PEG-PLA嵌段共聚物的合成及~(13)C NMR对平均链段长度的测定

本文报道聚乙二醇(PEG)在辛酸亚锡存在下与丙交酯(LA)反应合成PEG-PLA嵌段共聚物,用~(13)C NMR测定了共聚物的结构,估算了平均链段长度.实验结果表明,L_(PEG)在反应过程中保持不变,而L_(PLA)随反应时间和LA在原料配比中含量的增加而增加,呈逐步聚合反应特点.对聚合反应机理作了推测.     

聚电解质-磺化聚砜溶液的光散射

本文采用激光小角光散射法,测定了聚电解质-磺化聚砜(钠盐),在分别舍有NaNO_3、LiNO_3、LiCl、NaBr和NaI的DMF中各试样的表现分子量。结果表明,在含有0.07N NaNO_3的DMF中,磺化聚砜的表观分子量接近于试样的真实分子量。     

CHARACTERIZATION OF AMPHIPHILIC AND MICROPHASE SEPARATED GRAFT COPOLYMERS Ⅱ SURFACE CHARACTERIZATION AND IN VITRO BLOOD-COMPATIBILITY ASSESSMENT OF POLYSTYRENE-GRAFT-ω-STEARYLPOLY (ETHYLENE OXIDE)*

This paper reported the research results concerning the surface characterization ofpolystyrene-graft-w-stearyl poly(ethylene oxide) (PS-g-SPEO) by means of XPS,contactangle measurement and TEM, and its in vitro blood compatibility assessment by measuringthe plasma recalcification time (RT) and partial thromboplastin time (PTT). The XPSresults demonstrated that the surface and bulk composition of the PS-g-SPEO graftcopolymers differ remarkably from each other,and that SPEO component was constantlyenriched at the copolymer/air interface. Contact angle studies indicated that the surfacewater wettability can be adjusted effectively by changing the composition of the copolymer.PS-g-SPEO graft copolymers can undergo microphase separation as clearly illustrated byTEM photographs. The relationship between the surface properties of PS-g-SPEO graftcopolymer and its blood compatibility was also discussed.     

1-辛烯的Ziegler-Natta聚合动力学(Ⅰ)——稳态动力学规律

过去对C_6—C_(20)α-烯烃的Ziegler-Natta聚合动力学仅有少量研究,未发现与乙烯、丙烯的聚合行为有显著不同。但1-辛烯在烃类溶剂中的聚合是溶液聚合,这是与析出聚合的主要差别。本文发现并研究了1-辛烯以α-TiCl_3-AlEt_3催化在正庚烷中聚合时的特殊动力学行为,对此提出了初步解释。     

IMMOBILIZATION OF POTENTIALLY BIOACTIVE MOIETIES ONTO POLYETHER WITH POLY(ETHYLENE GLYCOL)-SULFONATE SPACER

A new reactive graft copolymer, poly(tetramthylene glycol) - graft-w-propyl sodiumsulfonate-poly(ethylene glycol) (PTMG-g-PEG-CH_2CH_2CH_2SO_3~-Na~+), was synthesizedby the cationic polymerization of a-w-bifunctional PEG macromonomer (O?CH_2—PEG——CH_2 CH_2 CH_2 SO_3 Na) and THF. The obtained copolymer exhibits the expected structureas indicated by the result of characterization. Two amino acids (L-arginine, L-tyrosine)were covalently attached to the copolymer after converting the sulfonate group to sulfonylchloride. So the new reactive graft copolymer (PTMG-g-PEG-CH_2CH_2CH_2SO_3~-Na~+) isexpected to be very useful in attachment of potentially bioactive moieties to polymer viaa hydrophilic PEG spacer.     

阳离子聚合合成聚苯乙烯大分子单体

<正> 近十年来,对大分子单体的合成和表征进行了较广泛的研究,其中尤以聚苯乙烯大分子单体研究得更多。Milkovich等用阴离子聚合合成了一系列具有不同端基的大分子单体。本文采用实验要求比阴离子简单的阳离子聚合方法,用对-氯甲基-β-溴乙苯和三     

STUDY ON THE MECHANISM OF 1-OCTENE ZIEGLER-NATTA POLYMERIZATION BASED ON THE NUMBER OF ACTIVE CENTERS

The number of active centers (C_p)-t and k_p-t profiles of Solvay type TiCl_3 - AlR_3 (R=C_2H_5, i-C_4H_9) or Stauffer AA TiCl_3-Al (C_2H_5)_3 catalyzed 1-octene polymerization were determined by using an acetyl chloride quenching method as well as kinetic data. The results show that in the studied systems k_p decreases when C_p increases, indicating the presence of two or more types of different active centers. The C_(p~(-t)) plots of the Solvay TiCl_3-AlR_3 systems show the presence of both stable active centers and unstable centers which decay in the polymerization process. The phenomena are explained based on a model of active center plurality. The increases of C_p in the induction periods are also discussed.     

聚氧乙烯交联网络-硫氰化钠络合体系离子电导的研究

合成了甲基丙烯酸聚氧乙烯酯大分子单体,其中含有少量双端酯化的单体。大分子单体经热交联,形成交联网络型聚氧乙烯,其与硫氰化钠形成的络合物的室温电导率较同类线型聚合物高二个数量级以上(～10^-5Ω^-1cm^-1/298K)。红外光谱表明:交联网络含较高的非晶成份。不同络合溶剂对形成的络合物聚集态有明显影响;络合盐浓度也对络合物结晶性有影响。     

苯乙烯-马来酸酐自由基共聚反应 (Ⅰ)苯乙烯-马来酸酐电荷转移络合反应

电荷转移络合反应机理是研究苯乙烯－马来酸酐自由基交替共聚反应机理的关键。本文简述了苯乙烯－马来酸酐电荷转移络合反应的研究进展。     

1-辛烯Ziegler-Natta聚合的活性中心多分散性——分子量分布及动力学的研究

本文通过对TiCl_3-Al(C_2H_5)_3聚合1-辛烯产物的双峰型分子量分布曲线用Schulz函数进行拟合、分峰处理,发现这种双峰型分布中的高分子量峰部分由一种活性中心生成,低分子量峰部分则由至少两种活性中心生成.将不同转化率时聚辛烯的分子量分布分峰拟合数据与聚合速率、活性中心数等测定数据相结合,得到了高分子量和低分子量两部分产物相应的活性中心上各自的动力学参数(增长速率常数、活性中心数、链转移常数等)及各自的聚合速率曲线,从而证实了多种活性中心的存在、它们催化特性的差异及与聚合物分子量分布增宽的关系.