C1 Symmetric 5-OMe-6-Alkyl Substituted Metallocenes

Abstract

The 5-OMe-6-tBu substitution of the indenyl fragment of the C1 symmetric catalyst is crucial to improve the EP molecular weight capability. The catalyst described in this document is also capable of producing other conventional polyolefins such as iPP, PE and EO copolymers. The added capability of high molecular weight EP copolymers can broaden the possibilities of the C1 symmetric system in the fields of RCP and ICP where such capability is required.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 307,477, filed February 7, 2022, the disclosure of which is incorporated herein by reference in its entirety.

[0002] Field Exemplary embodiments disclosed herein relate to polyolefin catalysts and methods for preparing polyolefins therewith. [Background technology]

[0003] background Olefin polymerization catalysts are of great utility in industry, and therefore there is interest in finding new catalyst systems, including catalyst activators, that enhance the polymerization activity of the catalyst and allow the production of polymers with specific properties, such as high melting points and high molecular weights. Catalysts for olefin polymerization are often based on metallocenes as catalyst precursors, which are activated with the aid of alumoxanes or with activators containing non-coordinating anions. Many of the patent publications using the 4-Ar-5-OMe-6-tBu indene scaffold are based on C2 symmetric metallocene systems. The first example of the 4-Ar-5-OMe-6-tBu indene scaffold was described by Resconi in WO2007 / 116034 in the context of C2 symmetric catalysts. Subsequent patent publications by Borealis describe the use of the 5-OMe-6-tBu indene scaffold in the context of symmetric (similarly substituted indenes) and asymmetric (different indene substitution) C2 symmetric metallocene catalysts (US2014 / 0221584, US2015 / 0259442, US2016 / 0002369). Related publications are EP3567061A1, WO2019 / 12110A1, WO2020 / 02349A1, WO2019 / 197383A1, and WO2020 / 157171A1. Recent patent activity on C1 symmetric catalysts for PP (WO2020 / 184887, US2019 / 0270833 and KR2019 / 0064338) uses catalysts described in WO2014 / 099303, WO2017 / 069854 and US9266910B2. Other notable patent publications include KR2020 / 00041169, KR2020 / 2250792, KR2020 / 2250794, and WO2020 / 96250A1. Other references of interest include U.S. Patent Nos. 5,416,177; 5,817,590; 8,202,958; 8,076,419; 7,531,605; 7,741,417; 6,355,747; 7,851,644; 7,081,543; 6,342,566; 6,960,676; 6,384,142; 6,472,474; U.S. Patent Publication Nos. 2011 / 0172375 and 2010 / 0152388; EP Patent Publication Nos. 0 277 004, 0 405 201, 0 798 306, 0 630 910; PCT Publication Nos. WO1991 / 002012, WO2001 / 062764, WO2001 / 068718, WO2004 / 005360, WO2001 / 048035, WO2003 / 035708; MA Giardello, et al. (1995) J. Am. Chem. Soc., v.117, pp. 12114-12129; and EA Sanginov, et al. (2006) Polymer Science, Series A, v.48(2), pp. 99-106. Summary of the Invention

[0004] summary The 5-OMe-6-tBu substitution of the indenyl backbone of the C1 symmetric catalyst is crucial to improve the EP molecular weight capability. The catalysts described in this document are also capable of producing other conventional polyolefins, such as iPP, PE and EO copolymers. The added capability of high molecular weight EP copolymers can broaden the possibilities of the C1 symmetric system in RCP and ICP fields where such capability is required. [Brief description of the drawings]

[0005] [Figure 1] 1 is an X-ray structure from a catalyst utilizing the technological advances of the present invention. [Diagram 2] Average catalyst activity in propylene polymerization is shown for a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 3A] 1 shows the average melting points of polypropylene prepared with a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 3B] 1 shows the average molecular weight capabilities of polypropylene prepared using a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 4A] The average catalyst activities are shown for PE / EO copolymers prepared with conventional catalysts and catalysts utilizing the technological advances of the present invention. [Figure 4B] The average molecular weight capabilities are shown for PE / EO copolymers prepared with a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 5A] 1 shows the average melting points of EO copolymers prepared using a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 5B] 1 shows the average octene content of EO copolymers prepared using a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 6] Representative catalyst activities are shown for EP copolymers using conventional catalysts and catalysts utilizing the technological advances of the present invention. [Figure 7A] Representative ethylene incorporation for EP copolymers of various compositions using a conventional catalyst and a catalyst utilizing the technological advances of the present invention are shown. [Figure 7B] 1 shows typical molecular weight capabilities of EP copolymers of various compositions using conventional catalysts and catalysts utilizing the technological advances of the present invention. [Figure 8] 1 shows slurry polymerization in the presence of propylene (iPP) and ethylene propylene mixtures using a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 9A] 1 shows the molecular weight capabilities of EP copolymers prepared in slurry polymerization using a conventional catalyst and a catalyst utilizing the technological advances of the present invention. [Figure 9B] EP copolymer compositions prepared by slurry polymerization using a conventional catalyst and a catalyst utilizing the technological advances of the present invention are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Detailed Description For purposes of this application and the claims appended hereto, the new numbering convention for the Periodic Table Groups will be used as set forth in Chemical and Engineering News, 63(5), p. 27 (1985). Thus, a "Group 4 metal" is an element in Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr. Unless otherwise indicated, "catalyst productivity" is a measure of how many grams of polymer (P) are produced using a polymerization catalyst containing Wg of catalyst (cat) over a period of time T hours; it can be expressed as P / (T×W) and can be expressed in units of gPgcat-1hr-1. Unless otherwise indicated, "conversion" is the amount of polymer converted to polymer product, reported as a mole %, and calculated based on the polymer yield and the amount of monomer fed to the reactor. Unless otherwise indicated, "catalyst activity" is a measure of how active the catalyst is, reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat).

[0007] An "olefin," sometimes referred to as an "alkene," is a straight-chain, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in the polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, the mer units in the copolymer are derived from ethylene in a polymerization reaction, and the derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer. A "polymer" has two or more identical or different mer units. A "homopolymer" is a polymer having mer units that are the same. A "copolymer" is a polymer having two or more mer units that are different from each other. A "terpolymer" is a polymer having three mer units that are different from each other. "Different," as used to refer to mer units, means that the mer units differ from each other by at least one atom or are isomerically different. Thus, the definition of copolymer as used herein includes terpolymers, etc. Oligomers are typically polymers having a low molecular weight (e.g., Mn less than 25,000 g / mol, preferably less than 2,500 g / mol) or a small number of mer units (e.g., 75 mer units or less). An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer that contains at least 50 mol% ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer that contains at least 50 mol% propylene-derived units, etc. For purposes of this application, ethylene shall be considered an alpha olefin.

[0008] For purposes of this application and the claims appended hereto, the term "substituted" means that a hydrogen radical has been replaced with a heteroatom or a heteroatom-containing group. For example, a "substituted hydrocarbyl" is a group made of carbon and hydrogen in which at least one hydrogen has been replaced with a heteroatom or a heteroatom-containing group. The term "heteroatom" refers to any Group 13-17 element except carbon. Heteroatoms include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term "heteroatom" can include the above elements with hydrogen attached, such as BH, BH2, SiH2, OH, NH, NH2, etc. The term "substituted heteroatom" refers to a heteroatom having one or more of its hydrogen atoms replaced by a hydrocarbyl or substituted hydrocarbyl group. Unless otherwise indicated (e.g., in the definitions of "substituted hydrocarbyl," "substituted aromatic," etc.), the term "substituted" means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3 (q is 1 to 10, each R * are independently hydrocarbyl or halocarbyl groups, and two or more R * may be attached to form a substituted or unsubstituted fully unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure) or at least one heteroatom is inserted within the hydrocarbyl ring.

[0009] The term "substituted hydrocarbyl" refers to a group in which at least one hydrogen atom of a hydrocarbyl group has been replaced with at least one heteroatom (e.g., a halogen, such as Br, Cl, F, or I) or heteroatom-containing group (e.g., a functional group, such as -NR * 2, -OR * , -SeR * , -TeR *, -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3. -GeR * 3. -SnR * 3. -PbR * 3 (q is 1 to 10, each R * are independently hydrocarbyl or halocarbyl groups, and two or more R * may be attached to form a substituted or unsubstituted fully unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure) or at least one heteroatom is inserted within the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" refers to a phenyl group having 1, 2, 3, 4, or 5 hydrogen groups replaced by hydrocarbyl or substituted hydrocarbyl groups. For example, a "hydrocarbyl-substituted phenyl" group can be represented by the formula:

[0010] [ka]

[0011] In the formula, R a , R b , R c , R d , and R e are each independently hydrogen, C1-C 40 Hydrocarbyl or C1-C 40 Substituted hydrocarbyl, heteroatom or heteroatom-containing group (wherein R a , R b , R c , R d , and R e at least one of R is not H; a , R b , R c , R d , and R e Two or more of these are combined to form C4-C 62It may form cyclic or polycyclic hydrocarbyl ring structures, or combinations thereof.

[0012] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also called polydispersity, is defined as Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mole. The following abbreviations may be used in this application: Me is methyl, Et is ethyl, Pr is propyl, cPR is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, MAO is methylalumoxane, Ind is indenyl, Cp is cyclopentadienyl, Flu is fluorenyl, OTf is triflate, and RT is room temperature (23° C. unless otherwise indicated).

[0013] A "catalyst system" is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. For purposes of this application and the claims appended hereto, when a catalyst system is described as comprising the neutral stable forms of the components, those skilled in the art will appreciate that the ionic forms of the components are the forms that react with monomers to produce polymers. In the present description, metallocene catalysts may be described as catalyst precursors, pre-catalyst compounds, metallocene catalyst compounds, or transition metal compounds, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into polymers. An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. A "neutral donor ligand" is a neutrally charged ligand that donates one or more electron pairs to a metal ion. Metallocene catalysts are defined as organometallic compounds having at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety), more frequently two π-bonded cyclopentadienyl or substituted cyclopentadienyl moieties.

[0014] For purposes of this application and the claims appended hereto with respect to metallocene catalyst compounds, the term "substituted" means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group, and ethyl alcohol is an ethyl group substituted with an -OH group. The terms "hydrocarbyl radical", "hydrocarbyl" and "hydrocarbyl group" are used interchangeably throughout this document. Similarly, the terms "group", "radical" and "substituent" are used interchangeably in this document. For the purposes of this disclosure, a "hydrocarbyl group" is defined as a group that contains hydrogen atoms and up to 100 carbon atoms and may be linear, branched or cyclic, and when cyclic, may be aromatic or non-aromatic. A "substituted hydrocarbyl" is a group made up of carbon and hydrogen in which at least one hydrogen has been replaced with a heteroatom or heteroatom-containing group.

[0015] The 5-OMe-6-tBu substitution of the indenyl fragment of the C1 symmetric catalyst is crucial to improve the EP molecular weight capability. The catalyst described in this document is also capable of producing other conventional polyolefins, such as iPP, PE and EO copolymers. The added capability of high molecular weight EP copolymers can broaden the possibilities of the C1 symmetric system in RCP and ICP fields where such capability is required. Propylene-ethylene random copolymers and EP rubber are interesting in the field of impact copolymers. However, C1 metallocene catalysts typically do not reach the high molecular weight capability of impact modifying phases such as EP rubber. More generally, metallocene catalysts with high molecular weight capability typically require very advanced synthesis as well as difficult rac / meso separation. Therefore, it is desirable to have a catalyst capable of producing both highly crystalline isotactic polypropylene and high molecular weight EP rubber in a cost-effective catalyst system. One such catalyst compound disclosed in the present application is based on 5-OMe-6-tBu substitution on the C1 symmetric backbone as shown in the following formula (I).

[0016] [ka]

[0017] During the ceremony: M is a Group 4 metal, preferably Hf, Ti or Zr; X 1 and X 2 are each a monovalent anionic ligand, or X 1 and X 2 are linked to form a metallocycle ring; R 1 ~R 4 are each independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, Substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C1-C 10 alkyl, and each R' is independently hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 is aryl; R 5 is hydrogen, unsubstituted C1-C 40Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, Substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C1-C 10 alkyl, and each R' is independently hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 is aryl; R 6 ~R 10 are each independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, Substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C1-C 10 alkyl, and each R' is independently hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 is aryl; R 14 and R 15 are each independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, Substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C1-C 10 alkyl, and each R' is independently hydrogen, halogen, C1-C 10 Alkyl, or C6-C10 is aryl; R 12 and R 13 each independently represents an unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, Substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, where R'' is C1-C 10 alkyl, and each R' is independently hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 is aryl; Optionally, R 12 and R 13 may be attached; and R 16 is unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, Substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, -R"-SiR"3, where R" is C1-C 10 alkyl, and each R' is independently hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 It is aryl.

[0018] Besides giving high crystallinity iPP with minimal regioerror, these catalysts are capable of producing high molecular weight EP copolymers with high activity and excellent ethylene incorporation (up to 50 wt%). Furthermore, the applicability of these catalysts for EO plastomers is also demonstrated in this paper. The expected applications of these types are likely to be in the production of random or impact copolymers with stiff (iPP) or soft (RCP) matrices. The production capabilities of these product compositions will be discussed in the future.

[0019] Examples of catalysts that utilize the technological advances of the present invention are as follows: [ka]

[0020] In this document, several conventional C1 symmetric catalysts (C1-C6) are used as comparative examples for the chemical species E1-E4 that utilize the technological advances of the present invention. Many commercial metallocene catalysts for polypropylene are based on C2 symmetric metallocenes. Although these catalysts are highly active, their cost-in-use is high due to the need for complex ligand synthesis and isomer resolution that typically leads to low yields. On the other hand, the use of C1 symmetric catalysts would be advantageous due to their ease of preparation and overall lower cost. This approach could theoretically narrow the cost gap between ZN and metallocene catalysts. The structures of the catalysts discussed in this document are shown below.

[0021] [ka]

[0022] These new catalysts E1-E4 are prepared according to the following synthetic scheme for the preparation of C1 symmetric 5-OMe-6-tBu substituted metallocenes. [ka]

[0023] Slow evaporation of a methylene chloride solution of catalyst E2 yielded X-ray quality crystals. The collected data confirms the predicted ligand binding. The corresponding X-ray structure is shown in Figure 1 (ellipsoids are at the 50% probability level). Catalysts E1-E3 were evaluated for propylene polymerization using MAO activator (500 equiv.) under high-throughput conditions with MAO activation. Figure 2 shows the average catalyst activity in propylene polymerization (conditions: [cat] = 30 nmol, [MAO] = 500 equiv. Polymerizations were performed at 70 °C and 100 °C). 3A and 3B show the average melting point and molecular weight capabilities of polypropylene prepared with a conventional catalyst and a catalyst utilizing the technological advances of the present invention. The activity of catalysts utilizing the technological advances of the present invention is generally lower than comparable catalysts in the same genus. However, the observed activities of >100 kg / mmol h are still considered to be quite high. Furthermore, catalysts utilizing the technological advances of the present invention provide relatively high iPP crystallinity along with melting points and Mw capabilities above 150°C similar to other catalysts in the genus. The high crystallinity of iPP is shown in Table 1 below. 13 This is confirmed by C NMR data.

[0024] [Table 1]

[0025] Most catalysts retain a high level of catalytic stereoselectivity, as shown in Table 1. For example, the 4-tBu series of catalysts (C1, C3, and E1) show progressive improvements in stereoselectivity from simple indene to the more highly substituted 5-OMe-6-tBu indene. As with the previous series, the choice of substituents on the 4-Ar moiety influences stereoregularity. Ethylene and ethylene-octene (EO) copolymerizations were carried out under high-throughput conditions with a fixed ethylene pressure of 115 psi (0.793 MPa). Figures 4A and 4B show the average catalyst activity and molecular weight capability for PE / EO copolymers (conditions: [cat] = 20 nmol, 115 psi (0.793 MPa) ethylene, 100°C). Figures 5A and 5B show the average melting point and average octene content of EO. Catalysts utilizing the technological advances of the present invention exhibit slightly reduced activity compared to other C1 symmetric catalysts and comparable Mw capabilities under most conditions. Octene composition remains comparable to other catalysts.

[0026] Ethylene propylene polymerizations were performed with varying amounts of propylene with ethylene pressure balanced to a total pressure of 140 psi (0.965 MPa). Based on AVIATO calculations, the range of ethylene composition in the feed is approximately 0.2-0.8 based on mole fraction relative to propylene. This type of screen allows for a variety of compositions (from semi-crystalline copolymers to pure EP rubber). Results are discussed below. Catalysts E1-E3 are capable of producing a variety of compositions at high activity (>200 kg / mmol·h). Compared to other catalysts used in this paper, the advantage of using the 5-OMe-6-tBu substituted system is the significantly improved EP Mw capability. This is a major challenge for C1 symmetric catalyst systems, which typically cannot achieve good Mw capability in ethylene copolymers. This capability could expand the utilization of C1 symmetric catalyst systems in areas not typically possible with previous C1 symmetric catalyst families. With careful consideration of the support, this could expand C1 catalyst capability in specialty / impact copolymer systems. Preferred supports include Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silicon oxide / clay, or mixtures thereof. Careful consideration of the support will affect what type of process will produce a particular polymer. For example, if you are looking to make an impact copolymer, you will choose a highly porous support with a high surface area. On the other hand, if you want to make a simple PP for fiber or molded articles, you will consider a smaller particle size support with low pore content to aid in volatiles.

[0027] FIG. 6 shows representative catalyst activities for EP copolymers (conditions: [cat]=20 nmol, 140 psi (0.965 MPa) total pressure, 70° C.). 7A and 7B show representative ethylene incorporation and molecular weight capabilities of EP copolymers of various compositions. Catalysts utilizing the technological advances of this invention can also be supported on conventional porous materials such as silica. Details regarding the support methods are provided in the experimental section below. These supported catalysts exhibit high activity as well as improved molecular weight capability of the EP copolymers. FIG. 8 shows slurry polymerizations in the presence of propylene (iPP) and ethylene propylene mixtures (EP). Condition iPP: 0.6 mg supported catalyst, 5 μmol TIBAL, 4 mL liquid propylene, 1 mL isohexane. Condition EP (250 psi): 0.6 mg supported catalyst, 5 μmol TIBAL, 2 mL liquid propylene, 3 mL isohexane, 70 psi ethylene. Condition EP (185 psi): 0.6 mg supported catalyst, 5 μmol TIBAL, 1 mL liquid propylene, 4 mL isohexane, 70 psi ethylene.

[0028] [Table 2]

[0029] 9A and 9B show the molecular weight capabilities and compositions of EP copolymers prepared by slurry polymerization. The data presented in Figures 7-9 show that supported catalysts E1-E4 utilizing the technological advances of the present invention exhibit relatively high (>10,000 g / mol) catalytic activity for EP copolymer production. The main advantages of the systems are their improved molecular weight capability and narrower PDI of the EP copolymers, which result in better quality rubbers that provide improved impact properties. Furthermore, the narrow polydispersity index (PDI) provided by catalysts E1-E4 is a very useful property in polypropylene fiber processing.

[0030] In this application, the terms "cocatalyst" and "activator" are used interchangeably and are defined as any compound capable of activating any one of the above catalyst compounds by converting the neutral catalyst compound to a catalytically active catalyst compound cation. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, and ionizing activators, which may be neutral or ionic conventional cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds, which abstract reactive σ-bonded metal ligands to render the metal complex cationic, resulting in a charge-balanced non-coordinating or weakly coordinating anion. Those skilled in the art will be able to select appropriate activators for use with catalysts utilizing the technical advances of the present invention. Activators that can be used with the technical advances of the present invention can be found in U.S. Pat. No. 9,266,910, the entire contents of which are incorporated herein by reference. Preferred activators include those in which the activator is either an alumoxane or a salt of a non-coordinating anion (NCA).

[0031] The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to a cation or coordinates only weakly to a cation, and thus remains sufficiently unstable to be displaced by a neutral Lewis base. A "compatible" non-coordinating anion is an anion that does not decompose to neutrality when the initial complex decomposes. Furthermore, the anion does not transfer anionic substituents or fragments to the cation to form a neutral transition metal compound and neutral by-products from the anion. A non-coordinating anion useful in accordance with the present application is an anion that is compatible and stabilizes the transition metal cation in the sense of balancing the ionic charge of the transition metal cation with +1, yet retains sufficient lability to allow displacement during polymerization. The minimum molar ratio of activator to catalyst compound is 1:1. Alternate preferred ranges are from 1:1 to 500:1, alternatively from 1:1 to 200:1, alternatively from 1:1 to 100:1, alternatively from 1:1 to 50:1.

[0032] In embodiments herein, the catalyst system may include an inert support material. Preferably, the support material is a porous support material, such as talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, or the like, or mixtures thereof. A person skilled in the art would be able to select a suitable support for use with a catalyst utilizing the technical advances of the present invention. Supports that can be used with the technical advances of the present invention can be found in U.S. Pat. No. 9,266,910, the contents of which are incorporated herein by reference in their entirety. Preferred supports include Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silicon oxide / clay, or mixtures thereof. In an embodiment herein, the technical advance of the present invention relates to a polymerization process in which a monomer (e.g., propylene) and, optionally, a comonomer are contacted with a catalyst system comprising an activator and at least one metallocene compound, as described above. The catalyst compound and the activator may be combined in any order and are typically combined prior to contact with the monomer. Polymerization processes usable with the technical advance of the present invention can be found in U.S. Pat. No. 9,266,910, the entire contents of which are incorporated herein by reference.

[0033] The technical advance of the present invention also relates to compositions of matter produced by the methods described herein. The process of some embodiments of the technical advance of the present invention produces olefin polymers, preferably polyethylene and polypropylene homopolymers and copolymers. In one embodiment, the polymers produced herein preferably contain 0-25 mol % (alternatively 0.5-20 mol %, alternatively 1-15 mol %, preferably 3-10 mol %) of one or more C3-C 20 Olefin comonomers (preferably C3-C 12ethylene comonomer with an α-olefin, preferably propylene, butene, hexene, octene, decene, dodecene, preferably propylene, butene, hexene, octene), or preferably 0 to 25 mol % (alternatively 0.5 to 20 mol %, alternatively 1 to 15 mol %, preferably 3 to 10 mol %) of one or more C2 olefin comonomers or C4-C 20 Olefin monomer (preferably ethylene or C4-C 12 It is a propylene copolymer with an alpha olefin, preferably ethylene, butene, hexene, octene, decene, dodecene, preferably ethylene, butene, hexene, octene.

[0034] Unless otherwise indicated, Mw, Mn, and MWD are determined by GPC as described in US 2006 / 0173123, pages 24-25, paragraphs

[0334] to

[0341] . In preferred embodiments of the present technical advancement, the propylene polymers produced can be isotactic polypropylene, atactic polypropylene and random, block or impact copolymers.

[0035] One or more types of C2-C 40 A process for preparing an alpha-olefin homopolymer or copolymer by introducing an olefin monomer and a catalyst system comprising a catalyst compound of formula (I) and optionally hydrogen into a reactor at a reactor pressure of 0.7 bar to 70 bar and a reaction temperature of 20° C. to 150° C., and obtaining an alpha-olefin homopolymer or copolymer. 40Comonomers may include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-pentene, vinylcyclobutane, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene, norbornene, vinylnorbornene, or ethylidenenorbornene comonomers. The olefin polymer or copolymer may have a Mw value of 1,000 to 1,000,000 g / mol, such as 5,000 to 500,000, such as 10,000 to 250,000, as measured by gel permeation chromatography. The olefin homopolymer or copolymer may have a Mw distribution with a polydispersity index of less than 10, more preferably less than 6, and more preferably less than 3. The propylene homopolymers and copolymers may have a melting point above 120° C., more preferably above 140° C., more preferably above 150° C. The ethylene-propylene copolymers may have a comonomer content of 0.1-99.9 wt %, such as 1-50 wt %, for example 2-20 wt %, for example 3-10 wt %. The ethylene-linear alpha olefin copolymers may have a linear alpha olefin content comonomer content of 0.1-50 wt %, for example 5-40 wt %, for example 10-30 wt %. EXAMPLES

[0036] experiment Preparation of dimethylsilyl(6-tert-butyl-4-(4-tert-butylphenyl)-5-methoxy-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst E1) 5-tert-Butyl-7-(4-tert-butylphenyl)-6-methoxy-2-methylindene. A sealable flask was charged with 7-bromo-5-tert-butyl-6-methoxy-2-methylindene (0.791 g, 2.68 mmol), 4-tert-butylphenylboronic acid (0.480 g, 2.70 mmol, 1.01 equiv), potassium carbonate (0.830 g, 6.01 mmol, 2.24 equiv), bis(dibenzylideneacetone)palladium (0.020 g, 0.035 mmol, 0.013 equiv), 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.030 g, 0.10 mmol, 0.038 equiv), and tetrahydrofuran (30 mL). Nitrogen-bubbled water (10 mL) was then added. The sealable flask was placed under a nitrogen atmosphere for 30 minutes before sealing the flask. The sealed flask was stirred and heated to 75° C. for 16 hours. The reaction was then cooled back to room temperature. The contents of the flask were transferred to a separate flask and concentrated in vacuo. The residue was partitioned between water (50 mL) and diethyl ether (50 mL). The organic phase was separated and the aqueous phase was further extracted with diethyl ether (50 mL). The combined diethyl ether extracts were washed with saturated aqueous potassium carbonate (50 mL) and then with brine (50 mL). The organic extracts were dried over anhydrous magnesium sulfate and filtered over a pad of silica, washing the product through the pad with additional diethyl ether (3×50 mL). The diethyl ether filtrate was concentrated in vacuo to give a yellow solid. The yellow solid was then dissolved in pentane (50 mL) and again filtered over a pad of silica, washing the product through the pad with additional pentane (3×50 mL). The pentane filtrate was concentrated in vacuo to give the product as a white solid (0.544 g, 58% yield). 1 H NMR (400 MHz, C6D6): δ 7.47 (d, 2H, J = 8.4 Hz), 7.41-7.33 (m, 3H), 6.43 (d, 1H, J = 2.2 Hz), 3.24 (s, 3H), 2.98 (s, 2H), 1.84 (s, 3H), 1.59 (s, 9H), 1.28 (s, 9H).

[0037] (6-(tert-butyl)-4-(4-(tert-butyl)phenyl)-5-methoxy-2-methyl-1H-inden-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane To a pre-cooled stirred solution of 5-tert-butyl-7-(4-tert-butylphenyl)-6-methoxy-2-methylindene (0.544 g, 1.56 mmol) in diethyl ether was added n-butyllithium (0.60 mL, 2.74 M in hexanes, 1.6 mmol, 1.05 equiv). The reaction was stirred at room temperature for 16 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum to give the lithiate as a white solid. The lithiate was dissolved in diethyl ether (40 mL). This solution was then added to a stirred solution of tetramethylcyclopentadienyldimethylsilyl trifluoromethanesulfonate (0.425 g, 1.56 mmol, 1 equiv) in diethyl ether. The reaction was stirred at room temperature for 1 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (3×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as a white foam (0.615 g, 75% yield). 1 H NMR (400 MHz, C6D6): δ 7.70 (d, 2H, J = 8.4 Hz), 7.61 (s, 1H), 7.43 (d, 2H, J = 8.4 Hz), 6.67 (s, 1H), 3.25 (s, 3H), 2.00 (s, 3H), 1.97 (s, 3H), 1.91 (s, 3H), 1.82 (s, 6H), 1.63 (s, 9H), 1.31 (s, 9H), -0.08 (s, 3H), -0.17 (s, 3H).

[0038] Lithium 6-(tert-butyl)-4-(4-(tert-butyl)phenyl)-1-(dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-id-1-yl)silyl)-5-methoxy-2-methyl-1H-inden-1-ide To a stirred solution of (6-(tert-butyl)-4-(4-(tert-butyl)phenyl)-5-methoxy-2-methyl-1H-inden-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (0.615 g, 1.17 mmol) in diethyl ether (50 mL) was added n-butyllithium (0.90 mL, 2.74 M in hexanes, 2.5 mmol, 2.1 equiv). The reaction was stirred at room temperature for 2 h. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was washed with pentane (10 mL) and filtered on a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a pale orange solid (0.366 g, 58% yield). 1 H NMR (400 MHz, THF-d8): δ 7.58 (d, 2H, J = 8.4 Hz), 7.49 (s, 1H), 7.37 (d, 2H, J = 8.4 Hz), 5.74 (s, 1H), 3.11 (s, 3H), 2.31 (s, 3H), 2.15 (s, 6H), 1.93 (s, 6H), 1.38 (s, 9H), 1.37 (s, 9H), 0.60 (s, 6H).

[0039] Dimethylsilyl(6-tert-butyl-4-(4-tert-butylphenyl)-5-methoxy-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst E1) To a stirred solution of lithium 6-(tert-butyl)-4-(4-(tert-butyl)phenyl)-1-(dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-id-1-yl)silyl)-5-methoxy-2-methyl-1H-inden-1-ide (0.366 g, 0.679 mmol) in diethyl ether (50 mL) was added zirconium chloride (0.155 g, 0.665 mmol, 0.979 equiv.) while washing the remaining zirconium chloride into the reaction with toluene (5 mL). The reaction was stirred at room temperature for 15 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (2×20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a sticky orange foam (0.443 g). The foam was stirred in pentane (20 mL) for 1 h resulting in a yellow suspension. The suspension was filtered over a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a yellow solid (0.253 g, 54% yield). 1 H NMR (400 MHz, CD2Cl2): δ 7.60-7.52 (m, 2H), 7.52-7.46 (m, 2H), 7.44 (s, 1H), 6.62 (s, 1H), 3.32 (s, 3H), 2.20 (s, 3H), 2.05 (s, 3H), 1.98 (s, 3H), 1.90 (s, 3H), 1.89 (s, 3H), 1.37 (s, 9H), 1.35 (s, 9H), 1.19 (s, 3H), 1.08 (s, 3H).

[0040] Preparation of dimethylsilyl(6-tert-butyl-5-methoxy-2-methyl-4-(o-tolyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (Catalyst E3) 5-tert-Butyl-6-methoxy-2-methyl-7-(o-tolyl)-indene A sealable flask was charged with 7-bromo-5-tert-butyl-6-methoxy-2-methylindene (0.776 g, 2.63 mmol), o-tolylboronic acid (0.357 g, 2.63 mmol, 1 equiv), potassium carbonate (0.799 g, 5.78 mmol, 2.2 equiv), bis(dibenzylideneacetone)palladium (0.015 g, 0.026 mmol, 0.01 equiv), 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.023 g, 0.079 mmol, 0.03 equiv), and tetrahydrofuran (30 mL). Nitrogen-bubbled water (10 mL) was then added. The sealable flask was placed under a nitrogen atmosphere for 30 minutes before sealing the flask. The sealed flask was stirred and heated to 80° C. for 17 hours. The reaction was then cooled to room temperature. The contents of the flask were transferred to a separate flask and concentrated in vacuo. The residue was partitioned between water (50 mL) and pentane (100 mL). The aqueous layer was drained and the organic layer was washed with saturated aqueous potassium carbonate followed by brine. The organic extract was dried over anhydrous magnesium sulfate and filtered over a silica pad, washing the product through the pad with additional pentane (3×50 mL). The pentane filtrate was concentrated in vacuo to give the product as a white solid (0.460 g, 57% yield, mixture of two isomers, 0.16:1 ratio). 1 H NMR (400 MHz, C6D6): main isomer δ 7.37 (s, 1H), 7.22-7.05 (m, 4H), 6.43 (q, 1H, J = 1.5 Hz), 3.19 (s, 3H), 2.98 (dt, 1H, J = 22.7, 1.1 Hz), 2.66 (dt, 1H, J = 22.5, 1.3 Hz), 2.17 (s, 3H), 1.83 (d, 3H, J = 1.5 Hz), 1.56 (s, 9H).

[0041] Lithium 6-tert-butyl-4-(o-tolyl)-5-methoxy-2-methylindenide To a pre-cooled stirred solution of 5-tert-butyl-6-methoxy-2-methyl-7-(o-tolyl)-indene (0.460 g, 1.50 mmol) in diethyl ether (50 mL) was added n-butyllithium (0.60 mL, 2.74 M in hexanes, 1.6 mmol, 1.1 equiv). The reaction was stirred at room temperature for 16 h. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was washed with hexanes (10 mL) and filtered on a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a white solid (0.469 g, 64% yield). 1 H NMR (400 MHz, C4D8O): δ 7.45-7.39 (m, 1H), 7.24-7.20 (m, 1H), 7.18 (s, 1H), 7.15-7.09 (m, 2H), 5.70 (d, 1H, J = 2.0Hz), 5.25 (d, 1H, J = 2.1 Hz), 3.16 (s. 3H), 2.25 (s, 3H), 2.20 (s, 3H), 1.42 (s, 9H).

[0042] (6-(tert-butyl)-5-methoxy-2-methyl-4-(o-tolyl)-1H-inden-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane To a stirred solution of lithium 6-tert-butyl-5-methoxy-2-methyl-4-(o-tolyl)-indenide (0.298 g, 0.954 mmol) in diethyl ether (50 mL) was added tetramethylcyclopentadienyldimethylsilyl trifluoromethanesulfonate (0.313 g, 0.954 mmol, 1 equiv). The reaction was stirred at room temperature for 3 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (3×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as a white foam (0.399 g, 86% yield, two isomers, 1:1.8 isomer ratio). 1H NMR (400 MHz, C6D6): integrated as mixed isomers δ 7.62 / 7.61 (s, 1H), 7.54-7.44 (m, 1H), 7.27-7.17 (m, 3H), 6.36 / 6.31 (s, 1H), 3.62 / 3.54 (s, 1H), 3.24 (br s, 1H), 3.20 / 3.19 (s, 3H), 2.30 / 2.29 (s, 3H), 1.98 / 1.97 (s, 6H), 1.90 (s, 3H), 1.83 (s, 6H), 1.600 / 1.596 (s, 9H), -0.10 / -0.16 (s, 3H), -0.19 / -0.22 (s, 3H).

[0043] Dimethylsilyl(6-tert-butyl-5-methoxy-2-methyl-4-(o-tolyl)-indenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst E3) To a stirred solution of (6-(tert-butyl)-5-methoxy-2-methyl-4-(o-tolyl)-1H-inden-1-yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (0.399 g, 0.823 mmol) in diethyl ether was added n-butyllithium (0.61 mL, 2.74 M in hexanes, 1.7 mmol, 2 equiv.). The reaction was stirred at room temperature for 16 h. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was washed with pentane (10 mL) and filtered on a plastic fritted funnel. The solid was collected and concentrated under high vacuum to give a pink solid. The pink solid was dissolved in diethyl ether (50 mL) and zirconium chloride (0.192 g, 0.823 mmol, 1 equiv.) was added to the stirred solution and the remaining zirconium chloride was washed into the reaction with toluene (5 mL). The reaction was stirred overnight at room temperature. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with dichloromethane (3×20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in pentane (10 mL) until a suspension formed. The resulting suspension was filtered over a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a yellow solid (0.181 g, 34% yield, 1:1.7 ratio of isomers A and B). 1H NMR (400 MHz, CD2Cl2): total combined isomers δ 7.76-7.70 (m, 1H), 7.46 (s, 1H), 7.44 (s, 1H), 7.36-7.14 (m, 6H), 7.02 (dd, 1H, J = 7.6, 1.5 Hz), 6.47 (s, 1H, used for ratio calculations, isomer B), 6.36 (s, 1H used for ratio calculations, isomer A), 3.34 (s, 3H), 3.31 (s, 3H), 2.57 (s, 3H), 2.20 (s, 3H), 2.18 (s, 3H), 2.07 (s, 3H), 2.044 (s, 3H), 2.037 (s, 3H), 1.98 (s, 6H), 1.95 (s, 3H), 1.92 (s, 3H), 1.91 (s, 3H), 1.90 (s, 3H), 1.36 (s, 9H), 1.35 (s, 9H), 1.19 (s, 3H), 1.18 (s, 3H), 1.08 (s, 3H), 1.07 (s, 3H).

[0044] Preparation of dimethylsilyl(4-(o-biphenyl)-6-tert-butyl-5-methoxy-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst E2) 7-(o-biphenyl)-5-tert-butyl-6-methoxy-2-methylindene A sealable flask was charged with 7-bromo-5-tert-butyl-6-methoxy-2-methylindene (0.812 g, 2.75 mmol), o-biphenylboronic acid (0.545 g, 2.75 mmol, 1 equiv), potassium carbonate (0.836 g, 6.05 mmol, 2.2 equiv), bis(dibenzylideneacetone)palladium (0.016 g, 0.028 mmol, 0.01 equiv), 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.024 g, 0.083 mmol, 0.03 equiv), and tetrahydrofuran (30 mL). Nitrogen-bubbled water (10 mL) was then added. The sealable flask was placed under a nitrogen atmosphere for 30 minutes before sealing the flask. The sealed flask was stirred and heated to 80° C. for 65 hours. The reaction was then cooled to room temperature. The contents of the flask were transferred to a separate flask and concentrated in vacuo. The residue was partitioned between water (100 mL) and diethyl ether (100 mL). The aqueous layer was drained and the diethyl ether layer was collected. The aqueous layer was further extracted with diethyl ether (2 x 50 mL). The combined diethyl ether extracts were washed with saturated aqueous potassium carbonate and then with brine. The organic extracts were dried over anhydrous magnesium sulfate and concentrated in vacuo to give an orange solid. The solid was dissolved in pentane (50 mL) and filtered over a silica pad. The product was further washed through the silica pad with additional pentane (3 x 50 mL) and then a mixture of diethyl ether and pentane (1:5 ratio of diethyl ether to pentane using 3 x 50 mL of the mixture). The combined filtrate was concentrated in vacuo to give the product as an off-white to yellow solid (0.964 g, 95% yield, 1:20 ratio of isomers). 1 H NMR (400 MHz, C6D6): Main isomer δ 7.49-7.44 (m, 1H), 7.37-7.32 (m, 1H), 7.28-7.17 (m, 5H), 7.01-6.93 (m, 3H), 6.39 (q, 1H, J = 1.6 Hz), 3.15 (s, 3H), 3.14 (d, 1H, J = 22.2 Hz), 2.73 (d, 1H, J = 22.8 Hz), 1.86-1.84 (m, 3H), 1.32 (s, 9H).

[0045] Lithium 7-(o-biphenyl)-5-tert-butyl-6-methoxy-2-methylindenide To a pre-cooled stirred solution of 7-(o-biphenyl)-5-tert-butyl-6-methoxy-2-methylindene (0.964 g, 2.62 mmol) in diethyl ether (50 mL) was added n-butyllithium (1.00 mL, 2.74 M in hexanes, 2.74 mmol, 1.05 equiv). The reaction was stirred at room temperature overnight. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was washed with hexanes (10 mL) and filtered on a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a white solid (0.748 g, 76% yield). 1 H NMR (400 MHz, C4D8O): δ 7.72-7.65 (m, 1H), 7.41-7.37 (m, 1H), 7.33-7.27 (m, 2H), 7.08 (s, 1H), 7.07-7.02 (m, 2H), 6.93-6.87 (m, 3H), 5.69 (d, 1H, J = 6.0 Hz), 5.51 (d, 1H, J = 2.1 Hz), 3.08 (s, 3H), 2.28 (s, 3H), 1.10 (s, 9H).

[0046] (4-(o-biphenyl)-6-(tert-butyl)-5-methoxy-2-methylindenyl)dimethyl(2,3,4,5-tetramethylcyclopentadienyl)silane To a stirred solution of lithium 7-(o-biphenyl)-5-tert-butyl-6-methoxy-2-methylindenide (0.748 g, 2.00 mmol) in diethyl ether (50 mL) was added tetramethylcyclopentadienyldimethylsilyl trifluoromethanesulfonate (0.656 g, 2.00 mmol, 1 equiv). The reaction was stirred at room temperature for 2 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (3×20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as a white foam (1.07 g, 98% yield). 1H NMR (400 MHz, C6D6): total combined isomers, δ 7.68-7.63 (m, 1H), 7.59-7.54 (m, 1H), 7.53-7.46 (m, 4H), 7.32-7.23 (m, 8H), 7.10-6.93 (m, 6H), 6.59 (s, 1H), 6.49 (s, 1H), 3.60 (s, 1H), 3.53 (s, 1H), 3.25-3.17 (m, 5H), 3.11 (s, 3H), 2.04 (s, 3H), 2.02 (s, 6H), 1.95 (s, 6H), 1.88 (s, 3H), 1.85 (s, 3H), 1.84 (s, 3H), 1.81 (s, 6H), 1.36 (s, 9H), 1.32 (s, 9H), -0.13 (s, 3H), -0.19 (s, 3H), -0.21 (s, 3H), -0.23 (s, 3H).

[0047] Dimethylsilyl(4-(o-biphenyl)-6-tert-butyl-5-methoxy-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst E2) To a stirred solution of (4-(o-biphenyl)-6-(tert-butyl)-5-methoxy-2-methylindenyl)dimethyl(2,3,4,5-tetramethylcyclopentadienyl)silane (1.07 g, 1.95 mmol) in diethyl ether (50 mL) was added n-butyllithium (1.5 mL, 2.74 M in hexanes, 4.1 mmol, 2.1 equiv). The reaction was stirred at room temperature for 70 min. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum to give a tan solid. The solid was dissolved in diethyl ether (50 mL) and zirconium chloride (0.455 g, 1.95 mmol, 1 equiv) was added and the remaining zirconium chloride was washed into the reaction with toluene (5 mL). The reaction was stirred at room temperature for 15 h. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was extracted with dichloromethane (50 mL, then 2×10 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in pentane (10 mL). The resulting suspension was filtered over a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a yellow solid (0.962 g, 70% yield). 1 H NMR (400 MHz, CD2Cl2): δ 7.94-7.87 (m, 1H), 7.49-7.40 (m, 3H), 7.31 (s, 1H), 7.09-7.01 (m, 3H), 6.95-6.89 (m, 2H), 6.60 (s, 1H), 3.26 (s, 3H), 2.24 (s, 3H), 2.06 (s, 3H), 1.99 (s, 3H), 1.90 (s, 3H), 1.83 (s, 3H), 1.18 (s, 3H), 1.10 (s, 3H), 0.99 (s, 9H).

[0048] Preparation of dimethylsilyl(4-(3,5-di-tert-butyl-4-methoxyphenyl)-6-tert-butyl-5-methoxy-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (Catalyst E4) 5-tert-butyl-7-(3,5-di-tert-butyl-4-methoxyphenyl)-6-methoxy-2-methylindene A sealable flask was charged with 7-bromo-5-tert-butyl-6-methoxy-2-methylindene (0.916 g, 3.26 mmol), 3,5-di-tert-butyl-4-methoxyphenylboronic acid (0.870 g, 3.29 mmol, 1 equiv), potassium carbonate (1.04 g, 7.50 mmol, 2.3 equiv), bis(dibenzylideneacetone)palladium (0.020 g, 0.035 mmol, 0.01 equiv), 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.030 g, 0.10 mmol, 0.03 equiv), and tetrahydrofuran (30 mL). Nitrogen-bubbled water (10 mL) was then added. The sealable flask was placed under a nitrogen atmosphere for 30 minutes before sealing the flask. The sealed flask was stirred and heated to 80° C. for 19 hours. The reaction was then cooled back to room temperature. The contents of the flask were transferred to a separate flask and concentrated in vacuo. The residue was partitioned between water (50 mL) and diethyl ether (50 mL). The aqueous layer was drained and the diethyl ether layer was collected. The aqueous layer was further extracted with diethyl ether (50 mL). The combined diethyl ether extracts were washed with brine (50 mL). The organic extracts were dried over anhydrous magnesium sulfate and concentrated in vacuo to give an orange solid. The solid was dissolved in isohexane (100 mL) and filtered over a silica pad. The product was further washed through the silica pad with additional isohexane (2×50 mL). The combined filtrates were concentrated in vacuo to give the product as a white solid (1.36 g, 96% yield). 1 H NMR (400 MHz, C6D6): δ 7.55 (s, 2H), 7.38 (s, 1H), 6.46 (q, 1H, J = 1.5 Hz), 3.47 (s, 3H), 3.25 (s, 3H), 3.14 (s, 2H), 1.85 (d, 3H, J = 1.5 Hz), 1.60 (s, 9H), 1.49 (s, 18H).

[0049] Lithium 4-(3,5-di-tert-butyl-4-methoxyphenyl)-6-tert-butyl-5-methoxy-2-methylindenide To a pre-cooled stirred solution of 7-(3,5-di-tert-butyl-4-methoxyphenyl)-5-tert-butyl-6-methoxy-2-methylindene (1.36 g, 3.14 mmol) in diethyl ether (50 mL) was added n-butyllithium (1.30 mL, 2.74 M in hexanes, 3.56 mmol, 1.1 equiv). The reaction was stirred at room temperature for 30 min. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was washed with hexanes (20 mL) and filtered on a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a white solid (1.30 g, 94% yield). 1 H NMR (400 MHz, C4D8O): δ 7.69 (s, 2H), 7.15 (s, 1H), 5.72 (dd, 1H, J = 2.1, 0.7 Hz), 5.65 (d, 1H, J = 2.1 Hz), 3.72 (s, 3H), 3.15 (s, 3H), 2.30 (s, 3H), 1.48 (s, 18H), 1.42 (s, 9H).

[0050] (4-(3,5-di-tert-butyl-4-methoxyphenyl)-6-(tert-butyl)-5-methoxy-2-methylindenyl)dimethyl(2,3,4,5-tetramethylcyclopentadienyl)silane To a stirred solution of tetramethylcyclopentadienyldimethylsilyl trifluoromethanesulfonate (0.972 g, 2.96 mmol, 1 equiv) in diethyl ether (20 mL) was added lithium 4-(3,5-di-tert-butyl-4-methoxyphenyl)-5-tert-butyl-6-methoxy-2-methylindenide (1.30 g, 2.96 mmol) in diethyl ether (50 mL). The reaction was stirred at room temperature for 1 h. The reaction was concentrated under a stream of nitrogen and then under high vacuum. The residue was extracted with pentane (40 mL, then 20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to give the product as a white foam (1.79 g, 98% yield). 1 H NMR (400 MHz, C6D6): δ 7.77 (s, 2H), 7.63 (s, 1H), 6.79 (s, 1H), 3.62 (s, 1H), 3.49 (s, 3H), 3.28 (s, 3H), 3.21 (br s, 1H), 2.03 (s, 3H), 1.98 (s, 3H), 1.90 (s, 3H), 1.82 (s, 6H), 1.64 (s, 9H), 1.54 (s, 18H), -0.08 (s, 3H), -0.18 (s, 3H).

[0051] Dimethylsilyl(4-(3,5-di-tert-butyl-4-methoxyphenyl)-6-tert-butyl-5-methoxy-2-methylindenyl)(2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride (catalyst E4) To a stirred solution of (4-(3,5-di-tert-butyl-4-methoxyphenyl)-6-(tert-butyl)-5-methoxy-2-methylindenyl)dimethyl(2,3,4,5-tetramethylcyclopentadienyl)silane (1.79 g, 2.92 mmol) in diethyl ether (50 mL) was added n-butyllithium (2.2 mL, 2.74 M in hexanes, 6.0 mmol, 2.1 equiv). The reaction was stirred at room temperature for 67 min. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum to give a foam. The foam was dissolved in diethyl ether (50 mL) and stirred, and zirconium chloride (0.679 g, 2.91 mmol, 1 equiv) was added and the remaining zirconium chloride was washed into the reaction with toluene (5 mL). The reaction was stirred at room temperature for 15 h. The reaction was concentrated under a stream of nitrogen and then concentrated under high vacuum. The residue was extracted with dichloromethane (50 mL, then 20 mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum. The residue was stirred in hexanes (40 mL). The resulting yellow suspension was filtered over a plastic fritted funnel. The filtered solid was collected and concentrated under high vacuum to give the product as a yellow solid (1.589 g, 70% yield). 1 H NMR (400 MHz, CD2Cl2): δ 7.88-7.11 (m, 3H), 6.61 (s, 1H), 3.72 (s, 3H), 3.30 (s, 3H), 2.21 (s, 3H), 2.05 (s, 3H), 1.99 (s, 3H), 1.90 (s, 3H), 1.88 (s, 3H), 1.44 (s, 18H), 1.36 (s, 9H), 1.19 (s, 3H), 1.08 (s, 3H).

[0052] High-throughput polymerization conditions: Unless otherwise stated, propylene homopolymerizations and ethylene-propylene copolymerizations (if any) were carried out in parallel pressure vessels as generally described in U.S. Patents US6,306,658; US6,455,316; US6,489,168; WO2000 / 009255; and Murphy et al. (2003) J. Am. Chem. Soc., v.125, pp. 4306-4317, each of which is fully incorporated herein by reference for U.S. purposes. Although individual amounts, temperatures, solvents, reactants, reactant ratios, pressures, and other variables may vary from polymerization run to polymerization run, a typical polymerization carried out in parallel pressure vessels is described below.

[0053] Metallocene-Based Propylene Polymerization: A pre-weighed glass vial insert and a disposable stir bar were fixed to each reactor in a reactor housing 48 individual reactors. The reactors were then closed and propylene was introduced into each vessel as a condensed gas liquid (typically 1 mL). Solvent (typically isohexane) was then added to bring the total reaction volume, including subsequent additions, to 5 mL, and the reactors were heated to their set temperature (usually about 50° C. to about 110° C.). The contents of the vessels were stirred at 800 rpm. An activator solution (typically 100-1000 molar equivalents of methylalumoxane (MAO) in toluene) was then injected into the reactor along with 500 microliters of toluene, followed by a toluene solution of catalyst (typically 0.50 mM in toluene, e.g., 20-40 nmol of catalyst) and another aliquot of toluene (500 microliters).

[0054] Equivalent weights are determined based on molar equivalents relative to the moles of transition metal in the catalyst complex. The reaction was then allowed to proceed until a predetermined amount of pressure was taken up by the reaction. At this point, the reaction was quenched by pressurizing the vessel with compressed air. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and inert atmosphere glove box and the volatile components were removed using a Genevac HT-12 centrifuge and a Genevac VC3000D vacuum evaporator operated at high temperature and reduced pressure. The vial was then weighed to determine the yield of polymer product. The resulting polymer was analyzed by Rapid GPC (see below) to determine molecular weight and DSC (see below) to determine melting point.

[0055] Preparation of silica-supported MAO (SMAO) In a Cellstar, 10.0 g of 200° C. calcined silica (DM-L403, AGC Chemicals) was suspended in approximately 100 mL of dry toluene and cooled to −20° C. in a freezer. After approximately 30 min of cooling, a 30% solution of MAO (15.8 g in toluene) was slowly added (over 10 min) to the stirred silica mixture. The reaction was allowed to warm back to room temperature with stirring for 1.5 h. After 1.5 h, the temperature was increased to 100° C. and the reaction was stirred for an additional 2.5 h. The temperature was then reduced to 55° C. before the mixture was filtered over a glass frit. The collected SMAO was then washed with toluene (2×50 mL) and pentane (2×50 mL) and dried in vacuum for 1 h. Yield: 14.1 g of free-flowing powder, calculated MAO absorption=7.1 mmol / g.

[0056] General procedure for catalyst loading 0.51 g of SMAO was suspended in 10 mL of toluene. With stirring, a solution of TIBAL (0.260 mL, 1 M) was added. The mixture was stirred for an additional 15 min at room temperature. After 15 min, 8.2 μmol of the desired metallocene was slowly added as a toluene solution (in approximately 1-2 mL of toluene). The mixture became green and slowly turned dark red. Each mixture was stirred for 2.5 h at room temperature. After 2.5 h, the mixture was filtered and the supported catalyst was washed with toluene (2×5 mL) and pentane (2×5 mL) and dried in vacuum to give the supported metallocene as a dark orange / red powder.

[0057] Test Method 13 C-NMR spectroscopy The polymer microstructure was determined by 13C-NMR spectroscopy, including the concentrations of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Samples were dissolved in d2-1,1,2,2-tetrachloroethane. Spectra were recorded at 125 °C using a 75 or 100 MHz NMR spectrometer. The polymer resonance peaks are referenced to mmmm = 21.8 ppm. The calculations involved in the characterization of the polymers by NMR follow the work of FA Bovey in "Polymer Conformation and Configuration" Academic Press, New York 1969 and J. Randall in "Polymer Sequence Determination, 13C-NMR Method", Academic Press, New York, 1977. The percent of methylene sequences of length 2, %(CH2)2, was calculated as follows: the integral of the methyl carbons between 14 and 18 ppm (which is the concentration corresponding to the number of methylenes in the length 2 sequence) divided by the integral of the methylene sequences of length 1 between 45 and 49 ppm plus the integral of the methyl carbons between 14 and 18 ppm, multiplied by 100. This is a minimum calculation of the amount of methylene groups contained in sequences of 2 or more, since sequences of more than 2 methylenes were excluded. Assignment based on HN Cheng and JA Ewen, Makromol. Chem. 1989, 190, 1931.

[0058] Rapid GPC Procedure: To measure molecular weight related values ​​by GPC, high temperature size 5 exclusion chromatography was performed using an automated "fast GPC" system generally described in U.S. Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, the contents of each of which are incorporated herein by reference in their entireties for U.S. purposes. The instrument has a series of three 30 cm x 7.5 mm linear columns, each containing PLgel 10 μm, Mix B. The GPC system was calibrated using polystyrene standards ranging from 580 to 3,390,000 g / mol. The system was operated at an eluent flow rate of 2.0 mL / min and an oven temperature of 165°C. 1,2,4-trichlorobenzene was used as the eluent. Polymer samples were dissolved in 1,2,4-trichlorobenzene at concentrations between 0.1 and 0.9 mg / mL. 250 uL of polymer solution was injected into the system. The concentration of polymer in the eluent was monitored using an evaporative light scattering detector (as shown by the example in Table 3) or a Polymer Char IR4 detector. Molecular weights given are relative to polystyrene standards and are uncorrected.

[0059] DSC procedure For high-throughput samples, melting points (T m ) was measured. Typically, 5-10 mg of molded or plasticized polymer was sealed in an aluminum pan and loaded into the instrument at about room temperature. The sample was pre-annealed at about 220°C for about 15 minutes and then cooled to about room temperature overnight. The sample was then heated to about 220°C at a heating rate of about 100°C / min, held at this temperature for at least about 5 minutes, and then cooled at a rate of about 50°C / min, typically to a temperature at least about 50°C below the crystallization temperature. Melting points were collected during the heating period.

[0060] All documents described herein, including any priority documents and / or testing procedures, are incorporated herein to the extent that they do not contradict the text, provided that any priority documents not specified in the originally filed application or filing are not incorporated herein by reference. As is apparent from the general description and specific embodiments above, the technical advances of the present invention have been demonstrated and described, but various modifications can be made without departing from the spirit and scope of the present invention. Accordingly, the present invention is not intended to be limited thereby. Similarly, the term "comprising" is deemed synonymous with the term "including" for purposes of Australian law. Similarly, there is a common understanding that whenever the transitional phrase "comprising" precedes a composition, element, or group of elements, it also contemplates the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" preceding the recitation of the composition, element, or group of elements, and vice versa.

[0061] Certain embodiments and features have been described with a set of numerical upper limits and a set of numerical lower limits. It should be understood that ranges including any combination of two values ​​are contemplated, for example, any combination of lower limits with any combination of upper limits, any combination of two lower limits, and / or any combination of two upper limits, unless otherwise indicated. Certain lower limits, upper limits, and ranges may appear in one or more claims below. All numerical values ​​are "about" or "approximately" designations and take into account experimental error and variations that would be expected by one of ordinary skill in the art. Any values ​​in the table may be subject to an additional ±10% at the end of the range defining their respective measurement or characteristic.

[0062] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent that they do not contradict this text. As is apparent from the general description and specific embodiments above, the forms of the present disclosure have been illustrated and described, but various modifications can be made without departing from the spirit and scope of the present invention. Thus, the present disclosure is not intended to be limited thereby. While this disclosure has been described with respect to certain embodiments and examples, it will be appreciated that those skilled in the art, having the benefit of this disclosure, may devise other embodiments which do not depart from the scope and spirit of the disclosure.

Claims

1. The following formula (I): 【Chemistry 1】 (In the formula, M is a Group 4 metal, preferably Hf, Ti or Zr; X 1 and X 2 are each a monovalent anionic ligand, or X 1 and X 2 are linked to form a metallocycle ring; R 1 ~R 4 are each independently hydrogen, unsubstituted C 1 -C 40 Hydrocarbyl, C 1 -C 40 Substituted Hydrocarbyl, Unsubstituted C 4 -C 62 Aryl, Substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR', -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 or -R''-SiR' 3 where R'' is C 1 -C 10 alkyl, and each R' is independently hydrogen, halogen, C 1 -C 10 Alkyl or C 6 -C 10 is aryl; R 5 is hydrogen, unsubstituted C 1 -C 40 Hydrocarbyl, C 1 -C 40 Substituted Hydrocarbyl, Unsubstituted C 4 -C 62 Aryl, Substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 or -R''-SiR' 3 where R'' is C 1 -C 10 alkyl, and each R' is independently hydrogen, halogen, C 1 -C 10 Alkyl or C 6 -C 10 is aryl; R 6 ~R 10 are each independently hydrogen, unsubstituted C 1 -C 40 Hydrocarbyl, C 1 -C 40 Substituted Hydrocarbyl, Unsubstituted C 4 -C 62 Aryl, Substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 or -R''-SiR' 3 where R'' is C 1 -C 10 alkyl, and each R' is independently hydrogen, halogen, C 1 -C 10 Alkyl or C 6 -C 10 is aryl; R 14 and R 15 are each independently hydrogen, unsubstituted C 1 -C 40 Hydrocarbyl, C 1 -C 40 Substituted Hydrocarbyl, Unsubstituted C 4 -C 62 Aryl, Substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 or -R''-SiR' 3 where R'' is C 1 -C 10 alkyl, and each R' is independently hydrogen, halogen, C 1 -C 10 Alkyl or C 6 -C 10 is aryl; R 12 and R 13 are each independently an unsubstituted C 1 -C 40 Hydrocarbyl, C 1 -C 40 Substituted Hydrocarbyl, Unsubstituted C 4 -C 62 Aryl, Substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 or -R''-SiR' 3 where R'' is C 1 -C 10 alkyl, and each R' is independently hydrogen, halogen, C 1 -C 10 Alkyl or C 6 -C 10 is aryl; Optionally, R 12 and R 13 may be attached; and R 16 is unsubstituted C 1 -C 40 Hydrocarbyl, C 1 -C 40 Substituted Hydrocarbyl, Unsubstituted C 4 -C 62 Aryl, Substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -R''-SiR' 3 where R'' is C 1 -C 10 alkyl, and each R' is independently hydrogen, halogen, C 1 -C 10 Alkyl or C 6 -C 10 is aryl) The catalyst compound represented by:

2. The catalyst compound is the following compound: 【Chemistry 2】 2. The catalyst compound of claim 1, comprising one or more of:

3. A catalyst system comprising the catalyst compound according to claim 1 or 2 and an activator.

4. 4. The catalyst system of claim 3, wherein the activator comprises methylalumoxane.

5. 1. A process for preparing isotactic polypropylene comprising the steps of:

4. The process comprising the steps of contacting propylene with the catalyst system of claim 3 and obtaining isotactic polypropylene.

6. 4. A method for preparing a copolymer comprising contacting ethylene and ethylene-octene with the catalyst system of claim 3 and obtaining a polyethylene / ethylene-octene copolymer.

7. 4. A process for preparing a copolymer comprising the steps of contacting ethylene and propylene with the catalyst system of claim 3 and obtaining an ethylene-propylene copolymer.

8. One or more types of C 2 -C 40 Introducing an olefin monomer, the catalytic system according to claim 3 and optionally hydrogen into a reactor at a reactor pressure of 0.7 bar to 70 bar and a reactor temperature of 20° C. to 150° C. and obtaining an alpha olefin homopolymer or copolymer, A process for preparing an alpha olefin homopolymer or copolymer.

9. Said C 2 -C 40 9. The process of claim 8, wherein the comonomer comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-pentene, vinylcyclobutane, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene, norbornene, vinylnorbornene, or ethylidenenorbornene.

10. 10. The method of any one of claims 8 to 9, wherein the olefin polymer or copolymer has a Mw value of from 1,000 to 1,000,000 g / mol, such as from 5,000 to 500,000, such as from 10,000 to 250,000, as measured by gel permeation chromatography.

11. 10. The process according to any one of claims 8 to 9, wherein the olefin homopolymer or copolymer has a Mw distribution with a polydispersity index of less than 10, more preferably less than 6, even more preferably less than 3.

12. The process according to any one of claims 8 to 11, wherein the olefin monomer is propylene.

13. The process according to any one of claims 8 to 11, wherein the propylene homopolymers and copolymers have a melting point above 120°C, more preferably above 140°C, even more preferably above 150°C.

14. 12. The method according to any one of claims 8 to 11, wherein the copolymer is an ethylene-propylene copolymer having a comonomer content of 0.1 to 99.9 wt%, such as 1 to 50 wt%, for example 2 to 20 wt%, such as 3 to 10 wt%.

15. 12. A method according to any one of claims 8 to 11, wherein the copolymer is an ethylene-linear alpha olefin copolymer having a linear alpha olefin content comonomer content of 0.1 to 50 wt%, such as 5 to 40 wt%, for example 10 to 30 wt%.

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