Single-reactor chain shuttle reaction for ethylene / vinylarene multiblock interpolymers

Abstract

A method for forming a composition comprising an ethylene / vinyl arene multi-block interpolymer, comprising polymerizing a mixture comprising ethylene, vinyl arene, and optionally an alpha-olefin in a single reactor in the presence of at least: a) a first metal complex selected from formula (A) as described herein; b) a second metal complex selected from formula (B) as described herein; and c) a chain shuttling agent selected from dialkyl zinc, trialkyl aluminum, or a combination thereof. The composition comprises an ethylene / vinyl arene multi-block interpolymer comprising at least one polymer structure selected from -(AR)-(AP)-(AR)-(AP)-(Structure 1), or (AR)-(AP)-(AR)-(AP)(Structure 2), wherein each (AR) segment independently comprises, in polymerized form, ethylene, greater than 10 mol % vinyl arene, and optionally an alpha-olefin, and each (AP) segment independently comprises ethylene, optionally up to 10 mol % vinyl arene, and optionally an alpha-olefin.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 127,343, 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. Chain shuttle technology is needed to produce other types of polymers, such as stereocontrolled ethylene / vinylarene block interpolymers, using single-reactor continuous solution polymerization.

[0003] In 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," isoprene-styrene chain shuttle polymerization using n-butylethylmagnesium, a lanthanide half-sandwich complex, and lanthanidocene is disclosed. The resulting multiblock structure has hard (styrene-rich) and soft (isoprene-rich) segments.

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

[0005] U.S. Patent No. 8623976 (Polymerization Catalyst Compositions Containing Metallocene Complexes and the Polymers Produced by Using the Same) states the following: a) the following: 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) Metallocene complexes containing a neutral Lewis base; b) Catalyst compositions comprising ionic compounds of non-ligand anions and cationic compounds, such as tetrakis(pentafluorophenyl)borate, are disclosed. These catalyst compositions are 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 discloses chain-shutling polymerization of styrene, isoprene, and butadiene using two different scandium catalysts and chain-shutling agents (TIBA). The polymerization results in regio- and stereospecific copolymerization of styrene, isoprene, and butadiene.

[0007] SS Park et al., Macromolecules 2017, 50, 6606-6616, Biaxial Chain Growth of Polyolefin and Polystyrene from 1,6-Hexanediylzinc Species for Triblock Copolymers discloses the preparation of triblock copolymers by initiating (anionic) styrene polymerization from polymeryl zincate species. Polyethylene / polypropylene copolymers are grown from dual-headed zinc species by using coordination chain transfer polymerization, followed by the addition of an anionic initiator (e.g., Me3SiCH2Li-(pmdeta)) and styrene monomer. Coordination chain transfer polymerization occurs in the presence of a transition metal (e.g., Zr or Hf) complex. Anionic polymerization is used to grow polystyrene endblocks that do not exhibit any 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 organozinc compounds, including those of formula 1, as shown therein, and styrene polymers or polyolefin-polystyrene block copolymers. The preparation method involves preparing an intermediate by coordination polymerization of an olefin monomer using a transition metal catalyst, and then partially inserting a styrene monomer into the intermediate by anionic polymerization. The transition metal catalyst includes a Zr metal compound represented by formulas 6A and 6B, as shown therein (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 copolymer melting temperature (T m ) can be modified by adjusting ethylene uptake, where ethylene uptake is, as a result, T m This leads to a decrease in performance. Chain shuttlering was not observed with Sc catalysts.

[0010] In "Synthesis of Ethylene-Styrene Copolymer Containing Syndiotactic Polystyrene Sequence by Trivalent Titanium Catalyst" by H. Hagihara et al., Polymer Journal 2012, 44, 147-154, the polymerization of syndiotactic styrene-ethylene copolymer using a trivalent titanium catalyst, tris(acetylacetonate)titanium (Ti(acac)3), is disclosed. Different polymers were produced by the Ti(acac)3 catalyst, which may be due to the presence of multiple oxidation states on this catalyst.

[0011] F. Lin et al., 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. The sequential addition of styrene, butadiene, and styrene monomers formed SBS triblocks. The SBS triblocks consisted of elastic polybutadiene sequences with 1,4 regularity and crystalline syndiotactic polystyrene. The SBS triblocks were hydrogenated to form SEBS.

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

[0013] U.S. Patent No. 8710143 (Catalyst Composition Comprising Shuttling Agent for Ethylene Multi-Block Copolymer Formation) discloses the following: (A) a first metal complex olefin polymerization catalyst, (B) a second metal complex olefin polymerization catalyst capable of preparing polymers with different chemical or physical properties from polymers prepared by catalyst (A) under equivalent polymerization conditions, and (C) polymerization of multi-block copolymers using a chain shuttle agent. Suitable monomers include ethylene and one or more addition polymerizable monomers such as 1-octene and styrene (see paragraph 16, lines 3-32). Suitable catalysts include metal complexes, where the metal is selected from groups 3-15, preferably 3-10, more preferably 4-8, and most preferably 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 therein (see paragraph 85, rows 12-30; paragraph 86, rows 21-52; paragraph 115, rows 21-116, row 23, and Tables 27 and 28).

[0014] Additional olefin block copolymers (OBCs) and related polymerizations are disclosed in the following references: U.S. Patent No. 7,915,192; U.S. Patent No. 8,124,709; U.S. Patent No. 8,501,885; U.S. Patent No. 8,716,400; European Patent No. 1,716,190; European Patent No. 1,926,763; and European Patent No. 2,582,747.

[0015] However, there is still a need for stereocontrolled ethylene / vinylarene multiblock interpolymers and their preparation using continuous solution polymerization in a single reactor. These needs have been met by the following inventions. [Overview of the Initiative]

[0016] In a first aspect, a method of forming a composition comprising an ethylene / vinyl aromatic multi-block interpolymer, comprising at least the following components a) to c): a) The following formula A:

[0017]

Chemical formula

[0018]

Chemical formula

[0019] In a second embodiment, a composition comprising an ethylene / vinylarene multiblock interpolymer, wherein the interpolymer comprises at least one polymer structure selected from structure 1 or structure 2 as shown below, where (AR) refers to a vinylarene-rich segment and (AP) refers to a vinylarene-poor segment. -(AR)-(AP)-(AR)-(AP)-(Structure 1), (AR)-(AP)-(AR)-(AP)(Structure 2), Each (AR) segment independently comprises, in its polymerized form, ethylene, vinylarene, and optionally alpha-olefin. Each (AP) segment independently comprises, in its polymerized form, ethylene, optionally vinylarene, and optionally alpha-olefin. Each (AR) segment independently contains more than 10 mol% vinylarene in its polymerized form, based on the total number of moles of polymerized monomers within the (AR) segment. A composition in which each (AP) segment independently contains 10 mol% or less of vinylarene in polymerization form, based on the total number of moles of polymerized monomers within the (AP) segment. [Brief explanation of the drawing]

[0020] [Figure 1] This figure shows the 1H NMR profile of CAT B. [Figure 2]This figure shows the 13C NMR profile of CAT B. [Figure 3] This graph shows the GPC profiles of syndiotactic polystyrene (sPS) polymers prepared from chain shuttle polymerization. From left to right, the GPC profiles start with peak maximum: Log M = 3.00: SP-3 (100 DEZ), SP-5 (100 TEA), SP-2 (25 DEZ), SP-4 (25 TEA), SP-1 (no CSA). [Figure 4] This graph shows Tm (determined by DSC) and the mole percentage or Tbb (determined by 13C NMR) of "back-to-back styrene incorporation" as a function of the mole percentage of polymerized (or incorporated) styrene (determined by 13C NMR), respectively. [Figure 5] This graph shows the weight-average molecular weight (Mw) (by GPC) and Tm (by DSC) as functions of the polymerization parameters described, respectively. [Figure 6] This graph shows the glass transition temperature (Tg) determined by DSC as a function of the molar percentage of polymerized octene in the polymer (determined from 13C NMR). [Figure 7] This figure shows the corresponding molar percentages (determined by 13C NMR spectroscopy) of ethylene, styrene, and octene in the final polymer prepared under reactor conditions (mol% ethylene, mol% styrene, and mol% octene) and terpolymerization conditions (CAT B and CAT A). [Modes for carrying out the invention]

[0021] Chain shuttle technology has been found to produce ethylene / vinylarene multiblock interpolymers via a binary catalyst in a single reactor. One catalyst produces vinylarene-poor segments (AP, soft blocks), while the other produces vinylarene-rich segments (AR, hard blocks). The addition of Al-based or Zn-based chain shuttle agents (CSAs), in the presence of both catalysts, produces compositions containing ethylene / vinylarene multiblock interpolymers. It has been found that the individual block properties can be tuned through the selection of compatible catalyst pairs, monomers, chain shuttle agents, and polymerization conditions.

[0022] It was also discovered that the catalyst used to produce segments poor in vinylarenes had the following properties: a) produced polymers with high intrinsic molecular weight; b) had a high chain shuttle constant determined by molecular weight reduction and narrowing of molecular weight distribution in the presence of CSA; c) had high alpha-olefin incorporation; d) T g However, the vinylarene (e.g., styrene) incorporation was low, similar to ethylene-based interpolymers that contain similar alpha-olefin incorporation but do not contain styrene incorporation; and e) produced polymers with low crystallinity.

[0023] The catalyst used to produce vinylarene-rich segments was found to have the following properties: a) high vinylarene (e.g., styrene) uptake; b) high "back-to-back" vinylarene insertion leading to syndiotactic configuration; c) high chain shuttle constant determined by molecular weight reduction and narrowing of molecular weight distribution in the presence of CSA; d) high activity in the presence of ethylene; and e) low alpha-olefin uptake.

[0024] As discussed above, in a first embodiment, the present invention provides a method for forming the compositions described above. The method of the present invention may include a combination of two or more embodiments described herein. Each component a, b, and c may independently include a combination of two or more embodiments described herein.

[0025] As discussed above, in a second embodiment, the present invention provides compositions as described above. The compositions of the present invention may include combinations of two or more embodiments described herein. Structure 1 and Structure 2 may each independently include combinations of two or more embodiments described herein.

[0026] When used herein, with respect to the structure of a metal complex, X 1 =X1, X 2 =X2, and Ar1=Ar 1 Ar2=Ar 2 Ar3=Ar 3 Please note that, etc. Also, when used in this specification, with respect to such structures, R1 = R 1 , R²=R 2 , R3=R 3 And so on. The notation "a~n" represents a sequence of numbers. a ~R n 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 It refers to.

[0027] The following embodiments apply to the method of the present invention.

[0028] In one embodiment, or in a combination of two or more embodiments described herein, formula A is the following structure (a11) or (a12):

[0029] [ka] From there, it is further selected from the structure (a11).

[0030] In one embodiment, or in a combination of two or more embodiments described herein, formula B is the following structure (b11) or (b12):

[0031] [ka] From there, it is further selected from the structure (b11).

[0032] In one embodiment, or in a combination of two or more embodiments described herein, the chain shuttle agent (component c) is selected from: Zn(CH2CH3)2, Al(CH2CH3)3, or a combination thereof.

[0033] In one embodiment, or in a combination of two or more embodiments described herein, the mixture comprises an alpha-olefin.

[0034] The present invention also provides compositions formed by the methods of the present invention of one or more embodiments described herein.

[0035] The following embodiments apply to the method or composition of the present invention.

[0036] In one embodiment, or a combination of two or more embodiments described herein, each (AR) segment of an ethylene / vinylarene multiblock interpolymer independently contains 15 mol% or more, or 20 mol% or more, or 25 mol% or more, or 30 mol% or more, or 35 mol% or more, or 40 mol% or more, or 45 mol% or more, or 50 mol% or more, or 55 mol% or more, or 60 mol% or more, based on the total number of moles of polymerized monomers in the (AR) segment. In one embodiment, or a combination of two or more embodiments described herein independently, each (AR) segment independently contains less than 100 mol%, or 98 mol% or less, or 96 mol% or less, or 94 mol% or less, or 92 mol% or less, or 91 mol% or less, based on the total number of moles of polymerized monomers in the (AR) segment.

[0037] In one embodiment, or in a combination of two or more embodiments described herein, with respect to the ethylene / vinylarene multiblock interpolymer, each (AR) segment independently contains 2.0 mol% or more, or 4.0 mol% or more, or 6.0 mol% or more, or 8.0 mol% or more, or 9.0 mol% or more, or 10 mol% or more, or 11 mol% or more, or 12 mol% or more, or 13 mol% or more, or 14 mol% or more, based on the total number of moles of polymerized monomers in the (AR) segment. In one embodiment, or in a combination of two or more embodiments described herein, each (AR) segment independently contains, in polymer form, ethylene in an amount of 80 mol% or less, or 77 mol% or less, or 75 mol% or less, or 73 mol% or less, or 70 mol% or less, or 65 mol% or less, or 60 mol% or less, or 55 mol% or less, or 50 mol% or less, or 45 mol% or less, or 40 mol% or less, based on the total number of moles of polymerized monomers in the (AR) segment.

[0038] In one embodiment, or in a combination of two or more embodiments as described herein, with respect to the ethylene / vinylarene multiblock interpolymer, each (AR) segment independently contains 20 mol% or more, or 30 mol% or more, or 40 mol% or more, or 50 mol% or more, or 60 mol% or more, or 70 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 92 mol% or more, or 94 mol% or more, or 96 mol% or more, or 98 mol% or more, or 99 mol% or more polymerized vinylarene in a “back-to-back” arrangement as shown below within the subsegment bb.

[0039] [ka] mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment. In one embodiment, or in a combination of two or more embodiments described herein, each (AR) segment independently contains 100 mol% or less of polymerized vinylarene in a “back-to-back” arrangement as shown in the subsegment bb above.

[0040] In one embodiment, or in a combination of two or more embodiments as described herein, with respect to the ethylene / vinylarene multiblock interpolymer, each (AR) segment independently contains 20 mol% or more, or 30 mol% or more, or 40 mol% or more, or 50 mol% or more, or 60 mol% or more, or 70 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 92 mol% or more, or 94 mol% or more, or 96 mol% or more, or 98 mol% or more, or 99 mol% or more polymerized vinylarene in a syndiotactic "back-to-back" arrangement as shown below within the subsegment sbb:

[0041] [ka] mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment. In one embodiment, or in a combination of two or more embodiments described herein, each (AR) segment independently contains 100 mol% or less of polymerized vinylarene in a “back-to-back” arrangement as shown in the subsegment sbb above.

[0042] In one embodiment, or in a combination of two or more embodiments described herein, the vinylarene in the ethylene / vinylarene multiblock interpolymer is styrene.

[0043] In one embodiment, or in a combination of two or more embodiments described herein, the ethylene / vinylarene multiblock interpolymer is an ethylene / alpha-olefin / vinylarene multiblock interpolymer, and further, an ethylene / alpha-olefin / vinylarene multiblock interpolymer.

[0044] In one embodiment, or in a combination of two or more embodiments described herein, the composition further comprises a polyethylene homopolymer, an ethylene / vinylarene copolymer, an ethylene / alpha-olefin copolymer, or a combination thereof.

[0045] Articles comprising at least one component, formed from compositions of one or more embodiments described herein, are also provided.

[0046] Vinylarene monomer Vinylarene monomers are aromatic monomers and include, but are 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), as well as functional group-containing derivatives such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropene, 4-phenylpropene, and α-methylstyrene. However, the monomers must be polymerizable under the conditions in which they are used.

[0047] Chain shuttle agent (CSA) The term "chain shuttle agent (CSA)" refers to a compound or mixture of compounds capable of inducing polymeryl exchange between at least two active catalytic sites of a catalyst included in the polymerization conditions. That is, the movement of polymer fragments occurs from or to one or more of the active catalytic sites. CSAs can, for example, chain-transfer between "AP (soft block) catalysts" and "AR (hard block) catalysts." 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, and diethylzinc.

[0048] Ethylene / vinylarene multiblock interpolymer Ethylene / vinylarene multiblock interpolymers are characterized by multiple (four or more) blocks or segments of two or more polymer monomer units, the blocks having different chemical or physical properties. Preferably, the segments are linked substantially linearly, rather than substantially branched or substantially star-shaped. In other embodiments, each block is randomly distributed along the polymer chain. As discussed, ethylene / vinylarene multiblock interpolymers contain two chemically distinct regions (referred to as "blocks") that are preferably linearly linked. In some embodiments, the blocks differ in the amount or type of incorporated comonomers, density, degree of crystallinity, type or degree of tacticity (isotactic or syndiotactic), or any other chemical or physical properties. Compared to conventional block interpolymers in the art, including interpolymers produced by sequential monomer addition, flow catalysts, or anionic polymerization techniques, the ethylene / vinylarene multiblock interpolymers exhibit polymer polydispersity (PDI or M) due to the effect of the (one or more) shuttle agents combined with the multiple catalysts used in their preparation. w / M n It is characterized by any of the following specific distributions: the block length distribution (or MWD), and / or the block number distribution.

[0049] definition Unless otherwise stated, implicitly from the context, or established convention 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.

[0050] The term “composition,” as used herein, includes a composition, as well as a mixture 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.

[0051] As used herein, the term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Thus, the general term polymer includes the terms homopolymer (used to refer to polymers 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 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") of each type.

[0052] As used herein, the term “interpolymer” refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term interpolymer includes the term copolymer (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0053] The term "olefin polymer," as used herein, refers to a polymer in its polymerized form comprising 50 wt% or more than half weight percent of an olefin such as ethylene or propylene (based on the weight of the polymer), and which may optionally contain one or more comonomers.

[0054] As used herein, the term "propylene polymer" refers to a polymer in its polymerized form that comprises a majority by weight percentage of propylene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0055] As used herein, the term "ethylene-based polymer" refers to a polymer in its polymerized form that contains 50 wt% or more than half weight percent ethylene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0056] As used herein, the term "vinylarene polymer" refers to a polymer in its polymerized form that comprises, in a majority weight percent, vinylarene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0057] As used herein, the term "styrene-based polymer" refers to a polymer in its polymerized form that comprises, in a majority weight percent, styrene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0058] The term "ethylene / alpha-olefin interpolymer," as used herein, refers to a random interpolymer in polymerization form comprising 50 wt% or majority by weight percent of ethylene (based on the weight of the interpolymer) and alpha-olefin.

[0059] The term "ethylene / alpha-olefin copolymer," as used herein, refers to a random copolymer in polymerization form comprising only two monomer types: 50 wt% or a majority by weight of ethylene (based on the weight of the copolymer) and alpha-olefin.

[0060] The term "ethylene / vinylarene copolymer," as used herein, refers to a random copolymer in polymerization form comprising only two monomer types: 50 wt% or a majority by weight of ethylene (based on the weight of the copolymer) and vinylarene.

[0061] When used herein, the term “majority by weight percent” refers to the amount of monomer present in the polymer (or interpolymer, or terpolymer or copolymer) in the maximum amount.

[0062] The term "ethylene / vinylarene multiblock interpolymer," as used herein, refers to a multiblock interpolymer comprising at least two vinylarene-rich (AR) segments and at least two vinylarene-poor (AP) segments. Each (AR) segment independently contains more than 10 mol% vinylarene in its polymerized form. Each (AP) segment independently contains 10 mol% or less vinylarene in its polymerized form. Each mol% is based on the total number of moles of polymerized monomers in each segment. The multiblock interpolymer comprises ethylene and vinylarene in its polymerized form, and may contain other monomer types. The term "ethylene / vinylarene multiblock copolymer," as used herein, refers to a multiblock copolymer comprising at least two vinylarene-rich (AR) segments and at least two vinylarene-poor (AP) segments, as discussed above. The multiblock copolymer comprises only two monomer types, ethylene and vinylarene, in its polymerized form.

[0063] The term "ethylene / alpha-olefin / vinylarene multiblock interpolymer," as used herein, refers to a multiblock interpolymer comprising at least two vinylarene-rich (AR) segments and at least two vinylarene-poor (AP) segments. Each (AR) segment independently contains more than 10 mol% vinylarene in its polymerized form. Each (AP) segment independently contains 10 mol% or less vinylarene in its polymerized form. Each mol% is based on the total number of moles of polymerized monomers in each segment. The multiblock interpolymer comprises ethylene, alpha-olefin, and vinylarene in its polymerized form, and may contain other monomer types. The term "ethylene / alpha-olefin / vinylarene multiblocker polymer," as used herein, refers to a multiblocker polymer comprising at least two vinylarene-rich (AR) segments and at least two vinylarene-poor (AP) segments, as discussed above. The multiblocker polymer comprises ethylene, alpha-olefin, and vinylarene as only three monomer types in its polymerized form.

[0064] The term "vinylarene," as used herein, refers to a compound containing "-CR=CHR' (wherein R and R' are independently H or alkyl)" bonded to an aromatic ring structure, such as a monocyclic, bicyclic, or tricyclic ring structure. The aromatic ring structure may contain or 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, and alpha-methylstyrene.

[0065] The term "alkylsilane group," as used herein, refers to a chemical group containing at least one -Si-R moiety (wherein 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).

[0066] The term "heteroatom" refers to an atom other than hydrogen or carbon (e.g., O, N, or P). The term "heteroatomic group" refers to a heteroatom or a chemical group containing one or more heteroatoms.

[0067] The terms "hydrocarbon," "hydrocarbyl group," and similar terms, as used herein, refer to the respective compounds or chemical groups, etc., that contain only carbon and hydrogen atoms.

[0068] The terms “heterohydrocarbon,” “heterohydrocarbyl group,” and similar terms, as used herein, refer to each hydrocarbon, or “hydrocarbyl group, etc.,” in which at least one carbon atom is substituted with a heteroatomic group (e.g., O, N, or P). A monovalent heterohydrocarbyl group may be bonded to the rest of the compound of interest via a carbon atom or via a heteroatom.

[0069] The terms “substituted hydrocarbon,” “substituted hydrocarbyl group,” and similar terms, as used herein, refer to each hydrocarbon or hydrocarbyl group, etc., in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0070] The terms “substituted heterohydrocarbon,” “substituted heterohydrocarbyl group,” and similar terms, as used herein, refer to each heterohydrocarbon or heterohydrocarbyl group, etc., in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0071] As used herein, the terms “aryl,” “aryl group,” and similar terms refer to one or more ring structures; for example, monovalent aromatic hydrocarbyl or aromatic hydrocarbyl groups, including monocyclic, bicyclic, or tricyclic ring structures.

[0072] As used herein, the terms “heteroaryl,” “heteroaryl group,” and similar terms refer to a monovalent aryl or aryl group, etc., in which at least one carbon atom of the skeletal ring structure is substituted with a heteroatom group.

[0073] The terms “substituted aryl,” “substituted aryl group,” and similar terms, as used herein, refer to an aryl or aryl group, etc., in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0074] The terms “substituted heteroaryl,” “substituted heteroaryl group,” and similar terms, as used herein, refer to a heteroaryl or heteroaryl group in which one or more hydrogen atoms are independently substituted by a heteroatomic group.

[0075] As used herein, the terms “arirene,” “arirene group,” and similar terms refer to one or more ring structures; for example, divalent aromatic hydrocarbylene or aromatic hydrocarbylene groups containing monocyclic, bicyclic, or tricyclic ring structures.

[0076] The terms “substituted arylene,” “substituted arylene group,” and similar terms, as used herein, refer to arylene or arylene groups, etc., in which one or more hydrogen atoms are independently substituted by heteroatomic groups.

[0077] The term "substitution or non-substitution (C1~C 30When used herein, "hydrocarbyl" and other similar terms refer to the range of all carbon atoms (e.g., 1 to 30) that a substituted or unsubstituted hydrocarbyl group may contain. Other monovalent chemical groups having the described carbon range (e.g., substituted or unsubstituted (C6 to C6) 20 Note that the aryl group is defined similarly.

[0078] The term "substitution or non-substitution (C1~C 30 The terms "heterohydrocarbyl" and other similar terms, as used herein, represent the range of total carbon atoms (e.g., 1 to 30) that a substituted or unsubstituted heterohydrocarbyl group may contain. Note that other monovalent chemical groups having the described carbon range are defined similarly.

[0079] The term "substitution or non-substitution (C6~C)" 20 The terms "arylene group" and other similar terms, as used herein, refer to the range of total carbon atoms (e.g., 2 to 6) that a substituted or unsubstituted arylene group may contain. Note that other divalent chemical groups having the described carbon range are defined similarly.

[0080] As used herein, the term “Lewis base” refers to a compound or chemical group that can donate an electron pair to a metal or another chemical group in relation to a metal complex, thereby forming a bond with the metal or another chemical group. Examples of Lewis bases include, but are not limited to, tetrahydrofuran (THF), diethyl ether, dimethylaniline, or trimethylphosphine.

[0081] The terms “syndiotacticity,” “syndiotactic,” and similar terms, as used herein, refer to the alternating stereochemical arrangement of two or more pendant aryl (e.g., phenyl) groups with respect to a polymerized vinylarene unit. See, for example, subsegment sbb.

[0082] The term "polymer structure" refers to either a portion of the polymer chain, as shown in Structure 1, or the entire polymer chain, as shown in Structure 2, with respect to the ethylene / vinylarene multiblock interpolymers of Structures 1 and 2.

[0083] The notation "AR" refers to a polymer segment of a multiblock interpolymer that contains more than 10 mol% vinylarene in its polymerization form. This notation refers to a "vinylarene-rich" segment.

[0084] The notation "AP" refers to a polymer segment of a multiblock interpolymer that contains 10 mol% or less of vinylarene in its polymerization form. This notation indicates a segment that is "poor in vinylarene."

[0085] The term "each segment" refers to an (AR) segment (or block) or (AP) segment (or block) located at the end of a polymer molecule or within a polymer molecule.

[0086] As used herein, the term “solution polymerization” refers to a polymerization process in which (one or more) monomers, (one or more) catalysts, and the resulting polymer are all soluble in a polymerization solvent or a solvent blend of two or more solvents.

[0087] As used herein, the term "continuous solution polymerization" refers to solution polymerization in which (one or more) monomers are continuously fed into a reactor and the polymer is continuously removed from the reactor.

[0088] As used herein, the term “metal complex” refers to a chemical structure comprising a metal or metal ion bonded and / or coordinated to one or more ligands (ions or molecules containing one or more electron pairs that can be shared with the metal). See, for example, the metal complexes of formulas A and B. Metal complexes typically derive their catalytic activity from the use of one or more cocatalysts.

[0089] As used herein, the term "scavenger" refers to a compound added to a polymerization reaction to remove or deactivate impurities or unwanted reaction products (e.g., oxygen). Some examples of scavengers include aluminum alkyl compounds such as MMAO and MMAO-3A.

[0090] The terms “comprising,” “including,” “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 any doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, auxiliaries, or compounds, whether polymeric or otherwise, unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, steps, or procedures from the scope of any subsequent description, except those not essential to the feasibility. The term “consisting of” excludes any components, steps, or procedures not specifically described or enumerated.

[0091] List of several methods and compositions A) A method for forming a composition comprising an ethylene / vinylarene multiblock interpolymer, comprising at least the following components a) to c): a) The following equation A:

[0092] [ka] (In the formula, X1 and X 2 Each of these can be substituted or not substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, further substituted or unsubstituted (C1~C 30 ) Hydrocarbyl, further selected from alkyl, X 1 and X 2 These may be joined by choice. Ar 1 and Ar 2 Each of these is independently a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group, R 52 (These are substituted or unsubstituted arylene groups.) A first metal complex selected from; b) The following equation B:

[0093] [ka] (In the formula, 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, further H, an alkyl group or alkylsilyl group, further alkyl group or alkylsilyl group, Q 1 and Q 2 Each of these is independently a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heterohydrocarbyl group, or a halogen, further comprising an aryl group, an alkylsilyl group, an alkoxy group, a halogen, or -NRR' (wherein R and R' are independently hydrocarbyl or SiR'' (wherein R'' is hydrocarbyl)), further comprising an aryl group, an alkylsilyl group, or an alkoxy group. L is a Lewis base, and each n is independently either 0 or 1. (Optionally, at least one L group and at least one Q group are connected, and optionally, at least one R group and at least one Q group are connected.) A second metal complex selected from; c) The following: Chain shuttle agents selected from dialkylzinc, trialkylaluminum, or combinations thereof A method comprising polymerizing a mixture containing ethylene, vinylarene, and optionally alpha-olefin in a single reactor in the presence of [a specific substance].

[0094] Regarding equation A, X 1 and X 2 Each of these independently performs substitution or non-substitution (C1~C 30 ) Hydrocarbyl, further alkyl, further X 1 =X 2 The method is as described in A above.

[0095] C] Expression A is the following structure (a11) or (a12):

[0096] [ka] From there, one of the above methods A] or B] is selected from the structure (a11).

[0097] Regarding formula B in D, R 1 ~R 5 Each of the above A] to C] is independently H, alkyl, further C1-C5 alkyl, further C1-C4 alkyl, further C1-C3 alkyl, further C1-C2 alkyl, and further methyl.

[0098] Regarding E] formula B, R 1 =R 2 =R 3 =R 4 =R 5 This is one of the methods A] to D] above.

[0099] F] Expression B is the following structure (b11) or (b12):

[0100] [ka] From there, one of the above methods A]~E] is selected from the structure (b11).

[0101] G] For formula B, L is selected from tetrahydrofuran (THF), diethyl ether, dimethylaniline, or trimethylphosphine, and further from THF, one of the methods A] to F] above.

[0102] For equation B, n=0, one of the methods A]~F] above.

[0103] I) The chain shuttle agent (component c) is selected from the following: Zn(CH2CH3)2, Al(CH2CH3)3, or a combination thereof, in any one of the above methods A) to H).

[0104] J) Polymerization is carried out by any one of the above methods A) to I), which is solution polymerization or continuous solution polymerization.

[0105] The above method J] provides a solution containing an aromatic solution, further containing toluene.

[0106] L) Polymerization occurs at a temperature of 80°C or higher, or 85°C or higher, or 90°C or higher, or 95°C or higher, or 100°C or higher, or 105°C or higher, or 110°C or higher, according to any one of the above methods A] to K].

[0107] M) Polymerization occurs at a temperature of 160°C or below, or 155°C or below, or 150°C or below, or 145°C or below, or 140°C or below, or 135°C or below, or 130°C or below, or 125°C or below, or one of the above methods A) to L).

[0108] N) Polymerization occurs at a pressure of 50 psig or higher, or 60 psig or higher, or 70 psig or higher, or 75 psig or higher, or 80 psig or higher, in any one of the above methods A] to M].

[0109] O) Polymerization occurs at a pressure of 120 psig or less, or 110 psig or less, or 100 psig or less, or 95 psig or less, or 90 psig or less, in any one of the above A]~N] methods.

[0110] P] The mixture contains alpha-olefins in any one of the above A]~O] methods.

[0111] Q] Alpha-olefins, C3~C 20 Alpha-olefins, and furthermore, C3~C 10 The above method of P] is 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, further 1-octene.

[0112] R] One of the above methods A] to Q], wherein the molar ratio of the metal of the first metal complex to the metal of the second metal complex is 0.03 or greater, or 0.1 or greater, or 0.5 or greater.

[0113] S) One of the above methods A] to R], wherein the molar ratio of the metal of the first metal complex to the metal of the second metal complex is 1000 or less, or 500 or less, or 100 or less.

[0114] T) Any one of the above methods A] to S], wherein the molar ratio of the chain shuttle agent metal to the total of the metals of the first metal complex and the second metal complex is 2.0 or greater, or 5.0 or greater, or 10 or greater, or 20 or greater, or 40 or greater, or 100 or greater.

[0115] U) The molar ratio of the chain shuttle agent metal to the total of the metals of the first metal complex and the second metal complex is 1000 or less, or 800 or less, or 500 or less, in any one of the above methods A] to T].

[0116] V] The first metal complex has a reactivity ratio of 50-1000, and further, 100-500, 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) One of the above methods A to U, having [...].

[0117] W] The second metal complex has a reactivity ratio of 1 to 10, 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) One of the above methods A to V, having [the specified condition].

[0118] X] A method of any one of the above A] to W] wherein the composition further comprises polyethylene homopolymer, ethylene / vinylarene copolymer, ethylene / alpha-olefin copolymer, or a combination thereof.

[0119] A composition formed by one of the following methods: Y, A, X.

[0120] A2] A composition comprising an ethylene / vinylarene multiblock interpolymer, wherein the interpolymer comprises at least one polymer structure selected from structure 1 or structure 2 as shown below, where (AR) refers to a vinylarene-rich segment and (AP) refers to a vinylarene-poor segment. -(AR)-(AP)-(AR)-(AP)-(Structure 1), (AR)-(AP)-(AR)-(AP)(Structure 2), Each (AR) segment independently comprises, in its polymerized form, ethylene, vinylarene, and optionally alpha-olefin. Each (AP) segment independently comprises, in its polymerized form, ethylene, optionally vinylarene, and optionally alpha-olefin. Each (AR) segment independently contains more than 10 mol% vinylarene in its polymerized form, based on the total number of moles of polymerized monomers within the (AR) segment. Each (AP) segment independently contains 10 mol% or less of vinylarene in its polymerized form, based on the total number of moles of polymerized monomers within the (AP) segment.

[0121] A2) above, wherein each (AR) segment independently contains 15 mol% or more, or 20 mol% or more, or 25 mol% or more, or 30 mol% or more, or 35 mol% or more, or 40 mol% or more, or 45 mol% or more, or 50 mol% or more, or 55 mol% or more, or 60 mol% or more of vinylarene in polymerized form, based on the total number of moles of polymerized monomers in the (AR) segment.

[0122] A2] or B2] above, wherein each (AR) segment independently contains less than 100 mol%, or 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 91 mol%, of vinylarene in polymerized form, based on the total number of moles of polymerized monomers within the (AR) segment.

[0123] A2] to C2] above, wherein each (AP) segment independently contains 0 mol% or more, or 0.2 mol% or more, or 0.4 mol% or more, or 0.6 mol% or more, or 0.8 mol% or more, or 1.0 mol% or more of vinylarene in polymerization form, based on the total number of moles of polymerized monomers in the (AP) segment.

[0124] E2] Ethylene / vinylarene multiblock interpolymer, one of the above compositions A2] to D2], wherein each (AP) segment independently contains 10 mol% or less, or 9.0 mol% or less, or 8.0 mol% or less, or 7.0 mol% or less, or 6.0 mol% or less, or 5.0 mol% or less vinylarene in polymerization form, based on the total number of moles of polymerized monomers in the (AP) segment.

[0125] F2]E2]Ethylene / vinylarene multiblock interpolymer, one of the above compositions A2-E2], wherein each (AR) segment independently contains 2.0 mol% or more, or 4.0 mol% or more, or 6.0 mol% or more, or 8.0 mol% or more, or 9.0 mol% or more, or 10 mol% or more, or 11 mol% or more, or 12 mol% or more, or 13 mol% or more, or 14 mol% or more of ethylene in polymerization form, based on the total number of moles of polymerized monomers in the (AR) segment.

[0126] G2] Ethylene / vinylarene multiblock interpolymer, one of the above compositions A2 to F2], wherein each (AR) segment independently contains ethylene in a polymerization form of 80 mol% or less, or 77 mol% or less, or 75 mol% or less, or 73 mol% or less, or 70 mol% or less, or 65 mol% or less, or 60 mol% or less, or 55 mol% or less, or 50 mol% or less, or 45 mol% or less, or 40 mol% or less.

[0127] A composition of any one of the above A2-G2], wherein each (AP) segment independently contains 50 mol% or more, 52 mol% or more, or 54 mol% or more, or 56 mol% or more, or 58 mol% or more, or 60 mol% or more, or 62 mol% or more, or 64 mol% or more, or 66 mol% or more, or 68 mol% or more, or 70 mol% or more of ethylene in polymerized form, based on the total number of moles of polymerized monomers in the (AP) segment.

[0128] I2]Ethylene / vinylarene multiblock interpolymer, one of the above A2-H2] compositions, wherein each (AP) segment independently contains ethylene in its polymerized form at a concentration of 100 mol% or less, or 98 mol% or less, or 96 mol% or less, or 94 mol% or less, or 92 mol% or less, or 90 mol% or less, based on the total number of moles of polymerized monomers within the (AP) segment.

[0129] J2]Ethylene / vinylarene multiblock interpolymer, one of the above compositions A2] to I2], wherein each (AR) segment independently contains 0 mol% or more, 1.0 mol% or more, or 2.0 mol% or more, or 3.0 mol% or more, or 4.0 mol% or more of alpha-olefin in polymerization form, based on the total number of moles of polymerized monomers within the (AR) segment.

[0130] A2] to J2] above, wherein each (AR) segment independently contains 10 mol% or less, 9.0 mol% or less, or 8.0 mol% or less, or 7.0 mol% or less, or 6.0 mol% or less of alpha-olefins in polymerization form, based on the total number of moles of polymerized monomers within the (AR) segment.

[0131] L2] Alpha-olefin, C3~C 20 Alpha-olefins, and furthermore, C3~C 10A composition of the above J2] or K2], which is an 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, further 1-octene.

[0132] For the ethylene / vinylarene multiblock interpolymer, a composition of any one of the above A2] to L2], in which each (AR) segment does not contain an alpha-olefin in the polymerized form.

[0133] For the ethylene / vinylarene multiblock interpolymer, a composition of any one of the above A2] to M2], in which each (AP) segment independently contains 0 mol% or more, 1.0 mol% or more, or 2.0 mol% or more, or 3.0 mol% or more, or 4.0 mol% or more, or 6.0 mol% or more, or 8.0 mol% or more, or 10 mol% or more of an alpha-olefin based on the total number of moles of the polymerized monomers in the (AP) segment in the polymerized form.

[0134] For the ethylene / vinylarene multiblock interpolymer, a composition of any one of the above A2] to N2], in which each (AP) segment independently contains 40 mol% or less, or 35 mol% or less, or 30 mol% or less, or 28 mol% or less, or 26 mol% or less, or 24 mol% or less, or 22 mol% or less, or 20 mol% or less of an alpha-olefin based on the total number of moles of the polymerized monomers in the (AP) segment in the polymerized form.

[0135] P2] The alpha-olefin is C3-C 20 alpha-olefin, further C3-C 10 A composition of the above N2] or O2], which is an 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, further 1-octene.

[0136] Q2] Regarding ethylene / vinylarene multiblock interpolymers, each (AR) segment independently comprises the following subsegments:

[0137] [ka] A composition comprising 20 mol% or more, or 30 mol% or more, or 40 mol% or more, or 50 mol% or more, or 60 mol% or more, or 70 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 92 mol% or more, or 94 mol% or more, or 96 mol% or more, or 98 mol% or more, or 99 mol% or more polymerized vinylarene in a "back-to-back" arrangement as shown, wherein the mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment, according to any one of the methods A] to X] above or any one of the compositions A2] to P2] above.

[0138] R2] An ethylene / vinylarene multiblock interpolymer in which each (AR) segment independently contains 100 mol% or less of polymerized vinylarene in a "back-to-back" arrangement as shown in the subsegment bb above, by any one of the above A]~X] or Q2] or in any one of the above A2]~Q2] compositions.

[0139] S2] Ethylene / vinylarene multiblock interpolymer, each (AR) segment independently contains 20 mol% or more, or 30 mol% or more, or 40 mol% or more, or 50 mol% or more, or 60 mol% or more, or 70 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 92 mol% or more, or 94 mol% or more, or 96 mol% or more, or 98 mol% or more, or 99 mol% or more polymerized vinylarene in a syndiotactic "back-to-back" arrangement as shown below within the subsegment sbb.

[0140] [ka] A composition of any one of the above methods A]~X] or Q2] or R2], where mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

[0141] T2]Ethylene / vinylarene multiblock interpolymer, wherein each (AR) segment independently contains 100 mol% or less of polymerized vinylarene in a syndiotactic "back-to-back" configuration as shown in the subsegment sbb above, by any one of the above A]~X] or Q2]~S2] or in any one of the above A2]~S2] compositions.

[0142] Regarding the U2]ethylene / vinylarene multiblock interpolymer, each (AP) segment independently contains 0 to 5.0 mol%, or 2.0 mol%, or 1.0 mol%, or 0.5 mol%, or 0.2 mol%, or 0.1 mol%, polymerized vinylarene present in a "back-to-back" configuration within subsegment bb as shown below.

[0143] [ka] A composition of any one of the above methods A]~X] or Q2]~T2], or any one of the above methods A2]~T2], where mol% is based on the total number of moles of polymerized vinylarene in the (AP) segment.

[0144] For V2] ethylene / vinylarene multiblock interpolymers, none of the polymerized vinylarenes within each (AP) segment are present in a "back-to-back" configuration as shown in the subsegment bb above, in any one of the above A]~X] or Q2]~U2] methods or any one of the above A2]~U2] compositions.

[0145] W2] Ethylene / vinylarene multiblock interpolymer, wherein vinylarene is styrene, by any one of the above A]~X] or Q2]~V2] or in any one of the above A2]~V2] compositions.

[0146] X2) is an ethylene / vinylarene multiblock interpolymer, further comprising an ethylene / alpha-olefin / vinylarene multiblock interpolymer, and an ethylene / alpha-olefin / vinylarene multiblock interpolymer, in any one of the above A]~X] or Q2]~W2] or any one of the above A2]~W2] compositions.

[0147] [Y2] The composition has a molecular weight distribution (MWD=M) of 2.5 or higher, or 2.6 or higher, or 2.7 or higher, or 2.8 or higher, or 2.9, or 3.0 or higher, or 3.1 or higher. w / M n A method of any one of the above A]~X] or Q2~X2] or a composition of any one of the above A2]~X2] having ).

[0148] Z2] A composition having a molecular weight distribution MWD of 20 or less, or 10 or less, or 8.0 or less, or 6.0 or less, or 5.5 or less, or 5.0 or less, or 4.5 or less, or 4.0 or less, by any one of the methods A]~X] or Q2]~Y2] above, or any one of the compositions A2]~Y2] above.

[0149] A3] A composition having a number average molecular weight (Mn) of 10,000 g / mol or more, or 12,000 g / mol or more, or 14,000 g / mol or more, or 16,000 g / mol or more, or 18,000 g / mol or more, according to any one of the methods A]~X] or Q2]~Z2] above, or any one of the compositions A2]~Z2] above.

[0150] B3] A composition having Mn of 100,000 g / mol or less, or 90,000 g / mol or less, or 80,000 g / mol or less, or 70,000 g / mol or less, or 65,000 g / mol or 60,000 g / mol or less, or 55,000 g / mol or less, by any one of the above A]~X] or Q2]~A3] or any one of the above A2]~A3].

[0151] [C3] Composition has a weight-average molecular weight (M) of 30,000 g / mol or more, 35,000 g / mol or more, 40,000 g / mol or more, and 45,000 g / mol or more. w A method or composition of any one of the above A]~X] or Q2]~B3], having ).

[0152] D3] A composition having Mw of 400,000 g / mol or less, or 350,000 g / mol or less, or 300,000 g / mol or less, or 250,000 g / mol or less, or 200,000 g / mol or less, by any one of the above A]~X] or Q2]~C3] or any one of the above A2]~C3] compositions.

[0153] E3] A composition having a melt index (I2) of 0.5 dg / min or more, or 1.0 dg / min or more, or 2.0 dg / min or more, or 5.0 dg / min or more, or 10 dg / min or more, by any one of the methods A] to X] or Q2] to D3] above, or any one of the compositions A2] to D3] above.

[0154] F3] A composition having a melt index (I2) of 1,000 dg / min or less, or 500 dg / min or less, or 250 dg / min or less, or 100 dg / min or less, or 50 dg / min or less, or 20 dg / min or less, by any one of the above A]~X] or Q2]~E3] or any one of the above A2]~E3].

[0155] The composition has a T of 100 °C or higher, or 120 °C or higher, or 150 °C or higher, or 200 °C or higher, or 220 °C or higher, or 230 °C or higher, or 240 °C or higher, or 250 °C or higher m and is any one of the methods of A] to X] or Q2] to F3] above or any one of the compositions of A2] to F3] above.

[0156] The composition has a T of 300 °C or lower, or 290 °C or lower, or 285 °C or lower, or 280 °C or lower, or 275 °C or lower, or 270 °C or lower, or 265 °C or lower m and is any one of the methods of A] to X] or Q2] to G3] above or any one of the compositions of A2] to G3] above.

[0157] The composition has a T of -75 °C or higher, or -70 °C or higher, or -65 °C or higher g and is any one of the methods of A] to X] or Q2] to H3] above or any one of the compositions of A2] to H3] above.

[0158] The composition has a T of 10 °C or lower, or 0 °C or lower, or -20 °C or lower, or -30 °C or lower, or -40 °C or lower, or -50 °C, or -55 °C or lower g and is any one of the methods of A] to X] or Q2] to I3] above or any one of the compositions of A2] to I3] above.

[0159] The composition is in a polymerized form and contains 5.0 mol% or more, or 10 mol% or more, or 12 mol% or more, or 14 mol% or more of vinylarene based on the total number of moles of the polymerized monomers in the composition, and is any one of the methods of A] to X] or Q2] to J3] above or any one of the compositions of A2] to J3] above.

[0160] L3] A composition comprising, in polymerization form, 60 mol% or less, or 55 mol% or less, or 50 mol% or less, or 45 mol% or less of vinylarene based on the total number of moles of polymerization monomers in the composition, by any one of the above methods A]~X] or Q2]~K3] or any one of the above compositions A2]~K3].

[0161] M3] A composition comprising 10 mol% or more, or 15 mol% or more, or 20 mol% or more, or 25 mol% or more of ethylene in polymerization form, based on the total number of moles of polymerization monomers in the composition, by any one of the above methods A]~X] or Q2]~L3] or any one of the above compositions A2]~L3].

[0162] The composition [N3] contains ethylene in a polymerized form in an amount of 90 mol% or less, or 85 mol% or less, or 80 mol% or less, or 78 mol% or less, or 76 mol% or less, or 74 mol% or less, or 72 mol% or less, or 70 mol% or less, based on the total number of moles of polymerized monomers in the composition, by any one of the above methods A]~X] or Q2]~M3] or any one of the above compositions A2]~M3].

[0163] The O3] composition comprises 2.0 mol% or more, 5.0 mol% or more, or 10 mol% or more, or 12 mol% or more, or 14 mol% or more, or 16 mol% or more of alpha-olefins in polymerization form, based on the total number of moles of polymerization monomers in the composition, by any one of the above A]~X] or Q2]~N3] or any one of the above A2]~N3] composition.

[0164] P3) A composition comprising 50 mol% or less, or 45 mol% or less, or 40 mol% or less, or 35 mol% or less of an alpha-olefin in polymerization form, based on the total number of moles of polymerization monomers in the composition, by any one of the above A]~X] or Q2]~O3] or any one of the above A2]~O3].

[0165] Q3] Alpha-olefins, C3~C20 Alpha-olefins, and furthermore, C3~C 10 A composition of any one of the above A]~X] or Q2]~P3] or O3] or P3], which is an 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, or further 1-octene.

[0166] For the composition R3], the molar ratio of block styrene (bb in AR) to isolated styrene is 2.0 or greater, 4.0 or greater, 6.0 or greater, 8 or greater, or 10 or greater, according to any one of the methods A]~X] or Q2]~Q3] above or any one of the compositions A2]~Q3] above.

[0167] S3] A composition in which the molar ratio of block styrene (bb in AR) to isolated styrene is 30 or less, or 25 or less, according to any one of the above methods A]~X] or Q2]~R3] or any one of the above compositions A2]~R3].

[0168] T3) A composition in which vinylarene is styrene, by any one of the above methods A]~X] or Q2]~S3] or any one of the above methods A2]~S3].

[0169] U3) an ethylene / vinylarene multiblock interpolymer is an ethylene / vinylarene / alpha-olefin multiblock interpolymer, and further an ethylene / vinylarene / alpha-olefin multiblock interpolymer, in any one of the above A]~X] or Q2]~T3] or in any one of the above A2]~T3] composition.

[0170] V3] A composition comprising a polyethylene homopolymer, an ethylene / vinylarene copolymer, an ethylene / alpha-olefin copolymer, or a combination thereof, by any one of the above methods A]~X] or Q2]~U3] or any one of the above compositions A2]~U3].

[0171] W3] Monomer type and / or quantity (one or more types), T m , T g M n M w In one or more features such as MWD, or any combination thereof, and furthermore, (one or more) monomer types and / or quantities, T m , T g A composition from A2 to V3 above, further comprising an ethylene / vinylarene multiblock interpolymer and a thermoplastic polymer different in one or more features, such as any combination thereof.

[0172] An article comprising at least one component formed from one of the compositions of X3]Y] or A2]~W3].

[0173] A method for forming any one of the compositions A2 to V3 on Y3, wherein at least the following a) to c): a) A first metal complex selected from the following formula A, as described above; b) A second metal complex selected from the following formula B, as described above; c) The following: Chain shuttle agents selected from dialkylzinc, trialkylaluminum, or combinations thereof A method comprising polymerizing a mixture containing ethylene, vinylarene, and optionally alpha-olefin in a single reactor in the presence of [a specific substance].

[0174] Test method Gel permeation chromatography (conventional) 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 chamber was set to 160°C, and the column chamber was set to 150°C. The columns were four AGILENT "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent was 1,2,4-trichlorobenzene, which contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was spurged nitrogen. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min.

[0175] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, which were arranged in a mixture of six "cocktails" with individual molecular weights separated by at least one decade. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at a concentration of 0.025 grams in 50 ml of solvent for molecular weights greater than 1,000,000, and 0.05 grams in 50 ml of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80°C 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)):

[0176] M ポリエチレン =A × (M ポリスチレン ) B (Equation 1) (wherein M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0).

[0177] A fifth-degree polynomial was used to fit the equivalent calibration points of each polyethylene. The linear homopolymer polyethylene standard was 120,000 M. wA was slightly adjusted (approximately 0.375-0.445) to compensate for the column resolution and band expansion effect obtained. The total plate count of the GPC column set was performed using decane (prepared at 0.04 g in 50 ml of TCB and dissolved for 20 minutes with gentle stirring). The plate count (Equation 2) and symmetry (Equation 3) for a 200 microliter injection are given by the following equations:

[0178]

number

[0179]

number

[0180] The sample was prepared semi-automatically using PolymerChar "Instrument Control" software, where the sample (targeting a weight of 2 mg / ml) and solvent (containing 200 ppm BHT) were added to a pre-nitrogen-spurged vial with a septum cap via a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours under low-speed shaking.

[0181] Mn (GPC) Mw(GPC) and M z(GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4-6, using PolymerChar GPCOne® Software, the IR chromatogram 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. Equations 4-6 are as follows:

[0182]

number

[0183] To monitor deviations over time, a flow marker (decane) was introduced to each sample via a micropump controlled by the PolymerChar GPC-IR system. Using this flow marker (FM), the pump flow rate (apparent flow rate) for each sample was linearly corrected by RV matching each decane peak in the sample (RV(FM sample)) with that of the decane peak in the narrow standard calibration (RV(FM calibrated)). It was then assumed that any temporal change in the decane marker peak was related to a linear shift in the flow rate (effective flow rate) over the entire operation. To facilitate the highest accuracy of RV measurement of the flow marker peak, the peaks of the flow marker concentration chromatogram were fitted to a quadratic equation using a least-squares fitting routine. The true peak position was then determined using the first derivative of the quadratic equation. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated as shown in Equation 7: Flow rate (effective) = Flow rate (apparent) * (RV(FM calibrated) / RV(FM sample))(Equation 7). Flow marker peak processing was performed via PolymerChar GPCOne(trademark) Software. The acceptable flow correction is such that the effective flow rate is within + / - 0.7% of the apparent flow rate.

[0184] Melt Index The melt index (I2) of ethylene-based polymers is measured according to ASTM D-1238, under conditions of 190°C / 2.16 kg. The melt flow rate (MFR) of propylene-based polymers is measured according to ASTM D-1238, under conditions of 230°C / 2.16 kg.

[0185] density Polymer plaques for density analysis are prepared using ASTM D4703. The density of the polymer is measured using ASTM D792, Method B.

[0186] Differential scanning calorimetry (DSC) Differential scanning calorimetry (DSC) was used to determine the T of ethylene (PE) polymer samples and styrene (PS) polymer samples. m , T c , T g The degree of crystallinity is measured. Approximately 5-8 mg of polymer sample is weighed and placed in a DSC pan. The lid is pressed onto the pan to ensure a closed atmosphere. Unless otherwise specified, the sample pan is placed in a DSC cell and then heated at a rate of 10°C / min to a temperature of 180°C for PE (300°C for PS). The sample is held at this temperature for 3 minutes. The sample is 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 is heated at a rate of 10°C / min until completely melted (second heating). Unless otherwise specified, the melting point (T) of each polymer is measured. m ) and glass transition temperature (T g The crystallization temperature (T) is determined from the second heating curve. c ) was determined from the first cooling curve. T m (Peak temperature) and T g This was recorded. The heat of fusion (H) was determined from the second heating curve. f) For PE, divide by the theoretical heat of fusion of 292 J / g (for syndiotactic PS it is 53 J / g), and multiply this amount by 100 to calculate the percent crystallinity (for example, % crystallinity = (Hf / 292 J / g) × 100 (for PE)).

[0187] 13 C NMR Each sample was prepared by adding approximately 2.7 g of stock solvent to 0.2 g of sample (polymer or 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 - 135 °C. Data was collected using a Bruker 600 MHz spectrometer equipped with a Bruker high - temperature CryoProbe. With a sample temperature of 120 °C, data was acquired using a pulse repetition delay of 7.3 seconds (delay 6 seconds + acquisition time 1.3 seconds), a flip angle of 90 degrees, and inverse - gate decoupling. All measurements were performed in lock mode on a non - rotating sample. The sample was homogenized immediately before insertion into a heated (125 °C) NMR sample changer and thermally equilibrated in the probe for 7 minutes before data acquisition.

[0188] For the analysis of each sample (polymer or polymer composition), the B1 carbon (quaternary carbon on the aromatic ring) signal at 145.0 - 147.7 ppm was used as the styrene contribution, and the molar amount of the polymerization monomer was calculated as follows (S = styrene, E = ethylene): Smol = Integral(145.0 - 147.7 ppm) Emol = (Integral(20.0 - 48.0 ppm) - 2 * Smol) / 2 S mol% = 100 * Smol / (Smol + Emol) E mol% = 100 - S mol%

[0189] [Chemical]

[0190] For the analysis of each sample (polymer or polymer composition), B1-4 ring carbon signals at 124.0 - 148.0 ppm were used as styrene contributions, 2B6 (22.0 - 23.5 ppm), and 3B6 (31.5 - 32.7 ppm) signals were used as octene contributions, and the molar amounts of the polymerization monomers were calculated as follows (S = styrene, E = ethylene, O = octene): Smol = Integral(124.0 - 148.0 ppm) / 6 Omol = (Integral(22.0 - 23.5 ppm) + Integral(31.5 - 32.7 ppm)) / 2 Emol = (Integral(11.8 - 48.0 ppm) - 2 * Smol - 8 * Omol) / 2 Smol% = 100 * Smol / (Smol + Omol + Emol) Omol% = 100 * Omol / (Smol + Omol + Emol) Emol% = 100 - Smol% - Omol%

[0191] [Chemical] Average styrene block length = 2 * (Integral T ββ + T βδ ) / Integral T βδ Ratio of block styrene to isolated styrene = (Integral T ββ + T βδ ) / Integral T δδ T ββ signal is a methine signal centered at approximately 41.6 ppm, and the T βδ signal is a methine signal centered at approximately 43.9 ppm, and the T δδThe signal is a methine signal centered around approximately 46.4 ppm. T ββ %=100 * Integral T ββ / Integral B1

[0192] 1 1H NMR Each sample was prepared by adding 130 mg of the sample (metal complex) to 3.25 g of tetrachloroethane-d2 containing 0.001 M Cr(acac)3 in a 10 mm NMR tube. The sample was purged for approximately 5 minutes by bubbling N2 into the solvent through a pipette inserted into the tube to prevent oxidation. The sample container was capped and sealed with TEFLON tape. The sample was heated and vortexed at 115°C to ensure homogeneity. 1 1H NMR was performed using a Bruker AVANCE 600MHz spectrometer equipped with a Bruker high-temperature cryoprobe, at a sample temperature of 120°C. 1 1H NMR was operated with a ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64 sec, and d 114 sec.

[0193] Determination of liquid-phase monomer concentration by gas-liquid equilibrium (VLE) calculation. Since olefin polymerization occurs in the liquid phase within a batch reactor, determining the reactant concentrations in the liquid phase is useful. This can be done experimentally by sampling the liquid phase and using online gas chromatography, or through spectroscopic techniques such as Fourier transform near-infrared spectroscopy or Raman spectroscopy. An alternative method is to accurately measure the amounts of each reactant and solvent added to the reactor, as well as the temperature and pressure, and then use a thermodynamic "equation of state" model to calculate the amounts of liquid and vapor phases present, as well as the composition of each phase. Suitable equations of state include the Redlich-Kwong-Soave[1], Peng-Robinson[2], or, more recently, the perturbed chain statistical associating fluid theory (PC-SAFT) equation of state[3]. Thermodynamic parameters can be obtained from the literature, and the equations can be solved in a spreadsheet or other computer calculation. Alternatively, commercial process simulation software can be used to solve a chosen equation of state model and determine the conditions within the batch reactor. Examples include ASPEN PLUS[4], CHEMCAD[5], or gPROMS[6]. ASPEN PLUS was used in experimental examples along with the PC-SAFT equation of state—see Figure 7.

[0194] [1] Soave, Giorgio. "Equilibrium constants from a modified Redlich-Kwong equation of state". Chemical Engineering Science. 27 (6): 1197-1203. [2] Peng, DY; Robinson, DB "A New Two-Constant Equation of State". Industrial and Engineering Chemistry: Fundamentals. 15: 59-64. [3] Gross, Joachim; Sadowski, Gabriele. "Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain Molecules". Industrial & Engineering Chemistry Research. 40 (4): 1244-1260. [4] https: / / www.aspentech.com / products / engineering / aspen-plus [5] https: / / www.chemstations.com / CHEMCAD / [6] https: / / www.psenterprise.com /

[0195] experiment Study 1: Analysis of vinylarene-rich (hard block) samples (C5Me5)Sc(CH2C6H4NMe2-o)2, CAT B synthesis

[0196] [ka] In a nitrogen-filled glove box, a 1 mL THF solution of Sc(CH2CH6H4NMe2-O)3 (0.300 g, 0.67 mmol) was added to a 1 mL THF solution of C5Me5H (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, and the residue was extracted with hexane and then filtered. The concentrated hexane solution was equilibrated at -30°C to yield yellow crystals (0.203 g, yield 65.5%). 1 1H NMR and 13 The 13C NMR spectrum is consistent with the literature report (Chem. Commun. 2007, 40, 4137-4139). Figure 1 shows the Sc complex (CAT B). 1 (H NMR) and Figure 2 ( 13 Please refer to (C NMR).

[0197] Chain shuttle experiment with Sc catalyst (CAT B) Toluene (final volume 8 mL), styrene (1 mL), and a magnetic stirring bar were placed in a glass vial. CAT B (5 umol), "amine, bis(hydrolyzyl hydride), methyl tetrakis(pentafluorophenyl)borate (1-) (1.2 equivalents)," and either the chain shuttle agent TEA or DEZ (25 or 100 umol) were sequentially added to the solution. A control solution without the chain shuttle agent was also prepared. Each mixture was heated at 100°C for 1 hour, then slowly cooled and quenched in methanol. The polymers were collected by filtration and dried under vacuum. Polymer properties are listed in Table 1 below. GPC profiles are shown in Figure 3. These polymerizations demonstrate the chain shuttle ability of CAT B in the presence of the chain shuttle agent. This is clearly shown by the data in Table 1, which shows a characteristic decrease in molecular weight and narrowing of the MWD compared to polymerization carried out in the presence of DEZ or TEA.

[0198] [Table 1]

[0199] Batch reactor polymerization setup (vinylarene-rich) The batch reactor setup consisted of a 600 mL Parr reactor controlled by a process control system. The reactor was equipped with an electric heating jacket, an internal cooling coil for temperature control, and an electrically heat-traced transfer line between the reactor and the reactor dump pot. Three feeds were available with the option of charging the solvent or monomer (50 mL) from a removable 1 liter cylinder. This cylinder was loaded inside an inert (N2) glove box and its contents were transferred to the reactor via nitrogen injection. The catalyst components and the chain shuttling agent were prepared inside the inert glove box and transferred to the reactor from the 50 mL cylinder via nitrogen transfer. The 1-octene cylinder was filled from the purified plant feed. Ethylene was supplied as a high purity grade from Airgas. For further purification, 1-octene and ethylene were passed through in-line beds of activated alumina, 13X molecular sieves, and Q5 material. The high pressure nitrogen for catalyst injection and purging was of ultra-high purity grade. Styrene was degassed immediately prior to addition into the reactor and the inhibitor was removed by passing the styrene feed through a plug of neutral alumina.

[0200] Ethylene, 1-octene, styrene polymerization: [Cp * Sc] catalyst - reactivity of CAT B Degassed anhydrous toluene was added to a 600 mL Parr reactor from a nitrogen-pressurized solvent cylinder using a mass flow meter, and the reactor agitator was set to 450 rpm. Styrene was injected via a high-pressure nitrogen-pressurized cylinder. When used, a predetermined amount of 1-octene was added to the reactor from a nitrogen-pressurized cylinder using a flow meter. Once 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 toluene solution of pre-prepared CAT B (typical input amount 22 μmol Sc), a 0.006 M solution of "amine, bis(hydroalkyl hydride), 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 compared to one equivalent of CAT B.

[0201] An ethylene flow of 200 mg / min was initiated while the overall reactor pressure was controlled to a programmed setpoint throughout the desired 10-minute operating time. After the mixing time, the agitator was stopped and the contents of the reactor were emptied into 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 2 below. See also Table 3. Interpolymers AR1-AR12 in Tables 2 and 3 are, for example, vinylarene-rich (hard block) segments of ethylene / octene / styrene multiblock interpolymers in monomer compositions, tacticity of polymerized vinylarene, T m and T g These represent the respective things.

[0202] [Table 2]

[0203] [Table 3]

[0204] Additional research - CAT B Figure 4 shows T m (Due to DSC measurement) and the mole percentage or T of "back-to-back styrene uptake" bb ( 13 (determined by 13C NMR) the mole percentage of polymerized (or incorporated) styrene, respectively. 13 This is shown as a function of (determined by 13C NMR). As seen in this figure, as the amount of ethylene (C2) uptake increases, the Tm of sPS is the same as that of pure sPS. m The temperature drops below (270℃), T bb The molar percentage also decreases. The samples include the batch reactor samples shown in Tables 2 and 3.

[0205] Figure 5 shows the weight-average molecular weight (M w ) (by GPC) and T m (Due to DSC) are shown as functions of the polymerization parameters described, respectively. As can be seen in this figure, the presence of a chain shuttle agent results in the presence of chain shuttles in the reaction mixture, and the molecular weight and T m This leads to a decrease in molecular weight or T. m It did not significantly affect the results. The samples were prepared according to the batch polymerization described above and using the conditions shown in Table 4.

[0206] [Table 4]

[0207] Data from Study 1 demonstrate the copolymerization characteristics of the scandium catalyst (CAT B) desirable for the intended chain shuttle polymerization, which requires the catalyst to prepare polystyrene or poly(styrene-co-ethylene) with a high melting temperature in the presence of an alpha-olefin such as 1-octene. For this scheme to succeed, the catalyst should preferably have high reactivity with styrene but very low reactivity with alpha-olefins. The table and figure above show high reactivity with styrene and ethylene but very low reactivity with 1-octene. In addition, the desirable chain shuttle characteristics are maintained, as can be seen from the decrease in molecular weight for polymerization carried out in the presence of DEZ or TEA.

[0208] Study 2: Analysis of vinylarene-poor (soft block) samples

[0209] [ka]

[0210] Ethylene, 1-octene, styrene polymerization: Reactivity of CAT A See the above discussion regarding batch reactor setup. Degassed anhydrous toluene was added to a 600 mL Parr reactor from a nitrogen-pressurized solvent cylinder using a mass flow meter, and the reactor agitator was set to 450 rpm. Styrene was injected via a high-pressure nitrogen-pressurized cylinder. A predetermined amount of 1-octene was added to the reactor from a nitrogen-pressurized cylinder using a flow meter. Once 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 toluene solution of the pre-prepared CAT A catalyst, a 0.006 M solution of "amine, bis(hydrohydrate-alkyl)methyl, 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 compared to CAT A (one equivalent).

[0211] An ethylene flow of 200 mg / min was initiated while the overall reactor pressure was controlled to a programmed setpoint throughout the desired 10-minute operating time. After the mixing time, the agitator was stopped and the reactor contents were emptied into 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 Tables 5 and 6 are, for example, the vinylarene-poor (soft block) segment of the ethylene / octene / styrene multiblock interpolymer in the monomer composition, the tacticity of the polymerized vinylarene, and T m and T g These represent the respective things.

[0212] [Table 5]

[0213] [Table 6]

[0214] Additional research - CAT A Figure 6 shows the glass transition temperature (T) determined by DSC. g ) is the molar percentage of polymerized octene in the polymer ( 13 (Determined from 13C NMR) is shown as a function of θ. As seen in this figure and Table 7 below, the presence of styrene in the reactor does not significantly affect the glass transition temperature and amorphous phase of the final polymer. Samples were prepared according to the batch polymerization described above (see Table 5) and using the conditions shown in Table 7.

[0215] [Table 7]

[0216] Data from Study 2 demonstrate the desirable copolymerization characteristics for the hafnium catalyst (CAT A) for the intended chain shuttle polymerization. Unlike the scandium catalyst (CAT B), this catalyst species is required to prepare polyethylene or poly(ethylene(ethyene)-co-1-octene) with minimal styrene incorporation. The catalyst should preferably have high reactivity with ethylene and alpha-olefins, and low reactivity with styrene. The table and figure above reveal high reactivity with ethylene and 1-octene, but low reactivity with styrene. This is also evident from the low styrene incorporation into the polymer, as determined by NMR. In addition, styrene is a T of the polymer. g This can increase the T in polymer products, which would be detrimental to performance in elastic applications, but would be detrimental to performance in polymer products. g Little to no increase was observed. Furthermore, a decrease in molecular weight, indicating chain shuttleping, was observed in the presence of TEA and CAT A.

[0217] Figure 7 shows the reactor conditions (mol% ethylene, mol% styrene, and mol% octene, each determined by VLE calculation, represented by white circles) and the corresponding molar percentages of ethylene, styrene, and octene in the final polymer prepared under terpolymerization conditions (each determined by 13C NMR spectroscopy, represented by squares and triangles). This figure illustrates the hypothetical orthogonal polymerization behavior of CAT A and CAT B. The samples used were the polymerization examples in Tables 2 and 5.

[0218] Study 3: Multiblock Interpolymer Analysis - Binary Catalysts and Chain Shuttles Batch reactor polymerization setup Binary catalytic polymerization was carried out in a 600 mL Parr batch reactor. The reactor was heated by an electric heating band and cooled by an internal cooling coil. Both the reactor and the heating / cooling system were controlled and monitored by a process computer. A dump valve was provided at the bottom of the reactor, thereby emptying the reactor contents into a glass dump pot. The dump pot had a constant N2 purge, which was discharged into the dump pot. The ethylene used for each polymerization was passed through a purification column consisting of Q5 and 3A molecular sieves to remove any oxygen and water. Anhydrous grade toluene from Acros Organics was sparged with nitrogen in a hood and transferred to a glove box. Molecular sieves were added to the toluene to remove water from the solvent. The high-pressure nitrogen was ultra-high purity grade supplied by Airgas or another supplier. Styrene obtained from Sigma Aldrich was degassed immediately before use and passed through neutral alumina to remove inhibitors.

[0219] Toluene, ethylene, styrene, and optionally octene were added to the reactor. Toluene was added to a 1-liter stainless steel cylinder inside a glove box and then added to the reactor using high-pressure nitrogen. After pre-injection of CSA (e.g., TEA or DEZ) was added along with the toluene, the reactor was heated and filled with solvent. The two control polymerizations did not have pre-injection of CSA. After the addition of toluene, the reactor agitator was operated at 1000 rpm while the reactor was heated to 120°C. When the reactor reached this temperature setpoint, the desired amount of ethylene was added to the reactor using a flow meter. Ethylene was added throughout the reaction to maintain the reaction pressure setpoint.

[0220] Two catalyst cocktails were prepared by mixing a scavenger, activator, and their respective catalysts in toluene inside an inert (N2) glove box. The scavenger, (one or more) activators, and catalysts were mixed with appropriate amounts of toluene to obtain solutions of the desired molar concentration. Each cocktail was drawn into a syringe, and the syringes were emptied into 20 mL glass vials with rubber septum caps under an N2 atmosphere (to maintain an inert atmosphere over the cocktails during transfer from the glove box to the reactor). The contents of the vials were transferred into a catalyst shot tank outside the glove box. After the reactor reached its target temperature setpoint of 120°C and both pressure and temperature reached steady states, the reactor was ready to operate. The "catalyst cocktails" were injected into the injector along with a constant low-pressure nitrogen purge to avoid contamination. The operating timer was started in the control system, and the "catalyst cocktails" were immediately injected into the reactor while the agitator was running at 1000 rpm. Two different catalyst cocktails were injected simultaneously. Within the first minute of successful polymerization, exothermic reactions and a decrease in reactor pressure were observed. Ethylene was added using a pressure controller to maintain the reactor pressure setpoint, as discussed above. The reactor was operated for the specified duration, typically 10 minutes. Before dumping the polymer at the end of the operation, the reactor dump pot was filled with 300 mL of methanol (inside the ventilation hood) to precipitate any polymer formed (methanol was not added if the amount of styrene added was large). A poly cap for the dump pot was used to avoid fumes when transferring the pot from the hood to the reactor. The polymer was dumped into methanol inside the dump pot. The precipitated polymer was collected by filtration and transferred to a labeled MYLAR tray. The polymer sample remained inside the ventilation hood, where the residual solvent was evaporated overnight. The reactor was then filled with toluene solvent and high-temperature washed at 180-190°C to ensure a clean reactor and avoid cross-contamination during subsequent polymerization. The trays containing the polymer products were transferred to a vacuum oven, where they were heated under vacuum up to 100°C for several hours to remove all residual solvent.After the trays had cooled to ambient temperature, the polymer products were weighed for yield / efficiency and submitted for polymer testing. The polymerization conditions are shown in Table 8. MB-1 to MB-8 are compositions containing multiblock interpolymers, respectively. The composition properties are shown in Table 9.

[0221] [Table 8]

[0222] [Table 9] Furthermore, the present invention encompasses the following embodiments. [1] A method for forming a composition comprising an ethylene / vinylarene multiblock interpolymer, comprising at least the following components a) to c): a) The following equation A: [ka] (In the formula, X 1 and X 2 Each of these can be independently substituted or not substituted (C 1 ~C 30 ) Hydrocarbyl, substituted or unsubstituted (C 1 ~C 30 ) Selected from heterohydrocarbils, X 1 and X 2 These may be joined by choice. Ar 1 and Ar 2 Each of these is independently a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group, R 52 (These are substituted or unsubstituted arylene groups.) A first metal complex selected from; b) The following equation B: [ka] (In the formula, R1 、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. Q 1 and Q 2 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, and each n is independently either 0 or 1. (Optionally, at least one L group and at least one Q group are connected, and optionally, at least one R group and at least one Q group are connected.) A second metal complex selected from; c) The following: Chain shuttle agents selected from dialkylzinc, trialkylaluminum, or combinations thereof A method comprising polymerizing a mixture containing ethylene, vinylarene, and optionally alpha-olefin in a single reactor in the presence of [a specific substance]. [2] Equation A is the following structure (a11) or (a12):

change

change

change

change

[10] The composition according to [9], wherein each (AR) segment of the ethylene / vinylarene multiblock interpolymer independently contains 15 mol% to less than 100 mol% of the vinylarene in polymerization form, based on the total number of moles of polymerized monomers in the (AR) segment.

[11] The composition according to [9] or

[10] , wherein each (AR) segment of the ethylene / vinylarene multiblock interpolymer independently contains 2 mol% to 80 mol% of the ethylene in polymerization form, based on the total number of moles of polymerized monomers in the (AR) segment.

[12] With respect to the ethylene / vinylarene multiblock interpolymer, each (AR) segment independently comprises the following subsegments bb:

change

[11] , comprising 20 mol% to 100 mol% polymerized vinylarene in a "back-to-back" arrangement as shown in [9], wherein the mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

[13] With respect to the ethylene / vinylarene multiblock interpolymer, each (AR) segment independently comprises the following subsegments sbb:

change

[12] , comprising 20 mol% to 100 mol% of polymerized vinylarene in a syndiotactic "back-to-back" configuration as shown in [9], wherein the mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

[14] The composition according to any one of the above [9] to

[13] , further comprising polyethylene homopolymer, ethylene / vinylarene copolymer, ethylene / alpha-olefin copolymer, or a combination thereof.

[15] An article comprising at least one component formed from a composition according to any one of the above [8] to

[14] .

Claims

1. A method for forming a composition comprising an ethylene / vinylarene multiblock interpolymer, comprising at least the following components a) to c): a) Equation A below: 【Chemistry 1】 (In the formula, X １ and X ２ Each of these can be independently substituted or not substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbils, X １ and X ２ These may be joined by choice. Ar １ and Ar ２ are each independently a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group, R ５２ (These are substituted or unsubstituted arylene groups.) A first metal complex selected from; b) Equation B below: 【Chemistry 2】 (In the formula, 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. Q １ and Q ２ 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, and each n is independently either 0 or 1. (Optionally, at least one L group and at least one Q group are connected, and optionally, at least one R group and at least one Q group are connected.) A second metal complex selected from; c) The following: Chain shuttle agents selected from dialkylzinc, trialkylaluminum, or combinations thereof A method comprising polymerizing a mixture containing ethylene, vinylarene, and optionally alpha-olefin in a single reactor in the presence of [a specific substance].

2. Formula A is the following structure (a11) or (a12): 【Transformation 3】 The method according to claim 1, selected from the following.

3. Equation B is the following structure (b11) or (b12): 【Chemistry 4】 The method according to claim 1 or 2, selected from the above.

4. The chain shuttle agent (component c) is as follows: Zn (CH ２ CH ３ ) ２ Al(CH) ２ CH ３ ) ３ The method according to any one of claims 1 to 3, or a combination thereof.

5. The method according to any one of claims 1 to 4, wherein the mixture comprises the alpha-olefin.

6. The ethylene / vinylarene multiblock interpolymer comprises two or more (AR) segments, each (AR) segment independently comprising the following subsegments bb: 【Transformation 5】 The method according to any one of claims 1 to 5, comprising 20 mol% to 100 mol% of polymerized vinylarene in a "back-to-back" arrangement as shown in, wherein the mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

7. The ethylene / vinylarene multiblock interpolymer comprises two or more (AR) segments, each (AR) segment independently comprising the following subsegments sbb: 【Transformation 6】 The method according to any one of claims 1 to 6, comprising 20 mol% to 100 mol% of polymerized vinylarene in a syndiotactic "back-to-back" arrangement as shown in, wherein the mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

8. A composition comprising an ethylene / vinylarene multiblock interpolymer, wherein the interpolymer comprises structure 1 or structure 2 as shown below. -(AR)-(AP)-(AR)-(AP)-(Structure 1), (AR)-(AP)-(AR)-(AP) (structure 2), It comprises at least one polymer structure selected from, where (AR) refers to a vinylarene-rich segment and (AP) refers to a vinylarene-poor segment. Each (AR) segment independently comprises, in polymerized form, ethylene, the vinylarene and optionally alpha-olefin. Each (AP) segment independently comprises, in polymerized form, ethylene, optionally the vinylarene and optionally the alpha-olefin. Each (AR) segment independently contains more than 10 mol% of the vinylarene in polymerized form, based on the total number of moles of polymerized monomers within the (AR) segment. Each (AP) segment independently contains, in its polymerized form, 10 mol% or less of the vinylarene based on the total number of moles of polymerized monomers within the (AP) segment. composition.

9. The composition according to claim 8, wherein each (AR) segment of the ethylene / vinylarene multiblock interpolymer independently contains 15 mol% to less than 100 mol% of the vinylarene in polymerization form, based on the total number of moles of polymerized monomers within the (AR) segment.

10. The composition according to claim 8 or 9, wherein each (AR) segment of the ethylene / vinylarene multiblock interpolymer independently contains 2 mol% to 80 mol% of the ethylene in polymerization form, based on the total number of moles of polymerized monomers within the (AR) segment.

11. Regarding the ethylene / vinylarene multiblock interpolymer, each (AR) segment independently comprises the following subsegments bb: 【Transformation 7】 The composition according to any one of claims 8 to 10, comprising 20 mol% to 100 mol% of polymerized vinylarene in a "back-to-back" arrangement as shown in, wherein the mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

12. Regarding the ethylene / vinylarene multiblock interpolymer, each (AR) segment independently comprises the following subsegments sbb: 【Transformation 8】 The composition according to any one of claims 8 to 11, comprising 20 mol% to 100 mol% of polymerized vinylarene in a syndiotactic "back-to-back" arrangement as shown in, wherein the mol% is based on the total number of moles of polymerized vinylarene in the (AR) segment.

13. The composition according to any one of claims 8 to 12, further comprising a polyethylene homopolymer, an ethylene / vinylarene copolymer, an ethylene / alpha-olefin copolymer, or a combination thereof.

14. An article comprising at least one component, formed from the composition according to any one of claims 8 to 13.

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