超支化聚苯乙烯-线型聚苯乙烯-超支化聚甲基丙烯酸甲酯三嵌段聚合物的合成与表征

合成了超支化聚苯乙烯-线型聚苯乙烯-超支化聚甲基丙烯酸甲酯三嵌段聚合物(HPS-b-LPS-b-HPMMA). 首先分别合成了带有炔基和溴的三硫代碳酸酯(ATC和BTC), 然后通过苯乙烯(St)的可逆加成-断裂链转移(RAFT)聚合, 制得端炔基和端基溴的线型聚苯乙烯大分子RAFT试剂, 然后将大分子RAFT试剂的溴末端转化为叠氮末端. 接着在大分子RAFT试剂存在情况下, 通过自缩合原子转移自由基共聚合(SCATRCP)分别制得端炔基超支化聚苯乙烯-线型聚苯乙烯(HPS-b-LPS)和端叠氮基超支化聚甲基丙烯酸甲酯-线型聚苯乙烯(HPMMA-b-LPS)两嵌段聚合物. 最后将两种两嵌段聚合物通过点击(click)反应偶合, 得到不对称的超支化-线型-超支化三嵌段聚合物HPS-b-LPS-b-HPMMA. 核磁共振氢谱(¹H NMR)、凝胶渗透色谱(GPC)结果表明, 所得产物分子量可控, 得到了预期结构的聚合物.     

基于炔类单体的点击聚合制备超支化聚合物

超支化聚合物由于其独特的树枝状结构和物理化学性质,已经得到了广泛关注及应用.而基于炔类单体的点击聚合作为一类简单、高效的聚合反应已被广泛用于超支化聚合物的制备.本文对近5年利用叠氮-炔和巯基-炔点击聚合制备超支化聚合物的工作进行了简要综述.其中,Cu(I)催化的叠氮-炔点击聚合可制备1?4-立构规整的超支化聚三唑;Ru(II)催化的叠氮-炔点击聚合可制备1?5-立构规整的超支化聚三唑;活化的炔类单体和叠氮单体的无金属催化点击聚合可得到1?4-异构体含量高(高达91.7%)的超支化聚合物;而光引发?热引发及自发的巯基-炔点击聚合可制备含硫的超支化聚合物.此外,对所制备的超支化聚合物的功能和应用进行了简单介绍,最后还简单讨论了点击聚合制备超支化聚合物方面的可能发展方向.     

三溴化金催化端炔与二芳基二硒醚反应合成炔基硒醚

炔基硒醚是合成一些有机硒化合物的重要起始物。本文研究发现,在三溴化金(Au Br3)催化下,端位炔和二芳基二硒醚在弱碱(如碳酸钾)存在下反应,生成炔基芳基硒醚,产率为69%~98%;在空气参与下,于80℃下进行反应,反应条件简单,且二硒醚的两个硒原子均可以被利用。二甲基亚砜(DMSO)是合适的溶剂,在极性较小的溶剂(如甲苯、四氢呋喃)中,此反应不能进行。芳基炔(如苯乙炔、对甲基苯乙炔、对氯苯乙炔等)、烯基炔(如环己烯乙炔)和烷基炔(如1-壬炔)均能顺利进行此反应。当芳基炔苯环的间位或邻位连有取代基时,反应产率较低(69%~82%),而对位无论是连有吸电子基还是给电子基,该反应均可以得到很高的产率(95%)。     

含全碳和多炔阴离子配体的银簇化合物的超分子组装及其结构研究

总结了我们在新型炔银簇化合物研究方面的最新进展. 这些化合物分为以下几种类型: (a)1,3,5-己三炔基和1,3,5,7-辛四炔基; (b)1,5-己二炔基; (c)经膦酸配体组装的乙炔基和烷基乙炔基; (d)苯乙炔基、 环烷基乙炔基和含氮杂环基乙炔基结构单元的银簇化合物; (e)经不同类型的银-碳配位键连接, 并进一步通过分子内/分子间作用力稳固其配位网络的炔银化合物. 我们还进一步讨论了溶剂、 配体的位阻大小和辅助配体类型对于多维配位网络结构的影响.     

含全碳和多炔阴离子配体的银簇化合物的超分子组装及其结构研究（英文）

总结了我们在新型炔银簇化合物研究方面的最新进展.这些化合物分为以下几种类型:(a)1,3,5-己三炔基和1,3,5,7-辛四炔基;(b)1,5-己二炔基;(c)经膦酸配体组装的乙炔基和烷基乙炔基;(d)苯乙炔基、环烷基乙炔基和含氮杂环基乙炔基结构单元的银簇化合物;(e)经不同类型的银-碳配位键连接,并进一步通过分子内/分子间作用力稳固其配位网络的炔银化合物.我们还进一步讨论了溶剂、配体的位阻大小和辅助配体类型对于多维配位网络结构的影响.     

“可点击”丙烯酸酯聚合物的合成及其巯-炔光交联研究

通过丙烯酰氯和1-乙炔基1-环己醇的酯化反应,制备了乙炔基功能化的丙烯酸酯功能单体1-乙炔基环己基丙烯酯(ECA)。以该单体与丙烯酸甲酯(MA)进行自由基聚合反应,合成了乙炔基功能化均聚物(PECA)和共聚物(PMA-co-PECA),用1 HNMR、FT-IR、GPC等对其结构进行了表征。结果表明:在自由基聚合过程中,ECA中的乙炔基得以保留,所得到的乙炔基功能化聚合物可溶于普通有机溶剂,如氯仿、二甲基亚砜、四氢呋喃、丙酮等。实时红外跟踪了PMA-co-PECA与三羟甲基丙烷三巯基丙酸酯经光引发的巯-炔反应,得到交联的聚合物网络,凝胶分数大于90%,表明聚合物链上保留的乙炔基与巯基的加成反应有较高的活性,可以通过硫醇-炔点击反应实现快速功能化。     

含芳杂环的超支化聚合物的合成与性能研究

在紫外光照射的条件下,以CpCo(CO)2为催化剂,通过3,5-双-(4-炔苯基)-4-苯基-1,2,4-三唑和2,5-双-(4-炔苯基)-1,3,4-(噁)二唑的双炔分别与1-辛炔的[2 2 2]环三聚反应,合成了一类含芳杂环的可溶于普通有机溶剂的新型超支化聚合物.采用红外光谱、核磁共振谱、热失重分析、紫外吸收光谱、荧光光谱、循环伏安法等方法对聚合物进行结构表征和性能测试.结果表明,聚合物具有优异的热稳定性,尤其是含三唑的聚合物热失重5%的分解温度在450℃以上;在800℃时,残余碳化率高达75%.在光激发的条件下,这类聚合物在二氯甲烷溶液中发射深蓝光,其荧光量子效率可达80%.电化学测试结果表明,这类含芳杂环聚合物具有较好的电子传输能力.     

含二乙炔类共轭聚合物的合成及性能研究

在以CuCl和四甲基乙二胺(TMEDA)作为催化剂和邻二氯苯作溶剂条件下,以二-(4-乙炔苯基)-4-辛氧基苯胺(M1)和3, 6-双(乙炔基)-N-辛基咔唑(M2)作为单体,通过Glaser-Hay氧化偶联反应合成了含有咔唑和三苯胺结构单元的聚芳烃二乙炔共轭聚合物.采用红外光谱、核磁共振谱、热失重分析、紫外吸收光谱和荧光光谱等方法对聚合物进行结构表征与性能测试.所得到的聚合物都溶于普通的有机溶剂(如四氢呋喃、二氯甲烷、氯仿、甲苯等).结果表明,聚合物具有优异的热稳定性,热失重5 %时,分解温度在400℃以上;在光激发的条件下,聚合物在二氯甲烷溶液中发射蓝光.     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

两亲性全季铵盐超支化聚合物的设计与合成及主-客体超分子着色应用研究

采用高效的巯基-炔点击化学与Menschutkin季铵化反应,合成了一种带有1个叠氮基、2个炔基和2个季铵盐基团的AB2型季铵盐单体,通过核磁共振、红外光谱、质谱等方法对单体结构进行了确认.将所得单体进行点击聚合,得到全季铵盐超支化聚合物,并用端叠氮基的长链烷烃封端,得到核亲水-壳憎水的两亲性超支化聚季铵盐.研究所得两亲性超支化聚合物对染料的装载性能,结果表明所合成的带正电荷两亲性聚合物对多种带负电荷的水性染料装载效果好,平均相转移率高达95%.进一步将装载染料的主-客体超分子复合物用于聚合物制品着色,发现其对SBS及PMMA等聚合物有很好的着色效果,着色均匀且不掉色,着色的膜色泽鲜艳透明.     

HYPERBRANCHED CONJUGATIVE MACROMOLECULES CONSTRUCTED FROM TRIPLE-BOND BUILDING BLOCKS

Polycyclotrimerization and polycoupling of acetylenic monomers respectively furnish hyperbranched polyarylenes and polyynes with high molecular weights(up to 1×10~6)in high yields(up to 99.9%).The polymers possess low intrinsic viscosities and high thermal stabilities,losing little of their weights when heated to＞400℃.Upon pyrolysis at＞800℃,the polymers graphitize with high char yields(up to 86%).Hyperbranched polyarylenes efficiently emit deep-blue to blue-green lights with fluorescence quantum yields up to 98% and strongly attenuate intense laser pulses with optical power-limiting performances superior to that of C_(60),a well-known optical lirniter.Poly(alkenephenylenes),poly(aroylarylenes)and polyynes are readily cross-linkable by UV irradiation,serving as excellent photoresist materials for the generation of patterns with nanometer resolution.Thin films of hyperbranched polyynes exhibit very high refractive indexes(n up to 1.86).The internal and terminal acetylene moieties of the polyynes readily form complexes with cobalt carbonyls,which can be transformed into soft ferromagnetic ceramics with high magnetic susceptibilities(M_s up to ca.118 emu/g)and near-zero magnetic losses.     

SYNTHESIS AND PROPERTIES OF POLY(AROMATIC DIACETYLENE)S CONTAINING FLUORENE

Novel fluorene-based poly(aromatic diacetylene)s have been synthesized by CuCl-catalyzed oxidative coupling of aromatic diynes.New aromatic diynes 2,7-diethynyl-9,9-bis(triphenylamine)fluorene(M_1)is synthesized by multistep reactions.The structures and properties of the polymers are characterized and evaluated by IR,NMR,TGA,UV, photoluminescence(PL),and cyclic voltammetry analyses.These polymers possess good thermal stability.All the polymers are completely soluble in coammon solvents such as toluene,TH...     

LINEAR AND HYPERBRANCHED POLYMERS WITH HIGH THERMAL STABILITY AND LUMINESCENCE EFFICIENCY

New acetylene monomers, 6-{[(1-naphthylethynyl-4-phenyl)carbonyl]oxy}-1-pheny-1-hexyne (1), 2, 5-diethynyl-thiophene (3), and 4,4'-diethynylbiphenyl(6) were synthesized. Homopolymerization of 1 and copolycyclotrimerizations of 3and 6 with 1-heptyne and 1-octyne have been achieved with WCl_6- and TaCl_5-Ph_4Sn catalysts, respectively, giving solublelinear disubstituted polyacetylene (2) and hyperbranched polyarylenes (5 and 8) with high molecular weights (up to 1.2×10~5) in high yields (up to 98%). The trictures and properties of the polymers are characterized and evaluated by IR, NMR,TGA, UV, photoluminescence (PL), and electroluminescence (EL) analyses. All the polymers possess high thermal stabilityand emit strong blue ligh upon photoexcitation. The intensity of the emitted light is greater than that of poly(1-phenyl-1-octyne), a well-known highly luminescent disubstituted polyacetylene. Little aggregation-induced red shift in the PL wasobserved in the thin films of the polymers. By constructing a multi-layer EL device, high EL quantum yield (0.18%) has beenachieved in 2, which are the best results for substituted polyacetylenes attainable so far.     

含空间位阻基团的超支化聚芴的合成、表征及稳定性研究

以1,3,5-间三溴苯和三(4-溴苯基)胺为支化核,引入9,10-二溴蒽和2,7-二溴-螺(芴-9,9-氧杂蒽)通过Suzuki反应与芴分别共聚,得到4种不同结构的超支化聚芴蓝光材料,对其结构及光物理性质进行了表征,根据退火前后荧光光谱的变化对其光谱热稳定性进行了研究.实验结果表明,引入超支化结构和高位阻基团,聚芴的荧光发射光谱热稳定性显著提高,绿光区发射现象几乎完全被抑制.     

超支化聚芴的合成与性能研究

采用2,7-二(4-羟基苯基)-9,9-二烷基芴(A2)与四对甲基苯磺酸季戊四醇酯(B4)通过A2+B4型缩聚反应合成了一系列共轭型超支化聚合物.利用紫外和荧光谱对聚合物予以表征,结果表明,此类聚合物均可发出稳定、纯正的蓝光.DSC和TGA显示,4种聚合物在150℃以下没有明显的相态变化,300℃以内无明显的热分解现象,这表明此类聚合物具有良好的热稳定性,有利于材料的发光效率及发光稳定性.     

Polycyclotrimerization of aromatic diynes: Synthesis,thermal stability,and light‐emitting properties of hyperbranched polyarylenes

New aromatic diyne monomers of 1,4‐diethynyl‐2,5‐(dihexyloxy)benzene ( 1 ), 1,6‐diethynyl‐2‐(hexyloxy)naphthalene ( 2 ), and 9,9‐bis(4‐ethynylphenyl)fluorene ( 3 ) are synthesized. Their homopolymerizations and copolymerizations with 1‐octyne ( 4 ) or phenylacetylene ( 5 ) are effected by TaBr₅–Ph₄Sn and CpCo(CO)₂–hν, giving soluble hyperbranched polyarylenes with high molecular weights (M_w up to ～ 2.9 × 10⁵) in high yields (up to 99%). The structures and properties of the polymers are characterized and evaluated by IR, NMR, UV, PL, and TGA analysis. The polymers show excellent thermal stability (T_d > 400 °C) and carbonize when pyrolyzed at 900 °C. Upon photoexcitation, the polymers emit deep blue light in the vicinity of ～400 nm with fluorescence quantum yields up to 92%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4249–4263, 2007     

CARBAZOLE-CONTAINING HYPERBRANCHED POLY（ARYLENEETHYNYLENE）S： SYNTHESIS, CHARACTERIZATION, AND PROPERTIES

New hyperbranched poly(aryleneethynylene)s containing carbazole moieties are synthesized in high yields(up to 87%)by polycyclotrimerization of 3,6-bis(4-ethynylphenyl)-9-octylcarbazole and its copolymerization with 1-octyne catalyzed by CpCo(CO)_2 in THF.The structures and properties of the polymers are characterized and evaluated by IR,NMR, TGA,UV,photoluminescence,and cyclic voltammetry analyses.All the polymers are soluble in common organic solvents and show outstanding thermal stability(≥430℃).They graphitize in high yields(up to 79%)when pyrolyzed at 800℃. Upon photoexcitation,the polymers emit a strong deep blue light of ca.400 nm with quantum yields larger than 60%.     

Synthesis and optical properties of hyperbranched polyarylenes and linear polyacetylenes

New hyperbranched polyarylenes (HPAs) and linear polyacetylenes (LPAs) containing chromophoric moieties were synthesized in high yields (up to 97%) by coablt- and tantalum-catalyzed polycyclotrimerizations and tungsten-catalyzed metathesis polymerizations, respectively. The polymers possessed high molecular weights (M_w up to 113 000 Da) and were completely soluble in common organic solvents. The HPAs emitted strong UV light of 400 nm in high quantum yields (Φ_F up to 0.98) and limited intense laser pulses, whose limiting threshold and signal suppress power were better than those of C₆₀, a well-known optical limiter. The electroluminescence (EL) devices of the LPAs emitted blue light of ∼460 nm and exhibited maximun brightness, current efficiency, and external quantum efficiency of 1118 cd/m², 1.53 cd/A, and 0.85%, respectively.     

SYNTHESES AND CHARACTERIZATIONS OF HYPERBRANCHED POLYPHENYLENES

Hyperbranched polymers have attracted much attention over the past decade because of the expectation that theirunique molecular shape, branching pattern and surface functionality may impart unusual properties. Methods forthe synthesis of hyperbranched polymers are, however, rather limited. Cyclotrimerization of alkynes to aromaticrings is a century-old reaction. Although chemists have intensively investigated cyclotrimerization of variousdiynes in the last century, their attention was mainly f…     

Tuning the optical properties of hyperbranched polymers through the modification of the end groups

Dye‐capped, hyperbranched, conjugated polymers were prepared by the modification of the peripheral bromo end groups of the hyperbranched polymer core with a palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction. The dye‐modified, hyperbranched polymers had high molecular weights and displayed good solubility in common organic solvents such as tetrahydrofuran, toluene, and chloroform. The structure of the dye‐modified, hyperbranched polymers was characterized by ¹H and ¹³C NMR and elemental analysis. The thermal properties of five kinds of hyperbranched polymers were investigated with thermogravimetric analysis and differential scanning calorimetry. The optical properties of the dye‐capped, hyperbranched polymers were investigated with ultraviolet‐absorption and fluorescence spectroscopy. The hyperbranched structure could effectively reduce the aggregation of the peripheral dyes. The emission colors of the hyperbranched polymers could be easily tuned by end‐group modification. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 111–124, 2007