Emulsion Copolymerization of Vinyl Acetate and Vinyl Silanes: Kinetics and Development of Microstructure

The batch emulsion copolymerization of vinyl acetate with different vinyl silane functional monomers (vinyl trimethoxysilane [VTMS], vinyl triethoxysilane [VTES], and vinyl silanetriol [VSTO]) is studied. The nature of the silane strongly affects the development of the microstructure and crosslinking ability of the latexes. A combination of techniques (Soxhlet extraction, centrifugation, assymetric‐flow field flow fractionation AF4/MALS/RI) shows that the factor controlling the molar mass and crosslinking density is the degree of hydrolysis of the alkoxysilane, producing higher molar masses and degrees of crosslinking when the degree of hydrolysis is high. Thus, the copolymer containing VSTO produced a very crosslinked latex, the one with VTMS produced a latex with a low degree of crosslinking in the wet state that can yield high degrees of crosslinking upon drying, and the latex with VTES do not produce significant amounts of crosslinking neither before nor after drying.     

Fe(II) Spin Crossover/Polymer Hybrid Materials: Investigation of the SCO Behavior via Temperature-Dependent Raman Spectroscopy,Physicochemical Characterization and Migration Release Study

Polymeric composites constitute an appealing class of materials with applications in various fields. Spin crossover (SCO) coordination complexes are switchable materials with potential use in data storage and sensors. Their incorporation into polymers can be considered an effective method for their wider practical application. In this study, Fe(II) SCO/polylactic acid hybrid polymeric composites have been prepared by film casting. The mononuclear coordination complex [Fe{N(CN)₂}₂(abpt)₂] was incorporated into polylactic acid. The morphological, structural and thermoanalytical characterization of the composite films were performed via scanning electron microscopy (SEM), attenuated total reflectance (ATR/FTIR), Raman spectroscopy and differential scanning calorimetry (DSC). In addition, the migration release study (MRS) of the SCO compound from the polymeric matrix into the food simulant 50% v/v water/ethanol solution was also examined via UV/Vis absorption. Of particular interest was the investigation of the SCO behavior of the coordination complex after its incorporation into the polymer matrix; it was accomplished by temperature-dependent micro-Raman spectroscopy. The described attempt could be considered a preparatory step toward the development of SCO-based temperature sensors integrated into food packaging materials.     

Organic‐acid mediated bulk polymerization of ε‐caprolactam and its copolymerization with ε‐caprolactone

Polyamides (PA) constitute one of the most important classes of polymeric materials and have gained strong position in different areas, such as textiles, fibers, and construction materials. Whereas most PA are synthesized by step‐growth polycondensation, PA 6 is synthesized by ring opening polymerization (ROP) of ε‐caprolactam (ε‐CLa). The most popular ROP methods involve the use of alkaline metal catalyst difficult to handle at large scale. In this article, we propose the use of organic acids for the ROP of ε‐CLa in bulk at 180 °C (below the polymer's melting point). Among evaluated organic acids, sulfonic acids were found to be the most effective for the polymerization of ε‐CLa , being the Brønsted acid ionic liquid: 1‐(4‐sulfobutyl)?3‐methylimidazolium hydrogen sulfate the most suitable due to its higher thermal stability. End‐group analysis by ¹H nuclear magnetic resonance and model reactions provided mechanistic insights and suggested that the catalytic activity of sulfonic acids was a function of not only the acid strength, but of the nucleophilic character of conjugate base as well. Finally, the ability of sulfonic acid to promote the copolymerization of ε‐CLa and ε‐caprolactone is demonstrated. As a result, poly(ε‐caprolactam‐co‐ε‐caprolactone) copolymers with considerably randomness are obtained. This benign route allows the synthesis of poly(ester amide)s with different thermal and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2394–2402     

Application of SSA thermal fractionation and X‐ray diffraction to elucidate comonomer inclusion or exclusion from the crystalline phases in poly(butylene succinate‐ran‐butylene azelate) random copolymers

Poly(butylene succinate‐ran‐butylene azelate) random copolyesters were thermally fractionated by successive self‐nucleation and annealing (SSA). The samples before and after SSA were analyzed by differential scanning calorimetry (DSC) and X‐ray diffraction (WAXS and SAXS). WAXS results indicate that a small degree of comonomer inclusion is present in the crystalline phases that are formed in the copolymers depending on composition: a PBS‐like unit cell or/and a PBAz‐like unit cell, thus confirming the isodimorphic behavior of the samples. SSA on the other hand demonstrated that the degree of comonomer exclusion during crystallization is far larger than comonomer inclusion, as judged by the increase in fractionation degree with compositions leading to the pseudo‐eutectic point. Furthermore, WAXS, SAXS, and SSA results show that the isodimorphic behavior is not highly dependent on kinetic factors, as the degree of comonomer inclusion or exclusion in the samples was not significantly altered by SSA thermal fractionation, a thermal treatment that promotes annealing and molecular segregation of defects to the amorphous regions of the material. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2346–2358     

Adhesives for Low-Energy Surfaces

Summary: The wetting and adhesive properties of model pressure-sensitive adhesives synthesised by miniemulsion polymerization were investigated. Wetting experiments of aqueous solutions of three different emulsifiers showed that Silwet L-77 (nonionic ethoxylated trisiloxane) was the best wetting agent. Probing adhesive properties, two different structure modifications of the polymer were investigated: a change in the polymer microstructure by the addition of a chain transfer agent and the introduction of a hydrophobic monomer into the polymer backbone. An addition of chain transfer agent was sufficient to obtain a polymer with a significantly different microstructure and, consequently, enhanced adhesion energy but reduced shear resistance. On the other hand, stearyl acrylate (SA) was employed as the hydrophobic monomer and the synthesis was carried out in miniemulsion polymerization which enables the incorporation of hydrophobic compounds without any diffusion limitations. There were almost no differences in the polymer microstructure, whereas, some differences were observed in adhesion properties.     

Molecular Dynamics of PGA Bioabsorbable Polymer During Isothermal Cold Crystallization

An investigation was carried out on the molecular dynamics of poly(glycolide) (PGA) in its completely amorphous state and during isothermal cold crystallization. Experimental results were generated over a wide range of frequency and temperature by broad-band dielectric spectroscopy (DRS). The variation of the average relaxation time (defined as τ= ½πf_max where f_max is the frequency at maximum loss for the main α relaxation) has been studied during cold crystallization and the temperature dependence of this average relaxation time for completely amorphous and crystallized samples has been analyzed. This behaviour has been modelled by Havriliak-Negami and Vogel-Fulcher equations. The sensitiveness of the segmental dynamics to the degree of crystallinity has been analyzed, taking into account the relaxing segments and the amorphous layers between lamellae. Supporting evidence about the thermal behaviour of the polymers has been obtained with DSC. Complementarily, the evolution of the morphologies obtained during crystallization processes has been followed by optical microscopy.     

The reverse self-dual serial cost-sharing rule

In this study we define a cost-sharing rule for cost-sharing problems. This rule is related to the serial cost-sharing rule defined by Moulin and Shenker (Econometrica 60:1009–1037, 1992). We give some formulas and axiomatic characterizations for the new rule. The axiomatic characterizations are related to some previous ones provided by Moulin and Shenker (J. Econ. Theory 64:178–201, 1994) and Albizuri (Theory Decis. 69:555–567, 2010).     

A detailed workforce planning model including non-linear dependence of capacity on the size of the staff and cash management

This paper introduces an original planning model which integrates production, human resources and cash management decisions, taking into account the consequences that decisions in one area may have on other areas and allowing all these areas to be coordinated. The most relevant characteristics of the planning problem are: (1) production capacity is a non-linear function of the size of the staff; (2) firing costs may depend on the worker who is fired; (3) working time is managed under a working time account (WTA) scheme, so positive balances must be paid to workers who leave the company; (4) there is a learning period for hired workers; and (5) cash management is included. A mixed integer linear program is designed to solve the problem. Despite the size and complexity of the model, it can be solved in a reasonable time. A numerical example, the main results of a computational experiment and a sensibility analysis illustrate the performance and benefits of the model.