Characterization and Apparent Kinetics of Polymerization of 1-Decene Catalyzed by Boron Trifluoride/Alcohol System

Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol system. Gas chromatography–mass spectrometry, proton nuclear magnetic resonance and ^(13) C nuclear magnetic resonance analysis confirmed dimer, trimer and tetramer structures of PAO. Each component contained branched chains with a 1,2 insertion of a head-to-tail link; a 2,1 insertion of a tail-to-tail link and a methyl-containing linked structure. At a low conversion rate, the reaction rate was related directly with the reaction temperature and the catalyst/1-decene concentration. An apparent kinetic equation for PAO formation was determined during 1-decene polymerization.

Apparent Kinetics of 1-Decene Polymerization Catalyzed Using the Ionic Liquid[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]

Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.

Study on Kinetics of Dissolving Biomass Using Sodium Hypochlorite in the Recovery of Poly-β-hydroxybutyrate

The effects of sodium hypochlorite concentration in the recovery of poly-β-hydroxybutyrate (PHB) are investigated. A simple reaction equation and a mathematical model describe the reaction kinetics. Results showed that the stoichiometric coefficient increases with increasing CAO/CBO, where CAO is the concentration of the active chlorine at t = 0 and CBO is the initial concentration of the non-PHB materials.

立构嵌段聚丁二烯的研制——Ⅰ.立构二嵌段聚丁二烯的合成

用二哌啶乙烷(DPE)作为丁二烯阴离子聚合的调节剂,n-BuLi为引发剂,环己烷为溶剂,合成出1,2-结构含量为100％的1,2-聚丁二烯(1,2-PB)和1,2-1,4-立构二嵌段聚丁二烯(1,2-1,4-PB)。30℃聚合时,DPE/n-BuLi(mol比)从1.0增加到10.0,表观增长反应速度常数 k_p″下降 32％;60℃聚合时,下降 47％。当 DPE/n-BuLi分别为 1.0、5.0和 10.0时,表观活化能分别为55.4、42.9和24.9kJ/mo1。生成1,2-PB和1,2-1,4-PB中1,2-PB嵌段的k_p″基本相等。

镍体系催化丁二烯聚合速率的影响因素

研究了Ni(naph)_2-Al(i-Bu)_3-BF_3·OEt_2(Ni-Al-B)催化体系各组分浓度、配比及丁二烯初始浓度[Bd]_0等在较大范围变化时丁二烯聚合的动力学行为。结果表明,在不同的实验条件下均存在-d[Bd]/dt=K[Bd]的动力学关系。固定[Al],[B] 改变 [Ni],当Al/Ni=6～16(摩尔比)时,K值无明显变化,表明体系中存在Ni(0),Ni(I)过量值。[Bd]_0提高,K值增大,Bd对活性中心稳定有利。

LLDPE prepared by in situ polymerization using a dual-functional catalytic system of Ti(On-Bu)_4 /AlEt_3-Et(Ind)_2-ZrCl_2/MAO

Linear low-density polyethylene (LLDPE) was prepared by in situ polymerization using a dual-functional catalytic system containing Et(Ind)2ZrCl2/MAO and Ti(On-Bu)4 /AlEt3 used as co-polymerization catalyst and dimeriza-tion catalyst, respectively. The catalytic system showed high activity and the polymer with low melting point, narrow molecular weight distribution (MWD) and low crystallinity was produced.

我国镍系顺丁橡胶聚合过程的工程分析及其改进 Ⅰ.釜式反应器聚合工艺

根据我国镍系顺丁橡胶的生产数据和工艺方案,对釜式丁二烯聚合工艺进行了动力学分析和工程分析。由分析结果推断,镍系催化剂的催化活性具有依温性和依时性两大特性,而釜式反应器的热不穗态操作特性则是过程偏离优化操作的主要根源。