Compatible thermoplastic starch/polyethylene blends by one‐step reactive extrusion

In the presence of dicumyl peroxide (DCP), the thermal plasticization of starch and its compatibilizing modification with polyethylene was accomplished by one‐step reactive extrusion in a single‐screw extruder at the same time. Because of the formation of polyethylene‐graft‐maleic anhydride (PE‐g‐MAH) during the extrusion, it was used as the compatibilizer between the thermoplastic starch and polyethylene. The blending samples were characterized by means of thermogravimetric analysis (TGA), scanning electron microscopy (SEM), dynamic thermal mechanical analysis (DTMA) and Fourier‐transform infrared (FTIR) analysis. The experimental results showed that in the presence of DCP the addition of MAH improved the mutual dispersion of molecules in thermoplastic starch and polyethylene. From TGA, we concluded that the thermal stability of the blends with MAH was improved compared with the blends without MAH. The DTMA and FTIR results indicated that, with the addition of MAH, the compatibility of molecules between thermoplastic starch and polyethylene in the blends was improved. Copyright © 2004 Society of Chemical Industry     

Use of maleic anhydride–grafted polyethylene as compatibilizer for HDPE–tapioca starch blends: Effects on mechanical properties

Tapioca starch in both glycerol‐plasticized and in unplasticized states was blended with high‐density polyethylene (HDPE) using HDPE‐g‐maleic anhydride as the compatibilizer. The impact and tensile properties of the blends were measured according to ASTM methods. The results reveal that blends containing plasticized starch have better mechanical properties than those containing unplasticized starch. High values of elongation at break at par with those of virgin HDPE could be obtained for blends, even with high loading of plasticized starch. Morphological studies by SEM microscopy of impact‐fractured specimens of such blends revealed a ductile fracture, unlike blends with unplasticized starch at such high loadings, which showed brittle fracture, even with the addition of compatibilizer. In general, blends of HDPE and plasticized starch with added compatibilizer show better mechanical properties than similar blends containing unplasticized starch. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 863–872, 2001     

Effects of glycerol and PE‐g‐MA on morphology,thermal and tensile properties of LDPE and rice starch blends

The effects of glycerol and polyethylene‐grafted maleic anhydride (PE‐g‐MA) on the morphology, thermal properties, and tensile properties of low‐density polyethylene (LDPE) and rice starch blends were studied by scanning electron microscopy (SEM), differential scanning calorimetry, and the Instron Universal Testing Machine, respectively. Blends of LDPE/rice starch, LDPE/rice starch/glycerol, and LDPE/rice starch/glycerol/PE‐g‐MA with different starch contents were prepared by using a laboratory scale twin‐screw extruder. The distribution of rice starch in LDPE matrix became homogenous after the addition of glycerol. The interfacial adhesion between rice starch and LDPE was improved by the addition of PE‐g‐MA as demonstrated by SEM. The crystallization temperatures of LDPE/rice starch/glycerol blends and LDPE/rice starch/glycerol/PE‐g‐MA blends were similar to that of pure LDPE but higher than that of LDPE/rice starch blends. Both the tensile strength and the elongation at break followed the order of rice starch/LDPE/glycerol/PE‐g‐MA blends > rice starch/LDPE/glycerol > LDPE/rice starch blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 344–350, 2004     

Photobiodegradation of low‐density polyethylene/banana starch films

The effects of the starch content, photosensitizer content, and compatibilizer on the photobiodegradability of low‐density polyethylene (LDPE) and banana starch polymer blend films were investigated. The compatibilizer and photosensitizer used in the films were PE‐graft‐maleic anhydride (PE‐g‐MA) and benzophenone, respectively. Dried banana starch at 0–20% (w/w) of LDPE, benzophenone at 0–1% (w/w) of LDPE, and PE‐g‐MA at 10% (w/w) of banana starch were added to LDPE. The photodegradation of the blend films was performed with outdoor exposure. The progress of the photodegradation was followed by determining the carbonyl index derived from Fourier transform IR measurements and the changes in tensile properties. Biodegradation of the blend films was investigated by a soil burial test. The biodegradation process was followed by measuring the changes in the physical appearance, weight loss, and tensile properties of the films. The results showed that both photo‐ and biodegradation rates increased with increasing amounts of banana starch, whereas the tensile properties of the films decreased. The blends with higher amounts of benzophenone showed higher rates of photodegradation, although their biodegradation rates were reduced with an increase in benzophenone content. The addition of PE‐g‐MA into polymer blends led to an increase in the tensile properties whereas the photobiodegradation was slightly decreased compared to the films without PE‐g‐MA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2725–2736, 2006     

Effect of epoxy functionalized compatibilizer on the mechanical properties of low‐density polyethylene/plasticized tapioca starch blends

A series of low‐density polyethylene (LDPE) blends with varying proportions of plasticized tapioca starch have been used for the study of their mechanical properties. A functionalized epoxy resin, namely, poly(ethylene‐co‐glycidyl methacrylate) has been used as the compatibilizer. The impact and tensile properties have been measured by standard ASTM methods. The mechanical properties are seen to improve significantly with the addition of the epoxy compatibilizer, approaching values close to those of virgin LDPE. The scanning electron micrographs of the compatibilized blends show ductile failure which evidently contribute to improved mechanical properties. © 2001 Society of Chemical Industry     

Effect of compatibilizer on the crystallization,rheological, and tensile properties of LDPE/EVOH blends

The effect of the compatibilizer on the crystallization, rheological, and tensile properties of low-density polyethylene (LDPE)/ethylene vinyl alcohol (EVOH) (70/30) blends was investigated. Maleic anhydride-grafted linear low-density polyethylene (LLD-g-MAH) was used as the compatibilizer in various concentrations (from 1 to 12 phr). The interesting effect of compatibilization on the crystallization kinetics of the blends was noted, and the correlation between the morphology and the rheological and tensile properties was also discussed. Morphological analysis showed that the blends exhibited a regular and finer dispersion of the EVOH phase when LLD-g-MAH was added. Nonisothermal crystallization exotherms of the compatibilized LDPE/EVOH blends showed the retarded crystallization of the dispersed EVOH phase, which probably resulted from the constraint effect of the grafted EVOH (EVOH-g-LLD) as well as the size reduction of the EVOH domains. The blends exhibited increased melt viscosity and storage modulus and also enhanced tensile properties with the addition of LLD-g-MAH, which seemed to be attributable to both dispersed particle-size reduction and improved interfacial adhesion. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1245–1256, 1998     

The effect of zinc oxide addition on the compatibilization efficiency of maleic anhydride grafted high‐density polyethylene compatibilizer for high‐density polyethylene/polyamide 6 blends

A high‐density polyethylene with grafted maleic anhydride units has been investigated as a compatibilizer for high‐density polyethylene with polyamide 6. The material acts as an effective compatibilizer, causing a marked reduction in dispersed phase size as well as an increase in tensile strength and toughness. Compatibilizer also affects the glass‐transition temperature, crystallization kinetics, and amount of crystalline material for certain blend compositions. The addition of zinc cations, which are effective in increasing ethylene‐acid copolymer compatibilizer performance in low‐density polyethylene/polyamide blends, has little, if any, effect on compatibilizer performance in these high‐density polyethylene/polyamide blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3871–3881, 2007     

LDPE/starch blends compatibilized with PE-g-MA copolymers

In the present study, low-density polyethylene (LDPE) and plasticized starch (PLST) blends, containing different percentages of PLST, were prepared. In these blends, two different polyethylene/maleic anhydride graft (PE-g-MA) copolymers containing 0.4 and 0.8 mol % anhydride groups, respectively, were added as compatibilizers at 10 wt % PLST. The compatibilization reaction was followed by FTIR spectroscopy. The morphology of the blends was studied using scanning electron microscopy (SEM). It was found that as the amount of anhydride groups in the copolymers increases a finer dispersion of PLST in the LDPE matrix is achieved. This is reflected in the mechanical properties of the blends and especially in the tensile strength. The blends compatibilized with the PE-g-MA copolymer containing 0.8 mol % anhydride groups have a higher tensile strength, which in all blends, even in those containing 20 and 30 wt % PLST, is similar to that of pure LDPE. The biodegradation of the blends followed the exposure to activated sludge. It was found that the compatibilized blends have only a slightly lower biodegradation rate compared to the uncompatibilized blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1503–1521, 1998     

Synthesis and tensile properties of a novel composite of Chlorella and polyethylene

A novel composite of the green microalga Chlorella sp. with polyethylene (PE) was synthesized through chemical modification of PE with maleic anhydride (MA), with respect to the biological fixation of CO₂ with Chlorella sp. The interaction of Chlorella grains with a PE matrix is strikingly enhanced by the chemical modification of PE with MA. The tensile strength of a Chlorella–MA‐modified PE composite (Ch–MPE) with a Chlorella content of 40 wt % is more than 2 times greater than that of a composite derived from unmodified PE. The marked increase in tensile strength is attributed to the formation of chemical bonds between Chlorella grains and the PE matrix, from IR and SEM studies. Because of the satisfactory thermal plasticity of Ch–MPE, it can be easily shaped into plate and dishlike moldings by a heat‐pressurizing method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 812–816, 2004     

Structure and properties of composites of polyethylene or maleated polyethylene and cellulose or cellulose esters

Composites of linear low‐density poly(ethylene‐co‐butene) (PE) or maleated linear low‐density poly (ethylene‐co‐butene) (M‐PE) and cellulose (CEL), cellulose acetate (CA), cellulose acetate propionate (CAP), or cellulose acetate butyrate (CAB) were prepared in an internal laboratory mixer with 20 wt % polysaccharide. The structure and properties of the composites were studied with tensile testing, dynamic mechanical thermal analysis, differential scanning calorimetry, extraction with a selective solvent, Raman spectroscopy, and X‐ray diffraction. Composites prepared with M‐PE presented yield stress and elongation values higher than those of composites prepared with PE, showing the compatibilizer effect of maleic anhydride. Dynamic mechanical thermal analysis performed for M‐PE–CEL, M‐PE–CA, M‐PE–CAP, and M‐PE–CAB composites showed one glass‐transition temperature (T_g) close to that observed for pure M‐PE, and for M‐PE–CAP, another T_g lower than that measured for the polysaccharide was observed, indicating partial mutual solubility. These findings were confirmed by the extraction of one phase with a selective solvent, gravimetry, and Raman spectroscopy. X‐ray diffraction showed that the addition of CEL, CA, CAP, or CAB had no influence on the lattice constants of PE or M‐PE, but the introduction of the reinforcing material increased the amorphous region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:402–411, 2007     

Influence of maleic anhydride on the compatibility of thermal plasticized starch and linear low‐density polyethylene

In the presence of dicumyl peroxide, the compatibility of thermal plasticized starch/linear low‐density polyethylene (TPS/LLDPE) blends using maleic anhydride (MAH) as compatibilizer was investigated. The thermal plasticization of starch and its compatibilizing modification with LLDPE was accomplished in a single‐screw extruder at the same time. We prepared three types of blends containing different percentages of TPS and MAH. The content of MAH based on LLDPE was 0, 1, and 2 wt %, respectively. The morphology of the blends was studied by SEM. It was found that, with the addition of MAH, the blends have good interfacial adhesion and finely dispersed TPS and LLDPE phases, which is reflected in the mechanical and thermal properties of the blends. The blends containing MAH showed higher tensile strength, elongation at break, and thermal stability than those of blends without MAH. The rheologic properties of the blends demonstrated the existence of processing. Finally, the dynamic thermal mechanical analysis results indicated that, with the addition of MAH, the compatibility between TPS and LLDPE in the blends was substantially improved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 686–695, 2004     

Lamination of high‐density polyethylene by bulk photografting and the mechanism of adhesion

The photolamination of high‐density polyethylene (HDPE) by bulk photografting is described, along with a discussion of the adhesion mechanism. HDPE can be photolaminated very easily with a thin poly(acrylic acid) layer, photopolymerized from acrylic acid, with very strong adhesion obtained after a short time of UV irradiation; the adhesion failure mode is polyethylene breakage. Thicker HDPE sheets require longer irradiation times for strong adhesion. Methacrylic acid or hydroxyethyl methacrylate provides no adhesion of HDPE at all after irradiation. When glycidyl acrylate is used alone between HDPE sheets, the peel strength of the photolaminated polyethylene is only approximately 320 N/m, but when glycidyl acrylate or hydroxyethyl methacrylate is grafted with acrylic acid, very good adhesion can be obtained. It is proposed that stronger adhesion is produced by a less branched grafted chain structure, which permits much more chain entanglement. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1097–1106, 2005     

马来酸酯淀粉对热敏感型纤维的低温粘合强度

碱性条件下,以马来酸酐为酯化剂,制备了一系列具有不同取代度的马来酸酯淀粉,探讨了取代度和温度对淀粉与纤维粘合强度的影响。结果表明,淀粉经马来酸酯变性,改善了淀粉对热敏感羊毛和粘胶纤维在较低温度下的粘合强度,且随着取代度的增加,粘合强度均逐渐增大;随着温度的降低,粘合强度下降的趋势均得到缓解。马来酸酯淀粉取代度0.04,温度50⁶5℃为宜。     

溶液法聚乙烯蜡接枝马来酸酐的表征

以溶液法合成了聚乙烯蜡接枝马来酸酐(PEW-g-MAH)。利用酸碱中和滴定法测定 PEW-g-MAH 中酸酐含量,借助红外光谱分析证明接枝物的存在,探讨了取样量、滴定温度对测试结果的影响,得到表征 PEW-g-MAH 的优化实验方法。结果表明,在温度70℃下取样量达到1.5g-2g 时,能得到较稳定的接枝率测试数据。     

Effects of reactive melt mixing on the morphology and thermal behavior of linear low-density polyethylene/rubber blends

Linear low-density polyethylene (LLDPE)/polybutadiene (PB) and LLDPE/poly(styrene-b-butadiene-b-styrene) (SBS) binary blends were prepared by simple melt mixing or by reactive blending in the presence of a free-radical initiator, and for comparison, pure LLDPE was treated under the same conditions with a comparable free-radical initiator concentration. The effect of the reactive melt mixing on the morphology of the blends was studied with transmission electron microscopy, and the corresponding particle size distributions were analyzed and compared to highlight the effects of the crosslinking and grafting phenomena. Thermal properties of the obtained materials were investigated with differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA). In particular, the effect of the reactive mixing parameters on the amorphous phase mobility was investigated. The influence of the chemical modification on the crystallization behavior of LLDPE, neat and blended with PB and SBS, was also studied with dynamic and isothermal differential scanning calorimetry tests, and the isothermal thermograms were analyzed in light of the Avrami equation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactive extrusion for the synthesis of nylon 12 and maleated low‐density polyethylene blends via the anionic ring‐opening polymerization of lauryllactam

Nylon 12 was successfully synthesized in a twin‐screw extruder via the anionic ring‐opening polymerization of lauryllactam (LL). Maleated low‐density polyethylene (LDPE–MAH) was added to improve the mechanical properties of nylon 12. The in situ blends of nylon 12 and LDPE–MAH were characterized by mechanical testing and scanning electron microscopy. With increasing LDPE–MAH content, the tensile strength and flexural strength decreased, whereas the blend had improved impact strength and achieved supertoughness when the content of LDPE–MAH was 30 wt %. In the in situ formed low‐density polyethylene‐g‐PA12 copolymer, the domain of the LDPE–MAH phase was finely dispersed in the nylon 12 matrix. The good interface between the two phases demonstrated that LDPE–MAH could be used as a macromolecular activator to induce the polymerization of LL. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhancement of pro‐degradant performance in polyethylene/starch blends as a function of distribution

The effect of pro‐degradant distribution in polyethylene (PE)/starch blends on ultraviolet (UV) photo‐oxidative degradation was investigated. Two kinds of pro‐degradants, Fe and Co‐based, were used in this study. The distribution of pro‐degradants in the different phases was varied by a dual step process using a side‐feed on a reactive extruder. The variation in mechanical properties and evaluation of carbonyl groups by FTIR were conducted to investigate the effect of degradation following exposure to UV photo‐oxidative degradation. It was found that the variation in mechanical properties was higher when the pro‐degradants were distributed in the PE phase. The concentration of carbonyl groups increased as a function of UV exposure, and the concentration of carbonyl groups was higher when the pro‐degradants were distributed in the PE phase. Micro‐cracking was observed on the interface between starch and PE after adding the pro‐degradants. When the pro‐degradants were distributed in high‐density polyethylene (HDPE) phase, the micro‐cracks mainly appeared in HDPE matrix, and the density of micro‐crack was higher. In general, the function of the pro‐degradants in PE/starch blends was enhanced when their distribution was varied within HDPE phase. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Interfacial tension measurements and evidence of order in high‐density polyethylene melts

Polyethylene (PE) is a widely used product commercially. However, our knowledge is incomplete about the properties of high‐density polyethylene (HDPE) at temperatures above its melting point, where solid crystals disappear. Recently, there has been increasing evidence from rheological, differential scanning calorimetry, and NMR studies that suggests the presence of microstructural order in the bulk of PE melts. In this study, the interfacial tension of HDPE melts in contact with silicone oil was measured with a spinning drop tensiometer in the same temperature range in which phase transitions have been observed in the bulk HDPE. Anomalous temperature dependence of interfacial tension was found between 200 and 230°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4061–4067, 2003     

Rheological and thermal properties of single‐site polyethylene blends

Branched polyethylenes, low‐density polyethylenes (LDPE1 and LDPE2) or long‐chain‐branched very low density polyethylenes (VLDPE2), were blended with very low density polyethylenes containing short branches (VLDPE1 and VLDPE3). The rheological and thermal measurements of the pure copolymers and their blends (VLDPE1–LDPE1, VLDPE1–LDPE2, VLDPE1–VLDPE2, and VLDPE2–VLDPE3) were taken by controlled stress rheometry and differential scanning calorimetry, respectively. The shear‐thinning effect became stronger with increasing long‐chain‐branched polymer compositions when it was correlated with the flow behavior index, and the extent of shear thinning was different for each blend set. Stronger shear thinning and a linear composition dependence of the zero‐shear viscosity were observed for the VLDPE1–LDPE1 and VLDPE1–LDPE2 blends. These blends followed the log additivity rule, and this indicated that they were miscible in the melt at all compositions. In contrast, a deviation from the log additivity rule was observed for the VLDPE1–VLDPE2 blend compositions with 50% or less VLDPE2 and for the VLDPE3–VLDPE2 blends with 50% or more VLDPE2. The thermal properties of the blends were consistent with the rheological properties. VLDPE1–LDPE1 and VLDPE1–LDPE2 showed that these blends were characteristic of a single‐component system at all compositions, whereas the phase separation (immiscibility) was detected only for VLDPE1–VLDPE2 blends with 50% or less VLDPE2 and for VLDPE3–VLDPE2 blends with 50% or more VLDPE2. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1549–1557, 2005     

Effect of grafted maleic anhydride content and recyclability of dynamically cured maleated natural rubber/polypropylene blends

Maleated natural rubbers (MNRs) were prepared using various levels of maleic anhydride (MA) at 4, 6, 8, 10, and 12 phr. Dynamically cured 60/40 MNR/PP blends with phenolic‐modified polypropylene (Ph‐PP) compatibilizer at a loading level of 5 wt % of PP were prepared by melt mixing process using sulfur vulcanization system. The influence of the level of MA on properties of the thermoplastic vulcanizates (TPVs) was studied. It was found that the mixing torque, apparent shear stress, shear viscosity, tensile strength, and hardness properties increased with increasing levels of the MA or grafted succinic anhydride groups in the MNR molecules. This is attributed to an increase in chemical interaction and reaction between methylol groups in the Ph‐PP molecules and polar functional groups in the MNR molecules upon increasing levels of the grafted succinic anhydride groups. As a consequence, compatibilizing block copolymers of MNR and PP blocks were formed. The block copolymers were capable of compatibilizing with MNR and PP blend components via the respective blocks. Recyclability of the MNR/PP TPVs was also studied. It was found that, after processing through a number of cycles by injection molding and extrusion processing, the TPV exhibited marginal decreases in mechanical properties. This corresponded to slightly increasing size of the dispersed vulcanized rubber domains. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008