负载双核茂金属催化剂催化乙烯聚合反应动力学研究

以SiO2为载体,制备了负载的双核茂金属[（η5-C5H5）Zr Cl2]2[μ,μ-（SiMe2）2（η5-allyl C5H2）2]/MAO/SiO2催化剂,以己烷为溶剂进行了淤浆条件下乙烯聚合反应,研究了扩散因素、乙烯聚合压力和聚合温度对乙烯淤浆聚合动力学参数的影响,测定了聚合反应级数和表观活化能,采用动力学和相对分子质量法计算了负载催化剂的活性中心浓度,并对链增长速率常数等动力学参数进行了计算.结果表明,以负载双核茂金属催化剂催化乙烯淤浆聚合反应速率对单体浓度呈1.11级依赖,反应活化能Ea为72.47 kJ/mol,活性中心浓度C＊为0.33 mol/mol,链增长速率常数Kp为1.06×106L.（mol.h）-1.     

Pt/Al2O3蜂窝状催化剂上NO选择性催化还原反应动力学研究

采用多次涂层和浸渍法制备了蜂窝状Pt/Al2O3催化剂，并在高空速和大气体流量条件下对无梯度循环式反应器和积分反应器上催化剂的活性进行了比较。同时采用循环式反应器对动力学数据进行了测定。根据Langmuir-Hinshelwood模型和实验结果，推测了NO-C3H6-O2体系的SCR反应机理，并导出了NO和C3H6反应速率的数学表达式。据此所计算的理论模拟值能够与实验值很好地吻合。实验结果表明，氧气浓度对NO和C3H6的反应速率有明显的影响，二者均随着氧浓度c (O2)的增加达到峰值，再增加氧气浓度时，C3H6的反应速率r(C3H6)保持不变，而NO反应速率r (NO)却下降，而且下降的程度随着温度的升高而加剧。同时，随着氧气浓度增加，r (NO)达到最大值时的温度亦随之下降。     

甲烷氧化偶联制烯烃的热力学平衡限度

选择适宜的热力学模型对甲烷氧化偶联制烯烃体系的热力学平衡进行分析，考察温度﹑压力﹑进料组成对体系组分的平衡限度影响。研究发现，在甲烷氧化偶联制烯烃体系中，H2、CO的生成相对容易，C2产物（C2H4、C2H6）不容易生成。通过计算，得到了该体系有利于烯烃生成的反应条件，500℃～800℃、1.5MPa、烷氧摩尔比为7。实验为甲烷氧化偶联反应器和催化剂的开发研究提供热力学依据。     

一种后过渡金属催化剂催化乙烯低聚动力学研究

设计并合成了一种新型的后过渡金属铁络合物 { [(2 ArNC(Me) ) 2 C5H3N]FeCl2 } (Ar =2 ,4 C6 H4(CH3) 2 ) ,研究了该络合物 甲基铝氧烷 (MAO)催化乙烯低聚 ,讨论了低聚反应温度、Al Fe摩尔比、催化剂浓度、反应压力等对催化剂活性及反应速率的影响 .本催化剂的最大特点是活性高 (在 30℃ ,3 0MPa时活性可达 4 2 6× 10 8goligomer·molFe·h- 1 )、初速度大 ,动力学曲线为衰减型 .     

侧链取代基含有氧原子的环戊二烯与席夫碱混合配体的镧系化合物催化甲基丙烯酸甲酯聚合

侧链取代基含有氧原子的环戊二烯与双水杨醛邻环己二胺席夫碱混合配体的镧系化合物[(η5:η1-MeOCH2CH2C5H4)Ln][(μ:η-OC20H20N2O)]2[(η5-MeOCH2CH2C5H4)Ln](Ln=Sm(1),Dy(2)),[(MeOCH2CH2C5H4)2Yb]2(OC20H20N2O)(3),[(C4H7OCH2C5H4)2Dy]2(OC20H20N2O)(4)与三乙基铝体系催化甲基丙烯酸甲酯(MMA)的聚合,可以得到高分子量(粘均分子量Mη>100,000),窄分子量分布(Mw/Mn<3)的聚甲基丙烯酸甲酯(PMMA).不同茂环上的取代基及稀土元素使这类化合物形成了不同的分子结构,并且影响了它们的催化活性.化合物(3)具有较高的活性(转化率∶54.1%,Mη=287.1×103).考察了催化剂浓度,助催化剂浓度,聚合温度和时间对化合物(3)/Al(Et)3体系催化聚合反应的影响,最佳聚合条件为:60℃,24h,MMA∶催化剂∶助催化剂(摩尔比)=1000∶1∶10.利用核磁,凝胶渗透色谱仪(GPC)等对聚合物进行表征.     

组合催化剂上丙烷选择氧化制丙烯酸

考察了在C3H8氧化脱氢的NiZrO催化剂和C3H6选择氧化的Mo基催化剂组成的组合催化剂上C3H8选择氧化制取丙烯酸的反应性能.结果表明,两个催化剂比例适当时,反应的丙烯酸收率可达最大.优化温度、烷氧比、空速以及N2含量等反应条件的结果发现,反应体系中O2的匮乏会严重影响反应性能.在有氧分布器的反应装置中对所选组合催化剂在优化的反应条件下进行了30h稳定性测试,结果表明,在340oC,反应性能基本稳定,C3H8转化率和丙烯酸选择性可分别维持在～20%和～74%.     

含分子内配位Ln←O键的稀土有机化合物催化甲基丙烯酸甲酯聚合

 采用含有分子内配位Ln←O键、茂(茚)和环辛四烯(COT)混合配体的稀土有机化合物与三乙基铝体系催化甲基丙烯酸甲酯(MMA)的聚合,可以得到高分子量(Mη＞100×103),窄分子量分布(Mw/Mn＜3)的聚甲基丙烯酸甲酯(PMMA). 不同的配体及稀土元素可以影响这类稀土有机化合物的催化聚合活性. 化合物(η5-MeOCH2CH2C5H4)Nd(η8-C8H8)(THF)具有较高的活性(转化率91.0%,Mη=115.2×103). 考察了催化剂和助催化剂浓度,以及聚合温度和时间对(η5-cyclo-C4H7OCH2C9H6)Dy(η8-C8H8)/AlEt3体系催化聚合反应的影响. 结果表明,最佳聚合条件为: n(MMA)∶n(催化剂)∶n(助催化剂)=1?200∶1∶5,θ=60 ℃,t=32 h. 利用核磁共振和凝胶渗透色谱等技术对聚合物进行了表征.     

钙钛矿型La0.8Sr0.2FeO3中的晶格氧用于甲烷选择氧化制取合成气

 用自燃烧法制备了钙钛矿型La0．8Sr0．2FeO3催化剂．用H2－TPR考察了催化剂表面的氧消耗过程，用程序升温表面反应（TPSR）研究了甲烷与催化剂表面氧物种的反应，用在线质谱脉冲反应和甲烷／氧切换反应研究了催化剂的晶格氧选择氧化甲烷制合成气．结果表明，催化剂上存在两种氧物种，无气相氧存在时，强氧化性氧物种首先将甲烷氧化为CO2和H2O；而后提供的氧化性较弱的晶格氧具有良好的甲烷部分氧化选择性，可将甲烷氧化为合成气CO和H2（选择性可达95％以上）．在900℃下的CH4／O2切换反应结果表明，甲烷能与La0．8Sr0．2FeO3中的晶格氧反应选择性地生成CO和H2，失去晶格氧的La0．8－Sr0．2FeO3能与气相氧反应恢复其晶格氧．在合适的反应条件下，用La0．8Sr0．2FeO3催化剂的晶格氧代替分子氧按Redox模式实现甲烷选择氧化制合成气是可能的．     

含氮原子桥联吡咯基稀土金属双核配合物的合成及催化ε-己内酯的开环聚合反应

RE(CH2SiMe3)3(THF)2和1.5 equiv.(C4H3NHCH2)2NCH3(1)反应合成得到含氮原子桥联吡咯基稀土金属双核配合物[η1∶η1∶η1-(C4H3NCH2)2NCH3]RE{μ-η5∶η5∶η1-(C4H3NCH2)2NCH3}RE[η1∶η1∶η1-(C4H3NCH2)2NCH3](THF)[RE=Y(2),Er(3),Yb(4)],所得配合物经过核磁共振、红外和元素分析表征,配合物2和4经单晶X-Ray进一步确认结构.同时研究了稀土配合物作为单一组分催化剂催化ε-内酯的开环聚合反应.     

新型二茂锆化合的（1，2—Ph2—4—PrCp）2ZrCl2的合成及催化烯烃聚合反应研究

3，4－二苯基环戊－2－烯－1－酮与丙基锂反应，经酸化脱水得新环戊二烯衍生物1，2－二苯基－4－丙基－1，3－环戊二烯（1）。用丁基锂处理1得到相应的环戊二烯基锂，再与ZrCl4在甲苯中反应，在立体阻碍二氯二茂锆化合物（1，2－Ph2-4-PrCp)2ZrCl2（2）。化合物和2均经元素分析和核磁共振谱学表征。经甲基铝氧烷（MAO）活化，化合物2在较低Al/Zr比条件下既可有效地催化乙烯聚合，生成高分子量，高熔化温度聚乙烯。2／MAO体系对丙烯聚合表现出高活性，生成低分子量齐聚物，其分子量随聚合温度的降低而升高。     

Coordination polymerization at very low amounts of methylaluminoxane as cocatalyst

The effect of very low amounts of methylaluminoxane as an activating cocatalyst in the coordination polymerization has been investigated in the syndiospecific polymerization of styrene with a half-sandwich metallocene catalyst in the presence of triisobutylaluminum at molar ratios of methylaluminoxane/transition metal from 0/1 to about 20/1 in comparison to the polymerization behavior at high molar methylaluminoxane (MAO)/metal ratios.As a result, there cannot be observed any polymerization reaction below a true molar ratio MAO/Ti of 6:1. At higher molar ratios until about 20, the polymerization conversion is increasing significantly with the MAO/Ti molar ratio.These observations and the results of the determination of the kinetic reaction order can be explained with Barron’s tert-butyl aluminoxane based model of MAO as a cage of six monomeric MAO units (AlOMe)₆ in contrast to Sinn’s MAO model of a cage of twelve monomeric units (AlOMe)₁₂ and are discussed with the results received at usually applied much higher MAO/transition metal ratios leading to a first-order dependence of the polymerization rate on the MAO concentration.From the thermal behavior of the syndiotactic polystyrenes synthesized it can be concluded, that the stereospecificity of the polymerization reaction is not affected by MAO at low MAO concentrations.     

自缩合乙烯基聚合体系中的环化效应

基于超支化高分子的生长代数模型,利用Monte Carlo模拟方法研究了不同溶剂条件下自缩合乙烯基聚合(SCVP)体系的环化效应.根据SCVP体系的反应机理给出含环反应的微分动力学方程,并通过环化反应的内在特征确定了分子间反应和内环化反应的速率常数.在此基础上,利用Monte Carlo模拟方法得到了高分子的数量分布函数、重均分子量、环数以及含环分子的链段分数等相关物理量,分析了环化效应对于体系平均物理量的影响.进一步根据模拟结果对单体浓度和溶剂效应等对内环化反应的影响予以分析.结果表明,环化效应取决于单体浓度和溶剂效应之间的协同作用,其中单体浓度在环化反应中起着主导作用.     

甲基铝氧烷的改性及其对乙烯聚合催化活性的影响

用BCl3为修饰剂制备了改性甲基铝氧烷(BMAO) 以二氯二茂锆为主催化剂、BMAO为助催化剂,考察了影响乙烯聚合活性的各种因素及其聚合动力学行为 与常用的甲基铝氧烷(MAO)相比,BMAO用于催化体系显著提高了乙烯聚合的催化活性.     

Kinetics and mechanisms of emulsion polymerization initiated by oil-soluble initiators. IV. Kinetic modeling of unseeded emulsion polymerization of styrene initiated by 2,2′-azobisisobutyronitrile

To explain the kinetic features of particle formation and growth in unseeded emulsion polymerization initiated by oil-soluble initiators, a mathematical kinetic model is proposed, based on the assumption that when initiator radicals or monomer radicals in the water phase enter monomer-solubilized emulsifier micelles, initiate polymerization, and propagate to a chain length which is long enough not to desorb from the micelles, the micelles are regarded to be transformed into polymer particles. It is demonstrated by comparing the experimental results obtained in the emulsion polymerization of styrene initiated by the oil-soluble initiator, 2,2'-azobisisobutyronitrile, with sodium lauryl sulfate as emulsifier that the proposed kinetic model satisfactorily explains the kinetic features such as the effects of initial emulsifier, initiator, and monomer concentrations on both the number of polymer particles produced and the monomer conversion versus time histories. © 1993 John Wiley & Sons, Inc.     

用甲基铝氧烷活化的氯化稀土催化剂合成高顺式窄分布聚丁二烯

以NdCl3.4L(配体L为膦酸三丁酯TBP、膦酸三苯酯TPP、膦酸二异辛酯P204)为主催化剂(简称[Nd])、甲基铝氧烷(MAO,简称[Al])为助催化剂和环己烷为溶剂,进行1,3-丁二烯聚合的研究.考察了配体对丁二烯聚合反应活性的规律及MAO用量、催化剂陈化时间、溶剂种类对聚合的影响;并对聚合物进行NMR,IR和GPC的表征.结果表明,3种配体的聚合活性顺序为TBP>P204>TPP;当[Al]/[Nd]为30时,聚合物的分子量分布指数达到1.20;30℃陈化时,聚丁二烯cis-1,4结构均大于97%;与正己烷、甲苯溶剂对比来看,环己烷体系所得聚合产物的分子量分布相对较窄、产率较高.     

Modeling of Ethylene Polymerization Kinetics over Supported Chromium Oxide Catalysts

Summary: Silica supported chromium oxide catalysts have been used for many years to manufacture polyethylene and they still account for more than 50% of world production of high‐density polyethylene. Along with its commercial success, the catalytic mechanism and polymerization kinetics of silica supported chromium oxide catalysts have been the subject of intense research. However, there is a lack of modeling effort for the quantitative prediction of polymerization rate and polymer molecular weight properties. The chromium oxide catalyzed ethylene polymerization is often characterized by the presence of an induction period followed by a steady increase in polymerization rate. The molecular weight distribution is also quite broad. In this paper, a two‐site kinetic model is developed for the modeling of ethylene polymerization over supported chromium oxide catalyst. To model the induction period, it is proposed that divalent chromium sites are deactivated by catalyst poison and the reactivation of the deactivated chromium sites is slow and rate controlling. To model the molecular weight distribution broadening, each active chromium site is assumed to have different monomer chain transfer ability. The experimental data of semibatch liquid slurry polymerization of ethylene is compared with the model simulations and a quite satisfactory agreement has been obtained for the polymerization conditions employed.

Polymerization rates at different reaction temperatures: symbols – data, lines – model simulations.     

负离子引发丙烯腈沉淀聚合动力学研究

从负离子引发丙烯腈沉淀聚合的亚微观过程出发,建立了动力学模型,并通过初生态沉淀聚集体联结方法数的叠加,推导出了动力学方程.在不同条件下(单体浓度、引发剂浓度、时间)对丙烯腈沉淀聚合进行了研究,用推导的动力学方程处理数据后发现实验数据与理论相吻合.丙烯腈负离子沉淀聚合的聚合反应为对单体浓度的一级反应,对引发剂浓度的一级反应,反应速率方程为Rp=k0[M]1.0[I]1.0.     

Use of block copolymer surfactants in the inverse-suspension polymerization of acrylamide

A comprehensive experimental investigation of the inverse microsuspension polymerization of acrylamide using an oil-soluble initiator and a block copolymeric surfactant whose hydrophobic miety is poly(12-hydroxystearic acid) and whose hydrophilic moeity is polyethylene oxide was carried out. It was found that the initial polymerization rate was first order with respect to molar monomer concentration, first order with respect to molar initiator concentration and zeroth order with respect to molar emulsifier concentration. Based on these experimental findings, a mechanism was proposed which includes initiation, propagation transfer to monomer and termination. It also includes transfer to impurities which are believed to be found in the surfactant. The kinetic model developed from the proposed mechanism is found to be in good agreement with the experimental conversion and weight-average molecular weight data. Comparing with sorbitan esters of fatty acids, the copolymeric surfactant provides higher polymerization rate and very high and linear molecular weight comparable to those obtained by solution polymerization.     

活化/失活反应对原子转移自由基共聚产物微观结构的影响

提出了一个可以处理原子转移自由基共聚及其产物微结构的模型,采用计算机模拟产生了包括活化/失活反应的ATRcP稳态增长反应链,得到了有关链段分布的信息.模拟发现,含有休眠过程的ATRcP产物与常规的自由基的相比组成结构和序列结构完全一致,即活化/失活反应不影响ATRcP产物的微组成与微序列结构.     

A new kinetic model for bulk polymerization of vinyl chloride based on two-phase hypothesis

A kinetic model has been developed for the bulk polymerization of vinyl chloride using Talamini's hypothesis of two-phase polymerization and a new concept of kinetic solubility which assumes that rapidly growing polymer chains have considerably greater solubility than the thermodynamic solubility of preformed polymer molecules of the same size and so can remain in solution even under thermodynamically unfavourable conditions. It is further assumed that this kinetic solubility is a function of chain length. The model yields a rate expression consistent with the experimental data for vinyl chloride bulk polymerization and moreover is able to explain several characteristic kinetic features of this system. Application of the model rate expression to the available rate data has yielded 2.36 × 10⁸l mol^?1 sec^?1 for the termination rate constant in the polymer-rich phase; as expected, this value is smaller than that reported for homogenous polymerization by a factor of 10–30.