Strengthening Interfacial Adhesion and Foamability of Immiscible Polymer Blends via Rationally Designed Reactive Macromolecular Compatibilizers.

Foams made of immiscible polymer blends have attracted great interest in both academia and industry, because of the integration of desirable properties of different polymers in a hybrid foam. However, the foamability and end-use properties are hampered because of the poor interfacial strength within the immiscible blends. Furthermore, few investigations have been carried out on the mechanisms by which interfacial strength and structure affect the foamability of polymer blends. In this work, two different reactive interfacial compatibilizers, i.e., poly(styrene-co-glycidyl methacrylate)-graft-poly(l-lactide) and poly(styrene-co-glycidyl methacry-late)-graft-poly(d-lactide), abbreviated as SG-g-PLLA and SG-g-PDLA, respectively, were designed and synthesized through reactive melt blending and subsequently applied to strengthen the interfacial strength and foamability of immiscible poly(butylene adipate-co-terephthalate) (PBAT)/poly(l-lactide) (PLLA) blends. Both compatibilizers could remarkably enhance the interfacial strength and foamability of the PBAT/PLLA blends, as evidenced by the significantly elongated dispersed phase in the resulting cocontinuous phase and more than 7000-fold increase in the cell density. Furthermore, the improved foamability was quantitively explained by the reduced gas diffusion and increased melt strength. Strikingly, the SG-g-PDLA introduced a stereocomplex crystal at the interface (i-SC), providing highly strengthened interfaces and nanoscale heterogeneous nucleation sites, which led to an energetically favorable cell nucleation. Moreover, foams with specifically laminated cell structures were fabricated by combining pressure-induced flow processing and i-SC strengthened interfaces. This work provides insight into the relationship between interfacial strength and formability of immiscible polymer blends and offers new possibilities for controlling cell morphologies and designing unique cell structures for polymer foams.

Enhancement of strength and toughness of bio-nanocomposites with good transparency and heat resistance by reactive processing.

Growing concerns in addressing environmental challenges are driving the rapid advancement of both bio-based and environmental friendly materials. Biodegradable polymers have been compounded with various nanofillers to fulfill the multiple requirements in real applications. However, current technologies remain to be improved in terms of the intrinsic inferior performance and the lack of interfacial interactions. In this work, we employed a facile route to develop bio-nanocomposites integrating multiple functionalities by reactive processing of polylactide and reactive boehmite nanorods. The grafting of polymer chains onto the surface of the nanorods encourages fully homogeneous dispersion of nanofillers with even 30 wt% loadings. Such nanocomposites exhibit simultaneously enhanced tensile strength, modulus, ductility, and impact strength. Moreover, the bio-based nanocomposites present promising features such as high transparency, improved flame resistance, and heat resistance. This work demonstrates exciting opportunities to produce bio-plastics with diverse functionalities in versatile applications of sustainable packaging industry and engineering plastics.

Interfacial Engineering with Rigid Nanoplatelets in Immiscible Polymer Blends: Interface Strengthening and Interfacial Curvature Controlling.

The interfacial nanoparticle compatibilization (INC) strategy has opened up a promising avenue toward simultaneous functionalization and interfacial engineering of immiscible polymer blends. While the INC mechanism has been well developed recently, few investigations have focused on rigid nanoplatelets because of the inherent steric hindrance of the surface-grafted polymer chains. Herein, surface-modified rigid nanoplatelets have been incorporated into an immiscible poly(l-lactide) (PLLA)/poly(butylene succinate) (PBSU) blend. It is demonstrated that the strong interfacial adhesion between PLLA and PBSU phases is promoted via molecular entanglements of the grafted chains on the surface of nanoplatelets with the individual components. A refined phase morphology with improved mechanical properties can be achieved with the addition of 5 wt % modified Gibbsite nanoplatelets. It was further found that the stiffness of nanoplatelets can change the geometry of the interface significantly. It is, therefore, indicated that the simultaneous interface strengthening and interfacial curvature controlling of rigid nanoplatelets originate from the selective swelling/collapse of the in situ-formed PLLA and PBSU grafts within the corresponding phase at the interface. Such a mechanism is confirmed by the Monte Carlo simulations. This work provides new opportunities for the fabrication of advanced polymer blend nanocomposites.

Reactive Comb Polymer Compatibilized Immiscible PVDF/PLLA Blends: Effects of the Main Chain Structure of Compatibilizer.

The compatibilizer with double comb structure has a superior compatibilizing effect for immiscible polymer blends due to the symmetrical structure on both sides of main chains. Extensive study related to the architectural effects of compatibilizer on the compatibilization has mainly focused on the side chains. We investigated the influence of the compatibilizer-main-chain structure on the compatibilizing effect for immiscible poly(vinylidene fluoride)/poly(L-lactic acid) (PVDF/PLLA) blends. Two reactive-comb compatibilizers with polystyrene (PS) and polymethylmethacrylate (PMMA) as main chains and PMMA as the side chains have been synthesized. PS is immiscible with both PLLA and PVDF, while PMMA is miscible with PVDF. It was found that both compatibilizers can improve the compatibility between the PLLA and PVDF, with different compatibilization effects. In the PVDF/PLLA (50/50) blends, 1 wt.% poly(styrene-co-glycidyl methacrylate)-graft-poly(methyl methacrylate) (RC-SG) tuned the morphology from the droplet-in-matrix structure to the co-continuous structure, while the blends with poly(methyl methacrylate-co-glycidyl methacrylate)-graft-poly(methyl methacrylate) (RC-MMG) kept the sea-island structure with even 3 wt.% loading. Moreover, RC-SG induces a wider co-continuous interval range than RC-MMG. The co-continuous structure obtained by RC-SG was also more stable than that by RC-MMG. It was further found that RC-SG-compatibilized PVDF/PLLA blends exhibit higher mechanical properties than the RC-MMG-compatibilized blends.

Enhanced Interfacial Adhesion by Reactive Carbon Nanotubes: New Route to High-Performance Immiscible Polymer Blend Nanocomposites with Simultaneously Enhanced Toughness, Tensile Strength, and Electrical Conductivity.

Physically anchoring carbon nanotubes (CNTs) onto the interface of immiscible polymer blends has been extensively reported; however, enhancement of physical properties of the blends has seldom been achieved. Herein, we used CNTs with reactive epoxide groups and long poly(methyl methacrylate) (PMMA) tails as a thermodynamic compatibilizer for immiscible poly vinylidene fluoride/poly l-lactide (PVDF/PLLA) blends. The CNTs acted as an efficient compatibilizer and bridged the two phases through physical entanglement and chemical reaction. The sea-island structure of the blend transformed into a bicontinuous structure for CNT contents greater than 3 wt %. The mechanical properties, including ductility and tensile strength, thermal properties, and electrical conductivities were all enhanced by the CNTs compatibilizer. This strategy thermodynamically compatibilized by reactive nanofillers paves the way for advanced blend nanocomposites.

Reactive Compatibilization: Formation of Double-Grafted Copolymers by In Situ Binary Grafting and Their Compatibilization Effect.

Reactive compatibilizers are usually used to enhance the compatibility of immiscible polymer blends. However, reactive linear compatibilizers containing reactive groups on the main chains form graft copolymers during reactive blending, and such graft copolymers with an asymmetric molecular structure are often "pulled in" or "pulled out" under mechanical shear. Double-grafted compatibilizers have a symmetric structure, and they usually exhibit higher compatibilizing efficiency. In this work, we propose a binary grafting strategy during melt blending to form compatibilizers located at the interface of an immiscible polymer blend. Specifically, poly(methyl methacrylate) (PMMA) oligomer with carboxylic end groups (PMMA-COOH) and poly(styrene-co-glycidyl methacrylate) (SG) copolymer were simultaneously incorporated into immiscible poly(vinylidene fluoride)/poly(l-lactic acid) (PVDF/PLLA) blends. The carboxylic acid groups of both the PMMA oligomer and PLLA can react with the epoxide groups on the SG main chains. Therefore, novel compatibilizing polymers with both PMMA and PLLA chains grafted onto the SG main chains form in situ. The grafted PMMA chains can entangle with PVDF, and the grafted PLLA chains are embedded in the PLLA phase, so the double-grafted copolymers act as effective compatibilizers for the PVDF/PLLA blends. Moreover, the effects of the PMMA molecular weight and PMMA loading (number of grafted PMMA side chains) on the compatibilization efficiency were investigated. The compatibilizing efficiency increases with increasing molecular weight and number of side chains in the ranges considered in this study. This one-pot synthesis of double-grafted compatibilizers by in situ grafting provides a new and simple method to prepare double-comb compatibilizers, and it offers the possibility of high-efficiency compatibilization.

Reactive Nanoparticles Compatibilized Immiscible Polymer Blends: Synthesis of Reactive SiO2 with Long Poly(methyl methacrylate) Chains and the in Situ Formation of Janus SiO2 Nanoparticles Anchored Exclusively at the Interface.

The exclusive location of compatibilizers at the interface of immiscible binary polymer blends to bridge the neighboring phases is the most important issue for fabricating desirable materials with synergistic properties. However, the positional stability of the compatibilizers at the interface remains a challenge in both scientific and technical points of view due to the intrinsic flexibility of compatibilizer molecules against aggressive processing conditions. Herein, taking the typical immiscible poly vinylidene fluoride (PVDF)/polylactic acid (PLLA) blend as an example, we demonstrate a novel approach, termed as the interfacial nanoparticle compatibilization (IPC) mechanism, to overcome the challenges by packing nanoparticles thermodynamically at the interface through melt reactive blending. Specifically, we have first synthesized nanosilica with both reactive epoxide groups and long poly(methyl methacrylate) (PMMA) tails, called reactive PMMA-graft-SiO2 (Epoxy-MSiO2), and then incorporated the Epoxy-MSiO2 into the PVDF/PLLA (50/50, w/w) blends by melt blending. PLLA was in situ grafted onto SiO2 by the reaction of the carboxylic acid groups with epoxide groups on the surface of SiO2. Therefore, the reacted SiO2 particles were exclusively located at the interface by the formation of the Janus-faced silica hybrid nanoparticles (JSNp) with pregrafted PMMA tails entangled with PVDF molecular chains in the PVDF phase and the in situ grafted PLLA chains embedded in the PLLA phase. Such JSNp with a distinct hemisphere, functioning as compatibilizer, can not only suppress coalescence of PVDF domains by its steric repulsion but also enhance interfacial adhesion via the selective interactions with the corresponding miscible phase. The interfacial location of JSNp is very stable even under the severe shear field and annealing in the melt. This IPC mechanism paves a new possibility to use the various types of nanoparticles as both effective compatibilizers and functional fillers for immiscible polymer blends.

Formation of Interfacial Janus Nanomicelles by Reactive Blending and Their Compatibilization Effects on Immiscible Polymer Blends.

Micellization of in situ formed graft copolymers during reactive blending is commonly observed. Numerous studies have been carried out to minimize the formation of micelles and enhance emulsification efficiency. Herein, we investigated the formation of interfacial Janus nanomicelles (JNMs) and their compatibilization effects on immiscible polymer blends when reactive graft copolymers (RGCs) are used as compatibilizers. Poly(styrene-co-glycidyl methacrylate)-graft-poly(methyl methacrylate) RGCs were synthesized and used as compatibilizers for immiscible poly(l-lactide) (PLLA)/poly(vinylidene fluoride) (PVDF) blends. Numerous nanomicelles were formed in situ during melt blending by grafting of PLLA onto the RGCs. The formation and location of JNMs depended not only on the molecular architecture of the RGCs but also on the melt processing sequence and molecular weight of the components. Interfacial JNMs can effectively improve the miscibility of polymer blends, thereby enhancing the performance of immiscible polymer blends.

Compatibilization of Immiscible Polymer Blends Using in Situ Formed Janus Nanomicelles by Reactive Blending.

Block or graft copolymers located at polymer-polymer interfaces have been considered as ideal compatibilizers for immiscible polymer blends. Herein, we report a novel compatibilization mechanism using Janus nanomicelles (JNMs) formed in situ at the polymer-polymer interface in immiscible polyvinylidene fluoride (PVDF)/polylactic acid (PLLA) blends. A small amount of a reactive graft copolymer, poly(styrene-co-glycidyl methacrylate)-graft-poly(methyl methacrylate) (P((S-co-GMA)-g-MMA)), is incorporated into the PLLA/PVDF blends by simple melt mixing. The in situ grafting of PLLA chains onto P((S-co-GMA)-g-MMA) during melt mixing leads to the formation of numerous JNMs with a shell structure consisting of PLLA and PMMA hemispheres. These JNMs are located at the PLLA/PVDF interface, where they behave as effective compatibilizers for the immiscible PLLA/PVDF blends. This interfacial micelle compatibilization (IMC) mechanism opens new opportunities to exploit interfacial emulsification using JNMs and should be of great significance in the compatibilization of polymer alloys.

Enhanced crystallization rate of poly(L-lactic acid) (PLLA) by polyoxymethylene (POM) fragment crystals in the PLLA/POM blends with a small amount of POM.

Phase diagrams and glass transition behaviors of poly(L-lactic acid)/polyoxymethylene (PLLA/POM) blends have been investigated in our previous work (Macromolecules 2013, 46, 5806-5814). In this work, the crystallization behaviors and physical properties of the PLLA/POM blends with the PLLA as the major component have been systematically studied. POM was crystallized into the fragment crystals that were finely dispersed in the PLLA matrix when cooling down from the melt of the blends. It was found that the POM fragment crystals accelerated the crystallization process of PLLA matrix and increased the final crystallinity of PLLA significantly in the blends. At the same time, the PLLA spherulites nucleated by POM fragment crystals were much smaller than those obtained from neat PLLA. It was further found that the crystallization rate of PLLA was quite dependent upon the POM loadings and the highest crystallization rate was observed at POM loadings of 7 wt %. It is considered that the POM fragment crystals take the nuclei role to initiate the crystallization of PLLA at low POM loadings, while a high content of POM in the blends leads to the large POM spherulites that cannot nucleate PLLA crystallization effectively. The obtained PLLA/POM blends at low POM loadings with small PLLA spherulites exhibited excellent optical transmittance and good mechanical performance.

Mechanical and thermal properties of eco-friendly poly(propylene carbonate)/cellulose acetate butyrate blends.

The eco-friendly poly(propylene carbonate) (PPC)/cellulose acetate butyrate (CAB) blends were prepared by melt-blending in a batch mixer for the first time. PPC and CAB were partially miscible because of the drastically shifted glass transition temperatures of both PPC and CAB, which originated from the specific interactions between carbonyl groups and hydroxyl groups. The incorporation of CAB into PPC matrix enhanced not only tensile strength and modulus of PPC dramatically, but also improved heat resistance and thermal stability of PPC significantly. The tensile strength and the modulus of PPC/CAB=50/50 blend are 27.7 MPa and 1.24 GPa, which are 21 times and 28 times higher than those of the unmodified PPC, respectively. Moreover, the elongation at break of PPC/CAB=50/50 blend is as high as 117%. In addition, the obtained blends exhibited good transparency, which is very important for the package materials. The results in this work pave new possibility for the massive application of eco-friendly polymer materials.