Linear poly(amide triazole)s derived from d‐glucose

The click reaction between azides and alkynes is been increasingly employed in the preparation of polymers. In this article, we describe the synthesis and click polyaddition reaction of a new A‐B‐type amide monomer—prepared from d ‐glucose as renewable resource—containing the alkyne and azide functions. Both Cu(I)‐catalyzed and metal‐free click polymerization methods were used to prepare glucose‐derived poly(amide triazole)s. The resulting polymers had weight‐average molecular weights in the 45,000–129,000 range and were characterized by GPC, IR, and NMR spectroscopies. Thermal and X‐ray diffraction studies revealed them to be amorphous. Their qualitative solubilities in various solvents and their water sorption have been studied. The poly(amide triazole)s having the alcohol functions protected as methyl ether were water‐soluble. The presence of the amide functions along the polymer chain made these polytriazoles degradable in the presence of sodium deuteroxide. The degradation was monitored by NMR analysis, and the degradation product was characterized by HRMS. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 629–638     

Novel Hyperbranched Poly([1,2,3]‐triazole)s Derived from AB2 Monomers by a 1,3‐Dipolar Cycloaddition

Summary: Novel hyperbranched poly([1,2,3]‐triazole)s were synthesized from several AB₂ monomers by a 1,3‐dipolar cycloaddition reaction. The compound 3,5‐bis(propargyloxy)benzyl azide was polymerized thermally at room temperature leading to 1,4‐ and 1,5‐disubstituted poly([1,2,3]‐triazole) and catalytically leading only to the 1,4‐disubstituted poly([1,2,3]‐triazole). Only the thermal reaction led to fully soluble products. The AB₂ monomers containing an internal alkyne A unit could be autopolymerized thermally under mild reaction conditions leading to soluble, high‐molecular‐weight hyperbranched poly([1,2,3] triazole)s. All products were characterized by detailed NMR investigations.

Synthesis route for polymers 8a and 8b .     

Preparation of Information‐Containing Macromolecules by Ligation of Dyad‐Encoded Oligomers

A simplified strategy for preparing non‐natural information‐containing polymers is reported. The concept relies on the successive ligation of oligomers that contain minimal sequence motifs. It was applied here to the synthesis of digitally‐encoded poly(triazole amide)s, in which propyl and 2‐methyl propyl motifs are used to code 0 and 1, respectively. A library of four oligo(triazole amide)s containing the information dyads 00, 01, 10, and 11 was prepared. These oligomers contain two reactive functions, that is, an alkyne and a carboxylic acid. Thus, they can be linked to another with the help of a reactive spacer containing azide and amine functions. Using two successive chemoselective steps, that is, azide‐alkyne Huisgen cycloaddition and carboxylic acid‐amine coupling, monodisperse polymers can be obtained. In particular, the library of dyads permits the implementation of any desired sequence using a small number of steps. As a proof‐of‐concept, the synthesis of molecular bytes 00000000 and 00000110 is described.     

含二氦杂萘酮结构全芳香杂环聚合物的研究进展

高性能高分子材料在高温下仍保持优异的综合性能,是航空航天、电子电气、高速轨道交通等重要高技术领域不可或缺的材料。在不牺牲耐热性能的前提下改善高性能聚合物的加工性能一直是国内外研究的热点。含二氮杂萘酮结构高性能聚合物是高性能高分子材料的新成员。本文主要综述了含二氮杂萘酮结构的聚芳醚（包括聚芳醚砜酮系列、聚芳醚腈砜酮系列、...     

Antibacterial activity of conjugated polyelectrolytes with variable chain lengths

Cationic poly(phenylene ethynylene)- (PPE-) based conjugated polyelectrolytes (CPEs) with six different chain lengths ranging in degree of polymerization from ～7 to ～49 were synthesized from organic-soluble precursor polymers. The molecular weight of the precursor polymers was controlled by the amount of a monofunctional "end-capping" agent added to the polymerization reaction. Cationic CPEs were prepared by quaternization of amine groups to tetraalkylammonium groups. Their structure-property relationships were investigated by observing their photophysical properties and antibacterial activity. The polymers were found to exhibit a chain-length dependence in their photophysical properties. It has also been observed that the polymers exhibit effective antibacterial activity against both Gram-positive and Gram-negative bacteria under UV irradiation, whereas they show little antibacterial activity in the dark. An effect of chain length on the light-activated antibacterial activity was also found: The shortest polymer (n=7) exhibited the most effective antibacterial activity against both Gram-positive and Gram-negative bacteria.     

Biodegradable synthetic and semisynthetic polymers

As a part of our continuing interest in the preparation of multifunctional polymeric materials and evaluation of their potential in pharmaceutical, medical and environmental fields, a survey on new polymeric systems of synthetic and semisynthetic origin, susceptible to bioerosion and/or biodegradation attack is presented. In particular, attention has been focused on the design, preparation and characterization of the following classes of hydrophilic and/or water-soluble polymeric materials: hydroxyl-containing poly(ester)s, hydroxyl-containing poly(amide)s, hydrophilic polymers containing carboxylic groups, perhydroxylated oligo- and poly(saccharide)s, oxidized poly(saccharide)s, and hybrid polymeric materials based on blends of carboxyl-containing synthetic polymers and proteins. The rationale of the research activity undertaken over the years is illustrated by focusing on some specific achievements of practical significance.     

Synthesis of Conjugated Hyperbranched Polytriazoles Containing Truxene Units by Click Polymerization

It has been a challenge to synthesize high molecular weight and soluble conjugated hyperbranched poly(1,2,3‐triazole)s (hb‐PTAs). In this paper a series of soluble hyperbranched polytriazoles, whose number‐average molecular weight (M_n) and polydispersity index ranged in (1.2–3.3)×10⁴ and 1.7–3.0, respectively, were synthesized with A₂+B₃ approach. In the polymerization process, diazides A1 – A4 and triyne B1 were used as A₂ and B₃ monomers; Cu(I)‐catalyst, THF and water were used as their reaction system. At room temperature the final molecular weight could be controlled through reaction time, so finally we obtained soluble conjugated hyperbranched poly(1,2,3‐triazole)s hb‐PTAs (1–4 ). The polymers were soluble in common organic solvents, and all emitted blue light; the films of polymers emitted yellow and blue light, due to the difference in the aggregation of their chromophoric units in the solid state. The thermal properties of the final copolymers were analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

Reduction‐cleavable hyperbranched polymers with limited intramolecular cyclization via click chemistry

In this contribution, we present new reduction‐cleavable hyperbranched disulfide bonds‐containing poly(ester triazole)s with limited intramolecular cyclization, which can be synthesized by the Cu(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) of A₂ monomer of dipropargyl 3,3′‐dithiobispropionate and B₃ monomer of tris(hydroxymethyl)ethane tri(4‐azidobutanoate). The hyperbranched poly(ester triazole)s possess numerous terminal groups and weight‐average molecular weight up to 20,400 g mol^?1 with a polydispersity index in the range 1.57–2.17. The CuAAC introduces rigid triazole units into the backbones of hyperbranched poly(ester triazole)s and reduces intramolecular cyclization, which is proved by topological analysis and ¹H NMR spectroscopy. The disulfide bonds on backbones endow the reduction‐cleavable feature to the hyperbranched poly(ester triazole)s at the presence of dithiothreitol. It gives a novel and convenient methodology for the synthesis of reduction‐responsive functional polymer with controlled topologies, and the reduction‐cleavable hyperbranched poly(ester triazole)s with limited intramolecular cyclization are expected to possess potential in the application of stimuli‐responsive anticancer drug nanocarriers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2374–2380     

Efficient tuning nonlinear optical properties: Synthesis and characterization of a series of novel poly(aryleneethynylene)s co‐containing BODIPY

A series of novel conjugated poly(aryleneethynylene)s (PAEs) co‐containing BODIPY have been synthesized and characterized, and their third‐order nonlinear optical properties were studied using the Z‐scan technique. Interestingly, by introducing the BODIPY skeleton into the PAE backbone, the polymers showed that their nonlinear optical properties were dependent on the BODIPY component. From poly‐4 to poly‐1, the third‐order nonlinear optical properties of the polymers enhanced regularly with the increase of the BODIPY component of the copolymers, indicating that the BODIPY component played decisive roles in enhancing the nonlinear optical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7401–7410, 2008     

Dielectric phenomena and electrical energy storage of poly(vinylidene fluoride) based high-k polymers

Since the discovery of relaxor ferroelectric behavior was firstly reported in irradiated poly(vinylidene fluoridetrifluoroethylene) (P(VDF-TrFE)) copolymer, many strategies have been developed to enhance the electrical energy storage capability, including copolymerization, grafting, blending and fabricating of multilayer. This review article mainly summarizes the recent progresses on these strategies and aims to motivate the development of novel PVDF-based polymers for electrical energy storage and dielectric applications.     

COMPARED PROPERTIES OF FLUORINATED HETEROCYCLIC COPOLYIMIDES

Various new fluorinated heterocyclic copolyimides have been synthesized by a polycondensation reaction of a diacid chloride containing imide, hexafluoroisopropylidene and methylene groups with aromatic or heteroaromatic diamines containing preformed phenylquinoxaline or 1,3,4-oxadiazole rings. Other fluorinated heterocyclic copolyimides have been prepared by a polycondensation reaction of the same diacid chloride with aromatic dihydrazides, bis(o-hydroxy-amine)s or a bis(o-carboxy-amine), resulting in intermediate polyhydrazides, poly(o-hydroxy-amide)s or poly(o-carboxy-amide), respectively, which were futher cyclodehydrated to the corresponding polyoxadia zole-imide, polybenzoxazole-imide or polybenzoxazinone-imide structure. These polymers showed good solubility in polar amidic solvents, such as N-methylpyrrolidinone (NMP) and dimethylformamide (DMF), and even in less polar liquids, like tetrahydrofurane or pyridine, except for those compounds containing benzoxazole rings which were less soluble, only on heating in NMP or DMF. The weight average molecular weight measured for tetrahydrofurane-fully-soluble polymers are in the range of 12800–26700 and the polydispersity is in the range of 2–5. All these polymers exhibited good thermal stability, with decomposition temperature being above 350°C, although somewhat lower than that of related polymers prepared by using fully aromatic diacid chlorides instead of the present ones containing methylene units. The glass transition temperature is in the range of 200–300°C. The dielectric constant measured for polymer films is in the range of 3.3–3.7. Tensile strength is in the range of 35–70 MPa, elongation to break between 30–40% and tensile modulus in the range of 170–330 MPa. A study of the relation between conformational parameters and properties of some of these polymers has been carried out by using the Monte Carlo method with an allowance for hindered rotation, and the values were compared with the experimental data and discussed in relation with the rigidity of the chains. The present polymers are potential candidates for use as high performance materials.     

Preparation of new poly(ester triazole) and poly(amide triazole) by “click chemistry”

New dialkynyl monomers containing furan and ester or amide units were prepared via three step reactions from ethyl furan-2-carboxylate. Their click polymerization with either poly(ethylene glycol) diazide or poly(tetrahydrofuran) diazide catalyzed by Cu(I) led to corresponding amorphous poly(ester triazole) and poly(amide triazole) with molecular weights in the range of (7–11) × 10³ and with glass transition temperatures in the range of ?35 and ?19°C. The temperature at 5% wt loss (T ₁₀), determined from TGA of polyazomethines were in the range 345–365°C indicating their good thermal stability.     

SYNTHESIS AND CHARACTERIZATION OF HETEROAROMATIC POLYMERS CONTAINING PYRIDINE MOIETIES

The progress on the molecular design, synthesis and characterizations of some kinds of pyridine-containing heteroaromatic polymers in main chain were reviewed in this paper, they would include polyimides (PIs), polypyrrolones (PPYs), poly(pyrrolone-imide)s (PPIs), and poly(pyrrolone-benzimidazone)s (PPBs) containing pyrldine moieties. The pyridine-containing polymers reported all exhibit good processability, excellent thermal properties and mechanical properties. However, the contribution of pyridine ring to polymers properties is still need to research further, the heteroarornatic polymers containing pyridine moieties have focused by more and more researchers.     

具可调光学性质的富勒烯聚合物

聚（Ｃ６０ 甲基丙烯酸甲酯）与聚（Ｃ６０ 苯乙烯）的ＴＨＦ溶液的透射光谱随浓度的增大而不断红移．这种异常的光谱位移可能与富勒烯的纳级（１０－９）簇的形成有关．用简单的办法来“调改”一物质的性质是科学家们长期梦寐以求的，而含Ｃ６０的聚合物正代表了这一群新奇的物质，它们的光学性质可以预期地和可逆地调变，只要简单改变一下浓度．     

SYNTHESIS AND CHARACTERIZATION OF HETEROAROMATIC POLYMERS CONTAINING PYRIDINE MOIETIES

1. INTRODUCTION The new kinds of heteroaromatic polymers have been important topics in polymer science fields since they were developed at 1960s in order to meet demands for heat-resistant plastics for space and military applications. Because heteroaromatic polymers exhibit excellent thermal and chemical stability, outstanding electrical and mechanical properties, good solvent resistance, and dimensional stability, these polymers have found usage as adhesives, coatings, matrix resins, film…     

含二氮杂荼酮结构新型聚芳醚系列高性能聚合物的合成与性能

从分子结构设计出发 ,以价廉易得的苯酚、苯酐为原料 ,经温和的工艺合成了结构全新的 4 ( 4′ 羟基苯基 ) 2 ,3 二氮杂萘 1 酮 (DHPZ) ,对其合成反应路线、合成反应动力学、反应机理进行了深入研究 .在大量实验研究基础上 ,结合分子立体结构的计算机模拟 ,确认其具有非共平面扭曲结构特征 ,其N—H键和O—H键具有类似的反应活性 ,是一种类似双酚的新单体 .以DHPZ与多种市售双卤单体如二氟二苯酮 (DFK)、二氯二苯砜 (DCS)、二氯二苯双酮 (DCKK)、二氯二苯腈 (DCBN)等经溶液亲核取代逐步聚合反应制得一系列含二氮杂萘酮结构的新型高性能聚醚砜 (PPES)、聚醚酮 (PPEK)、聚醚砜酮 (PPESK)、聚醚酮酮 (PPEKK)、聚醚砜酮酮(PPESKK)、聚醚腈酮 (PPENK)、聚醚腈砜 (PPENS)、聚醚腈砜酮 (PPENSK)等 ,对其结构进行了谱学表征 ,对其性能进行了全面测试 ,研究了其结构与性能关系 .谱学数据证明皆为无定型高聚物 .其玻璃化温度Tg 在 2 5 0～370℃之间 ,可以通过取代基团结构或主链上砜 酮基团比例进行调控 .在大量实验研究基础上 ,创造性提出“引入全芳环非共平面扭曲分子链结构赋予高聚物既耐高温又可溶解的优异综合性能”的分子结构设计理论 .在此分子设计理论指导下 ,设计并合成了含联苯二氮杂萘酮结构的新型二     

New directions in medical biosensors employing poly(3,4-ethylenedioxy thiophene) derivative-based electrodes

Demand is growing in the field of medical diagnostics for simple, disposable devices that also demonstrate fast response times, are easy to handle, are cost-efficient, and are suitable for mass production. Polymer-based microfluidic devices meet the requirements of cost efficiency and mass production and they are suitable for biosensor applications. Conducting polymer-based electrochemical sensors have shown numerous advantages in a number of areas related to human health, such as the diagnosis of infectious diseases, genetic mutations, drug discovery, forensics and food technology, due to their simplicity and high sensitivity. One of the most promising group of conductive polymers is poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives due to their attractive properties: high stability, high conductivity (up to 400–600 S/cm) and high transparency. This review paper summarizes newly developed methods associated with the application of PEDOT to diagnostic sensing.     

Poly(4-nitrophenyl)quinoxalines

Via the reaction of 4,4-bis(4-nitrophenylglyoxalyl)diphenyl ether with different bis(o-phenylenediamine)s, new poly(4-nitrophenyl)quinoxalines were synthesized, which are of interest as precursors for polymers containing protogenic groups. Some properties of the obtained polymers were studied. It was shown that the solubility of poly(4-nitrophenyl)quinoxalines in organic solvents and their viscosity characteristics are comparable with the parameters of polyphenylquinoxalines that do not bear nitro groups. A study of the thermal properties of the polymers showed that the introduction of nitro groups into polyphenylquinoxalines is accompanied by some increase in the glass transition temperature and a decrease in the onset temperature of runaway thermal degradation.     

Synthesis and photophysical properties of poly(aryleneethynylene)s bearing dialkylsilyl side substituents

A series of poly(aryleneethynylene)s bearing dialkylsilyl (-SiR₂H) side substituents has been synthesized by Sonogashira cross-coupling reactions of 1,4-diethynyl-2,5-bis(dialkylsilyl)benzene and diiodoarylene compounds. Their photophysical properties in solution have been studied. All of the polymers showed intense fluorescence with high quantum yield. Compared with their analogues containing para-phenylene units, the polymers with meta-phenylene units in the main chain showed absorption and emission maxima at shorter wavelengths, whereas the polymers having thiophenylene units in their backbones showed bathochromically shifted spectra. For polymers having the same conjugated parent backbone, silyl substituents have been found to exert negligible effect on their photophysical properties.     

Organic thin film pyrosensors

Recent developments in sensor technology show the suitability of thin pyroelectric films for the construction of pyroelectric sensor devices made from polymer materials. These materials are used for its advantageous thermal properties and also for its suitable frequency behaviour. Pyroelectrical measurements have been provided on thin films based upon poly(vinyl alcohol)s and poly(siloxane)s with azobenzene side chains. Relaxation behaviour and stability of poled pyroelectric polymers are discussed and related to the results of dipole relaxation measurements provided at our laboratories.