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RAFT Living Radical Polymerization and Self-Assembly

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A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (26 February 2018) | Viewed by 49505

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Special Issue Editor

Prof. Dr. Po-Chih Yang

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Guest Editor

Department of Chemical Engineering and Materials Science, Yuan Ze University, Taoyuan 32003, Taiwan
Interests: polymer modifications; radical polymerzation; self assembly; organic/inrganic composites; polymer coatings; biomedical applications
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Reversible addition-fragmentation chain transfer (RAFT) polymerization is one kind of well-established controlled/living radical polymerization (CLRP) methods (e.g., atom transfer radical polymerization, nitroxide-mediated radical polymerization, and RAFT polymerization) that exhibits numerous appealing characteristics for controlling the synthesis of a wide variety of macromolecular architectures, as well as maintaining molecular weight control, narrow molecular weight distributions, and functionality. The absence of catalysts and the ease of scaling up make RAFT one of the most versatile CLRP techniques. The use of CLRP methods has recently increased extensively in the preparation of block polymers, because using this method yields advantages such as an experimental setup, a wide range of functional monomers, and complex macromolecular architectures with well-defined end groups of narrow polydispersity in the CLRP. Amphiphilic block copolymers can form various self-assembled aggregates such as spherical micelles, vesicles, cylinders, gyroids, and lamellae through the selective interaction of the solvent with hydrophobic and hydrophilic blocks.

This Special Issue, “RAFT Living Radical Polymerization and Self-Assembly”, aims to provide a comprehensive collection of the newest developments in self-assembled materials area. The issue covers the synthesis, characterization, polymerization kinetics, self-assembly, and stimuli-responsive (i.e., pH, thermal, photo, and ion-responsive) behaviors of block polymers. Studies of reaction mechanisms, rational selection of reaction components and conditions, and various materials aspects, including methods to control molecular architecture and placement of functionalities, and applications will be welcome. Both original contributions and reviews are welcome.

Prof. Dr. Po-Chih Yang
Guest Editor

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Keywords

Reversible-fragmentation chain transfer polymerization (RAFT)
Self-assembly
Block copolymers
Stimuli-responsive
Amphiphilic
Polymerization kinetics
Microphase separation

Published Papers (6 papers)

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Research

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17 pages, 5859 KiB

Open AccessArticle

Study of theThermo-/pH-Sensitivity of Stereo-Controlled Poly(N-isopropylacrylamide-co-IAM) Copolymers via RAFT Polymerization

by Syang-Peng Rwei, Whe-Yi Chiang, Tun-Fun Way, Huynh Nguyen Anh Tuan and Ya-Chin Chang

Polymers 2018, 10(5), 512; https://doi.org/10.3390/polym10050512 - 09 May 2018

Cited by 13 | Viewed by 4458

Abstract

In this work, a smart copolymer, Poly(nipam-co-IAM) was synthesized by copolymerization of N-isopropylacrylamide (nipam) and itaconamic acid (IAM) through reversible addition-fragmentation chain-transfer (RAFT) polymerization. Poly(nipam-co-IAM) has been studied previously synthesized via radical polymerization without stereo-control, and this work used cumyl dithiobenzoate and Ytterbium(III) trifluoromethanesulfonate as RAFT and stereo-control agents, respectively. The stereo-control result in this work shows that tacticity affects the lower critical solution temperature (LCST) and/or the profile of phase separation of Poly(nipam-co-IAM). In the pH 7 and pH 10 buffer solutions, the P(nipam-co-IAM) copolymer solutions showed soluble–insoluble–soluble transitions, i.e., both LCST and upper critical solution temperature (UCST) transitions, which had not been found previously, and the insoluble to soluble transition (redissolved behavior) occurred at a relatively low temperature. The insoluble to soluble transition of P(nipam-co-IAM) in alkaline solution occurred at a temperature of less than 45 °C. However, the redissolved behavior of P(nipam-co-IAM) was found only in the pH 7 and pH 10 buffer solutions and this redissolved behavior was more prominent for the atactic copolymers than in the isotactic-rich ones. In addition, the LCST results under our experimental range of meso content did not show a significant difference between the isotactic-rich and the atactic P(nipam-co-IAM). Further study on the soluble-insoluble-soluble (S-I-S) transition and the application thereof for P(nipam-co-IAM) copolymers will be conducted. Full article

(This article belongs to the Special Issue RAFT Living Radical Polymerization and Self-Assembly)

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15 pages, 2409 KiB

Open AccessArticle

RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients

by Minh Ngoc Nguyen, André Margaillan, Quang Trung Pham and Christine Bressy

Polymers 2018, 10(2), 224; https://doi.org/10.3390/polym10020224 - 24 Feb 2018

Cited by 5 | Viewed by 5961

Abstract

Well-defined poly(tert-butyldimethylsilyl methacrylate)s (TBDMSMA) were prepared by the reversible addition-fragmentation chain transfer (RAFT) process using cyanoisopropyl dithiobenzoate (CPDB) as chain-transfer agents (CTA). The experimentally obtained molecular weight distributions are narrow and shift linearly with monomer conversion. Propagation rate coefficients (k_p) and termination rate coefficients (k_t) for free radical polymerization of TBDMSMA have been determined for a range of temperature between 50 and 80 °C using the pulsed laser polymerization-size-exclusion chromatography (PLP-SEC) method and the kinetic method via steady-state rate measurement, respectively. The CPDB-mediated RAFT polymerization of TBDMSMA has been subjected to a combined experimental and PREDICI modeling study at 70 °C. The rate coefficient for the addition reaction to RAFT agent (k_β1, k_β2) and to polymeric RAFT agent (k_β) is estimated to be approximately 1.8 × 10⁴ L·mol⁻¹·s⁻¹ and for the fragmentation reaction of intermediate RAFT radicals in the pre-equilibrium (k_-β1, k_-β2) and main equilibrium (k_-β) is close to 2.0 × 10⁻² s⁻¹. The transfer rate coefficient (k_tr) to cyanoisopropyl dithiobenzoate is found to be close to 9.0 × 10³ L·mol⁻¹·s⁻¹ and the chain-transfer constant (C_tr) for CPDB-mediated RAFT polymerization of TBDMSMA is about 9.3. Full article

(This article belongs to the Special Issue RAFT Living Radical Polymerization and Self-Assembly)

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25 pages, 1341 KiB

Open AccessArticle

Microphase Segregation of Diblock Copolymers Studied by the Self-Consistent Field Theory of Scheutjens and Fleer

by Merve Mocan, Marleen Kamperman and Frans A. M. Leermakers

Polymers 2018, 10(1), 78; https://doi.org/10.3390/polym10010078 - 17 Jan 2018

Cited by 8 | Viewed by 4800

Abstract

We used the self-consistent field (SCF) formalism of Scheutjens and Fleer (SF-SCF) to complement existing theoretical investigations on the phase behavior of block copolymer melts. This method employs the freely jointed chain (FJC) model for finite chain length and systematic differences exist compared to the classical SCF predictions. We focus on the critical and hexagonal (HEX) to lamellar (LAM) phase transition region at intermediate and strong segregations. Chain length (N) dependence of the critical point (

χ^{c r}

) was found to be

χ^{c r} N = 10.495 (1 + 4 / N)

. The characteristic spacing (D) of LAM was found as

D = 4 / 3 \sqrt{N}

at the critical conditions. We present SF-SCF predictions for the phases single gyroid (SG), double gyroid (DG) and hexagonally perforated lamellar (HPL), in the region where HEX and LAM compete. At

χ N = 30

N = 300

; we found SG and HPL were metastable with respect to LAM or HEX, DG was stable in a narrow region of the asymmetry ratio. In contrast to the latest predictions, at strong segregation

χ N = 120

, DG was found to be metastable. From the structural evolution of HPL, we speculate that this may be an intermediate phase that allows the system to go through various connectivity regimes between minority and majority blocks. Full article

(This article belongs to the Special Issue RAFT Living Radical Polymerization and Self-Assembly)

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6210 KiB

Open AccessArticle

Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

by Jianbo Tan, Xueliang Li, Jun He, Qin Xu, Yuxuan Zhang, Xiaocong Dai, Liangliang Yu, Ruiming Zeng and Li Zhang

Polymers 2017, 9(12), 681; https://doi.org/10.3390/polym9120681 - 06 Dec 2017

Cited by 8 | Viewed by 6782

Abstract

Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT) dispersion copolymerization of methyl methacrylate (MMA) and methyl methacrylic (MAA) for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition) were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag) composite microspheres were prepared by in situ reduction of AgNO₃ using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB) with NaBH₄ as a reductant. Full article

(This article belongs to the Special Issue RAFT Living Radical Polymerization and Self-Assembly)

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3468 KiB

Open AccessArticle

Polyisoprene-Silica Nanoparticles Synthesized via RAFT Emulsifier-Free Emulsion Polymerization Using Water-Soluble Initiators

by Dusadee Tumnantong, Garry L. Rempel and Pattarapan Prasassarakich

Polymers 2017, 9(11), 637; https://doi.org/10.3390/polym9110637 - 22 Nov 2017

Cited by 17 | Viewed by 6956

Abstract

Polyisoprene-silica (PIP-co-RAFT-SiO₂) nanoparticles were prepared via reversible addition–fragmentation chain-transfer (RAFT) emulsifier-free emulsion polymerization using water-soluble initiators, 4,4′-Azobis (4-cyanopentanoic acid) (ACP) and 2,2′-Azobis (2-methylpropionamidine) dihydrochloride (V50). The particle size of emulsion prepared using ACP initiator was smaller than that using V50 initiator because the V50 initiator was more active toward decomposition than the ACP initiator. A high monomer conversion (84%), grafting efficiency (83%) and small particle size (38 nm) with narrow size distribution were achieved at optimum condition. The PIP-co-RAFT-SiO₂ nanoparticles exhibited core–shell morphology with silica encapsulated with polyisoprene (PIP). The new PIP-SiO₂ nanoparticles could be applied as effective filler in rubber composites that possess good mechanical and thermal properties. Full article

(This article belongs to the Special Issue RAFT Living Radical Polymerization and Self-Assembly)

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Review

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26 pages, 12412 KiB

Open AccessReview

Recent Advances in RAFT Polymerization: Novel Initiation Mechanisms and Optoelectronic Applications

by Xiangyu Tian, Junjie Ding, Bin Zhang, Feng Qiu, Xiaodong Zhuang and Yu Chen

Polymers 2018, 10(3), 318; https://doi.org/10.3390/polym10030318 - 14 Mar 2018

Cited by 74 | Viewed by 19406

Abstract

Reversible addition-fragmentation chain transfer (RAFT) is considered to be one of most famous reversible deactivation radical polymerization protocols. Benefiting from its living or controlled polymerization process, complex polymeric architectures with controlled molecular weight, low dispersity, as well as various functionality have been constructed, which could be applied in wide fields, including materials, biology, and electrology. Under the continuous research improvement, main achievements have focused on the development of new RAFT techniques, containing fancy initiation methods (e.g., photo, metal, enzyme, redox and acid), sulfur-free RAFT system and their applications in many fields. This review summarizes the current advances in major bright spot of novel RAFT techniques as well as their potential applications in the optoelectronic field, especially in the past a few years. Full article

(This article belongs to the Special Issue RAFT Living Radical Polymerization and Self-Assembly)

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