界面聚合法制备聚脲多孔材料

发布时间：2018-05-10 19:07

本文选题：界面聚合 + 聚脲多孔材料　；参考：《济南大学》2017年硕士论文

【摘要】：本文以甲苯二异氰酸酯(TDI)和乙二胺(EDA)为单体通过界面聚合法制备出大粒径的多孔聚脲(PU)微球。探讨了针头内径和单体的滴加速率对PU微球尺寸的影响,研究了聚合时间、聚合温度、EDA与TDI的摩尔比等对PU微球形貌和结构的影响。通过对硝基苯甲醛(NBA)与PU多孔微球表面伯胺的反应测定了PU微球表面伯胺基含量,通过光学显微镜和扫描电子显微镜(SEM)对微球的形貌做了表征,通过压汞法对PU多孔微球的孔结构进行了表征,采用热重分析仪和差示扫描量热仪对PU多孔微球的热性能进行了表征,使用X-射线衍射仪测试了微球的结晶性能,使用核磁共振仪对PU的化学结构进行了表征。改变针头的内径及TDI单体的滴加速率,可制备粒径介于400~750?m的大小均一的多孔PU微球。当EDA与TDI的摩尔比为1:7,65°C反应5 h可制得表面光滑粒径均一的PU多孔微球。测得PU微球表面胺基基团密度为1.179×10-8 mmol/cm2(0.071/nm2)。SEM表征表明微球表面为粗糙的外壳,内部为多孔结构。PU多孔微球的比表面积为8.2m2/g,孔体积为0.4 cm3/g,孔隙率为31%。PU微球有良好的耐热性能,XRD对PU微球的结晶表征得到其结晶度为41%。核磁1H谱和13C谱测试表明,TDI液滴表面单体首先与连续相中的EDA反应形成硬壳,TDI随后与H2O反应直到聚合完成。当体系中EDA加入量过多时,形成的PU微球规整性变差。当EDA/TDI摩尔比为1.43时,制得的PU微球之间呈现串珠状排列且微球之间有聚合物相连。选用内径不同的针头,改变TDI的滴加速率可以改变串珠的尺寸和规整度。对串珠的形貌做表征,结果表明串珠表面光滑且分布有孔洞,内部为多孔结构。串珠孔体积为0.3 cm3/g,孔隙率为26%。改变针头的内径可以制得直径不同的棒状PU。当针头内经为300?m,且控制TDI单体的滴加速率在140 m L/h时可以制得粗细均匀的棒状PU。对其表面和内部形貌表征结果表明,棒状PU表面光滑,内部为多孔结构。
[Abstract]:In this paper, a large size porous polyurea (PUU) microspheres were prepared by interfacial polymerization with toluene diisocyanate (TDI) and ethylenediamine (EDA) as monomers. The effects of needle diameter and monomer dropping rate on the size of pu microspheres were investigated. The effects of polymerization time, polymerization temperature and molar ratio of EDA to TDI on the morphology and structure of pu microspheres were studied. The primary amine content on the surface of pu microspheres was determined by the reaction of p-nitrobenzaldehyde (NBA) with primary amine on the surface of pu porous microspheres. The morphology of pu microspheres was characterized by optical microscope and scanning electron microscope (SEM). The pore structure of pu porous microspheres was characterized by mercury injection method, the thermal properties of pu porous microspheres were characterized by thermogravimetric analyzer and differential scanning calorimeter, and the crystallization properties of pu porous microspheres were tested by X- ray diffractometer. The chemical structure of pu was characterized by NMR. By changing the inner diameter of the needle and the dropping rate of the TDI monomer, the porous pu microspheres with a diameter of 400 ~ 750m can be prepared. When the molar ratio of EDA to TDI is 1: 765 掳C for 5 h, the porous pu microspheres with uniform surface size can be prepared. The Amino group density on the surface of pu microspheres was 1.179 脳 10 ~ (-8) mmol/cm2(0.071/nm2).SEM. The results showed that the surface of pu microspheres was a rough shell. The specific surface area of porous microspheres is 8.2 m2 / g, the pore volume is 0.4 cm ~ 3 / g, and the porosity of 31%.PU microspheres has good heat resistance. The crystallinity of pu microspheres is 41%. NMR 1H and 13C spectra show that the surface monomer of TDI first reacts with EDA in continuous phase to form a hard shell TDI and then reacts with H2O until the polymerization is completed. When the amount of EDA in the system is too much, the regularity of the pu microspheres becomes worse. When the molar ratio of EDA/TDI is 1.43, the pu microspheres are arranged in series and the microspheres are connected with each other. The size and regularity of beads can be changed by changing the dropping rate of TDI with different inner diameter needles. The morphology of the beaded beads was characterized. The results showed that the surface of the beaded beads was smooth and the pores were distributed, and the inner structure of the beaded beads was porous. The volume of beaded pore is 0.3 cm 3 / g, and the porosity is 26%. The rod-shaped pu with different diameter can be obtained by changing the inside diameter of the needle. When the needle's internal passage is 300m, and the dropping rate of TDI monomer is controlled at 140ml / h, the rod shape can be obtained. The surface and internal morphologies of the pu show that the rod-like pu has a smooth surface and a porous structure.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ317;TB383.4

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