聚合物载体－稀土金属络合物的研究ⅩⅤ．聚（苯乙烯－丙烯酰胺）载体－氯化钕络合物对异戊二烯聚合的催化行为

研究了聚（苯乙烯－丙烯酰胺）（ＰＳＡＣ）载体－氯化钕（ＮｄＣｌ３）络合物对异戊二烯（Ｉｐ）聚合的催化行为．ＰＳＡＣ·ＮｄＣｌ３络合物保留了小分子稀土催化剂对双烯烃聚合的催化规律和高度的定向效应．络合物的催化活性随着Ｎｄ／Ｉｐ和Ａｌ／Ｎｄ比的增加而增加，所得聚异戊二烯的特性粘数［η］却随之下降．聚异戊二烯的顺式－１，４结构含量达９５％．此外，ＰＳＡＣ·ＮｄＣｌ３络合物的活性受ＰＳＡＣ和ＰＳＡＣ·ＮｄＣｌ３的组成与结构的影响．在一定的条件下，络合物的活性随着ＰＳＡＣ中功能团含量的增加而下降．ＰＳＡＣ中单体链节交替分布的程度越低，络合物的活性越高     

π－烯丙基稀土配合物的合成、结构及其催化烯烃聚合反应机理的研究 Ⅲ．LiLn（π－C_3H_5）_4·nD催化异戊二烯和苯乙烯均聚合反应的研究

本文研究了ＬｉＬｎ（π－Ｃ_３Ｈ_５）_４·ｎＤ（Ｌｎ＝Ｌａ、Ｔｂ，ｎ＝３；Ｌｎ＝Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｅｒ，ｎ＝２；Ｌｎ＝Ｙ、Ｄｙ，ｎ＝２．５；Ｄ为二氧六环）催化异戊二烯和苯乙烯的均聚合反应．其中，钇配合物的催化活性为最高．聚异戊二烯顺式－１，４链节含量在４３－８１％．聚合体系内少量给电子体的加入使聚合物中３，４－链节含量高达８４％．所得聚苯乙烯为无规结构．     

New method for resolving the enantiomeric composition of 2-methyltetrols in atmospheric organic aerosols

In order to facilitate the determination of the primary and secondary origin of atmospheric organic aerosols, a novel method involving chiral capillary gas chromatography coupled with mass spectrometry has been developed and validated. The method was focused on the analysis of 2-methylerythritol and 2-methylthreitol, considered to be tracers of secondary organic aerosols from the oxidation of atmospheric isoprene. The method was validated by performing various tests using authentic standards, including pure enantiomeric standards. The result showed that the analytical method itself does not affect the enantiomeric composition of the samples analyzed. The method was applied on atmospheric aerosols from a boreal forest collected in Aspvreten, Sweden and on laboratory samples obtained from liquid phase oxidation of isoprene and smog chamber experiments. Aerosol samples contained one enantiomer of 2-methylerythritol in significantly larger quantities than the others. In contrast, the liquid-phase oxidation of isoprene and its gas-phase oxidation in the smog chamber produced all enantiomers in equal quantities. The results obtained where the enantiomer fraction, EF, is larger than 0.50 suggest that 2-methyltetrols in atmospheric aerosols may also have biological origin. Information about the differences between enantiomer fractions obtained using this method brings new insights in the area of atmospheric aerosols.     

连续流动条件下含氮Beta分子筛催化甲缩醛-异丁烯Prins反应

采用高温氨气氮化法,制备了一系列含氮Beta分子筛样品,并在连续流动条件下,考察了其催化甲缩醛与异丁烯经Prins缩合制异戊二烯的反应性能.利用XRD、 N₂吸附/脱附、元素分析、 ²⁹SiMAS NMR、 NH₃-TPD、 CO₂-TPD和TG等方法对氮化分子筛的结构、酸碱性和反应后积碳进行了表征,研究了反应条件及样品的酸碱性对反应性能的影响.结果表明,以35%甲缩醛水溶液为反应物,在320℃、 2 MPa、异丁烯与甲缩醛摩尔比为7的适宜条件下,铵型Beta为前驱体制备的催化剂对甲缩醛的转化率达99%,异戊二烯的产率达85%.氮化后少量的酸性位和较多的碱性位有利于维持甲缩醛较高的转化率、较高的异戊二烯产率及较低的反应积碳量.催化剂再生6次后仍保持75%异戊二烯产率,样品中Si―N键削弱导致酸碱性变化是再生后反应性能下降的主要原因.     

高反式-1,4-丁二烯-异戊二烯共聚橡胶在轿车轮胎带束层中的应用研究

研究了高反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)的生胶性能及其在轿车轮胎带束层中的应用。结果表明,随丁二烯单体单元含量增加,TBIR生胶的玻璃化转变温度、结晶熔融焓、生胶强度和硬度逐渐降低。硫化胶性能测试表明,TBIR硫化胶的定伸应力、回弹性能以及耐老化性能优于NR硫化胶,TBIR-40硫化胶的拉伸强度和撕裂强度明显高于NR硫化胶。采用10~30份TBIR取代NR应用于轿车轮胎带束层配方,并用硫化胶拉伸强度、拉断伸长率、撕裂强度和钢丝帘线抽出力处于较高水平,定伸应力、硬度、回弹性能和耐老化性能较对比胶提高,含TBIR的轮胎带束层胶料具有更加优异的综合性能。DMA结果表明,NR与TBIR相容性较好,NR/TBIR并用硫化胶具有更低的内耗。TEM结果表明,NR/TBIR并用胶具有较好的填料分散性。     

影响异戊二烯大气光解形成二次有机气溶胶的环境因素研究

通过自制的烟雾腔系统研究羟基启动的异戊二烯光解形成二次有机气溶胶(SOA)过程中环境因素的影响.使用气溶胶粒径光谱仪测量了SOA的粒径分布,通过光解实验研究了光照时间、反应物浓度以及CH3ONO浓度对异戊二烯光解形成SOA的影响.结果表明,异戊二烯光解形成的SOA空气动力学直径在0.4 mm～1.4 mm之间,这些粒子的直径小于2.5μm的微细粒子很容易沉积在人体肺泡内,对人体健康产生很大危害;不管是SOA粒子的粒子数浓度还是质量数浓度都随着反应时间的增长、光照强度的增强和反应物浓度的增加而增加.该研究为大气颗粒物排放源的外场测量提供了非常有用的信息.     

Controlled/living radical polymerization of isoprene and butadiene in emulsion

A process for RAFT-controlled radical polymerization in emulsion [36] has been applied to the polymerizations of isoprene and of butadiene in emulsion systems, with the goal of producing latex particles containing block copolymers of acrylic acid (stabilizer and starting polymer), styrene (second polymer) and isoprene or butadiene (third polymer). The microstructure of the polymer chains was examined using dual-detection size-exclusion chromatography, and the nanostructure of the materials was investigated by differential scanning calorimetry and solid-state nuclear magnetic resonance. Reactions were always slow (although faster than the corresponding processes in solution), and exhibited limited reinitiation by isoprene when in emulsion. The materials containing isoprene exhibit a nanostructure with a phase separation into high-T_g polystyrene-rich domains and low-T_g polyisoprene-rich domains, revealed by DSC and NMR. This has the potential to lead to barrier materials with novel physical properties.     

Cationic polymerization of dienes VIII: Is the elimination of cross-linking by a bulky electron donor a general behavior in the presence of aluminium trichloride?

Previous works on the polymerization of 1,3-pentadiene initiated by aluminium trichloride in non polar solvent at room temperature in the presence of bulky electron donor (ED) as tri-p-tolylamine have highlighted a stabilization of the polymerizing actives centres by ED, which allowed a reduction of some side reactions and the formation of more precisely defined polypentadienes than ever by cationic polymerization in non polar medium. The aim of this research was to investigate the role of bulky EDs such as tri-p-tolylamine and similar compounds in polar medium in order to obtain if possible a complete control of the polymerization of isoprene and 1,3-pentadiene. The beneficial effect of tri-p-tolylamine was shown in the case of isoprene polymerization at room temperature, with an important reduction of the cross-linked fraction for long reaction times and strong reduction of termination reactions. At −30 °C in the presence of tri-p-tolylamine, polypentadienes more controlled than in non polar solvent could be obtained, with a nearly complete elimination of the cross-linked fraction, while keeping the microstructure approximately constant.     

四氯化钛/三异丁基铝体系催化降冰片烯与异戊二烯的共聚合

以传统Ziegler-Natta催化体系TiCl4/Al(#em/em#-Bu)3催化降冰片烯(NBE)和异戊二烯(IP)的共聚合, 制得可溶于常规有机溶剂的共聚物, 其数均分子量为2.0 × 104~6.5 × 104, 分子量分布指数为1.5~2.9, 降冰片烯结构摩尔含量为26%~60%. 考察了助催化剂用量、 聚合温度及2种单体投料比对共聚合的影响. 结果表明, 当降冰片烯与异戊二烯的投料摩尔比为4∶6时, 于40 ℃聚合6 h, 得到的共聚物产率为96%, 数均分子量为6.5×104, 降冰片烯结构含量45%. 用 1H NMR, 13CNMR, GPC和DSC等方法表征了共聚产物的微观结构与热性能. 13C NMR DEPT结果表明, 共聚反应中降冰片烯单体以加成方式聚合. DSC结果显示, 共聚物只有一个玻璃化转变温度(Tg=20~40 ℃). 通过Kelen-Tüdös方法得到2种单体的竞聚率分别为rNBE=0.07, rIP=0.44.