator Controller, Concentration Indicator Controller PIC: Pressure Indicator Controller, Pressure Indicator Fl: Flow Indicator, Flowmeter FC: Flow Controller, Flow Control
    4: percentage of crystallinity as a function of the mole percentage of incorporated ethylene for a copolymer without control (dashes) and for a copolymer according to the invention (dotted line)
    DETAILED DESCRIPTION OF THE INVENTION The invention relates to a copolymer of ethylene and butadiene comprising, statistically distributed, ethylene units, butadiene units, fra / 7s-1,2-cyclohexane units, the molar fraction of ethylene units in said copolymer being equal to or greater than 50%, based on the total number of moles of ethylene, butadiene and fra / 7s-1,2-cyclohexane units, characterized in that the microstructure of the copolymer is homogeneous.
    A copolymer is of homogeneous microstructure when for each of these units, at each instant of polymerization, the concentrations in the chain are identical or almost identical. Thus, for each of these units, at a given time, the concentration is identical or almost identical to its concentration at the instant just before and after, and thus at any time of the polymerization.
    In particular, in the copolymer of ethylene and butadiene the molar concentration in each of these units is constant throughout the copolymer chain. Thus, for a representative number of successive units defining a segment, present at the beginning, middle, end or at any other point in the copolymer chain, the concentration in ethylene units, butadiene units and transi, 2-cyclohexane units is identical or almost identical in each segment. A sequence of 10 units may be a representative number.
    Advantageously, the concentration of ethylene units, butadiene units, and trans-1, 2-cyclohexane units is identical or almost identical all along the copolymer chain. The concentration in each of the units can be determined in advance depending on the nature of the catalyst system chosen and the operating conditions (concentrations and monomer pressure in particular).
    Unlike the copolymers synthesized so far, we do not observe overconcentration in one of these units, especially at the beginning or end of the chain. In other words, the microstructure is free or significantly free of compositional gradient. Surprisingly, and of great interest, the control of the microstructure of the copolymer makes it possible to access copolymers having low levels of crystallinity even though the molar concentration in ethylene units is very important. Thus, it is possible to access copolymers having high levels of ethylene units and having a limited degree of crystallinity.
    In the copolymer according to the invention, the mole fraction of ethylene units, relative to the total number of moles of ethylene, butadiene and fra / 7s-1,2-cyclohexane units, is equal to or greater than 50 mol%. It advantageously ranges from 50 mol% to 99 mol%, more preferably from 50 mol% to 90 mol%, even more preferably from 65 mol% to 80 mol%, relative to the total mol% of mol. ethylene, butadiene and frans-1,2-cyclohexane units.
    Indeed, it is, by the present invention, possible to obtain copolymers having a high molar concentration in ethylene units while having a low crystallinity.
    Advantageously, the ethylene-butadiene copolymer according to the invention has a crystallinity of less than 25%, more preferably less than 15%, and even more advantageously less than 10%.
    According to a particularly advantageous embodiment of the invention, in the ethylene / butadiene copolymer the mole fraction of butadiene units, relative to the total number of moles of ethylene, butadiene and fra / s-1,2-cyclohexane units. in said copolymer is less than 50 mol%. The mole fraction of butadiene units advantageously varies from 1% to 35% by mole, relative to the total number of moles of ethylene, butadiene and trans-1,2-cyclohexane units.
    The butadiene units denote the 1,4 units of formula - (CH 2 -CH = CH-CH 2) -, of trans or cis configuration, and 1,2 of formula - (CH 2 -C (CH = CH 2)) -. The concentration in each of these units will also be constant throughout the copolymer chain. It will also be able to be determined in advance depending on the nature of the catalyst system chosen and the operating conditions (concentrations and monomer pressure in particular).
    Preferably, the copolymers according to the invention are such that they comprise trans-1,2-cyclohexane units, derived from an insertion of butadiene and ethylene, with a mole fraction greater than 0% and, again more preferential, equal to or greater than 1%, relative to the number of total moles of ethylene, butadiene and transi, 2-cyclohexane units.
    According to an exemplary embodiment of the invention, in the ethylene / butadiene copolymer, the mole fraction of f / ans-1,2-cyclohexane units is between 0% and 25%, advantageously ranging from 1% to 10%, relative to total number of moles of ethylene, butadiene and f / ans-1,2-cyclohexane units.
    According to another embodiment of the invention, in the ethylene / butadiene copolymer, the mole fraction of the trans-1, 2-cyclohexane units is between 0% and 25%, advantageously greater than 0% and less than or equal to 5%, based on the number of total moles of ethylene, butadiene and fra / 7s-1,2-cyclohexane units.
    For a given catalyst system, the relative concentration in each of the units is dependent on the concentration of monomers in the reaction medium, and therefore is dependent on the operating conditions in the reactor, in particular the ethylene pressure, the butadiene pressure and the monomer pressure at the reactor. within the reactor. Thus, irrespective of the reactivity ratios of the monomers with respect to the catalytic system used, the mole fractions of each of the units may be adjusted by the conditions for carrying out the polymerization.
    Advantageously, the copolymers of ethylene and butadiene according to the invention have a mass Mn ranging from 1,000 g / mol to 1,500,000 g / mol, more preferably ranging from 60,000 g / mol to 250,000 g / mol.
    According to another characteristic of the invention, the copolymers according to the invention have a polymolecularity index which is less than 2.5. Preferably, the index Ip of said copolymers is less than or equal to 2 and, even more preferably, this index Ip is less than or equal to 1.9. As with the molecular weights Mn, the polymolecularity indices Ip were determined in the present application by size exclusion chromatography (SEC technique described before the examples).
    The copolymers according to the invention preferably have a glass transition temperature Tg which is below 25 ° C. More specifically, these copolymers may for example have a temperature Tg between -45 ° C and -20 ° C.
    The copolymers according to the invention are advantageously elastomers. The subject of the invention is also a semi-continuous process for the preparation of a copolymer of ethylene and butadiene according to the invention, comprising the solution polymerization in a hydrocarbon solvent at a temperature of between 0 ° C. and 200 ° C. ° C, advantageously between 0 ° C and 120 ° C, ethylene and butadiene in the presence of a catalytic system for the formation of frans-1,2-cyclohexane units in the polymer chain, in a reactor, characterized in that the polymerization is carried out at constant temperature, at constant ethylene pressure and butadiene pressure, in that ethylene and butadiene are injected continuously and in a controlled manner into the reactor and that in the reaction medium, at each instant During polymerization, the concentrations of ethylene and butadiene are kept constant.
    The reactor is provided with stirring means.
    The process according to the invention is thus a controlled process, for which the quantities of ethylene and butadiene introduced are controlled, which are defined in particular as a function of the catalytic system chosen and the desired microstructure. This control makes it possible both to define the microstructure of the synthesized polymer, but also to define and maintain the ethylene pressure and the butadiene pressure constant. The polymerization step is advantageously carried out according to a semi-continuous process in solution in the presence of a catalytic system allowing the formation of 1,2-cyclohexane trans units with a continuous injection of the comonomers, ethylene and butadiene, in a stirred reactor to obtain a copolymer of homogeneous and statistical composition all along the chain.
    The specific control of the injection of co-monomers makes it possible to control the rate of incorporation of ethylene and butadiene and the homogeneity of the microstructure, thus making it possible to access copolymers of low crystallinity level.
    The catalytic system advantageously comprises at least two constituents, on the one hand a metallocene corresponding to the formula (I): [PiCp'XCp ^ Met] (I) - with:
    Met is a group comprising: o at least one scandium, yttrium or lanthanide atom, the atomic number of which is from 57 to 71, o at least one monovalent ligand belonging to the group of halogens, such as chlorine, iodine, bromine, fluorine, to the group of amides, alkyls or borohydrides, o optionally other constituents such as complexing molecules, belonging to the group of ethers or amines, P being a group, based on minus one silicon or carbon atom, bridging the two groups Cp1 and Cp2
    Cp1 and Cp2, are identical to each other or different from each other o when Cp1 and Cp2 are identical to each other, they are chosen from indenyls substituted in the 2-position, such as 2-methylindene, 2-phenylindene, among the fluorenyls, substituted or unsubstituted, such as fluorenyl, 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl, o when Cp1 and Cp2 are different from each other, Cp1 is chosen from fluorenyls, substituted or non, such as fluorenyl, 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl, Cp2 is chosen from cyclopentadienyls substituted at the 2-position and 5-position, such as tetramethylcyclopentadiene, among the indenyls substituted in the 2-position such as 2-methylindene, 2-phenylindene, among substituted fluorenyls, such as 2,7-ditertiobutyl-fluorenyl, 3,6-di-tert-butyl-fluorenyl. on the other hand a co-catalyst is an alkyl magnesium, an alkyl lithium, an alkyl aluminum, a Grignard reagent, or a mixture of these constituents. As substituted cyclopentadienyl, fluorenyl and indenyl groups, mention may be made of those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms. The choice of radicals is also oriented by accessibility to the corresponding molecules that are cyclopentadienes, fluorenes and substituted indenes, because they are commercially available or easily synthesizable.
    In the present application, in the case of the cyclopentadienyl group, the 2 (or 5) position refers to the position of the carbon atom which is adjacent to the carbon atom to which the bridging group P is attached, as shown in FIG. the diagram below.
    As a 2-substituted cyclopentadienyl group & 5, there may be mentioned more particularly the tetramethylcyclopentadienyl group.
    In the case of the indenyl group, the 2-position designates the position of the carbon atom which is adjacent to the carbon atom to which the bridging group P is attached, as shown in the diagram below.
    As 2-substituted indenyl groups, there may be mentioned more particularly 2-methylindenyl, 2-phenylindenyl. As substituted fluorenyl groups, there may be mentioned more particularly the 2,7-ditertiobutyl-fluorenyl and 3,6-ditertiobutyl-fluorenyl groups. The positions 2, 3, 6 and 7 respectively designate the position of the carbon atoms of the rings as represented in the diagram below, the position 9 corresponding to the carbon atom to which the bridging group P is attached.
    Advantageously, the metallocene is a metallocene of lanthanide. Preferably, the lanthanide metallocene is chosen from the compounds [Me2Si (Flu) 2Nd (BH4) 2Li (THF)], [Me2Si (Flu) 2Nd (BH4) (THF)], [Me2Si (2-Melnd) 2Nd ( BH4)], [Me2Si (C5Me4) (Flu) Nd (BH4)], [Me2Si (2-Melnd) (Flu) Nd (BH4)] and the cocatalyst is selected from dialkylmagnesians such as ethylbutylmagnesium or butyloctylmagnesium.
    The symbol "Flu" represents the fluorenyl group C13H8 and the symbol "Melnd" represents an indenyl group substituted in position 2 by a methyl.
    Such systems have for example been described in applications WO 2004/035639 and WO 2007/054224.
    Optionally, the catalytic system may comprise other constituents, chosen from ethers, aliphatic solvents, or other compounds known to those skilled in the art and compatible with such catalytic systems.
    The polymerization reaction of ethylene and butadiene in solution is carried out in one or more reactors in parallel. When several reactors according to the invention are in parallel, the timing management can be adjusted according to the manufacturing requirements and consistent with the prior stages of preparation of the reagents and subsequent recovery of the polymer.
    Each reactor must ensure an optimal mixing level between the gas phase and the liquid phase. By way of example, we can mention the internal stirring modules type hollow shaft and / or the recirculation modules of the gas phase via an outer loop with injection in the liquid phase.
    It is preferable to use reactors to hold and control at least 15 bars of pressure, preferably at least 200 bars of pressure. In fact, the ethylene pressure and the butadiene pressure must be constant throughout the polymerization in order to guarantee a homogeneous microstructure along the entire polymer chain, as well as the expected productivity levels.
    It is also preferable to use reactors with an effective temperature control device. For example, a double jacket, an internal condenser in the gas phase, a heat exchanger in the liquid phase, a cooler in the outer loop of gas recirculation.
    The polymerization temperature is advantageously between 0 ° C and 200 ° C, more preferably between 0 ° C and 120 ° C. The polymerization temperature is chosen according to the catalytic system and the product to be obtained. The temperature, which influences the macrostructure and the microstructure, is also controlled to keep it constant throughout the polymerization phase in the chosen range. .
    The ethylene pressure constant during the polymerization stage can advantageously range from 1 to 100 bar. The butadiene pressure, which is constant during the polymerization stage, can advantageously range from 1 to 100 bar. In particular, it has been found that the relative concentration in the different units can also be controlled by the ethylene pressure and the butadiene pressure.
    In a first variant, the monomer pressure ranges from 1 to 25 bar, more preferably from 4 to 25 bar, and the copolymer comprises trans-1,2-cyclohexane units in a molar fraction of between 0% and 25%, more advantageously ranging from 1 to 10%, relative to the number of total moles of ethylene, butadiene and trans-1,2-cyclohexane units.
    In another variant, the monomer pressure ranges from 25 to 100 bar, more preferably from 25 to 80 bar, and the copolymer comprises trans-1,2-cyclohexane units in a mole fraction of between 0% and 25%, more advantageously greater than 0% and less than or equal to 5%, relative to the number of total moles of ethylene, butadiene and trans-1,2-cyclohexane units.
    According to the invention, a monomer injection management system is coupled to the reactor to maintain constant ethylene pressure and butadiene pressure and thus guarantee a random polymer and composition gradient free along the chain.
    In a first mode of operation, this system for controlling the injection of the monomers may consist of a means for measuring the concentration of ethylene in the reaction medium and a means for measuring the concentration of butadiene in the reaction medium. reaction medium. Therefore, the injection rates of each of the two monomers are adjusted according to the measurement of the composition of the reaction medium. These adjustments are made to ensure a constant concentration at the ethylene and butadiene set point in the reaction medium.
    Thus, in this first mode of operation, the composition of the reaction medium is analyzed continuously and the injection rates of ethylene and butadiene are adjusted to maintain constant ethylene and butadiene concentrations in the reaction medium.
    In this mode of operation, the temperature is kept constant throughout the polymerization phase.
    In this mode of operation, butadiene is advantageously injected in liquid form.
    In this mode of operation, the ethylene is advantageously injected in gaseous form. By way of nonlimiting example, the measuring means can be carried out by absorbance type methods in the infrared range, absorbance type methods in the ultraviolet / visible range, or by gas chromatography.
    An example of a reactor according to this first mode of operation is shown in FIG. 1, the solvent and catalytic supply conduits not being shown, 1. Reactor 2A and 2B. Flow Control Valves 3. Ethylene Supply Line 4. Butadiene Supply Line 5. Means of Agitation 6. Reactor Drain 7. External Cooling of the Reactor 8. Drive Motor stirring 9A and 9B. Automatic controllers for the concentration of ethylene and butadiene in the reaction medium
    The reactor 1 comprises measuring means (not shown) for the concentration of ethylene and that of butadiene in the reaction medium, connected to an automatic controller of the concentration of ethylene and butadiene, respectively 9A and 9B, controlling the respective injection rates of ethylene fed by a conduit 3 and butadiene fed by a conduit 4 by the control valves 2A and 2B. The reactor comprises stirring means 5, here several pale. The temperature in the reactor is kept constant throughout the polymerization phase.
    In a second mode of operation, the injection rate of ethylene and butadiene is continuous and is adjusted to maintain a constant ethylene pressure and butadiene pressure in the reactor.
    In this mode of operation, the temperature is kept constant throughout the polymerization phase.
    In this mode of operation, the ethylene concentration in the reaction medium is kept constant by managing the pressure in the reactor with a continuous addition of ethylene. Indeed, by maintaining the constant ethylene pressure within the reactor and by continuously injecting ethylene at a rate that can vary, the ethylene consumption is compensated. The same goes for butadiene.
    In a first variant, the ethylene and butadiene are injected in a pre-determined flow rate ratio. Thus, the injection of the monomers is controlled by the ethylene pressure and the butadiene pressure of the reactor and by a flow rate ratio known by the various tools available to those skilled in the art (experimentation, numerical simulation), and adapted to catalytic system implemented.
    An example of a reactor according to this first mode of operation is shown in FIG. 2, the solvent and catalytic supply conduits not being shown. 1 Reactor 2A and 2B Flow Control Valves 3 Ethylene Supply Line 4 Butadiene Supply Line 5 Means of Agitation 6 Reactor Drain 7 External Cooling of the Reactor 8 Stirring Drive Motor 9 Automatic controller of the pressure of the reactor 10 and 11 Means of measurement of flow 12 Controller of the ratio of feed rates of ethylene and butadiene
    In this mode of operation, butadiene is advantageously injected in liquid form.
    In this mode of operation, the ethylene is advantageously injected in gaseous form.
    The reactor 1 comprises a means for measuring the pressure (not shown) in the reactor connected to an automatic controller of the pressure of the reactor 9 which slaves the flow rates of injection of ethylene and butadiene, respectively fed by a conduit. 3 and a pipe 4. The ethylene and butadiene pressures are kept constant while keeping the total pressure in the reactor constant. The injection rates of ethylene and butadiene, regulated by the opening of the respective valves 2A and 2B and measured respectively by flow measurement means 10 and 11, are furthermore controlled by a flow rate ratio controller. supply of ethylene and butadiene 12 to meet the preset flow ratio. The reactor comprises stirring means 5, here several pale. The temperature in the reactor is kept constant throughout the polymerization phase.
    In a second variant, a composition comprising ethylene and butadiene is injected at constant ethylene and butadiene concentrations.
    An example of a reactor according to this first mode of operation is shown in FIG. 3, the solvent and catalytic supply conduits not being shown. 1. Reactor 2. Flow control valve 3. Ethylene supply duct 4. Butadiene supply duct 5. Stirring means 6. Drain pipe 7. External cooling 8. Mobile drive motor 9. Automatic control of the reactor pressure
    The reactor 1 comprises a means for measuring the pressure (not shown) within the reactor, connected to an automatic controller of the pressure of the reactor 9 which slaves the injection flow rate of the ethylene / butadiene premix via a valve 2, ethylene and butadiene being fed respectively by a conduit 3 and a pipe 4. The ethylene and butadiene pressures are maintained constant by maintaining constant the total pressure within the reactor. The reactor comprises stirring means 5, here several pale. The temperature in the reactor is kept constant throughout the polymerization phase.
    In this mode of operation, the butadiene / ethylene mixture is advantageously injected in liquid or supercritical form. In fact, the injection can be at sufficiently high pressures, in particular from 52 to 250 bar, more preferably from 60 to 100 bar, and sufficiently low temperatures, in particular from 0 to 50.degree. C., more preferably from 5 to 50.degree. 25 ° C, to have a liquid mixture in order to adapt the injection conditions to existing technologies.
    The solution polymerization process generally comprises three major steps: Step 1: Preparation step Step 2: Polymerization step Step 3: Polymer recovery step
    Step 1: The objective of step 1 is to: • Purify the monomers (ethylene and butadiene) and the solvent if necessary • Prepare the catalytic system solution
    The purification techniques of the monomers and solvent depend on the nature of the impurities and their content. By way of example and without limitation, it can be mentioned that distillation or chemical adsorption techniques can be envisaged for the purification of the monomers or solvent.
    Examples of suitable solvents are C 2 -C 30 alkanes, C 4 -C 30 branched alkanes, C 5 -C 6 cyclic alkanes, C 6 -C 30 branched cyclic alkanes, C 6 -C 30 aromatic solvents, and mixtures thereof. of these products.
    The preparation of the catalytic system solution is a delicate step since this type of catalytic system does not tolerate the presence of air or practical products such as water or alcohols. The preparation is carried out with the purified and / or recycled polymerization solvent of the process.
    Step 2: Step 2 comprises the polymerization reaction as described above.
    Before the production phase, the reactor or reactors must be cleaned in such a way that the level of impurities present in the reactor is less than or equal to the level of impurities tolerated by the catalytic system. By way of example, the reactor can be washed with the purified solvent in step 1 and the level of impurities measured on the washing solvent.
    In another complementary or replacement mode, the reactor impurities harmful to the polymerization are neutralized by washing with an aluminum alkyl or alkyl magnesium solution. It is said that the reactor is rendered inert.
    The production timing is engaged after the cleaning phase. The timing which makes it possible to obtain the copolymer according to the invention is advantageously divided into three phases: • Phase 1) reactor loading
    Phase 1) begins with the charging of the reactor with the chosen amount of solvent or mixture of solvents. This phase is preferably carried out under an inert atmosphere, at the temperature of the targeted reaction and with the mixing system (s) operating at the desired rate.
    Then, the monomers are introduced while respecting the desired composition for the medium. The introduction of monomers ends when the reactor pressure reaches the desired pressure.
    Phase 1 is complete when the solvents and monomers are in the reactor at the desired pressure, temperature and monomer composition. • Phase 2) polymerization
    Phase 2) starts with the injection of the catalyst system solution into the reactor, at a desired quantity.
    The polymerization phase is continued with a continuous feed of the monomers according to one of the modes described above.
    Controlling the temperature and maintaining the constant ethylene pressure and butadiene pressure are essential to obtain the desired product.
    The cycle of phase 2 ends once the desired conversion to monomers has been achieved. The corresponding polymerization time is determined by the various tools available to those skilled in the art (experimentation, numerical simulation), and adapted to the catalytic system and to the experimental conditions used. • Phase 3) unloading and curing stoppage
    Phase 3 consists of draining the polymerization reactor. At the time of reactor emptying, the polymer solution is mixed with a terminating agent, or "stopper", to stop the polymerization reaction and deactivate the catalyst system. This agent can be an alcohol or any other chemical compound leading to the deactivation of the catalytic system. The reaction can be stopped in the reactor or outside (other reactor, tube, etc.).
    After completing phase 3), the polymerization step is complete.
    Step 3: Step 3) consists of: recovering the polymer from the solution and separating it from its solvent according to any method known to those skilled in the art, so as to isolate it and bring it to a volatile matter content less than 1% by weight, • recover the solvent and unconverted monomers and recycle all or part of them in step 1) if purification is necessary or wholly or partly in step 2 ) if purification is not necessary.
    For this, we can mention in a nonlimiting manner several recovery techniques known to those skilled in the art, such as: • Decantation, if two liquid phases can form under the separation conditions. One of the phases is rich in polymer and the other is rich in solvent and unreacted monomers. This technique may be possible if the mixture solvent, monomers and polymer allows it, and advantageous from an energy point of view. Often, this technique is present after step 2); • The flash, which consists of devolatilization separating the solvent and the unconverted monomers from the polymer by thermal effect or by the effect of a reduction of the pressure or both. Often this technique is present after step 2) or decantation; • Stripping, which consists in separating the solvent and unconverted monomers from the polymer by the presence of a third inert body such as nitrogen, steam. This step can be coupled with a thermal effect to improve the recovery of the polymer. Often, this technique is present after the devolatilization by flash; • Spinning, which consists of pressing elastomer particles to extract the liquid constituents contained inside the elastomer particles. Often, this technique is present after a stripping step; • Extrusion / flash, which consists of compressing the polymer at high pressures and at high enough temperatures to subsequently flash a flash. This makes it possible to devolatilize virtually all the solvent residues and unconverted monomers. Often, this technique is present after a spinning step or the flashing step. • Drying with a fluid, preferably hot, which removes solvent residues and unconverted monomers in the polymer. Often, this technique is present after a spinning step or the flash step;
    In a preferred mode of operation, the recovery of the polymer from the polymer solution is carried out by: 1 Concentration in a succession of flash steps to obtain a polymer solution concentrated to at least 15% by weight, preferably to at least 20% by weight weight and a gaseous flow of solvent and unconverted monomers free of impurities. This stream can be recycled in step 2). Stripping with water vapor to obtain the polymer with a hydrocarbon content (solvents and unconverted monomers) of less than 5% by weight, preferably less than 1% by weight. The gas stream rich in solvent, unconverted monomers and water vapor is sent to step 1) to be purified by decantation, distillation and / or chemical adsorption. The polymer stream after this step is composed of water and water-soaked polymer particles and less than 1% by weight of hydrocarbons. Filtration of the polymer particles and spinning to reduce the level of volatiles (hydrocarbons and water) to less than 5% by weight, preferably less than 3% by weight of volatile materials. 4 Compression at above 50 bar, heating at less than 250 ° C, extrusion and flash at atmospheric pressure to lower the level of volatile matter to less than 1% by weight. Drying with hot, dry air (~ 80 ° C) to wait for the specification in terms of volatile matter, usually less than 0.5% by weight. The subject of the invention is also the copolymer obtained by the process according to the invention. This copolymer is advantageously an elastomer.
    Compositions The invention also relates to a composition comprising a copolymer according to the invention, preferably an elastomer.
    The composition is advantageously a rubber composition, in particular a composition that can be used in the manufacture of a tire.
    According to an advantageous variant of the invention, the copolymer according to the invention is an elastomer. The copolymer according to the invention is particularly useful for the preparation of compositions as described in patent WO 2014/082919 A1 or WO 2014/114607 A1 in the name of the Claimants. If any other elastomers are used in the composition, the copolymer according to the invention constitutes the major fraction by weight of all the elastomers; it then represents at least 65%, preferably at least 70% by weight, more preferably at least 75% by weight of all the elastomers present in the elastomer composition. Also preferably, the copolymer according to the invention represents at least 95% (in particular 100%) by weight of all the elastomers present in the composition. Thus, the amount of copolymer according to the invention is in a range which varies from 65 to 100 phr, (parts by weight per hundred parts of total elastomer), preferably from 70 to 100 phr, and in particular from 75 to 100 phr. . Also preferably, the composition contains from 95 to 100 phr of copolymer according to the invention.
    The composition according to the invention may further comprise at least one (that is to say one or more) diene rubber as non-thermoplastic elastomer.
    By elastomer or "diene" rubber, it is to be understood in a known manner (one or more elastomers) are understood to come from at least a part (ie a homopolymer or a copolymer) of diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or not).
    By diene elastomer, it should be understood according to the invention any synthetic elastomer derived at least in part from diene monomers. More particularly, diene elastomer is any homopolymer obtained by polymerization of a conjugated diene monomer having 4 to 12 carbon atoms, or any copolymer obtained by copolymerization of one or more conjugated dienes with one another or with one or more vinylaromatic compounds. having from 8 to 20 carbon atoms. In the case of copolymers, these contain from 20% to 99% by weight of diene units, and from 1 to 80% by weight of vinylaromatic units. Conjugated dienes which may be used in the process according to the invention are especially suitable for 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di (C 1 -C 5 alkyl) -1,3 butadiene such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl 3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, etc. The diene elastomer of the composition according to the invention is preferably selected from the group of diene elastomers consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of styrene copolymers (SBR, SIR and SBIR), polybutadienes (BR), synthetic polyisoprenes (IR) and natural rubber (NR).
    Reinforcing charge
    When a reinforcing filler is used, it is possible to use any type of filler usually used for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler capable of reinforcing on its own, without any other means than an intermediate coupling agent, such as silica, or a blend of these two types of filler, in particular a black carbon and silica blend.
    In order to couple the reinforcing inorganic filler to the elastomer, an at least bifunctional coupling agent (or bonding agent) is used in known manner in order to ensure a sufficient chemical and / or physical connection between the inorganic filler (surface particles or aggregates of particles) and the elastomer according to the invention, in particular organosilanes or bifunctional polyorganosiloxanes.
    Various additives
    The rubber compositions in accordance with the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tires, for example pigments, protective agents such as anti-ozone waxes, chemical antioxidants, anti-oxidants, anti-fatigue agents, reinforcing or plasticizing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M) as described, for example, in the application WO 02/10269, a crosslinking system based on either sulfur, or sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators, adhesion promoters such as compounds based on cobalt, plasticizing agents, preferably non-aromatic or very weakly aromatic selected from the group consisting of hu naphthenic, paraffinic, MES oils, TDAE oils, ethers plasticizers, ester plasticizers (for example glycerol trioleate), hydrocarbon resins having a high Tg, preferably greater than 30 ° C, as described for example in the WO 2005/087859, WO 2006/061064 and WO 2007/017060, and mixtures of such compounds. The invention also relates to a tire of which one of the constituent elements comprises a composition according to the invention.
    The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given for illustrative and non-limiting in connection with the attached annexes.
    MEASUREMENTS AND TESTS USED FOR DETERMINATION OF MASS MASSES: Analysis by Steric Exclusion Chromatography of the Copolymers: a) For room temperature soluble copolymers in tetrahydrofuran (THF), the molar masses were determined by size exclusion chromatography in THF . Samples were injected using a "Waters 717" injector and a "Waters 515 HPLC" pump at a flow rate of 1 ml.min'1 into a series of "Polymer Laboratories" columns.
    This series of columns, placed in an enclosure thermostated at 45 ° C, is composed of: -1 precolumn PL Gel 5 pm, - 2 columns PL Gel 5 pm Mixed C, - 1 column PL Gel 5 pm-500 Å.
    The detection was carried out using a "Waters 410" refractometer
    Molecular weights were determined by universal calibration using polystyrene standards certified by "Polymer Laboratories" and dual detection with refractometer and viscometer coupling.
    Without being an absolute method, the SEC allows to apprehend the distribution of the molecular masses of a polymer. From Polystyrene type commercial standard products, the various number average masses (Mn) and weight (Mw) can be determined and the calculated polymolecularity index (Ip = Mw / Mn). b) For copolymers insoluble at room temperature in tetrahydrofuran, the molar masses were determined in 1,2,4-trichlorobenzene. They were first dissolved under heat (4 h at 150 ° C.) and then injected at 150 ° C. with a flow rate of 1 ml.min -1 in a "Waters Alliance GPCV 2000" chromatography equipped with three columns "Styragel" (2 columns "HT6E" and 1 column "HT2").
    The detection was carried out using a "Waters" refractometer.
    The molar masses were determined by relative calibration using polystyrene standards certified by "Polymer Laboratories".
    DETERMINATION OF MOTIONAL FRACTIONS
    Reference is made to the article "Investigation of ethylene / butadiene copolymers microstructure by 1H and 13C NMR, Llauro MF, Monnet C., Barbotin F., Monteil V., Spitz R., Beverage C., Macromolecules 2001,34, 6304 -6311 ", for a detailed description of the 13 H NMR and 13 C NMR techniques which have been specifically used in the present application to determine the mole fractions of these trans-1,2 cyclohexane units, as well as the ethylene, butadiene 1, 4-c / s and 1,4-trans butadiene.
    DETERMINATION OF CRYSTALLINITY
    The measurement of crystallinity is done by comparing the enthalpy of fusion observed in the case of RBEs. This endothermic phenomenon is observed during the thermogram analysis of the DSC (Differential Scanning Calorimetry) measurement. The measurement is made by going-back scanning from -150 ° C. to 200 ° C. under an inert atmosphere (helium) with a ramp of 20 ° C./min.
    The signal corresponding to the endothermic phenomenon (fusion) is integrated and the degree of crystallinity is the ratio between the measured enthalpy and that of the perfectly crystalline polyethylene (290J / g)% Crystallinity = (Enthalpy measured in J / g) / (theoretical enthalpy) 100% crystalline polyethylene in J / g)
    DETERMINATION OF THE VITREOUS TRANSITION TEMPERATURE
    The glass transition temperature, Tg, is measured in the present application by the Differential Scanning Calorimetry (DSC) technique on a "Setaram DSC 131" naming device. The temperature program used corresponds to a rise in temperature from -120 ° C. to 150 ° C. at a rate of 10 ° C./min. Reference may be made to the method described in application WO 2007/054224 (page 11).
    EXAMPLES
    The series of examples below is intended to illustrate some embodiments of the invention, leading to obtaining a homogeneous distribution of the different constituent units of copolymers of ethylene and butadiene.
    A first series of experimental examples illustrate the homogeneous distribution of the units during the polymerization, characterized by an analysis of the copolymer composition throughout the polymerization.
    A second series of experimental examples show that according to the invention, the homogeneous distribution of the units along the polymer chain can significantly shift the compromise crystallinity level as a function of the molar percentage of ethylene units.
    A final series of examples obtained by numerical simulation shows the ability to obtain a homogeneous distribution of the different units constituting copolymers of ethylene and butadiene under different operating conditions, in particular at higher molar concentrations of monomers in the reaction medium, and describes the composition of the accessible copolymers according to the invention.
    In the tables, the following abbreviations are used: E. = ethylene unit B. = butadiene unit B. 1,4 = butadiene unit, 4-trans or butadiene1,4-c / s B. 1,2 = butadiene-1 unit , 2 C. = trans-1,2-cyclohexane unit
    The percentages of the units are molar percentages, based on the number of total moles of ethylene, butadiene and transi, 2-cyclohexane units.
    Examples - Part A
    In this part is illustrated the copolymerization of ethylene and butadiene in a reactor of useful volume of 87.5 L. Two modes of management of the addition of monomers are envisaged, with or without drift of the composition, for two types monomer mixtures, as shown in the table below.
    Table 1
    Monomer butadiene composition (mol%) = total mole percentage of butadiene introduced (phase 1 + 2), relative to the number of total moles of monomers introduced (butadiene + ethylene, phases 1 + 2)
    The procedure for these four examples comprises the following steps: 1. Phase 1: reactor charging. The products below, in the amounts indicated in Table A-1, are introduced into an agitated, inert reactor: toluene (solvent); - Butyl-Octyl-Magnesium solution (BOMag) in toluene, used here to neutralize the impurities of the reactor, - ethylene, - optionally butadiene
    All these introductions are at atmospheric pressure, under an inert atmosphere of nitrogen and at room temperature. Once this phase is complete, the total pressure of the reactor is 8.5 bars. 2. Phase 2: polymerization
    The catalyst system, consisting of metallocene [Me2Si (Flu) 2Nd (BH4) 2Li (THF)] and the alkylating agent BOmag at atmospheric pressure, is introduced under an inert atmosphere of nitrogen and at room temperature. In Table A1, these quantities are constant and equivalent for all counterexamples C-EX1 and 2, and examples EX1 and EX2. These amounts can be determined by those skilled in the art according to the desired characteristics of the polymers to be synthesized. At this time, the temperature control system is set to maintain the reaction medium at 80 ° C, the polymerization starts and lasts until the desired monomer conversion is achieved.
    The examples differ from counterexamples in: (i) a discontinuous addition mode of butadiene and continuous addition of ethylene for counterexamples 1 and 2: additional amounts of monomers are introduced as and when the polymerization reaction consumes the monomers, continuously in the case of ethylene (in order to maintain the constant pressure equal to 8.5 bars), and discontinuously in the case of butadiene whose quantities are added manually and determined according to the conversion rate to monomers; (ii) a continuous addition method, for Examples 1 and 2, of ethylene and butadiene to obtain a copolymer of ethylene and butadiene having a homogeneous distribution of the different units: the amounts of ethylene and butadiene are added in a controlled manner depending on the composition of the liquid phase to monomers referred and to achieve a reactor pressure of 8.5 bar. 3. Phase 3,
    At the end of polymerization, the catalytic system is then deactivated by addition of methanol and antioxidants are added to the polymer solution. The solvent is evaporated and the polymer is dried. Samples are taken throughout the polymerization so as to analyze the composition of the copolymer over time.
    Table A-1 below describes the operating conditions for each of the four tests. Table A-2 shows the main characteristics of the copolymers thus obtained. Table A-3 below describes the average composition of the copolymer throughout the polymerization.
    Table A-1
    Table A-2
    Table A-3a Comparison for 20% Molar Butadiene Compositions
    Table A-3b Comparison for 30% Molar Butadiene Compositions
    These two tables A-3a and b illustrate that the percentage of each of the units of the copolymers according to the invention is constant throughout the polymerization, whereas for the counterexamples a fluctuation of the order of several% is observed between the first sample and the polymer recovered at the end of polymerization.
    Examples - Part B
    A series of copolymers was prepared according to a synthesis mode identical to that of the preceding counterexamples 1 and 2. The molar ratio of the ethylene units was determined, as well as the degree of crystallinity. Another series of copolymers was prepared according to a synthesis mode identical to that of Examples 1 and 2.
    The samples from each series constitute two populations, shown in Figure 4.
    This figure demonstrates, for the invention, a better compromise rate of crystallinity / rate of ethylene units: for the same molar level of ethylene, the crystallinity is lower for the copolymers according to the invention.
    Examples - Part C Copolymer according to the invention obtained by Numerical Simulation
    The polymerization conditions of ethylene and butadiene according to the invention imply that the concentration of each of the two monomers in the reaction medium remains constant. For any reaction of order greater than or equal to 1 with respect to the monomers, one of ordinary skill in the art infers, trivially, that the insertion rates of each unit in the chain also remain constant throughout the duration of the polymerization.
    In the particular case of the invention, the prediction of the microstructure is calculated by the following equations:
    Where: •% E is the molar percentage of ethylenic units in the chain •% B is the molar percentage of butadiene units (1,4 and 1,2) in the chain •% unitsc is the molar percentage of cyclic units in the chain • And R1 to R9 calculated as below if = 112 = k2% PE (B] 53 = fc3% P0 [£] 54 = 55 = k2% £ £ [£] R6 = kiWFSfiTfl ·] R7 = fc2% PBEE [B] S8 = k4% PBEE R9 = k5% PC [E] Where: • ki to k5 are constants
    • [E], [B] are the concentrations of ethylene, butadiene in mol / L •% PE,% PB,% PBE,% PBEE and% PC calculated according to the system of equations below:
    Where the values of k2, k3, k4 and k5 are measured experimentally and then reported to k1.
    The following table represents typical values of the values k2, k3, k4 and k5 relative to k1 for the catalytic systems that can be used according to the polymerization method described in the invention.
    Table 2
    This mathematical model makes it possible to predict the distribution of the ethylene, butadiene and 1,2-cyclohexane units of an elastomer produced according to the invention as a function of the constants k1 to k5 and the molar composition of ethylene and butadiene in the liquid phase. .
    Example of model validation for the metallocene [Me2Si (Flu) 2Nd (BH4) 2Li (THF)] catalyst system in the presence of butyloctyl magnesium
    For this catalytic system, in the case of a copolymerization of ethylene and butadiene performed identically to Examples 1 and 2 of Part A, we were able to determine the values given in Table 2 above, regardless of the value of k1 between 0 and 1020 L / mol / min, or higher. By way of example, the table below compares the results of Examples 1 and 2 according to the invention of Part A and the result obtained with the mathematical model and its constants.
    Table 3 According to this table, we conclude that the model makes it possible to predict the potentially attainable microstructures according to the invention.
    Example of microstructures attainable by the metallocene [Me2Si (Flu) 2Nd (BH4) 2Li (THF)] catalyst system in the presence of butyloctyl magnesium according to the mathematical model
    The examples below describe the microstructure obtained at different pressure levels, 5, 8.5 and 70 bar, for different compositions of the feed. The mole fraction of ethylene is between 0.5 and 0.99.
    The pressure is involved in the calculation of the total concentration of the monomers in the liquid phase. The equation below makes it possible to calculate the pressure of the reactor (P) in bar from the concentration of butadiene and ethylene in mol / L.
    This equation is valid for the system: ethylene, butadiene in the MCH solvent.
    The table below shows the prediction of accessible microstructures at 5 bars.
    Table 4
    The table below shows the prediction of accessible microstructures at 8.5 bars.
    Table 5
    The table below shows the prediction of accessible microstructures at 70 bar.
    Table 6
    In the three previous tables, Liq = liquid. The% ethylene (Liq) or% butadiene (Liq) percentage corresponding to the molar percentage of ethylene or butadiene in the reaction medium, relative to the total number of moles of butadiene and ethylene in the reaction medium. From the results of the tables above, we observe that the microstructure of the ethylene-butadiene copolymers made according to the invention can be controlled by controlling the composition of the reaction medium and the reactor pressure.
    For example: • for the pressure range 5 to 70 bar, the rate of 1,2-cyclohexane units may vary from a value close to 0%, but greater than 0%, to 10% • to 8.5 bars, the level of 1,2 cyclohexane units has a maximum of 7% for ethylene levels in the liquid phase of between 70% and 80% relative to the total monomers.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. A copolymer of ethylene and butadiene comprising, statistically distributed, ethylene units, butadiene units, transi, 2-cyclohexane units, the molar fraction of ethylene units in said copolymer being equal to or greater than 50%, relative to the total number of moles of ethylene, butadiene and frans-1,2-cyclohexane units, characterized in that the microstructure of the copolymer is homogeneous and thus the molar concentration in each of the units is constant all along the copolymer chain.
    [2" id="c-fr-0002]
    2. Copolymer of ethylene and butadiene according to claim 1, characterized in that the mole fraction of ethylene units varies from 50 mol% to 95 mol%, relative to the total number of moles of ethylene units, butadiene. and trans-1,2-cyclohexane.
    [3" id="c-fr-0003]
    3. Copolymer of ethylene and butadiene according to claim 1 or 2, characterized in that the mole fraction of fra / 7s-1,2-cyclohexane units is between 0 mol% and 25 mol%, relative to to the number of total moles of ethylene, butadiene and transi, 2-cyclohexane units.
    [4" id="c-fr-0004]
    4. Copolymer of ethylene and butadiene according to any one of the preceding claims, characterized in that it has a crystallinity of less than 20%, preferably less than 10%.
    [5" id="c-fr-0005]
    5. Semi-continuous process for preparing a copolymer of ethylene and butadiene according to any one of the preceding claims, comprising the solution polymerization in a hydrocarbon solvent, at a temperature between 0 ° C and 200 ° C , of ethylene and butadiene in the presence of a catalyst system for the formation of trans-'l, 2-cyclohexane cyclic units in the polymer chain, in a stirred reactor, characterized in that the polymerization is conducted at a constant temperature and at constant ethylene pressure and butadiene pressure, in that ethylene and butadiene are injected continuously into the reactor and that in the reaction medium, at each instant of the polymerization, the concentrations of ethylene and butadiene are constant.
    [6" id="c-fr-0006]
    6. Method according to claim 5, characterized in that the composition of the reaction medium is continuously analyzed and the injection rate of ethylene and butadiene are adjusted to maintain constant ethylene and butadiene concentrations in the reaction medium.
    [7" id="c-fr-0007]
    7. The method of claim 5, characterized in that the injection rate of ethylene and butadiene are adjusted to maintain a constant ethylene pressure and butadiene pressure in the reactor.
    [8" id="c-fr-0008]
    8. Process according to claim 7, characterized in that ethylene and butadiene are injected in a predetermined flow rate ratio.
    [9" id="c-fr-0009]
    9. Process according to claim 7, characterized in that a composition comprising ethylene and butadiene is injected at constant ethylene and butadiene concentrations.
    [10" id="c-fr-0010]
    10. Process according to any one of Claims 5 to 9, characterized in that the catalytic system comprises at least two constituents, on the one hand a metallocene corresponding to formula (I):

    (I) - with: Met being a group comprising: o at least one scandium atom, yttrium or a lanthanide atom, the atomic number of which is from 57 to 71, o at least one monovalent ligand, belonging to the group of halogens, such as chlorine, iodine, bromine, fluorine, amide, alkyl or borohydride group o optionally other components such as complexing molecules, belonging to the group of ethers or amines, P being a group , based on at least one silicon or carbon atom, bridging the two groups Cp1 and Cp2 Cp1 and Cp2, are identical to each other or different from each other when Cp1 and Cp2 are identical to each other; are selected from 2-substituted indenyls, such as 2-methylindene, 2-phenylindene, from fluorenyls, substituted or unsubstituted, such as fluorenyl, 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl, -fluorenyl, o when Cp1 and Cp2 are different from each other, Cp1 is chosen from fluorenyls, substituted or unsubstituted, such as fluorenyl, 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl, Cp2 is chosen from cyclopentadienyls substituted at the 2-position and 5-position, such as tetramethylcyclopentadiene; among the 2-substituted indenyls, such as 2-methylindene, 2-phenylindene, among the substituted fluorenyls, such as 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl. on the other hand a co-catalyst is an alkyl magnesium, an alkyl lithium, an alkyl aluminum, a Grignard reagent, or a mixture of these constituents.
    [11" id="c-fr-0011]
    11. Copolymer of ethylene and butadiene obtained by the process according to any one of claims 5 to 10, characterized in that the microstructure of the copolymer is homogeneous.
    [12" id="c-fr-0012]
    12. An ethylene-butadiene copolymer according to any one of claims 1 to 4 or claim 11, which is an elastomer.
    [13" id="c-fr-0013]
    13. Composition comprising a copolymer according to any one of claims 1 to 4 or 11 to 12.
    [14" id="c-fr-0014]
    14. A tire of which one of its constituent elements comprises a composition according to claim 13.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3390465B1|2021-05-19|Ethylene/butadiene copolymer of homogeneous microstructure
    EP3390466B1|2021-06-02|Ethylene and butadiene copolymer having a homogeneous microstructure
    WO2015018600A1|2015-02-12|Diene elastomer modified by coupling having silanol functions, synthesis method for same and rubber composition comprising it
    WO2013039152A1|2013-03-21|Polyolefin having terminal double bond, and method for producing same
    Cao et al.2011|Enhancing the thermal stability of poly | by removing the chains with weak links in a continuous polymerization
    Bykov et al.2012|Binary and ternary copolymers of norbornene and its derivatives with acrylates as novel materials for optoelectronics
    JP5835723B2|2015-12-24|Divinyl ether homopolymer, production method thereof and use thereof
    FR3065216A1|2018-10-19|CONTINUOUS SYNTHESIS OF COPOLYMER OF ETHYLENE AND BUTADIENE
    FR3065215A1|2018-10-19|CONTINUOUS SYNTHESIS OF COPOLYMER OF ETHYLENE AND BUTADIENE
    FR3041348A1|2017-03-24|TERPOLYMERS OF VINYLIDENE FLUORIDE, TRIFLUOROETHYLENE AND 1,3,3,3-TETRAFLUOROPROPENE
    WO2015101477A1|2015-07-09|Continuous process for the synthesis of a functionalized polyisoprene
    FR3060582A1|2018-06-22|PROCESS FOR THE PREPARATION OF POLYDIENE / POLYLACTIDE COPOLYMERS BY REACTIVE EXTRUSION
    WO2015101478A1|2015-07-09|Method for the continuous synthesis of a functionalised diene elastomer
    JP2021091896A|2021-06-17|Polyethylene resin composition
    WO2021053051A1|2021-03-25|Terpolymer of ethylene and 1,3-dienes
    WO2021053295A1|2021-03-25|Functional ethylene and 1,3-diene copolymers
    EP3720889A1|2020-10-14|Continuous method for producing a diene elastomer
    WO2020136331A1|2020-07-02|Grafted polymer bearing pendent cyclic carbonate functional groups
    FR3082205A1|2019-12-13|COPOLYMER OF ETHYLENE AND ISOPRENE
    WO2018115779A1|2018-06-28|Rubber composition comprising a polydiene-polylactide / copolymer
    同族专利:
    公开号 | 公开日
    CN108473624B|2021-07-27|
    US10822475B2|2020-11-03|
    FR3045612B1|2017-12-15|
    WO2017103543A1|2017-06-22|
    RU2726114C2|2020-07-09|
    US20180371214A1|2018-12-27|
    EP3390465A1|2018-10-24|
    RU2018126196A|2020-01-17|
    RU2018126196A3|2020-01-30|
    CN108473624A|2018-08-31|
    KR20180098582A|2018-09-04|
    EP3390465B1|2021-05-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2004035639A1|2002-10-16|2004-04-29|Societe De Technologie Michelin|Ethylene/butadiene copolymers, catalytic system of producing same and production of said polymers|
    EP2599808A1|2010-07-30|2013-06-05|Bridgestone Corporation|Method for controlling chain structure in copolymers|WO2020038761A1|2018-08-23|2020-02-27|Compagnie Generale Des Etablissements Michelin|Tyre having a composition comprising an ethylene-rich elastomer, a peroxide and a specific acrylate derivative|
    WO2020038763A1|2018-08-23|2020-02-27|Compagnie Generale Des Etablissements Michelin|Tyre having a composition comprising an ethylene-rich elastomer, a peroxide and a specific acrylate derivative|
    WO2020038762A1|2018-08-23|2020-02-27|Compagnie Generale Des Etablissements Michelin|Tyre having a composition comprising an ethylene-rich elastomer, a peroxide and a specific acrylate derivative|US3910862A|1970-01-30|1975-10-07|Gaf Corp|Copolymers of vinyl pyrrolidone containing quarternary ammonium groups|
    IN172494B|1986-12-19|1993-09-04|Exxon Chemical Patents Inc|
    IT1270253B|1994-06-20|1997-04-29|Spherilene Srl|ETHYLENE COPOLYMERS AND PROCEDURE FOR THE PREPARATION OF ETHYLENE POLYMERS|
    FR2799468B1|1999-10-12|2006-04-28|Michelin Soc Tech|CATALYTIC SYSTEM USABLE FOR THE COPOLYMERIZATION OF ETHYLENE AND A CONJUGATE DIENE, PROCESS FOR THE PREPARATION OF THIS CATALYTIC SYSTEM AND OF A COPOLYMER OF ETHYLENE AND A CONJUGATE DIENE|
    FR2866028B1|2004-02-11|2006-03-24|Michelin Soc Tech|PLASTICIZING SYSTEM FOR RUBBER COMPOSITION|
    FR2877348B1|2004-10-28|2007-01-12|Michelin Soc Tech|PLASTICIZING SYSTEM FOR RUBBER COMPOSITION|
    FR2889538B1|2005-08-08|2007-09-14|Michelin Soc Tech|PLASTICATING SYSTEM FOR COMBINING RUBBER.|
    RU2528410C1|2010-07-30|2014-09-20|Бриджстоун Корпорейшн|Copolymer, rubber composition, cross-linked rubber composition and tyre|
    FR2998574B1|2012-11-29|2015-01-16|Michelin & Cie|RUBBER COMPOSITION COMPRISING A HIGHLY SATURATED DIENIC ELASTOMER|
    FR3001223B1|2013-01-22|2015-03-06|Michelin & Cie|RUBBER COMPOSITION COMPRISING A HIGHLY SATURATED DIENIC ELASTOMER|FR3065215A1|2017-04-18|2018-10-19|Compagnie Generale Des Etablissements Michelin|CONTINUOUS SYNTHESIS OF COPOLYMER OF ETHYLENE AND BUTADIENE|
    法律状态:
    2016-12-22| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-23| PLSC| Publication of the preliminary search report|Effective date: 20170623 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1562573A|FR3045612B1|2015-12-17|2015-12-17|COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE|FR1562573A| FR3045612B1|2015-12-17|2015-12-17|COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE|
    US16/062,343| US10822475B2|2015-12-17|2016-12-16|Ethylene/butadiene copolymer of homogeneous microstructure|
    CN201680077057.9A| CN108473624B|2015-12-17|2016-12-16|Ethylene/butadiene copolymers of homogeneous microstructure|
    RU2018126196A| RU2726114C2|2015-12-17|2016-12-16|Ethylene-butadiene copolymer of homogeneous microstructure|
    EP16829259.7A| EP3390465B1|2015-12-17|2016-12-16|Ethylene/butadiene copolymer of homogeneous microstructure|
    KR1020187020352A| KR20180098582A|2015-12-17|2016-12-16|Homogeneous microstructure ethylene / butadiene copolymer|
    PCT/FR2016/053537| WO2017103543A1|2015-12-17|2016-12-16|Ethylene/butadiene copolymer of homogeneous microstructure|
    [返回顶部]