【作者】 毕福勇；

【导师】 姚薇；

【作者基本信息】 青岛科技大学 ， 材料学， 2007， 硕士

【摘要】 采用TiCl₄／MgCl₂-AlEt₃-DDS负载钛催化体系，在3L聚合釜中考察了氢气压力、n（DDS）／n（Ti）对聚丁烯-1等规度的影响。结果表明：当氢气压力为0.038MPa，n（DDS）／n（Ti）为1.3时，合成出等规度为94.1％的高等规度聚丁烯-1。实验还考察了等规度对聚丁烯-1的结构和性能的影响，等规度升高形成的球晶完善、结晶速率快、结晶度高、密度、硬度、热性能、拉伸强度、屈服应力、100％定伸应力、300％定伸应力、永久变形呈上升趋势，而韧性和扯断伸长率呈下降趋势。并把本实验室合成的高等规度聚丁烯-1与巴塞尔生产的高规度聚丁烯-1进行结构和性能的对比，结果表明：自制高等规度聚丁烯-1结晶完善、结晶度稍低、熔点高、Ⅱ型晶型向Ⅰ型晶型的转变速度快、相对分子量偏低，热稳定性、分子量分布和物理力学性能基本一致，自制高等规度聚丁烯-1已与国外工业化生产的高等规度聚丁烯-1非常接近，加快了国内高等规度聚丁烯-1工业化生产的步伐。采用自制的TiCl₄／MgCl₂-Al（i-Bu）₃负载钛催化体系，合成聚丁烯-1热塑性弹性（PBt-TPE）。在氢气存在条件下，采用本体聚合方法在3L聚合釜中考察了n（Al）／n（Ti）、n（Ti）／n（Bt）及反应温度对单体转化率、特性黏数、全同立构含量的影响。结果表明：当n（Al）／n（Ti）为300，反应温度为30℃，单体转化率达到最大值。采用溶液聚合方法在500ml聚合瓶中考察了陈化条件、反应温度、反应时间对单体转化率、结晶度、分子量、物理力学性能的影响。在陈化条件为：当n（Al）／n（Ti）为100，陈化温度为20℃，陈化时间为20min时，单体转化率最大，为82.5％；随着反应时间的增加，PBt-TPE的相对分子量增加，但分子量分布变窄；随着反应温度的升高，PBt-TPE的等规度、拉伸强度、撕裂强度、100％定伸应力和300％定伸应力以及硬度均先上升后下降，在T=30℃处各项力学性能达到最佳。在同样的聚合条件下，考察了本体聚合方法和溶液聚合方法对PBt-TPE的结构和性能的影响，溶液法合成的PBt-TPE的结晶度、等规度、特性黏数、硬度、密度、拉伸强度、扯断伸长率、永久形变、撕裂强度都比本体法合成的PBt-TPE大。更多还原

【Abstract】 Adopting TiCl₄/MgCl₂-AlEt₃-DDS catalyst system, the effects of hydrogen pressure and n（DDS）/n（Ti） on isotacticity of polybutene-1 were studied in 3L polymerizer. It was showed that: the optimal-polymerization conditions of high isotacticpolybutene- 1 （94.1%） are: Hydrogen pressure=0.038MPa,n（DDS）/n（Ti）= 1.3. The effects of isotacticity on structure and properties of polybutene-1 were also studied in this experiment. With the increasing of the isotacticity of polybutene-1, the perfect of spherulite, the speed of crystallization,density, hardness,the heating stability, tensile strength, jield strength, modulus at 100%,modulus at 300% and permanent set will go rise,while toughness and elongation at break will drop down. From the comparison of structure, and properties between self-made and abroad high isotactic polybutene-1, the perfect of spherutite, melting point and the speed of crystal transformation of self-made -polybutene-1 are higher than abroad sample, but the degree of crystallinity of self-made polybutene-t is siightly lower, self-made polybutene-1 coincides with abroad sample in most parts such as the heating stability, molecular polydispersity and mechanical properties. Self-made polybutene-1 gets much close to the abroad high isotactic polybutene-1 in both structure and properties, which will give a good prospect in industrializing high isotactic potybutene-1 at inland.Polybutene-1 thermoplastic elastomer （PBt-TPE） was synthesized with the TiCl₄/MgCl₂-Al（i-Bu）₃ catalyst system.The effects of n（A1）/n（Ti）, n（Ti）/n（Bt） and polymerization temperature on isotacticity, conversion ,and limiting viscosity number in 3L polymerizer in bulk polymerization at the presence of hydrogen pressure. It was showed that when n（A1）/n（Ti） is 300,polymerization temperature is30℃, the conversion reached its maximum. The effects of aging conditions, polymerization temperature and polymerization time on conversion, degree of crystallinity, relative molecular weight and mechanical properties in 500ml reaction bottle in solution polymerization.The conversion reached its maximum of 82.5%,when aging conditions were that n（Al）/n（Ti） is 100, aging temperature is 20℃and aging time is 20min. With the increase of polymerization time, relative molecular weight of PBt-TPE will rise while molecular polydispersity will become narrow. With the increase of polymerization temperature, isotacticity, tensile strenth, tear strength,modulus at 100%, modulus at 300% and hardness wiil increase first then decrease.There is the optimal properties when temperature is 3.0℃. On the same polymerization conditions, the effects of bulk polymerization and solution polymerization on structure and properties of PBt-TPE. Compared with bulk polymerization, isotacticity, the degree of crystallinity, limiting viscosity number, hardness, density, tensile strength, elongation at break, permanent set of PBt-TPE synthesized by solution polymerization were high.更多还原