等规聚丙烯成核剂的结构和构型分析

doi:10.11938/cjmr20192763

摘要/Abstract

摘要： 成核剂在聚丙烯的结晶过程中作为晶核，参与调节晶体的晶型、大小及其分布，促使形成不同性能的聚丙烯材料．成核剂促进聚合物结晶的机制是聚合物结晶领域的研究热点，但其结构对聚合物结晶的影响尚不清晰；而成核剂通常具有同分异构体，使其结构解析更加困难，但成核剂的结构解析是进一步研究其成核机理的基础．本文综合运用核磁共振（NMR）波谱、傅里叶变换-红外（FT-IR）光谱和扫描电镜能谱分析（SEM-EDS）表征了一种二元羧酸复合物类β晶型聚丙烯成核剂的结构和构型，结果表明该成核剂cis-△4-四氢邻苯二甲酸钙为消旋体，羧酸与钙以桥式螯合方式形成有机羧酸金属盐．

关键词: 聚丙烯, 成核剂, 桥式螯合, 结构和构型, 有机金属盐

Abstract: The nucleating agent acts as a crystal nucleus during polypropylene (PP) crystallization, affecting the structure and size distribution of the crystal, and in turn the properties of PP products. It is a hot research topic to study the mechanisms by which the nucleating agent promotes polymer crystallization. Currently it is still unclear how the structure of nucleating agent affects polymer crystallization. In addition, a nucleating agent may have different chemical structures due to isomerization, further complicating the nucleation mechanism study. Structural studies of nucleating agents are therefore the foundation of the nucleation mechanism studies. In this work, the structure and configuration of a β nucleating agent used in PP crystallization were studied by the combination of nuclear magnetic resonance (NMR) spectroscopy, Fourier transform-infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The FT-IR data suggested that the chelating way of calcium salt of cis-Δ4-tetrahydrophthalic acid in the nucleating agent belongs to the bridge type, while the cis-Δ4-tetrahydrophthalic acid is a mesomer.

Key words: polypropylene (PP), nucleating agent, bridge type chelating, structure and configuration, organic metal salts

中图分类号:

O482.53

温亮, 李春发. 等规聚丙烯成核剂的结构和构型分析[J]. 波谱学杂志, 2020, 37(3): 291-299.

WEN Liang, LI Chun-fa. Structure and Configuration Analyses of a Nucleating Agent for Isotactic Polypropylene Crystallization[J]. Chinese Journal of Magnetic Resonance, 2020, 37(3): 291-299.

参考文献

[1] LIBSTER D, ASERIN A, GARTI N. Advanced nucleating agents for polypropylene[J]. Polym Adv Tchnolo, 2007, 18(9):685-695.
[2] DANIEL A, JRJENG R, ANNETTE T, et al. Structural matching between the polymeric nucleating agent isotactic poly(vinylcyclohexane) and isotactic polypropylene[J]. Macromolecules, 2006, 39(8):2832-2840.
[3] MARKUS B, SANDRA G, DORIS H, et al. "Designer" nucleating agents for polypropylene[J]. Macromolecules, 2005, 38(9):3688-3695.
[4] PADDEN F J, KEITH H D. Spherulitic crystallization in polypropylene[J]. J Appl Phys, 1959, 30(10):1479-1484.
[5] TURNER-JONES A, COBBOLD A J M. The β crystalline form of isotactic polypropylene[J]. Polym Lett, 1968, 6(8):539-546.
[6] ZHAO S C, CAI Z, XIN Z. A highly active novel β-nucleating agent for isotactic polypropylene[J]. Polymer 2008, 49(11):2745-2754.
[7] CAO L, LI Q, SU Z Q, et al. Research progress of nucleating agents for iPP[J]. Chin Polym Bull, 2013, 4:146-150. 曹莉, 李青, 苏志强, 等. 聚丙烯成核剂研究进展[J]. 高分子通报, 2013, 4:146-150.
[8] JIANG C Q, ZHAO S C, WANG F, et al. A highly active β-nucleating agent for isotactic polypropylene[J]. China Plastics, 2014, 28(6):93-97. 姜昌泉, 赵世成, 王菲, 等. 新型高效聚丙烯β晶型成核剂[J]. 中国塑料, 2014, 28(6):93-97.
[9] ZHANG Y F, XIN Z. Effects of substituted aromatic heterocyclic phosphate salts on properties, crystallization, and melting behaviors of isotactic polypropylene[J]. J Appl Poly Sci, 2010, 100(6):4868-4874.
[10] LI C F, LIU G, WANG Q, et al. Analyzing pentaerythritol stearate homologs with NMR spectroscopy[J]. Chinese J Magn Reson, 2018, 35(3):363-373. 李春发, 刘广, 王芹, 等. 季戊四醇硬脂酸酯同系物的结构解析[J]. 波谱学杂志, 2018, 35(3):363-373.
[11] MA L G, LONG Y H. Determination of aromatic carbon mole ratio in oil samples by quantitative ¹³C NMR spectroscopy with DFSS methodology[J]. Chinese J Magn Reson, 2017, 34(1):8-15. 马琳鸽, 龙银花. ¹³C qNMR结合DFSS方法测定油品芳碳率[J]. 波谱学杂志, 2017, 34(1):8-15.
[12] SCHLERETH D D, JAMENO M L, DELA CAMPA J G. et al. Linear polyesters of diethylene glycol with cis-and trans-4-cyclohexene-1, 2-dicarboxylic acid. Synthesis, characterization and NMR structural study[J]. Eur Polym J, 1993, 29(10):1345-1350.
[13] 汉斯·茨魏费尔, 著. 欧育湘, 李建军, 译. 塑料添加剂手册(原著第五版)[M]. 北京:化学工业出版社, 2005.
[14] 翁诗甫. 傅里叶变换红外光谱分析[M]. 北京:化学工业出版社, 2010.
[15] QIN Y W, GUO S H, FENG J C, et al. Advanced in β-forms polypropylene and β-nucleating agents[J]. China Plastics, 20006, 20(3):7-13. 秦亚伟, 郭绍辉, 冯嘉春, 等. 聚丙烯的β晶型及β成核剂的研究进展[J]. 中国塑料, 2006, 20(3):7-13.
[16] 温亮. 基于杯
[8] 芳烃与小分子构筑的自组装成核剂对聚乳酸结晶过程的调控研究[D]. 上海:华东理工大学, 2011.
[17] ZHANG M, WANG J W, ZONG Y Y, et al. Research progress in the first-principles calculation of metal-hydrogen system[J]. Materials Science and Technology, 2018, 26(5):1-10. 张苗, 王继伟, 宗影影. 等. 金属-氢系统的第一性原理计算研究进展[J]. 材料科学与工艺, 2018, 26(5):1-10.