Biaxial Chain Growth of Polyolefin and Polystyrene from 1,6-Hexanediylzinc Species for Triblock Copolymers

Park, Seung Soo; Kim, Chung Sol; Kim, Sung‐Dong; Kwon, Soo Hyun; Lee, Hyun Mo; Kim, Tae Hee; Jeon, Jong Yeob; Lee, Hyun Ju

doi:10.1021/acs.macromol.7b01365

Cited by 29 publications

(47 citation statements)

References 68 publications

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“…Syntheses of polyethylene-block-polyester and polyethylene-block-polyether have been attempted with POs functionalized with -OH end groups, which were generated by treatment of the CCTP product (polyolefinyl) 2 Zn with O 2 [28][29][30][31]. We also discovered a method to grow polystyrene (PS) chains initiating from (polyolefinyl) 2 Zn that allows the syntheses of commercially more relevant PO-block-PS and PS-block-PO-block-PS in one-pot [32][33][34][35]. In those works, n-BuLi•(TMEDA) (TMEDA = tetramethylethylenediamine, i.e., Me 2 NCH 2 CH 2 NMe 2 ) and Me 3 SiCH 2 Li•(PMDTA) (PMDTA = pentamethyldiethylenetriamine, i.e., Me 2 NCH 2 CH 2 N(Me)CH 2 CH 2 NMe 2 ) were introduced to grow PS chains from (polyolefinyl) 2 Zn.…”

Section: Methodsmentioning

confidence: 99%

“…(Polyolefinyl) 2 Zn was prepared via coordinative chain transfer copolymerizations (CCTcoPs) performed using a pyridylamidohafnium catalyst (1 in Scheme 1) in methylcyclohexane at high temperatures of 90-110 • C by feeding ethylene/propylene mixed gases. Catalyst 1 is the best in performing CCTcoPs [22,33,[41][42][43]. It undergoes fast alkyl exchange with Zn sites to generate PO chains with a narrow molecular weight distribution [21,44].…”

Section: Attempts To Synthesize Block Copolymersmentioning

confidence: 99%

“…However, the amounts of the extracted homo-PSs were slightly higher (30-34% vs. 27-29%) and the molecular weight distributions of the extracted homo-PSs were broader than those in the case of pentylallyl-Li•(PMDTA) (M w /M n 1.38-1.52 vs. 1.23-1.25), indicating that pentylallyl-Li•(PMDTA) might be a better initiator than PhLi•(PMDTA) in growing PS chains from (polyolefinyl) 2 Zn. Previously, we introduced n-BuLi•(TMEDA) and Me 3 SiCH 2 Li•(PMDTA) as initiators for growing PS chains from the CCTP product (polyolefinyl) 2 Zn, mainly based on the model studies performed with R 2 Zn (R = Et, 1-hexyl, benzyl) [32,33]. Though significant performance differences could not be observed among pentylallyl-Li•(PMDTA), PhLi•(PMDTA), n-BuLi•(TMEDA), and Me 3 SiCH 2 Li•(PMDTA) in the model studies performed with (1-hexyl) 2 Zn (Table 2), the studies performed with actual (polyolefinyl) 2 Zn indicated that pentylallyl-Li•(PMDTA) and PhLi•(PMDTA) were superior to the previous initiators.…”

Section: Synthesis Of Po-block-psmentioning

confidence: 99%

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Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

et al. 2020

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Polyolefins (POs) are the most abundant polymers. However, synthesis of PO-based block copolymers has only rarely been achieved. We aimed to synthesize various PO-based block copolymers by coordinative chain transfer polymerization (CCTP) followed by anionic polymerization in one-pot via conversion of the CCTP product (polyolefinyl)2Zn to polyolefinyl-Li. The addition of 2 equiv t-BuLi to (1-octyl)2Zn (a model compound of (polyolefinyl)2Zn) and selective removal or decomposition of (tBu)2Zn by evacuation or heating at 130 °C afforded 1-octyl-Li. Attempts to convert (polyolefinyl)2Zn to polyolefinyl-Li were unsuccessful. However, polystyrene (PS) chains were efficiently grown from (polyolefinyl)2Zn; the addition of styrene monomers after treatment with t-BuLi and pentamethyldiethylenetriamine (PMDTA) in the presence of residual olefin monomers afforded PO-block-PSs. Organolithium species that might be generated in the pot of t-BuLi, PMDTA, and olefin monomers, i.e., [Me2NCH2CH2N(Me)CH2CH2N(Me)CH2Li, Me2NCH2CH2N(Me)Li·(PMDTA), pentylallyl-Li⋅(PMDTA)], as well as PhLi⋅(PMDTA), were screened as initiators to grow PS chains from (1-hexyl)2Zn, as well as from (polyolefinyl)2Zn. Pentylallyl-Li⋅(PMDTA) was the best initiator. The Mn values increased substantially after the styrene polymerization with some generation of homo-PSs (27–29%). The Mn values of the extracted homo-PS suggested that PS chains were grown mainly from polyolefinyl groups in [(polyolefinyl)2(pentylallyl)Zn]−[Li⋅(PMDTA)]+ formed by pentylallyl-Li⋅(PMDTA) acting onto (polyolefinyl)2Zn.

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Section: Methodsmentioning

confidence: 99%

Section: Attempts To Synthesize Block Copolymersmentioning

confidence: 99%

Section: Synthesis Of Po-block-psmentioning

confidence: 99%

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Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

et al. 2020

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“…In the other way, the styrene signals were observed at 7.2-5.0 ppm region ( Figure S2) in the 1 H NMR spectrum of a low molecular weight poly(ethylene-co-propylene), which was synthesized by feeding a high amount of 3 (Zn = 500 μmol) and by cutting the polymerization at an early stage (5 min). Preparation of the dialkylzinc species containing styrene moieties (3) was carried out through alkyl exchange between Et2Zn and the hydroboration product of divinylbenzene (Scheme 3) [42,48]. During the dynamic alkyl exchange process, the transient Et3B species was removed by evacuation at 0 °C, eventually leading to formation of the desired product, 3.…”

Section: Strategy For the Preparation Of Ps-block-po-block-psmentioning

confidence: 99%

“…In this case, the PS chains were grown preferentially from the R-groups present in R2Zn and also partially from the Me3SiCH2-moieties [42]. Thus, following completion of the CCTP reaction, the anionic initiator Me3SiCH2Li·(pmdeta) (150 μmol, [Li] …”

Section: Synthesis Of Ps-block-po-block-psmentioning

confidence: 99%

Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

et al. 2017

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Triblock copolymers of polystyrene (PS) and a polyolefin (PO), e.g., PS-block-poly(ethyleneco-1-butene)-block-PS (SEBS), are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH 2 =CHC 6 H 4 CH 2 CH 2 ) 2 Zn) was prepared, from which poly(ethylene-co-propylene) chains were grown via "coordinative chain transfer polymerization" using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me 3 SiCH 2 Li·(pmdeta) (pmdeta = pentamethyldiethylenetriamine). We found that the fraction of the extracted PS homopolymer was low (~20%) and that molecular weights were evidently increased after the styrene polymerization (∆M n = 27-54 kDa). Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS.

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Temporal Control over Two‐ and Three‐State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins

Wallace

Sita

2021

Angewandte Chemie

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A highly versatile new strategy for manipulating the molecular weight profiles, including breadth, asymmetry (skewness) and modal nature (mono‐, bi‐, and multimodal), of a variety of different polyolefins is reported. It involves temporal control over two‐ and three‐state living coordinative chain transfer polymerization (LCCTP) of olefins in a programmable way. By changing the identity of the R′ groups of the chain transfer agent, ER′n, with time, different populations of chains within a bi‐ or multimodal polyolefin product can be selectively tagged with different end‐groups. By changing the nature of the main‐group metal of the CTA, programmed manipulation of the relative magnitudes of the dispersities of the different maxima that make up the final MWD profile can be achieved. This strategy can be implemented with existing LCCTP materials and conventional reactor methods to provide access to scalable and practical quantities of an unlimited array of new polyolefin materials.

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Biaxial Chain Growth of Polyolefin and Polystyrene from 1,6-Hexanediylzinc Species for Triblock Copolymers

Cited by 29 publications

References 68 publications

Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

Temporal Control over Two‐ and Three‐State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins

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