Copolymerization of N‐vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control

Free‐radical copolymerizations of N‐vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) were investigated to synthesize temperature‐responsive reactive copolymers with minimized compositional heterogeneity. The average copolymer composition was determined by Fourier transform infrared and nuclear magnetic resonance techniques. The reactivity ratios for VCL and GMA were found to be 0.0365 ± 0.0009 and 6.44 ± 0.36 by the Fineman–Ross method and 0.039 ± 0.006 and 6.75 ± 0.29 by the Kelen–Tudos method, respectively. When prepared by batch polymerization, VCL–GMA copolymers had a highly heterogeneous composition and fractions of different solubilities in water. The use of a gradual feeding technique, which included the sequential addition of more reactive GMA monomer into the reaction, yielded copolymers with much more homogeneous composition. The produced copolymers with 0.9 and 0.11 fractional GMA contents preserved their temperature‐responsive properties and precipitated from aqueous solutions when the temperature exceeded 31 °C. The GMA units in the VCL–GMA copolymers were capable of reacting with amino end‐functionalized poly(ethylene oxide) at room temperature to produce poly(N‐vinylcaprolactam)–poly(ethylene oxide) graft copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 183–191, 2006     

I_2-KIO_3-AcOH-H_2O体系氧化3,5-环-24S-乙基-胆甾-22烯-6-酮反应的研究

油莱甾醇内酯(Brassinolide)(1)是一种高效的植物生长激素,其生理活性与侧链中C_(22)、C_(23)的构型密切相关。当C_(22)、C_(23)为S、S构型时,其活性仅为1的十分之一。在1的     

含有陡峭势阱和凹凸非线性项的Kirchhoff型问题的多重正解*

在这篇文章中, 作者研究涉及凹凸非线性项的Kirchhoff型问题-(a + b ∫R3|▽u|²dx) Δu + λV (x)u = μf(x)|u|^q?2u + |u|^p?2u, x ∈ R³,u ∈ H¹(R³),其中a,b > 0 是常数, λ, μ > 0 是参数, 1 < q < 2, 4 < p < 6 且 V 是一个非负连续位势. 在f(x) 和 V 的合适条件下,此问题正解的存在性和集中性能够通过Nehari 流形和Ekeland 变分原理得到.     

Synthesis of poly(n‐butyl acrylate) homopolymer and poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) triblock copolymer via AGET emulsion ATRP using a cationic surfactant

Cationic emulsions of triblock copolymer particles comprising a poly(n‐butyl acrylate) (PⁿBA) central block and polystyrene (PS) outer blocks were synthesized by activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Difunctional ATRP initiator, ethylene bis(2‐bromoisobutyrate) (EBBiB), was used as initiator to synthesize the ABA type poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) (PS‐PⁿBA‐PS) triblock copolymer. The effects of ligand and cationic surfactant on polymerizations were also discussed. Gel permeation chromatography (GPC) was used to characterize the molecular weight (M_n) and molecular weight distribution (MWD) of the resultant triblock copolymers. Particle size and particle size distribution of resulted latexes were characterized by dynamic light scattering (DLS). The resultant latexes showed good colloidal stability with average particle size around 100–300 nm in diameter. Glass transition temperature (T_g) of copolymers was studied by differential scanning calorimetry (DSC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 611–620     

Switchable Polymerization Triggered by Fast and Quantitative Insertion of Carbon Monoxide into Cobalt–Oxygen Bonds

A strategy that uses carbon monoxide (CO) as a molecular trigger to switch the polymerization mechanism of a cobalt Salen complex [salen=(R,R)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine] from ring-opening copolymerization (ROCOP) of epoxides/anhydrides to organometallic mediated controlled radical polymerization (OMRP) of acrylates is described. The key phenomenon is a rapid and quantitative insertion of CO into the Co−O bond, allowing for in situ transformation of the ROCOP active species (Salen)Co^III-OR into the OMRP photoinitiator (Salen)Co^III-CO₂R. The proposed mechanism, which involves CO coordination to (Salen)Co^III-OR and subsequent intramolecular rearrangement via migratory insertion has been rationalized by DFT calculations. Regulated by both CO and visible light, on-demand sequence control can be achieved for the one-pot synthesis of polyester-b-polyacrylate diblock copolymers (Đ<1.15).     

Switchable Polymerization Triggered by Fast and Quantitative Insertion of Carbon Monoxide into Cobalt–Oxygen Bonds

A strategy that uses carbon monoxide (CO) as a molecular trigger to switch the polymerization mechanism of a cobalt Salen complex [salen=(R,R)‐N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine] from ring‐opening copolymerization (ROCOP) of epoxides/anhydrides to organometallic mediated controlled radical polymerization (OMRP) of acrylates is described. The key phenomenon is a rapid and quantitative insertion of CO into the Co?O bond, allowing for in situ transformation of the ROCOP active species (Salen)Co^III‐OR into the OMRP photoinitiator (Salen)Co^III‐CO₂R. The proposed mechanism, which involves CO coordination to (Salen)Co^III‐OR and subsequent intramolecular rearrangement via migratory insertion has been rationalized by DFT calculations. Regulated by both CO and visible light, on‐demand sequence control can be achieved for the one‐pot synthesis of polyester‐b‐polyacrylate diblock copolymers (?<1.15).     

肟醚-酰胺衍生物的合成与生物活性研究

为了寻找高效、低毒的新农药,采用活性结构拼接法设计并合成了12个新型肟醚-酰胺类化合物,其结构均经1HNMR、IR、LC/MS及元素分析确证。初步生物活性测定结果显示,部分化合物具有明显的杀菌活性,其中化合物3a和3h在500mg/L的浓度下对小麦白粉病菌的盆栽活性均达80%以上。     

微乳液毛细管电动色谱法快速测定消炎利胆片中的穿心莲内酯和脱水穿心莲内酯

建立了微乳液毛细管电动色谱同时分析消炎利胆片中穿心莲内酯和脱水穿心莲内酯的方法。考察了缓冲溶液的浓度、pH值、十二烷基硫酸钠(SDS)以及助表面活性剂的含量对分离测定的影响。在由乙酸乙酯-SDS-正丁醇-30 mmol/L硼砂缓冲液(pH 9.5)（质量比为0.5∶0.6∶6.0∶92.9）组成的微乳液体系中,两种内酯在6 min内完成分离。该法简便、快速、选择性好,用于实际样品中穿心莲内酯和脱水穿心莲内酯的分析,获得了满意的结果。     

红黑排序混合算法收敛速度分析

The algorithm of applying the block Gauss elimination to the Red-Black or-dering matrix to reduce the order of the system then solve the reduced system byiterative methods is called Hybrid Red-Black Ordering algorithm.In this paper,we discuss the convergence rate of the hybrid methods combined with JACOBI,CG,GMRES(m).Theoretical analysis shows that without preconditioner thesethree hybrid methods converge about 2 times as fast as the corresponding natural ordering methods.For the case that all the eigenvalues is near the real axis, the GMRES(m) algorithm converges about 3 times faster than the natural ordering GMRES(m).Various numerical experiments are presented.For large scale prob-lem with preconditioners, numerical experiments show that the GMRES(m) hybrid methods converge from about 3 times to even 5 times as fast as the natural order-ing methods and the computing time is reduced to about 1/3 even 1/6 of that of the natural ordering methods.     

16O+natS全熔合激发函数

在入射能量为55—75MeV的范围内,借助于位置灵敏的△E-E望远镜系统测量了¹⁶O+^natS反应的全熔合激发函数并做了讨论分析,提取了模型参数.激发函数存在着粗结构,其峰位分别为EcM=38、43、48MeV.