稀土催化剂上丁二烯气相聚合的宏观动力学研究

The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium(Nd) was carried out.The effects of reaction temperature,reaction pressure,dispersing medium, and types of catalyst on kinetics of polymerization were investigated .A kinetic model with two kinds of active sites was proposed.The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant,and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.     

稀土钕催化剂上丁二烯气相聚合过程研究

在２升的卧式双轴自清洁型搅拌床反应器对负载型稀土催化剂催化的丁二烯气相聚合过程进行了实验研究。考察反应温度和压力等因素对聚合速率和分子量及其分布的影响。确定了合适的反应条件并获得了有关的动力学参数。     

丁二烯气相聚合动力学模型研究

以搅拌床反应器中负载型催化剂催化的丁二烯气相聚合动力学实验为基础,用失活行为不同的两种活性位组合失活模型模拟了丁二烯气相聚合的衰减型动力学行为。研究结果表明,用活性位的1级失活和1．5级失活的组合失活模型可以满意地描述聚合速率的衰减行为。     

用多粒模型模拟丁二烯气相聚合的颗粒增长

Gas phase polymerization of butadiene by neodymium catalyst was modeled. The effects of mass and heat transfer resistances in the external boundary layer and within particles, sorption of butadiene in polybutadiene,and deactivation of active sites on polymer particle growth and morphology were studied. Simulation results show that the effects of intraparticle mass and heat transfer resistances on the growth rate of polymer particles are insignificant, and that there is no significant effect of mass transfer resistance on the morphology of polymer particles.The simulation results were compared with the experimental results.     

丁二烯气相聚合过程中聚合物颗粒增长的动态研究

An experimental apparatus composed of microscope, video camera, image-processing, and mini reactor which can be used for real-time measurement of the growth of polymer particle in gas phase polymerization was built up to carry out dynamic study of gas phase polymerization of butadiene by heterogeneous catalyst based on neodymium(Nd). The studies of the shape duplication of polymer particles and catalyst particles and the growth rate of polymer paxticle were made. Results show that the appaxatus and procedure designed can be well utilizedto make dynamic observation and data collection of the growth of polymer particle in gas phase polymerization.A phenomenon of shape duplication of polymer particles and catalyst particles was observed by the real-time measurement. The result also concludes that the activity of individual catalyst particle is different, and the effect of reaction pressure on the growth of polymer particle is significant.     

丁二烯气相聚合产物分子量分布和粒径分布模型研究

对非均相催化的丁二烯气相聚合,基于聚合物多层模型,考虑催化剂颗粒间活性位初始浓度和粒径分布对聚合物分子量分布和粒径分布的影响,建立了聚合物分子量分布和粒径分布的数学模型。模拟了反应温度、催化剂颗粒间活性位初始浓度和粒径分布等因素的影响,结果表明。随着温度升高,聚合物颗粒平均粒径变小,粒径分布变窄,聚合物分子量变小,分子量分布变宽;催化剂颗粒间的活性组分负载越均匀,聚合物分子量越大,分子量分布和粒径分布越窄;随着催化剂平均粒径变大,聚合物分子量变小,分子量分布变宽,不存在催化剂颗粒粒径分布和聚合物颗粒粒径分布间的复制现象。模型模拟结果与实验结果吻合较好,可用于预测丁二烯气相聚合产物的分子量、分子量分布和粒径分布。     

气相法PE催化剂技术进展及研究设想

就国内外气相法ＰＥ催化剂的研究和技术进展进行综述，并对各种ＰＥ催化剂的制备和性能加以简要介绍，对齐鲁石油化工公司ＰＥ中试装置今后的研究工作提出的设想。     

气相法乙烯聚合铬系催化剂的性能研究

在小试及中试实验中,将ＱＣＰ－０１气相法铬系聚乙烯催化剂与工业Ｇ催化剂进行聚合活性及产物性能的对比,结果表明,改进后的ＱＣＰ－０１催化剂的催化均聚活性、共聚性能及聚合产物的主要性能均与Ｇ催化剂相当。     

Free Radical Polymerization of Acrylonitrile Using Potassium Peroxy Disulphate Initiator and a Phase Transfer Catalyst

Free radical polymerization of acrylonitrile with the di-site phase transfer catalyst 1,4-bis(tetramethylhexyl)ethylenediammonium bromide (TMHEDAB) was investigated using the water-soluble initiator PDS (potassium peroxydisulphate) and water-insoluble solvent ethylacetate in an aqueous-organic biphase system at 60±1°C under nitrogen atmosphere at fixed pH and ionic strength. Rp increased with the increase in concentration of the monomer, initiator and catalyst. The order of R_p, with respect to monomer and catalyst concentration was found to be unity and with respect to initiator was found to be 0.5. A suitable mechanism has been proposed and its significance was discussed. The polymers obtained were characterized by spectral studies such as FTIR, ¹H-NMR, XRD, DSC, and TGA.     

Ti—Mg催化剂乙烯气相聚合反应研究

研究了乙烯气相聚合Ｔｉ－Ｍｇ催化剂的聚合性能，常压气相聚合催化效率７～１１ｋｇＰＥ／ｇＴｉ，产物表观密度０．３０～０．３３ｇ／ｍｌ，产物颗粒２０～１２０目重量占８９％～９７％，加压搅拌床气相聚合，催化效率６１～８１ｋｇＰＥ／ｇＴｉ，产物表观密度０．３４～０．３５ｇ／ｍｌ，产物颗粒１０～１２０目重量占９１％～９６％。流化床惭烯／１－丁烯共聚合催化效率１００～１６９ｋｇＰＥ／ｇＴｉ，ＭＩ２．１６＝５．     

Radical Polymerization of n-BMA Using a Di-Site Phase Transfer Catalyst

The di-site phase transfer catalyzed radical polymerization of butyl methacrylate with the phase transfer catalyst N,N′-diheptyl-N,N,N′,N′-tetramethyl-1,2-ethanediammonium dibromide (DHTMEDADB) was carried out in an aqueous-organic biphase system at 60 ± 1°C under nitrogeneous atmosphere at fixed pH and ionic strength. A suitable kinetic scheme has been proposed and its significance was discussed. The polymers obtained were investigated and characterized (FTIR, ¹H-NMR and XRD studies).     

丁二烯聚合因素分析及预防措施

丁二烯聚合是影响装置运行质量的关键因素。分析了影响丁二烯聚合的因素,提出了通过控制系统中的氧及铁锈、减少设备管线死角、按量按点注入阻聚剂、采用新型阻聚剂和严格控制工艺操作条件等方法预防丁二烯聚合,保证装置的长周期运行,保证产品质量,杜绝安全事故的发生。     

镍系顺丁橡胶聚合反应控制探讨

本文主要结合茂名石化新开顺丁橡胶装置,通过顺丁橡胶聚合单元开车初期的调试,利用理论结合实践,总结聚合系统各组分催化剂之间的配方与通过不断调整各组分催化剂的配比积累的经验方法,探讨影响聚合反应的条件,优化控制项目,可更好地生产出优质门尼的顺丁橡胶,提高产品质量,使整个顺丁橡胶装置产生最佳的经济效益。     

环流流化床反应器中乙烯气相聚合反应研究

研究开发了１种新型的用于乙烯气相聚合反应的环流流化床反应器。通过对工业Ａ催化剂和实验室自制的ＱＣＰ－０１催化剂的乙烯气相聚合反应评价及聚合物产品的颗粒形态等方面的研究,认为环流流化床反应器具有聚合反应平稳、催化剂的聚合活性高、产品粒径分布均匀等特点,是１种具有良好应用前景的新型反应器。     

镍系丁二烯橡胶聚合反应影响因素及控制

聚合反应是生产丁二烯橡胶的核心工序,聚合反应进行的好坏,直接关系到橡胶的产量和质量。聚合反应的强弱受多种因素的影响,综合多种影响因素,将聚合反应控制稳定在指定的区间内,提高丁二烯橡胶的产品质量。通过聚合反应过程的分析,指出了影响聚合反应的因素,提出了几种控制聚合反应的强度的方法     

丁二烯气相聚合过程中的单体吸附效应和本征动力学模型

采用负载型稀土催化剂 ,在搅拌床反应器内进行丁二烯气相聚合动力学的研究 .考察了单体在聚合物小粒子中的吸附效应和单体压力与温度对聚合速率影响 ,在此基础上 ,提出了本体系的本征动力学模型     

低温乳聚丁苯橡胶反应器的稳态模拟

乳聚丁苯橡胶（ESBR）是最早实现工业化科耗量最大的合成橡胶胶种，对ESBR反应器的模拟一直是一难题。今在组分浓度分配、分析数据计算以及模型算法方面对现有反应器模型进行了改进，建立了能用于现场模拟的聚合釜模型。通过抽象为数个串联聚合釜的方法建立了置换塔模型，并确定了串联数目。讨论了总固体含量（TSC）和门尼粘度（ML）的模拟值与分析值间的差距，分析了引发剂、调节剂用量对ESBR产品质量的影响。结果表明，该模型能较好地反映和预测反应器的操作情况。     

乳化剂造成丁苯橡胶乳液聚合反应下降原因分析

乳化剂在丁苯橡胶低温乳液生产过程中起到至关重要的作用,它是保证聚合反应平稳进行的重要因素之一,其组成体系的参数波动会对聚合反应结果造成较大的影响,使得聚合反应胶乳的TSC和门尼值发生波动,甚至造成生产事故。对由乳化剂pH值和TSC波动造成聚合反应下降的原因做了分析。     

TiCl4/SiO2负载型催化剂用于丁二烯聚合Ⅱ.聚合条件及聚合动力学

使用以球磨法制备的 SiO2负载 TiCl4催化剂进行丁二烯溶液聚合,考察了聚合条件对催化效率的影响以及在 20～ 60℃下的聚合动力学。确定了适宜的聚合条件：以加氢汽油为溶剂, Al/Ti摩尔比为 20, Ti/Bd摩尔比为 2× 10－ 4, 50℃聚合 10 h以上。溶液聚合动力学研究结果表明,本体系在低转化率下为稳态聚合,其稳态聚合速率方程为 Rp=kpf[Ti]0[Bd],聚合的表观活化能为 11.4 kJ/mol。     

影响气相丙烯聚合反应的因素及改进措施

就聚丙烯装置的生产情况,分析了影响丙烯聚合反应的几个主要因素。通过降低原料杂质含量,选择合适的催化剂、改性剂、三乙基铝加入比例以及选择合适的反应温度、反应压力等措施来提高聚合反应的效率。