The crystallization and morphology of two linear diblock copolymers based on polymethylene (PM) and poly(vinylidene fluoride) (PVDF) with compositions PM₂₃-b-PVDF₇₇ and PM₃₈-b-PVDF₆₂ (where the subscripts indicate the relative compositions in wt%) were compared with blends of neat components with identical compositions. The samples were studied by SAXS (Small Angle X-ray Scattering), WAXS (Wide Angle X-ray Scattering), PLOM (Polarized Light Optical Microscopy), TEM (Transmission Electron Microscopy), DSC (Differential Scanning Calorimetry), BDS (broadband dielectric spectroscopy), and FTIR (Fourier Transform Infrared Spectroscopy). The results showed that the blends are immiscible, while the diblock copolymers are miscible in the melt state (or very weakly segregated). The PVDF component crystallization was studied in detail. It was found that the polymorphic structure of PVDF was a strong function of its environment. The number of polymorphs and their amount depended on whether it was on its own as a homopolymer, as a block component in the diblock copolymers or as an immiscible phase in the blends. The cooling rate in non-isothermal crystallization or the crystallization temperature in isothermal tests also induced different polymorphic compositions in the PVDF crystals. As a result, we were able to produce samples with exclusive ferroelectric phases at specific preparation conditions, while others with mixtures of paraelectric and ferroelectric phases.

We investigate for the first time the morphology and crystallization of two novel tetrablock quarterpolymers of polyethylene (PE), poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA) with four potentially crystallizable blocks: PE₁₈^7.1-b-PEO₃₇^15.1-b-PCL₂₆^10.4-b-PLLA₁₉^7.6 (Q1) and PE₂₉^9.5-b-PEO₂₆^8.8-b-PCL₂₃^7.6-b-PLLA₂₂^7.3 (Q2) (superscripts give number average molecular weights in kg/mol, and subscripts give the composition in wt %). Their synthesis was performed by a combination of polyhomologation (C1 polymerization) and ring-opening polymerization techniques using a ″catalyst-switch″ strategy, either ″organocatalyst/metal catalyst switch″ (Q1 sample, 96% isotactic tetrads) or ″organocatalyst/organocatalyst switch″ (Q2 sample, 84% isotactic tetrads). Their corresponding precursors—triblock terpolymers PE-b-PEO-b-PCL, diblock copolymers PE-b-PEO, and PE homopolymers—were also studied. Cooling and heating rates from the melt at 20 °C/min were employed for most experiments: differential scanning calorimetry (DSC), polarized light optical microscopy (PLOM), in situ small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS), and atomic force microscopy (AFM). The direct comparison of the results obtained with these different techniques allows the precise identification of the crystallization sequence of the blocks upon cooling from the melt. SAXS indicated that Q1 is melt miscible, while Q2 is weakly segregated in the melt but breaks out during crystallization. According to WAXS and DSC results, the blocks follow a sequence as they crystallize: PLLA first, then PE, then PCL, and finally PEO in the case of the Q1 quarterpolymer; in Q2, the PLLA block is not able to crystallize due to its low isotacticity. Although the temperatures at which the PEO and PCL blocks and the PE and PLLA blocks crystallize overlap, the analysis of the intensity changes measured by WAXS and PLOM experiments allows identifying each of the crystallization processes. The quarterpolymer Q1 remarkably self-assembles during crystallization into tetracrystalline banded spherulites, where four types of different lamellae coexist. Nanostructural features arising upon sequential crystallization are found to have a relevant impact on the mechanical properties. Nanoindentation measurements show that storage modulus and hardness of the Q1 quarterpolymer significantly deviate from those of the stiff PE and PLLA blocks, approaching typical values of compliant PEO and PCL. Results are mainly attributed to the low crystallinity of the PE and PLLA blocks. Moreover, the Q2 copolymer exhibits inferior mechanical properties than Q1, and this can be related to the PE block within Q1 that has thinner crystal lamellae according to its much lower melting point.

Polylactide (PLA) stereocomplexes (SCs) containing amorphous block copolymers have gained enormous interest due to their unique properties and wide range of potential applications. In this work, we report the synthesis and properties of non-covalent triblock terpolymers: polystyrene–SCPLA–polyisoprene (PS–SC–PI) via the stereocomplexation of PS-b-PDLA with PI-b-PLLA diblock copolymers through the solution-precipitation method. The diblock copolymers were prepared by combining the anionic polymerization high-vacuum technique with ring-opening polymerization (ROP). First, several well-defined ω-hydroxyl polystyrenes and polyisoprenes (PS-OH and PI-OH) with varied molecular weights were synthesized by anionic polymerization using sec-BuLi as the initiator. PS-OH and PI-OH were used as the macroinitiators for the ROP of DLA and LLA catalyzed by tin(II) 2-ethyl hexanoate to afford PS-b-PDLA and PI-b-PLLA. PS–SC–PIs were prepared by mixing PS-b-PDLA and PI-b-PLLA solutions (in dichloromethane) and precipitated into methanol. The molecular characteristics of the block copolymers were determined by ¹H NMR spectroscopy and size exclusion chromatography. The formation of PS–SC–PIs was evidenced by differential scanning calorimetry, X-ray diffraction, and Fourier-transform infrared, and circular dichroism spectroscopies. A preliminary study by atomic force microscopy reveals the thin-film phase behavior and the supramolecular organization of the PS–SC–PI.