聚丙烯酸修饰咔唑的电化学聚合及表征

合成了侧链带有咔唑的N-丙烯酰氧己基咔唑(MACZ),通过自由基聚合得到聚N-丙烯酰氧己基咔唑(PMACZ),在四氢呋喃含10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中,直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧己基咔唑)(PPMACZ)薄膜.PPMACZ薄膜具有良好的氧化还原性和热稳定性,电导率为1.34×10-5S·cm-1.1HNMR和红外光谱表明PMACZ二次聚合反应发生在咔唑单元的3,6位上,荧光光谱表明PPMACZ薄膜是一种良好的蓝色发光材料.     

8-丙烯酰氧喹啉及其聚合物与四溴化碳双组分体系敏化的丙烯腈光聚合

我们曾报道过8-丙烯酰氧喹啉本身在光照下可以聚合;8-丙烯酰氧喹啉(AQ)及其聚合物(PAQ)的喹啉环上的氮原子可以和双键缺电子单体如丙烯腈(AN)在紫外光下能形成激基复合物引发AN的光聚合,并且通过荧光分析证明AQ或PAQ还参与AN聚合物链中,含有氮杂环的烯类单体如N-乙烯基咔唑等不仅和缺电子化合物,和一些卤代烷如CCl_4、CBr_4等在激发下也可以形成激基复合物,进而可以引发烯类单体聚     

N-苯基咔唑取代的蓝光聚(2,7-咔唑)的合成与表征

采用Suzuki聚合方法并通过改变催化剂的投料量,合成了一系列具有不同分子量的N-苯基咔唑取代的蓝光聚(2,7-咔唑),并详细研究了分子量对聚合物的光物理、电化学和电致发光器件性质的影响.结果表明,刚性N-苯基咔唑侧链的引入,能够有效地调控主链之间的相互作用,提高蓝光的色纯度,并使得该系列聚合物的固态荧光量子效率高达0.40.同时,在热退火及器件工作过程中,没有观察到类似聚芴中绿光峰的出现,表明具有良好的光谱稳定性.单层聚合物电致发光器件的最大发光效率为0.33 cd/A,色坐标为(0.18,0.12).     

含Gemini表面活性剂结构单元的新型两亲聚电解质的合成及聚集行为

分别将Gemini型单体1,3-双(二甲基十四烷基溴化铵)-2-丙烯酰氧基丙烷(14G)或1,3-双(二甲基十六烷基溴化铵)-2-丙烯酰氧基丙烷(16G)与丙烯酰氧乙基三甲基氯化铵(DAC, D)共聚合反应, 合成了新型含Gemini表面活性剂结构单元的两亲性阳离子聚电解质(D14G和D16G). 采用稳态荧光、电导、动态光散射及透射电镜等手段研究了这些聚电解质在水溶液中的聚集行为. 结果表明, 临界聚集浓度(CAC)随着Gemini型表面活性剂单元含量的增加而减小, 同时随着Gemini型表面活性剂单元中疏水碳链长度的增加而降低. 这些聚电解质在水溶液中同时存在分子内和分子间两种类型的聚集体, 而且碳链越长, 形成分子内聚集体的倾向越强. 随着Gemini表面活性剂单元含量的增加, D14G溶液中聚集体的流体动力学半径(Rh)也有所增大, 而D16G溶液中的聚集体的流体动力学半径(Rh) 却略有减小.     

温敏两亲性接枝物PAM-g-PNIPAm的合成及表征

以巯基乙胺为分子量调节剂,以丙烯酰氯作为链端转化剂合成了不同分子量的端丙烯酰胺基聚(N-异丙基丙烯酰胺)(PNIPAm)大分子单体;与丙烯酰胺共聚合,合成了以PNIPAm为侧链的接枝聚丙烯酰胺.用FTIR和¹HNMR方法表征了接枝聚合物与大分子单体的组成.该接枝聚合物在水溶液中具有热缔合特性及明显的温敏增稠性,水溶液的粘度在32～50℃之间随温度增加而增加.     

含胺基功能性单体的聚合研究——Ⅷ.N-丙烯酰-N’-甲基吡嗪的合成、聚合及其聚合物的抗凝血性

<正> N—丙烯酰-N′-甲基吡嗪(AMP),N-甲基丙烯酰-N′-甲基吡嗪(MAMP)是丙烯酰胺,甲基丙烯酰胺的脂肪叔胺基N-取代物。聚丙烯酰胺是众所周知的医用水凝胶,其N-取代物也是甚多报道的生物相容性材料。以脂肪叔胺基取代的丙烯酰胺,除可期望其聚合物用作医用水凝胶外,分子内所含的叔胺基可以作为氧化还原引发体系的组分来引     

苯乙烯与N-取代马来酰亚胺的可逆加成-断裂链转移交替共聚合

研究了二硫代苯甲酸酯存在下偶氮二异丁腈引发苯乙烯(St)、St与N-对羟基苯基马来酰亚胺(HPM)、St与N-对(2-氯/溴丙酰氧基)苯基马来酰亚胺(CPPM/BPPM)的可逆加成-断裂链转移(RAFT)均/共聚,聚合物的结构由紫外-可见光(UV-Vis)与凝胶渗透色谱(GPC)表征.结果表明,St的RAFT均聚以及St与N-取代马来酰亚胺的RAFT共聚均呈现活性聚合特征,分子量随着转化率上升而增加,且分子量分布较窄.对于St的RAFT均聚,由于双基终止,聚苯乙烯(PSt)链中"戴帽效率"随着转化率上升逐渐下降.对于St与N-取代马来酰亚胺的RAFT共聚合,电荷转移复合物的形成显著地提高了共聚反应速度,并促进交替结构的形成.随后进行了以P(St-alt-BPPM)引发St的原子转移自由基聚合以制备梳型PSt,结果表明在强极性溶剂中进行的聚合过程失去可控性,所得产物分子量极宽,而在本体聚合中所得聚合物分子量相对较窄,有一定的可控性.     

含烷基侧链聚芴基苯并二噁唑聚合物的合成及性能研究

通过溶液缩聚的方法合成了一种含烷基侧链聚芴基苯并二噁唑聚合物(PBOPFx),讨论了聚合物的光物理性能、热性能和溶解性能.结果表明,在甲基磺酸(MSA)溶液中,PBOPFx紫外吸收显示出最大吸收峰为466 nm左右的蓝光发射,与PBO相比,最大紫外吸收峰和最大荧光发射峰均发生了明显红移,这是由于芴单元的引入,提高了聚合物的共轭程度,加强了对电子的束缚能力.此外,比较了PBOPFx在320 nm处和430 nm处激发得到的荧光发射光谱,预测聚合物中存在两种共轭单元,通过测定氧化还原曲线以及讨论stokes位移,验证了这个假设,但是由于两种共轭单元并没有出现明显的分离现象,同时还伴有电子传输杂化,致使PBOPFx主要显示出共轭长度大的单元的吸收和发射.另外由于芴单元中烷基侧链的存在,聚合物(PBOPFx)的热稳定性远低于聚亚苯基苯并二噁唑聚合物(PBO),起始分解温度在350℃左右,溶解性方面,PBOPFx有了很大的改善,在大多数有机溶剂中能较好溶解.     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

我们曾报道过同一分子中含有给电子生色基团和电子受体基团的一类功能性单体,如甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基代丙烯酰胺,N-(4-N′、N′)-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),8-丙烯酰氧喹啉(AQ),N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合以及单独或与过氧化二酰构成氧化还原体系以引发烯类单体的聚合研究。N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP)     

N-(2-乙烯氧乙基)-1,8-萘二甲酰亚胺聚合物与共聚物的荧光行为

<正> 我们曾报道过一系列含有给电子生色基团的丙烯酰类单体如甲基丙烯酸二甲氨基苄酯、N-(N′,N′-二甲氨基苯基)丙烯酰胺类、8-丙烯酰氧喹啉类、N-丙烯酰-N′-苯基哌嗪类、N-丙烯酰-N′-嘧啶哌嗪类、N-甲基丙烯酰氧乙基-N-甲基代苯胺等的合成、聚合、引发行为以及它们的聚合物的荧光行为。这些单体结构的共同点在于其双键为缺电子性而生色基团为给电子性,因而在荧光行为上,由于生成激基复合物或电荷转移而发生荧光     

Lyotropic and thermotropic phase transitions in films of ionene-alkyl sulfate complexes

Five [X,Y]-ionenes [(CH2)(X)N+(CH3)2(CH2)(Y)N+(CH3)2]nBr-(2n) were prepared (X = 3, 5; Y = 10, 12, 22). Using new preparation methods, dry, salt-free complexes with three n-alkyl sulfates (octyl, decyl, and dodecyl) were obtained. The ionenes and their complexes were characterized in methanol solution by light scattering, viscometry, and fluorescent probe studies. The solid materials were investigated by means of DSC, TG, and ATR-IR. Transparent films were formed from stoichiometric [3,10], [3,12], and [5,10]-ionene complexes with decyl and dodecyl sulfate. In the films, mesogenic phase transitions could be induced: dry films were optically isotropic; when exposed to elevated humidity, the films slowly became optically anisotropic because of a lyotropic transition to a hexagonal mesogenic phase. The relative humidity, at which the hexagonal phase developed, was distinct for each complex. The anisotropic phases were converted to isotropic in a thermotropic transition under controlled relative humidity at specific clearing temperatures, which were higher for dodecyl complexes than for decyl complexes. This thermotropic isotropic-anisotropic transition could be cycled several times, but partial hydrolysis of the alkyl sulfates reduced the reproducibility of transition points.     

含苯并硒二唑聚咔唑/芴类共轭聚电解质及其前驱体的合成与性能研究

采用Suzuki偶合反应合成了一系列新型的咔唑、芴和2,1,3-苯并硒二唑的共聚物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BSeD)及其相应的聚电解质衍生物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BSeD).在聚咔唑和芴中引入不同比例的2,1,3-苯并硒二唑(BSeD)单元,引起了由咔唑和芴链段向窄带隙苯并硒二唑(BSeD)单元有效的能量转移.通过对聚合物电致发光性能的研究,发现用聚(3,4-亚乙基二氧基噻吩)(PEDOT)或聚(3,4-亚乙基二氧基噻吩)/聚乙烯咔唑(PEDOT/PVK)作为空穴传输层时,器件的性能相差不大,表明咔唑的引入较明显的改善了聚合物的空穴注入性能.而且几乎所有的聚合物用高功函数铝作阴极的器件和用钡/铝作阴极的器件具有相近的发光性能,表明这类聚合物具有良好的电子注入性能.     

Dependence of the glass transition temperature of poly[N-(n-alkyloxy-carbonyl-methyl) Maleimides] and poly[N-(5-n-alkyloxycarbonyl-n-pentyl) Maleimides] on n-alkyl side-chain length

The glass transition temperature has been determined by a refractometric technique for two homologous series of poly[N-(n-alkyloxycarbonyl-methyl) maleimides] (PEMIS 1) and poly[N-(5-n-alkyloxycarbonyl-n-pentyl) maleimides] (PEMIS 5) with the outer part of the n-alkyl side-chain ranging in length from ethyl to decosyl for PEMIS 1 and from ethyl to decyl for PEMIS 5 and including only the even members of the series. The glass transition temperature is directly related to the number of methylene groups in the outer part of the n-alkyl side-chain (including terminal methyl) of the repeating unit. A semiempirical equation is presented that affords estimates of T_g that are in good agreement with the experimental data.     

INFLUENCE OF BACKBONE RIGIDITY ON THE LIQUID CRYSTALLINITY OF MESOGEN-CONTAINING POLYACETYLENES

Two acetylene polymers containing cyanobiphenyl-based mesogens,poly { 10-[ ((4'- cyano-4-biphenylyl ) oxy ) carbonyl] - 1 -decyne } (PA8CN ), which has a relativelyfiexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy)carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly (phenylacetylene )backbone, were synthesized using respectively WCl_6 and [Rh(nbd)Cl]_2 as the catalysts.PA8CN exhibits enantiotropic interdigitated smectic A phase (S_(Ad)) over a temperaturerange as wide as ca. 100℃, whereas PB12CN is non-mesomorphic, demonstrating thatthe backbone rigidity plays an important role in determining the liquid crystallinity of thepolyacetylenes.     

Photoinduced cyclization of 3-acyl-2-halo-1-[(ω-phenylethynyl)alkyl]indoles to azaheterocyclo[1,2,3-lm]-fused benzo[c]carbazoles

A one-pot synthesis of azaheterocyclo[1,2,3-lm]-fused benzo[c]carbazoles (2 and 3) has been developed by photocyclization of 3-acyl-2-halo-1-[(ω-phenylethynyl)alkyl] indoles (1) in good to excellent yields. All products are formed from 1 via two sequential photocyclization reactions. Two products, 9-chloro-7,8-dihydro-6H-benzo[c]pyrido[1,2,3-lm]carbazole (2a-h) and 7,8-dihydro-6H-benzo[c]pyrido[1,2,3-lm]carbazole (3a-h), are produced in the photocyclization of 2-halo-1-[(ω-phenylethynyl)alkyl]indole-3-carbaldehydes (1a-h). In contrast, only products 2a-h are produced in the photocyclization of 3-acetyl-2-chloro-1-[(ω-phenylethynyl)alkyl]indole-3-carbaldehydes (1o-t). The 9-H in 3a-h (n = 2) does originate from the formyl group in 1a-h via 1,5-hydrogen shift. The structures of three new products, 9-bromo-7,8-dihydro-6H-benzo[c]pyrido[1,2,3-lm]carbazole (2b), 9-chloro-10-methyl-7,8-dihydro-6H-benzo[c]pyrido[1,2,3-lm]carbazole (3h) and 12-chloro-7,8-dihydro-6H-benzo[c]pyrido[1,2,3-lm]carbazole (2w), have been corroborated by single-crystal X-ray structural analyses.     

Development of Carbazole and Bipyridine Copolymers as Novel Photovoltaic Materials

Summary: A novel acrylate polymer with a carbazole pendant group and bipyridine derivatives as side chains was synthesized, in which derivatives of bipyridine as electro-optic chromophores and carbazole as photoconductive moiety were covalently linked to the acrylate backbone. 2–(Carbazol-9-yl)ethyl methacrylate (CEM) and methacrylic 2-[5-(2-{5,5′-dimethyl-6′-[2-(5-pentylthiophen-2-yl)vinyl]-3,3′-bipyridin-6-yl}vinyl)thiophen-2-yl]ethyl methacrylate (BiPy) were synthesized and then copolymerized to give 99:1, 98:2, 92:8 (mol/mol) CEM/BiPy copolymers. Films of the copolymers blended with poly(3-octylthiophene) (P3OT) or poly(3-decylthiophene) (PDT) and sandwiched between the transparent ITO and Al electrode were examined for photovoltaic properties.     

Aromatic substitution by N-arylhydroxylamines—II : Generation of nitrenes from arylhydroxylamines and N-benzenesulfonylhydroxylamines and phosphorous pentoxide

Substitution of benzene by N-benzene- and N-(4-methylbenzenesulfonyl)hydroxylamines occurs in the presence of phosphorous pentoxide whereas N-methyl-N-benzenesulfonylhydroxylamine gave no substitution product under the same conditions. When N-(4-methylbenzenesulfonyl)hydroxylamine was treated with phosphorous pentoxide in pyridine, N-(4-methylbenzenesulfonimido)pyridinium ylide was formed. Nitrene intermediates are postulated to account for these products. Similarly carbazole was formed from 2-hydroxylamino[1,1′-biphenyl] and phosphorous pentoxide but with phosphorous pentachloride, 3- and 3-chloro-2-amino[1,1′-biphenyls] were formed, most likely via a nitrenium ion intermediate.     

Synthesis and Properties of New 2,6-Poly(phenylquinoline)s and Their Composites with 2,1,3-Benzothiadiazole

We synthesized 2,6-poly(phenylquinoline)s, the elementary polymer unit of which contained alkyl carbazole or alkyl indolo[3,2-b]carbazole moieties with C₁₂ and C₁₈ alkyl side chains at nitrogen atoms and the oxygen or phenylamine bridge group between the quinoline cycles. The synthesized polymers form heat-resistant coatings, for which the temperature for 5% weight loss is higher than 450°С. It is demonstrated that introduction of 10 wt % of 2,1,3-benzothiadiazole to the poly(phenylquinoline)s leads to an increase in the photosensitivity of the composite as compared with the original polymers. Structural-morphological studies of the synthesized poly(phenylquinoline)s and their composites were carried out.     

Preparation and properties of two new soluble carbazole-containing functional polyacetylenes

Two new functional polyacetylenes bearing carbazole group as pendant,poly {3-[（4-ethynylstyryl）-N-butyl]carba/ole}（P1） and poly{3-[4-（prop-2-ynyloxy）phenyl-N-butyl]carbazole}（P2）,were prepared using[Rh（nbd）Cl)₂-Et₃N as catalyst.The polymers were soluble in common organic solvents such as CHCl₃ and THK Their structures and properties were characterized and evaluated with FTIR,¹H NMR,UV,TGA,GPC,and CV,respectively.The results show that the polymers possess high thermal stability and well hole-injection property.