Haloaldehyde Polymers. XXX. Macromolecular Asymmetry as the Basis of Optical Activity in Polymers

The synthesis of polymers characterized by a preferred helical screw sense (macromolecular asymmetry) is a subject of considerable experimental interest. Here, we summarize our efforts toward the preparation of optically active polychloral in which asymmetry at the macromolecular level is the only factor contributing to the polymer's chiroptical properties. Through the use of chiral initiating species, we have prepared optically active polychloral with specific rotations reaching 4500° at the sodium D-line. The results of this work and the prospects for further investigation are outlined.     

Imine Oligomers and Polymers

Abstract

In the last few years, polymers with highly conjugated chains have attracted much attention because of their wide variety of applications in the field of electronics, opto‐electronics, and photonics. Polyimines (PIs) (polymeric Schiff bases) is a class of polymer family, which has been less reviewed. In this paper, we focus on the synthesis methods of PIs by polycondensation, using diamines or hydrazine and dialdehydes, diketones or quinone compounds, or by chemical and electrochemical polymerization of imine oligomers containing terminal oxidable groups (pyrrole, thiophene, furan, naphthalene, etc). PIs with liquid crystalline behavior or having rotaxane and dendrimer architectures are also discussed. Structure, thermal, opto‐electronic, electrical, and mechanical properties and some potential applications of this class of polymers are presented in the last chapters.     

Living Cationic Polymerization Toward Macromolecular Design: Synthesis of End-Functional Multiarmed Polymers

A series of multiarmed polymers with terminal functional groups have been synthesized on the basis of living cationic polymerizations of vinyl ethers and p-alkoxystyrenes. The syntheses were performed by two methods, one via living polymerizations with new multifunctional initiating systems followed by endcapping of the resultant multifunctional living polymers, and the other using designed silyl enol ethers as multifunctional terminators (coupling agents) that combine two to four end- functionalized linear living polymers. These two methodologies thus led to telechelic and 3- or 4-arm star polymers and macromonomers with hydroxyl, acetate, methacrylate, and styryl end functionalities.     

Oligomers and Polymers of Polyethers and Polyformals

Linear high molecular weight aromatic polyformals are readily obtained from biphenols and excess methylene chloride with solid sodium hydroxide or potassium hydroxide in the presence of a phase transfer catalyst or an aprotic dipolar solvent. By control of the stoichiometry bifunctional oligomers can be obtained which can subsequently be incorporated into a variety of block copolymers.     

Syntheses of Polymers and Oligomers Having Adenine Derivatives

Abstract

9-(2′,3′-Dihydroxyethyl)-8-bromoadenine was synthesized by the reaction of 9-(2′,3′-dihydroxyethyl)-adenine with bromine. The reaction of 9-(2′,3′-dihydroxyethyl)-8-bromoadenine with phosphorus oxychloride in trimethyl phosphate produced 9-(2′,3′-dihydroxypropyl)-8-bromoadenine-3′-phosphate. The condensation polymerization of 9-(2′,3′-dihydroxypropyI)-8-bromoadenine-3′-phosphate was conducted in refluxing dimethylformamide-water (9:1) using dicyclohexylcarbodiimide as a dehydrating agent. The oligomer obtained is soluble in water and has a molecular weight of more than 1000 according to gel-filtration measurement. This oligomer showed hypochromicity of 3°, with denatured yeast RNA. The condensation polymerization of 9(2′,3′-dihydroxypropyl)-8-bromoadenine-3′ -phosphate was also carried out using imidazole or a triethylamine-hydrochloric acid system.     

Reactive Polymers and Oligomers from Cyclic Ethers and Cyclic Sulfides

(2-Bromoethyl)oxirane is converted in 39% yield to poly-[(2-bromoethyl)oxirane] of inherent viscosity 1.99 dL/g. The AlEt₃/H₂O/AcAc system is a very effective initiator for the polymerization of (2-bromoethyl)oxirane. Poly[(2-bromoethyl)-oxirane] is a white elastomer, soluble in CHCl₃ and insoluble in CH₃OH. Polyether-urethane hydrogels are prepared by the room temperature crosslinking of poly[(3-hydroxypropyl)oxirane] with aliphatic or aromatic diisocyanates. These networks absorb 100–200% of their weights in water, and can be prepared in transparent form with potential application as biomaterials or contact lenses.     

硒吩聚合物/寡聚物有机光电材料研究进展

主要从光电性能角度总结了近几年硒吩聚合物/寡聚物在有机太阳能电池(OSCs)、场效应晶体管(FETs)、发光二级管(LED)等方面的研究进展。目前,基于聚硒吩并[3,4-b]硒吩-苯并二硒吩(PSeB2)(polyselenopheno[3,4-b]selenophene-co-benzodiselenophene)本体异质结太阳能电池器件的能量转化效率最高,达6.87%;场效应晶体管方面,基于PSeDPP(P28)器件的空穴迁移率最高达1.62cm2.V-1.s-1。基于PFO-DDSTQ(一种硒吩芴基聚合物)的发光二级管,表现出目前基于硒吩化合物的最长波长发光器件,EL光谱峰值约860nm。通过对研究者的研究成果的总结发现,在有机光电器件的应用领域中硒吩聚合物/寡聚物是一种极具应用前景的材料。     

Macromolecular Architecture-Nature as a Model for Degradable Polymers

Abstract

Nature usually combines polymers with short degradation times with polymers having long degradation times in an energy and material optimized process involving hierarchical systems. Sometimes a natural system of polymers has evolved to degrade in a month, sometimes in many years. The building blocks of the plant and animal kingdom are biopolymers which are either oxidizable or hydrolyzable. In natural composites, combinations of the two are common, e.g., in wood. Current trends in polymer research and marketing of plastics indicate an increasing demand for the development of a diversity of degradable polymer products with a predetermined service-life. We identify four main routes to design degradable polymers. The goal is to tailor-make a material which is more susceptible to environmental degradation factors (e.g., hydrolysis, biodegradation, photooxidation). The most convenient route is to use cheap synthetic bulk polymers and add a biodegradable or photooxidizable component. A more expensive solution is to change the chemical structure by introducing hydrolyzable or oxidizable groups in the repetitive chain of a synthetic polymer. The third route to degradable polymers is to use biopolymers or derivatives of these where the bacterial polyhydroxyalkanoates are perhaps the most studied material of them all. The fourth route is to tailor-make new hydrolyzable structures e.g., polyesters, polyanhydrides, and polycarbonates.     

Analysis of Polydispersity of Oligomers and Polymers by Adsorption Thin-Layer Chromatography

Abstract

Thin-layer chromatography/TLC/ has been widely used for the analysis of virtually all classes of low molecular weight organic substances.     

Synthesis of Functionally-Terminated Oligomers by Free Radical Ring-Opening Polymerization

Since free radical ring-opening polymerization made it possible to introduce functional groups, such as esters, carbonates, thioesters, and amides, into the backbone of an addition polymer, it was reasoned that simple hydrolysis of these copolymers would produce the desired oligomers that could be terminated with various combinations of hydroxyl, amino, thiol, and carboxy1 groups. Thus the copolymerization of 2-methylene-1,3-dioxepane and styrene (r1=0.021 and r2=22.6) gave a copolymer containing 10 mole-percent of an ester-containing unit with 100% ring opening at 120°C. Hydrolysis of this copolymer gave an oligomer terminated with a hydroxyl group and a carboxylie acid group. Similarly the copolymerization of 2-methylene-1,3-dioxepane and ethylene gave a series of biodegradable polyethylene copolymers containing 2.1 to 10.4% ester-containing units. Hydrolysis of these copolymers gave a series of ethylene oligomers with nine to forty-seven ethylene units and terminated with a hydroxyl group and a carboxylic acid group. By the same general method oligomers of various monomers that are terminated with a methylandno group and a carboxylic acid group from N-methyl-Z-methylene-1,3-oxazolidine and with a thiol group and a carboxyl group from Z-methylene-1,3-oxathiolane.     

Communication: Synthesis of Polylactosamine Oligomers by Disaccharide Polymerization

Polylactosamine chains, which consist of repeats of the disaccharide βGal(1→4)βGlcNAc(1 →3), are characteristic developmental and tumor associated carbohydrate markers found attached to both glycoproteins and glycolipids.^1,2 In addition to the accumulation of such sequences in a number of diseases, these structures are the immediate biosynthetic precursors to poly-Le^x determinants, {--βGal(1 →4)[αFuc(1 →3)βGlcNAc(1 →3)--)_n, which are recognized also as tumor associated antigens,^3-4 particularly in adenocarcinomas.⁵     

N-Metalla Hydridophosphazenes: Precursors for Heterobimetallic Complexes and Hydridophosphazene Oligomers and Polymers

Abstract

The tautomerisation of NH-aminophosphanes to the corresponding PH-imino-phosphoranes has been the subject of several experimental and theoretical studies^[1].     

Asymmetry of Monomer Unit Arrangements in Multicomponent Polymers

The concept of “flux” is proposed for quantitatively describing the manner in which the relative concentrations of three chain ends remain at a steady state in a terpolymerization. The flux is a measure of the net rate of transition from one chain end to another. If a terpolymerization remains at a steady state with respect to the relative concentrations of the three chain ends, then the flux must be either zero or some finite number which is independent of the choice of chain ends used to calculate it. It is a necessary and sufficient condition for Ham's concept of sequence reversibility to be true that the flux be zero. The flux calculated for many systems using reactivity ratio data is quite near zero. However, the calculations necessarily share the imprecision of reactivity ratio data. Ter-polymer sequence distribution data, if available, could be used in a proposed method of calculating flux.     

间氯苯胺的乳液聚合及聚合物链结构表征

聚苯胺以其良好的电化学稳定性和掺杂可逆性 ,成为一类优良的电活性聚合物 [1,2 ] ,但其溶解性差 ,限制了它的加工及应用 .用取代基对聚苯胺的结构进行修饰 ,可有效地提高其加工性能 [3,4 ] ,但有关含吸电子取代基的苯胺衍生物聚合的报道尚少 .Ranger等 [5]指出 ,含强吸电子取代基团的聚苯胺不易用化学氧化聚合方法制备 ,并提出被氧化单体中的 N7和 C4位置必须具有相近的电子自旋密度 ,才能进行“头 -尾”偶联 ,而含强吸电子取代基团的苯胺单体中这两个位置的反应能力是不等价的 ,但可采用与母体共聚的方法可制备含强吸电子取代基 (如— C…     

等离子体聚合及其聚合物的应用

本文着重综述了烃,含氮、氧的有机化合物,碳氟化合物以及有机硅化合物的等离子体聚合。同时还系统地介绍了等离子体聚合物在制备反渗透膜、分离膜、材料表面的涂层等方面的国内外的最新研究成果。     

Structural Design and Applications of Stereoregular Fused Thiophenes and Their Oligomers and Polymers

Abstract

Stereoregular fused thiophenes (SFTs: especially thieno[3,2-b]thiophene (TT) and dithieo[3,2-b:2′,3′-d]thiophene (DTT)), as stable conjugated structures deriving from thiophene ring enlargement, possess outstanding properties and special configuration, such as the superior carrier transfer efficiency and a high degree backbone of planarity. In comparison to stand-alone SFTs structures, oligomers and polymers containing different heteroaromatic units have been much widely researched and used in many fields. In decade, several important reviews have summarized the broad field of fused thiophenes including SFTs, and their synthesis and optoelectronic applications. Here, we critically present the structure–performance relationships and application of oligomers and polymers containing SFTs (exhibiting thiophene ring number from 2 to 7) units. First, the basic structures and properties of SFTs are briefly stated. Then, oligomers classified by extra conjugated heterocyclic attachments are carefully discussed, focusing on the structure–performance relationships for their optoelectronic applications including organic photovoltaic cells and organic field-effect transistors. Moreover, such relationships in polymers have been applied in much wider fields such as organic light-emitting diodes, electrochromic devices, thermoelectric devices, and supercapacitors are discussed. Finally, a summary and prospect are given. Through this review, instruction for molecular design and novel ideas for the future development of SFTs-contained are provided.     

聚合度3～6甲壳寡糖的制备与TOF-MS分析

本文用自制酸性蛋白酶粗酶液降解壳聚糖,研究了降解过程中温度、pH值、反应时间、酶用量及壳聚糖脱乙酰度(DD)对酶降解能力的影响。以85.5%脱乙酰度(DD)、分子量(Mw)为56.0×104的壳聚糖为底物,45℃、pH4.6降解数小时,降解产物由红外光谱、分子量测定(GPC)和基体辅助激光解吸电离飞行时间质谱(MALDI TOF MS)表征。主要降解产物的脱乙酰度有所降低;酶解8h,其水解产物用NaOH调至pH9无沉淀,9h分子量降为0.93×103,经MALDI TOF MS分析产物为聚合度3～6的甲壳寡糖,3～6糖中各糖含量分别为13.3%、27.3%、49.0%、10.1%。     

The Synthesis of Graft,Block, and Star Polymers Using Enolate-Initiated Anionic Polymerization

Abstract

Initiation of the polymerization of methacrylate monomers by enolate ions affords broad opportunities for the design of several types of macromolecules. Alone, or in combination with other techniques, enolate initiation provides routes to the preparation of well-Characterized graft copolymers, block copolymers (of both AB and BAB types), star polymers, and H-polymers. The general mechanism of polymerization initiated by lithiated esters and silyl ketene acetals is discussed, and examples are presented of the synthesis of each of the kinds of polymer molecules mentioned above.