CN103880769A - 杂多酸十三吗啉季铵盐及其制备方法和用途 - Google Patents
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Abstract
本发明公开了一种杂多酸十三吗啉季铵盐及其制备方法和用途,杂多酸十三吗啉季铵盐通过十三吗啉的烷基化和阴离子交换两步反应制备得到;该化合物作为环氧化催化剂在大豆油与过氧化氢环氧化反应制备环氧大豆油中的应用。本发明的优点是:杂多酸十三吗啉季铵作为大豆油制备环氧大豆油的催化剂,不但催化活性高、并且反应结束后易分离回收、重复使用性能好。
Description
技术领域
本发明涉及一种杂多酸十三吗啉季铵盐的制备方法。
背景技术
杂多酸具有独特的酸性和氧化还原性,且腐蚀性小,是大豆油与过氧化氢环氧化反应制备环氧大豆油良好的催化剂。但杂多酸水溶性好,在有机相中溶解性差,在实际应用过程中存在因分布不均匀所造成的不稳定的催化活性。同时,其水溶性好的特点使得回收困难,且与其它酸催化剂相比,价格偏高,价高又难以回收的缺点使其无法应用于工业化生产;负载型杂多酸催化剂降低了使用成本,同时在催化性能上有所改善,但离实际应用还需要进一步研究。本发明涉及到的杂多酸十三吗啉季铵盐属于阴离子为杂多酸的季铵盐型离子液体,由于其独特的分子结构,表现出优秀的相转移性能和环氧化催化性能;特别是它在反应温度时与反应物具有良好的溶解性能,使得反应几乎在均相进行;更为突出的是,该催化剂在较低的温度时能够从反应体系中凝固析出,分离简便,不需要作进一步的处理就能用于下一轮反应,因此特别适合于环氧大豆油的工业生产。
发明内容
本发明的目的在于提供一种催化性能优异、容易回收和重复使用的杂多酸十三吗啉季铵盐及其制备方法和用途。
本发明的技术解决方案是:
一种杂多酸十三吗啉季铵盐,其特征是:结构式为:
R为正丁基、正辛基、苄基、2-吡啶甲基,C13H27为正十三基,HPA-为[H2PW12O40]-或[H4PMo10V2O40]-。
一种所述的杂多酸十三吗啉季铵盐的制备方法,其特征是:包括下列步骤:
1)卤化十三吗啉季铵盐的制备:十三吗啉与等摩尔的卤代烃100~120℃反应24~72h,经重结晶,得淡黄色固体或粘稠物,即为卤化十三吗啉季铵盐;
2)杂多酸十三吗啉季铵盐的制备:上述第1)步所得卤化十三吗啉季铵盐溶解于1,2-二氯乙烷,加入等摩尔的杂多酸,加热回流,除去卤化氢,浓缩,得到杂多酸十三吗啉季铵盐。
所述卤代烃为正丁基溴、正辛基溴、苄基氯或2-氯甲基吡啶。
所述卤化氢为氯化氢或溴化氢。
一种杂多酸十三吗啉季铵盐作为环氧化催化剂在大豆油与过氧化氢环氧化反应制备环氧大豆油中的应用,其特征是:包括以下步骤:
按大豆油、催化剂杂多酸十三吗啉季铵盐的质量比为100:1~3投料,控制反应温度为45~65℃,搅拌下滴加30%的双氧水,双氧水滴加的量是大豆油的质量的40~80%,滴完后,保温反应1~8小时,冷却,催化剂呈固状或半固状析出,分离,催化剂可循环使用,有机层经干燥,得环氧大豆油产品。
本发明具有以下优点:
具相转移催化剂及氧化催化剂的双重功能。特别是在反应温度时与反应物具有良好的溶解性能,使得反应几乎在均相进行;更为突出的是,该催化剂在较低的温度时能够从反应体系中凝固析出,分离简便,不需要作进一步的处理就能用于下一轮反应,因此特别适合于环氧大豆油的工业生产。作为催化剂能循环使用多次,仍保持较高的活性。作为大豆油制备环氧大豆油的催化剂,简化了环氧大豆油的生产流程,并且生产过程基本无废水、绿色环保。
下面结合实施例对本发明作进一步说明。
具体实施方式
实施例1:十三吗啉季铵盐的制备
44.6g(0.150mol)十三吗啉与20.6g(0.150mol)正丁基溴120℃下搅拌反应48h,得黄色半固体粗品,经乙酸乙酯重结晶,得淡黄色固体的溴化十三吗啉正丁基铵63.2g,产率96.9%。
实施例2:磷钨酸正丁基十三吗啉铵盐的制备
4.3g(0.010mol)溴化正丁基十三吗啉铵与28.8g(0.010mol)H3PW12O40在100mL1,2-二氯乙烷中加热回流、搅拌反应,利用吸气装置吸收产生的溴化氢,直至无溴化氢气体产生,蒸馏除去溶剂,得到32.3g乳白色的磷钨酸正丁基十三吗啉铵盐,产率100%。
所得磷钨酸正基十三吗啉季铵盐的测定结果:
核磁共振氢谱(1H NMR,300MHz,D2O)δ3.67-3.61(m,2H),3.52-3.49(m,4H),3.24-3.22(m,4H),1.34-1.32(m,22H),1.73(m,4H),1.21(d,J=7.2Hz,6H),0.97(t,J=7.2Hz,3H),0.96(t,J=7.2Hz,3H)。
傅里叶变换红外光谱(溴化钾压片):3404cm-1(宽锋)为H-O键的伸缩振动峰;2959cm-1、2873cm-1为甲基C-H键的伸缩振动峰;2928cm-1为亚甲基C-H键的伸缩振动峰;1333cm-1为吗啉环上C-H键的弯曲振动峰;1463cm-1、1379cm-1为甲基C-H键的弯曲振动峰;1181cm-1为C-N+键的伸缩振动峰;1080cm-1、978cm-1、896cm-1、820cm-1为磷钨酸的特征吸收峰。
实施例3:环氧大豆油的制备
250mL三颈瓶上安装电动搅拌机、回流冷凝管,加100.0g大豆油(碘值130,酸值0.50)、2.0g磷钨酸正丁基十三吗啉铵盐催化剂于瓶中,控制反应温度55℃,搅拌下通过恒压滴液漏斗缓慢滴加65mL30%的双氧水,滴完,再保温反应3小时,冷却,过滤回收催化剂,分出有机相,经干燥后得环氧大豆油,产品经测定,环氧值为6.3%,碘值4.25g/100g,酸值0.35mg/g。
实施例4:催化剂重复使用性能
将前一轮分离所得催化剂用于下一轮试验,步骤同实例3,五轮试验所得的环氧大豆油的环氧值分别为6.3%、6.2%、6.3%、6.2%、6.1%,碘值分别4.25、4.30、4.20、4.33、4.38g/100g,酸值分别为0.35、0.37、0.40、0.44、0.48mg/g。
Claims (5)
1.一种杂多酸十三吗啉季铵盐,其特征是:结构式为:
R为正丁基、正辛基、苄基、2-吡啶甲基,C13H27为正十三基,HPA-为[H2PW12O40]-或[H4PMo10V2O40]-。
2.一种权利要求1所述的杂多酸十三吗啉季铵盐的制备方法,其特征是:包括下列步骤:
1)卤化十三吗啉季铵盐的制备:十三吗啉与等摩尔的卤代烃100~120℃反应24~72h,经重结晶,得淡黄色固体或粘稠物,即为卤化十三吗啉季铵盐;
2)杂多酸十三吗啉季铵盐的制备:上述第1)步所得卤化十三吗啉季铵盐溶解于1,2-二氯乙烷,加入等摩尔的杂多酸,加热回流,除去卤化氢,浓缩,得到杂多酸十三吗啉季铵盐。
3.根据权利要求2所述的杂多酸十三吗啉季铵盐的制备方法,其特征是:所述卤代烃为正丁基溴、正辛基溴、苄基氯或2-氯甲基吡啶。
4.根据权利要求2所述的杂多酸十三吗啉季铵盐的制备方法,其特征是:所述卤化氢为氯化氢或溴化氢。
5.一种权利要求1所述的杂多酸十三吗啉季铵盐作为环氧化催化剂在大豆油与过氧化氢环氧化反应制备环氧大豆油中的应用,其特征是:包括以下步骤:
按大豆油、催化剂杂多酸十三吗啉季铵盐的质量比为100:1~3投料,控制反应温度为45~65℃,搅拌下滴加30%的双氧水,双氧水滴加的量是大豆油的质量的40~80%,滴完后,保温反应1~8小时,冷却,催化剂呈固状或半固状析出,分离,催化剂可循环使用,有机层经干燥,得环氧大豆油产品。
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CN105566298A (zh) * | 2016-02-16 | 2016-05-11 | 顾伟 | 一种制备埃索美拉唑钠的方法 |
CN105732447A (zh) * | 2016-02-16 | 2016-07-06 | 顾伟 | 一种4,4’-二氯二苯砜的制备方法 |
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CN104707654A (zh) * | 2014-02-27 | 2015-06-17 | 南通大学 | 杂多酸十三吗啉季铵盐的用途 |
CN104707654B (zh) * | 2014-02-27 | 2017-01-11 | 南通大学 | 杂多酸十三吗啉季铵盐的用途 |
CN105566298A (zh) * | 2016-02-16 | 2016-05-11 | 顾伟 | 一种制备埃索美拉唑钠的方法 |
CN105732447A (zh) * | 2016-02-16 | 2016-07-06 | 顾伟 | 一种4,4’-二氯二苯砜的制备方法 |
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