Trends in industrial polymer research

In the past decades a shift in paradigm took place in industrial polymer research for structural materials. Only a few new polymers based on new monomeric building blocks were developed. The main focus is now on tailoring improved “old polymers” with well-defined structure and properties based on a set of low cost “old” monomers using controlled polymerization mechanisms.     

Electrogenerated Chemiluminescence of Pure Polymer Films and Polymer Blends

We recently reported the discovery of soliton‐like electrogenerated chemiluminescence (ECL) waves from pure conjugated polymer films and gold‐nanoparticles‐doped polymer films. In addition to a more detailed study of these polymer systems by changing the film thickness and the distribution of local leaks, we also apply the ECL wave phenomenon to polymer blends of conjugated and nonconjugated polymers. Poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) is used as the active material that is oxidized and produces ECL with the presence of a co‐reactant, tri‐n‐propylamine (TPA). Several factors such as film thickness, artificial leaks, and solubility of doped polymers are examined for their effects on the ECL behavior. When polystyrene (PS), less soluble in the electrolyte, is blended with F8BT, dotted ECL signals are observed and transported as waves. When poly(methyl methacrylate) (PMMA), more soluble in the electrolyte, is blended with F8BT, PMMA serves as local scratches and ECL waves are triggered simultaneously from the whole film.

     

Pattern Formation in Thin Polymer Films Containing Conducting Polyaniline

Summary: In the present work knowledge the authors tried to direct the phase separation process in a thin polymer composite film to manufacture a polymer pattern via self organisation of the blend components. The Au substrate was modified by applying with a PDMS stamp a pattern of alternating stripes of a self-assembled monolayer. This in turn influenced the microstructure of the blend, allowing for the production of elongated domains repeating the pattern of the substrate. The blends studied in this work contained conducting polyaniline doped with camphorsulfonic acid or diphenyl phosphate and polystyrene. The role of the dopant was to induce electrical conductivity in polyaniline as well as to improve its solubility in common organic solvents. The microstructure of thin films was analysed using atomic force microscopy (AFM), dynamic secondary ion mass spectroscopy (dSIMS) and optical microscopy.     

超临界CO2在高分子合成与制备中的应用

介绍超临界二氧化碳流体作为介质在高分子合成与制备中的研究进展。文中表明，可在超临界二氧化碳中实施氟代单体的自由基溶液聚合、甲基丙烯酸甲酯的分散聚合、丙烯酸的沉淀聚合、丙烯酰胺的反相乳液聚合以及异丁基乙烯基醚的阳离子聚合等多种聚合反应，可用超临界二氧化碳溶胀聚合法制备梯度共混物。此外，超临界二氧化碳还可用于聚合物分级和聚合物微孔、微纤与微球材料的制备等，显示出超临界二氧化碳是一种对环境无污染且价廉的     

Physical Properties of the Biodegradable Polymer Compositions Containing Natural Polyesters and their Synthetic Analogues

The thermal, mechanical and thermo-mechanical properties of polymer compositions, containing synthetic biodegradable polymers i.e. polylacide (PLA) and aliphatic-aromatic copolyester (BTA), natural biopolyester n-PHB and its synthetic atactic analog (a-PHB) were investigated. Thermal properties of the polymer compositions were studied by means of DSC . The compositions of various polymer weight ratio were tested. Compositions containing BTA and n-PHB create polyphase systems, what was confirmed by DSC. In this case the two Tg and two Tm values were observed. Polymer compositions containing PLA and BTA showed different behaviours. At the BTA content up to 30 weight % only one Tg and one Tm were indicated. At the increase of the BTA content to 50% weight and above, the two Tg, and two Tm were observed. Mixtures of BTA with n-PHB, PLA and with a-PHB show considerably greater values of the strain (ε) in comparison with initial polymers (n-PHB, PLA). It was found that in contrary to mixtures containing PLA, at the BTA content in the mixture with n-PHB above 50% of weights increases not only the strain, but also the stress at break (σ). Strong increase of the ε value in PLA/a-PHB mixtures with the content of a-PHB above 30% of weights were observed.     

Performance Enhancement of Polymer Solar Cells by Using Two Polymer Donors with Complementary Absorption Spectra

Performance enhancement of polymer solar cells (PSCs) is achieved by expanding the absorption of the active layer of devices. To better match the spectrum of solar radiation, two polymers with different band gaps are used as the donor material to fabricate ternary polymer cells. Ternary blend PSCs exhibit an enhanced short‐circuit current density and open‐circuit voltage in comparison with the corresponding HD‐PDFC‐DTBT (HD)‐ and DT‐PDPPTPT (DPP)‐based binary polymer solar cells, respectively. Ternary PSCs show a power conversion efficiency (PCE) of 6.71%, surpassing the corresponding binary PSCs. This work demonstrates that the fabrication of ternary PSCs by using two polymers with complementary absorption is an effective way to improve the device performance.

     

Grafting of Polymer Brushes from Xanthate-Functionalized Silica Particles

Monodisperse silica particles (SiPs) were surface-modified with a newly designed silane coupling agent comprising a triethoxysilane and an alkyl halide, namely, 6-(triethoxysilyl)hexyl 2-bromopropionate, which was further treated with potassium O-ethyl dithiocarbonate (PEX) to immobilize xanthate molecules on the particle surfaces. Surface-initiated macromolecular design via interchange of xanthates (MADIX) polymerization of vinyl acetate (VAc) was conducted with the xanthate-functionalized SiPs. The polymerization was well controlled and produced SiPs coated with poly(vinyl acetate) (PVAc) with a well-defined target molar mass and a graft density of about 0.2 chains nm⁻². Dynamic light scattering and TEM measurements revealed that the hybrid particles were highly dispersible in good solvents without any aggregation. The PVAc brushes were hydrolyzed with hydrochloric acid to produce poly(vinyl alcohol) brushes on the SiP surfaces. In addition, the number of xanthate molecules introduced on the SiP surfaces could be successfully controlled by adjusting the concentration of PEX. Thus, the SiPs have two functionalities: xanthates able to act as a MADIX chain-transfer agent and alkyl bromide initiation sites for atom transfer radical polymerization (ATRP). By using these unique bifunctional particles, mixed polymer brushes were constructed on the SiPs by MADIX of VAc followed by ATRP of styrene or methyl methacrylate.     

Electrochemically synthesized polymer of the plant substance embelin (2,5-dihydroxy-3-undecyl-1,4-benzoquinone)

Among the possible new materials for microelectronics, quinones have a number of significant advantages. Similarly, polymers with quinone functionality possess biodegradability. Because natural polymers are promising candidates for functional materials for the future, we have initiated studies on the polymers of natural products. In the present study, a natural quinone (a plant substance) extracted from Embelier libes distributed in the Kerala state of India was electrochemically polymerized and its properties were investigated. The redox activity, electrical conductivity, and biodegradability are discussed.     

活性聚合在星形聚合物合成中的应用

星形聚合物在近年来发展迅速,其结构、形态、合成方法与功能性是高分子科学的研究热点。本文主要从活性离子聚合手段与活性自由基聚合手段两方面对星形聚合物的合成方法进行分类,依托星形聚合物的单体选择、星形臂的特性以及整体功能性进行系统阐述,介绍近年来星形聚合物合成方法、形貌控制以及功能性质的最新研究进展。本文结合现阶段最新的研究成果,对星形聚合物在功能与应用之间的广泛前景与联系进行了展望与预测。     

可生物降解聚合物的现状及生物降解性研究

综述了可生物降解聚合物的现状及发展、影响生物降解性的因素和生物降解性的评价方法。     

高分子学科动态与国家自然科学基金2017指南

重点综述近年来高分子领域若干方向研究前沿进展与动态。对国家自然科学基金化学部高分子学科2016资助情况进行了介绍,给出了2017年项目申请指南。     

高分子化学中的活性/可控自由基聚合教学

活性/可控自由基聚合自20世纪90代被报道到现在经历了30余年的发展,其反应机理和相关理论比较成熟,对高分子化学和功能高分子材料产生重大的影响。而目前本科生高分子化学的教学中对该部分的内容没有足够的重视,很多专业受学时的限制并未对该部分的内容进行讲授,制约了学生的知识面和科学研究思维。针对如何将普通自由基聚合转变为可控/活性自由基聚合这一问题,通过问题的提出、寻找解决策略及其发展趋势等,循序渐进教学,启发学生进行知识创新,提高学生对知识的运用能力和解决问题的能力。     

Biodegradable Phosphorylcholine Polymer Hydrogels Cross‐Linked with Vinyl‐Functionalized Polyphosphate

A vinyl‐functionalized polyphosphate (PIOP) was synthesized by ring‐opening polymerization of 2‐isopropyl‐2‐oxo‐1,3,2‐dioxaphospholane and 2‐(2‐oxo‐1,3,2‐dioxaphosphoroyloxyethyl methacrylate) with triisobutylaluminum as an initiator. The number‐averaged molecular weight of the PIOP was 1.2 × 10⁴. The average number of vinyl groups in the PIOP is 2.20. Transparent hydrogels were prepared by the radical polymerization of 2‐methacryroyloxyethyl phosphorylcholine with PIOP as a cross‐linking reagent. These hydrogels may have many applications in the biomedical field because of their biodegradability and biocompatibility.

Synthetic route of PIOP.     

Degradable polymer blends. I. Screening of miscible polymers

Blends of biodegradable polymers having properties distinct from the individual polymer components, and that are suitable for use as carriers of pharmaceutically active agents, were prepared from two or more polyanhydrides, polyesters, and mixtures of polyanhydrides and low molecular weight polyesters. The blends have different properties than the original polymers, providing a mean for altering the characteristics of the polymeric matrix without altering the chemical structure of the component polymers. Aliphatic, aromatic, and copolymers of polyanhydrides were miscible in each other and formed less crystalline compositions with a single melting point which was lower than the melting point of the starting polymers. The polyesters: poly(lactide-glycolide), poly(caprolactone), and poly(hydroxybutyric acid) presented some miscibility in each other. However, the polyanhydrides were immiscible with the polyesters resulting in a complete phase separation both in solution or in melt mixing. Only low molecular weight polyesters (in the range of 2000) of lactide and glycolide, mandelic acid, propylenefumarate, and caprolactone presented some miscibility with polyanhydrides. Similarly, poly(orthoester) and hydroxybutyric acid polymers formed a uniform mixture with the anhydride polymers which had the two melting points of the original polymers. Drug release from polymer blends composed of poly(hydroxybutyric acid) or low molecular weight poly(lactic acid) with poly(sebacic anhydride) (PSA) showed a constant release of drug for periods from 2 weeks to several months as a function of the PSA content in the blend. Increasing the content of PSA, a fast degrading polymer, increases the release rate from the blend. © 1993 John Wiley & Sons, Inc.     

Direct Creation of Highly Conductive Laser‐Induced Graphene Nanocomposites from Polymer Blends

The current state‐of‐the‐art mixing strategies of nanoparticles with insulating polymeric components have only partially utilized the unique electrical conductivity of graphene in nanocomposite systems. Herein, this paper reports a nonmixing method of direct creation of polymer/graphene nanocomposites from polymer blends via laser irradiation. Polycarbonate‐laser‐induced graphene (PC‐LIG) nanocomposite is produced from a PC/polyetherimide (PC/PEI) blend after exposure to commercially available laser scribing with a power of ≈6 W and a speed of ≈2 cm s⁻¹. Extremely high electrical conductivities are obtained for the PC‐LIG nanocomposites, ranging from 26 to 400 S m⁻¹, depending on the vol% of the starting PEI phase in the blend. To the authors' knowledge, these conductivity values are at least one order of magnitude higher than the values that are previously reported for conductive polymer/graphene nanocomposites prepared via mixing strategies. The comprehensive microscopy and spectroscopy characterizations reveal a complete graphitization of the PEI phase with columnar microstructure embedded in the PC phase.     

Direct Cyclodextrin‐Mediated Ring Opening Polymerization of ϵ‐Caprolactone in the Presence of Yttrium Trisphenolate Catalyst

Unmodified β‐cyclodextrin has been directly used to initiate ring‐opening polymerization of ϵ‐caprolactone in the presence of yttrium trisphenolate. Well‐defined cyclodextrin (CD)‐centered star‐shaped poly(ϵ‐caprolactone)s have been successfully synthesized containing definite average numbers of arms (N_arm = 4–6) and narrow polydispersity indexes (below 1.10). The number‐average molecular weight ( ) and average molecular weight per arm ( ) are controlled by the feeding molar ratio of monomer to initiator. The prepared star‐PCL with of 2.7 × 10³ is in fully amorphous and that with of 13.3 × 10³ is crystallized. In addition, the obtained poly(e‐caprolactone) (PCL) stars with various molecular weights have different solubilities in methanol and tetrahydrofuran, which can be applied for further modifications.     

Polymer Photovoltaic Cells Based on Polymethacrylate Bearing Semiconducting Side Chains

Polymethacrylate with semiconducting side chains ( P1 ), synthesized by free radical polymerization, was used as a donor material for polymer solar cells. P1 is of high molecular weight (M _n = 82 kg mol⁻¹), good thermal stability, narrow band gap (1.87 eV), and low‐lying HOMO energy level (−5.24 eV). P1 possesses not only the good film‐forming ability of polymers but also the high purity of small organic molecules. Power conversion efficiencies (PCEs) of 0.63% and 1.22% have been obtained for solar cells with M1 :PC₇₁BM and P1 :PC₇₁BM as the active layers, respectively. With PC₆₁BM as the acceptor, PCEs of M1 and P1 based devices decrease to 0.61% and 0.76%, respectively. To the best of our knowledge, this is the first report that free radical polymerization can be used to prepare polymer donors for photovoltaic applications.     

Relation between Polymer Conformational Structure and Dynamics in Linear and Ring Polyethylene Blends

Atomistic molecular dynamics simulations of ring‐linear polyethylene blends are employed to understand the relationship between chain conformational structure and the melt dynamics of these blends. As observed in previous studies, this study confirms that ring polymers in pure melts do not exhibit screened excluded volume interactions, contrary to linear polymers. Moreover, the average molecular shapes of the rings are quite distinct from both swollen and ideal ring polymers under theta conditions, and instead rather resemble branched polymers with screened binary excluded volume interactions, e.g., percolation clusters. Upon adding linear chains to a melt of pure rings, we find significant swelling of the rings and a corresponding shape change that is qualitatively similar to dissolving rings in a small molecule good solvent. This swelling, arising from altered self‐excluded volume interactions, translates into a large decrease in ring diffusivity, an effect that becomes more amplified when the polymer melt is entangled.