Mechanistic transformations involving living and controlled/living polymerization methods

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.     

Telechelic polymers by living and controlled/living polymerization methods

Telechelic polymers, defined as macromolecules that contain two reactive end groups, are used as cross-linkers, chain extenders, and important building blocks for various macromolecular structures, including block and graft copolymers, star, hyperbranched or dendritic polymers. This review article describes the general techniques for the preparation of telechelic polymers by living and controlled/living polymerization methods; namely atom transfer radical polymerization, nitroxide mediated radical polymerization, reversible addition-fragmentation chain transfer polymerization, iniferters, iodine transfer polymerization, cobalt mediated radical polymerization, organotellurium-, organostibine-, organobismuthine-mediated living radical polymerization, living anionic polymerization, living cationic polymerization, and ring opening metathesis polymerization. The efficient click reactions for the synthesis of telechelic polymers are also presented.     

活性自由基聚合反应与多种结构聚合物的制备

介绍了原民移自由基聚合反应这一新型的活性自由基聚合方式,并综述了利用这种聚合方法制备的多种结构的聚合物,包括嵌段共取物,交替共聚物,接枝共聚物,星形聚合物,超支化聚合物,梳形聚合物等。     

Precise synthesis of polymers containing functional end groups by living ring-opening metathesis polymerization (ROMP): Efficient tools for synthesis of block/graft copolymers

This article summarizes recent examples for precise synthesis of (co)polymers containing functional end groups prepared by living ring-opening metathesis polymerization (ROMP) using molybdenum, ruthenium complex catalysts. In particular, this article reviews recent examples for synthesis of amphiphilic block/graft copolymers by adopting transition metal-catalyzed living ROMP technique. Unique characteristics of the living ROMP initiated by the molybdenum alkylidene complexes (so-called Schrock type catalyst), which accomplish precise control of the block segment (hydrophilic and hydrophobic) as well as exclusive introduction of functionalities at the polymer chain end, enable us to provide the synthesis of block copolymers varying different backbones by adopting the “grafting to” or the “grafting from” approach as well as “soluble” star shape polymers with controlled manner. The “grafting through” approach (polymerization of macromonomers) by the repetitive ROMP technique offers precise control of the amphiphilic block segments.     

Synthesis,properties, and practical application of hyperbranched polymers

The methods of synthesis of hyperbranched polymers are considered and systematized with main attention focused on such modern and promising procedures of crosslinking free-radical polymerization as living chain and intense chain transfer regimes. The synthetic approach to hyperbranched polymers via free-radical oxidative polymerization is the first to be put forth. The main problems concerning these polymers are formulated, and the recent advances in this field are generalized and elucidated.     

Preparation of pH-sensitive amphiphilic block star polymers,their self-assembling characteristics and release behavior on encapsulated molecules

Poly(ethylene glycol) (PEG), a polymer with excellent biocompatibility, was widely used to form nanoparticles for drug delivery applications. In this paper, based on PEG, a series of pH-sensitive amphiphilic block star polymers of poly(ethylene glycol)-block-poly(ethoxy ethyl glycidyl ether) (PEG-b-PEEGE) with different hydrophobic length were synthesized by living anionic ring-opening polymerization method. The products were characterized using ¹H NMR and gel permeation chromatography. These copolymers could self-assemble in aqueous solution to form micellar structure with controlled morphologies. Transmission electron microscopy showed that the nanoparticles are spherical or rodlike with different hydrophilic mass fractions. The pH response of polymeric aggregates from PEG-b-PEEGE was detected by fluorescence probe technique at different pH. A pH-dependent release behavior was observed and pH-responsiveness of PEG-b-PEEGE was affected by the hydrophobic block length. These results demonstrated that star-shaped polymers (PEG-b-PEEGE) are attractive candidates as anticancer drug delivery carriers.     

Hydrophilic modification of engineering polymers

Water-soluble carboxylated polymers were synthesized from engineering polymers via the metallation of poly(oxy-1,4-phenylenesulphonyl-1,4-phenyleneoxy-1,4-phenyleneisopropylidene-1, 4-phenylene) and poly(oxy-2,6-dimethyl-1,4-phenylene) with n-butyllithium followed by reaction with carbon dioxide. Interactions between lithium sites on the polymer backbones cause the precipitation of highly metallated polymers. Precipitation of PPO occurs at approximately 15% metallation based on polymer repeat unit. Reproducibility problems are encountered with highly metallated, precipitated polymers. An ester-functional comb-type graft copolymer is synthesized via the anionic polymerization of methyl methacrylate (MMA) from metallated sites on PPO. The ester functionalities can be transesterified with hydroxy functional reagents to yield well-defined comb-type graft terpolymers. Transesterification of oligomeric polyethylene glycol onto PPO-MMA yields a comb-type graft terpolymer with nonionic hydrophiles.     

Structure and properties of block polymers and multiphase polymer systems: an overview of present status and future potential

Work on the block polymers of styrene and butadiene indicates the potential of multiphase polymers of controlled solid state structure. The effect of chemical composition, molecular architecture (multichain ‘star’ shaped versus linear), block sequence length, processing conditions, and blending of homopolymer with the block polymers on their solid state morphology is discussed. Results on these block polymer systems indicate the future research directions in certain areas. Implications of these areas for polymers of controlled solid state structure to provide materials of desirable combination of properties are also considered.     

Architecture of nanostructured polymers by segregated domain crosslinking of block‐graft copolymer micelles

Polystyrene‐block‐polyisoprene (PS‐block‐PI; high 3,4‐structure) diblock copolymer was prepared by living anionic polymerization. For transfer into a reactive intermediate, the hydroxylation of the double bonds of PI block was achieved by hydroboration, followed by oxidation. Esterification of the hydroxy‐derivative with stearoyl chloride or decanoyl chloride resulted in block‐graft copolymers composed of PS (flexible chain)‐grafted long alkane (stretched chains). After partial chloromethylation of PS block copolymer, photofunctional N,N‐diethyldithiocarbamate (DC) groups were introduced into such pendant sites by reaction with the corresponding sodium salt. We studied the self‐assemblies of photofunctional block‐graft copolymers in a selective solvent, such as heptane, and constructed nanostructured polymers by crosslinking PS cores under UV irradiation. © 2001 Society of Chemical Industry     

Anionic Graft Polymerisation of Styrene from Polyisoprene. Dependence of Grafting Efficiency on Polyisoprene Structure

Styrene was grafted from polyisoprene forming poly(isoprene-g-styrene) graft polymers. N,N,N',N'-Tetramethylene diamine and s-butyllithium were used to create active centres on the polyisoprene backbone in cyclohexane under anionic living polymerisation conditions. The stereoregularity of polyisoprene is shown to influence the grafting efficiency. Addition of small amounts of tetrahydrofuran increased grafting efficiency and decreased polydispersity of the graft polymers obtained. Polystyrene branches are shown to be syndiotactic rich.     

Structurally controlled polymerizations of methacrylates and acrylates

Progress in the structure control of polymethacrylates and polyacrylates through stereospecific living polymerization are described. Three types of stereospecific living polymerizations have been developed for methacrylate polymerization: isotactic with t‐C₄H₉MgBr, syndiotactic with ­t‐C₄H₉Li/R₃Al, and heterotactic with t‐C₄H₉Li/bis(2,6‐di‐t‐butylphenoxy)methylaluminium [MeAl(ODBP)₂]. The last initiator system has been proved effective for monomer‐selective living copolymerization of methacrylates. The living nature of these polymerizations allows extensive use for the syntheses of stereoregular block polymers and copolymers, and end‐functionalized polymers such as macromonomers. Through stereospecific polymerizations and copolymerizations of macromonomers, comb polymers and graft copolymers with defined stereoregularities in the main chain and side chains could be obtained. Some properties of these stereoregular polymers are also described, including stereocomplex formation and solution viscosity. Stereospecific polymerizations of crotonates leading to diisotactic, diheterotactic and disyndiotactic polymers are also discussed. Supercritical fluid chromatography (SFC) has been proven to be useful for isolating uniform polymers from stereoregular poly(methyl methacrylate)s (PMMAs) with narrow molecular weight distribution. Uniform end‐functionalized polymers have been used to construct more elaborate uniform polymer architectures such as stereoblock, star, and comb polymers, and copolymers. The uniform polymers have been proven quite useful for the studies of the relationship between structures and properties such as glass transition temperature, melting temperature and solution viscosity. Particularly interesting is the use of isotactic and syndiotactic uniform PMMAs for the understanding of stereocomplex formation in certain solvents such as acetone. Furthermore, a uniform stereoblock PMMA was found to undergo intramolecular complexation in addition to intermolecular complexation in acetone. Uniform star and comb PMMAs were also prepared and found useful for discussing the effect of branching on the solution viscosity. © 2000 Society of Chemical Industry     

Polymer vectors via controlled/living radical polymerization for gene delivery

The design of efficient gene delivery vectors is a challenging task in gene therapy. Recent progress in living/controlled radical polymerizations (LRPs), in particular atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization providing a means for the design and synthesis of new polymeric gene vectors with well-defined compositions, architectures and functionalities is reviewed here. Polymeric gene vectors with different architectures, including homopolymers, block copolymers, graft copolymers, and star-shaped polymers, are conveniently prepared via ATRP and RAFT polymerization. The corresponding synthesis strategies are described in detail. The recent research activities indicate that ATRP and RAFT polymerization have become essential tools for the design and synthesis of advanced, noble and novel gene carriers.     

Temperature responsive bio-compatible polymers based on poly(ethylene oxide) and poly(2-oxazoline)s

This review covers the LCST behavior of two important polymer classes in aqueous solution, namely poly(2-oxazoline)s and systems whose thermo-responsiveness is based on their structural similarity to poly(ethylene oxide) (PEO). In order to elucidate the progress that has been made in the design of new thermo-responsive copolymers, experimental data that were obtained by different research groups are compared in detail. Copolymerization with hydrophilic or hydrophobic comonomers represents a suitable method to tune the coil to globule transition temperature of several homopolymers, and incorporation of other monomers provided further interesting features, such as pH responsiveness or sensing properties. In addition, living and controlled polymerization techniques enabled access to defined end groups and more advanced polymer architectures, such as graft copolymers or double responsive block copolymers. The effect of such structural variations on the temperature responsive behavior of the (co)polymers is discussed in detail.     

模型聚合物的制备

本文对模型聚合物（包括线型均聚物以及远螯聚合物、嵌段聚合物、环状聚合物、树枝状聚合物等特征结构的聚合物）的制备方法进行综述,并着重讨论了活性聚合在模型聚合物制备中的应用     

Borylated Polyolefins and their Applications

Different preparative routes for the attachment of organoboron moieties to polyolefins and applications of such materials are reviewed. Preparation from boron-functionalized monomers represents one possible synthetic strategy with free radical polymerization, Ziegler–Natta polymerization, and ring-opening metathesis polymerization methods as the most thoroughly studied procedures. Recent advances in the preparation of boron-containing polymers through polymer modification reactions provide an interesting alternative that allows for the facile preparation of well-defined organoboron polymers of various architectures including homo polymers, random copolymers, block copolymers, and telechelic polymers. New opportunities for organoboron polymers as supported catalysts, sensors, luminescent materials, device components, and precursors to ceramics are briefly discussed.     

Polyboranes, their synthesis and applications in functional polyolefins

This paper summarizes our research results on the synthesis of polyboranes and their applications in the functionalization of polyolefins. The method involves the borane monomers and transitional metal catalysts, such as Ziegler-Natta and metathesis catalysts. Our results show that most trialkylboranes are stable to a broad range of transitional metal catalysts. The borane-containing olefins can be homo- or copolymerized with olefins to the corresponding polyborane homo- and copolymers. The molecular weights of polyboranes are usually very high. Some of the reasons are attributed to the good solubility of polyboranes in hydrocarbon solutions during the polymerization processes. In turn, the borane groups in polymers are easily converted to other functional groups, such as hydroxyl groups, under mild conditions. Some high molecular weight functional polyolefins have been prepared with unique polymer structures, such as isotactic comb-like functional polymers, block copolymers, and alternating functional copolymers.     

RETRACTED ARTICLE: Towards understanding polyhydroxyalkanoates and their use

It is fact that Polymers and their products have changed the face of the world in all the field of the technology. They are the future of the coming up generation of the research of the world. But this is also fact that these synthetic non biodegradable polymers have created a tough situation for the living being for a healthy life. Polyhydroxyalkanoates are polyesters produced by bacteria as intracellular storage materials in response to a variety of nutritional and environmental conditions, such as nitrogen limitation Polyhydroxyalkanoates (PHAs) are gaining increasing attention in the biodegradable polymer market due to their promising properties such as high biodegradability in different environments, not just in composting plants, and processing versatility. Indeed among biopolymers, these biogenic polyesters represent a potential sustainable replacement for fossil fuel-based thermoplastics. Most commercially available PHAs are obtained with pure microbial cultures grown on renewable feedstocks (i.e.glucose) under sterile conditions but recent research studies focus on the use of wastes as growth media.PHA can be extracted from the bacteria cell and then formulated and processed by extrusion for production of rigid and flexible plastic suitable not just for the most assessed medical applications but also considered for applications including packaging, moulded goods, paper coatings, non-oven fabrics, adhesives, films and performance additives. The present paper reviews the PHAs, their main properties, processing aspects, commercially available ones, as well as limitations and related improvements being researched,with specific focus on potential applications of PHAs in packaging.     

Benzoin‐terminated polyurethane as macrophotoinitiator for synthesis of polyurethane–polymethyl methacrylate block copolymers

Macromolecular photoinitiators have attracted much attention in the recent years. They combine the properties of polymers with those of low‐molecular weight photoinitiators. These are polymers having side‐ or main‐chain photoreactive groups and can be used to make tailor‐made graft and block copolymers. Benzoin is an important photoinitiator, and polymers containing terminal photoactive benzoin group can initiate polymerization of vinylic monomers to give block copolymers. In the present case, we report the synthesis of polyurethane macrophotoinitiator with benzoin end group, which was subsequently used to synthesize polyurethane–polymethyl methacrylate block copolymers. The block copolymers were characterized by FTIR, ¹H NMR, TGA, scanning electron microscopic analysis, and solution viscometry studies. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

原子转移自由基聚合原理及应用

介绍了有关原子转移自由基聚合(ATRP)的聚合原理。最新研究表明:应用ATRP法进行聚合反应可以制备接枝聚合物、嵌段聚合物、超支化聚合物和其它有机/无机混合型聚合物等。ATRP在高分子聚合反应领域具有十分广阔的应用前景。     

Recent advances in stereocomplexation of enantiomeric PLA-based copolymers and applications

Poly(lactic acid) or poly(lactide) (PLA) is a biodegradable and biocompatible thermoplastic polymer, being derived from renewable resources such as corn and sugar cane. The building block of PLA, lactic acid is chiral and the polymerization of lactic acids (or lactides) leads to isotatic, syndiotatic and atactic/heterotactic PLA primary structures. The stereoselective interaction between two complementary enantiomeric PLLA and PDLA has led to enhanced physical properties such as mechanical properties, thermal resistance and hydrolytic stability compared with the parent polymers. Progress in controlled and/or living polymerization techniques combined with other new synthetic methodologies has facilitated the preparation of PLA-based copolymers with complex architectures such as diblock, triblock, multiblock, star-shape block, comb-shape block and various PLA-grafted structures. The utilization of stereocomplexation strategy to these newly developed copolymers has opened avenues to access a variety of new materials with unique characteristics, including novel chemical functionalities, bioactivities, and smart (responsive to external stimulus) properties tailored for specific applications. This review presents recent advancements in the synthesis of PLA-based block/graft copolymers having complex architectures, with emphasis on the enhanced material performances induced by PLA stereocomplex formation. The origin of the enhanced thermal mechanical property observed in PLA stereocomplex is first discussed. The strong interaction resulted from stereocomplexation in PLA based copolymers could be exploited not only for fabrication of advanced therapeutic delivery carriers and tissue engineering devices, but also for stabilizing colloidal systems in microparticles, micelles and hydrogels, that further broaden the applications of PLA that could not have been attained with single PLLA or its copolymers. The stereocomplexation could also be used to tailor the interface interactions between fillers and PLA matrix that lead to higher strength and toughness of PLA.