ON THE ORIGIN OF STRESS PEAK IN UNI-AXIAL STRETCHING OF AMORPHOUS POLYMERS

Rubber of high molar mass, like cis-polybutadiene, shows a stress peak on theenineering stress-strain curve during stretching at room temperature. In this work cis-polybutadiene samples were swollen in a poor solvent, CHCl_3/EtOH (1/1 v/v), for differenttimes. It was found that both the initial modulus and the stress peak on stretching de-creased in magnitude with increasing swelling time and the peak disappeared entirely after1 hour of swelling. On further swelling the initial modulus increased somewhat and a smallstress peak re-appeared after swelling for 2 h. The disappearance of the stress peak afterswelling is interpreted as the result of disruption of cohesional entanglements present in theinitial rubber sample. The re-appearance of a small stress peak and the increase of modu-lus on further swelling are interpreted as being of the same nature as the phenomenon ofanti-plasticization. It is the result of forming some new cohesional entanglements of largerbinding energies through longer range chain segmental motions excited after the disruptionof the previously existing cohesional entanglements in the rubber. Thus an understand-ing of the stress peak on stretching a high molar mass rubber and the phenomenon ofanti-plasticization on molecular level has been put forward.     

Synthesis, Characterization and Biological Activity of Diorganotin（IV） Complexes of N-（3,5-Dibromosalicylidene）-α-amino Acid

The diorganotin（Ⅳ） complexes of N-（3,5-dibromosalicylidene）-α-amino acid, R2Sn（2-O-3,5-Br2C6H2CH= NCHRCOO）（where R=H, Me, i-Pr, Bz; R＇=n-Bu, Cy）, were synthesized by the reactions of diorganotin dichlorides with in situ formed potassium salt of N-（3,5-dibromosalicylidene）-α-amino acid and characterized by elemental analysis, IR and NMR （^1H, ^13C and ^119Sn） spectra. The crystal structures of n-Bu2Sn（2-O-3,5-Br2C6H2CH= NCHRCOO）（R=i-Pr, Bz） and Cy2Sn（2-O-3,5-Br2C6H2CH=NCHRCOO）（R=Me, Bz） were determined by X-ray single crystal diffraction and showed that the tin atoms are in a distorted trigonal bipyramidal geometry to form five- and six-membered chelate rings with the tridentate ligand. Bioassay results indicated that the compounds possess better in vitro antitumour activity against three human tumour cell lines, HeLa, CoLo205 and MCF-7, than cis-platin and moderate anti-bacterial activity against two bacteria, E. coli and S. aureus.     

红外碳硫测定仪测定铁矿石中硫

采用红外碳硫仪对铁矿石中硫进行测定，通过对助熔剂各类、助熔剂的加入量，助熔剂的比例，称样量、试样加入顺序等条件进行试验，选择了测定铁矿石中硫的最佳条件，此法的测定范围为0．01％－4．0％。     

一个适用于Huggins常数K′较大的新的一点法特性粘数方程

本文提出了一个适用于Huggins常数较大(0.472≤K＇≤0.825)的聚合物-溶剂体系的新的一点法特性粘数方程[η]=ηsp/Cη~(1/2).并与其它四个一点法方程分别对19种聚合物的27种聚合物-溶剂体系的192个文献数据进行计算比较,发现本方程所得结果是十分满意的.因此,本方程的建立,扩大了用一点法求算聚合物特性粘数方法中K＇值的范围.     

含茂、非茂混合配体钛族络合物的合成与催化烯烃聚合的研究进展

目前金属有机钛族络合物的发展呈现出多元化的趋势:茂络合物、非茂络合物以及茂非茂混合配体络合物,而其中茂、非茂混合配体络合物是近年来发展的一个新亮点.关于茂钛族络合物、非茂钛族络合物近年已经有过许多的综述,而关于茂、非茂混合配体钛族络合物的综述却很少.综述了近年来茂、非茂混合配体钛族络合物合成与催化烯烃聚合的研究进展.     

自由基引发的可注射PLA-b-PEG-b-PLA大分子单体和α-CD超分子结构水凝胶的合成与表征

以数均分子量为6000的聚乙二醇为引发剂,以辛酸亚锡为催化剂引发丙交酯开环,再用甲基丙烯酸酐进行封端生成大分子单体.然后将大分子单体和α-环糊精混合,分别用维生素C和硫酸亚铁与过硫酸铵组成的氧化还原引发剂引发聚合,得到了两种不同结构的超分子结构水凝胶.用1HNMR,FTIR,TGA和XRD等分析测试手段对大分子单体及形成的水凝胶进行了表征.流变仪测试结果表明,该水凝胶固化时间合适,并具有可注射性.     

手性稀土配合物催化的亚膦酸酯对醛的不对称加成（Pudovik）反应研究

手性稀土配合物催化的亚膦酸酯对醛的不对称加成（Ｐｕｄｏｖｉｋ）反应研究钱长涛黄太生（中国科学院上海有机化学研究所金属有机化学开放实验室上海２０００３２）关键词对映选择性加成Ｐｕｄｏｖｉｋ反应手性镧配合物α－羟基膦酸酯分类号Ｏ６４３．３２光学纯的α－羟...     

胂叶立德与具有对三氟甲基苯基及双吸电子基团烯烃的反应研究

鉮盐1以碳酸钾为碱分别与含对三氟甲基苯基及双吸电子基团的烯烃2或3反应, 高产率、高立体选择性地合成了含对三氟甲基苯基的顺-1,2-环丙烷衍生物4或顺-2,3-二氢呋喃衍生物5, 并对其产物结构进行了确证.     

STUDIES ON POLY(ETHYLENE TEREPHTHA LATE)-POLY(TETRAMETHYLENE ETHER) MULTIBLOCK COPOLYMER.Ⅰ.COMPOSITIONAL HOMOGENEITY

The compositional homogeneity of a poly (ethylene terephthalate)-poly (tetramethylene ether) multiblock copolymer sample with low content of hard segment was examined by GPC, TLC, and solubility method. The copolymer sample was found to have a uniform composition as a function of elution volume over the major portion of sample from GPC method. However within one elution fraction, the copolymer chains, although having the same hydrodynamic volume, may have some difference in composition. Two fractions with different composition were obtained by precipitation in ethanol. Some low molar mass copolymers were also separated by a TLC technique from the copolymer sample.     

头孢唑酮与Triton X-100缔合体系的相互作用

抗生素头孢唑酮的加入使得非离子表面活性剂Triton X-100的表面活性降低. ¹H-NMR的结果表明，头孢唑酮增溶于胶束极性基团附近.头孢唑酮与Triton X-100胶束的结合常数随Triton X-100含量的增加而下降，但头孢唑酮在Triton X-100胶束相和水连续相之间的分配系数不随Triton X-100含量变化而变化.