CN110681875B - 一种异斯特维醇类金属凝胶及其制备方法和应用 - Google Patents
一种异斯特维醇类金属凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种异斯特维醇磺酸银类超分子凝胶及其制备方法和其在纳米银制备中的应用，属功能材料领域。该类凝胶剂是由天然产物异斯特维醇经酯化、磺化和成盐制备而成，具有磺酸银结构片段。结构如式1所示，其中R为烷烃基、芳香烃基。该类凝胶剂具有很好的凝胶性能，最低凝胶浓度低至0.2%w/v，并能通过绿色、方便的光致还原过程原位制备纳米银。该凝胶体系制备方法简单、成本低、溶剂可回收再利用。所制备的纳米银粒径均匀、方法简单，为纳米银的制备提供了一种便利的模板。
式1。
Description
技术领域
本发明公开了一种异斯特维醇磺酸银类超分子凝胶、其制备方法及其在纳米银制备中的应用，属功能材料领域。
背景技术
纳米金属粒子是尺寸小于100nm的超细金属粒子，是纳米科学中一个重要的研究方向。纳米银具有良好的光学、力学、热学和生物活性，所以其在光学器材、生物医学、高性能电极材料、涂料、导电浆料、传感器等领域具有广阔的应用前景。纳米金属粒子的制备一般有物理研磨法、惰性气体冷凝法、等离子体法、生物还原法、反相微乳液法以及液相还原法等。目前报道的制备法中，存在纳米银粒子粒径不均匀、易发生团聚等不足而需要分散剂，稳定剂和还原剂等，不但增加了成本、还会造成污染，因而不利于所制纳米银的广泛应用。
专利CN106180753B公开了一种琼脂糖凝胶制备纳米银的方法。该方法将银离子均匀的分布到凝胶体系中，利用琼脂糖的还原性使银离子被还原成纳米银粒子，但凝胶的制备需要加热冷却过程，自还原过程甚至需要1-15天的时间。201810939378.6专利报道了在溶液中制备纳米银，但用到了壳寡糖-水合肼硫脲衍生物作为还原剂，增加了成本，并且会带来污染。
相比于传统的制备方法，超分子凝胶能在低温下制备纯度高、粒度分布均匀、化学活性高的单、多组分混合物(分子级混合)的纳米金属粒子。此外，该方法制备的金属纳米粒子的尺寸大小及其形貌可通过改变反应物初始溶液的浓度和后期热处理过程来控制。因此，提供一种配位型银超分子凝胶体系，并以此为模板在自然光或者外加光源照射下实现纳米银粒子的制备具有重要的应用价值。
发明内容
为了克服上述现有技术的不足，本发明目的在于提供一种稳定性好，不容易发生团聚的异斯特维醇类超分子金属凝胶；另一目的在于提供其制备方法，简单、温和、低成本、绿色环保地制备目标物。
为实现本发明目的，本发明以异斯特维醇为原料，经酯化、磺化、成盐制备磺酸银类超分子凝胶。在具体操作中对反应底物、溶剂、温度、纯化过程等进行优化，提高收率，降低成本，并使所有溶剂都可回收再利用。
本发明采用的技术方案如下：
本发明所述异斯特维醇类超分子金属凝胶具有通式1所示结构：
其中R为正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正癸基、正十六烷基、苯乙基或苄基。
优选式2、式3和式4所示的异斯特维醇磺酸银类凝胶剂：
本发明提供了上述衍生物的合成方法，所述反应过程如下：
具体方法如下：
(1)加入缚酸剂，将异斯特维醇(化合物1)与卤代化合物在有机溶剂中反应，结束后蒸干溶剂，向其中加入稀盐酸洗涤粗品，过滤，干燥得化合物2。
所述溶剂采用DMF，DMSO，乙腈，乙酸乙酯，甲苯，二甲苯、四氢呋喃、二氧六环或乙醚中的一种或几种；卤代为氯代烃、溴代烃或碘代烃；缚酸剂采用KOH、NaOH、K2CO3或N,N-二甲氨基吡啶(DMAP)。
所述酯化过程反应温度选20-60℃；优选乙腈作溶剂，碘代烃为反应试剂在回流状态下反应。化合物1与卤代烃的摩尔比为1:1.2～1:2，优选1:1.5。
(2)低温下将浓硫酸滴加到乙酸酐中，滴加完毕后向体系内加入溶剂和化合物2反应至结束。蒸去溶剂得固体，体系中加入有机溶剂重结晶得化合物3。
所述反应溶剂为甲苯、二甲苯或冰乙酸，也可加入过量乙酸酐作溶剂；所述重结晶溶剂为乙酸乙酯、冰乙酸、甲醇和乙醇中的一种或几种。
优选冰醋酸做反应溶剂、乙酸乙酯-乙醇10:1做重结晶溶剂。
所述反应温度0～30℃，反应时间8～24小时。优选0～5℃。
浓硫酸选质量百分浓度90％以上，浓硫酸和乙酸酐摩尔比为1:5～10。
(3)向化合物3中加入重结晶溶液，再加入银盐水溶液或其有机溶液，洗涤后分出有机相，异斯特维醇磺酸银结晶析出，抽滤，少量水洗涤去除多余银盐和生成的酸。
所述重结晶溶剂为乙酸乙酯、乙醇、水、甲醇或甲苯的一种或几种，优选乙酸乙酯-乙醇体系，所述银盐为硝酸银、高氯酸银、四氟硼酸银、六氟磷酸银或氟化银。
银盐与化合物3的摩尔比3:1～1:1，优选1.05:1。
将异斯特维醇磺酸银分散到凝胶溶剂中室温静置体系凝胶化；也可将含有银盐的溶液加入到异斯特维醇磺酸3的溶液中实现原位凝胶化。
所述凝胶溶剂为氯仿、二氯甲烷、1,2-二氯乙烷，1,2-二溴乙烷，四氯化碳、溴丁烷、溴丙烷、异丙基溴、溴乙烷、甲苯，二甲苯、四氢呋喃中的一种或几种。
所述凝胶水溶液重量体积比为0.2％w/v-2％w/v。
本发明纳米银粒子的制备过程是将不同浓度的异斯特维醇磺酸银凝胶置于自然光或者254-365nm的紫外光下进行光致还原，随着反应时间进行体系逐渐变黑。
所述自然光光照时间为1-3天，254-365nm的紫外光还原时间10-50分钟。
与现有技术相比，本发明具有以下优点：
1.本发明制备了一种配位型超分子银凝胶，凝胶制备不需要加热冷却的过程从而实现原位凝胶化，制备方法简单，成本低，污染小，所有溶剂均可回收再利用。
2.因为银离子参与凝胶剂的自组装，在凝胶纤维上存在，稳定性好，制备出的纳米银粒子与凝胶体系的相容性好，有效避免了纳米银粒子发生团聚。
3.本发明采用的溶剂沸点低，易挥发，通过自然挥发或冷冻干燥即可除去，避免加热除去，后处理简单。
4.本发明采用室温下光还原制备纳米银，还原过程无需化学还原剂，绿色无污染，实验易操作，无需特殊仪器。
5.本发明制备的纳米银稳定性好，粒径均匀，通过凝胶浓度和还原时间的调节可使纳米银粒径在20-200nm范围内自由调控，为纳米银的制备提供一种便利的模板。
附图说明
图1为本发明异斯特维醇异丙酯磺酸银的二氯甲烷干凝胶扫描电镜图片。
图2为本发明异斯特维醇异丙酯磺酸银的二氯甲烷凝胶经光致还原20分钟的干凝胶扫描电镜图片。
具体实施方式
为了更好地实施本发明，现举实施例对本发明作进一步说明，但是这些实施例仅是用于说明本发明，不对本发明限制。
实施例1异斯特维醇异丙酯磺酸银的制备
将异斯特维醇(5g 16mmol)溶于乙腈(31mL)中，加入K2CO3(1.79g 32mmol)，在100mL烧瓶中用磁力搅拌器搅拌，待异斯特维醇溶解后，加入异丙基溴1.96g，回流反应6个小时，TLC监测反应进程，反应完全后，蒸去乙腈。向体系内加入质量百分含量5％稀盐酸200mL，搅拌洗涤，抽滤，反复用重蒸水洗涤，将滤饼收集烘干，得白色固体异斯特维醇异丙酯(化合物2)。
冰浴条件下，向50mL容量瓶中加入1mL浓硫酸，搅拌下用恒压漏斗将乙酸酐(6mL)逐滴加入浓硫酸中，滴加完毕后，继续搅拌10min，向乙酸酐-浓硫酸体系内加入异斯特维醇异丙酯3.7g。搅拌至反应完全，蒸干溶剂，加入150mL乙酸乙酯重结晶得化合物3。再加入质量百分含量10％硝酸银水溶液，洗涤后分出有机相，有机相静置析出白色固体，过滤，洗涤，干燥得异斯特维醇异丙酯磺酸银，收率90％。1H NMR(400MHz,DMSO-d6)δ4.81(m,1H),3.29(s,1H),2.77(d,J＝13.5Hz,1H),2.38(d,J＝10.9Hz,1H),2.17(m,1H),2.00(d,J＝13.0Hz,1H),1.75(m,1H),1.66–1.47(m,3H),1.31(m,3H),1.17(m,6H),1.12(s,1H),1.10(s,3H),1.05(m,1H),0.97(m,3H),0.85(m,4H),0.68(s,3H).13C NMR(101MHz,DMSO-d6)δ214.3,176.3,72.1,67.1,57.6,56.9,51.5,47.2,43.5,42.8,39.2,38.3,38.3,37.9,36.0,29.0,22.0,21.9,21.9,20.6,19.5,19.0,13.4.
实施例2异斯特维醇异丙酯磺酸银凝胶的制备
称取2mg上述制得的异斯特维醇异丙酯磺酸银化合物，加入到5mL耐压样品瓶中，加入氯仿凝胶溶剂后超声使凝胶剂分散，静置24小时。采用倒置法测试凝胶是否生成和最低凝胶浓度。通过梯度升温法测试不同凝胶浓度下的相变温度。
实施例3纳米银的制备
将异斯特维醇异丙酯磺酸银凝胶于瓶中置于自然光下照射3天或者用365nm紫外灯照射30分钟，体系逐渐变黑得纳米银凝胶体系。将制备的含纳米银的凝胶体系移到硅片上，自然晾干得干凝胶样品。喷金30秒后于扫描电子显微镜下观察凝胶形态。可以观察到凝胶剂自组装的带状纳米结构。经光还原之后纳米银均匀的附着在凝胶剂上。
Claims (2)
1.一种纳米银的制备方法，其特征在于：通过如下方法实现：
室温下将结构式1所示的异斯特维醇磺酸银类衍生物分散到凝胶溶剂中，对异斯特维醇磺酸银凝胶体系进行光还原制备纳米银，光源采用自然光或者254-365nm紫外光源；
其中R 为正丙基、异丙基、正丁基、异丁基、正戊基、正己基、正癸基、正十六烷基、苯乙基或苄基；
所述凝胶溶剂为氯仿、二氯甲烷、1,2-二氯乙烷，1,2-二溴乙烷，1,4-二溴丁烷、四氯化碳、溴丁烷，溴丙烷、异丙基溴、溴乙烷、正己烷、甲苯、二甲苯中的一种或几种。
2.如权利要求1所述的纳米银的制备方法，其特征在于，所述的凝胶水溶液重量体积比为0.2%w/v-2% w/v。
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