Two reactor chain shuttling reaction of ethylene / vinyl aromatic di- and tri-block interpolymers

Abstract

The invention provides a process for forming a composition comprising an ethylene / vinyl aromatic di- and / or tri-block interpolymer, the process comprising at least the following steps: A) polymerizing a mixture A comprising ethylene and optionally an alpha-olefin and optionally a vinyl aromatic hydrocarbon in the presence of at least the following in reactor A: a) a metal complex S selected from the following formulae S1, S2, S3, S4, or S5 as described herein; B) polymerizing a mixture B comprising ethylene, a vinyl aromatic hydrocarbon and optionally an alpha-olefin in the presence of at least the following in reactor B: b) a metal complex H selected from the following formulae H1 or H2 as described herein; and wherein step A occurs before step B, or vice versa, and feeding at least one chain shuttling agent into the first reactor. The invention provides a composition comprising an ethylene / vinyl aromatic di- or tri-block interpolymer as described herein.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 127,350, filed December 18, 2020, the full text of which is incorporated herein by reference. Background Technology

[0003] The catalytic production of olefin block copolymers (OBCs) via chain shuttle technology has yielded differentiated materials such as INFUSE and INTUNE olefin block copolymers. These copolymers are typically made from ethylene and α-olefins. The production of styrene block interpolymers using chain shuttle technology offers an attractive route for producing high-value polymers using continuous solution polymerization processes. High-value styrene polymers such as SEBS (styrene-ethylene / butene-styrene) are produced in batch processes via anionic polymerization initiated by organolithium compounds. This expensive polymerization involves the sequential addition of monomers followed by costly hydrogenation steps. Chain shuttle technology is needed to produce ethylene / vinyl aromatic diblock and triblock interpolymers using two-reactor continuous solution polymerization.

[0004] A. Valente et al., Angew. Chem., Int. Ed. 2014, 53, 4638-4641, Isoprene-Styrene Chain Shuttling Copolymerization Mediated by a Lanthanide Half-Sandwich Complex and a Lanthanidocene: Straightforward Access to a New Type of Thermoplastic Elastomers, discloses the chain shuttle polymerization of isoprene and styrene using n-butylethyl magnesium, a lanthanide half-sandwich complex, and lanthanidocene. The resulting multiblock structure has alternating hard segments (styrene-rich) and soft segments (isoprene-rich).

[0005] US Patent 2014 / 0088276 (Manufacturing Method for Multidimensional Polymer, and Multidimensional Polymer) discloses the polymerization of stereocontrolled (syndiotactic) block copolymers of styrene-type monomers with conjugated dienes (such as isoprene or butadiene) via chain shuttle technology and coordination chain transfer polymerization. The polymerization is carried out in the presence of a first catalyst and a second catalyst. Each of the first and second catalysts independently comprises: a) a Group 3 metal atom or a lanthanide metal atom, such as Sc; b) a Cp-type ligand containing a substituted or unsubstituted cyclopentadienyl derivative; c) a monoanionic ligand; and d) a neutral Lewis base.

[0006] U.S. Patent 8,623,976 (Polymerization Catalyst Compositions Containing Metallocene Complexes and the Polymers Produced by Using the Same) discloses a catalyst composition comprising: a) a metallocene complex containing:

[0007] i) Group 3 metal atoms or lanthanide metal atoms, such as Sc,

[0008] ii) Cp* ligands of substituted or unsubstituted cyclopentadienyl derivatives,

[0009] iii) Monoanion ligands,

[0010] iv) Neutral Lewis base;

[0011] b) Ionic compounds of non-ligand anions and cations, such as tetra(pentafluorophenyl)borate. This catalyst composition is used to polymerize various polymers, such as ethylene / styrene copolymers (see Examples 11-17). The polymerized styrene can be in the syndiotactic form.

[0012] L. Pan et al., Angew. Chem., Int. Ed. 2011, 50, 12012-12015, Chain-Shuttling Polymerization at Two Different Scandium Sites: Regio- and Stereospecific “One-Pot” Block Copolymerization of Styrene, Isoprene, and Butadiene, disclose chain-shutling polymerization of styrene, isoprene, and butadiene via two different catalysts and a chain shuttler (triisobutylaluminum, TIBA). These catalysts exhibit different monomer selectivity and stereoselectivity in the presence of TIBA, leading to regio- and stereo-oriented copolymerization of styrene, isoprene, and butadiene.

[0013] SSPark et al., Macromolecules 2017, 50, 6606-6616, Biaxial Chain Growth of Polyolefin and Polystyrene from 1,6-Hexanediylzinc Species for Triblock Copolymers, disclose the preparation of triblock copolymers by initiating (anionic) styrene polymerization from polymeryl zincate substances. Polyethylene / polypropylene copolymers are grown from biaxial zincate substances using coordination chain transfer polymerization followed by the addition of an anionic initiator (e.g., Me3SiCH2Li-(pmdeta)) and styrene monomers. The coordination chain transfer polymerization is carried out in the presence of transition metal (e.g., Zr or Hf) complexes. Therefore, anionic polymerization is used to grow polystyrene-terminated blocks that do not exhibit any stereoregularity.

[0014] Paper 18 / 0022852 (Organic Zinc Compound Comprising Polyolefin-Polystyrene Block Copolymer, and Method for Preparing the Same) discloses the preparation of organozinc compounds (such as organozinc compounds of Formula 1 shown herein, and comprising styrene-based polymers or polyolefin-polystyrene block copolymers). The preparation method comprises preparing an intermediate by coordinating polymerization of an olefin monomer using a transition metal catalyst, followed by partial insertion of a styrene monomer into the intermediate via anionic polymerization. The transition metal catalyst comprises Zr metal compounds represented by Formulas 6A and 6B, respectively, shown herein (see paragraphs

[0076] and

[0077] ).

[0015] Y. Luo et al., J. Am. Chem. Soc. 2004, 126, 13910-13911, Scandium Half-Metallocene-Catalyzed Syndiospecific Styrene Polymerization and Styrene-Ethylene Copolymerization: Unprecedented Incorporation of Syndiotactic Styrene-Styrene Sequences in Styrene-Ethylene Copolymers, disclose the polymerization of syndiotactic styrene-ethylene copolymers using scandium half-sandwich complexes. The melt temperature (Tm) of the copolymer can be altered by adjusting the ethylene incorporation, which leads to a decrease in Tm. No chain shuttle was observed when using the Sc catalyst.

[0016] H. Hagihara et al., Polymer Journal 2012, 44, 147-154, Synthesis of Ethylene-Styrene Copolymer Containing Syndiotactic Polystyrene Sequence by Trivalent Titanium Catalyst, discloses the polymerization of syndiotactic styrene-ethylene copolymers using the trivalent titanium catalyst tri(acetylacetone)titanium (Ti(acac)3). The Ti(acac)3 catalyst produces different polymers, which may be attributed to the presence of multiple oxidation sites on the catalyst.

[0017] F. Lin et al., Journal of Polymer Science, Part A: Polymer Chemistry 2017, 55, 1243-1249, Synthesis and Characterization of Crystalline Styrene-b-(Ethylene-co-Butylene)-b-Styrene Triblock Copolymers, disclosed the synthesis and characterization of crystalline styrene-b-(ethylene-co-butene)-b-styrene (SEBS). The cationic rare earth metal complex [(η 5-Flu-CH2-Py)Ho(CH2SiMe3)}(THF) is used for the living polymerization of butadiene and styrene. The sequential addition of styrene, butadiene, and styrene monomers forms SBS triblocks. The SBS triblocks consist of a 1,4 regularized elastic polybutadiene sequence and a syndiotactic polystyrene. The SBS triblocks are then hydrogenated to form SEBS.

[0018] B. Liu et al., Macromolecules 2016, 49, 6226-6231, Regioselective ChainShuttling Polymerization of Isoprene: An Approach to Access New Materials from Single Monomer, discloses the chain transfer polymerization of isoprene using pyridyl-methylenefluorenyl scandium complexes in combination with [Ph3C]B(C6F5)4 and iBu3Al. This polymerization produces high 1,4-selectivity for isoprene. Additional catalyst structures include “pyridyl-methylene-functionalized fluorenyl-coordinated rare earth metal complexes 1-9” as shown therein, wherein the metal is Sc, Y, Lu, Tm, Er, Ho, Dy, Tb, or Gd (see page 6227 (Figure 1)).

[0019] U.S. Patent 8,710,143 (Catalyst Composition Comprising Shuttling Agent for Ethylene Multi-Block Copolymer Formation) discloses the use of the following to polymerize multi-block copolymers: (A) a first metal complex olefin polymerization catalyst, (B) a second metal complex olefin polymerization catalyst capable of preparing polymers with chemical or physical properties different from those of polymers prepared by catalyst (A) under equivalent polymerization conditions, and (C) a chain shuttle. Suitable monomers include ethylene and one or more addition-polymerizable monomers, such as 1-octene and styrene (see column 16, lines 3-32). Suitable catalysts include metal complexes, wherein the metal is selected from groups 3-15, preferably groups 3-10, more preferably groups 4-8, and most preferably group 4 (Ti, Zr, and Hf). See, for example, column 19, lines 61 to column 20, lines 6. Ethylene / styrene multiblock polymers were prepared using catalysts A1 (Hf) and B1 (Zr), as shown therein (see column 85, rows 12-30; column 86, rows 21-52; column 115, rows 21 to 116, rows 23, and tables 27 and 28).

[0020] Other olefin block copolymers (OBCs) and related polymerizations are disclosed in the following references: U.S. Patent 7,915,192; U.S. Patent 8,124,709; U.S. Patent 8,501,885; U.S. Patent 8,716,400; EP1716190B1; EP1926763B1; and EP2582747B1.

[0021] However, there remains a need for chain shuttle technology to produce ethylene / stereoregular vinyl aromatic diblock and triblock interpolymers using continuous solution polymerization in a two-reactor system. The invention below addresses this need. Summary of the Invention

[0022] In a first aspect, a method for forming a composition comprising an ethylene / vinyl aromatic diblock interpolymer and / or an ethylene / vinyl aromatic triblock interpolymer, said method comprising at least the following steps:

[0023] A) Polymerize a mixture A comprising ethylene and optionally α-olefins and optionally vinyl aromatics in reactor A in the presence of at least the following: a) a metal complex S selected from the following: formula S1, formula S2, formula S3, formula S4 or formula S5:

[0024]

[0025] Where M 1 It is a metal selected from titanium (Ti), zirconium (Zr) or hafnium (Hf); and said metal is in an oxidation state of +2, +3 or +4.

[0026] Each X is independently selected from substituted or unsubstituted (C1-C1) groups. 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 () heteroalkyl group or -H; and each X is independently a monodentate or bidentate ligand;

[0027] n is 0, 1 or 2, and X can be a bidentate ligand if n is 1.

[0028] R 1 It is a bridging group containing 2 to 41 atoms other than hydrogen, and wherein optionally, R 1 The bond between M and M is a π bond;

[0029] R 2 Selected from substituted or unsubstituted (C1-C) 30 ) hydrocarbon group or substituted or unsubstituted (C1-C 30 Heterohydrocarbon groups;

[0030] J 1 It connects N and R 1It also contains 2 to 40 bridging groups, excluding hydrogen atoms, and optionally, the bridging groups contain elements capable of bonding with the metal (M) via electron-donating bonds. 1 Interacting N atoms; and

[0031] The metal complexes described therein are generally electrically neutral;

[0032]

[0033] Where M 1 It is a metal selected from titanium (Ti), zirconium (Zr) or hafnium (Hf); and said metal is in an oxidation state of +2, +3 or +4.

[0034] Each X is independently selected from substituted or unsubstituted (C1-C1) groups. 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 () heteroalkyl group or -H; and each X is independently a monodentate or bidentate ligand;

[0035] n is 0, 1 or 2, and X can be a bidentate ligand if n is 1.

[0036] R 3 and R 4 Each of them is independently selected from substituted or unsubstituted (C6-C) 20 ) aryl group or substituted or unsubstituted (C5-C 20 heteroaryl groups;

[0037] N and N are connected by the bridging group J 2 The bridging group comprises 2 to 40 atoms other than hydrogen, and optionally, the bridging group comprises an N atom capable of interacting with the metal via an electron-donating bond; and

[0038] The metal complexes described therein are generally electrically neutral;

[0039]

[0040] Where M 1 It is a metal selected from titanium (Ti), zirconium (Zr) or hafnium (Hf); and said metal is in an oxidation state of +2, +3 or +4.

[0041] Each X is independently selected from substituted or unsubstituted (C1-C1) groups. 30 Hydrocarbon group, substituted, unsubstituted (C1-C) 30 () heteroalkyl group or -H; and each X is independently a monodentate or bidentate ligand;

[0042] n is 0, 1 or 2, and X can be a bidentate ligand when n is 1;

[0043] R 5 Is it substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 heterohydrocarbon groups, -Si(R) C )3 or -H;

[0044] T 1 Selected from -O-, -S-, -N(R) N )- or –P(R P )-;

[0045] t is 1 or 2;

[0046] And among them T 1 and N through J 3 The bridging group represents a connection, wherein the bridging group comprises 4 to 50 atoms other than hydrogen;

[0047] In equation S3, each R P R N and R C Independently, it is either substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 ) heterohydrocarbon group or -H; and

[0048] The metal complexes described therein are generally electrically neutral;

[0049]

[0050] Where M 1 It is a metal selected from zirconium (Zr) or hafnium (Hf); and said metal is in an oxidation state of +2, +3 or +4;

[0051] Each X is independently selected from substituted or unsubstituted (C1-C1) groups. 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 () heteroalkyl group or -H; and each X is independently a monodentate or bidentate ligand;

[0052] n is 0, 1 or 2, and X can be a bidentate ligand when n is 1;

[0053] -T 2 -and-T 3 Each of the following is independently selected from -O-, -S-, -N(R) N )- or –P(R P )-;

[0054] R 6 and R 21 Each is independently selected from the following groups: –H, substituted or unsubstituted (C1-C) 40 ) hydrocarbon group, substituted or unsubstituted (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C 3. -P(R) P )2、-N(R N )2、-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R)-、(R C )2NC(O)-, halogens, groups having formula (I), groups having formula (II), and groups having formula (III):

[0055]

[0056] Where R 22–26 R 27–34 and R 35–43 Each of them is independently selected from substituted or unsubstituted (C1-C1) molecules. 40 ) hydrocarbon group, substituted or unsubstituted (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C 3. -P(R) P )2、-N(R N 2. -N=CHR C -OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R N )-、(R C )2NC(O)-, halogen or -H;

[0057] R 7–20 Each of them is independently selected from substituted or unsubstituted (C1-C1) molecules. 40) hydrocarbon group, substituted or unsubstituted (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C )3、-P(R P )2、-N(R N 2. -N=CHR C -OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R N )-、(R C )2NC(O)-, halogen or -H;

[0058] J 4 Is it substituted or unsubstituted (C1-C) 40 ) alkylene group or substituted or unsubstituted (C1-C 40 ) heteroalkylene group, wherein the substituted or unsubstituted (C1-C 40 The alkylene group has a portion comprising a linker backbone containing 1 to 10 carbon atoms, said portion being linked to the group T in formula S4. 2 and T 3 (J 4 (bonded with it); or the substituted or unsubstituted (C1-C) 40 The heteroalkyl group has a portion comprising a 1-atom to 10-atom linker backbone, said portion being linked to the group T in formula S4. 2 and T 3 Each of the 1 to 10 atoms in the 1-to-10-atom linker backbone is independently a carbon atom or a heteroatom of a heteroatom group, wherein each heteroatom group is independently O, S, S(O), S(O)2, Si(R)2, or S(O)2. C )2、Ge(R C )2、P(R C ) or N(R C ), where each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group or substituted or unsubstituted (C1-C 30 ) heterohydrocarbon group; and each R in formula S4 P R N And the rest of R C Independently, it is either substituted or unsubstituted (C1-C) 30) hydrocarbon group, substituted or unsubstituted (C1-C 30 ) heterohydrocarbon group or -H; and

[0059] The metal complexes described therein are generally electrically neutral; or

[0060]

[0061] Where M 1 It is a metal selected from titanium (Ti), zirconium (Zr), or hafnium (Hf); and

[0062] The metal is in an oxidation state of +2, +3 or +4;

[0063] Each X is independently selected from substituted or unsubstituted (C1-C1) groups. 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 () heteroalkyl group or -H; and each X is independently a monodentate or bidentate ligand;

[0064] n is 0, 1 or 2, and X can be a bidentate ligand when n is 1;

[0065] R 44-51 Each is independently selected from substituted or unsubstituted (C) 1-40 ) hydrocarbon group, substituted or unsubstituted (C1-C 40 heterohydrocarbon group, -Si(R) C )3 or –H; and optionally from R 44-51 Two or more groups are linked such that the cyclopentadienyl group is a substituted or unsubstituted indenyl group or a substituted or unsubstituted fluorenyl group; and wherein R C Selected from substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 Heterohydrocarbon group or -H;

[0066] O and O are connected by J 5 The bridging group represents a connection, wherein the bridging group comprises 1 to 30 atoms other than hydrogen; and

[0067] The metal complexes described therein are generally electrically neutral;

[0068] B) Polymerize a mixture B comprising ethylene, vinyl aromatics, and optionally α-olefins in reactor B in the presence of at least the following: b) a metal complex H selected from formula H1 or H2:

[0069]

[0070] Where M 2It is Ti, Sc, Y, or elements from the lanthanide series;

[0071] R 1 R 2 R 3 R 4 and R 5 Each is independently an H or a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterohydrocarbon group;

[0072] Q 1 Q 2 and Q 3 Each is independently a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterohydrocarbon group, or a halogen;

[0073] L is a Lewis base; and each n is independently 0 or 1; and m is an integer from 0 to 3;

[0074] Optionally, at least one L group and at least one Q group are linked, and optionally at least one R group and at least one Q group are linked;

[0075] The metal complexes described therein are generally electrically neutral;

[0076]

[0077] Where M 3 It is a metal selected from titanium (Ti), zirconium (Zr) or hafnium (Hf); and said metal is in an oxidation state of +2, +3 or +4.

[0078] Each Q is independently selected from substituted or unsubstituted (C1-C1) molecules. 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 () heteroalkyl group or -H; and each Q is independently a monodentate or bidentate ligand;

[0079] n is 0, 1 or 2, and X can be a bidentate ligand when n is 1;

[0080] R 1 and R 2 Each is independently a bridging group comprising 2 to 41 atoms other than hydrogen, and optionally, R 1 and R 2 Each can be an independently substituted or unsubstituted aryl group;

[0081] -Z 1 -and-Z 2 Each of the following is independently selected from -O-, -S-, -Se-, -N(R) N )- or –P(R P -; and where -Z1 -and-Z 2 Each of them can independently and optionally interact with the metal via an electron-donating bond;

[0082] Z 1 and Z 2 By J 5 The bridging group represents the connection, and the bridging group comprises 1 to 50 atoms other than hydrogen.

[0083] Where R P and R N Each is independently either substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 ) heterohydrocarbon group or -H; and

[0084] The metal complexes described therein are generally electrically neutral; and

[0085] Step A occurs before step B, and at least a portion of the reactor product in reactor A is transferred to reactor B; or step B occurs before step A, and at least a portion of the reactor product in reactor B is transferred to reactor A; and

[0086] If step A occurs before step B, then at least one chain shuttle is fed into reactor A; and

[0087] If step B occurs before step A, then at least one chain shuttle agent is fed into reactor B; and

[0088] Wherein the vinyl aromatic hydrocarbon in step A is the same as the vinyl aromatic hydrocarbon in step B; and the α-olefin in step A is the same as the α-olefin in step B.

[0089] In a second aspect, a composition comprising an ethylene / vinyl aromatic diblock copolymer or an ethylene / vinyl aromatic triblock copolymer, said diblock copolymer comprising at least one polymer structure selected from structure 1 shown below, and said triblock copolymer comprising at least one polymer structure selected from structure 2 or structure 3 shown below, wherein AR refers to vinyl-rich aromatics and AP refers to vinyl-poor aromatics:

[0090] (AR)-(AP)(Structure 1),

[0091] (AR)-(AP)-(AR)(Structure 2),

[0092] (AP)-(AR)-(AP)(Structure 3); and

[0093] Each (AR) segment independently comprises, in polymeric form, ethylene, the vinyl aromatic hydrocarbon, and optionally an α-olefin; and

[0094] Each (AP) segment independently comprises, in polymeric form, ethylene, optionally the vinyl aromatic hydrocarbon, and optionally the α-olefin; and

[0095] Each (AR) segment independently contains >10 mol% of the vinyl aromatic hydrocarbon in polymeric form, based on the total molar number of polymeric monomers in the (AR) segment; and

[0096] Each (AP) segment contains, in polymeric form, ≤10 mol% of the vinyl aromatic hydrocarbon, based on the total molar number of polymerized monomers in the (AP) segment. Attached Figure Description

[0097] Figure 1A This is a schematic diagram depicting the formation of ethylene / styrene diblock interpolymers. Each black box represents a vinyl-depleted aromatic block, which comprises ethylene, optional α-olefin, and optional vinyl aromatic in polymeric form. Each gray (pink) box represents a vinyl-rich aromatic block, which comprises ethylene, vinyl aromatic, and optional α-olefin in polymeric form.

[0098] Figure 1B This is a schematic diagram depicting the formation of ethylene / styrene triblock interpolymers. See the box description above.

[0099] Figure 2 The 1H NMR curve of CAT B was plotted.

[0100] Figure 3 The 13C NMR curve of CAT B was plotted.

[0101] Figure 4 The PPR data depicted the relationship between activity and CSA loading (μmole).

[0102] Figure 5 The relationship between PPR data, PS molecular weight (Mw), and CSA loading (μmole) was depicted.

[0103] Figure 6 The conventional GPC curves for the aforementioned syndiotactic polystyrene are plotted. The GPC curves from left to right, starting from Log M = 3.00, are: "sPS 3 (100DEZ polymer)", "sPS-5 (100TEA polymer)", "sPS-2 (25DEZ polymer)", "sPS-4 (25TEA polymer)", and "sPS-1 (CSA-free polymer)".

[0104] Figure 7The 1H NMR curves of triblock 2 (a composition containing ethylene / octene / styrene triblocks) were plotted.

[0105] Figure 8 The 13C NMR curves of triblock 2 were plotted.

[0106] Figure 9 GPC curves for triblock 1 (a composition containing ethylene / octene / styrene triblocks) were plotted. A dRI / UV dual detector was used. The GPC curves from left to right, starting at Log M = 4.00, are: UV curve, RI curve.

[0107] Figure 10A The conventional GPC curves for the mentioned samples are plotted. The GPC curves from left to right, starting from Log M = 3.00, are: triblock 2, IB-1 (in-reactor blend) (see Table 9).

[0108] Figure 10B The conventional GPC curves for the mentioned samples are plotted. The GPC curves from left to right starting at Log M = 2.00 are: IB-2 (in-reactor blend), triblock 3 (composition containing ethylene / octene / styrene triblocks), diblock 1 (composition containing ethylene / octene / styrene diblocks), and diblock 2 (composition containing ethylene / octene / styrene diblocks) (see Table 7).

[0109] Figure 11 The relationship between tensile stress and tensile strain of triblock 2 and IB-1 was depicted.

[0110] Figure 12 The conventional GPC curves for the aforementioned atactic polystyrene are plotted. The GPC curves from left to right starting from Log M = 2.00 are: "aPS-4 (100DEZ polymer)", "aPS-5 (25TEA polymer)", "aPS-3 (25DEZ polymer)", "aPS-1 (CAT C polymer only)", and "aPS-2 (CSA C and CSA polymer)".

[0111] Figure 13 The relationship between molecular weight (Mw) and polymerization efficiency in CAT D PPR data is depicted.

[0112] Figure 14 The relationship between CAT E PPR data and polymerization efficiency is depicted.

[0113] Figure 15 The relationship between CAT F PPR data, molecular weight (Mw), and polymerization efficiency is depicted. Detailed Implementation

[0114] Chain shuttle technology has been found to produce ethylene / vinyl aromatic diblock and triblock interpolymers via a dual-catalyst system in two reactors. For example, the catalyst (metal complex) used to form vinyl-poor aromatic segments (or blocks) in one reactor meets the following criteria: a) high native molecular weight, b) high chain shuttle constant, as determined by the decrease in molecular weight and narrowing of the molecular weight distribution in the presence of a CSA (chain shuttler), and c) high α-olefin incorporation. The catalyst (metal complex) used to form vinyl-rich aromatic segments (or blocks) in another reactor meets the following criteria: a) good activity for vinyl aromatic polymerization, b) high chain shuttle constant, as determined by the decrease in molecular weight and narrowing of the molecular weight distribution in the presence of a CSA, and c) compatibility with entrained residual monomers.

[0115] As discussed above, the present invention provides, in a first aspect, a method for forming a composition comprising an ethylene / vinyl aromatic diblock interpolymer and / or an ethylene / vinyl aromatic triblock interpolymer as described above. The method of the present invention may include a combination of two or more embodiments as described herein. Each step and component of the method of the present invention may include a combination of two or more embodiments as described herein.

[0116] As discussed above, in a second aspect, the present invention provides a composition comprising an ethylene / vinyl aromatics diblock copolymer or an ethylene / vinyl aromatics triblock copolymer as described above. The compositions of the present invention may comprise a combination of two or more embodiments as described herein. The diblock copolymer and the triblock copolymer may each comprise a combination of two or more embodiments as described herein.

[0117] Note that, as used in this article, regarding the structure of metal complexes, Ar1 = Ar 1 Ar2 = Ar 2 Ar3 = Ar 3 And so on. Moreover, as used in this article, for this type of structure, R1 = R 1 R2 = R 2 R3 = R 3 And so on. Here, "a to n" represents the marker R for consecutive numbers. a -R n It refers to R a R a+1 R a+2 ...R n For example, R 3 -R 7 It refers to R 3 R 4 R 5 R 6 R 7As used herein, for the metal complexes mentioned, the symbol "→" indicates a bond formed by an electron-donating pair (electron-donating bond). Note that pi (π) bonds are represented by straight lines in this article.

[0118] If applicable, the following embodiments are applicable to the methods and / or compositions of the present invention.

[0119] In one embodiment or a combination of two or more embodiments described herein, the metal complex S is selected from structure s1a1 or structure s1a2:

[0120]

[0121] In one embodiment or a combination of two or more embodiments described herein, the metal complex S is selected from formula S1 as described herein and further formula S1a; and the metal complex H is selected from formula H1 as described herein and further formula H1a or H1b.

[0122] In one embodiment or a combination of two or more embodiments described herein, the metal complex H is selected from the following formulas h1a1, h1a2, h1a3, h1b1, h1b2, h1b3, h2a1 or h2a2 as described herein.

[0123] In one embodiment or in a combination of two or more embodiments described herein, at least one chain shuttle is selected from the group consisting of alkyl zinc compounds, alkyl aluminum compounds, bi-ended chain shuttles, or combinations thereof.

[0124] In one implementation or in a combination of two or more implementations described herein, step A occurs before step B.

[0125] In one implementation or in a combination of two or more implementations described herein, step B occurs before step A.

[0126] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatic diblock copolymers or ethylene / vinyl aromatic triblock copolymers, the vinyl aromatic is styrene.

[0127] In one embodiment or in a combination of two or more embodiments described herein, mixture A comprises an α-olefin.

[0128] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatics diblock interpolymers or ethylene / vinyl aromatics triblock interpolymers, each (AR) segment independently comprises, in polymeric form, ≥15 mol%, or ≥20 mol%, or ≥25 mol%, or ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥45 mol%, or ≥50 mol%, or ≥55 mol%, or ≥60 mol% of vinyl aromatics, based on the total molar number of polymerizable monomers in the (AR) segment. In one embodiment or a combination of two or more embodiments described herein, each (AR) segment independently comprises, in polymeric form, <100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤91 mol% of vinyl aromatics, based on the total molar number of polymerizable monomers in the (AR) segment.

[0129] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatics diblock or triblock interpolymers, each (AP) segment independently comprises, in polymeric form, ≥0 mol%, or ≥0.2 mol%, or ≥0.4 mol%, or ≥0.6 mol%, or ≥0.8 mol%, or ≥1.0 mol% of vinyl aromatics, based on the total molar number of polymerizable monomers in the (AP) segment. In one embodiment or a combination of two or more embodiments described herein, each (AP) segment independently comprises, in polymeric form, ≤10 mol%, or ≤9.0 mol%, or ≤8.0 mol%, or ≤7.0 mol%, or ≤6.0 mol%, or ≤5.0 mol% of vinyl aromatics, based on the total molar number of polymerizable monomers in the (AP) segment.

[0130] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatic diblock interpolymers or ethylene / vinyl aromatic triblock interpolymers, each (AR) segment independently comprises, in polymeric form, ≥2.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥9.0 mol%, or ≥10 mol%, or ≥11 mol%, or ≥12 mol%, or ≥13 mol%, or ≥14 mol% of ethylene, based on the total molar number of polymerizable monomers in the (AR) segment. In one embodiment or a combination of two or more embodiments described herein, each (AR) segment independently comprises, in polymeric form, ≤80 mol%, or ≤77 mol%, or ≤75 mol%, or ≤73 mol%, or ≤70 mol%, or ≤65 mol%, or ≤60 mol%, or ≤55 mol%, or ≤50 mol%, or ≤45 mol%, or ≤40 mol% of ethylene, based on the total molar number of polymerizable monomers in the (AR) segment.

[0131] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatics diblock interpolymers or ethylene / vinyl aromatics triblock interpolymers, each (AP) segment independently comprises, in polymeric form, ≥50 mol%, ≥52 mol%, or ≥54 mol%, or ≥56 mol%, or ≥58 mol%, or ≥60 mol%, or ≥62 mol%, or ≥64 mol%, or ≥66 mol%, or ≥68 mol%, or ≥70 mol% of ethylene, based on the total molar number of polymerizable monomers in the (AP) segment. In one embodiment or a combination of two or more embodiments described herein, each (AP) segment independently comprises, in polymeric form, ≤100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤90 mol% of ethylene, based on the total molar number of polymerizable monomers in the (AP) segment.

[0132] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatic diblock interpolymers or ethylene / vinyl aromatic triblock interpolymers, ≥20 mol%, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol%, or ≥98 mol%, or ≥99 mol% of polymerized vinyl aromatics are present in the sub-segment bb in a “back-to-back” configuration as shown below:

[0133] And the mole % mentioned therein is based on the total number of moles of polymerized vinyl aromatics in the (AR) segment.

[0134] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatic diblock interpolymers or ethylene / vinyl aromatic triblock interpolymers, ≥20 mol%, or ≥40 mol%, or ≥60 mol%, or ≥80 mol%, or ≥85 mol%, or ≥90 mol%, or ≥92 mol%, or ≥94 mol%, or ≥96 mol%, or ≥98 mol%, or ≥99 mol% of polymerized vinyl aromatics are present in the sub-segment sbb in a syndiotactic "back-to-back" configuration as shown below:

[0135] And the mole % mentioned therein is based on the total number of moles of polymerized vinyl aromatics in the (AR) segment.

[0136] In one embodiment or a combination of two or more embodiments described herein, for ethylene / vinyl aromatic diblock interpolymers or ethylene / vinyl aromatic triblock interpolymers, no polymerized vinyl aromatics are present in each (AP) segment in a “back-to-back” configuration in the sub-segment bb as shown:

[0137] And the mole % is based on the total number of moles of polymerized vinyl aromatics in the (AP) segment.

[0138] A composition formed by the method of the present invention as described herein is also provided. An article comprising at least one component formed from the composition of the present invention is also provided.

[0139] Ethylene / vinyl aromatic diblock and triblock interpolymers

[0140] Examples of the formation of ethylene / vinyl aromatic diblock interpolymers and the formation of ethylene / vinyl aromatic triblock interpolymers are respectively in Figure 1A and Figure 1B The figures are schematically illustrated. According to these figures, in a first reactor, ethylene / α-olefin random copolymer “blocks” are generated using a first transition metal catalyst, directly bound to an organometallic reagent such as a zinc- or aluminum-based chain shuttle (CSA) or a diheaded chain shuttle (DHCSA). These resulting polymer-based zinc or polymer-based aluminum materials from the first reactor are transferred to a second reactor. The lifetime of the first transition metal catalyst (metal complex) is exhausted upon transfer of the contents of the first reactor to the second reactor. In the second reactor, styrene, ethylene, and optionally an α-olefin are polymerized in the presence of a second transition metal catalyst to produce random styrene / ethylene interpolymer “blocks.” The polymer-based zinc or polymer-based aluminum material from the first reactor then undergoes chain shuttle with the catalyst of the second reactor, causing the styrene / ethylene random “blocks” to grow onto the ethylene / α-olefin polymer chain, thereby producing the desired diblock (…). Figure 1A ) or three-block ( Figure 1B Interpolymers. Two types of random blocks (vinyl-rich aromatics or hard blocks and vinyl-depleted aromatics or soft blocks) differ in chemical or physical properties. Each block has two or more monomer types that are substantially randomly distributed within the block.

[0141] As discussed, ethylene / vinyl aromatic diblock and triblock interpolymers comprise two chemically distinct regions (referred to as “blocks”), preferably connected in a linear manner. In one embodiment, the blocks differ in the amount or type of comonomer incorporated, density, amount of crystallinity, type or degree of stereoregularity (isotactic or syndiotactic), or any other chemical or physical property. Compared to conventional block interpolymers in the art (including interpolymers produced by sequential monomer addition, cyclic catalysts, or anionic polymerization techniques), the ethylene / vinyl aromatic diblock and triblock interpolymers of the present invention are characterized by unique distributions in polymer polydispersity (PDI or Mw / Mn or MWD), block length distribution, and / or block number distribution due to the influence of the shuttle agent and multiple catalyst combinations used when preparing them in a dual-reactor configuration.

[0142] Vinyl aromatic monomers

[0143] Vinyl aromatic monomers are aromatic monomers and include, but are not limited to, aromatic vinyl compounds such as monoalkylstyrene or polyalkylstyrene (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene) and functionalized derivatives (such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene), provided that the monomer is polymerizable under the conditions employed.

[0144] Chain transfer agent (CSA)

[0145] The term "chain shuttle (CSA)" refers to a compound or mixture of compounds capable of inducing polymer group exchange between at least two active catalyst sites of a catalyst included in polymerization conditions. That is, polymer fragments can be transferred to or from one or more active catalyst sites. CSAs are capable of chain transfer between, for example, "AP (soft block) catalysts" and "AR (hard block catalysts)".

[0146] Suitable shuttles include, but are not limited to, group 1, 2, 12, or 13 metal compounds or complexes containing at least one substituted or unsubstituted hydrocarbon group, preferably hydrocarbon-substituted aluminum, gallium, or zinc compounds containing 1 to 12 carbons in each hydrocarbon group, and their reaction products with a proton source. Preferred hydrocarbon groups are alkyl groups, preferably straight-chain or branched C2-C8 alkyl groups. Chain shuttles include, but are not limited to, trialkylaluminum and dialkylzinc compounds, particularly triethylaluminum, tri(isopropyl)aluminum, tri(isobutyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, or diethylzinc. See U.S. Patent 8,710,143 (incorporated herein by reference).

[0147] Biheaded chain shuttles (e.g., Al-DHCSA and AlZn-DHCSA) are also suitable reagents. Biheaded chain shuttles include, but are not limited to, structures with the following formula: R1-[M-R2-] n -M-R1, where R1 and R2 are each independently hydrocarbons containing 1 to 20 carbons, n ≥ 1, and M = Zn. See also WO2018 / 064546 and U.S. Patent 8,501,885 (each incorporated herein by reference).

[0148] definition

[0149] Unless stated to the contrary, implied by the context or customary in the art, all parts and percentages are by weight, and all test methods are current methods as of the date of this disclosure.

[0150] As used herein, the term "composition" includes mixtures of materials comprising the composition as well as reaction byproducts and decomposition products formed from the materials of the composition. Any reaction byproducts or decomposition products are typically present in trace or residual amounts.

[0151] As used herein, the term "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. Therefore, the general term polymer includes the terms homopolymer (used to refer to polymers prepared from only one type of monomer; it should be understood that trace impurities may be incorporated into the polymer structure) and interpolymer, as defined below. Trace impurities (such as catalyst residues) may be incorporated into and / or within the polymer. Typically, polymers are stabilized with one or more stabilizers in very low amounts ("ppm").

[0152] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. The term interpolymer therefore includes the term copolymer (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0153] As used herein, the term "olefin-based polymer" refers to a polymer that contains 50% by weight or most of a weight of an olefin (such as ethylene or propylene) in polymeric form (based on the weight of the polymer) and optionally may contain one or more comonomers.

[0154] As used herein, the term "propylene-based polymer" refers to a polymer that contains a majority weight percentage of propylene (based on the weight of the polymer) in polymeric form and may optionally contain one or more comonomers.

[0155] As used herein, the term "ethylene-based polymer" means a polymer that contains 50% by weight or most of the weight of ethylene (based on the weight of the polymer) in polymeric form and optionally may contain one or more comonomers.

[0156] As used herein, the term "vinyl aromatic-based polymer" refers to a polymer that contains a majority weight percentage of vinyl aromatics (based on the weight of the polymer) in polymeric form and may optionally contain one or more comonomers.

[0157] As used herein, the term "styrene-based polymer" refers to a polymer that contains a majority weight percentage of styrene (based on the weight of the polymer) in polymeric form and may optionally contain one or more comonomers.

[0158] As used herein, the term "ethylene / α-olefin interpolymer" refers to a random interpolymer containing 50% by weight or most of the weight of ethylene (based on the weight of the interpolymer) and α-olefin in polymeric form.

[0159] As used herein, the term "ethylene / α-olefin copolymer" refers to a random copolymer in polymeric form comprising 50% by weight or most of the weight of ethylene (based on the weight of the copolymer) and α-olefin as the only two monomer types.

[0160] As used herein, the term "ethylene / vinyl aromatics" refers to a random copolymer in polymer form comprising 50% by weight or most of the weight of ethylene (based on the weight of the copolymer) and vinyl aromatics as only two monomer types.

[0161] As used in this article with respect to polymers (or interpolymers or terpolymers or copolymers), the phrase "major weight percentage" refers to the amount of monomer present in the polymer in the largest quantity.

[0162] As used herein, the term "ethylene / vinyl aromatics diblock interpolymer" refers to a diblock interpolymer comprising vinyl-rich aromatic (AR) segments and vinyl-depleted aromatic (AP) segments. See, for example... Figure 1A The AR segment contains >10 mol% vinyl aromatics in polymeric form. The AP segment contains ≤10 mol% vinyl aromatics in polymeric form. Each mol% is based on the total number of moles of polymeric monomers in the respective segment. Diblock copolymers contain ethylene and vinyl aromatics in polymeric form and may include other monomer types. As used herein, the term "ethylene / vinyl aromatics diblock copolymer" refers to a diblock copolymer containing both the vinyl-rich (AR) segment discussed above and the vinyl-poor (AP) segment discussed above. Diblock copolymers contain ethylene and vinyl aromatics as the only two monomer types in polymeric form.

[0163] As used herein, the term "ethylene / α-olefin / vinyl aromatic diblock interpolymer" refers to a diblock interpolymer comprising vinyl-rich aromatic (AR) segments and vinyl-depleted aromatic (AP) segments. See, for example... Figure 1A The AR segment contains >10 mol% vinyl aromatics in polymeric form. The AP segment contains ≤10 mol% vinyl aromatics in polymeric form. Each mol% is based on the total number of moles of polymeric monomers in the respective segment. Diblock interpolymers contain ethylene, α-olefins, and vinyl aromatics in polymeric form, and may include other monomer types. As used herein, the term "ethylene / α-olefin / vinyl aromatics diblock terpolymer" refers to a diblock terpolymer containing both the vinyl-rich (AR) segment discussed above and the vinyl-poor (AP) segment discussed above. Diblock terpolymers contain ethylene, α-olefins, and vinyl aromatics in polymeric form as the only three monomer types.

[0164] As used herein, the term "ethylene / vinyl aromatic triblock interpolymer" refers to a triblock interpolymer comprising two vinyl-rich aromatic (AR) segments and one vinyl-poor aromatic (AP) segment between the AR segments, or two vinyl-poor aromatic (AP) segments and one vinyl-rich aromatic (AR) segment between the AP segments. See, for example... Figure 1B The AR segment contains >10 mol% vinyl aromatics in polymeric form. The AP segment contains ≤10 mol% vinyl aromatics in polymeric form. Each mol% is based on the total number of moles of polymeric monomers in the respective segment. The triblock copolymer contains ethylene and vinyl aromatics in polymeric form and may include other monomer types. As used herein, the term "ethylene / vinyl aromatic triblock copolymer" refers to a triblock copolymer containing two vinyl-rich aromatic (AR) segments and one vinyl-poor aromatic (AP) segment as discussed above, or two vinyl-poor aromatic (AP) segments and one vinyl-rich aromatic (AR) segment as discussed above. Each AR segment and AP segment is described above. The triblock copolymer contains ethylene and vinyl aromatics as the only two monomer types in polymeric form.

[0165] As used herein, the term "ethylene / α-olefin / vinyl aromatic triblock interpolymer" refers to a triblock interpolymer comprising two vinyl-rich aromatic (AR) segments and one vinyl-poor aromatic (AP) segment between the AR segments, or two vinyl-poor aromatic (AP) segments and one vinyl-rich aromatic (AR) segment between the AP segments. See, for example... Figure 1BThe AR segment contains >10 mol% vinyl aromatics in polymeric form. The AP segment contains ≤10 mol% vinyl aromatics in polymeric form. Each mol% is based on the total number of moles of polymeric monomers in the respective segment. The triblock interpolymer contains ethylene, α-olefin, and vinyl aromatics in polymeric form, and may include other monomer types. As used herein, the term "ethylene / α-olefin / vinyl aromatic triblock terpolymer" refers to a triblock terpolymer containing, in polymeric form, two vinyl-rich aromatic (AR) segments and one vinyl-poor aromatic (AP) segment as discussed above, or two vinyl-poor aromatic (AP) segments and one vinyl-rich aromatic (AR) segment as discussed above. Each AR segment and AP segment is described above. The triblock terpolymer contains ethylene, α-olefin, and vinyl aromatics in polymeric form as the only three monomer types.

[0166] As used herein, the term "vinyl aromatic hydrocarbon" refers to a chemical compound comprising a "-CR=CHR' (where R and R' are each independently H or alkyl) bonded to an aromatic ring structure (such as a monocyclic, bicyclic, or tricyclic structure). The aromatic ring structure may or may not contain one or more heteroatom groups and may or may not be substituted by one or more heteroatom groups. Examples of vinyl aromatic hydrocarbons include, but are not limited to, styrene, 2-vinyltoluene, 4-vinyltoluene, and α-methylstyrene.

[0167] As used herein, the term "alkylsilyl group" refers to a chemical group comprising at least one -Si-R moiety, where R is an alkyl group. Some examples of such groups include the following: -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).

[0168] The term "heteroatom" refers to an atom other than hydrogen or carbon (e.g., O, N, or P).

[0169] The term "heteroatomic group" refers to a heteroatom or a chemical group containing one or more heteroatoms.

[0170] As used herein, the terms "hydrocarbon," "hydrocarbon group," and similar terms refer to the corresponding compounds or chemical groups containing only carbon and hydrogen atoms. The divalent "hydrocarbon group" is defined in a similar manner.

[0171] As used herein, the terms "heterohydrocarbon," "heteroalkyl group," and similar terms refer to the corresponding hydrocarbon or alkyl group in which at least one carbon atom is replaced by a heteroatom group (e.g., O, N, or P). A monovalent heteroalkyl group may be bonded to the remainder of the compound of interest via a carbon atom or via a heteroatom. A divalent "heteroalkylene group" is defined in a similar manner; and a divalent heteroalkylene group may be bonded to the remainder of the compound of interest via two carbon atoms or two heteroatoms, or carbon atoms and heteroatoms.

[0172] As used herein, the terms “substituted hydrocarbon,” “substituted hydrocarbon group,” and similar terms refer to the corresponding hydrocarbon or hydrocarbon group in which one or more hydrogen atoms are independently substituted by a heteroatom group.

[0173] As used herein, the terms “substituted heterohydrocarbon,” “substituted heterohydrocarbon group,” and similar terms refer to the corresponding heterohydrocarbon or heterohydrocarbon group in which one or more hydrogen atoms are independently substituted by heteroatom groups.

[0174] As used herein, the terms "aryl," "aryl group," and similar terms refer to a monovalent aromatic hydrocarbon group or aromatic hydrocarbon group that contains one or more ring structures (e.g., monocyclic, bicyclic, or tricyclic structures).

[0175] As used herein, the terms “heteroaryl,” “heteroaryl group,” and similar terms refer to monovalent aryl or aryl groups in which one or more carbon atoms of the main chain ring structure are independently replaced by heteroatom groups.

[0176] As used herein, the terms “substituted aryl,” “substituted aryl group,” and similar terms refer to an aryl or aryl group in which one or more hydrogen atoms are independently substituted by a heteroatom group.

[0177] As used herein, the terms “substituted heteroaryl,” “substituted heteroaryl group,” and similar terms refer to a heteroaryl or heteroaryl group in which one or more hydrogen atoms are independently substituted by a heteroatom group.

[0178] As used herein, the terms "arylene", "arylene group" and similar terms refer to divalent aromatic arylene groups or aromatic arylene groups that contain one or more ring structures (e.g., monocyclic, bicyclic or tricyclic structures).

[0179] As used herein, the terms “substituted arylene,” “substituted arylene group,” and similar terms refer to an arylene or arylene group in which one or more hydrogen atoms are independently substituted by a heteroatom group.

[0180] As used in this article, “substituted or unsubstituted (C1–C1)” 30"Hydrocarbon group" and other similar terms indicate the range of total carbon atoms that a substituted or unsubstituted hydrocarbon group may contain (e.g., 1 to 30). Note that other monovalent chemical groups having the mentioned carbon range (e.g., substituted or unsubstituted (C6-C5) groups) may also be included. 20 Aryl groups are defined in a similar manner.

[0181] As used in this article, “substituted or unsubstituted (C1–C1)” 30 "Heteroalkyl group" and other similar terms indicate the range of total carbon atoms that a substituted or unsubstituted heteroalkyl group may contain (e.g., 1 to 30). Note that other monovalent chemical groups having the mentioned carbon range are defined in a similar manner.

[0182] As used in this article, “substituted or unsubstituted (C6-C)” 20 "Arylidene group" and other similar terms indicate the range of total carbon atoms (e.g., 2 to 6) that a substituted or unsubstituted arylidene group may contain. Note that other divalent chemical groups having the mentioned carbon range are defined in a similar manner.

[0183] As used herein with respect to metal complexes, the term "bridging group" refers to a divalent organic group bonded to two atoms located at different points in the rest of the metal complex's structure. See, for example, formula S1(J 1 S2(J) 2 ), S3(J 3 S4(J) 4 ), S5(J 5 H2(J) 5 Each of the bridging groups in )

[0184] The phrase “bridging group comprising 2 to 40 atoms other than hydrogen” and similar phrases used in this article for metal complexes indicate the range of total atoms (e.g., 2 to 40) that a bridging group may contain, excluding hydrogen. Note that other bridging groups having the mentioned carbon range are defined in a similar manner.

[0185] As used herein with respect to metal complexes, the term "Lewis base" refers to a chemical compound or chemical group that can donate a pair of electrons to form a bond with a metal or another chemical group. Examples of Lewis bases include, but are not limited to, tetrahydrofuran (THF), diethyl ether, dimethylaniline, or trimethylphosphine.

[0186] As used herein with respect to polymerized vinyl aromatic units, the terms “syndiotactic stereoregularity,” “syndiotactic,” and similar terms refer to alternating stereochemical configurations of two or more side-chain aryl (e.g., phenyl) groups. See, for example, sub-chain segment sbb.

[0187] Regarding structures 1, 2, and 3, the term "polymer structure" refers to the entire molecule of the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer mentioned.

[0188] The designation "AR" for diblock or triblock interpolymers refers to polymer segments of the corresponding interpolymers containing >10 mol% vinyl aromatics in polymeric form. This designation indicates a "vinyl aromatics-rich" segment.

[0189] The designation "AP" for diblock or triblock interpolymers refers to polymer segments of the corresponding interpolymers containing ≤10 mol% vinyl aromatics in polymeric form. This designation indicates a "vinyl-poor aromatics" segment.

[0190] The phrase "each segment" in relation to AR segments (or blocks) or AP segments (or blocks) refers to an AR or AP segment located at the end of or within a polymer molecule. In diblock interpolymers, an AR segment is located at one end of the polymer molecule, and an AP segment is located at the other end. In triblock interpolymers, two AR segments are located at each end of the polymer molecule, and an AP segment is located between the two AR segments, or two AP segments are located at each end of the polymer molecule, and an AR segment is located between the two AP segments.

[0191] As used herein, the term "solution polymerization" refers to a polymerization process in which the monomer, catalyst, and the resulting polymer are all soluble in a polymerization solvent or a solvent blend of two or more solvents.

[0192] As used herein, the term "continuous solution polymerization" refers to solution polymerization in which monomers are continuously fed into a reactor and polymers are continuously removed from the reactor.

[0193] As used herein, the term "metal complex" refers to a chemical structure comprising a metal or metal ion bonded to and / or coordinated with one or more ligands (ions or molecules containing one or more pairs of electrons that can share with the metal). See, for example, metal complexes of formulas S1, S2, S3, S4, S5, H1, and H2. Metal complexes are typically made catalytically active by using one or more co-catalysts.

[0194] As used herein, the term "scavenger" refers to a compound added to a polymerization reaction to remove impurities or unwanted reaction products (such as oxygen) or to deactivate them. Examples of some scavengers include alkylaluminum compounds such as MMAO and MMAO-3A.

[0195] As used herein, the term "reactor product" refers to the final polymerized mixture in the reactor, which contains one or more polymers and typically contains a solvent.

[0196] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed using the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise. In contrast, the term “substantially constitutes” excludes any other components, steps, or procedures from any subsequently listed scope, except those not essential for operability. The term “consisting of” excludes any components, steps, or procedures not specifically described or listed.

[0197] List of some methods and compositions

[0198] A] A method for forming a composition comprising an ethylene / vinyl aromatic diblock copolymer and / or an ethylene / vinyl aromatic triblock copolymer, as well as further ethylene / vinyl aromatic diblock copolymers or ethylene / vinyl aromatic triblock copolymers, said method comprising at least the following steps:

[0199] A) Polymerize a mixture A comprising ethylene and optionally α-olefins and optionally vinyl aromatics in reactor A in the presence of at least the following: a) a metal complex S selected from the following: formula S1, formula S2, formula S3, formula S4 or formula S5:

[0200] As described above (see Summary of the Invention (SOI));

[0201] As stated above (see SOI); and regarding R 3 and R 4 Each of them is independently selected from substituted or unsubstituted (C6-C) 20 ) aryl group or substituted or unsubstituted (C5-C 20 ) heteroaryl group; further R 3 and R 4 Each of them is independently selected from substituted or unsubstituted (C6-C) 12 ) aryl group or substituted or unsubstituted (C5-C 11 heteroaryl groups;

[0202] As described above (see SOI);

[0203] As described above (see SOI);

[0204] As described above (see SOI);

[0205] B) Polymerize a mixture B comprising ethylene, vinyl aromatics, and optionally α-olefins in reactor B in the presence of at least the following:

[0206] The metal complexes described therein are generally electrically neutral; or

[0207] b) Metal complexes H selected from the following: formula H1 or formula H2:

[0208] As described above (see SOI);

[0209] As stated above (see SOI); and regarding R 1 and R 2 Each is independently a bridging group comprising 2 to 41 atoms other than hydrogen, and optionally, R 1 and R 2 Each can be an independently substituted or unsubstituted aryl group; further, R 1 and R 2 Each can be an arylene group (unsubstituted);

[0210] Step A occurs before step B, and further transfers ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight of reactor product from reactor A to reactor B; or step B occurs before step A, and further transfers ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight of reactor product from reactor B to reactor A; wherein each weight percentage is based on the total weight of the corresponding reactor product; and

[0211] If step A occurs before step B, then at least one chain shuttle is fed into reactor A; and

[0212] If step B occurs before step A, then at least one chain shuttle agent is fed into reactor B; and

[0213] Wherein the vinyl aromatic hydrocarbon in step A is the same as the vinyl aromatic hydrocarbon in step B; and the α-olefin in step A is the same as the α-olefin in step B.

[0214] B] According to the method described in A] above, the metal complex S is selected from the following: formula S1a or formula S2a:

[0215]

[0216] Where X 1 and X 2Each is independently selected from substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 X ) heteroalkyl group or -H, and other substituted or unsubstituted benzyl group or -H; and wherein X 1 and X 2 Connections can be made optionally;

[0217] Ar 1 and Ar 2 Each is independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0218] R 52 It is a substituted or unsubstituted aryl group;

[0219]

[0220] Where X 3 and X 4 Each is independently selected from substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 X ) heteroalkyl group or -H, and other substituted or unsubstituted benzyl group or -H; and wherein X 3 and X 4 Connections can be made optionally;

[0221] R 53 Selected from substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 ( ) heteroalkyl groups or -H, and other substituted or unsubstituted benzyl groups or -H;

[0222] Ar 3 and Ar 4 Each is independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0223] C] According to the method described in A] or B] above, wherein the metal complex S is selected from the following structures: s1a1, s1a2, s1a3, s1a4, s1a5, s2a1, s3a1, s3a2, s3a3, s4a1 or s5a1, and any combination of two or more of these structures:

[0224]

[0225]

[0226] D] The method according to any one of A]-C] (A] to C] above, wherein the metal complex S is selected from structure s1a1 or structure s1a2:

[0227]

[0228] E] According to the method described in A]-D] above, the metal complex H is selected from the following: formula H1a, formula H1b or formula H2a:

[0229] Where R 1 R 2 R 3 R 4 and R 5 Each is independently H, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterohydrocarbon group; and further is H, an alkyl group or an alkylsilyl group; and further is an alkyl group or an alkyl group.

[0230] methylsilyl group;

[0231] Q 1 and Q 2 Each is independently a substituted or unsubstituted hydrocarbon group; a substituted or unsubstituted heteroalkyl group; or a halogen; and further is an aryl group; an alkylsilyl group, an alkoxy group, a halogen, or -NRR', wherein R and R' are each independently a hydrocarbon group or SiR" where R" is a hydrocarbon group; and further is an aryl group, an alkylsilyl group, or an alkoxy group; and

[0232] L is a Lewis base, and each n is independently 0 or 1; and

[0233] Optionally, at least one L group and at least one Q group are linked, and optionally...

[0234] At least one R group and at least one Q group are connected;

[0235] Where R 1 R 2 R 3 R 4 and R 5 Each is independently H, a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterohydrocarbon group; and further is H, an alkyl group or an alkylsilyl group, and further is an alkyl group or an alkylsilyl group;

[0236] Q 1 Q 2 and Q 3Each is independently a substituted or unsubstituted hydrocarbon group; a substituted or unsubstituted heteroalkyl group; or a halogen; and further is an aryl group; an alkylsilyl group, an alkoxy group, a halogen, or -NRR', wherein R and R' are each independently a hydrocarbon group or SiR" where R" is a hydrocarbon group; and further is an aryl group, an alkoxy group, or a halogen; and

[0237] Optionally, at least one R group and at least one Q group are connected;

[0238] Where M 2 It is Ti, Hf, or Zr, and further, it is Zr or Hf, and further, it is Zr; and where

[0239] R 6 and R 8 Each is independently selected from the group consisting of: -H, substituted or unsubstituted (C1-C) 40 ) hydrocarbon group, substituted or unsubstituted (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C 3. -P(R) P )2、-N(R N )2、-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R)-、(R C )2NC(O)-, halogens, groups having formula (I), groups having formula (II), and groups having formula (III):

[0240]

[0241] Where R 31–35 R 41–48 and R 51–59 Each of them is independently selected from substituted or unsubstituted (C1-C1) molecules. 40 ) hydrocarbon group, substituted or unsubstituted (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C 3. -P(R) P )2、-N(R N 2. -N=CHR C -ORC -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;

[0242] R 7 and R 9 Each of them is independently selected from substituted or unsubstituted (C1-C1) molecules. 40 ) hydrocarbon group, substituted or unsubstituted (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C 3. -P(R) P )2、-N(R N 2. -N=CHR C -OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R N )-、(R C )2NC(O)-, halogen or -H;

[0243] R 10 It is optional, and if present, it is either substituted or unsubstituted (C1-C). 40 ) alkylene group or substituted or unsubstituted (C1-C 40 Heterohydrocarbon group;

[0244] R 11 It is optional, and if present, it is either substituted or unsubstituted (C1-C). 40 ) alkylene group or substituted or unsubstituted (C1-C 40 Heterohydrocarbon group;

[0245] Q1 and Q2 are each independently a substituted or unsubstituted hydrocarbon group or halogen, and further are aryl groups, alkoxy groups or halogens;

[0246] L is either substituted or unsubstituted (C1-C) 40 ) alkylene group or substituted or unsubstituted (C1-C 40 ) heteroalkylene group, wherein the substituted or unsubstituted (C1-C 40 The alkylene group has a portion comprising a 1-carbon to 10-carbon linker backbone, said portion being linked to two Z groups (L-bonded thereto) in the structure H2a; or the substituted or unsubstituted (C1-C) 40 The heteroalkyl group has a portion comprising a 1- to 10-atom linker backbone, said portion connecting two Z groups in structure H2a, wherein said substituted or unsubstituted (C1-C 40 Each of the 1 to 10 atoms in the 1- to 10-atom linker backbone of the heteroalkyl group is independently a carbon atom or a heteroatom of a heteroatom group, wherein each heteroatom group is independently O, S, S(O), S(O)2, Si(R)2, or S(O)2. C )2、Ge(R C )2、P(R C ) or N(R C ), where each R is independent C Is it substituted or unsubstituted (C1-C) 30 ) hydrocarbon group or substituted or unsubstituted (C1-C 30 ) heterohydrocarbon group; and each R in formula H2a P R N And the rest of R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, substituted or unsubstituted (C1-C 30 ) heterohydrocarbon group or -H; and

[0247] Z 1 and Z 2 Each of them is independently selected from -S, -N(R) N ) or -P(R P ), where R N and R P As defined above.

[0248] F] According to the method described in A]-E] above, wherein the metal complex H is selected from the following formulas: h1a1, h1a2, h1a3, h1b1, h1b2, h1b3, h2a1, or h2a2 (Note: Bn = benzyl group (Ph-CH2-)):

[0249]

[0250] G] The method according to any one of A]-F] above, wherein the metal complex S is selected from formula S1, and further selected from formula S1a.

[0251] H] The method according to any one of A]-F] above, wherein the metal complex S is selected from formula S2, and further selected from formula S2a.

[0252] I] The method according to any one of A]-F] above, wherein the metal complex S is selected from formula S3.

[0253] J] The method according to any one of A]-F] above, wherein the metal complex S is selected from formula S4.

[0254] K] The method according to any one of A]-F] above, wherein the metal complex S is selected from formula S5.

[0255] L] The method according to any one of A]-K] above, wherein the metal complex H is selected from formula H1, and further selected from formula H1a or formula H1b.

[0256] M] The method according to any one of A]-K] above, wherein the metal complex H is selected from formula H2, and further selected from formula H2a.

[0257] According to any one of A]-M] above, the at least one chain shuttle is selected from the group consisting of alkyl zinc compounds, alkyl aluminum compounds, double-ended chain shuttles, or combinations thereof.

[0258] O] According to any one of A]-N] above, the at least one chain shuttle agent is selected from the following: Zn(CH2CH3)2, Al(CH2CH3)3, Al-DHCSA, ZnAl-DHCSA or combinations thereof, and further selected from Al-DHCSA, ZnAl-DHCSA or combinations thereof.

[0259] P] The method according to any one of A]-O] above, wherein the at least one chain shuttle is added to reactor A.

[0260] Q] The method according to any one of A]-O] above, wherein the at least one chain shuttle agent is added to reactor B.

[0261] R] The method according to any one of A]-O] above, wherein the at least one chain shuttle is added to both reactor A and reactor B.

[0262] S] The method according to any one of A]-R] above, wherein step A occurs before step B.

[0263] According to the method described in S] above, unreacted monomers in reactor B are recycled back to reactor A.

[0264] U] The method according to any one of A]-R] above, wherein step B occurs before step A.

[0265] V] According to the method described in U] above, unreacted monomers in reactor A are recycled back to reactor B.

[0266] W] The method according to any one of A]-V] above, wherein the polymerization is solution polymerization, and further, continuous solution polymerization.

[0267] X] The method according to any one of A]-W] above, wherein in reactor A, the polymerization is carried out at a temperature of ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C, or ≥115°C.

[0268] Y] The method according to any one of A]-X] above, wherein in reactor A, the polymerization is carried out at a temperature of ≤200°C, or ≤190°C, or ≤180°C, or ≤170°C, or ≤160°C, or ≤150°C, or ≤145°C, or ≤140°C, or ≤135°C, or ≤130°C, or ≤125°C.

[0269] Z] The method according to any one of A]-Y] above, wherein in reactor B, the polymerization is carried out at a temperature of ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C, or ≥115°C.

[0270] A2] The method according to any one of A]-Z] above, wherein in reactor B, the polymerization is carried out at a temperature of ≤200°C, or ≤190°C, or ≤180°C, or ≤170°C, or ≤160°C, or ≤150°C, or ≤145°C, or ≤140°C, or ≤135°C, or ≤130°C, or ≤125°C.

[0271] B2] The method according to any one of A]-A2] above, wherein the polymerization in reactor A is carried out at a pressure of ≥90 psig, or ≥100 psig, or ≥110 psig, or ≥120 psig, or ≥130 psig, or ≥140 psig, or ≥150 psig, or ≥160 psig, or ≥170 psig, or ≥180 psig.

[0272] C2] The method according to any one of A]-B2] above, wherein the polymerization in reactor A is carried out at a pressure of ≤250 psig, or ≤240 psig, or ≤230 psig, or ≤220 psig, or ≤210 psig, or ≤200 psig.

[0273] D2] The method according to any one of A]-C2] above, wherein the polymerization in reactor B is carried out at a pressure of ≥90 psig, or ≥100 psig, or ≥110 psig, or ≥120 psig, or ≥130 psig, or ≥140 psig, or ≥150 psig, or ≥160 psig, or ≥170 psig, or ≥180 psig.

[0274] E2] The method according to any one of A]-D2] above, wherein the polymerization in reactor B is carried out at a pressure of ≤250psi, or ≤240psi, or ≤230psi, or ≤220psi, or ≤210psi, or ≤200psi.

[0275] F2] The method according to any one of A]-E2] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, the vinyl aromatic is styrene.

[0276] G2] The method according to any one of A]-F2] above, wherein the mixture A comprises the α-olefin.

[0277] [H2] According to the method described in G2 above, the α-olefin is a C3-C20 α-olefin, further a C3-C10 α-olefin, further a C3-C8 α-olefin, further a propylene, 1-butene, 1-hexene or 1-octene, further a propylene, 1-butene or 1-octene, further a 1-butene or 1-octene, further a 1-octene.

[0278] I2] According to any one of A]-H2] above, the mixture B contains the α-olefin.

[0279] According to the method described in I2 above, the α-olefin is a C3-C20 α-olefin, further a C3-C10 α-olefin, further a C3-C8 α-olefin, further a propylene, 1-butene, 1-hexene or 1-octene, further a propylene, 1-butene or 1-octene, further a 1-butene or 1-octene, further a 1-octene.

[0280] K2] The method according to any one of A]-J2] above, wherein the molar ratio of "metal of complex S" to "metal of complex H" is ≥0.03, or ≥0.1, or ≥0.5.

[0281] L2] The method according to any one of A]-K2] above, wherein the molar ratio of "metal of complex S" to "metal of complex H" is ≤1000, or ≤500, or ≤100.

[0282] M2] The method according to any one of A]-L2] above, wherein the molar ratio of "metal of chain shuttle" to "the sum of metal of complex S and metal of complex H" is ≥2.0, or ≥5.0, or ≥10, or ≥20, or ≥40, or ≥100.

[0283] [N2] According to any one of A]-M2] above, the molar ratio of "metal of chain shuttle" to "the sum of metal of complex S and metal of complex H" is ≤1000, or ≤800, or ≤500.

[0284] O2] The method according to any one of A]-M2] above, wherein the metal complex S has a reactivity ratio r of 50 to 1000, further 100 to 500. (乙烯)(乙烯基芳烃) =k (乙烯)(乙烯) / k (乙烯)(乙烯基芳 hydrocarbon).

[0285] P2] The method according to any one of A]-O2] above, wherein the metal complex H has a reactivity ratio r of 1 to 10. (乙烯)(乙烯基芳烃) =k (乙烯)(乙烯) / k (乙烯)(乙烯基芳烃) .

[0286] Q2] The method according to any one of A]-P2] above, wherein the composition further comprises a polyethylene homopolymer, an ethylene / vinyl aromatic copolymer, an ethylene / α-olefin copolymer or a combination thereof.

[0287] R2] A composition formed by the method according to any one of A]-Q2] above.

[0288] [A3] A composition comprising an ethylene / vinyl aromatic diblock interpolymer or an ethylene / vinyl aromatic triblock interpolymer, wherein the diblock interpolymer comprises at least one polymer structure selected from structure 1 shown below, and the triblock interpolymer comprises at least one polymer structure selected from structure 2 or structure 3 shown below, wherein AR refers to vinyl-rich aromatics and AP refers to vinyl-poor aromatics:

[0289] (AR)-(AP)(Structure 1),

[0290] (AR)-(AP)-(AR)(Structure 2),

[0291] (AP)-(AR)-(AP)(Structure 3); and

[0292] Each (AR) segment independently comprises, in polymeric form, ethylene, the vinyl aromatic hydrocarbon, and optionally an α-olefin; and

[0293] Each (AP) segment independently comprises, in polymeric form, ethylene, optionally the vinyl aromatic hydrocarbon, and optionally the α-olefin; and

[0294] Each (AR) segment independently contains >10 mol% of the vinyl aromatic hydrocarbon in polymeric form, based on the total molar number of polymeric monomers in the (AR) segment; and

[0295] Each (AP) segment contains, in polymeric form, ≤10 mol% of the vinyl aromatic hydrocarbon, based on the total molar number of polymerized monomers in the (AP) segment.

[0296] [B3] According to the composition described in [A3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AR) segment independently comprises, in polymeric form, ≥15 mol%, or ≥20 mol%, or ≥25 mol%, or ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥45 mol%, or ≥50 mol%, or ≥55 mol%, or ≥60 mol% of the vinyl aromatics, based on the total molar number of polymerizable monomers in the (AR) segment.

[0297] C3] According to the composition described in A3] or B3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AR) segment independently contains, in polymeric form, <100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤91 mol% of the vinyl aromatics based on the total molar number of polymerizable monomers in the (AR) segment.

[0298] D3] The composition according to any one of A3]-C3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AP) segment independently contains, in polymeric form, ≥0 mol%, or ≥0.2 mol%, or ≥0.4 mol%, or ≥0.6 mol%, or ≥0.8 mol%, or ≥1.0 mol% of the vinyl aromatics based on the total molar number of polymerizable monomers in the (AP) segment.

[0299] [E3] According to any one of A3]-D3] above, for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AP) segment independently contains, in polymeric form, ≤10 mol%, or ≤9.0 mol%, or ≤8.0 mol%, or ≤7.0 mol%, or ≤6.0 mol%, or ≤5.0 mol% of the vinyl aromatics based on the total molar number of polymerizable monomers in the (AP) segment.

[0300] F3] The composition according to any one of A3]-E3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AR) segment independently comprises, in polymeric form, ≥2.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥9.0 mol%, or ≥10 mol%, or ≥11 mol%, or ≥12 mol%, or ≥13 mol%, or ≥14 mol% of ethylene, based on the total molar number of polymerizable monomers in the (AR) segment.

[0301] G3] The composition according to any one of A3]-F3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AR) segment independently contains, in polymeric form, ≤80 mol%, or ≤77 mol%, or ≤75 mol%, or ≤73 mol%, or ≤70 mol%, or ≤65 mol%, or ≤60 mol%, or ≤55 mol%, or ≤50 mol%, or ≤45 mol%, or ≤40 mol% of ethylene, based on the total molar number of polymerizable monomers in the (AR) segment.

[0302] [H3] The composition according to any one of [A3]-G3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AP) segment independently comprises, in polymeric form, ≥50 mol%, ≥52 mol%, or ≥54 mol%, or ≥56 mol%, or ≥58 mol%, or ≥60 mol%, or ≥62 mol%, or ≥64 mol%, or ≥66 mol%, or ≥68 mol%, or ≥70 mol% of ethylene, based on the total molar number of polymerizable monomers in the (AP) segment.

[0303] I3] The composition according to any one of A3]-H3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AP) segment independently contains, in polymeric form, ≤100 mol%, or ≤98 mol%, or ≤96 mol%, or ≤94 mol%, or ≤92 mol%, or ≤90 mol% of ethylene based on the total molar number of polymerizable monomers in the (AP) segment.

[0304] J3] The composition according to any one of A3]-I3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AR) segment independently contains, in polymeric form, ≥0 mol%, ≥1.0 mol%, or ≥2.0 mol%, or ≥3.0 mol%, or ≥4.0 mol% of the α-olefin based on the total molar number of polymerizable monomers in the (AR) segment.

[0305] K3] The composition according to any one of A3]-J3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AR) segment independently contains, in polymeric form, ≤10 mol%, ≤9.0 mol%, or ≤8.0 mol%, or ≤7.0 mol%, or ≤6.0 mol% of the α-olefin based on the total molar number of polymerizable monomers in the (AR) segment.

[0306] L3] According to the composition described in J3] or K3] above, wherein the α-olefin is a C3-C20 α-olefin, further a C3-C10 α-olefin, further a C3-C8 α-olefin, further a propylene, 1-butene, 1-hexene or 1-octene, further a propylene, 1-butene or 1-octene, further a 1-butene or 1-octene, further a 1-octene.

[0307] M3] The composition according to any one of A3]-L3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AR) segment does not contain the α-olefin in polymeric form.

[0308] [N3] The composition according to any one of [A3]-M3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AP) segment independently comprises, in polymeric form, ≥0 mol%, ≥1.0 mol%, or ≥2.0 mol%, or ≥3.0 mol%, or ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥10 mol% of the α-olefin, based on the total molar number of polymerizable monomers in the (AP) segment.

[0309] O3] The composition according to any one of A3]-N3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each (AP) segment independently contains, in polymeric form, ≤40 mol%, or ≤35 mol%, or ≤30 mol%, or ≤28 mol%, or ≤26 mol%, or ≤24 mol%, or ≤22 mol%, or ≤20 mol% of the α-olefin, based on the total molar number of polymerizable monomers in the (AP) segment.

[0310] [P3] According to the composition described above [N3] or [O3], wherein the α-olefin is a C3-C20 α-olefin, further a C3-C10 α-olefin, further a C3-C8 α-olefin, further a propylene, 1-butene, 1-hexene or 1-octene, further a propylene, 1-butene or 1-octene, further a 1-butene or 1-octene, further a 1-octene.

[0311] Q3] The composition according to any one of A3]-P3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, ≥20 mol% or ≥40 mol% or ≥60 mol% or ≥80 mol% or ≥85 mol% or ≥90 mol% or ≥92 mol% or ≥94 mol% or ≥96 mol% or ≥98 mol% or ≥99 mol% of the polymerized vinyl aromatics are present in the sub-segment bb in a “back-to-back” configuration as shown below:

[0312] And the mole % mentioned therein is based on the total number of moles of polymerized vinyl aromatics in the (AR) segment.

[0313] R3] The composition according to any one of A3]-Q3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, ≤100 mol% of polymerized vinyl aromatics in each (AR) segment are present in the above sub-segment bb in a “back-to-back” configuration as shown below.

[0314] S3] The composition according to any one of A3]-R3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, ≥20 mol% or ≥40 mol% or ≥60 mol% or ≥80 mol% or ≥85 mol% or ≥90 mol% or ≥92 mol% or ≥94 mol% or ≥96 mol% or ≥98 mol% or ≥99 mol% of the polymerized vinyl aromatics are present in the sub-segment sbb in a syndiotactic "back-to-back" configuration as shown below:

[0315] And the mole % mentioned therein is based on the total number of moles of polymerized vinyl aromatics in the (AR) segment.

[0316] T3] The composition according to any one of A3]-S3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, ≤100 mol% of polymerized vinyl aromatics in each (AR) segment are present in the above sub-segment sbb in a syndiotactic "back-to-back" configuration as shown.

[0317] U3] The composition according to any one of A3]-T3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, in each (AP) segment, ≥0 and ≤5.0 mol%, or ≤2.0 mol%, or ≤1.0 mol%, or ≤0.5 mol%, or ≤0.2 mol%, or ≤0.1 mol% of polymerized vinyl aromatics are present in the sub-segment bb in a “back-to-back” configuration as shown below:

[0318] And the mole % is based on the total number of moles of polymerized vinyl aromatics in the (AP) segment.

[0319] V3] The composition according to any one of A3]-U3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, no polymerized vinyl aromatics are present in each (AP) segment in the above sub-segment bb in a "back-to-back" configuration as shown.

[0320] W3] The composition according to any one of A3]-V3] above, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, the vinyl aromatic is styrene.

[0321] X3] The composition according to any one of A3]-W3] above, wherein the ethylene / vinyl aromatic diblock interpolymer is an ethylene / α-olefin / vinyl aromatic diblock interpolymer and further is a ternary copolymer, or the ethylene / vinyl aromatic triblock interpolymer is an ethylene / α-olefin / vinyl aromatic triblock interpolymer and further is a ternary copolymer.

[0322] Y3] The composition according to any one of A3]-X3] above, wherein the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer has a Tm1 of ≥50°C, or ≥55°C, or ≥60°C, or ≥70°C and a Tm2 of ≥120°C, or ≥124°C, or ≥150°C, or ≥170°C, or ≥200°C, or ≥210°C, or ≥220°C, or ≥230°C.

[0323] Z3] The composition according to any one of A3]-Y3] above, wherein the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer has a Tm1 of ≤120°C, or ≤115°C, or ≤110°C, or ≤105°C and a Tm2 of ≤270°C, or ≤265°C, or ≤260°C, or ≤255°C, or ≤250°C, or ≤245°C.

[0324] A4] The composition according to any one of A3]-Z3] above, wherein the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer has a Tg1 of ≥-70°C, or ≥-68°C, or ≥-66°C, or ≥-64°C, or ≥-62°C, and a Tg2 of 2.0°C, or ≥5.0°C, or ≥10°C, or ≥15°C, or ≥20°C, or ≥30°C.

[0325] B4] The composition according to any one of A3]-A4] above, wherein the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer has a Tg1 of ≤-30°C, or ≤-32°C, or ≤-34°C, or ≤-36°C, or -38°C, or ≤-40°C, or ≤-42°C, or ≤-44°C, or ≤-46°C, and a Tg2 of ≤125°C, or ≤120°C, or ≤115°C, or ≤110°C, or ≤105°C.

[0326] C4] The composition according to any one of A3]-B4] above, wherein the composition has a molecular weight distribution (MWD = Mw / Mn) of ≥3.0, or ≥3.1, or ≥3.2, or ≥3.3, or 3.4, or ≥3.6, or ≥3.8, or ≥4.0.

[0327] D4] The composition according to any one of A3]-C4] above, wherein the composition has a molecular weight distribution (MWD) of ≤50, or ≤45, or ≤40, or ≤38, or ≤36, or ≤34, or ≤32, or ≤30, or ≤28, or ≤26.

[0328] E4] The composition according to any one of A3]-D4] above, wherein the composition has a number-average molecular weight distribution (Mn) of ≥4,000 g / mol, or ≥6,000 g / mol, or ≥8,000 g / mol, or ≥10,000 g / mol, or ≥12,000 g / mol.

[0329] F4] The composition according to any one of A3]-E4] above, wherein the composition has Mn of ≤100,000 g / mol, or ≤90,000 g / mol, or ≤80,000 g / mol, or ≤75,000 g / mol, or ≤70,000 g / mol, or 65,000 g / mol, or ≤60,000 g / mol, or ≤55,000 g / mol, or ≤50,000 g / mol, or ≤45,000 g / mol.

[0330] G4] The composition according to any one of A3]-F4] above, wherein the composition has a weight-average molecular weight distribution (Mw) of ≥50,000 g / mol, ≥55,000 g / mol, ≥60,000 g / mol, ≥65,000 g / mol, or ≥70,000 g / mol, or ≥75,000 g / mol, or ≥80,000 g / mol.

[0331] H4] The composition according to any one of A3]-G4] above, wherein the composition has a Mw of ≤500,000 g / mol, or ≤450,000 g / mol, or ≤400,000 g / mol, or ≤390,000 g / mol, or ≤380,000 g / mol, or ≤370,000 g / mol, or ≤360,000 g / mol.

[0332] I4] The composition according to any one of A3]-H4] above, wherein the composition has a melt index (I2) of ≥0.5 dg / min, or ≥1.0 dg / min, or ≥2.0 dg / min, or ≥5.0 dg / min, or ≥10 dg / min.

[0333] J4] The composition according to any one of A3]-I4] above, wherein the composition has a melt index (I2) of ≤1,000 dg / min, or ≤500 dg / min, or ≤250 dg / min, or ≤100 dg / min, or ≤50 dg / min, or ≤20 dg / min.

[0334] K4] The composition according to any one of A3]-J4] above, wherein the composition has a Tm of ≥200°C, or ≥205°C, or ≥210°C, or ≥215°C, or ≥220°C, or ≥225°C, or ≥230°C, or ≥235°C.

[0335] L4] The composition according to any one of A3]-K4] above, wherein the composition has a Tm of ≤300°C, or ≤290°C, or ≤285°C, or ≤280°C, or ≤275°C, or ≤270°C, or ≤265°C.

[0336] M4] The composition according to any one of A3]-L4] above, wherein the composition has a Tg of ≥-80°C, or ≥-75°C, or ≥-70°C, or ≥-69°C, or ≥-68°C, or ≥-67°C.

[0337] N4] The composition according to any one of A3]-M4] above, wherein the composition has a Tg of ≤-30°C, or ≤-35°C, or ≤-40°C, or ≤-45°C, or -50°C, or ≤-55°C, or ≤-60°C.

[0338] O4] The composition according to any one of A3]-N4] above, wherein, based on the total molar number of polymerizable monomers in the composition, the composition comprises, in polymeric form, ≥5.0 mol%, or ≥10 mol%, or ≥12 mol%, or ≥14 mol%, or ≥16 mol% of the vinyl aromatic hydrocarbon.

[0339] [P4] The composition according to any one of [A3]-[O4] above, wherein, based on the total molar number of polymerizable monomers in the composition, the composition comprises, in polymeric form, <50 mol%, or ≤45 mol%, or ≤40 mol%, or ≤35 mol%, or ≤30 mol% of the vinyl aromatic hydrocarbon.

[0340] Q4] The composition according to any one of A3]-P4] above, wherein, based on the total molar number of polymeric monomers in the composition, the composition comprises, in polymeric form, ≥30 mol%, or ≥35 mol%, or ≥40 mol%, or ≥42 mol%, or ≥44 mol%, or ≥46 mol%, or ≥48 mol%, or ≥50 mol% of ethylene.

[0341] R4] The composition according to any one of A3]-Q4] above, wherein, based on the total molar number of polymerizable monomers in the composition, the composition comprises, in polymeric form, <90 mol% or ≤85 mol% or ≤80 mol% or ≤78 mol% or ≤76 mol% or ≤74 mol% or ≤72 mol% or ≤70 mol% or ≤68 mol% of ethylene.

[0342] S4] The composition according to any one of A3]-R4] above, wherein, based on the total molar number of polymerizable monomers in the composition, the composition comprises, in polymeric form, ≥2.0 mol%, ≥5.0 mol%, or ≥10 mol%, or ≥12 mol%, or ≥14 mol%, or ≥16 mol%, or ≥18 mol%, or ≥20 mol% of the α-olefin.

[0343] [T4] The composition according to any one of [A3]-S4] above, wherein, based on the total molar number of polymerizable monomers in the composition, the composition comprises, in polymeric form, ≤50 mol%, or ≤45 mol%, or ≤40 mol%, or ≤35 mol%, or ≤30 mol%, or ≤28 mol% of the α-olefin.

[0344] U4] According to the composition described in S4] or T4] above, wherein the α-olefin is a C3-C20 α-olefin, further a C3-C10 α-olefin, further a C3-C8 α-olefin, further a propylene, 1-butene, 1-hexene or 1-octene, further a propylene, 1-butene or 1-octene, further a 1-butene or 1-octene, further a 1-octene.

[0345] V4] The composition according to any one of A3]-U4] above, wherein for the composition, the molar ratio of block styrene (bb in AR) to isolated styrene is ≥2.0 mol%, ≥4.0 mol%, or ≥6.0 mol%, or ≥8.0 mol%, or ≥10 mol%.

[0346] W4] The composition according to any one of A3]-V4] above, wherein for the composition, the molar ratio of block styrene (bb in AR) to isolated styrene is ≤30 mol%, or ≤25 mol%, or ≤20 mol%, or ≤18 mol%, or ≤16 mol%, or ≤14 mol%, or ≤12 mol%.

[0347] X4] The composition according to any one of A3]-W4] above, wherein the vinyl aromatic hydrocarbon is styrene.

[0348] Y4] The composition according to any one of A3]-X4] above, wherein the composition comprises an ethylene / vinyl aromatic diblock interpolymer, and further comprises an ethylene / vinyl aromatic diblock terpolymer.

[0349] Z4] The composition according to any one of A3]-Y4] above, wherein the composition comprises an ethylene / vinyl aromatic triblock interpolymer, and further comprises an ethylene / vinyl aromatic triblock terpolymer.

[0350] A5] The composition according to any one of A3]-Z4] above, wherein the composition further comprises a polyethylene homopolymer, an ethylene / vinyl aromatic copolymer, an ethylene / α-olefin copolymer or a combination thereof.

[0351] B5] The composition according to any one of A3]-A5] above, wherein the composition further comprises a thermoplastic polymer that differs from the ethylene / vinyl aromatic diblock polymer or the ethylene / vinyl aromatic triblock polymer in one or more characteristics such as monomer type and / or amount, Tm, Tg, Mn, Mw, MWD or any combination thereof and further in one or more characteristics such as monomer type and / or amount, Tm, Tg or any combination thereof.

[0352] C5] An article comprising at least one component formed of a composition according to any one of R2] or A3]-B5] above.

[0353] D5] A method for forming a composition according to any one of A3]-A5] above, the method comprising the following steps:

[0354] A) A mixture comprising ethylene and optionally α-olefins and optionally vinyl aromatics.

[0355] A is polymerized in reactor A in the presence of at least the following:

[0356] a) Metal complexes S selected from the following: formulas S1, S2, S3, S4 or S5 as described above;

[0357] B) Polymerize a mixture B comprising ethylene, vinyl aromatics, and optionally α-olefins in reactor B in the presence of at least the following:

[0358] b) Metal complexes H selected from the following: formula H1 or formula H2 as described above;

[0359] Step A occurs before step B, and further transfers ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight of reactor product from reactor A to reactor B; or step B occurs before step A, and further transfers ≥50% by weight, or ≥80% by weight, or ≥90% by weight, or ≥98% by weight of reactor product from reactor B to reactor A; wherein each weight percentage is based on the total weight of the corresponding reactor product; and

[0360] If step A occurs before step B, then at least one chain shuttle is fed into reactor A; and

[0361] If step B occurs before step A, then at least one chain shuttle agent is fed into reactor B; and

[0362] Wherein the vinyl aromatic hydrocarbon in step A is equal to the vinyl aromatic hydrocarbon in step B; and

[0363] And the α-olefin in step A is the same as the α-olefin in step B.

[0364] Test methods

[0365] Gel permeation chromatography (routine)

[0366] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector. The autosampler oven compartment was set at 160°C and the column compartment at 150°C. The columns were four Agilent "Mixed A" 30cm 20µm linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichlorobenzene containing 200ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume used was 200 μL, and the flow rate was 1.0 mL / min.

[0367] The GPC column assembly was calibrated using 21 polystyrene standards with narrow molecular weight distributions, ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures, with individual molecular weights spaced at least ten times apart. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, “0.025 g” of polystyrene standard was prepared in 50 mL of solvent; for molecular weights less than 1,000,000, “0.05 g” of polystyrene standard was prepared in 50 mL of solvent. The polystyrene standards were dissolved by gentle stirring at 80 °C for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

[0368] M 聚乙烯 =A×(M) 聚苯乙烯 ) B (Equation 1), where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0369] A fifth-order polynomial was used to fit the calibration point for the corresponding polyethylene equivalent. A small adjustment to A (approximately 0.375 to 0.445) was made to correct for column resolution and band broadening effects, resulting in a linear homopolymer polyethylene standard at 120,000 Mw. Total plate counts for the GPC column assembly were performed using decane (“prepared as 0.04 g in 50 mL TCB”, dissolved under slow stirring for 20 min). Plate counts (Equation 2) and symmetry (Equation 3) were measured at “200 μL injection” according to the following equations:

[0370] Where RV is the retention volume in milliliters, peak width is in milliliters, peak value is the maximum height of the peak, and 1 / 2 height is half the height of the peak value; and

[0371] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the position of the peak maximum, one-tenth height is 1 / 10 of the height of the peak maximum, and the latter peak refers to the tail of the peak at a slightly later retention volume compared to the peak maximum, and the former peak refers to the foreground of the peak at a slightly earlier retention volume compared to the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0372] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, in which the sample (target weight "2 mg / ml") and solvent (containing 200 ppm BHT) were added to a pre-bubbled, diaphragm-capped vial via a PolymerChar high-temperature autosampler. The sample was then dissolved at 160°C for two hours under "low-speed" oscillation.

[0373] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4-6, the PolymerChar GPCOne was used. TM The software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weight (Mn) obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) Mw (GPC) and Mz (GPC) The calculation is as follows: Equation 4-6 is as follows:

[0374]

[0375] and

[0376]

[0377] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal flow rate) for each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration. It was then assumed that any variation in the time of the decane marker peak was related to a linear variation in the flow rate (effective flow rate) over the entire run. To facilitate the highest accuracy in RV measurement of the flow marker peak, a least-squares fitting procedure was used to fit the peak values ​​of the flow marker concentration chromatogram to a quadratic equation. The true peak position was then solved using the first derivative of the quadratic equation. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7: Effective Flow Rate = Nominal Flow Rate * (RV(FM Calibration) / RV(FM Sample)) (Equation 7). (via PolymerChar GPCOne) TM The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within + / - 0.7% of the nominal flow rate.

[0378] Melt index

[0379] The melt index (I2) of ethylene-based polymers was measured according to ASTM D-1238 at 190°C / 2.16 kg. The melt flow rate (MFR) of propylene-based polymers was measured according to ASTM D-1238 at 230°C / 2.16 kg.

[0380] density

[0381] Polymer plates for density analysis were prepared using ASTM D4703. The density of the polymer was measured using ASTM D792, Method B.

[0382] Differential scanning calorimetry (DSC)

[0383] Differential scanning calorimetry (DSC) is used to measure Tm, Tc, Tg, and crystallinity in ethylene-based (PE) and styrene-based (PS) polymer samples. Weigh approximately 5 to 8 mg of the polymer sample and place it in the DSC pan. Tighten the lid on the pan to ensure a sealed atmosphere. Unless otherwise specified, place the sample pan in the DSC unit and heat it to 180°C (300°C for PS) at a rate of 10°C / min. Hold the sample at this temperature for three minutes. Then, cool the sample to -90°C (PS) at a rate of 10°C / min and hold it isothermally at this temperature for three minutes. Next, heat the sample to 10°C / min until completely melted (second heating). Unless otherwise specified, the melting point (Tm) of each polymer is... m ) and glass transition temperature (T g The crystallization temperature (T) is determined by the second heating curve. c The value (T) is determined by the first cooling profile. Record T. m (Peak temperature) and T g The heat of fusion (H) determined by the second heating curve can be used to... f Divide by the theoretical heat of fusion of 292 J / g for PE (53 J / g for syndiotactic PS) and multiply that amount by 100 to calculate the crystallinity percentage (e.g., crystallinity % = (Hf / 292 J / g) × 100 (for PE)).

[0384] 13 C NMR

[0385] Each sample was prepared by adding approximately 2.7 g of stock solvent to 0.2 g of sample (polymer, polymer composition, or metal complex) in a 10 mm NMR tube. The stock solvent was tetrachloroethane-d2 containing 0.025 M chromium acetylacetonate (relaxant). The samples were capped and sealed with TEFLON tape. The samples were dissolved and homogenized by heating the tube and its contents at 130–135 °C. Data were collected using a Bruker 600 MHz spectrometer equipped with a Bruker high-temperature CryoProbe. Data were acquired using a 7.3 sec pulse repetition delay (6 sec delay + 1.3 sec acquisition time), a 90 sec flip angle, and inverse gating decoupling at a sample temperature of 120 °C. All measurements were performed on non-rotating samples in locked mode. The samples were homogenized just before being inserted into the heated (125 °C) NMR sample transducer and thermally equilibrated in the probe for seven minutes prior to data acquisition.

[0386] For each sample (polymer or polymer composition) analysis, the B1 carbon (quaternary carbon on the aromatic ring) signal from 145.0 ppm to 147.7 ppm was used as the styrene contribution, and the molar amount of the polymerizing monomer was calculated as follows (S = styrene, E = ethylene):

[0387] Smol = integral (145.0 - 147.7 ppm)

[0388] Emol = (integral (20.0–48.0ppm)–2*Smol) / 2

[0389] S mole% = 100 * Smol / (Smol + Emol)

[0390] E mole% = 100 - S mole%

[0391]

[0392] For each sample (polymer or composition) analysis, the B1-4 ring carbon signals from 124.0 ppm to 148.0 ppm were used as contributions from styrene, and the 2B6 (22.0–23.5 ppm) and 3B6 (31.5–32.7 ppm) signals were used as contributions from octene. The molar amounts of the monomers were calculated as follows (S = styrene, E = ethylene, O = octene):

[0393] Smol = integral (124.0–148.0ppm) / 6

[0394] Omol = (integral (22.0–23.5ppm) + integral (31.5–32.7ppm)) / 2

[0395] Emol = (integral (11.8 – 48.0 ppm) – 2 * Smol - 8 * Omol) / 2

[0396] S mole% = 100 * Smol / (Smol + Omol + Emol)

[0397] O mol% = 100 * O mol / (S mol + O mol + E mol)

[0398] E mole% = 100 – S mole% - O mole%

[0399]

[0400] Average styrene block length = 2 * (integral T) ββ +T βδ ) / integral T βδ

[0401] The ratio of block styrene to separated styrene = (integral T) ββ+T βδ ) / integral T δδ

[0402] T ββ The signal is a methylene signal centered at 41.6 ppm, T βδ The signal is a methylene signal centered at 43.9 ppm, and T δδ The signal is a methine signal centered at 46.4 ppm.

[0403] T ββ % = 100 * integral T ββ / Points B1

[0404] 1H NMR

[0405] Each sample was prepared by adding 130 mg of sample (polymer or polymer composition or metal complex) to 3.25 g tetrachloroethane-d2 and 0.001 M Cr(AcAc)3 in a 10 mm NMR tube. The sample was washed with N2 bubbling through the solvent for approximately 5 minutes via a pipette inserted into the tube to prevent oxidation. The sample container was capped and sealed with TEFLON tape. The sample was heated and vortexed at 115 °C to ensure homogeneity. 1H NMR was performed on a Bruker AVANCE 600 MHz spectrometer equipped with a Bruker high-temperature CryoProbe and at a sample temperature of 120 °C. 1H NMR was run with ZG pulses, 4 scans, SWH 10,000 Hz, AQ 1.64 s, and D1 14 s.

[0406] Compression molding

[0407] Each polymer composition was compressed and molded into patches using a Carver press for physical testing. Each composition was compressed and molded according to ASTM D4703 at a controlled cooling rate of 190°C and 15°C / min.

[0408] Micro tensile testing - mechanical properties

[0409] The specimen was punched from the compression-molded patch using an ASTM D1708 die. The specimen was tested at a test speed of 5 in / min according to ASTM D1708.

[0410] experiment

[0411] I. Catalysts and chain shuttles

[0412] CAT A (see WO03 / 40195, WO04 / 24740 and US 8,501,885)

[0413] Synthesis of (C5Me5)Sc(CH2C6H4NMe2-o)2(CAT B)

[0414]

[0415] In a nitrogen-filled glove box, 1 mL of a THF solution of Sc(CH2CH6H4NMe2-o)3 (0.300 g, 0.67 mmol) was added to 1 mL of a THF solution of C5Me5H (0.105 mL, 0.67 mmol) in a 20 mL vial. The solution was heated at 70 °C for 12 hours. The solvent was removed under reduced pressure, the residue was extracted with hexane, and then filtered. The concentrated hexane solution was equilibrated at -30 °C to give yellow crystals (0.203 g, 65.5% yield). The 1H NMR and 13C NMR spectra were consistent with those reported in the literature (Chem. Commun. 2007, 40, 4137-4139). See also the Sc complex (CAT B). Figure 2 (1H NMR) and Figure 3 (13CNMR).

[0416] Sc(CH2C6H4NMe2-o)3 (CATC, a catalyst used for atactic polystyrene and for chain shuttle with zinc) Synthesis

[0417]

[0418] Synthesis of Sc(CH2C6H4NMe2-o)3: Anhydrous ScCl3 (1.938 g, 12.81 mmol) was suspended in 10 mL of THF. A THF solution (20 mL) of LiCH2C6H4NMe2-o (5.423 g, 28.43 mmol, 3 equivalents) was slowly added at room temperature. The mixture was stirred for 30 min, and the solvent was removed under reduced pressure. The residue was dissolved in 40 mL of toluene, and the lithium salt was removed by filtration. The solvent was removed from the filtrate under reduced pressure, and the residue was thoroughly washed with diethyl ether, filtered, and dried to give the product as a fine yellow solid. Yield = 2.17 g (38%). ¹H NMR (400 MHz, benzene-d6) δ 7.05–6.94 (m, 6H), 6.85–6.76 (m, 6H), 2.28 (s, 18H), 1.67 (s, 6H). 13C NMR (101 MHz, benzene-d6) δ 143.43, 143.15, 129.41, 126.67, 119.95, 117.89, 52.30–46.32 (m), 45.04.

[0419] Synthesis of Ti complexes:

[0420]

[0421] CAT D: The following procedure was performed in a glove box under a nitrogen atmosphere. Cp*TiCl3 (300 mg, 1.37 mmol) was dissolved in 5.2 mL of anhydrous diethyl ether in a 40 mL vial equipped with a stir bar and dried in an oven. The solution was cooled in a glove box freezer for 30 minutes. 2,4,6-Trimethoxy-lithium phenyloxide (184 mg, 1.37 mmol) was added to the CpTiCl3 solution with vigorous stirring. The reaction was warmed to room temperature and stirred overnight at room temperature. The reactants were then filtered, and the solid was washed with 2 mL of anhydrous diethyl ether. The filtrate and washes were combined. Volatiles were removed under vacuum, and a red solid was separated. The material was analyzed by 1H NMR spectroscopy; the crude material appeared to contain unreacted CpTiCl3. The crude product was dissolved in a minimal amount of dichloromethane, and the solution was separated into layers with diethyl ether. The solution was placed in a freezer overnight. The desired complex was separated as red crystals (250 mg, 57%). The product was analyzed by 1H NMR spectroscopy [(400MHz,C6D6)δ 6.57(s,2H), 6.01(s,5H), 2.16(s,6H), 2.08(s,3H)].

[0422]

[0423] CAT E: The following procedure was performed in a glove box under a nitrogen atmosphere. Cp*TiCl3 (400 mg, 1.38 mmol) was dissolved in 19 mL of anhydrous diethyl ether in an oven-dried 40 mL vial equipped with a stir bar. The solution was cooled in a glove box freezer for 30 minutes. 2,4,6-Trimethoxy-lithium phenyloxide (196 mg, 1.38 mmol) was added to the Cp*TiCl3 solution with vigorous stirring. The reaction was warmed to room temperature and stirred overnight at room temperature. The reactants were then filtered, and the solid was washed with 5 mL of anhydrous diethyl ether. The filtrate and washes were combined. Volatiles were removed under vacuum, and a red solid was separated. The material was analyzed by 1H NMR spectroscopy. The crude product was dissolved in a minimal amount of dichloromethane, and the solution was separated into layers with diethyl ether. The solution was placed in a freezer overnight. The desired complex was separated as red crystals (301 mg, 56%). The product was analyzed by 1H NMR spectroscopy [(400MHz, C6D6)δ 6.61(s,2H), 2.29(s,6H), 2.10(s,3H), 1.90(s,15H)]. Note: This material contains some unreacted Cp*TiCl3, which appears to co-crystallize with the desired compound.

[0424]

[0425] CAT F: In an oven-dried vial equipped with a stir bar, dissolve Cp*TiCl3 (200 mg, 0.69 mmol) in 7.5 mL of anhydrous diethyl ether. Place the solution in a glove box freezer for 20 minutes. Then remove the vial from the freezer. Add 1.0 mL (2.1 mmol) of 2.0 M benzyl magnesium chloride solution dropwise to the cooled stirred solution. Slowly heat the reaction mixture to room temperature and stir at room temperature for one hour. Filter the reaction mixture to remove solids and concentrate the yellow solution under vacuum. Separate the pale reddish-brown solid and analyze it by 1H NMR spectroscopy [1H NMR (400 MHz, benzene-d6) δ 6.93 (t, J = 7.3 Hz, 3H), 6.83–6.78 (m, 5H), 2.74 (d, J = 2.7 Hz, 6H), 1.62 (d, J = 0.7 Hz, 13H)]. Note: Aromatic proton peaks overlap with benzene solvent peaks.

[0426] Synthesis of Al-DHCSA

[0427]

[0428] In a glass vial, Al(iBu)3 (3.00 g, 15.13 mmol) and ENB (3.030 g, 25.21 mmol) were mixed with p-xylene (7 mL). The mixture was heated to 130 °C and held for 20 minutes. Isobutylene was allowed to drain. Then, a mixture of p,m-divinylbenzene (Alfa Aesar 80:20) (1.313 g, 10.08 mmol) was added, and the mixture was allowed to reequilibrate at 130 °C for three hours, then cooled to room temperature. After the reaction period (3 hours), the mixture was cooled to room temperature, and the resulting homogeneous solution was used as DHCSA.

[0429] Other chain shuttle agents (CSAs) used in this study include diethylzinc (DEZ) and triethylaluminum (TEA).

[0430] ZnAl-DHCSA (see WO2018 / 064546)

[0431]

[0432] (*The point of contact with the metal; a mixture of isomers)

[0433] II. Catalyst Screening

[0434] PPR screening for hard block Sc complexes (CATB)

[0435] A parallel pressure reactor (PPR) system was used to demonstrate the feasibility of styrene polymerization activity and the chain shuttle capability of the polymerization catalyst. The activity and molecular weight of a given styrene polymerization catalyst relative to the chain shuttler (CSA) loading were investigated. The chain shuttlers studied were diethylzinc (DEZ) and triethylaluminum (TEA), serving as models for polymer-based alkylzinc or polymer-based alkylaluminum substances, respectively. Al-Zn DHCSA was also used. The PPR screening conditions were as follows: [ISOPAR-E + MMAO-3A + T] + (styrene + CSA + "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine" + catalyst); catalyst loading = 0.25 μmole; MMAO-3A loading = 5 μmole; T = 105 °C, t = 15 min, [styrene] = 2.1 M (in toluene).

[0436] Screening the ability of CAT B to polymerize styrene in the presence of various model chain shuttles in PPR. Figure 4 This indicates that CAT B exhibits high efficiency for styrene polymerization (without CSA), and its catalytic activity is unaffected by the addition of TEA (the third circle from the top at CSA = 25 μmole, and the third and fourth circles from the top at CSA = 100 μmole) or Al-Zn DHCSA (the two upper merged circles at CSA = 25 μmole, and the two upper circles at CSA = 100 μmole). For this specific study, the catalytic activity was low in the presence of DEZ (the two lower merged circles at CSA = 25 μmole, and the two lower merged circles at CSA = 100 μmole). Figure 5 The data shows that the addition of CSA leads to a decrease in molecular weight, indicating that the catalyst participates in effective chain shuttle. Note that Al-Zn DHCSA is represented by two upper circles at CSA = 25 μmole and two upper circles at CSA = 100 μmole. TEA is represented by two merged lower circles at CSA = 25 μmole and two merged lower circles at CSA = 100 μmole.

[0437] Table 1 further illustrates the effect of adding 100 μmole of CSA on the polymerization of styrene with CAT B at 105 °C. Additionally, the polymerization of styrene with CAT B was examined in the presence of 1-octene. The PPR screening conditions were as follows: T = 105 °C, catalyst loading = 0.25 μmole, [styrene] = 2.1 M (in toluene), t = 15 min. As shown in Table 1, the catalyst activity and molecular weight were not affected by the addition of 1-octene, indicating that CAT B is compatible with the residual α-olefin monomer transferred from the first reactor to the second reactor. This data indicates that catalyst CAT B meets the above-described requirements for the second reactor (R2) catalyst (a)-c) (see Specific Embodiments).

[0438] Table 1: Effects of CSA and 1-octene on the polymerization of styrene with CATB.

[0439]

[0440] M = metal of catalyst (Sc)

[0441] Chain shuttle experiment of Sc catalyst CAT B

[0442] Toluene (final volume 8 mL), styrene (1 mL), and a magnetic stir bar were placed in a glass vial. CAT B (5 μmol), bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine (1.2 equivalents (equivalent to CAT B)), and TEA or DEZ (0, 25 μmol or 100 μmol) were added sequentially to the solution. The mixture was heated at 100 °C for one hour, then cooled and quenched in methanol. The polymer was collected by filtration and dried under vacuum. GPC results were obtained in… Figure 6 The results are shown in Table 2. Chain shuttle processes occurred, as indicated by the decrease in molecular weight and MWD (Mw / Mn) in the presence of DEZ or TEA compared to sPS-1.

[0443] Table 2: Syndiotactic polystyrene (sPS) prepared with and without zinc and aluminum chain shuttles

[0444]

[0445] III. Analysis of Vinyl-Rich Aromatics (Hard Block) and Vinyl-Depleted Aromatics (Soft Block)

[0446] Batch reactor polymerization unit

[0447] The batch reactor unit consists of a 600 mL Parr reactor controlled by a process control system. The reactor is equipped with an electrically heated jacket, internal cooling coils for temperature control, and electrically heated transfer lines between the reactor and the reactor pouring tank. Three feed options are available, allowing loading of either solvent or monomer from a removable 1-liter (50 mL) cylinder. This cylinder is loaded into an inert (N2) glove box, and its contents are transferred to the reactor via nitrogen injection. Catalyst components and chain shuttles are prepared in the inert glove box and transferred from the 50 mL cylinder to the reactor via nitrogen transfer. The “1-octene cylinder” is filled with purified plant feed. Ethylene is supplied by Airgas at high purity. For further purification, 1-octene and ethylene are passed through an inline bed of activated alumina, 13X molecular sieves, and Q5 material. The high-pressure nitrogen used for catalyst injection and purging is ultra-high purity. Styrene is degassed, and inhibitors are removed just before addition to the reactor by passing the styrene supply through a neutral alumina plug.

[0448] Polymerization of ethylene, 1-octene, and styrene: Reactivity of CAT B (vinyl-rich aromatic hydrocarbons)

[0449] Degassed anhydrous toluene was added from a nitrogen-pressurized solvent cylinder to a 600 mL Parr reactor using a mass flow meter, with the reactor agitator set to 450 rpm. Styrene was injected via a nitrogen-pressurized cylinder. When in use, a predetermined amount of 1-octene was added to the reactor from a nitrogen-pressurized cylinder using a flow meter. Once the reactor reached its initial temperature setpoint of 120°C, a predetermined amount of ethylene was added to the reactor using a flow meter, followed by the addition of the active catalyst solution. The catalyst solution was prepared by adding a pre-prepared Cp*ScR2 (CAT B) toluene solution (typically at a loading of 22 μmol Sc), a solution of 0.006 M "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)borate (1-)amine" activator in toluene (1.0-1.2 equivalents), and a solution of 0.05 M MMAO-3A in toluene (10 equivalents). Each "equivalent" corresponds to one equivalent of CAT B.

[0450] A flow of ethylene at 200 mg / min was initiated, while the total reactor pressure was maintained at the programmed setpoint throughout the desired ten-minute run time. After the mixing time, the agitator was stopped, and the reactor contents were poured into a pouring tank. The tank contents were poured into methanol, and the mixture was stirred. The polymer precipitate was filtered and dried in a vacuum oven at 130°C for six hours. The polymerization conditions and polymer properties are shown in Table 3 below. See also Table 4. The interpolymers AR1-AR12 in Tables 3 and 4 each represent the vinyl-rich aromatic (hard block) (AR) segments of ethylene / octene / -styrene diblock or triblock interpolymers in terms of, for example, monomer composition, stereoregularity of the polymerized vinyl aromatics, Tm, and Tg.

[0451]

[0452]

[0453] Polymerization of ethylene, 1-octene, and styrene: Reactivity of CATA (vinyl-depleted aromatics)

[0454] Degassed anhydrous toluene was added to a 600 mL Parr reactor from a nitrogen-pressurized solvent cylinder using a mass flow meter, with the reactor agitator set to 450 rpm. Styrene was injected via a high-pressure nitrogen-pressurized cylinder. A predetermined amount of 1-octene was added to the reactor from a nitrogen-pressurized cylinder using a flow meter. Once the reactor reached its initial temperature setpoint of 120 °C, a predetermined amount of ethylene was added to the reactor using a flow meter, followed by the addition of the active catalyst solution. The catalyst solution was prepared by adding a pre-prepared CATA catalyst toluene solution, a solution of 0.006 M "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)borate (1-)amine" activator in toluene (1.0-1.2 equivalents), and a solution of 0.05 MMAO-3A in toluene (10 equivalents). Each "equivalent" corresponds to one equivalent of CATA.

[0455] A flow of ethylene at 200 mg / min was initiated, while the total reactor pressure was maintained at the programmed setpoint throughout the desired ten-minute run time. After the mixing time, the agitator was stopped, and the reactor contents were poured into a pouring tank. The tank contents were poured into methanol, and the mixture was stirred. The polymer precipitate was filtered and dried in a vacuum oven at 130°C for six hours. The polymerization conditions and polymer properties are shown in Table 5 below. See also Table 6. The interpolymers AP1-AP11 in Table 6 each represent the vinyl-poor (soft block) (AP) segments of ethylene / octene / -styrene diblock or triblock interpolymers in terms of, for example, monomer composition, stereoregularity of the polymerized vinyl aromatics, Tm, and Tg.

[0456]

[0457]

[0458] IV. Dual-catalyst polymerization using chain shuttles

[0459] Batch reactor polymerization unit (double Parr reactor) – solution polymerization

[0460] The polymerization unit consists of two reactors (a 600 mL Parr reactor (reactor 1, R1) and a 2.0 L Parr reactor (reactor 2, R2), each controlled by a separate process control system). Both reactors are equipped with electrically heated jackets, internal cooling coils for temperature control, and electrically heated transfer lines between the reactors and from each reactor to the reactor pouring tank. Three feeds are available for either reactor, with the option of loading solvent or monomer from a removable “1 L sample cylinder.” The “1 L cylinder” is loaded into an inert (N2) glove box, and its contents are transferred to either reactor via nitrogen injection. Catalyst components and chain shuttles are prepared in the inert glove box and transferred from a “50 mL cylinder” to the respective reactor via nitrogen transfer. ISOPAR-E and 1-octene cylinders are filled with purified plant feed. Ethylene is supplied by Airgas at high purity. For further purification, 1-octene and ethylene are passed through an inline bed of activated alumina, a 13X moiré sieve, and Q5 material. The high-pressure nitrogen used for catalyst injection and purging is of ultra-high purity.

[0461] Batch reactor - solution polymerization - compositions containing triblock 2

[0462] A solution of Al-DHCSA (1.5 mL, 578 μmol) in 4 mL of ISOPAR-E was injected into a 600 mL Parr reactor (R1 (first reactor)) via high-pressure nitrogen injection. ISOPAR-E (121.4 g) was added to R1 from a nitrogen-pressurized solvent cylinder using a mass flow meter, and the reactor agitator was set to 450 rpm. A predetermined amount of 1-octene (20.4 g) was added to R1 from a nitrogen-pressurized cylinder using a flow meter. Once the reactor reached its initial temperature setpoint of 120 °C, a predetermined amount of ethylene (7.1 g) was added to the reactor using a flow meter, followed by the addition of the active catalyst solution. The catalyst solution was prepared by adding a solution of 0.25 mL of 0.005 M CATA in toluene, a solution of 0.25 mL of 0.006 M "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine" in toluene, and a solution of 0.25 mL of 0.05 M MMAO-3A in toluene to a vial containing 4 mL of toluene.

[0463] An ethylene flow rate of 200 mg / min was initiated, while the total reactor pressure was maintained at 192.7 psig (for R1) throughout the desired 10-minute run time. During the R1 run time, 200 mL of toluene was charged into the “2.0 L Parr” reactor (R2, the second reactor) via a nitrogen-pressurized small cylinder. The R2 agitator was set to 450 rpm, and the R2 initial temperature setpoint was set to 120 °C. When the run time (10 minutes) in R1 was completed, the agitators in both reactors (R1 and R2) were stopped. R1 was pressurized with nitrogen to transfer the contents of R1 to R2 via a preheating line. The catalyst (with a lifetime of less than 10 minutes) was used up when CA A entered the second reactor.

[0464] Once the contents were transferred, the R2 agitator was restarted. Styrene monomer (5 mL, 0.044 mol) was injected into R2 via a nitrogen-pressurized small cylinder, followed immediately by the addition of 200 mL of an active catalyst solution in toluene. The catalyst solution was prepared by adding a solution of 45 μmol of the Sc complex CAT B in toluene, 0.083 mL of 0.006 M "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine" (0.5 μmol) in toluene, and 0.100 mL of 0.05 M MMAO-3A (5 μmol) in toluene to a vial containing 4 mL of toluene. Exothermic reaction was observed after the catalyst addition. The R2 contents were stirred at 120 °C for one hour (for R2). After the reaction time, the R2 agitator was stopped, and the R2 contents were poured into a pouring tank. The tank contents were then poured into methanol and stirred overnight. The polymer precipitate (a composition containing an ethylene / octene / styrene triblock terpolymer (triblock 2)) was filtered and dried in a vacuum oven at 130°C for six hours (yield 11.6 g). NMR curves were obtained in... Figure 7 (1H NMR) and Figure 8 As shown in (13C NMR). Based on Figure 7 The peak integrals are based on the weight of the composition, which contains 30% by weight of polystyrene. The peaks representing the phenyl C-1 (δ 145.50), Sαα (δ 43.35), and Tββ (δ 40.61) peaks of the syndiotactic polystyrene block are shown in [the original text]. Figure 8 As shown in the image.

[0465] Other polymer compositions

[0466] Other polymer compositions are described below. Polymerization conditions and polymer composition properties are listed in Tables 7 and 8.

[0467] The process described above for triblock 2 was used to polymerize triblock 1 (a composition containing an ethylene / octene / styrene triblock 1 terpolymer), except for the following changes. A solution of Al-DHCSA (1.5 mL, 690 μmol) in 4 mL of ISOPAR-E was injected into a 600 mL Parr reactor (R1) via high-pressure nitrogen injection. An ethylene flow of 200 mg / min was initiated, while the total reactor pressure was maintained at 192.7 psig (for R1) throughout the desired 30-minute run. Styrene monomer (5 mL, 0.690 mmol) was injected into R2 via a nitrogen-pressurized small cylinder, followed immediately by the addition of an active catalyst solution of 200 mL in toluene. A catalyst solution was prepared by adding a solution of 0.240 mL of 0.0021 M Sc complex CAT B (0.5 μmol) in toluene, 0.083 mL of 0.006 M "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine" (0.5 μmol) in toluene, and 0.100 mL of 0.05 MMAO-3A (5 μmol) in toluene to a vial containing 4 mL of toluene. The polymer precipitate (containing the triblock composition) was filtered and dried in a vacuum oven at 130 °C for six hours (yield 13.0 g). For the detection of AR-AP coupling (vinyl-rich aromatics (hard block) - vinyl-depleted aromatics (soft block) S), a Malvern 305aHT GPC with a triple detector (dRI, DV, LS) connected to DiscovIR™ (FTIR) and PDA (UV-Vis) was used. GPC data are available in […]. Figure 9 The image shows the response of the HT GPC dRI / UV dual detector to dual-batch reactor operation, displaying uncoupled PS, uncoupled EO, and coupled PS. From... Figure 9 It can be seen that the formation of block interpolymers is characterized by "coupled PS" peaks.

[0468] Triblock 3 (a composition containing an ethylene / octene / styrene triblock terpolymer) is prepared according to the process of triblock 2 as described above, except for the variations mentioned in Table 7 below. Diblock 1 (a composition containing an ethylene / octene / styrene diblock terpolymer) is prepared according to the process of triblock 2 as described above, except that TEA (400 μmole) is used as the CSA, and except for the variations mentioned in Table 7 below. Diblock 2 (a composition containing an ethylene / octene / styrene diblock terpolymer) is prepared according to the process of triblock 2 as described above, except that DEZ (100 μmole) is used as the CSA, and except for the variations mentioned in Table 7 below.

[0469] Two in-reactor blends (IB-1 and IB-2) (without CSA) (each of the ethylene / octene random copolymer and the syndiotactic stereostyrene-based polymer) were prepared using the same method as that used for the triblock 2 above, but without pre-injection of Al-DHCSA, and except for the variations mentioned in Table 7 below.

[0470] Table 7: Polymerization conditions and composition properties

[0471]

[0472] Table 8: 13C NMR data of polymer compositions

[0473]

[0474] a) Each mole % of polymeric monomer is based on the total number of moles of all polymeric monomers in the composition.

[0475] b) Each % by weight of polymeric monomer is based on the total weight of all polymeric monomers in the composition.

[0476] c) The ratio of block styrene to separated styrene = (integral T) ββ +T βδ ) / integral T δδ *T was almost not detected. δδ .

[0477] GPC Research

[0478] Refer to the GPC procedure described above in the Test Methods section. A Polymer Char (Valencia, Spain) high-temperature gel permeation chromatography system consisting of an infrared concentration / composition detector (IR-5) was used for MW and MWD determinations. The carrier solvent was 1,2,4-trichlorobenzene (TCB). The autosampler and detector chambers were operated at 160°C, and the column chamber at 150°C. The GPC column assembly was calibrated using 21 polystyrene standards with narrow molecular weight distributions. The GPC curves are shown in Figures 10a and 10b. The GPC results are shown in Tables 7 and 9. For the molecular weight distribution of the polymer in the two reactors, the values ​​are polystyrene equivalent molecular weights. As can be seen from Table 9, the composition containing the triblock polymer exhibits a wider MWD compared to the in-reactor blend (IB-1).

[0479] Table 9: GPC (Routine) Results

[0480]

[0481] Tensile test study

[0482] The mechanical properties of the two polymer samples are shown in Table 10. See also: Figure 11 The sample exhibited elastic recovery behavior.

[0483] Table 10: Tensile test data.

[0484] Tri-segment 1 79 73％ 53％ Tri-segment 2 58 70％ 56％

[0485] V. Atactic polystyrene (aPS): CAT C

[0486] Polymerization experiment: Toluene (final volume 8 mL), styrene (1 mL), and a magnetic stir bar were placed in a glass vial. CAT C (5 μmol), "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine" (1.2 equivalents), and TEA or DEZ (0.25 μmol or 100 μmol) were added sequentially to the solution. The mixture was heated at 100 °C for one hour, then cooled and quenched in methanol. The polymer was collected by filtration and dried under vacuum. The results are shown in Table 11. GPC curves are shown in... Figure 12 As shown in the figure. These results indicate that chain shuttle processes occur, as indicated by the decrease in molecular weight and MWD (Mw / Mn) in the presence of DEZ or TEA.

[0487] Table 11: Randomized polystyrene prepared with and without scandium catalyst in the presence of zinc or aluminum chain shuttlers (aPS)

[0488]

[0489] VI.Ti complex

[0490] PPR screening of Ti complexes (CATD, CATE, and CATF)

[0491] A parallel pressure reactor (PPR) system was used to demonstrate the feasibility of styrene polymerization activity and the chain shuttle of each polymerization catalyst mentioned below. The activity and molecular weight of the given styrene polymerization catalyst candidates relative to the CSA loading were investigated. The CSAs studied were diethylzinc (DEZ, 25 μmole or 100 μmole) and triethylaluminum (TEA, 25 μmole or 100 μmole), serving as models for polymer-based alkyl zinc or polymer-based aluminum substances, respectively. The PPR screening conditions were as follows: [ISOPAR-E + MMAO-3A + T] + (styrene + CSA + "bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine" + catalyst); catalyst loading = 0.25 μmole; MMAO-3A loading = 50 μmole; T = 75 °C and 105 °C, t = 15 min, [styrene] = 2.1 M (in toluene).

[0492] Screening in PPR the ability of CAT D to polymerize styrene in the presence of the mentioned chain shuttle. Figure 13The addition of CSA indicates a decrease in molecular weight, suggesting that the catalyst participates in effective chain shuttle. CAT D exhibits relatively low styrene polymerization efficiency. The ability of CAT E to polymerize styrene in the presence of the mentioned chain shuttle was screened in PPR. Figure 14 The addition of CSA indicates a decrease in molecular weight, suggesting that the catalyst participates in effective chain shuttle. CAT E exhibits relatively low styrene polymerization efficiency. The ability of CAT F to polymerize styrene in the presence of the mentioned chain shuttle was screened in PPR. Figure 15 The addition of CSA indicates a decrease in molecular weight, suggesting that the catalyst participates in effective chain shuttle. CATF exhibits relatively low styrene polymerization efficiency.

Claims

1. A method for forming a composition comprising an ethylene / vinyl aromatics diblock interpolymer and / or an ethylene / vinyl aromatics triblock interpolymer, said method comprising at least the following steps: A) Polymerize a mixture A comprising ethylene and optionally α-olefins and optionally vinyl aromatics in reactor A in the presence of at least the following: a) a metal complex S selected from the following: formula S1, formula S2, formula S3, formula S4 or formula S5: ， Where M 1 It is a metal selected from titanium, zirconium, or hafnium; and said metal is in an oxidation state of +2, +3, or +4. Each X is independently selected from substituted or unsubstituted C1-C. 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 Heteroalkyl group or −H; and each X is independently a monodentate or bidentate ligand; n is 0, 1 or 2, and X can be a bidentate ligand when n is 1; R 1 It is a bridging group containing 2 to 41 atoms other than hydrogen, and wherein optionally, R 1 The bond between M and M is a π bond; R 2 Selected from substituted or unsubstituted C1-C 30 Hydrocarbon group or substituted or unsubstituted C1-C 30 heterohydrocarbon groups; J 1 It connects N and R 1 It also comprises a bridging group containing 2 to 40 atoms other than hydrogen, and optionally, the bridging group comprises a group capable of bonding with the M via an electron-donating bond. 1 Interacting N atoms; and The metal complexes described therein are generally electrically neutral; ， Where M 1 It is a metal selected from titanium, zirconium, or hafnium; and said metal is in an oxidation state of +2, +3, or +4. Each X is independently selected from substituted or unsubstituted C1-C. 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 Heteroalkyl group or −H; and each X is independently a monodentate or bidentate ligand; n is 0, 1 or 2, and X can be a bidentate ligand when n is 1; R 3 and R 4 Each of them is independently selected from substituted or unsubstituted C6-C. 20 The aryl group is either substituted or unsubstituted C5-C. 20 heteroaryl groups; N and N are connected by the bridging group J 2 The bridging group comprises 2 to 40 atoms other than hydrogen, and optionally, the bridging group comprises an N atom capable of interacting with the metal via an electron-donating bond; and The metal complexes described therein are generally electrically neutral; ， Where M 1 It is a metal selected from titanium, zirconium, or hafnium; and said metal is in an oxidation state of +2, +3, or +4. Each X is independently selected from substituted or unsubstituted C1-C. 30 Hydrocarbon group, substituted, unsubstituted C1-C 30 Heteroalkyl group or −H; and each X is independently a monodentate or bidentate ligand; n is 0, 1 or 2, and X can be a bidentate ligand when n is 1; R 5 Is it substituted or unsubstituted C1-C? 30 Hydrocarbon group or substituted or unsubstituted C1-C 30 heteroalkyl groups, −Si(R) C )3 or −H; T 1 Selected from −O−, −S−, −N(R) N - or –P(R) P )−; t is 1 or 2; And among them T 1 and N through J 3 The bridging group represents a connection, wherein the bridging group comprises 4 to 50 atoms other than hydrogen; In equation S3, each R P R N and R C C1-C is substituted or unsubstituted independently. 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 heteroalkyl groups or −H; and The metal complexes described therein are generally electrically neutral; ， Where M 1 It is a metal selected from zirconium or hafnium; and said metal is in an oxidation state of +2, +3 or +4. Each X is independently selected from substituted or unsubstituted C1-C. 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 Heteroalkyl group or −H; and each X is independently a monodentate or bidentate ligand; n is 0, 1 or 2, and X can be a bidentate ligand when n is 1; -T 2 -and-T 3 Each of the elements in - is independently selected from -O−, -S−, -N(R) N - or –P(R) P )−; R 6 and R 21 Each group is independently selected from the following: –H, substituted or unsubstituted C1-C. 40 Hydrocarbon group, substituted or unsubstituted C1-C 40 heterohydrocarbon group, −Si(R) C )3、−Ge(R C )3、−P(R P )2、−N(R N )2、−OR C 、−SR C ,-NO2,-CN,-CF3,R C S(O)−、R C S(O)2−、(R C )2C=N−、R C C(O)O−、R C OC(O)−、R C C(O)N(R)−、(R C )2NC(O)−, halogens, groups having formula (I), groups having formula (II), and groups having formula (III): Where R 22–26 R 27–34 and R 35–43 Each of them is independently selected from substituted or unsubstituted C1-C. 40 Hydrocarbon group, substituted or unsubstituted C1-C 40 heterohydrocarbon group, −Si(R) C )3、−Ge(R C )3、−P(R P )2、−N(R N )2、−N=CHR C -OR C 、−SR C ,-NO2,-CN,-CF3,R C S(O)−、R C S(O)2−、(R C )2C=N−、R C C(O)O−、R C OC(O)−、R C C(O)N(R N )−、(R C )2NC(O)−, halogen or -H; R 7–20 Each of them is independently selected from substituted or unsubstituted C1-C. 40 Hydrocarbon group, substituted or unsubstituted C1-C 40 heterohydrocarbon group, −Si(R) C )3、−Ge(R C )3、−P(R P )2、−N(R N )2、−N=CHR C -OR C 、−SR C ,-NO2,-CN,-CF3,R C S(O)−、R C S(O)2−、(R C )2C=N−、R C C(O)O−、R C OC(O)−、R C C(O)N(R N )−、(R C )2NC(O)−, halogen or -H; J 4 Is it substituted or unsubstituted C1−C? 40 Hydroxyl group or substituted or unsubstituted C1−C 40 Heteroalkyl groups, wherein the substituted or unsubstituted C1−C 40 The alkylene group has a portion comprising a linker backbone containing 1 to 10 carbon atoms, said portion being linked to the group T in formula S4. 2 and T 3 J 4 With T 2 and T 3 Bonding; or the substituted or unsubstituted C1−C 40 The heteroalkyl group has a portion comprising a 1-atom to 10-atom linker backbone, said portion being linked to the group T in formula S4. 2 and T 3 Each of the 1 to 10 atoms in the 1-to-10-atom linker backbone is independently a carbon atom or a heteroatom of a heteroatom group, wherein each heteroatom group is independently O, S, S(O), S(O)2, Si(R)2, or S(O)2. C )2、Ge(R C )2、P(R C ) or N(R C ), where each R C C1−C is independently substituted or unsubstituted. 30 Hydrocarbon group or substituted or unsubstituted C1−C 30 heterohydrocarbon group; and each R in formula S4 P R N And the rest of R C C1-C is substituted or unsubstituted independently. 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 heteroalkyl groups or −H; and The metal complexes described therein are generally electrically neutral; or ， Where M 1 It is a metal selected from titanium, zirconium, or hafnium; and said metal is in an oxidation state of +2, +3, or +4. Each X is independently selected from substituted or unsubstituted C1-C. 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 Heteroalkyl group or −H; and each X is independently a monodentate or bidentate ligand; n is 0, 1 or 2, and X can be a bidentate ligand when n is 1; R 44-51 Each is independently selected from substituted or unsubstituted C1-C. 40 Hydrocarbon group, substituted or unsubstituted C1-C 40 heterohydrocarbon group, −Si(R) C )3 or –H; and optionally from R 44-51 Two or more groups are linked such that the cyclopentadienyl group is a substituted or unsubstituted indenyl group or a substituted or unsubstituted fluorenyl group; and wherein R C Independently selected from substituted or unsubstituted C1-C 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 heteroalkyl group or −H; O and O are connected by J 5 The bridging group represents a connection, wherein the bridging group comprises 1 to 30 atoms other than hydrogen; and The metal complexes described therein are generally electrically neutral; B) Polymerize a mixture B comprising ethylene, vinyl aromatics, and optionally α-olefins in reactor B in the presence of at least the following: b) a metal complex H selected from formula H1 or H2: ， Where M 2 It is Ti, Sc, Y, or elements from the lanthanide series; R 1 R 2 R 3 R 4 and R 5 Each is independently an H or a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterohydrocarbon group; Q 1 Q 2 and Q 3 Each is independently a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterohydrocarbon group, or a halogen; L is a Lewis base; and each n is independently 0 or 1; and m is an integer from 0 to 3; and Optionally, at least one L group and at least one Q group are linked, and optionally at least one R group and at least one Q group are linked; The metal complexes described therein are generally electrically neutral; ， Where M 3 It is a metal selected from titanium, zirconium, or hafnium; and said metal is in an oxidation state of +2, +3, or +4. Each Q is independently selected from substituted or unsubstituted C1-C. 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 Heteroalkyl group or −H; and each Q is independently a monodentate or bidentate ligand; n is 0, 1 or 2, and optionally when n is 1, Q can be a bidentate ligand; R 1 and R 2 Each is independently a bridging group comprising 2 to 41 atoms other than hydrogen, and optionally, R 1 and R 2 Each can be an independently substituted or unsubstituted aryl group; -Z 1 -and-Z 2 Each of the elements in - is independently selected from -O−, -S−, -Se−, -N(R) N - or –P(R) P )−; and where -Z 1 -and-Z 2 Each of them can independently and optionally interact with the metal via an electron-donating bond; Z 1 and Z 2 By J 5 The bridging group represents the connection, and the bridging group comprises 1 to 50 atoms other than hydrogen. Where R P and R N Each is independently either substituted or unsubstituted C1-C 30 Hydrocarbon group, substituted or unsubstituted C1-C 30 heteroalkyl groups or −H; and The metal complexes described therein are generally electrically neutral; and Step A occurs before step B, and at least a portion of the reactor product in reactor A is transferred to reactor B; or step B occurs before step A, and at least a portion of the reactor product in reactor B is transferred to reactor A; and If step A occurs before step B, then at least one chain shuttle is fed into reactor A; and If step B occurs before step A, then at least one chain shuttle agent is fed into reactor B; and Wherein the vinyl aromatic hydrocarbon in step A is the same as the vinyl aromatic hydrocarbon in step B; and the α-olefin in step A is the same as the α-olefin in step B.

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

3. The method according to claim 1 or claim 2, wherein the metal complex S is selected from structure s1a1 or structure s1a2: or .

4. The method according to any one of claims 1 to 2, wherein the metal complex H is selected from the following formulas: h1a1, h1a2, h1a3, h1b1, h1b2, h1b3, h2a1, or h2a2, wherein Bn = benzyl group Ph-CH2-: , , , , , , or .

5. The method according to any one of claims 1 to 2, wherein the at least one chain shuttle is selected from the group consisting of alkyl zinc compounds, alkyl aluminum compounds, double-ended chain shuttles, or combinations thereof.

6. The method according to any one of claims 1 to 2, wherein step A occurs before step B.

7. The method according to any one of claims 1 to 2, wherein step B occurs before step A.

8. The method according to any one of claims 1 to 2, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, the vinyl aromatic is styrene.

9. The method according to any one of claims 1 to 2, wherein the mixture A comprises the α-olefin.

10. A composition formed by the method according to any one of claims 1 to 9.

11. The composition of claim 10, comprising an ethylene / vinyl aromatic diblock copolymer or an ethylene / vinyl aromatic triblock copolymer, wherein the diblock copolymer comprises at least one polymer structure selected from structure 1 shown below, and the triblock copolymer comprises at least one polymer structure selected from structure 2 or structure 3 shown below, wherein AR refers to vinyl-rich aromatics and AP refers to vinyl-poor aromatics: (AR)-(AP) Structure 1, (AR)-(AP)-(AR) Structure 2 (AP)-(AR)-(AP) Structure 3; and Each AR segment independently comprises, in polymeric form, ethylene, the vinyl aromatic hydrocarbon, and optionally an α-olefin; and Each AP segment independently comprises, in polymeric form, ethylene, optionally the vinyl aromatic hydrocarbon, and optionally the α-olefin; and Each AR segment independently contains >10 mol% of the vinyl aromatic hydrocarbon in polymeric form, based on the total molar number of monomers in the AR segment; and Each AP segment contains ≤10 mol% of the vinyl aromatic hydrocarbon in polymeric form, based on the total molar number of polymeric monomers in the AP segment.

12. The composition of claim 11, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each AR segment independently comprises, in polymeric form, 15 mol% to <100 mol% of the vinyl aromatics based on the total molar number of polymerizable monomers in the AR segment.

13. The composition according to claim 11 or claim 12, wherein for the ethylene / vinyl aromatics diblock interpolymer or the ethylene / vinyl aromatics triblock interpolymer, each AP segment independently comprises 0 mol% to 10 mol% of the vinyl aromatics in polymeric form, based on the total molar number of polymerizable monomers in the AP segment.

14. The composition according to any one of claims 11 to 12, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each AR segment independently comprises 2.0 mol% to 80 mol% ethylene in polymeric form, based on the total molar number of polymerizable monomers in the AR segment.

15. The composition according to any one of claims 11 to 12, wherein for the ethylene / vinyl aromatic diblock interpolymer or the ethylene / vinyl aromatic triblock interpolymer, each AP segment independently comprises 50 mol% to 100 mol% ethylene in polymeric form, based on the total molar number of polymerizable monomers in the AP segments.

16. The composition according to any one of claims 11 to 12, wherein for the ethylene / vinyl aromatic diblock or triblock interpolymer, ≥20 mol% of polymerized vinyl aromatics in each AR segment are present in the sub-segment bb in a "back-to-back" configuration as shown below: ; and wherein the mole % is based on the total number of moles of polymerized vinyl aromatics in the AR segment.

17. The composition according to any one of claims 11 to 12, wherein for the ethylene / vinyl aromatic diblock or triblock interpolymer, ≥20 mol% of the polymerized vinyl aromatic in each AR segment is present in the sub-segment sbb in a syndiotactic "back-to-back" configuration as shown below: ; and wherein the mole % is based on the total number of moles of polymerized vinyl aromatics in the AR segment.

18. The composition according to any one of claims 11 to 12, wherein for the ethylene / vinyl aromatic diblock or triblock interpolymer, no polymerized vinyl aromatics are present in each AP segment in a "back-to-back" configuration in the sub-segment bb as shown below: ; and wherein the mole % is based on the total number of moles of polymerized vinyl aromatics in the AP segment.

19. The composition according to any one of claims 11 to 12, wherein, for the ethylene / vinyl aromatic diblock or triblock interpolymer, the vinyl aromatic is styrene.

20. An article comprising at least one component formed of the composition according to any one of claims 10 to 19.

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