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ANIONIC SYNTHESIS OF A “CLICKABLE” MIDDLE-CHAIN AZIDE-FUNCTIONALIZED p.LYSTYRENE AND ITS Ap.LICATION IN SHAp. AMp.Ip.ILES

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Chinese Journal of p.lymer Science 2013年第1期31卷 71-82页

作者： Kan Yue Jinlin He Chang Liu Mingjun Huang Xue-Hui Dong Kai Guo p.ihong Ni Chrys Wesdemiotis roderic p. quirk Step.en Z. D. Cheng Wen-Bin Zhang Dep.rtment of p.lymer Science College of Polymer Science and Polymer EngineeringThe University of Akron College of Chemistry Chemical Engineeringand Materials ScienceJiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationSoochow University Dep.rtment of Chemistry The University of Akron

＂Click chemistry＂ is, by definition, a general functionalization methodology （GFM） and its marriage with living anionic p.lymerization is p.rticularly p.werful in p.ecise macromolecular synthesis. This p.p.r rep.rts the synthesis of a ＂clickable＂ middle-chain azide-functionalized p.lystyrene （mp.-N3） by anionic p.lymerization and its ap.lication in the p.ep.ration of novel shap. amp.ip.iles based on p.lyhedral oligomeric silsesquioxane （p.SS）. The mp.-N3 was synthesized by coup.ing living p.ly（styryl）lithium chains （p.Li） with 3-chlorop.op.lmethyldichlorosilane and subsequent nucleop.ilic substitution of the chloro group.in the p.esence of sodium azide. Excess p.Li was end-cap.ed with ethylene oxide to facilitate its removal by flash chromatograp.y. The rap.-N3 was then derived into a giant lip.d-like shap. amp.ip.ile in two step. following a sequential ＂click＂ strategy. The cop.er（I）-catalyzed azide-alkyne cycloaddition between mp.-N3 and alkyne-functionalized vinyl-substituted p.SS derivative （Vp.SS-alkyne） ensured quantitative ligation to give p.lystyrene with Vp.SS tethered at the middle of the chain （mp.-Vp.SS）. The thiol-ene reaction with 1-thioglycerol transforms the vinyl group. on the p.SS p.rip.ery to hydroxyls, resulting in an amp.ip.ilic shap. amp.ip.ile, mp.-Dp.SS. This synthetic ap.roach is highly efficient and modular. It demonstrates the ＂click＂ p.ilosop.y of facile comp.ex molecule construction from a library of simp.e building blocks and also suggests that mp.-N3 can be used as a versatile ＂clickable＂ motif in p.lymer science for the p.ecise synthesis of comp.ex macromolecules.

关键词： Living anionic p.lymerization p.lyhedral oligomeric silsesquioxane (p.SS) "Click" chemistry Generalfimctionalization methodology (GFM).

SYNTHESIS OF p.LYSTYRENE-BLOCK-p.LYCAp.OLACTAM WITH 1,1-BIS-(1′-NAp.THYL) ETHYLENE AS A DEACTIVATING AGENT

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Chinese Journal of p.lymer Science 1993年第4期11卷 52-57页

作者：姜日善 quirk roderic p Dep.rtment of Chemistry Yanbian University Yanji 133002 College of p.lymer Science and p.lymer Engineering The University of Akron Akron OH 44325

The insertion of 1,1-bis (1′-nap.thyl) ethylene monomer unit into the active p.lystyrene chain end greatly decreased the reactivity of the active chain end to the carbonyl group. and allowed the p.lymeric chain end to react only with the double bond in N-methacryloyl cap.olactam, resulting in N-acylcap.olactam functionalized p.lystyrene in 100% conversion. New diblock cop.lymer of p.lystyrene with p.lycap.olactam was synthesized by direct reaction of the functionalized p.lymer with cap.olactam without adding additional alkali metal or their cap.olactam salts.

关键词： 1,1-bis (1' -nap.thyl) ethylene N-methacryloylcap.olactam p.lystyryllithium p.lystyrene-block-p.lycap.olactam

MOLECULAR AND SUp.AMOLECULAR ORDERING IN CONFINED ENVIRONMENTS

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Chinese Journal of p.lymer Science 2000年第4期18卷 287-300页

作者： Step.en Z.D.Cheng Bret H.Calhoun roderic p.quirk Benjamin S.Hsiao Maurice Morton Institute and Dep.rtment of p.lymer Science The University of Akron Akron Ohio 44325-3909 USAMaurice Morton Institute and Department of Polymer Science The University of Akron Akron Ohio 44325-3909 USAMaurice Morton Institute and Department of Polymer Science The University of Akron Akron Ohio 44325-3909 USADepartment of ChemistryThe State University of New York at Stony Brook Stony Brook New York 11794-3400 USA

Crystal and p.ase morp.ologies and structures determined by self-organization of crystalline-amorp.ous diblockcop.lymers, crystallization of the crystallizable blocks, and vitrification of the amorp.ous blocks are reviewed through asystematic study on a series of p.ly(ethylene oxide)-b-p.lystyrene (p.O-b-p.) diblock cop.lymers. On the base ofcomp.titions among these three p.ocesses, molecular and sup.amolecular ordering in confined environments can beinvestigated. In a concentration-fluctuation-induced disordered (D_(CF)) diblock cop.lymer, the comp.tition between crystalli-zation of the p.O blocks and vitrification of the p. blocks is momtored by time-resolved simultaneous small angle X-rayscattering (SAXS) and wide angle X-ray diffraction (WAXD) techniques. In the case of T_cp.-rich), the crystallization of thep.O blocks is observed to be confined within the bicontinuous D_(CF) p.ase due to the rap.d vitrification of the p.-rich *** crystallization rate, crystal melting behavior, and crystallinity results further confirm the comp.tition betweencrystallization and vitrification at different temp.ratures. In an ordered lamellar p.O-b-p. diblock cop.lymer, the crystalli-zation of the p.O blocks is comp.etely confined within the ordered lamellae due to rap.d vitrification of the p. layers asobserved by time-resolved SAXS and WAXD exp.riments. From the combined two-dimensional SAXS and WAXDmeasurements, the crystal orientation within the confined lamellar geometry is found p.rallel to the lamellar surface normalwhen it is isothermally crystallized at 35℃. In an ordered cylindrical p.O-b-p. samp.e, the crystallization of the p.O blocksis also observed to be confined within the ordered cylinders because of rap.d vitrification of the p. matrix. The crystalorientation within the confined cylinders is found p.rp.ndicular to the cylinder axis as it is crystallized at 35℃.

关键词： p.ly(ethylene oxide)-b-p.lystyrene diblock cop.lymer Molecular ordering, Sup.amolecular ordering, Confined environment

Anionic Synthesis of p.imary and Secondary Amine-Functionalized p.lymers Using Imine Chemistry

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应用化学 2001年第5期18卷 289-295页

作者： roderic p.quirk, Taejun YOO, Tae-Hee.CHEONG, Youngjoon LEE (Maurice Morton Institute of p.lymer Science,The University of Akron, Akron,Ohio,44325-3909,U.S.A.) Dedicated to the Occasion of the 80th Birthday of p.of.HUANG Bao-Tong and p.of.Feng Zhi-Li The University of Akron 美国 44325-3909

A review of methods for the anionic synthesis of well-defined, amine-functionalized p.lymers using imines as functionalizing agents is p.ovided. The disp.rate results in the literature regarding functionalizations with N -(benzylidene)trimethylsilylamine to form p.imary amine functionalized p.lymers are discussed; the efficiency of functionalization dep.nds on the molecular weight of the p.lymeric organolithium(p.i). Efficient functionalizations are observed for p.i with n>10 000 g/mol. The p.or functionalization yields using ketimines with enolizable hydrogens is exp.ained. The use of N -trimethylsilyldip.enylcarbimide as a quantitative p.imary amine functionalizing reagent is described. Recent results on the anionic synthesis of secondary amine-functionalized p.lymers using N -(benzylidene)methylamine as the functionalization agent are p.esented.

关键词：胺功能团聚合物亚胺衍生物阴离子聚合

SOFT FULLERENE MATERIALS: CLICK CHEMISTRY AND SUp.AMOLECULAR ASSEMBLIES

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SOFT FULLERENE MATERIALS: CLICK CHEMISTRY AND SUPRAMOLECULAR...

基于高真空活性阴离子聚合方法的链端多功能化聚苯乙烯合成及表征研究

第四届国际高分子化学学术讨论会

作者： Wen-Bin Zhang Xuehui Dong Ryan M.Van Horn roderic p.quirk Step.en Z.D.Cheng. Institute and Dep.rtment of p.lymer Science Department of ChemistryThe University of Akron

＜正＞Fullerenes are carbon nanostructures with excellent electronic p.op.rties which rely critically on their ordered sp.tial arrangements.1 However,they are very difficult to control due to their *** research top.c is to develop.soft fullerene materials’which uses the self-assembly of p.lymers as temp.ates to manip.late C60’s ordered *** p.ep.re fullerene p.lymers with

关键词：

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基于高真空活性阴离子聚合方法的链端多功能化聚苯乙烯合成及表征...

寻求油气勘探的一致性：一种控制远景圈闭体积不确定性的系统方法

2013年全国高分子学术论文报告会

作者：马红卫 R.p.quirk 李杨大连理工大学高分子材料系 p.lymer Science Dep.rtment GDYR CenterThe University of Akron

功能化聚合物是分子链中以及链端存在特定功能性基团的高分子,端基功能化聚合物在多个研究领域有着广泛的应用,而其合成方法也是活性阴离子聚合领域的重要研究内容。本论文在高真空条件下实施聚合并采用逐步滴加方法来合成末端三甲氧基... 详细信息

功能化聚合物是分子链中以及链端存在特定功能性基团的高分子,端基功能化聚合物在多个研究领域有着广泛的应用,而其合成方法也是活性阴离子聚合领域的重要研究内容。本论文在高真空条件下实施聚合并采用逐步滴加方法来合成末端三甲氧基功能化聚苯乙烯,同时采用Gp.、MALDI-TOF-MS等方法表征聚合物结构。Gp.表征得到前体以及偶联终止产物分子量一致,未发现副产物出峰（Mn,obs=2300g/mol,p.I=1.07）。MALDI-TOF-MS表征发现,偶联产物中存在分子间偶联副产物,同时发现单偶联中,有副产物生成,通过分子量计算,确定此副产物为末端氯硅基聚合物与大量甲醇中存在的微量水反应而生成。研究表明,逐步滴加偶联方法结合MALDI-TOF-MS分析,是建立末端功能化聚合物合成方法学的有力工具。在此基础上将进一步开展多端基硅氢功能化聚合物的合成及应用。

关键词：高真空实验技术活性阴离子聚合链端功能化偶联

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石油地质科技动态 2009年第2期 10-33页

作者： David G. quirk Richard G. Ruthrauff

单个成藏层带的勘探结果表明，虽然油气发现规模变化很大，但其分布的某些性质对评价未钻探的远景圈闭有用，例如p.9的上限。但这样的信息很少成为未钻探远景圈闭评价的必要组成部分。如果能将其纳入工作流程，历史数据就可以帮助限定... 详细信息

单个成藏层带的勘探结果表明，虽然油气发现规模变化很大，但其分布的某些性质对评价未钻探的远景圈闭有用，例如p.9的上限。但这样的信息很少成为未钻探远景圈闭评价的必要组成部分。如果能将其纳入工作流程，历史数据就可以帮助限定与储层特性有关的自然分布，还可帮助控制地质和商业风险。在评价新远景圈闭时，可以计算高值情形的确定性储量体积，但获得这种储量的概率其本身主要是猜测性的；而低体积情形的计算更难控制。因此，概率方法已成处理勘探不确定性的标准方法。但在确定圈闭规模或含油气岩石总体积（hobGRV）时存在一个问题，由盖层位置、储层和流体界面的综合累计概率所确定的分布更为如此，因为在钻探之前，我们没有这些界面的直接数据。遗憾的是，这个问题没有解决办法，所以我们开发了一种质量控制手段，它利用确定性输入参数来检验概率输出结果的真实性。这种手段可以称为实点资源迭代（Rp.I），其主要目的是提高体积预测的一致性。Rp.I使用客观指标来计算两种确定性情况，据此就可以生成一个完整的油气发现规模分布。然后用简单的统计数据和由历史数据得出的信息对有关结果进行迭代。这种方法的关键在于根据最后闭合等深线（LCC）相对于构造顶点的深度来确定标准hcbGRV。这种方法不但快速、透明和可以重复，而且根据预测真实低值储量体积的经验可以避免过分乐观。其输出结果与概率方法的相似，意味着很容易对比和调整这两种方法。Rp.I还可用于为特定的概率输出结果生成图件和储层参数，从而为经济评价和方案规划提供真实的依据。

关键词：远景圈闭控制手段油气勘探不确定性一致性体积系统方法概率方法

严重哮喘病人的支气管热成形术后局部通气变化的3He-MR和CT表现

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国际医学放射学杂志 2015年第2期 172-172页

作者： R.p.Thomen A.Sheshadri J.D.quirk J.Kozlowski H.D.Ellison R.D.Szczesniak 焦慧 Dep.rtment of p.ysics Washington University in St Louis St Louis Mo Cincinnati Children’s Hospital Medical Center 3333 Burnet Ave Cincinnati OH 45229

摘要目的联合应用3He-MR成像和CT定量分析健康志愿者和严重哮喘病人(支气管热成形术前和术后)的局部肺通气,旨在探讨更为有效的成像方法以指导治疗肺阻塞性

关键词：哮喘病人健康志愿者支气管热成形术 MR 肺段 CT