Improving the marine biodegradability of poly(alkylene succinate)-based copolymers

Paliperidone palmitate depot microspheres based on biocompatible poly(alkylene succinate) polyesters as long-acting injectable formulations

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated into poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the ...

Poly(ethylene succinate) and poly(butylene succinate) are synthetic biodegradable polymers, and much attention is paid to study the properties of pure polymers and the polymers modified by different comonomers and filling materials. The literature data on the physical properties of these polymers vary widely depending on their method of preparation and subsequent modifications. Most of the studies deal with low- and moderate-molecular-weight polymers or commercial grade polymers, modified by different comonomers and chain-extension agents. The data on pure high-molecular-weight polymers are scarce. In this work, we have prepared high-molecular-weight (MW range of (1.4–1.8) × 105) poly(ethylene succinate) and poly(butylene succinate) by direct polycondensation at 200°C in a nitrogen flow without chain-extension agents. We have further studied the properties of pure polymers and examined the effect of different fillers (carbon nanotubes, SiO2, Aerosil®) on the mechanical and physical properties of these polymers. Because of high-molecular-weight, the polymers possess increased tensile and storage moduli and thermostability. Even very low filler contents (up to 1 wt %) have a pronounced influence on the polymer properties: the polymer tensile and the storage modulus increases, the elongation at break decreases, and the thermal stability of the polymers decreases slightly. The effects of fillers are less pronounced compared with those for low- and moderate-molecular-weight polymers. When mixed together, poly(ethylene succinate) and poly(butylene succinate) crystallize independently from each other as evident from the mechanical and thermal analysis data.

Synthesis and characterization of a novel multiblock copolyester containing poly(ethylene succinate) and poly(butylene succinate)

To study the effect of hyperbranched polyester with different kinds of terminal groups on the thermomechanical and dielectric properties of silica–epoxy resin composite, a molecular dynamics simulation method was utilized. Pure epoxy resin and four groups of silica–epoxy resin composites were established, where the silica surface was hydrogenated, grafted with silane coupling agents, and grafted with hyperbranched polyester with terminal carboxyl and terminal hydroxyl, respectively. Then the thermal conductivity, glass transition temperature, elastic modulus, dielectric constant, free volume fraction, mean square displacement, hydrogen bonds, and binding energy of the five models were calculated. The results showed that the hyperbranched polyester significantly improved the thermomechanical and dielectric properties of the silica–epoxy composites compared with other surface treatments, and the terminal groups had an obvious effect on the enhancement effect. Among them, epoxy composite modified by the hyperbranched polyester with terminal carboxy exhibited the best thermomechanical properties and lowest dielectric constant. Our analysis of the microstructure found that the two systems grafted with hyperbranched polyester had a smaller free volume fraction (FFV) and mean square displacement (MSD), and the larger number of hydrogen bonds and greater binding energy, indicating that weaker strength of molecular segments motion and stronger interfacial bonding between silica and epoxy resin matrix were the reasons for the enhancement of the thermomechanical and dielectric properties.

Temperature dependence of the molecular motion in the crystalline region of biodegradable poly(butylene adipate), poly(ethylene succinate), and poly(butylene succinate)

The synergetic effect of adding multi-walled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) on the thermomechanical properties and electric resistance of epoxy polymers were experimentally analyzed in this study. The total content of two employed carbon fillers were kept constant at 0.4 wt %, and seven filler ratios between two fillers (MWCNTs:GNPs), i.e., 10:0, 1:9, 3:7, 5:5, 7:3, 9:1, and 0:10, were considered in the experimental program to investigate the influences of employed nano-filler ratios on the viscoelastic and electrical properties of the studied nanocomposites. The thermomechanical properties and the sheet resistance of the nanocomposites were analyzed using a dynamic mechanical analyzer and four-point probe, respectively. Moreover, the thermogravimetric analyzer was utilized to measure the pyrolysis temperature of the nanocomposites. Experimental results show that the synergistic effect of adding two nano-fillers were clear for the improvement of the storage moduli, glass transition temperatures, and electric conductivity. Oppositely, the employment of two fillers has a slight effect on the pyrolysis temperatures of the studied nanocomposites. The composites with the MWCNT:GNP ratio of 1:9 display the most apparent enhancement of the thermomechanical properties. The improvement results from the uniform distribution and the high aspect ratio of GNPs. The addition of a small amount of MWCNTs provides more linkage in the matrix. Moreover, the specimens with the MWCNT:GNP ratio of 1:9 shows remarkable electrical properties, which result from the large contact surface areas of GNPs with each other. The employment of few MWCNTs plays an important bridging role between the layered GNPs.

Miscible blends of three crystalline polymers, namely poly(butylene succinate) (PBS), poly(ethylene succinate) (PES), and poly(oxyethylene) (POE), exhibited interpenetrating spherulites, where a spherulite of one component grows inside the spherulites of other components. PBS and PES were immiscible above the melting points, Tm, of these substances, while ternary blends with POE showed miscibility, which depended on the molecular weight of POE. PBS and PES exhibited the same spherulitic growth process as in a miscible binary blend when they were crystallized from a homogeneous ternary melt. Spherulites of PBS, which is the highest‐Tm component, filled the whole volume first when a miscible ternary blend was quenched below Tm of POE, the lowest‐Tm component. Then, the blends showed either two types of crystallization processes. One was successive nucleation and growth of PES and POE spherulites, that is, PES nucleated and developed spherulites inside the PBS spherulites and then POE spherulites grew inside the interlocked spherulites of PBS and PES. The other was simultaneous growth and the formation of interpenetrating spherulites of PES and POE inside the PBS spherulites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 706–711, 2010

Biodegradable polyesters are a promising solution for plastic pollution; however, their widespread adoption is hindered by their poor mechanical properties and lack of marine degradability. Conventional bulk property modifications cannot overcome this trade-off. Herein, the incorporation of polycaprolactone-grafted polyrotaxane, a mechanically interlocked supramolecular additive that modifies the polymer chain mobility and crystallization behavior, is demonstrated to simultaneously enhance the toughness and marine biodegradability of polyesters. Using poly(butylene succinate) as a model system, we demonstrate that the toughness increased by 300% without reducing the tensile strength and Young’s modulus. Remarkably, this molecular engineering approach creates a “multi-lock biopolymer” to enhance the marine biodegradation 4-fold, with UV exposure triggering accelerated degradation to 10-fold. This strategy provides a new pathway for the development of high-performance biodegradable plastics with tunable degradation profiles, thereby addressing both the mechanical and environmental challenges of sustainable polymers.

Producing high-performance materials from renewable carbon at high efficiency and ensuring a sustainable end-of-life scenario can notably reduce the CO2 footprint of the plastics industry. A recent example of such a material is poly(butylene xylosediglyoxylate) (PBX), a xylose-based polyester made in high yield from the hemicellulosic fraction of biomass. The well-rounded performance of PBX in terms of tensile strength, glass-transition temperature, and gas permeability makes it suitable for a range of market applications. However, PBX tends to be brittle (elongation at a break of 9.8%), depending on the manufacturing process. Herein, the rational tuning of PBX’s flexibility was investigated using compounding strategies with additives and the commercially available polyesters poly(butylene succinate) and poly[(butylene adipate)-co-(butylene terephthalate)] (PBAT). While the use of additives failed to improve the flexibility of PBX, the blending approach with PBAT led to materials with improved flexibility while retaining excellent thermomechanical and barrier properties. For example, the blending of PBX with 20 wt % PBAT led to elongations of break of 148% while maintaining a 1.6 GPa tensile modulus, a main glass transition of 89 °C, and only moderately disrupted barrier properties (OTR100 μm = 18 cm3/m2/day and WVTR100 μm = 44 g/m2/day). This advancement establishes a pathway toward the creation of biobased, flexible packaging materials with sustainable end-of-life.

ABSTRACTComposite materials consisting of poly(butylene succinate) (PBS) and montmorillonite (MMT), modified to various extents using trihexyltetradecylphosphonium chloride (THTDP) cations, were prepared using a simple melt intercalation technique. The surfactant contents were varied, i.e. 0.4, 0.6, 0.8, 1.0, and 1.2 times the cation exchange capacity (CEC) of the MMT. The intercalation of the surfactant molecules into MMT layers, confirmed by the increase in interlayer spacing and significant changes in the morphology of the modified MMT, facilitated the dispersion of the clay in the PBS matrix. The properties of the PBS-based composites were changed with increasing surfactant content. The melting and crystallization temperatures increased and the degree of crystallinity (χc) decreased. The storage modulus was significantly enhanced below the glass transition temperature (Tg), and Tg shifted to a higher temperature, with a maximum at a surfactant loading of 0.6 CEC. The mechanical properties, including tensile strength, flexural strength, flexural modulus and impact strength, increased and then decreased with surfactant loading, with the maximum observed also at a surfactant loading of 0.6 CEC. In conclusion, an ideal balance between thermal and mechanical properties can be obtained at a surfactant quantity equivalent to 0.6 times the clay CEC. Moreover, all the composites exhibited obvious improvement in thermal and mechanical properties as compared to those of neat PBS.

Two kinds of bio‐based polyesters were synthesized from 1,10‐decanediol (DD), dimethyl terephthalate (DMT) or 2,6‐naphthalene dicarboxylic acid (NDCA). Chemical structure, thermal properties and crystal structures, tensile properties and rheological properties were investigated. The glass transition temperature and melting temperature of poly(decamethylene 2,6‐naphthalate) (PDN) are higher than that of poly(decamethylene terephthalate) (PDT). Differential scanning calorimetry and wide‐angle X‐ray diffraction results suggested that PDT and PDN were semi‐crystalline polymers. Equilibrium melting points of PDT and PDN were 129.5°C and 167.1°C, respectively. Compared with PDT, PDN exhibited the higher tensile strength (36.8 MPa) and lower elongation at break (224%) and the complex viscosity of PDN is more sensitive to temperature and oscillation frequency. Compared with the current available bio‐based plastic poly(butylene succinate) (PBS), PDT and PDN exhibit higher melting temperature, faster crystallization rate and comparable tensile properties.

A phthalonitrile monomer (DPTP) containing pyridine with sulfide bonds was prepared and cured into polymers using different curing agents under the same temperature-programmed process. We characterized and comprehensively evaluated the effects of different curing agents on the thermal and thermomechanical properties of phthalonitrile resin, showing that the DPTP monomer cured with naphthalene-containing curing agent exhibited the best performance among the three polymers. Differential scanning calorimetric (DSC) investigation manifested that the melting point of the DPTP monomer was 61 °C, with a processing window of about 170 °C, suggesting the presence of a wide processing range. Thermogravimetric analysis (TGA) demonstrated the outstanding heat resistance, T5%, of 460 °C in nitrogen, at the same time demonstrating superior long-term stability compared with other commonly used polymer materials, which proves the long-term usage under high temperatures of 300 °C. Dynamic mechanical analysis (DMA) revealed that the storage modulus at 50 °C was 3315 MPa, and the glass transition temperature (Tg) of the polymer was more than 350 °C. Therefore, DPTP resins have favorable thermal stability as well as prominent thermomechanical properties.

Rapid, solvent-free synthesis of poly(1,4-butadiene) in ambient conditions is demonstrated by frontal ring-opening metathesis polymerization (FROMP) of 1,5-cyclooctadiene (COD). Furthermore, cross-linked copolymers with a wide range of tunable properties are readily prepared by FROMP of mixtures of COD and dicyclopentadiene (DCPD). Specifically, glass transition temperature and tensile modulus are varied from -90 to 114 °C and 3.1 MPa to 1.9 GPa, respectively, by controlling the comonomer ratio. Copolymers with subambient glass transition temperature exhibit robust elastomeric behavior, with the ability to repeatedly recover from large elastic deformations. As a demonstration of the capability of this manufacturing strategy, gradient materials are fabricated in less than a minute with spatially controlled properties for multistage shape memory actuation. This simple yet powerful manufacturing strategy enables rapid synthesis of copolymers ranging from elastomers to thermosets with precise control over thermomechanical properties.

The thermomechanical properties of a thin film of shape memory polymer of polyurethane series were investigated experimentally. Based on the experimental results, the dynamic mechanical properties, cyclic deformation properties at high temperature, thermomechanical cycling properties, creep and stress relaxation are discussed. The shape fixity with loading above the glass transition temperature followed by unloading below does not change under thermomechanical cycling. The residual strain is recovered in the vicinity of during the heating process. Several applications of the polymer are introduced.