Coionomeric mixtures of polyhydroxyethers and ethylene methacrylic acid copolymers. II. Compatibilizers for blends of polybutylene terephthalate and ethylene butyl acrylate copolymers

Blends of polybutylene terephthalate and ethylene butyl acrylate copolymers were studied at two extreme concentration levels so that each polymer would form, in turn, a particulate dispersed phase. The blends contained 5% by weight of a coionomeric compatibilizer, which was produced from 1 : 1 mixtures of a polyhydroxy ether of bisphenol A and the sodium ionomer of an ethylene methacrylic acid copolymer, using sodium ethoxide to enhance the formation of ionomeric clusters together with an A-B-A block oligomer to assist the solubilization of the two ionomeric polymers. In all cases the addition of the coionomeric compatibilizer mixture to the blend was found to decrease the size of the dispersed particles with a concomitant reduction in the interphase gap. It was also observed that the dispersed polymer exhibited a lower level of crystallinity and a slightly lower melting point than when it was present as a matrix, particularly for the case of the ethylene butylacrylate copolymer. The inability of the compatibilizer to completely prevent the formation of an interfacial gap which did not allow the blends to achieve more substantial improvements in mechanical properties, was attributed to the vast difference in crystallization temperature between the two polymers. © 1993 John Wiley & Sons, Inc.     

Polyolefin/layered silicate nanocomposites with functional compatibilizers

Polymer nanocomposites containing layered silicates have been considered as a new generation of composite materials due to their expected unique properties attributed to the high aspect ratio of the inorganic platelets. Nevertheless, addition of layered silicates to polyolefins mostly results in phase separated systems because of the incompatibility of the silicates with the non-polar polyolefins. Functional compatibilizers are required to enhance the interactions and alter the structure from phase separated micro-composites to intercalated and exfoliated nanocomposites. Commercial macromolecular compatibilizers (mainly maleic-anhydride-functionalized polyolefins) are most commonly used to improve the interfacial bonding between the fillers and the polymers whereas specifically synthesized functional homopolymers or copolymers have been utilized as well. In this article, we are reviewing a number of investigations, which studied the influence on the composite structure of various parameters like the compatilizer to inorganic ratio, the type and content of the functional groups and the molecular weight of the functional additive, the miscibility between the matrix polymer and the compatibilizer, the kind of surfactants modifying the inorganic surface, the processing conditions, etc. The most important results obtained utilizing maleic-anhydride-functionalized polyolefins are discussed first, whereas a summary is presented then of the studies performed utilizing other functional oligomers/polymers. X-ray diffraction and transmission electron microscopy studies supported by rheology indicate that the most important factor controlling the structure and the properties is the ratio of functional additive to organoclay whereas the miscibility between the matrix polymer and the compatibilizer is a prerequisite.     

Design of bicontinuous donor/acceptor morphologies for use as organic solar cell active layers

In recent works, we demonstrated the achievement of bicontinuous donor/acceptor morphologies by the addition of conjugated block copolymers to a blend of conjugated homopolymer donors and fullerene acceptors. However, the domain sizes resulting in experiments were much larger than those of interest for high‐performance organic solar cells. Moreover, a significant concentration of fullerene acceptors was present in the donor domains. Here, we utilize simulations to study the bicontinuous donor/acceptor morphologies that result for different parametric conditions. Using such results, we provide guidelines for how to blend polymer materials to give rise to bicontinuous phases with the smaller and more compositionally pure domains that are desirable for organic photovoltaic applications. Our results can be generalized to treat a large range of donor and acceptor monomers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 884–895     

Donor–acceptor rod–coil block copolymers comprising poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] and fullerene as compatibilizers for organic photovoltaic devices

The successful synthesis is described for a donor–acceptor rod–coil block copolymer comprising blocks of poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] (F6T2) and polystyrene functionalized with fullerene (PS(C₆₀)) (F6T2‐b‐PS(C₆₀)). This new material was obtained by combining Suzuki polycondensation with radical addition fragmentation chain transfer. The block copolymer was characterized by nuclear magnetic resonance, gel permeation chromatography, and optical spectroscopy methods. Photophysical data for (F6T2‐b‐PS(C₆₀)) and a related block copolymer (F6T2‐b‐PS(PCBM)) (PCBM, phenyl‐C61‐butyric acid methyl ester) are reported and their performance as compatibilizers in bulk heterojunction organic solar cells is assessed. It is demonstrated that the addition of the rod–coil block copolymers to the active layer extends the operational stability of organic photovoltaic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 888–903     

Influence of Reactive Compatibilizer on the Morphology,Rheological, and Mechanical Properties of Recycled Poly(Ethylene Terephthalate)/Polyamide 6 Blends

Recycled poly(ethylene terephthalate) (R-PET) and virgin polyamide 6 (PA6) blends compatibilized with glycidyl methacrylate grafted poly(ethylene-octene) (POE-g-GMA) were melt blended. The morphological, rheological and mechanical properties of the prepared blends were investigated by scanning electron microscopy, rheology, and an electromechanical testing instrument, respectively. All of the blends showed a droplet dispersion type morphology, and the PA6 particle size decreased with increase in the POE-g-GMA concentration. The storage modulus (G′), loss modulus (G′′), and complex viscosity (η*) of the blends significantly increased at low frequency with the addition of POE-g-GMA. In addition, ‘‘Cole-Cole’’ plots showed that the elasticity of the blends was also increased by raising the compatibilizer dosage. It was also found that 10 wt% of POE-g-GMA caused 88.46 and 171.05% increments in Charpy impact strength and elongation at break with only a 21.66% decrement in tensile strength.     

Combined effect of compatibilizer and carbon nanotubes on the morphology and electrical conductivity of PP/PS blend

In this work, maleic anhydride grafted styrene–ethylene–butadiene–styrene copolymer (SEBS‐g‐MA) and carbon nanotubes (CNTs) were introduced into the immiscible polypropylene/polystyrene (PP/PS) blend. Among the three polymer components, SEBS‐g‐MA has the strongest affinity to CNTs; thus, it exhibits dual effects to adjust the phase morphology of the blends and the dispersion state of CNTs in the blends. The experimental observations obtained from morphology characterizations using scanning electron microscope and transmission electron microscope confirm the selective localization of CNTs at the interface of the immiscible PP/PS blend. As a consequence, largely decreased percolation threshold is achieved when most of CNTs are selectively localized at the interface region between PP and PS. Copyright © 2014 John Wiley & Sons, Ltd.     

Stereospecific sequential block copolymerizations of styrene and 1,3‐butadiene with a C5Me5TiMe3/B(C6F5)3/Al(oct)3 catalyst

This article reports a new methodology for preparing highly stereoregular styrene (ST)/1,3‐butadiene (BD) block copolymers, composed of syndiotactic polystyrene (syn‐PS) segments chemically bonded with cis‐polybutadiene (cis‐PB) segments, through a stereospecific sequential block copolymerization of ST with BD in the presence of a C₅Me₅TiMe₃/B(C₆F₅)₃/Al(oct)₃ catalyst. The first polymerization step, conducted in toluene at ?25 °C, was attributed to the syndiospecific living polymerization of ST. The second step, conducted at ?40 °C, was attributed to the cis‐specific living polymerization of BD. The livingness of the whole polymerization system was confirmed through a linear increase in the weight‐average molecular weights of the copolymers versus the polymer yields in both steps, whereas the molar mass distributions remained constant. The profound cross reactivity of the styrenic‐end‐group active species with BD toward ST led to the production of syn‐PS‐b‐cis‐PB copolymers with extremely high block efficiencies. Because of the presence of crystallizable syn‐PS segments, this copolymer exhibited high melting temperatures (up to 270 °C), which were remarkably different from those of the corresponding anionic ST–BD copolymers, for which no melting temperatures were observed. Scanning electron microscopy pictures of a binary syn‐PS/cis‐PB blend with or without the addition of the syn‐PS‐b‐cis‐PB copolymers proved that it could be used as an effective compatibilizer for noncompatibilized syn‐PS/cis‐PB binary blends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1188–1195, 2005     

Understanding and controlling the structure of polypropylene/layered silicate nanocomposites

The miscibility and structure in polypropylene/layered silicate nanocomposites is systematically investigated utilizing a maleic-anhydride grafted polypropylene with a low degree of functionalization acting as the compatibilizer. The morphology of the hybrids can be modified from phase separated to almost completely exfoliated in a controlled way by varying the ratio α of the compatibilizer to the organophilized clay; this ratio α is found to be the most important parameter in determining the final structure whereas exfoliated structures can be obtained for α values of 9 or higher. Furthermore, utilization of a “masterbatch” procedure can enhance the degree of exfoliation even for smaller values of α; in that case, polypropylene is essentially mixed with the already dispersed “hairy” platelets. Investigation of the thermal stability of the micro- and nanocomposites shows that high degree of exfoliation is vital in increasing the temperature that the polymer starts to degrade. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2683–2695, 2008     

Natural source compatibilizers for olive waste/recycled polypropylene matrix composites

A simple, environmentally friendly process was developed for surface hydrophobization of cellulose-rich waste to improve their compatibility with recycled polypropylene (rPP), helping reduce costs while recycling environmentally problematic waste such as solid olive waste (also called olive pomace). In this study, an improvement of the interfacial bonding strength between the hydrophilic waste particles and the hydrophobic matrix was achieved by surface hydrophobization of the waste using a ring-opening polymerization reaction of epoxidized soy-bean oil (ESBO) with SnCl₂ as a catalyst. The treatment on cellulose based filter paper led to a contact angle of 128°. The composite containing treated olive pomace has shown an increase in the elongation of 92% and an increase in the stress at yield of 15%, indicating improved compatibility.     

Maleated glycidyl 3‐pentadecenyl phenyl ether with styrene: synthesis and application as compatibilizer in SBR/silica composite

Maleated glycidyl 3‐pentadecenyl phenyl ether with styrene (MGS) was synthesized from glycidyl 3‐pentadecenyl phenyl ether (GPPE), maleic anhydride (MAH) and styrene (St) in the presence of AIBN initiator at 80°C, and then the resultant MGS was applied as a compatibilizer to prepare SBR/silica composites. Meanwhile, the commercial compatibilizer bis‐(triethoxysilylpropyl) tetrasulfide (named Si69) added into composite was also prepared for comparison purpose. The synthetic MGS structure was characterized by GPC and FTIR, and SBR/silica compounds with different compatibilizer were analyzed using RPA, DMA and so on. The results showed that M?n and M?w of MGS were 19,538 g/mol and 23,790 g/mol, respectively. The curing time of compounds with MGS increased, whereas the maximum and minimum torques decreased. The addition of MGS decreased Payne effect of SBR/silica compounds, which implied an improvement of silica dispersion in the compounds. Bound rubber content of compound with MGS was about 1.7 times higher than the absence and 1.5 times higher than that with Si69. The tensile strength of the composites was improved by increasing compatibilizer loading, and the optimum value was observed at 6 phr of MGS. Meanwhile the use of MGS can improve the anti‐aging property of composite. According to DMA, the tanδ value at 0°C of composite with MGS was higher than composite without compatibilizer suggesting that MGS can improve the wet skid resistance of composite. The SEM analysis revealed that introduction of MGS enhanced the compatibility between SBR and silica. Copyright © 2015 John Wiley & Sons, Ltd.