FR3123915A1 - Synthesis of block polymers based on 1,3-diene and ethylene - Google Patents
Synthesis of block polymers based on 1,3-diene and ethylene Download PDFInfo
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- FR3123915A1 FR3123915A1 FR2106319A FR2106319A FR3123915A1 FR 3123915 A1 FR3123915 A1 FR 3123915A1 FR 2106319 A FR2106319 A FR 2106319A FR 2106319 A FR2106319 A FR 2106319A FR 3123915 A1 FR3123915 A1 FR 3123915A1
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- diene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000005977 Ethylene Substances 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title description 10
- 238000003786 synthesis reaction Methods 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 9
- 239000013256 coordination polymer Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- 229920006318 anionic polymer Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002734 organomagnesium group Chemical group 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 2
- 229920001577 copolymer Chemical group 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 4
- 229910052801 chlorine Inorganic materials 0.000 claims 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 229910052731 fluorine Inorganic materials 0.000 claims 2
- 239000011737 fluorine Substances 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 229910052747 lanthanoid Inorganic materials 0.000 claims 1
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 150000002901 organomagnesium compounds Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 125000002897 diene group Chemical group 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
- C08F297/086—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene the block polymer contains at least three blocks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
Abstract
L’invention concerne des polymères à blocs A-B-A et leur procédé de préparation par polymérisation d’éthylène ou d’un mélange contenant de l’éthylène et un 1,3-diène en présence au moins d’un métallocène de terre rare et d’un cocatalyseur de formule RB-(Mg-RA)m-Mg-RB , RB étant un groupe comprenant un noyau benzénique substitué par l’atome de magnésium, l’un des atomes de carbone du noyau benzénique en ortho du magnésium étant substitué par méthyle, éthyle, isopropyle ou formant un cycle avec l'atome de carbone qui est son plus proche voisin et qui est en méta du magnésium, l’autre atome de carbone du noyau benzénique en ortho du magnésium étant substitué par méthyle, éthyle ou isopropyle, RA une chaîne polymère d’un 1,3-diène ou d’un 1,3-diène et de styrène, m un nombre supérieur ou égal à 1. Le bloc central B des polymères à blocs a des unités diéniques, les blocs terminaux A des unités éthyléniques.The invention relates to A-B-A block polymers and their method of preparation by polymerization of ethylene or a mixture containing ethylene and a 1,3-diene in the presence of at least one rare earth metallocene and a cocatalyst of formula RB-(Mg-RA)m-Mg-RB , RB being a group comprising a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by methyl, ethyl, isopropyl or forming a ring with the carbon atom which is its nearest neighbor and which is meta to the magnesium, the other carbon atom of the benzene ring ortho to the magnesium being substituted by methyl, ethyl or isopropyl , RA a polymer chain of a 1,3-diene or of a 1,3-diene and styrene, m a number greater than or equal to 1. The central block B of block polymers has diene units, the blocks A terminals of the ethylenic units.
Description
Le domaine de la présente invention est celui des procédés de synthèse des polymères à blocs à base de 1,3-diène et d’éthylène qui contiennent au moins trois blocs. Plus particulièrement, le domaine de l’invention est celui des polymères à blocs qui comportent au moins un premier bloc comportant des unités d’un 1,3-diène et deux autres blocs comportant des unités d’éthylène, chaque bloc comportant des unités d’éthylène étant rattaché à une extrémité distincte du premier bloc.The field of the present invention is that of processes for the synthesis of block polymers based on 1,3-diene and ethylene which contain at least three blocks. More particularly, the field of the invention is that of block polymers which comprise at least a first block comprising units of a 1,3-diene and two other blocks comprising ethylene units, each block comprising units of ethylene being attached to a separate end of the first block.
Le document EP 2599809 A1 décrit la synthèse de polymères à bloc à base d’éthylène et de 1,3-butadiène. Ils sont synthétisés par une première étape de polymérisation d’éthylène, suivie d’une étape de polymérisation de 1,3-butadiène. Des polymères multiblocs sont synthétisés également en réitérant plusieurs fois la séquence composée de la polymérisation d’une première charge monomère d’éthylène et de la polymérisation d’une deuxième charge monomère de 1,3-butadiène. Comme la polymérisation est réalisée en présence d’un métallocène, les blocs constitutifs du polymère à blocs ont une microstructure typique d’une polymérisation catalytique, notamment un fort taux de cis pour les unités du 1,3-butadiène. En raison du procédé utilisé, la formation de chaque bloc supplémentaire après la synthèse d’un premier bloc requiert l’ajout d’une nouvelle charge monomère dans le milieu de polymérisation. Ainsi, la synthèse d’un polymère tribloc requiert d’utiliser trois charges monomères, la synthèse d’un pentabloc cinq charges monomères, etc. Or, chaque nouvel ajout d’une charge monomère dans un milieu de polymérisation au cours de la réaction de polymérisation complexifie le procédé de synthèse et s’accompagne généralement d’une désactivation d’une partie des sites actifs qui participent à la réaction de polymérisation, ce qui a pour effet de former des espèces polymères autres que le polymère à blocs visé.Document EP 2599809 A1 describes the synthesis of block polymers based on ethylene and 1,3-butadiene. They are synthesized by a first step of polymerization of ethylene, followed by a step of polymerization of 1,3-butadiene. Multiblock polymers are also synthesized by repeating several times the sequence composed of the polymerization of a first monomer charge of ethylene and the polymerization of a second monomer charge of 1,3-butadiene. As the polymerization is carried out in the presence of a metallocene, the constituent blocks of the block polymer have a typical microstructure of a catalytic polymerization, in particular a high cis content for the 1,3-butadiene units. Due to the process used, the formation of each additional block after the synthesis of a first block requires the addition of a new monomer charge in the polymerization medium. Thus, the synthesis of a triblock polymer requires the use of three monomer charges, the synthesis of a pentablock five monomer charges, etc. However, each new addition of a monomer charge in a polymerization medium during the polymerization reaction complicates the synthesis process and is generally accompanied by a deactivation of part of the active sites which participate in the polymerization reaction. , which has the effect of forming polymer species other than the targeted block polymer.
Le document WO2019/077232A1 décrit la synthèse de polymères à bloc par polymérisation d’éthylène ou d’un mélange d’éthylène et de 1,3-butadiène en présence d’un métallocène de néodyme activé par une réaction d’alkylation du métallocène avec un polymère anionique vivant. Les polymères à bloc préparés sont donc constitués d’un premier bloc caractérisé par une microstructure typique d’un polymère anionique et par un deuxième bloc caractérisé par une microstructure quant à elle typiquement obtenue par une polymérisation catalytique. Seule une des extrémités de chaîne du premier bloc est attachée à un bloc obtenu par polymérisation catalytique.Document WO2019/077232A1 describes the synthesis of block polymers by polymerization of ethylene or a mixture of ethylene and 1,3-butadiene in the presence of a neodymium metallocene activated by an alkylation reaction of the metallocene with a living anionic polymer. The block polymers prepared therefore consist of a first block characterized by a microstructure typical of an anionic polymer and by a second block characterized by a microstructure typically obtained by catalytic polymerization. Only one of the chain ends of the first block is attached to a block obtained by catalytic polymerization.
La Demanderesse a découvert un procédé de synthèse de polymères à bloc ayant une microstructure originale sans présenter les inconvénients mentionnés. Non seulement il permet de synthétiser des polymères comportant plus de deux blocs en limitant le nombre de charges monomères, mais aussi il donne accès à des polymères ayant un bloc de microstructure typique d’une polymérisation anionique dont les deux extrémités sont reliées chacune à un bloc distinct de microstructure typique d’une polymérisation catalytique.The Applicant has discovered a process for the synthesis of block polymers having an original microstructure without exhibiting the drawbacks mentioned. Not only does it make it possible to synthesize polymers comprising more than two blocks by limiting the number of monomer charges, but also it gives access to polymers having a microstructure block typical of an anionic polymerization whose two ends are each connected to a block distinct microstructure typical of catalytic polymerization.
Ainsi, un premier objet de l’invention est un procédé de préparation d’un polymère à blocs qui comprend la polymérisation de l’éthylène ou d’un mélange monomère contenant de l’éthylène et un premier 1,3-diène en présence d’un système catalytique à base au moins
d’un métallocène de formule (Ia) ou (Ib),
{P(Cp1)(Cp2)Y} (Ia)
Cp3Cp4Y (Ib)
d’un organomagnésien à titre de cocatalyseur,
Y désignant un groupe comportant un atome d’une terre rare,
Cp1, Cp2, Cp3et Cp4, identiques ou différents, étant choisis dans le groupe constitué par les groupes fluorényles, les groupes cyclopentadiényles et les groupes indényles, les groupes étant substitués ou non substitués,
P étant un groupe pontant les deux groupes Cp1et Cp2, et comprenant un atome de silicium ou de carbone,
l’organomagnésien étant un composé de formule (II)
RB-(Mg-RA)m-Mg-RB(II)
RBétant différent de RA,
RBétant un groupe comprenant un noyau benzénique substitué par l’atome de magnésium, l’un des atomes de carbone du noyau benzénique en ortho du magnésium étant substitué par un méthyle, un éthyle, un isopropyle ou formant un cycle avec l'atome de carbone qui est son plus proche voisin et qui est en méta du magnésium, l’autre atome de carbone du noyau benzénique en ortho du magnésium étant substitué par un méthyle, un éthyle ou un isopropyle,
RAétant une chaîne polymère d’un deuxième 1,3-diène ou d’un deuxième 1,3-diène et de styrène,
m étant un nombre supérieur ou égal à 1, de préférence égal à 1.Thus, a first object of the invention is a process for the preparation of a block polymer which comprises the polymerization of ethylene or of a monomer mixture containing ethylene and a first 1,3-diene in the presence of a catalytic system based at least
a metallocene of formula (Ia) or (Ib),
{P(Cp1)(cp2)Y} (Ia)
CP3CP4Y (Ib)
an organomagnesium as a cocatalyst,
Y denoting a group containing a rare earth atom,
CP1, Cp2, Cp3and CP4, identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted,
P being a group bridging the two groups Cp1and CP2, and comprising a silicon or carbon atom,
the organomagnesium being a compound of formula (II)
RB-(Mg-RHAS)m-Mg-RB(II)
RBbeing different from RHAS,
RBbeing a group comprising a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl, an isopropyl or forming a ring with the carbon atom which is its nearest neighbor and which is meta to magnesium, the other carbon atom of the benzene ring ortho to magnesium being substituted by a methyl, an ethyl or an isopropyl,
RHASbeing a polymer chain of a second 1,3-diene or a second 1,3-diene and styrene,
m being a number greater than or equal to 1, preferably equal to 1.
L’invention concerne aussi un polymère à blocs susceptible d’être obtenu par le procédé conforme à l’invention. Le polymère à blocs, autre objet de l’invention, est de formule A-B-A, le symbole A désignant un bloc terminal et représentant une chaîne polymère d’éthylène ou une chaîne polymère contenant des unités d’éthylène et des unités d’un premier 1,3-diène, le symbole B désignant un bloc central et représentant une chaîne polymère d’un deuxième 1,3-diène ou une chaîne copolymère d’un deuxième 1,3-diène et de styrène, le taux total des unités 1,2 et des unités 3,4 dans le bloc central représentant plus de 7% en mole des unités du deuxième 1,3-diène constitutives de la chaîne polymère du bloc central B.The invention also relates to a block polymer capable of being obtained by the process in accordance with the invention. The block polymer, another object of the invention, is of formula A-B-A, the symbol A designating a terminal block and representing an ethylene polymer chain or a polymer chain containing ethylene units and units of a first 1 ,3-diene, the symbol B designating a central block and representing a polymer chain of a second 1,3-diene or a copolymer chain of a second 1,3-diene and styrene, the total rate of units 1, 2 and 3,4 units in the central block representing more than 7% by mole of the units of the second 1,3-diene constituting the polymer chain of the central block B.
Claims (15)
d’un métallocène de formule (Ia) ou (Ib),
{P(Cp1)(Cp2)Y} (Ia)
Cp3Cp4Y (Ib)
d’un organomagnésien à titre de cocatalyseur,
Y désignant un groupe comportant un atome d’une terre rare,
Cp1, Cp2, Cp3et Cp4, identiques ou différents, étant choisis dans le groupe constitué par les groupes fluorényles, les groupes cyclopentadiényles et les groupes indényles, les groupes étant substitués ou non substitués,
P étant un groupe pontant les deux groupes Cp1et Cp2, et comprenant un atome de silicium ou de carbone,
l’organomagnésien étant un composé de formule (II)
RB-(Mg-RA)m-Mg-RB(II)
RBétant différent de RA,
RBétant un groupe comprenant un noyau benzénique substitué par l’atome de magnésium, l’un des atomes de carbone du noyau benzénique en ortho du magnésium étant substitué par un méthyle, un éthyle, un isopropyle ou formant un cycle avec l'atome de carbone qui est son plus proche voisin et qui est en méta du magnésium, l’autre atome de carbone du noyau benzénique en ortho du magnésium étant substitué par un méthyle, un éthyle ou un isopropyle,
RAétant une chaîne polymère d’un deuxième 1,3-diène ou d’un deuxième 1,3-diène et de styrène,
m étant un nombre supérieur ou égal à 1, de préférence égal à 1.Process for the preparation of a block polymer which comprises the polymerization of ethylene or of a monomer mixture containing ethylene and a first 1,3-diene in the presence of a catalytic system based at least
a metallocene of formula (Ia) or (Ib),
{P(Cp1)(cp2)Y} (Ia)
CP3CP4Y (Ib)
an organomagnesium as a cocatalyst,
Y denoting a group containing a rare earth atom,
CP1, Cp2, Cp3and CP4, identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted,
P being a group bridging the two groups Cp1and CP2, and comprising a silicon or carbon atom,
the organomagnesium being a compound of formula (II)
RB-(Mg-RHAS)m-Mg-RB(II)
RBbeing different from RHAS,
RBbeing a group comprising a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl, an isopropyl or forming a ring with the carbon atom which is its nearest neighbor and which is meta to magnesium, the other carbon atom of the benzene ring ortho to magnesium being substituted by a methyl, an ethyl or an isopropyl,
RHASbeing a polymer chain of a second 1,3-diene or a second 1,3-diene and styrene,
m being a number greater than or equal to 1, preferably equal to 1.
(BH4)(1+y)-Ly-Nx(III)
dans laquelle
L représente un métal alcalin choisi dans le groupe constitué par le lithium, le sodium et le potassium,
N représente une molécule d’un éther, de préférence diéthyléther ou tétrahydrofurane,
x, nombre entier ou non, est égal ou supérieur à 0,
y, nombre entier, est égal ou supérieur à 0.Process according to Claim 3, in which G denotes a chlorine atom or the group of formula (III)
(BH 4 ) (1+y)- Ly -N x (III)
in which
L represents an alkali metal chosen from the group consisting of lithium, sodium and potassium,
N represents a molecule of an ether, preferably diethyl ether or tetrahydrofuran,
x, whole number or not, is equal to or greater than 0,
y, integer, is equal to or greater than 0.
[Me2Si(Flu)2Nd(µ-BH4)2Li(THF)] (III-1)
[{Me2SiFlu2Nd(µ-BH4)2Li(THF)}2] (III-2)
[Me2SiFlu2Nd(µ-BH4)(THF)] (III-3)
[{Me2SiFlu2Nd(µ-BH4)(THF)}2] (III-4)
[Me2SiFlu2Nd(µ-BH4)] (III-5)
Flu représentant le groupe C13H8.Process according to any one of Claims 1 to 6, in which the metallocene is of formula (III-1), (III-2), (III-3), (III-4) or (III-5):
[Me 2 Si(Flu) 2 Nd(µ-BH 4 ) 2 Li(THF)] (III-1)
[{Me 2 SiFlu 2 Nd(µ-BH 4 ) 2 Li(THF)} 2 ] (III-2)
[Me 2 SiFlu 2 Nd(µ-BH 4 )(THF)] (III-3)
[{Me 2 SiFlu 2 Nd(µ-BH 4 )(THF)} 2 ] (III-4)
[Me 2 SiFlu 2 Nd(µ-BH 4 )] (III-5)
Flu representing the C 13 H 8 group.
X étant un halogène choisi dans le groupe constitué par le chlore, le fluor, le brome et l’iode, préférentiellement un atome de brome ou un atome de chlore,
RBétant un groupe comprenant un noyau benzénique substitué par l’atome de magnésium, l’un des atomes de carbone du noyau benzénique en ortho du magnésium étant substitué par un méthyle, un éthyle, un isopropyle ou formant un cycle avec l'atome de carbone qui est son plus proche voisin et qui est en méta du magnésium, l’autre atome de carbone du noyau benzénique en ortho du magnésium étant substitué par un méthyle, un éthyle ou un isopropyle,
RAétant une chaîne polymère d’un deuxième 1,3-diène ou d’un deuxième 1,3-diène et de styrène.Process according to any one of Claims 1 to 7, in which the compound of formula (II) is prepared by reaction of a living anionic polymer of formula LiR A Li with a halide of an organomagnesium compound of formula R B -Mg-X ,
X being a halogen chosen from the group consisting of chlorine, fluorine, bromine and iodine, preferably a bromine atom or a chlorine atom,
R B being a group comprising a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl, an isopropyl or forming a ring with the atom carbon which is its closest neighbor and which is meta to the magnesium, the other carbon atom of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl or an isopropyl,
R A being a polymer chain of a second 1,3-diene or of a second 1,3-diene and styrene.
R1et R5, identiques ou différents, représentant un méthyle ou un éthyle, de préférence un méthyle,
R2, R3et R4, identiques ou différents, étant un atome d’hydrogène ou un alkyle,
RAétant la chaîne polymère d’un deuxième 1,3-diène ou d’un deuxième 1,3-diène et de styrène,
m étant un nombre supérieur ou égal à 1, de préférence égal à 1.Process according to any one of Claims 1 to 11, in which the compound of formula (II) is of formula (IV-m)
R 1 and R 5 , identical or different, representing a methyl or an ethyl, preferably a methyl,
R 2 , R 3 and R 4 , identical or different, being a hydrogen atom or an alkyl,
R A being the polymer chain of a second 1,3-diene or of a second 1,3-diene and styrene,
m being a number greater than or equal to 1, preferably equal to 1.
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| FR2106319A FR3123915B1 (en) | 2021-06-15 | 2021-06-15 | Synthesis of block polymers based on 1,3-diene and ethylene |
| PCT/FR2022/051079 WO2022263744A1 (en) | 2021-06-15 | 2022-06-08 | Synthesis of block polymers based on 1,3-diene and ethylene |
| EP22735548.4A EP4355800A1 (en) | 2021-06-15 | 2022-06-08 | Synthesis of block polymers based on 1,3-diene and ethylene |
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| FR2106319A FR3123915B1 (en) | 2021-06-15 | 2021-06-15 | Synthesis of block polymers based on 1,3-diene and ethylene |
| FR2106319 | 2021-06-15 |
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| WO2007054224A2 (en) | 2005-11-09 | 2007-05-18 | Societe De Technologie Michelin | Borohydride metallocene complex of a lanthanide, catalytic system including said complex, polymerisation method using same and ethylene/butadiene copolymer obtained using said method |
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| WO2019077232A1 (en) | 2017-10-19 | 2019-04-25 | Compagnie Generale Des Etablissements Michelin | Method for synthesising polymer blocks |
-
2021
- 2021-06-15 FR FR2106319A patent/FR3123915B1/en active Active
-
2022
- 2022-06-08 EP EP22735548.4A patent/EP4355800A1/en active Pending
- 2022-06-08 WO PCT/FR2022/051079 patent/WO2022263744A1/en active Application Filing
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| WO1989004843A1 (en) | 1987-11-16 | 1989-06-01 | The Dow Chemical Company | Amine containing initiator system for anionic polymerization |
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| Publication number | Publication date |
|---|---|
| EP4355800A1 (en) | 2024-04-24 |
| WO2022263744A1 (en) | 2022-12-22 |
| FR3123915B1 (en) | 2024-07-26 |
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