Double reactor chain shuttle reaction for ethylene / vinyl alloy blocks and triblock interpolymers

Abstract

A process for forming a composition comprising an ethylene / vinyl arene diblock and / or triblock interpolymer, comprising at least the following steps: A) polymerizing a mixture A comprising ethylene and optionally an alpha-olefin and optionally a vinyl arene in a reactor A in the presence of at least: a) a metal complex S selected from the following: Formula S1, Formula S2, Formula S3, Formula S4, or Formula S5, as described herein; and B) polymerizing a mixture B comprising ethylene, vinyl arene and optionally an alpha-olefin in a reactor B in the presence of at least: b) a metal complex H selected from the following: Formula H1 or H2, as described herein, wherein step A occurs before step B or vice versa, and at least one chain shuttling agent is provided in the first reactor. A composition comprising an ethylene / vinyl arene diblock or triblock interpolymer, as described herein.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 127,350, filed on 18 December 2020, which is incorporated herein by reference in its entirety. [Background technology]

[0002] The catalytic production of olefin block copolymers (OBCs) via chain shuttle technology has resulted in differentiated materials such as INFUSE Olefin Block Copolymers and INTUNE Olefin Block Copolymers. Such copolymers are typically produced from ethylene and alpha-olefins. The use of chain shuttle technology for producing styrene-based block interpolymers presents an attractive route to high-value polymers using continuous solution polymerization processes. High-value styrene-based polymers, such as styrene-ethylene / butene-styrene (SEBS), are produced in batch processes via anionic polymerization initiated by organolithium compounds. This costly polymerization involves the continuous addition of monomers, followed by an expensive hydrogenation step. There is a need for chain shuttle technology for producing ethylene / vinyl ylene block and triblock interpolymers using double-reactor continuous solution polymerization.

[0003] A. Valente et al., Angew. Chem., Int. Ed. 2014, 53, 4638-4641, "Isoprene-Styrene Chain Shuttling Copolymerization Mediated by a Lanthanide Half-Sandwich Complex and a Lanthanidocene: Straightforward Access to a New Type of Thermoplastic Elastomers," discloses chain shuttle polymerization of isoprene and styrene using n-butylethyl-magnesium, a lanthanide half-sandwich complex, and lanthanidocene. The resulting multiblock structure has alternating hard (styrene-enriched) and soft (isoprene-enriched) segments.

[0004] U.S. Patent Application Publication No. 2014 / 0088276 (Manufacturing Method for Multidimensional Polymer, and Multidimensional Polyme) discloses the polymerization of stereocontrolled (syndiotactic) block copolymers of styrene-type monomers and conjugated dienes such as isoprene or butadiene by chain shuttle technique and coordination chain transfer polymerization. Polymerization is carried out in the presence of a first catalyst and a second catalyst. The first and second catalysts each independently contain: a) a group 3 metal atom or lanthanide metal atom, e.g., Sc; b) a Cp-type ligand containing a substituted or unsubstituted cyclopentadienyl derivative; c) a monoanionic ligand; and d) a neutral Lewis base.

[0005] U.S. Patent No. 8,623,976 (Polymerization Catalyst Compositions Containing Metallocene Complexes and the Polymers Produced by Using the Same) is as follows: a) i) Group 3 metal atoms or lanthanide metal atoms, e.g., Sc, ii) Cp of substituted or unsubstituted cyclopentadienyl derivatives * Ligand, iii) Monoanionic ligands, iv) A metallocene complex containing a neutral Lewis base, b) Disclosed is a catalyst composition comprising an ionic compound of a non-coordinating anion and a cation, such as tetrakis(penta-fluorophenyl)borate. The catalyst composition is used to polymerize various polymers, such as ethylene / styrene copolymers (see Examples 11-17). The polymerized styrene may be in a syndiotactic form.

[0006] L. Pan et al., Angew. Chem., Int. Ed. 2011, 50, 12012-12015, Chain-Shuttling Polymerization at Two Different Scandium Sites: Regio and Stereospecific "One-Pot" Block Copolymerization of Styrene, Isoprene, and Butadiene disclose chain-shutling polymerization of styrene, isoprene, and butadiene using two different catalysts and a chain-shutling agent (triisobutylaluminum, TIBA). These catalysts exhibit different monomer selectivity and stereoselectivity in the presence of TIBA, resulting in region-specific and stereospecific copolymerization of styrene, isoprene, and butadiene.

[0007] SSPark et al., in Macromolecules 2017, 50, 6606-6616, "Biaxial Chain Growth of Polyolefin and Polystyrene from 1,6-Hexanediylzinc Species for Triblock Copolymers," disclose the preparation of triblock copolymers by initiating (anionic) styrene polymerization from polymeryl zincate species. Polyethylene / polypropylene copolymers are grown from dual-head zinc species using coordination chain transfer polymerization, followed by the addition of an anionic initiator (e.g., Me3SiCH2Li-(pmdeta)) and styrene monomer. Coordination chain transfer polymerization is carried out in the presence of a transition metal (e.g., Zr or Hf) complex. Thus, anionic polymerization is used to grow polystyrene-terminated blocks that exhibit no stereoregularity.

[0008] U.S. Patent Application Publication No. 2018 / 0022852 (Organic Zinc Compound Comprising Polyolefin-Polystyrene Block Copolymer, and Method for Preparing the Same) discloses the preparation of an organozinc compound, such as one represented by chemical formula 1, comprising a styrene polymer or a polyolefin-polystyrene block copolymer, as shown in the document. This preparation method involves preparing an intermediate by coordination polymerization of an olefin monomer using a transition metal catalyst, and then inserting a portion of the styrene monomer into the intermediate by anionic polymerization. Examples of transition metal catalysts include Zr metal compounds represented by chemical formulas 6A and 6B, each of which is shown in the document (see paragraphs

[0076] and

[0077] ).

[0009] Y. Luo et al., J. Am. Chem. Soc. 2004, 126, 13910-13911, "Scandium Half-Metallocene-Catalyzed Syndiospecific Styrene Polymerization and Styrene-Ethylene Copolymerization: Unprecedented Incorporation of Syndiotactic Styrene-Styrene Sequences in Styrene-Ethylene Copolymers," discloses the polymerization of syndiospecific styrene-ethylene copolymers using a scandium half-sandwich complex. The melting temperature (Tm) of the copolymer can be modified by adjusting the ethylene incorporation, which results in a decrease in Tm. Chain shuttlering was not demonstrated with the Sc catalyst.

[0010] H. Hagihara et al., in Polymer Journal 2012, 44, 147-154, "Synthesis of Ethylene-Styrene Copolymer Containing Syndiotactic Polystyrene Sequence by Trivalent Titanium Catalyst," discloses the polymerization of syndiotactic styrene-ethylene copolymer using the trivalent titanium catalyst tris(acetylacetonato)titanium (Ti(acac)3). The Ti(acac)3 catalyst produced different polymers, which can be attributed to the presence of multiple oxidation sites in the catalyst.

[0011] F. Lin et al., in the Journal of Polymer Science, Part A: Polymer Chemistry 2017, 55, 1243-1249, "Synthesis and Characterization of Crystalline Styrene-b-(Ethylene-co-Butylene)-b-Styrene Triblock Copolymers," discloses the synthesis and characterization of crystalline styrene-b-(ethylene-co-butylene)-b-styrene (SEBS). Cationic rare earth metal complexes, [(η 5 -Flu-CH2-Py)Ho(CH2SiMe3)(THF) was used for the living polymerization of butadiene and styrene. SBS triblocks were formed by the sequential addition of styrene, butadiene, and styrene monomers. The SBS triblocks consisted of elastic polybutadiene sequences with 1,4 regularity and crystalline syndiotactic polystyrene. SEBS were formed by hydrogenating the SBS triblocks.

[0012] B. Liu et al., in Macromolecules 2016, 49, 6226-6231, "Regioselective Chain Shuttling Polymerization of Isoprene: An Approach to Access New Materials from Single Monomer," discloses chain transfer polymerization of isoprene using pyridyl-methylene fluorenyl scandium complexes in combination with [Ph3C]B(C6F5)4 and iBu3Al. The polymerization resulted in high 1,4-selectivity of isoprene. Additional catalytic structures include "pyridyl-methylene functionalized fluorenyl-linked rare earth metal complexes 1-9" as shown in the same document, where the metal is Sc, Y, Lu, Tm, Er, Ho, Dy, Tb, or Gd (see page 6227 (Chart 1)).

[0013] U.S. Patent No. 8,710,143 (Catalyst Composition Comprising Shuttling Agent for Ethylene Multi-Block Copolymer Formation) discloses the polymerization of a multi-block copolymer using: (A) a first metal complex olefin polymerization catalyst, (B) a second metal complex olefin polymerization catalyst capable of preparing a polymer with chemical or physical properties different from the polymer prepared by catalyst (A) under equivalent polymerization conditions, and (C) a chain shuttle agent. Suitable monomers include one or more addition polymerizable monomers such as ethylene, 1-octene, and styrene (see paragraph 16, lines 3-32). Suitable catalysts include metal complexes in which the metal is selected from Groups 3-15, preferably Groups 3-10, more preferably Groups 4-8, and most preferably Group 4 (Ti, Zr, and Hf). See, for example, paragraph 19, lines 61-20, line 6. Ethylene / styrene multiblock polymers were prepared using Cat.A1(Hf) and Cat.B1(Zr) as shown in the same document (see paragraph 85, lines 12-30, paragraph 86, lines 21-52, paragraph 115, paragraphs 21-116, line 23, and Tables 27 and 28).

[0014] Further olefin block copolymers (OBCs) and related polymerizations are disclosed in the following references: U.S. Patent Nos. 7,915,192, 8,124,709, 8,501,885, 8,716,400, European Patent Publication Nos. 1716190(B1), 1926763(B1), and 2582747(B1).

[0015] However, in double reactors using continuous solution polymerization, chain shuttle techniques for producing ethylene / stereoregular vinyl array blocks and triblock interpolymers remain necessary. This need is met by the following invention. [Overview of the Initiative]

[0016] In a first aspect, a process for forming a composition comprising an ethylene / vinylarene diblock interpolymer and / or an ethylene / vinylarene triblock interpolymer, comprising at least the following steps: A) In reactor A, the following: at least the following selected from chemical formula S1, chemical formula S2, chemical formula S3, chemical formula S4, or chemical formula S5: a) polymerizing a mixture A comprising ethylene, and optionally an alpha-olefin, and optionally a vinylarene, in the presence of a metal complex S,

[0017]

Chemical formula

[0018] [ka] In the formula, M 1 This is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), and the metal is in a formal oxidation state of +2, +3, or +4. Each X can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R 3 and R 4 Each of these can be independently substituted or not substituted (C6~C 20 ) Aryl group, or substituted or unsubstituted (C5~C 20 ) Selected from heteroaryl groups, N and N' are bridging groups J containing 2 to 40 atoms other than hydrogen. 2 The bridging group is linked by and optionally contains an N atom that can interact with the metal via an electron-donating bond. Metal complexes are generally charge-neutral.

[0019] [ka] In the formula, M 1 This is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), and the metal is in a formal oxidation state of +2, +3, or +4. Each X can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted, unsubstituted (C1~C 30) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R 5 is either a substitution or a non-substitution (C1~C 30 ) Hydrocarbyl group, or substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl group, -Si(R C )3, or -H, T 1~2 -O-, -S-, -N(R N )-, or -P(R P )- Selected from, t is either 1 or 2. T 1 And N contains 4 to 50 atoms other than hydrogen, J 3 It is connected by a bridging group represented by, Each R in equation S3 P , R N , and R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, (C1~C 30 ) Heterohydrocarbyl, or -H, Metal complexes are generally charge-neutral.

[0020] [ka] M 1 This is a metal selected from zirconium (Zr) or hafnium (Hf), and the metal is in a formal oxidation state of +2, +3, or +4. Each X can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. -T 2 - and -T 3 Each of these is independently -O-, -S-, -N(R N )-, or -P(R P )- Selected from, R 6 and R 21 Each of these is independently -H, substitution, or non-substitution (C1~C 40 ) Hydrocarbyl, substituted or unsubstituted (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C Selected from the group consisting of 2NC(O)-, halogens, radicals having formula (I), radicals having formula (II), and radicals having formula (III),

[0021] [ka] In the formula, R 22~26 , R 27~34 , and R 35~43 Each of these can be independently substituted or not substituted (C1~C 40 ) Hydrocarbyl, substituted or unsubstituted (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R CS(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, halogen, or -H, and is selected from R 7~20 each independently is a substituted or unsubstituted (C1-C 40 )hydrocarbyl, substituted or unsubstituted (C1-C 40 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, halogen, or -H, and is selected from J 4 is a substituted or unsubstituted (C1-C 40 )hydrocarbylene or substituted or unsubstituted (C1-C 40 )heterohydrocarbylene, and the substituted or unsubstituted (C1-C 40 )hydrocarbylene has a part (to which J 2 and T 3 in chemical formula S4 are attached) containing a linker skeleton of 1 to 10 carbon atoms connecting the groups T 4 in chemical formula S4, or the substituted or unsubstituted (C1-C 40 )heterohydrocarbylene has a part (to which J 2 and T 3It has a portion containing a linker skeleton of 1 to 10 atoms that connects the components, and each of the 1 to 10 atoms in the linker skeleton is independently a carbon atom or a heteroatomic group of a heteroatom group, and each heteroatomic group is independently O, S, S(O), S(O)2, Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) and each R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) is a heterohydrocarbyl, and each R in chemical formula S4 P , R N , and the remaining R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or -H, Metal complexes are either charge-neutral overall, or

[0022] [ka] In the formula, M 1 This is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf). The metal is in a formal oxidation state of +2, +3, or +4. Each X can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R 44~51 Each of these can be substituted or not substituted (C1~ 40 ) Hydrocarbyl, substituted or unsubstituted (C1~C 40 ) Heterohydrocarbyl, -Si(RC )3, or -H, selected optionally, R 44~51 Two or more of these groups are linked, and therefore the cyclopentadienyl group is a substituted or unsubstituted indenyl group, or a substituted or unsubstituted fluorenyl group, R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl or -H, O and O contain 1 to 30 atoms other than hydrogen, J 5 Connected by a bridging group represented by, Metal complexes are generally charge-neutral, step, B) A step in which a mixture B comprising ethylene, vinylarene, and optionally alphaolefin is polymerized in reactor B in the presence of at least: b) a metal complex H selected from the following chemical formulas H1 or H2,

[0023] [ka] In the formula, M 2 These are elements from Ti, Sc, Y, or the lanthanide series. R 1 , R 2 , R 3 , R 4 , and R 5 Each of these is independently H, or a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted heterohydrocarbyl group. Q 1 Q 2 , and Q 3 Each of these is independently a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heterohydrocarbyl group, or a halogen. L is a Lewis base, each n is independently either 0 or 1, and m is an integer between 0 and 3. At least one L group and at least one Q group are optionally connected, and at least one R group and at least one Q group are optionally connected. Metal complexes are generally charge-neutral.

[0024] [ka] M 3 This is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), and the metal is in a formal oxidation state of +2, +3, or +4. Each Q can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl or -H, where each Q is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R 1 and R 2 Each of these is an independent bridging group containing 2 to 41 atoms other than hydrogen, and R is optionally selected. 1 and R 2 Each of these can independently be a substituted or unsubstituted arylene group. -Z 1 - and -Z 2 Each of these is independently -O-, -S-, -Se-, -N(R N )-, or -P(R P )- Selected from, -Z 1 - and -Z 2 Each of these can independently and optionally interact with the metal via electron-donating bonds. Z 1 and Z 2 J contains 1 to 50 atoms other than hydrogen. 5 Connected by a bridging group represented by, R P and R N Each of these can be substituted or not substituted (C1~C 30) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or -H, Metal complexes are generally charge-neutral. Step A occurs before Step B, and at least a portion of the reactor product in reactor A is transferred to reactor B, or Step B occurs before Step A, and at least a portion of the reactor product in reactor B is transferred to reactor A. If step A occurs before step B, at least one chain shuttle agent is supplied into reactor A. If step B occurs before step A, at least one chain shuttle agent is supplied into reactor B. A process in which the vinylarene in step A is equal to the vinylarene in step B, and the alpha-olefin in step A is equal to the alpha-olefin in step B.

[0025] In a second embodiment, a composition comprising an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, wherein the diblock interpolymer comprises at least one polymer structure selected from Structure 1 as shown below, and the triblock interpolymer comprises at least one polymer structure selected from Structure 2 or Structure 3, respectively, as shown below, where AR refers to vinylarene enrichment and AP refers to vinylarene deficiency. (AR)-(AP)(Structure 1), (AR)-(AP)-(AR)(Structure 2), (AP)-(AR)-(AP)(Structure 3), and Each (AR) segment independently contains ethylene, vinylarene, and optionally alpha-olefin in its polymerized form. Each (AP) segment independently comprises, in its polymerized form, ethylene, optionally vinylarene, and optionally alpha-olefin. Each (AR) segment independently contains >10 mol% vinylarene in its polymerized form, based on the total number of moles of polymerized monomers in the (AR) segment. A composition in which each (AP) segment independently contains ≤10 mol% vinylarene in polymerized form, based on the total number of moles of polymerized monomers in the (AP) segment. [Brief explanation of the drawing]

[0026] [Figure 1A] This is a schematic diagram illustrating the formation of ethylene / styrene diblock interpolymers. Each black block represents a vinylarene-deficient block containing ethylene, optionally alpha-olefin, and optionally vinylarene in the polymerized form. Each gray (pink) block represents a vinylarene-enriched block containing ethylene, vinylarene, and optionally alpha-olefin in the polymerized form. [Figure 1B] This is a schematic diagram illustrating the formation of ethylene / styrene triblock interpolymers. See above for a description of the blocks. [Figure 2] The 1H NMR profile of CAT B is shown. [Figure 3] The 13C NMR profile of CAT B is shown. [Figure 4] PPR data: Shows activity versus CSA input volume (μmole). [Figure 5] PPR data: Shows PS molecular weight (Molecule Weight, Mw) versus CSA input amount (μmole). [Figure 6] The conventional GPC profiles of syndiotactic polystyrene as described are shown. The GPC profiles, from left to right, starting with Log M=3.00, are "sPS-3 (100 DEZ polymer)", "sPS-5 (100 TEA polymer)", "sPS-2 (25 DEZ polymer)", "sPS-4 (25 TEA polymer)", and "sPS-1 (no CSA polymer)". [Figure 7]The 1H NMR profile of Triblock 2 (a composition containing ethylene / octene / styrene triblock) is shown. [Figure 8] The 13C NMR profile of Triblock 2 is shown. [Figure 9] The GPC profile of Triblock 1 (a composition containing ethylene / octene / styrene triblock) is shown. A dRI / UV dual detector was used. The GPC profile is shown from left to right, starting with Log M=4.00, as UV profile, then RI profile. [Figure 10A] The conventional GPC profiles for the sample described are shown. The GPC profiles, from left to right, start with Log M=3.00 and include Triblock 2 and IB-1 (in-reactor blend) (see Table 9). [Figure 10B] The conventional GPC profiles for the sample described are shown. The GPC profiles, from left to right, starting with Log M=2.00, are IB-2 (in-reactor blend), Triblock 3 (composition containing ethylene / octene / styrene triblock), Diblock 1 (composition containing ethylene / octene / styrene diblock), and Diblock 2 (composition containing ethylene / octene / styrene diblock) (see Table 7). [Figure 11] The tensile stress versus tensile strain for Triblock 2 and IB-1 is shown. [Figure 12] The conventional GPC profiles of atactic polystyrene as described are shown. The GPC profiles, from left to right, starting with Log M=2.00, are "aPS-4 (100 DEZ polymer)", "aPS-5 (25:TEA polymer)", "aPS-3 (25 DEZ polymer)", "aPS-1 (CAT C only polymer)", and "aPS-2 (without CSA C and CSA polymer)". [Figure 13] CAT D PPR data: Shows molecular weight (Mw) versus polymerization efficiency. [Figure 14] CAT E PPR data: Shows molecular weight (Mw) versus polymerization efficiency. [Figure 15]CAT F PPR data: Shows molecular weight (Mw) versus polymerization efficiency. [Modes for carrying out the invention]

[0027] Chain shuttle technology has been found to produce ethylene / vinylarene diblocks and triblock interpolymers via a dual catalyst in two reactors. For example, the catalyst (metal complex) used to form a vinylarene-deficient segment (or block) in one reactor satisfies the following criteria: a) high natural molecular weight, b) high chain shuttle rate determined by reducing molecular weight and narrowing the molecular weight distribution in the presence of a chain shuttle agent (CSA), and c) high α-olefin content. The catalyst (metal complex) used to form a vinylarene-enriched segment (or block) in the other reactor satisfies the following criteria: a) good activity for vinylarene polymerization, b) high chain shuttle constant determined by reducing molecular weight and narrowing the molecular weight distribution in the presence of a CSA, and c) suitable for the remaining monomer carryover.

[0028] As discussed above, in a first embodiment, the present invention provides a process for forming compositions comprising ethylene / vinylarene diblock interpolymer and / or ethylene / vinylarene triblock interpolymer, as described above. The process of the present invention may comprise a combination of two or more embodiments as described herein. Each step or component of the process of the present invention may comprise a combination of two or more embodiments as described herein.

[0029] As discussed above, the present invention also provides, in a second embodiment, compositions comprising an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock copolymer, as described above. The compositions of the present invention may comprise combinations of two or more embodiments as described herein. The diblock interpolymer and the triblock interpolymer may each comprise combinations of two or more embodiments as described herein.

[0030] In this specification, when used, the structure of the metal complex is defined as Ar1=Ar 1 Ar2=Ar 2 Ar3=Ar 3 Please note that, etc. Also, when used in this specification, with respect to such a structure, R1=R 1 , R²=R 2 , R3=R 3 And so on. Also, "a to n" represents consecutive numbers, R a ~R n This notation is R a , R a+1 , R a+2 ,..., R n This refers to R. 3 ~R 7 R 3 , R 4 , R 5 , R 6 , R 7 This refers to the following. When used herein in relation to the metal complexes described, the notation "→" refers to a bond formed from a donor electron pair (electron-donating bond). In this specification, pi (π) bonds are shown as straight lines.

[0031] The following embodiments are applicable to the processes and / or compositions of the present invention.

[0032] In each embodiment described herein, or in a combination of two or more embodiments, the metal complex S is structure s1a1 or structure s1a2:

[0033] [ka] Selected from.

[0034] In each embodiment described herein, or in a combination of two or more embodiments, the metal complex S is selected from chemical formula S1, and further from chemical formula S1a, as described herein, and the metal complex H is selected from chemical formula H1, and further from chemical formula H1a or formula H1b, as described herein.

[0035] In each embodiment described herein, or in combination of two or more embodiments, the metal complex H is selected from the following chemical formulas described herein: h1a1, h1a2, h1a3, h1b1, h1b2, h1b3, h2a1, or h2a2.

[0036] In each embodiment described herein, or in combination of two or more embodiments, at least one chain shuttle agent is selected from: alkylzinc compounds, alkylaluminum compounds, dual-head chain shuttle agents, or combinations thereof.

[0037] In each embodiment described herein, or in combination of two or more embodiments, step A occurs before step B.

[0038] Each embodiment, or combination of two or more embodiments, described herein, Step B occurs before Step A.

[0039] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in one embodiment or a combination of two or more embodiments described herein, vinylarene is styrene.

[0040] In each embodiment described herein, or in combination of two or more embodiments, mixture A comprises an alpha-olefin.

[0041] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in each embodiment or combination of two or more embodiments described herein, each (AR) segment independently contains ≥15 mol%, or ≥20 mol%, or ≥25 mol%, or ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥45 mol%, or ≥50 mol%, or ≥55 mol%, or ≥60 mol%, based on the total number of moles of polymerized monomers in the (AR) segment. In each embodiment or combination of two or more embodiments described herein, each (AR) segment independently contains <100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤91 mol%, based on the total number of moles of polymerized monomers in the (AR) segment.

[0042] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in each embodiment or combination of two or more embodiments described herein, each (AP) segment independently contains ≥0 mol%, or ≥0.2 mol%, or ≥0.4 mol%, or ≥0.6 mol%, or ≥0.8 mol%, or ≥1.0 mol%, based on the total number of moles of polymerized monomers in the (AP) segment in the polymerization form. In each embodiment or combination of two or more embodiments described herein, each (AP) segment independently contains ≤10 mol%, or ≤9.0 mol%, or ≤8.0 mol%, or ≤7.0 mol%, or ≤6.0 mol%, or ≤5.0 mol%, based on the total number of moles of polymerized monomers in the (AP) segment in the polymerization form.

[0043] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in one embodiment or a combination of two or more embodiments described herein, each (AR) segment independently contains ≥2.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥9.0 mol%, or ≥10 mol%, or ≥11 mol%, or ≥12 mol%, or ≥13 mol%, or ≥14 mol% of ethylene in the polymerization form, based on the total number of moles of polymerized monomers in the (AR) segment. In each embodiment described herein, or in combination of two or more embodiments, each (AR) segment independently contains ≤80 mol%, or ≤77 mol%, or ≤75 mol%, or ≤73 mol%, or ≤70 mol%, or ≤65 mol%, or ≤60 mol%, or ≤55 mol%, or ≤50 mol%, or ≤45 mol%, or ≤40 mol%, based on the total number of moles of polymerized monomers in the (AR) segment.

[0044] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in each embodiment or combination of two or more embodiments described herein, each (AP) segment independently contains ≥50 mol%, ≥52 mol%, or ≥54 mol%, or ≥56 mol%, or ≥58 mol%, or ≥60 mol%, or ≥62 mol%, or ≥64 mol%, or ≥66 mol%, or ≥68 mol%, or ≥70 mol% of ethylene in the polymerization form, based on the total number of moles of polymerized monomers in the (AP) segment. In each embodiment or combination of two or more embodiments described herein, each (AP) segment independently contains ≤100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤90 mol% of ethylene in the polymerization form, based on the total number of moles of polymerized monomers in the (AP) segment.

[0045] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in one embodiment or a combination of two or more embodiments described herein, ≥20 mol%, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol%, or ≥98 mol%, or ≥99 mol% of polymerized vinylarenes in each (AR) segment are present in subsegment bb in a "back-to-back" configuration as shown below:

[0046] [ka] (Subsegment bb); mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

[0047] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in one embodiment or a combination of two or more embodiments described herein, ≥20 mol%, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol%, or ≥98 mol%, or ≥99 mol% of polymerized vinylarenes in each (AR) segment are present in a syndiotactic "back-to-back" configuration as shown below in subsegment sbb,

[0048] [ka] (Subsegment sbb), mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

[0049] With respect to ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, in one embodiment or a combination of two or more embodiments described herein, none of the polymerized vinylarenes in each (AP) segment are present in a "back-to-back" configuration as shown in subsegment bb.

[0050] [ka] (Subsegment bb), mol% is based on the total number of moles of polymerized vinylarene in segment (AP).

[0051] We also provide compositions formed from the processes of the present invention described herein. We also provide articles comprising at least one component formed from the compositions of the present invention.

[0052] Ethylene / vinyl alloy blocks and triblock interpolymers Examples of ethylene / vinylarene diblock interpolymer formation and ethylene / vinylarene triblock interpolymer formation are schematically shown in Figures 1A and 1B, respectively. According to these figures, ethylene / alpha-olefin random copolymer "blocks" directly bonded to organometallic reagents, such as zinc or aluminum-based chain shuttling agents (CSAs) or dual-headed chain shuttling agents (DHCSAs), are produced in a first reactor using a first transition metal catalyst. These polymeric zinc or polymeric aluminum species obtained in the first reactor are transferred to a second reactor. The lifetime of the first transition metal catalyst (metal complex) is spent until the contents of the first reactor are transferred to the second reactor. In the second reactor, styrene, ethylene, and optionally alpha-olefins are polymerized in the presence of a second transition metal catalyst to produce random styrene / ethylene interpolymer "blocks." Next, polymeric zinc or polymeric aluminum species from the first reactor undergo chain shuttle with the second reactor catalyst to grow styrene / ethylene random "blocks" on the ethylene / alpha-olefin polymer chain, producing the desired diblock (Figure 1A) or triblock (Figure 1B) interpolymer. The two types of random blocks (vinylarene-enriched, i.e., hard blocks, and vinylarene-deficient, i.e., soft blocks) have different chemical or physical properties. Each block has two or more monomer species distributed substantially randomly within the block.

[0053] As discussed, the ethylene / vinyl arene block and triblock interpolymers preferably contain two chemically distinct regions (referred to as "blocks") that are linked linearly. In one embodiment, the blocks differ in the amount or type of incorporated comonomers, density, degree of crystallinity, type or degree of stereoregularity (isotactic or syndiotactic), or any other chemical or physical properties. Compared to conventional block interpolymers, including interpolymers produced by continuous monomer addition, fluid catalysts, or anionic polymerization techniques, the ethylene / vinyl arene block and triblock interpolymers of the present invention are characterized by unique distributions of both polymer polydispersity (PDI or Mw / Mn or MWD), block length distribution, and / or block number distribution, due to the effect of the shuttling agent in combination with multiple catalysts used for their preparation in a dual reactor.

[0054] Vinylarene monomer Vinylarene monomers are aromatic monomers, including, but not limited to, aromatic vinyl compounds such as mono- or polyalkylstyrenes (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene), and functional group-containing derivatives such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropene, 4-phenylpropene, and α-methylstyrene. However, the monomers are polymerizable under the conditions in which they are used.

[0055] Chain shuttle agent (CSA) The term "chain shuttle agent (CSA)" refers to a compound or mixture of compounds that can cause polymeryl exchange between at least two active catalytic sites of a catalyst included in polymerization conditions. That is, the movement of polymer fragments occurs from one or more of the active catalytic sites, or from both. A CSA can perform chain transfer, for example, between an "AP (soft block) catalyst" and an "AR (hard block) catalyst."

[0056] Suitable shuttle agents include, but are not limited to, group 1, 2, 12, or 13 metal compounds or complexes comprising hydrocarbyl-substituted aluminum, gallium, or zinc compounds containing at least one substituted or unsubstituted hydrocarbyl group, preferably each hydrocarbyl group containing 1 to 12 carbon atoms, and their reaction products with a proton source. Preferred hydrocarbyl groups are alkyl groups, preferably linear or branched C2-C8 alkyl groups. Suitable chain shuttle agents include, but are not limited to, trialkylaluminum and dialkylzinc compounds, particularly triethylaluminum, tri(isopropyl)aluminum, tri(isobutyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, or diethylzinc. See U.S. Patent No. 8,710,143 (incorporated herein by reference).

[0057] Dual-head chain shuttle agents (e.g., Al-DHCSA and AlZn-DHCSA) are also suitable agents. The following chemical formula applies to dual-head chain shuttle agents: R1-[M-R2-] n -The structure M-R1 is an example, but is not limited to it, where R1 and R2 are each independently hydrocarbons containing 1 to 20 carbon atoms, n≧1, and M=Zn. See also International Publication No. 2018 / 064546 and U.S. Patent No. 8,501,885 (both incorporated herein by reference).

[0058] definition Unless otherwise stated, implied in the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0059] As used herein, the term “composition” includes a composition, as well as mixtures of materials including reaction by-products and decomposition products formed from the materials of the composition. Any reaction by-products or decomposition products are typically present in trace or residual amounts.

[0060] As used herein, the term “polymer” refers to a polymer compound prepared by polymerizing the same or different types of monomers. Thus, the general term polymer includes the term homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term interpolymer, as defined herein below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with one or more stabilizers in very small amounts ("ppm").

[0061] As used herein, the term “interpolymer” refers to a polymer prepared by the polymerization of at least two different types of monomers. Therefore, the term “interpolymer” includes the term “copolymer” (used to refer to a polymer prepared from two different types of monomers), and polymers prepared from two or more different types of monomers.

[0062] As used herein, the term “olefinic polymer” means a polymer that, in its polymeric form, comprises 50% by weight or more than half by weight percent of an olefin such as ethylene or propylene (based on the weight of the polymer), and may optionally contain one or more comonomers.

[0063] As used herein, the term "propylene-based polymer" refers to a polymer that, in its polymerized form, contains more than half weight percent of propylene (based on the weight of the polymer) and optionally may contain one or more comonomers.

[0064] As used herein, the term "ethylene-based polymer" refers to a polymer that, in its polymerized form, contains 50 weight percent or more than half weight percent of ethylene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0065] As used herein, the term "vinylarene-based polymer" refers to a polymer that, in its polymerized form, contains more than half weight percent of vinylarene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0066] As used herein, the term "styrene-based polymer" refers to a polymer that, in its polymerized form, contains more than half weight percent of styrene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0067] As used herein, the term "ethylene / alpha-olefin interpolymer" refers to a random interpolymer that, in its polymerized form, contains 50 weight percent or more than half weight percent of ethylene (based on the weight of the interpolymer) and an alpha-olefin.

[0068] As used herein, the term "ethylene / α-olefin copolymer" refers to a random copolymer that, in its polymerized form, contains 50 weight percent or more than half weight percent of ethylene and an alpha-olefin as only two monomer types (based on the weight of the copolymer).

[0069] As used herein, the term "ethylene / vinylarene copolymer" refers, in the polymerized form, to a random copolymer that contains (based on the weight of the copolymer) 50% by weight or more than half weight percent of ethylene and vinylarene as the only two monomer types.

[0070] As used herein, with respect to a polymer (or interpolymer or terpolymer or copolymer), the phrase "more than half weight percent" refers to the amount of the monomer that is present in the largest amount in the polymer.

[0071] As used herein, the term "ethylene / vinylarene diblock interpolymer" refers to a diblock interpolymer that includes a vinylarene-rich (AR) segment and a vinylarene-poor (AP) segment. For example, see Figure 1A. The AR segment contains > 10 mol% vinylarene in the polymerized form. The AP segment contains ≤ 10 mol% vinylarene in the polymerized form. Each mol% is based on the total number of moles of polymerized monomers in each segment. The diblock interpolymer contains ethylene and vinylarene in the polymerized form and may also contain other monomer types. As used herein, the term "ethylene / vinylarene diblock copolymer" refers to a diblock copolymer that includes a vinylarene-rich (AR) segment as discussed above and a vinylarene-poor (AP) segment as discussed above. The diblock copolymer contains ethylene and vinylarene as the only two monomer types in the polymerized form.

[0072] As used herein, the term “ethylene / alpha-olefin / vinylarene diblock copolymer” refers to a diblock interpolymer containing a vinylarene-enriched (AR) segment and a vinylarene-deficient (AP) segment. See, for example, Figure 1A. The AR segment contains >10 mol% vinylarene in its polymerized form. The AP segment contains ≤10 mol% vinylarene in its polymerized form. Each mol% is based on the total number of moles of polymerized monomer in each segment. The diblock interpolymer contains ethylene, alpha-olefin, and vinylarene in its polymerized form, and may contain other monomer types. As used herein, the term “ethylene / alpha-olefin / vinylarene diblocker polymer” refers to a diblocker polymer containing a vinylarene-enriched (AR) segment and a vinylarene-deficient (AP) segment, as discussed above. The diblocker polymer contains ethylene, alpha-olefin, and vinylarene as only three monomer types in its polymerized form.

[0073] As used herein, the term “ethylene / vinylarene triblock interpolymer” refers to a triblock interpolymer comprising either two vinylarene-enriched (AR) segments and one vinylarene-deficient (AP) segment located between the AR segments, or two vinylarene-deficient (AP) segments and one vinylarene-enriched (AR) segment located between the AP segments. See, for example, Figure 1B. An AR segment contains >10 mol% vinylarene in its polymerized form. An AP segment contains ≤10 mol% vinylarene in its polymerized form. Each mol% is based on the total number of moles of polymerized monomer in each segment. A triblock interpolymer may contain ethylene, vinylarene, and other monomer types in its polymerized form. As used herein, the term “ethylene / vinylarene triblock copolymer” refers to a triblock copolymer containing two vinylarene-enriched (AR) segments and one vinylarene-deficient (AP) segment, as discussed above, or containing two vinylarene-deficient (AP) segments and one vinylarene-enriched (AR) segment, as discussed above. Each AR segment and AP segment is as described above. In its polymerized form, the triblock copolymer contains ethylene and vinylarene as only two monomer types.

[0074] As used herein, the term “ethylene / alpha-olefin / vinylarene triblock interpolymer” refers to a triblock interpolymer comprising either two vinylarene-enriched (AR) segments and one vinylarene-deficient (AP) segment located between the AR segments, or two vinylarene-deficient (AP) segments and one vinylarene-enriched (AR) segment located between the AP segments. See, for example, Figure 1B. AR segments contain >10 mol% vinylarene in their polymerized form. AP segments contain ≤10 mol% vinylarene in their polymerized form. Each mol% is based on the total number of moles of polymerized monomer in each segment. Triblock interpolymers may contain ethylene, alpha-olefin, vinylarene, and other monomer types in their polymerized form. As used herein, the term "ethylene / alpha-olefin / vinylarene triblocker polymer" refers to a triblocker polymer that, in its polymerization form, contains either two vinylarene re-enriched (AR) segments and one vinylarene-deficient (AP) segment, or two vinylarene-deficient (AP) segments and one vinylarene-enriched (AR) segment, as discussed above. Each AR segment and AP segment is as described above. In its polymerization form, the triblocker polymer contains ethylene, alpha-olefin, and vinylarene as only three monomer types.

[0075] As used herein, the term "vinylarene" refers to a chemical compound containing "-CR=CHR' (wherein R and R' are each independently H or alkyl)" bonded to an aromatic ring structure, such as a monocyclic, bicyclic, or tricyclic ring structure. The aromatic ring structure may or may not contain one or more heteroatom groups, and may or may not be substituted with one or more heteroatom groups. Examples of vinylarenes include, but are not limited to, styrene, 2-vinyltoluene, and 4-vinyltoluene, as well as alpha-methylstyrene.

[0076] As used herein, the term “alkylsilane group” refers to a chemical group containing at least one -Si-R moiety, where R is alkyl. Some examples of such groups include: -CH2-Si(CH3)3, -CH2-Si(H)(CH3)2, -CH2-Si(H)2(CH3), -Si(CH3)3, -Si(H)(CH3)2, and -Si(H)2(CH3).

[0077] The term "heteroatom" refers to an atom other than hydrogen or carbon (e.g., O, N, or P).

[0078] The term "heteroatomic group" refers to a chemical group containing a heteroatom or one or more heteroatoms.

[0079] As used herein, the terms “hydrocarbon,” “hydrocarbyl group,” and similar terms refer to each compound or chemical group containing only carbon and hydrogen atoms. The divalent “hydrocarbylene group” is defined similarly.

[0080] As used herein, “heterohydrocarbon,” “heterohydrocarbyl group,” and similar terms refer to each “hydrocarbon” or “hydrocarbyl group,” for example, in which at least one carbon atom is substituted with a heteroatomic group (e.g., O, N, or P). A monovalent heterohydrocarbyl group may bond to the rest of the compound in question via a carbon atom or via a heteroatom. A divalent “heterohydrocarbylene group” is similarly defined, and a divalent heterohydrocarbylene group may bond to the rest of the compound in question via two carbon atoms, or two heteroatoms, or a carbon atom and a heteroatom.

[0081] As used herein, the terms “substituted hydrocarbon,” “substituted hydrocarbyl group,” and similar terms refer to each hydrocarbon group or hydrocarbyl group, etc., in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0082] As used herein, the terms “substituted heterohydrocarbon,” “substituted heterohydrocarbyl group,” and similar terms refer to each heterohydrocarbon or heterohydrocarbyl group in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0083] As used herein, the terms “aryl,” “aryl group,” and similar terms refer to a monovalent aromatic hydrocarbyl or aromatic hydrocarbyl group, etc., which include one or more cyclic structures, such as monocyclic, bicyclic, or tricyclic ring structures.

[0084] As used herein, the terms “heteroaryl,” “heteroaryl group,” and similar terms refer to monovalent aryl or aryl groups, etc., in which one or more carbon atoms in the skeletal ring structure are independently replaced by heteroatom groups.

[0085] As used herein, the terms “substituted aryl,” “substituted aryl group,” and similar terms refer to an aryl or aryl group in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0086] As used herein, the terms “substituted heteroaryl,” “substituted heteroaryl group,” and similar terms refer to a heteroaryl or heteroaryl group in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0087] As used herein, the terms “arirene,” “arirene group,” and similar terms refer to divalent aromatic hydrocarbylene or aromatic hydrocarbylene groups, etc., which include one or more cyclic structures, such as monocyclic, bicyclic, or tricyclic ring structures.

[0088] As used herein, the terms "substituted arylene," "substituted arylene group," and similar terms refer to arylene or arylene groups in which one or more hydrogen atoms are independently substituted by heteroatomic groups.

[0089] As used herein, the term "substituted or unsubstituted (C1-C 30 ) hydrocarbyl" and other similar terms refer to the range of the total number of carbon atoms that a substituted or unsubstituted hydrocarbyl radical may contain (e.g., 1 to 30). It should be noted that other monovalent chemical groups described with a carbon range (e.g., substituted or unsubstituted (C6-C 20 ) aryl group) are similarly defined.

[0090] As used herein, the term "substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl" and other similar terms refer to the range of the total number of carbon atoms that a "substituted or unsubstituted heterohydrocarbyl" may contain (e.g., 1 to 30). It should be noted that other monovalent chemical groups described with a carbon range are similarly defined.

[0091] As used herein, the term "substituted or unsubstituted (C6-C 20 ) arylene group" and other similar terms refer to the range of the total number of carbon atoms that a substituted or unsubstituted arylene group may contain (e.g., 2 to 6). It should be noted that other monovalent chemical groups described with a carbon range are similarly defined.

[0092] When used herein with respect to a metal complex, the term "bridging group" refers to a divalent organic group that is bonded to two atoms located at different points in the remaining structure of the metal complex. For example, refer to the bridging groups of each of formula S1(J 1 ), S2(J 2 ), S3(J 3 ), S4(J 4 ), S5(J 5 ), H2(J 5 ).

[0093] When used herein, the phrase "bridging group containing 2 to 40 atoms other than hydrogen" and similar phrases refer to, with respect to a metal complex, the range of all atoms other than hydrogen that a bridging group may contain (e.g., 2 to 40). It should be noted that other bridging groups described with a carbon range are similarly defined.

[0094] As used herein in relation to metal complexes, the term "Lewis base" refers to a chemical compound or chemical group capable of donating an electron pair to form a bond with a metal or another chemical group. Examples of Lewis bases include, but are not limited to, tetrahydrofuran (THF), diethyl ether, dimethylaniline, or trimethylphosphine.

[0095] As used herein with respect to polymerized vinylarene units, “syndiotacticity,” “syndiotactic,” and similar terms refer to the alternating stereochemical configuration of two or more pendant aryl (e.g., phenyl) groups. See, for example, subsegment sbb.

[0096] With respect to structures 1, 2, and 3, the term "polymer structure" refers to the entire molecule of the ethylene / vinylarene diblock interpolymer or ethylene / vinylarene triblock interpolymer mentioned.

[0097] The designation "AR" in relation to diblock or triblock interpolymers refers to the polymer segment of each interpolymer containing >10 mol% vinylarene in its polymerization form. This designation refers to the "vinylarene-enriched" segment.

[0098] The designation "AP" in relation to diblock or triblock interpolymers refers to the polymer segment of each interpolymer containing ≤10 mol% vinylarene in its polymerization form. This designation refers to the "vinylarene-deficient" segment.

[0099] With respect to AR segments (or blocks) or AP segments (or blocks), the phrase “each segment” refers to an AR segment or AP segment located at the end of a polymer molecule or within a polymer molecule. With respect to diblock interpolymers, an AR segment is located at one end of the polymer molecule, and an AP segment is located at the other end of the polymer molecule. With respect to triblock interpolymers, two AR segments are located at each end of the polymer molecule, with an AP segment located between these two AR segments, or two AP segments are located at each end of the polymer molecule, with an AR segment located between these two AP segments.

[0100] As used herein, the term “solution polymerization” refers to a polymerization process in which the monomers, catalysts, and the resulting polymer are all soluble in a polymerization solvent or a solvent blend of two or more solvents.

[0101] As used herein, the term “continuous solution polymerization” refers to solution polymerization in which monomers are continuously supplied to a reactor and polymers are continuously removed from the reactor.

[0102] As used herein, the term "metal complex" refers to a chemical structure comprising a metal or metal ion bonded to and / or coordinated to one or more ligands (ions or molecules containing one or more electron pairs that can be shared with a metal). See, for example, the metal complexes of chemical formulas S1, S2, S3, S4, S5, H1, and H2. Metal complexes are typically catalytically activated by the use of one or more cocatalysts.

[0103] As used herein, the term “scavenger” refers to a chemical compound added to a polymerization reaction to remove or deactivate impurities or undesirable reaction products (e.g., oxygen). Some examples of scavengers include aluminum alkyl compounds such as MMAO and MMAO-3A.

[0104] As used herein, the term “reactor product” refers to the final polymerization mixture in a reactor, which comprises one or more polymers and typically a solvent.

[0105] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymers or otherwise, unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, steps, or procedures that are not essential to the operability and excludes any other components, steps, or procedures from the scope of any subsequent detail. The term “consisting of” excludes any components, steps, or procedures that are not specifically specified or enumerated.

[0106] List of several processes and compositions A) A process for forming a composition comprising an ethylene / vinylarene diblock interpolymer and / or an ethylene / vinylarene triblock interpolymer, further comprising an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, wherein the process comprises at least the following steps: A) A step in which a mixture A comprising ethylene, optionally alpha-olefin, and optionally vinylarene, in reactor A, selected from the following: chemical formula S1, chemical formula S2, chemical formula S3, chemical formula S4, or chemical formula S5, at least a) in the presence of a metal complex S,

[0107] [ka] As described above (see Summary of the Invention (SOI)), (Chemical formula S1),

[0108] [ka] As described above (see SOI), (chemical formula S2), R 3 and R 4 Each of these can be independently substituted or not substituted (C6~C 20 ) Aryl group, or substituted or unsubstituted (C5~C 20 ) Selected from heteroaryl groups, and further, R 3 and R 4 Each of these can be independently substituted or not substituted (C6~C 12 ) Aryl group, or substituted or unsubstituted (C5~C 11 ) Selected from heteroaryl groups,

[0109] [ka] As described above (see SOI), (chemical formula S3),

[0110] [ka] As described above (see SOI), (chemical formula S4),

[0111] [ka] As described above (see SOI), (chemical formula S5), B) A step of polymerizing a mixture B comprising ethylene, vinylarene, and optionally alpha-olefin in reactor B in the presence of at least the following: Metal complexes are either charge-neutral overall, or b) A metal complex H selected from the following chemical formulas H1 or H2:

[0112] [ka] As mentioned above (see SOI), (chemical formula H1),

[0113] [ka] As mentioned above (see SOI), (chemical formula H2), R 1 and R 2 Each of these is an independent bridging group containing 2 to 41 atoms other than hydrogen, and R is optionally selected. 1 and R 2 Each of these can independently be a substituted or unsubstituted arylene group, and further R 1 and R 2 Each of these can independently be an arylene group (unsubstituted), Step A occurs before Step B, and at least a portion of the reactor product in reactor A, moreover ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight, is transferred to reactor B, or Step B occurs before Step A, and at least a portion of the reactor product in reactor B, moreover ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight, is transferred to reactor A, where each weight percentage is based on the total weight of each reactor product. If step A occurs before step B, at least one chain shuttle agent is supplied into reactor A. If step B occurs before step A, at least one chain shuttle agent is supplied into reactor B. A process in which the vinylarene in step A is equal to the vinylarene in step B, and the alpha-olefin in step A is equal to the alpha-olefin in step B. B] Metal complex S is selected from the following chemical formulas S1a or S2a:

[0114] [ka] In the formula, X 1 and X 2 Each of these can be substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or -H, further selected from substituted or unsubstituted benzyl, or H, X 1 and X 2 This is optional, They can be connected, Ar 1 and Ar 2 Each of these is independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 52 is a substituted or unsubstituted arylene group,

[0115] [ka] In the formula, X 3 and X 4 Each of these can be substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or -H, further selected from substituted or unsubstituted benzyl, or H, X 3 and X 4 They can be optionally linked, R 53 is either a substitution or a non-substitution (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or -H, further selected from substituted or unsubstituted benzyl, or -H Ar 3 and Ar 4 The process described in A] above, wherein each is independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. C] A metal complex S selected from the following structures s1a1, s1a2, s1a3, s1a4, s1a5, s2a1, s3a1, s3a2, s3a3, s4a1, or s5a1, and further combinations of two or more of these structures

[0116]

Chemical formula

[0117]

Chemical formula

[0118]

Chemical formula

[0119] [ka] (Formula H1b), where R 1 , R 2 , R 3 , R 4 , and R 5 Each of these is independently H, a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted heterohydrocarbyl group, and further H, an alkyl group, or an alkylsilyl group, Q 1 Q 2 , and Q 3 Each of the following is independently a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heterohydrocarbyl group, or a halogen, and furthermore an aryl group, an alkylsilyl group, an alkoxy group, a halogen, or -NRR', where R and R' are each independently a hydrocarbyl or SiR'', where R'' is a hydrocarbyl, and furthermore an aryl group, an alkoxy group, or a halogen. At least one R group and at least one Q group are optionally connected.

[0120] [ka] (Chemical formula H2a), where M 2is Ti, Hf, or Zr, further Zr or Hf, further Zr, R 6 and R 8 Each of these is independently -H, substitution or non-substitution (C1~C 40 ) Hydrocarbyl, substituted or unsubstituted (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C Selected from the group consisting of 2NC(O)-, halogens, radicals having formula (I), radicals having formula (II), and radicals having formula (III),

[0121] [ka] In the formula, R 31~35 , R 41~48 , and R 51~59 Each of these can be independently substituted or not substituted (C1~C 40 ) Hydrocarbyl, substituted or unsubstituted (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, RC C(O)N(R N )-, (R C ) Selected from 2NC(O)-, halogen, or -H, R 7 and R 9 Each of these can be independently substituted or not substituted (C1~C 40 ) Hydrocarbyl, substituted or unsubstituted (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) Selected from 2NC(O)-, halogen, or -H, R 10 This is optional, and if present, it can be substituted or not substituted (C1~C 40 ) Hydrocarbylene, or substituted or unsubstituted (C1~C 40 ) is a heterohydrocarbylene, R 11 This is optional, and if present, it can be substituted or not substituted (C1~C 40 ) Hydrocarbylene, or substituted or unsubstituted (C1~C 40 ) is a heterohydrocarbylene, Q1 and Q2 are each independently a substituted or unsubstituted hydrocarbyl group or a halogen, and furthermore an aryl group, an alkoxy group, or a halogen. L is either substituted or non-substituted (C1~C 40 ) Hydrocarbylene, or substituted or unsubstituted (C1~C 40 ) Heterohydrocarbylene, substituted or unsubstituted (C1~C 40Hydrocarbylene has a portion containing a linker skeleton of 1 to 10 carbon atoms that connects the two Z groups (to which L is bonded) in structure H2a, or substituted or unsubstituted (C1 to C 40 ) Heterohydrocarbylene has a portion containing a linker skeleton of 1 to 10 atoms that connects two Z groups in structure H2a, and is substituted or unsubstituted (C1 to C 40 Each of the 1 to 10 atoms in the linker skeleton of heterohydrocarbylene is independently a carbon atom or a heteroatom of a heteroatomic group, and each heteroatomic group is independently O, S, S(O), S(O)2, Si(R) C )2, Ge(R C )2, P(R C ), or N(R C ) And in the formula, each R C is either a substitution or a non-substitution (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) is a heterohydrocarbyl, and each R in structure H2a P , R N , and the remaining R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or -H, Z 1 and Z 2 Each of these is independently -S, -N(R N ), or -P(R P ) is selected from, R N and R P This refers to the processes described above in A] to D] as defined above. The metal complex H of [F] has the following chemical formulas: h1a1, h1a2, h1a3, h1b1, h1b2, h1b3, h2a1, or h2a2 (Note: Bn = benzyl group (Ph-CH2-)).

[0122] [ka] The process described in A] to E] above, selected from the above. G) The metal complex S is selected from chemical formula S1, and further from chemical formula S1a, according to any one of the above A) to F). The H] metal complex S is selected from chemical formula S2, and further from chemical formula S2a, according to any one of the above A] to F] processes. I) The metal complex S is selected from chemical formula S3, and the process is one of the above A) to F). J) Metal complex S is selected from chemical formula S4, and the process is one of the above A) to F). The K]metal complex S is selected from chemical formula S5, and the process is one of the above A] to F]. L] The metal complex H is selected from chemical formula H1, and further selected from chemical formula H1a or chemical formula H1b, in any one of the processes described in A] to K] above. M] Metal complex H is selected from chemical formula H2, and further from chemical formula H2a, in any one of the processes described in A] to K] above. N) At least one chain shuttle agent is selected from: alkyl zinc compounds, alkyl aluminum compounds, dual-head chain shuttle agents, or combinations thereof, for any one of A) to M) above, in the process described above. O] At least one chain shuttle agent is: Zn(CH2CH3)2, Al(CH2CH3)3, Al-DHCSA, ZnAl-DHCSA, or a combination thereof, further selected from Al-DHCSA, ZnAl-DHCSA, or a combination thereof, in any one of the processes described in A] to N] above. P) The process according to any one of A) to O) above, wherein at least one chain shuttle agent is added to reactor A. Q) The process according to any one of A) to O) above, wherein at least one chain shuttle agent is added to reactor B. R) The process according to any one of A) to O) above, wherein at least one chain shuttle agent is added to reactor A and reactor B. S) Step A is a process described in any one of A) to R) above, which occurs before Step B. T) The unreacted monomer in reactor B is recycled and returned to reactor A, as described in S) above. U) Step B is a process described in any one of A) to R) above, which occurs before Step A. V) The unreacted monomer in reactor A is recycled and returned to reactor B, as described in U) above. W) polymerization is a process described in any one of A) to V) above, which is solution polymerization or continuous solution polymerization. X) Polymerization occurs in reactor A at a temperature of ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C, or ≥115°C, according to any one of the processes described in A) to W) above. Y) Polymerization occurs in reactor A at a temperature of ≤200°C, or ≤190°C, or ≤180°C, or ≤170°C, or ≤160°C, or ≤150°C, or ≤145°C, or ≤140°C, or ≤135°C, or ≤130°C, or ≤125°C, according to any one of A) to X) above. Z) Polymerization occurs in reactor B at a temperature of ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C, or ≥115°C, according to any one of the processes described in A) to Y) above. A2) Polymerization occurs in reactor B at a temperature of ≤200°C, or ≤190°C, or ≤180°C, or ≤170°C, or ≤160°C, or ≤150°C, or ≤145°C, or ≤140°C, or ≤135°C, or ≤130°C, or ≤125°C, according to any one of A] to Z] above. B2] Polymerization in reactor A occurs at a pressure of ≥90 psig, or ≥100 psig, or ≥110 psig, or ≥120 psig, or ≥130 psig, or ≥140 psig, or ≥150 psig, or ≥160 psig, or ≥170 psig, or ≥180 psig, as described in any one of A] to A2] above. C2] Polymerization in reactor A occurs at a pressure of ≤250 psg, or ≤240 psg, or ≤230 psg, or ≤220 psg, or ≤210 psg, or ≤200 psg, as described in any one of A] to B2] above. D2] Polymerization in reactor A occurs at a pressure of ≥90 psig, or ≥100 psig, or ≥110 psig, or ≥120 psig, or ≥130 psig, or ≥140 psig, or ≥150 psig, or ≥160 psig, or ≥170 psig, or ≥180 psig, according to any one of A] to C2] above. E2] Polymerization in reactor B occurs at a pressure of ≤250 psg, or ≤240 psg, or ≤230 psg, or ≤220 psg, or ≤210 psg, or ≤200 psg, as described in any one of A] to D2] above. F2] The process according to any one of A] to E2] above, wherein the vinylarene is styrene in an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer. G2] Mixture A comprises an alpha-olefin, and the process is as described in any one of A] to F2] above. The process described in [G2] above, wherein the [H2] alpha-olefin is C3-C20 alpha-olefin, further C3-C10 alpha-olefin, further C3-C8 alpha-olefin, further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, and further 1-octene. I2] Mixture B is a process according to any one of A] to H] above, comprising an alpha-olefin. The process described in I2) above, wherein the alpha-olefin is C3-C20 alpha-olefin, further C3-C10 alpha-olefin, further C3-C8 alpha-olefin, further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, and further 1-octene. The process described in any one of A] to J2] above, wherein the molar ratio of the metal of complex S to the metal of complex H is ≥ 0.03, or ≥ 0.1, or ≥ 0.5. The process described in any one of A] to K2] above, wherein the molar ratio of the metal of complex S to the metal of complex H is ≤1000, or ≤500, or ≤100. The process described in any one of A] to L2] above, wherein the molar ratio of the "metal of the chain shuttle" to the "total of the metal of complex S and the metal of complex H" is ≥2.0, or ≥5.0, or ≥10, or ≥20, or ≥40, or ≥100. The process described in any one of A] to M2] above, wherein the molar ratio of the "metal of the chain shuttle" to the "total of the metal of complex S and the metal of complex H" is ≤1000, or ≤800, or ≤500. [O2]metal complex S is r (エチレン)(ビニルアレーン) =k (エチレン)(エチレン) / k (エチレン)(ビニルアレーン) A process according to any one of the above A] to M2], having a reactivity ratio of 50 to 1000, or more precisely, 100 to 500. [P2] Metal complex H is r (エチレン)(ビニルアレーン) =k (エチレン)(エチレン) / k (エチレン)(ビニルアレーン) A process according to any one of the above A to O2, having a reactivity ratio of 1 to 10. Q2] The process according to any one of A] to P2] above, further comprising a polyethylene homopolymer, an ethylene / vinylarene copolymer, an ethylene / alpha-olefin copolymer, or a combination thereof. R2] A composition formed from any one of the processes described in A) to Q2) above. A3] A composition comprising an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, wherein the diblock interpolymer comprises at least one polymer structure selected from Structure 1 shown below, and the triblock interpolymer comprises at least one polymer structure selected from Structure 2 or Structure 3 shown below, where AR refers to vinylarene enrichment and AP refers to vinylarene deficiency. (AR)-(AP)(Structure 1), (AR)-(AP)-(AR)(Structure 2), (AP)-(AR)-(AP)(Structure 3), and Each (AR) segment independently contains ethylene, vinylarene, and optionally alpha-olefin in its polymerized form. Each (AP) segment independently comprises, in its polymerized form, ethylene, optionally vinylarene, and optionally alpha-olefin. Each (AR) segment independently contains >10 mol% vinylarene in its polymerized form, based on the total number of moles of polymerized monomers in the (AR) segment. A composition in which each (AP) segment independently contains ≤10 mol% vinylarene in polymerized form, based on the total number of moles of polymerized monomers in the (AP) segment. B3] The composition according to A3] above, wherein each (AR) segment independently contains ≥15 mol%, or ≥20 mol%, or ≥25 mol%, or ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥45 mol%, or ≥50 mol%, or ≥55 mol%, or ≥60 mol%, based on the total number of moles of polymerized monomers in the (AR) segment in the polymerization form. C3] The composition according to A3] or B3] above, wherein each (AR) segment independently contains <100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤91 mol%, based on the total number of moles of polymerized monomers in the (AR) segment in the polymerization form. D3] The composition according to A3] to C3] above, wherein each (AP) segment independently contains ≥0 mol%, or ≥0.2 mol%, or ≥0.4 mol%, or ≥0.6 mol%, or ≥0.8 mol%, or ≥1.0 mol%, of an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, based on the total number of moles of polymerized monomers in the (AP) segment in the polymerization form. E3] The composition according to any one of A3] to D3] above, wherein each (AP) segment independently contains ≤10 mol%, or ≤9.0 mol%, or ≤8.0 mol%, or ≤7.0 mol%, or ≤6.0 mol%, or ≤5.0 mol%, of vinylarene in the polymerization form, based on the total number of moles of polymerized monomers in the (AP) segment. F3] The composition according to any one of A3] to E3] above, wherein each (AR) segment independently contains ≥2.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥9.0 mol%, or ≥10 mol%, or ≥11 mol%, or ≥12 mol%, or ≥13 mol%, or ≥14 mol%, based on the total number of moles of polymerized monomers in the (AR) segment in the polymerization form. G3] The composition according to any one of A3] to F3] above, wherein each (AR) segment independently contains ≤80 mol%, or ≤77 mol%, or ≤75 mol%, or ≤73 mol%, or ≤70 mol%, or ≤65 mol%, or ≤60 mol%, or ≤55 mol%, or ≤50 mol%, or ≤45 mol%, or ≤40 mol%, based on the total number of moles of polymerized monomers in the (AR) segment in the polymerization form. The composition according to any one of A3] to G3] above, wherein each (AP) segment independently contains ≥50 mol%, ≥52 mol%, or ≥54 mol%, or ≥56 mol%, or ≥58 mol%, or ≥60 mol%, or ≥62 mol%, or ≥64 mol%, or ≥66 mol%, or ≥68 mol%, or ≥70 mol%, based on the total number of moles of polymerized monomers in the (AP) segment. I3] With respect to an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, each (AP) segment independently contains ≤100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤90 mol%, based on the total number of moles of polymerized monomers in the (AP) segment, as described in any one of A3] to H3] above. J3] The composition according to any one of A3] to I3] above, wherein each (AR) segment independently contains ≥0 mol%, or ≥1.0 mol%, or ≥2.0 mol%, or ≥3.0 mol%, or ≥4.0 mol%, of an alpha-olefin in its polymerization form, based on the total number of moles of polymerized monomers in the (AR) segment. K3] The composition according to any one of A3] to J3] above, wherein each (AR) segment independently contains ≤10 mol%, ≤9.0 mol%, or ≤8.0 mol%, or ≤7.0 mol%, or ≤6.0 mol%, of an alpha-olefin in the polymerization form, based on the total number of moles of polymerized monomers in the (AR) segment. The composition according to any one of the above J3] to K3], wherein the L3]α-olefin is a C3-C20 alpha-olefin, further a C3-C10 alpha-olefin, further a C3-C8 alpha-olefin, further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, and further 1-octene. M3] Ethylene / vinyl arene diblock interpolymer or ethylene / vinyl arene triblock interpolymer, wherein each (AR) segment does not contain alpha-olefin in its polymerization form, as described in any one of A3] to L3] above. The composition according to any one of A3] to M3] above, wherein each (AP) segment independently contains ≥0 mol%, ≥1.0 mol%, or ≥2.0 mol%, or ≥3.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥10 mol%, based on the total number of moles of polymerized monomers in the (AP) segment in the polymerization form. O3) With respect to an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, each (AP) segment independently contains ≤40 mol%, or ≤35 mol%, or ≤30 mol%, or ≤28 mol%, or ≤26 mol%, or ≤24 mol%, or ≤22 mol%, or ≤20 mol%, based on the total number of moles of polymerized monomers in the (AP) segment, the composition according to any one of A3] to N3] above. The composition according to any one of the above N3] to O3], wherein the P3]α-olefin is a C3-C20 alpha-olefin, further a C3-C10 alpha-olefin, further a C3-C8 alpha-olefin, further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, and further 1-octene. Q3] For ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, ≥20 mol%, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol%, or ≥98 mol%, or ≥99 mol% of polymerized vinylarenes in each (AR) segment are present in subsegment bb in a "back-to-back" configuration as shown below.

[0123] [ka] (Subsegment bb), mol% is based on the total moles of polymerized vinylarene in the (AR) segment, according to any one of the above A3 to P3. R3] The composition according to any one of A3] to Q3] above, wherein in each (AR) segment, ≤100 mol% of polymerized vinylarene is present in the above subsegment bb in a "back-to-back" configuration as shown below. S3] For ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, ≥20 mol%, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol%, or ≥98 mol%, or ≥99 mol% of polymerized vinylarenes in each (AR) segment are present in the subsegment sbb in a syndiotactic "back-to-back" configuration as shown below.

[0124] [ka] (Subsegment sbb), mol% is based on the total moles of polymerized vinylarene in the (AR) segment, according to any one of the above A3 to R3] compositions. The composition according to any one of A3] to S3] above, wherein, for an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, ≤100 mol% of polymerized vinylarene in each (AR) segment is present in a syndiotactic "back-to-back" configuration as shown in the subsegment sbb described above. For ethylene / vinylarene diblock interpolymers or ethylene / vinylarene triblock interpolymers, polymerized vinylarenes in ≥0, ≤5.0 mol%, ≤2.0 mol%, ≤1.0 mol%, ≤0.5 mol%, ≤0.2 mol%, or ≤0.1 mol% in each (AP) segment are present in subsegment bb in a "back-to-back" configuration as shown below.

[0125] [ka] (Subsegment bb); mol% is based on the total moles of polymerized vinylarenes in the (AP) segment, according to any one of the above A3 to T3] compositions. The composition according to any one of A3] to U3] above, wherein, with respect to V3] ethylene / vinylarene diblock interpolymer or ethylene / vinylarene triblock interpolymer, none of the polymerized vinylarenes in each (AP) segment are present in a "back-to-back" configuration as shown in the subsegment bb described above. W3] The composition according to any one of A3] to V3] above, wherein the vinylarene is styrene, in the case of an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer. The composition according to any one of A3] to W3] above, wherein the X3] ethylene / vinylarene diblock interpolymer is an ethylene / alpha-olefin / vinylarene diblock interpolymer and further a terpolymer, or the ethylene / vinylarene triblock copolymer is an ethylene / alpha-olefin / vinylarene triblock interpolymer and further a terpolymer. Y3] The ethylene / vinylarene diblock interpolymer or ethylene / vinylarene triblock interpolymer has a Tm1 such that Tm2 is ≥50°C, or ≥55°C, or ≥60°C, or ≥70°C, and Tm2 is ≥120°C, or ≥124°C, or ≥150°C, or ≥170°C, or ≥200°C, or ≥210°C, or ≥220°C, or ≥230°C, according to any one of A3] to X3] above. Z3] The ethylene / vinylarene diblock interpolymer or ethylene / vinylarene triblock interpolymer has a temperature of ≤120°C, or ≤115°C, or ≤110°C, or ≤105°C, and Tm1 has a temperature of ≤270°C, or ≤265°C, or ≤260°C, or ≤255°C, or ≤250°C, or ≤245°C, as described in any one of A3] to Y3] above. A4] The ethylene / vinylarene diblock interpolymer or ethylene / vinylarene triblock interpolymer has a Tg1 such that Tg2 is ≥-70°C, or ≥-68°C, or ≥-66°C, or ≥-64°C, or ≥-62°C, and Tg2 is ≥-2.0°C, or ≥5.0°C, or ≥10°C, or ≥15°C, or ≥20°C, or ≥30°C, as described in any one of A3] to Z3] above. B4] The ethylene / vinylarene diblock interpolymer or ethylene / vinylarene triblock interpolymer is a composition according to any one of A3] to A4] above, having a Tg1 such that Tg2 is ≤-125°C, ≤-120°C, ≤-115°C, ≤110°C, or ≤105°C. C4] The composition is the composition according to any one of A3] to B4] above, having a molecular weight distribution (MWD = Mw / Mn) of ≥3.0, or ≥3.1, or ≥3.2, or ≥3.3, or ≥3.4, or ≥3.6, or ≥3.8, or ≥4.0. The composition described in A3] to C4] above has a molecular weight distribution MWD of ≤50, or ≤45, or ≤40, or ≤38, or ≤36, or ≤34, or ≤32, or ≤30, or ≤28, or ≤26. E4] The composition is the composition described in any one of A3] to D4] above, having a number-average molecular weight distribution (Mn) of ≥4,000 g / mol, or ≥6,000 g / mol, or ≥8,000 g / mol, or ≥10,000 g / mol, or ≥12,000 g / mol. F4] The composition is one of the compositions described above in A3] to E4], having Mn such that the amount of Mn is ≤100,000 g / mol, or ≤90,000 g / mol, or ≤80,000 g / mol, or ≤75,000 g / mol, or ≤70,000 g / mol, or ≤65,000 g / mol, or ≤60,000 g / mol, or ≤55,000 g / mol, or ≤50,000 g / mol, or ≤45,000 g / mol. The composition described in A3] to F4] above is a composition having a weight-average molecular weight distribution (Mw) of ≥50,000 g / mol, or ≥55,000 g / mol, or ≥60,000 g / mol, or ≥65,000 g / mol, or ≥70,000 g / mol, or ≥75,000 g / mol, or ≥80,000 g / mol. The H4] composition is the composition according to any one of the above A3] to G4] having Mw, wherein the H4] composition is ≤500,000 g / mol, or ≤450,000 g / mol, or ≤400,000 g / mol, or ≤390,000 g / mol, or ≤380,000 g / mol, or ≤370,000 g / mol, or ≤360,000 g / mol. I4] The composition is the composition according to any one of A3] to H4] above, having a melt index (I2) of ≥0.5 dg / min, or ≥1.0 dg / min, or ≥2.0 dg / min, or ≥5.0 dg / min, or ≥10 dg / min. J4] The composition is the composition according to any one of A3] to I4] above, having a melt index (I2) of ≤1,000 dg / min, or ≤500 dg / min, or ≤250 dg / min, or ≤100 dg / min, or ≤50 dg / min, or ≤20 dg / min. K4] The composition is the composition according to any one of A3] to J4] above, having Tm, wherein the temperature is ≥200°C, or ≥205°C, or ≥210°C, or ≥215°C, or ≥220°C, or ≥225°C, or ≥230°C, or ≥235°C. L4] The composition is the composition according to any one of A3] to K4] above, having Tm, which is ≤300°C, or ≤290°C, or ≤285°C, or ≤280°C, or ≤275°C, or ≤270°C, or ≤265°C. M4] The compositions are those described in any one of A3] to L4] above, having a Tg of ≥-80°C, or ≥-75°C, or ≥-70°C, or ≥-69°C, or ≥-68°C, or ≥-67°C. N4] composition, A composition according to any one of the above A3] to M4], having a Tg of ≤-30℃, or ≤-35℃, or ≤-40℃, or ≤-45℃, or ≤-50℃, or ≤-55℃, or ≤-60℃. The composition according to any one of the above A3] to N4], wherein the composition, in its polymerization form, contains ≥5.0 mol%, or ≥10 mol%, or ≥12 mol%, or ≥14 mol%, or ≥16 mol% of vinylarene, based on the total number of moles of polymerized monomers in the composition. P4] The composition is the composition according to any one of A3] to O4] above, wherein in its polymerization form, it contains <50 mol%, or ≤45 mol%, or ≤40 mol%, or ≤35 mol%, or ≤30 mol%, of vinylarene based on the total number of moles of polymerization monomers in the composition. Q4] The composition is the composition according to any one of A3] to P4] above, wherein in its polymerization form, it contains ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥42 mol%, or ≥44 mol%, or ≥46 mol%, or ≥48 mol%, or ≥50 mol%, based on the total number of moles of polymerized monomers in the composition. The composition according to any one of A3] to Q4] above, wherein the composition in the polymerization form contains ethylene in an amount of <90 mol%, or 85 mol%, or ≤80 mol%, or ≤78 mol%, or ≤76 mol%, or ≤74 mol%, or ≤72 mol%, or ≤70 mol%, or ≤68 mol%, based on the total number of moles of polymerization monomers in the composition. S4] The composition is the composition according to any one of A3] to R4] above, wherein in its polymerization form, it contains ≥2.0 mol%, or ≥5.0 mol%, or ≥10 mol%, or ≥12 mol%, or ≥14 mol%, or ≥16 mol%, or ≥18 mol%, or ≥20 mol% of alpha-olefin based on the total number of moles of polymerization monomers in the composition. The composition according to any one of the above A3] to S4], wherein the T4] composition contains ≤50 mol%, ≤45 mol%, or ≤40 mol%, or ≤35 mol%, or ≤30 mol%, or ≤28 mol% of alpha-olefins in its polymerization form, based on the total number of moles of polymerization monomers in the composition. The composition according to any one of the above S4] to T4], wherein the alpha-olefin is C3-C20 alpha-olefin, further C3-C10 alpha-olefin, further C3-C8 alpha-olefin, further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, and further 1-octene. The composition according to any one of A3] to U4] above, wherein the molar ratio of block styrene (bb in AR) to isolated styrene is ≥2.0 mol%, ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥10 mol. The composition according to any one of the above A3] to V4], wherein the molar ratio of block styrene (bb in AR) to isolated styrene is ≤30 mol%, or ≤25 mol%, or ≤20 mol%, or ≤18 mol%, or ≤16 mol%, or ≤14 mol%, or ≤12 mol%. X4] The composition according to any one of A3] to W4] above, wherein vinylarene is styrene. The composition Y4] is the composition according to any one of A3] to X4] above, comprising an ethylene / vinyl anelectobloc interpolymer and further an ethylene / vinyl anelectobloc terpolymer. Z4] Composition, A composition according to any one of the above A3] to Y4], comprising an ethylene / vinylarene triblock interpolymer, and further comprising an ethylene / vinylarene triblock terpolymer. A5] The composition is the composition according to any one of A3] to Z4] above, further comprising polyethylene homopolymer, ethylene / vinylarene copolymer, ethylene / alpha-olefin copolymer, or a combination thereof. B5] The composition is the composition according to any one of A3] to A5] above, further comprising a thermoplastic polymer different from ethylene / vinyl arene diblock interpolymer or ethylene / vinyl arene triblock interpolymer in one or more characteristics, for example, in the type and / or amount of monomer, Tm, Tg, Mn, Mw, MWD, or any combination thereof, and further comprising a thermoplastic polymer different from ethylene / vinyl arene diblock interpolymer or ethylene / vinyl arene triblock interpolymer in one or more characteristics, for example, in the type and / or amount of monomer, Tm, Tg, or any combination thereof. C5] An article comprising at least one component formed from one of the compositions described in R2] or A3] to B5] above. D5] A process for forming any one of the compositions described in A3] to A5] above, the following: A) In reactor A, a mixture A containing ethylene, optionally alpha-olefin, and optionally vinylarene is prepared as follows: a) A step of polymerization in the presence of a metal complex S) selected from the following chemical formulas as described above: chemical formula S1, chemical formula S2, chemical formula S3, chemical formula S4, or chemical formula S5, B) In reactor B, as described above, a step of polymerizing a mixture B comprising ethylene, vinylarene, and optionally alphaolefin in the presence of a metal complex H selected from the following chemical formulas H1 or H2: Step A occurs before Step B, and at least a portion of the reactor product in reactor A, moreover ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight, is transferred to reactor B, or Step B occurs before Step A, and at least a portion of the reactor product in reactor B, moreover ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight, is transferred to reactor A, where each weight percentage is based on the total weight of each reactor product. If step A occurs before step B, at least one chain shuttle agent is supplied into reactor A. If step B occurs before step A, at least one chain shuttle agent is supplied into reactor B. A process comprising the steps of: vinylarene in step A = vinylarene in step B, and alpha-olefin in step A = alpha-olefin in step B.

[0126] Test method Gel permeation chromatography (conventional type) The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160 degrees Celsius, and the column compartment to 150 degrees Celsius. The column consisted of four AGILENT "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was spurged with nitrogen. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min.

[0127] Calibration of the GPC column set was performed using 21 polystyrene standards with narrow molecular weight distributions ranging from 580 to 8,400,000, placed in six "cocktail" mixtures with at least a 10-fold gap between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared using 0.025 grams per 50 ml of solvent for molecular weights above 1,000,000, and 0.05 grams per 50 ml of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80 degrees Celsius for 30 minutes with gentle stirring. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Formula 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). M ポリエチレン =A × (M ポリスチレン ) B (Formula 1) (In the formula, M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0).

[0128] A quintic polynomial was used to fit the respective polyethylene equivalent calibration points. A slight adjustment (approximately 0.375 to 0.445) was made for A to correct the column resolution and band expansion effect so that the linear homopolymer polyethylene standard material could be obtained at 120,000 Mw. The total plate count of the GPC column set was performed using decane (prepared with 0.04 g in 50 ml of TCB and dissolved for 20 minutes with gentle stirring). Plate count (Equation 2) and symmetry (Equation 3) were measured using a 200 microliter injection according to the following formulas.

[0129]

number

[0130]

number

[0131] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software. The sample (target weight 2 mg / ml) and solvent (containing 200 ppm BHT) were added to septum-capped vials via a PolymerChar high-temperature automated sampler before nitrogen purging. The samples were dissolved at 160°C for 2 hours under "low-speed" shaking.

[0132] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was performed using PolymerChar GPCOne™ software, an IR chromatograph with the baseline subtracted at each equally spaced data acquisition point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4-6, based on the GPC results. Equations 4-6 are as follows:

[0133]

number

[0134] To monitor deviations over time, a flow rate marker (decane) was introduced to each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (apparent flow rate) for each sample by RV-matching each decane peak (RV(FM sample)) within the sample to that of the decane peak in the narrow standard calibration (RV(FM calibrated)). It was then hypothesized that any temporal changes in the decane marker peaks were related to a linear shift in the overall flow rate (effective flow rate). To facilitate the highest accuracy of RV measurements of the flow rate marker peaks, a least-squares fitting routine was used to fit the peaks of the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to determine the true peak position. After calibrating the system based on the flow rate marker peaks, the effective flow rate (with respect to the narrow standard calibration) was calculated as shown in Equation 7: Effective flow rate = Apparent flow rate. * (RV(FM calibrated) / RV(FM sample))(Equation 7). Flow marker peak processing was performed via PolymerChar GPCOne® software. Acceptable flow correction was set so that the effective flow rate was within + / - 0.7% of the apparent flow rate.

[0135] Melt Index The melt index (I2) of ethylene-based polymers was measured according to ASTM D-1238, under conditions of 190°C / 2.16 kg. The melt flow rate (MFR) of propylene-based polymers was measured according to ASTM D-1238, under conditions of 230°C / 2.16 kg.

[0136] density Polymer plaques for density analysis were prepared using ASTM D4703. The density of the polymer was measured using ASTM D792, Method B.

[0137] Differential Scanning Calorimetry (DSC) Differential scanning calorimetry (DSC) was used to measure the Tm, Tc, Tg, and crystallinity of ethylene (PE) and propylene (PS) samples. Approximately 5–8 mg of polymer sample was weighed and placed in a DSC dish. The lid was pressed onto the pan to ensure a closed atmosphere. Unless otherwise specified, the sample dish was placed in the DSC cell and then heated at 10°C / min to 180°C for PE (300°C for PS). The sample was held at this temperature for 3 minutes. The sample was then cooled at a rate of 10°C / min to -90°C for PE (-90°C for PS) and held isothermally at that temperature for 3 minutes. Next, the sample was heated at a rate of 10°C / min until completely melted (second heating). Unless otherwise specified, the melting point (T) of each polymer was measured. m ) and glass transition temperature (T g The crystallization temperature (T) is determined from the second thermal curve. c ) was determined from the first cooling curve. m (Peak temperature) and T g The following was recorded. The heat of fusion (H) was determined from the second heat curve. f The degree of crystallinity can be calculated by dividing (Hf / 292J / g) by the theoretical heat of fusion (292J / g for PE, 53J / g for PS) and multiplying this amount by 100 (for example, degree of crystallinity % = (Hf / 292J / g) × 100 (for PE)).

[0138] 13 C NMR Each sample was prepared by adding approximately 2.7 g of stock solvent to 0.2 g of sample (polymer, polymer composition, or metal complex) in a 10 mm NMR tube. The stock solvent was tetrachloroethane-d2 containing 0.025 M chromium acetylacetonate (relaxant). The sample was capped and sealed with Teflon tape. The sample was dissolved and homogenized by heating the tube and its contents at 130°C to 135°C. Data were acquired using a Bruker 600 MHz spectrometer equipped with a Bruker high-temperature cryoprobe. Data was acquired using a pulse repetition delay of 7.3 seconds (6-second delay + 1.3-second acquisition time), a flip angle of 90 degrees, and reverse gate decoupling at a sample temperature of 120°C. All measurements were performed on non-rotating samples in lock mode. The sample was homogenized immediately before insertion into a heated (125°C) NMR sample exchanger and thermally equilibrated in the probe for 7 minutes before data acquisition.

[0139] For the analysis of each sample (polymer or polymer composition), the B1 carbon (quaternary carbon on the aromatic ring) signal of 145.0–147.7 ppm was used as the styrene contribution, and the molar amount of polymerization monomer was calculated as follows (S = styrene, E = ethylene). Smol = integral value (145.0~147.7 ppm). Emol = (integral value (20.0~48.0 ppm) - 2) * Smol) / 2 Smol%=100 * Smol / (Smol+Emol) Emol% = 100 - Smol%

[0140] [ka]

[0141] For the analysis of each sample (polymer or composition), the B1-4 ring carbon signals at 124.0-148.0 ppm were used as the styrene contribution, and the 2B6 (22.0-23.5 ppm) and 3B6 (31.5-32.7 ppm) signals were used as the octene contribution. The molar amount of polymerization monomer was calculated as follows (S=styrene, E=ethylene, O=octene). Smol = Integral value (124.0~148.0 ppm) / 6 Omol = (Integral value (22.0~23.5 ppm) + Integral value (31.5~32.7 ppm)) / 2 Emol = (integral value (11.8~48.0 ppm) - 2) * Smol-8 * Omol) / 2 Smol%=100 * Smol / (Smol+Omol+Emol) 0 mol% = 100 * Omol / (Smol+Omol+Emol) Emol% = 100 - Smol% - 0mol%.

[0142] [ka] Average styrene block length = 2 * (integral value T) ββ +T βδ ) / integral value T βδ Ratio of block styrene to isolated styrene = (integral value T) ββ +T βδ ) / integral value T δδ T ββ The signal is a methine signal centered at 41.6 ppm, T βδ The signal is a methine signal centered at 43.9 ppm, and T δδ The signal is a methine signal centered around 46.4 ppm. T ββ %=100 * Integral value T ββ / Integral value B1

[0143] 1H NMR Each sample was prepared by adding 130 mg of the sample (polymer, polymer composition, or metal complex) to 3.25 g of tetrachloroethane-d2 containing 0.001 M Cr(AcAc)3 in a 10 mm NMR tube. To prevent oxidation, the sample was purged by passing N2 through the solvent for approximately 5 minutes via a pipette inserted into the tube. The sample container was capped and sealed with Teflon tape. The sample was heated to 115°C and vortexed to ensure homogeneity. ¹H NMR was performed on a Bruker AVANCE 600 MHz spectrometer equipped with a Bruker high-temperature cryoprobe at a sample temperature of 120°C. ¹H NMR was performed with a ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64 s, and D1 14 s.

[0144] Compression molding Each polymer composition was compression-molded into plaques for physical testing using a Carver press. Each composition was compression-molded at 190°C according to ASTM D4703 with controlled cooling at 15°C / min.

[0145] Micro-tensile testing - Mechanical properties Samples were punched out from compression-molded plaques using ASTM die D1708. The test specimens were tested according to ASTM D1708 at a test rate of 5 inches / minute.

[0146] experiment I. Catalysts and Chain Shuttling Agents

[0147] [ka] CAT A (see International Publication No. 03 / 40195, International Publication No. 04 / 24740, and U.S. Patent No. 8,501,885). (C5Me5)Sc(CH2C6H4NMe2-o)2, CAT B synthesis

[0148] [ka]

[0149] In a nitrogen-filled glove box, a THF solution of Sc(CH2CH6H4NMe2-o)3 (1 mL) (0.300 g, 0.67 mmol) was added to a THF solution of C5Me5H (1 mL) (0.105 mL, 0.67 mmol) in a 20 mL vial. The solution was heated at 70°C for 12 hours. The solvent was removed under reduced pressure, the residue was extracted with hexane, and then filtered. The concentrated hexane solution was equilibrated at -30°C to obtain yellow crystals (0.203 g, yield 65.5%). The ¹H NMR and ¹³C NMR spectra were consistent with literature reports (Chem.Commun. 2007, 40, 4137~4139). See Figure 2 (¹H NMR) and Figure 3 (¹³C NMR) for the Sc complex (CAT B).

[0150] Synthesis of Sc(CH2C6H4NMe2-o)3, CAT C catalyst for atactic polystyrene, and chain shuttle using zinc.

[0151] [ka] Synthesis of Sc(CH2C6H4NMe2-o)3: Anhydrous ScCl3 (1.938 g, 12.81 mmol) was suspended in 10 mL of THF. A THF solution (20 mL) of LiCH2C6H4NMe2-o (5.423 g, 28.43 mmol, 3 equivalents) was slowly added at room temperature. The mixture was stirred for 30 minutes, and the solvent was removed under reduced pressure. The residue was dissolved in 40 mL of toluene and then filtered to remove the lithium salt. The solvent was removed from the filtrate under reduced pressure, the residue was thoroughly washed with ether, filtered, and dried to obtain the product as a fine yellow solid. Yield = 2.17 g (38%). ¹H NMR (400 MHz, benzene-d6): δ 7.05~6.94 (m, 6H), 6.85~6.76 (m, 6H), 2.28 (s, 18H), 1.67 (s, 6H). ¹³C NMR (101 MHz, benzene-d6): δ 143.43, 143.15, 129.41, 126.67, 119.95, 117.89, 52.30~46.32 (m), 45.04.

[0152] Synthesis of Ti complexes:

[0153] [ka] CAT D: The following procedure was performed in a glove box under a nitrogen atmosphere. In an oven-dried 40 mL vial equipped with a stirring rod, Cp *TiCl3 (300 mg, 1.37 mmol) was dissolved in 5.2 mL of anhydrous diethyl ether. This solution was cooled in a glove box freezer for 30 minutes. Lithium 2,4,6-trimethoxyphenoxide (184 mg, 1.37 mmol) was added to the CpTiCl3 solution with vigorous stirring. The reaction mixture was warmed to room temperature and stirred overnight at room temperature. The reaction product was then filtered, and the solid was washed with 2 mL of anhydrous diethyl ether. The filtrate and washings were combined. Volatile substances were removed under vacuum, and the red solid was isolated. This material was analyzed by 1H NMR spectroscopy. The crude material appeared to contain unreacted CpTiCl3. The crude product was dissolved in the minimum amount of methylene chloride, and this solution was then layered with ether. This solution was left in a freezer overnight. The desired complex was isolated as red crystals (250 mg, 57%). The product was analyzed by 1H NMR spectroscopy [(400 MHz, C6D6)δ 6.57(s, 2H), 6.01(s, 5H), 2.16(s, 6H), 2.08(s, 3H)].

[0154] [ka]

[0155] CAT E: The following procedure was performed in a glove box under a nitrogen atmosphere. In an oven-dried 40 mL vial equipped with a stirring rod, Cp * TiCl3 (400 mg, 1.38 mmol) was dissolved in 19 mL of anhydrous diethyl ether. This solution was cooled in a glove box freezer for 30 minutes. Lithium 2,4,6-trimethoxyphenoxide (196 mg, 1.38 mmol) was added while vigorously stirring with Cp *The reaction mixture was added to a TiCl3 solution. The reaction mixture was heated to room temperature and stirred overnight at room temperature. The reaction product was then filtered, and the solid was washed with 5 mL of anhydrous diethyl ether. The filtrate and washings were combined. Volatile substances were removed under vacuum, and the red solid was isolated. This material was analyzed by 1H NMR spectroscopy. The crude product was dissolved in the smallest amount of methylene chloride, and this solution was then layered with ether. This solution was left in the freezer overnight. The desired complex was isolated as red crystals (301 mg, 56%). The product was analyzed by 1H NMR spectroscopy [(400 MHz, C6D6)δ 6.61(s,2H), 2.29(s,6H), 2.10(s,3H), 1.90(s,15H)]. Note: This material contains some unreacted Cp that appears to cocrystallize with the desired compound. * It contained TiCl3.

[0156] [ka]

[0157] CAT F: In an oven-drying vial equipped with a stirring rod, Cp * TiCl3 (200 mg, 0.69 mmol) was dissolved in 7.5 mL of anhydrous ether. The solution was placed in a glove box freezer for 20 minutes. The vial was then removed from the freezer. To the cooled and stirred solution, a 2.0 M solution of benzyl magnesium chloride (1.0 mL, 2.1 mmol) was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred at room temperature for 1 hour. The reaction mixture was filtered to remove the solid, and the yellow solution was reduced under vacuum. The reddish-brown solid was isolated and analyzed by 1H NMR spectroscopy [1H NMR (400 MHz, benzene-d 6) δ 6.93 (t, J=7.3 Hz, 3 H), 6.83~6.78 (m, 5 H), 2.74 (d, J=2.7 Hz, 6 H), 1.62 (d, J=0.7 Hz, 13 H)]. Note: Aromatic protons overlapped with the benzene solvent peak.

[0158] Synthesis of Al-DHCSA

[0159] [ka] Al(iBu)3 (3.00 g, 15.13 mmol) and ENB (3.030 g, 25.21 mmol) were mixed with p-xylene (7 mL) in a glass vial. The mixture was heated to 130°C for 20 minutes, allowing i-butene to be released. Then, a mixture of p,m-divinylbenzene (Alfa Aesar 80:20) (1.313 g, 10.08 mmol) was added, and the mixture was further equilibrated at 130°C for 3 hours, after which it was cooled to room temperature. After the reaction time (3 hours), the temperature of the mixture was cooled to room temperature, and the resulting homogeneous solution was used as DHCSA.

[0160] Other chain shuttle agents (CSAs) used in the experiments described herein include diethyl zinc (DEZ) and triethyl aluminum (TEA). ZnAl-DHCSA (see International Publication No. 2018 / 064546).

[0161] [ka] ( * Adhesion site on a metal; mixture of isomers).

[0162] II. Screening Catalysts PPR screening of Sc complexes (CAT B) against hard blocks. To demonstrate the feasibility of styrene polymerization activity and the chain-shutting ability of polymerization catalysts, a Parallel Pressure Reactor (PPR) system was employed. The activity and molecular weight of a given styrene polymerization catalyst in relation to the amount of chain-shutting agent (CSA) added were investigated. The chain-shutting agents examined were diethylzinc (DEZ) and triethylaluminum (TEA), respectively, as models for polymeric alkylzinc species and polymeric alkylaluminum species. Al-Zn DHCSA was also used. The PPR screening conditions were as follows: [ISOPAR-E + MMAO-3A + T] + (styrene + CSA + amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-) + catalyst). Catalyst input amount = 0.25 μmole. MMAO-3A input amount = 5 μmole; T = 105°C, t = 15 min, [styrene] = 2.1 M (in toluene).

[0163] CAT B was screened in PPR for its styrene polymerization ability in the presence of various model chain-shutting agents. Figure 4 demonstrates that CAT B exhibits high efficiency for styrene polymerization (without CSA) and that its catalytic activity is unaffected by the addition of TEA (third circle from the top at CSA=25 μmole, third and fourth circles from the top at CSA=100 μmole) or Al-Zn DHCSA (top two merged circles at CSA=25 μmole, and top two circles at CSA=100 μmole). For this particular study, catalytic activity was low in the presence of DEZ (two merged lower circles at CSA=25 μmole, and two merged lower circles at CSA=100 μmole). The data in Figure 5 shows that the addition of CSA results in a decrease in molecular weight, indicating that the catalyst is involved in effective chain shuttle action. Al-Zn DHCSA is represented by two upper circles at CSA=25μmole and two upper circles at CSA=100μmole. TEA is represented by two merged lower circles at CSA=25μmole and two merged lower circles at CSA=100μmole.

[0164] Table 1 further illustrates the effect of adding 100 μmole of CSA to styrene polymerization by CAT B at 105°C. Furthermore, styrene polymerization by CAT B was tested in the presence of 1-octene. The PPR screening conditions were as follows: T=105°C, catalyst input=0.25 μmole, [styrene]=2.1 M (in toluene), t=15 min. As shown in Table 1, the catalytic activity and molecular weight were not affected by the addition of 1-octene, indicating that CAT B is compatible with the residual alpha-olefin monomer transferred from the first reactor to the second reactor. This data demonstrates that catalyst CAT B satisfies the above-mentioned desired second reactor (R2) catalyst criteria (a)~c)) (see "Detailed Description of the Invention").

[0165] [Table 1] M = Catalyst metal (Sc)

[0166] Sc catalyst: Chain shuttle experiment for CAT B Toluene (final volume 8 mL), styrene (1 mL), and a magnetic stirring rod were placed in a glass vial. CAT B (5 μmol), amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-) (1.2 equivalents (equivalent to CAT B)), and either TEA or DEZ (0, 25 μmol, or 100 μmol) were sequentially added to the solution. This mixture was heated at 100°C for 1 hour and then cooled before quenching in methanol. The polymer was collected by filtration and dried under vacuum. GPC results are shown in Table 6. The results are also shown in Table 2. Compared to sPS-1, a chain shuttle process occurs, as indicated by the decrease in molecular weight and MWD (Mw / Mn) in the presence of DEZ or TEA.

[0167] [Table 2]

[0168] III. Analysis of vinylarene enrichment (hard block) and vinylarene deficiency (soft block) Batch reactor polymerization setup The batch reactor setup consisted of a 600 mL per reactor controlled by a process control system. The reactor featured an electrically heated jacket, an internal cooling coil for temperature control, and an electrically heated trace transfer line between the reactor and the reactor dump pot. Three feeds were available, with the option of introducing solvents or monomers from removable 1-liter (50 mL) cylinders. These cylinders were placed in an inert (N2) glove box, and the contents were transferred to the reactor via nitrogen injection. Catalyst components and chain shuttles were prepared in an inert glove box and transferred to the reactor via nitrogen transfer from a 50 mL cylinder. A "1-octene cylinder" was filled from the purification plant feed. Ethylene was supplied from Airgas as a high-purity grade. For further purification, 1-octene and ethylene were passed through an in-line bed of activated alumina, a 13x molecular sieve, and Q5 material. High-pressure nitrogen for catalyst injection and purging was of ultra-high-purity grade. The styrene was degassed, and the inhibitor was removed by passing the styrene feed through a neutral alumina plug immediately before adding it to the reactor.

[0169] Ethylene, 1-octene, styrene polymerization: Reactivity of CAT B (vinylarene enrichment) Degassed anhydrous toluene was added to a 600 mL per reactor from a nitrogen-pressurized solvent cylinder using a mass flow meter, and the reactor stirrer was set to 450 rpm. Styrene was injected through a high-pressure nitrogen-pressurized cylinder. At the time of use, a preset amount of 1-octene was added to the reactor from a nitrogen-pressurized cylinder using a flow meter. When the reactor reached the starting temperature setpoint of 120°C, a preset amount of ethylene was added to the reactor using a flow meter, followed by the addition of the activated catalyst solution. Cp *A catalyst solution was prepared by adding a pre-prepared toluene solution of ScR2 (CAT B) (usually added at a rate of 22 μmol Sc), a 0.006 M solution of amines, bis(hydrogenated tallow alkyl)methyl, a tetrakis(pentafluorophenyl)-borate(1-) activator (1.0-1.2 equivalents) in toluene, and a 0.05 M solution of MMAO-3A (10 equivalents) in toluene. Each "equivalent" is relative to 1 equivalent of CAT B.

[0170] The ethylene flow was started at 200 mg / min while controlling the overall reactor pressure to a programmed setpoint throughout the desired run time of 10 minutes. After the mixing time, the stirrer was stopped and the contents of the reactor were transferred to a dump pot. The contents of the pot were poured into methanol and the mixture was stirred. The polymer precipitate was filtered and dried in a vacuum oven at 130°C for 6 hours. The polymerization conditions and polymer properties are shown in Table 3 below. See also Table 4. In Tables 3 and 4, interpolymers AR1 to AR12 represent, for example, the vinylarene-enriched (hard block) (AR) segment, stereoregularity, Tm, and Tg of the polymerized vinylarene in the monomer composition of the ethylene / octene / -styrene diblock or triblock interpolymer, respectively.

[0171] [Table 3] General: Catalyst = 22 μmol [CAT B], 1.2 × "amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-)", 10 × MMAO, T = 120°C, t = 10 min, V = 600 mL

[0172] [Table 4] a Determined by 13C NMR, each mol% is based on the total number of moles of polymerization monomers in the interpolymer (representing vinylarene enrichment (hard block)).

[0173] Ethylene, 1-octene, styrene polymerization: Reactivity of CAT A (vinylarene deficiency) Degassed anhydrous toluene was added to a 600 mL per reactor from a nitrogen-pressurized solvent cylinder using a mass flow meter, and the reactor stirrer was set to 450 rpm. Styrene was injected through a cylinder pressurized with high-pressure nitrogen. A predetermined amount of 1-octene was added to the reactor from a nitrogen-pressurized cylinder using a flow meter. When the reactor reached the starting temperature setpoint of 120°C, a predetermined amount of ethylene was added to the reactor using a flow meter, followed by the addition of the activated catalyst solution. The catalyst solution was prepared by adding a pre-prepared toluene solution of CAT A catalyst, a 0.006 M solution of amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)-borate(1-) activator (1.0-1.2 equivalents) in toluene, and a 0.05 M solution of MMAO-3A in toluene (10 equivalents). Each "equivalent" is relative to 1 equivalent of CAT A.

[0174] The ethylene flow was started at 200 mg / min while controlling the overall reactor pressure to a programmed setpoint over a desired run time of 10 minutes. After the mixing time, the stirrer was stopped and the contents of the reactor were transferred to a dump pot. The contents of the pot were poured into methanol and the mixture was stirred. The polymer precipitate was filtered and dried in a vacuum oven at 130°C for 6 hours. The polymerization conditions and polymer properties are shown in Table 5 below. See also Table 6. Interpolymers AP1 to AP11 in Table 6 represent, for example, the vinylarene-deficient (soft block) (AP) segment of the ethylene / octene / styrene diblock or triblock interpolymer in the monomer composition, the stereoregularity of the polymerized vinylarene, Tm, and Tg, respectively.

[0175] [Table 5] General: Catalyst = 6-8 μmol CAT A, 1.2 × "amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-)", 10 × MMAO, T=120℃, t=10 min, V=600 mL.

[0176] [Table 6] Note: The mol% values ​​for styrene in the table were calculated to include only the styrene present in E / O / S terpolymers, assuming the absence of back-to-back styrene. This is based on the observation that CAT A does not polymerize styrene under homopolymerization conditions. Attactic polystyrene was assumed to arise from thermally generated PS. a Each mol% based on the total number of moles of polymerization monomers in the interpolymer represents a vinylarene deficiency (soft block).

[0177] IV. Double catalytic polymerization using chain shuttle agents Batch reactor polymerization setup (dual-per-reactor) - solution polymerization The polymerization setup consisted of two reactors, namely a 600 mL per reactor (reactor 1, R1) and a 2.0 L per reactor (reactor 2, R2), each controlled by a process control system. Both reactors were equipped with electrically heated jackets, internal cooling coils for temperature control, and electrically heated trace transfer lines between reactors and from each reactor to the reactor dump pot. Three feeds were available for either reactor, with the option of supplying solvent or monomer from a removable 1 L sample cylinder. The 1 L cylinders were placed in an inert (N2) glove box, and the contents were transferred to either reactor via nitrogen injection. Catalyst components and chain shuttles were prepared in an inert glove box and transferred to each reactor via nitrogen transfer from a 50 mL cylinder. ISOPAR-E and 1-octene cylinders were filled from the purification plant feed. Ethylene was supplied from Airgas as high-purity grade. For further purification, 1-octene and ethylene were passed through an in-line bed of activated alumina, a 13x molecular sieve, and Q5 material. High-pressure nitrogen was used for catalyst injection and purging, resulting in ultra-high purity grade.

[0178] Batch reactor-solution polymerization-composition containing Triblock 2 A 600 mL Par reactor (R1 (first reactor)) was filled with a solution of Al-DHCSA (1.5 mL, 578 μmol) in 4 mL of ISOPAR-E by high-pressure nitrogen injection. ISOPAR-E (121.4 g) was added to R1 from a nitrogen-pressurized solvent cylinder using a mass flow meter, and the reactor stirrer was set to 450 rpm. A predetermined amount of 1-octene (20.4 g) was added to R1 from a nitrogen-pressurized cylinder using a flow meter. When the reactor reached the starting temperature setpoint of 120 °C, a predetermined amount of ethylene (7.1 g) was added to the reactor using a flow meter, followed by the addition of the activated catalyst solution. A catalyst solution was prepared by adding 0.25 mL of a 0.005 M solution of CAT A in toluene, 0.25 mL of a 0.006 M solution of amines, bis(hydrogenated tallow alkyl)methyl, and tetrakis(pentafluorophenyl)borate(1-) in toluene, and 0.25 mL of a 0.05 M solution of MMAO-3A in toluene to a vial containing 4 mL of toluene.

[0179] Throughout the desired run time of 10 minutes (for R1), the ethylene flow was started at 200 mg / min while controlling the overall reactor pressure to 192.7 psig. During the run time of R1, 200 mL of toluene was filled into the "2.0 L Parr" reactor (R2, the second reactor) via a small cylinder pressurized with nitrogen. The stirrer in R2 was set to 450 rpm, and the starting temperature setpoint for R2 was set to 120°C. When the run time (10 minutes) in R1 was complete, the stirrers in both reactors (R1 and R2) were stopped. R1 was pressurized with nitrogen to transfer its contents to R2 via a preheated line. CAT A (lifetime less than 10 minutes) was consumed when this catalyst entered the second reactor.

[0180] After transferring the contents, the stirrer in R2 was restarted. Styrene monomer (5 mL, 0.044 mol) was injected into R2 via a small cylinder pressurized with nitrogen, and immediately afterward, the activated catalyst solution in 200 mL of toluene was added. A catalyst solution was prepared by adding Sc complex CAT B in 45 μmol of toluene, a 0.006 M solution of amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(penta-fluorophenyl)borate (1-) (0.5 μmol) in 0.083 mL of toluene, and a 0.05 M solution of MMAO-3A (5 μmol) in 0.100 mL of toluene to a vial containing 4 mL of toluene. After the addition of the catalyst, exothermic reaction was observed. The contents of R2 were stirred at 120 °C for a run time of 1 hour (for R2). After the reaction time, the stirrer for R2 was stopped, and the contents of R2 were transferred to a dump pot. The contents of the pot were poured into methanol and stirred overnight. The polymer precipitate (composition containing ethylene / octene / styrene triblocker polymer (Triblock 2)) was filtered and dried in a vacuum oven at 130 °C for 6 hours (yield 11.6 g). NMR profiles were shown in Figure 7 (1H NMR) and Figure 8 (13C NMR). The results are shown in NMR. Based on the peak integration in Figure 7, the composition contained 30% by weight of polymerized styrene, based on the weight of the composition. The peaks representing phenyl C-1 (δ145.50), Sαα (δ43.35), and Tββ (δ40.61) of the syndiotactic polystyrene block are shown in Figure 8.

[0181] Additional polymer composition The additional polymer compositions are described below. The polymerization conditions and polymer composition properties are listed in Tables 7 and 8.

[0182] Triblock 1 (a composition containing ethylene / octene / styrene triblock 1 terpolymer) was polymerized using the process described above for Triblock 2, with the following modifications: A 600 mL par reactor (R1) was filled with a solution of Al-DHCSA (1.5 mL, 690 μmol) in 4 mL of ISOPAR-E by pressurized nitrogen injection. An ethylene flow of 200 mg / min was started, while controlling the total reactor pressure to 192.7 psig over a desired run time of 30 minutes (for R1). Styrene monomer (5 mL, 0.690 mmol) was injected into R2 via a small nitrogen-pressurized cylinder, and immediately thereafter, an activated catalyst solution in 200 mL of toluene was added. A catalyst solution was prepared by adding a 0.0021 M solution of Sc complex CAT B (0.5 μmol) in 0.240 mL of toluene, a 0.006 M solution of amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)-borate (1-) (0.5 μmol) in 0.083 mL of toluene, and a 0.05 M solution of MMAO-3A (5 μmol) in 0.100 mL of toluene to a vial containing 4 mL of toluene. The polymer precipitate (composition containing the triblock) was filtered and dried in a vacuum oven at 130°C for 6 hours (yield 13.0 g). To detect AR-AP bonding (vinylarene enriched (hard block) - vinylarene deficient (soft block) S), a Malvern 305a HT with a triple detector (dRI, DV, LS) connected to DiscovIR™ (FT IR) and PDA (UV-Vis) was used. GPC was employed. The GPC data is shown in Figure 9 [HT GPC dRI / UV dual detector response to dual-batch reactor run, showing unbound PS, unbound EO, and bound PS]. As can be seen in Figure 9, the formation of block interpolymers appears as a "bound PS" peak.

[0183] Triblock 3 (a composition containing ethylene / octene / styrene triblock co-polymer) was prepared according to the process for Triblock 2 shown above, except for the modifications described in Table 7 below. Diblock 1 (a composition containing ethylene / octene / styrene diblock terpolymer) was prepared according to the process for Triblock 2 shown above, except for the use of TEA (400 μmole) as the CSA and the modifications described in Table 7 below. Diblock 2 (a composition containing ethylene / octene / styrene diblock terpolymer) was prepared according to the process for Triblock 2 shown above, except for the use of DEZ (100 μmole) as the CSA and the modifications described in Table 7 below.

[0184] Instead of CSA, two in-reactor blends (IB-1 and IB-2), which were ethylene / octene random copolymer and syndiotactic styrene polymer, respectively, were prepared using the same process as used for Triblock 2 described above, without pre-injection with Al-DHCSA, except for the modifications described in Table 7 below.

[0185] [Table 7]

[0186] [Table 8] A) Each polymer monomer in mol% based on the total number of moles of polymer monomers in the composition. b) Weight percent of each polymerized monomer based on the total weight of the polymerized monomers in the composition. c) Ratio of block styrene to isolated styrene = (integral value T) ββ +T βδ ) / integral value T δδ . * T δδ It was hardly detected.

[0187] GPC research Refer to the GPC procedure in the section on test methods above. A PolymerChar (Valencia, Spain) high-temperature gel permeation chromatography system consisting of an infrared concentration / composition detector (IR-5) was used to determine MW and MWD. ​​The support solvent was 1,2,4-trichlorobenzene (TCB). The autosampler and detector compartments were operated at 160°C, and the column compartment was operated at 150°C. The GPC column set was calibrated using 21 polystyrene standards with narrow molecular weight distributions. The GPC profiles are shown in Figures 10a and 10b. The GPC results are shown in Tables 7 and 9. For the molecular weight distribution of the double reactor polymer, the values ​​are the polystyrene equivalent molecular weights. As can be seen in Table 9, compositions containing triblock polymers have a broader MWD compared to the in-reactor blend (IB-1).

[0188] [Table 9]

[0189] Tensile Test Research The mechanical properties of the two polymer samples are shown in Table 10. See also Figure 11. The samples exhibit elastic recovery behavior.

[0190] [Table 10]

[0191] V. Atactic Polystyrene (aPs): CAT C Polymerization Experiment: Toluene (final volume 8 mL), styrene (1 mL), and a magnetic stirring rod were placed in a glass vial. CAT C (5 umol), amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-) (1.2 equivalents), and either TEA or DEZ (0, 25, or 100 umol) were sequentially added to the solution. This mixture was heated at 100°C for 1 hour and then cooled before quenching in methanol. The polymer was collected by filtration and dried under vacuum. The results are shown in Table 11. The GPC profile is shown in Figure 12. These results indicate that a chain shuttle process occurs, as shown by the decrease in molecular weight and MWD (Mw / Mn) in the presence of DEZ or TEA.

[0192] [Table 11]

[0193] VI.Ti complex PPR screening of Ti complexes (CAT D, CAT E, and CAT F) As described below, a parallel pressure reactor (PPR) system was employed to demonstrate the feasibility of styrene polymerization activity and chain shuttle of each polymerization catalyst. The activity and molecular weight of given styrene polymerization catalyst candidates in relation to the amount of CSA input were investigated. The CSAs examined were diethylzinc (DEZ, 25 μmole or 100 μmole) and triethylaluminum (TEA, 25 μmole or 100 μmole), respectively, as models of polymeric alkylzinc species and polymeric aluminum species. The PPR screening conditions were as follows: [ISOPAR-E + MMAO-3A + T] + (styrene + CSA + "amine, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-) + catalyst). Catalyst input = 0.25 μmole. MMAO-3A input = 50 μmol. T = 75°C and 105°C, t = 15 min, [styrene] = 2.1 M (in toluene).

[0194] CAT D was screened by PPR for its styrene polymerization ability in the presence of the mentioned chain shuttle agent. Figure 13 demonstrates that the addition of CSA results in a decrease in molecular weight, indicating that the catalyst is involved in effective chain shuttle action. CAT D shows relatively low efficiency for styrene polymerization. CAT E was screened by PPR for its styrene polymerization ability in the presence of the mentioned chain shuttle agent. Figure 14 demonstrates that the addition of CSA results in a decrease in molecular weight, indicating that the catalyst is involved in effective chain shuttle action. CAT E shows relatively low efficiency for styrene polymerization. CAT F was screened by PPR for its styrene polymerization ability in the presence of the mentioned chain shuttle agent. Figure 15 demonstrates that the addition of CSA results in a decrease in molecular weight, indicating that the catalyst is involved in effective chain shuttle action. CAT F shows relatively low efficiency for styrene polymerization. This application also relates to the following aspects. (1) A process for forming a composition comprising an ethylene / vinylarene diblock interpolymer and / or an ethylene / vinylarene triblock interpolymer, At least the following steps: A) A step in which a mixture A comprising ethylene, optionally alpha-olefin, and optionally vinylarene, in reactor A, selected from the following: chemical formula S1, chemical formula S2, chemical formula S3, chemical formula S4, or chemical formula S5, at least a) in the presence of a metal complex S, [ka] In the formula, M 1 is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), wherein the metal is in a formal oxidation state of +2, +3, or +4. Each X is independently substituted or non-substituted (C 1 ~C 30 ) Hydrocarbyl, substituted or unsubstituted (C 1 ~C 30 ) Selected from heterohydrocarbyl or -H, where each X is They are independently monosect or bisect ligands. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R 1 This is a bridging group containing 2 to 41 atoms other than hydrogen, and R can be optionally selected. 1 The bond between and M is a pi bond, R 2 Independently, substitution or non-substitution (C 1 ~C 30 ) Hydrocarby group, or substituted or unsubstituted (C 1 ~C 30 ) is a heterohydrocarbyl group, J 1 N and R 1 A bridging group that connects and and contains 2 to 40 atoms other than hydrogen, and optionally the bridging group contains an N atom that can interact with the metal (M1) via an electron-donating bond. The aforementioned metal complex is charge-neutral overall.

change

change

change

change

change

change

change

change

change

change

change

change

Claims

1. A process for forming a composition comprising an ethylene / vinylarene diblock interpolymer and / or an ethylene / vinylarene triblock interpolymer, comprising at least the following steps: A) A step in which a mixture A is polymerized in reactor A, the mixture A comprising ethylene, optionally alpha-olefin, and optionally vinylarene, selected from chemical formula S1, S2, S3, S4, or S5, at least a) in the presence of a metal complex S, 【Chemistry 1】 In the formula, M １ is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), wherein the metal is in a formal oxidation state of +2, +3, or +4. Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R １ This is a bridging group containing 2 to 41 atoms other than hydrogen, and R is optionally selected. １ The bond between and M is a pi bond, R ２ is independently a substituted or unsubstituted (C １ -C ３０ ) hydrocarbyl group, or a substituted or unsubstituted (C １ -C ３０ ) heterohydrocarbyl group, J １ N and R １ A bridging group that connects and contains 2 to 40 atoms other than hydrogen, and optionally, the bridging group is connected to the metal (M) via electron-donating bonds. １ It contains an N atom that can interact with ) The aforementioned metal complex is charge-neutral overall. 【Chemistry 2】 In the formula, M １ is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), wherein the metal is in a formal oxidation state of +2, +3, or +4. Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R ３ and R ４ Each of these independently can be substituted or not substituted (C ６ ~C ２０ ) Aryl group, or substituted or unsubstituted (C ５ ~C ２０ ) Selected from heteroaryl groups, N and N' are bridging groups J containing 2 to 40 atoms other than hydrogen. ２ The bridging group is linked by and optionally contains an N atom that can interact with the metal via an electron-donating bond. The aforementioned metal complex is charge-neutral overall. 【Transformation 3】 In the formula, M １ is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), wherein the metal is in a formal oxidation state of +2, +3, or +4. Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substituted, unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R ５ is either substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl group, or substituted or unsubstituted (C １ ~C ３０ ) Heterohydrocarbyl group, -Si(R Ｃ ) ３ , or -H, T １ is -O-, -S-, -N(R Ｎ )-, or-P(R Ｐ ) - Selected from, t is either 1 or 2. T １ And N contains 4 to 50 atoms other than hydrogen, J ３ It is connected by a bridging group represented by, Each R in equation S3 Ｐ , R Ｎ , and R Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, (C １ ~C ３０ ) Heterohydrocarbyl, or -H, The aforementioned metal complex is charge-neutral overall. 【Chemistry 4】 In the formula, M １ is a metal selected from zirconium (Zr) or hafnium (Hf), wherein the metal is in a formal oxidation state of +2, +3, or +4. Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. -T ２ - and -T ３ Each of these is independently -O-, -S-, and -N(R) Ｎ )-, or-P(R Ｐ ) - Selected from, R ６ and R ２１ Each of these independently represents -H, substitution, or non-substitution (C １ ~C ４０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ ,-Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C = N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ Selected from the group consisting of NC(O)-, halogens, radicals having formula (I), radicals having formula (II), and radicals having formula (III), 【Transformation 5】 Wherein, R ２２～２６ , R ２７～３４ , and R ３５～４３ each independently is selected from a substituted or unsubstituted (C １ -C ４０ ) hydrocarbyl, a substituted or unsubstituted (C １ -C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -N=CHR Ｃ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ )-, (R Ｃ ) ２ NC(O)-, a halogen, or -H, R ７～２０ Each of these independently can be substituted or not substituted (C １ ~C ４０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ ,-Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ -N=CHR Ｃ , -OR Ｃ , -SR Ｃ , -NO ２ -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C = N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R) Ｎ ) -, (R Ｃ ) ２ Selected from NC(O)-, halogen, or -H, J ４ is either substitution or non-substitution (C １ ~C ４０ ) Hydrocarbylene or substituted or unsubstituted (C １ ~C ４０ ) is a heterohydrocarbylene, and the substituted or unsubstituted (C １ ~C ４０ Hydrocarbylene is a compound of the group T in chemical formula S4. ２ and T ３ A portion containing a linker skeleton of 1 to 10 carbon atoms that connects them (J ４ (is bonded) or has substitution or non-substitution (C １ ~C ４０ ) Heterohydrocarbylene is a compound of the group T in chemical formula S4. ２ and T ３ It has a portion containing a linker skeleton of 1 to 10 atoms that connects the following, and each of the 1 to 10 atoms of the linker skeleton is independently a carbon atom or a heteroatomic group of heteroatoms, and each heteroatomic group is independently O, S, S(O), S(O) ２ , Si(R Ｃ ) ２ , Ge(R Ｃ ) ２ , P(R Ｃ ), or N (R Ｃ ) and each R Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, or substituted or unsubstituted (C １ ~C ３０ ) is a heterohydrocarbyl, and each R in chemical formula S4 Ｐ , R Ｎ , and the remaining R Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Heterohydrocarbyl, or -H, The aforementioned metal complex is either charge-neutral overall, or 【Transformation 6】 In the formula, M １ is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), wherein the metal is in a formal oxidation state of +2, +3, or +4. Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each X is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, X can be a bidentate ligand. R ４４～５１ Each of these can be independently substituted or not substituted (C １ ~ ４０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ , or -H is selected, and R is optionally selected. ４４～５１ Two or more of these groups are linked, and therefore the cyclopentadienyl group is a substituted or unsubstituted indenyl group, or a substituted or unsubstituted fluorenyl group, R Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, O and O contain 1 to 30 atoms other than hydrogen, J ５ Connected by a bridging group represented by, The aforementioned metal complex is charge-neutral overall, step, B) In reactor B, at least the following: b) In the presence of a metal complex H selected from the following chemical formulas H1 or H2, ethylene, vinylarene, and The step of optionally polymerizing a mixture B containing an alpha-olefin, 【Transformation 7】 In the formula, M ２ These are elements from Ti, Sc, Y, or the lanthanide series. R １ , R ２ , R ３ , R ４ , and R ５ Each of these is independently H, or a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted heterohydrocarbyl group. Q １ Q ２ , and Q ３ Each of these is independently a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heterohydrocarbyl group, or a halogen. L is a Lewis base, each n is independently either 0 or 1, and m is an integer between 0 and 3. At least one L group and at least one Q group are optionally connected, and at least one R group and at least one Q group are optionally connected. The aforementioned metal complex is charge-neutral overall. 【Transformation 8】 M ３ is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf), wherein the metal is in a formal oxidation state of +2, +3, or +4. Each Q can be independently substituted or not substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each Q is independently a monodentate or bidentate ligand. n is 0, 1, or 2, and optionally, when n is 1, Q can be a bidentate ligand. R １ and R ２ Each of these is a bridging group containing 2 to 41 atoms other than hydrogen, and R is optionally selected. １ and R ２ Each of these can independently be a substituted or unsubstituted arylene group. -Z １ - and -Z ２ Each of these is independently -0-, -S-, -Se-, -N(R Ｎ )-, or-P(R Ｐ ) - Selected from, -Z １ - and -Z ２ Each of these can independently and optionally interact with the metal via electron-donating bonds. Z １ and Z ２ J contains 1 to 50 atoms other than hydrogen. ５ Connected by a bridging group represented by, R Ｐ and R Ｎ Each of these can be independently substituted or not substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Heterohydrocarbyl, or -H, The aforementioned metal complex is charge-neutral overall and includes a step, Step A occurs before Step B, and at least a portion of the reactor product in reactor A is transferred to reactor B, or Step B occurs before Step A, and at least a portion of the reactor product in reactor B is transferred to reactor A. If step A occurs before step B, at least one chain shuttle agent is supplied into reactor A. If step B occurs before step A, at least one chain shuttle agent is supplied into reactor B. A process in which, if vinylarene is included in step A, the vinylarene in step A is the same as the vinylarene in step B, and the alpha-olefin in step A is the same as the alpha-olefin in step B.

2. The process according to claim 1, wherein the metal complex S is selected from chemical formula S1 and the metal complex H is selected from chemical formula H1.

3. The metal complex S has structure s1a1 or structure s1a2: 【Chemistry 9】 A process according to claim 1 or 2, selected from the above.

4. The metal complex H has the following chemical formulas: h1a1, h1a2, h1a3, h1b1, h1b2, h1b3, or h2a2 (Note: Bn = benzyl group (Ph-CH) ２ -)) 【Chemistry 10】 A process according to any one of claims 1 to 3, selected from the above.

5. The process according to any one of claims 1 to 4, wherein the at least one chain shuttle agent is selected from: alkylzinc compounds, alkylaluminum compounds, dual-head chain shuttle agents, or a combination thereof.

6. The process according to any one of claims 1 to 5, wherein step A occurs before step B.

7. The process according to any one of claims 1 to 5, wherein step B occurs before step A.

8. The process according to any one of claims 1 to 7, wherein the vinylarene in the ethylene / vinylarene diblock interpolymer or the ethylene / vinylarene triblock interpolymer is styrene.

9. The process according to any one of claims 1 to 8, wherein the mixture A comprises the alpha-olefin.

Images