CN105498698B - 一种多孔型含氮柔性长链的桥联聚倍半硅氧烷的制备方法 - Google Patents
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Abstract
本发明公开了一种多孔型含氮柔性长链的桥联聚倍半硅氧烷的简单制备方法。本方法先将3‑氯丙基三甲氧基硅烷与二乙烯三胺反应，得到含氮柔性长链的桥联单体；再将其在催化剂作用下于一定温度下自然凝胶，抽提、干燥后即得最终产品。该制备方法简单，无须另外添加致孔剂，所得产品氮功能基含量高且具有较高的比表面积和孔隙度，对Au3+和Ag+显示了优异的吸附性能。
Description
技术领域
本发明涉及多孔型含氮柔性长链的桥联聚倍半硅氧烷吸附剂的制备方法及其所制得的产品。
背景技术
吸附材料是一类利用材料本身能发生吸附－解吸作用以达到物质的分离、净化目的的材料，应用领域十分广泛。一般认为，理想的吸附材料应具有高孔隙度、高吸附量、高选择性及在恶劣条件下的高稳定性，并且为了便于日后的大规模工业生产，降低生产成本，其合成方法要尽量简单，重复性好，并在合成过程中可以对最终产物的物理化学性质及结构—吸附性能进行调控。从这个角度看，桥联聚倍半硅氧烷成为一类颇具吸引力的吸附材料。
用于制备这类杂化材料的单体在结构上具有一个显著的特点，即单体由有机桥联基团和功能化的烷基硅烷组成。通过改变有机基团可以对杂化材料的整体性能(如孔径、热稳定性、折射率、介电常数等) 进行精细调控。公开号为CN 102372851的中国发明专利公开了桥联聚倍半硅氧烷气凝胶及其制备方法；公开号为CN 101747361的中国发明专利公开了含环氧基的硅烷单体与含氨基的硅烷单体或二元胺进行反应制备桥联单体的方法；公开号为CN 103450247的中国发明专利公开了一种芳基桥联倍半硅氧烷单体的制备方法，包括二卤代芳烃与金属镁进行格氏反应制得格氏试剂，以及格氏试剂与三乙氧基氯硅烷进行亲核取代反应生成芳基桥联倍半硅氧烷单体；公开号为CN103204871和CN103204870的中国发明专利公开了含硫桥联倍半硅氧烷单体及其制备方法与应用。上述桥联单体中桥联基团多为短链的刚性结构，制备凝胶材料时成孔性较好，但是若作为吸附材料使用时，其螯合功能基含量明显不足。
含氮功能基对各种金属离子具有很好的螯合作用。本课题组曾以含环氧基团的硅烷偶联剂和多胺为原料，合成了一系列多胺桥联聚倍半硅氧烷吸附材料，在合成中发现，由于桥联基团的柔顺性和羟基之间的氢键作用使桥之间缠结现象十分严重，必须加入致孔剂十六烷基三甲基溴化铵（CTAB）和起骨架支撑作用的四乙氧基硅烷才能得到多孔型材料，而这些试剂的加入，虽然增加了材料的比表面积却降低了材料中功能基的含量，从而降低了材料的吸附性能。且合成后期需要去除致孔剂CTAB，过程繁琐，残留的CTAB也会影响材料的性能。。
发明内容
本课题旨在用简单的方法，无须添加致孔剂，合成多孔型且氮功能基含量高的桥联聚倍半硅氧烷吸附材料，并将其应用于水溶液中金、银离子的富集分离。本发明的目的可以通过如下措施来达到：（1）将3-氯丙基三甲氧基硅烷分散到乙醇溶液中，加入二乙烯三胺，在氮气保护下加热搅拌反应一定时间，得到二乙烯三胺桥联单体的乙醇溶液，置于聚丙烯瓶中密封保存。（2）将桥联单体乙醇溶液中加入氢氧化钠溶液，在一定温度下凝胶、陈化后，用无水乙醇和盐酸抽提，真空干燥后得最终产品。本发明与已有技术相比具有如下优点：合成工艺简单，反应条件温和，时间短，易控制，合成效率高；制备过程中 “三废”产生，该吸附剂价格低廉，机械稳定性和化学稳定性好；对金、银等贵金属离子具有相当优异的吸附能力。
本发明的目的还可通过如下具体措施来实现：
实施例1：
于三颈瓶中分别加入100 ml乙醇，22 ml 3-氯丙基三甲氧基硅烷和10 ml 二乙烯三胺，在70℃氮气保护下机械搅拌回流12 h，得到二乙烯三胺桥联单体的乙醇溶液，置于聚丙烯瓶中密封保存。
向40ml上述单体的乙醇溶液中加入 4ml浓度为0.014g/ml 氢氧化钠溶液，在室温条件下自然凝胶。凝胶完成后，于70℃下陈化4小时，85℃下陈化4天，然后取出凝胶研磨，并室温干燥。将干燥后的凝胶置于索氏提取器中抽提72小时，采用无水乙醇（270 ml）和盐酸（37%，15 ml）作为溶剂。之后将产品放在60℃真空干燥箱中干燥，得淡黄色桥联聚倍半硅氧烷产品，比表面积可达215 m2g-1。
实施例2：
于三颈瓶中分别加入100 ml乙醇，22 ml 3-氯丙基三甲氧基硅烷和5 ml 二乙烯三胺，在85℃氮气保护下机械搅拌回流12 h，得到二乙烯三胺桥联单体的乙醇溶液，置于聚丙烯瓶中密封保存。
向40ml上述单体的乙醇溶液中加入 2ml浓度为0.014g/ml 氢氧化钠溶液，在30℃下自然凝胶。凝胶完成后，于70℃下陈化4小时，85℃下陈化4天，然后取出凝胶研磨，并室温干燥。将干燥后的凝胶置于索氏提取器中抽提72小时，采用无水乙醇（270 ml）和盐酸（37%，15 ml）作为溶剂。之后将产品放在60℃真空干燥箱中干燥，得淡黄色桥联聚倍半硅氧烷产品，比表面积可达220 m2g-1。
应用实例1：
对Au3+的吸附。称取20 mg吸附材料置于碘量瓶中，分别加入20 ml 5×10-3 mol/l的金离子溶液，在25 ℃，120r/min的振荡箱里，振荡48h后，静置，取上层清液。用原子吸收分光光度计测定溶液中的金属离子浓度。根据吸附前后金属离子浓度的变化，计算其对Au3+离子的饱和吸附量为4.488 mmolg-1。
应用实例2：
对Ag+的吸附。称取20 mg吸附材料置于碘量瓶中，分别加入20 ml 5×10-3 mol/l的银离子溶液，在25 ℃，120r/min的振荡箱里，振荡48h后，静置，取上层清液。用原子吸收分光光度计测定溶液中的金属离子浓度。根据吸附前后金属离子浓度的变化，计算CPTS-DETA对Ag+离子的饱和吸附量为4.746 mmolg-1。
Claims (2)
1.一种多孔型含氮柔性长链的桥联聚倍半硅氧烷的制备方法，其特征在于该制备方法由如下两个步骤组成：
(1) 将3-氯丙基三甲氧基硅烷分散于乙醇中，加入二乙烯三胺，在氮气保护下加热搅拌反应一定时间，得到含氮柔性长链的桥联单体乙醇溶液；
(2) 于桥联单体乙醇溶液中，加入氢氧化钠水溶液，于一定温度下凝胶、陈化，过滤出固体，经无水乙醇和盐酸抽提、真空干燥后得最终产品多孔型含氮柔性长链的桥联聚倍半硅氧烷吸附剂，
其中：
所述步骤(1) 需在氮气保护下进行，在制备桥联单体的反应中，二乙烯三胺与3-氯丙基三甲氧基硅烷的摩尔比为1∶(1～10)；反应温度为20～90℃；反应时间为5～24h；所述桥联单体与氢氧化钠的摩尔比为1∶(0.001～0.01)，反应温度为20～90℃，反应时间为4～72h。
2.根据权利要求1所述的多孔型含氮柔性长链的桥联聚倍半硅氧烷的制备方法，其特征在于该产品用于水溶液中Au3+、Ag+的高效富集回收。
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| CN101747361A (zh) * | 2008-12-04 | 2010-06-23 | 中国科学院化学研究所 | 一种桥联聚倍半硅氧烷及其单体与它们的制备方法 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5476985A (en) * | 1994-12-16 | 1995-12-19 | Uop | Process for separating linear and branched hydrocarbons using alkylene-bridged polysilsesquioxanes |
| CN101747361A (zh) * | 2008-12-04 | 2010-06-23 | 中国科学院化学研究所 | 一种桥联聚倍半硅氧烷及其单体与它们的制备方法 |
| WO2012012311A2 (en) * | 2010-07-23 | 2012-01-26 | The Regents Of The University Of California | Compositions and methods for synthesis of organic-silica hybrid materials |
| CN103450248A (zh) * | 2013-09-13 | 2013-12-18 | 合肥学院 | 一种含芳环桥联倍半硅氧烷单体的制备方法 |
Non-Patent Citations (3)
| Title |
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| "Syntheses of diethylenetriamine-bridged polysilsesquioxanes and their structure–adsorption properties for Hg(II) and Ag(I)";Changmei Sun et al.;《Chemical Engineering Journal》;20131210;第240卷;第369-378页 * |
| "Syntheses of polyamine-bridged polysilsesquioxanes hybrid materials combining sol-gel processing and molecular imprinting applied to selective adsorption for copper";Changmei Sun et al.;《Materials Chemistry and Physics》;20150107;第153卷;第307-315页 * |
| "桥联聚倍半硅氧烷及其在吸附领域中的应用";李春雪等;《离子交换与吸附》;20121031;第28卷(第5期);第469-480页 * |
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| CN105498698A (zh) | 2016-04-20 |
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