新型金属钴催化剂催化亚胺与一氧化碳的交替共聚及相关反应的研究
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摘要
多肽作为一种重要的生物高分子材料,在生命系统起着重要的作用,在材料、催化、制药等应用领域有着广泛的应用。多年以来,多肽的合成一直是人们研究的热点,关于多肽的合成也有很多方法,但几乎所有的方法都是以氨基酸为原料,来构建肽的结构。这些传统的合成方法不仅在原子经济性上有很大的不足,产生大量的副产物,而且步骤繁琐,价格昂贵。近些年来,受到烯烃和一氧化碳在金属催化剂的催化下生成聚酮类的高分子聚合物的启发,科学家们便开始尝试用相似结构的亚胺与一氧化碳交替共聚合成多肽高分子材料,而这些研究的关键就是找到一种合适的催化剂。
本课题组在2007年曾首次报道了金属钴催化剂成功地催化了亚胺与CO的交替共聚。在此基础上,本文对该催化反应所用的钴催化剂的种类进行拓展,开发出新的具有更好的物理及化学性能的催化剂。同时,还通过原位红外技术对聚合反应所涉及的机理及动力学进行了广泛的研究。此外,实现了活性聚合并得到了含有不同肽链结构的嵌段共聚物。具体研究内容如下：
1.开发出了五种稳定的可以催化亚胺与CO交替共聚的催化剂,其中三种为首次分离得到的酰基四羰基钻化合物,我们对其分别进行了X-ray单晶衍射分析,确定了它们的酰基四羰基钴结构,同时还分离鉴定了它们对应的三苯基膦配位的酰基钻结构并对它们的结构进行了对比。对几种催化剂的催化性能进行了评价,其中三种催化剂表现出活性聚合的特征,催化脂肪系亚胺与CO共聚得到的聚合物的分子量分布都比较窄。特别是第Ⅱ代催化剂44是专门为了解决24在聚合刚开始时的引发问题而设计并合成的,使得该聚合反应真正成为活性聚合。
2.利用原位红外技术研究了从烷基钴23到酰基钴24的转化动力学,测定了该反应的热力学参数及动力学参数,利用所得热力学参数解释了实验过程中观察到的平衡移动现象。测得的动力学活化参数呈现出较低的能垒(17.8Kcal mol-1),表明羰基化反应很容易发生,这对于以后的聚合机理的研究有重要的指导意义。
3.利用原位红外技术监测了聚合反应的过程并测定了聚合反应的反应动力学。分别测定了反应对亚胺、CO、催化剂的反应级数及不同反应溶剂中聚合反应的速度及聚合效果,测定了30-80℃范围内各温度下的反应速率常数,并运用Eyring方程测定了反应的活化吉布斯自由能为20.4Kcal mol-1。
4.通过实验发现24催化的聚合物的分子量随转化率的增加而线性增加,而且可以得到端基功能化的聚合物,判定了该聚合反应已经具备活性聚合的必要条件。接下来进行了嵌段聚合的实验,运用原位红外监测技术通过分批加入单体的方法得到了一条聚合物链中含有不同肽链结构的嵌段共聚物。聚合物的分子量随嵌段数的增加而线性增加,但是分子量分布略宽,主要是由于在聚合的第一阶段存在的引发过程导致的。为了消除引发过程对聚合活性的影响,设计并合成了具有一个聚合物结构单元的第Ⅱ代催化剂44。用原位红外监测44催化亚胺与CO的交替共聚反应发现已经完全没有了引发过程。得到的聚合物的分子量分布都是比较窄的,特别是得到的嵌段聚合物的分子量分布也是很窄的,而且聚合物的分子量更接近于理论分子量。所以可以认为最终我们实现了该新型聚合反应的活性聚合并得到了嵌段聚合物。
利用化合物44进行了聚合物端基的研究。结果表明44可以很容易的与苄胺、甲醇、水等亲核试剂反应,生成相应的酰胺、酯和羧酸化合物,在此指导下又得到了端基分别为酯基及羧基的端基功能化的多肽聚合物。我们还分离得到了44缓慢分解生成的产物49,化合物49的五元环的恶唑烷酮结构对我们进一步完善聚合反应的机理起到了关键的作用。
最终在结合之前所有的实验现象并参考本课题组理论计算的结果的基础上,确定了整个聚合反应过程的反应机理。
Polypeptides are important biopolymers that play an important role in biological systems as well as in fields of applications such as materials, catalysis and pharmaceuticals. Over the past years, very useful methods have been developed for polypeptide synthesis.But most of the methods are based on the use of amino acids as starting materials, which require expensive cost and tedious procedures alongwith large amount of by-products. Inspired by the well-studied copolymerization of alkenes and CO to produce polyketones, chemists had attempted to find a suitable catalyst to catalize the copolymerization of imines and CO to produce polypeptides. Our group have reported the first copolymerization of imines with CO using a cobalt catalyst. Based on this successful study, we have expanded the type of new cobalt catalyst with highly stability and efficiency in this thesis. Additionally, a study of the mechanism and kinetics of the carbonylation as well as polymerization were carried out extensively by utilizing in situ IR technique. Moreover, living polymerization research was carried out and block polymers containing different peptide chains were obtained. Details are listed as follows:
1. A total of5new cobalt catalysts with highly stability were developed,3of which were first isolated as acyl cobalt tetracarbonyls and their structure were determined by X-ray diffraction as well as their PPh3derivatives. Catalytic performances of the five catalysts were evaluated and three of them displayed characteristics of living polymerization behavior. Especially for complex44, which was designed for eliminating the initiation of the polymerization, was found as a real living catalyst.
2. In situ IR technique was employed to study the kinetics of transformation from alkyl cobalt23to acyl cobalt24. Thermodynamic and kinetic parameters of the reaction were determined. Activation of kinetic parameters presented a low energy barrier (17.8Kcal mol-1), which was in accordance with the experimental observations that the carbonylation reactions occurs easily. This research exhibited important guiding significance for the further study of the polymerization mechanism.
3. The mechanism and kinetics study of polymerization reaction was carried out by ultlizing in situ IR technique. The reaction orders on imine, CO, catalyst as well as the solvent dependence were determined respectively. An Eyring plot was carried out by determining the rate constants at varying temperature from30to80℃and provided an energy barrier20.4Kcal mol-1.
4. Complex24exhibited a living behavior which typically showed a linear increase of molecular weight with conversion and end-functionalized polypeptides was generated. Block copolymerization was carried out via sequential monomer addition, which was monitored by in situ IR, generating block copolymers containing different peptides in a polymer chain. The polymer showed a linear increase of molecular weight with block number but exhibited somewhat broadened molecular weight distributions, which was mainly due to the initiation in the first stage of the polymerization process. In order to eliminate the influence of initiation on polymerization activity, the second generation catalyst44was designed and synthesized. As expected, no initiation was observed during the copolymerization processure. The polymer, especially for the block copolymers, showed narrow polydispersities and molecular weight was more agreement with the theoretical value. Thus,44exhibited true living behavior. Research of polymer end group was also carried out using complex44. The results indicated that44could easily react with nucleophilic reagent such as benzylamine, methanol and water, providing the corresponding amide, ester and carboxylic acid compounds. We also isolated compound49from the slow decomposition of44. The five membered ring oxazolidinone structure of compound49played a key role in completing the mechanism of polymerization. Finally, on the basis of combining the experiment observations and kinetic parameters as well as the results of theoretical calculation, the reaction mechanism of the polymerization process is completed.
本课题组在2007年曾首次报道了金属钴催化剂成功地催化了亚胺与CO的交替共聚。在此基础上,本文对该催化反应所用的钴催化剂的种类进行拓展,开发出新的具有更好的物理及化学性能的催化剂。同时,还通过原位红外技术对聚合反应所涉及的机理及动力学进行了广泛的研究。此外,实现了活性聚合并得到了含有不同肽链结构的嵌段共聚物。具体研究内容如下：
1.开发出了五种稳定的可以催化亚胺与CO交替共聚的催化剂,其中三种为首次分离得到的酰基四羰基钻化合物,我们对其分别进行了X-ray单晶衍射分析,确定了它们的酰基四羰基钴结构,同时还分离鉴定了它们对应的三苯基膦配位的酰基钻结构并对它们的结构进行了对比。对几种催化剂的催化性能进行了评价,其中三种催化剂表现出活性聚合的特征,催化脂肪系亚胺与CO共聚得到的聚合物的分子量分布都比较窄。特别是第Ⅱ代催化剂44是专门为了解决24在聚合刚开始时的引发问题而设计并合成的,使得该聚合反应真正成为活性聚合。
2.利用原位红外技术研究了从烷基钴23到酰基钴24的转化动力学,测定了该反应的热力学参数及动力学参数,利用所得热力学参数解释了实验过程中观察到的平衡移动现象。测得的动力学活化参数呈现出较低的能垒(17.8Kcal mol-1),表明羰基化反应很容易发生,这对于以后的聚合机理的研究有重要的指导意义。
3.利用原位红外技术监测了聚合反应的过程并测定了聚合反应的反应动力学。分别测定了反应对亚胺、CO、催化剂的反应级数及不同反应溶剂中聚合反应的速度及聚合效果,测定了30-80℃范围内各温度下的反应速率常数,并运用Eyring方程测定了反应的活化吉布斯自由能为20.4Kcal mol-1。
4.通过实验发现24催化的聚合物的分子量随转化率的增加而线性增加,而且可以得到端基功能化的聚合物,判定了该聚合反应已经具备活性聚合的必要条件。接下来进行了嵌段聚合的实验,运用原位红外监测技术通过分批加入单体的方法得到了一条聚合物链中含有不同肽链结构的嵌段共聚物。聚合物的分子量随嵌段数的增加而线性增加,但是分子量分布略宽,主要是由于在聚合的第一阶段存在的引发过程导致的。为了消除引发过程对聚合活性的影响,设计并合成了具有一个聚合物结构单元的第Ⅱ代催化剂44。用原位红外监测44催化亚胺与CO的交替共聚反应发现已经完全没有了引发过程。得到的聚合物的分子量分布都是比较窄的,特别是得到的嵌段聚合物的分子量分布也是很窄的,而且聚合物的分子量更接近于理论分子量。所以可以认为最终我们实现了该新型聚合反应的活性聚合并得到了嵌段聚合物。
利用化合物44进行了聚合物端基的研究。结果表明44可以很容易的与苄胺、甲醇、水等亲核试剂反应,生成相应的酰胺、酯和羧酸化合物,在此指导下又得到了端基分别为酯基及羧基的端基功能化的多肽聚合物。我们还分离得到了44缓慢分解生成的产物49,化合物49的五元环的恶唑烷酮结构对我们进一步完善聚合反应的机理起到了关键的作用。
最终在结合之前所有的实验现象并参考本课题组理论计算的结果的基础上,确定了整个聚合反应过程的反应机理。
Polypeptides are important biopolymers that play an important role in biological systems as well as in fields of applications such as materials, catalysis and pharmaceuticals. Over the past years, very useful methods have been developed for polypeptide synthesis.But most of the methods are based on the use of amino acids as starting materials, which require expensive cost and tedious procedures alongwith large amount of by-products. Inspired by the well-studied copolymerization of alkenes and CO to produce polyketones, chemists had attempted to find a suitable catalyst to catalize the copolymerization of imines and CO to produce polypeptides. Our group have reported the first copolymerization of imines with CO using a cobalt catalyst. Based on this successful study, we have expanded the type of new cobalt catalyst with highly stability and efficiency in this thesis. Additionally, a study of the mechanism and kinetics of the carbonylation as well as polymerization were carried out extensively by utilizing in situ IR technique. Moreover, living polymerization research was carried out and block polymers containing different peptide chains were obtained. Details are listed as follows:
1. A total of5new cobalt catalysts with highly stability were developed,3of which were first isolated as acyl cobalt tetracarbonyls and their structure were determined by X-ray diffraction as well as their PPh3derivatives. Catalytic performances of the five catalysts were evaluated and three of them displayed characteristics of living polymerization behavior. Especially for complex44, which was designed for eliminating the initiation of the polymerization, was found as a real living catalyst.
2. In situ IR technique was employed to study the kinetics of transformation from alkyl cobalt23to acyl cobalt24. Thermodynamic and kinetic parameters of the reaction were determined. Activation of kinetic parameters presented a low energy barrier (17.8Kcal mol-1), which was in accordance with the experimental observations that the carbonylation reactions occurs easily. This research exhibited important guiding significance for the further study of the polymerization mechanism.
3. The mechanism and kinetics study of polymerization reaction was carried out by ultlizing in situ IR technique. The reaction orders on imine, CO, catalyst as well as the solvent dependence were determined respectively. An Eyring plot was carried out by determining the rate constants at varying temperature from30to80℃and provided an energy barrier20.4Kcal mol-1.
4. Complex24exhibited a living behavior which typically showed a linear increase of molecular weight with conversion and end-functionalized polypeptides was generated. Block copolymerization was carried out via sequential monomer addition, which was monitored by in situ IR, generating block copolymers containing different peptides in a polymer chain. The polymer showed a linear increase of molecular weight with block number but exhibited somewhat broadened molecular weight distributions, which was mainly due to the initiation in the first stage of the polymerization process. In order to eliminate the influence of initiation on polymerization activity, the second generation catalyst44was designed and synthesized. As expected, no initiation was observed during the copolymerization processure. The polymer, especially for the block copolymers, showed narrow polydispersities and molecular weight was more agreement with the theoretical value. Thus,44exhibited true living behavior. Research of polymer end group was also carried out using complex44. The results indicated that44could easily react with nucleophilic reagent such as benzylamine, methanol and water, providing the corresponding amide, ester and carboxylic acid compounds. We also isolated compound49from the slow decomposition of44. The five membered ring oxazolidinone structure of compound49played a key role in completing the mechanism of polymerization. Finally, on the basis of combining the experiment observations and kinetic parameters as well as the results of theoretical calculation, the reaction mechanism of the polymerization process is completed.
引文
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