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    • 专利摘要:
    The present invention relates to a copolymer of ethylene and butadiene comprising, statistically distributed, ethylene units and butadiene units, the molar fraction of ethylene units in said copolymer being equal to or greater than 50%, relative to the number of total moles of ethylene and butadiene 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:FR3045613A1
    申请号:FR1562575
    申请日:2015-12-17
    公开日:2017-06-23
    发明作者:Nuno Pacheto；Julien Thuilliez
    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 patents EP1092731A1, US 2005 / 0239639A1, EP 0 526 955, WO 2005 / 028526A1 and US2009270578A1.
    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 is particularly concerned with copolymers based on ethylene and butadiene which do not comprise 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. The different units that can be found in these copolymers are ethylene units and butadiene 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, 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 units. and butadiene, characterized in that the microstructure of the copolymer is homogeneous and thus the molar concentration in each of the units is constant throughout the copolymer chain.
    The mole fraction of ethylene units advantageously varies from 50 mol% to 95 mol%, based on the total number of moles of ethylene and butadiene units.
    The mole fraction of ethylene units advantageously varies from 70 mol% to 88 mol%, based on the total number of moles of ethylene and butadiene units. 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 catalyst system, in a stirred reactor, characterized in that the polymerization is conducted at 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.
    In a variant, the composition of the reaction medium is analyzed continuously and the injection rate of ethylene and butadiene is adjusted to maintain constant ethylene and butadiene concentrations in the reaction medium.
    The temperature is kept constant.
    In another variant, the injection flow rate of ethylene and butadiene is 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 atom, yttrium or lanthanide atom, whose atomic number is from 57 to 71, o at least one monovalent ligand, belonging to the group of halogens, such as chlorine, l, 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 at least a silicon or carbon atom, bridging the two groups Cp1 and Cp2
    Cp1 and Cp2 are identical to one another or different from each other and chosen from the group consisting of cyclopentadienyl, indenyl and fluorenyl groups, these groups possibly being substituted or unsubstituted
    Each of the Cp1 and Cp2 being bound to a lanthanide atom, scandium or yttrium
    The case where the Cp1 and Cp2 are both identical fluorenyls is excluded from the invention or on the other hand one or more organometallic compounds as cocatalyst or alkylating agent. 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.
    In a variant, the ethylene / butadiene copolymer according to the invention is an elastomer. In another variant, the copolymer of ethylene and butadiene according to the invention is a semi-crystalline polymer. The subject of the invention is also a composition, in particular a composition, comprising a copolymer of ethylene and butadiene according to the invention. In a variant, this composition is a rubber composition. 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 result 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
    DETAILED DESCRIPTION OF THE INVENTION The subject of the invention is a copolymer of ethylene and butadiene comprising, statistically distributed, ethylene units and butadiene 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 and butadiene 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 of ethylene units and butadiene units is identical or nearly identical in each segment. A sequence of 10 units may be a representative number.
    Advantageously, the concentration of ethylene units and butadiene 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, overconcentration is not observed in one of these units, especially at the beginning or at the end of the chain. In other words, the microstructure is free or significantly free of compositional gradient.
    Control of the microstructure of the copolymer makes it possible to access copolymers of identical microstructure at any instant during the polymerization, which makes it possible, for example, to access samples of the same microstructure at different times of the polymerization. In the copolymer according to the invention, the mole fraction of ethylene units, relative to the total number of moles of ethylene and butadiene units, is greater than 50 mol%. It advantageously ranges from 50 mol% to 99 mol%, more preferably from 50 mol% to 90 mol%, more preferably from 70 mol% to 88 mol%, or more advantageously from 65 mol%. at 80 mol%, based on the total number of moles of ethylene and butadiene units.
    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 and butadiene 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 and butadiene units.
    The butadiene units denote the 1,4 units of formula - (CH 2 -CH = CH-CH 2) -, of trans or cis configuration, and the 1,2 units 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).
    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 suitable catalyst system in a reactor, characterized in that the polymerization is conducted at constant temperature, ethylene pressure and butadiene pressure constants in that ethylene and butadiene are injected continuously and controlled in the reactor and that in the reaction medium, at each instant of the 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 suitable catalytic system 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 catalyst systems for the synthesis of copolymers according to the invention are chosen by those skilled in the art, so as not to allow the formation of 1,2-cyclohexane trans units within the polymer chain. The catalytic system advantageously comprises at least two constituents, on the one hand a metallocene corresponding to formula (I): [P (Cp1) (Cp2) Met] (I) - with:
    Met is a group comprising: o at least one scandium atom, yttrium or lanthanide atom, whose atomic number is from 57 to 71, o at least one monovalent ligand, belonging to the group of halogens, such as chlorine, l, 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 at least one silicon or carbon atom, bridging the two groups Cp1 and Cp2
    Cp1 and Cp2, are identical to one another or different from each other, and being selected from the group consisting of cyclopentadienyl, indenyl and fluorenyl groups, these groups possibly being substituted or unsubstituted
    Each of the Cp1 and Cp2 being bound to a lanthanide, scandium or yttrium atom The case where the Cp1 and Cp2 are both identical fluorenyls is excluded from the invention o on the other hand one or more organometallic compounds as co- catalyst or alkylating agent, the organometallic compound being an alkyl magnesium, an alkyl lithium, an alkyl aluminum or a Grignard reagent. 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 [Me 2 Si (3- (CH 3) 3 Si-C 5 H 3) 2 NdCl], [Me 2 Si (3- (CH 3) 3 Si-C 5 H 3) 2 Nd (BH 4) (THF) 2], [ MezSKS-'Bu-CsHsfeNdCl], [Me2Si (3 -Bu-C5H3) 2Nd (BH4) (THF) 2], [Me2Si (C5H4) 2Nd (BH4)], [Me2Si (C5Me4) 2Nd (BH4)], [Me2Si (Cp) (Flu) Nd (Cl)] [Me2Si (Cp) (Flu) Nd (BH4) (THF)], [Me2Si (Cp) (2.7 - (Bu) 2-
    Flu) Nd (BH4) (THF)] and [MezSKCpXS.e-OBujz-FlujNdiBH ^ THF)] 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 EP1092731A1, US 2005 / 0239639A1, EP 0 526 955, WO 2005 / 028526A1 and US2009270578A1.
    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.
    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 injection rates of ethylene fed by a conduit 3 and butadiene fed by a conduit 4. 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. It is the same 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 used.
    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 conduit 4.
    The ethylene and butadiene pressures are kept 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 such solvents are C 2 to C 30 alkanes, C 4 to C 30 branched alkanes, C 5 to C 6 cyclic alkanes, C 8 to C 30 branched cyclic alkanes, C 6 to 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 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 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. This copolymer is advantageously a semi-crystalline polymer.
    Compositions The invention also relates to a composition comprising a copolymer according to the invention.
    In a variant, the ethylene / butadiene copolymer according to the invention is an elastomer. In another variant, the copolymer of ethylene and butadiene according to the invention is a semi-crystalline polymer of homogeneous microstructure.
    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 In this case, 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 on behalf 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 way (one or more elastomers) are understood to come from at least a part (ie a homopolymer or a copolymer) of diene monomers (monomers carrying 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 dienic 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 can 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 chosen from 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 novolac 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 in a series of columns. Polymer Laboratories
    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 room temperature insoluble copolymers 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" chromatograph equipped with three columns "Styragel" (2 columns "HT6E" and 1 column "HT2").
    The detection was carried out using a "Waters" refractometer.
    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 the RBEs. This endothermic phenomenon is observed during the thermogram analysis of the DSC (Differential Scanning Calorimetry) measurement. The measurement is carried out by forward 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
    Examples -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 skilled in the art trivially infers 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 catalytic systems described by the invention, the prediction of the microstructure is calculated by the following equations: RI + R3% unitsE = RI + R 2 + R 3 + "4
    ° / gmativesB = 1 - ®emotifsE Where: •% motivesE is the molar percentage of the ethylenic units in the chain •% motifsB is the molar percentage of the butadiene units (1,4 and 1,2) in the chain • And R1 to R4 calculated as below RI = kP1% PE [E] R2 = 'κΡ2ΨοΡΕ [Β] R3 = kP3 ψΰΡΒ [Ε] R4 = kP,% PB [B] Where: • ki to k4 are constants
    • [E], [B] are the concentrations of ethylene, butadiene in mol / L •% PE,% PB, calculated according to the system of equations below:
    Or : . % And | iq = [E] / ([E] + [B]). % Bd | iq = [B] / ([E] + [B])
    The values of k2, k3, k4 and k5 are measured experimentally and then reported at k1.
    This mathematical model makes it possible to predict the distribution of the ethylene and butadiene units of an elastomer produced according to the invention and as a function of the constants k1 to k4 and the molar composition of ethylene and butadiene in the liquid phase.
    Example for the catalyst system consisting of metallocene [Me2Si (Cp) (Flu) Nd (BH4) (THF)] in the presence of butyloctyl magnesium
    For this catalytic system, according to the methods known to those skilled in the art, copolymerization tests of ethylene and butadiene were carried out by maintaining a constant composition of monomers in the reaction medium. We have been able to determine the following model values based on experimental tests, inspired by those described in Angewandte Chemie, Int Ed, 2005, Volume 44, Issue 17, pages 2593-2596 but controlling the flow rate. injection of the monomers according to the invention.
    Using the mathematical model described above and the constants of the table above, we have estimated the accessible microstructures for this chemical system. The table below shows a sample of the simulation results for this particular case.
    % And | iq% patterns E% patterns B% And | iq% patterns E% patterns B 1% 8% 92% 60% 51% 49% 2% 14% 86% 70% 53% 47% 5% 25% 75% 75% 54% 46% 10% 34% 66% 80% 56% 44% 15% 39% 61% 85% 59% 41% 20% 42% 58% 90% 63% 37% 25% 44% 56% 95% 71% 29% 30% 45% 55% 98% 83% 17% 40% 48% 52% 99% 90% 10% 50% 49% 51%
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. A copolymer of ethylene and butadiene comprising, statistically distributed, ethylene units and butadiene 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 units ethylene and butadiene, 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 molar fraction of ethylene units varies from 50 mol% to 95 mol%, relative to the total number of moles of ethylene and butadiene units. .
    [3" id="c-fr-0003]
    3. Copolymer of ethylene and butadiene according to claim 1, characterized in that the molar fraction of ethylene units varies from 70 mol% to 88 mol%, relative to the total number of moles of ethylene and butadiene units. .
    [4" id="c-fr-0004]
    4. 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, in a stirred reactor, characterized in that the polymerization is carried out at 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.
    [5" id="c-fr-0005]
    5. Method according to claim 4, characterized in that the composition of the reaction medium is analyzed continuously and the injection rate of ethylene and butadiene is adjusted to maintain in the reaction medium constant ethylene and butadiene concentrations.
    [6" id="c-fr-0006]
    6. Method according to claim 4, characterized in that the injection rate of ethylene and butadiene is adjusted to maintain a constant ethylene pressure and butadiene pressure in the reactor.
    [7" id="c-fr-0007]
    7. Method according to claim 6, characterized in that the ethylene and butadiene are injected at a predetermined flow ratio.
    [8" id="c-fr-0008]
    8. Process according to claim 7, characterized in that a composition comprising ethylene and butadiene is injected at constant ethylene and butadiene concentrations.
    [9" id="c-fr-0009]
    9. Process according to any one of claims 4 to 8, characterized in that the catalytic system comprises at least two constituents, on the one hand a metallocene corresponding to the formula (I): [P (Cp1) (Cp2) Met ] (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, to the group of amides, alkyls or borohydrides or possibly other constituents 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 one another or different from each other and chosen from the group consisting of cyclopentadienyl groups, indenyls, fluorenyls, these groups for Whether or not each of Cp1 and Cp2 is bonded to a scandium, yttrium or lanthanide atom, the case where the Cp1 and Cp2 are both identical fluorenyls is excluded from the invention on the other hand by one or more organometallic compounds as cocatalyst or alkylating agent.
    [10" id="c-fr-0010]
    10. Copolymer of ethylene and butadiene obtained by the process according to any one of claims 4 to 9, characterized in that the microstructure of the copolymer is homogeneous.
    [11" id="c-fr-0011]
    An ethylene-butadiene copolymer according to any one of claims 1 to 3 or claim 10 which is an elastomer.
    [12" id="c-fr-0012]
    An ethylene-butadiene copolymer according to any of claims 1 to 3 or claim 10 which is a semi-crystalline polymer.
    [13" id="c-fr-0013]
    13. Composition comprising a copolymer according to any one of claims 1 to 3 or 10 to 12.
    [14" id="c-fr-0014]
    14. A tire of which one of the constituent elements comprises a composition according to claim 13.
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    US10844149B2|2020-11-24|
    US20180371129A1|2018-12-27|
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    引用文献:
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    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|
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    FR3001223B1|2013-01-22|2015-03-06|Michelin & Cie|RUBBER COMPOSITION COMPRISING A HIGHLY SATURATED DIENIC ELASTOMER|FR3085683B1|2018-09-11|2020-10-23|Michelin & Cie|PNEUMATIC|
    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
    FR1562575A|FR3045613B1|2015-12-17|2015-12-17|COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE|FR1562575A| FR3045613B1|2015-12-17|2015-12-17|COPOLYMER OF ETHYLENE AND BUTADIENE OF HOMOGENEOUS MICROSTRUCTURE|
    CN201680074306.9A| CN108602919B|2015-12-17|2016-12-16|Ethylene and butadiene copolymers of homogeneous microstructure|
    EP16829260.5A| EP3390466B1|2015-12-17|2016-12-16|Ethylene and butadiene copolymer having a homogeneous microstructure|
    BR112018012365-0A| BR112018012365A2|2015-12-17|2016-12-16|homogeneous microstructure ethylene and butadiene copolymer|
    RU2018123148A| RU2726197C9|2015-12-17|2016-12-16|Ethylene and butadiene copolymer with homogeneous microstructure|
    JP2018531349A| JP2019504148A|2015-12-17|2016-12-16|Ethylene and butadiene copolymers with uniform microstructure|
    US16/061,655| US10844149B2|2015-12-17|2016-12-16|Ethylene and butadiene copolymer having a homogeneous microstructure|
    KR1020187020404A| KR20180096694A|2015-12-17|2016-12-16|Ethylene and butadiene copolymers having a uniform microstructure|
    PCT/FR2016/053538| WO2017103544A1|2015-12-17|2016-12-16|Ethylene and butadiene copolymer having a homogeneous microstructure|
    SA518391793A| SA518391793B1|2015-12-17|2018-06-12|Ethylene and butadiene copolymer of homogeneous microstructure|
    US16/926,236| US20200339716A1|2015-12-17|2020-07-10|Ethylene and butadiene copolymer having a homogeneous microstructure|
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