CN107698742A - 苯并二噻吩二酮基共轭微孔聚合物制备及其光催化应用 - Google Patents
苯并二噻吩二酮基共轭微孔聚合物制备及其光催化应用 Download PDFInfo
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Abstract
本发明公开了一类简易制备的苯并二噻吩二酮基新型共轭微孔聚合物(CMPs)在催化硫醚氧化应用上的优良性能。本发明突破性地发现常温时该聚合物能在光照条件下催化硫醚的氧化反应。所制得的该类CMPs具有良好的紫外吸收，大比表面积，很好的热稳定性及化学稳定性，同时能够高效催化硫醚的氧化，并获得高选择性，且能实现循环使用，其针对性地在有机合成反应类型中硫醚氧化方面具有重要的应用价值和应用前景。
Description
技术领域
本发明属于催化功能材料制备和应用领域。具体涉及一类苯并二噻吩二酮基共轭微孔聚合物(CMPs)的制备，以及作为光催化剂的应用。
背景技术
众所周知，随着经济的不断发展，能源的日趋枯竭，找寻可持续发展的绿色新能源来改变现在严峻的能源形势已成为世界各国科学者最为重视的目标。在现有的诸多新能源中，太阳能因为其在地球上储量丰富、照射范围广以及清洁无污染的优点而受到广泛关注。2008年，MacMillan课题组在可见光条件下用Ru(bpy)3Cl2作为光催化剂，成功催化醛基的α位不对称烷基化(Science， 2008，322，77-80)，在光致氧化还原催化领域引起了极大的关注，许多以金属配合物及有机染料为光敏剂的可见光化学催化反应相继被报道。
亚砜作为一类重要的有机化合物和有机合成中间体，在医药、农药和精细化工合成等方面有非常重要的用途。亚砜一般由硫醚直接氧化而得，该反应的副产物主要是砜。目前，光催化硫醚氧化所使用的催化剂主要是金属配合物及有机染料。然而，有机染料的稳定性较差，金属配合物成本较高，同时作为均相催化剂，分离与循环使用很复杂，难提取、难回收，大大限制了它们的大规模应用。
共轭微孔聚合物是一类具有扩展共轭体系的材料，具有高比表面积、可调控的孔结构、好的热稳定性和化学稳定性等优势，同时针对均相催化剂的局限性，有机多孔聚合物作为异相催化剂在后处理、回收和重复使用方面体现出显著的优势。Kian Ping Loh课题组报道了基于咔唑的共轭微孔聚合物作为光催化剂应用于硫醚氧化，转化率达到99％以上，但选择性一般(ACS Catal，2016,6, 3594-3599)。
发明内容
本发明的第一个目的在于公布我们构建的一种简单快速合成的新型苯并二噻吩二酮基溴代物的方法。
本发明的第二个目的在于制备了一种新型苯并二噻吩二酮基共轭微孔聚合物中。
本发明的第三个目的在于实现了新型苯并二噻吩二酮共轭微孔聚合物对硫醚氧化的光催化应用。
本发明提供了一种新型苯并二噻吩二酮共轭微孔聚合物，具有式I结构：
其中，设计为如下结构式中任意一种：
所述的聚合物是粉末状或颗粒状。
所述的聚合物平均孔径范围是0.5～100nm。
本发明对于苯并二噻吩二酮基新型共轭微孔聚合物的合成设计为，苯并二噻吩二酮溴代物和单元在Pd(pph3)4和CuI催化下发生Sonogashira偶联反应，即得；
所述反应中单元和苯并二噻吩二酮以等摩尔官能团的比例加入进行聚合反应。
所述的Sonogashira偶联反应在惰性气体保护下，在100℃下反应72-96h。
所述的实验进行过程中都以液氮冷冻反应物和无水溶剂，以空气泵严格除去氧气。
所述反应的催化剂Pd(pph3)4与反应官能团的摩尔比例为6:100，CuI与反应官能团的摩尔比例为1:10。
所述的新型苯并二噻吩二酮基共轭微孔聚合物是能高效氧化硫醚，同时具有高选择性的材料。
所述聚合物氧化硫醚的催化实验设计为研磨及冻干后的聚合物粉末光照条件下加入到甲基苯基硫醚的乙醇溶液中进行。
所述聚合物粉末氧化硫醚的催化实验设计为298K，氧气气氛条件下进行。
所述聚合物粉末催化氧化硫醚的实验结果使用核磁共振氢谱分析计算转化率和选择性。
相对现有技术，本发明的技术方案的优势在于：本发明基于一种新型苯并二噻吩二酮基共轭微孔聚合物，具有大的比表面积和高化学稳定以及热稳定性。在光照条件下，较为温和的催化硫醚的氧化，该催化剂获得高转化率的同时能获得高选择性，转化率达到99％以上，选择性达到31：1，能有效的催化硫醚的氧化。而且作为异相催化剂，便于分离和回收，而且具有重复使用的优势。因此，本发明设计的苯并二噻吩二酮基聚合物对硫醚的氧化具有广泛的应用前景。
附图说明
【图1】是例1中苯并二噻吩二酮上溴后的核磁图。单体M1氢谱图。
【图2】是例2中苯并二噻吩二酮溴代物及苯并二噻吩二酮基共轭微孔聚合物CMP-CSU-1及单体的红外光谱。红外图谱。TEB为1,3,5-三乙炔基苯， BDD为苯并二噻吩二酮溴代物，CMP-CSU-1为二者反应制备的聚合物。
【图3】催化甲基苯基硫醚的实验结果核磁。甲基苯基硫醚催化实验结果氢谱图
具体实施方式
以下实施例是对本发明的进一步说明，而不是限制本发明。
本发明具体实施方式中含苯并二噻吩二酮基共轭微孔聚合物在Nicolet- 6700型红外光谱仪上进行FT-IR证实，用KBr压片制样。聚合物热稳定测试：热失重分析(TGA)聚合物的分解温度测试在美国TA公司产SDT Q600V8.0同步热分析仪上进行，在氮气氛围下，升温速率10℃/min，测试温度范围为 30～800℃，取5％热失重温度作为聚合物分解温度。聚合物气体吸附性能性能测试：聚合物比表面积和孔径分布Micro ASAP 2000静态容量法比表面及孔径分析仪上测量，孔径分布和孔容来源于气体的吸附等温曲线的密度泛函理论(DFT)气孔模型计算得出。
一种苯并二噻吩二酮基共轭微孔聚合物，其合成路线如下：
实施例1
称取苯并二噻吩二酮(220mg，1mmol)溶于30mL无水CHCl3，快速用移液枪取液溴(400mg，2.5mmol)混合10mL无水CHCl3加入恒压滴液漏斗中，脱气，N2保护，低温反应釜中-15℃下缓慢滴加液溴和无水CHCl3的混合溶液 1h，搅拌24h；加入饱和硫代硫酸钠溶液萃取液溴，有机层有无水硫酸钠干燥 2h，过滤，旋干有机层，快速过柱(PE：DCM＝2:1)，收集得到亮黄色固体苯并二噻吩二酮溴代物(M1)(198mg，产率：90％)。
1H NMR(400MHz,CDCl3):δ7.69(m,2H)
参考例1
N,N-二甲基噻吩-3-甲酰胺(16.3g,105.0mmol)和N-溴代琥珀酰亚胺 (NBS,41.1g,231.1mmol)加入150mL DMF,室温下避光搅拌2小时。随后水洗，用乙酸乙酯萃取，有机相用无水硫酸镁干燥，过滤后将有几层旋干，过柱。得到黄色固体。
将黄色固体(4.9g,15.4mmol,40mL)溶解在乙醚当中，冰浴条件下缓慢滴加叔丁基锂(15.3mmol,2.5M in hexane)。滴加结束后恢复到室温，随后加入饱和NH4Cl水溶液(30mL)，收集沉淀，随后过柱。得到黄色固体M1(1.3g,37％)
实施例2
称取单体苯并二噻吩二酮溴代物M1(66mg，0.17mmol)和1,3,5-三炔基苯(54mg，0.36mmol)置于25ml的单口烧瓶中，加入加入12mL DMF和36mL TEA,混合溶液将粉末溶解后，用液氮将溶液冷冻后脱气，N2保护，以常温的水解冻，将上述操作(冷冻，脱气，解冻)依次重复3次，冷冻时加入 Pd(pph3)4(22mg，6mol％)，CuI(6mg，10mol％)，脱气，N2保护，将冷冻，脱气，解冻依次重复3次后，由常温升温至100℃，滴加苯并二噻吩二酮溴代物(134mg,0.33mmol)一小时，搅拌反应96h。装置降温至室温后将浑浊液抽滤，将滤渣于5mol/L的HCl溶液中搅拌2h后抽滤，依次以THF，氯仿，丙酮将滤渣分别索提12h，改用甲醇索提48h。冷冻干燥3d，得到土黄色粉末CMP- CSU-1(124mg，产率：48％)。
实施例3
称取单体甲基苯基硫醚(124mg，1mmol)，HCl(20mol％),EtOH(4ml) 和20mgCMP-CSU-1,在氧气氛围下，距离20w LED灯5cm照射下室温搅拌20h。通过TCL判断原料反应完毕，即反应结束，将反应液离心，分离催化剂CMP- CSU-1，取上层清液用水洗HCl,DCM萃取,得到淡黄色油状物(122mg，产率： 98％)。
聚合物的热失重分解温度为322℃，比表面积达到627m2/g，孔容为 0.592cm3g-1，平均孔径分布在1.2nm。
经红外图谱分析可知(图2)，单体1,3,5-三炔基苯的炔基上的C-H伸缩振动吸收带出现在3277cm-1处，而聚合物相应位置上该C-H伸缩振动吸收带消失，说明炔端基处发生反应；此外，其C≡C在2190cm-1处的振动峰在聚合物图谱的相应位置有所出现；在2200左右为醌的特征峰，在聚合物能找到与之相对应的峰；结合单体及聚合物的图谱和官能团出峰位置，峰强度等，我们可确定该反应的较充分进行。
以上列举的一系列苯并二噻吩二酮基共轭微孔聚合物的合成及单体进行的可行性分析的应用实例只对本发明做具体说明，通过实施例对本发明进行具体描述，实施例只用于对本发明进行进一步说明，而不是对本发明保护范围的限定，该领域的技术人员可以根据本发明作出一些非本质的改进和调整。
Claims (5)
1.一种苯并二噻吩二酮基新型共轭微孔聚合物，其特征在于，具有式I结构：
其中，设计为如下结构式中任意一种：
2.根据权利要求1所述的聚合物，其特征在于，所述的聚合物是粉末状或颗粒状，平均孔径范围是0.5～100nm。
3.一种如权利要求1所述的溴代苯并二噻吩二酮单体，其特征在于用液溴和并二噻吩二酮一步反应制备得到单体。
4.一种如权利要求1所述的苯并二噻吩二酮基新型共轭微孔聚合物材料，其特征在于，单元和单体在Pd(pph3)4和CuI催化下发生Sonogashira偶联反应，即得。
5.一种如权利要求1～2任一项所制备的新型苯并二噻吩二酮基的共轭微孔聚合物材料的应用，其特征在于，所述的新型苯并二噻吩二酮基的共轭微孔聚合物应用于高转化率和高选择性地光催化硫醚氧化反应。
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