【作者】 蒋可志；

【导师】 冯建跃； 陈关喜；

【作者基本信息】 浙江大学 ， 应用及分析化学， 2005， 硕士

【摘要】 聚醚表面活性剂在水中以分子状态存在,稳定性高,不具毒性,与其他类型的表面活性剂相溶性好,并具有良好的抑泡效果、乳化能力和洗涤作用,已广泛地应用于许多工业部门以及民用洗涤等各个领域。随着石油工业的发展,聚醚类表面活性剂产量和品种一直在上升。聚醚类表面活性剂分子量通常变化比较大,其组成及结构都比较复杂,而这些差异都会明显地改变聚合物的物化性质。所以,至今为止聚醚类化合物的结构表征仍是一个方兴未艾的大课题。 本研究合成了两种叔丁基苯二酚聚氧化乙烯齐聚物和一种聚氧化乙烯（EO）氧化丙烯（PO）嵌段共聚物（EP3）,分别利用硅胶柱层析、凝胶渗透色谱、红外光谱、核磁共振(¹H谱、¹³C谱、DEPT谱)以及傅立叶变换离子回旋共振质谱（ESI-FT-ICR-MS）进行了比较系统的表征研究: 1.对叔丁基苯二酚聚氧化乙烯进行质谱分析,利用FT-ICR-MS的超高质量精度,确定谱图中各峰所对应的分子式。将谱图中各系列峰的精确质量对其聚合度进行线性拟合,求算聚合单体精确质量,并根据末端基质量计算其聚合度。发现它们质谱图中都存在二叔丁基苯二酚聚氧化乙烯的一系列离子峰,并利用谱图中各个系列峰的质量及其谱峰强度,计算出样品中主成分的聚合参数以及其相对含量。 2.对EP3聚醚化合物,以硅胶做固定相,采用氯仿—乙醇做流动相进行梯度淋洗,发现聚合物根据其极性大小,由弱至强（化合物EO含量由少至多）逐渐被淋洗出来。从EP3样品分离出聚环氧丙烷组分和EO/PO嵌段共聚物,并得到红外、凝胶渗透色谱和核磁共振(¹H-NMR和¹³C-NMR谱图)的证实。 3.根据¹H-NMR数据,计算EP3经柱层析分离出两个流分中的EO/PO单元比例分别为0.4/10.0和16.6/10.0。利用核磁DEPT谱图,并参考文献数据,对EP3经柱分离出组分的¹³C-NMR谱图中各峰进行归属。并且,从¹³C-NMR谱图中获得EP3各流分的结构信息:从谱图信息确认该聚合物是EO/PO嵌段聚合物,而且其嵌段次序为PO-EO-PO,也存在一些PO-EO二嵌段序列化合物。 4.对EP3柱层析分离出的两个组分进行了ESI-FT-ICR-MS分析。利用其超高质量精度,确定各组分峰的分子式,并计算各分子式中EO、PO单元数目:利用其超高分辨能力,检测出质量仅在小数点后第二位存在差别的组分,并发现EO/PO共聚物中,EO更多还原

【Abstract】 As an important member of nonion surfactant, polyethers are nontoxic, have a good stability for its existing in water in the form of molecule, behaves well dissolution with other kinds of surfactants, and shows wonderful capability of antifoam, emulsification and detergent. It has been widely used in many household and industrial for these superiorities, and the kinds and the capacities of it are increasing with the development of the petroleum industry. Usually, the polyethers have a relatively large molecular weight, and are very complex in its components and structure. However, some of these differences will arouse great difference in the polymer’s properties. So far, the structural analysis of nonion surfactants is either a challenge work for analysts.In this paper, polyoxyethylene 4-tert-butyl-cresol, polyoxyethylene 2-tert-butyl-benzene-1,2-diol and oxyethylene- oxypropylene copolymer(EP3) are synthesized, and identified roundly by many modern methods as follows:1. The samples of 4-ter-butyl — benzene-1,2-diol poly oxyethylene and 2-ter-butyl-benzenz-1,2-diol poly oxyethylene were analyzed by using FT-ICR-MS. It was found that FT-ICR-MS is a good method for identifying the oligomer with relative sample components. The molecular formulas of the peaks in the spectra were obtained by taking the super mass accuracy of FT-MS. From the plot of mass weight of each series of peaks in the spectra Vs its polymerization degree, the accurate mass of the repeat unit was attained, and the real polymerization degree of each peak was obtained according to the mass of the end groups. A series of peaks raised from the impurity of polyoxyethylene di-tert-butyl-benzene-diol were detected in both of the spectra. The polymerization parameter and the content of main component in the samples were acquired on the basis of the data in the mass spectra.2. The copolymer sample EP3 was seperated by liquid column chromatography, which used silicon gel (300 mesh) as stationary phase and chloroform - ethanol as the mobile phase gradient eluantion program. The components were eluted according to its polarity from the weak to the strong. Besides, the components of polyoxypropythene and the PO/EO/PO block copolymer were separated from the sample, which were identified by IR, ~1H-NMR and13C-NMR.3. The EO/PO molar ratio of the two components of EP3, which were separated by liquid column chromatography, was acquired by using ’H-NMR data. The assignment of the 13C-NMR peaks of the EP3 components were made with the help of its DEPT spectra and reference data. And from the 13C-NMR data, many structure information were obtained: the sample was identified to be a block copolymer, and its sequence to be PO/EO/PO, and some two block of the copolymer PO/EO components were also detected; the molar ratios of EO/PO were calculated either.4. The two components of EP3 were analyzed by using FT-ICR-MS. The molecular formulas of the peaks in the mass spectra were obtained according to the super mass accuracy of FT-MS, and two components with molecular weight difference at 0.03amu were separated and identified by taking the advantage of its the super mass resolution. It was found that some of the end group in the polymer has lost hydroxyl and formed double carbon bond —O— CH=CH—CH3, which was confirmed by IR spectra, and that the more content of EO, the more easily it loses hydroxyl. Besides, great difference of the ratio and serious mass discrimination was found to be in the measurement of the intricate copolymer by ESI-MS.更多还原