几种高分子材料的域结构、分子动力学和相互作用的固体NMR研究
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摘要
聚3-羟基丁酸酯(PHB)是微生物细胞在其生长的特定时期在胞内合成的具有相应生物功能的聚羟基烷酸酯类物质,是一种具有潜在的广泛应用前景的生物可降解的高分子材料。由于天然的PHB其较高的结晶度和较窄的温度处理范围,它在应用过程中受到较大的局限性。人们将结构相似的单体3-羟基戊酸(HV)与3-羟基丁酸(HB)共聚形成共聚物(PHBV)以后,显著改善了PHB的物理机械性能,譬如:冲击强度和韧性有所增加,而硬度脆性有一定程度的下降。人们虽然在这些降解高分子材料的开发、制备和物理机械性能以及这些材料的应用等方面有很多研究,但是有关分子水平的问题并未得到系统的探索。因此,我们针对这些分子基础问题(结构域特征和分子动力学等)做了一些初步的研究。
全氟磺酸树脂(Nafion)是杜邦公司生产的一种燃料电池电极薄膜材料,其较低的使用温度(<100℃)严重地限制了它的应用范围。人们发现,当把层状硅酸盐(蒙脱土)和Nafion合成为有机无机纳米复合材料之后,在一定程度上提高了它的使用温度。虽然这种复合材料很容易合成出来并且已经运用到了实际工业应用之中,但是这种热稳定性提高的原因却不甚清楚。我们试图通过固体NMR等分析方法从微观相互作用方面来认识这种宏观性能改善的原因。
我们使用固体13C CP MAS、13C SPE MAS NMR以及XRD方法测定了PHB和两种PHBV的结晶度(Xc),发现随着HV的引入它们的Xc逐渐减小。研究同时发现在测量Xc的这几种方法中13C SPE MAS NMR误差较小。实验中我们利用质子弛豫诱导谱编辑(PRISE)、质子自旋扩散(Spin-diffusion)等固体NMR技术研究了PHB以及不同含量HV的PHBV的结构域特征和相应结构域的运动性。实验结果表明随着HV含量的增加,它们的非晶相结构域尺寸增大,晶相结构域尺寸减小,可以看出HV的引入导致PHB的结构域特征的变化是其宏观性能改善的原因。
我们进一步通过低分辨固体NMR测量了PHB和PHBV的变温质子弛豫时间(T1, T1ρ, T2),然后通过理论拟合获得了它们不同运动状态的分子运动相关频率(τc)和分子活化能(Ea)等动力学信息,研究发现随着HV含量的增加,分子运动加快,活化能减小,我们在分子水平上认识了HV的引入使得PHB宏观性能改善的微观原因。
我们还通过溶胶凝胶法合成了燃料电池电极薄膜(Nafion)和层状硅酸盐(蒙脱土)纳米复合材料来提高Nafion的使用温度,FT-IR和29Si MAS NMR实验结果表明在杂化材料中虽然质子化的十二烷基胺修饰的蒙脱土(MMT)的引入没有导致MMT的骨架结构发生明显变化,而且Nafion也没有插入到MMT的层间,但是TGA分析表明杂化材料中的Nafion的热稳定性比纯的Nafion高。我们通过一系列固体NMR技术包括19F MAS、1H-13C CP MAS NMR和1H-13C HETCOR 2D NMR实验初步证实了这种材料的热稳定性的提高可能是由于MMT表面吸附的NH3+与Nafion?侧链上的SO3-之间存在较强的静电相互作用,我们初步可以认为这种相互作用是导致电极材料性能改善的原因。
Poly(3-hydroxybutyrate) is one of the most applicative biodegradable polymers. However, its industrial application remains limited, owing to several inherent deficiencies including poor mechanical properties such as brittleness due to its high crystallinity and narrow thermal processing range. To overcome these drawbacks, a number of copolymers with other similar hydroxyalkanoate monomer units have been developed such as poly(3-hydroxybutyrate-co-3-hydroxyvalerate), [P(HB-HV)]. Compared with PHB, these copolymers exhibit outstanding improvement of physical/mechanism properties such as reduced brittleness and enhanced flexibility. Although the preparation and its physical/mechanism properties had been investigated extensively, less work has been done for answering the questions about the molecular basis of them and the relationship between the micaostructural and dynamic properties and their macroscopic properties.
Nafion is one of the most promising proton-exchange membranes used in direct methanol fuel cell (DMFC). In practice, normal Nafion? materials are not applicable for DMFC due to poor mechanical stability at temperature above 100oC. In order to develop the higher temperature electrolyte materials, many attempts have, so far, been made by modifying the Nafion? membrane with various nonconductive inorganic materials. However, little information is available on the molecular basis of such thermal stability improvement. In addition, there are few reports dealing with the molecular structure of these composite materials, the interactions between the inorganic and organic species at the molecular level and structure-property relationships which will undoubtedly be useful for future development of materials.
In this dissertation, combined with XRD various solid state NMR techniques including 13C CP MAS、13C SPE MAS NMR, proton relaxation induced spectra editing, 1H spin-diffusion have been employed to investigate the crystallnility and domain structural character. The experimental results show that with the content of HV increasing their crystallinity decrease, domain size of amorphous region increase and domain size of rigid region decrease, which can be seen at the molecular lever that introduction of HV results in the macroscopic properties improvement of PHB.
Furthermore, 1H variable temperature relaxation time (T1, T1ρand T2) measurements have been employed to investigate the molecular motional parameters such as molecular rotational correlation time (τ0) and active energy (Ea) in the PHB and its copolymers PHBV. The results imply that the higher the content of HV, the faster the molecular motion, the lower the molecular active energy, which can be correlated to their structural and molecular dynamic properties at the molecular lever.
A series of nanocomposites have been prepared from perfluorosulfonylfluoride copolymer resin (Nafion?) and layered montmorillonite (MMT) modified with protonated dodecylamine by conventional sol-gel intercalation. FT-IR and 29Si MAS NMR results showed no significant alteration to the lattice structure of m-MMT and addition of the organically modified MMT led to moderate improvement of the thermal stability of Nafion? resin though the resin was not intercalated into the m-MMT. 19F MAS, 1H-13C CP MAS and HETCOR 2D NMR experimental results, combined with XRD and element analysis, indicated strong interactions between NH3+ group of surface absorption of dodecylamine and the SO3- group of the resin side chain. It is concluded that interactions between the resin and the surface absorbed organic modifier probably have some contributions to the resin thermal stability enhancement resulting from addition of m-MMT.
全氟磺酸树脂(Nafion)是杜邦公司生产的一种燃料电池电极薄膜材料,其较低的使用温度(<100℃)严重地限制了它的应用范围。人们发现,当把层状硅酸盐(蒙脱土)和Nafion合成为有机无机纳米复合材料之后,在一定程度上提高了它的使用温度。虽然这种复合材料很容易合成出来并且已经运用到了实际工业应用之中,但是这种热稳定性提高的原因却不甚清楚。我们试图通过固体NMR等分析方法从微观相互作用方面来认识这种宏观性能改善的原因。
我们使用固体13C CP MAS、13C SPE MAS NMR以及XRD方法测定了PHB和两种PHBV的结晶度(Xc),发现随着HV的引入它们的Xc逐渐减小。研究同时发现在测量Xc的这几种方法中13C SPE MAS NMR误差较小。实验中我们利用质子弛豫诱导谱编辑(PRISE)、质子自旋扩散(Spin-diffusion)等固体NMR技术研究了PHB以及不同含量HV的PHBV的结构域特征和相应结构域的运动性。实验结果表明随着HV含量的增加,它们的非晶相结构域尺寸增大,晶相结构域尺寸减小,可以看出HV的引入导致PHB的结构域特征的变化是其宏观性能改善的原因。
我们进一步通过低分辨固体NMR测量了PHB和PHBV的变温质子弛豫时间(T1, T1ρ, T2),然后通过理论拟合获得了它们不同运动状态的分子运动相关频率(τc)和分子活化能(Ea)等动力学信息,研究发现随着HV含量的增加,分子运动加快,活化能减小,我们在分子水平上认识了HV的引入使得PHB宏观性能改善的微观原因。
我们还通过溶胶凝胶法合成了燃料电池电极薄膜(Nafion)和层状硅酸盐(蒙脱土)纳米复合材料来提高Nafion的使用温度,FT-IR和29Si MAS NMR实验结果表明在杂化材料中虽然质子化的十二烷基胺修饰的蒙脱土(MMT)的引入没有导致MMT的骨架结构发生明显变化,而且Nafion也没有插入到MMT的层间,但是TGA分析表明杂化材料中的Nafion的热稳定性比纯的Nafion高。我们通过一系列固体NMR技术包括19F MAS、1H-13C CP MAS NMR和1H-13C HETCOR 2D NMR实验初步证实了这种材料的热稳定性的提高可能是由于MMT表面吸附的NH3+与Nafion?侧链上的SO3-之间存在较强的静电相互作用,我们初步可以认为这种相互作用是导致电极材料性能改善的原因。
Poly(3-hydroxybutyrate) is one of the most applicative biodegradable polymers. However, its industrial application remains limited, owing to several inherent deficiencies including poor mechanical properties such as brittleness due to its high crystallinity and narrow thermal processing range. To overcome these drawbacks, a number of copolymers with other similar hydroxyalkanoate monomer units have been developed such as poly(3-hydroxybutyrate-co-3-hydroxyvalerate), [P(HB-HV)]. Compared with PHB, these copolymers exhibit outstanding improvement of physical/mechanism properties such as reduced brittleness and enhanced flexibility. Although the preparation and its physical/mechanism properties had been investigated extensively, less work has been done for answering the questions about the molecular basis of them and the relationship between the micaostructural and dynamic properties and their macroscopic properties.
Nafion is one of the most promising proton-exchange membranes used in direct methanol fuel cell (DMFC). In practice, normal Nafion? materials are not applicable for DMFC due to poor mechanical stability at temperature above 100oC. In order to develop the higher temperature electrolyte materials, many attempts have, so far, been made by modifying the Nafion? membrane with various nonconductive inorganic materials. However, little information is available on the molecular basis of such thermal stability improvement. In addition, there are few reports dealing with the molecular structure of these composite materials, the interactions between the inorganic and organic species at the molecular level and structure-property relationships which will undoubtedly be useful for future development of materials.
In this dissertation, combined with XRD various solid state NMR techniques including 13C CP MAS、13C SPE MAS NMR, proton relaxation induced spectra editing, 1H spin-diffusion have been employed to investigate the crystallnility and domain structural character. The experimental results show that with the content of HV increasing their crystallinity decrease, domain size of amorphous region increase and domain size of rigid region decrease, which can be seen at the molecular lever that introduction of HV results in the macroscopic properties improvement of PHB.
Furthermore, 1H variable temperature relaxation time (T1, T1ρand T2) measurements have been employed to investigate the molecular motional parameters such as molecular rotational correlation time (τ0) and active energy (Ea) in the PHB and its copolymers PHBV. The results imply that the higher the content of HV, the faster the molecular motion, the lower the molecular active energy, which can be correlated to their structural and molecular dynamic properties at the molecular lever.
A series of nanocomposites have been prepared from perfluorosulfonylfluoride copolymer resin (Nafion?) and layered montmorillonite (MMT) modified with protonated dodecylamine by conventional sol-gel intercalation. FT-IR and 29Si MAS NMR results showed no significant alteration to the lattice structure of m-MMT and addition of the organically modified MMT led to moderate improvement of the thermal stability of Nafion? resin though the resin was not intercalated into the m-MMT. 19F MAS, 1H-13C CP MAS and HETCOR 2D NMR experimental results, combined with XRD and element analysis, indicated strong interactions between NH3+ group of surface absorption of dodecylamine and the SO3- group of the resin side chain. It is concluded that interactions between the resin and the surface absorbed organic modifier probably have some contributions to the resin thermal stability enhancement resulting from addition of m-MMT.
引文
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