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KR-102963866-B1 - Ethylene copolymer and catalyst mixture for manufacturing ethylene copolymer

KR102963866B1KR 102963866 B1KR102963866 B1KR 102963866B1KR-102963866-B1

Abstract

A copolymer comprising repeating units derived from ethylene, at least one C3 - C20 -α-olefin, at least one non-conjugated diene, and at least one dipolymerizable diene is provided, wherein the copolymer has (i) an intensity ratio (D) of 0.5 or less and (ii) a molecular weight distribution (MWD) of R or greater, wherein R depends on the branching index (g'(III)) of the copolymer, and R is (-27.7 x g'(III)) + 29.2 when g'(III) is 0.90 or less, and R is 4.3 when g'(III) is greater than 0.90 and up to 0.99. A catalyst composition for producing such a copolymer comprising at least two different metal complexes, a process for producing the catalyst composition, a process for producing the copolymer, and an article obtained using the copolymer are also provided.

Inventors

  • 베르나르도, 라파엘레
  • 반 도레마엘레, 헤라르뒤스
  • 반 메이렌돈크, 와우터르
  • 윈드뮐러르, 페터르

Assignees

  • 아란세오 네덜란즈 비.브이.

Dates

Publication Date
20260513
Application Date
20210315
Priority Date
20200316

Claims (17)

  1. (a) ethylene, (b) at least one C3 - C20 α-olefin, (c) at least one dipolymerizable diene, and (d) a copolymer comprising repeating units derived from at least one non-conjugated diene having 6 to 30 carbon atoms that is not the dipolymerizable diene, The above copolymer is, (i) having an intensity ratio (D) of 0.5 or less when measured by C 13 -NMR spectroscopy, and (ii) having a branching index (δ△) of 5° to 50°, wherein δ△ is the difference between the phase angle (δ) measured at a frequency of 0.1 rad/sec and the phase angle (δ) measured at a frequency of 100 rad/sec by dynamic mechanical analysis (DMA) at 125°C; (iii) having a branch index (g'(III)) of 0.50 to 0.99; (iv) having a molecular weight distribution (MWD) greater than or equal to R, where R depends on the branch index (g'(III)) of the copolymer, wherein R is (-27.7 x g'(III)) + 29.2 when g'(III) is 0.90 or less, and R is 4.3 when g'(III) is greater than 0.90 up to 0.99 at most; The above g'(III) and the molecular weight distribution are measured by gel permeability size exclusion chromatography, and The copolymer comprises 30% to a maximum of 85% by weight of units derived from ethylene, 5% to 50% by weight of units derived from C3 - C20 α-olefins, and 2% to 20% by weight of units derived from non-conjugated dienes other than the dipolymerizable dienes, wherein the weight% is based on the total weight of the polymer, i.e., 100% by weight, and A copolymer in which at least one of the above-mentioned dual polymerizable dienes is selected from the group consisting of 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclo-hexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenyl-cyclohexane, 1-isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane, dicyclopentadiene, 1,4-cyclohexadiene, 5-vinyl-2-norbornene (VNB), 2,5-norbornene, and combinations thereof.
  2. A copolymer according to claim 1, characterized in that g'(III) is 0.70 to 0.98 or 0.80 to 0.97 and the phase angle difference (△δ) is 5° to 35°.
  3. A copolymer according to claim 1, characterized in that the MWD is 4.5 to 50.
  4. A copolymer according to claim 1, wherein the strength ratio (D) is in the range of 0.02 to 0.4 or less.
  5. A copolymer according to claim 1, wherein the C3 - C20 α-olefin is selected from propylene.
  6. A copolymer according to claim 1, wherein the non-conjugated diene having 6 to 30 carbon atoms is selected from vinylcyclohexene, dicyclopentadiene, cyclooctadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and combinations thereof.
  7. A copolymer according to claim 1, containing 2% to 6.7% by weight of a unit derived from a non-conjugated diene.
  8. A copolymer according to claim 1, wherein at least one C3 - C20 -α-olefin comprises propylene, at least one non-conjugated diene comprises 5-ethylidene-2-norbornene (ENB), and at least one dipolymerizable diene monomer comprises 5-vinyl-2-norbornene (VNB).
  9. A copolymer according to claim 1, wherein at least one dual polymerizable diene comprises 5-vinyl-2-norbornene (VNB), and the content of units derived from VNB is 0.05 wt% to 5 wt% or 0.5 wt% to 5 wt%.
  10. In claim 1, the polymerization is obtained using a first metal complex and a second metal complex, wherein the first metal complex corresponds to the chemical formula (1): [Chemical Formula (1)] CyLMZ p [In the above formula, M is selected from titanium, hafnium, or zirconium; Z is an anionic ligand selected from the group consisting of halogens, C1-10 alkyl groups, C7-20 aralkyl groups, C6-20 aryl groups, C1-20 hydrocarbon-substituted amino groups, and combinations thereof; p is 1 or 2 and; L is a ligand according to chemical formula (2) or: [Chemical Formula (2)] (In the above formula, the ligand (L) is covalently bonded to the metal (M) through its imine nitrogen atom, and Sub 1 is a C1 - C20 alkyl residue or a C6 - C20 aryl residue, which may be unsubstituted or substituted with a substituent selected from halogens and C1 - C3 alkyl groups; Sub 2 represents the general formula -NR4R5 , wherein R4 and R5 are independently selected from the group consisting of aliphatic C1 - C20 hydrocarbyl, halogenated C1 - C20 aliphatic hydrocarbyl, aromatic C6 - C20 hydrocarbyl, and halogenated aromatic C6 - C20 hydrocarbyl residues, or R4 forms a heterocyclic ring together with R5 or Sub 1 ); L corresponds to the general chemical formula (2b): [General Chemical Formula (2b)] (In the above formula, the amidine-containing ligand is covalently bonded to the metal (M) through the imine nitrogen atom ( N₂ ); S is a -CH₂- unit, t is an integer representing 1, 2, 3, and 4, Sub 3 represents an aliphatic or aromatic, cyclic or linear substituent comprising a group 14 atom through which Sub 3 is bonded to the amine nitrogen atom ( N₁ ); Sub 4 is a C₂ unit in which two carbon atoms can be sp₂ or sp₃ hybridized, wherein the C₂ unit may be substituted by one or more halogen atoms or by one or more C₁ - C₁₀ alkyl groups or C₁ - C₁₀ alkoxy groups); Cy is a cyclopentadienyl ligand that may contain one or more substituents selected from the group consisting of a halogen and aromatic or aliphatic, linear or branched or cyclic residues comprising 1 to 20 carbon atoms; Cy is selected from unsubstituted or substituted indenyl ligands, substituted cyclopentadienyl ligands containing at least three methyl groups, or S-heterocyclic ligands corresponding to formula (2e): [Chemical formula (2e)] (In the above chemical formula (2e), R1 and R2 are individually selected from the group consisting of hydrogen, halogens, C1 - C10 alkyl, C5 - C10 cycloalkyl, and C1 - C4 -alkyl- or C1 - C4 -dialkylamino-substituted or unsubstituted phenyls, R1 and R2 form a C1 - C4 -alkyl-substituted or unsubstituted aliphatic C5 - C6 -cycloalkene ring together with the two double-bonded carbon atoms of the thiophene ring to which they are connected, and R3 , R4 , and R5 are individually selected from the group consisting of hydrogen, C1 - C4 alkyl, phenyl, and C1 - C4 -alkyl- and/or halogen-substituted phenyl)]; The above second metal complex is a bis-indeneyl complex and is a copolymer corresponding to the chemical formula (3): [Chemical Formula (3)] J-Ind 2 -MX 2 (In the above formula, Ind 2 represents two indenyl ligands to which the metal (M) is bonded, wherein these indenyl ligands are additionally connected to each other through a linker (J); said indenyl ligands may be substituted or unsubstituted; J represents a divalent bridge connecting the two indenyl ligands ( In₂ ); wherein J is (a) a cyclic unit ((R a 2 J') n ), wherein each J' is independently C or Si, n is 1 or 2, and each R a is independently a hydrocarbyl substituted or unsubstituted with C1 to C20 , and at least two R a are connected together to form a saturated or partially saturated or aromatic cyclic or fused ring structure in which at least one J' is incorporated ((R a 2 J') n ), and (b) an acyclic unit (R b 2 J'), wherein each R b is selected from a C1 - C9 linear or branched hydrocarbyl in which each R b can be independently hydrogen, unsubstituted or substituted, and each J' is independently C or Si, and is selected from an acyclic unit (R b 2 J'); M is selected from titanium, hafnium, or zirconium; Each X is independently a monovalent anionic ligand selected from the group consisting of a halogen, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group, and a C1-20 hydrocarbon-substituted amino group).
  11. In claim 1, the polymerization is obtained using a first metal complex and a second metal complex, wherein the first metal complex corresponds to the chemical formula (1): [Chemical Formula (1)] CyLMZ p [In the above formula, M is selected from titanium, hafnium, or zirconium; Z is an anionic ligand selected from the group consisting of halogens, C1-10 alkyl groups, C7-20 aralkyl groups, C6-20 aryl groups, C1-20 hydrocarbon-substituted amino groups, and combinations thereof; p is 1 or 2 and; L is a ligand according to chemical formula (2) or: [Chemical Formula (2)] (In the above formula, the ligand (L) is covalently bonded to the metal (M) through its imine nitrogen atom, and Sub 1 is a C1 - C20 alkyl residue or a C6 - C20 aryl residue, which may be unsubstituted or substituted with a substituent selected from halogens and C1 - C3 alkyl groups; Sub 2 represents the general formula -NR4R5 , wherein R4 and R5 are independently selected from the group consisting of aliphatic C1 - C20 hydrocarbyl, halogenated C1 - C20 aliphatic hydrocarbyl, aromatic C6 - C20 hydrocarbyl, and halogenated aromatic C6 - C20 hydrocarbyl residues, or R4 forms a heterocyclic ring together with R5 or Sub 1 ); L corresponds to the general chemical formula (2b): [General Chemical Formula (2b)] (In the above formula, the amidine-containing ligand is covalently bonded to the metal (M) through the imine nitrogen atom ( N₂ ); S is a -CH₂- unit, t is an integer representing 1, 2, 3, and 4, Sub 3 represents an aliphatic or aromatic, cyclic or linear substituent comprising a group 14 atom through which Sub 3 is bonded to the amine nitrogen atom ( N₁ ); Sub 4 is a C₂ unit in which two carbon atoms can be sp₂ or sp₃ hybridized, wherein the C₂ unit may be substituted by one or more halogen atoms or by one or more C₁ - C₁₀ alkyl groups or C₁ - C₁₀ alkoxy groups); Cy is a cyclopentadienyl ligand that may contain one or more substituents selected from the group consisting of a halogen and aromatic or aliphatic, linear or branched or cyclic residues comprising 1 to 20 carbon atoms; Cy is selected from unsubstituted or substituted indenyl ligands, substituted cyclopentadienyl ligands containing at least three methyl groups, or S-heterocyclic ligands corresponding to formula (2e): [Chemical formula (2e)] (In the above chemical formula (2e), R1 and R2 are individually selected from the group consisting of hydrogen, halogens, C1 - C10 alkyl, C5 - C10 cycloalkyl, and C1 - C4 -alkyl- or C1 - C4 -dialkylamino-substituted or unsubstituted phenyls, R1 and R2 form a C1 - C4 -alkyl-substituted or unsubstituted aliphatic C5 - C6 -cycloalkene ring together with the two double-bonded carbon atoms of the thiophene ring to which they are connected, and R3 , R4 , and R5 are individually selected from the group consisting of hydrogen, C1 - C4 alkyl, phenyl, and C1 - C4 -alkyl- and/or halogen-substituted phenyl)]; The above second metal complex is a bis-indeneyl complex and is a copolymer corresponding to the chemical formula (3): [Chemical Formula (3)] J-Ind 2 -MX 2 (In the above formula, Ind 2 represents two indenyl ligands to which the metal (M) is bonded, wherein these indenyl ligands are additionally connected to each other through a linker (J); each of the indenyl ligands (Ind) may be substituted or unsubstituted and contains one to seven alkyl substituents having one to three carbon atoms; J is selected from ( H₃C ) ₂Si , ( H₅C₂ ) ₂Si , ( H₇C₃ )₂Si , H₂C , H₃CHC , ( H₃C ) ₂C , ( H₅C₂ ) ₂Si , and ( H₇C₃ ) ₂Si ; M represents zirconium; Both X are selected from C1 - C10 alkyl groups).
  12. A process for manufacturing an ethylene copolymer according to claim 1, A process comprising the step of copolymerizing ethylene, the at least one C3 - C20 -α-olefin, the at least one non-conjugated diene, and the at least one dipolymerizable diene monomer in the presence of a first metal complex and a second metal complex, wherein the first and second metal complexes are each selected from those defined in claim 10 or claim 11.
  13. A process according to claim 12 further comprising the presence of at least one activator (b) and optionally at least one scavenger (c).
  14. An extruded article comprising a polymer according to claim 1, wherein the polymer is at least partially cured.
  15. As a process for manufacturing extruded articles, The step of providing a formulation comprising a polymer according to claim 1, and A process comprising the step of extruding the above mixture through at least one mold.
  16. A composition comprising a first and second metal composite, The first metal complex above corresponds to the chemical formula (1): [Chemical Formula (1)] CyLMZ p [In the above formula, M is selected from titanium, hafnium, or zirconium; Z is an anionic ligand selected from the group consisting of halogens, C1-10 alkyl groups, C7-20 aralkyl groups, C6-20 aryl groups, C1-20 hydrocarbon-substituted amino groups, and combinations thereof; p is 1 or 2 and; L is a ligand according to chemical formula (2) or: [Chemical Formula (2)] (In the above formula, the ligand (L) is covalently bonded to the metal (M) through its imine nitrogen atom, and Sub 1 is a C1 - C20 alkyl residue or a C6 - C20 aryl residue, which may be unsubstituted or substituted with a substituent selected from halogens and C1 - C3 alkyl groups; Sub 2 represents the general formula -NR4R5 , wherein R4 and R5 are independently selected from the group consisting of aliphatic C1 - C20 hydrocarbyl, halogenated C1 - C20 aliphatic hydrocarbyl, aromatic C6 - C20 hydrocarbyl, and halogenated aromatic C6 - C20 hydrocarbyl residues, or R4 forms a heterocyclic ring together with R5 or Sub 1 ); L corresponds to the general chemical formula (2b): [General Chemical Formula (2b)] (In the above formula, the amidine-containing ligand is covalently bonded to the metal (M) through an imine nitrogen atom ( N₂ ); S is a -CH₂- unit, t is an integer representing 1, 2, 3, and 4, Sub 3 represents an aliphatic or aromatic, cyclic or linear substituent comprising a group 14 atom through which Sub 3 is bonded to the amine nitrogen atom ( N₁ ); Sub 4 is a C₂ unit in which two carbon atoms can be sp₂ or sp₃ hybridized, wherein the C₂ unit may be substituted by one or more halogen atoms or by one or more C₁ - C₁₀ alkyl groups or C₁ - C₁₀ alkoxy groups); Cy is a cyclopentadienyl ligand that may contain one or more substituents selected from the group consisting of a halogen and aromatic or aliphatic, linear or branched or cyclic residues comprising 1 to 20 carbon atoms; Cy is selected from unsubstituted or substituted indenyl ligands, substituted cyclopentadienyl ligands containing at least three methyl groups, or S-heterocyclic ligands corresponding to formula (2e): [Chemical formula (2e)] (In the above chemical formula (2e), R1 and R2 are individually selected from the group consisting of hydrogen, halogens, C1 - C10 alkyl, C5 - C10 cycloalkyl, and C1 - C4 -alkyl- or C1 - C4 -dialkylamino-substituted or unsubstituted phenyls, R1 and R2 form a C1 - C4 -alkyl-substituted or unsubstituted aliphatic C5 - C6 -cycloalkene ring together with the two double-bonded carbon atoms of the thiophene ring to which they are connected, and R3 , R4 , and R5 are individually selected from the group consisting of hydrogen, C1 - C4 alkyl, phenyl, and C1 - C4 -alkyl- and/or halogen-substituted phenyl)]; The above second metal complex is a bis-indeneyl complex and is a composition corresponding to the chemical formula (3): [Chemical Formula (3)] J-Ind 2 -MX 2 (In the above formula, Ind 2 represents two indenyl ligands to which the metal (M) is bonded, wherein these indenyl ligands are additionally connected to each other through a linker (J); said indenyl ligands may be substituted or unsubstituted; J represents a divalent bridge connecting the two indenyl ligands ( In₂ ); wherein J is (a) a cyclic unit ((R a 2 J') n ), wherein each J' is independently C or Si, n is 1 or 2, and each R a is independently a hydrocarbyl substituted or unsubstituted with C1 to C20 , and at least two R a are connected together to form a saturated or partially saturated or aromatic cyclic or fused ring structure in which at least one J' is incorporated ((R a 2 J') n ), and (b) an acyclic unit (R b 2 J'), wherein each R b is selected from a C1 - C9 linear or branched hydrocarbyl in which each R b can be independently hydrogen, unsubstituted or substituted, and each J' is independently C or Si, and is selected from an acyclic unit (R b 2 J'); M is selected from titanium, hafnium, or zirconium; Each X is independently a monovalent anionic ligand selected from the group consisting of a halogen, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group, and a C1-20 hydrocarbon-substituted amino group).
  17. delete

Description

Ethylene copolymer and catalyst mixture for manufacturing ethylene copolymer The present disclosure relates to an elastomeric ethylene copolymer having improved extrusion properties. The present disclosure also relates to a catalyst mixture and a polymerization process for producing a copolymer. The present disclosure also relates to an extruded article made of a copolymer. Elastomerical ethylene copolymers are generally processed in the form of formulations. That is, copolymers are mixed with one or more fillers and other optional components to form so-called formulations. Often, ethylene copolymers that produce desired good mechanical properties, such as high tensile strength and low compressive strain, result in formulations that are difficult and costly to process because large forces must be applied to process them. One approach to overcome these problems has focused on attempts to reduce the viscosity of the formulation by adding various components to the formulation. Instead of using a single copolymer, blends of copolymers with different Mooney viscosities have been used to reduce the viscosity of the formulation, for example, by adding one or more copolymers with lower Mooney viscosity. This approach involves a step of blending them after the polymers are manufactured, or a step of blending them during polymerization to provide so-called "in-situ blends" or "reactor blends." Other methods include a step of adding oil to the formulation as a lubricant ("processing oil") or "extension oil" to provide an "oil-extensioned" ethylene copolymer. The extension oil is incorporated into the polymer structure, for example, by adding the extension oil to the polymer during the production process prior to the isolation of the polymer. While these approaches can result in a reduction in the viscosity of the formulation, they generally come at the expense of a reduction in the mechanical performance of the formulation. Another approach has focused on developing new catalysts for the production of ethylene copolymers to replace the commonly used Ziegler-Natta catalyst. The creation of these new catalysts is based on molecular metal-organic complexes, such as metallocene complexes or post-metallocene complexes, which enable better control of the polymer structure during polymerization, particularly better control of the polymer's branching pattern and microstructure. Different metallocene catalysts can produce different polymer structures and have different polymerization activities for the monomers used in the production of ethylene copolymers. Metallocene-based catalysts exhibit different activities regarding the incorporation of comonomers into the ethylene polymer backbone. A metallocene catalyst reported to be highly active for the incorporation of non-conjugated dienes is described in WO2005/090418 A1. Although it is known that ethylene copolymers can be produced using these types of catalysts that exhibit good mechanical properties, there is still a need to provide ethylene copolymers that not only provide formulations with good mechanical properties such as tensile strength and compressive strain, but also have improved extrusion behavior. Preferably, such polymers can be produced at a low cost. Figure 1 is a photograph of an extruded strip of a copolymer mixture obtained from an extrusion experiment. Figure 2 is a photograph of the Garvey profile used in the extrusion experiment. In the following description, the standard may be used. Unless otherwise indicated, the standard is used for the version in effect as of March 1, 2020. For example, if no version is in effect on that date because the standard has expired, this version is referred to as being in effect on the date closest to March 1, 2020. In the following description, the amount of a component of the composition or polymer may be expressed as "weight percentage," "wt.%," or "weight%." The terms "weight percentage," "wt.%," or "weight%" are used interchangeably and are based on the total weight of each component of the composition or polymer, i.e., 100%. This means that the total amount of the various components of the composition or polymer is 100 weight%. The copolymer according to the present disclosure is a copolymer of ethylene and at least three additional comonomers. This means that the copolymer comprises repeating units derived from ethylene and at least three additional comonomers. Preferably, the copolymer comprises at least 30 wt.% to a maximum of 85 wt.% of units derived from ethylene. More preferably, the copolymer according to the present disclosure comprises 41 wt.% to 80 wt.%, most preferably 45 wt.% to 74 wt.% of units derived from ethylene. The weight percentages are based on the total weight of the copolymer. In addition to units derived from ethylene, the copolymer according to the present disclosure has repeating units derived from (i) one or more C3 - C20 -α-olefins, preferably C3 - C12 -α-olefins, (ii) at least one non-conju