聚对苯二甲酸丁二醇酯二聚体热降解机理的理论研究

采用密度泛函理论(DFT)方法 M06-2X/6-311G(d)研究了聚对苯二甲酸丁二醇酯(PBT)二聚体的热降解机理,对PBT二聚体热解过程设计了八条可能反应路径,计算了每条反应路径的各基元反应步的热力学及动力学参数。计算结果表明,在PBT初始热解过程中,主链发生协同反应的反应能垒明显低于自由基反应的能垒,因此,通过协同反应生成的对苯二甲酸、对苯二甲酸单丁烯酯、对苯二甲酸二丁烯酯和二对苯二甲酸-1,4-丁二酯是PBT初始热解主要产物。主链通过六元环过渡态进行的协同反应的反应能垒低于通过四元环过渡态的,PBT主链的断裂主要通过六元环过渡态的协同反应而进行。此外,还讨论了PBT主要产物的二次降解反应,研究发现,在二次降解反应过程中主要以协同反应为主,生成1,3-丁二烯、四氢呋喃、苯、CO₂、苯甲酸等主要产物。     

阻燃高抗冲聚苯乙烯热降解研究

利用热失重-红外联用仪(TGA-IR)分析了高抗冲聚苯乙烯(HIPS)的热降解过程,结合热裂解气相色谱-质谱联用仪(Py-GC/MS)分析了HIPS的热裂解产物,利用化学方程式阐述了HIPS自由基降解反应.对十溴二苯乙烷、三氧化二锑复配阻燃体系的热降解过程进行了研究,讨论了阻燃HIPS的凝聚相阻燃、气相阻燃机理.实验表明,HIPS燃烧时主要发生β-断裂,大量烟雾主要由苯乙烯、甲苯、α-甲基苯乙烯、苯乙烷、丁二烯等组成,其中凝聚相主要是1,3,5-三苯基苯乙烯及其他部分低聚物.在不同的温度下,阻燃HIPS的热裂解产物不同,在较高的温度下,小分子化合物明显增多.     

硫代乙酰胺光化学反应机理的理论研究

用B3LYP, MP2和CASSCF方法, 采用cc-pVDZ和6-31++G**基组, 研究了硫代乙酰胺在基态和最低三态上消除硫化氢以及其它光解离反应, 并考虑了单个溶剂分子参与反应对质子迁移反应的影响, 得到了消除硫化氢反应的反应机理, 计算结果可以很好地解释实验结果. 进而用CASSCF方法计算了第一激发单态上的各驻点, 以及各交叉点. 计算结果表明, 在S1和T1态上发生除分子内转动以外的化学反应的可能性比较小, 当分子被激发到S2态上时, 将通过S2/S1交叉点到S1态, 在S1态上的分子有两条途径去活化, 通过S1/S0交叉点到热基态, 通过S1/T1交叉点系间窜越到T1态. 因而得出CH3CSNH2发生光解离反应的可能性不大. 基于此, 可将硫代酰胺结构引入蛋白或多肽中, 有望在不破坏分子整体结构的情况下对其进行光化学研究.     

CH_3SH+CN微观反应机理的理论研究

采用BMC-CCSD//B3LYP/6-311G(d,p)方法对CH3SH+CN反应机理进行了详细的理论研究.反应中涉及的各稳定点的构型、振动频率和零点能在B3LYP/6-311G(d,p)水平下计算得到,计算结果表明,该反应存在两种反应机理,5条可能的反应通道.SN2机理由于能垒太高,与直接氢抽提机理相比可以忽略.该反应的最可行通道为CN中的C原子进攻SH中的H原子经由一个前期和一个后期分子络合物生成产物CH3S和HCN.计算得到的反应焓变与已有实验值非常吻合.     

C_2H_3·与NO反应机理的理论研究

采用密度泛函B3LYP/6-311G**和高级电子相关耦合簇CCSD(T)/6-311G**方法计算研究了C2H3·与NO反应的机理,全参数优化了反应势能面上各物种的几何构型,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证.研究结果表明,C2H3·与NO是一多通道多步骤的反应,经过缔合、氢转移和离解等复杂过程,最终得到5种产物(P1～P5).     

基于DFT密度泛函理论的聚酯热降解反应机理研究

本文应用密度泛函理论（DFT）研究钛系催化剂催化聚酯热降解的反应机理。分别以Ti(OEt)4化合物以及Ti(OEt)3 阳离子化合物为催化剂,探讨了二苯甲酸乙二酯（EDB）解聚反应的Lewis酸催化热降解反应机理（M1机理）和烷氧基配位催化热降解反应机理（M2机理）。结果表明,Lewis酸催化热降解反应机理在两种催化剂下的解聚反应能垒与无催化剂反应非常相似,未表现出明显促进作用;Ti(OEt)3 催化剂在M2机理中明显降低了解聚反应能垒,是聚酯热降解反应的催化活性中心。经轨道相互作用分析发现,阳离子催化剂和反应物EDB之间存在较为明显的轨道相互作用。     

O(3P)+O2H→OH+O2反应机理的密度泛函理论研究

用密度泛函理论方法研究了O(3P)与O2H反应生成羟基和氧分子的反应机理. 在PW91/6-31+G水平上用梯度解析技术全自由度优化上述反应物、产物和反应路径上的中间体及过渡态几何构型, 并通过频率振动分析加以确认, 计算IRC反应路径及中间体异构化过程, 确定了此反应的可能反应通道. 结果表明: 该反应是多通道多步骤的强放热反应. 首先形成顺式或反式O3H富能中间体, 此过程无能垒; 然后跨过一个能垒分解成产物OH和O2. 通道IM1→TS1比IM2→TS2克服的能垒要大, 反应放热372.822 kJ*mol-1. IM1TS3IM2 可相互转化.     

气相中La催化乙烯脱氢及C-C键耦合的理论研究

采用密度泛函理论中的B3LYP方法研究了气相中过渡金属La在二、四重态势能面上催化C2H4的反应机理。全参数优化了二、四重态势能面上各个驻点的几何构型,同时对过渡态进行了频率分析,使用内禀反应坐标（IRC）方法验证了过渡态的准确性,通过AIM理论和NBO分析方法对主要的驻点进行了键分析,并对2IM1、2IM3进行了态密度分析。结果表明：La与C2H4的反应存在两种可能的路径,反应在二重态势能面上进行且均为放热反应。键分析表明初始复合物中La与C2H4分子之间为共价作用。     

己烷催化异构化反应中氢溢流机理的理论研究

采用密度泛函理论(DFT)在B3LYP/6-311++ G**//B3LYP/6-311G*水平下, 对正己烷(C6H14)催化异构化反应中的氢溢流机理进行了理论探讨. 通过对振动模式分析和内禀反应坐标(IRC)计算确认了各可能反应的过渡态. 同时在MP2/6-311++G**水平上对各驻点做了单点能计算和零点能校正, 计算出各反应通道的活化能, 进而确定了该反应的主反应通道, 其活化能为42.52 kJ/mol.     

F~2+2HCl→2HF+Cl~2反应机理的密度泛函理论研究

用密度泛函理论(DFT)B3LYP方法,在6-311G^*^*基组下,计算研究了反应F~2+2HCl→2HF+Cl~2的机理。求得各可能反应途径的系列过渡态,并通过振动分析和内禀反应坐标(IRC)分析加以证实。比较反应能垒(理论计算活化能)发现,标题反应若以分子与分子作用机理进行,则需克服的最大能垒为150.63kJ.mol^-^1;若以F~2分子先裂解为F原子再反应的机理进行,则需越过能垒154.82kJ.mol^-^1,求得反应F+HCl→HF+Cl的线形和三角形两种过渡态,以三角形较稳定;求得反应HCl+Cl→H+Cl~2的两种过渡态,以线形较稳定。     

半纤维素模型化合物热解机理的理论研究

针对半纤维素模型化合物4-O-甲基葡萄糖醛酸的热解,提出了六种可能的反应路径,对各种反应路径中的反应物、产物、中间体和过渡态的结构进行了几何结构全优化,计算了各步反应的标准动力学参数。结果表明,4-O-甲基葡萄糖醛酸热解时,首先通过分子内的氢原子转移发生开环反应而形成链状中间体,然后中间体进一步分解,主要产物是甲醇、乙醇醛、2-羟基-3-甲氧基丁醛酸、乙二醛和2-羟基丁醛酸等;主要的热解竞争产物是甲酸、CO_2、CO、4-羟基-3-丁烯酮和甲基乙烯醚等。在半纤维素的热解中,CO_2是通过不饱和反应物或中间体脱羧基反应而形成,乙酸则是通过脱O-乙酰基反应而形成。     

Investigation of the thermal degradation process of polystyrene brominated on the ring

The results of investigation of the degradation process of polystyrene brominated on the ring via an ionic route have been presented. Using thermogravimetric (TG) and differential thermal analysis (DTA) methods, the course of degradation of polymer samples with different bromine content has been described. Introducing of bromine on the aromatic ring influenced the initial decomposition temperature (IDT) and the temperature corresponding to the maximum of decomposition rate (T _m). The samples have been pyrolyzed at 300°C and some pyrolysis products were identified by means of gas chromatography/mass spectrometry. Finally, the possible mechanism of degradation was presented.     

O-乙酰基-吡喃木糖热解反应机理的理论研究

为了从微观上理解半纤维素热解过程及其主要产物的形成演变机理,采用密度泛函理论方法B3LYP/6-31G++(d,p),对O-乙酰基-吡喃木糖的热解反应机理进行了量子化学理论研究。在热解过程中,O-乙酰基-吡喃木糖中的O-乙酰基首先脱出,形成乙酸和中间体IM₁,该步反应能垒为269.4 kJ/mol。IM₁进一步发生开环反应形成IM₂,开环反应能垒较低,为181.8 kJ/mol。对中间体IM₂设计了四种可能的热解反应途径,对各种反应的反应物、产物、中间体和过渡态的结构进行了能量梯度全优化,计算了各热解反应途径的热力学和动力学参数。计算结果表明,反应路径(4)和反应路径(2)是O-乙酰基-吡喃木糖热解的主要反应通道,乙酸、乙醛、乙醇醛、丙酮、CO、CO₂、CH₄等小分子产物是热解的主要产物。这与相关实验结果分析是一致的。     

CHF_2CF_2CH_2OCHF_2与OH自由基反应机理的理论研究

采用从头算和密度泛函方法研究了多通道反应CHF2CF2CH2OCHF2+OH→产物的反应机理.首先在BMK/6-311+G(d,p)水平下优化了稳定点的几何构型并计算了振动频率;然后在BMC-CCSD水平下,对势能面进行高水平能量校正.结果表明,此反应存在提氢和取代两类反应通道,但是无论从动力学还是从热力学分析,提氢反应通道才是主要的反应通道,且从-CH2-基团上提取氢原子的提氢通道是主要的反应通道.     

Toward efficient functionalization of polystyrene backbone through ketene chemistry: Synthesis,characterization, and DFT study

In this study, polystyrene was functionalized with Meldrum's acid toward the introduction of the ketenes (CCO) system to its backbone for producing a dramatically reactive intermediate. Meldrum's acid, as a ketene source, was reacted by poly(styrene-co-p-chloromethyl styrene) through a simple nucleophilic reaction to synthesize poly(styrene-co-styryl Meldrum's acid). Then, the pendant Meldrum's acid under thermal treatment converted to ketene intermediate resulting in highly reactive polystyrenes derivatives, which rapidly reacted by nucleophilic reagents to afford ultimate organic building blocks. The polystyrene derivatives were characterized using elemental analysis, FT-IR, high-resolution solid-state NMR, thermogravimetric analysis (TGA), and differential thermogravimetric analysis (DTG). To clarify the evolutionary mechanisms of polystyrene products, density functional theory (DFT) method B3LYP with the 6–311++G(2d,p) basis set was used. We studied the preparation of polystyrene model compounds through Meldrum's acid thermolysis and nucleophilic substitution. The kinetic and thermodynamic parameters in all reactions and the structural and electronic properties of all molecules were calculated. These data exhibited that based on Gibbs Free energy values, the structure of syndiotactic polystyrene is more stable than that of isotactic polystyrene. Furthermore, it was found that the presence of an electron donor or acceptor substituent on the polystyrene structure affects the electronic bandgap.     

Theoretical study on the aggregation-induced emission mechanism of anthryl-tetraphenylethene

Since the concept of aggregation-induced emission (AIE) was proposed by Benzhong Tang's research group in 2001, the exploration of the mechanism of AIE and the development of new high-performance AIE materials have been the focus and goal of this field. On the basis of a large number of experiment results, AIE mechanism has been well explained by lots of works, such as restricted intramolecular motion (RIM), J-aggregate et al. As tetraphenylethlene (TPE) molecules are stacked, the rotation of the benzene ring rotor is blocked, and the energy attenuation is released in the form of radiation, showing the AIE effect. In order to further explore the AIE effect of TPE, we performed electronic structure, spectrum simulation, and AIE mechanism calculations of the anthryl-tetraphenylethene (TPE-an) monomer and dimer in the gas phase, tetrahydrofuran (THF), and aqueous solutions at the B3LYP/6-31G** level. The calculation results show that TPE-an molecule is in a propeller-like configuration, and its fluorescence intensity is weak; compared with the monomer, the fluorescence intensity of the dimer increases by 87% in aqueous solution; the fluorescence intensity in the gas phase, THF solution, and aqueous solution gradually enhances with the increase of the degree of aggregation, which are consistent with the experimental results. The enhancement of fluorescence intensity is caused by the change of molecular structure caused by aggregation. This detailed AIE luminescence mechanism will provide theoretical guidance for AIE material design.     

CH3SS与OH自由基反应机理的理论研究

应用密度泛函理论(DFT)对CH3SS与OH自由基单重态反应机理进行了研究.在B3PW91/6-311+G(d,p)水平上优化了反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型,用内禀反应坐标(IRC)计算和频率分析方法对过渡态进行了验证.在QCISD(T)/6-311++G(d,p)水平上计算了各物种的单点能,并对总能量进行了零点能校正.研究结果表明,CH3SS与OH反应为多通道反应,有5条可能的反应通道.反应物首先通过不同的S—O键相互作用形成具有竞争反应机理的中间体IM1和IM2.再经过氢迁移、脱氢和裂解等机理得到主要产物P1(CH2SS+H2O),次要产物P2(CH2S+HSOH),P3(CH3SH+1SO)和P4(CH2SSO+H2),其中最低反应通道的势垒为174.6kJ.mol-1.     

Mechanisms of thermal degradation of polystyrene,polymethacrylonitrile, and their copolymers on flash pyrolysis

The mechanism of thermal degradation of homopolymers of styrene (St) and methacrylonitrile (MAN) and their copolymers was investigated theoretically and experimentally by the pyrolysis gas chromatography using a Curie-point pyrolyzer. Poly(St-co-MAN)s generate dimers and trimers as well as monomers by flash pyrolysis. Parameter α was proposed to account for the competition between the back-biting reaction and depolymerization. The back-biting parameter α is defined as the ratio of rate constants, α = k_bb/k_dp, where k_bb is the rate constant for the back-biting reaction and k_dp is that for depolymerization. The back-biting process is followed by β-scission, where dimer and trimer are generated, and directly correlated with the C—H bond dissociation energies in the polymer chain. Using the back-biting parameter α, where 1/α is equal to the zip length n in depolymerization, the boundary effect for the difference of monomer yields from the homopolymers of St and MAN and their copolymers is well explained. The calculated values of boundary effect parameters, β_St and β_MAN, agreed well with the experimental results. It was found that thermal degradation mechanisms of homo- and copolymers of vinyl compounds can be analyzed comprehensively using the back-biting parameter α and the boundary effect parameter β. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2315–2330, 1998     

Catalytic degradation of polystyrene using HUSY catalysts

Summary The addition of carbon dioxide to phenyl glycidyl ether (PGE) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports : (1) soluble poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC) [C1], (2) insoluble poly(ST-DVB-VBC) [C2], (3) macroporous poly(ST-DVB-VBC) [C3], (4) poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC)-MMT [C4] (5) modified MCM-41 [C5]. The addition of carbon dioxide to PGE can be considered as a pseudo-first order process with respect to the concentration of PGE. The pseudo-first order rate constant for the catalysts decreased in the series C1&gt;C3&gt;C2&gt;C4&gt;C5. The activation energy for C1 to C5 catalysts was 8.6, 20.9, 19.9, 23.9, and 26.8 kJ/mol, respectively. The immobilized catalysts can be reused in least 4 successive runs without any considerable loss of their initial reactivities.