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

Abstract

The present invention provides a composition comprising an ethylene / vinyl anelonge block and / or triblock interpolymer, and a process for forming the said composition. [Solution] A composition comprising an ethylene / vinylarene diblock interpolymer or an ethylene / vinylarene triblock interpolymer, wherein the diblock interpolymer comprises at least one polymer structure selected from Structure 1 shown below, and the triblock interpolymer comprises at least one polymer structure selected from Structure 2 or Structure 3, where AR refers to vinylarene enrichment and AP refers to vinylarene deficiency. (AR)-(AP)(Structure 1) (AR)-(AP)-(AR)(Structure 2) (AP)-(AR)-(AP)(Structure 3)

Description

[Technical Field]

[0001] Cross-reference of related applications This application is based on U.S. Provisional Patent Application No. 63 / 127,35, filed on 18 December 2020. Claiming the benefit of priority of application No. 0, this provisional application is incorporated herein by reference in its entirety. It can be done. [Background technology]

[0002] Olefin block copolymers via chain shuttle technology The catalyst generation of olyme (OBC) results in INFUSE Olefin Block Copolymers and INTUNE Olefin Block Copolymer Differentiated materials such as er have emerged. Such copolymers are typically made of ethylene and It is made from alpha-olefins. It produces styrene-based block interpolymers. By using chain shuttle technology, high value can be achieved using a continuous solution polymerization process. This presents an attractive route to polymers. Styrene-ethylene / butene-styrene (styr High-value styrene polymers such as ene-ethylene / butene-styrene (SEBS) are organic Produced in a batch process via anionic polymerization initiated by lithium compounds. This expensive polymerization involves the continuous addition of monomers, followed by an expensive hydrogenation step. It is done using a double reactor continuous solution polymerization process to build ethylene / vinyl alloy blocks and The need for chain shuttle technology to produce reblock interpolymers There is.

[0003] A.Valente et al., Angew.Chem.,Int.Ed.2014,53,4 638-4641,Isoprene-Styrene Chain Shuttlin g Copolymerization Mediated by a Lanthan ide Half-Sandwich Complex and a Lanthani docene:Straightforward Access to a New T Type of Thermoplastic Elastomers is n-butylethylene Using ru-magnesium, lanthanide half-sandwich complex, and lanthanidocene The present invention discloses the chain shuttle polymerization of isoprene and styrene. The resulting multi-block structure consists of alternating hard (styrene-enriched) segments and soft (styrene-enriched) segments. It has a soprene-enriched segment.

[0004] U.S. Patent Application Publication No. 2014 / 0088276 (Manufacturing Me thod for Multidimensional Polymer,and Mu (Il-dimensional Polyme) is a chain shuttle technology and coordination Chain transfer polymerization of styrene-type monomers and conjugated dienes such as isoprene or butadiene. The polymerization of stereochemically controlled (syndiotactic) block copolymers is disclosed. Polymerization is carried out in the presence of a first catalyst and a second catalyst. The first catalyst and the second catalyst are Each independently, the following: a) Group 3 metal atoms or lanthanide metal atoms, e.g., Sc, b ) Cp-type ligands containing substituted or unsubstituted cyclopentadienyl derivatives, c) monoanio It contains ligands and d) a neutral Lewis base.

[0005] U.S. Patent No. 8,623,976 (Polymerization Catalyst) Compositions Containing Metallocene Com plexes and the Polymers Produced by Usin g the Same) is as follows: a) below: i) Group 3 metal atoms or lanthanide metal atoms, e.g., Sc, ii) Cp of substituted or unsubstituted cyclopentadienyl derivatives * Ligand, iii) Monoanionic ligands, iv) A metallocene complex containing a neutral Lewis base, b) Ionic compounds of non-coordinating anions and cations, e.g., tetrakis(penta- The present invention discloses a catalyst composition comprising fluorophenyl borate. The catalyst composition comprises Used to polymerize various polymers such as ethylene / styrene copolymers (Example 1) (See 1-17). Polymerized styrene can 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 Copolymeriz Styrene, Isoprene, and Butadiene , two different catalysts and chain shuttle agents (triisobutylaluminum (triiso Styrene, isoprene, and butadiene chains using butylaluminum (TIBA). Shuttle polymerization is disclosed. These catalysts differ in the presence of TIBA. It exhibits nomeric selectivity and stereoselectivity, resulting in styrene, isoprene, and butadiene This results in region-specific and stereospecific copolymerization.

[0007] SSPark et al., Macromolecules 2017, 50, 6606-6 616,Biaxial Chain Growth of Polyolefin a nd Polystyrene from 1,6-Hexanediylzinc S pecies for Triblock Copolymers are polymeryl zincate. Preparation of triblock copolymers by initiating (anionic) styrene polymerization from seeds. The manufacturing process is disclosed. Using coordination chain transfer polymerization, a dual-head zinc species is converted to polyethylene. The n / polypropylene copolymer is grown, followed by an anionic initiator (e.g., Me3S iCH2Li-(pmdeta)) and styrene monomer are added. Coordination chain transfer polymerization is performed. This is carried out in the presence of a transition metal (e.g., Zr or Hf) complex. Therefore, anions Polymerization is used to grow polystyrene-terminated blocks that do not exhibit any stereoregularity. .

[0008] U.S. Patent Application Publication No. 2018 / 0022852 (Organic ZincCom) pound Comprising Polyolefin-Polystyrene Block Copolymer,and Method for Preparing The Same) is, as shown in the same document, a styrene polymer or polio Refine-polystyrene block copolymers, including organozinc compounds such as those of chemical formula 1. The preparation method is disclosed. This preparation method uses a transition metal catalyst to produce an olefin monomer. After preparing an intermediate by coordination polymerization, the intermediate is converted to styrene by anionic polymerization. This includes inserting a portion of the nomer. Examples of transition metal catalysts include those of chemical formula 6A and chemical formula 6B. Examples of Zr metal compounds represented by are shown in the same document (paragraph

[0076] ). (and see

[0077] ).

[0009] Y. Luo et al., J. Am. Chem. Soc. 2004, 126, 13910-139 11,Scandium Half-Metallocene-Catalyzed S yndiospecific Styrene Polymerization and Styrene-Ethylene Copolymerization: Unpre cedented Incorporation of Syndiotactic S tyrene-Styrene Sequences in Styrene-Ethy lene Copolymers uses scandium half-sandwich complexes. The polymerization of styrofoam-specific styrene-ethylene copolymers is disclosed. The melting temperature of the copolymer is disclosed. The degree (Tm) can be changed by adjusting the ethylene incorporation, The integration results in a reduction in Tm. In Sc catalysts, chain shuttle This was not proven.

[0010] H. Hagihara et al., Polymer Journal 2012, 44, 147. -154,Synthesis of Ethylene-Styrene Copol ymer Containing Syndiotactic Polystyrene Sequence by Trivalent Titanium Catalyst This is trivalent titanium catalyst tris(acetylacetonate)titanium (Ti(acac)3) The polymerization of syndiotactic styrene-ethylene copolymer is disclosed using T. The i(acac)3 catalyst may be attributed to the presence of multiple oxidation sites in this catalyst. Different polymers were produced.

[0011] F. Lin et al., Journal of Polymer Science, Part A:Polymer Chemistry 2017,55,1243-1249,Sy nthesis and Characterization of Crystallization ine Styrene-b-(Ethylene-co-Butylene)-bS Tyrene Triblock Copolymers are crystalline styrene-b-(E The synthesis and characterization of ethylene-co-butylene)-b-styrene (SEBS) are disclosed. Cationic rare earth metal complexes, [(η 5 -Flu-CH2-Py)Ho(CH2SiM [e3](THF) was used in the living polymerization of butadiene and styrene. Styrene, buta SBS triblock was formed by the sequential addition of diene and styrene monomer. Liblock is an elastic polybutadiene sequence with 1,4 regularity and crystalline syndiotactic It was made of polystyrene. SEBS was formed by hydrogenating SBS triblock.

[0012] B. Liu et al. Macromolecules 2016, 49, 6226-6231 Regioselective Chain Shuttling Polymeriz ation of Isoprene:An Approach to Access New Materials from Single Monomer is [Ph3C Pyridyl-methylenefluorenyl, when combined with B(C6F5)4 and iBu3Al. The chain transfer polymerization of isoprene using a scandium complex is disclosed. This resulted in high 1,4-selectivity for Len. Additional catalyst structures include those shown in the same document. "This includes pyridyl-methylene-functionalized fluorenyl-linked rare earth metal complexes 1-9, where gold The genera are Sc, Y, Lu, Tm, Er, Ho, Dy, Tb, or Gd (p. 6227) See Chart 1).

[0013] U.S. Patent No. 8,710,143 (Catalyst Composition Co.) mprising Shuttling Agent for Ethylene Mu The lti-Block Copolymer Formation is as follows: (A) 1 (B) A metal complex olefin polymerization catalyst, prepared by catalyst (A) under equivalent polymerization conditions. A second method allows for the preparation of polymers that have different chemical or physical properties from the polymers that have been prepared. Using a metal complex olefin polymerization catalyst and a (C) chain shuttle agent, a multi-chain Polymerization of rock copolymers is disclosed. Suitable monomers include ethylene and 1- Examples include one or more addition polymerizable monomers such as octene and styrene (Section 16, Section 3) (See lines 32). Suitable catalysts include metals belonging to groups 3-15, preferably 3-10. Group 4, more preferably Group 4 to Group 8, most preferably Group 4 (Ti, Zr, and Hf) Examples of metal complexes include those shown in paragraph 19, lines 61-20, and line 6. And. Ethylene / styrene multiblock polymer, Cat.A1(Hf) and Cat. Using B1(Zr), each was prepared as shown in the same document (section 85, section 12~ Line 30, paragraph 86, lines 21-52, paragraph 115, paragraphs 21-116, line 23, and (See Tables 27 and 28.)

[0014] Further information on olefin block copolymers (OBCs) and related polymerization can be found in the following references. U.S. Patent No. 7,915,192, U.S. Patent No. 8,124,709, U.S. Patent No. 8, Patent No. 501,885, U.S. Patent No. 8,716,400, European Patent Application Publication No. 171619 Patent No. 0(B1), European Patent Application Publication No. 1926763(B1), and European Patent Application Publication No. This is disclosed in patent number 2582747(B1).

[0015] However, in a double reactor using continuous solution polymerization, ethylene / stereoregularity Chains for producing nialanegeblock and triblock interpolymers Shuttle technology is still needed. This need is met by the following inventions. It is being done. [Overview of the project]

[0016] In the first embodiment, ethylene / vinyl anedenide block interpolymer and / or This forms a composition containing ethylene / vinylarene triblock interpolymer. The process involves at least the following steps: A) In reactor A, the following: chemical formula S1, chemical formula S2, chemical formula S3, chemical formula S4, and The compound is selected from chemical formula S5, and at least the following: a) in the presence of a metal complex S, comprising Rhenium, and optionally an alpha-olefin, and optionally a vinylarene a step of polymerizing mixture A,

[0017]

Chemical formula

[0018]

Chemical formula

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

[0020] [ka] M 1 It is a metal selected from zirconium (Zr) or hafnium (Hf), and gold The genus is in a formal oxidation state of +2, +3, or +4. Each X can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substitution or is non-substitution (C1~C 30) Selected from heterohydrocarbyl or -H, each X independently And it is a monosect ligand or a bisect ligand, n is 0, 1, or 2, and optionally when n is 1, X is a bidentate ligand. Possible, -T 2 - and -T 3 Each of these is independently -O-, -S-, -N(R N )-, or- P(R P )- Selected from, R 6 and R 21 Each of these is independently -H, substitution, or non-substitution (C1~C 40 ) Hydro Calville, substituted or unsubstituted (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -N O2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)- , halogen, radical having formula (I), radical having formula (II), and formula (III Selected from the group consisting of radicals having ),

[0021] [ka] In the formula, R 22~26 , R 27~34 , and R 35~43 Each of them can be independently replaced or k is non-substitution (C1~C40 ) Hydrocarbyl, substituted or unsubstituted (C1-C 40 ) Heterohydrocarbyl, -Si(R )3, -Ge(R C )3, -P(R C )2, -N(R P )2 N , -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)- , R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, halogen, or -H, and is selected from R 7~20 each of which is, independently, substituted or unsubstituted (C1-C 40 ) Hydrocarbyl, substituted or unsubstituted (C1-C ) Heterohydrocarbyl, -Si(R 40 )3, C -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -S R C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C =N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2 NC(O)-, halogen, or -H, and is selected from J 4 is substituted or unsubstituted (C1-C​​40 ) Hydrocarbylene or substituted or unsubstituted Exchange(C1~C 40 ) Heterohydrocarbylene, substituted or unsubstituted (C1~C 40 ) Hydrocarbylene is a compound of the group T in chemical formula S4. 2 and T 3 Linking 1 to 10 carbon atoms The part of the atom that includes the linker skeleton (J 4 (which is joined) or has substitution or k is non-substitution (C1~C 40 ) Heterohydrocarbylene is a compound of the group T in chemical formula S4. 2 and T 3 It has a portion containing a linker skeleton of 1 to 10 atoms that connects the atoms, and 1 to 10 atoms of phosphorus Each of the 1 to 10 atoms in the Kerr skeleton is independently a carbon atom or a heteroatom group of heteroatoms Each heteroatom group is independently O, S, S(O), S(O)2, Si(R) C )2 , Ge(R C )2, P(R C ), or N(R C ) and each R C They can be replaced independently or k is non-substitution (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) It is a heterohydrocarbyl, and each R in the chemical formula S4 P , R N , and the remaining R C It is independent Substitution or non-substitution (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~ C 30 ) Heterohydrocarbyl, or -H, Metal complexes are either charge-neutral overall, or

[0022] [ka] In the formula, M 1 It is made from titanium (Ti), zirconium (Zr), or hafnium (Hf). The metal to be selected, The metal is in a formal oxidation state of +2, +3, or +4. Each X can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substitution or is non-substitution (C1~C 30 ) Selected from heterohydrocarbyl or -H, each X independently And it is a monosect ligand or a bisect ligand, n is 0, 1, or 2, and optionally when n is 1, X is a bidentate ligand. Possible, R 44~51 Each of these can be substituted or not substituted (C1~ 40 ) Hydrocarbyl , substitution or non-substitution (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, or - Selected from H, and optionally R 44~51 Two or more of these units are linked together, Therefore, the cyclopentadienyl group is a substituted or unsubstituted indenyl group, or substituted or R is an unsubstituted fluorenyl group, C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or - Selected from H, O and O contain 1 to 30 atoms other than hydrogen, J 5 The crosslinking group represented by They are connected, Metal complexes are generally charge-neutral, step, B) In reactor B, at least the following: b) Select from the following chemical formulas H1 or H2 In the presence of the selected metal complex H, ethylene, vinylarene, and optionally, Alf A step of polymerizing a mixture B containing an olefin,

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

[0024] [ka] M 3 It is selected from titanium (Ti), zirconium (Zr), or hafnium (Hf). It is a metal that is in a formal oxidation state of +2, +3, or +4. Each Q can be independently substituted or not substituted (C1~C 30 ) Hydrocarbyl, substitution or is non-substitution (C1~C 30 ) Selected from heterohydrocarbyl or -H, each Q is independently And it is a monosect ligand or a bisect ligand, n is 0, 1, or 2, and optionally when n is 1, X is a bidentate ligand. Possible, R 1 and R 2 Each of these is an independent bridging group containing 2 to 41 atoms other than hydrogen, and Selectively, R 1 and R 2 Each of these can independently be a substituted or unsubstituted arylene group. -Z 1 - and -Z 2 Each of these is independently -O-, -S-, -Se-, -N(R N ) -, or -P(R P )- Selected from, -Z 1 - and -Z 2 Each of these is an electron, independently It can optionally interact with metals through donor bonding, Z 1 and Z 2 J contains 1 to 50 atoms other than hydrogen. 5 The crosslinking group represented by Therefore, they are connected, R P and R N Each of these can be substituted or not substituted (C1~C 30 ) Hydrocarbil , substitution or non-substitution (C1~C 30 ) Heterohydrocarbyl, or -H, Metal complexes are generally charge-neutral. Step A occurs before Step B and involves at least a portion of the reactor products in reactor A. The mixture is transferred to reactor B, or step B occurs before step A and the reaction takes place. At least a portion of the reactor product in reactor B is transferred to reactor A. If step A occurs before step B, at least one chain shuttle The agent is supplied into reactor A. If step B occurs before step A, at least one chain shuttle The agent is supplied into reactor B. The vinylarene in step A is equal to the vinylarene in step B, and in step A The alpha-olefin is the alpha-olefin in step B of the process.

[0025] In a second embodiment, ethylene / vinyl anedenide block interpolymer or ethylene A composition comprising a len / vinylarene triblock interpolymer, and diblock The interpolymer is composed of at least one selected from Structure 1, as shown below. The rimer structure is included, and the triblock interpolymer is structured as shown below. It comprises at least one polymer structure selected from 2 or 3, and AR is vinyl allergen. ¹ refers to ¹¹ enrichment, while AP refers to vinylarene deficiency. (AR)-(AP)(Structure 1), (AR)-(AP)-(AR)(Structure 2), (AP)-(AR)-(AP)(Structure 3), and Each (AR) segment independently, in its polymerized form, is composed of ethylene, vinyl allergen, etc. , and optionally containing alpha-olefin, Each (AP) segment independently polymerizes into ethylene, optionally. The compound comprises vinylarene and optionally alpha-olefin. Each (AR) segment independently determines the total amount of polymerized monomers in the (AR) segment. Based on the number of moles, the polymerized form contains >10 mol% vinylarene. Each (AP) segment independently determines the total amount of polymerized monomers in the (AP) segment. Based on the number of moles, the polymerized form contains ≤10 mol% vinylarene. composition. [Brief explanation of the drawing]

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

[0027] Chain shuttle technology uses a dual catalyst in two reactors to process ethylene / bacterial It was discovered that it produces nialene block and triblock interpolymers. For example, a vinylarene-deficient segment (or block) is formed in one of the reactors. The catalyst (metal complex) used for this purpose must meet the following criteria: a) have a high natural molecular weight, b) In the presence of a chain shuttling agent (CSA), molecular weight A high chain shuttling rate is determined by reducing the molecular weight distribution and narrowing the molecular weight distribution. And, and 3) the α-olefin is present in a high concentration. In the other reactor, vinyl The catalyst (metal complex) used to form the lane enrichment segment (or block) is The following indicators: a) good activity for vinylarene polymerization, b) in the presence of CSA Chain chatrins were determined by reducing the molecular weight and narrowing the molecular weight distribution. The requirements are met: a high constant and c) compatibility with the remaining monomer carryover.

[0028] As discussed above, in its first embodiment, the present invention provides ethylene / bi as described above. Nylarene diblock interpolymer and / or ethylene / vinylarene tripolymer The present invention provides a process for forming a composition containing a buck interpolymer. The invention may include a combination of two or more embodiments as described herein. Each step or component of the process is a combination of two or more embodiments described herein. It may include wasabi.

[0029] As discussed above, the present invention also, in a second embodiment, provides ethylene as described above. / Vinylarene triblock interpolymer or ethylene / vinylarene triblock The present invention provides a composition containing goji polymer. The composition of the present invention is as described herein, 2 This may include combinations of more than one embodiment. Diblock interpolymer and triblock Quinter polymers are combinations of two or more embodiments as described herein. It may include se.

[0030] In this specification, when used, the structure of the metal complex is defined as Ar1=Ar 1 , Ar² = Ar 2 Ar3=Ar 3 Please note that the above is the case. Also, in this specification When used in this way, with respect to such a structure, R1 = R 1 , R²=R 2 , R3=R 3 etc. And, "a to n" represents consecutive numbers, R a ~R n This notation is R a , R a+1 , R a+2 ,..., R n This refers to R. 3 ~R 7 R 3 , R 4 , R 5 , R 6 , R 7 This refers to the metal complex described herein, where it is used in reference to the metal complex described. The notation "u" refers to a bond formed from a donor electron pair (electron-donating bond). In this specification, This shows a pi (π) bond as a straight line.

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

[0032] In each of the embodiments described in this specification, or combinations of two or more embodiments, the metal complex S has the structure s1a1 or the structure s1a2: is selected from:

[0033]

Chemical formula

[0034] In each of the embodiments described in this specification, or combinations of two or more embodiments, the metal complex S is selected from the chemical formula S1 described in this specification, and more specifically from the chemical formula S1a, and the metal complex H is, as described in this specification, selected from the chemical formula H1, and more specifically from the chemical formula H1a or the formula H1b is selected from: In each of the embodiments described in this specification, or combinations of two or more embodiments, the metal complex H is selected from the following chemical formulas h1a1, h1a2, h1a3 is selected from:

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

[0036] In each of the embodiments described in this specification, or combinations of two or more embodiments, at least one chain shuttling agent is selected from: alkyl zinc compounds, alkyl aluminum compounds, dual head chain shuttling agents, or combinations thereof. is selected from:

[0037] In each of the embodiments described in this specification, or combinations of two or more embodiments, Step A occurs before Step B.

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

[0039] Ethylene / vinylarene diblock interpolymer or ethylene / vinylarene With respect to the triblock interpolymer, each embodiment described herein, or In combinations of two or more embodiments, vinylarene is styrene.

[0040] Each embodiment, or combination of two or more embodiments, described herein, Mixture A contains alpha-olefin.

[0041] Ethylene / vinylarene diblock interpolymer or ethylene / vinylarene With respect to the triblock interpolymer, each embodiment described herein, or In combinations of two or more embodiments, each (AR) segment independently undergoes polymerization. Based on the total number of moles of polymerization monomers in the (AR) segment, ≥15 mol%, or ≥20 mol%, or ≥25 mol%, or ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥45 mol%, or ≥50 mol%, or ≥55 mol%, or comprising ≥60 mol% vinylarene. Each embodiment described herein, Alternatively, in a combination of two or more embodiments, each (AR) segment is independently a polymerized form In this state, based on the total number of moles of polymerization monomers in the (AR) segment, <100 mo 1% or ≤98 mol% or ≤96 mol% or ≤94 mol% or ≤92 mol% Contains 1% or ≤91 mol% of vinylarene.

[0042] Ethylene / vinylarene diblock interpolymer or ethylene / vinylarene With respect to the triblock interpolymer, each embodiment described herein, or In combinations of two or more embodiments, each (AP) segment independently undergoes polymerization. In this case, based on the total number of moles of polymerization monomers in the (AP) segment, ≥0 mol%, or is ≥0.2 mol%, or ≥0.4 mol%, or ≥0.6 mol%, or ≥0.8 mol Each contains 1% or ≥1.0 mol% of vinylarene. In the configuration, or combination of two or more embodiments, each (AP) segment is independent. In the polymerization form, based on the total number of moles of polymerization monomers in the (AP) segment, ≤ 1 0 mol%, or ≤9.0 mol%, or ≤8.0 mol%, or ≤7.0 mol%, or It contains ≤6.0 mol% or ≤5.0 mol% vinylarene.

[0043] Ethylene / vinylarene diblock interpolymer or ethylene / vinylarene With respect to the triblock interpolymer, each embodiment described herein, or In combinations of two or more embodiments, each (AR) segment independently undergoes polymerization. Based on the total number of moles of polymerization monomers in the (AR) segment, ≥2.0 mol% , or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥9.0 mol%, or ≥10 mol%, or ≥11 mol%, or ≥12 mol%, or ≥13 Each contains 1 mol%, or ≥14 mol%, of ethylene. In one or more embodiments, each (AR) segment is independent of the other. In the combined form, based on the total number of moles of the polymerized monomers in the (AR) segment, ≤ 80 m ol%, or ≤ 77 mol%, or ≤ 75 mol%, or ≤ 73 mol%, or ≤ 70 m ol%, or ≤ 65 mol%, or ≤ 60 mol%, or ≤ 55 mol%, or ≤ 50 m ol% contains ethylene of ≤ 45 mol%, or ≤ 40 mol%.

[0044] For the ethylene / vinylarene diblock interpolymer or ethylene / vinylarene triblock interpolymer, in each embodiment described herein, or in a combination of two or more embodiments, each (AP) segment is independently in the polymerization form and contains ≥ 50 mol%, [[ID=​​​​​​​​​​​​​​​​​​​​%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, Alternatively, polymerized vinylarenes in a concentration of ≥94 mol%, ≥96 mol%, ≥98 mol%, or ≥99 mol%. However, in subsegment bb, it exists in a "back-to-back" configuration as shown below. ,

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

[0047] Ethylene / vinylarene diblock interpolymer or ethylene / vinylarene With respect to the triblock interpolymer, each embodiment described herein, or In combinations of two or more embodiments, as shown in the following subsegment sbb, ≥20 mol%, or ≥40 mol%, or ≥60 mol% in each (AR) segment, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol%, or ≥98 mol%, or ≥99 mol% Polymerized vinylarenes, in subsegment sbb, have the following syndio It exists in a tactical "back-to-back" configuration,

[0048] [ka] (Subsegment sbb), mol%, polymerized vinyl array in segment (AR) Based on the total number of moles of n.

[0049] Ethylene / vinylarene diblock interpolymer or ethylene / vinylarene With respect to the triblock interpolymer, each embodiment described herein, or In combinations of two or more embodiments, polymerized vinylarenes are present in each (AP) segment. In all cases, the configuration is a "back-to-back" configuration as shown in subsegment bb. Not present,

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

[0051] Compositions formed from the processes of the present invention described herein are also provided. The article also provides an article comprising at least one component formed from a composition.

[0052] Ethylene / vinyl alloy blocks and triblock interpolymers Formation of ethylene / vinyl alenide block interpolymer and ethylene / vinyl Examples of lane triblock interpolymer formation are schematically shown in Figures 1A and 1B, respectively. These diagrams show that organometallic reagents, for example, zinc or aluminum-based chains Shuttle agent (CSA) or dual-headed chain shuttle agent (dual-headed Ethylene / alpha-olefin directly bound to chain shuttling agent (DHCSA) The random copolymer "block" is converted in the first reactor using a first transition metal catalyst. These polymeryl zinc or polymeryl aluminum obtained in the first reactor are generated. The nium species is transferred to the second reactor. The lifetime of the first transition metal catalyst (metal complex) is as follows: The time elapsed until the contents of reactor 1 are transferred to reactor 2. Styrene, ethylene, and optionally alpha-olefins are second transition metals. Polymerized in the presence of a catalyst, random styrene / ethylene interpolymer "blocks" Next, polymeryl zinc or polymeryl aluminum species from the first reactor are produced. It then undergoes chain shuttle with the second reactor catalyst, resulting in styrene / ethylene random The "block" is grown on an ethylene / alpha-olefin polymeryl chain, and desired This produces a diblock (Figure 1A) or triblock (Figure 1B) interpolymer. Random blocks of different types (vinylarene-enriched, i.e., hard blocks, and vinylarenes) Blocks lacking in pulp (i.e., soft blocks) have different chemical or physical properties. Each block is made of pulp. It has two or more monomer types that are distributed substantially randomly within the pack.

[0053] As discussed, ethylene / vinyl alloy blocks and triblock intermediates The rimer is preferably composed of two chemically distinct regions (referred to as "blocks") bonded linearly. (includes). In one embodiment, the block is the amount of incorporated comonomer or Type, density, degree of crystallinity, stereoregularity (isotactic or syndiotactic) The type or degree of ) or any other chemical or physical properties are different. Includes interpolymers produced by nomer addition, fluid catalyst, or anionic polymerization technology. Compared to conventional block interpolymers, the present invention provides ethylene / vinyl alloy Block and triblock interpolymers are used in their preparation in a dual reactor. Due to the effect of the shuttling agent in combination with multiple catalysts used, both poly Specific distribution of multidispersion (PDI, Mw / Mn, or MWD), block length It features a unique distribution of both the distribution and / or the number of blocks.

[0054] Vinylarene monomer Vinylarene monomers are aromatic monomers, mono- or poly-alkylstyrene monomers. (Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p -dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene Aromatic vinyl compounds such as (including ) as well as o-chlorostyrene and m-chlorostyrene p-chlorostyrene, divinylbenzene, 3-phenylpropene, 4-phenylpropene Examples include functional group-containing derivatives such as α-methylstyrene, but are not limited to these. However, monomers can be polymerized under the conditions in which they are used.

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

[0056] Suitable shuttling agents include at least one substituted or unsubstituted hydrocarbyl group, Preferably, each hydrocarbyl group contains 1 to 12 carbon atoms. 1, 2 comprising a um, gallium, or zinc compound and its reaction product with a proton source. Examples include, but are not limited to, metal compounds or complexes of groups 12 or 13. The hydrocarbyl group is an alkyl group, preferably a linear or branched C2-C8 alkyl group. It is a group. As chain shuttling agents, trialkylaluminum and diaryl Zinc compounds, especially triethylaluminum, tri(isopropyl)aluminum, tri (Isobutyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl) Examples include, but are not limited to, aluminum, triethylgallium, or diethylzinc. Not applicable. See U.S. Patent No. 8,710,143 (incorporated herein by reference). Teru.

[0057] Dual head chain shuttle agents (e.g., Al-DHCSA and AlZn-D HCSA is also a suitable drug. The following are suitable as dual-head chain shuttle agents: Chemical formula: R1-[M-R2-] n -The structure of the M-R1 is one example, but it is not limited to this. In the formula, R1 and R2 are each independently hydrocarbons containing 1 to 20 carbon atoms, n ≥ 1 and M = Zn. International Publication No. 2018 / 064546 and U.S. Publication No. 8, See also publications 501,885 (each incorporated herein by reference).

[0058] definition Unless otherwise stated, unless implicitly stated in the context, or if it is customary in the art, To the extent that, all parts and percentages are based on weight, and all test methods are as of the filing date of this disclosure. It is the latest model.

[0059] As used herein, the term “composition” means the composition, as well as the materials of the composition. The mixture of materials includes reaction by-products and decomposition products formed from the reaction. The product or its decomposition products are typically present in trace or residual amounts.

[0060] As used herein, the term "polymer" refers to the same or different types of materials. This refers to polymer compounds prepared by polymerizing polymers. Therefore, polymers The general term is homopolymer (even when trace amounts of impurities are incorporated into the polymer structure). Under the understanding that such polymers exist, it is used to refer to polymers prepared from only one type of monomer. This includes the terms "interpolymer" as defined below in this specification. Trace amounts of impurities, such as residues in the polymer, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with one or more stabilizers in very small amounts ("ppm") ru.

[0061] As used herein, the term “interpolymer” means at least two different species This refers to polymers prepared by the polymerization of monomers of a certain type. Therefore, interpolymers. The term copolymer (a polymer prepared from two different types of monomers) (used to refer to a monomer), and prepared from two or more different types of monomers. Contains polymers.

[0062] As used herein, the term "olefin polymer" means, in its polymerized form, ( (Based on the weight of the polymer) 50% by weight or more than half by weight of ethylene or propylene A polymer containing an olefin such as lene, which may optionally contain one or more comonomers. To point.

[0063] As used herein, the term "propylene polymer" refers to a polymerized form (Po (Based on the weight of the rim) Contains a majority of half weight percent of propylene, and optionally one or more This refers to polymers that may contain the above-mentioned comonomers.

[0064] As used herein, the term "ethylene-based polymer" means (poly (Based on the weight of the product) Contains 50% by weight or more than half by weight of ethylene, if desired This refers to a polymer that may contain one or more comonomers.

[0065] As used herein, the term "vinylarene polymer" refers to the polymerization form. In this case, (based on the weight of the polymer) it contains a majority of half-weight percent of vinylarene, This refers to a polymer that may selectively contain one or more comonomers.

[0066] As used herein, the term "styrene polymer" refers to the polymerized form. , containing a majority of half-weight percent styrene (based on the weight of the polymer), and optionally 1 This refers to a polymer that may contain one or more comonomers.

[0067] As used herein, "ethylene / alpha-olefin interpolymer" and The term refers to a polymerization form, where 50% by weight or more than half by weight (based on the weight of the interpolymer) A random interpolymer containing a certain percentage of ethylene and alpha-olefin. — refers to.

[0068] As used herein, the term "ethylene / α-olefin copolymer" means In polymerization, 50% by weight or more than half by weight (based on the weight of the copolymer) A random compound containing ethylene and alpha-olefin as only two monomer types. It refers to polymers.

[0069] As used herein, the term "ethylene / vinylarene copolymer" means In polymerization, 50% by weight or more than half by weight (based on the weight of the copolymer) A random copolymer containing ethylene and vinylarene as only two monomer types. — refers to.

[0070] When used herein, polymers (or interpolymers or terpolymers or co Regarding polymers, the phrase "majority by weight percent" means that the most abundant amount in the polymer is present. This refers to the amount of monomer used.

[0071] When used herein, "ethylene / vinyl anedenide block interpolymer" The terms "vinylarene-enriched (AR) segment" and "vinylarene-deficient (AP) segment" refer to the vinylarene-enriched (AR) segment and the vinylarene-deficient (AP) segment. This refers to a diblock interpolymer containing segments. See, for example, Figure 1A. The AR segment, in its polymerization form, contains >10 mol% vinylarene. The P segment contains ≤10 mol% vinylarene in its polymerization form. The percentage is based on the total number of moles of polymerization monomers in each segment. Diblock interpolymer In its polymerization form, it contains ethylene, vinylarene, and may also contain other monomer types. As used herein, "ethylene / vinyl alloy block copolymer" The terminology discussed above is the vinylarene-enriched (AR) segment, and the terminology discussed above is also discussed above. As described, a diblock copolymer containing a vinylarene-deficient (AP) segment. This refers to a diblock copolymer, which in its polymerization form consists of ethylene and vinylarenes. It is included as a monomer type of horn only.

[0072] When used herein, "ethylene / alpha-olefin / vinylalene dipropyl alcohol" The term "rock copolymer" refers to vinylarene-enriched (AR) segments and vinylarenes. This refers to diblock interpolymers containing lane-deficient (AP) segments. For example, see Figure 1. See A. The AR segment is a vinyl array in polymerization form, >10 mol% It contains. The AP segment contains ≤10 mol% vinylarene in its polymerization form. Each mol% is based on the total number of moles of polymerization monomer in each segment. Terpolymers, in their polymerization form, are composed of ethylene, alpha-olefins, and vinyl arrays. It contains ethylene / aluminum and may contain other monomer types. When used herein, it is referred to as "ethylene / aluminum". The term "fluoroolefin / vinyl alloy blocker polymer" is discussed above. As described above, the vinylarene-enriched (AR) segment and, as discussed above, vinyl Diblock refers to a diblock polymer containing an arene-deficient (AP) segment. Terpolymers, in their polymerization form, consist of ethylene, alpha-olefin, and vinylarene. It includes only three monomer types.

[0073] When used herein, "ethylene / vinyl arene triblock interpolymer" The term "-" refers to two vinylarene-enriched (AR) segments and the space between AR segments. Either one vinylarene-deficient (AP) segment located at or two vinylarenes Deficient (AP) segments and one vinylarene enriched (A) located between AP segments Refers to a triblock interpolymer containing any of the R) segments. For example, Figure 1B See below. The AR segment, in its polymerization form, is >10 mol% vinylarene. The AP segment contains ≤10 mol% vinylarene in its polymerization form. Each mol% is based on the total number of moles of polymerization monomer in each segment. Triblockin The terpolymer, in its polymerization form, contains ethylene, vinylarene, and other monomer species. May include other. When used herein, "ethylene / vinyl arene triblock The term "polymer" refers to two vinylarene-enriched (AR) polymers, as discussed above. Includes a compound and one vinylarene-deficient (AP) segment, or as considered above. As you suspected, there are two vinylarene-deficient (AP) segments and one vinylarene array. This refers to a triblock copolymer containing an AR-enriched (AR) segment. Each AR segment and The AP segment is as described above. The triblock copolymer is in its polymerization form. It contains ethylene and vinylarenes as only two monomer types.

[0074] When used herein, "ethylene / alpha-olefin / vinyl arenetri The term "block interpolymer" refers to two vinylarene-enriched (AR) segmented polymers. A vinylarene-deficient (AP) segment located between the T and AR segments, or Two vinylarene-deficient (AP) segments and one vinylarene located between the AP segments A triblock interpolymer containing any of the nylarene-enriched (AR) segments Refers to Figure 1B, for example. The AR segment, in its polymerized form, is >10mo Contains 1% vinylarene. The AP segment, in its polymerized form, is ≤10 mol% Contains vinylarene. Each mol% is based on the total number of moles of polymerization monomer in each segment. Triblock interpolymers are polymerized in the form of ethylene, alpha-olefins. Vinylarenes may be included, and other monomer types may be included. "Ethylene / alpha-olefin / vinyl arene triblocker polymer" The term refers to the polymerization form, as discussed above, two vinylarene enriched (A R) segment and one vinylarene-deficient (AP) segment, or as discussed above As such, there are two vinylarene-deficient (AP) segments and one vinylarene-enriched segment. Refers to a triblocker polymer containing any of the AR segments. The AP segment is as described above. The Triblocker polymer is in polymerization form In this, ethylene, alpha-olefin, and vinylarene are used as three monomers. Included as a type.

[0075] As used herein, the term "vinylarene" refers to a monocyclic, bicyclic, or Aromatic ring structures such as tricyclic ring structures are bonded to "-CR=CHR' (wherein R and R' are, This refers to chemical compounds containing (each independently being either H or alkyl). The aromatic ring structure is one The above heteroatomic groups may or may not be present, and one or more heteroatomic groups may be present. They may or may not be substituted. Examples of vinylarenes include styrene. Examples include 2-vinyltoluene, 4-vinyltoluene, and alpha-methylstyrene. These are possible, but are not limited to these.

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

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

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

[0079] As used herein, the terms "hydrocarbon," "hydrocarbyl group," and related terms are used herein. The term "similar" refers to each compound or chemical group that contains only carbon atoms and hydrogen atoms. Divalent " The term "hydrocarbylene group" is defined similarly.

[0080] As used herein, "heterohydrocarbons," "heterohydrocarbyl groups," and similar terms Similar terms include, for example, a heteroatom group in which at least one carbon atom is (e.g., O, N, or This refers to each "hydrocarbon" or "hydrocarbyl group" that is substituted with P). The rhodocarbyl group, via a carbon atom or a heteroatom, connects to the rest of the compound in question. It can bond to substances. A divalent "heterohydrocarbylene group" is similarly defined as a divalent hetero A hydrocarbylene group consists of two carbon atoms, or two heteroatoms, or a carbon atom and a heteroatom. It can bind to the remaining compound of the target via the α atom.

[0081] As used herein, the terms "substituted hydrocarbon" and "substituted hydrocarbyl group" are used in this specification. The term, and similar terms, refers to a group in which one or more hydrogen atoms are independently substituted with heteroatomic groups. This refers to various hydrocarbon groups or hydrocarbyl groups, etc.

[0082] As used herein, "substituted heterohydrocarbon" and "substituted heterohydrocarbyl group" The term "heteroatomic group" and similar terms refer to a group in which one or more hydrogen atoms are independently positioned in a heteroatomic group. This refers to the various heterohydrocarbons or heterohydrocarbyl groups that have been replaced.

[0083] As used herein, the terms “aryl,” “aryl group,” and similar terms are used. The word includes one or more ring structures, such as monoring, biring, or triring ring structures. This refers to aromatic hydrocarbyl groups or aromatic hydrocarbyl groups of a certain valence.

[0084] As used herein, the terms "heteroaryl" and "heteroaryl group" And similar terms refer to a structure in which one or more carbon atoms in a skeletal ring structure are independently placed in a heteroatomic group. This refers to the monovalent aryl or aryl group that has been replaced.

[0085] As used herein, the terms "substituted aryl," "substituted aryl group," and A similar term is Ally, where one or more hydrogen atoms are independently substituted by heteroatomic groups. This refers to groups such as aryl or aryl groups.

[0086] As used herein, "substituted heteroaryl" and "substituted heteroaryl group" are used in this specification. The term and similar terms refer to a group in which one or more hydrogen atoms are independently substituted with heteroatomic groups. This refers to heteroaryl groups or heteroaryl groups that are present in a heteroaryl or heteroaryl group.

[0087] As used herein, the terms “arirene,” “arirene group,” and similar terms are used herein. The term includes one or more ring structures, such as monoring, biring, or triring ring structures. This refers to valence aromatic hydrocarbylene or aromatic hydrocarbylene groups, etc.

[0088] As used herein, the terms "substituted arylene" and "substituted arylene group" And similar terms refer to a group in which one or more hydrogen atoms are independently substituted with heteroatomic groups. This refers to groups such as arylene or allylene.

[0089] As used herein, "substitute or non-substitute (C1-C) 30 ) Hydrocarbyl The terms and other similar terms refer to the total carbon that a substituted or unsubstituted hydrocarbyl radical may contain. This indicates the range of the number of atoms (e.g., 1 to 30). Note that other monovalent chemistry terms also specify the carbon range. Base (for example, substitution or non-substitution (C6~C) 20 The aryl group is similarly defined. Please take note.

[0090] As used herein, "substitute or non-substitute (C1-C) 30 ) Heterohydrocarbyl The term "and other similar terms may include "substituted or unsubstituted heterohydrocarbyl" This indicates the range of the total number of carbon atoms (e.g., 1 to 30). Note that other carbon ranges are also listed. Note that monovalent chemical groups are defined similarly.

[0091] When used herein, "substitute or non-substitute (C6~C)" 20 ) Arylene group The terms and other similar terms refer to the range of the total number of carbon atoms that a substituted or unsubstituted arylene group may contain. (For example, 2 to 6) is indicated. Other monovalent chemical groups with specified carbon ranges are similarly defined. Please note that this is a matter of principle.

[0092] As used herein with respect to metal complexes, the term "crosslinking group" refers to the residue of the metal complex. This refers to a divalent organic group that is bonded to two atoms located at different points in the structure of an atom. For example, Formula S1(J 1 ), S2(J 2 ), S3(J 3 ), S4(J 4 ), S5(J 5 ), H2(J 5 Refer to each of the bridging sites in ).

[0093] As used herein, "a bridging group containing 2 to 40 atoms other than hydrogen" and similar The phrase, with respect to metal complexes, refers to the range of all atoms other than hydrogen that the bridging group may contain (e.g., 2-40). This indicates (number of units). Note that other bridging groups with specified carbon ranges are defined similarly. I want to.

[0094] As used herein in relation to metal complexes, the term "Lewis base" refers to a pair of electrons. This refers to a chemical compound or chemical group that can be donated to form a bond with a metal or another chemical group. Examples of Lewis bases include tetrahydrofuran (THF) and die. Examples include methyl ether, dimethylaniline, or trimethylphosphine, but these Not limited.

[0095] When used herein with respect to polymerized vinylarene units, "Syndiotacticite" "Yi", "Syndiotactic", and similar terms refer to two or more pendant reels (e.g.) For example, it refers to the stereochemical configuration of alternating phenyl groups. Teru.

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

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

[0098] The notation "AP" in relation to diblock or triblock interpolymers indicates the polymerization form In this state, the polymer segment of each interpolymer containing ≤10 mol% vinylarene This refers to the "vinylarene deficiency" segment.

[0099] Regarding AR segments (or blocks) or AP segments (or blocks) The phrase "each segment" refers to A located at the end of the polymer molecule or within the polymer molecule. Refers to R segment or AP segment. Regarding diblock interpolymers, AR segment The segment is located at one end of the polymer molecule, and the AP segment is located at the other end of the polymer molecule. To place. Regarding triblock interpolymers, two AR segments are polymer molecules. Located at each end, the AP segment is located between these two AR segments, Alternatively, two AP segments are located at each end of the polymer molecule, and the AR segment is... It is located between these two AP segments.

[0100] As used herein, the term “solution polymerization” refers to monomers, catalysts, and formed All polymers are soluble in the polymerization solvent or a solvent blend of two or more solvents. This refers to Seth.

[0101] As used herein, the term “continuous solution polymerization” means that monomers are continuously injected into a reactor. This refers to solution polymerization, in which a polymer is supplied to a reactor and continuously extracted from the reactor.

[0102] When used herein, the term "metal complex" refers to one or more ligands (metals and A metal or a molecule (containing one or more electron pairs that can be shared) that is bonded to and / or coordinated to This refers to a chemical structure containing metal ions. For example, chemical formulas S1, S2, S3, S4, S5, H See 1 and the metal complex of H2. Metal complexes typically use one or more cocatalysts. It is activated catalytically by use.

[0103] As used herein, the term "scavenger" means impurities or unwanted substances. Chemicals added to polymerization reactions to remove or deactivate reaction products (e.g., oxygen). This refers to a mixture. Some examples of scavengers include MMAO and MMAO-3A. Examples include aluminum alkyl compounds.

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

[0105] The terms "comprising," "including," and "having" , and their derivatives, whether or not they are specifically disclosed, This is not intended to exclude the existence of additional components, steps, or procedures. To avoid ambiguity, patent claims are made through the use of the term "comprising". All compositions, whether polymers or otherwise, unless otherwise stated. , may include any additional additives, adjuvants, or compounds. In contrast, "from essential The term "becomes" excludes anything that is not essential to operability and is within the scope of any subsequent detail. The term "consists of" excludes any other components, steps, or procedures. Eliminate any components, steps, or procedures that are not specifically defined or enumerated.

[0106] List of several processes and compositions A) Ethylene / vinyl alloy block interpolymer and / or ethylene / vinyl A process for forming a composition containing a luarene triblock interpolymer, further Ethylene / vinyl arrenthe block interpolymer or ethylene / vinyl arrenthe A reblockable interpolymer, wherein the above process involves at least the following steps: A) In reactor A, the following: chemical formula S1, chemical formula S2, chemical formula S3, chemical formula S4, and The compound is selected from chemical formula S5, and at least the following: a) in the presence of a metal complex S, The compound comprises len, and optionally alpha-olefins, and optionally vinylarenes. , a step of polymerizing mixture A,

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

[0108] [ka] As described above (see SOI), (chemical formula S2), R 3 and R 4 Each of them is independent Then, substitution or non-substitution (C6~C 20 )aryl group, or substituted or unsubstituted (C5 ~C 20 ) Selected from heteroaryl groups, and further, R 3 and R 4 Each of them is independent Established, substitution or non-substitution (C6~C 12 )aryl group, or substituted or unsubstituted (C 5~C 11 ) Selected from heteroaryl groups,

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

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

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

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

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

[0114] [ka] In the formula, X 1 and X 2 Each of these can be substituted or not substituted (C1~C 30 ) Hydroca Rubill, substitution or non-substitution (C1~C 30 ) Heterohydrocarbyl, or -H, Furthermore, a selection is made from substituted or unsubstituted benzyl, or H, and X 1 and X 2 This is optional , They can be connected, Ar 1 and Ar 2 Each is independently a substituted or unsubstituted aryl, or substituted or It is an unsubstituted heteroaryl group, R 52 is a substituted or unsubstituted arylene group,

[0115] [ka] In the formula, X 3 and X 4 Each of these can be substituted or not substituted (C1~C 30 ) Hydroca Rubill, substitution or non-substitution (C1~C 30 ) Heterohydrocarbyl, or -H, further placed Selected from substitution or non-substituted benzyl, or H, X 3 and X 4 This is optional, and can be linked. It can be done, R 53 is either a substitution or a non-substitution (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) Heterohydrocarbyl, or -H, further substituted or unsubstituted benzyl, Or selected from -H, Ar 3 and Ar 4 Each is independently a substituted or unsubstituted aryl, or substituted or The process described in A] above, wherein the group is an unsubstituted heteroaryl group. C] The following structures s1a1, s1a2, s1a3, s1a4, s1a5, s2a1, s3 a1, s3a2, s3a3, s4a1, or s5a1, and any two of these structures The metal complex S selected from the above combinations,

[0116] [ka] Furthermore, a metal complex S selected from two or more combinations of these structures, and the aforementioned A The process described in ] or ]. D] Metal complex S has structure s1a1 or structure s1a2:

[0117] [ka] The process described in one of the above A] to C](A] to C] is selected from . E] The metal complex H is selected from the following chemical formulas H1a, H1b, or H2a. ,

[0118] [ka] (Chemical formula H1a), where R 1 , R 2 , R 3 , R 4 , and R 5 Each of them is independent of H, A substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted heterohydrocarbyl group. Furthermore, it is H, an alkyl group, or an alkylsilyl group, and further, an alkyl group or alkylsilyl It is a lyl group, Q 1 and Q 2 Each of these independently comprises a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted hydrocarbyl group. A substitute heterohydrocarbyl group, or halogen, and furthermore, an aryl group, an alkylsilyl group, or an alcohol. The compound is a xyl group, a halogen, or -NRR', where R and R' are each independently a hydroxyl group. Rubyl or SiR'', where R'' is a hydrocarbyl, further aryl, or alkyl group. It is a silyl group or an alkoxy group, L is a Lewis base, and each n is independently either 0 or 1. At least one L group and at least one Q group are optionally connected, and optionally Selectively, at least one R group and at least one Q group are connected.

[0119] [ka] (Formula H1b), where R 1 , R 2 , R 3 , R 4 , and R 5 Each of them is independent of H, Substituted or unsubstituted hydrocarbyl groups, or substituted or unsubstituted heterohydrocarbyl groups It is further H, alkyl group, or alkylsilyl group, and further alkyl group, or It is a chlorosilyl group, Q 1 Q 2 , and Q 3 Each of these independently consists of a substituted or unsubstituted hydrocarbyl group, and a substituted group. Alternatively, an unsubstituted heterohydrocarbyl group, or a halogen, and furthermore, an aryl group, an alkyl silicone R is a group, an alkoxy group, a halogen, or -NRR', where R and R' are each independently The formula is hydrocarbil or SiR'', where R'' is hydrocarbil, and furthermore, aryl It is a group, an alkoxy group, or a halogen, At least one R group and at least one Q group are optionally connected.

[0120] [ka] (Chemical formula H2a), where M 2 is Ti, Hf, or Zr, further Zr or Hf, further Z r is, R 6 and R 8 Each of these is independently -H, substitution or non-substitution (C1~C 40 ) Hydrocarb Lu, substitution or non-substitution (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge (R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O -, R C OC(O)-, RC C(O)N(R)-, (R C )2NC(O)-, halogen, A radical having formula (I), a radical having formula (II), and a radical having formula (III). Selected from a group consisting of dicals,

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

[0122] [ka] The process described in A] to E] above, selected from the above. G] The metal complex S is selected from chemical formula S1, and further from chemical formula S1a, as described above in A]~F] The process described in any one of the following. The H] metal complex S is selected from chemical formula S2, and further from chemical formula S2a, as described above (A) to F). The process described in any one of the following. I) The metal complex S is selected from chemical formula S3, one of the above A) to F) The process described below. J] Metal complex S is selected from chemical formula S4, one of the above A] to F] The process described below. The K] metal complex S is selected from chemical formula S5, one of the above A] to F]. The process described below. The L]metal complex H is selected from chemical formula H1, and further from chemical formula H1a or chemical formula H1b. The process described in any one of the above A] to K]. The metal complex H is selected from the chemical formulas H2 and H2a, as described above (A) to K). The process described in any one of the following. N] At least one chain shuttle agent is: alkyl zinc compound, alkyl Aluminum compounds, dual-head chain shuttle agents, or combinations thereof A process described in any one of the above A]~M], selected from the above. O] At least one chain shuttle agent is: Zn(CH2CH3)2, A l(CH2CH3)3, Al-DHCSA, ZnAl-DHCSA, or combinations thereof Furthermore, select from Al-DHCSA, ZnAl-DHCSA, or a combination thereof. The process described in any one of the above A]~N] is performed. P] At least one chain shuttle agent is added to reactor A, as described above A]~ The process described in any one of the following [O]. Q] At least one chain shuttle agent is added to reactor B, as described above in A]~ The process described in any one of the following [O]. R] At least one chain shuttle agent is added to reactor A and reactor B. The process described in any one of the above A] to O]. S] Step A occurs before step B, one of the above A]~R] The process described below. T] Unreacted monomers in reactor B are recycled and returned to reactor A, as described above in S] The process described. U] Step B occurs before step A, one of the above A]~R] The process described below. V] Unreacted monomers in reactor A are recycled and returned to reactor B, as described in U] above. The process described. W) polymerization is either solution polymerization or continuous solution polymerization, or any of the above A) to V) The process described in one document. X] Polymerization in reactor A occurs at ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C , or occurs at a temperature of ≥110°C, or ≥115°C, any of the above A]~W] The process described in one of the documents. In reactor A, polymerization occurs at ≤200°C, or ≤190°C, or ≤180°C, or ≤17 0°C, or ≤160°C, or ≤150°C, or ≤145°C, or ≤140°C, or ≤13 The above-mentioned A]~X] occurs at temperatures of 5°C, or ≤130°C, or ≤125°C. The process described in either one of the following. Z] Polymerization occurs in reactor B at ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C , or occurs at a temperature of ≥110°C, or ≥115°C, any of the above A]~Y] The process described in one of the documents. A2] Polymerization in reactor B occurs at ≤200°C, or ≤190°C, or ≤180°C, or ≤1 70°C, or ≤160°C, or ≤150°C, or ≤145°C, or ≤140°C, or ≤1 Occurs at temperatures of 35°C, or ≤130°C, or ≤125°C, among the above A]~Z] The process described in any one of the following. B2] Polymerization in reactor A occurs at ≥90 psig, or ≥100 psig, or ≥110 psig. sig, or ≥120psig, or ≥130psig, or ≥140psig, or ≥ 150 psig, or ≥160 psig, or ≥170 psig, or ≥180 psig A process described in any one of the above A] to A2], which occurs under pressure. C2] Polymerization in reactor A is ≤250 psg, or ≤240 psg, or ≤230 ps Occurs at pressures of g, or ≤220 psg, or ≤210 psg, or ≤200 psg. The process described in any one of the above A] to B2]. D2] Polymerization in reactor A occurs at ≥90 psig, or ≥100 psig, or ≥110 psig. sig, or ≥120psig, or ≥130psig, or ≥140psig, or ≥ 150 psig, or ≥160 psig, or ≥170 psig, or ≥180 psig A process described in any one of the above A] to C], which occurs at the pressure. E2] Polymerization in reactor B is ≤250 psg, or ≤240 psg, or ≤230 ps Occurs at pressures of g, or ≤220 psg, or ≤210 psg, or ≤200 psg. The process described in any one of the above A] to D2]. F2] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, the vinylarene is styrene, as mentioned above. The process described in one of the following A to E2. G2] Mixture A contains any of the above A] to F2], including an alpha-olefin. The process described in one of the documents. [H2] alpha-olefins are C3-C20 alpha-olefins, and further C3-C1 0 alpha-olefin, further C3-C8 alpha-olefin, further propylene, 1- Butene, 1-hexene or 1-octene, and further propylene, 1-butene or 1-octene Furthermore, 1-butene or 1-octene, and further 1-octene, as described in G2 above. Rothes. I2] Mixture B contains one of the above A]~H2] which contains an alpha-olefin The process described above. [J2] Alpha-olefins include C3-C20 alpha-olefins, and further C3-C1 0 alpha-olefin, further C3-C8 alpha-olefin, further propylene, 1- Butene, 1-hexene or 1-octene, and further propylene, 1-butene or 1-octene Furthermore, 1-butene or 1-octene, and further 1-octene, as described in I2] above. Rothes. K2] The molar ratio of the metal of complex S to the metal of complex H is ≥ 0.03, or ≥ 0 A process described in any one of the above A]~J2], where 0.1 or ≥0.5. L2] The molar ratio of the metal of complex S to the metal of complex H is ≤1000 or ≤5 A process described in any one of the above A] to K2], where 00 or ≤ 100. M2] "Total of the metals of complex S and complex H" for the "metals of the chain shuttle agent" The molar ratio to is ≥2.0, or ≥5.0, or ≥10, or ≥20, or ≥40, The process described in any one of the above A]~L2], where ≥ 100. N2] "Metal of chain shuttle agent" "Total of the metal of complex S and the metal of complex H" The molar ratio to is ≤1000, or ≤800, or ≤500, as described above for A]~M The process described in any one of the following two items. [O2]metal complex S is r (エチレン)(ビニルアレーン) =k (エチレン)(エチレン ) / k (エチレン)(ビニルアレーン) The range is 50-1000, and even further, 100-500. The process described in any one of the above A] to M2], having a reactivity ratio. [P2] Metal complex H is r (エチレン)(ビニルアレーン) =k (エチレン)(エチレン ) / k (エチレン)(ビニルアレーン) The above-mentioned A has a reactivity ratio of 1 to 10. The process described in one of the following: ]~O2]. Q2] The composition is polyethylene homopolymer, ethylene / vinyl arene copolymer, The above further includes ethylene / alpha-olefin copolymers, or combinations thereof. The process described in any one of A] to P2]. R2] A composition formed from any one of the processes described in A) to Q2) above. A3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy A composition comprising the laen triblock interpolymer, wherein the diblock interpolymer The polymer comprises at least one polymer structure selected from Structure 1 shown below, and the above Triblock interpolymers each consist of a minimum number of structures selected from Structure 2 or Structure 3 shown below. It contains at least one polymer structure, where AR refers to vinylarene enrichment and AP is vinyl This refers to a shortage of luarene. (AR)-(AP)(Structure 1), (AR)-(AP)-(AR)(Structure 2), (AP)-(AR)-(AP)(Structure 3), and Each (AR) segment independently, in its polymerized form, is composed of ethylene, vinyl allergen, etc. , and optionally containing alpha-olefin, Each (AP) segment independently polymerizes into ethylene, optionally. The compound comprises vinylarene and optionally alpha-olefin. Each (AR) segment independently determines the total amount of polymerized monomers in the (AR) segment. Based on the number of moles, the polymerized form contains >10 mol% vinylarene. Each (AP) segment independently determines the total amount of polymerized monomers in the (AP) segment. Based on the number of moles, the polymerized form contains ≤10 mol% vinylarene. composition. B3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AR) segment is independently heavy In the combined form, based on the total number of moles of polymerized monomers in the (AR) segment, ≥ 15m ol%, or ≥20mol%, or ≥25mol%, or ≥30mol%, or ≥35m ol%, or ≥40mol%, or ≥45mol%, or ≥50mol%, or ≥55m The composition according to A3 above, comprising ol% or ≥60 mol% of vinylarene. C3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AR) segment is independently heavy In the combined form, based on the total number of moles of polymerized monomers in the (AR) segment, <100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 The above-mentioned A3] or B3] contains mol% or ≤91 mol% vinylarene. The composition of. D3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AP) segment is independently heavy In the combined form, based on the total number of moles of polymerization monomers in the (AP) segment, ≥ 0 mo 1%, or ≥0.2 mol%, or ≥0.4 mol%, or ≥0.6 mol%, or ≥0 The above-mentioned A3-C3] contain 0.8 mol% or ≥1.0 mol% vinylarene. The composition described. E3] Ethylene / vinyl alloy block interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AP) segment is independently heavy In the combined form, based on the total number of moles of polymerization monomers in the (AP) segment, ≤ 10m ol%, or ≤9.0mol%, or ≤8.0mol%, or ≤7.0mol%, or ≤ The above-mentioned A3-D3] contain 6.0 mol% or ≤5.0 mol% of vinylarene. A composition as described in any one of the following. F3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AR) segment is independently heavy In the combined form, based on the total number of moles of polymerized monomers in the (AR) segment, ≥ 2.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥9.0 mol%, or ≥10 mol%, or ≥11 mol%, or ≥12 mol%, or It contains ≥13 mol% or ≥14 mol% ethylene, one of the above A3 to E3] Any one of the compositions described. G3] Ethylene / vinyl alloy block interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AR) segment is independently heavy In the combined form, based on the total number of moles of polymerized monomers in the (AR) segment, ≤ 80 m ol%, or ≤77mol%, or ≤75mol%, or ≤73mol%, or ≤70m ol%, or ≤65mol%, or ≤60mol%, or ≤55mol%, or ≤50m The above-mentioned A3-F contain 100% or ≤45 mol% or ≤40 mol% ethylene. The composition described in any one of [3]. H3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AP) segment is independently heavy In the combined form, based on the total number of moles of polymerized monomers in the (AP) segment, ≥ 50 m ol%, ≥52mol%, or ≥54mol%, or ≥56mol%, or ≥58mol %, or ≥60 mol%, or ≥62 mol%, or ≥64 mol%, or ≥66 mol The above A3-G3] contain %, or ≥68 mol%, or ≥70 mol% ethylene. A composition as described in any one of the following. I3] Ethylene / vinyl alloy block interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AP) segment is independently heavy In the combined form, based on the total number of moles of polymerization monomers in the (AP) segment, ≤ 100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 One of the above-mentioned A3 to H3] containing mol% or ≤90 mol% ethylene The composition described above. J3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AR) segment is independently heavy In the combined form, based on the total number of moles of polymerization monomers in the (AR) segment, ≥ 0 mo 1% or ≥1.0 mol%, or ≥2.0 mol%, or ≥3.0 mol%, or ≥4 Contains 0.0 mol% alpha-olefin, as described in one of the above A3] to I3] The composition of the material. K3] Ethylene / vinyl alloy block interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AR) segment is independently heavy In the combined form, based on the total number of moles of polymerization monomers in the (AR) segment, ≤ 10m ol%, ≤9.0mol%, or ≤8.0mol%, or ≤7.0mol%, or ≤6. Contains 0 mol% alpha-olefin, as described in any one of the above A3 to J3]. The composition of. L3]α-olefins are C3-C20 alpha-olefins, and further C3-C10 alpha-olefins. Alpha-olefins, further C3-C8 alpha-olefins, further propylene, 1-butene , 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, or any of the above J3 to K3] which are 1-octene. The composition described in one of the following. M3] Ethylene / vinyl alloy block interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AR) segment is a polymerization form. Furthermore, it does not contain alpha-olefins, as described in any one of the above A3 to L3] composition. N3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AP) segment is independently heavy In the combined form, based on the total number of moles of polymerization monomers in the (AP) segment, ≥ 0 mo 1%, ≥1.0 mol%, or ≥2.0 mol%, or ≥3.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥10 mol% of alpha A composition comprising α-olefin, as described in any one of the above A3 to M3. O3) Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, each (AP) segment is independently heavy In the combined form, based on the total number of moles of polymerization monomers in the (AP) segment, ≤ 40 m ol%, or ≤35mol%, or ≤30mol%, or ≤28mol%, or ≤26m ol%, or ≤24mol%, or ≤22mol%, or ≤20mol% alpha-o A composition containing refin, as described in any one of the above A3] to N3]. P3]α-olefins are C3-C20 alpha-olefins, and further C3-C10 alpha-olefins. Alpha-olefins, further C3-C8 alpha-olefins, further propylene, 1-butene , 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, or any of the above N3 to O3, which are 1-octene. The composition described in one of the following. Q3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy For lane triblock interpolymers, ≥20 mol in each (AR) segment. %, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol %, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol %, or ≥98 mol%, or ≥99 mol%, of polymerized vinylarene is subsegmented In Tobb, it exists in a "back-to-back" configuration as shown below,

[0123] [ka] (Subsegment bb), mol% is polymerized vinylarene in segment (AR). A composition according to any one of the above A3 to P3, based on the total moles of [A3] to [P3]. R3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy For lane triblock interpolymers, in each (AR) segment, ≤100 mo 1% polymerized vinylarene is present in the subsegment bb described above as follows: It exists in a "back-to-back" configuration, as described in one of the above A3]~Q3] composition. S3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy For lane triblock interpolymers, ≥20 mol in each (AR) segment. %, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol %, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol %, or ≥98 mol%, or ≥99 mol%, of polymerized vinylarene is subsegmented In the tsbb, the following syndiotactic "back-to-back" configuration is used. exist,

[0124] [ka] (Subsegment sbb), mol%, polymerized vinyl array in segment (AR) A composition according to any one of the above A3 to R3, based on the total moles of n. T3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy For lane triblock interpolymers, ≤100 mo in each (AR) segment 1% polymerized vinylarene is as shown in the subsegment sbb described above. Any of the above A3]~S3] exist in a gneotactic "back-to-back" configuration. The composition described in one of the following. U3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy For lane triblock interpolymers, ≥0 and ≤ in each (AP) segment. 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 is subsegmented In ntbb, it exists in a "back-to-back" configuration as shown below.

[0125] [ka] (Subsegment bb); mol% is polymerized vinylarene in segment (AP). A composition according to any one of the above A3 to T3, based on the total moles of [A3] to T3]. V3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding lane triblock interpolymers, polymerized vinyl in each (AP) segment All of the Allen models are "back-to-back" as shown in the subsegment bb above. A composition that does not exist in any of the above A3] to U3]. W3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Regarding the lane triblock interpolymer, vinylarene is styrene, A composition according to any one of A3 to V3 described above. X3] Ethylene / vinyl alloy block interpolymer is ethylene / alpha -Olefin / vinyl alloy block interpolymer and further terpolymer Alternatively, ethylene / vinylarene triblock copolymer is ethylene / alpha -Olefin / vinylarene triblock interpolymer and further terpolymer or a composition as described in any one of the above A3] to W3]. Y3] Ethylene / vinylalene diblock interpolymer or ethylene / vinylalene Lane Triblock Interpolymers are suitable for temperatures of ≥50°C, or ≥55°C, or ≥60°C, or ≥70℃, and Tm2 ≥120℃, or ≥124℃, or ≥150℃, or ≥170℃, Or having Tm1 which is ≥200℃, or ≥210℃, or ≥220℃, or ≥230℃ The composition described in any one of the above A3 to X3. Z3] Ethylene / vinyl alloy interpolymer or ethylene / vinyl alloy Lane Triblock Interpolymers are suitable for use at ≤120°C, or ≤115°C, or ≤110°C. , or ≤105℃, and Tm2 is ≤270℃, or ≤265℃, or ≤260℃, The above A3 has Tm1 which is ≤255℃, or ≤250℃, or ≤245℃. A composition as described in any one of the following: ~Y3]. A4] Ethylene / vinyl alloy block interpolymer or ethylene / vinyl alloy Lane Triblock Interpolymers are suitable for use at ≥-70°C, or ≥-68°C, or ≥-66°C. , or ≥-64℃, or ≥-62℃, and Tg2 is ≥-2.0℃, or ≥5.0℃, or The above-mentioned Tg1 is such that is ≥10℃, or ≥15℃, or ≥20℃, or ≥30℃. A composition as described in any one of A3 to Z3. B4] Ethylene / vinyl alloy block interpolymer or ethylene / vinyl alloy Lane Triblock Interpolymers are suitable for temperatures ≤-30°C, ≤-32°C, or ≤-34°C. , or ≤-36℃, or ≤-38℃, or ≤-40℃, or ≤-42℃, or ≤-44℃ , or ≤-46℃, and Tg2 is ≤-125℃, or ≤120℃, or ≤115℃, or It has a Tg1 of ≤110℃ or ≤105℃, and is one of the above A3]~A4]. The composition described in one of the following. [C4] Composition has a value of ≥3.0, or ≥3.1, or ≥3.2, or ≥3.3, or ≥3. The molecular weight distribution (MWD = Mw / M) is 4, or ≥3.6, or ≥3.8, or ≥4.0. A composition according to any one of the above A3] to B4], having n). [D4] composition, ≤50, or ≤45, or ≤40, or ≤38, or ≤36, or ≤ Having a molecular weight distribution MWD of 34, or ≤32, or ≤30, or ≤28, or ≤26. The composition described in any one of the above A3 to C4. E4] Composition, ≥4,000 g / mol, or ≥6,000 g / mol, or ≥8, 000 g / mol, or ≥10,000 g / mol, or ≥12,000 g / mol The set has a number-average molecular weight distribution (Mn) as described in any one of the above A3 to D4]. A finished product. The F4 composition has a concentration of ≤100,000 g / mol, or ≤90,000 g / mol, or ≤80,000 g / mol, or ≤75,000 g / mol, or ≤70,000 g / m³ ol, or ≤65,000 g / mol, or ≤60,000 g / mol, or ≤55,0 It is 00 g / mol, or ≤50,000 g / mol, or ≤45,000 g / mol. A composition according to any one of the above A3 to E4, comprising Mn. [G4] Composition has a concentration of ≥50,000 g / mol, or ≥55,000 g / mol, or ≥ 60,000 g / mol, or ≥65,000 g / mol, or ≥70,000 g / mol l, or ≥75,000 g / mol, or ≥80,000 g / mol, weight-average fraction A composition having a particle distribution (Mw), as described in any one of the above A3 to F4. The H4 composition has a concentration of ≤500,000 g / mol, or ≤450,000 g / mol, is ≤400,000 g / mol, or ≤390,000 g / mol, or ≤380,000 0 g / mol, or ≤370,000 g / mol, or ≤360,000 g / mol A composition according to any one of the above A3 to G4, having Mw. I4] The composition is ≥0.5 dg / min, or ≥1.0 dg / min, or ≥2.0 dg / min. Or having a melt index (I2) of ≥ 5.0 dg / min or ≥ 10 dg / min The composition described in any one of the above A3 to H4. [J4] Compositions are ≤1,000 dg / min, or ≤500 dg / min, or ≤250 dg / min Meltoy A composition according to any one of the above A3] to I4], having index (I2). The K4 composition is suitable for temperatures of ≥200°C, or ≥205°C, or ≥210°C, or ≥215°C. Tm is ≥220°C, or ≥225°C, or ≥230°C, or ≥235°C. , the composition described in any one of the above A3 to J4. [L4] composition, ≤300℃, or ≤290℃, or ≤285℃, or ≤280℃, The temperature is ≤275℃, or ≤270℃, or ≤265℃, and has Tm, as described above in A3]~ The composition described in any one of K4. M4] composition, ≥-80℃, or ≥-75℃, or ≥-70℃, or ≥-69℃, It has a Tg of ≥-68℃ or ≥-67℃, and is one of the above A3]~L4]. The composition described in one. N4] composition, ≤-30℃, or ≤-35℃, or ≤-40℃, or ≤-45℃, or ≤-50℃, or It has a Tg of ≤-55℃ or ≤-60℃, and is one of the above A3]~M4]. The composition described in one. The O4 composition, in its polymerization form, is based on the total number of moles of polymerized monomers in the composition. ≥5.0 mol%, or ≥10 mol%, or ≥12 mol%, or ≥14 mol%, or This includes ≥16 mol% vinylarene, as described in any one of the above A3-N4]. The composition of. [P4] The composition, in its polymerization form, is based on the total number of moles of polymerized monomers in the composition. <50 mol%, or ≤45 mol%, or ≤40 mol%, or ≤35 mol%, or Contains ≤30 mol% vinylarene, as described in any one of the above A3 to O4] composition. Q4] In terms of polymerization form, the composition is determined based on the total number of moles of polymerized monomers in the composition. ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥42 mol%, or Ethyl ≥44 mol%, or ≥46 mol%, or ≥48 mol%, or ≥50 mol% A composition containing Len, as described in any one of the above A3 to P4. The R4 composition, in its polymerization form, is based on the total number of moles of polymerized monomers in the composition. <90 mol%, or 85 mol%, or ≤80 mol%, or ≤78 mol%, or ≤ 76 mol%, or ≤74 mol%, or ≤72 mol%, or ≤70 mol%, or ≤ A composition according to any one of the above A3] to Q4], comprising 68 mol% ethylene. S4] The composition, in its polymerization form, is based on the total number of moles of polymerized monomers in the composition. ≥2.0 mol%, or ≥5.0 mol%, or ≥10 mol%, or ≥12 mol%, or ≥14 mol%, or ≥16 mol%, or ≥18 mol%, or ≥20 mol% A composition comprising an alpha-olefin, as described in any one of the above A3] to R4]. The T4 composition, in its polymerization form, is based on the total number of moles of polymerized monomers in the composition. ≤50 mol%, ≤45 mol%, or ≤40 mol%, or ≤35 mol%, or ≤3 The above-mentioned A3-S4] contain 0 mol% or ≤28 mol% of alpha-olefin. A composition as described in any one of the following. U4] Alpha-olefins include C3-C20 alpha-olefins, and further C3-C1 0 alpha-olefin, further C3-C8 alpha-olefin, further propylene, 1- Butene, 1-hexene or 1-octene, and further propylene, 1-butene or 1-octene Furthermore, 1-butene or 1-octene, and further 1-octene, as described above in S4]~T4] The composition described in any one of the following. Regarding the V4 composition, block styrene (bb in AR) relative to isolated styrene The molar ratio is ≥2.0 mol%, ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 The composition described in any one of the above A3 to U4 is mol%, or ≥10 mol. thing. Regarding the W4 composition, the isolation of block styrene (bb in AR) relative to styrene The molar ratio is ≤30 mol%, or ≤25 mol%, or ≤20 mol%, or ≤18 mol%. The above A is 1%, or ≤16 mol%, or ≤14 mol%, or ≤12 mol%. A composition as described in any one of [3] to [V4]. X4] Vinylarene is styrene, as stated in any one of the above A3]~W4]. The composition of. The Y4 composition is an ethylene / vinyl alloy block interpolymer, and furthermore, ethylene Any of the above A3]~X4] containing a len / vinylalene diblocker polymer The composition described in one. Z4] Composition, Ethylene / vinylarene triblock interpolymer, and further ethylene / vinylarene The following describes any one of the above A3] to Y4], including a lane triblocker polymer. composition. A5] Composition: polyethylene homopolymer, ethylene / vinylarene copolymer, The above further includes ethylene / alpha-olefin copolymers, or combinations thereof. A composition as described in any one of A3 to Z4. B5] The composition has one or more characteristics, for example, the type and / or amount of monomers. , Tm, Tg, Mn, Mw, MWD, or any combination thereof, further, In one or more features, for example, the type and / or amount of monomer, Tm, Tg, or In any of these combinations, ethylene / vinyl anedi block intermediate Thermoplastic polymers different from ethylene / vinyl arene triblock interpolymers A composition according to any one of the above A3] to A5], further comprising a rimer. C5] Formed from one of the compositions described above in R2] or A3] to B5] An article comprising at least one component. D5] Process for forming any one of the compositions described in A3] to A5] above And, as follows: A) In reactor A, ethylene, optionally alpha-olefin, and optionally A mixture A containing vinylarene, at least the following: a) Each as described above: Chemical formula S1, Chemical formula S2, Chemical formula S3, Chemical formula S4, and The process involves polymerization in the presence of a metal complex (S) selected from chemical formula S5, B) In reactor B, as described above, at least the following: b) the following chemical formula H1 or In the presence of a metal complex H selected from the chemical formula H2, ethylene, vinylarene, and other metals are produced. A step of selectively polymerizing a mixture B containing an alpha-olefin, Step A occurs before Step B, and at least a portion of the reactor products in reactor A Furthermore, if ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight It is transferred to reactor B, or step B occurs before step A, and in reactor B At least a portion of the reactor product, and moreover, ≥50% by weight, or ≥80% by weight, or ≥ 90% by weight, or ≥98% by weight, is transferred to reactor A, and each weight percentage is equal to the total weight of each reactor product. Based on quantity, If step A occurs before step B, at least one chain shuttle The agent is supplied into reactor A. If step B occurs before step A, at least one chain shuttle The agent is supplied into reactor B. The vinylarene in step A is equal to the vinylarene in step B, and in step A The alpha-olefin is an alpha-olefin in step B, and includes Hmm, process.

[0126] Test method Gel permeation chromatography (conventional type) The chromatography system is equipped with an internal IR5 infrared detector (IR5) Poly High-temperature GPC chromatography of merChar GPC-IR (Valencia, Spain) It consisted of a graph. Set the autosampler oven compartment to 160 degrees Celsius. The column compartment was set to 150 degrees Celsius. The column has four AGILEN T "Mixed A" was a 30cm, 20-micron linear mixed-bed column. Chromatography The solvent for the graphi is 200 ppm of butylated hydroxytoluene. It was 1,2,4-trichlorobenzene containing toluene (BHT). The solvent source was nitrogen. A spurged injection was performed. The injection volume used was 200 microliters, and the flow rate was 1. The flow rate was 0 milliliters / minute.

[0127] Calibration of the GPC column set with 2 molecular weights in the range of 580 to 8,400,000 This was carried out using a single polystyrene standard material with a narrow molecular weight distribution, and there were small differences between the individual molecular weights. The standard substance was placed in six "cocktail" mixtures with at least a 10-fold interval between them. Purchased from ilent Technologies. Molecular weight over 1,000,000. For the solvent, "0.025 grams in 50 milliliters" is less than 1,000,000. Regarding molecular weight, the concentration is "0.05 grams per 50 milliliters of solvent" for the polystyrene standard substance. The following was prepared: The polystyrene standard was dissolved at 80 degrees Celsius for 30 minutes with gentle stirring. The peak molecular weight of the polystyrene standard was converted to the polyethylene molecular weight using formula 1. (Williams and Ward, J. Polym. Sci., Polym) (As described in Let., 6, 621 (1968)). M ポリエチレン =A × (M ポリスチレン ) B (Formula 1) (In the formula, M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0) ).

[0128] A quintic polynomial was used to fit each polyethylene equivalent calibration point. For A By making slight adjustments (approximately 0.375 to 0.445), the column resolution and band expansion effect are improved. The linear homopolymer polyethylene standard material was corrected so that it could be obtained at 120,000 Mw. The total plate count of the GPC column set was decanted (TCB "0 in 50 ml" The procedure was performed using a solution prepared with 0.04g and dissolved for 20 minutes while gently stirring. To count (Equation 2) and symmetry (Equation 3) are expressed by the following formula for "200 microliter injection" The measurements were taken according to the instructions.

[0129]

number

[0130]

number

[0131] Sample from PolymerChar "Instrument Control" software Prepared semi-automatically using a WEAR, the sample and solvent (target weight 2 mg / ml) (Containing 200 ppm BHT) via PolymerChar high-temperature automatic sampler The sample was then added to the septum-capped vial before nitrogen purging. The sample was then subjected to "low-speed" shaking. Then, it was dissolved at 160 degrees Celsius for 2 hours.

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

[0133]

number

[0134] To monitor deviations over time, the PolymerChar GPC-IR system is used. A flow marker (decane) was introduced into each sample via a controlled micropump. Flow rate markers (FM) are used to determine the respective decane peaks (RV) within the sample. (FM sample)) and the Decane peak within the narrow standard calibration (RV (FM calibrated)) By matching the RV (Reverse Voltage), the pump flow rate (apparent flow rate) of each sample is linearly compensated for. It was used to correct it. Then, any time change in the decan marker peak was used throughout the entire run. It was estimated that this is related to the linear shift of the flow rate (effective flow rate). To facilitate the highest accuracy of V measurement, a least squares fitting routine is used to measure the flow rate. The peaks of the concentration chromatogram were fitted to a quadratic equation. Next, the first-order derivative of the quadratic equation was obtained. The true peak position was determined using a function. The system was calibrated based on the flow marker peak. After that, the effective flow rate (with respect 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 rate meter Kapeak processing is performed via PolymerChar GPCOne™ software. The process was carried out as follows: The acceptable flow rate correction is such that the effective flow rate is within + / - 0.7% of the apparent flow rate. It was meant to be.

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

[0136] density Polymer plaques for density analysis are prepared using ASTM D4703. The polymer density was measured using MD792, Method B.

[0137] Differential Scanning Calorimetry (DSC) Differential scanning calorimetry (DSC) was used to analyze ethylene (PE) samples and propylene The Tm, Tc, Tg, and crystallinity of polystyrene (PS) samples were measured. Approximately 5-8 mg of polystyrene was used. The sample was weighed and placed in a DSC dish. The lid was pressed onto the pan to ensure a sealed atmosphere. Unless otherwise specified, place the sample dish in a DSC cell, and then incubate at 10°C / min for PE. The sample was heated to a temperature of 180°C (300°C for PS). The sample was then heated at this temperature for 3 minutes. It was kept. Afterwards, the sample was heated at a rate of 10°C / min, to -90°C for PE (and for PS). The sample was cooled to -90°C and kept isothermally at that temperature for 3 minutes. Next, the sample was completely dissolved. It was heated at a rate of 10°C / min until melted (second heating). Unless otherwise specified, each poly Melting point of Mar (T m ) and glass transition temperature (T g The crystallization temperature is determined from the second thermal curve. (T c ) was determined from the first cooling curve. m(Peak temperature) and T g This was recorded. 2 The heat of fusion (H) determined from the heat curve f ) In the case of PE, the theoretical heat of fusion is 292 J / g (PS In this case, divide by 53 J / g and multiply this amount by 100 to obtain the degree of crystallinity. It is possible to calculate cents (for example, crystallinity % = (Hf / 292J / g) × 100) (In the case of PE).

[0138] 13 C NMR Approximately 2.7g of stock solvent was added to a 0.2g sample (polymer) in a 10mm NMR tube. Each sample was prepared by adding it to a polymer composition or a metal complex. Tok solvent contains 0.025M chromium acetylacetonate (relaxant) in a tetra- It was chloroethane-d2. The sample was capped and sealed with Teflon tape. The sample is dissolved by heating the tube and its contents at 130°C to 135°C. So, it was made uniform. The data was obtained using a Bruker high-temperature cryoprobe. Acquired using an ER 600MHz spectrometer. 7.3-second pulse repetition delay (6 seconds) (Delay + 1.3 second acquisition time), 90-degree flip angle, and inverse at a sample temperature of 120°C. Data was acquired using gate decoupling. All measurements were performed in non-locked mode. The procedure was performed with rotating samples. Immediately before inserting them into the heated (125°C) NMR sample exchanger, The sample was homogenized and thermally equilibrated in the probe for 7 minutes before data acquisition.

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

[0140] [ka]

[0141] For the analysis of each sample (polymer or composition), 124.0–148.0 ppm of B Using the 1-4 ring carbon signal as the styrene contribution, 2B6 (22.0-23.5 ppm) ) and the 3B6 (31.5~32.7 ppm) signal were used as octene contributions during polymerization. The molar amounts of monomers were calculated as follows (S=styrene, E=ethylene, O=octene). ). Smol = Integral value (124.0~148.0 ppm) / 6 Omol = (integral value (22.0~23.5 ppm) + integral value (31.5~32.7 ppm) m)) / 2 Emol = (integral value (11.8~48.0 ppm) - 2) * Smol-8 * Omol) / 2 Smol%=100 * Smol / (Smol+Omol+Emol) 0 mol% = 100 * Omol / (Smol+Omol+Emol) Emol% = 100 - Smol% - 0mol%.

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

[0143] 1H NMR Each sample contains 130 mg of the sample (polymer or polymer composition or metal complex). , 3.25 g of tetra 0.001 M Cr(AcAc)3 in a 10 mm NMR tube It was prepared by adding it to chloroethane-d2. To prevent oxidation, it was inserted into the tube. By passing N2 through the pipette for approximately 5 minutes, the sample is parsed. I did that. I capped the sample container and sealed it with Teflon tape. I put the sample in 115 The mixture was heated to °C and vortexed to ensure homogeneity. ¹H NMR was performed at the Bruker high temperature. With a Bruker AVANCE 600MHz spectrometer equipped with CryoProbe, 1 The procedure was performed at a sample temperature of 20°C. 1H NMR was performed using a ZG pulse, four scans, and SW. The test was conducted at H10,000Hz, AQ1.64s, and D11 14s.

[0144] Compression molding Each polymer composition was placed on a plaque for physical testing using a Carver press. Compression molding was performed. Each composition was subjected to ASTM D4 at 190°C while controlled cooling at 15°C / min. It was compression molded according to 703.

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

[0146] experiment I. Catalysts and Chain Shuttling Agents

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

[0148] [ka]

[0149] In a nitrogen-filled glove box, Sc(CH2CH6H4NMe2-O)3 dissolved in THF. The liquid (1 mL) (0.300 g, 0.67 mmol) is placed in a 20 mL vial of C5Me5 It was added to a THF solution (0.105 mL, 0.67 mmol) of H (1 mL). The solution was 7 The mixture was heated at 0°C for 12 hours. The solvent was removed under reduced pressure, the residue was extracted with hexane, and then filtered. The concentrated hexane solution was equilibrated at -30°C, producing yellow crystals (0.203g, yield 65%). 5% was obtained. The ¹H NMR and ¹³C NMR spectra were consistent with those reported in the literature (C hem.Commun.2007,40,4137~4139). Sc complex (CAT B See Figures 2 (1H NMR) and 3 (13C NMR) in the document.

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

[0151] [ka] Synthesis of Sc(CH2C6H4NMe2-o)3: Anhydrous ScCl3 (1.938g, 12 LiCH2C6H4NMe2-o( A 20 mL solution of 5.423 g, 28.43 mmol, 3 equivalents of THF is slowly dissolved at room temperature. The mixture was added. After stirring this mixture for 30 minutes, the solvent was removed under reduced pressure. The residue was 40 The solution was dissolved in mL of toluene, then filtered to remove the lithium salt. The solvent was then filtrated under reduced pressure. Remove from the substrate, thoroughly wash the residue with ether, filter, and dry to obtain a fine yellow product. Obtained as a solid. Yield = 2.17 g (38%). 1H NMR (400 MHz, benzene). -d6)δ7.05~6.94(m,6H),6.85~6.76(m,6H),2.2 8(s,18H), 1.67(s,6H). 13C NMR (101MHz, benzene- d6)δ143.43,143.15,129.41,126.67,119.95,1 17.89, 52.30~46.32(m), 45.04.

[0152] Synthesis of Ti complexes:

[0153] [ka] CAT D: The following procedure was performed in a glove box under a nitrogen atmosphere. A stirring rod was equipped. In an oven-dried 40 mL vial, Cp * TiCl3 (300mg, 1.37 mmol) was dissolved in 5.2 mL of anhydrous diethyl ether. This solution was then placed in a glove bottle. It was cooled in a freezer for 30 minutes. Lithium 2,4,6-trimethoxyphenoxide ( Add 184 mg (1.37 mmol) to the CpTiCl3 solution while stirring vigorously. The reaction mixture was heated to room temperature and stirred overnight at room temperature. Then, the reaction product was filtered. The solid was then washed with 2 mL of anhydrous diethyl ether. The filtrate and washing solution were combined. The material was removed under vacuum, and the red solid was isolated. This material was analyzed by 1H NMR spectroscopy. The crude material appeared to contain unreacted CpTiCl3. The crude product was prepared in the smallest possible amount. It was dissolved in methylene chloride, and then this solution was layered with ether. This solution was placed in a freezer. It was left overnight. The desired complex was isolated as red crystals (250 mg, 57%). The product was divided into 1H NMR spectroscopy [(400MHz,C6D6)δ6.57(s,2H),6.01(s, The analysis was performed using [5H), 2.16(s,6H), and 2.08(s,3H)].

[0154] [ka]

[0155] CAT E: The following procedure was performed in a glove box under a nitrogen atmosphere, equipped with a stirring rod. In an oven-dried 40 mL vial, Cp * TiCl3 (400mg, 1.38m) Dissolve (mol) in 19 mL of anhydrous diethyl ether. This solution was placed in a glove box. It was cooled in the freezer for 30 minutes. Lithium 2,4,6-trimethoxyphenoxide (19 (6 mg, 1.38 mmol) is mixed vigorously with Cp * Added to TiCl3 solution The reaction mixture was heated to room temperature and stirred overnight at room temperature. Then, the reaction product was filtered. The solid was washed with 5 mL of anhydrous diethyl ether. The filtrate and washing solution were combined. Volatile substances The undercoat was removed under vacuum, and the red solid was isolated. This material was analyzed by 1H NMR spectroscopy. The crude product was dissolved in the smallest amount of methylene chloride, and this solution was then layered with ether. This solution was left in the freezer overnight. The desired complex was isolated as red crystals (301 mg, 56%). The product was analyzed by 1H NMR spectroscopy [(400MHz, C6D6)δ6.61(s, (2H), 2.29(s,6H), 2.10(s,3H), 1.90(s,15H) That's what I analyzed. Note: This material appears to cocrystallize with the desired compound. Unresponsive Cp * It contained TiCl3.

[0156] [ka]

[0157] CAT F: In an oven-drying vial equipped with a stirring rod, Cp * TiCl3(200 (mg, 0.69 mmol) was dissolved in 7.5 mL of anhydrous ether. The solution was then prepared in a glove box. Placed in the freezer for 20 minutes. Then, removed the vial from the freezer. Cooled and stirred. To the mixed solution, add a 2.0 M solution of benzyl magnesium chloride (1.0 mL, 2.1 mmol) The solution was added dropwise. The reaction mixture was slowly warmed to room temperature, and the reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered to remove the solid, and the yellow solution was reduced under vacuum. The result was a reddish-brown color. The solid was isolated and analyzed by ¹H NMR spectroscopy [¹H NMR (400 MHz, Benzene-d 6)δ6.93(t,J=7.3Hz,3H),6.83~6.78(m ,5H),2.74(d,J=2.7Hz,6H),1.62(d,J=0.7Hz,1 (3H) Note: Aromatic protons overlapped with the benzene solvent peak.

[0158] Synthesis of Al-DHCSA

[0159] [ka] Al(iBu)3 (3.00g, 15.13 mmol) and EN in a glass vial. B (3.030 g, 25.21 mmol) was mixed with p-xylene (7 mL). The mixture was heated to 130°C for 20 minutes. The elimination of i-butene was allowed. Then, p, m-Divinylbenzene (Alfa Aesar 80:20) (1.313g, 10.0 Add 8 mmol of the mixture, equilibrate the mixture at 130°C for a further 3 hours, and then at room temperature. It was cooled to room temperature. After the reaction time (3 hours), the temperature of the mixture was cooled to room temperature, and the resulting homogeneous solution was obtained. The liquid was used as DHCSA.

[0160] Other chain shuttle agents (CSAs) used in the experiments described herein include dieth Diethyl zinc (DEZ) and triethyl aluminum (T EA) is one example. ZnAl-DHCSA (see International Publication No. 2018 / 064546).

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

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

[0163] CAT B's styrene polymerization capability in the presence of various model chain shuttling agents We screened for this using PPR. Figure 4 shows that CAT B undergoes styrene polymerization (CSA It shows high efficiency against (shi), and the catalytic activity is TEA (CSA = 25 μmole) The third circle from the top in CSA=100μmole and (4th circle) or Al-Zn DHCSA (CSA=25μmole, upper two circles) The effect of adding the circle (the upper two circles at CSA = 100 μmole) This demonstrates that it is not the case. In this particular study, catalytic activity was found to be in the presence of DEZ. It was low (two merged lower circles at CSA=25μmole, and CSA= (Two merged lower circles in 100 μmole). The data in Figure 5 shows the results after CSA addition. However, this has shown that it results in a decrease in molecular weight, and that the catalyst is effective in chain cycles. This indicates involvement in cattailing. Furthermore, Al-Zn DHCSA is CSA Two upper circles at =25 μmole and two upper circles at CSA=100 μmole It is represented by circles. TEA is two merged under CSA=25μmole It is represented by a square circle and two merged lower circles at CSA = 100 μmole. .

[0164] Table 1 shows the results of 100 μmole of CS for styrene polymerization by CAT B at 105°C. The effect of adding A is further demonstrated. Furthermore, the polymerization of styrene by CAT B is shown in the presence of 1-octene. The tests were conducted under the following conditions: T=105℃, Catalyst input amount = 0.25 μmole, [styrene] = 2.1 M (in toluene), t = 15 min As shown in Table 1, catalytic activity and molecular weight are affected by the addition of 1-octene. However, this is because CAT B is transferred from the first reactor to the second reactor, and the residual alpha- This demonstrates compatibility with olefin monomers. This data shows that catalyst CAT B is compatible with the above-mentioned Demonstrate that the desired second reactor (R2) catalyst criteria (a) to c)) are met ("Invention" (See "Detailed explanation").

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

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

[0167] [Table 2]

[0168] III. Analysis of vinylarene enrichment (hard block) and vinylarene deficiency (soft block) Block analysis Batch reactor polymerization setup The batch reactor setup is controlled by a process control system and consists of 600 mL units. It consisted of a per reactor. The reactor had an electric heating jacket and an internal cooling unit for temperature control. It is equipped with an electric heating trace transfer line between the reactor and the reactor dump pot. There is an option to add the solvent or monomer from a removable 1-liter (50 mL) cylinder. Three supplies were available. This cylinder in an inert (N2) glove box The contents were introduced into the reactor and transferred to the reactor via nitrogen injection. Catalyst components and chain shuttle The ring agent is prepared in an inert glove box and transferred from a 50 mL cylinder via nitrogen transfer. It was transferred to the reactor. The "1-octene cylinder" was filled from the refining plant supply. Chilene was supplied from Airgas as a high-purity grade. For further purification, 1 - Octene and ethylene in an in-line bed of activated alumina, 13x molecular sieve, and Q5 material. It was passed through. The high-pressure nitrogen used for catalyst injection and purging was of ultra-high purity grade. The ethylene is degassed, and the styrene feed is passed through a neutral alumina plug immediately before being added to the reactor. The inhibitor was removed by allowing it to pass through the solution.

[0169] Ethylene, 1-octene, styrene polymerization: Reactivity of CAT B (vinylarene enrichment) Degassed anhydrous toluene is poured from a nitrogen-pressurized solvent cylinder using a mass flow meter. It was added to a 00 mL per reactor, and the reactor stirrer was set to 450 rpm. Styrene was added. It was injected through a cylinder pressurized with high-pressure nitrogen. When used, a preset amount of 1-octane was injected. The nitrogen was added to the reactor from a nitrogen-pressurized cylinder using a flow meter. Once the starting temperature set to 20°C is reached, a predetermined amount of ethylene is introduced using a flow meter. The catalyst was added to the vessel, and then the activated catalyst solution was added. Cp * ScR2(CAT B)(Normal pitch The input volume is 22 μmol (Sc) of a pre-prepared toluene solution containing "amines and amines" in toluene. A 0.006 M solution of methyl (hydrogenated beef tallow alkyl), tetrakis(pentafluoromethyl) Nyl-borate(1-) activator (1.0-1.2 equivalents), and MMA in toluene. A catalyst solution was prepared by adding a 0.05 M solution (10 equivalents) of O-3A. Each "equivalent" is relative to one equivalent of CAT B.

[0170] Throughout the desired 10-minute run time, the pressure throughout the reactor is controlled to a programmed setpoint. While doing so, the ethylene flow was started at 200 mg / min. After the mixing time, the stirrer was stopped. The contents of the reactor were transferred to a dump pot. The contents of the pot were poured into methanol, and the mixture was added. The mixture was stirred. The polymer precipitate was filtered and dried in a vacuum oven at 130°C for 6 hours. The conditions for acceptance and polymer properties are shown in Table 3 below. See also Table 4. The ingredients in Tables 3 and 4 Turpolymers AR1 to AR12 each have, for example, a monomer composition of ethylene / o Vinylarene enrichment of kuten / -styrene diblock or triblock interpolymers (Hard block) (AR) segment, stereoregularity of polymerized vinylarene, Tm and Represents Tg

[0171] [Table 3] General: Catalyst = 22 μmol [CAT B], 1.2 × "amines, bis(hydrogenated beef tallow) Methyl tetrakis(pentafluorophenyl)borate (1-), 10 × M MAO, T=120℃, t=10min, V=600mL

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

[0173] Ethylene, 1-octene, styrene polymerization: Reactivity of CAT A (vinylarene deficiency) Degassed anhydrous toluene is poured from a nitrogen-pressurized solvent cylinder using a mass flow meter. It was added to a 00 mL per reactor, and the reactor stirrer was set to 450 rpm. Styrene was added. It was injected through a cylinder pressurized with high-pressure nitrogen. A predetermined amount of 1-octene was injected via flow Using a measuring device, the substance was added to the reactor from a nitrogen-pressurized cylinder. The reactor was open at 120°C. Once the initial temperature set point is reached, a predetermined amount of ethylene is added to the reactor using a flow meter. Next, the activated catalyst solution was added. CAT A catalyst was added in a pre-prepared toluene solution. In the ene, "amines, bis(hydrogenated tallow alkyl)methyl 0.006 M solution, tetrak S(pentafluorophenyl)-borate(1-) activator (1.0-1.2 equivalents), And by adding a 0.05 M solution (10 equivalents) of MMAO-3A in toluene A catalyst solution was prepared. Each "equivalent" is relative to one equivalent of CAT A.

[0174] Throughout the desired 10-minute run time, the pressure throughout the reactor is controlled to a programmed setpoint. While doing so, the ethylene flow was started at 200 mg / min. After the mixing time, the stirrer was stopped. The contents of the reactor were transferred to a dump pot. The contents of the pot were poured into methanol, and the mixture was added. The mixture was stirred. The polymer precipitate was filtered and dried in a vacuum oven at 130°C for 6 hours. The conditions for compatibility and polymer properties are shown in Table 5 below. See also Table 6. Interpolymers in Table 6 AP1 to AP11 are, for example, in the monomer composition ethylene / octene / sodium Vinylarene deficiency in Chilenzblock or Triblock interpolymers (soft blocks) The (AP) segment represents the stereoregularity, Tm, and Tg of the polymerized vinylarene.

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

[0176] [Table 6] Note: The mol% values ​​for styrene in the table are for cases where back-to-back styrene does not exist. Based on this premise, the calculation was performed to include only the styrene present in the E / O / S terpolymer. This is based on the observation that CAT A does not polymerize styrene under homopolymerization conditions. Atactic polystyrene was assumed to arise from thermally generated PS. a Inter Each mol% is based on the total number of moles of polymerization monomers in the polymer, and vinylarene deficiency (so (Represents a soft block.)

[0177] IV. Double catalytic polymerization using chain shuttle agents Batch reactor polymerization setup (dual-per-reactor) - solution polymerization The polymerization setup consists of two reactors, namely a 600 mL per reactor (reactor 1, It consists of R1) and a 2.0L per reactor (reactor 2, R2), each with a process control system Controlled by Tem. Both reactors have electric heating jackets and internal cooling for temperature control. Coils, and electric heating trace transfer lines between reactors and from each reactor to the reactor dump pot. It is equipped with a removable "1L sample cylinder" into which the solvent or monomer is added. Three feed options were available in any of the reactors. The contents are placed in an inert (N2) glove box and injected with nitrogen. It was transferred to the reactor. The catalyst components and chain shuttle agent were placed in an inert glove box. The mixture was prepared and transferred from a "50 mL cylinder" to each reactor via nitrogen transfer. ISOPAR -E and 1-octene cylinders were filled from the refinery plant feed. Ethylene was high Supplied from Airgas as a purity grade. For further purification, 1-octene and Ethylene was passed through an in-line bed of activated alumina, a 13x molecular sieve, and Q5 material. The high-pressure nitrogen used for catalyst injection and purging was of ultra-high purity grade.

[0178] Batch reactor-solution polymerization-composition containing Triblock 2 In a 600 mL Par reactor (R1 (first reactor)), 4 mL of ISOPAR-E A solution of Al-DHCSA (1.5 mL, 578 μmol) was filled by high-pressure nitrogen injection. ISOPAR-E (121.4g) was dissolved under nitrogen pressure using a mass flow meter. The mixture was added to R1 from the catalyst cylinder, and the reactor stirrer was set to 450 rpm. 1-octene (20.4g) is added to a nitrogen-pressurized cylinder using a flow meter, and R1 It was added. When the reactor reached the starting temperature set point of 120°C, a predetermined amount of ethylene was added. (7.1g) was added to the reactor using a flow meter, and then the activated catalyst solution was added. 0.25 mL of a 0.005 M solution of CAT A in toluene, and "amines, amines, S(hydrogenated beef tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate( 1) 0.25 mL of a 0.006 M solution of MMAO-3A in toluene By adding the solution to vials containing 0.25 mL and 4 mL of toluene, the catalyst solution is dissolved. The liquid was prepared.

[0179] Throughout the desired run time of 10 minutes (for R1), the total pressure in the reactor was 192.7 ps. While controlling with ig, the ethylene flow was started at 200 mg / min during the execution time of R1. In the "2.0L Parr" reactor (R2, the second reactor), a small silicate was pressurized with nitrogen. 200 mL of toluene was filled via the duct. The stirrer R2 was set to 450 rpm. The starting temperature setting point for R2 was set to 120°C. The execution time (10 minutes) in R1 was completed. At that time, the stirrers in both reactors (R1 and R2) were stopped. Preheat the contents of R1. R1 was pressurized with nitrogen to transfer to R2 via the line below. CAT A (less than 10 minutes) The lifespan of this catalyst was consumed when it entered the second reactor.

[0180] After transferring the contents, the R2 stirrer was restarted. Styrene monomer (5 mL, 0.044 mL) The ol) was injected into R2 via a small cylinder pressurized with nitrogen, and immediately afterwards, 200m An activated catalyst solution was added in L of toluene. The Sc complex CAT was added in 45 μmol of toluene. B. Amines, bis(hydrogenated tallow alkyl)methyl in 0.083 mL of toluene, 0.0 of tetrakis(penta-fluorophenyl)borate (1-) (0.5 μmol) 0.06M solution, 0.05M solution of MMAO-3A (5 μmol) in 0.100 mL of toluene The catalyst solution is prepared by adding the liquid to a vial containing 4 mL of toluene. After the catalyst was added, heat generation was observed. The contents of R2 were heated at 120°C for 1 hour (in the case of R2). The mixture was stirred for the duration of the reaction. After the reaction time, the stirrer in R2 was stopped, and the contents of R2 were removed. The contents were transferred to a dump pot. The contents of the pot were poured into methanol and stirred overnight. Polymer precipitation. Contains ethylene / octene / styrene triblock terpolymer (Triblock 2) The composition was filtered and dried in a vacuum oven at 130°C for 6 hours (yield 11.6g). The NMR profiles are shown in Figure 7 (1H NMR) and Figure 8 (13C NMR). Based on the peak integral, the composition contains 30% by weight of polymerized styrene, based on the weight of the composition. It contained phenyl C-1 (δ145) in syndiotactic polystyrene blocks. Figure 8 shows peaks indicating 0.50), Sαα (δ 43.35), and Tββ (δ 40.61). show.

[0181] Additional polymer composition Additional polymer compositions are described below. Polymerization conditions and polymer composition properties are shown in Table 7 and Table List them in section 8.

[0182] Triblock 1 (contains ethylene / octene / styrene triblock 1 terpolymer) Using the above process for Triblock 2, except for the following changes, the composition (which is used) is prepared. Polymerization was carried out. In a 600 mL Par reactor (R1), 4 mL of Al- in ISOPAR-E was added. A solution of DHCSA (1.5 mL, 690 μmol) was filled by high-pressure nitrogen injection. 3 Throughout the desired run time of 0 minutes (for R1), the total pressure in the reactor was 192.7 psig. While controlling the flow, the ethylene flow was started at 200 mg / min. Styrene monomer (5m L (0.690 mmol) is injected into R2 through a small cylinder pressurized with nitrogen, and Immediately afterward, an activated catalyst solution in 200 mL of toluene was added. A 0.0021 M solution of the Sc complex CAT B (0.5 μmol) in 0.083 mL Toluene contains amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafull 0.006 M solution of olophenyl)-borate (1-) (0.5 μmol), 0.100 A 0.05 M solution of MMAO-3A (5 μmol) in mL of toluene is added to 4 mL of toluene. A catalyst solution was prepared by adding it to a vial containing . Polymer precipitate ( The composition containing Liblock was filtered and dried in a vacuum oven at 130°C for 6 hours. Yield 13.0g). AR-AP bond (vinylarene enriched (hard block)-vinylarene) To detect lane shortage (soft block) S), DiscovIR™ (FT I R) and a triple detector (dRI, DV, LS) connected to a PDA (UV-Vis) The Malvern 305a HT GPC was used. The GPC data is shown in Figure 9. [For dual-batch reactor execution, showing unbonded PS, unbonded EO, and bonded PS] [HT GPC dRI / UV dual detector response]. As can be seen in Figure 9, block Interpolymer formation appears as a "bound PS" peak.

[0183] Triblock 3 (contains ethylene / octene / styrene triblock co-polymer) The composition) is modified as shown above, except for the changes described in Table 7 below. Prepared according to the process for 2. Diblock 1 (ethylene / octene / styrene di A composition containing a blocker polymer, with TEA (400 μmole) as CSA. Except for the use of the above-mentioned Triblock 2 and the changes listed in Table 7 below, Prepared according to the following process: Diblock 2 (ethylene / octene / styrene diblock) A composition containing a culter polymer is used, with DEZ (100 μmole) as the CSA. Except for the changes made to Triblock 2 as shown above, and the changes listed in Table 7 below, Prepared according to Rothes's method.

[0184] Instead of CSA, they are ethylene / octene random copolymer and syndiotactic, respectively. Two reactor blends (IB-1 and IB-2), which are ethylene polymers, were each subjected to A Without performing a preliminary injection of l-DHCSA, and with the exception of the changes listed in Table 7 below, the above triblock It was prepared using the same process as used for C2.

[0185] [Table 7]

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

[0187] GPC research Refer to the GPC procedure in the section on the above test methods. Infrared concentration / composition detector (IR-5) or PolymerChar (Valencia, Spain) High-temperature gel permeation chromatography A Graph system was used to determine MW and MWD. ​​The support solvent was 1,2,4-tri It was chlorobenzene (TCB). The autosampler and detector compartment was The operation was performed at 160°C, and the column compartment was operated at 150°C. GPC column set Calibration was performed using 21 polystyrene standard materials with narrow molecular weight distributions. The rfile is shown in Figures 10a and 10b. The GPC results are shown in Tables 7 and 9. Double inversion The molecular weight distribution of the polymer is the equivalent molecular weight of polystyrene. See Table 9. To enable extraction, compositions containing triblock polymers are used in the reactor blend (IB-1 It has a broader MWD compared to ).

[0188] [Table 9]

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

[0190] [Table 10]

[0191] V. Atactic Polystyrene (aPs): CAT C Polymerization experiment: In a glass vial, toluene (final volume 8 mL), styrene (1 mL), and A magnetic stirring rod was inserted. CAT C (5µmol), "amines, bis(hydrogenated beef tallow aluminum) Methyl tetrakis(pentafluorophenyl)borate (1-) (1.2 equivalents) Then, either TEA or DEZ (0, 25, or 100 umol) is added to the solution sequentially. This mixture was heated at 100°C for 1 hour, and then quenched in methanol. The mixture was then cooled. The polymer was collected by filtration and dried under vacuum. The results are shown in Table 11. The GPC profile is shown in Figure 12. These results are obtained in the presence of DEZ or TEA. As indicated by the decrease in molecular weight and MWD(Mw / Mn) in the chain, This indicates that a shuttling process is occurring.

[0192] [Table 11]

[0193] VI.Ti complex PPR screening of Ti complexes (CAT D, CAT E, and CAT F) As described below, the feasibility of styrene polymerization activity and the chain shuttle of each polymerization catalyst To demonstrate the ring, a parallel pressure reactor (PPR) system was employed. CSA input amount The activity and molecular weight of a given styrene polymerization catalyst candidate were investigated. The CSA examined was: Each of the following serves as a model for a polymerylalkylzinc species or a polymerylaluminum species. Zinc (DEZ, 25 μmole or 100 μmole) and triethylaluminum ( The screening conditions were TEA, 25 μmole, or 100 μmole. The result was as follows: [ISOPAR-E+MMAO-3A+T]+(styrene+C SA+ "Amine, bis(hydrogenated beef tallow alkyl)methyl, tetrakis(pentafluorophosphate) (Nyl)borate (1-) + catalyst). Catalyst input amount = 0.25 μmole. MMAO-3A input Input volume = 50 μmol. T = 75°C and 105°C, t = 15 min, [styrene] = 2.1 M ( (In toluene).

[0194] The styrene polymerization of CAT D in the presence of the chain shuttle agent mentioned above. Capabilities were screened using PPR. Figure 13 shows the results after CSA addition. This demonstrates that it leads to a reduction in molecular weight, and that the catalyst is effective in chain shuttling. This indicates that it is involved in styrene polymerization. CAT D has a relatively low efficiency. This shows that CAT E, in the presence of the chain shuttle agent mentioned, The polymerization ability was screened using PPR. Figure 14 shows the polymerization ability after the addition of CSA. As a result, it has been demonstrated that it leads to a decrease in molecular weight, and that the catalyst is effective in chain shuttles. This indicates involvement in the ring. CAT E is relatively low for styrene polymerization. It shows high efficiency. CAT F, in the presence of the chain shuttle agent mentioned, Styrene polymerization ability was screened using PPR. Figure 15 shows the results with the addition of CSA. As a result, it has been demonstrated that this leads to a decrease in molecular weight, and that the catalyst effectively chain This indicates that it is involved in shuttleping. CAT F is relative to styrene polymerization. It exhibits relatively low efficiency.

Claims

1. Ethylene / vinyl alloy block interpolymer and / or ethylene / vinyl alloy A process for forming a composition comprising a laentriblock interpolymer, At least the following steps: A) In reactor A, the following: chemical formula S1, chemical formula S2, chemical formula S3, chemical formula S4, or The is selected from chemical formula S5, and at least the following: a) in the presence of a metal complex S, eth The compound comprises len, and optionally alpha-olefins and optionally vinylarenes. , a step of polymerizing mixture A, 【Chemistry 1】 where M １ is titanium (Ti), zirconium (Zr), or hafnium (Hf), or A metal selected from among, the metal being in a formal oxidation state of +2, +3, or +4. the law of nature, Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substitution or non-substitution (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each X is They are independently monosect or bisect ligands. n is 0, 1, or 2, and optionally, when n is 1, X is a bidentate ligand. It could be, R １ This is a bridging group containing 2 to 41 atoms other than hydrogen, and R is optionally selected. １ and M The bond between them is a pi bond, R ２ is, independently, a substituted or unsubstituted (C １ -C ３０ ) hydrocarbyl group, or a substituted Or non-substitution (C １ ~C ３０ ) is a heterohydrocarbyl group, J １ N and R １ A bridging group that connects and contains 2 to 40 atoms other than hydrogen. Furthermore, optionally, the crosslinking group is connected to the metal (M) via electron-donating bonds. １ ) and mutual work It contains N atoms that can be used, The aforementioned metal complex is charge-neutral overall. 【Chemistry 2】 In the formula, M １ It is made from titanium (Ti), zirconium (Zr), or hafnium (Hf). A selected metal, which is in a formal oxidation state of +2, +3, or +4. 、 Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substitution or is non-substitutive (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, each X independently And it is a monosect ligand or a bisect ligand, n is 0, 1, or 2, and optionally, when n is 1, X is a bidentate ligand. Possible, R ３ and R ４ Each of these independently can be substituted or not substituted (C ６ ~C ２０ ) aryl group, or substitution or non-substitution (C ５ ~C ２０ ) Selected from heteroaryl groups, N and N' are bridging groups J containing 2 to 40 atoms other than hydrogen. ２ It is connected by , optionally, the crosslinking group interacts with the metal via electron-donating bonds. It contains an N atom that can form The aforementioned metal complex is charge-neutral overall. 【Transformation 3】 In the formula, M １ It is made from titanium (Ti), zirconium (Zr), or hafnium (Hf). A selected metal, which is in a formal oxidation state of +2, +3, or +4. 、 Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substitution, non-position Exchange (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, each X independently It is a monosect ligand or a bisect ligand. n is 0, 1, or 2, and optionally, when n is 1, X is a bidentate ligand. Possible, R ５ is either substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl group, or substituted or non-hydrocarbyl group Substitution (C １ ~C ３０ ) Heterohydrocarbyl group, -Si(R Ｃ ) ３ , or -H, T １ is -O-, -S-, -N(R Ｎ )-, or-P(R Ｐ ) - Selected from, t is either 1 or 2. T １ And N contains 4 to 50 atoms other than hydrogen, J ３ By the crosslinking group represented by They are connected in this way. Each R in equation S3 Ｐ , R Ｎ , and R Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, (C １ ~C ３０ ) Heterohydrocarbyl, or -H, The aforementioned metal complex is charge-neutral overall. 【Chemistry 4】 In the formula, M １ This is a metal selected from zirconium (Zr) or hafnium (Hf). Furthermore, the aforementioned metal is in a formal oxidation state of +2, +3, or +4. Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substitution or is non-substitutive (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, each X independently And it is a monosect ligand or a bisect ligand, n is 0, 1, or 2, and optionally, when n is 1, X is a bidentate ligand. Possible, -T ２ - and -T ３ Each of these is independently -O-, -S-, and -N(R) Ｎ ) - or - P(R) Ｐ ) - Selected from, R ６ and R ２１ Each of these independently represents -H, substitution, or non-substitution (C １ ~C ４０ ) Hydro Calville, substituted or unsubstituted (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ 、-Ge(R Ｃ ) ３ 、-P(R Ｐ ) ２ 、-N(R Ｎ ) ２ 、-OR Ｃ 、-SR Ｃ 、-N O ２ 、-CN、-CF ３ 、R Ｃ S(O) - R Ｃ S(O) ２ -、(R Ｃ ) ２ C N - R Ｃ C(O)O-、R Ｃ OC(O)-、R Ｃ C(O)N(R)-、(R Ｃ ) ２ NC(O)- , halogen, radical having formula (I), radical having formula (II), and formula (III Selected from the group consisting of radicals having ), 【Transformation 5】 wherein, R ２２～２６ , R ２７～３４ , and R ３５～４３ each independently represents a substituted or k is non-substitution (C １ ~C ４０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ４０ ) Hetero Drocarbil, -Si(R Ｃ ), -Ge(R ３ ), -P(R Ｃ ), -N(R ３ ), -P(R Ｐ ), -N(R ２ ), -N(R Ｎ ), ２ 、-N=CHR Ｃ 、-OR Ｃ 、-SR Ｃ 、-NO ２ 、-CN、-CF ３ 、R Ｃ S(O)- 、R Ｃ S(O) ２ -、(R Ｃ ) ２ C=N-、R Ｃ C(O)O-、R Ｃ OC(O)-、R Ｃ C(O)N(R) Ｎ ) -, (R Ｃ ) ２ Selected from NC(O)-, halogen, or -H, R ７～２０ Each of these independently can be substituted or not substituted (C １ ~C ４０ ) Hydro-carb Lu, substitution or non-substitution (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ 、-P(R Ｐ ) ２ 、-N(R Ｎ ) ２ 、-N=CHR Ｃ 、-OR Ｃ 、-S R Ｃ 、-NO ２ 、-CNN、-CF ３ ,R Ｃ S (O) - R Ｃ S (O) ２ -、(R Ｃ ) ２ C =N-、R Ｃ C(O)O-、R Ｃ OC(O)-、R Ｃ C(O)N(R Ｎ )-、(R Ｃ ) ２ Selected from NC(O)-, halogen, or -H, J ４ is either substituted or non-substituted (C １ ~C ４０ ) Hydrocarbylene or substituted or unsubstituted Exchange (C １ ~C ４０ ) is a heterohydrocarbylene, and the substituted or unsubstituted (C １ ~C ４０ Hydrocarbylene is a compound of the group T in chemical formula S4. ２ and T ３ Linking 1 to 10 carbon atoms The part containing the carbon atom linker skeleton (J ４ (which are joined together) or substitute Or non-substitution (C １ ~C ４０ ) Heterohydrocarbylene is a compound of the group T in chemical formula S4. ２ and T ３ It has a portion that includes a linker skeleton of 1 to 10 atoms that connects the 1 to 10 atoms Each of the 1 to 10 atoms in the linker skeleton is independently a carbon atom or a heteroatom group. It is an atomic group, and each heteroatom group is independently O, S, S(O), S(O) ２ , Si(R Ｃ ) ２ , Ge(R Ｃ ) ２ , P(R Ｃ ), or N (R Ｃ ) and each R Ｃ It is, independently, placed Replacement or non-substitution (C １ ~C ３０ ) Hydrocarbyl, or substituted or unsubstituted (C １ ~C ３０ ) is a heterohydrocarbyl, and each R in chemical formula S4 Ｐ , R Ｎ , and the remaining R Ｃ teeth, Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted ( C １ ~C ３０ ) Heterohydrocarbyl, or -H, The aforementioned metal complex is either charge-neutral overall, or 【Transformation 6】 In the formula, M １ It is made from titanium (Ti), zirconium (Zr), or hafnium (Hf). A selected metal, which is in a formal oxidation state of +2, +3, or +4. 、 Each X is independently substituted or non-substituted (C １ ~C ３０ ) Hydrocarbyl, substitution or is non-substitutive (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, each X independently And it is a monosect ligand or a bisect ligand, n is 0, 1, or 2, and optionally, when n is 1, X is a bidentate ligand. Possible, R ４４～５１ Each of these can be independently substituted or not substituted (C １ ~ ４０ ) Hydrocalcyl , substitution or non-substitution (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ , or - Selected from H, and arbitrarily selected, R ４４～５１ Two or more of these units are linked together, Therefore, the cyclopentadienyl group is a substituted or unsubstituted indenyl group, or substituted or R is an unsubstituted fluorenyl group, Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) Heterohydrocarbyl, or - Selected from H, O and O contain 1 to 30 atoms other than hydrogen, J ５ By the crosslinking group represented by They are connected, The aforementioned metal complex is charge-neutral overall, step, B) In reactor B, at least the following: b) Select from the following chemical formulas H1 or H2 In the presence of a selected metal complex H, ethylene, vinylarene, and The step of optionally polymerizing a mixture B containing an alpha-olefin, 【Transformation 7】 In the formula, M ２ These are elements from Ti, Sc, Y, or the lanthanide series. R １ , R ２ , R ３ , R ４ , and R ５ Each of these independently corresponds to H, or substitution or non-substitution. A hydrocarbyl group, a substituted or unsubstituted heterohydrocarbyl group, Q １ Q ２ , and Q ３ Each of these independently consists of a substituted or unsubstituted hydrocarbyl group, A substituted or unsubstituted heterohydrocarbyl group, or a halogen, L is a Lewis base, each n is independently either 0 or 1, and m is an integer between 0 and 3. And, At least one L group and at least one Q group are optionally connected, Selectively, at least one R group and at least one Q group are connected. The aforementioned metal complex is charge-neutral overall. 【Transformation 8】 M ３ The material can be selected from titanium (Ti), zirconium (Zr), or hafnium (Hf). The metal is in a formal oxidation state of +2, +3, or +4. Each Q can be independently substituted or not substituted (C １ ~C ３０ ) Hydrocarbyl, substitution or k is non-substitution (C １ ~C ３０ ) Selected from heterohydrocarbyl or -H, where each Q is independent It is a single-seat ligand or a double-seat ligand. n is 0, 1, or 2, and optionally, when n is 1, Q is a bidentate ligand. It could be, R １ and R ２ Each of these is an independent bridging group containing 2 to 41 atoms other than hydrogen. Optionally, R １ and R ２ Each of these can independently be a substituted or unsubstituted arylene group. -Z １ - and -Z ２ Each of these is independently -0-, -S-, -Se-, -N(R Ｎ )-, or-P(R Ｐ ) - Selected from, -Z １ - and -Z ２ Each of these is independent of the electric It can optionally interact with the metal via child-donating bonding, Z １ and Z ２ J contains 1 to 50 atoms other than hydrogen. ５ Crosslinking group represented by Connected by, R Ｐ and R Ｎ Each of these can be independently substituted or not substituted (C １ ~C ３０ ) Hydrogalbi Lu, substitution or non-substitution (C １ ~C ３０ ) Heterohydrocarbyl, or -H, The aforementioned metal complex is charge-neutral overall. Step A occurs before Step B and involves at least a portion of the reactor products in reactor A. The mixture is transferred to reactor B, or step B occurs before step A and the reaction takes place. At least a portion of the reactor product in reactor B is transferred to reactor A. If step A occurs before step B, at least one chain chatlin The guting agent is supplied into reactor A, If step B occurs before step A, at least one chain chatlin The guting agent is supplied into reactor B, The vinylarene in step A is the same as the vinylarene in step B, The alpha-olefin in step A is the same as the alpha-olefin in step B. The process.

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

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

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

5. The at least one chain shuttle agent is: alkyl zinc compound, alkyl Aluminum compounds, dual-head chain shuttle agents, or combinations thereof A process according to any one of claims 1 to 4, selected from the above.

6. Step A occurs before Step B, according to any one of claims 1 to 5. Seth.

7. Step B occurs before Step A, according to any one of claims 1 to 5. Seth.

8. The ethylene / vinyl anedenid block interpolymer or the ethylene / vinyl Regarding the arene triblock interpolymer, the vinylarene is styrene. The process according to any one of claims 1 to 7.

9. The mixture A comprises the alpha-olefin as described in any one of claims 1 to 8. The loading process.

10. A composition formed by the process described in any one of claims 1 to 9.

11. Ethylene / vinylarene diblock interpolymer or ethylene / vinylarene A composition comprising a triblock interpolymer, wherein the diblock interpolymer However, as shown below, it comprises at least one polymer structure selected from structure 1. The triblock interpolymer is structure 2 or structure 3, as shown below. It comprises at least one polymer structure selected from, and AR indicates vinylarene enrichment. AP refers to a vinylarene deficiency. (AR)-(AP) (Structure 1), (AR)-(AP)-(AR) (Structure 2), (AP)-(AR)-(AP) (Structure 3), Each (AR) segment independently contains ethylene and vinyl in its polymerized form. arenes, and optionally alpha-olefins, Each (AP) segment independently polymerizes into ethylene, optionally in its polymerized form. The material comprises the vinylarene and optionally the alpha-olefin. Each (AR) segment independently contains the polymerized monomer in the (AR) segment. Based on the total number of moles, in the polymerized form, >10 mol% of the vinylarene Includes, Each (AP) segment independently contains the polymerized monomer in the (AP) segment. Based on the total number of moles, in the polymerized form, ≤10 mol% of the vinylarene A composition containing the following:

12. The ethylene / vinyl anedenid block interpolymer or the ethylene / vinyl Regarding the arene triblock interpolymer, each (AR) segment is independent. Based on the total number of moles of polymerized monomers in the (AR) segment, the polymerization form In claim 11, the present invention comprises 15 mol% to <100 mol% of the vinylarene. The composition described.

13. The ethylene / vinyl anedenid block interpolymer or the ethylene / vinyl Regarding the arene triblock interpolymer, each (AP) segment is independent. Based on the total number of moles of polymerized monomers in the (AP) segment, the polymerization form Claim 11 or 12, wherein the present invention comprises 0 mol% to 10 mol% of the vinylarene. The composition described above.

14. The ethylene / vinyl anedenid block interpolymer or the ethylene / vinyl Regarding the arene triblock interpolymer, each (AR) segment is independent. Based on the total number of moles of polymerized monomers in the (AR) segment, the polymerization form In which any of claims 11 to 13, comprising 2.0 mol% to 80 mol% ethylene. The composition described in item 1.

15. The ethylene / vinyl anedenid block interpolymer or the ethylene / vinyl Regarding the arene triblock interpolymer, each (AP) segment is independent. Based on the total number of moles of polymerized monomers in the (AP) segment, the polymerization form In which any of claims 11 to 14, comprising 50 mol% to 100 mol% ethylene. The composition described in item 1.

16. The aforementioned ethylene / vinylalene interpolymer or triblock interpolymer Regarding the polymer, ≥20 mol% of the polymerized vinyl in each (AR) segment The lane is "back to back" in subsegment bb as shown below. It exists in a "to back" configuration. 【Chemistry 11】 (Subsegment bb), the mol% is polymerized vinyl in the (AR) segment. A composition according to any one of claims 11 to 15, based on the total number of moles of arenes.

17. The aforementioned ethylene / vinylalene interpolymer or triblock interpolymer Regarding the polymer, ≥20 mol% of the polymerized vinyl in each (AR) segment The lane is syndiotactic in subsegment sbb as shown below: It exists in a "back-to-back" configuration, 【Chemistry 12】 (Subsegment sbb), the mol% is the polymerized vinyl in the (AR) segment. The composition according to any one of claims 11 to 16, based on the total number of moles of lurene.

18. The aforementioned ethylene / vinylalene interpolymer or triblock interpolymer Regarding the polymer, any of the polymerized vinylarenes in each (AP) segment is In segment bb, there exists a "back-to-back" configuration as shown below. Without doing so, 【Chemistry 13】 (Subsegment bb), the mol% is polymerized vinyl in the (AP) segment. The composition according to any one of claims 11 to 17, based on the total number of moles of arenes.

19. The aforementioned ethylene / vinylalene interpolymer or triblock interpolymer Any of claims 11 to 18, wherein the vinylarene in the polymer is styrene. The composition described in item 1.

20. at least one composition formed from the composition according to any one of claims 10 to 19 An article containing elements.

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