• 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 a 1,3-diene of formula CH2 = CR-CH = CH2, in which the ethylene units represent between 50% and 95% by moles of ethylene units and units of 1 , 3-diene, and 1,3-diene units of 1,2 and 3,4 configuration represent more than 50 mol% of 1,3-diene units, the R symbol representing a hydrocarbon chain having 3 to 20 carbon atoms. Such a copolymer has an improved compromise between crystallinity level and stiffness and allows the range of ethylene-rich diene copolymers to be extended into rubber compositions.
    公开号:FR3078973A1
    申请号:FR1852305
    申请日:2018-03-19
    公开日:2019-09-20
    发明作者:Vincent LAFAQUIERE；Emma MORESO
    申请人:Compagnie Generale des Etablissements Michelin SCA；
    IPC主号:
    专利说明:

    The field of the invention is that of copolymers of conjugated diene and of ethylene, rich in ethylene unit and usable as elastomers in a rubber composition for tires.
    The most widely used diene elastomers in the manufacture of tires are polybutadienes, polyisoprenes, in particular natural rubber, and copolymers of 1,3-butadiene and styrene. What these elastomers have in common is the high molar proportion of diene units in the elastomer, generally much greater than
    50%, which can make them sensitive to oxidation, especially under the action of ozone.
    The Applicant has described elastomers which, on the contrary, are relatively poor in diene units, in particular with a view to reducing their sensitivity to oxidation phenomena. These elastomers are for example described in document WO 2007054223.
    These are copolymers of 1,3-butadiene and ethylene containing more than 50% by mole of ethylene unit. These elastomers are called diene elastomers rich in ethylene.
    The ethylene-rich copolymers of 1,3-butadiene and ethylene are crystalline and their crystallinity increases with the level of ethylene. The presence of crystalline parts in the copolymer can be problematic when the copolymer is used in a rubber composition. The melting of the crystalline parts of the copolymer resulting in a reduction in its rigidity, a rubber composition containing such a copolymer and used in a tire also sees its rigidity decrease when it is brought to temperatures equal to or exceeding the melting temperature of the parts crystalline, which may be the case during the repeated braking and acceleration phases of the tire.
    This dependence on stiffness as a function of temperature can therefore lead to uncontrolled fluctuations in the performance of the tire. It is advantageous to have diene polymers rich in ethylene units whose crystallinity is reduced, or even eliminated.
    In WO 2,07054224, the Applicant has described diene copolymers rich in ethylene which have reduced aistallinity. These copolymers are copolymers of 1,3-butadiene and ethylene which additionally contain 6-membered saturated hydrocarbon ring units. However, these copolymers introduced into a rubber composition can confer too high rigidity on the rubber composition. The high rigidity of the rubber composition is attributed to an equally high rigidity of the elastomer. High stiffness of a rubber composition can be problematic, as it too can make the rubber composition 40 unsuitable for certain applications.
    2018PAT00087FR
    To produce these ethylene and 1,3-butadfen copolymers rich in ethylene and comprising 6-membered saturated hydrocarbon cyclic units, the Applicant has developed a catalytic system based on a metallocene and an organomagnesium, such as this is described for example in document WO 2007054224, the metallocene being of the following formula:
    P (Cp 1 ) (Cp 2 ) Nd (BH4) ii n .yL / -N x
    Cp and Cp z , identical or different, being chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula CuH g , P being a group bridging the two groups Cp 2 and Cp 2 and representing a group ZR 3 R 4 , Z representing a silicon or carbon atom, R 'and R 4 , identical or different, each representing an alkyl group comprising from 1 to 20 carbon atoms, preferably a methyl, y, an integer being equal or greater than 0, x, whole number or not, being equal to or greater than 0, L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium, N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran.
    Pursuing its aim of synthesizing diene elastomers rich in ethylene, the Applicant has discovered a new polymer which makes it possible to solve the problems mentioned.
    Thus a first object of the invention is a copolymer, preferably elastomer, of ethylene and of 1,3-diene of formula (!) Which comprises ethylene units and. l, 3 ~ dfene units, your ethylene units representing between 50% and 95% by moles of the ethylene units and of the 1,3-diene units, and the 1,3-diene units of configuration 1,2 and 3 , 4 representing more than 50% by mole of the units of 1,3-diene,
    CR-CH-CH-CH (!) the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms.
    Another subject of the invention is a process for the preparation of the copolymer in accordance with the invention.
    The invention also relates to a rubber composition based on at least one elastomer according to the invention and of a crosslinking system, as well as a tire which comprises the rubber composition according to the invention.
    THE DETAILED DESCRIPTION OF THE INVENTION
    In the present description, any range of values designated by the expression between a and b represents the domain of values greater than : 'a and less than b (that is to say bounds a
    2018PAT00087EN and b excluded) while any range of values designated by the expression from a to b means the range of values from a to b (i.e. including the strict limits a and b).
    The expression “based on” used to define the constituents of a catalytic system or of a composition means the mixture of these constituents, or the product of the reaction of part or all of these constituents. between them.
    Unless otherwise indicated, the levels of the units resulting from the insertion of a monomer into a copolymer are expressed in molar percentage relative to the totality of the monomer units of the copolymer.
    The compounds mentioned in the description can be of fossil origin or bio-based. In the latter case, they can be, partially or totally, from biomass or obtained from renewable raw materials from biomass. The monomers are concerned in particular.
    The 1,3-diene of formula (I) as defined above and useful for the needs of the invention being a substituted 1,3-diene, the 1,3-diene can give rise to units of configuration 1,2 represented by formula (1), of configuration 3.4 represented by formula (2) and of configuration 1.4, the trans form of which is represented below by formula (3).

    (1)

    As is also well known, the ethylene unit is a motif unit - (CHrCHa) -.
    The copolymer according to the invention is a copolymer of ethylene and 1,3-diene, which implies that the monomeric units of the co-polymer are units resulting from the polymerization of ethylene and of 1,3-diene. The copolymer therefore comprises ethylene units and 1,3-diene units. According to any one of the embodiments of the invention, the 1,3-diene useful for the needs of the invention is a single compound, that is to say a single (in English "one") , 3-diene of formula (!) Or is a mixture of 1,3-dienes of formula (!), The 1,3-dienes of the mixture differentiating from each other by the group represented by the symbol R.
    The essential characteristic of the copolymer of ethylene and of 1,3-diene according to the invention is to comprise between 50% and 95% by mole of ethylene unit. In other words, the
    2018PAT00087FR ethylene units represent between 50% and 95% by moles of the ethylene units and of the 1,3-diene units. another essential characteristic is also to include units of 1,3-diene which are more than 50% by mole of units of 1,3-diene of configuration 1,2 and 3,4. In other words, the 1,3-diene units, whether they are of the 1,2 or 3,4 configuration, represent more than 50 mol% of the 1,3-diene units. The complement to 100% by mole of the 1,3-diene units in the copolymer consists of all or part of 1,3-diene units of configuration 1.4. According to any one of the embodiments of the invention, preferably more than half of the units of the 1,3-diene of configuration 1,4 are of 1,4-trans configuration, more preferably all the units of 1,3 -diene of configuration 1,4 are of configuration 1,4-trans.
    In the formula (I) of 1,3-diene useful for the needs of the invention, the hydrocarbon chain represented by the symbol R can be a straight or branched chain, in which case the symbol R represents a straight or branched chain. Preferably, the hydrocarbon chain is acyclic, in which case the symbol R represents an acyclic chain. In formula (I), the hydrocarbon chain represented by the symbol R can be saturated or unsaturated, in which case the symbol R represents a saturated or unsaturated chain. Preferably, the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms.
    According to a preferred embodiment of the invention, in the copolymer in accordance with the invention, the ethylene units represent at least 60% by mole of the ethylene units and of the 1,3-diene units. More preferably, the ethylene units represent from 60 to 90% by mole of the ethylene units and of the 1,3-diene units.
    According to a more preferred embodiment of the invention, in the copolymer according to the invention, the ethylene units represent at least 70 mol% of the ethylene units and of the 1,3-diene units. More preferably, the ethylene units represent from 70% to 90% by mole of the ethylene units and of the 1,3-diene units.
    Preferably, the copolymer in accordance with the invention has a glass transition temperature below -35 ° C, in particular between -SCfC and -35 a C.
    More preferably, the copolymer according to the invention is an elastomer.
    The copolymer according to the invention can be prepared by a process which comprises the copolymerization of ethylene and 1,3-diene in the presence of a catalytic system based on at least one metallocene of formula (II) and of an organomagnesium of formula (III)
    (fl) (III)
    2018PAT00087FR
    Cp 1 fit Cp 2 , identical or different, being chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula c 13 h 8 .
    P being a group bridging the two groups Cp 1 and Cp * and representing a group
    ZR 3 R 4 , Z representing a silicon or carbon atom, P and R 4 , which may be identical or different, each representing an akey group comprising from 1 to 20 carbon atoms, preferably a methyl, y, an integer being equal to or greater than 0, x, an integer or not, being equal or greater at 0,
    L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium,
    N representing a molecule of an ether, preferably ethyl ether or tetrahydrofuran,
    R 1 and R 3 , identical or different, representing a carbon group.
    As substituted fluorenyl 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 guided by the accessibility to the corresponding molecules which are substituted fluorenes, because the latter are available commercially or easily synthesized.
    Mention may more particularly be made, as substituted fluorenyl groups, of the 2,7-ditertiobutyîe-fluorényie and 3,6-ditertiobutyîe * fluorényîe groups. Positions 2, 3, 6 and 7 respectively designate the position of the carbon atoms of the rings as shown in the diagram below, position 9 corresponding to the carbon atom to which the P bridge is attached.
    The catalytic system can be prepared in a traditional manner by a process analogous to that described in patent application WO 2007054224. For example, the organomagnesium solvent and the metallocene are reacted typically with a temperature ranging from 20 to 80 ° C. in a hydrocarbon solvent. for a period of between 5 and 60 minutes. The catalytic system is generally prepared in a hydrocarbon solvent, aliphatic such as methylcyclohexane or aromatic such as toluene. Generally after its synthesis, îe
    2018PAT00087FR catalytic system is used as it is in the process for synthesizing the copolymer according to the invention.
    The metallocene used to prepare the catalytic system can be in the form of powder, crystallized or not, or in the form of single crystals. The metallocene can be in a monomer or dimer form, these forms depending on the method of preparation of the metallocene, as for example that is described in patent application WO 2007054224. The metallocene can be prepared in a traditional manner by a process analogous to that described in patent application WO 2007054224, in particular by reaction under inert and anhydrous conditions of the salt of an alkali metal of the ligand with a rare earth borohydride in a suitable solvent, such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to a person skilled in the art After reaction, the metallocene is separated from the reaction by-products by techniques known to a person skilled in the art, such as filtration or precipitation in a second solvent. The metallocene is finally dried and isolated in solid form.
    Like any synthesis carried out in the presence of an organo-metallic compound, the synthesis of the metalfocene and that of the catalytic system takes place under anhydrous conditions under an inert atmosphere. Typically, the reactions are carried out from solvents and anhydrous compounds under anhydrous nitrogen or argon.
    Preferably, the metallocene is of formula (IIa), (Lib), (Ile), (III) or (Ile) in which the symbol Plu has the fluorenyl group of formula Ci 3 H 3 .
    [{Me 2 SiFlu2Nd (p-BH 4 ) 2Li (THF) hJ (Ha) [Me 2 SiFlu 2 Nd (p-BH 4 ) AîrHF) l (Ub) [Me 2 SiFlu 2 Nd (p-BH 4 ) ( THF)] (IIc)
    Ê {Me SiFlu 2 Nd (p ~ BH 4 ) (THF) k] (lld) [Me 2 SiFîu 3 Nd (p-BH4Î (Ile)
    The organomagnesium useful for the needs of the invention is of formula MgR 1 R z in which R 1 and R 2 , identical or different, represent a carbon group. Carbon group means a group which contains one or more carbon atoms. Preferably, R 1 and R 3 contain 2 to 10 carbon atoms. More preferably, R 1 and R each represents an alkyl. The organomagnesium is advantageously a dialkyimagnesium, better butyiethylmagnesium or butyloctylmagnesium, even better butyloctylmagnesés'fum.
    According to any one of the embodiments of the invention, the molar ratio of the organomagnesium to the metal Nd constituting the metallocene is preferably within a range from 1 to 100, more preferably is greater than or equal to 1 and less than 10. The range of values from 1 to less than 10 is in particular more favorable for obtaining copolymers of high molar masses.
    2Ô18PAT00087FR
    Those skilled in the art also adapt the polymerization conditions and the concentrations of each of the reactants (constituents of the catalytic system, monomers) according to the material (tools, reactors) used to carry out the polymerization and the various chemical reactions. As is known to a person skilled in the art, the copolymerization as well as the handling of the monomers, of the catalytic system and of the polymerization solvent (s) takes place under anhydrous conditions and under an inert atmosphere. The polymerization solvents are typically hydrocarbon, aliphatic or aromatic solvents.
    The polymerization is preferably carried out in solution, continuously or discontinuously, the polymerization solvent can be a hydrocarbon, aromatic or aliphatic solvent. Examples of polymerization solvents that may be mentioned include toluene and methylcyclohexane. The monomers can be introduced into the reactor containing the polymerization solvent and the catalytic system or conversely the catalytic system can be introduced into the reactor containing the polymerization solvent and the monomers. The copolymerization is typically carried out under anhydrous conditions and in the absence of oxygen, in the possible presence of an inert gas. The polymerization temperature generally varies in a range from 30 to 15CTC, preferably from 30 to 120 ° C. Preferably, the copolymerization is carried out at constant ethylene pressure.
    The polymerization can be stopped by cooling the polymerization medium. The polymer can be recovered according to conventional techniques known to a person skilled in the art, for example by precipitation, by evaporation of the solvent under reduced pressure or by stripping with steam.
    According to any one of the embodiments of the invention, the incorporation of 1,3-diene and ethylene into the growing polymer chain is preferably statistical. The copolymer according to the invention is advantageously a random copolymer.
    The copolymer according to the invention, in particular when it is elastomer, can be used in a rubber composition.
    The rubber composition, another object of the invention, has the characteristic of comprising the elastomer according to the invention and a crosslinking system.
    The crosslinking system can be based on sulfur, sulfur donors, peroxides, bismaleimides or their mixtures. The crosslinking system is preferably a vulcanization system, that is to say a system based on sulfur (or a sulfur-donating agent) and on a primary vulcanization accelerator.
    2018PAT00087FR base can be added various secondary accelerators or activators of known vulcanization such as zinc oxide, stearic acid or equivalent compounds, guanidic derivatives (in particular diphenylguanidine), or known retarders of vulcanization.
    According to a preferred embodiment of the invention, the rubber composition comprises a reinforcing filler. The rubber composition can comprise any type of so-called reinforcing filler, known for its capacity to reinforce a rubber composition which can be used for the manufacture of tires, for example an organic filler such as carbon black, an inorganic reinforcing filler such as 10 silica to which is associated in known manner a coupling agent, or a mixture of these two types of filler. Such a reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than a micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm. The level of reinforcing filler is adjusted by a person skilled in the art according to the use of the rubber composition.
    the rubber composition may further contain other additives known for use in rubber compositions for tires, such as plasticizers, anti-ozonants, antioxidants.
    The rubber composition in accordance with the invention is typically produced in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first working phase or thermomechanical kneading (phase 25 called "non-productive"). ) at high temperature, up to a maximum temperature of between 130 ° C and 200 e C, followed by a second phase of mechanical working (phase called "productive") to a lower temperature, typically less than 110 ° C, for example between 40 e C and 100 ° C, finishing phase during which the crosslinking system is incorporated.
    The rubber composition according to the invention, which can either be in the raw state (before crosslinking or vulcanization), or in the cooked state (after crosslinking or vulcanization), can be used in a semi-finished article for tires.
    The tire, another object of the invention, comprises the rubber composition according to the invention defined under any one of the embodiments of the invention.
    The aforementioned characteristics of the present invention, as well as others, will be better understood on reading the following description of several exemplary embodiments of the invention, given by way of illustration and not limitation.
    2O18PATDOO87FR it. EXAMPLES OF EMBODIMENT OF THE INVENTION
    1) Synthesis of polymers:
    In the synthesis of copolymers in accordance with the invention, the 1,3-diene used (myrcene) is a 1,3-diene of formula (I) in which R is a hydrocarbon group having 6 carbon atoms of formula CH a -CH2-CH “CMe 2 .
    All the reagents are obtained commercially except the metallocenes [(Me 2 SiFlu 2 Nd (pBFUhLifTHF)}] and [Me 2 SîCpFluNd (p-BH4hü (THF)] which are prepared according to the procedures described in patent applications WO 2007054224 and WO 2007054223.
    BOMAG butyloctylmagnesium (20% in heptane, C = 0.88 mol L ' 1 ) comes from Chemtura and is stored in a Schlenk tube under an inert atmosphere. The ethylene, of N35 quality, comes from the company Air Liquide and is used without prior purification. Myrcene (purity> 95%) is obtained from Slgma-Aldrich.
    1.1- Control synthesis: Example 1 the polymer is synthesized according to the following procedure:
    In a 500 ml glass reactor containing 300 m! of toluene, the cocatalyst, butyloctylmagnesium (BOMAG) and then the metailocene are added | Me 2 SiCpFiuNd (pBHi ^ LHTHF}], The duration of alkylation is 10 minutes, the reaction temperature is 20 20 C. The respective quantities constituents of the catalytic system are shown in Table 2. Next, the monomers are added in the respective proportions indicated in Table 2, ethylene (Eth) and 1,3-butadien (Bde) being, in the form of a gaseous mixture The polymerization is carried out at 80 ° C. and at a constant ethylene pressure of 4 bars.
    The polymerization reaction is stopped by cooling, degassing of the reactor and addition of 10 ml of ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered by drying in an oven under vacuum until constant mass. The mass weighed makes it possible to determine the average catalytic activity of the catalytic system expressed in kilogram of polymer synthesized per mole of neodymium metal and per hour (kg / mol.h).
    1.2 “Example not in accordance with the invention: Example 2 the polymer is synthesized according to the following procedure:
    In a 500 ml glass reactor containing 300 ml of methyicyclohexane, the cocatalyst, butyloctyl magnesium (BOMAG) is added, followed by the metallocene [MesSiiFluhNdlpBH 4 ) 2 Li (THF)]. The alkylation time is 10 minutes, the reaction temperature is 20 ° C. The respective amounts of the constituents of the catalytic system are shown in Table 2. Next, the monomers are added in the respective proportions indicated in Table 2, ethylene (Eth) and 1,3-butadiene (Bde) being in the form of a gas mixture. The polymerization is carried out at 80 ° C. and at a constant ethylene pressure of 4 bars.
    201SPAT00087FR
    The polymerization reaction is stopped by cooling, degassing of the reactor and addition of 10 ml of ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered by drying in a vacuum oven to constant mass. The weighed mass makes it possible to determine the average catalytic activity of the catalytic system 5 expressed in kilograms of polymer synthesized per mole of neodymium metal and per hour (kg / mol.h).
    1.3- Examples in accordance with the invention: Examples 3 to 5
    The polymers are synthesized according to the following procedure:
    In a 500 ml glass reactor containing 300 ml of methylcyclohexane, the cocatalyst, butyloctylmagnesium (8OMAG) and then the metallocene [Me2Si (Flu) 2 Nd (pBI'fahUCFHF)] are added. The alkylation time is 10 minutes, the reaction temperature is 20 ° C. The respective amounts of the constituents of the catalytic system are shown in Table 2. Then, the myrcene is added to the reactor before the injection of ethylene gaseous. The polymerization is carried out at 80 ° C. and at a constant ethylene pressure of 4 bars.
    The polymerization reaction is stopped by cooling, degassing of the reactor and addition of 10 ml of ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered by drying in an oven under vacuum to constant mass. The mass weighed makes it possible to determine the average catalytic activity of the catalytic system expressed in kilograms of polymer synthesized per mole of neodymium metal and per hour (kg / mol.h).
    The characteristics of the polymers are given in Tables 3 and 4.
    2) Determination of the microstruclose of polymers:
    The spectral characterization and the measurements of the microstructure of ethylene copolymer and 1,3-dien (myrcene) are carried out by Nuclear Magnetic Resonance (NMR) spectroscopy.
    Spectrometer: For these measurements, a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe.
    Experiments: The 1H experiments are recorded using a radiofrequency pulse 35 with a tilt angle of 30, the number of repetitions is
    128 with a 5 second recycling delay. The 1H1.3C NMR correlation experiments HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) are recorded with a repetition number of 128 and a number of increments of 128. The experiments are carried out at 25 ° C. .
    2018PAT00087FR
    Sample preparation: 25 mg of sample are dissolved in 1 mL of deuterated chloroform (CDCI3).
    - Calibration of the sample: The axes of the chemical displacements 1 H and 13 C are calibrated with respect to the protonated impurity of the solvent (CHCIî) at Ôih = 7.2 ppm and § 33C = 77 ppm,
    - Spectral allocation: The signals of the 1,3-diene insertion forms A, B and C (diagram
    1) were observed on the different spectra recorded. According to S. Georges et al. f (S. Georges, M. Brîa, P. Zinck and M. Visseaux, Polymer 55 (2014) 3869-3878), the signal of the 10 group ~ CH = n ° 8 characteristic of the form C presents chemical shifts X H and 13 C identical to the group -CH = n ° 3.
    The chemical shifts of the signals characteristic of the patterns A, B and C are presented in Table 1. The patterns A, B and C correspond respectively to the units of configuration 3,4, configuration 1,2 and configuration 1,4-trans .
    Table 1: Allocation of the 1 H and n C signals of Fthylene-Myrcene copolymers
    (Ppm) diac (ppm) Group 5.54 146.4 S ' 5.07 124.6 3 + 8 4.97-4.79 112.0 9 ' 4.67 108.5 7 2.06 26.5 4 2.0 -1.79 31.8 5 + 5 '+ 5 44.5 8 1.59 25.9 and 17.0 1 1.2 36.8 ~ 24.0 Cbb ethylene
    2018PAT00087R θ'-l
    Diagram 1
    X
    of
    o in
    O
    adisoooivdsioe
    The quantifications were carried out from the integration of the NMR spectra 10a using the Topspin software.
    The integrated signals for the quantification of the different patterns are:
    S Ethylene: signal at 1.2 ppm corresponding to 4 protons
    S Total Myrcene: signed! n ”l (1.59 ppm} corresponding to 6 protons
    Form A: signal n ° 7 (4.67 ppm) corresponding to 2 protons' Z Form B: signal n '8' (5.54 ppm) corresponding to 1 protons
    The quantification of the microstructure is carried out in molar percentage (molar%) 10 as follows: molar% of a motif = 1H integral of a motif * 100 / Σ (1H integrals of each motif)
    3) Determination of the stiffness of the polymers (raw):
    The measurements are carried out on an Anton Paar rheometer model MCR301 in mode
    1S Shearing with cylindrical specimens of controlled geometry (thickness between 1.5mm and 3mm and diameter between 22mm and 28mm). The sample is subjected to a sinusoidal shear stress, at a fixed temperature (corresponding to the end of the passage of the glass transition of the elastomer on a temperature scan at 10 Hz), and over a frequency range from 0.01 Hz to 100Hz. The rigidity value retained as being the rigidity of the rubbery plate of the sample is the value of the shear modulus G ′ for the frequency at which the loss modulus G reaches its minimum, in accordance with the method described by C. Liu, J. He, E. van Ruymbeke, R. Keunings, C. Bailly, Evaluation of different methods for the determination of the plateau modulas and the entanglement molecular weight, Polymer 47 (2006) 4461-4479.
    4) Determination of the glass transition temperature of the polymers:
    The glass transition temperature is measured using a differential scanning calorimeter (Caiorlmeteff) according to standard ASTM D3418 (1999).
    5) Determination of the degree of crystallinity of the polymers .;
    The I5O 11357-3: 2011 standard is used to determine the temperature and enthalpy of melting and crystallization of the polymers used by differential scanning calorimetry (DSC). The reference enthalpy of polyethylene is 277.1 J / g (from Handbook of Polymer 4th Edition, J. BRANDRUP, E. H. IMMERGUT, and E. A. GRULKE, 1999) ôl.Résuffatsj:
    In Example 1 (control), the diene copolymer rich in ethylene and synthesized by polymerization of ethylene and 1,3-butadiene in the presence of the metallocene IMeîSÎCpFluNdÎp-BH ^ iLÎiTHF)] has a high crystallinity (31%) which may make it unsuitable for certain uses.
    2018PAT00087FR
    In Example 2 (non-conforming), the ethylene-rich diene copolymer synthesized in the presence of the metallocene [Me 2 S i (Fl u) ^ Nd (μ-B (TH F)) has cyclic units. Although it contains a level of ethylene comparable to that of the control, it is not crystalline. However, it has a relatively high rigidity which can make it unsuitable for certain uses.
    In Examples 3 to 5 (conforming), the ethylene-rich diene copolymers are copolymers of ethylene and of myrcene. In Example 3, the copolymer has an ethylene content comparable to that of the copolymers of Examples 1 and 2, but without having their drawbacks. Indeed, it has the advantage both of not being crystalline and of having a significantly lower rigidity than the copolymer of Example 2.
    In Example 4, the copolymer is much richer in ethylene (85%) than the control copolymer of Example 1 (74%) and yet it is much less crystalline (17%) than the control copolymer (31%). .
    In Example 5, the copolymer has a higher myrcene level than the copolymers of Examples 3 and 4. It is not crystalline and also has a lower rigidity. Examples 5 to 5 illustrate that a variation in the myrcene level in the copolymer makes it possible to improve the compromise in rate of rigidity and crystallinity of the diene polymers rich in ethylene compared to the copolymers of ethylene and of 1,3 butadiene.
    In summary, the replacement of 1,3-butadiene with a 1,3-diene of formula CHi-CR-CH ^ CEh, R representing a hydrocarbon chain having 3 to 20 carbon atoms, like myrcene, makes it possible to synthesize polymers ethylene-rich diene compounds with an improved compromise between the crystallinity rate and the rigidity and of widening the field of application of the ethylene-rich diene copolymers in rubber compositions.
    2018PAT00087FR
    Table 2:

    2018PAT00087FR
    LH
    O m
    CM CM
    2018PAT00087FR
    Table 4:
    权利要求:
    Claims (21)
    [1" id="c-fr-0001]
    claims
    1. Copolymer of ethylene and a 1,3-diene of formula (I) which comprises ethylene units and 1,3-diene units, the ethylene units representing between 50% and 95% by moles of the ethylene units and 1,3-diene units, and the 1,3-diene units of configuration 1,2 and 3,4 representing more than 50% by mole of the 1,3-diene units,
    CH 2 = CR-CH = CH 2 (I) the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms.
    [2" id="c-fr-0002]
    2. Copolymer according to claim 1, in which the ethylene units represent at least 60 mol% of the ethylene units and of the 1,3-diene units.
    [3" id="c-fr-0003]
    3. Copolymer according to claim 1 or 2 wherein the ethylene units represent from 60 to 90% by mole of the ethylene units and of the 1,3-diene units.
    [4" id="c-fr-0004]
    4. Copolymer according to any one of claims 1 to 3, in which the ethylene units represent at least 70 mol% of the ethylene units and of the 1,3diene units.
    [5" id="c-fr-0005]
    5. Copolymer according to any one of claims 1 to 4 in which the ethylene units represent from 70% to 90% by mole of the ethylene units and of the 1,3diene units.
    [6" id="c-fr-0006]
    6. Copolymer according to any one of claims 1 to 5 in which the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms.
    [7" id="c-fr-0007]
    7. Copolymer according to any one of claims 1 to 6 in which the symbol R represents an acyclic chain.
    [8" id="c-fr-0008]
    8. Copolymer according to any one of claims 1 to 7 in which the symbol R represents a linear or branched chain.
    [9" id="c-fr-0009]
    9. Copolymer according to any one of claims 1 to 8 in which the symbol R represents a saturated or unsaturated chain.
    [10" id="c-fr-0010]
    10. Copolymer according to any one of claims 1 to 9, which copolymer has a glass transition temperature of less than -35 ° C.
    [11" id="c-fr-0011]
    11. Copolymer according to any one of claims 1 to 10, which copolymer has a glass transition temperature between -90 ° C and -35 ° C.
    2018PAT00087FR
    [12" id="c-fr-0012]
    12. Copolymer according to any one of claims 1 to 11, which copolymer is a random copolymer.
    [13" id="c-fr-0013]
    13. Copolymer according to any one of claims 1 to 12, which copolymer is an elastomer.
    [14" id="c-fr-0014]
    14. Process for the preparation of a copolymer defined in any one of claims 1 to 13, which comprises the polymerization of ethylene and of 1,3-diene in the presence of a catalytic system based on at least one metallocene of formula (II) and an organomagnesium of formula (III)
    Ρ ^ ρ ^ ρ 2 ) Νά (ΒΗ 4 ) (1 + γ) .Ι. γ -Ν χ (II)
    MgR 1 R 2 (III)
    Cp 1 and Cp 2 , identical or different, being chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula Ci 3 H 8 .
    P being a group bridging the two groups Cp 1 and Cp 2 and representing a group ZR 3 R 4 , Z representing a silicon or carbon atom, R 3 and R 4 , identical or different, each representing an alkyl group comprising of 1 with 20 carbon atoms, preferably methyl, y, whole number being equal to or greater than 0, x, whole number or not, being equal or greater than 0,
    L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium,
    N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran,
    R 1 and R 2 , identical or different, representing a carbon group.
    [15" id="c-fr-0015]
    15. The method of claim 14 wherein the metallocene is of formula (IIa), (IIb), (Ile), (lld) or (Ile) [{Me 2 SiFlu 2 Nd (p-BH 4 ) 2Li (THF) } 2] (lia) [Me 2 SiFlu 2 Nd (p-BH 4 ) 2Li (THF)] (llb) [Me 2 SiFlu 2 Nd (p-BH 4 ) (THF)] (Ile) [{Me 2 SiFlu2Nd (p-BH 4 ) (THF)} 2 ] (lld) [Me 2 SiFlu 2 Nd (p-BH 4 )] (Ile) the symbol Flu having the fluorenyl group of formula Ci 3 H 8 .
    [16" id="c-fr-0016]
    16. Method according to any one of claims 14 to 15 in which R 1 and R 2 contain 2 to 10 carbon atoms.
    2018PAT00087FR
    [17" id="c-fr-0017]
    17. Method according to any one of claims 14 to 16 in which R 1 and R 2 each represent an alkyl.
    [18" id="c-fr-0018]
    18. Method according to any one of claims 14 to 17 in which
    5 the organomagnesium is a dialkylmagnesium, preferably butylethylmagnesium or butyloctylmagnesium, more preferably butyloctylmagnesium.
    [19" id="c-fr-0019]
    19. A rubber composition based at least on a copolymer defined in claim 13 and on a crosslinking system.
    [20" id="c-fr-0020]
    20. The rubber composition according to claim 19, which comprises a reinforcing filler.
    [21" id="c-fr-0021]
    21. A tire which comprises a rubber composition defined in any one
    15 of claims 19 to 20.
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    同族专利:
    公开号 | 公开日
    WO2019180356A1|2019-09-26|
    FR3078973B1|2020-04-03|
    CN111801361A|2020-10-20|
    JP2021517194A|2021-07-15|
    EP3768737A1|2021-01-27|
    US20210054118A1|2021-02-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3480599A|1965-09-28|1969-11-25|Goodrich Co B F|Unsaturated interpolymers of linear aliphatic heptadienes and/or heptatrienes and alpha-olefins|
    FR2179772A1|1972-03-29|1973-11-23|Du Pont|
    US5837791A|1994-07-06|1998-11-17|Mitsui Petrochemical Industries, Ltd.|Unsaturated copolymer of ethylene and process for preparing the same|FR3104596A1|2019-12-17|2021-06-18|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION|FR2893028B1|2005-11-09|2008-02-15|Michelin Soc Tech|METALOCENE COMPLEX BOROHYDRIDE OF LANTHANIDE, INCORPORATING CATALYTIC SYSTEM, POLYMERIZATION METHOD USING THE SAME, AND ETHYLENE / BUTADIENE COPOLYMER OBTAINED BY THIS PROCESS|
    FR2893029B1|2005-11-09|2009-01-16|Michelin Soc Tech|METALOCENE COMPLEX BOROHYDRIDE OF LANTHANIDE, INCORPORATING CATALYTIC SYSTEM, POLYMERIZATION METHOD USING THE SAME, AND ETHYLENE / BUTADIENE COPOLYMER OBTAINED BY THIS PROCESS|FR3100815B1|2019-09-18|2022-01-28|Michelin & Cie|rubber composition|
    FR3104487B1|2019-12-17|2021-11-05|Michelin & Cie|ELASTOMERIC LAMINATE|
    法律状态:
    2019-03-22| PLFP| Fee payment|Year of fee payment: 2 |
    2019-09-20| PLSC| Publication of the preliminary search report|Effective date: 20190920 |
    2020-03-19| PLFP| Fee payment|Year of fee payment: 3 |
    2021-03-23| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1852305|2018-03-19|
    FR1852305A|FR3078973B1|2018-03-19|2018-03-19|COPOLYMER OF ETHYLENE AND A 1,3-DIENE|FR1852305A| FR3078973B1|2018-03-19|2018-03-19|COPOLYMER OF ETHYLENE AND A 1,3-DIENE|
    PCT/FR2019/050598| WO2019180356A1|2018-03-19|2019-03-18|Copolymer of ethylene and a 1,3-diene|
    EP19720937.2A| EP3768737A1|2018-03-19|2019-03-18|Copolymer of ethylene and a 1,3-diene|
    JP2020547361A| JP2021517194A|2018-03-19|2019-03-18|Copolymer of ethylene and 1,3-diene|
    CN201980016297.1A| CN111801361A|2018-03-19|2019-03-18|Copolymers of ethylene and 1, 3-dienes|
    US16/981,804| US20210054118A1|2018-03-19|2019-03-18|Copolymer of ethylene and a 1,3-diene|
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