跳跃二烯烃提氢反应的机理研究
发布时间：2018-10-11 12:12
【摘要】：研究目的跳跃二烯烃的两个双键是孤立二烯烃中距离最短的,其双键之间亚甲基上的碳氢键的键能低具有很高的反应活性,因而备受关注,本文通过不同类型的氢受体与跳跃二烯烃反应力求深入研究提氢反应的反应机制,研究氢供体构型、氢受体类型以及取代基对反应热力学属性与动力学参数的影响,进一步研究结构与反应之间的关系,揭示原子转移反应的本质。研究方法本文采用量子化学中密度泛函理论(DFT)的B3LYP泛函在6-31g(d)基组和6-311++g(d,p)基组上优化反应物与产物的结构,得到相应的能量,用M062X泛函在6-311++g(d,p)基组上计算激发态的相关能量,采用Ki SThel P程序计算反应速率常数和隧穿因子,利用Multiwfn程序得到基态到激发态的电子密度差图和基态到相应激发态的跃迁密度矩阵图。以氢转移反应作为研究对象,对比线性过渡态(TS)与非线性TS的差别,探讨氢供体的刚性与柔性对提氢反应的影响,根据激发态硫杂蒽酮类(TXs)光引发剂(PI)与亚油酸甲酯(MLO)和油酸甲酯(MO)的反应,研究光活性三线态物质引发的提氢反应的具体机理。通过对不同类型的提氢反应的研究加深对氢原子转移反应机理的理解。通过实时红外法研究硫醇-烯烃聚合动力学,选择油酸蔗糖酯(O-170)、1,10-癸二硫醇(DDT)与1173或二苯甲酮(BP)这两个体系,研究不同浓度的组分、不同PI、不同光照时间、不同光照强度和不同单体对转化率的影响。实验结果由2,5-庚二烯(HD)与苯甲酰自由基(BR)类型氢受体反应为模型,根据Boltzmann分布和裂解能计算结果判断2,5-庚二烯的最稳定构型为HD(Boltzmann分布所占百分比为85.04%,BDE为68.7kcal/mol)。BR常来源于裂解型PI的光解,如1173,184,2959等,其中2959的键裂解能最低(61.3kcal/mol),三甲基苯甲酰自由基(TMBR)常来源于含磷裂解型PI的光解,如TPO,TPO-L和BAPO等,其中BAPO的C-P键裂解能最低(59.6kcal/mol)。BR与氢供体反应TS夹角在误差范围内可视为拟线性TS,三甲基BR与氢供体反应TS夹角为非线性。根据内禀反应坐标(IRC)得到从反应物复合物到鞍点的活化能、形变能和相互作用能随反应进程的关系图,结果显示随着反应进程的推进,活化能和形变能逐渐升高,而相互作用能则逐渐下降。非线性TS反应的活化能和形变能高于拟线性TS反应。根据键能键级(BEBO)理论,得到拟线性TS反应裂键指数比非线性TS小,根据Evans-Polanyi关系,得到拟线性TS反应Polanyi因子比非线性TS大。这些数据表明:非线性TS构型与反应物复合物更接近,为似反应物型,而拟线性TS构型与产物复合物更接近,为产物型。Ki SThel P程序计算结果显示,自由基诱发的提氢反应隧穿因子较大(3.5-4.0),而光活性三线态硫杂蒽酮类诱导的提氢反应隧穿因子较小(1.1-1.8),接近于自由基加成反应(1.1)。拟线性TS反应速率常数比非线性TS大3-4个数量级。根据M062X泛函在6-311++g(d,p)基组上计算光活性三线态氢受体(TXs)的垂直激发能、绝热激发能和重组能,结果表明,三线态的垂直激发能与绝热激发能小于单线态的垂直激发能与绝热激发能,而三线态的重组能则大于单线态,由此证实,三线态的反应活性远远大于基态。由Multiwfn程序得到跃迁密度矩阵图和电子密度差图,结果显示TXs从基态到激发态,主要是羰基上的电子激发,反应位点以羰基基团为主。三线态与基态的键角键长发生了改变,推测是由于电子结构重新排布的结果。TXs分别与MO和MLO反应,与MLO反应的活化能较小,反应速率常数较大。所有TS角均在线性误差范围内,均为拟线性TS。与自由基诱发的提氢反应相比,光活性三线态物质诱发的提氢反应的相互作用能较大,是活化能的重要组成部分。1173裂解产生的BR与DDT反应的活化能大于BP与DDT反应的活化能。实时红外研究结果表明,转化率和反应速率受反应物种类、反应物浓度、光照强度、光照时间等的影响。O-170、DDT与1173或BP三体系中,O-170、DDT、1173/BP摩尔比为反应摩尔比2:2:4时,1173体系转化率与反应速率均达到最大,若1173过量或不足,则反应速率与转化率均下降,但BP过量时,转化率与反应速率继续升高;若DDT不足,转化率随DDT浓度下降而下降,DDT的浓度对转化率和反应速率的影响,BP体系比1173体系更明显;若O-170不足反应摩尔比时,转化率反而下降,O-170的浓度对转化率和反应速率的影响,BP体系比1173体系更明显;相同配比时1173体系的转化率大于BP体系的转化率。结论由变形能相互作用能模型和BEBO理论得知,非线性TS反应的活化能和变形能比拟线性TS反应大,非线性TS出现比拟线性TS推迟出现,此外,由于变形受限,反应物的刚性与柔性会影响TS出现的早晚。TXs PI的电子激发主要集中在两个苯环间的羰基上,单线态激发能高于三线态,三线态重组能较大,由于电子结构的改变,最优三线态几何构型与基态时相比发生了改变,使三线态羰基夺取氢原子的能力增强。三线态TXs PI与跳跃二烯间的亚甲基氢反应时TS的出现比与普通双键?位的亚甲基的反应更早,活化能更低,反应速率更快,光活性三线态诱导的提氢反应,TS基本都呈线性。光照时间越长,转化率越高;光照强度越大,反应速率越快;BP难溶于O-170和DDT混合物中,故O-170、DDT与1173配方优于O-170、DDT与BP配方。
[Abstract]:The two double bonds of the jump diolefins are the shortest in isolated diolefins, and the bond energy of the carbon hydrogen bonds between the double bonds of the two double bonds is low and has very high reaction activity, The effects of hydrogen donor configuration, hydrogen acceptor type and substituent on reaction thermodynamic properties and kinetic parameters were studied by different types of hydrogen acceptors and hopping diolefin reactions, and the relationship between structure and reaction was further studied. The essence of atom transfer reactions is revealed. In this paper, the structure of reactants and products is optimized in 6-31g (d) group and 6-311 ++ g (d, p) groups by using the B3LYP functional theory of quantum chemistry intermediate density functional theory (DFT). The electron density difference map of the ground state to the excited state and the transition density matrix of the ground state to the corresponding excited state are obtained by using the Ki SThel P program. Based on the difference between the linear transition state (TS) and the non-linear TS, the influence of the rigidity and flexibility of the hydrogen donor on the hydrogen-stripping reaction was discussed. The specific mechanism of hydrogen-stripping reaction initiated by optically active triplet state substance was studied according to the reaction of the excited state sulfur heteropolyketone (TXs) photoinitiator (PI) with methyl linoleate (MLO) and methyl oleate (MO). The understanding of hydrogen atom transfer reaction mechanism is deepened through the study of different types of hydrogen stripping reactions. By studying the polymerization kinetics of thiol-olefins by real-time infrared method, the two systems of sucrose ester (O-170), 1, 10-dithiodithiol (SO) and 1173 or benzophenone (BP) were selected to study the components of different concentrations, different PI and different illumination time. Effects of different light intensity and different monomer on conversion rate. The experimental results were determined by the reaction of 2,5-heptalene (HD) with the benzene-free radical (BR) type hydrogen acceptor, and the stable configuration of 2,5-heptalene was determined according to Boltzmann distribution and pyrolysis energy. The most stable configuration of the 2,5-heptalene was HD (85. 04% for Boltzmann distribution and 68. 7mol/ mol for BDE). BR often comes from photolysis of lysing PI, such as 1173, 184, 2959, etc., where 2959 bond cleavage can be the lowest (61. 3mol/ mol), and trimethylbenzene free radical (TMBR) is often derived from photolysis of phosphorus-containing cleavage type PI, such as TPO, TPO-L and BAPO, etc. The cleavage energy of the C-P bond of BAPO can be the lowest (59. 6mol/ mol). The included angle of the reaction TS of BR and hydrogen donor can be regarded as quasi-linear TS in the error range, and the included angle between trimethylBR and hydrogen donor is non-linear. According to the intrinsic reaction coordinate (IRC), the activation energy, deformation energy and interaction energy from the reactant complex to the saddle point are obtained. The results show that the activation energy and deformation can be gradually increased with the advancing of the reaction process, and the interaction energy gradually decreases. The activation energy and deformation of the nonlinear TS reaction can be higher than that of the quasi-linear TS. According to the key-energy-key-level (BEBO) theory, the quasi-linear TS reaction crack bond index is smaller than that of the non-linear TS, and the proposed linear TS reaction Polanyi factor is larger than the non-linear TS according to the Langmuir-Polanyi relation. These data indicate that the non-linear TS configuration is closer to the reactant complex and is of a quasi-reactant type, while the proposed linear TS configuration is closer to the product complex as a product type. The results of the Ki-SThel P program show that the radical-induced hydrogen-stripping reaction tunnel wear factor is large (3,5-4.0), while the photoreactive triplet sulfur heteropolyketide-induced hydrogen-stripping reaction tunnel wear factor is smaller (1,1-1.8), close to the free radical addition reaction (1,1). The quasi-linear TS reaction rate constant is 3-4 orders of magnitude larger than the non-linear TS. The vertical excitation energy, adiabatic excitation energy and recombination energy of photoreactive triplet hydrogen receptors (TXs) were calculated on 6-311 ++ g (d, p) groups according to the M062X functional group. The results show that the vertical excitation energy and adiabatic excitation energy of triplet states can be less than the vertical excitation energy and adiabatic excitation energy of singlet state. The recombination energy of triplet state is larger than singlet state, thus confirming that the reaction activity of triplet state is far greater than the ground state. The transition density matrix diagram and the electron density difference map are obtained by the Multiwfn program. The results show that the TXs is excited from the ground state to the excited state, mainly the electron excitation on the electron beam, and the reaction site is mainly composed of the chromophore group. The bond length of the three-wire state and the ground state has changed, presumably due to the re-arrangement of the electronic structure. TXs were reacted with MO and MLO respectively, and the activation energy of the reaction with MLO was small and the reaction rate constant was large. All TS angles are within the linear error range and are quasi-linear TS. Compared with free radical-induced hydrogen-stripping, the interaction energy of the hydrogen-assisted reaction induced by the photoactive triplet state substance can be larger, which is an important part of the activation energy. The activation energy of the BR and the hydrogen cyanide reaction generated by the pyrolysis of 1173 is greater than the activation energy of the BP and the hydrogen cyanide reaction. The results of real-time infrared studies show that the conversion rate and reaction rate are influenced by reactant species, reactant concentration, illumination intensity, illumination time, etc. When the molar ratio of O-170, 1173, and 1173/ BP was 2: 2: 4, the conversion rate and reaction rate of 1173 system reached the maximum. If 1173 excess or insufficient, the reaction rate and conversion rate were all decreased, but when BP was over, the conversion rate and reaction rate continued to increase. If the reaction rate was insufficient, Compared with 1173 system, the conversion rate and the reaction rate decreased, the conversion rate decreased, and the concentration of O-170 was more obvious than 1173 system. The conversion rate of 1173 system was higher than that of BP system at the same ratio. The results show that the activation energy and deformation of the non-linear TS reaction can be compared with the linear TS due to the interaction energy model of the deformation energy and the BEBO theory, and the non-linear TS is compared with the linear TS. In addition, due to the limited deformation, the rigidity and flexibility of the reactant affect the occurrence of TS. The electron excitation of TXs PI is mainly focused on the triplet state between the two benzene rings, the excitation energy of singlet state can be higher than triplet state, the recombination energy of triplet state can be larger, because of the change of the electronic structure, the optimal three-wire state geometry is changed compared with the ground state, The ability to capture hydrogen atoms in triplet states is enhanced. The ratio of the presence of TS to the normal double bond at the time of the methylene-hydrogen reaction between the three-wire TXs PI and the hopping diene? The reaction of methylene in position is earlier, the activation energy is lower, the reaction rate is faster, the photoactivity triplet state induced hydrogen stripping reaction, TS is basically linear. The longer the illumination time, the higher the conversion rate, the higher the illumination intensity, the faster the reaction rate, the higher the BP difficult to dissolve in the O-170 and the water-soluble mixture, so the O-170, the BSF and 1173 formulations are better than the O-170, the Nafion and the BP formula.
【学位授予单位】：广州医科大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25
本文编号：2264147
[Abstract]:The two double bonds of the jump diolefins are the shortest in isolated diolefins, and the bond energy of the carbon hydrogen bonds between the double bonds of the two double bonds is low and has very high reaction activity, The effects of hydrogen donor configuration, hydrogen acceptor type and substituent on reaction thermodynamic properties and kinetic parameters were studied by different types of hydrogen acceptors and hopping diolefin reactions, and the relationship between structure and reaction was further studied. The essence of atom transfer reactions is revealed. In this paper, the structure of reactants and products is optimized in 6-31g (d) group and 6-311 ++ g (d, p) groups by using the B3LYP functional theory of quantum chemistry intermediate density functional theory (DFT). The electron density difference map of the ground state to the excited state and the transition density matrix of the ground state to the corresponding excited state are obtained by using the Ki SThel P program. Based on the difference between the linear transition state (TS) and the non-linear TS, the influence of the rigidity and flexibility of the hydrogen donor on the hydrogen-stripping reaction was discussed. The specific mechanism of hydrogen-stripping reaction initiated by optically active triplet state substance was studied according to the reaction of the excited state sulfur heteropolyketone (TXs) photoinitiator (PI) with methyl linoleate (MLO) and methyl oleate (MO). The understanding of hydrogen atom transfer reaction mechanism is deepened through the study of different types of hydrogen stripping reactions. By studying the polymerization kinetics of thiol-olefins by real-time infrared method, the two systems of sucrose ester (O-170), 1, 10-dithiodithiol (SO) and 1173 or benzophenone (BP) were selected to study the components of different concentrations, different PI and different illumination time. Effects of different light intensity and different monomer on conversion rate. The experimental results were determined by the reaction of 2,5-heptalene (HD) with the benzene-free radical (BR) type hydrogen acceptor, and the stable configuration of 2,5-heptalene was determined according to Boltzmann distribution and pyrolysis energy. The most stable configuration of the 2,5-heptalene was HD (85. 04% for Boltzmann distribution and 68. 7mol/ mol for BDE). BR often comes from photolysis of lysing PI, such as 1173, 184, 2959, etc., where 2959 bond cleavage can be the lowest (61. 3mol/ mol), and trimethylbenzene free radical (TMBR) is often derived from photolysis of phosphorus-containing cleavage type PI, such as TPO, TPO-L and BAPO, etc. The cleavage energy of the C-P bond of BAPO can be the lowest (59. 6mol/ mol). The included angle of the reaction TS of BR and hydrogen donor can be regarded as quasi-linear TS in the error range, and the included angle between trimethylBR and hydrogen donor is non-linear. According to the intrinsic reaction coordinate (IRC), the activation energy, deformation energy and interaction energy from the reactant complex to the saddle point are obtained. The results show that the activation energy and deformation can be gradually increased with the advancing of the reaction process, and the interaction energy gradually decreases. The activation energy and deformation of the nonlinear TS reaction can be higher than that of the quasi-linear TS. According to the key-energy-key-level (BEBO) theory, the quasi-linear TS reaction crack bond index is smaller than that of the non-linear TS, and the proposed linear TS reaction Polanyi factor is larger than the non-linear TS according to the Langmuir-Polanyi relation. These data indicate that the non-linear TS configuration is closer to the reactant complex and is of a quasi-reactant type, while the proposed linear TS configuration is closer to the product complex as a product type. The results of the Ki-SThel P program show that the radical-induced hydrogen-stripping reaction tunnel wear factor is large (3,5-4.0), while the photoreactive triplet sulfur heteropolyketide-induced hydrogen-stripping reaction tunnel wear factor is smaller (1,1-1.8), close to the free radical addition reaction (1,1). The quasi-linear TS reaction rate constant is 3-4 orders of magnitude larger than the non-linear TS. The vertical excitation energy, adiabatic excitation energy and recombination energy of photoreactive triplet hydrogen receptors (TXs) were calculated on 6-311 ++ g (d, p) groups according to the M062X functional group. The results show that the vertical excitation energy and adiabatic excitation energy of triplet states can be less than the vertical excitation energy and adiabatic excitation energy of singlet state. The recombination energy of triplet state is larger than singlet state, thus confirming that the reaction activity of triplet state is far greater than the ground state. The transition density matrix diagram and the electron density difference map are obtained by the Multiwfn program. The results show that the TXs is excited from the ground state to the excited state, mainly the electron excitation on the electron beam, and the reaction site is mainly composed of the chromophore group. The bond length of the three-wire state and the ground state has changed, presumably due to the re-arrangement of the electronic structure. TXs were reacted with MO and MLO respectively, and the activation energy of the reaction with MLO was small and the reaction rate constant was large. All TS angles are within the linear error range and are quasi-linear TS. Compared with free radical-induced hydrogen-stripping, the interaction energy of the hydrogen-assisted reaction induced by the photoactive triplet state substance can be larger, which is an important part of the activation energy. The activation energy of the BR and the hydrogen cyanide reaction generated by the pyrolysis of 1173 is greater than the activation energy of the BP and the hydrogen cyanide reaction. The results of real-time infrared studies show that the conversion rate and reaction rate are influenced by reactant species, reactant concentration, illumination intensity, illumination time, etc. When the molar ratio of O-170, 1173, and 1173/ BP was 2: 2: 4, the conversion rate and reaction rate of 1173 system reached the maximum. If 1173 excess or insufficient, the reaction rate and conversion rate were all decreased, but when BP was over, the conversion rate and reaction rate continued to increase. If the reaction rate was insufficient, Compared with 1173 system, the conversion rate and the reaction rate decreased, the conversion rate decreased, and the concentration of O-170 was more obvious than 1173 system. The conversion rate of 1173 system was higher than that of BP system at the same ratio. The results show that the activation energy and deformation of the non-linear TS reaction can be compared with the linear TS due to the interaction energy model of the deformation energy and the BEBO theory, and the non-linear TS is compared with the linear TS. In addition, due to the limited deformation, the rigidity and flexibility of the reactant affect the occurrence of TS. The electron excitation of TXs PI is mainly focused on the triplet state between the two benzene rings, the excitation energy of singlet state can be higher than triplet state, the recombination energy of triplet state can be larger, because of the change of the electronic structure, the optimal three-wire state geometry is changed compared with the ground state, The ability to capture hydrogen atoms in triplet states is enhanced. The ratio of the presence of TS to the normal double bond at the time of the methylene-hydrogen reaction between the three-wire TXs PI and the hopping diene? The reaction of methylene in position is earlier, the activation energy is lower, the reaction rate is faster, the photoactivity triplet state induced hydrogen stripping reaction, TS is basically linear. The longer the illumination time, the higher the conversion rate, the higher the illumination intensity, the faster the reaction rate, the higher the BP difficult to dissolve in the O-170 and the water-soluble mixture, so the O-170, the BSF and 1173 formulations are better than the O-170, the Nafion and the BP formula.
【学位授予单位】：广州医科大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25
【参考文献】
相关期刊论文 前5条
1 韦美菊;贾德强;陈飞武;;TiO_2基态和激发态的几何结构、激发能和偶极矩[J];物理化学学报;2013年07期
2 马玉臣;刘成卜;;研究激发态的多体格林函数理论[J];化学进展;2012年06期
3 孙倩;王金婷;张立敏;杨茂萍;;光致噻吨酮与胺类、酚类、醇类的电子转移和氢转移反应[J];物理化学学报;2010年09期
4 王金婷;孙倩;葛爱民;潘洋;张立敏;俞书勤;;核苷酸和芳香酮的电子转移和质子转移反应研究[J];光谱学与光谱分析;2010年04期
5 郭银明;张教强;杨永峰;唐晓春;陈少杰;;巯基/烯紫外光聚合反应体系的研究及其应用[J];中国胶粘剂;2008年06期
相关硕士学位论文 前2条
1 徐冰冰;硫醇/烯类单体的光聚合研究[D];北京化工大学;2013年
2 陈丽云;脂肪替代品——蔗糖多油酸酯的合成方法及分析研究[D];暨南大学;2001年
，本文编号：2264147
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2264147.html
教材专著
