Alternating Copolymerization Involving Zwitterions

We would like to dedicate this article to P. H. Plesch, a pioneer of cationic polymerization and a mentor and friend for many of those who are now at the forefront of this field of science. He passed away 5 March 2013 at the age of 95. We will miss him. Abstract: This short, introductory review covers the still rapidly growing and industrially important field of ring opening polymerization (ROP). The review is organized according to mechanism (radical ROP (RROP), cationic ROP (CROP), anionic ROP (AROP) and ring-opening metathesis polymerization (ROMP)) rather than monomer classes. Nevertheless, the different groups of cyclic monomers are considered (olefins, ethers, thioethers, amines, lactones, thiolactones, lactams, disulfides, anhydrides, carbonates, silicones, phosphazenes and phosphonites) and the mechanisms by which they can be polymerized involving a ring-opening polymerization. Literature up to 2012 has been considered but the citations selected refer to detailed reviews and key papers, describing not only the latest developments but also the evolution of the current state of the art.

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“…This copolymerization takes place without any initiator or catalyst and additional details are available in the literature [158]. …”

Section: Other Ring-opening Polymerizationsmentioning

confidence: 99%

Ring-Opening Polymerization—An Introductory Review

Nuyken

Pask²

2013

Polymers

355

265

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“…[1][2][3] The following may be cited as typical examples: cationic ring-opening polymerizations of cyclic ethers, 4 cyclic imino ethers, 2,5-7 and cyclic phosphorous compounds 8,9 and zwitterionic polymerizations. 10,11 Through these polymerizations, several varieties of functional polymers have been developed, and they include oxygen-, nitrogen-, and phosphorus-containing functional groups such as chelating polymers, scaffolds for polymeric drugs, biocompatible materials, nonionic polymer surfactants, and supramolecular systems. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] I once worked on Ziegler-Natta catalysts for a norbornene ring-opening polymerization; this was the first research project in which I was involved.…”

Section: Cellulose Synthesismentioning

confidence: 99%

“…10,11 Through these polymerizations, several varieties of functional polymers have been developed, and they include oxygen-, nitrogen-, and phosphorus-containing functional groups such as chelating polymers, scaffolds for polymeric drugs, biocompatible materials, nonionic polymer surfactants, and supramolecular systems. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] I once worked on Ziegler-Natta catalysts for a norbornene ring-opening polymerization; this was the first research project in which I was involved. Also, I studied the organic chemistry of new transition-metalcatalyzed synthetic reactions 17,18 and the reaction mechanisms of carbocationic chemistry.…”

Section: Cellulose Synthesismentioning

confidence: 99%

Challenge of synthetic cellulose

Kobayashi

2004

J. Polym. Sci. A Polym. Chem.

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This article focuses on why and how the chemical synthesis of cellulose was accomplished. The synthesis of cellulose was an important, challenging problem for half a century in polymer chemistry. For the synthesis, a new method of enzymatic polymerization was developed. A monomer of β‐D‐cellobiosyl fluoride (β‐CF) was designed and subjected to cellulase catalysis, which led to synthetic cellulose for the first time. Cellulase is a hydrolysis enzyme of cellulose; cellulase, inherently catalyzing the bond cleavage of cellulose in vivo, catalyzes the bond formation via the polycondensation of β‐CF in vitro. It is thought that the polymerization and hydrolysis involve a common intermediate (transition state). This view led us to a new concept, a transition‐state analogue substrate, for the design of the monomer. The preparation of cellulase proteins with biotechnology revealed the enzymatic catalytic functions in the hydrolysis and polymerization to cellulose. High‐order molecular structures were in situ formed and observed as fibrils (cellulose I) and spherulites (cellulose II). In situ small‐angle neutron scattering measurements suggested a fractal surface formation of a synthetic cellulose assembly. The principle of cellulose synthesis was extended to the synthesis of other natural polysaccharides, such as xylan and amylose, and unnatural polysaccharides. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 693–710, 2005

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“…Certain combinations of nucleophiles and electrophiles undergo polymerization without the need for initiator [Culbertson, 2002;Kobayashi and Saegusa, 1985;Kobayashi and Uyama, 2002;Saegusa, 1977Saegusa, , 1979Saegusa, , 1981. The polymerization, referred to as zwitterion polymerization, proceeds via zwitterion intermediates.…”

Section: -12d Zwitterion Polymerizationmentioning

confidence: 99%

Ring‐Opening Polymerization

Odian

2004

Principles of Polymerization

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A wide variety of cyclic monomers have been successfully polymerized by the ring-opening process [Frisch and Reegan, 1969; Ivin and Saegusa, 1984;Saegusa and Goethals, 1977]. This includes cyclic amines, sulfides, olefins, cyclotriphosphazenes, and N-carboxy-a-amino acid anhydrides, in addition to those classes of monomers mentioned above. The ease of polymerization of a cyclic monomer depends on both thermodynamic and kinetic factors as previously discussed in Sec. 2-5.The single most important factor that determines whether a cyclic monomer can be converted to linear polymer is the thermodynamic factor, that is, the relative stabilities of the cyclic monomer and linear polymer structure [Allcock, 1970;Sawada, 1976]. Table 7-1 shows the semiempirical enthalpy, entropy, and free-energy changes for the conversion of cycloalkanes to the corresponding linear polymer (polymethylene in all cases) [Dainton and Ivin, 1958;Finke et al. 1956]. The lc (denoting liquid-crystalline) subscripts of ÁH, ÁS, and ÁG indicate that the values are those for the polymerization of liquid monomer to crystalline polymer.Polymerization is favored thermodynamically for all except the 6-membered ring. Ringopening polymerization of 6-membered rings is generally not observed. The order of thermodynamic feasibility is 3,4 > 8 > 5,7 which follows from the previous discussion (Sec. 2-5c) on bond angle strain in 3-and 4-membered rings, eclipsed conformational strain in the 5-membered ring, and transannular strain in 7-and 8-membered rings. One notes that RING-OPENING POLYMERIZATION RING-OPENING POLYMERIZATION

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Alternating Copolymerization Involving Zwitterions

Cited by 20 publications

References 67 publications

Ring-Opening Polymerization—An Introductory Review

Ring-Opening Polymerization—An Introductory Review

Challenge of synthetic cellulose

Ring‐Opening Polymerization

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