Grafting Modification And Immobilizing MTO Of Halloysite

Epoxy soybean oil has been the main component of plasticizer. Catalyzing epoxidation of soybean oil is becoming the main point of industrialization. Modifying carriers has attracted considerable interests. The preparation and application of modified carriers has been reported on different areas of chemical engineering. Immobolizing Re on modified halloysite can catalyze epoxidation of soybean oil, as a modified carrier. The advantages of modified carriers are as follow: clean, high selectivity, and high yields of products, recovery and recycling. This study is about the preparation of modifying natural nanotube carriers and its application on epoxidation of soybean oil. The main researching works and results are as follows.Halloysite nanotubes are modified by in situ polymerization and "live" polymerization, separately. To achieve in situ polymerization, amino groups are grafted by silane coupling agent Z6020, then anchored double bond on HNTs by amidation, at last, P-4VP chains are attached onto the wall of HNTs. FT-IR, DTA-TG, are introduced to characterize different products. The successful immobilization of P-4VP is indicated by FT-IR. DTA shows the immobilization of P-4VP. TG shows the results of weight loss. The rate of mNTs, vNTs, pNTs are 7.22%,9.43%,15.3%, separately.To achieve "live" polymerization on nanotubes, the initiators are introduced to graft HNTs. With aluminum (amphoteric hydroxide) in HNTs, the initiator 2-bromoisobutyrate bromide is easy initiated onto the -OH of HNTs. Me6tren, CuCl and CuCl2 are used as coordinate agent, catalyst and passivator, separately to achieve Surface Initiated Atom Transfer Radical Polymerization (SI-ATRP). The molecular weight can be controlled by adjusting the polymerization time of the SI-ATRP. The chemical composition of the nanotubes at various stages of modification is characterized by FT-IR, TGA, H1-NMR and GPC. The results shows that grafting polymerization of P-4VP can be achieved by in situ polymerization, the degree of branching increased in the company of extended hours by SI-ATRP. M-NTs, M-IPNTs and M-SPNTs are obtained by immobilizing MTO on HNTs, IPNTs and SPNTs respectively. The immobilization of MTO is characterized by TEM and UV. The result shows that M-NTs lead to the coacervate of MTO; But on modified carriers, MTO distribute on the polymer surface uniformly. The degree of immobilizing MTO increased with increasing molecule weight.MTO, M-NTs, M-IPNTs and M-SPNTs are used to catalyze epoxidation of soybean oil, separately. H1-NMR is performed to characterize epoxydation. The result shows that, to in situ polymerization, the conversion of M-IPNTs is higher than MTO, the conversion of M-NTs is lowest. To the spiceman modified by ATRP, the conversion of soybean oil increased with increasing load degree. The order of M-SPNTs is 12 h>6 h>3 h.