萘基/菲基双取代喹喔啉单体衍生二炔基-烷氧基苯共聚物的制备及光谱性质

Synthesis of Two Disubstituted Monomers of Quinoxaline and Alternating Copolymerization with 2,5-Di Dodecyloxy-1,4-Diethynylbenzene and Optical Properties

以苯并噻二唑为初始原料,通过硝化、还原、缩合等反应合成了2种新型单体5,10-二溴-2,3,7,8-二萘基双喹喔啉(M1)和5,10-二溴-2,3,7,8-二菲基双喹喔啉(M2)。2种单体分别与1,4-二炔基-2,5-二氧十二烷基苯共聚,得到了2种新型共轭共聚物,聚(2,3,7,8-二萘基双喹喔啉-二炔基-2,5-二氧十二烷基苯)(P1)(产率86.1%)和聚(2,3,7,8-二菲基双喹喔啉-二炔基-2,5-二氧十二烷基苯)(P2)(产率41.6%)。所得单体通过红外光谱、核磁共振等进行了表征。单体和聚合物的紫外-可见吸收光谱中M1的最大吸收波长在339nm,354nm处出现。M2的最大吸收波长分别在304nm,317nm处出现双吸收峰外,在长波431nm,459nm处出现双吸收峰。P1的最大吸收波长在448nm处出现,在305nm和317nm处出现2个吸收峰。P2在短波处吸收峰分别在350nm,368nm处出现。单体荧光光谱图中分别在480nm和579nm出现最大发射峰。聚合物分别在487nm和478nm处出现最大发射峰。得到的共聚物通过X射线衍射发现结晶性较差。

Benzo-thiadiazole as primary material,5,10-dibromo-2,3,7,8-acenaphthene-quinoxaline(M1)and5,10-dibromo-2,3,7,8-phenanthrene quinoxaline(M2)synthesized by nitration,reduction,and condensation reaction.Its alternating copolymers of poly(2,5-didodecyloxy-1,4-diethynyl-phenylene-alt-2,3,7,8-diacenaphthenequinoxaline)(P1)and poly(2,5-didodecyloxy-1,4-diethynyl-phenylene-alt-2,3,7,8-diphenanthrenequinoxaline)(P2)were prepared with 2,5-didodecyloxy-1,4-diethynlbenzene by Sonogashira reaction.And these structures of monomers were characterized by FT-IR and 1 H-NMR.In the UV-Vis absorbance of the monomers and polymers,maximum absorption wavelength of M1 appears at 339 nm,354nm and 317 nm,436nm in CHCl3 respectively.The maximum absorption wavelength of the monomer M2 appears double absorption peaks at 304 nm,317nm;in long wave appear double absorption peaks at 431 nm,459nm.The maximum absorption wavelength of polymer P1 appears at 448 nm,two absorption peaks appear at 305 nm and 317 nm.The photoluminescence(PL)spectra of monomers show that that maximum emission peaks appear at 480 nm and 579 nm respectively,and the maximum emission peaks of polymers appear at 487 nm and 478 nm respectively.The XRD patterns of polymers obtained by X-ray diffraction(XRD)show lower crystallinity.