Functionalization of polyolefins and elastomers with an oxazoline compound

The aim of this work was to graft ricinoloxazoline maleinate (OXA) onto polyethylene (PE), and onto an ethylene propylene copolymer (E/P) and styrene ethylene/butylene styrene copolymer (SEBS), by melt free radical grafting in a twin‐screw midiextruder. A study was made of the effects of the initial monomer and peroxide concentrations and of temperature on the degree of grafting, on the amount of residual monomer, and on the molecular weight. The initial monomer and peroxide concentrations were 1.5–9.0 wt % and 0.15–0.90 wt %, respectively. The grafting yield was found to increase with the initial monomer and peroxide concentrations. Grafting yields up to 2.1 wt % for PE, 2.3 wt % for E/P and 2.7 wt % for SEBS were achieved. The degree of grafting also varied considerably with the temperature. E/P and SEBS decomposed with low initial monomer and peroxide concentrations, but crosslinked with raising the initial concentrations. Polyethylene crosslinked even with low initial concentrations, but with a suitable choice of peroxide grafted polyethylene could be produced with good grafting yields and without gel formation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 877–885, 1999     

Compatibilization of polyethylene/polyamide 6 blends with oxazoline‐functionalized polyethylene and styrene ethylene/butylene styrene copolymer (SEBS)

Study was made of the compatibilization of polyethylene/polyamide 6 (PE/PA6) blends with a ricinoloxazoline maleinate grafted polyethylene and styrene ethylene/butylene styrene copolymer. The blends were prepared in a twin‐screw midiextruder, and the specimens for mechanical tests were injection molded with a mini‐injection molding machine. The effect of compatibilizing on the mechanical properties and the morphology of the blends was studied. The toughness and ductility of the blends were substantially improved as a result of the compatibilization. Simultaneously, the strength and stiffness were slightly reduced. Morphological studies showed that the particle size was reduced and the adhesion of the dispersed phase to the matrix was improved by the compatibilization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1443–1450, 1999     

Comparison of carboxylated and maleated polypropylene as reactive compatibilizers in polypropylene/polyamide‐6,6 blends

Using reactive extrusion, polypropylene is functionalized with maleic anhydride and compared on an equimolar basis to polypropylene that is functionalized with an asymmetric, carboxylic acid containing peroxide. The grafting efficiency for the asymmetric peroxide is double that obtained for the maleic anhydride system. Moreover, the asymmetric peroxide yields a functionalized material with minimal molecular weight degradation and desirable mechanical properties, relative to maleic anhydride‐grafted polypropylene. In compatibilized blends of polypropylene and nylon 6,6, the polypropylene that was functionalized with the asymmetric peroxide is found to be an improved compatibilizer compared to that of maleic anhydride‐grafted polypropylene. The differences in mechanical properties of the two different functionalized polypropylene materials and their respective blends are rationalized on the basis of the grafting efficiency, molecular weight degradation during reactive extrusion, and effect of free functional species on the ability to form graft copolymers in compatibilized blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2398–2407, 2001     

Metallocene‐based functionalized polyolefins as compatibilizers in polyolefin nanocomposites

This article reports a study of some functionalized polyolefins evaluated as compatibilizers in polyethylene nanocomposites. The functionalized polymers were prepared by direct metallocene‐mediated copolymerizations of ethylene and a functional comonomer. The prepared nanocomposites were evaluated for mechanical and barrier property enhancement. A good combination of mechanical and barrier properties was obtained with the metallocene‐based functionalized polyethylene. The toughness–stiffness balance was better than or comparable to that achieved with conventional functionalized polymers such as maleic anhydride grafted polyethylene. The results also indicated that these metallocene‐based functionalized polyolefins, when used as compatibilizers, could have relatively higher molar masses and lower functionality than those of conventional post‐reactor‐modified compatibilizers, and so the drawbacks associated with the latter could be avoided. Their inherent properties could also further improve the final nanocomposite properties. This was attributed to the more homogeneous nature of metallocene‐catalyzed polymers in comparison with post‐reactor‐modified products. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1094–1100, 2004     

Effects of olefin‐based compatibilizers on the morphology,thermal and mechanical properties of ABS/polyamide‐6 blends

In this study, commercially available epoxidized and maleated olefinic copolymers, EMA‐GMA (ethylene‐methyl acrylate‐glycidyl methacrylate) and EnBACO‐MAH (ethylene‐n butyl acrylate‐carbon monoxide‐maleic anhydride), were used at 0, 5, and 10% by weight to compatibilize the blend composed of ABS (acrylonitrile‐butadiene‐styrene) terpolymer and PA6 (polyamide 6). Compatibilizing performance of these two olefinic polymers was investigated from blend morphologies, thermal and mechanical properties as a function of blend composition, and compatibilizer loading level. Scanning electron microscopy (SEM) studies showed that incorporation of compatibilizer resulted in a fine morphology with reduced dispersed particle diameter at the presence of 5% compatibilizer. The crystallization behavior of PA6 phase in the blends was explored for selected blend compositions by differential scanning calorimetry (DSC). At high compatibilizer level a decrease in the degree of crystallization was observed. In 10% compatibilizer containing blends, formation of γ‐crystals was observed contrary to other compatibilizer compositions. The behavior of the compatibilized blend system in tensile testing showed the negative effect of using excess compatibilizer. Different trends in yield strengths and strain at break values were observed depending on compatibilizer type, loading level, and blend composition. With 5% EnBACO‐MAH, the blend toughness was observed to be the highest at room temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 926–935, 2007     

Impact-modified poly(styrene-co-acrylonitrile) blends containing both oxazoline-functionalized poly(ethene-co-1-octene) elastomers and poly(styrene-co-maleic anhydride) as compatibilizer

Blends of a poly(styrene-co-acrylonitrile) (SAN) with poly(ethene-co-1-octene) rubber (EOR) were investigated. An improved toughness–stiffness balance was obtained when adding as a compatibilizer a blend consisting of oxazoline-functionalized EOR, prepared by grafting EOR with oxazoline-functional maleinate, and poly(styrene-co-maleic anhydride) (SMA), which is miscible with SAN. Enhanced interfacial adhesion was evidenced by the improved dispersion of the EOR in the SAN matrix and the reduced glass transition temperature of the dispersed EOR phase. Morphology studies using transmission electron microscopy revealed formation of an interphase between the matrix and the rubber particles. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1685–1695, 1999     

不同热塑性弹性体增韧聚甲醛

在比较乙烯-辛烯共聚热塑性弹性体(POE)、氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)和凝胶丁腈弹性体(GNBE)增韧聚甲醛(POM)的力学性能基础上,研究了GNBE增韧POM共混物的应力一应变、断裂形貌和热稳定性。结果表明,以GNBE改性POM共混物的力学性能最好。当以质量分数为6％的酚醛树脂为增容剂时,用质量分数为20％的GNBE增韧POM,共混物缺口冲击强度为21．6kJ／m^2,扯断伸长率为133．0％,拉伸强度为33．8MPa。当GNBE质量分数为10％时,POM／GNBE共混物应变为未改性POM的2倍。试样缺口冲击断裂形貌分析表明,POM的断裂表面光滑平整,是典型的脆性断裂;而POM／GNBE共混物的断裂表面粗糙。加入质量分数为20％,的GNBE,POM／GNBE共混物在空气气氛中的热失重温度有明显的提高。     

Effectiveness of functionalized polyolefins as compatibilizers for polyethylene/wood flour composites

The effects of various types of compatibilizers on the mechanical properties of high‐density polyethylene/wood flour (HDPE/WF) composite were investigated. Functionalized polyolefins such as maleated and acrylic acid grafted polyethylenes, maleated polypropylene (PPgMA) and styrene‐ethylene/butylene‐styrene triblock copolymer (SEBSgMA) were incorporated to reduce the interfacial tension between the polyethylene matrix and the wood filler. Among them, it was found that maleated linear low‐density polyethylene (LLDPEgMA) gave maximum tensile and impact strength of the composites, presumably because of better compatibility with the HDPE matrix. Similar but less enhanced improvements in the mechanical properties, depending on the compatibilizer loading, were seen for the SEBSgMA system. Whereas acrylic acid grafted high‐density polyethylene (HDPEgAA) and maleated polypropylene (PPgMA) only slightly improved tensile modulus and tensile strength; and they both increased with increasing loadings of compatibilizers. A scanning electron microscopic study was employed to reveal the interfacial region and confirm these findings. In addition, dynamical mechanical thermal measurements also revealed the interaction between filler and matrix, and FTIR spectroscopy was used to assign the chemical fixation and the various chemical species involved at the surface of the wood fillers before and after surface treatment.     

热塑性弹性体的反应挤出动态硫化

介绍了制备热塑性动态硫化胶的反应挤出动态硫化技术的发展历史,系统论述了该技术的特点、工艺条件、硫化速率及硫化过程。     

聚碳酸酯—聚苯乙烯的反应性挤出共混研究（Ⅱ）

用ＤＳＣ进一步研究了ＰＣ／ＰＳ共混物的相容性。考察了在ＰＣ／ＰＳ混合过程中加入ＲＰＳ对机械力学性能的影响,结果表明：ＲＰＳ显示良好的增容作用,使反应性挤出共混物的拉伸强度,弯曲强度和冲击强度都高于相应的非反应性共混物。     

Reactively formed block and graft copolymers as compatibilizers for polyamide 66/PS blends

Phthalic anhydride terminated polystyrene (PS-An) and styrene-maleic anhydride copolymer (SMA) were compared as a compatibilizer at low loadings (<10 wt%) in 70/30 polyamide 66 (PA66)/polystyrene (PS) blends. Compatibilization efficiency was judged by morphology of the blends and the extent of interfacial coupling to copolymer. Fluorescent labels of functional PS's (anthracene and pyrene for PS-An and SMA, respectively) allowed the detection of small amounts of reactively formed block (PA66-b-PS) or graft copolymer (SMA-g-PA66) in the blends via gel permeation chromatography with a fluorescence detector. Extremely fast reactions giving >60% conversion in 0.5 min mixing were observed regardless of the molecular weight, the structure, and the amount of the functional PS's. Interfacial stability of the reactively formed copolymers was estimated by micelle formation in the bulk phases and the interfacial coverage, Σ. PS-An with higher molecular weight (37 kg/mol) was most effective as a compatibilizer at the interface, showing less tendency to form microemulsions by suppressing interfacial roughening. However, a large portion of PA66-b-PS from low molecular weight PS-An (10 kg/mol) and SMA-g-PA66 from random functional SMA (16 kg/mol) migrated to the bulk phase to form micelles even at <2 wt% loadings. Blends of PA66 with syndiotactic PS compatibilized with PS-An gave very similar morphology to the PA66/PS blends indicating that these conclusions apply also to PA66/sPS blends.     

Influence of in situ compatibilization on in situ formation of low‐density polyethylene/polyamide 6 blends by reactive extrusion

Low‐density polyethylene/polyamide 6 (LDPE/PA6) blends were in situ formed by reactive extrusion, in which in situ polymerization of ε‐caprolactam (CL) and in situ copolymerization of maleic anhydride grafted low‐density polyethylene (LDPE‐MA) and CL took place simultaneously. The latter reaction could be considered as in situ compatibilization, and the influence of in situ compatibilization on the morphologies, thermal properties, and rheological behaviors of the blends was investigated in this work. Scanning electron microscopy showed that the in situ compatibilization could dramatically reduce the dispersed phase sizes and narrow the size distribution. The thermal properties indicated that in differential scanning calorimetry (DSC) cooling scans, fractionated crystallization of the PA6 component was observed in all cases and was promoted with increasing the amount of LDPE‐MA. The DSC second heating scans showed the in situ compatibilization could stimulate the formation of the less stable γ‐crystalline form of PA6 in the blends. Dynamic rheological experiments revealed the in situ compatibilization had enhanced the viscosity, storage modulus, and loss modulus of the blend and reduce the corresponding slope values of the storage modulus and loss modulus. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of montmorillonite modification on the behaviour of polyamide/polystyrene blends

BACKGROUND: In nanocomposites with multiphase matrices, the addition of layered silicate not only has a reinforcing effect, but also changes significantly the morphology, namely the size and the structure of the dispersed phase. In this paper, we focus on systems with polyamide 6 (PA6)/polystyrene (PS) matrices. The effect of clay was studied over the whole composition range together with the simultaneous variation of basic parameters influencing the structure and mechanical behaviour, i.e. the clay treatment type and mixing protocol. RESULTS: At all compositions, remarkable refinements of both particulate and co‐continuous structures by clay were found. This effect and a significant shift of the glass transition temperature of blend components were more pronounced for clay with less polar treatment as a result of distinct localization of clay in the interfacial area (due to its lower affinity for PA6 phase). An increase in modulus was found at all compositions, whereas strength and toughness were enhanced at low PS contents only, as a consequence of small particle size and enhanced interfacial bonding. CONCLUSIONS: The results presented indicate that nanosilicates can effectively influence the structure and properties of PA6/PS blends. Copyright © 2008 Society of Chemical Industry     

Mechanical properties and morphology of LCP/ABS blends compatibilized with a styrene–maleic anhydride copolymer

A co‐polyester liquid crystalline polymer (LCP) was melt blended with an acrylonitrile–butadiene–styrene copolymer (ABS). LCP fibrils are formed and a distinct skin/core morphology is observed in the injection moulded samples. At higher LCP concentration (50 wt%), phase inversion occurs, where the dispersed LCP phase becomes a co‐continuous phase. While the tensile strength and Young's modulus remain unchanged with increasing LCP content up to 30 wt% LCP, a significant enhancement of the modulus at 50 wt% LCP is observed due to the formation of co‐continuous morphology. The blend modulus is lower than the values predicted by the rule of mixtures, suggesting a poor interface between the LCP droplets and ABS matrix. A copolymer of styrene and maleic anhydride (SMA) was added in the LCP/ABS blends during melt blending. It is observed that SMA has a compatibilizing effect on the blend system and an optimum SMA content exists for mechanical properties enhancement. SMA improves the interfacial adhesion, whereas excess of SMA reduces the LCP fibrillation. Copyright © 2003 Society of Chemical Industry     

热塑性弹性体的挤出和螺杆设计

概述了热塑性弹性体的挤出加工条件和挤出螺杆的设计要求,并通过分析比较指出,对于某一类热塑性能体的挤出加工来说,即便其组成材料相同而中是组分比例有差异,也很难从整体上给出统一的加工条件和螺杆设计的特定规则。     

GMA对高分子共混体系的反应增容

介绍了甲基丙烯酯缩水甘油酯类大分子增容剂制备的方法及原理,甲基丙烯酯缩水甘油酯对聚酰胺合金、聚酯合金、聚烯烃合金、生物降解高分子合金及高分子复合材料等的反应增容及原理。综述了相关的研究进展。     

Oxazoline‐containing compatibilizers for polyamide/SAN and polyamide/ABS blends

Polyamide (PA) and acrylonitrile/butadiene/styrene copolymer (ABS) may appear as a mixture in the recycled plastic stream. The incompatibility of these blends results in a blend with poor mechanical properties. The aim of this work is to partially convert the nitrile groups of the acrylonitrile/styrene copolymer (SAN) into oxazoline groups by reaction with aminoethanol (AE). Such modified SAN (SAN‐m) can react with the amine or carboxylic acid end groups of PA, and therefore used as compatibilizers for blends of PA with ABS. SAN‐m was found to reduce the SAN‐domain size in the PA/SAN‐blends. The initial acrylonitrile content of SAN‐m had a strong influence on the degree of conversion into oxazoline groups and on the compatibilizing effect. Mechanical properties of SAN‐m compatibilized PA/ABS blends were investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 449–455, 2002     

Modelling of the Nonlinear Behavior of Compatibilized Polyethylene/Polyamide Blends in Shear and Extensional Flows

We have studied the effect of the amount Φ_c of a reactive compatibilizer on the rheological properties of a polyethylene/polyamide blend, under steady shear and transient extensional flows. Here, we propose to describe the viscosity η(γ) and the first normal stress coefficient γ₁(γ) using a Carreau‐type power‐law model, which is a three‐parameter model. A single model is sufficient to express the behavior of γ₁(γ) On the other hand, the complete η(γ) curve is described by the superposition of two Carreau models, in relation to the presence of two relaxation mechanisms. Moreover, the extentional viscosity η_E(?), estimated using the end pressure drop observed in capillary flow experiments, is expressed by a two‐parameter power‐law model.     

Compatibilizing efficiency of copolymer precursors for immiscible polymer blends

An anhydride‐terminated polystyrene (PS‐b‐Anh) as a block copolymer precursor and a copolymer (PS‐co‐TMI) of styrene (St) and 3‐isopropenyl‐α,α‐dimethylbenzene isocyanate (TMI) as a graft copolymer precursor are chosen to investigate the effect of the type of the copolymer precursor on its compatibilizing and stabilizing efficiency for polymer blends. Results show that during the melt blending of the PS and PA6, the addition of PS‐b‐Anh dramatically decreases the size of the dispersed phase domains, irrespective of its molecular weight. This indicates that a diblock copolymer PS‐block‐PA6 (PS‐b‐PA6) is formed by a reaction between the terminal anhydride moiety of the PS‐b‐Anh and the terminal amine group of the PA6. When PS/PA6 (30/70) blends are annealed at 230°C for 15 min, their morphologies are much more stable in the presence of the PS‐b‐Anh block copolymer precursor than in the presence of the PS‐co‐TMI graft copolymer precursor. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ternary reactive blends of nylon‐6 matrix with dispersed rigid brittle polymer and elastomer

Except by elastomers, the toughness of nylon‐6 (N‐6) can be improved by the addition of rigid poly(styrene‐co‐maleic anhydride) (SMA). In this case, strength and stiffness are also enhanced. Combination of SMA with maleated ethylene‐propylene rubber or styrene‐ethene/butene‐styrene with a total content below 15% gives a ternary blend having a toughness level close to elastomer toughening, whereas the strength and stiffness reached at least the Nylon‐6 values. An explanation is a synergistic combination of both elastomer and rigid polymer toughening mechanisms. An opposite effect on mechanical behavior was found with high contents of both additives. Except for worsened strength and stiffness, in some cases, a higher elastomer content even did not enhance the toughness. This effect can be explained by too fine phase structure found, causing the matrix ligament dimension to be below its minimum critical value. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1404–1411, 1999