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聚对苯二甲酸乙二酯/双酚配合物通过熔融后缩聚的结晶与热行为

Crystallization and Thermal Behaviors of Poly(ethylene terephthalate)/Bisphenols Complexes through Melt Post-Polycondensation.

作者信息

Chen Shichang, Xie Shangdong, Guang Shanshan, Bao Jianna, Zhang Xianming, Chen Wenxing

机构信息

Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China.

Zhejiang Provincial Key Laboratory of Fiber Materials and Manufacturing Technology, Zhejiang Sci-Tech University, Hangzhou 310018, China.

出版信息

Polymers (Basel). 2020 Dec 19;12(12):3053. doi: 10.3390/polym12123053.

Abstract

Three kinds of modified poly(ethylene terephthalate) (PET) were prepared by solution blending combined with melt post-polycondensation, using 4,4'-thiodiphenol (TDP), 4,4'-oxydiphenol (ODP) and hydroquinone (HQ) as the bisphenols, respectively. The effects of TDP, ODP and HQ on melt post-polycondensation process and crystallization kinetics, melting behaviors, crystallinity and thermal stability of PET/bisphenols complexes were investigated in detail. Excellent chain growth of PET could be achieved by addition of 1 wt% bisphenols, but intrinsic viscosity of modified PET decreased with further bisphenols content. Intermolecular hydrogen bonding between carbonyl groups of PET and hydroxyl groups of bisphenols were verified by Fourier transform infrared spectroscopy. Compare to pure PET, both the crystallization rate and melting temperatures of PET/bisphenols complexes were reduced obviously, suggesting an impeded crystallization and reduced lamellar thickness. Moreover, the structural difference between TDP, ODP and HQ played an important role on crystallization kinetics. It was proposed that the crystallization rate of TDP modified PET was reduced significantly due to the larger amount of rigid benzene ring and larger polarity than that of PET with ODP or HQ. X-ray diffraction results showed that the crystalline structure of PET did not change from the incorporation of bisphenols, but crystallinity of PET decreased with increasing bisphenols content. Thermal stability of modified PET declined slightly, which was hardly affected by the molecular structure of bisphenols.

摘要

通过溶液共混结合熔融后缩聚的方法制备了三种改性聚对苯二甲酸乙二酯(PET),分别使用4,4'-硫代二苯酚(TDP)、4,4'-氧代二苯酚(ODP)和对苯二酚(HQ)作为双酚。详细研究了TDP、ODP和HQ对PET/双酚复合物的熔融后缩聚过程、结晶动力学、熔融行为、结晶度和热稳定性的影响。添加1 wt%的双酚可实现PET优异的链增长,但改性PET的特性粘度会随着双酚含量的进一步增加而降低。通过傅里叶变换红外光谱证实了PET羰基与双酚羟基之间的分子间氢键。与纯PET相比,PET/双酚复合物的结晶速率和熔融温度均明显降低,表明结晶受到阻碍且片晶厚度减小。此外,TDP、ODP和HQ之间的结构差异对结晶动力学起着重要作用。有人提出,由于TDP改性PET中刚性苯环数量较多且极性比ODP或HQ改性的PET大,其结晶速率显著降低。X射线衍射结果表明,双酚的加入并未改变PET的晶体结构,但PET的结晶度随着双酚含量的增加而降低。改性PET的热稳定性略有下降,这几乎不受双酚分子结构的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13d3/7766347/20af0cf692ee/polymers-12-03053-sch001.jpg

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