The reversible addition-fragmentation chain transfer(RAFT) miniemulsion polymerization of vinyl acetate mediated by xanthate

The reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization of vinyl acetate （VAc） mediated by methyl （methoxycarbonothioyl） sulfanyl acetate （MMSA） was carried out. The results showed that polymerizations initiated by AIBN and KPS proceeded in a controlled way. The RAFT miniemulsion polymerization of VAc initiated by KPS showed the shorter inhibition period, higher propagation rate coefficient and final conversion than those in experiment initiated by AIBN. When the monomer conversion reached 25%, the polydispersity index （PDI） of polymer became broad, which was related to chain transfer reaction in RAFT miniemulsion of VAc.

Synthesis of polystyrene-styrene/butadiene diblock copolymers via reversible addition-fragmentation chain transfer miniemulsion polymerization

Polystyrene-styrene/butadiene diblock copolymers were synthesized via reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization.During the polymerization process,the molecular weight distribution was narrow and the numerical molecular weight of the copolymers increased with increasing conversion of monomers,which was close to the theoretical.FT-IR and ^1H NMR results indicated that the microstructure of the polymer was mainly 1,4-trans-butadiene with small amount of 1,2-units,and composition in the copolymers was obtained.

Evaluation of the clenbuterol imprinted monolithic column prepared by reversible addition-fragmentation chain transfer polymerization

To make more homogenous organic monolithic structure, reversible addition-fragmentation chain transfer （RAFT） process was employed in the synthesis of the clenbuterol imprinted polymer. In the synthesis, the influence of synthetic conditions on the polymer structure and separation efficiency was studied. The result demonstrated that the imprinted columns prepared with RAFT process have higher column efficiency and selectivity than the columns prepared with conventional polymerization in the present study, which may result from the higher surface area, smaller pore size and the narrower globule size distribution in their structures. The result indicated that RAFT polymerization provided better conditions for the clenbuterol imprinted monolithic polymer preparation. 2009 Xiang Chao Dong. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Grafting of MIPs from PVDF Membranes via Reversible Addition-fragmentation Chain Transfer Polymerization for Selective Removal of p-Hydroxybenzoic Acid

Effective molecularly imprinted membranes（MIMs） were developed as an efficient adsorbent for the selective removal ofp-hydroxybenzoic acid（p-HB） from acetylsalicylic acid（ASA, aspirin）. The MIMs were grafted successfully from poly（vinylidene fluoride） microfiltration membranes via reversible addition-fragmentation chain transfer（RAFT） polymerization. The graft copolymerization of acrylic acid（AA） in the presence of template p-hydroxybenzoic acid led to molecularly imprinted polymer（MIP） film coated membranes. The obtained MIMs were characterized by scanning electron microscopy（SEM）, Fourier transform infrared spectrophotometer（FTIR） and Raman spectra, and batch mode adsorption studies were carried ont to investigate the specific adsorption equilibrium, kinetics and selective recognition properties of different MIMs. The kinetic properties of the MIMs could be well described by the pseudo-second-order rate equation. Selective permeation experiments were performed to evaluate the permeation selectivity of the p-HB imprinted membranes. The observed performances of the MIMs are applicable to the further purification of aspirin. Keywords Acetylsalicylic acid; Reversible addition-fragmentation chain transfer; Molecularly imprinted membrane; p-Hydroxybenzoic acid; Selective adsorption

嵌段分散剂在制备水性无树脂色浆中的应用

采用可逆加成-断裂链转移自由基聚合(RAFT)合成了嵌段共聚物聚(丙烯酸铵-co-甲氧基聚乙二醇丙烯酸酯-co-甲氧基聚丙二醇丙烯酸酯)-b-(丙烯酸丁酯-co-苯乙烯-co-乙烯基吡啶)。用红外光谱测试了共聚物的组成,采用凝胶色谱测试了聚合物的“活性”特征。将嵌段共聚物用作水性分散剂,制备了碳黑色浆和有机颜料色浆。测试色浆的黏度、储存稳定性和与基础漆的相容性,表征了分散剂的应用性能,并与市场上的水性分散剂进行对比。结果显示,用嵌段共聚物分散剂制备的色浆比用市售分散剂制备的色浆储存稳定性好、展色性高。

考虑乘客反向换乘的城市轨道交通快慢车停站方案

城市轨道交通网络化、高频度的运营为乘客提供了灵活的出行方案,制订多种快慢车停站方案,可以更好地满足不同乘客的乘车偏好,实现更大选择空间,提高运营效能。阐述乘客的反向换乘行为,采用广义出行费用和Logit模型量化计算乘客多样化出行意愿,建立可体现乘客反向换乘情况的快慢车停站方案模型,利用计算机仿真求解模型。结果显示,全线乘客的总旅行时间比仅考虑同向换乘与"站站停"方案分别减少0.34%和4.45%,表明兼顾乘客反向换乘行为制订的快慢车停站方案能够提升轨道交通的运营效率。

Degradable and Recyclable Polymers by Reversible Deactivation Radical Polymerization

Reversible deactivation radical polymerization(RDRP)provides unprecedented control over polymer composition,size,functionality,and topology.Various materials,such as linear polymers,star polymers,branched polymers,graft polymers,polymer networks,and hybrid materials,have been prepared by RDRP.The ability to control polymer topology also enabled precision synthesis of well-defined polymer topologies with degradable functional groups located at specific locations along a polymer chain.This review outlines progress in the synthesis of degradable polymers designed by RDRP,organized by topology and synthetic route.Recent progress in the depolymerization of polymers using RDRP mechanisms is highlighted and critically discussed.

Molecularly Imprinted Polymers on Chloromethyl Polystyrene Resin Prepared via RAFT Polymerization

Surface molecularly imprinted polymers （SMIP） was prepared via the reversible addition-fragmentation chain transfer （RAFT） polymerization on the chloromethyl polystyrene resin （CPR） in the presence of the template D-phenylalanine. The structure of SMIP was characterized by FTIR and SEM. The adsorption behavior of D-phenylalanine of SMIP was preliminarily investigated.

Effect of Phase Separation Size on the Properties of Self-healing Elastomer

Regulation of phase structure has been recognized as one of the most effective ways to fabricate self-healing polymers with high mechanical strength.The mechanical properties of the resultant polymers are certainly affected by the size of separated phase domain.However,the study on this aspect is absence,because it can hardly exclude the influence of variation in monomer proportion required for tuning the separated phase size.Here,we report the first study on tuning the phase size through reversible addition-fragmentation chain transfer(RAFT)polymerization without changing the proportion of monomers.As expected,the size of separated phase has been successfully mediated from 15 nm to 9 nm by tuning the molecular weight of the chain transfer agent.It is found that the mechanical strength and the self-healing efficiency of the resultant polymers increase simultaneously with the decrease of phase size.The study on the formation kinetics of hydrogen bonds reveals that the decrease of phase size can facilitate the re-bonding rate of hydrogen bonds,even if the migration of polymer chains is restricted.

Synthesis of Self-assembled Star/Linear Block Copolymer Blends via Aqueous RAFT Dispersion Polymerization

Reversible addition-fragmentation chain transfer(RAFT)-mediated polymerization-induced self-assembly(PISA)of star block copolymer and linear block copolymer using a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is reported.With this formulation,star block copolymer and diblock copolymer were formed simultaneously to generate colloidally stable star/linear block copolymer assemblies.Size exclusion chromatography(SEC)analysis confirmed the presence of two types of polymers in the final samples.The molar ratio of the star-like macro-RAFT agent and the linear macro-RAFT agent has a significant impact on the morphology of polymer assemblies.It was found that increasing the amount of star-like macro-RAFT agent facilitated the formation of higher-order morphologies.Additionally,effects of other reaction parameters including the length/number of the arm of the star-like macro-RAFT agent,degree of polymer(DP),monomer concentration on the morphology of star/linear block copolymer assemblies were also investigated.We expect that this work will offer new possibilities for the scalable preparation of polymer assemblies with unique structures and functions.

Enzyme-assisted Photoinitiated Polymerization-induced Self-assembly in Continuous Flow Reactors with Oxygen Tolerance

Polymerization-induced self-assembly(PISA)is an emerging method for the preparation of block copolymer nano-objects at high concentrations.However,most PISA formulations have oxygen inhibition problems and inert atmospheres(e.g.argon,nitrogen)are usually required.Moreover,the large-scale preparation of block copolymer nano-objects at room temperature is challenging.Herein,we report an enzyme-assisted photoinitiated polymerization-induced self-assembly(photo-PISA)in continuous flow reactors with oxygen toleranee.The addition of glucose oxidase(GOx)and glucose into the reaction mixture can consume oxygen efficiently and constantly,allow the flow photo-PISA to be performed under open-air conditions.Polymerization kinetics indicated that only a small amount of GOx(0.5 μmol/L)was needed to achieve the oxygen tolerance.Block copolymer nano-objects with different morphologies can be prepared by varying reaction conditions including the degree of polymerization(DP)of core-forming block,monomer concentration,reaction temperature,and solvent composition.We expect this study will provide a facile platform for the large-scale production of block copolymer nano-objects with different morphologies at room temperature.

Mechanism study and molecular design in controlled/“living” radical polymerization

This tutorial review summarizes recent progress in the research field of controlled/"living" radical polymerization (CLRP) from Soochow University.The present paper gives a broad overview of the mechanism study and molecular design in CLRP.The mechanism study in CLRP aided by microwave,initiated by γ-radiation at low temperature,mediated by iron,in reversible addition-fragmentation chain transfer (RAFT) polymerization and the mechanism transfer between different CLRP processes are reviewed and summarized.The molecular design in CLRP,especially in RAFT polymerization for mechanism study,and in achieving tailor-made functional polymers is studied and discussed in the later part.

Preparation of ABA triblock copolymer assemblies through “one-pot” RAFT PISA

Poly(N,N-dimethyl acrylamide)-block-poly(styrene)-block-poly(N,N-dimethyl acrylamide)(PDMAc-bPSt-b-PDMAc)amphiphilic triblock copolymer micro/nano-objects were synthesized through reversible addition-fragmentation chain transfer(RAFT)dispersion polymerization of St mediated with poly(N,Ndimethyl acrylamide)trithiocarbonate(PDMAc-TTC-PDMAc)bi-functional macromolecular RAFT agent.It is found that the morphology of the PDMAc-b-PSt-b-PDMAc copolymer micro/nano-objects like spheres,vesicles and vesicle with hexagonally packed hollow hoops(HHHs)wall can be tuned by changing the solvent composition.In addition,vesicles with two sizes(600 nm,264 nm)and vesicles with HHHs features were also synthesized in high solid content systems(30 wt%and 40 wt%,respectively).Besides,as compared with typical AB diblock copolymers(A is the solvophilic,stabilizer block,and B is the solvophobic block),ABA triblock copolymers tend to form higher order morphologies,such as vesicles,under similar conditions.The finding of this study provides a new and robust approach to prepare block copolymer vesicles and other higher order micelles with special structure via PISA.

Recent advances in “living”/controlled radical polymerization of phosphorus-containing monomers and their potential applications

Special research attention has been paid to phosphorus-containing materials and their corresponding applications. This mini review considers recent publications devoted to the "living"/controlled radical(co)polymerization of phosphorus-containing monomers. In addition, different properties of the polymers involved in the phosphonate group in various chemical environments are demonstrated, and their potential applications are briefly discussed.

RAFT Copolymerization of Glycidyl Methacrylate and N,N-Dimethylaminoethyl Methacrylate

In this work, copolymerization of two functional monomers, glycidyl methacrylate （GMA） and N,N-dimethylaminoethyl methacrylate （DMAEMA）, was firstly carried out via reversible addition-fragmentation chain transfer （RAFT） polymerization successfully. The copolymerization kinetics was investigated under the molar ratio of n[GMA＋DMAEMA]o/n[AIBN]o/n[CPDN]o=300/1/3 at 60℃. The copolymerization showed typical ＂living＂ features such as first-order polymerization kinetics, linear increase of molecular weight with monomer conversion and narrow molecular weight distribution. The reactivity ratios of GMA and DMAEMA were calculated by the extended Kelen-Tudos linearization methods. The epoxy group of the copolymer PGMA-co-PDMAEMA remained intact under the conditions of RAFT copolymerization and could easily be post-modified by ethylenedia- mine. Moreover, the modified copolymer could be used as a gene carrier.