首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化...首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化剂催化合成环氧化大豆油的催化性能。结果表明:以叔丁基过氧化氢(TBHP)为氧化剂,固体催化剂对大豆油的环氧反应具有良好的催化性能,相比于催化剂1(磺酸化低聚苯乙烯基膦酸-磷酸氢锆),在相同的条件下,催化剂2(磺酸化聚(苯乙烯-苯乙烯膦酸)-磷酸氢锆)表现出更高的催化活性(产率:58.6% vs 53.3%),这主要归因于催化剂2拥有更大的比表面积、孔容以及孔径,为底物和催化剂的接触提供足够的催化场所。催化剂2重复使用7次后,催化活性未见明显降低。第8次反应结束后,将其置于2 mol·L^-1稀盐酸中静置过夜后,在进行第9和10次循环时,催化活性又得以恢复。展开更多
The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO4)1.34[O3PCH2N- (CH2CO2H)2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO4)2-x [O3PCH2N(CH...The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO4)1.34[O3PCH2N- (CH2CO2H)2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO4)2-x [O3PCH2N(CH2CO2H)2]x·H2O (ZPPMIDA) by the reaction of zirconium oxychloride with phosphonic acid and H2O3PCH2N(CH2CO2H)2 in the designed x range of 0 < x < 2, which had been monitored by using the phosphorus integration value ratio of HPO42- and [O3PCH2N(CH2CO2H)2]2- group in the 31P MAS NMR spectra. After intercala- tion of n-butyl amine, the 31P chemical shift of HPO42- group at - 8.0￣- 10.0 ppm moved to 6.0 ppm with a change of 14.0￣16.0 ppm and that of [O3PCH2N(CH2CO2H)2]2- group at - 29.1 ppm changed only 0.5 ppm. Due to the pil- lared effect of [O3PCH2N(CH2CO2H)2]2- groups on the interlayer spacing, intercalated amines such as n-butylamine, n-hexyl amine and n-octyl amine easily reacted with HPO42- group in ZPPMIDA (x=0.66) rather than that in α- ZrP, and carboxylic group (-CO2H) in ZPPMIDA (x=0.66).展开更多
Chloromethyl-zirconium oligo-polystyrenyl-phosphonatephosphate was used as the support of salen Mn(Ⅲ) which was synthesized by statistical method.The chloromethyl group of the support reacted with the free hydroxy of...Chloromethyl-zirconium oligo-polystyrenyl-phosphonatephosphate was used as the support of salen Mn(Ⅲ) which was synthesized by statistical method.The chloromethyl group of the support reacted with the free hydroxy of salen,and then with Mn(OAc)2·4H2O,so a new type of salen Mn(Ⅲ) catalyst supported on zirconium oligo-polystyrenyl-phosphonate-phosphate was synthesized.The catalyst was characterized by IR,SEM,element analysis and BET surface area.展开更多
文摘首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化剂催化合成环氧化大豆油的催化性能。结果表明:以叔丁基过氧化氢(TBHP)为氧化剂,固体催化剂对大豆油的环氧反应具有良好的催化性能,相比于催化剂1(磺酸化低聚苯乙烯基膦酸-磷酸氢锆),在相同的条件下,催化剂2(磺酸化聚(苯乙烯-苯乙烯膦酸)-磷酸氢锆)表现出更高的催化活性(产率:58.6% vs 53.3%),这主要归因于催化剂2拥有更大的比表面积、孔容以及孔径,为底物和催化剂的接触提供足够的催化场所。催化剂2重复使用7次后,催化活性未见明显降低。第8次反应结束后,将其置于2 mol·L^-1稀盐酸中静置过夜后,在进行第9和10次循环时,催化活性又得以恢复。
文摘The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO4)1.34[O3PCH2N- (CH2CO2H)2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO4)2-x [O3PCH2N(CH2CO2H)2]x·H2O (ZPPMIDA) by the reaction of zirconium oxychloride with phosphonic acid and H2O3PCH2N(CH2CO2H)2 in the designed x range of 0 < x < 2, which had been monitored by using the phosphorus integration value ratio of HPO42- and [O3PCH2N(CH2CO2H)2]2- group in the 31P MAS NMR spectra. After intercala- tion of n-butyl amine, the 31P chemical shift of HPO42- group at - 8.0￣- 10.0 ppm moved to 6.0 ppm with a change of 14.0￣16.0 ppm and that of [O3PCH2N(CH2CO2H)2]2- group at - 29.1 ppm changed only 0.5 ppm. Due to the pil- lared effect of [O3PCH2N(CH2CO2H)2]2- groups on the interlayer spacing, intercalated amines such as n-butylamine, n-hexyl amine and n-octyl amine easily reacted with HPO42- group in ZPPMIDA (x=0.66) rather than that in α- ZrP, and carboxylic group (-CO2H) in ZPPMIDA (x=0.66).
文摘Chloromethyl-zirconium oligo-polystyrenyl-phosphonatephosphate was used as the support of salen Mn(Ⅲ) which was synthesized by statistical method.The chloromethyl group of the support reacted with the free hydroxy of salen,and then with Mn(OAc)2·4H2O,so a new type of salen Mn(Ⅲ) catalyst supported on zirconium oligo-polystyrenyl-phosphonate-phosphate was synthesized.The catalyst was characterized by IR,SEM,element analysis and BET surface area.
