末端含苯乙烯结构的超支化荧光聚合物的合成及性能

以季戊四醇、1,2,4-偏苯三甲酸酐和环氧氯丙烷为原料,合成超支化聚合物,利用合成聚合物分子外围的羧基与亚硫酰氯反应使其分子外围的羧基酰氯化,通过傅-克酰化反应将苯乙烯引入到超支化聚合物分子末端,得到末端含苯乙烯结构的超支化荧光聚合物。采用红外光谱、热分析及荧光光谱等手段表征了聚合物的结构,研究了其热稳定性及荧光性能与结构的关系。将苯乙烯接到超支化聚合物分子外围得到的聚合物具有较好的热稳定性,其荧光特性表现为:激发波长为254nm时,其发射光谱的峰值为500nm～506nm;激发波长为365nm时,其发射光谱峰值在361nm～365nm。     

末端环氧化超支化荧光聚合物的合成

通过季戊四醇、偏苯三酸酐、环氧氯丙烷合成超支化聚酯,利用合成聚合物分子外围的羧基与二缩水甘油醚、甲萘胺反应,形成末端官能化超支化荧光聚合物,在获得荧光聚合物的同时,不仅保留了超支化聚合物的良好的相溶性,其热性能也得到了改善;通过DSC、TG、红外光谱、荧光光谱等手段研究了合成聚合物的热稳定性,及结构与荧光性能的关系。     

ATRP法制备水溶性荧光温敏聚合物P(NIPAM-co-NBDAE)

以4-氯-7-硝基-2,1,3-苯并口恶唑(NBD-Cl)为原料,首先合成了荧光单体4-(2-丙烯酸胺乙基酯)-7-硝基-2,1,3-苯并口恶唑(NBDAE),然后以2-溴异丁酸乙酯(t-EBiB)为引发剂,CuCl/Me6TREN为催化剂,采用原子转移自由基聚合(ATRP),与温敏性单体N-异丙基丙烯酰胺(NIPAM)共聚,得到水溶性无规共聚物P(NIPAM-co-NBDAE)。对产物进行了1H-NMR,GPC,UV-Vis及荧光光谱仪(FL)表征。结果表明,成功制备了多分散系数小于1.20的窄分布荧光水溶性共聚物,并研究了该聚合物荧光强度随温度的变化。在PNIPAM的相变温度(30℃)以下,该聚合物在水溶液中荧光较弱;而在PNIPAM的相变温度(30℃)以上,该聚合物的荧光强度随PNIPAM疏水转变而显著增强。     

一种超支化共轭聚合物的合成与2,4-二硝基甲苯的荧光猝灭

以2,4,6-三甲基均三嗪和甲酰基咔唑、二甲酰基咔唑为原料,通过羟醛缩合反应合成了化合物I及超支化荧光共轭聚合物II,其中I可以视为II的组成单体。聚合物II在常见有机溶剂中有较好的溶解度,其X射线衍射谱图中2θ=24.2°的位置有1个较宽的峰;其吸收和荧光光谱与I的相比仅有轻微红移(3nm),这些结果都说明聚合物II分子间没有紧密的π-π堆积作用。聚合物II的荧光强度是化合物I的2倍。2,4-二硝基甲苯对其荧光猝灭研究结果表明,超支化聚合物II具有比化合物I更大的荧光猝灭常数(Ksv=95.52L/mol),表现出了一定的分子导线效应。     

一种超支化碱溶性感光聚合物的合成及性能

以己二酸和三羟甲基丙烷为原料,通过羧基和羟基的酯化反应反复扩链聚合,生成外围含有羧基和羟基的超支化聚合物,利用超支化聚合物分子外围的羧基与甲基丙烯酸缩水甘油酯(GMA)的环氧基进行开环加成反应,生成超支化碱溶性感光聚合物。反应过程通过体系的酸值变化进行跟踪,并研究了树脂组成对感光性和碱溶性的影响。结果表明,合成聚合物的碱溶性不仅与树脂的酸值有关,还受分子中己二酸链段含量的影响,而感光性能与反应物分子中-COOH/-OH物质的量比和分子外围感光基团含量有关,通过调整合成树脂的配方可得到具有较好感光性能的超支化碱溶性感光聚合物。     

超支化聚合物的合成及在丙烯酸乳液中的应用

以季戊四醇为"核",与1,2,4-偏苯三酸酐和环氧氯丙烷反应合成超支化聚合物,并通过马来酸酐进行端基改性,合成了以羟基和/或羧基为末端基的水溶性超支化聚合物(HBPs),通过FT-IR1、H-NMR对结构进行了表征。然后将该超支化聚合物(HBPs)应用于BA/VAc/AA丙烯酸共聚物压敏胶粘剂(PSAs)乳液中。发现超支化聚合物的加入提高了胶粘剂的稳定性和粘接性能。以羧基为末端基的超支化聚合物(HBP-B)加入量为0.5%时,胶粘剂互相矛盾的两个性能——持粘力与剥离强度同时达到最大值。     

阳离子超支化聚合物电解质的合成及离子传导性能研究

以间苯三酚、1,2,4-偏苯三酸酐和环氧氯丙烷为原料合成不同支化度的超支化聚合物(HBP),利用合成的超支化聚合物外围的氯原子与N-甲基咪唑进行离子化反应,制备含咪唑阳离子的超支化聚合物电解质(HBPE)。利用1H-NMR、FT-IR、DSC、TG和复阻抗谱分析等对HBPE的化学结构,热力学性能和离子传导性能进行了研究,结果表明,该聚合物电解质室温离子电导率可达2.3×10-4S/cm,热稳定性在270℃以上。     

超支化TAPOB/BPADA-聚酰亚胺的制备与表征

合成了三氨基单体-1,3,5-三(4-氨基苯氧基)苯(TAPOB),利用其和二酸酐单体-双酚A二酸酐(BPADA)反应,制备了端酸酐基超支化聚酰胺酸和超支化聚酰亚胺。通过红外光谱和核磁谱图检测,表明得到了目标聚合物。超支化聚酰亚胺具有中等分子量和较宽的分子量分布,进一步测试表明,聚合物的特征黏度和线性聚酰亚胺相比较低很多。超支化聚酰亚胺保留了线性聚酰亚胺的优良热性能,同时超支化聚合物溶解性能大为改善,在室温下可溶解于常见的强极性溶剂。     

含有不同烷氧基侧链的聚对苯乙炔(PPV)衍生物的合成与性能表征

采用强碱去卤缩合法合成了聚(2-甲氧基-5-丁氧基)对苯乙炔(PMOBOPV),聚(2-甲氧基-5-辛氧基)对苯乙炔(PMOCOPV),(2-甲氧基-5-异辛氧基)对苯乙炔(iso-PMOCOPV)和聚(2-甲氧基-5-十二烷氧基)对苯乙炔(PMODOPV)四种含有不同烷氧基侧链的聚对苯乙炔(PPV)的衍生物。利用傅里叶变换红外光谱、核磁共振谱、热失重曲线、紫外-可见光吸收光谱和光致发光光谱对聚合物的结构和性能进行了表征。并通过实验确定了适宜的合成反应条件,例如催化剂和原料配比、叔丁醇钾的用量等。结果表明合成的聚合物具有良好的热稳定性和溶解性,聚合物的紫外吸收波长最大在492nm,荧光光谱的最大发射波长在555nm左右。     

两个新型芳香四元羧酸的合成及荧光性质

以1,4-二溴苯,二苯胺等为原料经Buchwald-Hartwig芳胺化、溴化、Suzuki偶联、Heck和水解等反应合成两个新型长链芳香四元羧酸,即N,N,N’,N’-四[4-(4’-羧基)联苯基]-1,4-苯二胺(4)和N,N,N’,N’-四[4-(2-羧基乙烯基)苯基]-1,4-苯二胺(6)。其结构经1 H NMR,13 C NMR和高分辨质谱表征。通过UV-Vis和荧光光谱(FL)考察了目标产物的光物理性能。结果表明,化合物4和6紫外吸收峰分别为254,360和254,374nm,分别以360和374nm为激发波长,化合物4和6的钠盐水溶液的最大发射波长分别为530和525nm,具有发绿光的性质,同时也有较好的荧光量子效率。     

Synthesis of polyhydroxybenzoxazole-based colorimetric chemosensor for anionic species

Poly[2-(2′-hydroxyphenyl)benzoxazole] is prepared by the two step procedures of Suzuki coupling polymerization with corresponding monomers followed by the deprotection of benzyl group. The polymer in dimethylformamide (DMF) solution is applicable to colorimetric sensing fluoride anion, which shows a color change from colorless to yellow. High sensitivity to fluoride anion compared to other anions such as phosphate, chloride, and sulfate is ascribed to the high coordination ability of the 2-(2′-hydroxyphenyl)benzoxazole moiety in the polymer chain.     

1,8-萘酰亚胺类聚合荧光材料的合成及光学性能

以-4溴-1,8-萘二甲酸酐、二乙烯三胺（DETA）及三聚氯氰（CNC）为原料,经酰胺化、亲核取代反应合成了一种荧光单体,通过傅里叶变换红外光谱对其进行结构表征,并使其与丙烯酰胺按照一定比例聚合,得到一种能溶于水的聚合荧光材料。考察了荧光单体及聚合物的紫外可见吸收和荧光光谱,研究表明,聚合物的Δσ（3964 cm-1）...     

Precise synthesis of asymmetric star-shaped polymers by coupling reactions of new specially designed polymer anions with chain-end-functionalized polystyrenes with benzyl bromide moieties

We have developed a novel methodology using polymer anions specially designed to comprise either of the three same or different polymer segments for the synthesis of well-defined regular and asymmetric star-shaped polymers. The polymer anion was prepared by the addition reaction of living anionic polymer to in-chain-functionalized polymer with 1,1-diphenylethylene (DPE) moiety and in situ coupled with chain-end-functionalized polystyrene with two or four benzyl bromide moieties. Although the anions located at the cores of 3-armed star polymers were believed to be highly sterically hindered, the coupling reactions proceeded virtually quantitatively under the conditions in THF at – 78 °C for 24 h. Regular 7-armed A₇ and 13-armed A₁₃ star-shaped polystyrenes as well as quite new asymmetric 7-armed A₂B₂C₂D and 13-armed A₄B₄C₄D star-shaped polymers were synthesized in ca. 100% yields. Four polymer segments, A, B, C, and D, were, poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), poly(4-methylstyrene), and polystyrene prepared by sec-BuLi-initiated living anionic polymerization. Thus, three same or different polymer chains could be simultaneously introduced into either two or four benzyl bromide reaction sites only by one-step coupling reaction with the above-prepared polymer anion. The resulting star-shaped polymers all were well-defined in architecture and precisely controlled in-chain length and composition. Accordingly, they have a high molecular weight and structural homogeneity. Among them, asymmetric star-shaped polymers synthesized herein are the first successful examples comprised of four plural different polymer segments. As expected, new morphologies with nanoscopic ordered structures applicable to nanotechnology have been expressed.     

Facile electrosynthsis of poly (pyrene-1-sulfonic acid sodium salt) film: A good candidate for blue light-emitting diodes applications

Pyrene-1-sulfonic acid sodium salt (PyS) was chemically synthesized, and its polymer film, poly (pyrene-1-sulfonic acid sodium salt) (PPyS), was successfully electropolymerized by direct anodic oxidation both in aqueous and boron trifluoride diethyl etherate (BFEE) systems. The PPyS films showed good redox activity and structural stability even in SA. The impedance spectra of PPyS films indicated that the electron transfer resistance was about 23 Ω. The fluorescent result exhibited that the emission band of PPyS was red-shifed at least 76 nm in comparison with the monomer. Both the impedance and the fluorescent spectra demonstrated that the PPyS films were good semiconducting polymer and excellent blue-light-emitting materials, respectively.     

含苯并噁唑半芳香聚酰胺的合成与表征

为了得到同时具有优良耐热性能和易加工性能的新型半芳香聚酰胺,以5-氨基-2-(对氨基苯)苯并噁唑(ABO)和己二酸基于Yamazaki磷酸化过程合成了聚己二酰对苯撑苯并噁唑二胺(BO6).研究了反应温度对聚合物分子量的影响,并通过FTIR、1H-NMR对其结构进行了表征;利用DSC、TG对其热性能进行了研究.结果表明:反应温度在90℃左右时高聚物获得了最高的粘数.该聚合物的耐热性较脂肪族聚酰胺有较大幅度的提高,同时该聚合物具有较好的耐溶剂性能.     

新型含铱共聚物的合成及表征

利用2-对甲苯基吡啶(ptpy)、对乙烯基苯甲酸(VBA)和三水合氯化铱(IrCl_3·H_2O)配位,得到了铱配合物单体Ir(ptpy)_2(VBA),再将其与乙烯基咔唑共聚制得了一种含铱配合物的新型聚合物.通过元素分析、FT-IR光谱和~1H NMR谱等对Ir(ptpy)-2(VBA)和聚合物的结构进行了表征.凝胶色谱仪(GPC)测试结果表明,聚合物的数均分子量(Mn)为8230.此外还研究了Ir(ptpy)_2(VBA)和聚合物的紫外-可见(UV-vis)吸收光谱和光致发光(PL)光谱.光致发光光谱测试结果表明,聚合物在固态时,主体咔唑基团向客体铱配合物基团有着较为有效的能量转移.聚合物在501nm处有较强的金属配合物三重态的磷光发射峰,是一种绿色磷光材料.     

P(LMA-MA)两亲性梳型聚合物的合成与表征

采用溶液聚合方式,合成了具有两亲性梳型结构的聚甲基丙烯酸十二酯-马来酸酐共聚物P(LMA-MA)。使用傅里叶变换红外光谱(FT-IR)、核磁共振(1H-NMR)等检测手段对聚合物的组成结构进行了表征。在选择性溶剂(水)中制备了P(LMA-MA)两亲性梳型聚合物的胶束,通过Zeta电位粒径分析仪和透射电子显微镜(TEM)探讨了两亲性梳型聚合物在胶束化过程中胶束形态和尺寸的影响因素。实验表明,由于两亲性梳型聚合物的结构特点,P(LMA-MA)形成200nm以上尺寸的胶束;在浓度范围0.5 g/L-1.75 g/L、温度范围25℃-50℃和pH值范围4-8时,胶束可稳定形成和存在。     

Towards nanoporous polymer thin film-based drug delivery systems

A nanoporous polymer thin film has been developed as a potential platform for drug delivery. The film was fabricated by a light-induced polymerization process in which non-reactive solvent was first separated from photopolymer (dipentaerythritol penta-/hexa-acrylate as the monomer) and then removed from polymer via evaporation, yielding pores with diameters between 20 and 40 nm. Loading and release of Rhodamine B (drug model molecules) on both porous and non-porous thin films proved that nanopores enhanced the film's effectiveness in encapsulating and releasing the drug model molecules, which was attributed to the high surface-to-volume ratio of nanoporous film. Ultrasound-enhanced cumulative and pulsatile release revealed the advantages of ultrasound in controlled drug delivery.     

Enhanced electrooptical active materials based on n-hexyl group flexible isolation in NLO chromophores

Two principally novel organic nonlinear optical chromophores (1 and 2) with flexible (n-hexyl group) or rigid isolated (benzyl group) group are designed and successfully synthesized. The prepared chromophores were characterized by MS, ¹H-NMR and UV–Vis spectra. Their thermal stability was studied by thermal gravimetric analyzer and differential scanning calorimetry. Poled films of the chromophores doped in amorphous polycarbonate afford the maximum electro-optic tensor coefficient (r₃₃) equal to 39 pm/V, 63 pm/V for chromophore 1 and chromophore 2, respectively at the wavelength 1,064 nm. The reason of so large differences between these two chromophores’ linear electrooptics coefficients were explained within a framework of performed quantum chemical calculations and it is crucially dependent on distances between the chromophore molecules and the polymer chains.