Z-type and R-type macro-RAFT agents in RAFT dispersion polymerization – another mechanism perspective on PISA

Yu, Mingguang; Tan, Jianbo; Yang, Jianwen; Zeng, Zhaohua

doi:10.1039/c6py00605a

Cited by 20 publications

(25 citation statements)

References 54 publications

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“…A key point is the ability of both blocks to form the so-called microphase-separated domains on a nanoscale level driven by their polarity difference, i.e., the difference in their mixing parameter χ. − For this, block copolymers were obtained by first polymerizing the macromonomers VBmPEOz , which feature a styrene-functionalized mPEOz chain, using DDMAT as a RAFT agent to achieve perfect control over the radical polymerization (Scheme ). Consequently, a macro-RAFT agent based on styrene repeating units with grafted PEO side chains was obtained ( PVBmPEOz ). Subsequently, PVBmPEOz was used for the chain extension with styrene to eventually obtain the block copolymer PVBmPEOz- b -PS (hereinafter denoted as BPz) .…”

Section: Results and Discussionmentioning

confidence: 99%

Styrene-Based Poly(ethylene oxide) Side-Chain Block Copolymers as Solid Polymer Electrolytes for High-Voltage Lithium-Metal Batteries

Butzelaar

Röring

Mach

et al. 2021

ACS Appl. Mater. Interfaces

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Herein, we report the design of styrene-based poly(ethylene oxide) (PEO) side-chain block copolymers featuring a microphase separation and their application as solid polymer electrolytes in high-voltage lithium-metal batteries. A straightforward synthesis was established, overcoming typical drawbacks of PEO block copolymers prepared by anionic polymerization or ester-based PEO side-chain copolymers. Both the PEO side-chain length and the LiTFSI content were varied, and the underlying relationships were elucidated in view of polymer compositions with high ionic conductivity. Subsequently, a selected composition was subjected to further analyses, including phase-separated morphology, providing not only excellent self-standing films with intrinsic mechanical stability but also the ability to suppress lithium dendrite growth as well as good flexibility, wettability, and good contacts with the electrodes. Furthermore, good thermal and electrochemical stability was demonstrated. To do so, linear sweep and cyclic voltammetry, lithium plating/stripping tests, and galvanostatic overcharging using high-voltage cathodes were conducted, demonstrating stable lithium-metal interfaces and a high oxidative stability of around 4.75 V. Consequently, cycling of Li||NMC622 cells did not exhibit commonly observed rapid cell failure or voltage noise associated with PEO-based electrolytes in Li||NMC622 cells, attributed to the high mechanical stability. A comprehensive view is provided, highlighting that the combination of PEO and high-voltage cathodes is not impossible per se.

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Section: Results and Discussionmentioning

confidence: 99%

Styrene-Based Poly(ethylene oxide) Side-Chain Block Copolymers as Solid Polymer Electrolytes for High-Voltage Lithium-Metal Batteries

Butzelaar

Röring

Mach

et al. 2021

ACS Appl. Mater. Interfaces

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“…Also very active over the last 3 years was the group of Tan at Guangdong University (China) that reported dispersion photo-PISA in methanol/water mixtures (isobornyl acrylate [209,210] and MMA [211] for chain extension) and in water (2-hydroxylpropyl methacrylate [212][213][214][215]) as depicted in Fig. 29).…”

Section: Adaptation To Photoinitiationmentioning

confidence: 99%

Photopolymerization in dispersed systems

Jasinski

Zetterlund

Braun

et al. 2018

Progress in Polymer Science

129

115

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Zero-VOC technologies combining ecological and economic efficiency are destined to occupy a growing place in the polymer economy. Today, Polymerization in dispersed systems and Photopolymerization are the two major key players. The hybrid technology based on photopolymerization in dispersed systems has emerged as the next technological frontier, not only to make processes even more efficient and eco-friendly, but also to expand the range of polymer products and properties. This review summarizes the current knowledge in research relevant to this field in an exhaustive way. Firstly, fundamentals of photoinitiated polymerization in dispersed systems are given to show the favourable context for developing this emerging technology, its specific features as well as the distinctive equipment and materials necessary for its implementation. Secondly, a state-of-the-art and critical review is provided according to the seven main processing methods in dispersed systems: emulsion, microemulsion, miniemulsion, dispersion, precipitation, suspension, and aerosol.

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“…Another advantage of diblock copolymer nano-objects prepared via the Z-RAFT-mediated photo-PISA is that the corona block and the core-forming block can be cleaved easily by removing the trithiocarbonate group (see Figure a). This feature enables the preparation of stabilizer-free nanoparticles and hollow nanomaterials. , Treating RAFT-derived polymers with excess initiator is a common strategy to remove the RAFT reactive group . Herein, mPEG 45 -P t BA 209 vesicles (prepared at 30% w/w t BA concentration) were treated with 50-fold SPTP via the exposure of 405 nm visible light for 5 h. Precipitation occurred during this process due to the absence of stabilizer on the particle surface.…”

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confidence: 99%

“…37 When using a Z-type macro-CTA, the RAFT reactive groups located on the particle surface do not have access to control the polymerization inside, leading to a certain degree of uncontrolled polymerization. For example, the Zeng group and us 38 recently reported that the use of a Z-type macro-CTA for thermally initiated PISA of styrene only led to the formation of polydisperse micron-sized particles with broad molar mass distributions (M w /M n > 2.80).…”

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confidence: 99%

Expanding the Scope of Polymerization-Induced Self-Assembly: Z-RAFT-Mediated Photoinitiated Dispersion Polymerization

Tan

Zeng

et al. 2018

ACS Macro Lett.

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In this communication, we developed the first well-controlled Z-RAFT (RAFT = reversible addition− fragmentation chain transfer) mediated polymerization-induced self-assembly (PISA) formulation based on photoinitiated RAFT dispersion polymerization of tert-butyl acrylate (tBA) in ethanol/water (60/40, w/w) at room temperature using a Z-type macromolecular chain transfer agent (macro-CTA). Polymerizations proceeded rapidly via the exposure of visible-light irradiation (405 nm, 0.45 mW/cm 2 ) with high monomer conversion (>95%) being achieved within 1 h. A variety of polymer nano-objects (spheres, worms, and vesicles) with narrow molar mass distributions were prepared by this Z-RAFT mediated PISA formulation. Silver nanoparticles were loaded with the vesicles via in situ reduction, which can be used as a catalyst for the reduction of methylene blue (MB) in the presence of NaBH 4 . Finally, gel permeation chromatography (GPC) analysis demonstrated that the corona block and the core-forming block could be cleaved by treating with excess initiator. This novel PISA formulation will greatly expand the scope of PISA and provide more mechanistic insights into the PISA research.

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Z-type and R-type macro-RAFT agents in RAFT dispersion polymerization – another mechanism perspective on PISA

Abstract: The location of RAFT groups plays a key role for the living polymerization process and the formation of nano-objects in RAFT dispersion polymerization.

Cited by 20 publications

References 54 publications

Styrene-Based Poly(ethylene oxide) Side-Chain Block Copolymers as Solid Polymer Electrolytes for High-Voltage Lithium-Metal Batteries

Styrene-Based Poly(ethylene oxide) Side-Chain Block Copolymers as Solid Polymer Electrolytes for High-Voltage Lithium-Metal Batteries

Photopolymerization in dispersed systems

Expanding the Scope of Polymerization-Induced Self-Assembly: Z-RAFT-Mediated Photoinitiated Dispersion Polymerization

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