EPR studies on regio-selective H-abstraction by “magic blue” reagent from polymers

The radical reactions of polyolefin and olefin copolymers (4-9), polydienes and diene coplymers (10-15), and polysiloxane (16) with “magic blue” reagent containing H-abstracting agent-bis{perfluoro-1-[1-(2-fluorosulfonyl)ethoxy]ethyl}nitroxide [FSO₂CF₂CF₂OCF(CF₃)]₂N(O) (2)and spin trap-perfluoro-1-nitroso-[1-(2-fluoro-sulfonyl)ethoxy]ethane FSO₂CF₂CF₂OCF(CF₃)NO (3) were studied by EPR detection of the spin adducts of the corresponding polymeric radicals generated in the H-abstraction step to the spin trap 3, namely, the nitroxides FSO₂CF₂CF₂OCF(CF₃)N(O) (polymer-H) 17-29. EPR studies have provided information about the regio-selectivity of H-abstraction, the subsequent radical steps followed H-abstraction and grounded a possibility of employing “magic blue” reagent in polymer modification via H-abstraction-initiated grafting polymerization.     

Separation characteristics of phenyl-containing stationary phases for gas chromatography based on silarylene-siloxane copolymer chemistries

The solvation parameter model is used to characterize the retention properties of five open-tubular column stationary phases (ZB-5 ms, DB-5 ms, DB-XLB, DB-17 ms, and DB-35 ms) based on silarylene-siloxane copolymer chemistries at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and regression models for varied compounds are used to establish the selectivity equivalence of the silarylene-siloxane copolymer stationary phases and to compare their separation characteristics with poly(dimethyldiphenylsiloxane) stationary phases containing a nominally similar concentration of phenyl groups. These studies demonstrate that ZB-5 ms and DB-5 ms are selectivity equivalent. DB-XLB is significantly more dipolar and polarizable than DB-5 ms. In general terms, the silarylenesiloxane copolymer stationary phases are slightly less cohesive and more dipolar and polarizable with similar hydrogen-bond basicity to the poly(dimethyldiphenylsiloxane) stationary phases they were designed to replace. None of the silarylenesiloxane copolymer or poly(dimethyldiphenylsiloxane) stationary phases are hydrogen-bond acidic. Selectivity differences between the two types of stationary phase are temperature dependent and tend to be smaller at higher temperatures within the temperature range studied. Consequently, selectivity differences cannot be globalized without reference to the temperature for the comparison.     

Cryo-FIB-Preparation and Cryo-SEM Investigation of Gold Nanolayers Used as Absorber for Laser Welding of Polymer Foils

The morphology of welded polymer foils was investigated by Scanning Electron Microscopy (SEM) using Focused Ion Beam (FIB) technology for cross-sectional preparation. Due to the sensitive structure of the copolymer Ethylene Tetrafluororethylene (ETFE), FIB preparation and SEM investigation were performed at cryo conditions. A gold nanolayer was used as absorber for the laser beam to weld the transparent copolymer foils. The embedding of the gold nanolayer inside the welding seam and its influence on the mechanical stability of the welding seams was demonstrated.     

Temperature- and pH-responsive star amphiphilic block copolymer prepared by a combining strategy of ring-opening polymerization and reversible addition-fragmentation transfer polymerization

The star-shaped poly(ε-caprolactone)-b-poly(2-(dimethylamino)ethyl methacrylate) (HPs-Star-PCL-b-PDMAEMA) was synthesized by ring-opening polymerization and reversible addition-fragmentation chain transfer (RAFT) polymerization. Star-shaped polycaprolactones (HPs-Star-PCL) were synthesized by the bulk polymerization of ε-caprolactone (CL) with a hyperbranched polyester initiator and tin 2-ethylhexanoate as a catalyst. The number-average molecular weight of these polymers linearly increased with the increase of the molar ratio of CL to hyperbranched initiator. HPs-Star-PCL was converted into a HPs-star-PCL-RAFT by an esterification of HPs-Star-PCL and 4-cyanopentanoic acid dithiobenzoate. Star amphiphilic block copolymer HPs-Star-PCL-b-PDMAEMA was obtained via RAFT polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA). The molecular weight distribution of HPs-Star-PCL-b-PDMAEMA was narrow. Furthermore, the micellar properties of HPs-Star-PCL-b-PDMAEMA in water were studied at various temperatures and pH values by means of dynamic light scattering (DLS). The results indicated that the star copolymers had the pH- and temperature-responsive properties. The release behaviors of model drug aspirin from the star polymer indicated that the rate of drug release could be effectively controlled by pH value and temperature.     

分子水平研究不同嵌段结构苯乙烯/丁二烯共聚物的表面结构

利用具有准单分子层灵敏度的和频振动光谱(SFG)、原子力显微镜(AFM)和接触角(CA)测定技术研究链结构和溶剂对苯乙烯(S)/丁二烯(B)嵌段共聚物表面准分子层化学结构形成的影响.结果表明,两嵌段共聚物SB比三嵌段共聚物SBS更有利于聚丁二烯(PB)组分在膜表面富集.利用PB的选择性溶剂环己烷做溶剂时,SB膜表面层完全由纯的PB组分组成,而SBS表面则是聚苯乙烯(PS)与PB二组分共存.利用PS的选择性溶剂甲苯做溶剂时,SB与SBS表面都是PS与PB二组分共存,其中SBS表面PS组分的含量更高.原因是由于溶剂影响嵌段共聚物分子在溶液中的构象从而影响溶剂挥发后聚合物表面结构的形成.     

聚乳酸-b-聚(N~ε-苄氧羰基-L-赖氨酸)-b-聚乙二醇的合成与表征

用端氨基聚乳酸做引发剂,在DMF中引发Nε-苄氧羰基-L-赖氨酸酐(Lys(Z)-NCA)聚合,合成了端氨基聚(Nε-苄氧羰基-L-赖氨酸)-b-聚乳酸两嵌段共聚物.以端羧基聚乙二醇经NHS活化与端氨基聚(Nε-苄氧羰基-L-赖氨酸)-b-聚乳酸偶联,合成了聚(乳酸-b-Nε-苄氧羰基-L-赖氨酸-b-乙二醇)三嵌段聚合物.利用IR、1H-NMR、GPC和TEM对它们的结构、形态进行了表征,结果表明,所合成的分子量可控、分子量分布窄(Mw/Mn=1.07)的嵌段共聚物,酰化反应产率达70%以上.同时聚乙二醇和Nε-苄氧羰基-L-赖氨酸被引入到聚乳酸主链中,在聚合物侧链脱保护后有望改善聚乳酸的细胞亲和性。     

P(VDF-co-TrFE-co-CTFE)-g-SPS共聚物的合成表征

采用商业聚(偏氟乙烯-co-三氟氯乙烯)(P(VDF-co-CTFE)为原料,结合氢化反应、ATRP和磺化反应系统合成了一系列聚(偏氟乙烯-co-三氟乙烯-co-三氟氯乙烯)-g-磺化聚苯乙烯(P(VDF-co-TrFE-co-CTFE)-g-SPS)共聚物.重点研究了测试环境(如温度和相对湿度)、聚合物微观结构(接枝密度,接枝长度等)对聚合物形貌、吸水率和质子传导率的影响.研究表明,在接枝量相同的情况下,随着接枝密度的降低,聚合物的相分离更加明显,亲水相从孤岛型逐渐转变为部分连续型;聚合物的吸水率随磺酸基摩尔含量增加而提高;聚合物的质子传导率随着温度的提高和湿度的降低而降低;在较低温度下,聚合物的电导率随接枝密度的增加而降低,而在较高温度下,聚合物的电导率随接枝密度的增加而升高.组成优化的P(VDF-co-TrFE-co-CTFE)-g-SPS共聚物在30～120℃和高湿度条件下,其质子传导率明显优于Nafion112膜.     

具有温度敏感和荧光特性的侧链查尔酮共聚物的研究

采用2,2′-偶氮二异丁腈作为引发剂,将N-异丙基丙烯酰胺和4-甲基丙烯酰氧基-4′-二甲氨基查尔酮单体,在四氢呋喃溶剂中通过自由基共聚制备了一系列具有溶剂和温度双重敏感荧光特性的侧链查尔酮共聚物,并通过红外光谱、核磁共振氢谱和紫外-可见光谱对其结构进行表征,通过吸光度法测定了共聚物中查尔酮单元的含量.研究了侧链查尔酮共聚物的温敏性以及溶剂极性和温度双重敏感的荧光特性.结果表明,侧链查尔酮共聚物是一类具有最低临界溶解温度(LCST)的温敏性聚合物,其LCST温度随着共聚物中查尔酮含量的增加而降低;随着溶剂极性的增加,侧链查尔酮共聚物的紫外-可见最大吸收波长红移,其荧光发光波长红移并且发光强度先增强后降低,具有溶剂极性敏感的荧光特性;同时对比侧链查尔酮共聚物水溶液低温和高温下的荧光,发现低温下几乎无荧光,高温下其荧光得到明显增强,其荧光具有可逆的温度"开/关"特性。     

向列相液晶共聚物作为β晶成核剂对等规聚丙烯结晶结构与热性能的影响

采用接枝聚合的方法,合成了一种新型聚硅氧烷类向列相液晶共聚物(LCP-H4),然后将LCP-H4与PP在一定工艺条件下密炼共混,得到了一系列的共混样品,采用WAXD、POM与DSC等研究了LCP-H4作为成核剂对PP样品结晶结构、形态与热性能的影响.结果表明,具有独特"液晶"性能的LCP-H4为PP结晶提供了更多的带自由能的晶核与较多的活性点,起到了异相成核的作用,既提高了PP的结晶速度、结晶温度和结晶度,又减小了球晶的尺寸,同时也改变了PP的结晶结构、形态及热力学与动力学,诱导出了β晶.此外,随着增加LCP-H4的含量及结晶温度,对应PP试样的β晶含量(Kβ)呈现先增加后降低的趋势,当LCP-H4含量为0.9%,在128℃等温结晶1h,对应成核PP的Kβ最大,为54%.     

完全交替结构乙烯-丙烯共聚物的制备与表征

对顺-1,4含量为100%的高顺式聚异戊二烯(HCPI)进行加氢反应,得到了序列结构高度规整的乙烯-丙烯交替共聚物(alt-EP).所用的HCPI有适当的分子量(Mn=41×104)和极窄的分子量分布(Mw/Mn=1.02).HCPI的加氢反应以环烷酸镍和三异丁基铝为催化剂,在60℃和4.0MPa氢压的条件下反应3h,加氢产物的加氢度为100%.GPC测试结果显示所得乙烯-丙烯交替共聚物保持了窄分布的特点,表明HCPI加氢后未发生交联和降解反应;NMR,FTIR和广角X射线衍射测试结果表明此乙烯-丙烯交替共聚物具有高度规整的序列结构,为完全交替结构的乙烯-丙烯共聚物.并通过TGA和DSC对乙烯-丙烯交替共聚物的热性能进行了表征.