Isoconversional Curing and Degradation Kinetics Study of Self-assembled Thermo-responsive Resin System Bearing Oxime and Iminium Groups

This paper demonstrates synthesis of a self-assembled resin system containing p-acetylpyridine oxime, formaldehyde and p-methoxyacetophenone moieties in main chain and thermally cross-linkable periphery oxime groups, and application as antimicrobial coating in biomedical applications. The post-polymerization conversion from oxime into iminium groups was observed by heating scan, with exothermic peaks being at 194 to 247°C. Various degradation models including the Flynn-Wall-Ozawa (F-W-O), Kissinger-Akahira-Sunose (K-A-S), Tang (T) and Friedman (F) methods were employed to check the thermal stability of self-assembly by computing apparent activation energy. It has also exhibited strong biocidal properties against gram-positive and gram-negative bacteria, and fungi until the macrochain retains some positive charge. The obtained results prove that the structure of links, which combine the hydrophobic pyridine rings with the hydrophilic iminium groups, is responsible for the high biocidal activity of the resin system.     

Synthesis and Characterization of Novel Liquid Crystalline Epoxy Resin with Low Melting Point

A liquid crystalline epoxy resin (LCE) having α-methylstilbene as a mesogenic unit and an ethylene-oxy unit as a spacer (DGE(C2-MS-C2)) was synthesized and characterized. DGE (C2-MS-C2) has a lower melting point (MP) compared to the diglycidylether of 4,4′-dihydroxy-α-methylstilbene (DGEDHMS). The curing of DGE (C2-MS-C2) with diaminodiphenylethane (DDEt) in a mesophase generated a liquid crystalline (LC) network, which have a more highly layered structure than DGEDHMS. The LC network showed extensively large fracture energy on a tensile test. Introducing spacers outside the mesogen unit promotes the mesogen unit to form a highly ordered structure, which enhances the versatility of LC epoxy resins.     

Synthesis and Characterization of Novel Liquid Crystalline Epoxides with Lateral Substituent Showing Imposing Shape Memory Properties

In this work, a series of novel shape memory liquid crystalline (LC) epoxides with lateral substituent were prepared and characterized. Dynamic mechanical analysis (DMA) and shape memory testing were used to investigate on the thermo-mechanical properties and shape memory effects of prepared samples. The results showed that the modulus in the rubbery region (E_R ) decreased as the length of lateral alkyl group increases. And more than 95% of the deformation can be fixed as the sample was cooled down below the glass transition temperature (T_g), which was determined by differential scanning calorimetry (DSC) measurement, and can be recovered completely as heating. Effects of the curing agent and substituent on the shape memory behavior were also studied. We found that LC epoxides cured by aromatic diamine have a higher recovery speed. The recovering speeds of the shape memory decreased as the length of lateral alkyl group inscreased. The local ordered structures and the lateral substituent played an important role in shape memory effects.     

Effect of Polymerizable Photoinitiators on the UV‐polymerization behaviors of photosensitive polysiloxane

In this contribution, three polymerizable benzophenone photoinitiators containing maleimide group including 4‐maleimidebenzophenone (MBP), 4‐chlorine‐4′‐maleimide benzophenone (CMBP), and 4‐maleimide‐4′‐[(4‐maleimide)thiophenyl]benzophenone (MMTBP) were designed and synthesized to enhance the polymerization degree of photosensitive polysiloxane containing methacryloxy active groups (MAPSO). The polymerization behaviors of the MAPSO cured by different photoinitiators were investigated using Fourier transform infrared (FTIR). It was noted that the MAPSO initiated by MMTBP showed a high carbon–carbon double bond conversion above 80% because of the existence of thiophenyl group which could generate more radicals from the photolysis reaction at the C? S bond. In addition, the thermal stability of the UV‐cured MAPSO were studied by thermogravimetric analysis (TGA), the result showed that the initial 5% mass loss (T _5%) and residual weight percent at 800 °C in nitrogen of the UV‐cured MAPSO initiated by MMTBP systems was 200 °C and 33.8%. Thus, this work provides a new perspective and efficient strategy to improve the polymerization degree of UV‐curable polysiloxanes with carbon–carbon double bonds. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1696–1705     

Relation between interfacial shear strength and compressive strength of carbon fiber/epoxy resin composite strands

The mechanism with which the fiber-matrix interfacial strength exerts its influence on the compressive strength of fiber reinforced composites has been studied by measuring the axial compressive strength of carbon fiber/epoxy resin unidirectional composite strands having different levels of interfacial shear strength. The composite strands are used for experiments in order to investigate the compressive strength which is not affected by the delamination taking place at a weak interlayer of the laminated composites. The interfacial strength is varied by applying various degrees of liquid-phase surface treatment to the fibers. The efficiency of the compressive strength of the fibers utilized in the strength of the composite strands is estimated by measuring the compressive strength of the single carbon filaments with a micro-compression test. The compressive strength of the composite strands does not increase monotonically with increasing interfacial shear strength but showes lower values at higher interfacial shear strengths. With increasing interfacial shear strength, the suppression of the interfacial failure in the misaligned fiber region increases the compressive strength, while at higher interfacial shear strengths, the enhancement of the crack sensitivity decreases the compressive strength.     

Cross‐linking and properties of rubber magnetic composites cured with different curing systems

Rubber magnetic composites were prepared by incorporation of strontium ferrite into rubber compounds based on acrylonitrile butadiene rubber and ethylene propylene diene monomer rubber. The sulfur, peroxide, and mixed sulfur/peroxide curing systems were introduced as cross‐linking agents for rubber matrices. The aim was to investigate the influence of curing system composition on curing process and cross‐link density of composite materials. Then, static and dynamic mechanical properties and thermal and magnetic characteristics were investigated in relation to the cross‐link density of rubber magnetic composites and structure of the formed cross‐links. The changes of dynamical and physicomechanical properties were in close correlation with the change of cross‐link density, whereas the tensile strength of magnetic composites showed increasing trend with increasing amount of peroxide in mixed curing systems. On the other hand, thermal conductivity and magnetic characteristics were found not to be dependent on the curing system composition.     

Further Studies on the Anionic Copolymerization of Styrene and Glycidyl Methacrylate in Toluene

Sequential anionic copolymerization of styrene and glycidyl methacrylate (GMA) was performed with the protection of argon under normal pressure, where styrene, GMA, toluene, THF, n-butyllithium and a small amount of lithium chloride (LiCl) were used as first monomer, second monomer, solvent, polar reagent, initiator and additive, respectively. Polystyrene-b-poly(glycidyl methacrylate) diblock copolymers (PS-b-PGMA) with well-defined structure and narrow molecular weight distribution were prepared by the copolymerization reaction of poly(styryl)lithium with GMA under certain temperatures. The copolymers were characterized using gel permeation chromatography (GPC), ¹H-NMR, ¹³C-NMR, thin layer chromatography (TLC) and hydrochloric acid-dioxane argentimetric methods. The effects of additives, copolymerization temperature and THF dosage on the copolymerization were studied. No chain transfer reaction of anionic polymerization of styrene in toluene was observed. Slightly broader molecular weight distribution of PS-b-PGMA was observed with the increase the GMA repeat units. Using THF/toluene blend solvent could reduce the polydispersity index (M _w /M _n ) and dissolve the copolymer better than toluene alone. Lower temperature (< -40°C) and LiCl are required to prepare PS-b-PGMA with narrower molecular weight distribution.     

Strong covalent bonding modulated graphene oxide/epoxy interfacial enhancement and advanced corrosion resistance

Abstract

Chemically functionalized graphene oxide [multi-amino functionalized graphene oxide (MAGO)] was achieved by building covalent bonds between graphene oxide (GO) and a small molecule containing benzene structure and multi-amino groups. Fourier transform infrared, X-ray diffraction, X-ray photo electron spectroscopy and TEM-EDX results certified that the molecule was successfully grafted onto GO nanosheets. Subsequently, functionalized GO was incorporated into waterborne epoxy (EP) coating through ball-milling method. This molecular design can significantly improve the dispersion of MAGO in EP matrix, as well as the compatibility and interaction between MAGO and EP. Compared with GO/EP, the water absorption of MAGO/EP decreased from 4.38 to 2.59%, the adhesion strength of MAGO/EP increased from 4.72 to 6.32?MPa after immersion of 40?days in 3.5% NaCl solution. Incorporation of 1?wt% of MAGO into EP matrix prominently improved the long-term corrosion resistance. The impedance modulus of GO/EP coating decreased by four orders after 40 days immersion, while that of MAGO/EP coating only decreased by one order. The impedance modulus was still 1.47?×?10⁸ Ω cm², and two-time constant wasn’t detected for MAGO/EP coating. This research developed a novel green anticorrosion coating with enhanced durability for metal protection.