SOLID-PHASE SYNTHESIS OF 2''''—5'''' OLIGOADENYLATE——2''''—5''''A CORE

With phosphotriester approach, the 2'—5' linked oligonucleotide——2'—5'A core was synthesized by using cross-linked polyacrylmorpholide resin as the support and the mesitylene sulfonyl chloride and N-methylimidazole as the condensing agent. Synthesizing the 2'—5'A core with this method has not yet been described. The yields that each of the protected monomers was attached to the polymeric support were satisfactory, i.e., 100%, 60% and 91% respectively.For the synthesis, we improved the methods for preparing the polymeric support and a series of intermediates. For this reason, the yields of the products were markedly increased and the operations to separate the products from the by-products and reagents were simplified.     

合成聚乙烯基苯甲酸树脂的研究(Ⅰ)——用氯甲基化交联聚苯乙烯一步法合成

本文用硝酸一步法将大孔氯甲基化交联聚苯乙烯树脂小球(氯球)氧化成聚乙烯基苯甲酸树脂。经红外光谱鉴定,推测了反应的机理。     

合成聚乙烯基苯甲酸树脂的研究(Ⅱ)——由氯甲基化交联聚苯乙烯树脂按二步法合成

用两种二步法将交联度6％的大孔氯甲基化聚苯乙烯树脂制成了聚乙烯基苯甲酸树脂,产品氯含量均为零。     

THE MECHANISM OF COPOLYMERIZATION OF VINYL AND DIVINYL MONOMER Ⅵ: A STUDY ON THE MECHANISM OF THE STRUCTURE FORMATION OF CROSSLINKED POLYSTYRENE

In order to study the mechanism of the formation of maeroporous copolymer, the overall reaction kinetics, phase separation and gelation of the S/EGDM in the presence of inert solvents and the physical properties of the eopolymer were investigated and compared with the corresponding system of S/DVB and S/DVB/MMA. The formation of the network structure of the macroreticular polymer was studied and a model of the mechanism suggested.     

在乳液体系里制备过氧化氫基聚苯乙烯及其在接枝聚合上的应用

用不同分子量的聚苯乙烯在乳液体系中进行过氧化氢基化反应,然后测定这些产品的特性粘数,HPO值(每1,000个苯乙烯结构单元中所合的过氧化氢基平均数目)等。在过氧化氢基聚苯乙烯的红外光谱里,可以在3,200—3,600厘米~(-1)吸收区里观察到过氧化氢基的吸收带,其吸收强度随着HPO值的增大而加强。最后用这些大分子过氧化物引发甲基丙烯酸甲酯及苯乙烯聚合,得到接枝聚合物。经过分离提纯后,用下列的方法: (1)浊度滴定; (2)热机械性能的测试; (3)水解后测定交换量; (4)红外吸收光谱;证明它们是接枝共聚物。     

以脂肪醇为致孔剂的苯乙烯-二乙烯苯共聚体的合成及其膦酰胺化反应

本文以异辛醇或2-乙基丁醇为致孔剂,合成了一系列苯乙烯-二乙烯苯大孔共聚体。通过对共聚体物理结构的测定,讨论了影响共聚体物理结构的主要因素。经乙酰化,膦化反应后的共聚体可以与二正丁胺作用制得膦酰胺树脂。研究了交联聚苯乙烯膦酰氯与二正丁胺反应的影响因素,同时考察了经膦酰胺化反应后共聚体物理结构所发生的变化。     

以球形碳化树脂为载体用水合肼法还原4,4′—二硝基二苯醚制备4,4′—二氨基二苯醚

以新型吸附剂—球形碳化树脂为载体,用三价铁盐作催化剂,在醇介质中,用水合肼法还原4,4’—(二硝基)二苯醚制备4,4’-(二氨基)二苯醚。详细研究了载体结构,载体用量,催化剂用量等反应条件对产率的影响。     

2′-5′连接寡聚核苷酸——2′-5′A核的固相合成

本文用磷酸三酯法,在交联聚丙烯酰吗福啉载体上,以1,3,5-三甲苯磺酰氯(MS)加N-甲基咪唑(N-Mein)为缩合剂,合成了2′-5′相连的寡聚腺苷酸——2′-5′A核。每个保护的单体接到载体上的收率是令人满意的,分别是100％,64％和89％。在合成过程中,我们对合成一系列中间体和制备载体的方法进行了改进,使产物收率大大提高,分离操作得以简化。     

化学分析法测定MMA／EGDM共聚物中的悬挂双键

本文采用催化碘量法研究MMA/EGDM共聚物中的悬挂双键(Pendent double bonds)。     

THE OVERALL KINETICS OF FREE RADICAL (CO)POLYMERIZATION WITH HIGHLY DIFFUSION CONTROLLED TERMINATION

The overall reaction rate kinetics of polymerization of diethyleneglycol dimethacrylate and copolymerization of it with styrene in bulk and in the presence of inert diluents were investigated. Theresults indicated that these reactions can be treated as free radical polymerization with highly diffu-sion controlled termination reaction in which the termination rate constant is an empirically derivedfunction of monomer conversion: K_t=K_(to)(1-c ln[M]/ [M_0])~(-1) in which K_(to) is the initial terminationrate constant and c is a factor related to the magnitude of diffusion co?re The following equationof monomer conversion as a function of time could then be derived: U=1-exp {1/c [1-(1+ckt/2)~2]}in which k=K_P(R_i/2K_(to))~(1/2) and t is the time of reaction. Excellent agreement between the theoreticaland experimental overall reaction kinetic curves was obtained. The equation is valid for crosslinkingand noncrosslinking free radical polymerizations in which the self-acceleration effcct is effective fromthe very beginning of the reaction. The equation can be expressed in a more generally applicableform: U=1--exp{1/e[1--(1+?t/n)~n] in which n≥0.