The present article examines the aging behavior in the marine environment of some representative flexible plastic packaging films including supermarket plastic bags made of low‐density polyethylene (LDPE), polyethylene terephthalate (PET) films, polyamide–polyethylene (PAPE) films and films made of a material under the commercial name Mater‐Bi®. The effect of aging was studied by Fourier transform infrared spectroscopy, differential scanning calorimetry, and tension including creep‐recovery tests. The polyethylene films were not hydrolytically degraded during aging in seawater, and the polyethylene chains did not undergo any substantial chain scission. The PET films after exposure for 8 months in seawater did not suffer any substantial degradation, and the PET chains were plasticized by the absorbed water. After prolonged exposure to seawater (12 months), the PET films started to degrade. The PAPE film underwent extensive chemical and structural changes during aging in seawater as result of plasticization and hydrolysis of the polyamide (PA) component in combination with an eventual loosening of the tie layer. Mater‐Bi® film underwent a severe deterioration during aging in seawater due to the hydrolysis of the starch and polycaprolactone components. All films exhibited a marked degradation of their tensile properties after exposure to accelerating aging conditions under UV radiation. POLYM. ENG. SCI., 59:E432–E441, 2019. © 2019 Society of Plastics Engineers

This review article aims to cover the most recent advances regarding the synthesis of linear ABC-type triblock terpolymers and star-shaped polymers by RAFT polymerization, as well as their self-assembly properties in aqueous solutions. RAFT polymerization has received extensive attention, as it is a versatile technique, compatible with a great variety of functional monomers and reaction conditions, while providing exceptional and precise control over the final structure, with well-defined side-groups and post-polymerization engineering potential. Linear triblock terpolymers synthesis can lead to very interesting novel ideas, since there are countless combinations of stimuli/non-stimuli and hydrophilic/hydrophobic monomers that someone can use. One of their most interesting features is their ubiquitous ability to self-assemble in different nanostructures depending on their degree of polymerization (DP), block composition, solubilization protocol, internal and external stimuli. On the other hand, star-shaped polymers exhibit a more stable nanostructure, with a distinct crosslinked core and arm blocks that can also incorporate stimuli-responsive blocks for “smart” applications.

We report on the utilization of the amphiphilic poly[quaternized (2-(N,N-dimethylamino) ethyl methacrylate)]-co-(lauryl methacrylate))-b-poly[(oligo ethylene glycol) methyl ether methacrylate] QP(DMAEMA-co-LMA)-b-POEGMA cationic diblock terpolymer aggregates as nanocarriers for insulin delivery applications. QP(DMAEMA-co-LMA)-b-POEGMA random diblock terpolymer is derived from the chemical modification of the precursor amino diblock copolymer via quaternization, producing permanent positive charges on the macromolecular chain. The QP(DMAEMA-co-LMA)-b-POEGMA diblock terpolymer as well as its amino precursor investigated self-assemble in aqueous media, forming aggregates. In vitro cytotoxicity and in vivo biocompatibility studies on QP(DMAEMA-co-LMA)-b-POEGMA and its amino precursor aggregates, showed good cytocompatibility and biocompatibility. QP(DMAEMA-co-LMA)-b-POEGMA aggregates were chosen to be complexed with insulin due to their self-assembly features and the permanent positive charge in each amino group. QP(DMAEMA-co-LMA)-b-POEGMA aggregates were complexed with insulin through electrostatic interactions. Light scattering techniques were used in order to study the ability of the polymer aggregates to complex with insulin, to determine critical physicochemical parameters such as size, mass, and surface charge of the stable complexes and study the effect of salt addition on their properties. The results showed that in both cases, the complexation process was successful and as the insulin concentration increases, nanosized complexes of different physicochemical characteristics (mass, size, surface charge) and spherical morphology are formed. UV-Vis and fluorescence spectroscopy studies showed that no conformational changes of insulin occurred after the complexation.

A series of completely amorphous polymer brushes composed of grafted copolymer electrolytes based on the ioncontaining block of poly(acrylic acid-co-oligo ethylene glycol acrylate) (P(AA-co-OEGA)) doped with LiCF 3 SO 3 (LiTf) or LiN(SO 2 CF 3 ) (LiTFSI) and the glassy polystyrene (PS) block are synthesized and studied with respect to the structural, thermomechanical, and ion conduction properties. The incorporation of some AA units into the ion-conducting phase provides a trade-off between increased mechanical stability and anion/cation complexation. Consequently, the P(AA-co-OEGA) block can be engineered to simultaneously support ion conduction while exhibiting enhanced mechanical stability. Between the two anions ([Tf − ] vs [TFSI − ]), it is the latter that better supports the Li-ion transport. Diblock copolymer electrolytes doped with the larger anion ([TFSI − ]) suppress ion complexation and give rise to superior ion conduction properties (by about 2 orders of magnitude), as compared to that of the smaller anion ([Tf − ]). Overall, the PS-b-P(AA-co-OEGA)/LiTFSI diblock-random copolymer electrolyte with salt concentration, r = 0.08 (r is defined as the molar ratio of Li ions to EO units), best combines the required mechanical stability (storage modulus, G′ ∼ 10 8 Pa) with a relatively high dc-conductivity (σ dc ∼ 10 −6 S•cm −1 ) at an ambient temperature (for application as solid polymer electrolytes (SPEs) in Li-ion batteries). This work suggests routes toward further improving the mechanical stability via the random incorporation of acids into the ion-containing block of nanophase-separated electrolytes.

This work focuses on the synthesis of novel amphiphilic block terpolymers of the type poly[(2‐(N,N‐dimethylamino) ethyl methacrylate)‐co‐(lauryl methacrylate)]‐b‐poly[(oligo ethylene glycol) methyl ether methacrylate] (P(DMAEMA‐co‐LMA)‐b‐POEGMA)) by reversible addition‐fragmentation chain transfer polymerization. The cationic amphiphilic polyelectrolyte analogs P(QDMAEMA‐co‐LMA)‐b‐POEGMA are obtained through quantitative quaternization of the DMAEMA segments. Molecular characterization by size exclusion chromatography, nuclear magnetic resonance, and Fourier Transform Infrared spectroscopies indicates the successful synthesis of these novel series of block terpolymers. The amine forms of the block copolymers respond to pH and temperature changes in aqueous solutions by forming unimolecular or multichain nanoaggregates of varying size, micropolarity, and internal structure, as indicated by light scattering and fluorescence spectroscopy techniques. At neutral and basic pH, the existence of micellar like nanoassemblies is observed in the solutions of P(DMAEMA‐co‐LMA)‐b‐POEGMA terpolymers, while aggregation into micellar‐like clusters take place at temperature values above room temperature due to the presence of the hydrophobic LMA segments. Unexpectedly, the cationic polyelectrolytes P(QDMAEMA‐co‐LMA)‐b‐POEGMA counterparts show temperature responsiveness as a consequence of the amphiphilicity of the polymeric system.