Metal complex catalysts for the polymerization of olefins.

Abstract

General formula (I): CyLMZ p A catalyst composition for the polymerization of olefinic monomers comprising a metal complex corresponding to (I), wherein Cy represents a ligand bound to the metal of the metal complex, said ligand having a cyclopentadienyl unit which is either substituted or unsubstituted, M is the metal of the metal complex and is selected from Group 4 metals, Z is an anionic ligand, p is 1 or 2, and L is an amidinate ligand of formula (II): Sub1Sub2N(II), wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom and Sub1 is aliphatic and cyclic substituents. A catalyst composition, wherein Sub1 represents either a substituent or an aromatic substituent, and Sub2 corresponds to the general formula (III): -NR1R2(III), where R1 and R2 are identical or different and are selected from acyclic, linear or branched, saturated aliphatic hydrocarbon residues having 4 to 24 carbon atoms, where R1 and R2 are both linear or R1 is linear and R2 is branched, and where the hydrocarbon chain of R1 or R2 may be interrupted one or more times by oxygen or nitrogen atoms. Also provided are polymers obtained by a process using this composition and a process for making a polymer using this composition. JPEG2024515951000012.jpg33170

Description

[Technical field]

[0001] The present disclosure relates to metal complexes for the polymerization of olefins, polymerization processes for making olefin polymers and polymers obtained thereby. [Background technology]

[0002] Polymerization of olefins using metallocene or post-metallocene catalysts is well known. For example, the cyclopentadienyl amide catalysts described in International Patent Application WO2005090418A1 are capable of producing ethylene / α-olefin copolymers having high molecular weights.

[0003] However, there is a continuing need to further develop new catalysts for the polymerization of olefins, in particular for making ethylene copolymers of high molecular weight, preferably above 200 kg / mol. Summary of the Invention [Means for solving the problem]

[0004] Thus, in one embodiment, a metal complex of formula (I) CyLMZ p (I) A catalyst composition comprising: During the ceremony, Cy represents a ligand bound to the metal of the metal complex, the ligand having a cyclopentadienyl unit which is either substituted or unsubstituted; M is the metal of the metal complex and is selected from Group 4 metals; Z is independently selected from neutral or anionic ligands bound to the metal M, where the neutral ligands are selected from conjugated dienes having 4 to 40 carbon atoms, optionally substituted one or more times with a substituent selected from the group consisting of hydrocarbyl, silyl, halocarbyl, and combinations thereof, and where the anionic ligands are selected from -H, -F, -Cl, -Br, -I, -pseudohalogen, -C1~12 -Alkyl, -OC 1~12 -Alkyl, -C(=O)C 1~12 -Alkyl, -acetylacetonate, C 1~12 Alkyl biscarboxylates, -phenyl, -O-phenyl, -Si(C 1~12 -Alkyl)3, -Ge(C 1~12 -alkyl)3, -N(C 1~12 -alkyl)2, -P(C 1~12 )-Alkyl)2, -SC 1~12 -alkyl (all present in their anionic form), and combinations thereof; p is 1 or 2; L is an amidinate ligand of formula (II) [ka] wherein the amidine-containing ligand is covalently bonded to the metal M via an imine nitrogen atom, Sub1 represents either an aliphatic and cyclic or aromatic substituent, Sub1 contains 6 to 20 carbon atoms, and Sub2 represents a group of general formula (III): -NR1R2(III) wherein R1 and R2 are the same or different and are selected from acyclic, linear or branched, saturated aliphatic hydrocarbon residues having 4 to 24 carbon atoms, where either R1 and R2 are both linear, or R1 is linear and R2 is branched, and where the hydrocarbon chain of R1 or R2 may be interrupted one or more times by oxygen or nitrogen atoms or may carry one or more halogen atoms.

[0005] In one embodiment, R1 and R2 are both linear.

[0006] In another embodiment, there is provided a method for preparing a polymer comprising units derived from ethylene, comprising the steps of: (a) providing a monomer composition comprising ethylene; (b) providing said catalyst composition comprising said metal complex; (c) contacting at least a portion of the monomer composition with a catalyst composition to produce a polymer. A method is provided, comprising:

[0007] In a further aspect there is provided the use of said metal complex as a polymerization catalyst for producing a polymer comprising units derived from ethylene.

[0008] In another aspect, there is provided a polymer obtainable by this method.

[0009] In yet another aspect, an article is provided comprising a cured polymer of the polymer obtained by this method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] For a complete understanding of the present disclosure and its advantages, reference is made to the following detailed description.

[0011] It should be understood that the various aspects and embodiments of the detailed description disclosed herein are intended to illustrate specific ways of making and using the disclosure, and do not limit the scope of the disclosure when considered in conjunction with the claims and the detailed description. It will also be understood that features from various aspects and embodiments of the disclosure may be combined with features from various aspects and embodiments of the disclosure.

[0012] In the following description, the terms "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any additional elements, steps or procedures, whether or not they are specifically disclosed.

[0013] In the following description, some descriptive standards may be used. Unless otherwise indicated, the standards are used in the version that came into force on March 1, 2020. If there is no version in force as of that date, for example because the standard has expired, the version in force on the date closest to March 1, 2020 is referenced.

[0014] In the following description, amounts of components of compositions or polymers may be interchangeably referred to as "weight percent," "wt.%," or "% by weight." The terms "weight percent," "wt.%," or "% by weight" are used interchangeably and are based on the total weight of the composition or polymer, respectively, which total weight is 100% unless otherwise indicated.

[0015] The term "phr" means parts per hundred rubber, i.e., the weight percentage based on the total amount of rubber, which is set to 100%.

[0016] Ranges specified in this disclosure include, disclose and include all values ​​between the endpoints of the range, unless otherwise specified.

[0017] The term "substituted" is used to describe a hydrocarbon-containing organic compound in which at least one hydrogen atom has been replaced with a chemical entity other than hydrogen, which chemical entity is referred to interchangeably herein as a "substituent," "residue," or "radical." For example, the term "methyl group substituted with fluorine" refers to a fluorinated methyl group, which includes the groups -CF3, -CHF2, and -CH2F. The term "unsubstituted" is intended to describe a hydrocarbon-containing organic compound in which none of the hydrogen atoms have been replaced. For example, the term "unsubstituted methyl group" refers to methyl, i.e., -CH3.

[0018] The catalyst composition according to the present disclosure contains at least one metal complex as described below. The composition may contain only the metal complex according to the present disclosure, or the composition may contain one or more additional components.

[0019] Metal complexes The metal complexes according to the present disclosure have the formula (I): CyLMZ p (I) where: Cy M is a Group 4 metal; Z is an anionic ligand; p is 1 or 2; L is a ligand of formula (II) [ka] where the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom.

[0020] Sub1 is either an aliphatic and cyclic substituent or an aromatic substituent and contains 6 to 20 carbon atoms.

[0021] Preferably, Sub1 is a substituted or unsubstituted C6-C 20 It represents an aryl residue, preferably unsubstituted phenyl or substituted phenyl having one or more substituents selected from halogen (preferably fluorine) and C1-C4 alkyl.

[0022] In one embodiment, Sub1 is preferably disubstituted in the ortho position.

[0023] Specific examples of Sub1 include, but are not limited to, 2,6-dimethylphenyl, 2,6-dichlorophenyl, or 2,6-difluorophenyl.

[0024] Sub2 is a compound represented by the general formula (III) -NR1R2(III) where R1 and R2 are the same or different and are independently selected from acyclic, linear or branched, saturated aliphatic hydrocarbons having 4 to 24 carbon atoms, where either R1 and R2 are both linear, or R1 is linear and R2 is branched. In one embodiment, R1 or R2 is interrupted one or more times by an oxygen atom or a nitrogen atom, or R1 or R2 or both bear one or more halogen atoms.

[0025] In one embodiment, R1 is selected from n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and n-tridecyl.

[0026] In one embodiment, R1 and R2 are both linear.

[0027] In another embodiment, R1 and R2 are the same.

[0028] Ligand Cy The ligand Cy of formula (I) is selected from unsubstituted cyclopentadienyl and substituted cyclopentadienyl. Preferably, the substituent is an N-heterocyclic or S-heterocyclic substituent, C 1~20 - Linear, branched or cyclic alkyl substituents, C6-C 12 The linear or branched alkyl substituents may be unsubstituted or may themselves be substituted with one or more halogens. The cyclic alkyl, heterocyclic and aryl substituents may be unsubstituted or may themselves be substituted with one or more halogens, one or more C1-C 10 Linear or branched alkyl, one or more C1-C 10 Linear or branched oxoalkyl, C5-C 10 -cycloalkyl, dialkylamino groups where alkyl is C1-C6 alkyl, and combinations thereof which may themselves be substituted.

[0029] C1~C20 Examples of alkyl substituents include, but are not limited to, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C4H9 (including isomers), -C6H 13 (including isomers), or -C 10 H 21 (including isomers), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenylcyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, isopropyldodecyl, adamantyl, norbornyl, tricyclo[5.2.1.0]decyl, fluoromethyl, difluoromethyl, methoxymethyl, and trifluoromethyl.

[0030] C6~C 12 Examples of aryl substituents include, but are not limited to, phenyl, or biphenyl (including isomers) and phenyl having one or more alkyl substituents having 1 to 6 carbon atoms, such as, but not limited to, methylphenyl, trimethylphenyl, cyclohexylphenyl, naphthyl, butylphenyl, or butyldimethylphenyl. Further examples include N,N-dimethylaminobenzyl, N,N-dimethylaminomethyl, diphenyl-phosphinomethyl.

[0031] Examples of cyclically substituted cyclopentadienyl include unsubstituted indenyl, unsubstituted fluorenyl, and substituted indenyl and substituted fluorenyl, where the substituents are one or more halogens, one or more C1-C 10 Straight or branched alkyl, C5-C 10 It is selected from cycloalkyl, dialkylamino groups where alkyl is C1 to C6 alkyl, and combinations thereof.

[0032] Examples of N-heterocyclic substituted cyclopentadienyls or S-heterocyclic substituted cyclopentadienyls include, but are not limited to, those corresponding to formulas (1) and (2) set forth below.

[0033] Heterocyclic cyclopentadienyls represented by formula (1): [ka] is an indole-fused cyclopentadienyl, where R 1 means, for each index m, independently, a C1-C4-alkyl group substituting a hydrogen atom on a benzene ring, m is a number from 0 to 4, preferably from 0 to 2, and more preferably 0; R 2 is unsubstituted or has one or more C1 to C 10 -C1-C alkyl group, one or more C1-C dialkylamino groups or a combination thereof; 10 -Alkyl, C5-C 10 -Cycloalkyl or C6-C 10 -aryl, R 3 , R 4 and R 5 is hydrogen, C1-C4 alkyl, or C6-C 10 -aryl.

[0034] Heterocyclic substituted cyclopentadienyl represented by formula (2) [ka] is a thiophene-fused cyclopentadienyl, R 1 and R 2 are independently hydrogen, halogen, C1-C 10 Alkyl, C5-C 10 Cycloalkyl and C6-C 10 aryl; or R 1 and R 2 together with the two double-bonded carbon atoms of the thiophene ring to which they are attached, form an unsubstituted or C1-C4 alkyl-substituted aliphatic C5-C6 cycloalkene ring; R 3 , R 4 and R 5are each independently hydrogen, C1-C4 alkyl, and C6-C 10 aryl.

[0035] In one embodiment of the present disclosure, Cy is a substituted cyclopentadienyl containing at least one methyl substituent. In a preferred embodiment of the present disclosure, the ligand Cy is selected from cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl and pentamethylcyclopentadienyl.

[0036] M The metal M of the metallocene complex of the present disclosure is a Group 4 metal. For the purposes of this disclosure, the term "Group 4 metal" refers to the conventional IUPAC nomenclature. Preferably, the metal M is selected from the group consisting of titanium, zirconium, and hafnium. In a particularly preferred embodiment of the present invention, the metal M is titanium. The metal is in an oxidation state such that the overall metal complex is neutral.

[0037] Ligand Z In one embodiment of the present disclosure, the ligand Z is a neutral ligand and is selected from a conjugated diene. The diene ligand may be bonded to the metal M in either the s-trans configuration (π-bonded) or the s-cis configuration (either π-bonded or σ-bonded). Preferably, the conjugated diene contains 4 to 40 carbon atoms and may be optionally substituted one or more times with substituents independently selected from the group consisting of hydrocarbyl, silyl, halocarbyl, or combinations thereof. Examples of suitable neutral ligands include, but are not limited to, butadiene, isoprene, 1,3-pentadiene, 1,4-diphenyl-1,3-butadiene; 2,3-diphenyl-1,3-butadiene; 3-methyl-1,3-pentadiene; 1,4-dibenzyl-1,3-butadiene; 2,4-hexadiene; 2,4,5,7-tetramethyl-3,5-octadiene; 2,2,7,7-tetramethyl-3,5-octadiene; 1,4-ditolyl-1,3-butadiene; 1,4-bis(trimethylsilyl)-1,3-butadiene; and 2,3-dimethylbutadiene.

[0038] In a preferred embodiment of the present disclosure, the ligand Z is anionic. Preferably, the ligand Z is -H, -F, -Cl, -Br, -I, -pseudohalogen, -C 1~12 -Alkyl, -OC 1~12 -Alkyl, -C(=O)C 1~12 -Alkyl, -acetylacetonate, C 1~12 Alkyl biscarboxylates, -phenyl, -O-phenyl, -Si(C 1~12 -Alkyl)3, -Ge(C 1~12 -alkyl)3, -N(C 1~12 -alkyl)2, -P(C 1~12 )-Alkyl)2, -SC 1~12 -alkyl, and combinations thereof; preferably -C 1~12-alkyl, where these ligands are in their anionic form. For the purposes of this specification, pseudohalogens are halogen polyatomic analogs that are similar in chemical properties to true halogens and can be substituted for halogens in some types of chemical compounds. Suitable examples include, but are not limited to, -CN, -OCN, -SCN, or -N3.

[0039] Preferably, the anionic ligand Z is -CH3, -benzyl, -Si(CH3)3, -CH2-Si(CH3)3, -phenyl, and -OC 1~12 -Alkyl, -N(C 1~12 -alkyl)2, -F, and -Si(C 1~12 and Z is selected from the group consisting of the anions of -phenyl (e.g., methoxyphenyl, dimethoxyphenyl, N,N-dimethylaminophenyl, bis(N,N-dimethylamino)phenyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, perfluorophenyl, trimethylsilylphenyl, bis(trimethylsilyl)phenyl, tris(trimethylsilyl)phenyl) substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of -alkyl)3; preferably, Z is a methyl anion.

[0040] In one embodiment of the present disclosure, the compound comprises two ligands Z, preferably both ligands Z are identical, preferably the index p is 2, and each of the two ligands Z is a methyl anion.

[0041] In one embodiment of the present disclosure, the metal complex corresponds to formula (I) where M is titanium.

[0042] In one embodiment of the disclosure, the metal complex corresponds to formula (I), where p is 2 and Z is the anionic -CH3.

[0043] In one embodiment of the present disclosure, the metal complex corresponds to formula (I), wherein Cy is selected from methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, and pentamethylcyclopentadienyl.

[0044] In one embodiment of the present disclosure, the metal complex corresponds to formula (I) where Sub1 is phenyl and 2,6-difluorophenyl.

[0045] polymerization Ethylene-containing polymers can be produced by using the catalyst composition according to the present disclosure. The metal complexes can be used alone or in combination with other polymerization catalysts, or in combination with one or more optional scavengers and activators, and combinations thereof.

[0046] Thus, in another aspect of the disclosure, there is provided a process for the preparation of a polymer comprising units derived from ethylene, comprising the steps of: (a) providing a monomer composition containing ethylene; (b) providing a catalyst composition comprising at least one metal complex according to the present disclosure; (c) contacting at least a portion of the monomer composition with at least a portion of the catalyst composition to polymerize the monomer composition. A method is provided, comprising:

[0047] The method may further include, optionally, providing at least one scavenger and / or, optionally, providing at least one activator. The activator and scavenger may be components of the catalyst composition comprising the metal complex of the present disclosure, or they may be provided separately, for example, as separate feed streams.

[0048] The monomer composition may be polymerized to produce a polymer having a broad or narrow molecular weight distribution (Mw / Mn). In one embodiment, a polymer having a molecular weight distribution (Mw / Mn) of 1.80 to 30 or 2 to 10 may be produced.

[0049] Polymers with high or low Mooney viscosities can be produced. In one embodiment, the polymer produced by the present method has a Mooney viscosity ML1+4 of at least 40 at 125° C. and a Mooney viscosity ML1+8 of 100 or less at 150° C. In one embodiment of the present disclosure, the polymer has a Mooney viscosity ML1+4 of about 40 to about 100 at 125° C. In another embodiment of the present disclosure, the polymer has a Mooney viscosity ML1+8 of about 50 to about 100 at 150° C.

[0050] High or low weight average molecular weight (Mw) polymers can be produced by the methods of the present disclosure, hi one embodiment, the polymer has an (Mw) of at least greater than 200,000 g / mol, for example, from about 200,000 g / mol to about 600,000 g / mol.

[0051] Polymers with high or low number average molecular weight (Mn) can be produced, hi one embodiment, the polymers produced by the method according to the present disclosure have an Mn of 40,000 g / mol to 250,000 g / mol.

[0052] Branched or linear polymers may be produced using the method according to the present disclosure. The branching level of the branched polymer may be high, medium or low. The polymer branching level may be characterized by the parameter Δδ. Δδ, expressed in degrees, is the difference between the phase angle δ at a frequency of 0.1 rad / sec and the phase angle δ at a frequency of 100 rad / sec, as measured by Dynamic Mechanical Spectroscopy (DMS) at 125° C. and 10% strain. This quantity Δδ is a measure of the amount of long chain branching structure present in the polymer and is introduced in HC Booij, Kautschuk+Gummi Kunststoffe, Vol. 44, No. 2, pages 128-130, which is incorporated herein by reference. In one embodiment of the present disclosure, polymers with Δδ between 2 and 65 may be produced.

[0053] The polymers produced by the method according to the present disclosure may be monomodal, or they may be bimodal or multimodal. The polymers may have a molecular weight distribution characterized by two peaks or one peak and one shoulder in the case of bimodal polymers, or three or more peaks or two shoulders in the case of multimodal polymers, in a diagram obtained by gel permeation chromatography (GPC). Reactor blends may also be produced, which means that the polymers are produced in at least two different reaction vessels and combined by mixing, typically wet mixing, i.e., by mixing the reaction mixture. Block or graft polymers may also be produced.

[0054] Ethylene-containing polymers: The polymers that can be produced by using the catalyst composition according to the present disclosure contain units derived from ethylene, and the monomer composition provided in the method according to the present disclosure contains at least ethylene.Preferably, the polymers produced by the method according to the present disclosure are ethylene copolymers, more preferably ethylene / α-olefin copolymers.

[0055] Ethylene / α-olefin polymers: In one embodiment of the present disclosure, the polymer produced using the catalyst composition according to the present disclosure is an ethylene / α-olefin polymer. The ethylene / α-olefin polymer is a copolymer of ethylene and at least one other α-olefin and, optionally, one or more additional comonomers. Ethylene / α-olefin polymers can be produced that contain at least 20% by weight (based on the total weight of the polymer) of units derived from ethylene and may contain up to 80 weight percent (wt%) of units derived from ethylene. In one embodiment, the ethylene-α-olefin copolymer of the present disclosure contains 40-70% by weight, preferably 44-65% by weight, of units derived from ethylene. The weight percentage is based on the total weight of the copolymer.

[0056] In addition to units derived from ethylene, polymers according to the present disclosure may contain units derived from one or more other α-olefins.

[0057] Alpha-Olefins: An α-olefin is an olefin that has a single aliphatic carbon-carbon double bond. The double bond is located at the terminal (α-position) of the olefin. α-olefins can be aromatic or aliphatic, linear, branched, or cyclic. Typically, α-olefins have from 3 to 20 carbon atoms.

[0058] As α-olefin, the formula: H2C=X-CH3 where X represents an aliphatic alkylene residue having 1 to 17 carbon atoms, which may be linear or branched. Preferably, the branches, independently of one another, contain 1 to 3 carbon atoms.

[0059] In a preferred embodiment, the α-olefin has the formula: H2C=CH-(CH2) n Examples include those represented by the formula -CH3, where n=1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17.

[0060] Preferred examples of α-olefins 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.

[0061] One or more α-olefins may be used in combination. Preferably, the polymer contains at least 5% or at least 10% by weight of units derived from one or more α-olefins. Polymers containing up to 57% by weight, more preferably up to 55% by weight of units derived from one or more α-olefins (weight percentages (wt%) based on the total weight of the polymer) may be produced. Preferably, ethylene-α-olefin copolymers contain 17-57% by weight of total units derived from one or more α-olefins. Preferably, the polymer contains propylene.

[0062] Non-conjugated dienes: Ethylene / α-olefin polymers can be produced that, in addition to ethylene and an α-olefin, further contain units derived from one or more non-conjugated dienes as comonomers.

[0063] A non-conjugated diene is a polyene containing at least two carbon-carbon double bonds, which are non-conjugated and may be in a chain, a ring, a ring system or a combination thereof. The carbon-carbon double bonds are separated by at least two carbon atoms. The polyene may have endocyclic and / or exocyclic double bonds and may have substituents, which may be the same or different. Preferably, the non-conjugated diene is aliphatic, more preferably aliphatic and alicyclic. Suitable non-conjugated dienes include, for example, aromatic polyenes, aliphatic polyenes and alicyclic polyenes, preferably polyenes having 6 to 30 carbon atoms (C6 to C8). 30 -Polyenes, more preferably C6-C 30Specific examples of non-conjugated dienes include, but are not limited to, 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, 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,Examples of the non-conjugated dienes include 6-undecadiene, 9-methyl-1,8-undecadiene, dicyclopentadiene and mixtures thereof. Preferred non-conjugated dienes include alicyclic polyenes. The alicyclic dienes have at least one cyclic unit. In a preferred embodiment, the non-conjugated dienes are selected from polyenes having at least one endocyclic double bond and optionally at least one exocyclic double bond. Preferred examples include dicyclopentadiene (DCPD), 5-methylene-2-norbornene and 5-ethylidene-2-norbornene (ENB), with ENB being particularly preferred. In one embodiment, the copolymer of the present disclosure contains only ENB as the non-conjugated diene. While the above dienes typically contain one double bond that participates in polymerization, the other double bond may not be polymerized and thus provide a curing site for the polymer.

[0064] Further examples of non-conjugated dienes include doubly polymerizable dienes, i.e., non-conjugated dienes including dienes in which both non-conjugated double bonds can be polymerized. Such dienes can introduce polymer branching sites for the production of long chain branches and can contribute to branched polymer structures. Examples include, but are not limited to, vinyl-substituted aliphatic monocyclic and non-conjugated dienes, vinyl-substituted bicyclic and non-conjugated aliphatic dienes. Such doubly polymerizable dienes can cause or contribute to the formation of polymer branches. Examples of aliphatic dipolymerizable 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 12Preferred are αω linear dienes (e.g., 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene). The dipolymerizable dienes may be further substituted with at least one group containing a heteroatom from Groups 13 to 17, such as O, S, N, P, Cl, F, I, Br, or combinations thereof.

[0065] Examples of aromatic non-conjugated polyenes include vinylbenzene (including its isomers) and vinyl-isopropenylbenzene (including its isomers).

[0066] In a preferred embodiment of the present disclosure, the dipolymerizable diene is selected from dicyclopentadiene (DCPD), 5-vinyl-2-norbornene (VNB), 1,7-octadiene, and 1,9-decadiene, with 5-vinyl-2-norbornene (VNB) being most preferred.

[0067] In an exemplary embodiment of the present disclosure, ethylene / α-olefin copolymers containing at least 3 wt.% and up to and including 15 wt.% units derived from one or more non-conjugated dienes may be produced.

[0068] In another embodiment of the present disclosure, a polymer containing a non-conjugated diene selected from 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 1,7-octadiene, 1,9-decadiene, dicyclopentadiene (DCPD) or a combination thereof is produced. Preferably, the copolymer of the present disclosure contains 0.05% to 5% by weight, more preferably 0.10% to 3% by weight or 0.15% to 1.2% by weight of units derived from VNB (all weight percentages based on the total weight of the ethylene-α-olefin-copolymer). In another embodiment, ethylene / α-olefin copolymers containing units derived from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene may be produced, for example, the ethylene / α-olefin copolymers produced may contain 2-15 wt. % of units derived from ENB and 0.05-4 wt. % of units derived from VNB.

[0069] Ethylene / α-olefin copolymers, which may or may not contain units derived from other comonomers, may be produced by the process according to the present disclosure. The sum of units derived from ethylene, α-olefin and, optionally, non-conjugated dienes may be greater than 90% by weight, greater than 99% by weight (including 100% by weight), based on the total weight of the ethylene / α-olefin polymer.

[0070] Chain transfer agent: The polymerization may include the use of one or more chain transfer agents to control the molecular weight of the polymer. Preferred chain transfer agents include hydrogen (H2) and diethyl zinc and combinations thereof.

[0071] Activator: One or more activators, also referred to interchangeably herein as "cocatalysts", may be used in the polymerization. The presence of a cocatalyst typically increases the rate at which the catalyst polymerizes olefins. The cocatalyst may also affect the molecular weight, branching, comonomer content, or other properties of the polymer. The cocatalyst is typically introduced into the reactor together with the catalyst, e.g., as part of the catalyst composition, but may also be introduced separately from the catalyst, e.g., in a separate feed stream.

[0072] Exemplary cocatalysts include, but are not limited to, boron-containing activators. In a preferred embodiment, the activator (b) is selected from a borane (C1) or a borate (C2 or C3).

[0073] Suitable boron activators (C1) may be represented by the general formula BQ1Q2Q3.

[0074] Suitable borate activators represented by (C2) can be represented by the general formula: G(BQ1Q2Q3Q4).

[0075] Suitable borate activators represented by (C3) may be represented by the general formula: (JH)(BQ1Q2Q3Q4), In the activator represented by (C1), B is boron and Q1-Q3 are substituted or unsubstituted aryl groups, preferably phenyl groups. Suitable substituents include, but are not limited to, halogen, preferably fluoride, and C1-C 40 Hydrocarbyl, preferably C1-C 20 Specific examples of the activator represented by (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, and phenyl-bis(pentafluorophenyl)borane.

[0076] In the activator represented by (C2), G is an inorganic or organic cation, B is boron, Q1 to Q3 are the same as in (C1), and Q4 is also a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl. The substituents include, but are not limited to, halogen, preferably fluoride, and C1 to C 40 Hydrocarbyl, preferably C1-C 20 Examples of the borate group (BQ1Q2Q3Q4) include, but are not limited to, 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(pentafluoro-phenyl)borate, tetrakis(3,5-bistrifluoromethylphenyl)borate, and the like. Examples of G include ferrocenium cation, alkyl-substituted ferrocenium cation, silver cation, and the like. Examples of the organic cation G include triphenylmethyl cation, and the like. G is preferably a carbenium cation, particularly preferably a triphenylmethyl cation.

[0077] In the activator represented by (C3), J represents a neutral Lewis base, (JH) represents a Bronsted acid, B is boron, and Q1 to Q4 and the borate group (BQ1Q2Q3Q4) are both the same as in (C2). Specific examples of the Bronsted acid (JH) include trialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium, and triarylphosphonium. Specific examples of the activator represented by (C3) include, but are not limited to, 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(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethyl Examples of suitable tetrakis(pentafluorophenyl)borate include 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, and tri(dimethylphenyl)-phosphonium-tetrakis(pentafluorophenyl)borate.

[0078] Other cocatalysts include aluminum alkyls, such as, but not limited to, trialkylaluminum, trimethylaluminum, triethylaluminum, tri-isobutylaluminum, or tri-n-octylaluminum. Other examples include alkylaluminum halides, such as, but not limited to, diethylaluminum chloride, dimethylaluminum chloride, and ethylaluminum sesquichloride. Further examples include alumoxanes, including methylalumoxane (MAO), tetraisobutylalumoxane (TIBAO), or hexaisobutylalumoxane (HIBAO).

[0079] Scavenger: Impurities can adversely affect catalysts by reducing their activity. Compounds that react with such impurities and convert them into compounds that are harmless to catalytic activity are called scavengers by those skilled in the art of polymerization. Scavenger can be used in the method according to the present disclosure. Examples of scavengers include, but are not limited to, alkylaluminum compounds such as trimethylaluminum, triethylaluminum, tri-isobutylaluminum, and trioctylaluminum. In some cases, the scavenger can also act as a cocatalyst. In this case, the scavenger is generally applied in excess of the amount required to fully activate the catalyst.

[0080] In one embodiment of the process according to the present invention, the molar ratio of the activator provided in step (c) of the process to the metallocene compound according to the present invention is from 10:1 to 1:1, preferably 2:1, preferably 1:2.

[0081] The scavenger, preferably an aluminum-containing scavenger, may be used in combination with a sterically hindered hydrocarbon or heterohydrocarbon, preferably a sterically hindered phenol or amine. Specific examples of sterically hindered hydrocarbons and heterohydrocarbons include, but are not limited to, tert-butanol, iso-propanol, 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, etc. A preferred sterically hindered compound is 4-methyl-2,6-tert-butylphenol.

[0082] In the method of producing a polymer according to the present disclosure, a monomer composition is contacted with a catalyst composition according to the present disclosure. The contacting can be carried out in the gas phase. The contacting can also be carried out in the presence of one or more solvents, for example, in a solution or slurry. The polymerization can be carried out in a solution or slurry under pressure and temperature where a gas phase is not formed. Preferred solvents include one or more hydrocarbon solvents. Suitable solvents include C 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 150, 105, 150, 1000, 15 ... 5~12 Hydrocarbons are included.

[0083] The process may be carried out at reaction temperatures and pressures known in the art for the polymerization of such polymers. The polymerization may be carried out as a solution polymerization or as a slurry polymerization or as a polymerization in gas phase. Preferably, the polymerization is carried out as a solution polymerization. Typical reaction temperatures include 20°C to 150°C or 60°C to 140°C. In one embodiment of the present disclosure, the metallocene compound is used in the polymerization, preferably a solution polymerization, at reaction temperatures as high as 130°C and at pressures suitable for keeping the monomers in the liquid or dissolved phase, for example.

[0084] The catalyst composition may be used alone or in combination with one or more other catalysts other than the metal complexes of the present disclosure, such as metallocene catalysts, preferably bis-indenyl catalysts.

[0085] The polymerization to produce the polymer can be carried out in a single reactor or in multiple reactors. The catalyst composition can be added to a first reactor and another reactor, and the catalyst composition can be the same or different in the first and second reactors. The polymerization can be carried out in multiple reactors connected in series or in parallel. In parallel polymerization, the resulting polymer mixture can be combined to provide a so-called reactor blend, i.e., a wet blend of two or more polymer compositions.

[0086] Other Aspects of the Disclosure In another aspect of the disclosure, there is provided a polymer obtainable by the process according to the invention as described above. In one embodiment, the polymer is an ethylene propylene rubber (EPM) or an ethylene propylene diene monomer rubber (EPDM).

[0087] In another aspect of the present disclosure, there is provided an article containing the polymer obtained by the method described herein or by use of the metal complex according to the present disclosure, at least partially cured. If the polymer is curable, the article preferably contains the polymer in at least partially cured form.

[0088] Another aspect of the present disclosure relates to the use of a metal complex according to the present disclosure as a polymerization catalyst for polymerizing a monomer composition as defined above.

[0089] Another aspect of the present disclosure provides a supported catalyst comprising a metal complex or catalyst composition according to the present disclosure on a support material. The supported catalyst may optionally further contain a scavenger or an activator or a combination of a scavenger and an activator. The support material may be a solid material with a high surface area, to which at least one metal complex of the present disclosure is fixed. Typically, the activity of a heterogeneous catalyst occurs at the surface atoms. As a result, great efforts are made to maximize the surface area of ​​the catalyst. One suitable method for increasing the surface area includes distributing the catalyst over the support material. The support material may be inert or may participate in the catalytic reaction. Preferably, the support material is selected from the group consisting of silica, magnesium halides (e.g., MgF2, MgCl2, MgBr2, MgI2), zeolites, alumina, polystyrene, polypropylene, polyethylene, polyamide, polyester, and combinations thereof. EXAMPLES

[0090] The following examples further illustrate the present disclosure, without intending to limit the disclosure to these examples.

[0091] method Test Method Comonomer Composition Fourier transform infrared spectroscopy (FT-IR) can be used to determine the composition of the copolymer according to ASTM D3900 (revised 2017) for the C2 / C3 ratio and according to D6047 (revised 2017) for the diene content of pressed polymer films.

[0092] phase angle measurement Polymer branching can be determined by phase angle measurement on 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 and the phase angle δ measured at a frequency of 100 rad / s, as determined by dynamic mechanical analysis (DMA) at 125° C. Δδ is a measure of the presence of long chain branches in the polymer structure. The lower the value of Δδ, the more long chain branches are present in the polymer, as introduced by HC Booij, in Kautschuk + Gummi Kunststoffe, Vol. 44, No. 2, pages 128-130, 1991, which is incorporated herein by reference.

[0093] Size Exclusion Chromatography with Differential Viscometry (SEC-DV) The molecular weight distribution (MWD), weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity (Mw / Mn) and intrinsic viscosity can be determined by gel permeation size exclusion chromatography (GPC / SEC). A Polymer Char GPC from Polymer Characterization SA (Valencia, Spain) can be used. The size exclusion chromatograph can be equipped with an online viscometer (Polymer Char V-400 viscometer), an online infrared detector (IR5 MCT), with three AGILENT PL OLEXIS columns (7.5 x 300 mm) and a Polymer Char autosampler. Universal calibration of the system can be performed using polyethylene (PE) standards.

[0094] Polymer samples can be weighed into the vials of a Polymer Char autosampler (with a concentration range of 0.3-1.3 mg / ml). In the autosampler, the vials are automatically filled with the solvent (1,2,4-trichlorobenzene stabilized with 1 g / l di-tertbutyl-paracresol (DBPC)). The samples are placed in a high temperature oven (160° C.) for 4 hours. After this dissolution time, the samples are automatically filtered by an in-line filter before being injected into the column. The chromatographic system is operated at 160° C. The flow rate of the 1,2,4-trichlorobenzene eluent is 1.0 mL / min. The chromatograph includes an integrated online infrared detector (IR5 MCT) for concentration and an integrated Polymer Char online viscometer.

[0095] General Operating Steps: All experiments to prepare metal complexes were carried out under an atmosphere of argon or nitrogen using standard Schlenk line or dry box techniques. Solvents were degassed by sparging with nitrogen and dried by passing through a column of an appropriate desiccant. Deuterated solvents were dried over CaH2, distilled under reduced pressure, and stored under nitrogen in PTFE valved ampoules. NMR samples were prepared under nitrogen in 5 mm WILMAD 507-PP tubes equipped with J.YOUNG PTFE valves. 1 H, 19 F and 13 C-{ 1 H} spectra were recorded at ambient temperature and the residual protic solvent ( 1 H) or solvent ( 13 C) Resonances are internally referenced and reported relative to tetramethylsilane (d=0 ppm). Chemical shifts are given in δ (ppm) and coupling constants in Hz. NMR spectra were recorded on a BRUKER Avance 400 spectrometer.

[0096] General procedure for preparing metal complexes: The metal complex is treated with the same molar amount of Cp *The reaction was carried out at room temperature with TiMe3. The reaction time was less than 2 hours. In a typical experiment, 5.7 mg of Cp * TiMe3 (0.025 mmol) was dissolved in 5 ml of toluene. The ligand (0.025 mmol) was also dissolved in 5 ml of toluene. Both solutions were combined to produce the metal complex. The resulting solution was diluted with toluene to 25 ml before it was used in the polymerization experiments. The metal complex was prepared in situ and used immediately.

[0097] Cp * TiMe3, Cp * It was prepared by dissolving TiCl3 in hexane and adding the methyllithium solution to diethyl ether. The mixture was stirred for 4 hours and the solvent was evaporated. The solid was redissolved, filtered and the solvent was evaporated. The product was dissolved in pentane and stored in a freezer at -80°C. After 3 days, large crystals formed. The mixture was filtered to obtain high purity ( 1 Pure material (73%) was obtained, 95% by H-NMR.

[0098] The ligands were prepared by reacting the respective amines (HN-R1R2) with benzonitrile. The reactions were carried out under a nitrogen atmosphere by using standard Schlenk techniques. Solvents and reagents were dried before use. In a typical reaction, 9.58 mmol of benzonitrile in 15 mL of toluene was stirred overnight over calcium hydride to remove moisture, after which the calcium hydride was filtered off. A solution of the amine (9.88 mmol) in 10 ml of toluene was separately prepared and a 3 M solution of methylmagnesium chloride in tetrahydrofuran (3.36 ml, 9.78 mmol) was added to it dropwise with stirring. The resulting mixture was stirred at 50° C. for 1.5 hours. The suspension was cooled to room temperature, after which the benzonitrile solution was added. The reaction mixture was stirred at 70° C. for 18 hours. The reaction mixture was cooled to room temperature, water was added (15 ml), and the reaction was stirred at room temperature for an additional hour. The organic phase was separated and washed with water (2×15 mL). The aqueous phase was extracted with diethyl ether (3 x 15 mL). The combined organic phases were dried over magnesium sulfate. The magnesium sulfate was filtered off and the solvent was evaporated. The ligand was an oil and was purified by column chromatography (silica gel with a solution of hexane and ethyl acetate (1:1 v / v) and 1% triethylamine).

[0099] Ligands in which Sub1 was 2,6-difluorophenyl were prepared in the same manner, except that 2,6-difluorobenzonitrile was used instead of benzonitrile.

[0100] Various metal complexes of the following general structure ((CH3)5Cp-Ti-(CH3)2)(NC(Sub1)(Sub2)) (wherein Cp represents cyclopentadienyl) were prepared using various ligands L, i.e., various residues Sub1 and Sub2, respectively, as shown in the following general formula and in Table 1 below. [ka]

[0101] [Table 1]

[0102] General procedure for polymerization Polymerizations were carried out using catalysts from Table 1. The monomers were polymerized in a 1 L volume batch reactor at 90° C. with 7 bar ethylene (C2) and propylene (C3) pressures for 10 minutes in pentamethylheptane (PMH). Unless otherwise specified, the catalysts from Table 1 were used in an amount of 0.07 μmol. The ethylene / propylene ratio was 400 / 200 nL / hr. Polymerizations were carried out in the presence of 84.1 mmol of ENB, 84.1 mmol of VNB, 0.14 μmol of tritylium tetrakis(perfluorophenyl)borate, 450 μmol of ztiisobutylaluminium, and 900 μmol of 4-methyl-2,6-di-tert-butylphenol. Hydrogen was used as chain transfer agent at 0.35 nL / hr. The polymerization results are shown in Table 2.

[0103] [Table 2]

[0104] The results in Table 2 show that catalysts according to the invention having at least one linear residue R1 gave polymers with higher molecular weights compared to catalysts in which both R1 and R2 are branched. This behavior was observed for substituted and unsubstituted residues Sub1. It should be noted that the results of experiments 9 to 12 were already obtained at almost half the catalyst concentration.

Claims

1. General formula (I): CyLMZ ｐ (I) A catalyst composition for the polymerization of olefinic monomers comprising a metal complex corresponding to During the ceremony, Cy represents a ligand bound to the metal of said metal complex, said ligand having a cyclopentadienyl unit which is either substituted or unsubstituted; M is the metal of said metal complex and is selected from Group 4 metals; Z is independently selected from neutral or anionic ligands bound to said metal M, wherein said neutral ligands are selected from conjugated dienes having from 4 to 40 carbon atoms which may be optionally substituted one or more times with substituents selected from the group consisting of hydrocarbyl, silyl, halocarbyl, and combinations thereof, and said anionic ligands are all present in their anionic form, -H, -F, -Cl, -Br, -I, -pseudohalogen, -C １～１２ -alkyl, -O-C １～１２ -Alkyl, -C(=O)C １～１２ -Alkyl, -acetylacetonate, C １～１２ Alkyl biscarboxylates, -phenyl, -O-phenyl, -Si(C １～１２ -alkyl) ３ , -Ge(C １～１２ -alkyl) ３ , -N(C １～１２ -alkyl) ２ , -P(C １～１２ )-alkyl) ２ , -S-C １～１２ -alkyl, and combinations thereof; p is 1 or 2; L is of formula (II): 【Chemistry 1】 wherein the amidine-containing ligand is covalently bonded to the metal M through its imine nitrogen atom; １ represents either an aliphatic and cyclic substituent or an aromatic substituent; １ contains 6 to 20 carbon atoms; ２ is represented by the general formula (III): | １ ( ２ (_=) where R １ and R ２ are the same or different and are selected from acyclic, linear or branched, saturated aliphatic hydrocarbon residues having 4 to 24 carbon atoms, where R １ and R ２ are both linear, or R １ is linear, R ２ is branched, R １ Or R ２ wherein said hydrocarbon chain may be interrupted one or more times by oxygen or nitrogen atoms, or may contain one or more halogen atoms.

2. Sub ２ is represented by the general formula (III): | １ ( ２ (_=) where R １ 2. The catalyst composition of claim 1, wherein is selected from n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and n-tridecyl.

3. Sub ２ is represented by the general formula (III): | １ ( ２ (_=) where R １ and R ２ The catalyst composition of claim 1 or claim 2, wherein both are linear.

4. Sub １ represents an unsubstituted aryl residue or halogen, C １ ~C ４ C having one or more substituents selected from alkyl and combinations thereof ６ ~C １０ Catalyst composition according to claim 1, which represents an aryl residue.

5. Sub １ But fluorine, C １ ~C ４ 10. The catalyst composition of claim 1, wherein the substituents are selected from phenyl and ortho-para-disubstituted phenyl, with the substituents being selected from alkyl and combinations thereof.

6. 10. The catalyst composition of claim 1, wherein M is titanium.

7. 2. The catalyst composition of claim 1, wherein p is 2 and each Z represents methyl in anionic form.

8. Cy is an N- or S-heterocyclic substituent, C １～２０ linear, branched or cyclic alkyl substituents of ６ ~C １２ represents a cyclopentadienyl substituted with one or more substituents independently selected from the group consisting of an aryl substituent, and a silane, wherein the substituents may be unsubstituted or may be selected from the group consisting of one or more halogens, one or more C １ ~C １０ linear or branched alkyl, one or more C １ ~C １０ linear or branched oxoalkyl of ５ ~C １０ Cycloalkyl, alkyl is C １ ~C ６ 10. The catalyst composition of claim 1, which may itself be substituted with an alkyl, dialkylamino group, or combinations thereof.

9. Cy, (i) -CH ３ , -CH ２ CH ３ , -CH ２ CH ２ CH ３ , -CH(CH ３ ) ２ , -C ４ H ９ (including isomers), -C ６ H １３ cyclopentadienyl having 1 to 5 substituents selected from (including isomers), fluoromethyl, difluoromethyl, trifluoromethyl, methoxymethyl, and combinations thereof; (ii) a ring-substituted cyclopentadienyl selected from unsubstituted indenyl, unsubstituted fluorenyl, substituted indenyl, and substituted fluorenyl, the substituents being one or more halogens, one or more C １ ~C １０ Linear or branched alkyl, C ５ ~C １０ -Cycloalkyl, alkyl is C １ ~C ６ cyclically substituted cyclopentadienyls selected from alkyl, dialkylamino groups, and combinations thereof; (iii) Formula (1): 【Chemistry 2】 The N-heterocyclic substituted cyclopentadienyl corresponding to: (In the formula, R １ C which replaces a hydrogen atom of the benzene ring for each index m １ ~C ４ - represents alkyl, m is a number from 0 to 4, preferably from 0 to 2, more preferably 0; R ２ is unsubstituted or has one or more C １ ~C １０ - alkyl group, one or more C １ ~C ４ -substituted with dialkylamino groups or combinations thereof, １ ~C １０ -Alkyl, C ５ ~C １０ -cycloalkyl or C ６ ~C １０ - represents aryl, R ３ , R ４ and R ５ is hydrogen, C １ ~C ４ -Alkyl, or C ６ ~C １０ -aryl); (iv) Formula (2): 【Chemistry 3】 S-heterocyclic substituted cyclopentadienyl represented by the formula: (In the formula, R １ and R ２ are each independently hydrogen, halogen, C １ ~C １０ Alkyl, C ５ ~C １０ Cycloalkyl, and C ６ ~C １０ aryl; or R １ and R ２ together with the two double-bonded carbon atoms of the thiophene ring to which they are attached are unsubstituted or １ ~C ４ -Alkyl-substituted, aliphatic C ５ ~C ６ - forms a cycloalkene ring, R ３ , R ４ and R ５ are each independently hydrogen, C １ ~C ４ Alkyl, and C ６ ~C １０ -aryl) 2. The catalyst composition of claim 1, wherein the substituted cyclopentadienyl is selected from the group consisting of:

10. 2. The catalyst composition of claim 1, wherein Cy is selected from methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, and pentamethylcyclopentadienyl.

11. 1. A process for preparing a polymer comprising units derived from ethylene, comprising the steps of: (a) providing a monomer composition comprising ethylene; (b) providing a catalyst composition according to any one of claims 1 to 10; (c) optionally providing at least one scavenger; (d) optionally providing at least one activating agent; and (e) contacting at least a portion of said monomer composition with said catalyst composition to produce a polymer. A method comprising:

12. the polymer is an ethylene / α-olefin copolymer, the monomer composition comprises ethylene, propylene, and at least one non-conjugated diene having from 6 to 30 carbon atoms, preferably selected from dicyclopentadiene (DCPD), 5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, and combinations thereof; and The method according to claim 11, wherein the polymer preferably has a weight average molecular weight of from 200,000 g / mol to 600,000 g / mol.

13. A polymer obtainable by the method according to claim 11.

14. 12. An article comprising a cured polymer of the polymer obtainable by the method of claim 11.

15. Use of a metal complex as defined in any one of claims 1 to 10 as a polymerization catalyst for producing a polymer comprising units derived from ethylene.

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