固体核磁共振定量分析聚丙烯催化剂中的有机组分
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摘要
利用固体核磁共振的~(13)C交叉极化魔角旋转(CP/MAS)和定量交叉极化魔角旋转(QCP/MAS)实验技术对聚丙烯DQ催化剂的组成进行定性及定量分析。建立了DQ催化剂中不同有机组分的QCP/MAS表征方法,考察了接触时间和转速对信号增强的影响,在选定接触时间为200μs,转动频率为8 kHz的实验条件下,测定了DQ催化剂中不同含碳官能团的增强因子及有机组分的物质的量比例。结合气相色谱–质谱联用实验结果证明,在制备过程中,未经陈化处理的DQ催化剂原料间发生化学反应,产生了邻苯二甲酸酐、邻苯二甲酸二乙酯等活性组分。超高效液相色谱实验数据显示,是否进行陈化这一步骤,所得聚丙烯催化剂产品中引入的邻苯二甲酸二乙酯含量差异明显。
Solid-state nuclear magnetic resonance(NMR) methods including ~(13)C cross polarization/magic angle spinning nuclear magnetic resonance(CP/MAS NMR), ~(13)C quantitative cross polarization/magic angle spinning(QCP/MAS) NMR experiments were performed to analyze the organic components in polypropylene DQ-catalyst. The QCP NMR method was been applied to quantitatively characterize CP enhancement factors for carbon and mole fractions of organic components in catalyst, and the in?uence of CP contact time and MAS rate on the quantitative results were studied.The results combining GC–MS data showed that the chemical reaction existed during aging process in preparation of DQcatalyst, and produced phthalic anhydride and diethyl phthalate. Data from UPLC analysis showed that whether or not to undergo aging process the content of diethyl phthalate in the product of polypropylene catalyst was signi?cantly different.
Solid-state nuclear magnetic resonance(NMR) methods including ~(13)C cross polarization/magic angle spinning nuclear magnetic resonance(CP/MAS NMR), ~(13)C quantitative cross polarization/magic angle spinning(QCP/MAS) NMR experiments were performed to analyze the organic components in polypropylene DQ-catalyst. The QCP NMR method was been applied to quantitatively characterize CP enhancement factors for carbon and mole fractions of organic components in catalyst, and the in?uence of CP contact time and MAS rate on the quantitative results were studied.The results combining GC–MS data showed that the chemical reaction existed during aging process in preparation of DQcatalyst, and produced phthalic anhydride and diethyl phthalate. Data from UPLC analysis showed that whether or not to undergo aging process the content of diethyl phthalate in the product of polypropylene catalyst was signi?cantly different.
引文
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[2]化工部北京化工研究院.烯烃聚合用的球形催化剂:中国,93102795.0[P].1993-03-29.
[3]中国石油化工股份有限公司北京化工研究院.用于烯烃聚合反应的球形催化剂组分及其催化剂:中国,200410062291.3[P].2004-07-05.
[4]中国石油化工股份有限公司北京化工研究院.烯烃聚合用的球形催化剂组份、制备方法和应用及球形催化剂:中国,1036011C[P].1997-10-01.
[5]仝钦宇,杨芝超,杜亚锋,等.预络合技术在气相聚丙烯工艺上的应用[J].石油化工,2018,47(1):43-47.
[6]CHADWICK J C,MIEDEMA A,SUDMEIJER O.Hydrogen activation in propene polymerization with MgCl2-supported zieglernatta catalysts:the effect of the external donor[J].Macromol Chem Phys,1994,195(1):167-172.
[7]CHADWICK J C,VAN KESSEL G M M,SUDMEIJER O.Regio-and stereospecificity in propene polymerization with MgCl2-supported ziegler-natta catalysts:effects of hydrogen and the external Donor[J].Macromol Chem Phys,1995,196(5):1 431-1 437.
[8]王超,吴爱芹,刘爱芹,等.固体核磁共振法测定硫化丁苯橡胶中的苯乙烯[J].化学分析计量,2017,26(5):82-84.
[9]LUCIER B E G,CHEN S,HUANG Y.Characterization of metalorganic frameworks:unlocking the potential of solid-state NMR[J].Acc Chem Res,2018,51(2):319-330.
[10]孙毅,陈艳可,李建平,等.固体核磁共振中膜蛋白双交叉极化效率与动力学参数相关的定量分析[J].波谱学杂志,2017,34(3):257-265.
[11]SHU J,CHEN Q,ZHANG S M.Quantification of cross polarization with relaxation compensated reciprocity relation in NMR[J].Chem Phys Lett,2008,462(1-3):125-128.
[12]顾佳丽,张田田,赵辉鹏,等.耗时短、通用性强的固体核磁共振交叉极化定量检测方法[J].高等学校化学学报,2018,39(3):463-469.
[13]DUAN P,SCHMIDT-ROHR,K.Composite-pulse and partially dipolar dephased multi CP for improved quantitative solid-state13C NMR[J].J Magn Reson,2017,285:68-78.
[14]NAITO A,TASEI Y,NISHIMURA A,et al.Packing arrangements and intersheet interaction of alanine oligopeptides as revealed by relaxation parameters obtained from high-resolution13C solid-state NMR[J].J Phys Chem B,2017,121(38):8 946-8 955.
[15]RAYA J,HIRSCHINGER J.Sensitivity enhancement by multiplecontact cross-polarization under magic-angle spinning[J].JMagn Reson,2017,281:253-271.