Poly (N-Isopropyl Acrylamide-<i>Co</i>-Vanillin Acrylate) Dual Responsive Functional Copolymers for Grafting Biomolecules by Schiff’s Base Click Reaction

This article reports on the synthesis of acrylate monomer from renewable material. Vanillin was selected to be the start material to produce new monomer called vanillin acrylate and abbreviated by (VA). It has been successfully investigated by 1H, 13C NMR, IR and UV and all results were in logic state. The next step was to synthetize three different thermo-responsive functional copolymers by incorporation of three different molar ratios of vanillin acrylate (10, 20, 30 mol%) with N-Isopropylacrylamide via free radical polymerization by AIBN as initiator in solution. All copolymers were deduced by 1NMR and IR and all showed the presence of aldehyde group. The copolymer was used for grafting of tryptophan and β-alanine through the chemical link between amino group and the active aldehyde group by click reactions to form Schiff’s base imine compounds. Moreover, polymers were also elucidated by 1HNMR, IR and UV, Size Exclusion Chromatography (SEC) was used for the molecular weight determination, differential scanning calorimeter (DSC) for glass temperature of solid polymers, XRD for crystallinity. UV-vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution not only in deionized water but in pH5 and pH11. The mount of conversation and linked amino acid was determined by UV-vis Spectroscopy.

SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distribution.H...

SYNTHESIS OF A HYPERBRANCHED POLY(AROYLARYLENE) CONTAINING TRIAZOLE AND FLUORENE FUNCTIONALITIES BY CLICK CHEMISTRY AND METAL-FREE,REGIOSELECTIVE POLYCYCLOTRIMERIZATION

A new bis(aroylacetylene) containing tfiazole and fluorene moieties is synthesized by click chemistry. Polycyclotrimerization of the monomer is catalyzed by piperidine in refluxed dioxane,furnishing a regioregular poly(aroylarylene) in a satisfactory yield.The hyperbranched structure of the polymer is characterized spectroscopically with satisfactory results.The polymer enjoys no metal detriment and is soluble in common organic solvents such as tetrahydrofuran (THF),chloroform,dichloromethane (DCM),and N,N-...

Synthesis and Characterization of Heterocyclic Functionalized Polymers by Click Reaction: Preparation of Magnetic Nanocomposites and Studies on Their Thermal, Mechanical, Photophysical and Metal Ions Removal Properties

This work reports synthesis and characterization of heterocyclic functionalized polymers, poly（triazole-etherimidazole）s（PTAEI）, from a dialkyne-terminated compound, 3-（4,5-bis（4-（propargyloxy）phenyl）-1H-imidazol-2-yl）-9-ethyl-9H-carbazole, by using click reaction. PTAEIs were characterized and their properties such as solubility, thermal, mechanical, photophysical and metal ions adsorption were investigated. These polymers had weight average molar masses（Mw） in the range of 19100-26700 g/mol, exhibited excellent solubility in polar aprotic solvents and formed low-colored flexible thin films by solution casting method. They exhibited good thermal stability with glass transition temperatures（Tg） between 160 °C and 211 °C and 10% weight loss temperatures（T10%） in the range of 308-426 °C. Nanocomposites of PTAEIs with epoxide-terminated Fe3O4 showed that strong interfacial interaction between inorganic particles and the polymer matrix contributed to the enhanced thermal and mechanical properties. The photoluminescence intensity of the PTAEIs increased and the spectra red shifted with increasing Fe3O4 content. The PTAEIs and nanocomposites were tested for their extraction capability of metal ions from aqueous solutions either individually or in the mixture.

In-chain functionalization through the combination of ring opening copolymerization and oxime "Click" reaction towards X-ray opaque polylactide copolymers

X-ray imaging functionalization of biodegradable polyesters is a great demand and challenge in biomedical applications.In this work,a strategy of in-chain functionalization through the combination of ring opening copolymerization and oxime "Click" postfunctionalization was developed towards X-ray opaque polylactide copolymers.A functionalized cyclic carbonate was first synthesized and used as comonomer of polylactide copolymers,which were subjected to postfunctionalization of oxime "Click" reaction towards iodinated polylactide copolymers.The chemical structure and physical properties of the target products were traced and confirmed.In vitro cytotoxicity evaluation with 3T3-Swiss albino by Alamar blue demonstrated a low cytotoxicity.The X-ray radiopacity was analyzed by Micro-CT and quantified by Hounsfield Units value,which could be tailorable by the feedstock.It is a promising X-ray visible implantable biomaterial in biomedical applications.

Synthesis of Alkyne-functionalized Polymers via Living Anionic Polymerization and Investigation of Features during the Post-“thiol-yne” Click Reaction

"Thiol-yne" click reaction has already been widely applied in synthesis and modification of new polymer structures or novel materials due to its specific features. However, in most studies, only chain-end strategy was employed when using the di-addition feature of thiol-yne reaction, thus the in-chain di-addition strategy could endow us with a broader space to develop the synthesis of advanced polymers. Therefore, in this paper, the features of in-chain mono and di-addition were investigated when modifying the alkynefunctionalized polymers to prepare grafted polymers via thiol-yne click reaction. The results showed that it is almost impossible to obtain the in-chain di-adducts even under excess feeding of chain-end thiol-functionalized grafts, while only the in-chain mono-adducts could be obtained efficiently. Further researches investigated that the controlled grafting could be encountered when carrying out the thiol-yne click reaction between chain-end alkyne-functionalized polystyrenes and chain-end thiol-functionalized polystyrenes under proper feedings. Therefore, the effect of steric?hindrance might be the primary reason for the alternative grafting via thiol-yne click reaction between in-chain and chain-end alkyne-functionalized polymers.

Thermo-responsive topological metamorphosis in covalent-and-supramolecular polymer architectures

Topological metamorphosis represents a powerful approach to modulate the properties of polymers.However,it still remains a major challenge to achieve the tunability of bulk mechanical properties via topological transformation in supramolecular polymer systems.Herein,we couple the covalent polymer and supramolecular polymer in a single system—referred to as covalent-and-supramolecular polymer(CSP)—to realize a thermo-responsive macromolecular metamorphosis.The CSP is able to topologically switch from grafted polymer to cross-linked network by taking advantage of synergistic dynamic covalent interactions and host–guest interactions.Benefiting from the topologically structural transformation,brittleness intrinsically evolves into toughness in our CSP architectures with minimum change of their molecular compositions from furan–maleimide to anthracene–maleimide linkers.Our work demonstrates that supramolecular polymers are a promising platform to design smart materials not only due to their inherent stimuli-responsive properties but also because of their abilities in determining bulk mechanical properties of polymers with alterable topological structures.

Recent Advances of CuAAC Click Reaction in Building Cyclic Polymer

Cyclic polymers have attracted more and more attentions in recent years because of their unique topological structures and characteristic properties in both solution and bulk state. There are relatively few reports on cyclic polymers, partly because of the more demanding synthetic procedures. In recent years, 'click' reaction, especially Cu(I)-catalyzed azide-alkyne cycloaddition(CuAAC), has been widely utilized in the synthesis of cyclic polymer materials because of its high efficiency and low susceptibility to side reactions. In this review, we will focus on three aspects:(1) Constructions of monocyclic polymer using CuAAC 'click' chemistry;(2) Formation of complex cyclic polymer topologies through CuAAC reactions;(3) Using CuAAC 'click' reaction in the precise synthesis of molecularly defined macrocycles. We believe that the CuAAC click reaction is playing an important role in the design and synthesis of functional cyclic polymers.

点击化学交联用于提升有机太阳能电池活性层的稳定性

本文制备了以BDT为核心,侧链末端引入可交联的乙烯基的聚合物给体材料。采用三元共聚的合成方法,引入3%和5%含量的乙烯基片段,合成了材料CT-1和CT-2。随后基于材料自身的光电性能测试、器件活性层的形貌测试以及器件的光伏性能测试,分析了乙烯基片段的引入量与交联前后性能改变的内在联系。结果表明,适量的乙烯基交联不仅可以提升材料的稳定性,器件的光电转化效率(PCE)也得到了提高,其中CT-1与受体BTP-eC9制备的器件,其PCE达到了14%。

Polymer Synthesis Based on Self-Accelerating 1,3-Dipolar Cycloaddition Click Reactions

This review reports our recent work on developing polymer synthesis methods based on a self-accelerating double-strain-promoted 1,3-dipole-alkyne cycloaddition(DSPDAC)click reaction.In DSPDAC,the cycloaddition of 1,3-dipole with the first alkyne of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne(DIBOD)activates the second unreacted alkyne,which reacts with 1,3-dipole much faster than the original alkyne of DIBOD.When using DIBOD and bis-dipole compounds as monomer pairs,the self-accelerating property of DSPDAC allows us to develop a stoichiometric imbalance-promoted step-growth polymerization method.It could produce polymers with ultrahigh molecular weight in the presence of excess DIBOD monomers.When using DIBOD to ring-close linear polymers with 1,3-dipole end groups,the self-accelerating property of DSPDAC facilitates us to develop a unique bimolecular ring-closure method.It could efficiently prepare pure cyclic polymers in the presence of excess DIBOD small linkers to linear polymer precursors.

材料科学中的点击化学

近年来,点击(click)化学反应以其高产率、高选择性以及对各种官能团和反应条件优异的耐受性成为材料科学家们手中有力的研究工具。本文综述了点击化学的概念、特点、反应机理及应用。重点介绍了点击化学反应在聚合物、表面修饰、纳米材料方面的研究进展,并分析了点击化学目前存在的不足及今后发展趋势。

基于巯基-炔的“点击”化学研究进展

"点击"化学由于具有原料易得、反应条件温和、高的产率和选择性等特点,已受到人们的广泛关注。巯基-炔反应是近年来被证实的一种新型"点击"反应,具有简单、高效以及通用等特性。本文综述了"点击"化学的定义、特点、发展历程及应用,系统介绍了巯基-炔"点击"反应的机理及其在制备功能分子和表面修饰方面的研究进展,主要包括树枝状聚合物、超支化聚合物、网状聚合物、功能材料等的制备和材料的表面改性。最后对巯基-炔"点击"反应的发展前景进行了展望。

组装合成超分子液晶聚合物动态功能材料

从电荷转移相互作用、离子相互作用及氢键组装三个方面综述了通过分子自组装合成超分子液晶聚合物近年来的最新研究成果 ,总结了这类体系作为动态功能材料在器件化及应用方面所取得的重要进展 。

SH固沙机理的微观探讨

SH是新型高分子固化材料,可用于广大沙漠区固沙,为环境修复材料。采用红外光谱,扫描电镜结合电子能谱等现代分析方法,初步揭示了SH固沙的本质,从微观上探讨了SH固沙强度形成的机理。研究结果表明,SH与沙子结合以后,SH本身的官能团对沙子没有化学键的结合,只表现出微弱的氢键及范得华力的影响;固沙强度主要是物理化学作用而形成的。氢键作用、吸附作用和絮凝作用等赋予了沙子很好的机械强度和优良的耐水性能而达到固沙的目的。

ATRP与点击化学结合制备树状星型聚合物

A new approach to the synthesis of dendrimer-like star polymer,[(PMMA)2PSt]4,was presented via the combination of atom transfer radical polymerization(ATRP) and ckick chemistry.Firstly four-arm bromine-terminated polystyrene(PSt-Br)4 was obtained from ATRP of styrene using pentaerythritol tetra(2-bromoisobutyrate) as an initiator,and the(PSt-Br)4 was efficiently converted to the azido-terminated polymers[(PSt-N3)4] through the bromine substitution reaction with sodium azide.Furthermore,the(PSt-N3)4 reacted with propargyl 2,2-bis[2-(bromomethyl)propionato]propionyrate via a click reaction,1,3-dipolar cycloaddition reaction,and the polymer[(PSt-Br2)4] containing eight end-bromine was obtained.The(PSt-Br2)4 could further serve as a macroinitiator for the ATRP of methyl methacrylate(MMA).Accordingly,the dendrimer-like star polymer,[(PMMA)2PSt]4 was successfully prepared.The structure of [(PMMA)2PSt]4 was characterized via IR,1H NMR,GPC and DSC.

赤泥矿物表面电性与高分子官能团选择絮凝

研究含不同离子官能团絮凝剂对单一硅矿物悬浮液和多组分矿物悬浮液的絮凝沉降效果,分析官能团对悬浮赤铁矿和硅石微粒凝聚吸附性质。采用高分子絮凝剂替代中性淀粉可使悬浮矿物表面吸附更多的有机杂质,提高絮凝澄清率。通过聚合物选择,可获得工业浸出渣的分离条件。悬浮浆液中矿物微粒的表面电性是选择絮凝的基础。

新型拓扑结构聚合物的研究进展

目的展望新型拓扑结构聚合物研究的前沿进展,为进一步研究提供借鉴。方法文献综述。结果遵循"晶体工程"原理,人们合成出许多具有新颖拓扑结构的配位聚合物。将近年国内外和本课题组得到的具有新颖拓扑结构的配位聚合物进行归类,对其前驱体的选择与应用前景进行了探讨。结论新颖拓扑结构的配位聚合物具有潜在的应用前景,对合成结构新颖聚合物有指导作用。

材料化学专业《功能高分子材料》课程教学探索与改革

功能高分子具有多学科交叉性、边缘性和前沿性。本文从我校材料化学专业《功能高分子材料》课程的教学特点出发,对该课程的教学进行了一些相关方面的探索,如教学内容的选择,教学方法和手段的现代化、多样化,学生实践能力的培养,以及考核方式的改革创新等方面。这些对提高学生的学习效果起到了重要的积极作用。

高分子化学中一些重要概念的定义

高分子化学中有几个重要的概念,但在教科书中没有给出明确的定义,这给高分子化学教学带来许多困难。文中确切定义了结构单元、重复单元、聚合度和数均聚合度等基本概念,举例阐述这些概念及其之间的关系。给出缩聚体系平均官能度、基团量比和过量分率的定义,推导出数均聚合度分别对平均官能度、基团量比和过量分率的方程式,给出在特定缩聚体系中套用数均聚合度方程时,基团量比和过量分率的表达式。