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Special Issue "Living Polymerization Techniques"

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

Deadline for manuscript submissions: closed (29 February 2012)

Special Issue Editor

Guest Editor
Dr. Graeme Moad (Website)

CSIRO Materials Science and Engineering, Bag 10, Clayton South, Victoria 3169, Australia
Fax: +61 395 452 446
Interests: polymer design and synthesis; polymerization kinetics and mechanism; reversible deactivation radical polymerization (e.g., RAFT, NMP); reactive extrusion

Special Issue Information

Dear Colleagues,

This volume on living polymerization processes is intended to embrace all polymerization processes which show living characteristics. These characteristics include the ability to control molecular weight and molecular weight distribution, polymer composition and synthesize a variety of polymer architectures which including blocks and stars.

The classical living polymerization method is anionic polymerization. IUPAC have recommended that the term “living polymerization” be reserved for polymerizations that proceed in the absence irreversible termination (A.D. Jenkins, R.I. Jones, G. Moad. Pure Appl. Chem. 2010, 82, 483-491). The term “reversible deactivation radical polymerization” has been coined to describe those radical polymerization such as atom transfer radical polymerization (ATRP), nitroxide mediated polymerization (NMP) and radical polymerization with reversible addition-fragmentation chain transfer (RAFT), which inevitably involve termination but which, with appropriate selection of reagents and reaction conditions, display most of the attributes associated with living polymerization. Some forms of ionic polymerization should similarly be termed reversible deactivation polymerizations.

Other forms of polymerization potentially included in this volume are some forms of cationic polymerization, group transfer polymerization, metathesis polymerization, catalyst transfer polymerization, Grignard metathesis polymerization (GRIM) and ring opening polymerization. There is no intention to be restrictive.

Dr. Graeme Moad
Guest Editor

Keywords

  • living polymerization
  • reversible deactivation polymerization
  • polymer synthesis
  • mechanisms
  • anionic
  • radical
  • cationic
  • ring opening
  • group transfer
  • catalyst transfer
  • metathesis

Published Papers (4 papers)

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Research

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Open AccessArticle Synthesis of Star Poly(N-vinylcarbazole) by Microwave-Assisted Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT)
Polymers 2012, 4(2), 1183-1194; doi:10.3390/polym4021183
Received: 27 February 2012 / Revised: 12 April 2012 / Accepted: 4 May 2012 / Published: 15 May 2012
Cited by 6 | PDF Full-text (184 KB) | HTML Full-text | XML Full-text
Abstract
Controlled radical polymerization of N-vinylcarbazole (NVK) via microwave-assisted reversible addition-fragmentation chain transfer (RAFT) polymerization is described. As chain transfer agent, 1,3,5-benzyl tri (diethyldithiocarbamate), was used. The chain transfer agent, containing a 1.3.5-trisubstituted benzene ring as core and three dithiocarbamate functionalities attached [...] Read more.
Controlled radical polymerization of N-vinylcarbazole (NVK) via microwave-assisted reversible addition-fragmentation chain transfer (RAFT) polymerization is described. As chain transfer agent, 1,3,5-benzyl tri (diethyldithiocarbamate), was used. The chain transfer agent, containing a 1.3.5-trisubstituted benzene ring as core and three dithiocarbamate functionalities attached through an intermediate for fragmenting covalent bonds, led to poly(N-vinylcarbazole) (PVK) with star architecture. Polymerizations were carried out in 1,4-dioxane as solvent, at 70 °C, and studied for different polymerization times and monomer/CTA/initiator ratios. The SEC molecular weight curves exhibit a trimodal distribution, assigned to the linear and star-star coupling polymers, accompanying the real star polymer (as main product). Full article
(This article belongs to the Special Issue Living Polymerization Techniques)
Open AccessArticle Synthesis of Well-Defined, Water-Soluble Hyperbranched Polyamides by Chain-Growth Condensation Polymerization of AB2 Monomer
Polymers 2012, 4(2), 1170-1182; doi:10.3390/polym4021170
Received: 12 March 2012 / Revised: 18 April 2012 / Accepted: 8 May 2012 / Published: 14 May 2012
Cited by 9 | PDF Full-text (435 KB) | HTML Full-text | XML Full-text
Abstract
Condensation polymerization of 5-aminoisophthalic acid methyl ester 1 bearing a N-tri(ethylene glycol) methyl ester (TEG) chain as an AB2 monomer was conducted and the properties of the resulting hyperbranched polyamides (HBPA) were investigated. When the polymerization of 1 was carried [...] Read more.
Condensation polymerization of 5-aminoisophthalic acid methyl ester 1 bearing a N-tri(ethylene glycol) methyl ester (TEG) chain as an AB2 monomer was conducted and the properties of the resulting hyperbranched polyamides (HBPA) were investigated. When the polymerization of 1 was carried out with N-methyl core initiator 2b at various feed ratios of 1 to 2b ([1]0/[2b]0) in the presence of LiHMDS and LiCl at −10 °C, the Mn values of the obtained HBPA increased in proportion to the [1]0/[2b]0 ratio from 7 to 46 (Mn = 3810–18600), retaining a narrow molecular weight distribution (Mw/Mn = 1.11–1.19). The HBPA was soluble in water, and a 0.25 wt.−% aqueous solution of the HBPA exhibited a lower critical solution temperature (LCST). The cloud point was 21–23 °C, which is about 30 °C lower than that of the corresponding poly(m-benzamide) with the N-TEG unit. Full article
(This article belongs to the Special Issue Living Polymerization Techniques)
Figures

Open AccessArticle Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization
Polymers 2011, 3(4), 1944-1971; doi:10.3390/polym3041944
Received: 7 September 2011 / Revised: 17 October 2011 / Accepted: 9 November 2011 / Published: 11 November 2011
Cited by 8 | PDF Full-text (849 KB) | HTML Full-text | XML Full-text
Abstract
Various types of controlled/living radical polymerizations, or using the IUPAC recommended term, reversible-deactivation radical polymerization (RDRP), conducted inside nano-sized reaction loci are considered in a unified manner, based on the polymerization rate expression, Rp = kp[M]K[Interm [...] Read more.
Various types of controlled/living radical polymerizations, or using the IUPAC recommended term, reversible-deactivation radical polymerization (RDRP), conducted inside nano-sized reaction loci are considered in a unified manner, based on the polymerization rate expression, Rp = kp[M]K[Interm]/[Trap]. Unique miniemulsion polymerization kinetics of RDRP are elucidated on the basis of the following two factors: (1) A high single molecule concentration in a nano-sized particle; and (2) a significant statistical concentration variation among particles. The characteristic particle diameters below which the polymerization rate start to deviate significantly (1) from the corresponding bulk polymerization, and (2) from the estimate using the average concentrations, can be estimated by using simple equations. For stable-radical-mediated polymerization (SRMP) and atom-transfer radical polymerization (ATRP), an acceleration window is predicted for the particle diameter range, . For reversible-addition-fragmentation chain-transfer polymerization (RAFT), degenerative-transfer radical polymerization (DTRP) and also for the conventional nonliving radical polymerization, a significant rate increase occurs for . On the other hand, for  the polymerization rate is suppressed because of a large statistical variation of monomer concentration among particles. Full article
(This article belongs to the Special Issue Living Polymerization Techniques)

Review

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Open AccessReview Controlled Photoradical Polymerization Mediated by 2,2,6,6-Tetramethylpiperidine-1-Oxyl
Polymers 2012, 4(2), 1125-1156; doi:10.3390/polym4021125
Received: 1 March 2012 / Revised: 13 April 2012 / Accepted: 19 April 2012 / Published: 2 May 2012
Cited by 4 | PDF Full-text (832 KB) | HTML Full-text | XML Full-text
Abstract
In recent years, controlled photoradical polymerization has been established using 2,2,6,6-tetramethylpiperidine-1-oxyl as a mediator. This review article will describe the molecular weight control, polymerization mechanism, influence of initiator structure, effect of substituents supported on photo-acid generator, stability of the propagating chain end, [...] Read more.
In recent years, controlled photoradical polymerization has been established using 2,2,6,6-tetramethylpiperidine-1-oxyl as a mediator. This review article will describe the molecular weight control, polymerization mechanism, influence of initiator structure, effect of substituents supported on photo-acid generator, stability of the propagating chain end, photo-latency of the polymerization, molecular design, and an application to heterogeneous polymerization in an alcoholic medium. Full article
(This article belongs to the Special Issue Living Polymerization Techniques)

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