Ethylene copolymers and catalyst compositions for producing ethylene copolymers

Abstract

Ethylene and at least one C3-C 20 A copolymer comprising repeat units derived from an α-olefin, at least one non-conjugated diene, and at least one dipolymerizable diene, the copolymer having (i) an intensity ratio D≦0.5 and (ii) a molecular weight distribution (MWD)≧R, where R is dependent on the branching index g′(III) of the copolymer: when g′(III)≦0.90, R is −27.7×g′(III)+29.2; when g′(III) is >0.90 and is ≦0.99, R is 4.3. Also provided are catalyst compositions for producing such copolymers, comprising at least two different metal complexes, methods for producing the catalyst compositions, methods for producing the copolymers, and articles obtained using the copolymers.

Description

Technical Field

[0001] The present disclosure relates to an elastomeric ethylene copolymer having improved extrusion characteristics. The present disclosure further relates to a catalyst mixture and a polymerization method for producing the copolymer. The present disclosure also relates to an extruded article produced using the copolymer.

Background Art

[0002] Elastomeric ethylene copolymers are generally processed in the form of compounds. That is, the copolymer is mixed with one or more fillers and other optional components to form a so-called compound. In many cases, ethylene copolymers that result in desired good mechanical properties, such as high tensile strength and low compression set, result in compounds that are difficult or costly to process because strong forces need to be applied for their processing.

[0003] One way to overcome this problem has focused on attempts to reduce the viscosity of the compound by adding various components to the compound. Instead of using one copolymer, blends of copolymers with different Mooney viscosities are used to reduce the viscosity of the compound, for example by adding one or more copolymers with a lower Mooney viscosity. This method involves blending the polymers after they are prepared or blending them during polymerization to obtain a so-called "in-situ blend" or "reactor blend". Another method involves either adding oil to the compound as a lubricant ("process oil") or adding oil as an "extender oil" to obtain an "oil-extended" ethylene copolymer. The extender oil is incorporated into the polymer structure, for example, by adding the extender oil to the polymer during the production process before the polymer is isolated. Although the viscosity of the compound can be reduced by these methods, these methods generally may sacrifice a reduction in the mechanical performance of the compound.

[0004] Another approach focuses on the development of novel catalysts to replace the conventionally used Ziegler-Natta catalysts for the production of ethylene copolymers. This new generation of catalysts is based on molecular metal-organic complexes such as metallocene complexes or post-metallocene complexes, and can more fully control the polymer structure during polymerization, particularly the branching pattern and microstructure of the polymer. Different metallocene catalysts can form different polymer structures and may have different polymerization activities with respect to the monomers used in the production of ethylene copolymers. Metallocene-based catalysts exhibit various activities regarding the incorporation of comonomers into the ethylene polymer backbone. Metallocene catalysts with high activity regarding the incorporation of non-conjugated dienes are described in (Patent Document 1). Although it has been found that ethylene copolymers with good mechanical properties can be prepared using these types of catalysts, there is still a need to provide ethylene copolymers that not only have good mechanical properties such as tensile strength and compression set, but also have improved extrusion behavior and can obtain compounds with such properties. Advantageously, such polymers can be produced at low cost.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0006] The inventors have found that polymers with special monomer compositions and polymer structures not only have good mechanical properties but can also be processed by extrusion without showing surface defects. Such polymers have a controlled structure and a defined level of branching depending on their molecular weight distribution. These polymers are composed of ethylene and at least one C3-C 20-α-olefin, at least one non-conjugated diene, and units derived from at least one diene having two double bonds, and the polymerization of the monomers is carried out in the presence of a first transition metal catalyst and a second metal catalyst, and optionally in the presence of one or more activators, and optionally in the presence of one or more scavengers.

[0007] Thus, in one aspect, (a) ethylene, (b) at least one C3-C 20 α-olefin, (c) at least one diene having two double bonds, (d) at least one non-conjugated diene having 6 to 30 carbon atoms other than the diene having two double bonds, a copolymer comprising repeating units derived therefrom, wherein the copolymer (i) an intensity ratio D of ≦0.5 as measured by C 13 -NMR spectroscopy, and (ii) a branching index Δδ of 5 to 50 (where Δδ is the difference between the phase angle δ measured at a frequency of 0.1 rad / s by dynamic mechanical analysis (DMA) at 125°C and the phase angle δ measured at a frequency of 100 rad / s); (iii) a branching index g'(III) between 0.50 and 0.99, and (iv) a molecular weight distribution (MWD) of ≧R [R depends on the branching index g'(III) of the copolymer, when g'(III) ≦0.90, R is -27.7×g'(III)+29.2; when g'(III)>0.90 and 0.99 or less, R is 4.3], and having, g'(III) and the molecular weight distribution are determined by gel permeation size exclusion chromatography, the copolymer comprises units derived from 30 wt% to 85 wt% ethylene, units derived from 5 to 80 wt% C3-C 20 α-olefin, and units derived from 2 wt% to 20 wt% non-conjugated dienes other than the diene having two double bonds, where the wt% is based on the total weight of the polymer which is 100 wt%, At least one double-bonded diene is selected from the group consisting of 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 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-norbornadiene, and combinations thereof. A copolymer is provided.

[0008] In another aspect, a method for producing a copolymer includes copolymerizing ethylene, at least one C 3~ C 20 -α-olefin, at least one non-conjugated diene, and at least one double-bonded diene monomer in the presence of at least one first metal complex (the first metal complex and the second metal complex). The first metal complex has the formula (1): CyLMZ p (1) where: Cy is a cyclopentadienyl ligand that can preferably contain one or more substituents selected from the group consisting of a halogen, and an aromatic or aliphatic, linear, branched, or cyclic residue containing 1 to 20 carbon atoms; M is selected from titanium, hafnium, or zirconium; Z is an anionic ligand selected from the group consisting of a halogen, a C 1~10 alkyl group, a C 7~20 aralkyl group, a C 6~20 aryl group, a C 1~20 hydrocarbon-substituted amino group, and combinations thereof; p is 1 or 2, preferably 2; L has the formula (2):

Chemical formula

Chemical Formula

[0009] In another aspect, an extruded article is provided that includes the copolymer, wherein the copolymer is at least partially cured.

[0010] In another aspect, a method for manufacturing an extruded article is provided, which includes providing a compound including the copolymer, preferably in at least partially cured form, and extruding the compound through at least one die.

[0011] In yet another aspect, a composition comprising a first and a second metal complex is provided.

[0012] Hereinafter, the copolymer, the catalyst, and the method for producing the copolymer, the catalyst, and the use of the copolymer will be described in more detail.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0014] In the following description, multiple standards can be used. Unless otherwise specified, these standards are used in the editions that were valid as of March 1, 2020. For example, if a standard has expired and there is no edition valid on that date, the edition closest to March 1, 2020 and valid on that date is referred to.

[0015] In the following description, the amounts of the components of a composition or a polymer can be indicated by "weight percent", "wt.%", or "weight %". The terms "weight percent", "wt.%", or "weight %" are used synonymously and are based on the total weight of the composition or polymer, which is 100% respectively. This means that the total amount of the various components of the composition or polymer is 100 weight %.

[0016] The copolymers according to the present disclosure are copolymers of ethylene and at least three additional comonomers. This means that the copolymers contain repeating units derived from ethylene and at least three additional comonomers. Preferably, the copolymers contain units derived from at least 30 weight percent (wt%) and up to 85 wt% ethylene. More preferably, the copolymers according to the present disclosure contain units derived from 41 to 80 wt%, most preferably 45 to 74 wt% ethylene. The weight percent values are based on the total weight of the copolymer.

[0017] In addition to the units derived from ethylene, the copolymers according to the present disclosure have repeating units derived from (i) one or more C3-C 20 -α-olefins, preferably C3-C 12 -α-olefins, (ii) at least one non-conjugated diene, and (iii) at least one di-functional diene.

[0018] C3-C 20 -α-olefin C3-C 20 -α-olefins (hereinafter referred to as "C3-C 20An α-olefin (also called an alpha olefin) is an olefin containing 3 to 20 carbon atoms and having one aliphatic carbon-carbon double bond. The double bond is located at the front end (alpha position) of the olefin. The α-olefin may be aromatic or aliphatic, linear, branched, or cyclic. Examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Alpha olefins can be used in combinations. Preferred alpha-olefins are aliphatic C3-C 12 α-olefins, more preferably aliphatic linear C3-C4 α-olefins, and most preferably propylene (C3 α-olefin) and 1-butene (C4 α-olefin). Propylene is most preferred.

[0019] Preferably, the copolymer contains units derived from C3-C 20 α-olefins up to 80% by weight, more preferably up to 50% by weight (all weight percent values (wt%) are based on the total weight of the copolymer). Preferably, the copolymer contains a total of 5-80% by weight of units derived from C3-C 20 α-olefins, more preferably a total of 15-45% by weight or 25-45% by weight of units derived from C3-C 20 α-olefins. Preferably, the copolymer contains 5-80% by weight, more preferably 15-45% by weight, and most preferably 25-45% by weight of units derived from propylene (all weight percent values (wt%) are based on the total amount of the copolymer).

[0020] Non-conjugated diene A non-conjugated diene is a polyene containing at least two double bonds, and these double bonds are non-conjugated within a chain, ring, ring structure, or a combination thereof. The polyene can have double bonds inside and / or outside the ring, and can be unsubstituted or have the same or different types of substituents. The plurality of double bonds are separated by at least two carbon atoms. To a considerable extent, only one of the non-conjugated double bonds is converted by the polymerization catalyst. Therefore, a non-conjugated diene can provide a curing site in the polymer.

[0021] The non-conjugated diene is preferably aliphatic, more preferably alicyclic and aliphatic.

[0022] Suitable non-conjugated dienes include aromatic polyenes, aliphatic polyenes, and alicyclic polyenes, preferably polyenes having 6 to 30 carbon atoms (C6-C 30 -polyene, more preferably C6-C 30Specific examples of non-conjugated dienes include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1,6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene ene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6 -methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 1,5,9-decatriene, 6-methyl-1,6-Undecadiene, 9-methyl-1,8-undecadiene, dicyclopentadiene, and mixtures thereof may be mentioned. Dicyclopentadiene can be used as a diene having two double bonds or as a non-conjugated diene, in which case dicyclopentadiene is used in combination with at least one diene having two double bonds or at least one non-conjugated diene.,

[0023] Preferred non-conjugated dienes include alicyclic polyenes. The alicyclic diene has at least one cyclic unit. In a preferred embodiment, the non-conjugated diene is selected from polyenes having at least one double bond within the ring and optionally at least one double bond outside the ring. Preferred examples include dicyclopentadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene (ENB), and ENB is particularly preferred.

[0024] Examples of aromatic non-conjugated polyenes include vinylbenzene (including its isomers) and vinylisopropenylbenzene (including its isomers).

[0025] In a typical embodiment of the present disclosure, the copolymer contains units derived from one or more non-conjugated dienes in an amount of 20% by weight or less. In a preferred embodiment, the copolymer contains units derived from one or more non-conjugated dienes in an amount of 2 to 12% by weight. In a preferred embodiment, the copolymer contains units from ENB in an amount of up to 20% by weight, more preferably 2 to 12% by weight of units derived from ENB, or 3.5 to 6.7% by weight of units derived from ENB (all % by weight are based on the total weight of the copolymer).

[0026] Diene having two double bonds The double - functionality diene is selected from vinyl - substituted aliphatic monocyclic and non - conjugated dienes, vinyl - substituted bicyclic and non - conjugated aliphatic dienes, alpha - omega linear dienes and non - conjugated dienes, both of whose unsaturated sites are polymerizable by a coordination catalyst (e.g., a Ziegler - Natta vanadium catalyst or a metallocene - type catalyst). Thus, the double - functionality monomer can form polymer branches during polymerization. Examples of double - functionality dienes include 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, and 1,4 - cyclohexadiene. Non - conjugated vinylnorbornene and C8 - C 12 alpha - omega linear dienes (e.g., 1,7 - octadiene, 1,8 - nonadiene, 1,9 - decadiene, 1,10 - undecadiene, 1,11 - dodecadiene) are preferred. The double - functionality diene may be further substituted with at least one group containing a heteroatom of groups 13 - 17, such as O, S, N, P, Cl, F, I, Br, or combinations thereof.

[0027] In a preferred embodiment of the present disclosure, the double - functionality diene is selected from 2,5 - norbornene, 5 - vinyl - 2 - norbornene (VNB), 1,7 - octadiene, and 1,9 - decadiene, with 5 - vinyl - 2 - norbornene (VNB) being most preferred.

[0028] Preferably, the copolymer of the present disclosure contains from 0.05 wt% to 5 wt%, more preferably from 0.10 wt% to 3 wt% or from 0.2 wt% to 1.2 wt% or at least from 0.5 to 5 wt% or up to 3 wt% or up to 1.2 wt% of one or more double - functionality dienes, more preferably units derived from VNB (all weight percentage values are based on the total weight of the copolymer).

[0029] In a preferred embodiment, the copolymer of the present disclosure includes units derived from 5-ethylidene-2-norbornene and 5-vinylnorbornene. In a more preferred embodiment, the copolymer includes units derived from ethylene, propylene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene.

[0030] Intensity Ratio The intensity ratio (abbreviated as "D" herein) is a measure related to the microstructure of the polymer, particularly the regioregularity of the incorporation of C3-C 20 alpha-olefins into the polymer main chain, and is described, for example, in European Patent Application Publication No. 10 88 836 A1 by Koda and Kawasaki, which is incorporated herein by reference. The intensity ratio represents the ratio of CH2-units at different positions selected from C3-C 20 alpha-olefins to the tertiary carbon atoms in the polymer main chain. This shows the different arrangements of CH2-units from the following propylene.

Chemical formula

[0031] The CH2-unit may be adjacent to two tertiary carbon atoms (described as "Sαα" herein) or may be adjacent to one secondary carbon atom and one tertiary carbon atom (described as "Sαβ" herein).

[0032] 13In the 13C-NMR spectrum, signals at different positions in the spectrum are obtained by these (Sαα) and (Sαβ) carbon units. For example, one signal (Sαα) becomes the signal of CH2 adjacent to two tertiary carbon atoms, and the other signal (Sαβ) becomes the signal of CH2 adjacent to one tertiary carbon atom and one secondary carbon atom. From the ratio of the intensity of the signal of carbon atom Sαβ to the intensity of the signal of carbon atom Sαα, the intensity ratio D is obtained. The larger the value of D, the higher the positional irregularity of the orientation of the α-olefin bond, and the more 2,1 insertion of α-olefin in the polymer chain. The smaller the value of D, the higher the positional regularity of the α-olefin bond orientation, and the less 2,1 insertion of α-olefin in the polymer chain.

[0033] Ethylene copolymers obtained using Ziegler-Natta catalysts (i.e., non-metallocene type catalysts based on transition metals, particularly vanadium halides) are considered to have an intensity ratio D greater than 0.5. Therefore, an intensity ratio D of 0.5 or less means that the polymer is obtained without using a Ziegler-Natta catalyst and is obtained, for example, by a metallocene type catalyst. As used herein, "metallocene type catalyst" means an organometallic catalyst in which the metal is bonded to at least one cyclic ligand, preferably at least one cyclopentadienyl ligand or at least one indenyl ligand.

[0034] The ethylene copolymer according to the present disclosure has an intensity ratio D of 0.5 or less and thus cannot be obtained by using a Ziegler-Natta catalyst. The ethylene copolymer according to the present disclosure can be obtained by a combination of a first and a second metal complex, and both the second and the first catalysts are metallocene type catalysts, such as the first and second catalysts described herein. Typically, the ethylene copolymer according to the present disclosure has an intensity ratio of 0.5 or less, for example, 0.01 to 0.4 or less, or 0.03 to 0.3, or 0.05 to 0.02, or more than 0.06 and 0.4 or less.

[0035] Molecular weight distribution (MWD) and g’(III) The molecular weight distribution (MWD) is the ratio of the weight average molar mass (Mw) of the copolymer to the number average molar mass, i.e., MWD = Mw / Mn. The MWD can be determined by gel permeation size exclusion chromatography (GPC-SEC).

[0036] It has been found that good extrusion properties, particularly extrusion where the surface effect does not decrease or decreases, can be achieved by polymers having a specific relationship between the MWD and the degree of branching. The copolymers according to the present disclosure have a molecular weight distribution (MWD) that also varies depending on their branching level. The MWD of the polymers according to the present disclosure is equal to or greater than the value of R. The value of R varies depending on the value of g’(III). g’(III) is the branching index and indicates the degree of branching in the polymer structure as described in WO 99 / 00434 A1 of the international patent application of Evens et al. (incorporated herein by reference including the references described therein).

[0037] Accordingly, the molecular weight distribution of the polymers according to the present disclosure depends on the degree of branching in the polymer structure determined by the parameter g’(III). The parameter g’(III) is one of the indicators of the branching of the polymer based on the hydrodynamic radius. As the degree of branching is greater, g’(III) becomes smaller. When g’(III) ≤ 0.90, R is determined from the result of multiplying the value of g’(III) by (-27.7) and then adding 29.2, i.e., R = -27.7 × g’(III)+29.2. When g’(III) exceeds 0.90 and is 0.99 or less, R is 4.3.

[0038] [Number] is determined by the formula: g’(III) = ([η] / [η] * ) 1+α wherein [η] is the measured weight average (or bulk) intrinsic viscosity of the ethylene copolymer in units of dl / g; [η] *is the apparent weight average (or bulk) intrinsic viscosity of the linear copolymer of the same ethylene-α-olefin composition in units of dL / g.

[0039] α is the Mark Houwink exponent. For a linear polymer in an ideal solvent, α is 0.725. As used herein, to determine g`(III), 1 + α is 1.725.

[0040] In one embodiment, the copolymer of the present disclosure has a degree of branching corresponding to g’(III) of about 0.50 to 0.99. In another embodiment of the present disclosure, the copolymer has a degree of branching corresponding to g’(III) of 0.70 to 0.98. In another embodiment, the copolymer according to the present disclosure has a degree of branching corresponding to g’(III) of 0.75 to 0.95, or 0.80 to 0.97.

[0041] In another embodiment, the copolymer of the present disclosure, separately or in addition to this, has an MWD greater than 4.1. In one embodiment, the copolymer of the present disclosure has an MWD of 4.2 to 120, or 4.2 to 50 or 4.2 to 10. In one embodiment, the copolymer of the present disclosure has an MWD of at least 4.2 or at least 4.5, for example 4.0 to 9.5.

[0042] The copolymer according to the present disclosure has a Mooney viscosity ranging from 20 Mooney units (MU) at 100 °C with ML1+4 to 120 MU at 150 °C with ML1+8. In one embodiment, the copolymer according to the present disclosure has a Mooney viscosity of 56 to 120 at 150 °C with ML1+8. In one embodiment, the copolymer according to the present disclosure has a Mooney viscosity of 20 to 90 at 125 °C with ML1+4, or 20 to 90 at 100 °C with ML1+4.

[0043] The ethylene-α-olefin copolymer according to the present disclosure preferably has a weight average molecular weight (Mw) of at least 40,000 g / mol, particularly 40,000 to 800,000 g / mol.

[0044] Preferably, the ethylene-α-olefin copolymer according to the present disclosure branches with a Δδ between 2 and 50, more preferably between 5 and 35 or between 10 and 30. Δδ, expressed in degrees, is the difference between the phase angle δ at a frequency of 0.1 rad / s and the phase angle δ at a frequency of 100 rad / s, measured by dynamic mechanical spectroscopy (DMS) at 125°C. Thus, the branching parameter Δδ is one of the indicators of the branching of the polymer in the molten or fluid state.

[0045] Catalyst The copolymer according to the present disclosure can be obtained by polymerizing monomers in the presence of a first metal complex and a second metal complex. Preferably, the metal complexes are used in combination. However, the polymerization using these metal complexes can be carried out sequentially, for example, by first polymerizing in the presence of the first metal catalyst and subsequently in the presence of the second metal complex, or by carrying out the polymerization in the presence of the first metal complex, separately carrying out the polymerization in the presence of the second metal complex, and subsequently combining these separate reaction mixtures, for example, by obtaining a reactor blend.

[0046] First metal complex The first metal complex contains a metallocene catalyst, which is of formula (1): CyLMZ p (1), corresponding to where Cy is preferably a cyclopentadienyl ligand containing one or more substituents selected from the group consisting of a halogen and an aromatic or aliphatic, linear, branched or cyclic residue containing 1 to 20 carbon atoms; M is a Group 4 metal, Z is an anionic ligand, [[ID=2**]] p is 1 or 2, preferably 2, and L is a ligand according to formula (2):

Chemical formula

[0047] The ligand L is covalently bonded to the metal M via its imine nitrogen atom. Sub1 in formula (2) is a group 14 atom, preferably a substituent containing a carbon atom, that bonds Sub1 to the imine carbon atom. Sub2 in formula (2) is a group 15 heteroatom, preferably a substituent containing a nitrogen atom, that bonds Sub2 to the imine carbon atom. In a preferred embodiment, L is an aminidate.

[0048] To show the chemical structure of the first metal complex, the following metal complexes are specified by the chemical structure of formula (2a). Here, Cy is a pentamethylcyclopentadienyl ligand, M is titanium, p is 2, Z is both methyl (Me), and L is as per formula (2).

Chemical formula

[0049] Preferred embodiment of the first metal complex (catalyst A) M: In a preferred embodiment, M in formula (1) represents titanium (Ti), zirconium (Zr), or hafnium (Hf), more preferably titanium.

[0050] Z: In a preferred embodiment, Z is selected from the group consisting of a halogen, a C 1~10 alkyl group, a C 7~20 aralkyl group, a C 6~20 aryl group, or a C 1~20 hydrocarbon-substituted amino group. More preferably, Z is a halogen atom and a C 1~10It is selected from an alkyl group. Most preferably, Z is selected from the group consisting of Cl, F, Br, methyl, benzyl, methyltrimethylsilyl, phenyl, methoxyphenyl, dimethoxyphenyl, N,N-dimethylaminophenyl, bis-(N,N-dimethylamino)phenyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, perfluorophenyl, trialkylsilylphenyl, bis(trialkylsilyl)phenyl, and tris(trialkylsilyl)phenyl. Most preferably, Z is methyl or benzyl. When p is 2, Z may be the same or can be selected from combinations of the above residues. In a preferred embodiment, p is 2, both residues Z are the same, preferably both are methyl.

[0051] L: In a preferred embodiment, Sub1 of formula (2) is a substituted or unsubstituted C6-C 20 aryl residue or a substituted or unsubstituted C1-C 20 alkyl residue. Preferably Sub1 is selected from substituted or unsubstituted C6-C 20 aryl residues. Preferably, Sub1 is selected from phenyl, phenyl having at least one, preferably two substituents selected from halogen and alkyl, preferably methyl groups. Preferably Sub1 is selected from 2,6-dimethylphenyl, 2,6-dichlorophenyl, or 2,6-difluorophenyl. In another embodiment of the present disclosure, Sub1 of formula (2) represents a C1-C 20 alkyl residue. Typical examples of such alkyl residues include linear, branched, or cyclic alkyl residues having 1 to 20 carbon atoms. These alkyl residues may be unsubstituted or halogen, amide, silyl, or C6-C 20It may be substituted with a substituent selected from the group consisting of an aryl group and combinations thereof. In a preferred embodiment, Sub1 represents methyl, hexyl, cyclohexyl, isopropyl, tert-butyl, benzyl, trifluoromethyl, 2,6-dimethylbenzyl, 2,6-difluorobenzyl, or 2,6-dichlorobenzyl.

[0052] In a preferred embodiment, Sub2 of formula (2) is of the general formula -NR 4 R 5 wherein R 4 and R 5 are independently selected from the group consisting of aliphatic C1-C 20 hydrocarbyl, halogenated C1-C 20 aliphatic hydrocarbyl, aromatic C6-C 20 hydrocarbyl, and halogenated aromatic C6-C 20 hydrocarbyl residues, or R 4 optionally forms a heterocyclic ring together with R 5 or Sub1. In one embodiment, Sub2 is an aliphatic straight-chain residue. Preferred examples of Sub2 include, but are not limited to, dialkylamides, preferably dimethylamide, diethylamide, diisopropylamide, or piperidinyl.

[0053] Specific examples of L include N,N-dimethylacetimidamidinato, N,N-diisopropylacetimidamidinato, diisopropylacetimidamidinato, N,N-dicyclohexylacetimidamidinato, N-(2,6-dimethylphenyl)-N-ethylacetimidamidinato, N,N-dimethylisobutylimidamidinato, N,N-diisopropylisobutylimidamidinato, N,N-dicyclohexylisobutylimidamidinato, N-(2,6-dimethylphenyl)-N-ethylisobutylimidamidinato, N,N-dimethylcyclohexanecarboximidamidinato, N,N-diisopropylcyclohexanecarboximidamidinato, N,N-dicyclohexylcyclohexanecarboximidamidinato, N-(2,6-dimethylphenyl)-N-ethylcyclohexanecarboximidamidinato, N,N-dimethylpivalimidamidinato, N,N-diisopropylpivalimidamidinato, N,N-dicyclohexylpivalimidamidinato, N-(2,6-dimethylphenyl)-N-ethylpivalimidamidinato, 2,2,2-trifluoro-N,N-dimethylacetimidamidinato, 2,2,2-trifluoro-N,N-diisopropylacetimidamidinato, N,N-dicyclohexyl-2,2,2-trifluoroacetimidamidinato, N-(2,6-dimethylphenyl)-N-ethyl-2,2,2-trifluoroacetimidamidinato, 2-(phenyl)-N,N-dimethylacetimidamidinato, 2-(phenyl)-N,N-diisopropylacetimidamidinato, N,N-dicyclohexyl-2-(phenyl)acetimidamidinato, 2-(phenyl)-N-(2,6-dimethylphenyl)-N-ethylacetimidamidinato, 2-(2,6-dimethylphenyl)-N,N-dimethylacetimidamidinato, 2-(2,6-dimethylphenyl)-N,N-diisopropylacetimidamidinato, N,N-dicyclohexyl-2-(2,6-dimethylphenyl)acetimidamidinato, N,2-bis(2,6-dimethylphenyl)-N-ethylacetimidamidinato, 2-(2,6-difluorophenyl)-N,N-dimethylacetimidamidinato, 2-(2,6-Difluorophenyl)-N,N-diisopropylacetimidamidate, N,N-dicyclohexyl-2-(2,6-difluorophenyl)acetimidamidate, 2-(2,6-difluorophenyl)-N-(2,6-dimethylphenyl)-N-ethyl-acetimidamidate, N,N-dimethylbenzimidamidate, N,N-diisopropylbenzimidamidate, N,N-dicyclohexylbenzimidamidate, N-(2,6-dimethylphenyl)-N-ethylbenzimidamidate, N,N-dimethyl-1-naphthimidamidate, N,N-diisopropyl-1-naphthimidamidate, N,N-dicyclohexyl-1-naphthimidamidate, N-(2,6-dimethylphenyl)-N-ethyl-1-naphthimidamidate, N,N,2,6-tetramethylbenzimidamidate, N,N-diisopropyl-2,6-dimethylbenzimidamidate, N,N-dicyclohexyl-2,6-dimethylbenzimidamidate, N-(2,6-dimethylphenyl)-N-ethyl-2,6-dimethylbenzimidamidate, 2,6-difluoro-N,N-dimethylbenzimidamidate, 2,6-difluoro-N,N-diisopropyl-benzimidamidate, N,N-dicyclohexyl-2,6-difluorobenzimidamidate, N-(2,6-dimethylphenyl)-N-ethyl-2,6-difluorobenzimidamidate, 2,6-dichloro-N,N-dimethylbenzimidamidate, 2,6-dichloro-N,N-diisopropylbenzimidamidate, 2,6-dichloro-N,N-dicyclohexylbenzimidamidate, 2,6-dichloro-N-(2,6-dimethylphenyl)-N-ethylbenzimidamidate are mentioned, but are not limited thereto. Preferred examples are 2,6-difluoro-N,N-piperidinylbenzimidamidate, 2,4-difluoro-N,N-diisopropylbenz-imidamidate, 2,4,6-trifluoro-N,N-diisopropylbenz-imidamidate, 3,5-difluoro-N,N-diisopropylbenzimidamidate, pentafluoro-N,N-diisopropylbenz-imidamidate, 2,6-difluoro-N,N - Diisopropylbenz - imidamidinate, and N,N - Diisopropylbenzimidamidinate.,

[0054] According to another preferred embodiment of the present disclosure, L is of the general formula (2b):

Chemical formula

[0055] Sub3 in formula (2b) represents an aliphatic or aromatic cyclic or linear substituent containing a Group 14 atom that binds Sub3 to the amine nitrogen atom N 1 .

[0056] In a preferred embodiment of the present disclosure, Sub3 is independently selected from alkyl, alkenyl, and alkynyl residues having 1 to 20 carbon atoms, or aromatic residues having 6 to 20 carbon atoms. In each case, the residue may be unsubstituted or substituted with a halogen, amide, silyl, or aryl group. Examples of Sub3 include, but are not limited to, methyl, n - propyl, i - propyl, tert - butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, cyclododecyl, octadecyl, adamantyl, 1 - butenyl, 2 - butenyl, propenyl, unsubstituted phenyl, or substituted phenyl. Preferably, Sub3 represents phenyl, naphthyl, 2,6 - dimethylphenyl, 2,6 - dichlorophenyl, or 2,6 - difluorophenyl.

[0057] Sub4 in formula (2b) has two carbon atoms with sp 2 or sp 3It may be a C2 unit that is hybridized. Optionally, the C2 unit is substituted by one or more halogen atoms or by one or more C1-C 10 alkyl group or C1-C 10 alkoxy group.

[0058] In another preferred embodiment of the present disclosure, L is of general formula 2c)

Chemical formula

[0059] In another embodiment of the present disclosure, L is of general formula 2d):

Chemical formula

[0060] In a preferred embodiment of the present disclosure, L corresponds to general form 2c) in which each of R1 to R4 represents a hydrogen atom, or L corresponds to general formula 2d) in which each of R5 to R8 represents a hydrogen atom, or R5 is a fluorine atom. According to this preferred embodiment, Sub3 is selected from methyl, n-propyl, i-propyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, cyclododecyl, octadecyl, adamantyl, 1-butenyl, 2-butenyl, propenyl, phenyl, naphthyl, 2,6-dimethylphenyl, 2,6-dichlorophenyl, or 2,6-difluorophenyl, and t is 1.

[0061] Cy: Cy is a substituted cyclopentadienyl ligand. This ligand can contain one or more substituents. Typically, the 5-membered carbon ring of this ligand is usually bonded to the metal by a π-type bond in the adoption of η 5 -coordination. The substituents are preferably selected from the group consisting of a halogen and an aromatic or aliphatic, linear or branched or cyclic residue containing 1 to 20 carbon atoms.

[0062] In one embodiment, the cyclopentadienyl ligand may be substituted with at least one cyclic group. In one embodiment, the cyclopentadienyl ligand is substituted with a cyclic substituent to form, for example, an indenyl ligand. This indenyl ligand is, for example, selected from the group consisting of a halogen and an aliphatic, linear or branched or cyclic residue selected from the group consisting of an aromatic containing 1 to 20 carbon atoms, and may or may not be substituted with a substituent selected from the group consisting of a cyclic residue.

[0063] In one embodiment, the cyclopentadienyl ligand is substituted with at least one heterocyclic substituent, preferably an S heterocyclic substituent, and has the formula (2e):

Chemical formula

[0064] In a preferred embodiment, Cy is a cyclopentadienyl ligand substituted with at least three methyl groups. This means that three hydrogens of the ring are substituted with methyl groups, in other words, this ligand can have three methyl groups. Cy can additionally or alternatively have substituents R 1 and R 2 .

[0065] R 1preferably means a halogen, especially F, Cl, and Br, or an aromatic or aliphatic, straight-chain or branched residue having from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms, or from 1 to 6 carbon atoms or from 1 to 3 carbon atoms. These residues may be unsubstituted or substituted hydrocarbon residues. Preferably the residue is unsubstituted. Examples of unsubstituted hydrocarbon residues include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-pentyl, sec-pentyl, tert-pentyl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenylcyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, isopropyldodecyl, adamantyl, norbornyl, tricyclo[5.2.1.0]decyl, or aryl groups such as phenyl, benzyl, methylphenyl, trimethylphenyl, cyclohexylphenyl, naphthyl, butylphenyl, and butyldimethylphenyl, but are not limited thereto.

[0066] Typical examples of substituents in the substituted residues include heteroatom-containing hydrocarbon residues, halogens, especially F, Cl, and Br, and halogen-containing hydrocarbons. Heteroatom-containing hydrocarbons typically contain elements of group 15 or 16, such as N, P, O, and S. Specific examples include fluorophenyl, trifluoromethylphenyl, and fluoromethyl, difluoromethyl, and trifluoromethyl, N,N-dimethylaminobenzyl, N,N-dimethylaminomethyl, methoxymethyl, diphenylphosphinomethyl, aminoethyl, and sulfur heterocycles. Preferably, R 1 is unsubstituted or fluorine-substituted, more preferably, R 1 is methyl.

[0067] R 2preferably represents a substituted or unsubstituted hydrocarbon residue containing 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Such hydrocarbon residues include aliphatic linear or branched hydrocarbon groups, such as methyl, ethyl, n-propyl, allyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-pentyl, sec-pentyl, tert-pentyl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenylcyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, isopropyldodecyl, adamantyl, norbornyl, tricyclo[5.2.1.0]decyl. Examples of linear or branched aromatic hydrocarbon groups include, for example, phenyl, benzyl, methylphenyl, trimethylphenyl, cyclohexylphenyl, naphthyl, butylphenyl, or butyldimethylphenyl. In one embodiment, R 2 is methyl. This residue may be substituted. Examples of substituents include halogen, especially F, Cl, and Br. Specific examples include fluorophenyl, trifluoromethylphenyl, and fluoromethyl, difluoromethyl, and trifluoromethyl. Substituents also include heteroatom-containing hydrocarbons, and these heteroatoms are elements of groups 15 and 16, such as nitrogen, phosphorus, oxygen, and sulfur. Specific examples of heteroatom-containing substituents include, but are not limited to, N,N-dimethylaminobenzyl, N,N-dimethylaminomethyl, methoxymethyl, diphenylphosphinomethyl, cyanoethyl, and sulfur heterocycles. Preferably, R 2 is unsubstituted.

[0068] In a preferred embodiment, R 1 is an unsubstituted hydrocarbon residue containing 1 to 10 carbon atoms, and R 2 represents a methyl group. In a more preferred embodiment, R 2 is methyl, and R 1is a C1-C6 hydrocarbon group or fluorophenyl. Most preferably, R 1 and R 2 are both methyl.

[0069] In a preferred embodiment, Cy is an indenyl ligand, preferably this indenyl ligand is unsubstituted. In another preferred embodiment, Cy is a cyclopentadienyl ligand. Preferably, this cyclopentadienyl ligand is substituted and contains the aforementioned residues R 1 and R 2 . Preferably, Cy contains the aforementioned residues R 1 and R 2 and in addition contains a cyclopentadienyl ligand with three methyl groups. In a more preferred embodiment, Cy is a cyclopentadienyl ligand containing three methyl groups and where R 1 and R 2 are also methyl groups.

[0070] In a preferred embodiment of the present disclosure, the first metal complex corresponds to formula (1), where M is Ti, Z is selected from the group consisting of chlorine, preferably C1-C4-alkyl, more preferably methyl, p is 2, Cy is a cyclopentadienyl or indenyl ligand, preferably a cyclopentadienyl preferably substituted with a fluorophenyl group or with four methyl groups one of which is due to R 2 , and R 1 is selected from hydrogen and C1-C3 aliphatic groups, preferably methyl, L is selected from the group consisting of N,N-dialkylarylamidinates, preferably selected from N,N-diisopropylbenzamidinates, 2,6-difluoro-N,N-diisopropylbenzamidinates, 2,6-difluoro-N,N-piperidinylbenzamidinates.

[0071] Particularly preferred examples of the first metal complex according to formula (1) include ((CH3)5Cp-Ti-(CH3)2)(NC(Ph)(NC5H 10 ), Ind-Ti-(Cl2)(NC(Ph)(NC5H 10 N), Cp-Ti-Cl2(NC(Ph)(iPr2N), ((CH3)5Cp-Ti-(CH3)2)(NC(2,6-C6H3Cl2)(N((CH(CH3)2)2, ((C4H9)Cp-Ti-(CH3)2)(NC(2,6-C6H3F2)(N((CH(CH3)2)2, ((C6F5)Cp-Ti-(CH3)2)(NC(2,6-C6H3F2)(N((CH(CH3)2)2, Ind-Ti-(CH3)2)(NC(2,6-C6H3F2)(N((CH(CH3)2)2, ((CH3)5Cp-Ti-(CH3)2)(NC(2,6-C6H3F2)(N((CH(CH3)2)2.

[0072] In the above formula, "Cp" means cyclopentadienyl, "Ph" means phenyl, "Ind" means indenyl, and "iPr" means isopropyl.

[0073] Second metal complex The second metal complex includes a bridged Group 4 transition metal metallocene catalyst having two indenyl ligands, and is also referred to herein as a "bisindenyl metal complex". Such a metal complex is also referred to herein as a bisindenyl metallocene compound. The two indenyl ligands may both be unsubstituted, or both may be substituted, or one may be substituted and the other may not be substituted. Preferably, both indenyl ligands are the same.

[0074] The second metal catalyst is represented by formula (3): J-Ind2-MX2(3) and can be represented by.

[0075] In formula (3), J represents a divalent bridging group. The bridging group preferably connects two indenyl ligands by a C atom or an Si atom of the bridging group. Preferably, the bridging group is bonded to carbon atoms from each of the two 5-membered rings of the indenyl ligand. The bridging group may be a straight-chain or branched hydrocarbon group, or a straight-chain or branched hydrocarbon group containing one or more heteroatoms, such as one or more Si atoms, oxygen atoms, or combinations thereof.

[0076] M is a Group 4 transition metal (e.g., titanium, hafnium, or zirconium, preferably zirconium).

[0077] Each X is independently a monovalent anionic ligand, or two X's are linked to bond to a metal atom to form a metallacycle ring, or two X's are linked to form a chelate ligand, a diene ligand, or an alkylidene ligand. Each X is independently selected from the group consisting of a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, dienes, amines, phosphines, ethers, and combinations thereof. Two X's may form part of a fused ring or a ring structure. In certain embodiments, each X is independently selected from halides and C1-C5 alkyl groups. For example, each X may be chloro, bromo, methyl, ethyl, propyl, butyl, or pentyl group.

[0078] In a preferred embodiment, each X is independently selected from the group consisting of halogen, C 1~10 alkyl group, C 7~20 aralkyl group, C 6~20 aryl group, C 1~20 hydrocarbon-substituted amino group. In a preferred embodiment, each X is a methyl group.

[0079] Ind2 represents two indenyl ligands that are bonded to metal M and further linked to each other via a bonding group J. The indenyl ligand may be substituted or unsubstituted, preferably unsubstituted.

[0080] In the perspective view, the second metal catalyst has the formula (3’): [Chemical formula] It can be represented by

[0081] In formula (3’), J, M, and X have the same meaning and preference as described above for formula (3). Each R of the two indenyl ligands 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently selected from hydrogen, C1-C 20 substituted or unsubstituted hydrocarbyl. In a preferred embodiment, each R of each indenyl ligand 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is hydrogen, that is, the indenyl ligand is unsubstituted.

[0082] In one embodiment, J is a cyclic unit. In such an embodiment, J is represented by the formula (R a 2J’) n , where each J’ is independently C or Si (J’ is preferably Si), n is 1 or 2, and each R a is independently a C1-C 20 substituted or unsubstituted hydrocarbyl, provided that two or more R a are linked to each other to form a saturated or partially saturated or aromatic cyclic or fused ring structure containing at least one J’. R aSpecific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenylcyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, isopropyldodecyl, adamantyl, norbornyl, tricyclo[5.2.1.0]decyl. These groups may be aromatic, and aryl groups can also be cited as such. Specific examples of aryl groups include phenyl, benzyl, methylphenyl, trimethylphenyl, cyclohexylphenyl, naphthyl, butylphenyl, and butyldimethylphenyl. Substituents include halogen, especially F, Cl, and Br. R substituted with (halogen) a Specific examples of the group include, but are not limited to, fluorophenyl and trifluoromethylphenyl. Specific examples of heteroatom-containing substituents include, for example, N,N-dimethylaminobenzyl, diphenylphosphinomethyl, and sulfur heterocycles.

[0083] Specific examples of J when J' is silicon include cyclopentamethylenesilylene, cyclotetramethylenesilylene, cyclotrimethylenesilylene, etc. Specific examples of the J group when J' is carbon include cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, etc. Such metal complexes having a cyclic bridging group are described, for example, in International Publication No. WO 2016 / 114914 A1 pamphlet in which it is reported that vinyl-terminal chain ends are formed. However, as another advantage of the present disclosure, the formation of vinyl-terminal chain ends is not necessary for the production of the polymers according to the present disclosure. This increases the degree of freedom in the types of chain transfer agents that can be used for polymer production and molecular weight control.

[0084] In a preferred embodiment, the bridging group J is a linear or branched unit, but not a cyclic unit. In such an embodiment, J is represented by the formula R b 2J', where each R bis independently selected from hydrogen, and C1-C9 linear or branched hydrocarbyl which may be unsubstituted or substituted. Unsubstituted R b Examples include, but are not limited to, methyl, ethyl, n-propyl, allyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-pentyl, sec-pentyl, tert-pentyl, heptyl, octyl, nonyl, decyl. The hydrocarbyl may be substituted, for example, with one or more halogens, particularly F, Cl, and Br. Specific examples include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, and combinations thereof. Substituents also include hydrocarbon substituents containing one or more heteroatoms selected from Group 15 and 16 elements such as nitrogen, phosphorus, oxygen, and sulfur. Specific examples of such substituents include, for example, N,N-dimethylaminomethyl, methoxymethyl, cyanoethyl, and combinations thereof.

[0085] J’ is C or Si, preferably Si. More preferably J is selected from (H3C)2Si, (H5C2)2Si, (H7C3)2Si, H2C, H3CHC, (H3C)2C, (H5C2)2Si, (H7C3)2Si, and most preferably J is (H3C)2Si.

[0086] In a preferred embodiment, both X are C1-C 10Selected from alkyl groups, more preferably both X are the same, and most preferably both X are methyl. In this preferred embodiment, M is selected from zirconium, and each indenyl ligand contains 1 to 7 alkyl substituents having 1 to 3 carbon atoms, and more preferably each indenyl ligand is unsubstituted. In this preferred embodiment, J is linear or branched but not cyclic, and more preferably J is selected from (H3C)2Si, (H5C2)2Si, (H7C3)2Si, H2C, H3CHC, (H3C)2C, (H5C2)2Si, (H7C3)2Si, and most preferably J is (H3C)2Si.

[0087] The catalyst compound may be of the rac type or the meso type.

[0088] Catalyst composition Preferably, the first and second metal complexes are used in combination. These can be used as a catalyst composition containing both the first and second metal complexes. Alternatively, the first and second metal complexes may not be used in the same composition and can be used as separate compositions. Preferably, the first and second metal complexes are combined to form one catalyst composition containing them.

[0089] The ratio of the first metal complex to the second metal complex may be adjusted so that the Group 4 metal of the first metal complex is at a certain molar ratio to the Group 4 metal of the second catalyst complex. Preferably, the molar ratio of the Group 4 metal of the first metal complex to the Group 4 metal of the second metal complex is 1:0.1 to 1:100, particularly 1:0.2 to 1:80, and more preferably 1:0.5 to 1:10. In a preferred embodiment of the present disclosure, the catalyst mixture contains the first and second metal complexes in an amount such that the molar ratio of the Group 4 metal of the first metal complex to the Group 4 metal of the second catalyst complex is about 1:1 to 1:3.

[0090] The catalyst composition can also contain additional catalysts. Preferably, the catalyst mixture according to the present disclosure contains more than 95% by weight, particularly more than 99% by weight, of the first metal complex and the second metal complex based on the total weight of the catalyst mixture.

[0091] One or more activators (b) and optionally one or more scavengers (c) can be used in the catalyst composition, or they can be added separately, for example, before or together with the supply of the monomer to the catalyst mixture.

[0092] Activators (b) for single-site catalysts well known in the art can be used. The activator often contains group 13 atoms such as boron or aluminum.

[0093] In a preferred embodiment, the activator (b) is selected from borane (C1), borate (C2 or C3). Preferably, a combination of one or more activators by C1, C2, and C3 is used in combination with one or more scavengers by (c).

[0094] Suitable boron activators (C1) can be represented by the general formula BQ1Q2Q3.

[0095] Suitable borate activators by (C2) can be represented by the general formula G(BQ1Q2Q3Q4).

[0096] Suitable borate activators by (C3) can be represented by the general formula (J-H)(BQ1Q2Q3Q4).

[0097] In the activator by (C1), B is boron, and Q1 to Q3 are substituted or unsubstituted aryl groups, preferably phenyl groups. Suitable substituents include halogen, preferably fluoride, and C1-C 40 hydrocarbyl, preferably C1-C 20Examples include, but are not limited to, alkyl or aromatic groups. Specific examples of the activator according to (C1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenyl-bis(pentafluorophenyl)borane, etc., and tris(pentafluorophenyl)borane is most preferred.

[0098] In the activator according to (C2), G is an inorganic or organic cation, B is boron, Q1 to Q3 are the same as those in (C1), and Q4 is also a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl. Substituents include halogen, preferably fluoride, and C1-C 40 hydrocarbyl, preferably C1-C 20 Examples include, but are not limited to, alkyl or aromatic groups. Specific examples of the borate group (BQ1Q2Q3Q4) include tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluorophenyl)borate, tetrakis(3,5-bistrifluoromethylphenyl)borate, etc., but are not limited thereto. Specific examples of G include ferrocenium cation, alkyl-substituted ferrocenium cation, silver cation, etc. Specific examples of the organic cation G include triphenylmethyl cation, etc. G is preferably a carbenium cation, particularly preferably triphenylmethyl cation.

[0099] In the activator according to (C3), J represents a neutral Lewis base, (J-H) represents a Brønsted acid, B is boron, and both Q1 to Q4 and the borate group (BQ1Q2Q3Q4) are the same as those in (C2). Specific examples of the Brønsted acid (J-H) include trialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium, and triarylphosphonium. Specific examples of the activator according to (C3) include triethylammonium tetrakis(pentafluorophenyl)-borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium-tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bistrifluoromethyl-phenyl)borate, N,N-dimethyl-anilinium tetrakis(pentafluoro-phenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium-tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium-tetrakis(3,5-bistrifluoromethyl-phenyl)borate, diisopropyl-ammonium tetrakis(pentafluorophenyl)borate, dicyclohexyl-ammonium tetrakis-(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(dimethylphenyl)-phosphonium-tetrakis(pentafluorophenyl)borate, etc., but are not limited thereto, and tri(n-butyl)ammonium-tetrakis(pentafluorophenyl)borate or N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate is most preferred.

[0100] Preferably, the boron-containing activator is selected from the activators according to (C2), more preferably triphenylmethyltetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyltetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyltetrakis(3,4,5-trifluorophenyl)borate, triphenylmethyl-tetrakis(2,3,4-trifluorophenyl)borate, triphenylmethylphenyltris(pentafluorophenyl)borate, and triphenyl-methyl-tetrakis(3,5-bistrifluoromethylphenyl)borate. Most preferably, the activator contains triphenyl-methyltetrakis(pentafluorophenyl)borate.

[0101] The scavenger (c) is a compound that reacts with impurities that are toxic to the catalyst and can thus extend the life of the catalyst.

[0102] In another preferred embodiment of the present disclosure, the scavenger (c) is the reaction product thereof with a hydrocarbyl of a metal or metalloid of Groups 1 to 13 or at least one sterically hindered compound containing an atom of Group 15 or 16. Preferably, the Group 15 or 16 atom of the sterically hindered compound has a proton. Specific examples include butyllithium, dihydrocarbylmagnesium, and hydrocarbylzinc, including their isomers, and their reaction products with sterically hindered compounds or acids such as HF, HCl, and HBr.

[0103] In another preferred embodiment, examples of the scavenger (c) include one or more organoaluminum compounds (E). The organoaluminum compounds according to (E) can also function as activators, but these are referred to as scavengers in the present specification.

[0104] Suitable organic aluminum-based scavengers (E) include compounds having a carbon-aluminum bond. Examples of suitable scavengers by (E) preferably include organoaluminum by (E1) to (E4).

[0105] The scavenger by (E1) is an organoaluminum compound represented by the general formula T 1 a AlZ 3-a .

[0106] The scavenger by (E2) is a cyclic aluminoxane having a structure represented by the general formula {-Al(T 2 )-O-} b .

[0107] The scavenger by (E3) is a linear aluminoxane represented by the general formula T 3 {-Al(T 3 )-O-} c AlT 3 2.

[0108] The scavenger by (E4) is an alkylaluminoxane, preferably methylaluminoxane (MAO).

[0109] In the above formula, each of T 1 , T 2 , and T 3 is a hydrocarbon group, and each T 1 , T 2 , and T 3 may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. "a" represents a number satisfying 0 < a ≤ 3, "b" is an integer of 2 or more, and "c" is an integer of 1 or more.

[0110] The hydrocarbon group in (E1), (E2), or (E3) is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group.

[0111] Specific examples of the organoaluminum compound according to (E1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, etc.; dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, etc.; alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, etc.; dialkylaluminum hydride such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, etc. Trialkylaluminum is preferred, and triethylaluminum, triisobutylaluminum, and trioctylaluminum (TOA) are most preferred.

[0112] Specific examples of the cyclic or linear aluminoxane according to (E2) and (E3) include T 2 and T 3 which are, independently of each other, an alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, neopentyl group, etc., b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, T 2 and T 3 represent a methyl group or an isobutyl group, and b is from 2 to 40, and c is from 1 to 40. Specific examples of (E4) include, but are not limited to, methylaluminoxane (MAO).

[0113] In a preferred embodiment of the present disclosure, a combination of at least one activator by C1, C2, or C3 and at least one scavenger by (E) is used for polymerization. Preferred scavengers by (E) include scavengers of (E1) and MAO. Preferably, at least one another scavenger by (E) is used in combination with a sterically hindered hydrocarbon containing a heteroatom of Group 15 or 16 (preferably atoms of O, N, P, and S, more preferably heteroatoms of O and N), preferably a sterically hindered phenol. Specific examples of the sterically hindered hydrocarbon include, but are not limited to, tert-butanol, isopropanol, triphenylcarbinol, 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butylaniline, 4-methyl-2,6-di-tert-butylaniline, 4-ethyl-2,6-di-tert-butylaniline, diisopropylamine, di-tert-butylamine, diphenylamine, and the like.

[0114] Preferred combinations include triphenylcarbenium tetrakis-perfluorophenylborate triisobutylaluminum, 4-methyl-2,6-tert-butylphenol.

[0115] The molar ratio of the first and second metal complexes used: scavenger is preferably in the range of 0.1:1000 to 0.1:10, more preferably in the range of 0.1:1000 to 0.1:300, and most preferably in the range of 0.1:500 to 1:100.

[0116] The molar ratio of the activator used to the first and second metal complexes is preferably in the range of 5:1 to 1:1.

[0117] Polymerization method The copolymer according to the present disclosure is ethylene and at least one C 3~ C 20It can be prepared by a method comprising copolymerization of an α-olefin, at least one non-conjugated diene, and at least one double-bonded diene monomer in the presence of the aforementioned first and second metal complexes.

[0118] The polymerization can be carried out in the gas phase, in slurry, or in solution in an inert solvent, preferably a hydrocarbon solvent.

[0119] This polymerization can be carried out in various polymerization zones. A polymerization zone is a vessel in which the polymerization is carried out and can be either a batch reactor or a continuous reactor. When multiple reactors are used (e.g., multiple reactors connected in series or parallel), each reactor is regarded as a separate polymerization zone.

[0120] The first and second metal complexes can be premixed with an activator or can be mixed within the polymerization zone. Similarly, the first and second metal complexes can be premixed and fed together into the polymerization zone or can be added separately for in-situ mixing. Thus, the addition and mixing can be continuous or in a batch mode, and the same or different activators can be used for each catalyst system.

[0121] Preferred solvents include one or more hydrocarbon solvents. Suitable solvents include C 5~12 hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, pentamethylheptane, hydrogenated naphtha, their isomers, and mixtures thereof. The polymerization can be carried out at a temperature of 10 to 250 °C depending on the product formed. Most preferably, when the polymerization is carried out in solution, it is carried out at a temperature above 50 °C.

[0122] In a preferred embodiment, the polymerization includes the use of one or more chain transfer agents to control the molecular weight of the polymer. A preferred chain transfer agent is hydrogen (H2).

[0123] Compound polymer composition The copolymers provided herein can be cured (crosslinked) in the presence of a curing agent. That is, the copolymers are curable.

[0124] In another embodiment of the present disclosure, the polymer composition produced herein further comprises one or more additional polymers and / or additives, thereby forming a compounded polymer composition. For example, the processes of various embodiments can further include blending an ethylene copolymer according to the present disclosure with one or more additional polymer components and / or additives. Generally, any additional polymer components and / or any additives or other additional components suitable for conventional EP or EPDM formulations will be suitable for compounding. Suitable additives include those well-known in the art of elastomer formulations such as EPDM formulations. Examples of additives include: extender oils; plasticizers; processing aids such as fatty acids, waxes, etc.; antioxidants (such as hindered phenols such as those commercially available under the trade names IRGANOX 1010 or IRGANOX 1076); phosphites (such as those commercially available under the trade name IRGAFOS 168); curing agents or crosslinking agents (either or both curing agents and aids such as zinc oxide, peroxides, phenolic resins, etc.); fillers (such as carbon black, calcium carbonate, clay, silica, etc.); antiozonants; scorch inhibitors; non-stick additives; tackifiers (such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, stearates of alkali metals and glycerol, and hydrogenated rosin, etc.); UV stabilizers; heat stabilizers; antiblocking agents; release agents; antistatic agents; pigments; colorants; dyes; talc; and any one or more of other additives well-known in the art, but not limited thereto. "Extender oil" means a compound containing carbon and hydrogen and being liquid at 25°C. Examples of extender oils include various paraffins and paraffin blends, de-aromaticated aliphatic hydrocarbons, high-purity hydrocarbon fluids, polyalphaolefins, polybutene, mineral oils, etc. The above compounds may be curable. The above compounds can also be cured, i.e., they contain one or more curing agents and a curing reaction may be taking place.

[0125] Use The ethylene copolymers (including their compounds) according to the present disclosure can be used in various end - uses including any use suitable for EP or EPDM copolymers. The ethylene copolymers (including their compounds) according to the present disclosure can be particularly suitable for extrusion molding and can be extruded into one or more dies, particularly for manufacturing extruded articles.

Examples

[0126] Test Methods Composition of Comonomers Regarding the C2 / C3 ratio, in accordance with ASTM D3900 (revision date 2017), and regarding the diene content of the pressed polymer film, in accordance with ASTM D6047 (revision date 2017), the composition of the copolymer was determined using Fourier transform infrared spectroscopy (FT - IR).

[0127] Phase Angle Measurement The branching of the polymer was determined by measuring the phase angle with a Montech MDR 3000 moving die rheometer using the parameter Δδ. Δδ (expressed in degrees) is the difference between the phase angle δ measured at a frequency of 0.1 rad / s by dynamic mechanical analysis (DMA) at 125 °C and the phase angle δ measured at a frequency of 100 rad / s. Δδ is one measure of the presence of long - chain branches in the polymer structure. The smaller the value of Δδ, the more long - chain branches are present in the polymer, as introduced by H.C. Booij in Kautschuk + Gummi Kunststoffe, Vol. 44, No. 2, pages 128 - 130, 1991, which is incorporated herein by reference.

[0128] Size Exclusion Chromatography with Differential Viscosity Measurement (SEC - DV) The molecular weight distribution (MWD) and intrinsic viscosity for determining the branching degree g’(III) were determined by gel permeation size exclusion chromatography (GPC / SEC-DV) using differential viscometry with Polymer Char GPC from Polymer Characterization S.A, Valencia, Spain. An online viscometer (Polymer Char V-400 viscometer), an online infrared detector (IR5 MCT), three AGILENT PL OLEXIS columns (7.5×300 mm), and a Polymer Char autosampler were attached to the size exclusion chromatograph. Universal calibration of the system was performed using polyethylene (PE) standards.

[0129] The polymer sample was weighed into a vial of the PolymerChar autosampler (at a concentration in the range of 0.3 - 1.3 mg / ml). In the autosampler, the vial was automatically filled with a solvent (1,2,4-trichlorobenzene) stabilized with 1 g / l of di-tert-butylparacresol (DBPC). The sample was maintained in a high-temperature oven (160 °C) for 4 hours. After this dissolution time, the sample was automatically filtered through an in-line filter before being injected onto the column. This chromatographic system was operated at 160 °C. The flow rate of the 1,2,4-trichlorobenzene eluent was 1.0 mL / min. This chromatograph was equipped with a built-in online infrared detector (IR5 MCT) for concentration and a built-in PolymerChar online viscometer.

[0130] To determine the branching degree g’(III), the weight-average intrinsic viscosity [η] of the ethylene copolymer was determined by size exclusion chromatography (SEC-DV) using differential viscometry.

[0131] For the α-olefins of the ethylene copolymers tested, the viscosity of the linear polyethylene-based polymer was corrected according to the principles developed in Th.G.Scholte, N.L.J.Meijerink, H.M.Schoffeleers, A.M.G.Brands, J.of Appl.Pol.Sci., Vol,29, 3763-3782(1984), and International Patent Application Publication No. 99 / 00434A1 of Evens et al. (both are incorporated herein by reference), to obtain the apparent weight average viscosity [η] of the linear reference copolymer having the same ethylene-α-olefin composition. * The degree of branching was determined by the Mark-Houwink equation giving the relationship between the molecular weight (M) and the intrinsic viscosity [η] of the copolymer: [η]=KM a where K and a are Mark-Houwing parameters, which are determined depending on the individual polymer-solvent system. For a pure copolymer without long-chain branching, the relationship between log(η) and log(M) is represented by a linear relationship. Long-chain branching causes a deviation from the linear relationship between log(η) and log(M). As the degree of branching increases, the linearity of the relationship between log(η) and log(M) decreases. The molecular weight distribution (MWD) and the degree of branching of the elastomeric copolymer can be determined using a combination of size exclusion chromatography and differential viscosity measurement (SEC-DV). According to universal calibration, the main log([η i ×M i ) vs. retention volume = constant ([η i represents the intrinsic viscosity, M i is the molecular weight, and "i" is the i-th elution fraction in the SEC-DV chromatogram).

[0132] Comparing the experimental Mark-Houwink equation with the Mark-Houwink equation of the linear polymer used as a reference gives information about the degree of branching. Branching is understood to be a branch in a polymer chain that is longer than a branch resulting from the incorporation of one molecule of an α-olefin or polyene.

[0133] The reference Mark Houwink equation depends on the average ethylene / α-olefin composition of the polymer. According to Th.G.Scholte, N.L.J.Meijerink, H.M.Schoffeleers, A.M.G.Brands, J.of Appl.Pol.Sci., Vol,29, 3763 - 3782(1984), which is incorporated herein by reference, for the Mark-Houwink equation of linear ethylene-propylene (EP) reference copolymers: [η] * =(1 - 1 / 3W3) (l+α) K PE (Mv * ) a is maintained, where: [η] * is the apparent weight average intrinsic viscosity (in dl / g) of a linear copolymer having an ethylene / α-olefin composition corresponding to that of the ethylene copolymer tested; K PE is the Mark-Houwink constant of linear polyethylene (PE); a is the Mark-Houwink constant of a linear polyolefin copolymer; Mv * is:

Number

[0134] K PE and a are determined experimentally for the solvent and temperature used in SEC-DV (K PE is 4.06×10 measured in 1,2,4-trichlorobenzene at 135°C, -4 and a is 0.725 measured in 1,2,4-trichlorobenzene at 135°C). Mv* is determined from linear PE reference polymers of the same molecular weight.

[0135] In the case of an ethylene copolymer having propylene as an α-olefin, W3 is the weight fraction of propylene. W3 is calculated by the formula: W3 = C3 / (C3 + C2), where C2 and C3 represent the ethylene content and propylene content (in units of mass%) of the ethylene copolymer, respectively. The amounts of the diene monomer and non-conjugated diene monomer are small, and their presence is * ignored with respect to the determination of [η]. If there are also other α-olefin units, their amounts are also ignored, and the calculation is based on the propylene content as described above. In the case of an ethylene copolymer having an α-olefin copolymer other than propylene and no propylene, the value of [η] * is corrected according to the guidelines shown in the aforementioned paper by Th.G. Scholte et al. cited above.

[0136] Mooney viscosity The Mooney viscosity of the copolymer sample was measured in accordance with ISO 289 with the revision date of 2015 using a biaxially stretched PP (thickness 20 μm) film provided by Perfon. The measurement conditions were ML(1 + 4) at 125 °C.

[0137] The Mooney viscosity of the compound (measurement conditions of ML(1 + 4) at 100 °C) was measured in accordance with DIN 53523-3 (using NatureFlex NP / 28 μm, manufactured by Putz Folien, D-65232 Taunusstein Wehen).

[0138] Strength ratio (D) 13 The strength ratio was determined by 13C NMR. The copolymer sample was dissolved in C2D2Cl4 at 100 °C, and DBPC (di-tert-butylparacresol) was added as a stabilizer. On a Bruker Avance spectrometer operating at 500 MHz ( 13 125 MHz in the case of 13C) equipped with a 10 mm probe head heated to 100 °C 1313C NMR spectra were recorded using a standard PowerGate® decoupling pulse sequence with a relaxation delay of 20 s and a total of 512 scans. The data were processed using Bruker TopSpin 3 with a line broadening of 1 Hz for Fourier transformation. The intensity ratio D was calculated from the ratio of the peak intensities of the CH2-groups (Sαα) in the immediate vicinity of two tertiary carbon atoms and the CH2-groups (Sαβ) in the immediate vicinity of one tertiary and one secondary atom. C3~C 20 In the case of propylene as the α-olefin, the signal of the carbon atom Sαβ was the sum of the resonances at 34.7 ppm and 35.6 ppm. The signal of the carbon atom Sαα was at 42 - 48 ppm. Since signals from some dienes may appear in this region, correction of the signals from such dienes was carried out. Dividing the area (integration) of the signal of the carbon atom Sαβ by the area (integration) of the signal of the carbon atom Sαα gives the so-called intensity ratio D. The calculation was performed using integrals corrected for the baseline, and the baseline correction was done manually around the region of interest.

[0139] Cat A The first catalyst (Cat A) has the general formula ((CH3)5Cp-Ti-(CH3)2)(NC(2,6-C6H3F2)(N((CH(CH3)2)2 or is an amidinato titanium complex abbreviated as Me5CpTiMe2(NC(2,6-F2Ph)( i Pr2N), where "Me" represents "methyl" and i Pr represents "isopropyl". The catalyst was prepared as described for compound 10M in WO 2005 / 090418 A1 (incorporated herein by reference).

[0140] A solution of methylmagnesium bromide (16.5 mL, 3.0 M solution in diethyl ether, 49.5 mmol) was added to a solution of Me5CpTiCl2(NC(2,6-F2Ph)(iPr2N) (12.18 g, 24.7 mmol) in toluene (100 mL) at -78 °C. The reaction mixture was stirred at room temperature for 18 h. The reaction mixture was filtered and the solvent was removed from the filtrate under reduced pressure. Hexane (100 mL) was added to the residue and triturated to give 10.9 g of the pure product as a yellow powder (97%). These crystals were 1 1H NMR (300 MHz) (CDCI3) δ (ppm): 7.8 (d pent, 1H), 7.0 (dd, 2H), 4.0 (bs, 1H) 3,8 (sept, 1H), 1.9 (s, 15H), 1.8 (d, 6H), 1.3 (d, 6H), 0.0 (s, 6H), and 13 13C-NMR (75.5 MHz) (CDCI3) δ (ppm): 157.3 (dd, J = 248 Hz and J = 8 Hz), 146.5, 127.1 (t, J = 10 Hz), 118.7,1 17.2 (t, J = 25 Hz), 110.3 (m), 50.5, 47.1, 45.9, 20.1, 19.4, 10.3.

[0141] Cat B The second crystal (Cat B) is the zirconocene catalyst Me2Si(Ind)2ZrMe2, where "Me" represents "methyl" and "Ind" represents the "indenyl" ligand. This catalyst was synthesized by Spalek et alii, Angew. Chem. Int. Ed. Engl. 28 (1989), no. 11, and Bochmann et alii, Organometallics, vol 13, No. 6, 1994.

[0142] Examples 1, 2, and 3 (E1, E2, E3) The polymerization to obtain the polymers of Examples E1, E2, and E3 was carried out as follows. The polymerization was carried out in two solution polymerization reactors connected in series, each filled with liquid. The volume of both reactors was 3 liters. The feed stream was purified by contacting it with various absorption media to remove impurities that deactivate the catalyst, such as water, oxygen, and polar compounds. The process was continuous for all feed streams. The pre-mixed solvent (a mixture of hexane isomers with a boiling range of 65 °C to 70 °C), propene, ethylene, diene, di-functional diene monomer, hydrogen, triisobutylaluminum (TIBA), and 2,6-di-tert-butyl-4-methyl-phenol (BHT) were pre-cooled before being fed to the reactors. A solution containing a mixture of the first and second metal complexes (CAT A / CAT B) and a solution of a tetrakis-perfluorophenylborate triphenylcarbenium activator (TBF20) were fed separately to the reactors. The molar ratio of TIBA / BHT was 1 / 1, and the feed rate of TIBA was 1.2 mmol / h. The molar ratio of TBF20 / (Cat A + Cat B) was 2 / 1. The total pressure was 20 barg. Further details are shown in Table 1. The supply of hydrogen was adjusted so that the desired polymer Mooney viscosity as shown in Table 1 was achieved. The pressure was maintained at 20 barg. The polymer solution was withdrawn from the second reactor via the discharge line, where a solution of Irganox® 1076 in isopropanol was added to stop further polymerization and stabilize the polymer. Subsequently, the remaining monomers and solvents were removed by a continuous steam distillation process to obtain a polymer crumb.

[0143] The resulting EPDM polymers were dried in a batch manner on a mill.

[0144] The composition and properties of the EPDM polymers E1, E2, and E3 are also shown in Table 1. These EPDM polymers had a broad MWD and significant branching.

[0145]

Table 1

[0146] In Table 1, T1 is the temperature in Reactor 1, T2 is the temperature in Reactor 2, Prod means the polymer production rate in units of grams per hour, and C2 means units derived from ethylene. The remainder of the polymer was composed of units derived from propylene.

[0147] As shown in Table 2, the polymers prepared as described above (Examples 1 and 2, E1, E2, E3) were compared with EPDM polymers having the same comonomer composition but different preparations and different microstructures and macrostructures (Comparative Examples 1 to 3, C1, C2, C3, and C4). The copolymers of C2 and C3 were prepared using a Ziegler-Natta catalyst. The copolymer of C1 was prepared using only Catalyst A. The copolymer of C4 was prepared using a combination of a monocyclopentadienyl titanium catalyst (CH3)4CH(CH3)2Cp-Ti-(CH3)2(NC(2,6-C6H3F2)NC5H 10 ) and a monoindenyl-titanium complex [(indenyl)-Ti(CH3)2(NC(C6H5)(N((CH(CH3)2)2] as the second metal complex. The intensity ratio was not measured but is considered to be less than 0.5.

[0148]

Table 2

[0149] Preparation and Properties of Compounds Using polymers C1 to C4, E1, E2, and E3 and the components listed in Table 3, compounds were prepared. These compounds were prepared on a closed mixer (GK1,5 E1 from Harburg-Freudenberger Maschinenbau GmbH; ram pressure 8 bar, 50 rpm, 72% filling degree, and total mixing time 5 minutes). The curing system was added on an open mill (roll diameter 200 mm; roll temperature 20 rpm, 40 °C, and friction 1.22).

[0150]

Table 3

[0151] For these compounds, tests of mechanical properties and elastic properties were conducted. Test plates (with thicknesses of 2 mm and 6 mm) were prepared from the compounds and press-cured at 180 °C for times corresponding to 1.1 times and 1.25 times the t90 value (t90 is the time until 90% of the maximum torque is reached during rheometer measurement). For these compounds, tests of the Mooney viscosity and ΔS of the compounds were conducted. Rheometry data (ΔS = torque difference MH - ML at 180 °C) were obtained in accordance with DIN 53529. For the cured samples, tests of compression set (CS), tensile strength at break (TS), and elongation at break (EB) were conducted. The compression set (CS) was determined in accordance with DIN ISO 815. The Shore A hardness (H) was determined in accordance with DIN ISO 7629-1. The tensile strength at break (TS) and elongation at break (EB) were determined in accordance with DIN ISO 37. The results are shown in Table 4.

[0152]

Table 4

[0153] Extrusion experiment: With the following settings, profiles were extruded from the uncured compound through a Garvey profile (die diameter 4 mm, shown in Figure 2) in a Brabender 19 mm extruder: · Housing / die, and screw temperature = 100 °C · Measurement time = 60 seconds · Roll speed = 50 rpm · Nozzle diameter = 4 mm

[0154] The extruded strips obtained from the extrusion experiments are shown in Fig. 1. The profiles formed from copolymer E1 (profile a) in Fig. 1), E2 (profile b) in Fig. 1), and E3 (profile f) in Fig. 1) were of high quality and had a smooth surface. The profiles obtained using the comparative polymers C1, C2, and C3 had a less smooth surface and showed various surface defects (profiles c), d), and e) shown in Fig. 1). From C4, extrudates with properties similar to those of E1 and E2 were obtained (not shown in Fig. 1), but had a much higher branching density (smaller Δδ) and a higher diene (ENB) content (compare Table 2), and thus had a much higher manufacturing cost.

[0155] The mechanical properties of the compounds made from the polymers according to the present disclosure and the comparative polymers do not differ significantly and are sufficient in both cases (compare Table 4), but the polymers according to the present disclosure have a much improved extrusion behavior as confirmed by the extrusion tests (compare Fig. 1), and / or can be manufactured at a lower manufacturing cost, as shown by the above experiments.

Claims

1. (a) ethylene, (b) at least one C ３ ~C ２０ α-olefins, (c) at least one dipolymerizable diene; (d) at least one non-conjugated diene having 6 to 30 carbon atoms other than the dipolymerizable diene; A copolymer comprising repeat units derived from The copolymer is (i) C １３ an intensity ratio D measured by NMR spectroscopy of less than or equal to 0.5; (ii) a branching index Δδ of 5° to 50° (where Δδ is the difference between the phase angle δ measured by dynamic mechanical analysis (DMA) at 125° C. at a frequency of 0.1 rad / s and the phase angle δ measured at a frequency of 100 rad / s); (iii) a branching index g′(III) between 0.50 and 0.99; (iv) a molecular weight distribution (MWD) greater than or equal to R, where R depends on the branching index g'(III) of the copolymer, such that when g'(III) is less than or equal to 0.90, R is -27.7 x g'(III) + 29.2; and when g'(III) is greater than 0.90 up to 0.99, R is 4.3; and and g'(III) and the molecular weight distribution are determined by gel permeation size exclusion chromatography; The copolymer comprises from 30% to 85% by weight of units derived from ethylene and from 5 to 80% by weight of C ３ ~C ２０ comprising units derived from an α-olefin and 2% to 20% by weight of units derived from a non-conjugated diene other than said dipolymerizable diene, said weight percentages being based on the total weight of said copolymer, which is 100% by weight; 10. A copolymer wherein the at least one dipolymerizable diene is selected from the group consisting of 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 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-norbornadiene, and combinations thereof.

2. 2. The copolymer according to claim 1, wherein g'(III) is between 0.70 and 0.98 or between 0.80 and 0.97, and the phase angle difference Δδ is between 5° and 35°.

3. 3. Copolymer according to claim 1 or 2, characterized in that the MWD is between 4.5 and 50.

4. The copolymer according to any one of claims 1 to 3, wherein the intensity ratio D is in the range of from 0.02 to 0.

4.

5. Said C ３ ~C ２０ A copolymer according to any one of claims 1 to 4, wherein the α-olefin is selected from propylene.

6. 6. The copolymer of claim 1, wherein the non-conjugated diene having 6 to 30 carbon atoms comprises vinylcyclohexene, dicyclopentadiene, cyclooctadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and combinations thereof.

7. A copolymer according to any one of claims 1 to 6, comprising from 2% to 6.7% by weight of units derived from a non-conjugated diene.

8. The at least one C ３ ~C ２０ 8. The copolymer of any one of claims 1 to 7, wherein the -α-olefin comprises propylene, the at least one non-conjugated diene comprises 5-ethylidene-2-norbornene (ENB), and the at least one dipolymerizable diene monomer comprises 5-vinyl-2-norbornene (VNB).

9. 9. The copolymer of any one of claims 1 to 8, wherein the at least one dipolymerizable diene comprises 5-vinyl-2-norbornene (VNB) and the content of units derived from VNB is from 0.05 wt% to 5 wt%, or from 0.5 wt% to 5 wt%.

10. 10. A method for producing the copolymer of any one of claims 1 to 9 by polymerization using a first metal complex and a second metal complex, comprising the steps of: The first metal complex is represented by formula (1): CyLMZ ｐ (1) Corresponding to, During the ceremony, Cy is a cyclopentadienyl ligand, which may contain one or more substituents selected from the group consisting of halogens and aromatic or aliphatic linear, branched or cyclic residues containing 1 to 20 carbon atoms, or Cy is an unsubstituted or substituted indenyl ligand, a substituted cyclopentadienyl ligand having at least three methyl groups, or a ligand of formula (2e): 【Chemical 1】 (In formula (2e), R １ and R ２ are individually hydrogen, halogen, C １ ~C １０ Alkyl, C ５ ~C １０ Cycloalkyl and unsubstituted or C １ ~C ４ -Alkyl or C １ ~C ４ -phenyl substituted with dialkylamino, or R １ and R ２ are unsubstituted or C together with the two double-bonded carbon atoms of the thiophene ring to which they are attached. １ ~C ４ -Alkyl-substituted aliphatic C ５ ~C ６ - forms a cycloalkene ring, R ３ , R ４ , and R ５ are individually hydrogen, C １ ~C ４ Alkyl, phenyl, and C １ ~C ４ - selected from the group of phenyl substituted with alkyl and / or halogen; M is titanium, p is 2, and Z is methyl or benzyl. and an S heterocyclic ligand corresponding to M is selected from titanium, hafnium, or zirconium; Z is a halogen, C １～１０ Alkyl group, C ７～２０ Aralkyl group, C ６～２０ Aryl group, C １～２０ an anionic ligand selected from the group consisting of hydrocarbon-substituted amino groups, and combinations thereof; p is 1 or 2; L is represented by the formula (2): 【Chemistry 2】 where the ligand L is eutectic bonded to the metal M through its imine nitrogen atom, and １ is unsubstituted or is selected from halogen and C １ ~C ３ C may be substituted with a substituent selected from alkyl groups; １ ~C ２０ Alkyl residue or C ６ ~C ２０ is an aryl residue; ２ is represented by the general formula -NR ４ R ５ represents R ４ and R ５ are independently aliphatic C １ ~C ２０ Hydrocarbyl residue, halogenated C １ ~C ２０ Aliphatic hydrocarbyl residue, aromatic C ６ ~C ２０ Hydrocarbyl residues, and halogenated aromatic C ６ ~C ２０ or R ４ is R ５ or Sub １ together with or L is a group represented by the general formula (2b): 【Chemistry 3】 wherein the amidine-containing ligand is an imine nitrogen atom N ２ is covalently bonded to the metal M via - ２ -unit, t is an integer and represents 1, 2, 3, or 4, and Sub ３ Is, Sub ３ to the amine nitrogen atom N １ represents an aliphatic or aromatic cyclic or linear substituent containing a Group 14 atom bonded to ４ is a molecule in which two carbon atoms are sp ２ or sp ３ C, which may be mixed ２ unit, and the C ２ The unit may be joined by one or more halogen atoms or by one or more C １ ~C １０ Alkyl group or C １ ~C １０ may be substituted with an alkoxy group) Corresponding to; The second metal complex is a bisindenyl complex and has the formula (3): J-Ind ２ -MX ２ (3); [During the ceremony, Ind ２ represents two indenyl ligands bonded to a metal M and further linked to each other via a linking group J; said indenyl ligands may be substituted or unsubstituted; J represents a bond between said two indenyl ligands (In ２ ) ; where J represents a divalent bridging group linking (a) cyclic units (R ａ ２ J') ｎ wherein each J′ is independently C or Si, n is 1 or 2, and each R ａ are independently １ ~C ２０ is a substituted or unsubstituted hydrocarbyl of the formula ａ are linked together to form a saturated, partially saturated or aromatic ring or fused ring structure containing at least one J′, and (b) an acyclic unit R ｂ ２ J′ (wherein each R ｂ are independently hydrogen, unsubstituted or substituted C １ ~C ９ linear or branched hydrocarbyl, and each J' is independently C or Si; M is selected from titanium, hafnium, or zirconium; Each X is independently a halogen, C １～１０ Alkyl group, C ７～２０ Aralkyl group, C ６～２０ aryl groups, and C １～２０ a monovalent anionic ligand selected from the group consisting of hydrocarbon-substituted amino groups. A manufacturing method corresponding to the above.

11. In formula (3), M represents zirconium; Both Xs are C １ ~C １０ alkyl groups, Both indenyl ligands Ind are unsubstituted or substituted and have 1 to 7 alkyl substituents having 1 to 3 carbon atoms, J is linear or branched but not cyclic, and J is (H ３ C) ２ Si, (H ５ C ２ ) ２ Si, (H ７ C ３ ) ２ Si, H ２ C, H ３ CHC, (H ３ C) ２ C, (H ５ C ２ ) ２ Si, and (H ７ C ３ ) ２ Si, The method of claim 10.

12. ethylene and the at least one C ３～ C ２０ 12. A method for producing the copolymer of any one of claims 1 to 9, comprising the step of copolymerizing an -α-olefin, said at least one non-conjugated diene, and said at least one dipolymerizable diene monomer in the presence of at least one first metal complex, wherein said first and second metal complexes are as defined in claim 10 or 11.

13. 13. The method of claim 12, further comprising in the presence of at least one activating agent (b), and optionally at least one scavenger (c).

14. An extruded article comprising the copolymer of any one of claims 1 to 9, wherein the copolymer is at least partially cured.

15. A method for producing an extruded article, comprising the steps of providing a compound comprising the copolymer of any one of claims 1 to 9 and extruding said compound through at least one die.

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