Recent Advances in Living Cationic Polymerization with Emerging Initiation/Controlling Systems

Chen, Yinan; Zhang, Lu; Jin, Yi; Lin, Xinrong; Chen, Mao

doi:10.1002/marc.202100148

Cited by 29 publications

(26 citation statements)

References 110 publications

(134 reference statements)

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“…Several reviews exist that thoroughly discuss recent innovations in living polymerization chemistry, − MBCP synthesis, and coupling reactions, , so herein we will only highlight several key examples of how synthetic developments have enabled advancements in the field of blend compatibilization. Early studies largely focused on amorphous polymer compatibilizers (as those polymers could be directly attained from anionic polymerization), but the development of improved catalysts and chemistries have enabled the study of semicrystalline blends which are far more industrially relevant.…”

Section: Synthetic Methodsmentioning

confidence: 99%

Linear, Graft, and Beyond: Multiblock Copolymers as Next-Generation Compatibilizers

Self

Zervoudakis

Peng

et al. 2022

JACS Au

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Properly addressing the global issue of unsustainable plastic waste generation and accumulation will require a confluence of technological breakthroughs on various fronts. Mechanical recycling of plastic waste into polymer blends is one method expected to contribute to a solution. Due to phase separation of individual components, mechanical recycling of mixed polymer waste streams generally results in an unsuitable material with substantially reduced performance. However, when an appropriately designed compatibilizer is used, the recycled blend can have competitive properties to virgin materials. In its current state, polymer blend compatibilization is usually not cost-effective compared to traditional waste management, but further technical development and optimization will be essential for driving future cost competitiveness. Historically, effective compatibilizers have been diblock copolymers or in situ generated graft copolymers, but recent progress shows there is great potential for multiblock copolymer compatibilizers. In this perspective, we lay out recent advances in synthesis and understanding for two types of multiblock copolymers currently being developed as blend compatibilizers: linear and graft. Importantly, studies of appropriately designed copolymers have shown them to efficiently compatibilize model binary blends at concentrations as low as ∼0.2 wt %. These investigations pave the way for studies on more complex (ternary or higher) mixed waste streams that will require novel compatibilizer architectures. Given the progress outlined here, we believe that multiblock copolymers offer a practical and promising solution to help close the loop on plastic waste. While a complete discussion of the implementation of this technology would entail infrastructural, policy, and social developments, they are outside the scope of this perspective which instead focuses on material design considerations and the technical advancements of block copolymer compatibilizers.

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Section: Synthetic Methodsmentioning

confidence: 99%

Linear, Graft, and Beyond: Multiblock Copolymers as Next-Generation Compatibilizers

Self

Zervoudakis

Peng

et al. 2022

JACS Au

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“…Researchers have created various glycopolymers using vinyl monomers that include sugar as building blocks. Living polymerization is defined as a method that does not involve the termination or transfer of chain segments during the polymerization process [ 34 ]. Controlled polymerization, on the other hand, refers to those in which the termination of the polymer is hindered but not entirely eliminated by the introduction of a dormant species into the system [ 35 ].…”

Section: Glycopolymer Synthesis Methodologiesmentioning

confidence: 99%

Glycopolymer-Based Materials: Synthesis, Properties, and Biosensing Applications

et al. 2022

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Glycopolymer materials have emerged as a significant biopolymer class that has piqued the scientific community's attention due to their potential applications. Recently, they have been found to be a unique synthetic biomaterial; glycopolymer materials have also been used for various applications, including direct therapeutic methods, medical adhesives, drug/gene delivery systems, and biosensor applications. Therefore, for the next stage of biomaterial research, it is essential to understand current breakthroughs in glycopolymer-based materials research. This review discusses the most widely utilized synthetic methodologies for glycopolymer-based materials, their properties based on structure–function interactions, and the significance of these materials in biosensing applications, among other topics. When creating glycopolymer materials, contemporary polymerization methods allow precise control over molecular weight, molecular weight distribution, chemical activity, and polymer architecture. This review concludes with a discussion of the challenges and complexities of glycopolymer-based biosensors, in addition to their potential applications in the future. Graphical Abstract

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“…Finally, this photocontrolled RAFT process can also be expanded to realize temporal and spatial control by an "on/off" switch of UV irradiation and a painting-on-a-surface approach, respectively. Since photoinduced controlled/"living" radical polymerization can be readily activated or deactivated by manipulating light irradiation, [42,43] the temporal control of this process was first investigated by using DMA as a model monomer. As shown in Figure 4 and Table S2 (Supporting Information), when the reaction mixture was exposed to UV light for 3 min, the monomer conversion was ≈13%.…”

Section: Temporal and Spatial Controlmentioning

confidence: 99%

Oxygen‐Demanding Photocontrolled RAFT Polymerization Under Ambient Conditions

Peng

Liu

Wang

et al. 2022

Macromol. Rapid Commun.

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A photocontrolled reversible addition−fragmentation chain transfer (RAFT) process is developed by initiating polymerization through a 1,3‐diaminopropane‐triethylborane (DAPTB)−diphenyl iodonium salt (Ph2I+) complex (DAPTB/Ph2I+) under ambient temperature and atmospheric conditions. Upon demand, this air‐stable DAPTB/Ph2I+ complex is photolyzed to liberate a reactive triethylborane that consumes atmospheric oxygen and generates ethyl radicals, which initiate and mediate RAFT polymerization. Controlled RAFT polymerization is thus achieved without any prior deoxygenation using a novel RAFT chain transfer agent, BP‐FSBC, which contains both benzophenone and sulfonyl fluoride moieties. Furthermore, the kinetics of polymerization reveal that the reaction process is rapid, and well‐defined polymers are produced by a 61% conversion of 2‐hydroxyethyl acrylate (HEA) within 7 min and 77% conversion of N,N‐dimethylacrylamide (DMA) within 10.5 min. The temporal and spatial control of this photopolymerization is also demonstrated by an “on/off” switch of UV irradiation and a painting‐on‐a‐surface approach, respectively. In addition, active chain ends are demonstrated by preparing block copolymers by chain extension and click sulfur(VI)‐fluoride exchange postreaction using RAFT‐derived macrochain transfer agents.

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Recent Advances in Living Cationic Polymerization with Emerging Initiation/Controlling Systems

Cited by 29 publications

References 110 publications

Linear, Graft, and Beyond: Multiblock Copolymers as Next-Generation Compatibilizers

Linear, Graft, and Beyond: Multiblock Copolymers as Next-Generation Compatibilizers

Glycopolymer-Based Materials: Synthesis, Properties, and Biosensing Applications

Oxygen‐Demanding Photocontrolled RAFT Polymerization Under Ambient Conditions

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