聚烯烃弹性体自由基历程改性的化学流变学研究
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摘要
在聚合物反应加工过程中,聚合物材料及其它组成物的各尺度内部结构经历着复杂的物理与化学变化,构成了强烈的非线性问题。除了化学反应本质因素外,外加流场的作用影响在聚合物加工过程中也是十分重要的,这使得聚合物熔体反应时的化学流变学是需解决的核心科学问题之一。流场对于聚烯烃反应加工的影响显而易见,但对于流场作用下的自由基反应机理与动力学理论体系以前并没有建立,这是聚合物反应加工当前的一个研究工作热点与前沿课题,具有重要的理论意义和重要的工程应用背景。本文以聚烯烃弹性体(Polyolefin elastomer, POE)熔体的均相自由基反应过程为研究对象(POE/DCP),通过化学流变学方法,对该过程中流场对反应机理、反应速率、反应物大分子链拓扑结构的影响开展了研究,发现了静态条件下POE自由基反应的一些新的机理与动力学历程,提出了简单剪切流场中POE自由基反应机理,揭示了流场作用下大分子链运动对化学反应的影响,创立了一种表征长支链聚烯烃分子结构的流变学方法,初步实现了通过反应加工流场控制POE产物拓扑结构。本论文主要研究内容及结果如下:
1.静态下通过顺磁共振方法有效识别了POE/过氧化物反应体系中各种自由基信号的超精细结构与强度的变化,首次发现了对应于叔碳自由基的7线EPR信号,得出了反应过程中伯碳自由基的出现及其持续的时间强烈依赖于聚烯烃中共聚单体含量的结论;但是除偶合与歧化双基终止反应外,并没有观测到降解反应的存在。结合EPR数据和在线流变测量对整个反应过程进行了动力学过程分析,运用大分子反应动力学理论,分析得出了偶合与歧化反应速率系数随体系粘度增大而减小的动力学方程。研究结果表明,反应受大分子链扩散过程控制,高浓反应体系的偶和速率系数与粘度之间的标度关系与低于理论预测值,系为很高的体系粘度降低反应链扩散系数所致。
2.通过化学流变学方法以及GPC,NMR等表征手段提出了简单剪切流场(瞬态剪切和振荡剪切)中POE/过氧化物的反应机理,并在相关大分子反应动力学理论的基础上半定量地揭示了简单剪切的作用机制:存在临界剪切流场强度阀值,低于此值只发生偶合反应,高于此值体系除偶合反应外还会发生降解反应;降解反应发生与否由两断裂产物之间的相对距离决定,即受对流与扩散控制;降解反应首先在长支化的偶合产物上发生,随着剪切流场的强度增强,线形链发生断裂降解的几率增高,而长支链的有效断裂点越来越接近于长支化点;当大分子链的两叔碳原子中间仅相隔一个CH2单元的叔碳自由基生成时,容易发生降解反应,这种断裂降解源结构的浓度直接影响降解反应的临界剪切流场强度阀值。
3.复杂加工流场对POE/DCP长支链产物拓扑结构的调控:在密炼机中对POE进行过氧化物改性,逼近反应加工实际过程,在温度补偿下考察加工流场对产物拓扑结构的影响。根据降解反应首先发生在长支链(Long Chain Branching, LCB)上的结论,可由流场强度来控制LCB产物的支链长度和含量;当长支链断裂后其长度不再足以发生缠结时,即表示该长支链退化为线形链,可以通过调控流场改变LCB支链长度以及LCB含量。虽然转速这一参量不能很好的描述具体的加工流场,但对于聚合物链的裁剪还是具有指导性意义。另外加工流场对LCB性质仅具有一个可调控的窗口,加工过程中不同流场的实施形式能够更加细化产物中的LCB水平,升高温度并不会促进降解反应。
4.通过非线性流变实验和傅立叶变换流变学对含长支链的反应产物做出了表征分析,在连续性cDCR-CS理论模型的基础上定义了一种全新的与聚合物链的分子量及分子量分布无关的量化长支链LCB结构因子。与涉及到稀溶液性质所定义的LCB结构因子相比,具有操作性更为便捷简单的优势。
5.通过目前能较为成功预测聚合物线性粘弹性的“Branch on branch”(BOB)理论模型,考察了对称星形、不对称星形、“H”形、梳形、以及Cayley tree形聚合物的vGP图特征,以及分子链参数对其的影响,并将各种拓扑结构的聚合物的特征转变与此前报道的实验值分别进行比较,结果吻合得很好。在勾勒出长支链聚合物的vGP拓扑图的基础上,提出了判断长支链聚合物拓扑结构的具体步骤,初步建立了由线性粘弹性来表征长支链聚合物的流变学方法。但是对于梳形聚合物与不对称星形聚合物来说,在一定范围内单凭线性粘弹性是难以进行区分的,这表明线性流变学在表征长支链聚合物时是存在局限的。
All structures on different scales inside polymer materials experience various complicated physical and chemical alterations during the reacting processing, which is ready to form a heavily nonlinear problem in substance. Besides the chemical reaction, the effect of applied flow field is more important, which makes chemorheology, one important hotspot of the present researches about reacting processing of polymer, to be the core issue to resolve. So it is very essential for us to reveal how the chemical raction of polymer proceeds under the flow; however the mechanism and the kinetics of polymer reaction in the flow field are unclear so far. In this thesis, the reaction behavior of polyolefin elastomer (POE) via the free radical mechanism is focused, and the purpose is to investigate the role that the flow field plays in the reaction mechanism, the reaction rate and the topological structure of the products of the macromolecular reactions. This doesn’t only has the engineering background but also the theoretical significance. Firstly, some new reaction mechanisms of POE initiated by peroxides (POE/DCP) in static state were discovered and the rheokinetic analysis was carried out which was different from what the researchers had already acquired; Secondly, the mechanism under simple shear flow was proposed and the effect of polymer chains’movements on the chemical reaction was revealed; Finally, the feasibility of preliminary tailoring of LCB through complex flow field was evaluated in the torque rheometer with the compensation of temperature. And a new long chains branched (LCB) index (DLCB) was defined from nonlinear oscillatory shear was founded, which could be a map to quantify LCB level by Fourier Transform Rheology (FTR); The main content and the results are as followed:
1. Peroxide-initiated reaction of POE was studied at elevated temperatures using an on-line electron paramagnetic resonance (EPR) spectrometer. It is clear that the reaction process experienced the free radical mechanisms. Notable changes in signal hyperfine structures, the intensities and the lifetimes of the radicals were recognized. A kind of 7-line EPR signal corresponding to the ternary carbon radical was discovered for the first time. Whether the primary carbon radical appears and the lifetime are both dependent on the co-monomer content of POE. A rheokinetic analysis was made by correlating the EPR data and the rheogical responses recorded by the rotational rheometer. The kinetic coefficients of coupling and disproportionating reactions are not fixed, but the functions of the reacting time or the system viscosity, which indicates the reaction is diffusion controlled. The scaling between termination coefficient and viscosity is lower than what de Gennes predicted on the base of theory, which should be induced by the low diffusion coefficient for such system with plenty of reactive sites.
2. The mechanism of reaction of POE initiated by peroxides under the simple shear, including transient shear flow and oscillatory shear flow, was paid attention to, which’s the important instruction for the actual reacting processing. There’s an intensity threshold of shear flow, above which degrading behavior throughβ-scission of the ternary carbon macroradicals could be observed besides the coupling reaction. Degradation depentent on the distance between the two parts created byβ-scission is controlled by diffusion and the shear flow field imposed upon the reaction system. Moreover, degradation starts on the products of long chain branching (LCB) and the probability of degradation on linear chains increases with the intensity of shear flow. Taking into consideration that the key factor favoring tertiary carbons as sites for scission was the distance between branches, the chain scission is possible when there were two tertiary carbons in a chain separated by only one carbon atom, which has been confirmed by 13C-NMR spectroscopy. The concentration of such structures affect the intensity threshold of shear flow for degradation.
3. The feasibility of preliminary tailoring of LCB through complex flow field was evaluated in the torque rheometer, for the reaction of melt POE with peroxides at elevated temperatures. With the compensation of temperature, the strength of complex shear flow could be the only factor affecting the reaction kinetics and mechanism. According to the fact that degradation starts on LCB firstly, the length and the concentration of long chain branching can be controlled by the intensity of flow field. What’s more, a certain amount of LCB degraded to be linear chains again due to the scission approaching the branching point in intense mixing condition. Although the rotational speed can not represent the complex flow field exactly, all the characterizations can give the significant instruction to tailor the polymer architecture more or less. In addition, there’s only one adjustable window of the topological structure and content of LCB here through altering the processing flow field. High temperature can not promote the degradation.
4. One new LCB index (DLCB) was defined from nonlinear oscillatory shear followed by Fourier Transform Rheology (FTR) on the base of cDCR-CS model, through which a map to quantify LCB level could be founded. This index is independent on the molecular weight and the distribution of polymer chains, and is more convenient compared with the one defined from the characters of polymer melt rheology and diluted solution.
5. The characteristics of vGP plot of various long chains branching, including symmetric star, asymmetric star, H-shaped, comb and Caylay tree polymers, have been evaluated by BOB model, which could predict the linear viscoelasticity of polymer very successfully so far. The characteristic transitions of various LCB in vGP polt were compared with the ones acquired from the experimental data in publishments and good agreement has been obtained. The protocol for characterization of the topological structure of LCB was raised according to the vGP map of topology. However, it is difficult to distinguish the asymmetric star and comb polymers only by the linear viscoelasticity.
1.静态下通过顺磁共振方法有效识别了POE/过氧化物反应体系中各种自由基信号的超精细结构与强度的变化,首次发现了对应于叔碳自由基的7线EPR信号,得出了反应过程中伯碳自由基的出现及其持续的时间强烈依赖于聚烯烃中共聚单体含量的结论;但是除偶合与歧化双基终止反应外,并没有观测到降解反应的存在。结合EPR数据和在线流变测量对整个反应过程进行了动力学过程分析,运用大分子反应动力学理论,分析得出了偶合与歧化反应速率系数随体系粘度增大而减小的动力学方程。研究结果表明,反应受大分子链扩散过程控制,高浓反应体系的偶和速率系数与粘度之间的标度关系与低于理论预测值,系为很高的体系粘度降低反应链扩散系数所致。
2.通过化学流变学方法以及GPC,NMR等表征手段提出了简单剪切流场(瞬态剪切和振荡剪切)中POE/过氧化物的反应机理,并在相关大分子反应动力学理论的基础上半定量地揭示了简单剪切的作用机制:存在临界剪切流场强度阀值,低于此值只发生偶合反应,高于此值体系除偶合反应外还会发生降解反应;降解反应发生与否由两断裂产物之间的相对距离决定,即受对流与扩散控制;降解反应首先在长支化的偶合产物上发生,随着剪切流场的强度增强,线形链发生断裂降解的几率增高,而长支链的有效断裂点越来越接近于长支化点;当大分子链的两叔碳原子中间仅相隔一个CH2单元的叔碳自由基生成时,容易发生降解反应,这种断裂降解源结构的浓度直接影响降解反应的临界剪切流场强度阀值。
3.复杂加工流场对POE/DCP长支链产物拓扑结构的调控:在密炼机中对POE进行过氧化物改性,逼近反应加工实际过程,在温度补偿下考察加工流场对产物拓扑结构的影响。根据降解反应首先发生在长支链(Long Chain Branching, LCB)上的结论,可由流场强度来控制LCB产物的支链长度和含量;当长支链断裂后其长度不再足以发生缠结时,即表示该长支链退化为线形链,可以通过调控流场改变LCB支链长度以及LCB含量。虽然转速这一参量不能很好的描述具体的加工流场,但对于聚合物链的裁剪还是具有指导性意义。另外加工流场对LCB性质仅具有一个可调控的窗口,加工过程中不同流场的实施形式能够更加细化产物中的LCB水平,升高温度并不会促进降解反应。
4.通过非线性流变实验和傅立叶变换流变学对含长支链的反应产物做出了表征分析,在连续性cDCR-CS理论模型的基础上定义了一种全新的与聚合物链的分子量及分子量分布无关的量化长支链LCB结构因子。与涉及到稀溶液性质所定义的LCB结构因子相比,具有操作性更为便捷简单的优势。
5.通过目前能较为成功预测聚合物线性粘弹性的“Branch on branch”(BOB)理论模型,考察了对称星形、不对称星形、“H”形、梳形、以及Cayley tree形聚合物的vGP图特征,以及分子链参数对其的影响,并将各种拓扑结构的聚合物的特征转变与此前报道的实验值分别进行比较,结果吻合得很好。在勾勒出长支链聚合物的vGP拓扑图的基础上,提出了判断长支链聚合物拓扑结构的具体步骤,初步建立了由线性粘弹性来表征长支链聚合物的流变学方法。但是对于梳形聚合物与不对称星形聚合物来说,在一定范围内单凭线性粘弹性是难以进行区分的,这表明线性流变学在表征长支链聚合物时是存在局限的。
All structures on different scales inside polymer materials experience various complicated physical and chemical alterations during the reacting processing, which is ready to form a heavily nonlinear problem in substance. Besides the chemical reaction, the effect of applied flow field is more important, which makes chemorheology, one important hotspot of the present researches about reacting processing of polymer, to be the core issue to resolve. So it is very essential for us to reveal how the chemical raction of polymer proceeds under the flow; however the mechanism and the kinetics of polymer reaction in the flow field are unclear so far. In this thesis, the reaction behavior of polyolefin elastomer (POE) via the free radical mechanism is focused, and the purpose is to investigate the role that the flow field plays in the reaction mechanism, the reaction rate and the topological structure of the products of the macromolecular reactions. This doesn’t only has the engineering background but also the theoretical significance. Firstly, some new reaction mechanisms of POE initiated by peroxides (POE/DCP) in static state were discovered and the rheokinetic analysis was carried out which was different from what the researchers had already acquired; Secondly, the mechanism under simple shear flow was proposed and the effect of polymer chains’movements on the chemical reaction was revealed; Finally, the feasibility of preliminary tailoring of LCB through complex flow field was evaluated in the torque rheometer with the compensation of temperature. And a new long chains branched (LCB) index (DLCB) was defined from nonlinear oscillatory shear was founded, which could be a map to quantify LCB level by Fourier Transform Rheology (FTR); The main content and the results are as followed:
1. Peroxide-initiated reaction of POE was studied at elevated temperatures using an on-line electron paramagnetic resonance (EPR) spectrometer. It is clear that the reaction process experienced the free radical mechanisms. Notable changes in signal hyperfine structures, the intensities and the lifetimes of the radicals were recognized. A kind of 7-line EPR signal corresponding to the ternary carbon radical was discovered for the first time. Whether the primary carbon radical appears and the lifetime are both dependent on the co-monomer content of POE. A rheokinetic analysis was made by correlating the EPR data and the rheogical responses recorded by the rotational rheometer. The kinetic coefficients of coupling and disproportionating reactions are not fixed, but the functions of the reacting time or the system viscosity, which indicates the reaction is diffusion controlled. The scaling between termination coefficient and viscosity is lower than what de Gennes predicted on the base of theory, which should be induced by the low diffusion coefficient for such system with plenty of reactive sites.
2. The mechanism of reaction of POE initiated by peroxides under the simple shear, including transient shear flow and oscillatory shear flow, was paid attention to, which’s the important instruction for the actual reacting processing. There’s an intensity threshold of shear flow, above which degrading behavior throughβ-scission of the ternary carbon macroradicals could be observed besides the coupling reaction. Degradation depentent on the distance between the two parts created byβ-scission is controlled by diffusion and the shear flow field imposed upon the reaction system. Moreover, degradation starts on the products of long chain branching (LCB) and the probability of degradation on linear chains increases with the intensity of shear flow. Taking into consideration that the key factor favoring tertiary carbons as sites for scission was the distance between branches, the chain scission is possible when there were two tertiary carbons in a chain separated by only one carbon atom, which has been confirmed by 13C-NMR spectroscopy. The concentration of such structures affect the intensity threshold of shear flow for degradation.
3. The feasibility of preliminary tailoring of LCB through complex flow field was evaluated in the torque rheometer, for the reaction of melt POE with peroxides at elevated temperatures. With the compensation of temperature, the strength of complex shear flow could be the only factor affecting the reaction kinetics and mechanism. According to the fact that degradation starts on LCB firstly, the length and the concentration of long chain branching can be controlled by the intensity of flow field. What’s more, a certain amount of LCB degraded to be linear chains again due to the scission approaching the branching point in intense mixing condition. Although the rotational speed can not represent the complex flow field exactly, all the characterizations can give the significant instruction to tailor the polymer architecture more or less. In addition, there’s only one adjustable window of the topological structure and content of LCB here through altering the processing flow field. High temperature can not promote the degradation.
4. One new LCB index (DLCB) was defined from nonlinear oscillatory shear followed by Fourier Transform Rheology (FTR) on the base of cDCR-CS model, through which a map to quantify LCB level could be founded. This index is independent on the molecular weight and the distribution of polymer chains, and is more convenient compared with the one defined from the characters of polymer melt rheology and diluted solution.
5. The characteristics of vGP plot of various long chains branching, including symmetric star, asymmetric star, H-shaped, comb and Caylay tree polymers, have been evaluated by BOB model, which could predict the linear viscoelasticity of polymer very successfully so far. The characteristic transitions of various LCB in vGP polt were compared with the ones acquired from the experimental data in publishments and good agreement has been obtained. The protocol for characterization of the topological structure of LCB was raised according to the vGP map of topology. However, it is difficult to distinguish the asymmetric star and comb polymers only by the linear viscoelasticity.
引文
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