Internal plasticization of poly(vinyl) chloride using glutamic acid as a branched linker to incorporate four plasticizers per anchor point

Internal plasticization of polyvinyl chloride (PVC) using thermal azide‐alkyne Huisgen dipolar cycloaddition between azidized PVC and electron‐poor acetylenediamides incorporating a branched glutamic acid linker resulted in incorporation of four plasticizing moieties per attachment point on the polymer chain. A systematic study incorporating either alkyl or polyethylene glycol esters provided materials with varying degrees of plasticization, with depressed T_g values ranging from ?1 °C to 62 °C. Three interesting trends were observed. First, T_g values of PVC bearing various internal plasticizers were shown to decrease with increasing chain length of the plasticizing ester. Second, branched internal plasticizers bearing triethylene glycol chains had lower T_g values compared to those with similar length long‐chain alkyl groups. Finally, thermogravimetric analysis of these internally plasticized PVC samples revealed that these branched internal plasticizers bearing alkyl chains are more thermally stable than similarity branched plasticizers bearing triethylene glycol units. These internal tetra‐plasticizers were synthesized and attached to PVC‐azide in three simple synthetic steps. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1821–1835     

Synthesis,self-assembly,and photomechanical actuator performance of a sequence-defined polyviologen crosslinker

ABSTRACT

Although it is well known that viologen radical cations can self-assemble into stacks or complexes on account of radical-radical pairing interactions, it has only recently been demonstrated that reduction of main-chain polyviologens integrated into hydrogel networks can trigger actuation. In these earlier examples, hydrogels comprising oligoethylene glycol-based polyviologens and poly(ethylene glycol) were functionalized with terminal azide groups to prepare ‘click’-based gels. Here, we report a new structural design for the functional polyviologen that consists of main-chain viologen subunits separated by hexamethylene groups instead of glycols and is capped at each end with styrene groups. Activation of this viologen-based macrocrosslinker was achieved using chemical- and photoreduction methods and its ability to undergo intramolecular chain-folding was monitored by absorption spectroscopy. Acrylate-based organogels and hydrogels were also prepared and a comparison was carried out to assess the actuator performance in each gel in terms of the rate of contraction and changes in stiffness.     

Covalent Grafting of BPin functions on Carbon Nanotubes and Chan–Lam–Evans Post-Functionalization

The chemical functionalization of carbon nanotubes is often a prerequisite prior to their use in various applications. The covalent grafting of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BPin) functional groups directly on the surface of multi- and single-walled carbon nanotubes, activated by nucleophilic addition of nBuLi, was carried out. Thermogravimetric analysis (TGA) coupled with mass spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) confirmed the efficiency of this methodology and proved the integrity and covalent grafting of the BPin functional groups. These groups were further reacted with various nucleophiles in the presence of a copper(II) source in the conditions of the aerobic Chan–Lam–Evans coupling. The resulting materials were characterized by TGA, XPS and ToF-SIMS. This route is efficient, reliable and among the scarce reactions that enable the direct grafting of heteroatoms at carbonaceous material surfaces.     

Fluorescent core-shell polymer particles containing luminophore dyes: synthesis and optical response to acetone

Monodisperse dye-containing crosslinked particles are promising for application in novel optical chemical sensors due to their intrinsic sensitivity. However, preparation of these particles in aqueous media still remains a challenge, since luminophores inhibit radical processes or else cannot embed into polymer chains because of difference in monomer reactivity ratios. In this work, novel dye-containing monodisperse crosslinked particles were prepared and characterized. In order to obtain dye-containing monodisperse crosslinked particles, we studied seed copolymerization of styrene in the presence of divinylbenzene. The influence of nature and concentration of the used comonomers and co-solvents on shape, size distributions and surface characteristics of the particles formed was investigated. Shapes and diameters of the particles were analyzed by DLS, TEM and SEM. The data of SEM and optical spectroscopy studies demonstrated that the synthesized particles were able to self-assemble into thin-film three-dimensional ordered structures. Finally, the structures under study are promising for development of sensor devices with optical response to acetone.     

Dispirocycles: Platforms for the Construction of High-Performance Host Materials for Phosphorescent Organic Light-Emitting Diodes

Spirocyclic compounds such as 9,9′-spirobifluorene (SBF) are becoming more and more attractive for use as host materials in organic optoelectronic devices. Herein, two dispirocycles, namely, dispiro[fluorene-9,9′-anthracene-10′,9′′-fluorene] and 10,10′′-diphenyl-10H,10′′H-dispiro[acridine-9,9′-anthracene-10′,9′′-acridine], were used for the construction of host materials 1 – 4 . The attached triphenylamino group determines the thermal, photophysical, electrochemical, and charge-transport properties, and therefore they have different electroluminescent performances. The device based on dispiro[fluorene-9,9′-anthracene-10′,9′′-fluorene] ( 2 ) and 10,10′′-diphenyl-10H,10′′H-dispiro[acridine-9,9′-anthracene-10′,9′′-acridine] ( 3 ) molecular platforms exhibited external quantum efficiencies of greater than 21 % with a very high power efficiency (≈100 lm W⁻¹). These results demonstrate the potential of extending the application of dispirocyclic molecular platforms with inherent rigidity for developing highly efficient host materials for organic light-emitting diodes.     

Catalytic activity of nanocrystalline ZnM2O4 (M = Fe,Co) prepared via simple and facile synthesis of thermal decomposition of mixed metal complexes of Schiff bases generated from α-ketobutyric acid and diaminoguanidine

Metal complexes ([ML₂], where M = Fe, Co, or Zn; HL = 2-[(6-ethyl-5-oxo-4,5-dihydro-2H-[1,2,4]triazin-3-ylidene)-hydrazono]-butyric acid, C₉H₁₃N₅O₃) of a Schiff base derived from α-ketobutyric acid (α-KBA) and diaminoguanidine (Damgu) were synthesized and characterized using elemental, spectral, and thermal studies. The metal complexes exhibited similar decomposition behavior, with a highly exothermic final decomposition step resulting in the formation of metal oxides. Isomorphism among the complexes was revealed using a powder X-ray diffraction (PXRD) technique. Solid solution precursors ([Zn_1/3M_2/3(L)₂], where M = Fe, Co) were synthesized and characterized using various physico-chemical techniques. A thermal decomposition technique was used to prepare spinel-type zinc cobaltite (ZnCo₂O₄) and zinc ferrite (ZnFe₂O₄) nanocrystalline particles with the synthesized single source precursors. Structural studies using PXRD ascertained the predominant crystal phase to be spinel. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed a mean nanoparticle size of 18 ± 2 nm. Magnetic measurements revealed a weak magnetic behavior in the synthesized spinels. In the aqueous phase, the spinels exhibited catalytic activity, reducing 4-nitrophenol (4-NP) in the presence of NaBH₄ at room temperature. Additionally, the study demonstrated that the catalyst can be recovered and reused for five cycles with a more than 85% conversion efficiency.     

A conjugated alkyne functional bicyclic polybenzoxazine with superior heat resistance

A difunctional benzoxazine (coPh‐apa) with a conjugated alkyne group is synthesized by the oxidative coupling reaction from a monocycle‐benzoxazine (Ph‐apa) containing an alkyne group. A model compound, 1,4‐diphenylbutadiyne (coPa), is used to study the curing reaction process of coPh‐apa by DSC, Fourier transform infrared spectroscopy, and ¹³C NMR, and the results suggest that the conjugated alkyne groups are involved in the crosslinking reaction via the trimerization reaction of the conjugated alkynyl groups and the Diels–Alder reaction. Furthermore, thermal properties of the polybenzoxazine are studied by dynamic thermomechanical analysis and thermogravimetric analysis. A glass‐transition temperature (T_gs) of as high as 412 °C and a char yield of 75.6% at 800 °C under nitrogen are obtained with the aid of the conjugated alkyne groups. Its excellent heat resistance dominates most thermosetting resins and will serve for heat shields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1587–1592     

Synthesis of Organosilyl-Functionalized Cage-Type Germanoxanes Containing Fluoride Ions

Eight corners of a double-four ring cage-type germanoxane, containing a fluoride ion, were successfully silylated by the combination of chlorosilanes and silazanes. Three different silyl groups, trimethylsilyl, dimethylsilyl, and dimethylvinylsilyl, were attached on the corners of germanoxane cage. The solubility and reactivity of the cage modified with dimethylvinylsilyl groups were significantly increased, allowing for further reaction. Hydrosilylation reaction between dimethylvinylsilylated cage geramanoxanes and dimethylsilylated cage siloxanes afforded porous solids. Functionalization of the corners of germanoxanes with silyl groups should provide valuable building blocks in various functional materials.     

Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

RAFM钢TIG焊和电子束焊疲劳性能实验和分析模拟

利用ANSYS 对低活化铁素体马氏体(RAFM)钢进行非熔化极气体保护焊(TIG 焊)与电子束焊的抗疲劳模拟分析，再利用SDS200 电液伺服疲劳试验机对TIG 焊和电子束焊的两种RAFM 钢试件进行实验。通过施加相同梯度负荷对TIG 焊和电子束焊试件进行焊缝的疲劳性能实验。与实验结果对比分析，结果显示电子束焊优于 TIG 焊，但在一定负载下可以用TIG 焊代替电子束焊。