Ambient Temperature Synthesis of Poly(dichlorophosphazene) with Molecular Weight Control

Honeyman, Charles H.; Manners, Ian; Morrissey, Christopher T.; Allcock, Harry R.

doi:10.1021/ja00131a040

Cited by 242 publications

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“…There are many methods for the synthesis of polyphosphazenes due to presence of different substituents, but an easy route for the synthesis of polyphosphazenes at controlled temperature is living cationic polymerization [5,31,34,35]. By this method, polyphosphazene block co-polymers are synthesized conveniently and polyphosphazenes are produced with wide range of different macromolecule block structures; for example, polyphosphazene-block-polyphosphazene copolymers [5], poly(ethylene oxide)-block-polyphosphazene co-polymers [36,37] and polystyrene-block polymer phosphazene co-polymers [38,39].…”

Section: Cationic/anionic Condensation Polymerizationmentioning

confidence: 99%

“…By this method, polyphosphazene block co-polymers are synthesized conveniently and polyphosphazenes are produced with wide range of different macromolecule block structures; for example, polyphosphazene-block-polyphosphazene copolymers [5], poly(ethylene oxide)-block-polyphosphazene co-polymers [36,37] and polystyrene-block polymer phosphazene co-polymers [38,39]. These polymers are utilized for biomedical applications.…”

Section: Cationic/anionic Condensation Polymerizationmentioning

confidence: 99%

“…These polymers are utilized for biomedical applications. In 1995, Allcock and co-workers synthesized polyphosphazenes from monomer trichloro-(trimethylsilyl)-phosphoarnimine (Cl 3 P=NSiMe 3 ) in the presence of PCl 5 as initiator through cationic living polymerization [5]. The reaction mechanism is shown in Fig.…”

Section: Cationic/anionic Condensation Polymerizationmentioning

confidence: 99%

“…Tel. : (86-571) 8795-3200; Fax: (86-571) 8795-1612; e-mail: opl_wl@dial.zju.edu.cn monomer trichloro-(trimethylsilyl)-phosphoarnimine (Cl 3 P=NSiMe 3 ) in the presence of PCl 5 as initiator through cationic living polymerization [5].…”

Section: Introductionmentioning

confidence: 99%

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Recent Research Progress in the Synthesis of Polyphosphazene and Their Applications

Amin

Wang

et al. 2009

Designed Monomers and Polymers

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Designed Monomers and Polymers provides a forum for the prompt publication of peer-reviewed, English-language papers on all areas of macromolecular design and application. Emphasis will be placed on the macromolecular preparations including the synthesis, characterization and application of monomers. The experimental part should be provided in such detail (including specific observations, precautionary notes, use of new materials, techniques and their possible problems, etc.) that it could be reproduced by any researcher wishing to repeat the work. The subjects of supramolecular science, initiators, macroinitiators for macromolecular design, as well as the kinetics, mechanism and modeling aspects of polymerization, will be included too. This journal will provide an interface between organic and polymer chemistries and aims to bridge the gap between monomer synthesis and the design of new polymers. The subject of monomers may include old monomers but new methods of synthesis. Author(s) must show the evidence for polymerization (including polycondensation, sequential combination, oxidative coupling, radiation, plasma polymerization, etc.) for new monomers. The field of monomers encompasses functional prepolymers of various architecture, such as hyperbranched polymers, telechelic polymers, macromonomers, or dendrimers. In particular, articles on monomers have been scattered over a vast number of journals: there is no polymer journal that covers a specialized subject such as monomers, whereas monomers are the building blocks of polymers. Designed Monomers and Polymers seeks to redress the balance by providing an international forum for addressing the issue of monomers and the art and science of macromolecular design. Issues will contain: review articles of topical areas, full research papers, short research papers, book reviews, conference reports, and conferences of note. Subscription InformationThe price for Volume 12 (2009) is EUR 951/US$ 1398, including postage and handling charges, as well as access to the electronic version. The price of the electronic version only is EUR 856/US$ 1258. Despatch of issues/electronic access will commence only after receipt of correct payment. Subscription orders should be sent to: Brill Academic Publishers, P.O. Box 9000, 2300 PA Leiden, The Netherlands (orders@brill.nl). Publishing OfficeVSP (an imprint of Brill Academic Publishers), P.O. Box 9000, 2300 PA Leiden, The Netherlands. Tel.: (31-71) 535-3500; Fax: (31-71) 531-7532; e-mail: stm@brill.nl; website: www.brill.nl/dmp Submission of a paper for publication implies the transfer of the copyright from the author(s) to the publisher (as far as copyright may be transferable).© 2009 Koninklijke Brill NV (VSP is an imprint of Brill Academic Publishers) All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise without the prior permission from the copyright holder.Typeset by VTEX, Vilniu...

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Section: Cationic/anionic Condensation Polymerizationmentioning

confidence: 99%

Section: Cationic/anionic Condensation Polymerizationmentioning

confidence: 99%

Section: Cationic/anionic Condensation Polymerizationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Recent Research Progress in the Synthesis of Polyphosphazene and Their Applications

Amin

Wang

et al. 2009

Designed Monomers and Polymers

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“…[15][16][17] However, condensation polymers with precisely controlled molecular weights and low polydispersities have not been obtained because of insolubility of polymers and of contamination of conventional step-growth polycondensation. The cationic polycondensation of phosphoranimines [18][19][20][21] and the polycondensation of dimethylsulfoxonium methylide initiated by trialkylboranes [22][23][24][25][26][27] yield well-defined polyphospahzenes and polymethylenes, respectively, but the structures of these propagating groups are different from the polymerizable groups of the monomers, and the monomers do not essentially react with each other.…”

mentioning

confidence: 99%

Chain-Growth Polycondensation: Living Polymerization Nature in Polycondensation and Approach to Condensation Polymer Architecture

Yokozawa

Yokoyama

2004

Polym J

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ABSTRACT:In this review article, polycondensation that proceeds in a chain-growth polymerization manner (''chain-growth polycondensation'') for well-defined condensation polymers are described. Our approach to chaingrowth polycondensation is (1) activation of polymer end group by substituent effects changed between monomer and polymer and (2) phase-transfer polymerization in biphase composed of monomer store phase and polymerization phase. In the approach (1), a variety of condensation polymers such as aromatic polyamides, aromatic polyesters, aromatic polyethers, poly(ether sulfone), and polythiophene with defined molecular weights and low polydispersities were obtained. Their polycondensations had all of the characteristics of living polymerization: a linear correlation between molecular weights and monomer conversion maintaining low polydispersities, and control over molecular weights by the feed ratio of monomer to initiator. Taking advantage of the nature of living polymerization in this polycondensation, we synthesized diblock copolymers of different kinds of aromatic polyamides and of aromatic polyamide and conventional polymers such as poly(ethylene glycol), polystyrene, and poly(tetrahydrofuran), as well as triblock copolymers and star polymers containing aromatic polyamide units. Some copolymers were arranged in a supramolecular self-assembly. In the approach (2), the polycondensation of solid monomer dispersed in organic solvent with a phase transfer catalyst (PTC) was carried out, where solid monomer did not react with each other, and the monomer transferred to organic solvent with PTC reacted with an initiator and the polymer end group selectively in organic solvent, to yield well-defined polyesters.KEY WORDS Chain-Growth Polycondensation / Polycondensation / Living Polymerization / Controlled Polymerization / Architecture / Polyamides / Polyesters / Polyethers / Polythiophenes / Polymerization can be classified into two categories: chain polymerization and step polymerization. Chain polymerization is initiated by the reaction of monomer and initiator, and then monomers react with the propagating group of polymers. If the chain polymerization proceeds in a living polymerization manner, the molecular weight of polymer is controlled by the feed ratio of monomer to initiator and the molecular weight distribution is narrow. In addition, the molecular weight increases in proportion to monomer conversion while retaining low polydispersity over the whole conversion range.On the other hand, step polymerization is initiated by the reaction of monomers with each other, and propagation involves the reactions of all kinds of oligomers with themselves, as well as the reactions of those oligomers with monomers. Therefore, it is difficult to control the molecular weight of polymer, and polymer possesses a broad molecular weight distribution. Plotting the molecular weight values and the polydispersity against monomer conversion, the molecular weight does not increase much in the initial and middle stage and is acce...

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The synthesis of functional polyphosphazenes and their surfaces

Allcock

1998

Appl. Organometal. Chem.

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The macromolecular substitution approach for the synthesis of polyphosphazenes provides access to many different polymers. However, it precludes the use of reagents that contain two or more functional groups because such compounds would cause extensive crosslinking of the chains. This presents a problem because many of the uses for which polyphosphazenes seem ideally suited require the presence of-OH,-COOH,-NH 2 ,-SO 3 H,-PR 2 and other functional units in the side-chain structure. We have developed two approaches to introduce such active sites: (1) protection-deprotection reactions; and (2) direct reactions of active reagents with the organic side-groups of non-functional poly(organophosphazenes). These methods have been applied both at the molecular level and in the form of reactions carried out only at polymer surfaces. The resultant polymers have special properties that are valuable in the microencapsulation of sensitive biological agents; in the formation of hydrophobic, hydrophilic, or adhesive surfaces; in crosslinking reactions; and in the development of solid polymer electrolytes, bio-erodible polymers, pH-triggered hydrogels, polymer blends and interpenetrating polymer networks. Overall, more than 700 different polyphosphazenes are now known, and a large number of these are functional macromolecules targeted for specific property combinations and uses.

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Ambient Temperature Synthesis of Poly(dichlorophosphazene) with Molecular Weight Control

Cited by 242 publications

References 0 publications

Recent Research Progress in the Synthesis of Polyphosphazene and Their Applications

Recent Research Progress in the Synthesis of Polyphosphazene and Their Applications

Chain-Growth Polycondensation: Living Polymerization Nature in Polycondensation and Approach to Condensation Polymer Architecture

The synthesis of functional polyphosphazenes and their surfaces

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