聚合物热分解机理的理论研究
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摘要
近年来,聚合物的热分解反应机理的理论研究成为最具活力的研究领域。本文对几类聚合物反应机理进行了计算和模拟。具体方法是以聚合物的重复单元作为计算模型,得到各类高聚物的结构特征量子化学参数,通过对聚合物单体反应机理的研究来探讨聚合物的相关反应机理。
本文采用量子化学方法系统研究了如下3个体系;(1)聚丁烯二酸二乙酯的热分解反应机理;(2)聚氯乙烯脱去氯化氢的热分解反应机理;(3)聚β-羟基丁二酸的热分解反应机理。
首先,对聚丁烯二酸二乙酯的热分解反应机理进行了理论研究。在HF/6-31G(d)和B3LYP/6-31G(d)水平上计算了3条可能的反应路径。他们分别是路径(Ⅰ),(Ⅱ)和(Ⅲ)。并且在相同水平上计算了聚丁烯二酸二乙酯热分解反应中反应物、过渡态和产物的平衡构型、振动频率和能量,并在B3LYP/6-31G(d)水平上经过内禀反应坐标(IRC)分析加以证实。结果表明,三条路径反应的活化能活化能遵从以下顺序:Ⅲ>Ⅱ>Ⅰ,因此路径(Ⅰ)为主要的反应路径。
其次,用密度泛函理论方法(B3LYP),在6-31G*水平上对聚氯乙烯(PVC)脱去氯化氢热分解反应的机理进行了理论研究,计算了3条可能的最低能量反应路径。计算了氯乙烯脱去氯化氢分子反应中反应物、过渡态和产物的平衡构型、振动频率和能量,并进一步在B3G3水平上进行了能量计算。经过内禀反应坐标分析(IRC)加以证实。结果表明氯化氢的催化作用作为离子反应机理是热分解反应的主要途径之一,在B3LYP/6-31G(d)水平上路径(2)和路径(3)的活化能分别是55.1 kcal/mol和41.5 kcal/mol。
最后,对聚β-羟基丁二酸的热分解反应机理进行了研究。采用密度泛函理论(DFT),在B3LYP/6-31G(d)水平上对反应过程中反应物、过渡态和产物的平衡构型、振动频率和能量进行了理论计算。结果表明此热分解反应经历了三个阶段的拉链式反应。产生反丁烯二酸,然后脱水生成酐。本文所建立的各种模型精确,可靠。本文从理论上对几种聚合物的热降解机理进行了分析和研究。结果表明密度泛函理论能够对聚合物热分解反应机理提供合理的几何结构和相对反应能量。为各种聚合物反应机理的理论探究也提供一定的指导作用。
Recently, the thermal decomposition mechanism of polymer mechanism becomes one of the most active fields. The chemical descriptors of polymers were choosed, used to calculate and predict the property or reaction mechanism of polymers. The quantum chemical descriptors or topology descriptors are obtained directly from repeating units of polymers. Discussing the reation mechanism from monomers of polymers, the calculated results indicate the mechanism of polymer. The paper applied the quantum methods and systematically studied the following three systems. (1) the thermal decomposition of model compounds for Poly (dialkyl fumarate), (2) the thermal dehydrochlorination of model compounds for poly (vinyl chloride), (3) the thermal decomposition of model compounds forβ-Poly (L-malate).
Firstly, the thermal decomposition of model compounds for poly (dialkyl fumarate) was investigated theoretically. The three minimum energy paths of the possible reactions were calculated at the HF/6-31G (d) and B3LYP/6-31G(d) levels. Three favorable paths were found (path (Ⅰ) , path (Ⅱ) and path (Ⅲ) ). Geometries, structures, and energies were evaluated for reactants, products, and transition states of the proposed pathways at the HF/6-31G (d) and B3LYP/6-31G (d) levels. The transition states of possible reaction pathways was obtained at B3LYP/6-31G (d) level and verified by internal reaction coordinate (IRC) analysis. The activation energies for the three reaction paths are in the following order:Ⅲ>Ⅱ>Ⅰ. It has been found that the path (Ⅰ) is considered as the main path for the thermal decomposition of model compounds for poly (dialkyl fumarate).
Secondly, the thermal decomposition mechanism of HCl elimination reaction of polyvinyl chloride (PVC) is investigated using density function theory with B3LYP/6-31G* method. The three minimum energy paths of the possible reactions were calculated. The geometries, structures, and energies were evaluated for reactants, products, and transition states of the proposed pathways at the B3LYP/6-31G(d) level. To obtain more reliable thermal enthalpies and activation energies, calculations were also carried out using the composite G3B3 approach. The transition state of possible reaction pathway was obtained and verified by internal reaction coordinate (IRC) analysis. The result shows that the ionic reaction mechanism of decomposition mechanism of HCl elimination reaction of vinyl chloride is a main reactive channel. The activation energies of path (2) and path (3) are 55.1 kcal/mol and 41.5 kcal/mol at the B3LYP/6-31G(d) level, respectively.
At last, the thermal decomposition of model compounds forβ-Poly (L-malate) was investigated theoretically. The geometries, structures, and energies were evaluated for reactants, products, and transition states of the proposed pathways at the B3LYP/6-31G(d) levels. It was found that poly (β, L-malic acid) depolymerized by an unzipping mechanism with generation of fumaric acid which is then partially converted in a mixture of maleic acid and anhydride.
The models in this paper are proved to be accurate and reliable. The thermal decomposition of model compounds for some polymers was investigated theoretically. The results indicate that the density functional theory can provide reasonable and relative energies, and it was applied for the theoretical study the thermal decomposition mechanism.
本文采用量子化学方法系统研究了如下3个体系;(1)聚丁烯二酸二乙酯的热分解反应机理;(2)聚氯乙烯脱去氯化氢的热分解反应机理;(3)聚β-羟基丁二酸的热分解反应机理。
首先,对聚丁烯二酸二乙酯的热分解反应机理进行了理论研究。在HF/6-31G(d)和B3LYP/6-31G(d)水平上计算了3条可能的反应路径。他们分别是路径(Ⅰ),(Ⅱ)和(Ⅲ)。并且在相同水平上计算了聚丁烯二酸二乙酯热分解反应中反应物、过渡态和产物的平衡构型、振动频率和能量,并在B3LYP/6-31G(d)水平上经过内禀反应坐标(IRC)分析加以证实。结果表明,三条路径反应的活化能活化能遵从以下顺序:Ⅲ>Ⅱ>Ⅰ,因此路径(Ⅰ)为主要的反应路径。
其次,用密度泛函理论方法(B3LYP),在6-31G*水平上对聚氯乙烯(PVC)脱去氯化氢热分解反应的机理进行了理论研究,计算了3条可能的最低能量反应路径。计算了氯乙烯脱去氯化氢分子反应中反应物、过渡态和产物的平衡构型、振动频率和能量,并进一步在B3G3水平上进行了能量计算。经过内禀反应坐标分析(IRC)加以证实。结果表明氯化氢的催化作用作为离子反应机理是热分解反应的主要途径之一,在B3LYP/6-31G(d)水平上路径(2)和路径(3)的活化能分别是55.1 kcal/mol和41.5 kcal/mol。
最后,对聚β-羟基丁二酸的热分解反应机理进行了研究。采用密度泛函理论(DFT),在B3LYP/6-31G(d)水平上对反应过程中反应物、过渡态和产物的平衡构型、振动频率和能量进行了理论计算。结果表明此热分解反应经历了三个阶段的拉链式反应。产生反丁烯二酸,然后脱水生成酐。本文所建立的各种模型精确,可靠。本文从理论上对几种聚合物的热降解机理进行了分析和研究。结果表明密度泛函理论能够对聚合物热分解反应机理提供合理的几何结构和相对反应能量。为各种聚合物反应机理的理论探究也提供一定的指导作用。
Recently, the thermal decomposition mechanism of polymer mechanism becomes one of the most active fields. The chemical descriptors of polymers were choosed, used to calculate and predict the property or reaction mechanism of polymers. The quantum chemical descriptors or topology descriptors are obtained directly from repeating units of polymers. Discussing the reation mechanism from monomers of polymers, the calculated results indicate the mechanism of polymer. The paper applied the quantum methods and systematically studied the following three systems. (1) the thermal decomposition of model compounds for Poly (dialkyl fumarate), (2) the thermal dehydrochlorination of model compounds for poly (vinyl chloride), (3) the thermal decomposition of model compounds forβ-Poly (L-malate).
Firstly, the thermal decomposition of model compounds for poly (dialkyl fumarate) was investigated theoretically. The three minimum energy paths of the possible reactions were calculated at the HF/6-31G (d) and B3LYP/6-31G(d) levels. Three favorable paths were found (path (Ⅰ) , path (Ⅱ) and path (Ⅲ) ). Geometries, structures, and energies were evaluated for reactants, products, and transition states of the proposed pathways at the HF/6-31G (d) and B3LYP/6-31G (d) levels. The transition states of possible reaction pathways was obtained at B3LYP/6-31G (d) level and verified by internal reaction coordinate (IRC) analysis. The activation energies for the three reaction paths are in the following order:Ⅲ>Ⅱ>Ⅰ. It has been found that the path (Ⅰ) is considered as the main path for the thermal decomposition of model compounds for poly (dialkyl fumarate).
Secondly, the thermal decomposition mechanism of HCl elimination reaction of polyvinyl chloride (PVC) is investigated using density function theory with B3LYP/6-31G* method. The three minimum energy paths of the possible reactions were calculated. The geometries, structures, and energies were evaluated for reactants, products, and transition states of the proposed pathways at the B3LYP/6-31G(d) level. To obtain more reliable thermal enthalpies and activation energies, calculations were also carried out using the composite G3B3 approach. The transition state of possible reaction pathway was obtained and verified by internal reaction coordinate (IRC) analysis. The result shows that the ionic reaction mechanism of decomposition mechanism of HCl elimination reaction of vinyl chloride is a main reactive channel. The activation energies of path (2) and path (3) are 55.1 kcal/mol and 41.5 kcal/mol at the B3LYP/6-31G(d) level, respectively.
At last, the thermal decomposition of model compounds forβ-Poly (L-malate) was investigated theoretically. The geometries, structures, and energies were evaluated for reactants, products, and transition states of the proposed pathways at the B3LYP/6-31G(d) levels. It was found that poly (β, L-malic acid) depolymerized by an unzipping mechanism with generation of fumaric acid which is then partially converted in a mixture of maleic acid and anhydride.
The models in this paper are proved to be accurate and reliable. The thermal decomposition of model compounds for some polymers was investigated theoretically. The results indicate that the density functional theory can provide reasonable and relative energies, and it was applied for the theoretical study the thermal decomposition mechanism.
引文
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