Naphthalimide‐phthalimide derivative based photoinitiating systems for polymerization reactions under blue lights

Naphthalimide‐phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well‐known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 665–674     

Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations

The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399     

Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants

The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093     

Facile fabrication of fast recyclable and multiple self‐healing epoxy materials through diels‐alder adduct cross‐linker

A reversibly cross‐linked epoxy resin with efficient reprocessing and intrinsic self‐healing was prepared from a diamine Diels‐Alder (DA) adduct cross‐linker and a commercial epoxy oligomer. The newly synthesized diamine cross‐linker, comprising a DA adduct of furan and maleimide moieties, can cure epoxy monomer/oligomer with thermal reversibility. The reversible transition between cross‐linked state and linear architecture endows the cured epoxy with rapid recyclability and repeated healability. The reversibly cross‐linked epoxy fundamentally behaves as typical thermosets at ambient conditions yet can be fast reprocessed at elevated temperature like thermoplastics. As a potential reversible adhesive, the epoxy polymer with adhesive strength values about 3 MPa showed full recovery after repeated fracture‐thermal healing processes. The methodology explored in this contribution provides new insights in modification of conventional engineering plastics as functional materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2094–2103     

Thermally Crosslinkable and Chemically Modifiable Aromatic Polyesters Possessing Pendant Propargyloxy Groups

New aromatic (co)polyesters containing pendant propargyloxy groups were synthesized by phase transfer‐catalyzed interfacial polycondensation of 5‐(propargyloxy)isophthaloyl chloride (P‐IPC) and various compositions of P‐IPC and isophthaloyl chloride with bisphenol A. FTIR and NMR spectroscopic data, respectively, revealed successful incorporation of pendant propargyloxy groups into (co)polyesters and formation of (co)polyesters with desired compositions. (Co)polyesters exhibited good solubility in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran and could be cast into transparent, flexible, and tough films from chloroform solution. Inherent viscosities and number average molecular weights of (co)polyesters were in the range 0.77–1.33 dL/g and 43,600–118,000 g/mol, respectively, indicating the achievement of reasonably high‐molecular weights. The 10% weight loss temperatures of (co)polyesters were in the range 390–420 °C, demonstrating their good thermal stability. (Co)polyesters exhibited T_g in the range 146–170 °C and T_g values decreased with increase in mol % incorporation of P‐IPC. The study of non‐isothermal curing by DSC indicated thermal crosslinking of (co)polyesters via propargyloxy groups. The utility of pendant propargyloxy group was demonstrated by post‐modification of the selected copolyester with 1‐(4‐azidobutyl)pyrene, 9‐(azidomethyl)anthracene, and azido‐terminated poly(ethyleneglycol) monomethyl ether via copper(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction. FTIR and ¹H NMR spectra confirmed that click reaction was quantitative. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 588–597     

Synthesis and Self-Assembly of Mixed-Graft Block Copolymers

Mixed-graft block copolymers (mGBCPs) consist of two or more types of polymeric side chains grafted on a linear backbone in a random, alternating, or pseudo-alternating sequence. They can phase-separate with the backbone serving as the interface of the blocks, and the side chains dominate their self-assembly behavior. mGBCPs are an accessible polymer architecture for exploring the idea of encoding polymer properties through the macromolecular architecture, as there are two distinct structural components that can be tuned: the backbone and the side chains. In this Concept article, the current literature on the synthesis of mGBCPs is reviewed, and the advantages and disadvantages of each synthetic method are noted. The self-assembly of mGBCPs is also discussed where possible. Finally, directions for future research on mGBCP synthesis and self-assembly are suggested.     

Arbitrage‐free call option surface construction using regression splines

In this work, we suggest a novel quadratic programming‐based algorithm to generate an arbitrage‐free call option surface. The empirical performance of the proposed method is evaluated using S&P 500 Index call options. Our results indicate that the proposed method provides a more precise fit to observed option prices than other alternative methodologies. Copyright © 2014 John Wiley & Sons, Ltd.     

Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities

Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710     

Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks

Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.     

Norbornene derivatives from a metal‐free,strain‐promoted cycloaddition reaction: New building blocks for ring‐opening metathesis polymerization reactions

The preparation of new ring opening metathesis polymerization (ROMP) monomers using a 1,3‐dipolar cycloaddition between aryl azides and norbornadiene is described. Various norbornenetriazolines, obtained through a solvent‐and catalyst‐free reaction, can subsequently be incorporated into polymer backbones through ROMP reactions. Furthermore, thermal decomposition of the triazoline moiety can allow for further polymer functionalization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2357–2362