自由基引发剂对重油加氢裂化的影响研究

在高压釜式反应器中考察了添加过氧化特二丁基(DTBP)、偶氮二异丁腈(AIBN)和单质碘(I2)三种自由基引发剂对克拉玛依蜡油、孤岛减压渣油加氢裂化反应的影响。在氢气初始压力7.0 MPa,反应1 h的条件下,对引发剂用量、催化剂用量、反应温度等影响因素进行了考察。结果表明,添加自由基引发剂后,重油的加氢裂化转化率,轻质油收率以及HDS、HDN都明显增加。添加质量分数5 000×10-6或10 000×10-6引发剂后,蜡油和减压渣油加氢裂化的轻质油收率最大可增加10%、13%,HDS和HDN最大可增加11%和7%左右。采用较少的催化剂用量或较低的反应温度即可以实现较高的重油转化率和轻质油收率。相对而言,DTBP和I2的促进作用优于AIBN。添加引发剂前后的加氢裂化的产物分布对比说明,引发剂的加入有利于蜡油或渣油原料一次裂化产物的生成。     

减压渣油供氢剂减黏裂化研究

减黏裂化作为一种不生成焦炭的热加工方法主要涉及两类化学反应,裂解反应和缩合反应。裂解反应使减压渣油的平均分子量及其胶团直径变小,改善渣油的倾点和黏度;缩合反应使减压渣油及其中间产物中的芳烃、烯烃等缩合成大分子量产物,产生新的胶核,甚至生成焦炭。常规减黏裂化过程中,这两类化学反应主要与反应温度和反应时间有关。在热作用下渣油中的大分子裂解为H／C原子比相对较高的饱和烃自由基和H／C原子比相对较低的芳香性自由基。后者还可失去自身的环烷氢而使其H／C原子比进一步降低。如果体系中有足量的氢化芳烃存在,那么氢化芳烃分子上的活泼氢就可能转移到芳香性自由基的单电子位,将自由基封闭,从而阻止芳香性自由基之间的相互缩合,抑制使分子长大的缩合反应。如果体系中的氢化芳烃含量不足。则热反应体系中就没有足够的活泼氢将芳香性自由基封闭,芳香性自由基缩合反应的几率较高,造成过早地生焦。这种来自渣油分子自身的活泼氢的化学行为与渣油热反应生焦诱导期有一定关系。     

减黏裂化产物的长期储存稳定性

利用不同储存条件下,减黏产物运动黏度、酸值、质量损失、胶质和沥青质含量的变化,研究了委内瑞拉奥里常渣减黏产物长期储存稳定性的影响因素。结果表明,氧化缩聚、轻组分挥发和无氧缩聚作用影响减黏产物的长期储存稳定性,其中氧化缩聚作用最显著。热反应结束后,减黏产物中自由基并没有完全进行链终止反应,室温下自由基继续发生反应,减黏产物的稳定性与其中所含的自由基密切相关。不同储存条件下产物的沥青质和胶质的芳碳率均略低于减黏产物,沥青质间并没有发生缩聚,不易产生分层现象,减黏产物较稳定。     

双官能度自由基引发剂应用研究的进展

双官能度引发剂在自由基聚合中的应用不断受到重视，本文介绍了常用的双官能度引发剂，并综述了其在制备嵌段共聚物及引发乙烯类单体（如苯乙烯、氯乙烯、丙烯酰胺等）聚合的研究进展。     

引发剂结构对原子转移自由基聚合反应的影响

研究了三种不同结构的引发剂,溴代乙酸乙酯（EBrA)、α-溴代丁乙酯（EBrB)、α－溴代异丁酸乙酸（EBriB)引发的苯乙烯的原子转移自由基聚合反应（ATRP）。发现EBrA引发的苯乙烯的ATRP不是“活性”聚合。EBriB引发的苯乙烯的ATRP引发效率不够高,也不是典型的“活性”聚合。EBrB引发的苯乙烯的ATRP是较为典型的“活性”聚合：聚合物的分子量可以通过调节单体／引发剂的投料量及反应时间来控制,所得聚合物的分子量分布很窄,且有随转化率的增加而逐渐变窄的趋势。     

固体酸／碱和引发剂促进渣油轻质化的初步研究

在塔河常渣悬浮床加氢转化体系中，外加固体酸、固体碱和自由基引发剂的方法用于促进渣油轻质化。结果发现，固体酸USY、HY和固体碱CaO、MgO不同程度地改变了渣油加氢裂化反应的生焦率和裂化转化率，其中对于生焦率的促进效果明显。自由基引发剂偶氮二异丁腈和过氧化特二丁基显著改变了塔河常渣裂化产物分布，有效地促进了渣油热裂化反应。渣油加氢裂化产物中气体收率和生焦率略有增加，裂化产物收率明显上升，尾油收率明显下降。随着自由基引发剂质量分数的增加，上述变化趋势更加明显。低温下自由基引发剂的改善效果明显优于在较高温度下的的改善效果。就以上两种引发剂相比，过氧化特二丁基的作用明显优于偶氮异丁腈。     

催化剂和供氢剂对渣油模型化合物裂化反应选择性的影响

供氢剂与分散性催化剂协同作用对于传统的煤液化体系和渣油加氢裂化体系非常重要。通过活化分子氢及煤分子，使液化反应在较低的温度下进行以减少副反应，继而提高氢转移效率，增加液体产物产率。供氢剂和催化剂起促进煤分子裂化的作用。将供氢剂与催化剂的协同作用应用于渣油加     

环氧树脂的紫外光引发阳离子／自由基固化

研究了两类阳离子引发剂复合苯基硫钅翁盐和芳茂铁盐的紫外光引发活性以及它们分别与自由基引发剂的复合体系的增强光引发活性，并讨论了强氧化剂异丙苯过氧化氢对于芳茂铁盐引发效率的促进作用以及适量多元醇对于提高阳离子固化体系交联度所起的作用     

用稳定自由基聚合及光引发聚合制备嵌段共聚物

介绍了稳定自由基聚合的反应原理、引发剂设计，以及用稳定自由基聚合制备嵌段共聚物的几种方法：连续加料法、双官能团引发剂法和一步法。对于光引发聚合的原理及硫自由基的稳定性对聚合反应的影响也进行了讨论。     

自由基型光引发剂简介及研究进展

随着人们环保意识的提高,光聚合技术由于其高效、环保的优势,在近十多年来得到了蓬勃发展,成为目前最为先进的技术之一。本文介绍了在光聚合体系中作为关键组分的光引发剂的种类和作用机理,并重点综述了近几年来自由基型光引发剂的研究进展。     

委内瑞拉减压渣油供氢热转化基础研究

在热反应装置上考察了委内瑞拉合成原油减压渣油的供氢热转化与常规减黏裂化两种过程,利用显微镜观察了这两种反应体系的相态变化规律,研究了两种生成油的安定性并对两种残渣油的四组分组成进行了分析。结果表明,在反应温度为425℃时,随着反应时间的延长,采用显微镜能够清晰观察到无定型小体形成、长大及聚集的相态变化历程,两种过程残渣油的胶质与沥青质含量均呈下降趋势;相比常规减黏裂化,供氢热转化过程中供氢剂能够抑制无定型小体的长大、延缓相分离、抑制焦的形成、改善生成油安定性。     

Stable free radical polymerization of n-butyl acrylate in the presence of high-temperature initiators

Living radical polymerizations of acrylate are known to be difficult to achieve using TEMPO as a mediator. The stable free radical polymerization (SFRP) of acrylate tends to stop at low monomer conversion due to the accumulation of TEMPO in the medium as a result of unavoidable bimolecular termination. Rather than solving this problem by destroying the excess nitroxide using ascorbic acid or glyceraldehyde associated with pyridine as reported recently, high temperature initiators were used to slowly and continuously generate new radicals throughout the polymerization to consume the excess TEMPO molecules. Polymerizations of n-butyl acrylate initiated by the alkoxyamine unimer (1-benzoyloxy)-2-phenyl-2-(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)ethane (BST) were performed between 130 °C and 134 °C in the presence of a series of high temperature peroxide and azo initiators. The best results in this study were obtained by the continuous addition of small amounts of di-tert-amyl peroxide throughout the polymerization. Under these conditions, the acrylate polymerizations fulfilled the criteria of a controlled polymerization process although the molecular weight distributions were slightly broad (M_w/M_n ∼ 1.5).     

Decomposition kinetics of free radical initiators in micellar solutions

The kinetic parameters of thermal decomposition of initiators, azo-bis-isobutyronitrile (AIBN) and dicyclohexyl peroxydicarbonate (PC), have been measured in aqueous micellar solutions of sodium dodecylsulfate (SDS), cetyltrimethylammonium bromide (CTAB), and egg lecithin. The inhibitor technique and acceptors of free radicals have been used to estimate the efficiency of the initiation during AIBN decomposition. The rate constant of PC decomposition in a SDS micellar solution is the same as inn-decane. CTAB and lecithin accelerate the rate of PC decomposition. Mechanisms of surfactant effect on the PC decomposition are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1752–1757, October, 1994.The work was financially supported in part by the International Science Foundation (ISF) (Grant No. MAQ 000).     

Synthesis and radical polymerization properties of thermal radical initiators based on o‐imino‐isourea: The effect of the alkyl side chain on the radical initiation temperature

Four types of thermal radical initiators (TRIs) that are based on o‐imino‐isourea with cyclohexyl and isopropyl groups were successfully synthesized, namely, C‐HexDCC, DiiprDCC, C‐HexDIC, and DiiprDIC. The free radical polymerization and thermal properties of those synthesized TRIs were determined via differential scanning calorimetry (DSC) (using n‐butyl acrylate) and thermogravimetric analysis (TGA), respectively. The TRI derivatives showed peak temperatures (T_max) from 89 to 97 °C in n‐butyl acrylate, and DiiprDIC, with isopropyl groups on both sides of the N O group, showed the lowest peak temperatures. The rates of N O bond homolysis (k_d) of all the TRIs were calculated from their half‐lives determined using real‐time nuclear magnetic resonance (NMR) spectroscopy, and their theoretical bond dissociation energies (BDEs) were calculated using density functional theory (DFT) calculations. The free radical polymerization of n‐butyl acrylate using each TRI was efficiently determined from T_peak of the DSC curves; conversions depending on polymerization temperature (80, 90, and 100 °C) were monitored to observe kinetic information of TRIs during polymerization. Furthermore, to investigate the use of TRIs in curing, we applied them to an automotive clear coating system and monitored the real‐time evolution of the elastic modulus (G′) during thermal curing using a rheometer for representative DiiprDIC. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1749–1756     

HPLC-ECD检测羟自由基方法的研究

采用高效液相色谱结合库仑阵列多电极检测器体系(HPLC-ECD)建立了一套操作简便、高效、快速测定羟自由基的方法,并探究了检测的灵敏性,浓度和响应因子之间的线性关系,系统的稳定性等.2,3-二羟基苯甲酸(2,3-DHBA)、 2,5-二羟基苯甲酸(2,5-DHBA)以及水杨酸(SA)的相关系数分别为0.9999、 0.9996、 0.9968.2,3-DHBA和2,5-DHBA的检出限都低于0.1 ng/mL,SA的检出限均低于10 ng/mL,各种物质的方法回收率为100.5%～102.9%.