Liquid Crystalline and Light Emitting Polyacetylenes: Synthesis and Properties of Biphenyl-Containing Poly(1-alkynes) with Different Functional Bridges and Spacer Lengths
Liquid Crystalline and Light Emitting Polyacetylenes: Synthesis and Properties of Biphenyl-Containing Poly(1-alkynes) with Different Functional Bridges and Spacer Lengths
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DOI：
10.1021/ma011406e
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发表时间：
2002-01
期刊：
影响因子：
5.5
通讯作者：
J. Lam;Yuping Dong;K. Cheuk;Jingdong Luo;Z. Xie;H. Kwok;Z. Mo;B. Tang
中科院分区：
文献类型：
--
作者：
J. Lam;Yuping Dong;K. Cheuk;Jingdong Luo;Z. Xie;H. Kwok;Z. Mo;B. Tang
合成了具有不同桥基和间隔基长度的联苯-(联苯)-(联苯基)(3和4)及其聚合物(1和2)，研究了结构变化对其性能的影响，特别是对其介晶性和光致发光行为的影响。乙炔单体3(3)[HC⋮C(CH2)3O−BIPH−OCO(CH2)10CH3]和4(M)[HC⋮C(CH2)MOCO−BIPH−OCO(CH2)10CH3，m=3，4]。当3(3)显示对向异性晶体E和SMB中间相时，其结构表亲4(3)只显示单性SMB相。然而，当间隔基团长度增加到4时，会形成对映异构型的SMA和SMB中间相。Mo-、W-、Rh-和Fe基催化剂对单体的聚合都有影响，其中WCl6-−Ph_4Sn型催化剂的聚合效果最好(分离率高达85%，相对分子质量高达59000)。用红外光谱、紫外光谱、核磁共振、热重分析、差示扫描量热法、偏光显微镜、X射线衍射仪和荧光光谱分析对聚合物进行了表征。与1(3)相比，2(3)显示红色...
Biphenyl- (Biph-) containing 1-alkynes (3 and 4) and their polymers (1 and 2) with varying bridge groups and spacer lengths were synthesized and the effects of the structural variation on their properties, especially their mesomorphism and photoluminescence behaviors, were studied. The acetylene monomers 3(3) [HC⋮C(CH2)3O−Biph−OCO(CH2)10CH3] and 4(m) [HC⋮C(CH2)mOCO−Biph−OCO(CH2)10CH3, m = 3, 4] were prepared by sequential etherization and esterification reactions of 1-alkynes. While 3(3) exhibits enantiotropic crystal E and SmB mesophases, its structural cousin 4(3) displays only a monotropic SmB phase. Enantiotropic SmA and SmB mesophases are, however, developed when the spacer length is increased to 4. Polymerizations of the monomers are effected by Mo-, W-, Rh-, and Fe-based catalysts, with the WCl6−Ph4Sn catalyst giving the best results (isolation yield up to 85% and Mw up to 59000). The polymers were characterized by IR, UV, NMR, TGA, DSC, POM, XRD, and PL analyses. Compared to 1(3), 2(3) shows a red...