Synthesis and Characterization of an Exact Polystyrene-<i>graft</i>-polyisoprene: A Failure of Size Exclusion Chromatography Analysis

Lee, Sanghoon; Lee, Hyojoon; Chang, Taihyun; Hirao, Akira

doi:10.1021/acs.macromol.6b02811

Cited by 24 publications

(24 citation statements)

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“…This can be explained by the fact that SEC is a relative method and hydrodynamic radii for the amphiphilic P2VP‐grafted PS‐ b ‐PI strongly differ compared to PS homopolymers which were used as SEC standards. A remarkable failure of SEC for grafted PI chains with PS was recently described by the Hirao group . Therefore, values obtained from the NMR spectra for the purified samples are closer to the absolute values for molar masses compared to results obtained by SEC.…”

Section: Resultssupporting

confidence: 64%

“…Polybutadiene (PBd) segments were grafted with polystyrene (PS) by anionic polymerization after hydrosilylation of the PBd backbone with pendant chlorosilane moieties . Very recently, the Hirao group reported on the preparation and analysis of precisely grafted polystyrene‐ block ‐polyisoprenes, via iterative anionic polymerization and a graft reaction using diphenylethylene (DPE) functional groups …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Appold

Rüttiger

Kuttich

et al. 2017

Macro Chemistry & Physics

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Common stimuli include temperature, pH, light, redox reagents, and electrical fields. [16][17][18][19][20][21][22][23] Block copolymers featuring polyvinylpyridine (PVP) segments have attracted enormous attention due to their ability to undergo microphase separation, metal ion complexation, nanoparticle complexation, as well as participate in hydrogen bonding. [24] Stamm and co-workers have reported extensively on poly(styrene-block-(4-vinylpyridine)) (PS-b-P4VP) as a system. For example, they have reported on the influence of hydrogen bonding for poly(styrene-block-(4-vinylpyridine)) (PS-b-P4VP) for microphase separation, [25] the use of sacrificial PS-b-P4VP networks as carbon precursors, [26] the use of PS-b-P4VP as polymer templates for the preparation of highly ordered arrays of metallic nanodots, [27] and the preparation of P4VP-based block copolymers for helically arranged nanoparticle complexation in cylindrical domains. [28] Besides their structure formation capabilities, PVPs have been used as pH-responsive homopolymers, or as reversibly addressable segments in smart block copolymer architectures featuring protonated pyridinium moieties. [16] For example, Li et al. reported on the pH responsiveness of Au@PVP particles, and their application as pHresponsive bimetallic catalysts. [29] Furthermore, responsive P4VP-based cross-linked films have been used as pH sensors and as surfaces with controllable surface wettability. [30] The group of Eisenberg has also reported on the morphological changes in PS-b-P4VP micelles as a function of pH range. [31] Additionally, multi-stimuli-responsive block copolymers featuring a poly(2-vinylpyridine) (P2VP)-containing block segment were investigated in thin films, [32] as micelles in water, [33,34] and as smart nanocapsules. The latter have been advantageously used for the triggered release of different payloads from the capsules' interior. [21,35] As another impressive example, PSb-P4VP was the first polymer under investigation for creating integral asymmetric membranes with highly uniform pore sizes. [36] The complexation of the P4VP block segments with copper(II) ions was utilized for a stabilization of the PS-b-P4VP micelles in solution and hence a high reproducibility of uniform pore structures was achieved. [37,38] Besides copper(II) salts, other transition metals like nickel(II), cobalt(II), and iron(II) are also capable of influencing the self-organization of Anionic PolymerizationsFunctional block copolymers are a highly relevant material platform for many potential applications in fields of nanolithography, drug delivery, and separation technologies. Here, poly(2-vinylpyridine) (P2VP)-grafted diblock copolymers consisting of polystyrene-block-polyisoprene (PS-b-PI) backbone are synthesized via an iterative anionic grafting-to polymerization strategy. P2VP macro anions having molar masses of 1.1, 3.6, and 9.9 kDa are grafted to PS-b-PI block copolymers featuring 37 mol% 1,2-polyisoprene moieties. Prior to the grafting-to strategy, the PS-b-PI is subjected to pl...

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Section: Resultssupporting

confidence: 64%

Section: Introductionmentioning

confidence: 99%

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Appold

Rüttiger

Kuttich

et al. 2017

Macro Chemistry & Physics

View full text Add to dashboard Cite

show abstract

“…Advances in high‐temperature gradient interaction chromatography (TGIC) will help polymer chemists gain deeper insight into the block copolymers with complicated architectures. For example, a recent TGIC study, accompanied by liquid chromatography at critical condition (LCCC) analysis, revealed that the multigraft copolymers synthesized by the iterative method are actually highly heterogeneous in graft copolymer architecture, rather than homogenous as indicated by conventional size exclusive chromatography (SEC) analysis . Getting a more realistic assessment of the true structure of graft copolymer products will in return allow chemists.…”

Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Multigraft Copolymer Thermoplastic Elastomers: Superelastomers

Wang

et al. 2017

Macro Chemistry & Physics

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worldwide elastomer market, as sealants, coatings, adhesives, sporting good components, automotive parts, footwear, and as biomedical materials. [1] Prepared by living anionic polymerization, styrenic thermoplastic elastomers (S-TPEs), including polystyrene-blockpolyisoprene-block-polystyrene (SIS) and polystyrene-block-polybutadiene-blockpolystyrene (SBS), were first developed by Holden and Millkvich in the early 1960s and have since then become widely used in our daily life. [2,3] The exceptional mechanical properties of S-TPEs are attributed to the microphase separation between the two chemically incompati ble domains where hard polystyrene (PS) domains serve as physical cross-links for the soft polybutadiene (PB) or polyisoprene (PI) matrix. Mechani cal properties, such as tensile strength, Young's modulus, and elasticity, are tunable based on volume fractions of hard and soft domains. One limitation of S-TPEs is the restricted upper service temperature (UST), which is limited by the glass transition temperature (T g ) of polystyrene (T g ≈ 100 °C). When the service temperature is approaching 100 °C, softening of PS domains disrupts the physical cross-links, leading to a sharp drop of storage modulus. Numerous studies have been carried to increase the UST of S-TPEs by either replacing polystyrene with another higher T g polymer [4][5][6][7][8] or using catalytic hydrogenation to fully saturate PS into polyvinylcyclohexane (T g ≈ 150 °C). [9] With recent advances in living/controlled polymerization, various nonlinear architectures, including star, [10][11][12][13][14] graft, and cyclic [15,16] architectures, or their combinations, [17][18][19][20] have been synthesized during the past three decades. These nonlinear macromolecular architectures deliver additional parameters for chemists to use in tuning mechanical properties, as well as incorporating additional functionality to TPEs [21] (Figure 1).In this short review, we focus on the progress in design and synthesis of well-defined multigraft copolymers and their application as thermoplastic elastomers. Progress in precise synthesis of graft copolymers and mechanical properties of multigraft copolymers is first summarized. Recent work on all-acrylic graft copolymer TPEs and a low-cost emulsion polymerization approach to prepare multigraft copolymers are introduced subsequently. Finally, we finish the review with conclusions and some future prospectives. Living Anionic PolymerizationsThermoplastic elastomers (TPEs) have been widely studied because of their recyclability, good processibility, low production cost, and unique performance. The building of graft-type architectures can greatly improve mechanical properties of TPEs. This review focuses on the advances in different approaches to synthesize multigraft copolymer TPEs. Anionic polymerization techniques allow for the synthesis of well-defined macromolecular structures and compositions, with great control over the molecular weight, polydispersity, branch spacing, number of branch points, and branch point ...

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“…In general, size‐exclusion chromatography (SEC) is the most widely used tool to characterize polymers and provides the molar mass and molar mass distribution with respect to the hydrodynamic volume of the polymers usually using linear polystyrenes with narrow molar mass distributions as calibration standards . However, it is difficult to obtain accurate analysis of complex polymers with different topologies using SEC alone because polymers with the same hydrodynamic volume but different topologies may coelute . No doubt, it is necessary to combine SEC with other methods, such as normal‐phase temperature gradient interaction chromatography (NP‐TGIC), reversed‐phase temperature gradient interaction chromatography (RP‐TGIC), solvent gradient interaction chromatography (SGIC), and liquid chromatography at critical condition (LCCC) to form a two‐dimensional detection system to characterize complex polymers.…”

Section: Introductionmentioning

confidence: 99%

Characterization of mixed solutions of hyperbranched and linear polystyrenes by a combination of size‐exclusion chromatography and analytical ultracentrifugation

Zhang

Hao

Gao

et al. 2020

Journal of Polymer Science

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Separation and characterization on mixed solutions of hyperbranched and linear polystyrenes was achieved using size‐exclusion chromatography (SEC) as the first dimension and analytical ultracentrifugation (AUC) as the second dimension. The results show that linear and hyperbranched polystyrenes with similar hydrodynamic sizes (one fraction from SEC) can be separated by AUC according to the molar mass, and the separation efficiency decreases with the increasing of the retention volume in SEC. Moreover, the molar masses determined by AUC are consistent with the values measured by SEC‐refractive index (RI) and SEC‐multi‐angle light scattering (MALS) detection. Furthermore, the result shows that the separation efficiency decreases with the increasing of the subchain length of hyperbranched polystyrenes. Our study lays a solid foundation for future studies to separate polymers with different topologies by a combination of SEC and AUC.

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Synthesis and Characterization of an Exact Polystyrene-graft-polyisoprene: A Failure of Size Exclusion Chromatography Analysis

Cited by 24 publications

References 50 publications

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Design and Synthesis of Multigraft Copolymer Thermoplastic Elastomers: Superelastomers

Characterization of mixed solutions of hyperbranched and linear polystyrenes by a combination of size‐exclusion chromatography and analytical ultracentrifugation

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