水溶性聚合物和两亲聚合物——10.两亲聚合物PAMC_(16)S的自组装有序膜

用自组装技术在金(纯金和经阳极氧化的金)表面上获得了新型两亲聚合物PAMC_(16)S的有序膜。用接触角测试,XPS谱和电化学分析等方法对自组装膜进行了表征。根据膜表面的润湿性,金表面的自组装膜是疏水的,亲水的磺酸基团连于金表面,而疏水的碳氢链从表面伸展出。XPS实验结果支持金表面上单层膜的疏水结构。聚合物单层膜复盖的金电极起到含有针孔缺陷的阻膈型电极的作用。单层膜在法拉第反应中显示很强的吸附稳定性,说明聚合物LB膜在潜在应用中有其特有的特点。     

水溶性聚合物和两亲聚合物18.2—丙烯酰胺基烷磺酸类两亲单体

２－丙烯酰胺基烷磺酸的溶解行为和胶体化学性质明显随烷基长短而异，由于手性碳原子的存在，与其相邻亚甲基的质子峰在ＨＮＭＲ谱上清楚地发生分裂，研究了２－丙烯酰胺基十六烷磺酸（ＡＭＣ１６Ｓ）在水／二氧六环混合溶剂中的聚合动力学和胶体化化学性质，发现聚合速度和所得聚合物分子量均均在水／二氧六环体积比为１～１／２时出现最小值，临界胶束浓度随混合溶剂中二氧六环含量的增加而增加，当水／二氧六环体积比为１／２～１     

水溶性聚合物和两亲聚合物:14.丙烯酰胺/2-丙烯酰胺基十六烷磺酸铵无规共聚物

水溶液中用硫酸亚铁-异丙苯过氧化氢氧化还原引发体系合成了丙烯酰胺(AM)/2-丙烯酰胺基十六烷磺酸铵(AMC_(16)SNH_4)无规共聚物。用元素分析、IR、~(13)C-NMR和~1H-NMR对其进行了表征。对水溶液性质的研究结果表明,与部分水解聚丙烯酰胺相比,这种新型共聚物有着优异的耐盐性、耐温性和贮存稳定性。     

水溶性聚合物和两亲聚合物18．2－丙烯酰胺基烷磺酸类两亲单体

２－丙烯酰胺基烷磺酸的溶解行为和胶体化学性质明显随烷基长短而异。由于手性碳原子的存在，与其相邻亚甲基的质子峰在~１ＨＮＭＲ谱上清楚地发生分裂。研究了２－丙烯酰胺基十六烷磺酸（ＡＭＣ１６Ｓ）在水／二氧六环混合溶剂中的聚合动力学和胶体化学性质。发现聚合速度和所得聚合物分子量均在水／二氧六环体积比为１～１／２时出现最小值，临界胶束浓度随混合溶剂中二氧六环含量的增加而增加，当水／二氧六环体积比为１／２～１／４时，观察不到胶束化现象。     

水溶性聚合物和两亲聚合物 16.聚苯乙烯/聚丙烯酰胺嵌段聚合物的合成和表征

采用聚偶氮酯引发剂,合成了聚苯乙烯/聚丙烯酰胺嵌段聚合物(PSt/PAM)。考察了含偶氮基聚苯乙烯预聚物(pre-PSt)在1,4-二氧六环中引发AM的聚合反应行为,讨论了影响第二单体转化率和聚苯乙烯均聚物含量的因素。用元素分析、溶解性、红外光谱、DSC、TG和裂解色谱表征了PSt/PAM嵌段聚合物。     

水溶性聚合物和两亲聚合物19．磺化液体聚丁二烯──种新型液膜用表面活性剂

一种新的聚工二烯型表面活性剂ＬＹＦ经液体聚了二烯磺化方法制备而得，并应用于液膜分离研究之中。发现无论内水相是酸性还是碱性，由该表面活性剂制得的Ｗ／Ｏ型乳状液在稳定性、溶胀率和破乳诸方面均具有令人满意的综合性能。为深入了解液膜的稳定性，我们测定了处于两种水相间的双分子膜的强度。发现由ＬＹＦ所形成的双分子膜具有最大的膜强值，优于聚异丁烯型的表面活性剂ＥＣＡ４３６０和ＥＭ３０１．     

Synthesis and characterization of a novel AB2 monomer and corresponding hyperbranched poly(arylene ether phosphine oxide)s

A novel AB₂ monomer, 4‐(fluorophenyl)‐4′,4″‐(bishydroxyphenyl) phosphine oxide, was synthesized. The monomer was successfully polymerized to a modest molecular weight with various catalysts, including K₂CO₃ and Cs₂CO₃/Mg(OH)₂. Hyperbranched polymers exhibited exceptionally high thermal stability and solubility in conventional polar organic solvents and basic water solutions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3736–3741, 2000     

Synthesis and properties of novel polymers having S-methyldibenzothiophenium salt moieties

A polymer having dibenzothiophenium salt moieties [poly(sulfonium salt), 2 ] was prepared by the reaction of poly(2-vinyldibenzothiophene) ( 1 ) with CH₃I and AgBF₄ in CH₂ClCH₂Cl at room temperature for 24 h. The obtained polymer 2 was found to contain 71% of the methyldibenzothiophenium tetrafluoroborate unit. A monomer carrying the sulfonium salt moiety, i.e., 5-methyl-2-vinyldibenzothiophenium tetrafluoroborate ( 4 ), was independently prepared and subjected to radical polymerization to give a polymer ( 5 ) in 88% yield (methyldibenzothiophenium tetrafluoroborate unit: 79%). The thermal decompositions of 2 and 5 took place in two steps; the first step involved the formation of polymer 1 by demethylation. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1779–1784, 1998     

水溶性荧光共轭聚合物MPS-PPV的聚合新方法及其荧光波长调控的研究

在NaOH/C2H5OH/DMF溶液中,实现了水溶性阴离子荧光共轭聚合物聚-[5-甲氧基-2-(3-磺酰化丙氧基)-1,4-苯撑乙烯](MPS-PPV)单体的快速聚合并提高了聚合产率。通过改变溶液中NaOH的浓度,实现了对聚合物荧光发射波长的调控。对聚合物进行了元素分析、红外光谱以及分子量的表征,并探讨了不同聚合条件下得到的MPS-PPV的荧光和紫外光谱变化。研究了过氧化氢对MPS-PPV荧光的影响,为基于荧光聚合物的新型传感器的研制提供了新思路。     

Studies on the thermotropic liquid crystalline polymer. XII. Synthesis and properties of crosslinkable thermotropic liquid crystalline homo- and copoly(ether-ester)s

A series of crosslinkable thermotropic liquid crystalline poly(ether-ester)s and copoly(ether-ester)s was prepared. All of the polymers were crosslinked by thermal treatment or photo-irradiation upon heating. The thermal stability and thermal crosslinking reaction of these polymers were investigated. These polymers also could be crosslinked by copolymerization with vinyl monomers, such as styrene or methyl methacrylate. The crosslinked polymers exhibited thermotropic liquid crystalline behavior after softening by heating. The phase behavior of linear polymers and crosslinked polymers was studied by differential scanning calorimetry (DSC) and an optical polarizing microscope equipped with a heating stage. © 1995 John Wiley & Sons, Inc.     

Comparison of micelles formed by amphiphilic star block copolymers prepared in the presence of a nonmetallic monomer activator

In this article, we describe the synthesis of PEG‐b‐polyester star block copolymers via ring‐opening polymerization (ROP) of ester monomers initiated at the hydroxyl end group of the core poly(ethylene glycol) (PEG) using HCl Et₂O as a monomer activator. The ROP of ε‐caprolactone (CL), trimethylene carbonate (TMC), or 1,4‐dioxan‐2‐one (DO) was performed to synthesize PEG‐b‐polyester star block copolymers with one, two, four, and eight arms. The PEG‐b‐polyester star block copolymers were obtained in quantitative yield, had molecular weights close to the theoretical values calculated from the molar ratio of ester monomers to PEG, and exhibited monomodal GPC curves. The crystallinity of the PEG‐b‐polyester star block copolymers was determined by differential scanning calorimetry and X‐ray diffraction. Copolymers with a higher arm number had a higher tendency toward crystallization. The crystallinity of the PEG‐b‐polyester star block copolymers also depended on the nature of the polyester block. The CMCs of the PEG‐b‐PCL star block copolymers, determined from fluorescence measurements, increased with increasing arm number. The CMCs of the four‐arm star block copolymers with different polyester segments increased in the order 4a‐PEG‐b‐PCL < 4a‐PEG‐b‐PDO < 4a‐PEG‐b‐PLGA < 4a‐PEG‐b‐PTMC, suggesting a relationship between CMC and star block copolymer crystallinity. The partition equilibrium constant, K_v, which is an indicator of the hydrophobicity of the micelles of the PEG‐polyester star block copolymers in aqueous media, increased with decreasing arm number and increasing crystallinity. A key aspect of the present work is that we successfully prepared PEG‐b‐polyester star block copolymers by a metal‐free method. Thus, unlike copolymers synthesized by ROP using a metal as the monomer activator, our copolymers do not contain traces of metals and hence are more suitable for biomedical applications. Moreover, we confirmed that the PEG‐b‐polyester star block copolymers form micelles and hence may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2084–2096, 2008     

Synthesis and characterization of pyrene bearing amphiphilic miktoarm star polymer and its noncovalent interactions with multiwalled carbon nanotubes

A novel amphiphilic miktoarm star polymer, polystyrene‐poly(ethylene glycol)‐poly(methyl methacrylate), bearing a pyrene group at the end of PS arm (Pyrene‐PS‐PEG‐PMMA) was successfully synthesized via combination of atom transfer radical polymerization and click chemistry. The structure and composition of the amphiphilic miktoarm star polymer were characterized by gel permeation chromatography and ¹H NMR. The functionalization of multiwalled carbon nanotubes (MWCNTs) via “π–π” stacking interactions with pyrene‐PS‐PEG‐PMMA miktoarm star polymer was accomplished and the resulting polymer‐MWCNTs hybrid was analyzed by using ¹H NMR, UV–vis, fluorescence spectroscopy, and thermal gravimetric analysis. The high‐resolution transmission electron microscopy and analytical techniques aforementioned confirmed that the noncovalent functionalization of MWCNT's with the amphiphilic miktoarm star polymer was successfully achieved. The MWCNT/pyrene‐PS‐PEG‐PMMA exhibited significant dispersion stability in common organic solvents such as dimethyl formamide, chloroform, and tetrahydrofuran. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly(azomethine) Rotaxanes: Novel Water Soluble Supramolecular Polymers with High Molar Mass

A novel type of supramolecular poly(azomethine) was synthesized by the polycondensation of an inclusion complex of β‐cyclodextrin/poly(oxypropylene)diamine with one of β‐cyclodextrin/terephthaldehyde and a subsequent reaction with [60]fullerene as the end capping agent. Molar mass determination by gel permeation chromatography showed that the polymers had a high molar mass (about 150 kg · mol⁻¹) with a very narrow polydispersity. Isothermal titration calorimetric studies confirmed that each poly‐(oxypropylene)diamine unit could host seven cyclodextrin molecules, which was further supported by ¹H NMR spectroscopy and molecular modeling studies. Additional characterization by ¹³C NMR and FT‐IR spectroscopy, as well as by thermogravimetric analysis, confirmed the structure of the cyclodextrin‐based polyrotaxane.