Citation: Han Zhu, Xun Da, Chen Lu, Yi-xian Wu. Isothermal Crystallization Kinetics and Crystal Morphology of Polybutadiene/Silica Hybrid Materials[J]. Acta Polymerica Sinica, ;2018, 0(5): 656-664. doi: 10.11777/j.issn1000-3004.2017.170241 shu

Isothermal Crystallization Kinetics and Crystal Morphology of Polybutadiene/Silica Hybrid Materials

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029

Corresponding author: Yi-xian Wu, wuyx@mail.buct.edu.cn
Received Date: 27 August 2017
Revised Date: 29 September 2017
Available Online: 1 March 2018

Effect of SiO₂ content on cis-1,4 microstructure content of butadiene (Bd) units, intrinsic viscosity ([η]) and thermal stability of hybrid materials (PB-Si) were studied, in which SiO₂ nanoparticles were covalently attached and pendants along high cis polybutadiene (PB) macromolecular chains. Isothermal crystallization characteristics and SiO₂ dispersion in PB matrix of PB-Si hybrid and PB/SiO₂ blend (PB/Si) with the same SiO₂ contents were conducted. The microstructure of Bd units in PB-Si was characterized by Fourier transform infrared spectroscopy (FTIR) and the cis-1,4 content was determined based on the characteristic absorption in FTIR spectrum. The SiO₂ content of PB-Si was measured by thermal gravimetric analysis (TGA). The intrinsic viscosity of PB-Si in toluene was tested by Ubbelohde viscometer. Effects of SiO₂ content and microstructure (cis -1,4 configuration) on the isothermal crystallization kinetics, crystal morphology and spherulite growth rate of the hybrid materials at low temperatures were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM) equipped with in situ heating and cooling device. The results show that the intrinsic viscosity and the cis-1,4 contents of Bd units of PB-Si remained almost the same, and thermal stability could be improved with increasing SiO₂ content in the materials when SiO₂ content was less than 2.5%. For two series of PB-Si-Ni and PB-Si-Nd hybrids, their cis-1,4 contents were determined to be around 96.6% and 98.6% respectively. PB-Si hybrid materials exhibited a much higher crystallization rate compared to PB/Si blends by keeping the cis-1,4 contents and SiO₂ content at the same. The crystallization rate increased by introducing a small amount of covalently linked SiO₂ nanoparticle pendants along the macromolecular chains. The crystallization of PB-Si hybrid materials could be accelerated and the half-crystallization time (t_1/2) decreased with increasing SiO₂ content. PB-Si-Nd hybrid materials with highly linear chains possessed a higher crystallization rate than PB-Si-Ni with short branched chains by keeping cis-1,4 content and SiO₂ at the same. The crystallization rate of PB-Si-Nd hybrid materials could be further increased with increasing both SiO₂ and cis-1,4 contents. The Avrami exponents (n) for PB-Si hybrid materials with various topological structures were determined to be in the range of 2.0 − 3.0, which indicated a three-dimensional spherulite growth of PB-Si under isothermal condition at low crystallization temperature. The growth rate of spherulites increased with the increase in SiO ₂ content while keeping other conditions almost the same. The crystallization rate could increase with increased cis-1,4 content, linearity of chain structure and SiO₂ content.
- High cis polybutadiene,
- Hybrid materials,
- Chain structure,
- Isothermal crystallization kinetics
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