CN106883381A - 一种bodipy基共轭微孔聚合物及其制备方法与碘吸附应用 - Google Patents
一种bodipy基共轭微孔聚合物及其制备方法与碘吸附应用 Download PDFInfo
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- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 51
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011630 iodine Substances 0.000 title claims abstract description 50
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 31
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- 238000002360 preparation method Methods 0.000 title claims description 3
- 230000021615 conjugation Effects 0.000 title 1
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- 238000012360 testing method Methods 0.000 claims description 4
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims description 3
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- 125000000304 alkynyl group Chemical group 0.000 abstract description 7
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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Abstract
本发明公开了一类简易制备的BODIPY基新型共轭微孔聚合物(CMPs)在碘蒸气吸附应用上的优良性能。本发明突破性地发现常温时BODIPY单元的2，6位上的H在碘蒸气环境下能够被I所替换，基于前人报道的离子键，炔基，苯环，杂原子氢键等与碘蒸气有较强作用力，本发明目的性地引入以上单元，在合成，检测，吸附条件等优化明确的情况下突出比较说明含2，6位活泼H的BODIPY单元及其他单元在碘蒸气吸附方面的优良性能。所制得的该类CMPs具有丰富的2，6位活泼H，大比表面积，很好的热稳定性及化学稳定性，同时对碘单质具有高亲和力及吸附能力，且能实现循环使用，其针对性地在碘蒸气捕获方面具有重要的应用价值和应用前景。
Description
技术领域
本发明涉及一类简易制备的BODIPY基新型共轭微孔聚合物(CMPs)在碘蒸气吸附应用上的优良性能，基于我们发现的小分子BODIPY单元的2，6位活泼H与碘蒸气在常温下的化学作用，重点研究在于选择合适的合成条件制备高比表面，高孔容的聚合物并研究BODIPY单元的2，6位活泼H对碘蒸气的化学吸附及吸附促进性能。
背景技术
核能因社会对能源的需求日益增长在人类的日常生活越来越重要。而目前关键问题是如何安全有效地处理从铀燃料的核裂变中所产生的核废料。其中,放射性碘因其非常长的半衰期(1.57×107年)且能够影响到人类的代谢而成为了研究热点，因此,找到安全有效的放射性碘单质的捕获方法是当前急需解决的问题(Acta Chim.Sinica 2016,74,67)。有机多孔聚合物因其大比表面，热稳定性，良好的重复利用性等性能使其在环境问题方面(如碘单质吸附)的利用备受关注。
吉林大学裘式纶老师组以早期合成的PAF-1(SBET＝5600m2g-1)和JUC-Z2(SBET＝2081m2g-1)两种材料用于碘蒸气的吸附，在298K和40Pa条件下，PAF-1和JUC-Z2的碘蒸气吸附量分别为1.86g·g-1，1.44g·g-1。作者表示多孔材料的比表面积和孔容在碘蒸气吸附方面起着关键的作用；此外拉曼光谱表明客体分子以I5-的方式存在于孔道内，这表明客体I2与该富电子的骨架具有广泛的电荷转移(J.Mater.Chem.A,2014,2,7179)。大连化物所邓伟侨老师组创新性地将前人的报道的CMPs成功合成CMPNs并将其重复用于碘蒸气的吸附，在343K和1bar条件下，最高吸附量达208wt％(α＝(m2-m1)/m1×100wt％)。作者表示正是由于CMPN-3的SBET和总孔容比较高才使其具备对碘蒸汽较好的吸附性能，这佐证了裘式纶老师的观点(J.Mater.Chem.A,2015,3,87)。朱广山老师组目标性地合成了一类带电荷的多孔芳香骨架(PAF-23，PAF-24，PAF-25)，其所构造的富含炔基，苯环，离子键三种活性位点的PAF在骨架的“呼吸”作用下实现了对碘蒸气的超高效吸附，在348K和1bar条件下，该类PAF 最佳吸附性能为2.76g·g-1，同时核磁验证B+与I2也存在相互作用(Angew.Chem.,Int.Ed.,2015,54,12733)。
发明内容
本发明的第一个目的在于公布我们发现了BODIPY单元的2，6位活泼H与碘蒸气在常温常压下能发生化学反应。
本发明的第二个目的在于针对性地将具有2，6位活泼H的BODIPY单元便捷地引入到共轭微孔聚合物中。
本发明的第三个目的在于将制备的BODIPY基共轭微孔聚合物实现对碘单质(溶剂中碘，碘蒸气)强有效吸附和超容量储备功能应用。
本发明提供了一种新型BODIPY基共轭微孔聚合物，具有式I结构：
其中，设计为如下结构式中任意一种：
设计为如下结构式中任意一种
式2-6～2-8中，n为0～3的整数。
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BODIPY基新型共轭微孔聚合物的合成设计为，单元和单体(1,3-二溴苯-5-BODIPY派生物)在Pd(pph3)4和CuI催化下发生Sonogashira偶联反应，即得；
所述反应中单元和单体(1,3-二溴苯-5-BODIPY派生物)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BODIPY基的共轭微孔聚合物应用于制备对碘单质(溶液中碘，碘蒸气)具有强吸收和超容量储备功能的吸附材料。
所述聚合物应用前均以120-140℃活化处理及研磨。
所述聚合物对溶剂中的碘单质的吸附实验设计为研磨及活化后的聚合物粉末加入到碘单质的正己烷溶液中进行。
所述聚合物粉末对碘蒸气的吸附实验条件设计为348K和373K，真空条件下进行。
所述聚合物吸附碘蒸气后的样品的碘单质释放实验设计为样品加入乙醇溶液中进行。
本发明的效果和益处在于：本发明基于小分子BODIPY单元对碘蒸气的强化学吸附作用及前人的工作，针对性地构造具有丰富的与碘单质作用的官能团的BODIPY基共轭微孔聚合物。该类多孔聚合物具备苯环，炔基，BODIPY单元及2，6位活泼H，对碘单质(溶剂中碘，碘蒸气)具有强亲和力和高吸附性能。该类聚合物具有高化学稳定和热稳定性能，具有优良的重复利用性，且2，6位活泼H与碘单质发生化学反应后被I替代，有利于进一步碘单质吸附的进行。因此，本发明涉及的BODIPY基聚合物对碘单质的吸附具有广泛的应用前景。
附图说明
【图1】是例1中BODIPY单体2和碘薰后单体2'的核磁图。
【图2】是例2中BODIPY共轭微孔聚合物BDP-CMP-1及单体的红外光谱；单体1为1,3,5-三乙炔基苯，单体2为3,5-二溴基苯-1-BODIPY(Me)，BDP-CMP-1为二者反应制备的聚合物。
【图3】为吸附装置简图。
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BODIPY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。
实施例1
称取3,5-二溴苯甲醛(264mg，1mmol)溶于150ml无水CH2Cl2，快速称取2,4-二甲基吡咯(190mg，2mmol)并加入溶液中，滴加三氟乙酸(TFA)2滴后，脱气，N2保护，于室温下搅拌过夜；称取2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ，227mg，1mmol)溶于50ml无水CH2Cl2后加入反应溶液中，脱气，N2保护，室温下搅拌8-10h；量取3ml N,N-二异丙基乙胺(DIEA)加入并搅拌10min，冰浴条件下加入3ml三氟化硼乙醚络合溶液，脱气，N2保护下络合4-6h。直接旋蒸干溶剂，过硅胶柱提纯(PE：DCM＝2:1)，收集得到浅红色晶体3,5-二溴苯-1-BODIPY(Me)(115mg，产率：24％)。
1H NMR(500MHz,CDCl3):δ7.80(t,J＝2.5Hz,1H),7.44(d,J＝2.5Hz,2H),6.01(s,2H),2.55(s,6H),1.49(s,6H).
称取单体3,5-二溴苯-1-BODIPY(Me)(单体2，10mg，0.02mmol)溶解于2ml CH2Cl2中，将该溶液均匀涂抹在大号硅胶板上，烘干试剂后置于碘盒中16h，将硅胶板上硅胶尽数刮下后以足量CH2Cl2将板上物质溶解后得到红色溶液，旋蒸除去溶剂后以硅胶柱提纯(PE：DCM＝5:1)，得到红色粉末3,5-二溴苯-1-BODIPY-I(Me)(单体2'，15mg，产率：100％)。
1H NMR(500MHz,CDCl3):δ7.86(s,1H),7.41(d,J＝2Hz,2H),2.64(s,6H),1.51(s,6H).
实施例2
称取单体3,5-二溴苯-1-BODIPY(153mg，0.32mmol)和1,3,5-三炔基苯(48mg，0.32mmol)于25ml的单口烧瓶中，加入8ml DMF和TEA(DMF：TEA＝1:1)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℃，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、H2SO4混合溶液中搅拌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，在改用蒸馏水索提24h。冷冻干燥3d，得到暗红色粉末BDP-CMP-1(156mg，产率：104％)。
聚合物的热失重分解温度为375℃，比表面积达到637m2/g，孔容为0.92cm3g-1，平均孔径分布在4.9nm。
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2110cm-1处的振动峰在聚合物图谱的相应位置有所出现；与此同时，3,5-二溴苯-1-BODIPY在2925cm-1处出现的甲基上C-H伸缩振动峰在聚合物相应位置出现，而700-900cm-1之间C-Br的伸缩振动在聚合物中存在，但其峰强度明显减弱，表明C-Br键的明显减少；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。
经固体核磁碳谱分析：10ppm处为BODIPY单元上甲基上碳的化学位移；90ppm处为炔基两端相连碳的化学位移；120ppm和135ppm处的峰分别为1,3,5-三乙炔基苯上与炔基相连的碳临近的碳和炔基相连的碳临近碳化学位移。
BDP-CMP-2，NBDP-CMP的合成及检测分析均与上述操作类似。
实施例3
称取19.8mg粉末BDP-CMP-1平铺于碘量瓶中，在锥型瓶底部铺好10g高纯度碘单质，组装好装置(如图3)，严格抽真空后放于348K的真空干燥箱中保持48h，吸附完成后将粉末倒出称其质量为76.6mg(2.87g/g)。
以上列举的一系列BODIPY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 (6)
1.一种BODIPY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：
(BODIPY色团)设计为如下结构式(2系列)中任意一种
式2-6～2-8中，n为0～3的整数。
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BODIPY基新型共轭微孔聚合物材料，其特征在于，单元和单体(1,3-二溴苯-5-BODIPY派生物)在Pd(pph3)4和CuI催化下发生Sonogashira偶联反应，即得。
4.一种如权利要求1～2任一项所制备的新型BODIPY基的共轭微孔聚合物材料的应用，其特征在于，所述的新型BODIPY基的共轭微孔聚合物应用于制备对碘单质(溶液中碘，碘蒸气)具有强吸收和超容量储备功能的吸附材料。
5.如权利要求4所述的应用，其特征在于，权利要求1中的聚合物粉末对碘蒸气的吸附实验条件设计为348K和373K，真空条件下开始进行。
6.权利要求5中吸附碘蒸气后的样品的碘单质释放实验设计为样品加入乙醇溶液中进行。
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| CN109180912A (zh) * | 2018-09-21 | 2019-01-11 | 台州学院 | 基于三聚氯氰和二苯并噻吩的共轭微孔聚合物及其制备方法 |
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| CN115572373A (zh) * | 2022-11-04 | 2023-01-06 | 山东大学 | 一种用于有机染料吸附的有机多孔聚合物及其制备方法 |
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