Tough and Sustainable Graft Block Copolymer Thermoplastics

Zhang, Jiuyang; Li, Tuoqi; Mannion, Alexander M.; Schneiderman, Deborah K.; Bates, Frank S.

doi:10.1021/acsmacrolett.6b00091

Cited by 95 publications

(108 citation statements)

References 41 publications

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“…The brittleness does hinder its applications ranging from packaging materials to medical implants . To improve the elongation at break and impact strength, various modifier polymers (e.g., rubber or other polymers with excellent flexibility) have been widely employed to blend with PLLA . The binary blend, however, always undergoes phase separation because of weak interfacial interaction and poor miscibility between PLLA and other polymers.…”

Section: Methodsmentioning

confidence: 99%

Fabrication of PLLA with High Ductility and Transparence by Blending with Tiny Amount of PVDF and Compatibilizers

Zhang

et al. 2019

Macro Materials & Eng

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Poly(L‐lactic acid) (PLLA) with high ductility and transparence is fabricated by a blending tiny amount of polyvinylidene fluoride (PVDF) and reactive comb compatibilizers (RCC). Upon blending, the reaction between terminal carboxyl groups in PLLA and expoxy groups in RCC produces graft copolymer (PLLA‐g‐poly(methyl methacrylate) (PMMA)), which locates at the PVDF/PLLA interface due to the balanced stress on two sides. On the one hand, the PVDF domain size decreases remarkably with the help of compatibilization, accounting for the excellent transparence. On the other hand, the interface is enhanced significantly, resulting in an activated PLLA layer surrounding PVDF domains. The thickness exhibits higher magnitude because of the high molecular weight of grafted PLLA (relative to premade compatibilizers). During uniaxial tension, the activated PLLA layers (in addition to PVDF) can cause effective energy absorption and dissipation in the case of percolation of them, which is the reason for the better ductility. These results provide an efficient strategy to improve the ductility and transparence simultaneously.

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Section: Methodsmentioning

confidence: 99%

Fabrication of PLLA with High Ductility and Transparence by Blending with Tiny Amount of PVDF and Compatibilizers

Zhang

et al. 2019

Macro Materials & Eng

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“…Generally, there are three methods to synthesize graft polymers: (1) the “grafting from” method, where comonomers can propagate from initiation sites that are incorporated onto the polymer backbone ( Scheme a ); (2) the “grafting onto” method, where the backbone is endowed with randomly distributed functional groups that are capable of coupling with end‐functionalized graft chains (Scheme b); (3) the “grafting through” method, where macromonomers with polymerizable terminal group are copolymerized with comonomers, and the branches are “sewn” into the main chain (Scheme c).…”

Section: Precise Synthesize Of Multigraft Copolymers By Iterative Methodsmentioning

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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“…A simple and scalable synthetic procedure was used to make hydroxypropyl methylcellulose (HPMC) lightly grafted with poly(β‐methyl‐δ‐valerolactone)‐ b ‐PLLA diblock copolymer . HPMC‐ g ‐(PMVL‐ b ‐PLLA) polymers, described in this letter, used inexpensive and renewable precursors and provided exceptional rheological and mechanical properties attractive for a broad range of applications, which include packaging, medical equipment, and textiles.…”

Section: Applications Of Crystallizable Block Copolymersmentioning

confidence: 99%

“…Contrarily, linear (AB) n multiblock polymers have shown considerable promise for their ability to decouple the T ODT from the total molar mass. Zhang et al . studied fully sustainable HPMC‐ g ‐(PMVL‐ b ‐PLLA) using a facile two‐step sequential addition approach.…”

Section: Applications Of Crystallizable Block Copolymersmentioning

confidence: 99%

Recent progress in block copolymer crystallization

Horn

Steffen

O'Connor

2018

Polymer Crystallization

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Block copolymers (BCPs) are important for technological advances in numerous industries, including but not limited to, electronics, biomedical, optics, environmental, and infrastructure. Because of their ubiquity, it is important to understand their hierarchical phase behavior to tune their macroscopic properties for efficient use. These macroscopic properties are derived from the microscopic self‐assembled structures. One unique form of hierarchical assembly exists when one or more of the polymeric blocks form lamellar crystals. These crystals are integral to understanding and predicting the macroscopic behavior. This review reports on recent advances in crystallization of BCPs, including bulk and solution assembly. Reports highlighting development in fundamental processes regarding crystallization mechanisms and behavior as well as for the design of practical applications are included.

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Tough and Sustainable Graft Block Copolymer Thermoplastics

Cited by 95 publications

References 41 publications

Fabrication of PLLA with High Ductility and Transparence by Blending with Tiny Amount of PVDF and Compatibilizers

Fabrication of PLLA with High Ductility and Transparence by Blending with Tiny Amount of PVDF and Compatibilizers

Design and Synthesis of Multigraft Copolymer Thermoplastic Elastomers: Superelastomers

Recent progress in block copolymer crystallization

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