End‐Group‐Functionalized Poly(α‐olefinates) as Non‐Polar Building Blocks: Self‐Assembly of Sugar–Polyolefin Hybrid Conjugates

Thomas, Tessy S.; Hwang, Wonseok; Sita, Lawrence R.

doi:10.1002/anie.201600035

Cited by 61 publications

(66 citation statements)

References 63 publications

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“…The further growth of polymer chains initiating from (polyolefinyl) 2 Zn may be useful for the syntheses of PO-based block copolymers [27]. 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].…”

Section: Methodsmentioning

confidence: 99%

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%

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

et al. 2020

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“…We have previously reported that sugar-polyolefin conjugates can be conveniently obtained through the chemical linking of apolar saccharide "head" group with ahydrophobic "tail" derived from an end-group functionalized poly(aolefinate) (xPAO)o ft unable molecular weight and very narrow molecular weight distribution, also known as polydispersity. [16,17] Thex PAOp recursors are,i nt urn, prepared through the transition-metal-mediated living coordinative chain transfer polymerization (LCCTP) of acommon a-olefin monomer,s uch as propene and 4-methyl-1-pentene (4M1P). [18] Importantly,t hrough programmed variations in molecular weight and the space-filling requirements of the polyolefin pendant side chain, awide variety of occupied free volumes for the hydrophobic domain of sugar-polyolefin conjugates can be easily designed and synthesized.…”

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confidence: 99%

“…[18] Importantly,t hrough programmed variations in molecular weight and the space-filling requirements of the polyolefin pendant side chain, awide variety of occupied free volumes for the hydrophobic domain of sugar-polyolefin conjugates can be easily designed and synthesized. [16] In the present report, ultra-low molecular weight amorphous, atactic azido-terminated poly(4-methyl-1-pentene) (N 3 -aPMP) (2), with an umber-average molecular weight index, M n ,o f1 .0 kDa and ap olydispersity index, (= M w / M n ), of 1.05, where M w is the weight-average molecular weight index, was prepared through the LCCTP of af ixed amount of 4M1P using previously published methods. [16,18] As shown in Figure 2, sugar-polyolefin conjugate 1 was next prepared in high yield through the copper-mediated "click" reaction between 2 and the cellobiose propargyl amide derivative 3.A fter purification, matrix-assisted laser desorption ionization (MALDI) mass spectrometry of 1 provided M n and values of 1.4 Da and 1.05, respectively,a nd this material was shown to exist by 1 HNMR spectroscopy as an on-interconverting 3:1m ixture of b and a stereochemical anomers.…”

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An Exceptionally Stable and Scalable Sugar–Polyolefin Frank–Kasper A15 Phase

2019

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One-component" soft material Frank-Kasper (FK) phases are an intriguing structural form of matter that possess periodically ordered structures arising from the self-reconfiguration and close packingo fa ni nitial assembly of identical "deformable" spheres into two or more size-or shape-distinct sets of particles.S ignificant challenges that must still be addressed to advance the field of soft matter FK phases further,h owever,i nclude their rare and unpredictable occurrence,u ncertain mechanisms of solid-state assembly,a nd low thermodynamic stability.H ere we show that ar eadily-accessible sugar-polyolefin conjugate quantitatively produces an exceptionally stable solid-state FK A15 phase through arapid and irreversible thermotropic order-order transition, which contrary to other prevailing proposed mechanisms,d oes not require mass transfer between particles or large structural reorganization in the bulk to establish unit cell non-equivalency.Our results provide the basis for arealistic strategy for obtaining practical and scalable quantities of adiverse range of sugar-polyolefin FK A15 phases with unique intrinsic physical properties and chemical reactivities not previously seen in such systems.Periodically-ordered, "one-component" soft matter Frank-Kasper (FK) phases,w hich arise from the topological close packing (TCP) of "deformable" sphere-shaped particles,have now been experimentally verified for amphiphilic liquid crystals and dendrons,b lock copolymers," giant" molecules and surfactants,a nd colloidal nanoparticles. [1][2][3][4][5][6][7][8][9] Frank and Kasper [10] originally developed the concept of TCP to rationalize how the complex crystal structures of certain intermetallic alloys arise through the packing of asymmetric polyhedra that are associated with different sets of atoms that define ap articular coordination number, CNx, where x = 12,14,15, or 16. Forexample,asshown in Figure 1, the unit cell of the cubic FK A15 (Pm3 n)p hase,w hich is found for some bimetallic alloys with A 3 Bstoichiometry (e.g. Nb 3 Sn), can be seen as arising from two crystallographically equivalent B sites that reside within CN12 distorted icosahedra, while six equivalent face-shared As ites are associated with CN14 polyhedra. Other commonly encountered bimetallic FK phases include the Laves C14 and C15 structures for A 2 B alloys (e.g.MgZn 2 ), and the complex s phase for AB alloys of

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“…[1][2][3][4] Potentially,t he macromolecular engineering of PE through the control of its primary structure (that is,c haracteristics such as average molar mass,m olarmass distribution (MMD), [5][6][7][8] branching density,a nd the introduction of functional groups [9][10][11][12][13] )isexpected to fabricate new polyolefin-based high value-added materials.T he development of new catalysts for coordination polymerizations led to significant advances for high-density PE synthesis,enabling living polymerizations,end-group functionalities,and copolymerization with polar monomers.I nc ontrast, similar advances for low-density PE remain aformidable challenge,despite the continuous developments in the field of controlled radical polymerizations (CRPs,o rr eversible-deactivation radical polymerizations,RDRPs).…”

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confidence: 99%

Controlled Radical Polymerization of Ethylene Using Organotellurium Compounds

et al. 2017

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The first successfully controlled radical polymerization (CRP) of ethylene is reported using several organotellurium chain-transfer agents (CTAs) under mild conditions (70 8 8C, 200 bar of ethylene) within the concept of organotellurium-mediated radical polymerization (TERP). In contrast to preceding works on CRPs of ethylene applying reversible addition-fragmentation chain-transfer (RAFT), the TERP system provided ah igh livingness and chain-end functionalization of polyethylene chains.Molar-mass distributions with dispersities between 1.3 and 2.1 were obtained up to average molar masses of 5000 gmol À1 .Asinthe RAFT system, the high reactivity of the growing polyethylenyl radical led to an inherent side reaction. Fort he presented TERP systems, however,this side reaction did not result in dead chains,while it could even be effectively suppressed by ag ood choice of the CTA.

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End‐Group‐Functionalized Poly(α‐olefinates) as Non‐Polar Building Blocks: Self‐Assembly of Sugar–Polyolefin Hybrid Conjugates

Cited by 61 publications

References 63 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

An Exceptionally Stable and Scalable Sugar–Polyolefin Frank–Kasper A15 Phase

Controlled Radical Polymerization of Ethylene Using Organotellurium Compounds

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