Abstract:In the field of propellant and polymer-bonded explosives (PBX), energetic polymers may bring poor mechanical properties for bulky groups and polarity. To get rid of the defects, plasticizers with low molecular weight can enhance the flexibility and processability of propellants through monotonous mixing. However, the migration of plasticizers over time may severely disrupt the mechanical property of energetic polymers. In contrast to general plasticization, internal plasticization can regulate flexibility from… Show more
“…The increasing interest in branched copolymers as self-assembly nanocarriers has led to several studies focused on establishing a way to synthesize branched structures with the same composition as linear polymers [142]. To achieve this, varying the number of arms linked to the central core, along with controlling molecular weight, has been suggested as a means of providing flexible and less viscous branched copolymers [143][144][145]. Controlling the molecular weight becomes increasingly necessary for polymers that exhibit crystalline behavior, such as polycaprolactone (PCL), which exhibits an amorphous character as long as the polymeric chain is short, thereby enhancing hydrophobic interactions between the polymer and the encapsulated drug [146,147].…”
Section: Exploring the Potential Of Multi-arm Polymers As Nanocarriersmentioning
Controlled drug delivery is a crucial area of study for improving the targeted availability of drugs; several polymer systems have been applied for the formulation of drug delivery vehicles, including linear amphiphilic block copolymers, but with some limitations manifested in their ability to form only nanoaggregates such as polymersomes or vesicles within a narrow range of hydrophobic/hydrophilic balance, which can be problematic. For this, multi-arm architecture has emerged as an efficient alternative that overcame these challenges, with many interesting advantages such as reducing critical micellar concentrations, producing smaller particles, allowing for various functional compositions, and ensuring prolonged and continuous drug release. This review focuses on examining the key variables that influence the customization of multi-arm architecture assemblies based on polycaprolactone and their impact on drug loading and delivery. Specifically, this study focuses on the investigation of the structure–property relationships in these formulations, including the thermal properties presented by this architecture. Furthermore, this work will emphasize the importance of the type of architecture, chain topology, self-assembly parameters, and comparison between multi-arm structures and linear counterparts in relation to their impact on their performance as nanocarriers. By understanding these relationships, more effective multi-arm polymers can be designed with appropriate characteristics for their intended applications.
“…The increasing interest in branched copolymers as self-assembly nanocarriers has led to several studies focused on establishing a way to synthesize branched structures with the same composition as linear polymers [142]. To achieve this, varying the number of arms linked to the central core, along with controlling molecular weight, has been suggested as a means of providing flexible and less viscous branched copolymers [143][144][145]. Controlling the molecular weight becomes increasingly necessary for polymers that exhibit crystalline behavior, such as polycaprolactone (PCL), which exhibits an amorphous character as long as the polymeric chain is short, thereby enhancing hydrophobic interactions between the polymer and the encapsulated drug [146,147].…”
Section: Exploring the Potential Of Multi-arm Polymers As Nanocarriersmentioning
Controlled drug delivery is a crucial area of study for improving the targeted availability of drugs; several polymer systems have been applied for the formulation of drug delivery vehicles, including linear amphiphilic block copolymers, but with some limitations manifested in their ability to form only nanoaggregates such as polymersomes or vesicles within a narrow range of hydrophobic/hydrophilic balance, which can be problematic. For this, multi-arm architecture has emerged as an efficient alternative that overcame these challenges, with many interesting advantages such as reducing critical micellar concentrations, producing smaller particles, allowing for various functional compositions, and ensuring prolonged and continuous drug release. This review focuses on examining the key variables that influence the customization of multi-arm architecture assemblies based on polycaprolactone and their impact on drug loading and delivery. Specifically, this study focuses on the investigation of the structure–property relationships in these formulations, including the thermal properties presented by this architecture. Furthermore, this work will emphasize the importance of the type of architecture, chain topology, self-assembly parameters, and comparison between multi-arm structures and linear counterparts in relation to their impact on their performance as nanocarriers. By understanding these relationships, more effective multi-arm polymers can be designed with appropriate characteristics for their intended applications.
“…Energetic materials hold significant importance in several domains, such as aerospace, military weaponry, resource exploitation, etc. − As a result, there is a growing trend toward the use of energetic polymer binders, which aim to provide excellent mechanical properties and increase the overall energy level of solid rocket propellants and PBXs. − Generally, the preparation of energetic polymers involves the introduction of energetic groups, which can reduce the flexibility of their bulky volume and high polarity. To overcome this defect, copolymerization is considered a viable method to achieve intramolecular plasticization by modifying the regularity of the backbone structure. , This commonly used method typically improves flexibility by increasing the proportion of soft chains, which can lead to a decrease of energetic groups, thereby lowering energy levels. − …”
In the field of energetic materials (EMs), soft chains are copolymerized with energetic polymers to improve flexibility. However, this often makes it difficult to achieve simultaneous optimization of the energy level and flexibility due to the random sequence. In this study, a simple approach is presented to develop energetic sequencecontrolled polymers (ESCPs), alternate copolymers poly(3,3-bis(azidomethyl)oxetaneglycol) (P(BAMO-alt-EG)) and poly(3,3-bis(azidomethyl)oxetane-tetrahydrofuran) (P(BAMO-alt-THF)), through click reactions. This approach provides the potential to design and control mechanical and thermal properties in propellant binders by introducing various segments and regulating the sequence structure. These polymers display excellent thermal stability and demonstrate that regulated shorter segmental length promoted better flexibility and less residual carbon content without compromising the energy level of the propellant. The obtained kinetic parameters prove that P(BAMO-alt-EG) released higher heat and accelerated the thermolysis process compared to P(BAMO-alt-THF). These results demonstrate the potential of highly alternating ESCPs as a potential energetic propellant binder.
The self‐plasticization, i.e., the increase in the polymer chains' mobility by including its monomer, has a major impact on a polymer's structural, thermal, and mechanical properties. In this study, differential scanning calorimetry (DSC), optical and Raman microscopies, thermo‐mechanical analysis (TMA), size exclusion chromatography equipped with a multi‐angle light scattering detector (SEC‐MALS), and X‐ray diffraction analysis (XRD) are used to investigate the effect of thermally induced self‐plasticization of poly‐(p‐dioxanone), PDX, on the crystal growths from the amorphous and molten states. Significant changes in the crystallization behavior and mechanical properties of PDX are found only for samples self‐plasticized at the depolymerization temperature (Td) above 150 °C. The intense self‐plasticization leads to the decrease of the crystallization temperature, increase of the crystal growth rapidity, disappearance of the distinct α→α’ polymorphic transition, reduction of the overall melting temperature, and segregation of the redundant monomer. Although the morphology of the crystalline phase has a major impact on the mechanical properties of PDX, the self‐plasticization itself does not seem to result in any major changes in the magnitude, localization, or morphology of formed crystallites (these are primarily driven by the temperature of crystal growth). The manifestation of the variable activation energy concept is discussed for the present crystallization data.
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