A copper‐based reverse atom‐transfer radical polymerization process for the living radical polymerization of polyacrylonitrile

The reverse atom‐transfer radical polymerization (RATRP) technique using CuCl₂/2,2′‐bipyridine (bipy) complex as a catalyst was applied to the living radical polymerization of acrylonitrile (AN). A hexasubstituted ethane thermal iniferter, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was firstly used as the initiator in this copper‐based RATRP initiation system. A CuCl₂ to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution, but also provides rather rapid reaction rate. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 57.4 kJ mol^?1. Because the polymers obtained were end‐functionalized by chlorine atoms, they were used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/bipy catalyst system via a conventional ATRP process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 226–231, 2006     

Synthesis of polyacrylonitrile via reverse atom transfer radical polymerization catalyzed by FeCl3/isophthalic acid

FeCl₃ coordinated by isophthalic acid was first used as a catalyst in the azobisisobutyronitrile‐initiated reverse atom transfer radical polymerization of acrylonitrile. N,N‐Dimethylformamide was used as a solvent to improve the solubility of the ligand. An FeCl₃‐to‐isophthalic acid ratio of 0.5 not only gave the best control of the molecular weight and its distribution but also provided rather a rapid reaction rate. The effects of different solvents on the polymerization of acrylonitrile were also investigated. The rate of the polymerization in N,N‐dimethylformamide was faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in N,N‐dimethylformamide. The rate of polymerization increased with increasing polymerization temperature, and the apparent activation energy was calculated to be 59.9 kJ mol^?1. Reverse atom transfer radical polymerization was first used to successfully synthesize acrylonitrile polymers with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.22. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 219–225, 2006     

Divinylsiloxane‐bisbenzocyclobutene‐based polymer modified with polystyrene–polybutadiene–polystyrene triblock copolymers

Divinylsiloxane‐bisbenzocyclobutene (DVS‐bisBCB) polymer has very low dielectric constant and dissipation factor, good thermal stability, and high chemical resistance. The fracture toughness of the thermoset polymer is moderate due to its high crosslink density. A thermoplastic elastomer, polystyrene–polybutadiene–polystyrene triblock copolymer, was incorporated into the matrix to enhance its toughness. The cured thermoset matrix showed different morphology when the elastomer was added to the B‐staged prepolymer or when the elastomer was B‐staged with the DVS‐bisBCB monomer. Small and uniformly distributed elastomer domains were detected by transmission electron micrographs (TEM) in the former case, but TEM did not detect a separate domain in the latter case. A high percentage of the polystyrene–polybutadiene–polystyrene triblock copolymer could be incorporated into the DVS‐bisBCB thermoset matrix by B‐staging the triblock copolymer with the BCB monomer. The elastomer increased the fracture toughness of DVS‐bisBCB polymer as indicated by enhanced elongation at break and increased K1c values obtained by the modified edge‐lift‐off test. Elastomer modified DVS‐bisBCB maintained excellent electrical properties, high T_g and good thermal stability, but showed higher coefficient of linear thermal expansion values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1591–1599, 2006     

Photocrosslinked poly(vinylbenzophenone)‐core micelles via mild Friedel–Crafts benzoylation of polystyrene amphiphiles

Photocrosslinkable poly(vinylbenzophenone)‐containing polymers were synthesized via a one‐step, Friedel–Crafts benzoylation of polystyrene‐containing starting materials [including polystyrene, polystyrene‐block‐poly(tert‐butyl acrylate), polystyrene‐block‐poly(ethylene oxide), polystyrene‐block‐poly(methyl methacrylate), and polystyrene‐block‐poly(n‐butyl acrylate)] with benzoyl trifluoromethanesulfonate as a benzoylation reagent. The use of this mild reagent (which required no added Lewis acid) permitted polymers with well‐defined compositions and narrow molecular weight distributions to be synthesized. Micelles formed from one of these benzoylated polymers, [polystyrene_0.25‐co‐poly(vinylbenzophenone)_0.75]₁₁₅‐block‐poly(acrylic acid)₁₄, were then fixed by the irradiation of the micelle cores with UV light. As the irradiation time was increased, the pendent benzophenone groups crosslinked with other chains in the glassy micelle cores. Dynamic light scattering, spectrofluorimetry, and Fourier transform infrared spectroscopy were all used to verify the progress of the crosslinking reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2604–2614, 2006     

Probing the use of small‐angle light scattering for characterizing structure of titanium dioxide/low‐density polyethylene nanocomposites

Small‐angle light scattering (SALS) measurements were used to study the structure of titanium dioxide (TiO₂)/low‐density polyethylene (LDPE) nanocomposites. The results showed that the scattering from LDPE crystalline structures and the scattering from TiO₂ nanoparticles can be resolved and separated. It is shown that the independent effects of crystallization conditions and the presence of nanoparticle aggregates on the spherulitic structure of the LDPE matrix can be determined by analyzing the scattering patterns using the methods proposed. From the SALS results, we conclude that the nanoparticle surface chemistry affects both nucleation of spherulites and their structure particularly under rapid cooling conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1084–1095, 2006     

三种瓜环与4,4′-联吡啶及N,N′-二甲基4,4′-联吡啶盐酸盐相互作用的研究

以七元瓜环(Q[7])和新型椭圆型改性瓜环———对称四甲基取代六元瓜环(TM eQ[6])为主体,4,4′-联吡啶的盐酸盐(44)以及N,N′-二甲基4,4′-联吡啶的盐酸盐(dm44)为客体的主客体相互作用进行了考察.实验结果表明,Q[7]与客体44及dm44作用体系中,客体为了更有效地被主体Q[7]包结,在Q[7]内腔中呈倾斜状分布的几率最高.用核磁共振、循环伏安以及紫外吸收光谱对实验结果进行了印证和补充,验证了TM eQ[6]与客体44及dm44可发生较强的相互作用,形成一维的自组装超分子结构.核磁共振以及循环伏安方法的实验结果表明,没有观察到Q[6]与客体44及dm44的明显作用,而紫外吸收光谱方法证实,Q[6]与客体44确实存在一定的相互作用,比较主客体的结构特征,该作用体系也可能存在自组装的一维超分子结构等多种作用形式.     

绕圆柱体自由表面磁流体流动和传热的研究

本文对在不同雷诺数下,绕圆柱体的磁流体自由表面流动及传热进行了模拟,分析了磁场对绕流圆柱尾迹和涡分离的影响,获得了两种雷诺数下的电磁力密度、流场和温度场分布。结果表明,磁场不仅影响了流动的形态,而且对湍流有抑制作用,降低了自由表面的更新机制,从而减少了传热能力;在相同的Hartmann数下,相比低雷诺数下的流动换热情况,高雷诺数下的湍流不能被完全抑制,自由表面与尾迹的相互作用也较强,因而自由表面换热也较强。     

Optosensing of hydrochloric acid based on the fluorescence quenching of a flavone copolymer

An optical fiber sensor for the continuous determination of hydrochloric acid is presented. It is based on the fluorescence quenching of a flavone containing copolymer membrane by hydrochloric acid. The quenching efficiency is greatly enhanced in the presence of Fe(III). This enhancement is attributed to the primary inner filter effect, as well as the formation of a complex between the 4′-N,N-dimethylaminoflavone group in the copolymer and the Fe(III) species extracted from hydrochloric acid solution. The optical response is linear and reversible for 0.10–6.00 mol L^–1 HCl with a response time of the order of a second. The standard deviations for repeated alternative measurements of 0.20 and 2.00 mol L^–1 hydrochloric acid are 0.32% and 0.46% (n = 10), respectively, indicating a good reproducibility. Because of the covalently bonding of the dye to polymer, the sensor exhibits also a good stability. Selectivity has also been evaluated for some potential interferents. The sensor in conjunction with a flow-injection system can be used for on-line determination of hydrochloric acid.     

低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究

在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。