Directed polymer synthesis for industrial application

In the present survey the limitations for the industrial application of polymer syntheses are discussed as well as the directions, syntheses may go. As particular examples the living anionic polymerization and the respective ring-opening polymerization and copolymerization are discussed. Under the aspect of future developments some examples of biotechnological polymerization and particular features of biopolymers are given     

稀土催化剂在高分子合成中的开拓应用

综述了40多年来我国在高分子合成领域中开拓应用稀土催化剂,在双烯烃、炔烃、环氧烷烃、环硫烷烃、二氧化碳共聚、丙交酯、己内酯和环碳酸酯等聚合方面取得的主要进展。     

Polymerization in nanostructured media: applications to the synthesis of associative polymers

Some recent developments obtained by free radical polymerization in nanostructured media are presented. The characteristic features of the confined media like the large overall interfacial area and the particular microenvironment are taken advantage to yield novel materials with interesting properties. The examples considered here include the synthesis of i) thermosensitive polyampholytes by polymerization in bicontinuous microemulsions, ii) ionomers by polymerization in inverse microemulsions and iii) multicompartment polymeric micelles by means of an aqueous micellar polymerization process. The characteristics inherent to each of these syntheses are discussed.     

New developments in the synthesis of block and graft copolymers via anionic and cationic methods

Ionic living polymerization methods are well suited for the synthesis of macromolecules of known structure, molecular weight and composition, and exhibiting low fluctuations in composition and in molecular weight. They were the first to allow the synthesis of well characterized block and graft copolymers. The present paper discusses a number of recent developments concerning these syntheses based on anionic or cationic living polymerization.     

基于ATRP技术的多嵌段共聚物研究进展

原子转移自由基聚合(ATRP)技术是合成结构规整性聚合物的有效途径。综述了近十年来采用ATRP技术合成多嵌段共聚物的研究进展。从引发剂、共聚单体和反应条件等方面讨论了ABA型、ABC型和ABCBA型等类型多嵌段共聚物的合成、性质与潜在应用。对原子转移自由基聚合技术在合成功能性多嵌段共聚物中的应用前景进行了展望。     

Anionic methods for synthesis of star polymers

Leading position among numerous methods for synthesis of star polymers is occupied, as regards their potential and diversity, by techniques based on the anionic polymerization. The review considers five basic approaches to application of the anionic polymerization mechanisms in relation to an agent used or procedure employed (methods with polyfunctional coupling agents, multifunctional initiators, polymerizing and nonpolymerizing divinyl agents; multistage methods, methods using C₆₀ fullerene). All groups of syntheses are illustrated by examples, and advantages of methods for synthesis of various homo- and heteroarm star structures are demonstrated. Particular attention is given to syntheses with C₆₀ fullerene. The potential of C₆₀ fullerene as a coupling agent for “living” polymer chains and methods for conversion of polymeric derivatives of C₆₀ (hexaadducts) to polyfunctional macroinitiators of anionic polymerization are described and techniques for functionalization of polymeric fullerene derivatives and their coupling into structures with a complex controllable architecture are presented.     

Some Rare Earth Metallic Organohydrides with Biindenyl as the Ligand

Introduction It is well known that organometallic hydrides of rare earth metals are the catalysts and reducing reagents for the catalysis polymerization of alkenes and the catalysis hydrogenation of alkenoalkynes. There are four methods for the syntheses of organometallic hydrides of rare earth metals:(1) the thermal atomization of metals, i.e., the interaction of a rare earth metal with alkenes with a terminal alkyne;(2) the Ln—Cσ bond is broken with H_2;(3) metal-     

双桥连二环戊二烯基金属有机化合物的研究进展

综述了双桥连二戊二烯基金属有机化合物的研究进展，根据桥链以及金属原子 的不同，分别讨论了它们的合成、结构及在催化烯烃聚合上的应用。     

FI catalysts: new olefin polymerization catalysts for the creation of value-added polymers

This contribution reports the discovery and application of phenoxy-imine-based catalysts for olefin polymerization. Ligand-oriented catalyst design research has led to the discovery of remarkably active ethylene polymerization catalysts (FI Catalysts), which are based on electronically flexible phenoxy-imine chelate ligands combined with early transition metals. Upon activation with appropriate cocatalysts, FI Catalysts can exhibit unique polymerization catalysis (e.g., precise control of product molecular weights, highly isospecific and syndiospecific propylene polymerization, regio-irregular polymerization of higher alpha-olefins, highly controlled living polymerization of both ethylene and propylene at elevated temperatures, and precise control over polymer morphology) and thus provide extraordinary opportunities for the syntheses of value-added polymers with distinctive architectural characteristics. Many of the polymers that are available via the use of FI Catalysts were previously inaccessible through other means of polymerization. For example, FI Catalysts can form vinyl-terminated low molecular weight polyethylenes, ultra-high molecular weight amorphous ethylene-propylene copolymers and atactic polypropylenes, highly isotactic and syndiotactic polypropylenes with exceptionally high peak melting temperatures, well-defined and controlled multimodal polyethylenes, and high molecular weight regio-irregular poly(higher alpha-olefin)s. In addition, FI Catalysts combined with MgCl(2)-based compounds can produce polymers that exhibit desirable morphological features (e.g., very high bulk density polyethylenes and highly controlled particle-size polyethylenes) that are difficult to obtain with conventionally supported catalysts. In addition, FI Catalysts are capable of creating a large variety of living-polymerization-based polymers, including terminally functionalized polymers and block copolymers from ethylene, propylene, and higher alpha-olefins. Furthermore, some of the FI Catalysts can furnish living-polymerization-based polymers catalytically by combination with appropriate chain transfer agents. Therefore, the development of FI Catalysts has enabled some crucial advances in the fields of polymerization catalysis and polymer syntheses.     

Development of solvent-free acrylic pressure-sensitive adhesives

The present publication describes a problem to develop solvent-free acrylic pressure-sensitive adhesives (PSA). Solvent-free PSA are established materials for the manufacturing of various self-adhesive products. Only by means of these acrylic PSA was it possible to succeed in drafting the present surprisingly efficient generation of double-sided pressure-sensitive adhesive tapes, medical products, protective masking films, films for the graphics market, and various specialty products. New applications and technical specifications stimulate the continuous development of new methods of polymerization of solvent-free acrylates. New syntheses of solvent-free acrylic PSA include polymerization in the reactor with removal of the solvent and polymerization on the carrier. The polymerization process is connected with UV-crosslinking.     

Mechanochemical Synthesis of Stimuli Responsive Microgels

Mechanochemical approaches are widely used for the efficient, solvent-free synthesis of organic molecules, however their applicability to the synthesis of functional polymers has remained underexplored. Herein, we demonstrate for the first time that mechanochemically triggered free-radical polymerization allows solvent- and initiator-free syntheses of structurally and morphologically well-defined complex functional macromolecular architectures, namely stimuliresponsive microgels. The developed mechanochemical polymerization approach is applicable to a variety of monomers and allows synthesizing microgels with tunable chemical structure, variable size, controlled number of crosslinks and reactive functional end-groups.     

Synthesis and properties of stereoregular fluoro-polymers via ring-opening metathesis polymerization of fluorinated norbornenes and norbornadienes. An overview and progress report

Since the first report of the ring-opening metathesis polymerization of fluorinated monomers in 1979 considerable advances in precision and control of such syntheses have been achieved through the introduction of well defined initiators. It is now possible to carry out well controlled living and stereoregular polymerizations. The products of such syntheses can display unusually high relaxed dielectric constants, an observation which is crucial to the assignment of their tacticities and probably significant with regard to possible applications of this type of material.     

Preparation of Polymer Membranes for Fuel Cells by Radiation Graft Polymerization

Publications on the use of radiation graft polymerization for the manufacture of polymer membranes for fuel cells are systematized and generalized. Data on the syntheses, structures, and physicochemical properties of the membranes are given. The areas of practical applications of the membranes are demonstrated. The review mainly surveys works published in the past decade.     

A personal journey on using polymerization in aqueous dispersed media to synthesize polymers with branched structures

This short review is dedicated to celebrate Prof.Shoukuan Fu's 80 th birthday by discussing several of my accomplished projects over the past twenty years,which all applied radical polymerization in aqueous dispersed media for producing polymers with branched structures.These projects include the use of microemulsion polymerization for syntheses of fluorescent nanoparticles,hairy nanoparticles and hyperbranched polymers;the use of miniemulsion polymerization for synthesis of star polymers and light-emitting nanoparticles;the use of seeded emulsion polymerization for synthesis of hairy nanoparticles and hyperstar polymers;and the use of precipitation polymerization for synthesis of hollow polymer nanocapsules.Discussion of these projects demonstrates intriguing features of polymerization in biphasic dispersed media via either conventional radical polymerization or controlled radical polymerization to effectively regulate the branched structure of functional polymers.     

环碳酸酯开环聚合物制备、性能和应用研究进展

综述了近年来环碳酸酯开环均聚与共聚产物的制备、性能与应用研究进展     

A personal journey on using polymerization in aqueous dispersed media to synthesize polymers with branched structures

Several projects were discussed to demonstrate the intriguing power of radical polymerization in aqueous dispersed media to regulate the branched structures in functional polymeric nanomaterials.     

单分散大粒径聚合物微球的合成及应用

单分散，大粒径聚合物微球是近２０年来开发的一类球形高分子粒子，在标准计量、情报信息、化学化工、医学免疫及生物化学等许多领域里有着广阔的应用前景，其合成和应用在高分子科学领域里已成为人们致力于研究和开发的热门课题。     

Ligated anionic polymerization: An innovative elf-atochem technology for the polymerization of (meth)acrylates

Admittedly performing materials, (meth)acrylic polymers, used in a wide variety of applications, are traditionally produced by radical polymerization processes. The extension of living polymerization, originally developed for dienes and vinyl-aromatics, to (meth)acrylic polymers, would be an interesting opening to a variety of products with a large scope of properties and applications. However, this method suffers from chemical and technical limitations when applied to (meth)acrylates under the usual conditions of solvent and temperature. We report how alkoxy alkoxides-based systems combined with a recent Elf Atochem process offer attractive conditions for ultra-fast anionic polymerization of (meth)acrylates at high solid content. Applications to cost effective syndiotactic poly(methyl methacrylate) and block copolymers syntheses are described.     

Asymmetric polymerization of methacrylates

The syntheses of optically active polymers having helical conformation from bulky methacrylates are reviewed focusing on selected topics. The monomers include triphenylmethyl methacrylate and its analogues. Asymmetric anionic polymerization of the monomers gives isotactic, optically active polymers having a helical structure with excess helicity. The isotactic content and the extent of helical‐sense excess depend on the monomer structure and the reaction conditions. In the case of methacrylates, completely isotactic and single‐handed helical polymers can be produced by asymmetric anionic polymerization (helix‐sense‐selective polymerization). Asymmetric radical polymerization is also possible for this class of monomer. Some of the helical polymers show chiral recognition ability toward a wide range of racemic compounds. Polymers having main‐chain configurational chirality are also discussed.     

Lithium Camphor initiated Anionic Polymerization of C_(60) and Styrene

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