A novel and simple method of preparation of poly(styrene-b-2-vinylpyridine) block copolymer of narrow molecular weight distribution: living anionic polymerization followed by mechanism transfer to controlled/“living” radical polymerization (atrp)
15 May 2000-Journal of Macromolecular Science, Part A (Taylor & Francis Group)-Vol. 37, Iss: 6, pp 621-631
TL;DR: In this article, a block copolymer of styrene and 2-vinylpyridine with narrow molecular weight distribution is reported, where the transformation of the polymerization mechanism from living anionic to controlled/living radical polymerization (ATRP) is described.
Abstract: A novel and simple method of preparation of a block copolymer of styrene and 2-vinylpyridine with narrow molecular weight distribution is reported. The novelty lies in the transformation of the polymerization mechanism from living anionic to controlled/“living” radical polymerization (ATRP). Thus, anionic polymerization of styrene is carried out in benzene using sec-butyllithium as the initiator followed by termination with ethylene oxide to prepare hydroxy-terminated polystyrene (PS-OH). PS-OH is converted to chloride-terminated polystyrene (PS-Cl) by a displacement reaction involving thionyl chloride and pyridine in benzene. PS-Cl is used to initiate the heterogeneous ATRP of 2-vinylpyridine in p-xylene with CuCl/2,2′-bipyridine system. The polymers synthesized are characterized by gel permeation chromatography (GPC), thin layer chromatography (TLC), IR and proton NMR spectroscopies.
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3,096 citations
15 Jul 2004
TL;DR: In this article, the synthesis and solution characteristics of both natural and synthetic polymers are discussed, focusing on polynucleotides, polypeptides, and polysaccharides for naturally occurring polymers.
Abstract: Water-soluble (co)polymers represent a diverse class of macromolecules ranging from naturally occurring biopolymers such as polysaccharides and most polypeptides to wholly man-made materials. Such materials have found a wide-range of applications. In this article we detail the synthesis and solution characteristics of both natural and synthetic polymers. Emphasis is placed on polynucleotides, polypeptides, and polysaccharides for naturally occurring polymers, while the discussion regarding synthetic materials is divided into sections dealing with neutral, anionic, cationic, and zwitterionic species. Special attention is given to recent advances in synthetic methodologies which now allow the tailoring of synthetic materials with precisely controlled microstructures, predetermined molecular weights, narrow molecular weight distributions, and complex topologies.
Finally, we detail some of the self-assembly characteristics of both high molecular weight statistical copolymers and lower molecular weight block copolymers in aqueous media with an emphasis on those materials which undergo phase transitions and/or conformational changes in response to an applied stimulus.
Keywords:
water-soluble polymers;
naturally occurring polymers;
polynucleotides;
polypeptides;
proteins;
polysaccharides;
nonionic polymers;
polyelectrolytes;
polyzwitterions;
polyampholytes;
polybetaines
346 citations
TL;DR: In this paper, a review of transformation reactions involving living and controlled/living polymerization methods is presented, including step-growth, conventional and controlled free radical, cationic, anionic, group transfer, activated monomer Ziegler-Natta and metathesis reactions.
Abstract: This review is prepared on the occasion of the 50th anniversary of the historic discovery of living anionic polymerization by Michael Szwarc. This process enabled preparation, with good control of polymer architecture, of well-defined polymers such as block and graft copolymers, star polymers, macrocycles, and functional polymers. Transformation reactions provide a facile route to synthesis of block copolymers that cannot be made by a single polymerization mode. A variety of transformation reactions involving step-growth, conventional and controlled free radical, cationic, anionic, group transfer, activated monomer Ziegler–Natta and metathesis reactions are known. In this article, transformation reactions involving living and controlled/living polymerization methods are reviewed. Other possibilities of combining different polymerization methods namely, macromonomer technique, coupling reactions, dual polymerizations and click chemistry are described. Preparation of star and miktoarm-star block copolymers by using mechanistic transformations is also presented.
314 citations
Additional excerpts
...PSt PVP [37] PIP-b-PSt PSt [38] PSt-co-PAN PSt, PtBA, PBA, PGA, PMMA [39]...
[...]
...ARTICLE IN PRESS aPolymer abbreviations: PSt, polystyrene; PVP, poly(vinyl pyrolidone); PIP, polyisoprene; PMA, poly(methyl acrylate); PMMA, poly(methyl methacrylate); PB, polybutadiene; PBA, poly(butyl acrylate); PFS, poly(ferrocenyldimethylsilanes); PEO, poly(ethylene oxide); PtBA, poly(t-butyl acrylate); PCL, poly(ecaprolactone); PE, polyethylene; PBu, polybutylene; PAcSt, poly(4-acetoxystyrene); PP, polypropylene; PHMA, poly(hexyl methacrylate); PtBMA, poly(t-butyl methacrylate); PDMAEMA, poly(dimethylamino)ethyl methacrylate); PMAA, poly (methacrylic acid); PODMA, poly(n-octadecyl methacrylate); PHEMA, poly(2-hydroxyethyl methacrylate); PEGMA, poly ((ethylene glycol) methacrylate); POEGMA, poly(oligo(ethylene glycol) methyl ether methacrylate); PDMS, poly(dimethylsiloxane); PLL, polylactide; PBzA, poly(benzyl acrylate); PAN, polyacrylonitrile, PGA, poly(glycidyl acrylate); PMMEMA, poly(monomethyl ether methacrylate)....
[...]
...Polybutadiene-b-polystyrene (PB-b-PSt) [28–30], polydimethylsiloxane-b-polystyrene (PDMS-b-PSt) [31], (PEO-b-PSt) [32] and poly(ethylene oxide)-bpoly(4-vinyl pyridine) (PEO-b-PVP) [33] copolymers were synthesized by terminating the corresponding living anionic polymerization with a suitable TEMPO derivative and subsequent NMP. Stable nitroxyl radicals can also be incorporated into polymers as side groups....
[...]
TL;DR: In this article, the authors reported the polymerization of N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) directly in aqueous media utilizing 4-cyanopentanoic acid dithiobenzoate (CTP) as the chain transfer agent.
Abstract: Controlled radical polymerization (CRP) combines the benefits of the robust nature of conventional radical polymerization with the ability to prepare advanced macromolecular architectures common to living polymerization techniques. Of the major CRP techniques, the reversible addition−fragmentation chain transfer (RAFT) technique appears to be the most tolerant of aqueous reaction conditions and a variety of monomer functionalities. To date, however, there have been no reports of the RAFT polymerization of a cationic (meth)acrylamido monomer directly in aqueous media. Herein we report the polymerization of N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) directly in aqueous media utilizing 4-cyanopentanoic acid dithiobenzoate (CTP) as the chain transfer agent (CTA). Polymerization in water at neutral pH allowed a moderate level of control over the polymerization up to 50% conversion. Polymerization in an aqueous buffer (pH = 5), on the other hand, afforded excellent control up to 98% conversion (Mn = 38 ...
125 citations
114 citations
References
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TL;DR: In this paper, the authors present a method for the synthesis of organic compounds using Spectroscopic methods and Spectral Spectral Methods (SSTM) with a focus on alicyclic and aliphatic compounds.
Abstract: 1. Organic synthesis 2. Experimental techniques. 3. Spectroscopic methods. 4. Solvents and reagents. 5. Aliphatic compounds. 6. Aromatic compounds. 7. Selected alicyclic compounds. 8. Selected heterocyclic compounds. 9. Investigation and characterisation of organic compounds. 10. Physical constants of organic compounds.
6,578 citations
TL;DR: In this paper, free radical polymerization was used to obtain polystyrene and poly(styrene-co-butadiene) with narrow polydispersity (1.19-1.36) in the presence of 2,2,6, 6,6-tetramethyl-1-piperidinyloxy using benzoyl peroxide as initiator
Abstract: Polystyrene and poly(styrene-co-butadiene) with narrow polydispersity (1.19-1.36) could be obtained by free radical polymerization in solution, bulk or suspension in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy using benzoyl peroxide as initiator
1,863 citations
15 Mar 1996
TL;DR: Anionic and living polymerization: Living polymerization - definitions, consequences and criteria general aspects of anionic polymerization are discussed in this paper, where anionic synthesis of polymers with well-defined structures is discussed.
Abstract: Part 1 Structure and bonding in carbanionic compounds: structure of carbanions and organometallic compounds stabilities of carbanionic species ion pairs, free ions and stereochemistry in carbanionic chemistry. Part 2 Introduction to anionic and living polymerization: living polymerization - definitions, consequences and criteria general aspects of anionic polymerization. Part 3 Kinetics and mechanism in anionic polymerization: initiation reactions in anionic polymerization - kinetics of addition of organolithium compounds to vinyl monomer propagation reactions - kinetics and mechanism for styrenes and dienes in hydrocarbon solvents with lithium as counterion termination and chain transfer reactions stereochemistry of polymerization copolymerization. Part 4 Anionic synthesis of polymers with well-defined structures: functionalized polymers and macromonomers block copolymers star polymers graft copolymers. Part 5 Commercial applications of anionically prepared polymers: commercial applications of anionically polymerized products - an overview polydiene rubbers styrene-diene rubbers styrenic thermoplastic elastomers applications of styrenic thermoplastic rubbers in plastics modifications, adhesives and footwear clear impact-resistant polystyrene nonfunctional telechelic prepolymers. Part 6 Polar monomers: anionic polymerization of methyl methacrylate and related polar monomers block polymers prepared via anionic ring-opening polymerization.
1,000 citations