Reactive compatibilization of LLDPE/PS blends with a new type of Lewis acid as catalyst

The reactive compatibilization of LLDPE/PS (50/50 wt%) was achieved by Friedel–Crafts alkylation reaction with a combined Lewis acids (Me₃SiCl and InCl₃·4H₂O) as catalyst. The graft copolymer at the interface was characterized by Fourier transform infrared spectroscopy and the morphology of the blends was analysized by scanning electron microscopy. It was found that the combined Lewis acids had catalytic effect on Friedel–Crafts alkylation reaction between LLDPE and PS, and the catalytic effect was maximal when the molar ratio of InCl₃·4H₂O to Me₃SiCl was 1:5. The graft copolymer LLDPE–g–PS was formed via the F–C reaction and worked as a tailor-made compatibilizer to reduce the interfacial tension. The mechanical properties of reactive blend with combined Lewis acids as catalyst was notably improved compared to that of physical LLDPE/PS blend and serious degradation had been decreased compared to the reactive blend system with AlCl₃ as catalyst; we interpreted the above results in term of acidity of combined Lewis acids.     

Improvement of mechanical properties for PP/PS blends by in situ compatibilization

The effect of the in situ compatibilization on the mechanical properties of PP/PS blends was investigated. The application of Friedel-Crafts alkylation reaction to the PP/PS-blend compatibilization was assessed. Styrene/AlCl₃ was used as catalyst system. The graft copolymer (PP-g-PS) formed at the interphase showed relatively high emulsifying strength. Scission reactions, occurring in parallel with grafting, were verified for PP and PS at high catalyst concentration, but no crosslinking reactions were detected. Tensile tests were performed on dog-bone specimens of the blends. Both elongation at break and toughness increased with catalyst concentration. At 0.7% AlCl₃, a maximum was reached, which amounted to five times the value of the property for the uncompatibilized blend. At higher catalyst concentrations these properties decreased along with the PP molecular weight due to chain-scission reactions. On the other hand, the tensile strength did not change with the catalyst concentration. The in situ compatibilized blends showed considerable improvement in mechanical properties, but were adversely affected by chain scissions at high catalyst contents.     

Reactive compatibilization of PA6/LDPE blends with an ethylene-acrylic acid copolymer and a low molar mass bis-oxazoline

A sample of polyamide-6 (PA) was blended with low density polyethylene (LDPE) in the 80/20 wt/wt ratio, either without and with 2 phr of an ethylene-acrylic acid copolymer (EAA), Which was known to behave as a compatibilizer precursor, and the effect of the addition of small amounts (0.2 or 0.35 phr) of a fourth component, 2,2′-(1,3-phenylene)-bis(2-oxazoline) (PBO), was investigated. The reactions of PBO with EAA, PA and their blends were studied by recording as a function of time the torque applied to the blending apparatuses and by studying the solubility behavior of the products in formic acid. The PALDPE blends were prepared in a co-rotating twin screw extruder and were characterized by Molau tests, differential scanning calorimetry, scanning electron microscopy, rheology, and determination of the ultimate mechanical properties, including impact tests. The results indicate that the effectiveness of EAA as a compatibilizer precursor is considerably enhanced when PBO is added into the blends. It is thought that the reactions of PBO with the free carboxyl groups of EAA and with the amine or carboxyl end groups of PA run, at least in part, toward the formation of PA-g-EAA copolymers acting as the true compatibilizers for these blends.     

POE/SAN的原位增容

通过扭矩测定,傅里叶变换红外光谱、差示扫描量热法分析等方法研究了苯乙烯-丙烯腈共聚物(SAN)与聚烯烃弹性体(POE)大分子间的Friedel-Crafts烷基化反应。结果表明:适量无水AlCl3可以引发SAN与POE发生Friedel-Crafts烷基化反应,生成的POE-g-SAN接枝共聚物起到了原位增容POE/SAN共混物的作用,提高了其力学性能;当m(POE)/m(SAN)为60.0∶40.0,反应温度为180℃,AlCl3用量为0.4 phr时,POE/POE-g-SAN/SAN共混物性能较好;进一步提高AlCl3用量,SAN分子结构中侧链氰基与铝离子络合作用增强,导致SAN分散相聚集,POE/POE-g-SAN/SAN共混物刚性下降。     

原位增容PS/LLDPE共混物的结构与性能

在熔融状态下,利用大分子之间的Friedel-Crafts烷基化反应就地增容聚苯乙烯(PS)/线型低密度聚乙烯(LL-DPE)共混物。考察了AlCl3用量对高PS含量PS/LLDPE(80/20,质量比,下同)共混物的PS接枝百分比和力学性能的影响,同时研究了增容前后共混物的热性能与微观结构。结果表明,在PS/LLDPE共混物中加入0.4份的AlCl3,PS的接枝百分比较高;与简单共混体系相比,共混物力学性能与热稳定性都有所提高,同时PS也有一定程度的降解。     

Phase morphology and stability of co-continuous (PPE/PS)/PA6 and PS/PA6 blends: effect of rheology and reactive compatibilization

(PPE/PS)/PA6 and PS/PA6 blends were prepared by means of melt-extrusion. They were compatibilized using the reactive styrene-maleic anhydride copolymer with 2 wt% maleic anhydride (SMA2). The effect of compatibilization on the phase inversion and the stability of the resulting co-continuous blend structures were investigated using scanning electron microscopy, dissolution and extraction experiments. The onset of co-continuity shifted towards lower PA6 concentrations according to the change in blend viscosity ratio. The melting order of the components inside the extruder could result in a change in the observed co-continuity interval in slowly developing phase morphologies. The unmodified co-continuous blends were not stable and did break-up into a droplet/matrix type of morphology upon annealing in the melt depending on the blend composition. Although the stability of the threads during annealing improved upon compatibilization because of the lower resulting interfacial tension, the decreased possibility for recombination and coalescence during flow reduced the co-continuous region for the compatibilized blends. It is proposed that a dynamic equilibrium between break-up and recombination phenomena after the initial network formation is necessary to maintain the network structure.     

The morphology and mechanical properties of dynamic packing injection molded PP/PS blends

As a part of long-term project aimed at super polyolefin blends, in this work, we report the mechanical reinforcement and phase morphology of the immiscible blends of polypropylene (PP) and polystyrene (PS) achieved by dynamic packing injection molding (DPIM). The shear stress (achieved by DPIM) and interfacial interaction (obtained by using styrene-butadiene-styrene (SBS) as a compatibilizer) have a great effect on phase morphology thus mechanical properties. The shear-induced morphology with core in the center and oriented zone surrounding the core was observed in the cross-section areas of the samples. The phase inversion was also found to shift towards lower PS content under shear stress, at 70 wt% in the core and 30 wt% in the oriented zone, compared with 80 wt% for static samples (without shear). The tensile strength, tensile modules and impact strength were found largely increase by means of either shear stress or compatibilizer. The PS particle size is greatly reduced with adding of SBS, and the reduced particle size results in greater resistance to deformation, which causes the co-continuous structure at oriented zone change into droplet morphology. The morphology resulting from blending and processing was discussed based on effect of interfacial tension, shear rate, phase viscosity ratio and composition. The observed change of mechanical properties was explained based on the combined effect of phase morphology (droplet-matrix or co-continuous phase) and molecular orientation under shear stress.     

聚苯乙烯／聚乙烯塑料合金相容剂的研究进展

比较了ＰＳ／ＰＥ共混合金的相容剂接枝共聚物ＰＥ－ｇ－ＰＳ及嵌段共聚物ＳＥＢ对合金增容效果的贡献。叙述了嵌段共聚物用量，结构，分子量，微结构对合金增容效果的影响。     

Rheological and mechanical properties of compatibilized polystyrene/ethylene vinyl acetate blends

In this study, a blend of polystyrene (PS)/ethylene vinyl acetate (EVA) (PS/EVA, 90 : 10 wt %) was compatibilized with three different block copolymers, in which their end blocks were compatible with either styrene or EVA. The compatibilized blends with different compositions were prepared using a twin‐screw extruder and injection molded into the required test specimens. Mechanical properties of the blends, such as tensile properties and Charpy impact strength, morphology of tensile fractured surfaces, rheological properties, and thermal properties, were investigated. The results show that the interaction between the dispersed and continuous phase can be improved by the addition of a compatibilizer. Appreciable improvement in the impact strength of the blend with 15 wt % of compatibilizer C (polystyrene‐block‐polybutadiene) was observed. Its mechanical properties are comparable to those of the commercial high‐impact polystyrene, STYRON 470. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2071–2082, 2004     

Localized compatibilization in immiscible blends of thermoplastic polyurethane and ethylene‐octylene copolymer

To prepare thermoplastic polyurethane (TPU)/ethylene‐octylene copolymer (POE) blends, which are thermodynamically immiscible, maleated POE and aminated POE were incorporated as compatibilizers. Effect of addition of the compatibilizers and their contents on morphology, coalescence, and mechanical properties of TPU/POE blends were investigated. The microstructural observation revealed that the compatibilizers are located at the interface in the blends, forming a stable interfacial layer. As a result, the dispersed phase particle size was greatly reduced and tensile properties of the blends were significantly improved. POE‐NH₂ provides the blends with higher compatibility than POE‐MA. The interfacial interaction offered by the compatibilizers was found to be a function of the amount of the reactive groups grafted onto POE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

In situ compatibilization of polystyrene and polyurethane blends by using poly(styrene-co-maleic anhydride) as reactive compatibilizer

Blends of polystyrene (PS) and polyurethane (PU) elastomer were obtained by melt mixing, using poly(styrene-co-maleic anhydride) (SMA) containing 7 wt % of maleic anhydride groups as a reactive compatibilizer. Polyurethanes containing polyester flexible segments, PU-es, and polyether flexible segments, PU-et, were used. These polyurethanes were crosslinked with dicumyl peroxide or sulfur to improve their mechanical properties. The anhydride groups of SMA can react with the PU groups and form an in situ graft copolymer at the interface of the blends during their preparation. The rheological behavior was accompanied by torque versus time curves and an increase in the torque during the melt mixing was observed for all the reactive blends, indicating the occurrence of a reaction. Solubility tests, gel permeation chromatography, and scanning electronic microscopy confirmed the formation of a graft copolymer generated in situ during the melt blending. These results also indicate that this graft copolymer contains C C bond between SMA and PU chains. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2514–2524, 2001     

Miscibility,phase behavior,and mechanical properties of ternary blends of poly(vinyl chloride)/polystyrene/chlorinated polyethylene-graft-polystyrene

The effectiveness of chlorinated polyethylene-graft-polystyrene (CPE-g-PS) as a polymeric compatibilizer for immiscible poly(vinyl chloride)/polystyrene (PVC/PS) blends was investigated. The miscibility, phase behavior, and mechanical properties were studied using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), Izod impact tests, tensile tests, and scanning electron microscopy (SEM). DSC and DMA studies showed that PVC is immiscible with chlorinated polyethylene (CPE) in CPE-g-PS, whereas the PS homopolymer is miscible with PS in CPE-g-PS. The PVC/PS/CPE-g-PS ternary blends exhibit a three-phase structure: PVC phase, CPE phase, and PS phase that consisted of a PS homopolymer and PS in CPE-g-PS. The mechanical properties showed that CPE-g-PS interacts well with both PVC and PS and can be used as a polymeric compatibilizer for PVC/PS blends. CPE-g-PS can also be used as an impact modifier for both PVC and PS. SEM observations confirmed, after the addition of CPE-g-PS, improvement of the interfacial adhesion between the phases of the PVC/PS blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 995–1003, 1998     

Polystyrene and polyether polyurethane elastomer blends compatibilized by SMA: Morphology and mechanical properties

Blends of polystyrene (PS) and the polyether polyurethane elastomer (PU‐et) were prepared by melt mixing using poly(styrene‐co‐maleic anhydride) (SMA) containing 7 wt % of maleic anhydride as a compatibilizer. The polyurethane in the blends was crosslinked using dicumyl peroxide or sulfur. The content of maleic anhydride was varied in the blends through the addition of different SMA amounts. The morphology of the blends was analyzed by SEM and a drastic reduction of both the domain size and its distribution was observed with increase of the anhydride content in the blends. The morphology of the PU‐et blends also showed dependence on the crosslinker agent used for the elastomer, and larger domains were obtained for the elastomer phase crosslinked with dicumyl peroxide. The mechanical properties of the blends were evaluated by flexural and impact strength tests. The blend containing 0.5 wt % of maleic anhydride and 20 wt % of PU‐et crosslinked with sulfur showed the highest strength impact, which was three times superior to the PS strength impact, and the blends containing 20 wt % of PU‐et crosslinked with dicumyl peroxide showed the highest deflection at break independent of the anhydride content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 830–837, 2002     

Dynamic mechanical behavior of high‐density polyethylene/ethylene vinyl acetate copolymer blends: The effects of the blend ratio,reactive compatibilization,and dynamic vulcanization

The effects of the blend ratio, reactive compatibilization, and dynamic vulcanization on the dynamic mechanical properties of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends have been analyzed at different temperatures. The storage modulus of the blend decreases with an increase in the EVA content. The loss factor curve shows two peaks, corresponding to the transitions of HDPE and EVA, indicating the incompatibility of the blend system. Attempts have been made to correlate the observed viscoelastic properties of the blends with the blend morphology. Various composite models have been used to predict the dynamic mechanical data. The experimental values are close to those of the Halpin–Tsai model above 50 wt % EVA and close to those of the Coran model up to 50 wt % EVA in the blend. For the Takayanagi model, the theoretical value is in good agreement with the experimental value for a 70/30 HDPE/EVA blend. The area under the loss modulus/temperature curve (LA) has been analyzed with the integration method from the experimental curve and has been compared with that obtained from group contribution analysis. The LA values calculated with group contribution analysis are lower than those calculated with the integration method. The addition of a maleic‐modified polyethylene compatibilizer increases the storage modulus, loss modulus, and loss factor values of the system, and this is due to the finer dispersion of the EVA domains in the HDPE matrix upon compatibilization. For 70/30 and 50/50 blends, the addition of a maleic‐modified polyethylene compatibilizer shifts the relaxation temperature of both HDPE and EVA to a lower temperature, and this indicates increased interdiffusion of the two phases at the interface upon compatibilization. However, for a 30/70 HDPE/EVA blend, the addition of a compatibilizer does not change the relaxation temperature, and this may be due to the cocontinuous morphology of the blends. The dynamic vulcanization of the EVA phase with dicumyl peroxide results in an increase in both the storage and loss moduli of the blends. A significant increase in the relaxation temperature of EVA and a broadening of the relaxation peaks occur during dynamic vulcanization, and this indicates the increased interaction between the two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2083–2099, 2003     

Reactive processing compatibilization of direct injection molded polyamide‐6/poly(ethylene terephthalate) blends

Finely dispersed blends of polyamide 6 (PA‐6) and poly(ethylene terephthalate) (PET) were obtained by direct injection molding throughout the full composition range. The blends comprised a probably pure PA‐6 phase, and a PET phase that was apparently pure in PET‐rich blends and contained slight reacted PA‐6 amounts in PA‐6‐rich blends. This very complex morphology was characterized by the presence of dispersed particles at three levels and by a very large interface area/dispersed phase volume ratio. The linear ductility behavior was attributed to both the presence of reacted copolymers and the large interface area/dispersed volume ratio, and the synergism in both the Young's modulus and yield stress to the increased orientation of the blends related to that of the pure components. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 564–574, 2005     

Effects of the Competition between Grafting Reaction and Decomposition on the Miscibility and Rheological Behaviors of PS/POE Blends in the Presence of AlCl3

For increasing the compatibility of polystyrene (PS) and polyolefin elastomer (POE) blends, a Lewis acid catalyst, aluminium chloride (AlCl₃), was adopted to initiate the Friedel-Crafts alkylation reaction and induce the formation of PS-graft-POE copolymer. The dynamic mechanical and rheological tests were used to study the effects of catalyst content on the miscibility and rheological behaviors. The results showed that the viscosity increased and the MFI decreased with the increase of the catalyst content. However, when the catalyst content was overmuch, the viscosity decreased and the MFI increased. The variety of miscibility and rheological behaviors of PS/POE blends was the results of the competition between in situ graft reaction and decomposition of blending compounds.     

Effect of various added compatibilizers on the crystalline structure of polypropylene homopolymer/polybutylene terephthalate and polypropylene copolymer/polybutylene terephthalate polymer blends

Blends of semicrystalline isotactic polypropylene homopolymer and polypropylene copolymer with polybutylene terephthalate with different compatibilizers [i.e., styrene acrylonitrile, Surlyn, styrene–ethylene–butadiene styrene (SEBS), block copolymer and SEBS block copolymer grafted with maleic anhydride] were prepared by melt blending. Wide angle‐X‐ray scattering patterns of injection moldings were obtained. The crystallinity index and d‐spacing were calculated with different concentrations of different compatibilizers. X‐ray results in the structural investigation of the compatibilized blends correlated well with the different compatibilizer concentrations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1190–1193, 2003     

Reactive compatibilization of polystyrene/poly(ethylene–co–vinyl acetate) (EVA) blends

A reactive compatibilizer, mercapto‐functionalized EVA (EVASH), in combination with styrene‐butadiene block copolymer (SBS), was used to compatibilize the blends of polystyrene (PS) and ethylene–vinyl acetate copolymer (EVA). The reactive compatibilization was confirmed by the presence of insoluble material and from dynamic‐mechanical analysis. In addition to a more uniform morphology with small phase size, the compatibilization also provided excellent stabilization of the morphology, with an almost complete suppression of coarsening during annealing. As a consequence, a substantial increase on the elongation at break without significant influence on ultimate tensile strength was achieved for compatibilized blends with different compositions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 14–22, 2006     

Morphology and rheology of HDPE/LCP blends compatibilized by a novel PE-g-LCP copolymer

A novel graft copolymer (PE-g-LCP) consisting of polyethylene (PE) backbones and liquid crystalline polymer (LCP) branches was synthesized via reactive blending of an acrylic acid-functionalized PE (Escor 5000 by Exxon) with a semiflexible LCP (SBH 1 : 1 : 2 by Eniricerche S.p.A.). The crude reactive blending product (COP) was shown by investigation of the fractions soluble in boiling toluene and xylene and of the residue to contain unreacted Escor and SBH, together with the graft copolymer forming the interphase. The compatibilizing activity of COP for PE/SBH blends, compared to that of pure Escor, was investigated using two PE grades. The COP addition into 80/20 PE/SBH blends caused a much stronger reduction of the SBH droplet dimensions and morphology stabilization than did that of pure Escor. The rheological behavior of the samples showed that COP leads to a slight increase of interfacial adhesion in the melt as well and that the effect is more pronounced when lower molar mass PE grade is used as the blend matrix. Melt-spinning tests demonstrated that deformation of the SBH droplets into highly oriented fibrils can be obtained for the blends of lower molar mass PE, compatibilized with small amounts of the novel PE-g-SBH copolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2069–2077, 1999