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Low dielectric constant (k) polymers with excellent comprehensive properties are useful materials in the microelectronics industry as matrix resins or encapsulation layers. With the inherent low polarization, high reactivity, good processability, and low cost, poly(dicyclopentadiene) (PDCPD) has received considerable attention as low‐k materials. However, its practical application is limited by the relatively high thermal expansion and k value. Herein, three norbornene‐functionalized polyhedral oligomeric silsesquioxanes (POSSs) with T8, T10, and T12 polyhedral cores are synthesized and employed for enhancing the dielectric and comprehensive properties of PDCPD via reactive blending. The results show that these POSSs have good compatibility with PDCPD matrix and nano‐dispersed POSSs particles could be obtained. As a result, the materials' properties can be largely enhanced by varying the POSS content and POSS size. Especially, PT12N12‐40 (40 wt% of T12N12) shows the lowest k value (2.1) and coefficient of thermal expansion (63.4 ppm°C−1), highest glass transition temperature (202.5 °C), yield strength (78.0 MPa), and elastic modulus (2.36 GPa), along with excellent hydrophobicity. This study highlights a useful strategy to fabricate high‐performance low‐k polymer nanocomposites by using larger POSS and reactive blending, which provides useful materials for the future microelectronic industry and high frequency communication. [ABSTRACT FROM AUTHOR]

Constructing stereocomplex (SC) crystallites at the interface of poly(L‐lactide) (PLLA)/elastomer blends represent a promising strategy to develop heat‐resistant and super‐tough PLLA materials because such SC crystallites can behave as not only nucleator to accelerate crystallization of PLLA matrix but also interfacial binder to strengthen interface. The properties of blends could be largely dominated by the SC interfacial layer, however, it is still unclear how the interfacial structure affects nucleating efficiency and interfacial strength. Herein, taking PLLA/poly(ethylene‐co‐methyl acrylate‐graft‐poly(D‐lactide)) (EMA‐g‐PDLA) blends as an example, EMA‐g‐PDLA bearing different chain lengths and grafting densities is prepared to tailor the size and packing density of interface‐localized SC crystallites. The results indicate that the interfacial structure and properties of the blends have been successfully manipulated. Compared with low‐graft‐density long PDLA chains, high‐graft‐density short ones can readily collaborate with PLLA chains to form numerous SC crystallites with smaller size and higher packing density at the interface and thus dramatically enhance the impact toughness and matrix crystallization rate. Moreover, the toughness is dominated by the content of SC crystallites, but the matrix crystallization is determined by their size and packing density. The work provides a new understanding of SC structure controlling the properties of PLLA/elastomer blends. [ABSTRACT FROM AUTHOR]

The nucleation efficiency (NE) of stereocomplex crystallites (SCs) formed in asymmetric poly(L‐lactide)/poly(D‐lactide) (PLLA/PDLA) blends is generally unsatisfactory because the competition between stereocomplexation and chain mixing involved in the melt‐mixing process can cause low formation efficiency and even severe aggregation of SCs. Herein, it is attempted to achieve high‐efficient formation of finely dispersed SCs particles by designing a unique melt‐mixing procedure, where the mixing of PLLA with 0.75 wt% PDLA is first performed at elevated temperatures (far above the melting temperature of SCs) to allow the homogeneous mixing of PLLA/PDLA chains and then at a low temperature (slightly above that of homocrystallites) to permit the full stereocomplexation of the premixed chains. It is found that the SCs formed in the blends exhibit unexpectedly low NEs (e.g., 54.5%), much inferior to that (73.6%) in the counterpart without undergoing premixing. This is because the introduction of premixing leads to a remarkable deterioration in the amount of SCs particles formed, despite decreased particle size, highlighting that the direct mixing at low temperatures of 170–180 °C (about 20–30 °C lower than that used in common melt‐processing of PLA) is more effective for the construction of SCs with superior NE. The mechanisms for these striking findings are discussed. [ABSTRACT FROM AUTHOR]

Stereocomplex (SC) crystallization can prominently improve the physico-chemical properties of poly(l -lactide)/poly(d -lactide) (PLLA/PDLA) blends, yielding a novel polylactide (PLA) material. However, the predominant formation of SC crystals in the melt-processing of high-molar-mass (high-MW, >100 kg/mol) enantiomeric PLA blends remains a huge challenge due to the competition between SC crystallization and homocrystallization. Herein, double-grafted copolymer having both PLLA and PDLA side chain has been designed and synthesized as an efficient crystallization promoter for the harvest of SC crystals in the high-MW PLLA/PDLA blends. The results show that, with the addition of such a copolymer, the blends can preferentially crystallize into SC crystals in both isothermal and non-isothermal conditions. Promisingly, the SC crystals can be exclusively formed by adding only small amounts (e.g., 0.5 wt%) of the copolymer, without the formation of any homocrystals. This interesting observation can be interpreted by the crucial role of the unique copolymer in suppressing the phase separation of the opposite PLA enantiomers upon melting as an efficient compatibilizer and then encouraging the generation of alternatingly arranged PLLA/PDLA chain clusters favored for SC nucleation and crystal growth. These findings provide new inspiration for the development of high-performance PLA with desirable SC crystallizability. [Display omitted] [ABSTRACT FROM AUTHOR]

In recent years, rubber toughened polypropylene (PP) blends have been extensively investigated with special regard to the importance of PP matrix properties (e.g., crystal morphology and structure) in tailoring the toughening efficiency. Unfortunately, although high melt flowability is indispensable to the processing of polymers into complex thin-wall products, it remains a huge challenge to achieve a marvelous balance between stiffness and toughness in the blends with relatively low matrix molecular weight. Herein, taking PP/EPR (ethylene-propylene copolymer) blends as an example, the combined effects of matrix molecular weight and crystallinity on the mechanical properties of PP/EPR blends have been examined in both experiment and theory. The experimental results show that decreasing molecular weight leads to significant deterioration in notched impact toughness, tensile strength and Young's modulus. Impressively, the toughness loss caused by the decrease of molecular weight can be well-compensated by a slight reduction in the matrix crystallinity, without evidently sacrificing the strength and modulus, demonstrating an improved stiffness-toughness balance. Theoretical analysis indicates that the impact toughness of PP/EPR blends is heavily dependent on the chain entanglement density (v e) of PP matrix, and a linear relationship between critical interparticle distance (ID c) and the v e 1/3 has been verified from both experiment and theory. Moreover, it is interesting to find that decreasing matrix crystallinity can increase the v e of low-molecular-weight PP matrix, which enables the effective toughening at lower concentration of EPR and thus gives rise to less loss in the strength and modulus. We believe this work not only gives a new insight into the role of chain entanglement in the toughening but also provides a promising guidance for the design of high-performance PP with high melt flowability. [Display omitted] • Combined effects of M n and crystallinity on the toughening efficiency of PP/EPR blends were studded. • The relationship between the ID c and v e of PP matrix i.e. ID c ∼ v e 1/3 , was given for the first time. • Matrix with higher M n or lower crystallinity has higher v e , exhibiting larger ID c. • Toughness loss caused by decreasing M n can be compensated by reducing crystallinity. • Low-viscosity PP/EPR blends with good toughness-stiffness balance were obtained. [ABSTRACT FROM AUTHOR]